U.S. patent application number 15/525508 was filed with the patent office on 2018-10-11 for laminate and laminated glass.
This patent application is currently assigned to KURARAY CO., LTD.. The applicant listed for this patent is KURARAY CO., LTD.. Invention is credited to Koichiro ISOUE, Takuya KOBAYASHI, Takeshi KUSUDOU, Taiga YUI.
Application Number | 20180290436 15/525508 |
Document ID | / |
Family ID | 55954419 |
Filed Date | 2018-10-11 |
United States Patent
Application |
20180290436 |
Kind Code |
A1 |
YUI; Taiga ; et al. |
October 11, 2018 |
LAMINATE AND LAMINATED GLASS
Abstract
A laminate with excellent sound insulating properties and
bending strength and a laminated glass using the laminate are
provided. The laminate contains a layer A and a plurality of layers
B. The layer A includes a composition, which contains a resin
having a peak at which a tan .delta. as measured by conducting a
complex shear viscosity test under a condition at a frequency of 1
Hz in accordance with JIS K 7244-10 is maximum at -40 to 30.degree.
C. The layer A is laminated between at least two of the layers B,
in which a shear storage modulus at a temperature of 25.degree. C.
as measured by conducting a complex shear viscosity test under a
condition at a frequency of 1 Hz in accordance with JIS K 7244-10
is 1.30 MPa or more.
Inventors: |
YUI; Taiga; (Kurashiki-shi,
JP) ; ISOUE; Koichiro; (Kurashiki-shi, JP) ;
KOBAYASHI; Takuya; (Kurashiki-shi, JP) ; KUSUDOU;
Takeshi; (Kurashiki-shi, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
KURARAY CO., LTD. |
Kurashiki-shi |
|
JP |
|
|
Assignee: |
KURARAY CO., LTD.
Kurashiki-shi
JP
|
Family ID: |
55954419 |
Appl. No.: |
15/525508 |
Filed: |
November 10, 2015 |
PCT Filed: |
November 10, 2015 |
PCT NO: |
PCT/JP2015/081667 |
371 Date: |
May 9, 2017 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
E06B 3/6715 20130101;
B32B 17/10559 20130101; B32B 17/10761 20130101; B32B 2605/006
20130101; B32B 2307/734 20130101; B32B 17/1055 20130101; B32B 25/08
20130101; B32B 17/10036 20130101; B32B 17/10577 20130101; B60J
7/043 20130101; B32B 17/10678 20130101; B32B 17/10788 20130101;
B32B 25/042 20130101; B32B 17/10743 20130101; B32B 17/1077
20130101; B32B 2309/105 20130101; B32B 2307/30 20130101; B32B
17/10633 20130101; B32B 17/10605 20130101; B32B 2307/412 20130101;
B32B 2307/542 20130101; B32B 17/10165 20130101; B60J 1/001
20130101; B32B 17/10724 20130101; B60J 1/02 20130101; B32B 17/10587
20130101; E06B 3/66 20130101; E06B 3/6707 20130101; B32B 2307/102
20130101; B60J 1/08 20130101; B60J 1/18 20130101 |
International
Class: |
B32B 17/10 20060101
B32B017/10; E06B 3/67 20060101 E06B003/67; B60J 1/00 20060101
B60J001/00 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 10, 2014 |
JP |
2014-228354 |
Dec 5, 2014 |
JP |
2014-246710 |
Claims
1. A laminate, comprising: a layer A including a composition
containing a resin having a peak at which a tan .delta. as measured
by conducting a complex shear viscosity test under a condition at a
frequency of 1 Hz in accordance with JIS K 7244-10 is maximum at a
temperature of from -40 to 30.degree. C.; and a plurality of layers
B, wherein the layer A is laminated between at least two of the
layers B, and a film thickness of the layer A is 20 .mu.m or
more.
2. The laminate according to claim 1, wherein a shear storage
modulus of the laminate at a temperature of 25.degree. C. as
measured by conducting a complex shear viscosity test under a
condition at a frequency of 1 Hz in accordance with JIS K 7244-10
of 1.30 MPa or more.
3. The laminate according to claim 2, wherein the resin is a
thermoplastic elastomer.
4. The laminate according to claim 1, wherein a shear storage
modulus of the layer A at a temperature of 25.degree. C. as
measured by conducting a complex shear viscosity test at a
frequency of 1 Hz in accordance with JIS K 7244-10 is 0.6 to 3.0
MPa.
5. The laminate according to claim 1, wherein a shear storage
modulus of the layers B at a temperature of 25.degree. C. as
measured by conducting a complex shear viscosity test under a
condition at a frequency of 1 Hz in accordance with JIS K 7244-10
is 10 MPa or more.
6. The laminate according to claim 1, wherein a shear storage
modulus of the laminate at a temperature of 50.degree. C. as
measured by conducting a complex shear viscosity test under a
condition at a frequency of 1 Hz in accordance with HS K 7244-10 is
1.3 MPa or more.
7. The laminate according to claim 1, wherein when a laminated
glass prepared by using the laminate as an interlayer film for
glass is subjected to a damping test by a central exciting method,
a maximum loss factor at a frequency of 2,000 Hz and at a
temperature of 0 to 50.degree. C. is 0.2 or more.
8. The laminate according to claim 1, wherein when a laminated
glass obtained by interposing the laminate between two sheets of
glass having a width of 50 mm, a length of 300 mm, and a thickness
of 3 mm is subjected to a damping test by a central exciting method
to measure a loss factor in a tertiary mode, a width of the
temperature range where the loss factor is 0.2 or more is
15.degree. C. or more.
9. The laminate according to claim 1, wherein in interposing the
laminate between two sheets of float glass having a length of 300
mm, a width of 25 mm, and a thickness of 1.9 mm, a loss factor at a
quaternary resonance frequency as measured at 20.degree. C. by a
central exciting method is 0.2 or more, and a bending rigidity at
the quaternary resonance frequency in accordance with ISO 16940
(2008) is 150 Nm or more.
10. The laminate according to claim 1, wherein with respect to a
laminated glass prepared by interposing the laminate between
glasses having a thickness 2 mm and holding for contact bonding
under conditions at a temperature of 140.degree. C. and at a
pressure of 1 MPa for 60 minutes, a loss factor .alpha. at
20.degree. C. and at 2,000 Hz as measured by a damping test by a
central exciting method is 0.2 or more; and with respect to the
laminated glass after holding at 18.degree. C. for one month, a
ratio .beta./.alpha. of a loss factor 13 at 20.degree. C. and at
2,000 Hz as measured by a damping test by a central exciting method
to the loss factor .alpha. is 0.70 or more.
11. The laminate according to claim 10, wherein the ratio
.beta./.alpha. is 0.80 or more.
12. The laminate according to claim 10, wherein the ratio
.beta./.alpha. is 1.20 or less.
13. The laminate according to claim 1, wherein with respect to a
laminated glass containing the laminate after holding the laminated
glass at 18.degree. C. for one month, a loss factor .beta. at
20.degree. C. and at 2,000 Hz as measured by a damping test by a
central exciting method is 0.2 or more; and with respect to a
laminated glass after heating the laminated glass having been held
at 18.degree. C. for one month at 100.degree. C. for 24 hours, a
ratio .gamma./.beta. of a loss factor .gamma. at 20.degree. C. and
at 2,000 Hz as measured by a damping test by a central exciting
method to the loss factor .beta. is 0.80 or more and 1.30 or
less.
14. The laminate according to claim 13, wherein the ratio
.gamma./.beta. is 1.20 or less.
15. The laminate according to claim 13, wherein the ratio
.gamma./.beta. is 0.87 or more and 1.20 or less.
16. The laminate according to claim 1, wherein at least one of the
layers B is a layer containing at least one thermoplastic resin
selected from the group consisting of a polyvinyl acetal resin, an
ionomer resin, and an adhesive functional group-containing
polyolefin-based polymer.
17. The laminate according to claim 1, wherein the layers B are
layers containing at least one thermoplastic resin selected from
the group consisting of a polyvinyl acetal resin, an ionomer resin,
and an adhesive functional group-containing polyolefin-based
polymer.
18. The laminate according to claim 16, wherein a content of a
plasticizer in the at least one of the layers B is 50 parts by mass
or less based on 100 parts by mass of the thermoplastic resin.
19. The laminate according to claim 16, wherein a content of a
plasticizer in the at least one of the layers B is 30 parts by mass
or less based on 100 parts by mass of the thermoplastic resin.
20. The laminate according to claim 16, wherein a content of a
plasticizer in the at least one of the layers B is 25 parts by mass
or less based on 100 parts by mass of the thermoplastic resin.
21. The laminate according to claim 16, wherein a content of a
plasticizer in the at least one of the layers B is less than 20
parts by mass based on 100 parts by mass of the thermoplastic
resin.
22. The laminate according to claim 16, wherein the at least one
thermoplastic resin is a polyvinyl acetal resin, and a content of a
plasticizer in the at least one of the layers B containing the
polyvinyl acetal resin is 25 parts by mass or less based on 100
parts by mass of the polyvinyl acetal resin.
23. The laminate according to claim 18, wherein the plasticizer is
an ester-based plasticizer or an ether-based plasticizer each
having a melting point of 30.degree. C. or lower and a hydroxyl
value of 15 to 450 mgKOH/g or less.
24. The laminate according to claim 18, wherein the plasticizer is
an ester-based plasticizer or an ether-based plasticizer each being
amorphous and having a hydroxyl value of 15 to 450 mgKOH/g or
less.
25. The laminate according to claim 16, wherein the at least one
thermoplastic resin is a polyvinyl acetal resin, and a viscosity
average polymerization degree of the polyvinyl acetal resin is 100
to 5,000.
26. The laminate according to claim 16, wherein the at least one
thermoplastic resin is a polyvinyl acetal resin, which is obtained
from a polyvinyl alcohol having a viscosity average polymerization
degree of 300 to 1,000.
27. The laminate according to claim 26, wherein a content of a
polyvinyl alcohol unit of the polyvinyl acetal resin is 5 to 35 mol
%.
28. The laminate according to claim 16, wherein the at least one
thermoplastic resin is a polyvinyl acetal resin, which is polyvinyl
butyral.
29. The laminate according to claim 1, wherein the resin is a
thermoplastic elastomer, which is a block copolymer.
30. The laminate according to claim 29, wherein the block copolymer
is a block copolymer having a hard segment and a soft segment, or a
hydrogenated product of the polymer.
31. The laminate according to claim 30, wherein the block copolymer
is a block copolymer having a hard segment and a soft segment, and
a content of the hard segment in the block copolymer is 5 to 40% by
mass relative to a total amount of the block copolymer.
32. The laminate according to claim 29, wherein the block copolymer
is a block copolymer having an aromatic vinyl polymer block and an
aliphatic unsaturated hydrocarbon polymer block, or a hydrogenated
product of the polymer.
33. The laminate according to claim 32, wherein the block copolymer
is a block copolymer having an aromatic vinyl polymer block and an
aliphatic unsaturated hydrocarbon polymer block, and a content of
an aromatic vinyl monomer unit in the block copolymer is 5 to 40%
by mass relative to monomer units in total in the block
copolymer.
34. The laminate according to claim 1, wherein a height of the peak
of the resin in the layer A at which a tan .delta. is maximum is
0.5 or more.
35. The laminate according to claim 1, wherein the layer A contains
two or more thermoplastic elastomers having a different peak
temperature of the tan .delta. from each other.
36. The laminate according to claim 35, wherein the two or more
thermoplastic elastomers contain a copolymer of an aromatic vinyl
monomer and an aliphatic unsaturated monomer, or a hydrogenated
product of the copolymer.
37. The laminate according to claim 1, wherein the layer A contains
two or more thermoplastic elastomers having a different peak
temperature of the tan .delta. by 5.degree. C. or more from each
other.
38. The laminate according to claim 1, wherein the layer A includes
two or more layers, each of the two or more layers contains the
resin, which is a thermoplastic elastomer, and a peak temperature
of the tan .delta. of the thermoplastic elastomers contained
respectively in the two or more layers of the layer A is different
from each other by 5.degree. C. or more.
39. The laminate according to claim 1, wherein a peak temperature
of the tan .delta. of the layer A is -20.degree. C. or lower, and a
film thickness of the layer A is 20 to 120 .mu.m, a peak
temperature of the tan .delta. of the layer A is higher than
-20.degree. C. and -15.degree. C. or lower, and a film thickness of
the layer A is 50 to 200 .mu.m, or a peak temperature of the tan
.delta. of the layer A is higher than -15.degree. C., and a film
thickness of the layer A is 80 to 300 .mu.m.
40. The laminate according to claim 38, wherein a ratio of a total
thickness of the layers A to a total thickness of the layers B
ranges from 1/30 to 1/1.
41. The laminate according to claim 7, wherein when preparing the
laminated glass, a transmittance at a wavelength of 1,500 nm is 50%
or less.
42. The laminate according to claim 1, wherein a heat insulating
material is contained in at least one layer of either the layer A
or the layers B.
43. The laminate according to claim 1, comprising one or more heat
insulating fine particles selected from the group consisting of
tin-doped indium oxide, antimony-doped tin oxide, zinc antimonate,
lanthanum hexaboride, a metal element composite tungsten oxide, a
phthalocyanine compound, and a naphthalocyanine compound.
44. The laminate according to claim 1, wherein in a three-point
bending test of a laminated glass obtained by interposing the
laminate between two sheets of float glass having a length of 26
mm, a width of 76 mm, and a thickness of 2.8 mm, a breaking
strength measured at a temperature of 20.degree. C., an
inter-fulcrum distance of 55 mm, and a test speed of 0.25 mm/min is
0.5 kN or more.
45. A laminated glass, comprising: the laminate according to claim
1, and glass.
46. The laminated glass according to claim 45, which is a
windshield for automobile, a side glass for automobile, a sunroof
for automobile, a rear glass for automobile, or a glass for head-up
display.
47. The laminated glass according to claim 45, wherein the glass is
a thin sheet glass having a thickness of 2.8 mm or less.
48. The laminated glass according to claim 45, comprising: glass on
one side of the laminated glass and another glass on the other side
of the laminated glass, a thickness of the glass of one side is 1.8
mm or more, a thickness of the glass of the other side is 1.8 mm or
less, and a difference in thickness between the respective glasses
is 0.2 mm or more.
Description
TECHNICAL FIELD
[0001] The present invention relates to a laminate. In more detail,
the present invention relates to a laminate having excellent sound
insulating properties and bending strength with respect to a
laminated glass prepared therefrom and using a polyvinyl acetal
film. Also, the present invention relates to a laminate and a
laminated glass in which a lowering of sound insulating performance
in a high-frequency region to be caused due to a coincidence
phenomenon is suppressed and which are excellent in sound
insulating properties. Furthermore, the present invention relates
to a laminate and a laminated glass in which a time-dependent
change of sound insulating performance after preparation of the
laminated glass is small and which are excellent in stability of
sound insulating performance. In addition to the above, the present
invention relates to a laminate and a laminated glass which are
excellent in sound insulating properties over a broad temperature
range.
BACKGROUND ART
[0002] Polyvinyl acetals represented by polyvinyl butyral are
excellent in adhesion to or compatibility with various organic or
inorganic base materials and solubility in organic solvents, and
they are widely utilized as various adhesives or binders for
ceramic, various inks, paints, and the like as well as safety glass
interlayer films.
[0003] Among those, films containing a polyvinyl acetal and a
plasticizer are widely utilized as an interlayer film for laminated
glass because they are excellent in adhesion to a glass and
transparency and also in mechanical strength and flexibility (the
interlayer film for laminated glass will be hereinafter also
referred to simply as "interlayer film").
[0004] Now, it is known that though glass plates which are used for
a windowpane and the like are excellent in durability and
daylighting properties, a damping performance (tan .delta. against
bending vibration) is very small. For this reason, a lowering of
sound insulating properties to be caused due to a resonance state
occurred by vibration of a glass and incident sonic wave, namely a
coincident effect is remarkable.
[0005] In the case of constructing a glass in a place for which
sound insulation is required, such as a window, etc., there have
hitherto been employed a method of making the thickness of glass
thick to enhance a sound insulating effect by weight, and a method
of using a laminated glass prepared by laminating two or more
sheets of glass plate and an interlayer film to enhance a sound
insulating effect. In the latter method of using an interlayer
film, the sound insulating properties of a windowpane are improved
by using the interlayer film having a damping performance, and the
interlayer film also has ability of converting vibration energy
into heat energy, thereby absorbing the vibration energy.
[0006] As for a method of improving sound insulating properties,
there is proposed an interlayer film in which a polystyrene
elastomer is laminated by a plasticized polyvinyl acetal-based
resin (see, for example, Patent Literature 1). However, in the
present proposal, the bending strength is not sufficient, so that
in order to apply it in a place where an external load influences,
such as glass building materials for building and sunroofs or rear
glasses for automobile, there was room for more improvements.
[0007] In addition, there are proposed an interlayer film for
laminated glass and a laminated glass composed of polyvinyl butyral
and having certain impact resistance and sound insulating
properties (see, for example, Patent Literature 2). However, in the
present proposal, the bending strength is not sufficient, so that
in order to apply it in a place where an external load influences,
such as glass building materials for building and sunroofs or rear
glasses for automobile, there was room for more improvements.
[0008] For this reason, as properties of interlayer films for
laminated glass, besides the matters that transparency is high and
that the glass is not shattered at the time of breakage, there are
required excellent sound insulating properties against a sound
inside and outside a building, and furthermore, a certain bending
strength depending upon a construction place of windowpane.
[0009] Now, in the automobile field, for the purpose of reducing
the weight of a vehicle to improve fuel efficiency, thinning of
glass is being advanced in recent years. However, when the glass is
thinned, a coincidence threshold frequency (the coincidence
threshold frequency means a lowest frequency in a frequency region
where a coincidence effect in which the sound insulating
performance falls in a high-frequency region as compared with that
expected by the mass law) shifts toward the high-frequency side, so
that the sound insulating performance in a high-frequency region is
lowered. In the conventional laminated glasses using an interlayer
film having sound insulating properties, the above-described
phenomenon is liable to take place, so that improvements were
required. Under such circumstances, as for interlayer films for
laminated glass with improved sound insulating properties in a
high-frequency region, there were proposed a method of adjusting a
thickness of each layer of a laminate and a hydroxyl group quantity
of a polyvinyl acetal resin (see, for example, Patent Literature
3), a method of selecting a polyvinyl acetal resin and a
plasticizer in each layer such that a cloud point of a plasticizer
solution obtained from a polyvinyl acetal resin and a plasticizer
constituting each layer of a laminate is a prescribed relation
(see, for example, Patent Literature 4), a method of crosslinking a
sound insulating layer (see, for example, Patent Literature 5), a
method of using a plasticizer such that a difference in an SP value
from a polyvinyl acetal resin is a prescribed value or more (see,
for example, Patent Literature 6), and the like. However, in any of
the methods, an improvement of the sound insulating properties in a
high-frequency region was not sufficient.
[0010] Meanwhile, in preparing a laminated glass, a heat treatment
using an autoclave or the like is conducted. However, when a
general multi-layered interlayer film is heated, an interlayer
migration of plasticizer occurs, so that distribution of the
plasticizer changes. After preparation of the laminated glass, the
distribution of the plasticizer turns to the original state with a
lapse of time at ordinary temperature; however, till then, in view
of the fact that the plasticizer migrates into other layer,
physical properties, such as sound insulating properties, etc.,
become instable. For that reason, in the case of preparing a
laminated glass using the conventional multi-layered interlayer
film, it was needed to hold the prepared laminated glass for a
certain period of time until the sound insulating performance is
stabilized. This holding time is problematic from the viewpoint of
productivity, and an improvement was required in laminated glasses
having a sound insulating function.
[0011] On the other hand, in recent years, in the automobile field
or construction field, for the purpose of reducing the weight,
thinning of a laminated glass has been required. However, in
contemplating to make the laminated glass thin, there was
encountered such a problem that the sound insulating properties of
the laminate glass are lowered. For that reason, there was required
a laminated glass capable of realizing the sound insulating
properties at a high level even by conducting thinning.
[0012] In addition, even in interlayer films for laminated glass
having high sound insulating properties at ordinary temperature,
there was involved such a problem that the sound insulating
properties are largely lowered in the summer season or winter
season. For that reason, a laminated glass capable of revealing the
sound insulating properties at a high level over a broad
temperature range was required.
[0013] Besides, there are proposed those in which a sound
insulating layer is constituted of three layers of PVB film (see,
for example, Patent Literature 3, etc.) and the like. However, in
all of them, the sound insulating properties could not be revealed
at a high level over a broad temperature range.
CITATION LIST
Patent Literature
[0014] Patent Literature 1: JP 2007-91491A
[0015] Patent Literature 2: WO 2005/018969A
[0016] Patent Literature 3: JP 2013-107821A
[0017] Patent Literature 4: JP 2013-032260A
[0018] Patent Literature 5: JP 2012-214305A
[0019] Patent Literature 6: WO 2012/043817A
SUMMARY OF INVENTION
Technical Problem
[0020] The present invention solves the above-described problems.
That is, a first object of the present invention is to provide a
laminate with excellent sound insulating properties and a laminated
glass using the same.
[0021] The present invention solves the above-described problems.
That is, a second object of the present invention is to provide a
laminate with excellent sound insulating properties and bending
strength and a laminated glass using the same.
[0022] In addition, a third object of the present invention is to
provide a laminate and a laminated glass in which a lowering of
sound insulating performance in a high-frequency region to be
caused due to a coincidence phenomenon is suppressed and which are
excellent in sound insulating properties.
[0023] Furthermore, a fourth object of the present invention is to
provide a laminate and a laminated glass in which a time-dependent
change of sound insulating performance after preparation of the
laminated glass is small and which are excellent in stability of
sound insulating performance.
[0024] In addition to the above, a fifth object of the present
invention is to provide a laminate and a laminated glass which are
excellent in sound insulating properties over a broad temperature
range.
Solution to Problem
[0025] The present invention is concerned with a laminate
comprising a layer A including a composition containing a resin
having a peak at which a tan .delta. as measured by conducting a
complex shear viscosity test under a condition at a frequency of 1
Hz in accordance with JIS K 7244-10 is maximum, in the range of
from -40 to 30.degree. C.; and a plurality of layers B, the layer A
being laminated between at least two of the layers B.
[0026] Furthermore, in the present invention, the laminate is
preferably a laminate in which a shear storage modulus at a
temperature of 25.degree. C. as measured by conducting a complex
shear viscosity test under a condition at a frequency of 1 Hz in
accordance with JIS K 7244-10 is 1.30 MPa or more.
[0027] Furthermore, in the present invention, the laminate is
preferably a laminate in which the resin is a thermoplastic
elastomer.
[0028] Furthermore, in the present invention, the laminate is
preferably a laminate in which a shear storage modulus of the layer
A at a temperature of 25.degree. C. as measured by conducting a
complex shear viscosity test at a frequency of 1 Hz in accordance
with JIS K 7244-10 is 0.6 to 3.0 MPa.
[0029] Furthermore, in the present invention, the laminate is
preferably a laminate in which a shear storage modulus of the
layers B at a temperature of 25.degree. C. as measured by
conducting a complex shear viscosity test under a condition at a
frequency of 1 Hz in accordance with JIS K 7244-10 is 10 MPa or
more.
[0030] Furthermore, in the present invention, the laminate is
preferably a laminate in which a shear storage modulus of the
laminate at a temperature of 50.degree. C. as measured by
conducting a complex shear viscosity test under a condition at a
frequency of 1 Hz in accordance with JIS K 7244-10 is 1.3 MPa or
more.
[0031] Furthermore, in the present invention, the laminate is
preferably a laminate in which when a laminated glass prepared by
using the laminate as an interlayer film for glass is subjected to
a damping test by a central exciting method, a maximum loss factor
at a frequency of 2,000 Hz and at a temperature of 0 to 50.degree.
C. is 0.2 or more.
[0032] Furthermore, in the present invention, the laminate is
preferably a laminate in which when a laminated glass obtained by
interposing the laminate between two sheets of glass having a width
of 50 mm, a length of 300 mm, and a thickness of 3 mm is subjected
to a damping test by a central exciting method to measure a loss
factor in a tertiary mode, a width of the temperature range where
the loss factor is 0.2 or more is 15.degree. C. or more.
[0033] Furthermore, in the present invention, the laminate is
preferably a laminate in which in interposing the laminate between
two sheets of float glass having a length of 300 mm, a width of 25
mm, and a thickness of 1.9 mm, a loss factor at a quaternary
resonance frequency as measured at 20.degree. C. by a central
exciting method is 0.2 or more, and a bending rigidity at the
quaternary resonance frequency in accordance with ISO 16940 (2008)
is 150 Nm or more.
[0034] Furthermore, in the present invention, the laminate is
preferably a laminate in which with respect to a laminated glass
prepared by interposing the laminate between glasses having a
thickness 2 mm and holding for contact bonding under conditions at
a temperature of 140.degree. C. and at a pressure of 1 MPa for 60
minutes, a loss factor .alpha. at 20.degree. C. and at 2,000 Hz as
measured by a damping test by a central exciting method is 0.2 or
more; and with respect to the laminated glass after holding at
18.degree. C. for one month, a ratio .beta./.alpha. of a loss
factor .beta. at 20.degree. C. and at 2,000 Hz as measured by a
damping test by a central exciting method to the loss factor
.alpha. is 0.70 or more.
[0035] Furthermore, in the present invention, the laminate is
preferably a laminate in which the ratio .beta./.alpha. is 0.80 or
more.
[0036] Furthermore, in the present invention, the laminate is
preferably a laminate in which the ratio .beta./.alpha. is 1.20 or
less.
[0037] Furthermore, in the present invention, the laminate is
preferably a laminate in which with respect to a laminated glass
containing the laminate after holding the laminated glass at
18.degree. C. for one hour, a loss factor .beta. at 20.degree. C.
and at 2,000 Hz as measured by a damping test by a central exciting
method is 0.2 or more; and with respect to a laminated glass after
heating the laminated glass having been held at 18.degree. C. for
one month at 100.degree. C. for 24 hours, a ratio .gamma./.beta. of
a loss factor .gamma. at 20.degree. C. and at 2,000 Hz as measured
by a damping test by a central exciting method to the loss factor
.beta. is 0.80 or more and 1.30 or less.
[0038] Furthermore, in the present invention, the laminate is
preferably a laminate in which the ratio .gamma./.beta. is 1.20 or
less.
[0039] Furthermore, in the present invention, the laminate is
preferably a laminate in which the ratio .gamma./.beta. is 0.87 or
more and 1.20 or less.
[0040] Furthermore, in the present invention, the laminate is
preferably a laminate in which at least one of the layers B is a
layer containing at least one thermoplastic resin selected from the
group consisting of a polyvinyl acetal resin, an ionomer resin, and
an adhesive functional group-containing polyolefin-based
polymer.
[0041] Furthermore, in the present invention, the laminate is
preferably a laminate in which the layers B are a layer containing
at least one thermoplastic resin selected from the group consisting
of a polyvinyl acetal resin, an ionomer resin, and an adhesive
functional group-containing polyolefin-based polymer.
[0042] Furthermore, in the present invention, the laminate is
preferably a laminate in which a content of a plasticizer in the
layer or layers B is 50 parts by mass or less based on 100 parts by
mass of the thermoplastic resin.
[0043] Furthermore, in the present invention, the laminate is
preferably a laminate in which a content of a plasticizer in the
layer or layers B is 30 parts by mass or less based on 100 parts by
mass of the thermoplastic resin.
[0044] Furthermore, in the present invention, the laminate is
preferably a laminate in which a content of a plasticizer in the
layer or layers B is 25 parts by mass or less based on 100 parts by
mass of the thermoplastic resin.
[0045] Furthermore, in the present invention, the laminate is
preferably a laminate in which a content of a plasticizer in the
layer or layers B is less than 20 parts by mass based on 100 parts
by mass of the thermoplastic resin.
[0046] Furthermore, in the present invention, the laminate is
preferably a laminate in which a content of a plasticizer in the
layer or layers B containing a polyvinyl acetal resin is 25 parts
by mass or less based on 100 parts by mass of the polyvinyl acetal
resin.
[0047] Furthermore, in the present invention, the laminate is
preferably a laminate in which the plasticizer is an ester-based
plasticizer or an ether-based plasticizer each having a melting
point of 30.degree. C. or lower and a hydroxyl value of 15 to 450
mgKOH/g or less.
[0048] Furthermore, in the present invention, the laminate is
preferably a laminate in which the plasticizer is an ester-based
plasticizer or an ether-based plasticizer each being amorphous and
having a hydroxyl value of 15 to 450 mgKOH/g or less.
[0049] Furthermore, in the present invention, the laminate is
preferably a laminate in which a viscosity average polymerization
degree of the polyvinyl acetal resin is 100 to 5,000.
[0050] Furthermore, in the present invention, the laminate is
preferably a laminate in which a viscosity average polymerization
degree of polyvinyl alcohol used for synthesis of the polyvinyl
acetal resin is 300 to 1,000.
[0051] Furthermore, in the present invention, the laminate is
preferably a laminate in which a content of a vinyl alcohol unit of
the polyvinyl acetal resin is 5 to 35 mol %.
[0052] Furthermore, in the present invention, the laminate is
preferably a laminate in which the polyvinyl acetal resin is
polyvinyl butyral.
[0053] Furthermore, in the present invention, the laminate is
preferably a laminate in which the thermoplastic elastomer is a
block copolymer.
[0054] Furthermore, in the present invention, the laminate is
preferably a laminate in which the block copolymer is a block
copolymer having a hard segment and a soft segment, or a
hydrogenated product of the polymer.
[0055] Furthermore, in the present invention, the laminate is
preferably a laminate in which a content of the hard segment in the
block copolymer is 5 to 40% by mass relative to the total amount of
the block copolymer.
[0056] Furthermore, in the present invention, the laminate is
preferably a laminate in which the block copolymer is a block
copolymer having an aromatic vinyl polymer block and an aliphatic
unsaturated hydrocarbon polymer block, or a hydrogenated product of
the polymer.
[0057] Furthermore, in the present invention, the laminate is
preferably a laminate in which a content of an aromatic vinyl
monomer unit in the block copolymer is 5 to 40% by mass relative to
the whole of the monomer units in the block copolymer.
[0058] Furthermore, in the present invention, the laminate is
preferably a laminate having the layer A in which a height of the
peak at which a tan .delta. is maximum is 0.5 or more.
[0059] Furthermore, in the present invention, the laminate is
preferably a laminate in which the layer A contains two or more
thermoplastic elastomers having a different peak temperature of the
tan .delta. from each other.
[0060] Furthermore, in the present invention, the laminate is
preferably a laminate in which the at least two thermoplastic
elastomers having a different peak temperature of the tan .delta.
from each other contain a copolymer of an aromatic vinyl monomer
and an aliphatic unsaturated monomer, or a hydrogenated product of
the copolymer.
[0061] Furthermore, in the present invention, the laminate is
preferably a laminate in which the layer A contains two or more
thermoplastic elastomers having a different peak temperature of the
tan .delta. by 5.degree. C. or more from each other.
[0062] Furthermore, in the present invention, the laminate is
preferably a laminate in which the layer A includes two or more
layers, and a peak temperature of the tan .delta. of thermoplastic
elastomers contained respectively in the at least two layers of the
layer A is different from each other by 5.degree. C. or more.
[0063] Furthermore, in the present invention, the laminate is
preferably a laminate in which a peak temperature of the tan
.delta. of the layer A is -20.degree. C. or lower, and a film
thickness of the layer A is 20 to 120 .mu.m, a peak temperature of
the tan .delta. of the layer A is higher than -20.degree. C. and
-15.degree. C. or lower, and a film thickness of the layer A is 50
to 200 .mu.m, or a peak temperature of the tan .delta. of the layer
A is higher than -15.degree. C., and a film thickness of the layer
A is 80 to 300 .mu.m.
[0064] Furthermore, in the present invention, the laminate is
preferably a laminate in which a ratio of a sum total of the
thickness of the layers A to a sum total of the thickness of the
layers B ((sum total of the thickness of the layers A)/(sum total
of the thickness of the layers B)) is in the range of from 1/30 to
1/1.
[0065] Furthermore, in the present invention, the laminate is
preferably a laminate in which when preparing a laminated glass, a
transmittance at a wavelength of 1,500 nm is 50% or less.
[0066] Furthermore, in the present invention, the laminate is
preferably a laminate in which a heat insulating material is
contained in at least one layer of either the layers A or the
layers B.
[0067] Furthermore, in the present invention, the laminate is
preferably a laminate in which one or more heat insulating fine
particles selected from the group consisting of tin-doped indium
oxide, antimony-doped tin oxide, zinc antimonate, lanthanum
hexaboride, a metal element composite tungsten oxide, a
phthalocyanine compound, and a naphthalocyanine compound.
[0068] Furthermore, in the present invention, the laminate is
preferably a laminate in which in a three-point bending test of a
laminated glass obtained by interposing the laminate between two
sheets of float glass of 26 mm in length.times.76 mm in
width.times.2.8 mm in thickness, a breaking strength (temperature:
20.degree. C., inter-fulcrum distance: 55 mm, test speed: 0.25
mm/min) is 0.5 kN or more.
[0069] The present invention is concerned with a laminated glass
including a constitution of the laminate in the inside thereof.
[0070] Furthermore, in the present invention, the laminated glass
is preferably a laminated glass which is a windshield for
automobile, a side glass for automobile, a sunroof for automobile,
a rear glass for automobile, or a glass for head-up display.
[0071] Furthermore, in the present invention, the laminated glass
is preferably a laminated glass in which the glass constituting the
laminated glass is a thin sheet glass having a thickness of 2.8 mm
or less.
[0072] Furthermore, in the present invention, the laminated glass
is preferably a laminated glass in which a thickness of the glass
of one side is 1.8 mm or more, a thickness of the glass of the
other side is 1.8 mm or less, and a difference in thickness between
the respective glasses is 0.2 mm or more.
Advantageous Effects of Invention
[0073] By using the laminate according to the present invention, as
a first effect, a laminated glass with excellent sound insulating
characteristics and bending strength can be prepared. According to
this, it becomes possible to apply the laminated glass in a place
where an external load influences, and sound insulating properties
are required, such as glass building materials for building and
sunroofs or rear glasses for automobile. Meanwhile, in view of the
fact that the laminated glass is excellent in bending strength, it
also becomes possible to make a glass to be used for the laminated
glass thin, and weight reduction of the laminated glass can be
realized without impairing the strength of the laminated glass.
[0074] In addition, according to the present invention, as a second
effect, it is possible to prepare a laminate and a laminated glass
in which a lowering of sound insulating performance in a
high-frequency region to be caused due to a coincidence phenomenon
is suppressed and which are excellent in sound insulating
properties.
[0075] Furthermore, according to the present invention, as a third
effect, it is possible to provide a laminate and a laminated glass
in which a time-dependent change of sound insulating performance
after preparation of the laminated glass is small and which are
excellent in stability of sound insulating performance.
[0076] In addition to the above, according to the present
invention, as a fourth effect, it is possible to provide a laminate
and a laminated glass which are excellent in sound insulating
properties over a broad temperature range.
BRIEF DESCRIPTION OF DRAWINGS
[0077] FIG. 1 is an example of a cross-sectional view of a
constitution of a laminate.
[0078] FIG. 2 is an example of measurement results of shear storage
modulus and tan .delta. of a laminate.
DESCRIPTION OF EMBODIMENTS
[0079] Embodiments of the present invention are hereunder
described, but it should not be construed that the present
invention is limited to the present embodiments.
[0080] The laminate of the present invention is a laminate
comprising the layer A laminated between the at least two layers
B.
[Layer A]
[0081] A response of stress when distortion of a sinusoidal
waveform is applied to a viscoelastic body is defined as a complex
modulus. At this time, a phase shift is generated between the
sinusoidal wave of distortion to be applied and the sinusoidal wave
of stress obtained as the response, and this phase difference is
expressed in terms of .delta.. In addition, the complex modulus is
expressed in terms of an equality using a complex number, and a
real part of the complex modulus is called a storage modulus,
whereas an imaginary part thereof is called a loss modulus. In
particular, in the case of measuring dynamic viscoelastic
characteristics of a viscoelastic body in a shear mode, they are
called a complex shear modulus, a shear storage modulus, and a
shear loss modulus, respectively. A value obtained by dividing the
loss modulus by the storage modulus is called a loss tangent and
expressed in terms of tan .delta.. The value of tan .delta. is a
loss factor, and it is meant that the higher the loss factor at a
certain temperature, the higher the sound insulating properties at
that temperature.
[0082] When the value of tan .delta. in a construct composed of two
kinds of viscoelastic bodies is plotted at every measuring
temperature, in general, a bimodal curve is revealed as shown in
FIG. 2. A peak (maximum point) on the low-temperature side is a
peak derived from a relatively soft viscoelastic body, and a peak
(maximum point) on the high-temperature side is a peak derived from
a relatively hard viscoelastic body. In the present embodiment, the
peak on the low-temperature side is a peak derived from the layer A
(in the case where plural peaks are present, the instant peak means
a highest peak), and the peak on the high-temperature side is a
peak derived from the layer B.
[0083] The layer A which is used for the laminate of the present
invention includes a composition containing a specified resin. By
constituting the layer A by the composition containing a specified
resin, the sound insulating properties of the resulting laminate
can be improved.
(Peak Temperature of Tan .delta.)
[0084] The resin to be contained in the layer A which is used in
the present invention has a peak at which a tan .delta. as measured
by conducting a complex shear viscosity test under a condition at a
frequency of 1 Hz in accordance with JIS K 7244-10 is maximum at
-40.degree. C. or higher, more preferably at -30.degree. C. or
higher, and still more preferably at -20.degree. C. or higher. In
addition, the resin to be contained in the layer A has a peak at
which the tan .delta. is maximum at 30.degree. C. or lower, more
preferably at 10.degree. C. or lower, and still more preferably at
0.degree. C. or lower. When the peak at which the tan .delta. of
the resin to be contained in the layer A is maximum is present at
30.degree. C. or lower, excellent sound insulating properties are
exhibited in a temperature region where the layer A is used as a
laminated glass. When the peak at which the tan .delta. of the
resin to be contained in the layer A is maximum is present at
-40.degree. C. or higher, the shear storage modulus of the layer A
is a suitable value, and the sound insulating properties in a
high-frequency region are excellent.
[0085] Specifically, the tan .delta. of the resin to be contained
in the layer A is measured by the method described in the Examples
as described later. As a method of adjusting the peak at which the
tan .delta. of the resin to be contained in the layer A is maximum
to -40 to 30.degree. C., there are, for example, exemplified a
method of using a thermoplastic elastomer having a content of a
hard segment (for example, an aromatic vinyl polymer block) of 5%
by mass or more and 40% by mass or less relative to the total
amount of a block copolymer (for example, a block copolymer having
an aromatic vinyl polymer block and an aliphatic unsaturated
hydrocarbon polymer block); a method of controlling a structure of
a soft segment, for example, allowing a content ratio of a branched
monomer in a conjugated diene block, a ratio of a 1,4-bond, a
1,2-bond, and a 3,4-bond, or a hydrogenation ratio to fall within
an appropriate range; and the like.
[0086] With respect to the content ratio of the branched monomer,
for example, in the case of a copolymer of butadiene and isoprene,
a content ratio of an isoprene unit in the copolymer is preferably
20% by mass or more, and more preferably 50% by mass or more. With
respect to the ratio of the 1,4-bond, the 1,2-bond, and the
3,4-bond, a ratio of a sum total of the 1,2-bond and the 3,4-bond
is preferably 20 mol % or more, more preferably 30 mol % or more,
and still more preferably 40 mol % or more, and especially
preferably 50 mol % or more relative to a sum total of the
1,4-bond, the 1,2-bond, and the 3,4-bond. The hydrogenation ratio
is preferably 60 mol % or more, more preferably 65 mol % or more,
still more preferably 70 mol % or more, and especially preferably
75 mol % or more.
[0087] The layer A which is used in the present invention may be
composed of only a specified resin or may be one including the
resin and other component. The layer A has a peak at which a tan
.delta. as measured by conducting a complex shear viscosity test
under a condition at a frequency of 1 Hz in accordance with JIS K
7244-10 is maximum preferably at -40.degree. C. or higher, more
preferably at -30.degree. C. or higher, and still more preferably
at -20.degree. C. or higher. In addition, the layer A has a peak at
which the tan .delta. is maximum at 30.degree. C. or lower, more
preferably at 10.degree. C. or lower, and still more preferably at
0.degree. C. or lower. When the peak at which the tan .delta. of
the layer A is maximum is present at 30.degree. C. or lower,
excellent sound insulating properties are liable to be exhibited in
a temperature region where the layer A is used as a laminated
glass. When the peak at which the tan .delta. of the layer A is
maximum is present at -40.degree. C. or higher, the shear storage
modulus of the layer A is a suitable value, and when formed as a
laminated glass, the resulting laminated glass tends to become
excellent in sound insulating properties in a high-frequency
region.
[0088] Specifically, the tan .delta. of the layer A is measured by
the method described in the Examples as described later. As a
method of adjusting the peak at which the tan .delta. of the layer
A is maximum to -40 to 30.degree. C., there are, for example,
exemplified a method of using, as the resin to be contained in the
layer A, a resin having a peak at which a tan .delta. as measured
by conducting a complex shear viscosity test under a condition at a
frequency of 1 Hz in accordance with JIS K 7244-10 is maximum at
-40 to 30.degree. C.; and the like.
[0089] As described later, it is preferred that the laminate of the
present invention contains a thermoplastic elastomer in the layer
A. Then, it is preferred that the layer A containing a
thermoplastic elastomer contains two or more thermoplastic
elastomers having a different peak temperature of tan .delta. (a
temperature of the peak at which the tan .delta. is maximum) from
each other. The sound insulating properties become high in the
vicinity of a specified temperature related to the peak temperature
of tan .delta., and hence, in view of the fact that the layer A
containing a thermoplastic elastomer contains two or more
thermoplastic elastomers having a different peak temperature of tan
.delta. from each other, the sound insulating properties can be
enhanced over a broader temperature range.
[0090] In addition, in order to reveal suitable sound insulating
characteristics in the vicinity of room temperature, it is
preferred to regulate the peak temperature of tan .delta. in the
complex shear viscoelasticity test under a condition at a frequency
of 1 Hz to 0.degree. C. or lower, more preferably -5.degree. C. or
lower, and especially preferably -10.degree. C. or lower. In that
case, by using an elastomer having a physical or chemical
crosslinking site, a slippage of glasses at a high temperature at
which the laminated glass is exposed can be suppressed. In
addition, by using a thermoplastic elastomer as the elastomer, it
is possible to conduct the film formation by a coextrusion method,
and hence, such is especially preferred.
[0091] In addition, the at least two thermoplastic elastomers
having a different peak temperature of tan .delta. from each other
are preferably a thermoplastic elastomer including a copolymer of
an aromatic vinyl monomer and a vinyl monomer or a conjugated diene
monomer, or a hydrogenated product of the copolymer. The copolymer
of an aromatic vinyl monomer and a vinyl monomer or a conjugated
diene monomer, or the hydrogenated product of the copolymer has
suitable viscoelasticity. For that reason, in view of the fact that
such a thermoplastic elastomer is included in the laminate,
suitable sound insulating properties are revealed.
[0092] Furthermore, by forming a laminate having the layer A
containing a thermoplastic elastomer as an internal layer and a
layer B serving as an adhesive layer as each of outermost layers,
an interlayer film for laminated glass having improved sound
insulating properties while improving adhesion to a glass can be
provided.
[0093] In addition to the above, in the two or more thermoplastic
elastomers having a different peak temperature of tan .delta. from
each other, which are included in the layer A containing a
thermoplastic elastomer, a difference in the peak temperature of
tan .delta. is preferably 5.degree. C. or more, more preferably
10.degree. C. or more, and still more preferably 15.degree. C. or
more. When the difference in the peak temperature of tan .delta. is
less than 5.degree. C., a width of the temperature range where the
loss factor is 0.2 or more is narrow, so that the sound insulating
properties over a broad temperature range tend to be hardly
revealed.
[0094] Furthermore, in the laminate of the present invention, when
the layer A containing a thermoplastic elastomer is composed of two
or more layers, a difference between the peak temperature of tan
.delta. of the thermoplastic elastomer to be contained in at least
one layer A and the peak temperature of tan .delta. of the
thermoplastic elastomer to be contained in the other layer A is
preferably 5.degree. C. or more, more preferably 10.degree. C. or
more, and still more preferably 15.degree. C. or more. When the
difference in the peak temperature of tan .delta. between the
thermoplastic elastomers to be contained in the at least two layers
A is less than 5.degree. C., a width of the temperature range where
the loss factor is 0.2 or more is narrow, so that the sound
insulating properties over a broad temperature range tend to be
hardly revealed.
(Peak Height of Tan .delta.)
[0095] In the layer A which is used in the present invention, a
height of at least one peak of tan .delta. as measured by
conducting a complex shear viscosity test under a condition at a
frequency of 1 Hz in accordance with JIS K 7244-10 is preferably
0.5 or more, more preferably 0.75 or more, and still more
preferably 0.8 or more. In addition, from the viewpoint of further
improving the sound insulating properties, in the layer A, the
height of the peak at which the tan .delta. is maximum is
preferably 1.0 or more, more preferably 1.3 or more, and still more
preferably 1.5 or more. In the layer A, when the height of the peak
of tan .delta. is less than 0.5, the sound insulating properties of
the resulting interlayer film for laminated glass tend to become
low.
[0096] As a method of obtaining the layer A satisfying the
above-described conditions, there is exemplified a method of using,
for the layer A, a resin in which a height of at least one peak of
tan .delta. as measured by conducting a complex shear viscosity
test under a condition at a frequency of 1 Hz in accordance with
JIS K 7244-10 is 0.5 or more.
[0097] In the resin to be contained in the layer A which is used in
the present invention, the height of at least one peak of tan
.delta. as measured by conducting a complex shear viscosity test
under a condition at a frequency of 1 Hz in accordance with JIS K
7244-10 is preferably 0.5 or more, more preferably 0.75 or more,
and still more preferably 0.8 or more. In addition, from the
viewpoint of further improving the sound insulating properties, in
the resin to be contained in the layer A, the height of the peak at
which the tan .delta. is maximum is preferably 1.0 or more, more
preferably 1.3 or more, and still more preferably 1.5 or more. In
the resin to be contained in the layer A, when the height of the
peak of tan .delta. is less than 0.5, the sound insulating
properties of the resulting interlayer film for laminated glass
tend to become low.
[0098] As a method of regulating the height of the peak of tan
.delta. in the resin to be contained in the layer A to 0.5 or more,
there are, for example, exemplified a method of using a
thermoplastic elastomer having a content of a hard segment (for
example, an aromatic vinyl polymer block) of 40% by mass or less,
and more preferably 30% by mass or less relative to the total
amount of block copolymers (for example, a block copolymer having
an aromatic vinyl polymer block and an aliphatic unsaturated
hydrocarbon polymer block); a method of using a thermoplastic
elastomer having a soft segment in which a ratio of a branched
diene (for example, isoprene) component in copolymerization of a
linear diene (for example, butadiene) and a branched diene
(isoprene) is 10% by mass or more, and more preferably 30% by mass
or more; a method of using a thermoplastic elastomer having a soft
segment in which a ratio of a content of a 1,2-bond relative to a
sum total of a content of a 1,4-bond and a content of a 1,2-bond in
a diene monomer is 20 mol % or more, and more preferably 40 mol %
or more; and besides, a method of adjusting the kinds of monomers
constituting a hard segment or a soft segment, binding forms, glass
transition temperatures of the respective segments per se, and the
like; and the like.
[0099] From the viewpoint of further improving the sound insulating
properties, the glass transition temperature of the resin to be
contained in the layer A is preferably 10.degree. C. or lower, and
more preferably -5.degree. C. or lower. A lower limit of the glass
transition temperature of the resin to be contained in the layer A
is not particularly limited, and the glass transition temperature
of the resin to be contained in the layer A is preferably
-50.degree. C. or higher, and more preferably -40.degree. C. or
higher. Differential scanning calorimetry (DSC) may be adopted for
the measurement method of glass transition temperature.
(Shear Storage Modulus)
[0100] From the viewpoint of preparing a laminated glass in which a
time-dependent change of sound insulating properties is small or
preparing a laminate with excellent sound insulating properties
over a broad temperature range, a shear storage modulus of the
layer A which is used in the present invention (or the resin to be
contained in the layer A) at a temperature of 25.degree. C. as
measured by conducting a complex shear viscosity test at a
frequency of 1 Hz in accordance with JIS K 7244-10 is preferably
0.1 MPa or more, more preferably 0.2 MPa or more, and still more
preferably 0.3 MPa or more. In addition, from the above-described
viewpoint, the shear storage modulus of the layer A is preferably
5.0 MPa or less, more preferably 4.0 MPa or less, still more
preferably 3.0 MPa or less, yet still more preferably 1.0 MPa or
less, especially preferably 0.8 MPa or less, and particularly
preferably 0.6 MPa or less. When the shear storage modulus of the
layer A is less than 0.1 MPa, there is a concern that handling
properties in producing the laminate are deteriorated, or
unevenness of film thickness is caused. In addition, when the shear
storage modulus of the layer A is more than 5.0 MPa, a damping
performance as the interlayer film for laminated glass becomes low,
so that the function as a sound insulating film tends to be
lowered.
[0101] The layer A in which the shear storage modulus is 0.1 MPa or
more and 5.0 MPa or less can be, for example, obtained by a method
of adjusting the content of the hard segment (for example, an
aromatic vinyl polymer block) by selecting, as the resin to be
contained in the layer A, a thermoplastic elastomer that is a resin
constituted of a hard segment and a soft segment, as a block
copolymer, with a content of the hard segment being 5% by mass or
more and 30% by mass or less; or a method of adjusting the kinds of
monomers constituting a hard segment or a soft segment, binding
forms, glass transition temperatures of the respective segments per
se, and the like.
[0102] Furthermore, from the viewpoint of preparing a laminated
glass in which a lowering of sound insulating performance in a
high-frequency region to be caused due to a coincidence phenomenon
is suppressed and which is excellent in sound insulating
properties, a shear storage modulus of the layer A which is used in
the present invention (or the resin to be contained in the layer A)
at a temperature of 25.degree. C. as measured by conducting a
complex shear viscosity test at a frequency of 1 Hz in accordance
with JIS K 7244-10 is preferably 0.6 MPa or more, more preferably
0.8 MPa or more, and still more preferably 1.0 MPa or more. In
addition, from the above-described viewpoint, the shear storage
modulus of the layer A is preferably 3.0 MPa or less, more
preferably 2.0 MPa or less, and still more preferably 1.5 MPa or
less. When the shear storage modulus of the layer A is less than
0.6 MPa, the rigidity of the laminate tends to be lowered. In
addition, when the shear storage modulus of the layer A is more
than 3.0 MPa, the moldability or handling properties tend to be
lowered.
[0103] The layer A in which the shear storage modulus is 0.6 MPa or
more and 3.0 MPa or less can be, for example, obtained by a method
of adjusting the content of the hard segment by using a block
copolymer (for example, a block copolymer having an aromatic vinyl
polymer block and an aliphatic unsaturated hydrocarbon polymer
block) as the resin to be contained in the resin composition
constituting the layer A and using a thermoplastic elastomer having
a content of the hard segment (for example, an aromatic vinyl
polymer block) of 14% by mass or more and 40% by mass or less
relative to the total amount; or a method of adjusting the kinds of
monomers constituting a hard segment or a soft segment, binding
forms, glass transition temperatures of the respective segments per
se, and the like.
[0104] Among energies generated by an external force and a strain
against a body, the shear storage modulus is an index of a
component stored inside the body and can be determined from a
relation between dynamic modulus and temperature under a constant
heating rate in measurement temperature in a strain control type
dynamic viscoelasticity instrument.
[0105] Though the measurement condition of the shear storage
modulus can be properly set, for example, the measurement can be
conducted by setting at a frequency of 1 Hz and at a temperature of
-40 to 100.degree. C. A test system in JIS K 7244-10 includes a
stress control system and a strain control system.
[0106] A parallel-plate oscillatory rheometer can be used for a
testing instrument in JIS K 7244-10. The parallel-plate oscillatory
rheometer is constituted of two coaxial rigid parallel disks. The
dynamic viscoelastic characteristics, such as a shear loss modulus,
a shear storage modulus, etc., can be measured by placing a test
sheet between the disks and fixing one of the disks and vibrating
the other disk at a fixed frequency.
[0107] A diameter of the disk is generally 20 mm or more and 50 mm
or less, and a thickness of the test sheet is defined as a distance
between the disks. In order to minimize a measurement error, it is
desired to use a test sheet of about 3 g or more and 5 g or less
and allow the thickness of the test sheet to fall within the range
of 0.5 mm or more and 3 mm or less. In addition, a ratio of the
diameter of the disk to the thickness of the test sheet is
desirably in the range of 10 or more and 50 or less. The test sheet
is formed in a disk shape by means of injection molding,
compression molding, or cutting-out from the sheet. Besides, a
pellet, a liquid, or a molten polymer may be filled between the
disks. In addition, a gap between the two flat plates is completely
filled by the test sheet.
[0108] In the strain control system, distortion of a sinusoidal
waveform at a fixed angular frequency is applied, and a sinusoidal
torque and a phase difference between torque and angular
displacement generated as a result are measured. A torque
measurement instrument is connected to the flat plate of one side,
and a torque necessary for deforming the test sheet is measured. An
angular displacement measurement instrument is connected to the
flat plate on the movable side, and an angular displacement and a
frequency are measured. Either a torque of sinusoidal waveform or
an angular displacement is given to the test sheet at a fixed
frequency, and the shear loss modulus and the shear storage modulus
are determined from the measured torque and displacement and the
test sheet dimension.
[0109] In addition, it is necessary to heat a testing instrument to
the testing temperature, thereby rendering the testing instrument
in a thermal equilibrium state. It is desired that the testing
temperature is measured by bringing a thermometer into contact with
the disk on the immobile side or burying the thermometer in the
disk on the immobile side. Heating is conducted by means of forced
convection, high-frequency heating, or an appropriate method. The
test sheet and the disk are thoroughly held until the testing
instrument reaches the thermal equilibrium state at the testing
temperature such that measured values of the shear loss modulus and
the shear storage modulus do not change. An equilibrium time is
desirably 15 minutes or more and 30 minutes or less.
(Thermoplastic Elastomer)
[0110] Though the resin to be used in the layer A is not
particularly limited, for example, from the viewpoint of making
both the moldability and the sound insulating properties compatible
with each other, it is preferred to use a thermoplastic elastomer
(sometimes referred to simply as "elastomer"). Examples of the
thermoplastic elastomer include thermoplastic elastomers, such as a
polystyrene-based elastomer (soft segment: polybutadiene,
polyisoprene, etc./hard segment: polystyrene), a polyolefin-based
elastomer (soft segment: ethylene propylene rubber/hard segment:
polypropylene), a polyvinyl chloride-based elastomer (soft segment:
polyvinyl chloride/hard segment: polyvinyl chloride), a
polyurethane-based elastomer (soft segment: polyether, polyester,
or polycarbonate/hard segment: polyurethane), a polyester-based
elastomer (soft segment: aliphatic polyester/hard segment: aromatic
polyester), a polyether ester-based elastomer (soft segment:
polyether/hard segment: polyester), a polyamide-based elastomer
(soft segment: polypropylene glycol, polytetramethylene ether
glycol, polyester, or polyether/hard segment: polyamide <nylon
resin>), a polybutadiene-based elastomer (soft segment:
amorphous butyl rubber/hard segment: syndiotactic 1,2-polybutadiene
resin), an acrylic elastomer (soft segment: polyacrylate ester/hard
segment: polymethyl methacrylate), etc. It is to be noted that the
above-described thermoplastic elastomers may be used solely or may
be used in combination of two or more thereof.
[0111] A content of the hard segment in the thermoplastic elastomer
is preferably 5% by mass or more, more preferably 7% by mass or
more, still more preferably 8% by mass or more, yet still more
preferably 10% by mass or more, even yet still more preferably 14%
by mass or more, especially preferably 16% by mass or more, and
most preferably 18% by mass or more relative to the total amount of
the thermoplastic elastomer. A content of the hard segment is
preferably 40% by mass or less, more preferably 30% by mass or
less, still more preferably 20% by mass or less, and especially
preferably 15% by mass or less relative to the total amount of the
thermoplastic elastomer. When the content of the hard segment is
less than 5% by mass, there is a tendency that the molding of the
layer A is difficult, the height of the peak of tan .delta. is
small, the bending rigidity of the laminate is small, or the sound
insulating properties in a high-frequency region is lowered. When
the content of the hard segment is more than 40% by mass, there is
a tendency that the characteristics as the thermoplastic elastomer
are hardly exhibited, the stability of sound insulating performance
is lowered, or the sound insulating characteristics in the vicinity
of room temperature are lowered.
[0112] A content of the soft segment in the thermoplastic elastomer
is preferably 60% by mass or more, more preferably 70% by mass or
more, still more preferably 80% by mass or more, and especially
preferably 85% by mass or more relative to the total amount of the
thermoplastic elastomer. The content of the soft segment is
preferably 95% by mass or less, more preferably 92% by mass or
less, still more preferably 90% by mass or less, yet still more
preferably 88% by mass or less, even yet still more preferably 86%
by mass or less, especially preferably 84% by mass or less, and
most preferably 82% by mass or less relative to the total amount of
the thermoplastic elastomer. When the content of the soft segment
is less than 60% by mass, the characteristics as the thermoplastic
elastomer tend to be hardly exhibited. When the content of the soft
segment is more than 95% by mass, there is a tendency that the
molding of the layer A is difficult, the height of the peak of tan
.delta. is small, the bending rigidity of the laminate is small, or
the sound insulating properties in a high-frequency region are
lowered. Here, in the case where a plurality of the thermoplastic
elastomers is mixed, the contents of the hard segment and the soft
segment in the thermoplastic elastomer are each considered as an
average value of the mixture.
[0113] From the viewpoint of making both the moldability and the
sound insulating properties compatible with each other, it is more
preferred to use a block copolymer having a hard segment and a soft
segment as the thermoplastic elastomer. Furthermore, from the
viewpoint of further improving the sound insulating properties, it
is preferred to use a polystyrene-based elastomer.
[0114] In addition, crosslinked rubbers of natural rubber, isoprene
rubber, butadiene rubber, chloroprene rubber, nitrile rubber, butyl
rubber, ethylene propylene rubber, urethane rubber, silicone
rubber, chlorosulfonated polyethylene rubber, acrylic rubber,
fluorine rubber, and the like may be used as the thermoplastic
elastomer.
[0115] The thermoplastic elastomer is preferably a copolymer of an
aromatic vinyl monomer and a vinyl monomer or a conjugated diene
monomer, or a hydrogenated product of the copolymer. From the
viewpoint of making both the function as a rubber exhibiting sound
insulating properties and the function as a plastic compatible with
each other, the copolymer is preferably a block copolymer having an
aromatic vinyl polymer block and an aliphatic unsaturated
hydrocarbon polymer block, for example, a polystyrene-based
elastomer.
[0116] In the case where a copolymer having an aromatic vinyl
polymer block and a vinyl polymer block or a conjugated diene
polymer block, for example, a block copolymer having an aromatic
vinyl polymer block and an aliphatic unsaturated hydrocarbon
polymer block is used as the thermoplastic elastomer, the binding
form of these polymer blocks is not particularly limited, and it
may be any of a linear binding form, a branched binding form, a
radial binding form, and a combined binding form of two or more
thereof. Of those, a linear binding form is preferred.
[0117] When the aromatic vinyl polymer block is expressed as "a",
and the aliphatic unsaturated hydrocarbon polymer block is
expressed as "b", examples of the linear binding form include a
diblock copolymer expressed by a-b, a triblock copolymer expressed
by a-b-a or b-a-b, a tetrablock copolymer expressed by a-b-a-b, a
pentablock copolymer expressed by a-b-a-b-a or b-a-b-a-b, an
(a-b).sub.nX type copolymer (X represents a coupling residual
group, and n represents an integer of 2 or more), and a mixture
thereof. Of those, a diblock copolymer or a triblock copolymer is
preferred, and the triblock copolymer is more preferably a triblock
copolymer expressed by a-b-a.
[0118] A sum total of an aromatic vinyl monomer unit and an
aliphatic unsaturated hydrocarbon monomer unit in the block
copolymer is preferably 80% by mass or more, more preferably 95% by
mass or more, and still more preferably 98% by mass or more
relative to the whole of the monomer units. It is to be noted that
a part or the whole of the aliphatic unsaturated hydrocarbon
polymer blocks in the block copolymer may be hydrogenated.
[0119] A content of the aromatic vinyl monomer unit in the block
copolymer is preferably 5% by mass or more, more preferably 7% by
mass or more, still more preferably 8% by mass or more, yet still
more preferably 14% by mass or more, especially preferably 16% by
mass or more, and most preferably 18% by mass or more relative to
the whole of the monomer units of the block copolymer. A content of
the aromatic vinyl monomer unit is preferably 40% by mass or less,
more preferably 30% by mass or less, still more preferably 25% by
mass or less, especially preferably 20% by mass or less, and most
preferably 15% by mass or less relative to the whole of the monomer
units of the block copolymer.
[0120] When the content of the aromatic vinyl monomer unit in the
block copolymer is less than 5% by mass, there is a tendency that
the molding of the layer A is difficult, a slippage of glasses is
caused due to heat, the height of the peak of tan .delta. is small,
the bending rigidity of the laminate is small, or the sound
insulating properties in a high-frequency region are lowered. When
the content of the aromatic vinyl monomer unit in the block
copolymer is more than 40% by mass, there is a tendency that the
characteristics as the thermoplastic elastomer are hardly
exhibited, or the stability of sound insulating performance is
lowered.
[0121] The content of the aromatic vinyl monomer unit in the block
copolymer can be determined from a charge ratio of the respective
monomers in synthesizing the block copolymer, or the measurement
results of .sup.1H-NMR or the like of the block copolymer. In the
Examples of the present specification, a proportion of the monomer
species was determined from the measurement results of .sup.1H-NMR,
and the proportion of each monomer was described in terms of % by
mass. Here, in the case where a plurality of the block copolymers
is mixed, the content of the aromatic vinyl monomer unit in the
block copolymer is considered as an average value of the
mixture.
[0122] In the aromatic vinyl polymer block, a monomer other than
the aromatic vinyl monomer may be copolymerized so long as its
amount is small. A proportion of the aromatic vinyl monomer unit in
the aromatic vinyl polymer block is preferably 80% by mass or more,
more preferably 95% by mass or more, and still more preferably 98%
by mass or more relative to the whole of the monomer units in the
aromatic vinyl polymer block.
[0123] Examples of the aromatic vinyl monomer constituting the
aromatic vinyl polymer block include styrene; alkylstyrenes, such
as .alpha.-methylstyrene, 2-methylstyrene, 3-methylstyrene,
4-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene,
4-dodecylstyrene, etc.; arylstyrenes, such as
2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene,
1-vinylnaphthalene, 2-vinylnaphthalene, etc.; halogenated styrenes;
alkoxystyrenes; vinylbenzoate esters; and the like. These aromatic
vinyl monomers may be used solely or may be used in combination of
two or more thereof.
[0124] A content of the aliphatic unsaturated hydrocarbon monomer
unit in the block copolymer is preferably 60% by mass or more, more
preferably 70% by mass or more, still more preferably 75% by mass
or more, yet still more preferably 80% by mass or more, and
especially preferably 85% by mass or more relative to the whole of
the monomer units of the block copolymer. The content of the
aliphatic unsaturated hydrocarbon monomer unit in the block
copolymer is preferably 95% by mass or less, more preferably 92% by
mass or less, still more preferably 90% by mass or less, yet still
more preferably 88% by mass or less, even yet still more preferably
86% by mass or less, especially preferably 84% by mass or less, and
most preferably 82% by mass or less relative to the whole of the
monomer units of the block copolymer.
[0125] When the content of the aliphatic unsaturated hydrocarbon
monomer unit in the block copolymer is less than 60% by mass, there
is a tendency that the characteristics as the thermoplastic
elastomer are hardly exhibited, or the stability of sound
insulating performance is lowered. When the content of the
aliphatic unsaturated hydrocarbon monomer unit in the block
copolymer is more than 95% by mass, there is a tendency that the
molding of the layer A is difficult, the height of the peak of tan
.delta. is small, the bending rigidity of the laminate is small, or
the sound insulating properties in a high-frequency region are
lowered.
[0126] The content of the aliphatic unsaturated hydrocarbon monomer
unit in the block copolymer can be determined from a charge ratio
of the respective monomers in synthesizing the block copolymer, or
the measurement results of .sup.1H-NMR or the like of the block
copolymer. In the Examples of the present specification, a
proportion of the monomer species was determined from the
measurement results of .sup.1H-NMR, and the proportion of each
monomer was described in terms of % by mass. Here, in the case
where a plurality of the block copolymers is mixed, the content of
the aliphatic unsaturated hydrocarbon monomer unit in the block
copolymer is considered as an average value of the mixture.
[0127] In the aliphatic unsaturated hydrocarbon polymer block, a
monomer other than the aliphatic unsaturated hydrocarbon monomer
may be copolymerized so long as its amount is small. A proportion
of the aliphatic unsaturated hydrocarbon monomer unit in the
aliphatic unsaturated hydrocarbon polymer block is preferably 80%
by mass or more, more preferably 95% by mass or more, and still
more preferably 98% by mass or more relative to the whole of the
monomer units in the aliphatic unsaturated hydrocarbon polymer
block.
[0128] Examples of the aliphatic unsaturated hydrocarbon monomer
constituting the aliphatic unsaturated hydrocarbon polymer block
include ethylene, propylene, 1-butene, 1-pentene, 1-hexene,
1-heptene, 1-octene, 1-nonene, 1-decene, 4-phenyl-1-butene,
6-phenyl-1-hexene, 3-methyl-1-butene, 4-methyl-1-butene,
3-methyl-1-pentene, 4-methyl-1-pentene, 3-methyl-1-hexene,
4-methyl-1-hexene, 5-methyl-1-hexene, 3,3-dimethyl-1-pentene,
3,4-dimethyl-1-pentene, 4,4-dimethyl-1-pentene, vinylcyclohexane,
hexafluoropropene, tetrafluoroethylene, 2-fluoropropene,
fluoroethylene, 1,1-difluoroethylene, 3-fluoropropene,
trifluoroethylene, 3,4-dichloro-1-butene, butadiene, isoprene,
dicyclopentadiene, norbornene, acetylene, and the like. These
aliphatic unsaturated hydrocarbon monomers may be used solely or
may be used in combination of two or more thereof.
[0129] From the viewpoints of easiness of availability and handling
properties, the aliphatic unsaturated hydrocarbon monomer is
preferably an aliphatic unsaturated hydrocarbon having 2 or more
carbon atoms, and more preferably an aliphatic hydrocarbon having 4
or more carbon atoms, and is preferably an aliphatic unsaturated
hydrocarbon having 12 or less carbon atoms, and more preferably an
aliphatic hydrocarbon having 8 or less carbon atoms. Among those,
butadiene, isoprene, and a combination of butadiene and isoprene
are preferred.
[0130] In addition, from the viewpoints of easiness of availability
and handling properties as well as easiness of synthesis, the
aliphatic unsaturated hydrocarbon monomer is preferably a
conjugated diene. From the viewpoint of improving the heat
stability, in the case of using a conjugated diene as the
constituent unit of the aliphatic unsaturated hydrocarbon polymer
block, the block is preferably a hydrogenated product resulting
from hydrogenating a part or the whole thereof. On that occasion, a
hydrogenation ratio is preferably 80% or more, and more preferably
90% or more. The hydrogenation ratio as referred to herein is a
value obtained by measuring an iodine value of the block copolymer
before and after the hydrogenation reaction.
[0131] From the viewpoints of mechanical characteristics and
molding processability, a weight average molecular weight of the
block copolymer is preferably 30,000 or more, and more preferably
50,000 or more. From the viewpoints of mechanical characteristics
and molding processability, the weight average molecular weight of
the block copolymer is preferably 400,000 or less, and more
preferably 300,000 or less. A ratio (Mw/Mn) of weight average
molecular weight to number average molecular weight of the block
copolymer is preferably 1.0 or more. The ratio (Mw/Mn) of weight
average molecular weight to number average molecular weight of the
block copolymer is preferably 2.0 or less, and more preferably 1.5
or less. Here, the weight average molecular weight refers to a
weight average molecular weight in terms of polystyrene determined
by the gel permeation chromatography (GPC) measurement, and the
number average molecular weight refers to a number average
molecular weight in terms of polystyrene determined by the GPC
measurement.
[0132] Though a production method of the block copolymer is not
particularly limited, the block copolymer can be, for example,
produced by an anionic polymerization method, a cationic
polymerization method, a radical polymerization method, or the
like. For example, in the case of anionic polymerization, specific
examples thereof include:
[0133] (i) a method of successively polymerizing an aromatic vinyl
monomer, a conjugated diene monomer, and subsequently an aromatic
vinyl monomer by using an alkyllithium compound as an
initiator;
[0134] (ii) a method of successively polymerizing an aromatic vinyl
monomer and a conjugated diene monomer by using an alkyllithium
compound as an initiator and subsequently adding a coupling agent
to undergo coupling;
[0135] (iii) a method of successively polymerizing a conjugated
diene monomer and subsequently an aromatic vinyl monomer by using a
dilithium compound as an initiator; and the like.
[0136] In the case of using a conjugated diene as the aliphatic
unsaturated hydrocarbon monomer, by adding an organic Lewis base on
the occasion of anionic polymerization, a 1,2-bond quantity and a
3,4-bond quantity of the thermoplastic elastomer can be increased,
and the 1,2-bond quantity and the 3,4-bond quantity of the
thermoplastic elastomer can be easily controlled by the addition
amount of the organic Lewis base. By controlling them, the peak
temperature or height of tan .delta. can be adjusted.
[0137] Examples of the organic Lewis base include esters, such as
ethyl acetate, etc.; amines, such as triethylamine,
N,N,N',N'-tetramethylethylenediamine (TMEDA), N-methylmorpholine,
etc.; nitrogen-containing heterocyclic aromatic compounds, such as
pyridine, etc.; amides, such as dimethylacetamide, etc.; ethers,
such as dimethyl ether, diethyl ether, tetrahydrofuran (THF),
dioxane, etc.; glycol ethers, such as ethylene glycol dimethyl
ether, diethylene glycol dimethyl ether, etc.; sulfoxides, such as
dimethyl sulfoxide, etc.; ketones, such as acetone, methyl ethyl
ketone, etc.; and the like.
[0138] In the case of subjecting the unhydrogenated
polystyrene-based elastomer to a hydrogenation reaction, the
hydrogenation reaction can be conducted by dissolving the obtained
unhydrogenated polystyrene-based elastomer in a solvent inert to a
hydrogenation catalyst or using the unhydrogenated
polystyrene-based elastomer without being isolated from a reaction
liquid, and allowing the unhydrogenated polystyrene-based elastomer
to react with hydrogen in the presence of a hydrogenation catalyst.
The hydrogenation ratio is preferably 60% or more, more preferably
80% or more, and still more preferably 90% or more.
[0139] Examples of the hydrogenation catalyst include Raney nickel;
heterogeneous catalysts in which a metal, such as Pt, Pd, Ru, Rh,
Ni, etc., is supported on a carrier, such as carbon, alumina,
diatomaceous earth, etc.; Ziegler-based catalysts composed of a
combination of a transition metal compound with an alkylaluminum
compound, an alkyllithium compound, etc.; metallocene-based
catalysts; and the like. The hydrogenation reaction can be
generally conducted under conditions at a hydrogen pressure of 0.1
MPa or more and 20 MPa or less and at a reaction temperature of
20.degree. C. or higher and 250.degree. C. or lower for a reaction
time of 0.1 hours or more and 100 hours or less.
(Other Additive Components)
[0140] In the layer A, an antioxidant, an ultraviolet ray absorber,
a photostabilizer, an antiblocking agent, a pigment, a dye, a heat
insulating material, and the like may be added as other components,
if desired. Examples of the antioxidant, the ultraviolet ray
absorber, and the photostabilizer include those to be contained in
the layer B as described later.
[0141] The laminate can be given a heat insulating function, and a
transmittance at wavelength of 1500 nm can be regulated to 50% or
less when the a laminated glass is formed, by incorporating the
heat insulating material, for example, an inorganic heat insulating
fine particle or a heat insulating compound into the layer A The
heat insulating material is described later in detail.
[0142] In the case where a component other than the thermoplastic
elastomer is contained in the layer A, in the composition
containing the thermoplastic elastomer constituting the layer A,
the content of the thermoplastic elastomer component is preferably
60% by mass or more, more preferably 70% by mass or more, still
more preferably 80% by mass or more, especially preferably 90% by
mass or more, and most preferably 95% by mass or more. When the
content of the thermoplastic elastomer in the layer A is less than
60% by mass, there is a tendency that the characteristics as the
thermoplastic elastomer are hardly exhibited, or the optical
characteristics are impaired.
[0143] In the laminate of the present invention, the thermoplastic
elastomer is contained in an amount of preferably 5% by mass or
more, more preferably 10% by mass or more, and still more
preferably 13% by mass or more in the laminate. When the content of
the thermoplastic elastomer in the laminate is less than 5% by
mass, the sound insulating properties tend to be lowered.
[Layer B]
[0144] In the layer B which is used for the laminate of the present
invention, a shear storage modulus at a temperature of 25.degree.
C. as measured by conducting a complex shear viscosity test at a
frequency of 1 Hz in accordance with JIS K 7244-10 is preferably 1
MPa or more, and more preferably 2 MPa or more. When the shear
storage modulus at a temperature of 25.degree. C. is less than 1
MPa, there is a tendency that stickiness of the layer B increases,
and the process passing properties in a production process of a
laminated glass are lowered. Furthermore, in the case where it is
necessary to compensate for a lowering of strength of the laminated
glass following thinning (weight reduction) of glass, the shear
storage modulus at a temperature of 25.degree. C. is preferably
10.0 MPa or more. For example, by using the B layer whose shear
storage modulus at a temperature of 25.degree. C. is 10.0 MPa or
more as an outermost layer, a laminate with excellent handling
properties can be obtained. The shear storage modulus at a
temperature of 25.degree. C. is preferably 12.0 MPa or more, more
preferably 20.0 MPa or more, still more preferably 40.0 MPa or
more, especially preferably 60.0 MPa or more, and most preferably
80.0 MPa or more. When the shear storage modulus under the
above-described condition is less than 10.0 MPa, there is a
tendency that suitable shear storage modulus and maximum loss
factor cannot be kept, and the sound insulating properties or
bending rigidity of the interlayer film for laminate glass is
lowered. The layer B having a shear storage modulus of 10.0 MPa or
more can be, for example, obtained by regulating an amount of a
plasticizer to 50 parts by mass or less based on 100 parts by mass
of a thermoplastic resin, such as a polyvinyl acetal resin, etc. In
addition, an upper limit of the shear storage modulus at 25.degree.
C. is not particularly limited, and it is preferably 900 MPa or
less from the viewpoints of moldability and handling properties of
the laminate.
[0145] In the laminate of the present invention, it is preferred
that the layer B serving as the outermost layer contains at least
one thermoplastic resin selected from the group consisting of a
polyvinyl acetal resin, an ionomer, an ethylene.vinyl acetate
copolymer, and an adhesive functional group-containing polyolefin.
When the layer B serving as the outermost layer is constituted of a
composition containing the above-described thermoplastic resin, the
weather resistance or strength of the interlayer film for laminated
glass can be improved, or the bending strength or penetration
resistance of the resulting laminated glass can be improved. For
example, from the viewpoint of the matter that a safety glass with
low glass scattering properties at the time of breakage can be
prepared when the laminate of the present invention is put into
practical use as an interlayer film for laminated glass, or the
like, the layer B composed of a composition containing a polyvinyl
acetal resin is preferred. In particular, it is preferred that the
layer B serving as the outermost layer is constituted of polyvinyl
butyral.
[0146] In addition, as for the layer B of the present invention, in
interposing the laminate of the present invention between two
sheets of float glass having a length of 300 mm, a width of 25 mm,
and a thickness of 1.9 mm, the laminate is selected in such a
manner that a loss factor at a quaternary resonance frequency as
measured at 20.degree. C. by a central exciting method is 0.2 or
more, and a bending rigidity at the quaternary resonance frequency
as calculated in accordance with ISO 16940 (2008) is 150 Nm or
more. The resin satisfying such prescriptions is not particularly
limited, and examples thereof include the above-described
thermoplastic resins and the like.
[0147] Furthermore, it is preferred that the resin which is used
for the layer B of the present invention includes a resin having
adhesion to a glass. The resin having such properties is not
particularly limited, and examples thereof include the
above-described thermoplastic resins and the like.
[0148] In the case of using a composition containing a
thermoplastic resin, such as a polyvinyl acetal resin, etc., as the
layer B, the layer B contains the thermoplastic resin in an amount
of preferably 40% by mass or more, more preferably 50% by mass or
more, still more preferably 60% by mass or more, especially
preferably 80% by mass or more, and much more preferably 90% by
mass or more. The layer B may be constituted of only the
thermoplastic resin. When the content of the thermoplastic resin in
the layer B is smaller than 40% by mass, the bending strength of
the resulting laminated glass tends to be lowered.
(Ionomer)
[0149] A kind of the ionomer is not particularly limited, and
examples thereof include resins having a constituent unit derived
from ethylene and a constituent unit derived from an
.alpha.,.beta.-unsaturated carboxylic acid, in which at least a
part of the .alpha.,.beta.-unsaturated carboxylic acid is
neutralized with a metal ion. As the metal ion, there is, for
example, a sodium ion. In the ethylene..alpha.,.beta.-unsaturated
carboxylic acid copolymer serving as a base polymer, a content
proportion of the constituent unit of an .alpha.,.beta.-unsaturated
carboxylic acid is preferably 2% by mass or more, and more
preferably 5% by mass or more. In addition, the content proportion
of the constituent unit of an .alpha.,.beta.-unsaturated carboxylic
acid is preferably 30% by mass or less, and more preferably 20% by
mass or less. In the present invention, from the standpoint of
easiness of availability, an ionomer of an ethylene-acrylic acid
copolymer and an ionomer of an ethylene.methacrylic acid copolymer
are preferred. As for examples of the ethylene-based ionomer, there
can be exemplified a sodium ionomer of an ethylene.acrylic acid
copolymer and a sodium ionomer of an ethylene.methacrylic acid
copolymer as especially preferred examples.
[0150] Examples of the .alpha.,.beta.-unsaturated carboxylic acid
constituting the ionomer include acrylic acid, methacrylic acid,
maleic acid, monomethyl maleate, monoethyl maleate, maleic
anhydride, and the like. Of those, acrylic acid or methacrylic acid
is especially preferred.
(Adhesive Functional Group-Containing Polyolefin-Based Polymer)
[0151] The adhesive functional group-containing polyolefin-based
polymer is a polyolefin-based polymer having an adhesive functional
group given thereto. In the layer B of the laminate of the present
invention, by further incorporating the adhesive functional
group-containing polyolefin-based polymer, the adhesion of the film
obtained by molding the resin composition constituting the layer B
to a glass can be improved. In addition, in the case where the
adhesive functional group-containing polyolefin-based polymer and
the polyvinyl acetal resin are mixed and used in combination, the
adhesive functional group-containing polyolefin-based polymer works
as a compatibilizing agent between the polyvinyl acetal resin and
the thermoplastic polyolefin-based resin, and hence, the
transparency of the film obtained by molding the resin composition
can be improved.
[0152] Examples of the adhesive functional group that the adhesive
functional group-containing polyolefin-based polymer include a
carboxyl group, a boronic acid group, a silanol group, an epoxy
group, an isocyanate group, an acid anhydride group, a (meth)
acryloyloxy group, a hydroxyl group, an amide group, a halogen
atom, such as a chlorine atom, etc., and the like. In the case
where the adhesive functional group-containing polyolefin-based
polymer and the polyvinyl acetal resin are mixed with or brought
into contact with each other and used, a carboxyl group, a boronic
acid group, a silanol group, an epoxy group, or an isocyanate group
is preferred from the standpoint of reactivity with the hydroxyl
group in the polyvinyl acetal resin. Though a production method of
the adhesive functional group-containing polyolefin-based polymer
is not particularly limited, the adhesive functional
group-containing polyolefin-based polymer can be, for example,
obtained by reaction of olefin and a monomer having an adhesive
functional group by a known method through random copolymerization,
block copolymerization, graft copolymerization, or graft reaction.
Of those, random copolymerization, graft copolymerization, or graft
reaction is preferred, and a graft reaction product obtained
through graft reaction is more preferred. It is to be noted that
the graft reaction product as referred to herein means a product in
which the majority of graft side chains is one to which one monomer
but not a polymer is added, as in maleic anhydride modification.
Besides, the adhesive functional group-containing polyolefin-based
polymer is also obtained by subjecting a polyolefin-based resin to
a reaction, such as oxidation, chlorination, etc., by a known
method. In addition, an ethylene.vinyl acetate copolymer and the
like can be used as the adhesive functional group-containing
polyolefin.
[0153] Propylene is preferred as the olefin which is used for the
adhesive functional group-containing polyolefin-based polymer. The
adhesive functional group-containing polyolefin-based polymer may
also be a polymer obtained through copolymerization of propylene
with an .alpha.-olefin other than propylene and a monomer having an
adhesive functional group. Examples of the .alpha.-olefin include
ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene,
4-methyl-1-pentene, cyclohexene, and the like. The .alpha.-olefin
can be copolymerized with a monomer having an adhesive functional
group, and there is exemplified a method, such as random
copolymerization, block copolymerization, graft copolymerization,
etc. A proportion of a structural unit derived from such an
.alpha.-olefin other than propylene relative to the whole of the
structural units is preferably 0 mol % or more, and it is
preferably 45 mol % or less, more preferably 35 mol % or less, and
still more preferably 25 mol % or less.
[0154] Examples of the monomer having an adhesive functional group
include vinyl acetate, vinyl chloride, ethylene oxide, propylene
oxide, acrylamide, and an unsaturated carboxylic acid or its ester
or anhydride. Of those, an unsaturated carboxylic acid or its ester
or anhydride is preferred. Examples of the unsaturated carboxylic
acid or its ester or anhydride include (meth)acrylic acid, a
(meth)acrylate ester, maleic acid, maleic anhydride, fumaric acid,
itaconic acid, itaconic anhydride, himic acid, himic anhydride, and
the like. Of those, maleic acid and maleic anhydride are more
preferred. These monomers having an adhesive functional group may
be used solely or may be used in combination of two or more
thereof.
[0155] From the viewpoints of adhesion of the film to a glass and
transparency, as the adhesive functional group-containing
polyolefin-based polymer, polypropylene or a styrene-diene-based
elastomer each containing a carboxyl group as the adhesive
functional group, namely an (anhydrous) carboxylic acid-modified
polypropylene-based resin or an (anhydrous) carboxylic
acid-modified styrene-diene-based elastomer, is preferred, and in
particular, an (anhydrous) maleic acid-modified polypropylene-based
resin or an (anhydrous) maleic acid-modified styrene-diene-based
elastomer is more preferred.
[0156] Besides, examples of a monomer copolymerizable with the
olefin include alkyl acrylates, such as methyl acrylate, ethyl
acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate,
isobutyl acrylate, n-hexyl acrylate, isohexyl acrylate, n-octyl
acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, etc.; and
methacrylate esters, such as methyl methacrylate, ethyl
methacrylate, n-propyl methacrylate, isopropyl methacrylate,
n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate,
isohexyl methacrylate, n-octyl methacrylate, isooctyl methacrylate,
2-ethylhexyl methacrylate, etc. These (meth)acrylate esters may be
used solely or may be used in combination of two or more
thereof.
[0157] A proportion of the adhesive function group is preferably 1
.mu.eq/g or more, more preferably 2 .mu.eq/g or more, and optimally
3 .mu.eq/g or more relative to the whole of the structural units of
the adhesive functional group-containing polyolefin-based polymer.
The proportion of the adhesive function group is preferably 1,500
.mu.eq/g or less, more preferably 700 .mu.eq/g or less, and
optimally 500 .mu.eq/g or less relative to the whole of the
structural units of the adhesive functional group-containing
polyolefin-based polymer. When the proportion of the adhesive
functional group is smaller than 1 .mu.eq/g, there is a tendency
that a dispersed particle diameter of the polyolefin-based resin
becomes high, and cloudiness becomes vigorous, whereas when it is
more than 1,500 .mu.eq/g, there is a tendency that when recycled,
gelation is liable to be caused.
[0158] In the present invention, the adhesive functional
group-containing polyolefin-based polymer can play a role as the
above-described thermoplastic polyolefin-based resin. Accordingly,
the thermoplastic resin which can be used in the present invention
also includes a thermoplastic resin not containing an adhesive
functional group-free thermoplastic polyolefin-based resin but
containing only an adhesive functional group-containing
polyolefin-based polymer as the thermoplastic polyolefin-based
resin as one of preferred embodiments.
[0159] In the case where the adhesive functional group-containing
polyolefin-based polymer and the polyvinyl acetal resin are brought
into contact with each other and used, a content of the adhesive
functional group-containing polyolefin-based polymer is preferably
0.3 parts by mass or more, more preferably 0.6 parts by mass or
more, and still more preferably 1 part by mass or more based on 100
parts by mass of the thermoplastic elastomer. When the content of
the adhesive functional group-containing polyolefin-based polymer
is less than 0.5 parts by mass, compatibility between the polyvinyl
acetal resin and the thermoplastic polyolefin-based resin tends to
be not sufficient.
[0160] On the occasion of melt kneading the laminate for recycle
use as the polyvinyl acetal resin layer, in the case where the
thermoplastic elastomer and the polyvinyl acetal resin are mixed, a
content of the thermoplastic elastomer is preferably 0.5 parts by
mass or more, more preferably 1 part by mass or more, and more
preferably 3 parts by mass or more based on 100 parts by mass of
the polyvinyl acetal resin. In addition, the content of the
thermoplastic elastomer is preferably 50 parts by mass or less, and
more preferably 40 parts by mass or less based on 100 parts by mass
of the polyvinyl acetal resin. When the content of the
thermoplastic elastomer is less than 0.5 parts by mass, trimming
recycling properties tend to become inferior, whereas when it is
more than 50 parts by mass, a haze tends to be deteriorated.
[0161] A content of the adhesive functional group-containing
polyolefin-based polymer is preferably 0.3 parts by mass or more,
more preferably 0.6 parts by mass or more, and still more
preferably 1 part by mass or more based on 100 parts by mass of the
thermoplastic elastomer. When the content of the adhesive
functional group-containing polyolefin-based polymer is smaller
than 0.3 parts by mass, an effect for compatibilizing the polyvinyl
acetal resin and the thermoplastic polyolefin-based resin with each
other tends to be not sufficient.
(Polyvinyl Acetal Resin)
[0162] An average degree of acetalization of the polyvinyl acetal
resin is preferably 40 mol % or more, and it is preferably 90 mol %
or less. When the average degree of acetalization is less than 40
mol %, the compatibility with a solvent, such as a plasticizer,
etc., is not preferred. When the average degree of acetalization is
more than 90 mol %, there is a concern that the reaction for
obtaining the polyvinyl acetal resin takes a long time, so that
such is not preferred from the process standpoint. The average
degree of acetalization is more preferably 60 mol % or more, and
from the viewpoint of water resistance, it is still more preferably
65 mol % or more. In addition, the average degree of acetalization
is more preferably 85 mol % or less, and still more preferably 80
mol % or less.
[0163] A content of the vinyl acetate unit of the polyvinyl acetal
resin is preferably 30 mol % or less. When the content of the vinyl
acetate unit is more than 30 mol %, blocking is liable to be caused
at the time of producing the polyvinyl acetal resin, so that the
production is hardly achieved. The content of the vinyl acetate
unit is more preferably 20 mol % or less.
[0164] A content of the vinyl alcohol unit of the polyvinyl acetal
resin is preferably 5 mol % or more, more preferably 10 mol % or
more, still more preferably 15 mol % or more, yet still more
preferably 18 mol % or more, even yet still more preferably 20 mol
% or more, even still more preferably 22 mol % or more, and yet
even still more preferably 25 mol % or more. The content of the
vinyl alcohol unit of the polyvinyl acetal resin is preferably 50
mol % or less, more preferably 45 mol % or less, still more
preferably 40 mol % or less, yet still more preferably 35 mol % or
less, even yet still more preferably 30 mol % or less, yet even
still more preferably 25 mol % or less, and especially preferably
20 mol % or less.
[0165] When the content of the vinyl alcohol unit is smaller than 5
mol %, there is a tendency that the adhesion to a glass is lowered,
or the strength of the layer B is lowered. In addition, in the case
where a compound having a hydroxyl group as described later is used
as the plasticizer, there is a tendency that it is impossible to
allow the hydroxyl group that the plasticizer has and the polyvinyl
acetal resin to have a sufficient interaction (hydrogen bond), and
as a result, the compatibility between the polyvinyl acetal resin
and the plasticizer becomes unpreferable, so that the plasticizer
is liable to migrate into another resin layer. When the content of
the vinyl alcohol unit is more than 50 mol %, there is a tendency
that the water resistance is lowered, or it becomes difficult to
control the penetration resistance or impact resistance function
required for an interlayer film as the safety glass. In addition,
there is a tendency that compatibility with a solvent, such as a
plasticizer, etc., is lowered to cause bleedout of the plasticizer,
or hygroscopicity of the laminate becomes high, so that humidity
resistance is lowered, or whitening is liable to be caused.
[0166] The polyvinyl acetal resin is generally constituted of a
vinyl acetal unit, a vinyl alcohol unit, and a vinyl acetate unit,
and these respective units can be, for example, measured by the
"Testing Methods for Polyvinyl Butyral" of JIS K 6728 or a nuclear
magnetic resonance method (NMR).
[0167] In the case where the polyvinyl acetal resin contains a unit
other than the vinyl acetal unit, by measuring a unit quantity of
vinyl alcohol and a unit quantity of vinyl acetate and subtracting
these both unit quantities from a vinyl acetal unit quantity in the
case of not containing a unit other than the vinyl acetal unit, the
remaining vinyl acetal unit quantity can be calculated.
[0168] The polyvinyl acetal resin can be produced by a
conventionally known method, and representatively, the polyvinyl
acetal resin can be produced by acetalization of polyvinyl alcohol
with an aldehyde. Specifically, there is exemplified a method in
which polyvinyl alcohol is dissolved in warm water, the resulting
aqueous solution is held at a prescribed temperature, for example,
0.degree. C. or higher, preferably 10.degree. C. or higher and
90.degree. C. or lower, and preferably 20.degree. C. or lower, the
necessary acid catalyst and aldehyde are added, the acetalization
reaction is allowed to proceed while stirring, and subsequently,
the reaction temperature is increased to 70.degree. C. to conduct
aging, thereby accomplishing the reaction, followed by
neutralization, water washing, and drying to obtain a powder of the
polyvinyl acetal resin; or the like.
[0169] A viscosity average polymerization degree of polyvinyl
alcohol serving as a raw material of the polyvinyl acetal resin is
preferably 100 or more, more preferably 300 or more, still more
preferably 400 or more, yet still more preferably 600 or more, even
yet still more preferably 700 or more, yet even still more
preferably 750 or more, especially preferably 900 or more, and most
preferably 1,200 or more. When the viscosity average polymerization
degree of polyvinyl alcohol is too low, there is a concern that the
penetration resistance or creep resistance properties, particularly
creep resistance properties under high-temperature and
high-humidity conditions, such as those at 85.degree. C. and at 85%
RH, are lowered. In addition, the viscosity average polymerization
degree of polyvinyl alcohol is preferably 5,000 or less, more
preferably 3,000 or less, still more preferably 2,500 or less,
especially preferably 2,300 or less, and most preferably 2,000 or
less. When the viscosity average polymerization degree of polyvinyl
alcohol is more than 5,000, there is a concern that the molding of
a resin film is difficult.
[0170] Furthermore, for the purpose of improving lamination
aptitude of the resulting interlayer film for laminated glass to
obtain a laminated glass with a much more excellent appearance, the
viscosity average polymerization degree of polyvinyl alcohol is
preferably 1,800 or less, more preferably 1,500 or less, still more
preferably 1,100 or less, and especially preferably 1,000 or less.
In addition, in the case where the laminate of the present
invention is interposed as an interlayer film for laminated glass
between thin-film glasses and used as a laminated glass, in order
to enhance the bending strength of the resulting laminated glass,
it is preferred to make the quantity of the plasticizer small.
However, when the quantity of the plasticizer is made small, the
moldability tends to be lowered, and hence, from the viewpoint of
ensuring preferred moldability, it is preferred to allow the
viscosity average polymerization degree of polyvinyl alcohol to
fall within the foregoing range.
[0171] It is to be noted that since the viscosity average
polymerization degree of the polyvinyl acetal resin coincides with
the viscosity average polymerization degree of polyvinyl alcohol
serving as a raw material, the above-described preferred viscosity
average polymerization degree of polyvinyl alcohol coincides with
the preferred viscosity average polymerization degree of the
polyvinyl acetal resin.
[0172] It is preferred to set the vinyl acetate unit of the
resulting polyvinyl acetal resin to 30 mol % or less, and hence, it
is preferred to use polyvinyl alcohol having a saponification
degree of 70 mol % or more. When the saponification degree of
polyvinyl alcohol is less than 70 mol %, there is a concern that
transparency or heat resistance of the polyvinyl acetal resin is
lowered, and also, there is a concern that the reactivity with the
aldehyde is lowered, too. The saponification degree is more
preferably 95 mol % or more.
[0173] The viscosity average polymerization degree and
saponification degree of polyvinyl alcohol can be, for example,
measured in accordance with the "Testing Methods for Polyvinyl
Alcohol" of JIS K 6726.
[0174] The aldehyde which is used for acetalization of polyvinyl
alcohol is preferably an aldehyde having 1 or more and 12 or less
carbon atoms. When the carbon number of the aldehyde is more than
12, the reactivity of the acetalization is lowered, and moreover,
blocking of the resin is liable to be generated during the
reaction, and the synthesis of the polyvinyl acetal resin is liable
to be accompanied with difficulties.
[0175] The aldehyde is not particularly limited, and examples
thereof include aliphatic, aromatic, or alicyclic aldehydes, such
as formaldehyde, acetaldehyde, propionaldehyde, n-butyl aldehyde,
isobutyl aldehyde, valeraldehyde, n-hexyl aldehyde, 2-ethylbutyl
aldehyde, n-heptyl aldehyde, n-octyl aldehyde, n-nonyl aldehyde,
n-decyl aldehyde, benzaldehyde, cinnamaldehyde, etc. Of those,
aliphatic aldehydes having 2 or more and 6 or less carbon atoms are
preferred, and above all, butyl aldehyde is especially preferred.
In addition, the above-described aldehydes may be used solely or
may be used in combination of two or more thereof. Furthermore, a
small amount of a polyfunctional aldehyde or an aldehyde having
other functional group, or the like may also be used in combination
in an amount in the range of 20% by mass or less.
[0176] The polyvinyl acetal resin is most preferably polyvinyl
butyral. As the polyvinyl butyral, modified polyvinyl butyral
obtained by subjecting polyvinyl alcohol-based polymer obtained by
saponifying a copolymer of a vinyl ester and other monomer to
butyralization with butyl aldehyde can be obtained. Here, examples
of the other monomer include .alpha.-olefins, such as ethylene,
propylene, n-butene, isobutylene, etc.; acrylate esters, such as
methyl acrylate, ethyl acrylate, n-butyl acrylate, i-butyl
acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, dodecyl
acrylate, octadecyl acrylate, etc.; methacrylate esters, such as
methyl methacrylate, ethyl methacrylate, n-butyl methacrylate,
i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl
methacrylate, dodecyl methacrylate, octadecyl methacrylate, etc.;
acrylamides and derivatives thereof, such as acrylamide,
N-methylacrylamide, N-ethylacrylamide, N,N-dimethylacrylamide,
diacetone acrylamide, acrylamidepropanesulfonic acid and a salt
thereof, acrylamidepropyldimethylamine and a salt or quaternary
salt thereof, N-methylolacrylamide and a derivative thereof, etc.;
methacrylamides and derivatives thereof, such as methacrylamide,
N-methylmethacrylamide, N-ethylmethacrylamide,
methacrylamidepropanesulfonic acid and a salt thereof,
methacrylamidepropyldimethylamine and a salt or quaternary salt
thereof, N-methylolmethacrylamide and a derivative thereof, etc.;
vinyl ethers, such as methyl vinyl ether, ethyl vinyl ether,
n-butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl ether,
dodecyl vinyl ether, stearyl vinyl ether, etc.; nitriles, such as
acrylonitrile, methacrylonitrile, etc.; vinyl halides, such as
vinyl chloride, vinyl fluoride, etc.; vinylidene halides, such as
vinylidene chloride, vinylidene fluoride, etc.; allyl compounds,
such as allyl acetate, allyl chloride, etc.; maleate esters or
maleic anhydride; vinyl silyl compounds, such as
vinyltrimethoxysilane, etc.; isopropenyl acetate; and the like.
However, the other monomer is not limited thereto. In the case of
copolymerizing such other monomer, in general, such other monomer
is used in a proportion of less than 10 mol % relative to the vinyl
carboxylate compound. Besides, as the other monomer, styrene and
styrene derivatives, monomers having a hydroxyl group, a carboxyl
group, or a carboxylate group, and the like can be used.
[0177] In the layer B, as a component other than the thermoplastic
resin, such as the polyvinyl acetal resin, etc., a plasticizer, an
antioxidant, an ultraviolet ray absorber, a photostabilizer, an
adhesion modifier, an antiblocking agent, a pigment, a dye, a heat
insulating material (for example, an inorganic heat insulating fine
particle or an organic heat insulating material each having
infrared absorption ability), and the like may be added, if
desired.
(Plasticizer)
[0178] Though the plasticizer which is used for the layer B of the
present invention is not particularly limited, carboxylic acid
ester-based plasticizers, such as monovalent carboxylic acid
ester-based or polyvalent carboxylic acid ester-based plasticizers,
etc.; phosphate ester-based plasticizers; organic phosphite
ester-based plasticizers; and the like can be used. Besides,
polymeric plasticizers, such as carboxylic acid polyester-based,
carbonic acid polyester-based, or polyalkylene glycol-based
plasticizers, etc.; ester compounds of a hydroxycarboxylic acid and
a polyhydric alcohol, such as castor oil, etc.; and
hydroxycarboxylic acid ester-based plasticizers, such as an ester
compound of a hydroxycarboxylic acid and a monohydric alcohol,
etc., can also be used.
[0179] The monovalent carboxylic acid ester-based plasticizer is a
compound obtained through a condensation reaction between a
monovalent carboxylic acid, such as butanoic acid, isobutanoic
acid, hexanoic acid, 2-ethylbutanoic acid, heptanoic acid, octylic
acid, 2-ethylhexanoic acid, lauric acid, etc., and a polyhydric
alcohol, such as ethylene glycol, diethylene glycol, triethylene
glycol, tetraethylene glycol, polyethylene glycol, polypropylene
glycol, glycerin, etc., and specific examples of the compound
include triethylene glycol di-2-diethylbutanoate, triethylene
glycol diheptanoate, triethylene glycol di-2-ethylhexanoate,
triethylene glycol dioctanoate, tetraethylene glycol
di-2-ethylbutanoate, tetraethylene glycol diheptanoate,
tetraethylene glycol di-2-ethylhexanoate, tetraethylene glycol
dioctanoate, diethylene glycol di-2-ethylhexanoate, PEG#400
di-2-ethylhexanoate, triethylene glycol mono-2-ethylhexanoate, a
fully or partially esterified compound of glycerin or diglycerin
with 2-ethylhexanoic acid, and the like. "PEG#400" as referred to
herein expresses a polyethylene glycol having an average molecular
weight of 350 to 450.
[0180] As the polyvalent carboxylic acid ester-based plasticizer,
there are exemplified compounds obtained through a condensation
reaction between a polyvalent carboxylic acid, such as adipic acid,
succinic acid, azelaic acid, sebacic acid, phthalic acid,
isophthalic acid, terephthalic acid, trimellitic acid, etc., and an
alcohol having 1 to 12 carbon atoms, such as methanol, ethanol,
butanol, hexanol, 2-ethylbutanol, heptanol, octanol,
2-ethylhexanol, decanol, dodecanol, butoxyethanol,
butoxyethoxyethanol, benzyl alcohol, etc. Specific examples of the
compound include dihexyl adipate, di-2-ethylbutyl adipate, diheptyl
adipate, dioctyl adipate, di-2-ethylhexyl adipate, di(butoxyethyl)
adipate, di(butoxyethoxyethyl) adipate, mono(2-ethylhexyl) adipate,
dibutyl sebacate, dihexyl sebacate, di-2-ethylbutyl sebacate,
dibutyl phthalate, dihexyl phthalate, di(2-ethylbutyl) phthalate,
dioctyl phthalate, di(2-ethylhexyl) phthalate, benzylbutyl
phthalate, didodecyl phthalate, and the like.
[0181] Examples of the phosphoric acid-based plasticizer or
phosphorous acid-based plasticizer include compounds obtained
through a condensation reaction between phosphoric acid or
phosphorous acid and an alcohol having 1 to 12 carbon atoms, such
as methanol, ethanol, butanol, hexanol, 2-ethylbutanol, heptanol,
octanol, 2-ethylhexanol, decanol, dodecanol, butoxyethanol,
butoxyethoxyethanol, benzyl alcohol, etc. Specific examples of the
compound include trimethyl phosphate, triethyl phosphate, tripropyl
phosphate, tributyl phosphate, tri(2-ethylhexyl) phosphate,
tri(butoxyethyl) phosphate, tri(2-ethylhexyl) phosphite, and the
like.
[0182] As the carboxylic acid polyester-based plasticizer, there
may be used carboxylic acid polyesters obtained through alternate
copolymerization between a polyvalent carboxylic acid, such as
oxalic acid, malonic acid, succinic acid, adipic acid, suberic
acid, sebacic acid, dodecane diacid, 1,2-cyclohexanedicarboxylic
acid, 1,3-cyclohexanedicarboyxlic acid, 1,4-cyclohexanedicarboxylic
acid, etc., and a polyhydric alcohol, such as ethylene glycol,
diethylene glycol, triethylene glycol, tetraethylene glycol,
1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol,
1,3-butylene glycol, 1,4-butylene glycol, 1,2-pentanediol,
1,5-pentanediol, 2,4-pentanediol, 1,2-hexanediol, 1,6-hexanediol,
3-methyl-1,5-pentanediol, 3-methyl-2,4-pentanediol,
1,2-heptanediol, 1,7-heptanediol, 1,2-octanediol, 1,8-octanediol,
1,2-nonanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol,
1,2-decanediol, 1,10-decanediol, 1,2-dodecanediol,
1,12-dodecanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol,
1,4-cyclohexanediol, 1,2-bis(hydroxymethyl)cyclohexane,
1,3-bis(hydroxymethyl)cyclohexane,
1,4-bis(hydroxymethyl)cyclohexane, etc.; polymers of
hydroxycarboxylic acids (hydroxycarboxylic acid polyesters) of an
aliphatic hydroxycarboxylic acid, such as glycolic acid, lactic
acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid,
4-hydroxybutyric acid, 6-hydroxyhexanoic acid, 8-hydroxyhexanoic
acid, 10-hydroxydecanoic acid, and 12-hydroxydodecanoic acid, or a
hydroxycarboxylic acid having an aromatic ring, such as
4-hydroxybenzoic acid, 4-(2-hydroxyethyl)benzoic acid, etc.; and
carboxylic acid polyesters obtained through ring opening
polymerization of a lactone compound, such as an aliphatic lactone
compound, e.g., .gamma.-butyrolactone, .gamma.-valerolactone,
.delta.-valerolactone, .beta.-methyl-.delta.-valerolactone,
.delta.-hexanolactone, .epsilon.-caprolactone, lactide, etc., a
lactone compound having an aromatic ring, phthalide, or the like. A
terminal structure of such a carboxylic acid polyester is not
particularly limited, and it may be a hydroxyl group or a carboxyl
group, or it may also be an ester bond resulting from allowing a
terminal hydroxyl group or a terminal carboxyl group to react with
a monovalent carboxylic acid or a monohydric alcohol.
[0183] Examples of the carbonic acid polyester-based plasticizer
include carbonic acid polyesters obtained through alternate
copolymerization of a polyhydric alcohol, such as ethylene glycol,
diethylene glycol, triethylene glycol, tetraethylene glycol,
1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol,
1,3-butylene glycol, 1,4-butylene glycol, 1,2-pentanediol,
1,5-pentanediol, 2,4-pentanediol, 1,2-hexanediol, 1,6-hexanediol,
3-methyl-1,5-pentanediol, 3-methyl-2,4-pentanediol,
1,2-pentanediol, 1,7-heptanediol, 1,2-octanediol, 1,8-octanediol,
1,2-nonanediol, 1,9-nonanediol, 2-methyl-1,8-octnediol,
1,2-decanediol, 1,10-decanediol, 1,2-dodecanediol,
1,12-dodecanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol,
1,4-cyclohexanediol, 1,2-bis(hydroxymethyl)cyclohexane,
1,3-bis(hydroxymethyl)cyclohexane,
1,4-bis(hydroxymethyl)cyclohexane, etc. and a carbonate ester, such
as dimethyl carbonate, diethyl carbonate, etc., by means of an
ester interchange reaction. Though a terminal structure of such a
carbonic acid polyester compound is not particularly limited, it
may be a carbonate ester group, a hydroxyl group, or the like.
[0184] Examples of the polyalkylene glycol-based plasticizer
include polymers obtained through ring opening polymerization of an
alkylene oxide, such as ethylene oxide, propylene oxide, butylene
oxide, oxetane, etc., with a monohydric alcohol, a polyhydric
alcohol, a monovalent carboxylic acid, or a polyvalent carboxylic
acid as an initiator.
[0185] Examples of the hydroxycarboxylic acid ester-based
plasticizer include monohydric alcohol esters of a
hydroxycarboxylic acid, such as methyl ricinoleate, ethyl
ricinoleate, butyl ricinoleate, methyl 6-hydroxyhexanoate, ethyl
6-hydroxyhexanoate, and butyl 6-hydroxyhexnoate; polyhydric alcohol
esters of a hydroxycarboxylic acid, such as ethylene glycol
di(6-hydroxyhexanoic acid) ester, diethylene glycol
di(6-hydroxyhexanoic acid) ester, triethylene glycol
di(6-hydroxyhexanoic acid) ester, 3-methyl-1,5-pentanediol
di(6-hydroxyhexanoic acid) ester, 3-methyl-1,5-pentanediol
di(2-hydroxybuturic acid) ester, 3-methyl-1,5-pentanediol
di(3-hydroxybutyric acid) ester, 3-methyl-1,5-pentanediol
di(4-hydroxybutyric acid) ester, triethylene glycol
di(2-hydroxybutyric acid) ester, glycerin tri(ricinoleic acid)
ester, and di(1-(2-ethylhexyl)) L-tartarate; and castor oil.
Besides, polyhydric alcohol ester compounds of a hydroxyl
carboxylic acid in which a number of k groups derived from a
hydroxycarboxylic acid are replaced with a group derived from a
carboxylic acid not containing a hydroxyl group or with a hydrogen
atom can also be used, and as such a hydroxyl carboxylic acid
ester, those obtained by a conventionally known method can also be
used.
[0186] In the present invention, these plasticizers may be used
solely or may be used in combination of two or more thereof.
[0187] In the case where the plasticizer is contained in the layer
B, from the viewpoints of compatibility with the resin
(particularly, the polyvinyl acetal resin) to be used for the layer
B together with the plasticizer, low migration properties into
another layer, and enhancement of non-migration properties, it is
preferred to use an ester-based plasticizer or an ether-based
plasticizer, each of which has a melting point of 30.degree. C. or
lower and a hydroxyl value of 15 mgKOH/g or more and 450 mgKOH/g or
less, or an ester-based plasticizer or an ether-based plasticizer,
each of which is amorphous and has a hydroxyl value of 15 mgKOH/g
or more and 450 mgKOH/g or less. The term "amorphous" as referred
to herein means that a melting point is not observed at a
temperature of -20.degree. C. or higher. The hydroxyl value is
preferably 15 mgKOH/g or more, more preferably 30 mgKOH/g or more,
and optimally 45 mgKOH/g or more. In addition, the hydroxyl value
is preferably 450 mgKOH/g or less, more preferably 360 mgKOH/g or
less, and optimally 280 mgKOH/g or less. Examples of the
ester-based plasticizer include polyesters satisfying the
above-described prescriptions (e.g., the above-described carboxylic
acid polyester-based plasticizer and carbonic acid polyester-based
plasticizers, etc.) and hydroxycarboxylic acid ester compounds
(e.g., the above-described hydroxycarboxylic acid ester-based
plasticizers, etc.), and examples of the ether-based plasticizer
include polyether compounds satisfying the above-described
prescriptions (e.g., the above-described polyalkylene glycol-based
plasticizers, etc.).
[0188] A content of the plasticizer is preferably 50 parts by mass
or less, more preferably 40 parts by mass or less, still more
preferably 30 parts by mass or less, yet still more preferably 20
parts by mass or less, even yet still more preferably 10 parts by
mass or less, especially preferably 6 parts by mass or less, and
most preferably 0 part by mass (namely, the plasticizer is not
contained) based on 100 parts by mass of the thermoplastic resin,
such as the polyvinyl acetal resin, etc. When the content of the
plasticizer is more than 50 parts by mass based on 100 parts by
mass of the thermoplastic resin, such as the polyvinyl acetal
resin, etc., there is a tendency that the handling properties of
the laminate are deteriorated, or the shear storage modulus of each
of the layer B and the laminate is lowered. In addition, there is a
tendency that a time-dependent change of sound insulating
properties after preparation of the laminated glass becomes large,
so that the stability of sound insulating performance is lowered.
It is to be noted that two or more plasticizers may also be used in
combination.
[0189] A compound having a hydroxyl group can be used as the
plasticizer. A proportion of the content of the compound having a
hydroxyl group relative to the total amount of the plasticizer to
be used for the layer B is preferably 10% by mass or more, more
preferably 15% by mass or more, still more preferably 20% by mass
or more, yet still more preferably 50% by mass or more, even yet
still more preferably 70% by mass or more, especially preferably
80% by mass or more, and most preferably 90% by mass or more. The
proportion of the content of the compound having a hydroxyl group
relative to the total amount of the plasticizer to be used for the
layer B is preferably 100% by mass or less, more preferably 90% by
mass or less, and still more preferably 80% by mass or less. The
compound having a hydroxyl group has high compatibility with the
resin, particularly the polyvinyl acetal resin or ionomer and is
low in migration properties into another resin layer, and hence, a
laminate with excellent stability in sound insulating performance
can be obtained.
(Other Additive Components)
[0190] Examples of the antioxidant include phenol-based
antioxidants, phosphorus-based antioxidants, sulfur-based
antioxidants, and the like. Of those, phenol-based antioxidants are
preferred, and alkyl-substituted phenol-based antioxidants are
especially preferred.
[0191] Examples of the phenol-based antioxidant include
acrylate-based compounds, such as
2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl
acrylate,
2,4-di-t-amyl-6-(1-(3,5-di-t-amyl-2-hydroxyphenyl)ethyl)phenyl
acrylate, etc.; alkyl-substituted phenol-based compounds, such as
2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol,
octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate,
2,2'-methylene-bis(4-methyl-6-t-butylphenol),
4,4'-butylidene-bis(4-methyl-6-t-butylphenol),
4,4'-butylidene-bis(6-t-butyl-m-cresol),
4,4'-thiobis(3-methyl-6-t-butylphenol),
bis(3-cyclohexyl-2-hydroxy-5-methylphenyl)methane,
3,9-bis(2-(3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyl
oxy)-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane,
1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane,
1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl) benzene,
tetrakis(methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate)methan-
e, triethylene glycol
bis(3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate), etc.;
triazine group-containing phenol-based compounds, such as
1,3,5-tris(2,6-dimethyl-3-hydroxy-4-t-butylbenzyl)-1,3,5-triazine-2,4,6(1-
H,3H,5H)-trione,
6-(4-hydroxy-3,5-di-t-butylanilino)-2,4-bis-octylthio-1,3,5-triazine,
6-(4-hydroxy-3,5-dimethylanilino)-2,4-bis-octylthio-1,3,5-triazine,
6-(4-hydroxy-3-methyl-5-t-butylanilino)-2,4-bis-octylthio-1,3,5-triazine,
2-octylthio-4,6-bis-(3,5-di-t-butyl-4-oxyanilino)-1,3,5-triazine,
etc.; and the like.
[0192] Examples of the phosphorus-based antioxidant include
monophosphite-based compounds, such as triphenyl phosphite,
diphenylisodecyl phosphite, phenyldiisodecyl phosphite,
tris(nonylphenyl) phosphite, tris(dinonylphenyl) phosphite,
tris(2-t-butyl-4-methylphenyl) phosphite, tris(2,4-di-t-butyl)
phosphite, tris(cyclohexylphenyl) phosphite,
2,2-methylenebis(4,6-di-t-butylphenyl)octyl phosphite,
9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,
10-(3,5-di-t-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanth-
rene-10-oxide,
10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene, etc.;
diphosphite-based compounds, such as
4,4'-butylidene-bis(3-methyl-6-t-butylphenyl-di-tridecylphosphite),
4,4'-isopropylidene-bis(phenyl-di-alkyl(C12-C15) phosphite),
4,4'-isopropylidene-bis(diphenylmonoalkyl(C12-C15)phosphite),
1,1,3-tris(2-methyl-4-di-tridecylphosphite-5-t-butylphenyl) butane,
tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylene phosphite, etc.;
and the like. Of those, monophosphite-based compounds are
preferred.
[0193] Examples of the sulfur-based antioxidant include dilauryl
3,3'-thiodipropionate, distearyl 3,3-thiodipropionate, lauryl
stearyl 3,3'-thiodipropionate,
pentaerythritol-tetrakis-(.beta.-lauryl-thiopropionate),
3,9-bis(2-dodecylthioethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane,
and the like.
[0194] These antioxidants can be used solely or in combination of
two or more thereof. A compounding amount of the antioxidant is
preferably 0.001 parts by mass or more, and more preferably 0.01
parts by mass or more based on 100 parts by mass of the
thermoplastic resin. In addition, the compounding amount of the
antioxidant is preferably 5 parts by mass or less, and more
preferably 1 part by mass or less based on 100 parts by mass of the
thermoplastic resin. When the amount of the antioxidant is smaller
than 0.001 parts by mass, there is a concern that the sufficient
effects are hardly exhibited, whereas even when it is more than 5
parts by mass, remarkable effects are not expected.
[0195] In addition, examples of the ultraviolet ray absorber
include benzotriazole-based ultraviolet ray absorbers, such as
2-(5-methyl-2-hydroxyphenyl)benzotriazole,
2-[2-hydroxy-3,5-bis(.alpha.,.alpha.'-dimethylbenzyl)phenyl]-2H-benzotria-
zole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole,
2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole,
2-(3,5-di-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole,
2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole,
2-(2'-hydroxy-5'-t-octylphenyl)triazole, etc.; hindered amine-based
ultraviolet ray absorbers, such as 2,2,6,6-tetramethyl-4-piperidyl
benzoate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,
bis(1,2,2,6,6-pentamethyl-4-piperidyl)-2-(3,5-di-t-butyl-4-hydroxybenzyl)-
-2-n-butylmalonate,
4-(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy)-1-(2-(3-(3,5-di-t-buty-
l-4-hydroxyphenyl)propionyloxy)ethyl)-2,2,6,6-tetramethylpiperidine,
etc.; benzoate-based ultraviolet ray absorbers, such as
2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate,
hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate, etc.; and the like. An
addition amount of such an ultraviolet ray absorber is preferably
10 ppm or more, and more preferably 100 ppm or more on the basis of
a mass relative to the thermoplastic resin. In addition, the
addition amount of the ultraviolet ray absorber is preferably
50,000 ppm or less, and more preferably 10,000 ppm or less on the
basis of a mass relative to the thermoplastic resin. When the
addition amount of the ultraviolet ray absorber is smaller than 10
ppm, there is a concern that the sufficient effects are hardly
exhibited, whereas even when the addition amount of the ultraviolet
ray absorber is more than 50,000 ppm, remarkable effects are not
expected. These ultraviolet ray absorbers can also be used in
combination of two or more thereof.
[0196] Examples of the photostabilizer include hindered amine-based
materials, such as "ADEKA STAB LA-57 (a trade name)", manufactured
by Adeka Corporation and "TINUVIN 622 (a trade name)", manufactured
by Ciba Specialty Chemicals Inc.
[0197] In addition, it is also possible to control the adhesion of
the resulting laminate to a glass or the like, if desired. As a
method of controlling the adhesion, in general, there are
exemplified a method of adding an additive to be used as an
adhesion modifier of a laminated glass, a method of adding an
additive of every sort for modifying the adhesion, and the like. By
such a method, an interlayer film for laminated glass containing an
adhesion modifier and/or an adhesive of every sort for modifying
the adhesion is obtained.
[0198] As the adhesion modifier, for example, those disclosed in WO
03/033583A can be used; alkali metal salts and alkaline earth metal
salts are preferably used; and examples thereof include salts of
potassium, sodium, magnesium, and the like. Examples of the salt
include salts of organic acids, such as octanoic acid, hexanoic
acid, butyric acid, acetic acid, formic acid, etc.; inorganic
acids, such as hydrochloric acid, nitric acid, etc.; and the
like.
[0199] Though an optimal addition amount of the adhesion modifier
varies with the additive to be used, it is preferably adjusted in
such a manner that an adhesive force of the resulting laminate to a
glass is generally adjusted to 3 or more and 10 or less in a pummel
test (described in WO 03/033583A or the like). In particular, in
the case where high penetration resistance is required, the
addition amount of the adhesion modifier is more preferably
adjusted in such a manner that the adhesive force is 3 or more and
6 or less, whereas in the case where high glass scattering
preventing properties are required, the addition amount of the
adhesion modifier is more preferably adjusted in such a manner that
the adhesive force is 7 or more and 10 or less. In the case where
high glass scattering preventing properties are required, it is
also a useful method that the adhesive modifier is not added.
[Laminate (Interlayer Film for Laminated Glass)]
[0200] The laminate of the present invention is composed of a
laminate in which the layer A having the above-described properties
is laminated between the at least two layers B having the
above-described properties. By taking such a constitution, a
laminate with excellent sound insulating properties and bending
strength is obtained. The laminate of the present invention can be
suitably used as an interlayer film for laminated glass.
[0201] A production method of the laminate of the present invention
is not particularly limited, the laminate may be produced by a
method in which after uniformly kneading the resin composition
constituting the layer B, the layer B is prepared by a known film
formation method, such as an extrusion method, a calender method, a
pressing method, a casting method, an inflation method, etc., the
layer A is prepared with the resin by the same method, and these
layers may be laminated by means of press molding or the like, or
the layer B, the layer A, and other necessary layer may be molded
by a co-extrusion method.
[0202] Among the known film formation methods, in particular, a
method of producing a laminate using an extrusion machine is
suitably adopted. A resin temperature at the time of extrusion is
preferably 150.degree. C. or higher, and more preferably
170.degree. C. or higher. In addition, the resin temperature at the
time of extrusion is preferably 250.degree. C. or lower, and more
preferably 230.degree. C. or lower. When the resin temperature is
too high, there is a concern that the used resin causes
decomposition, thereby deteriorating the resin. Conversely, when
the temperature is too low, discharge from the extrusion machine is
not stabilized, resulting in causing a mechanical trouble. In order
to efficiently remove a volatile material, it is preferred to
remove the volatile material by measure of pressure reduction from
a vent port of the extrusion machine.
[0203] In the laminate of the present invention, a shear storage
modulus at a temperature of 25.degree. C. as measured by conducting
a complex shear viscosity test under a condition at a frequency of
1 Hz in accordance with JIS K 7244-10 is preferably 1.30 MPa or
more, more preferably 2.00 MPa or more, and still more preferably
3.00 MPa or more. In the case where the shear storage modulus under
the above-described conditions is 1.30 MPa or more, on the occasion
of using the laminate for a laminated glass, the bending strength
is improved. On the other hand, from the viewpoints of making the
appearance of the interlayer film for laminated glass more
favorable and making the production of a laminated glass easy, in
the laminate, the shear storage modulus under the above-described
conditions is preferably 10.0 MPa or less, more preferably 8.00 MPa
or less, and still more preferably 6.00 MPa or less. The laminate
in which the shear storage modulus as measured under the
above-described conditions is 1.30 MPa or more can be, for example,
obtained by laminating a layer A including a composition containing
an elastomer having a peak at which a tan .delta. is maximum, in
the range of from -40 to 30.degree. C. and a plurality of layers B
having a shear storage modulus at a temperature of 25.degree. C. of
10.0 MPa or more in such a manner that the layer A is interposed
between the at least two layers B.
[0204] In the laminate (interlayer film for laminated glass) of the
present invention, a shear storage modulus at a temperature of
50.degree. C. as measured by conducting a complex shear viscosity
test under a condition at a frequency of 1 Hz in accordance with
JIS K 7244-10 is preferably 1.30 MPa or more, more preferably 1.50
MPa or more, and still more preferably 2.00 MPa or more. In the
case where the above-described shear storage modulus is 1.30 MPa or
more, in particular, even when the temperature of the laminate
increases to 50.degree. C. or higher, the bending strength is
improved on the occasion of using the laminate for a laminated
glass. On the other hand, from the viewpoints of making the
appearance more favorable and making the production of a laminated
glass easy, in the laminate, the shear storage modulus under the
above-described condition is preferably 6.00 MPa or less, more
preferably 4.00 MPa or less, and still more preferably 3.00 MPa or
less. The laminate having a shear storage modulus at a temperature
of 50.degree. C. as measured under the above-described condition of
1.30 MPa or more can be obtained by laminating a layer A including
a composition containing an elastomer having a peak at which a tan
.delta. is maximum, in the range of from -40 to 30.degree. C. and a
plurality of layers B having a shear storage modulus at a
temperature of 25.degree. C. of 10.0 MPa or more in such a manner
that the layer A is interposed between the at least two layers
B.
[0205] A film thickness of the layer A is preferably 20 .mu.m or
more, more preferably 25 .mu.m or more, still more preferably 30
.mu.m or more, especially preferably 50 .mu.m or more, and most
preferably 100 .mu.m or more. In addition, the film thickness of
the layer A is preferably 500 .mu.m or less, more preferably 400
.mu.m or less, and still more preferably 300 .mu.m or less. When
the film thickness of the layer A is less than 20 .mu.m, the sound
insulating properties tend to be lowered, whereas when the film
thickness of the layer A is more than 400 .mu.m, there is a
tendency that when a laminated glass is prepared, mechanical
characteristics, such as penetration resistance, etc., are
deteriorated, so that a safety performance as a laminated glass is
impaired. In the case where a plurality of the layers A is included
in the laminate of the present invention, it is preferred that a
total thickness of the entirety of the layer A satisfies the
foregoing range.
[0206] A film thickness of the layer B is preferably 100 .mu.m or
more, more preferably 150 .mu.m or more, and still more preferably
200 .mu.m or more. The film thickness of the layer B is preferably
650 .mu.m or less, more preferably 500 .mu.m or less, still more
preferably 350 .mu.m or less, and yet still more preferably 300
.mu.m or less. When the film thickness of the layer B is less than
100 .mu.m, there is a tendency that the bending rigidity of the
laminate is small, so that the sound insulating properties in a
high-frequency region are lowered, whereas when the film thickness
of the layer B is more than 650 .mu.m, there is a tendency that the
sound insulating properties are lowered regardless of the frequency
region, or a time-dependent change of sound insulating performance
is liable to be caused, so that the stability of sound insulating
performance is lowered.
[0207] A total thickness of the entirety of the layer B is
preferably 300 .mu.m or more, more preferably 400 .mu.m or more,
still more preferably 500 .mu.m or more, and especially preferably
600 .mu.m or more. The total thickness of the entirety of the layer
B is preferably 750 .mu.m or less, more preferably 720 .mu.m or
less, and still more preferably 700 .mu.m or less. When the total
thickness of the entirety of the layer B is 300 .mu.mm or more, the
bending strength of the laminate tends to become large, whereas
when the total thickness of the entirety of the layer B is 750
.mu.m or less, the moldability is improved, so that the resulting
laminate is liable to be wound up by a roll.
[0208] A ratio of the total thickness of the layer A to the total
thickness of the layer B ((total thickness of the layer A)/(total
thickness of the layer B)) is preferably 1/1 or less, more
preferably 1/2 or less, and still more preferably 1/3 or less. The
ratio of the total thickness of the layer A to the total thickness
of the layer B is preferably 1/30 or more, more preferably 1/15 or
more, still more preferably 1/6.5 or more, and especially
preferably 1/5 or more. When the above-described ratio is smaller
than 1/30, the sound insulating effect of the laminate tends to
become small. On the other hand, when the above-described ratio is
more than 1/1, there is a tendency that the bending rigidity of the
laminate becomes small, the sound insulating properties in a
high-frequency region are lowered, a time-dependent change of sound
insulating performance is liable to be caused, so that the
stability of sound insulating performance is lowered, or the shear
storage modulus of the laminate is lowered, so that the bending
strength of the laminate is lowered.
[0209] For example, in the case where the thermoplastic elastomer
to be contained in the layer A is only one kind (or, even in the
case where two or more kinds of thermoplastic elastomers are
contained in the layer A, when thermoplastic elastomers in which a
difference in the peak temperature of tan .delta. is less than
5.degree. C. are used), when the peak temperature of tan .delta. of
the thermoplastic elastomer layer is -20.degree. C. or lower, a
film thickness of the thermoplastic elastomer layer is preferably
20 .mu.m or more, and more preferably 30 .mu.m or more, and it is
preferably 120 .mu.m or less, and more preferably 100 .mu.m or
less. When the peak temperature of tan .delta. of the layer A
containing the thermoplastic elastomer is higher than -20.degree.
C. and -15.degree. C. or lower, the film thickness of the layer A
containing the thermoplastic elastomer is preferably 50 .mu.m or
more, and more preferably 70 .mu.m or more, and it is preferably
200 .mu.m or less, and more preferably 160 .mu.m or less. When the
peak temperature of tan .delta. of the layer A containing the
thermoplastic elastomer is higher than -15.degree. C., the film
thickness of the layer A containing the thermoplastic elastomer is
preferably 80 .mu.m or more, and more preferably 100 .mu.m or more,
and it is preferably 300 .mu.m or less, and more preferably 260
.mu.m or less. When the film thickness of the layer A containing
the thermoplastic elastomer falls outside the preferred range,
there is a tendency that the sound insulating properties at room
temperature are lowered, or the bending strength of the resulting
laminated glass is lowered.
[0210] A film thickness of the layer B is preferably 50 .mu.m or
more, and more preferably 100 .mu.m or more. The film thickness of
the layer B is preferably 1,000 .mu.m or less, and more preferably
500 .mu.m or less. When the film thickness of the layer B is less
than 50 .mu.m, there is a tendency that the bending strength of the
laminate becomes small, or the sound insulating properties in a
high-frequency region are lowered.
[0211] As shown in FIG. 1, the laminate in the present embodiment
has a lamination constitution in which a layer A 1 is interposed
between a layer B 2a and a layer B 2b. Though the lamination
constitution in the laminate is determined depending upon the
purpose, it may be, in addition to the lamination constitution of
(layer B)/(layer A)/(layer B), a lamination constitution of (layer
B)/(layer A)/(layer B)/(layer A), or (layer B)/(layer A)/(layer
B)/(layer A)/(layer B). When the laminate is a two-layer
constitution as in (layer A)/(layer B), the sound insulating
properties or bending strength of the interlayer film for laminated
glass tends to be lowered.
[0212] One or more layers may also be included as a layer (referred
to as "layer C") other than the layers A and B. For example,
lamination constitutions, such as (layer B)/(layer A)/(layer
C)/(layer B), (layer B)/(layer A)/(layer B)/(layer C), (layer
B)/(layer C)/(layer A)/(layer C)/(layer B), (layer B)/(layer
C)/(layer A)/(layer B)/(layer C), (layer B)/(layer A)/(layer
C)/(layer B)/(layer C), (layer C)/(layer B)/(layer A)/(layer
B)/(layer C), (layer C)/(layer B)/(layer A)/(layer C)/(layer
B)/(layer C), (layer C)/(layer B)/(layer C)/(layer A)/(layer
C)/(layer B)/(layer C), etc., may be adopted. In addition, in the
above-described lamination constitution, the components in the
layer C may be identical with or different from each other. This is
also applicable to the components in the layer A or the layer
B.
[0213] It is to be noted that a layer composed of a known resin is
usable as the layer C. For example, polyethylene, polypropylene,
polyvinyl chloride, polystyrene, polyvinyl acetate, polyurethane,
polytetrafluoroethylene, an acrylic resin, a polyamide, a
polyacetal, a polycarbonate, a polyester inclusive of polyethylene
terephthalate and polybutylene terephthalate, a cyclic polyolefin,
polyphenylene sulfide, polytetrafluoroethylene, a polysulfone, a
polyether sulfone, a polyarylate, a liquid crystal polymer, a
polyimide, and the like can be used. In addition, in the layer C, a
plasticizer, an antioxidant, an ultraviolet ray absorber, a
photostabilizer, an antiblocking agent, a pigment, a dye, a heat
insulating material (for example, an inorganic heat insulating fine
particle or an organic heat insulating material each having
infrared absorption ability), and the like may also be added, if
desired.
[0214] The laminate can be given a heat insulating function, and a
transmittance at wavelength of 1500 nm can be regulated to 50% or
less when the a laminated glass is formed, by incorporating the
heat insulating material, for example, an inorganic heat insulating
fine particle or a heat insulating compound into the laminate of
the present invention. The heat insulating fine particle may be
contained in any of the layer A and the layer B, and the layer C to
be included, if desired. The heat insulating fine particle may be
contained in only any one of the layers, or may be contained in the
plural layers. In the case of incorporating the insulating fine
particle, from the viewpoint of suppressing the optical unevenness,
it is preferred that the insulating fine particle is contained in
the at least one layer A. Examples of the heat insulating fine
particle include a metal-doped indium oxide, such as tin-doped
indium oxide (ITO), etc., a metal-doped tin oxide, such as
antimony-doped tin oxide (ATO), etc., a metal-doped zinc oxide,
such as aluminum-doped zinc oxide (AZO), etc., a metal element
composite tungsten oxide represented by a general formula:
M.sub.mWO.sub.n (M represents a metal element; m is 0.01 or more
and 1.0 or less; and n is 2.2 or more and 3.0 or less), zinc
antimonate (ZnSb.sub.2O.sub.5), lanthanum hexaboride, and the like.
Of those, ITO, ATO, and a metal element composite tungsten oxide
are preferred, and a metal element composite tungsten oxide is more
preferred. Examples of the metal element represented by M in the
metal element composite tungsten oxide include Cs, Tl, Rb, Na, K,
and the like, and in particular, Cs is preferred. From the
viewpoint of heat insulating properties, m is preferably 0.2 or
more, and more preferably 0.3 or more, and it is preferably 0.5 or
less, and more preferably 0.4 or less.
[0215] A content of the heat insulating fine particle is preferably
0.01% by mass or more, more preferably 0.05% by mass or more, still
more preferably 0.1% by mass or more, and especially preferably
0.2% by mass or more relative to the whole of the resins used for
the layers constituting the laminate. In addition, the content of
the heat insulating fine particle is preferably 5% by mass or less,
and more preferably 3% by mass or less. When the content of the
heat insulating fine particle is more than 5% by mass, there is a
concern that the transmittance of visible rays is influenced. From
the viewpoint of transparency of the laminate, an average particle
diameter of the heat insulating fine particle is preferably 100 nm
or less, and more preferably 50 nm or less. It is to be noted that
the average particle diameter of the heat insulating particle as
referred to herein means one measured by a laser diffraction
instrument.
[0216] Examples of the heat insulating compound include
phthalocyanine compounds, naphthalocyanine compounds, and the like.
From the viewpoint of further improving the heat insulating
properties, it is preferred that the heat insulating compound
contains a metal. Examples of the metal include Na, K, Li, Cu, Zn,
Fe, Co, Ni, Ru, Rh, Pd, Pt, Mn, Sn, V, Ca, Al, and the like, with
Ni being especially preferred.
[0217] A content of the heat insulating compound is preferably
0.001% by mass or more, more preferably 0.005% by mass or more, and
still more preferably 0.01% by mass or more relative to the whole
of the resins used for the layers constituting the laminate. In
addition, the content of the heat insulating compound is preferably
1% by mass or less, and more preferably 0.5% by mass or less. When
the content of the heat insulating compound is more than 1% by
mass, there is a concern that the transmittance of visible rays is
influenced.
[0218] In addition, it is preferred that a concave and convex
structure, such as a melt fracture, an embossing, etc., is formed
on the surface of the laminate of the present invention by a
conventionally known method. A shape of the melt fracture or
embossing is not particularly limited, and those which are
conventionally known can be adopted.
[0219] In addition, a total film thickness of the laminate is
preferably 20 .mu.m or more, and more preferably 100 .mu.m or more.
In addition, the total film thickness of the laminate is preferably
10,000 .mu.m or less, and more preferably 3,000 .mu.m or less. When
the film thickness of the laminate is too thin, there is a concern
that in preparing a laminated glass, lamination cannot be achieved
well. The film thickness of the laminate being too thick results in
an increase of the costs, and hence, such is not preferred.
[Laminated Glass]
[0220] When the constitution of the laminate of the present
invention is included in the inside of a glass, it is possible to
obtain a laminated glass with excellent bending strength, a
laminated glass with excellent sound insulating properties,
particularly sound insulating properties in a high-frequency
region, a laminated glass with excellent sound insulating
properties and stability of sound insulating performance, and a
laminated glass with excellent sound insulating properties over a
broad temperature range.
[0221] For that reason, the laminated glass of the present
invention can be suitably for a windshield for automobile, a side
glass for automobile, a sunroof for automobile, a rear glass for
automobile, or a glass for head-up display; a building member for a
window, a wall, a roof, a sunroof, a sound insulating wall, a
display window, a balcony, a handrail wall, or the like; a
partition glass member of a conference room, etc.; and the like. In
the case where the laminated glass including the constitution of
the laminate of the present invention in the inside thereof is
applied to a glass for head-up display, a cross-sectional shape of
the laminate to be used is preferably a shape in which an end
surface side of one side is thick, whereas an end surface side of
the other side is thin. In that case, the cross-sectional shape may
be a shape in which the whole is a wedge shape in such a manner
that it becomes gradually thin from the end surface side of one
side toward the end surface side of the other side, or may be a
shape in which a part of the cross section is a wedge shape such
that the thickness is identical until an arbitrary position between
the end surface of one side and the end surface of the other side,
and it becomes gradually thin from the foregoing arbitrary position
toward the end surface of the other side.
[0222] In general, two sheets of glass are used for the laminated
glass of the present invention. Though a thickness of the glass
constituting the laminated glass of the present invention is not
particularly limited, it is preferably 100 mm or less. In addition,
since the laminate of the present invention is excellent in bending
strength, even when a laminated glass is prepared by using a thin
sheet glass having a thickness of 2.8 mm or less, weight reduction
of the laminated glass can be realized without impairing the
strength of the laminated glass. From the viewpoint of weight
reduction, with respect to the thickness of the glass, a thickness
of at least one sheet of glass is preferably 2.8 mm or less, more
preferably 2.5 mm or less, still more preferably 2.0 mm or less,
and especially preferably 1.8 mm or less. In particular, by
regulating a thickness of the glass of one side to 1.8 mm or more,
regulating a thickness of the glass of the other side to 1.8 mm or
less, and regulating a difference in thickness between the
respective glasses to 0.2 mm or more, a laminated glass in which
thinning and weight reduction have been realized without impairing
the bending strength can be prepared. The difference in thickness
between the respective glasses is preferably 0.5 mm or more.
(Sound Insulating Properties)
[0223] The sound insulating properties of the laminated glass can
be evaluated in terms of a loss factor obtained by a damping test
by a central exciting method. The damping test is a test for
evaluating what value does the loss factor take by the frequency or
temperature. When the frequency is fixed, a loss factor that
becomes maximum in a certain temperature range is called a maximum
loss factor. In accordance with the damping measurement by a
central exciting method, a value of loss factor relative to a
frequency at a fixed temperature is obtained. In order to obtain a
maximum loss factor, the measurement is carried out by varying the
temperature to 0, 10, 20, 30, 40, and 50.degree. C., respectively,
and a linear form of the loss factor relative to the temperature at
a fixed frequency can be obtained from the obtained value. The
maximum loss factor is an index expressing a virtue of damping, and
specifically, it is an index expressing how fast the bending
vibration generated in a platy material decays. Namely, the maximum
loss factor is an index of sound insulating properties, and it may
be said that the higher the maximum loss factor of a laminated
glass, the higher the sound insulating properties of the laminated
glass are.
[0224] In the present embodiment, in the case where a laminated
glass is prepared by using the laminate as an interlayer film for
laminated glass, and the resulting laminated glass is subjected to
a damping test by a central exciting method, the maximum loss
factor at a frequency of 2,000 Hz and at a temperature of 0 to
50.degree. C. is preferably 0.20 or more, more preferably 0.25 or
more, and still more preferably 0.28 or more. In the case where the
maximum loss factor under the above-described conditions is less
than 0.20, the sound insulating properties of the laminated glass
are poor, so that the resulting laminated glass is not suited for
an application aiming at the sound insulation. The laminated glass
in which the maximum loss factor as measured under the
above-described conditions is 0.20 or more can be obtained by
laminating a layer A including a composition containing an
elastomer having a peak at which a tan .delta. is maximum, in the
range of from -40 to 30.degree. C. and a plurality of layers B
having a shear storage modulus at a temperature of 25.degree. C. as
measured by conducting a complex shear viscosity test of 10.0 MPa
or more in such a manner that the layer A is interposed between the
at least two layers B.
(Sound Insulating Properties in a High-Frequency Region)
[0225] Here, from the viewpoint that a laminated glass capable of
suppressing a lowering of the sound insulating performance in a
high-frequency region to be caused due to a coincidence phenomenon,
when the laminate of the present invention is interposed between
two sheets of float glass having a length of 300 mm, a width of 25
mm, and a thickness of 1.9 mm to prepare a laminated glass, a loss
factor at a quaternary resonance frequency as measured at
20.degree. C. by a central exciting method is preferably 0.2 or
more, more preferably 0.4 or more, and still more preferably 0.6 or
more. When the loss factor at a quaternary resonance frequency is
less than 0.2, the sound insulating properties tend to become not
sufficient. In order to regulate the loss factor at a quaternary
resonance frequency to 0.2 or more, for example, it is possible to
achieve such by a method of using a material in which a content of
the hard segment is a prescribed proportion or more (for example,
14% by mass or more) relative to the thermoplastic elastomer
constituting the layer A and regulating a ratio of the total
thickness of the layer A to the total thickness of the layer B
serving as a protective layer of the laminate to a prescribed
portion or more (for example, 1/6.5 or more), or other method.
[0226] The loss factor at a quaternary resonance frequency can be,
for example, measured by the following method. The laminate is
interposed between two sheets of commercially available float glass
(300 mm in length.times.25 mm in width.times.1.9 mm in thickness),
and a laminated glass is prepared by a vacuum bagging method
(condition: the temperature is increased from 30.degree. C. to
160.degree. C. for 60 minutes, followed by holding at 160.degree.
C. for 30 minutes). Thereafter, the center of the laminated glass
is fixed to a tip portion of an exciting force detector built in an
impedance head of an exciter of a mechanical impedance instrument,
a vibration is given to the center of the laminated glass at a
frequency in the range of from 0 to 10,000 Hz, and an exciting
force and an acceleration waveform at this point are detected,
thereby conducting a damping test of the laminated glass by a
central exciting method. A mechanical impedance at an exciting
point (the center of the laminated glass to which a vibration is
given) is determined on the basis of the obtained exciting force
and a speed signal obtained by integrating an acceleration single;
and in an impedance curve obtained by setting the frequency on the
abscissa and the mechanical impedance on the ordinate,
respectively, the loss factor of the laminated glass at a
quaternary resonance frequency can be determined from a frequency
expressing a peak of the quaternary mode and a half-width
value.
[0227] In addition, from the viewpoint of preparing a laminated
glass capable of suppressing a lowering of the sound insulating
performance in a high-frequency region to be caused due to a
coincidence phenomenon, when the laminate of the present invention
is interposed between two sheets of float glass having a length of
300 mm, a width of 25 mm, and a thickness of 1.9 mm to prepare a
laminated glass, a bending rigidity at the quaternary resonance
frequency as calculated in accordance with ISO 16940 (2008) is
preferably 150 Nm or more, and more preferably 200 Nm or more. When
the bending rigidity at a quaternary resonance frequency is less
than 150 Nm, the coincidence phenomenon is liable to be generated,
so that the sound insulating properties in a high-frequency region
tends to be lowered. In order to regulate the bending rigidity at a
quaternary resonance frequency to 150 Nm or more, for example, it
is possible to achieve such by a method of using a material in
which a content of the hard segment is a prescribed proportion or
more (for example, 14% by mass or more) relative to the
thermoplastic elastomer constituting the layer A and regulating a
ratio of the total thickness of the layer A to the total thickness
of the layer B serving as a protective layer of the laminate to a
prescribed portion or less (for example, 1/1 or less), or other
method.
[0228] In addition, an acoustic transmission loss at 6,300 Hz as
calculated in accordance with ISO 16940 (2008) by using the loss
factor and bending rigidity at a quaternary resonance frequency is
preferably 43 dB or more, and more preferably 45 dB or more. An
acoustic transmission loss at 8,000 Hz is preferably 50 dB or more,
and more preferably 53 dB or more. An acoustic transmission loss at
10,000 Hz is preferably 56 dB or more, and more preferably 60 dB or
more.
(Stability of Sound Insulating Performance)
[0229] Here, from the viewpoint of preparing a laminated glass in
which a time-dependent change of sound insulating performance after
preparation of the laminated glass is small and which is excellent
in stability of sound insulating performance, the laminate of the
present invention is preferably a laminate having the layer A
located between the at least two layers B and satisfying such that
with respect to a laminated glass prepared by interposing the
laminate of the present invention between glasses having a
thickness 2 mm and holding for contact bonding under conditions at
a temperature of 140.degree. C. and at a pressure of 1 MPa for 60
minutes, a loss factor .alpha. at 20.degree. C. and at 2,000 Hz as
measured by a damping test by a central exciting method is 0.2 or
more, and with respect to the laminated glass after holding at
18.degree. C. for one month, a ratio .beta./.alpha. of a loss
factor .beta. at 20.degree. C. and at 2,000 Hz as measured by a
damping test by a central exciting method to the loss factor
.alpha. is 0.70 or more; or a laminate having the layer A located
between the at least two layers B and satisfying such that with
respect to a laminated glass containing the laminate after holding
the laminated glass at 18.degree. C. for one month, a loss factor
.beta. at 20.degree. C. and at 2,000 Hz as measured by a damping
test by a central exciting method is 0.2 or more, and with respect
to a laminated glass after heating the laminated glass having been
held at 18.degree. C. for one month at 100.degree. C. for 24 hours,
a ratio .gamma./.beta. of a loss factor .alpha. at 20.degree. C.
and at 2,000 Hz as measured by a damping test by a central exciting
method to the loss factor .beta. is 0.80 or more and 1.30 or
less.
[0230] As a method of obtaining a laminate capable of satisfying
the prescribed requirements for the laminated glass regarding the
loss factors .alpha., .beta., and .gamma. as measured by a damping
test by a central exciting method as described later, for example,
there are exemplified the following methods of constituting the
laminate.
[0231] A first constitution is a constitution in which the layer A
is a layer containing a block copolymer having at least one
aromatic vinyl polymer block and at least one aliphatic unsaturated
hydrocarbon polymer block, or a hydrogenated product of the
copolymer; the layer B is a layer containing an ionomer resin or a
polyvinyl acetal resin and not containing a plasticizer or
containing a plasticizer, and in the case of containing a
plasticizer, a content of the plasticizer is more than 0 and 30
parts by mass or less (preferably 25 parts by mass or less, more
preferably 20 parts by mass or less, still more preferably 15 parts
by mass or less, and especially preferably 10 parts by mass or
less) based on 100 parts by mass of the resin; and a ratio of a
total thickness of the layer A to a total thickness of the layer B
((total thickness of the layer A)/(total thickness of the layer B))
is in the range of from 1/30 to 1/3.
[0232] In addition, a second constitution is a laminate having the
layer A located between the at least two layers B and having a
constitution in which the layer A is a layer containing a block
copolymer having at least one aromatic vinyl polymer block and at
least one aliphatic unsaturated hydrocarbon polymer block, or a
hydrogenated product of the copolymer; and the layer B is a layer
containing an ionomer resin or a polyvinyl acetal resin and not
containing a plasticizer or containing a plasticizer, and in the
case of containing a plasticizer, a content of the plasticizer is
more than 0 and 25 parts by mass or less (preferably 20 parts by
mass or less, more preferably 15 parts by mass or less, still more
preferably 10 parts by mass or less, and especially preferably 3
parts by mass or less) based on 100 parts by mass of the resin. In
this case, a ratio of a total thickness of the layer A to a total
thickness of the layer B is preferably in the range of from 1/30 to
1/1. In addition, as the block copolymer, it is preferred to use
the block copolymer as explained in the section of the layer A.
[0233] It is to be noted that on the occasion of adopting these
constitutions, it is preferred to use, as the ionomer resin or
polyvinyl acetal resin, the ionomer resin or polyvinyl acetal resin
as explained in the section of the layer B. These constitutions
merely exemplify the constitution of the laminate of the present
invention, and the laminate of the present invention is not limited
to these constitutions. In addition, the plasticizer which may be
contained in the layer B to be used for these constitutions is
preferably an ester-based plasticizer or an ether-based plasticizer
each having a melting point of 30.degree. C. or lower or being
amorphous and also having a hydroxyl value of 15 to 450 mgKOH/g or
less.
[0234] In the laminated glass obtained from the laminate of the
present invention, which is prepared by interposing the laminate
between two sheets of glass having a thickness 2 mm and contact
bonding under conditions at a temperature of 140.degree. C. and at
a pressure of 1 MPa for 60 minutes, the laminated glass after
preparation (for example, immediately after preparation) has a loss
factor .alpha. at 20.degree. C. and at 2,000 Hz as measured by a
damping test by a central exciting method of 0.2 or more,
preferably 0.25 or more, and more preferably 0.30 or more. When the
loss factor .alpha. under the above-described conditions is 0.2 or
more, the laminated glass has thoroughly high sound insulating
properties. It is to be noted that the terms "immediately after
preparation of the laminated glass" mean a time within 2 hours
after the laminated glass is prepared and finished with cooling to
room temperature.
[0235] In addition, with respect to the laminated glass after
holding the prepared laminated glass at 18.degree. C. for one
month, a ratio .beta./.alpha. of a loss factor 13 at 20.degree. C.
and at 2,000 Hz as measured by a damping test by a central exciting
method to the loss factor .alpha. is preferably 0.70 or more, more
preferably 0.80 or more, and still more preferably 0.87 or more. In
addition, .beta./.alpha. is preferably 1.20 or less, and more
preferably 1.10 or less. When .beta./.alpha. is 0.70 or more, the
stability of sound insulating performance is improved. On the other
hand, when .beta./.alpha. is 1.20 or less, the holding time can be
shortened.
[0236] In addition, with respect to a laminated glass after heating
the laminated glass having been held at 18.degree. C. for one month
at 100.degree. C. for 24 hours, a ratio .gamma./.beta. of a loss
factor .gamma. at 20.degree. C. and at 2,000 Hz as measured by a
damping test by a central exciting method to the loss factor .beta.
is preferably 0.80 or more, more preferably 0.87 or more, and still
more preferably 0.90 or more. In addition, .gamma./.beta. is 1.30
or less, preferably 1.20 or less, and more preferably 1.10 or less.
When .gamma./.beta. is 0.80 or more, or 1.30 or less, the stability
of sound insulating performance can be improved, and the holding
time can be shortened.
(Sound Insulating Properties Over a Broad Temperature Range)
[0237] Here, from the viewpoint of obtaining a laminated glass with
excellent sound insulating properties over a broad temperature
range, a maximum loss factor in a tertiary mode as measured by a
central exciting method is preferably 0.2 or more, more preferably
0.23 or more, and still more preferably 0.25 or more. When the loss
factor in a tertiary mode is less than 0.2, the sound insulating
properties tend to be not sufficient. In order to regulate the loss
factor in a tertiary mode to 0.2 or more, for example, it is
possible to achieve such by a method of using, as an internal layer
(layer A) serving as a sound insulating layer, a layer having a
peak at which a tan .delta. as measured by conducting a complex
shear viscosity test under a condition at a frequency of 1 Hz in
accordance with JIS K 7244-10 is maximum, in the range of
-40.degree. C. or higher and 30.degree. C. or lower (the peak will
be sometimes abbreviated as "peak temperature of tan .delta.") or,
as the thermoplastic elastomer constituting the layer A, an
elastomer in which a content of the hard segment is a prescribed
portion or less (for example, 50% by mass or less), and regulating
a thickness of the internal layer (layer A) serving as a sound
insulating layer to 20 .mu.m or more, or other method. In addition,
a loss factor at 20.degree. C. is preferably 0.2 or more, and more
preferably 0.25 or more. When the loss factor at 20.degree. C. is
less than 0.2, the sound insulating properties at room temperature
tend to be not sufficient. In order to regulate the loss factor at
20.degree. C. to 0.2 or more, for example, there is exemplified a
method of allowing a balance between the peak temperature of tan
.delta. of the layer A and the thickness of the layer A to fall
within an appropriate range.
[0238] The loss factor in a tertiary mode can be, for example,
measured by the following method. The laminate is interposed
between two sheets of commercially available float glass (50 mm in
width.times.300 mm in length.times.3 mm in thickness), and a
laminated glass is prepared by a vacuum bagging method (condition:
the temperature is increased from 30.degree. C. to 160.degree. C.
for 60 minutes, followed by holding at 160.degree. C. for 30
minutes). Thereafter, the center of the laminated glass is fixed to
a tip portion of an exciting force detector built in an impedance
head of an exciter of a mechanical impedance instrument, a
vibration is given to the center of the laminated glass at a
frequency in the range of from 0 to 8,000 Hz, and an exciting force
and an acceleration waveform at this point are detected, thereby
conducting a damping test of the laminated glass by a central
exciting method. A mechanical impedance at an exciting point (the
center of the laminated glass to which a vibration is given) is
determined on the basis of the obtained exciting force and a speed
signal obtained by integrating an acceleration single; and the loss
factor of the laminated glass can be determined from a frequency
expressing a peak of the tertiary mode and a half-width value.
[0239] A width of the temperature range where the loss factor is
0.2 or more can be determined from the loss factor determined by
the above-described method. The width of the temperature range
where the loss factor is 0.2 or more is preferably 15.degree. C. or
more, more preferably 20.degree. C. or more, still more preferably
23.degree. C. or more, and especially preferably 25.degree. C. or
more. When the width of the temperature range where loss factor is
0.2 or more is less than 15.degree. C., the sound insulting
properties over a broad temperature range cannot be revealed, so
that the sound insulating properties of the laminated glass in a
low-temperature region and/or a high-temperature region tend to be
lowered.
[0240] Examples of a method of widening the width of the
temperature range where the loss factor is 0.2 or more include a
method of optimizing the thickness of the internal layer (layer A)
according to the kind of the thermoplastic elastomer;
[0241] a method of using a mixture of two or more thermoplastic
elastomers having a different peak temperature of tan .delta. from
each other as the internal layer (layer A); a method in which the
internal layer (layer A) is composed of two or more layers, and a
thermoplastic elastomer having a peak temperature of tan .delta.
different from a peak temperature of tan .delta. of a thermoplastic
elastomer used for the at least one layer is used for the layer
different from the foregoing layer; a method in which as two or
more thermoplastic elastomers having a different peak temperature
of tan .delta. from each other, those having a large difference in
the peak temperature of tan .delta. are used; and the like. In
general, even in the case of using a mixture of two kinds of
elastomers, those two elastomers are compatibilized with each other
to exhibit one peak; however, in the case where two peaks are
observed, any one of the peak temperatures of tan .delta. may be
included in the range prescribed in the present invention.
(Heat Insulating Properties)
[0242] In the case where the laminated glass of the present
invention includes a heat insulating material, a transmittance at a
wavelength of 1,500 nm is preferably 50% or less, and more
preferably 20% or less. When the transmittance at a wavelength of
1,500 nm is 50% or less, there is a tendency that a shield factor
of infrared rays is high, so that heat insulating performance of
the laminated glass is improved.
(Haze)
[0243] In the laminated glass of the present invention, when the
laminate having a thickness of 0.75 mm is laminated between two
sheets of float glass having a thickness of 2 mm, a haze thereof is
preferably less than 5, preferably less than 3, still preferably
less than 2, especially preferably less than 1, and most preferably
less than 0.5. When the haze is 5 or more, the transparency of the
laminated glass tends to be lowered. The haze of the laminated
glass can be, for example, measured in accordance with JIS K
7136.
(Breaking Strength)
[0244] In a laminated glass obtained by interposing the laminate of
the present invention between two sheets of float glass of 26 mm in
length.times.76 mm in width.times.2.8 mm in thickness, a breaking
strength thereof in a three-point bending test (temperature:
20.degree. C., inter-fulcrum distance: 55 mm, test speed: 0.25
mm/min) is preferably 0.3 kN or more, more preferably 0.5 kN or
more, and still more preferably 0.6 kN or more. When the breaking
strength as measured under the above-described conditions is less
than 0.3 kN, the strength of the laminated glass tends to be
lowered.
(Production Method of Laminated Glass)
[0245] It is possible to produce the laminated glass of the present
invention by a conventionally known method. Examples thereof
include a method of using a vacuum laminator, a method of using a
vacuum bag, a method of using a vacuum ring, a method of using a
nip roll, and the like. In addition, a method in which after
temporary contact bonding, the resultant is put into an autoclave
process can also be supplementarily conducted.
[0246] In the case of using a vacuum laminator, for example, a
known instrument which is used for production of a solar cell is
used, and the assembly is laminated under a reduced pressure of
1.times.10.sup.-6 MPa or more and 3.times.10.sup.-2 MPa or less at
a temperature of 100.degree. C. or higher and 200.degree. C. or
lower, and especially 130.degree. C. or higher and 170.degree. C.
or lower. The method of using a vacuum bag or a vacuum ring is, for
example, described in the specification of European Patent No.
1235683, and for example, the assembly is laminated under a
pressure of about 2.times.10.sup.-2 MPa at 130.degree. C. or higher
and 145.degree. C. or lower.
[0247] With respect to the preparation method of a laminated glass,
in the case of using a nip roll, for example, there is exemplified
a method in which after conducting first temporary contact bonding
at a temperature of a flow starting temperature of the polyvinyl
acetal resin or lower, temporary contact bonding is further
conducted under a condition close to the flow starting temperature.
Specifically, for example, there is exemplified a method in which
the assembly is heated at 30.degree. C. or higher and 100.degree.
C. or lower by an infrared heater or the like, then deaerated by a
roll, and further heated at 50.degree. C. or higher and 150.degree.
C. or lower, followed by conducting contact bonding by a roll to
achieve bonding or temporary bonding.
[0248] In addition, a laminated glass may also be prepared by
gathering and laminating glasses in which the layer B is coated on
the both surfaces of the layer A such that the constitution of the
laminate of the present invention is included in the inside of the
laminated glass.
[0249] Though the autoclave process which is supplementarily
conducted after the temporary contact bonding is variable depending
upon the thickness or constitution of a module, it is, for example,
carried out under a pressure of 1 MPa or more and 15 MPa or less at
a temperature of 120.degree. C. or higher and 160.degree. C. or
lower for 0.5 hours or more and 2 hours or less.
[0250] The glass to be used on the occasion of preparing a
laminated glass is not particularly limited. Inorganic glasses,
such as a float sheet glass, a polished sheet glass, a figured
glass, a wired sheet glass, a heat-ray absorbing glass, etc., and
besides, conventionally known organic glasses, such as polymethyl
methacrylate, polycarbonate, etc., and the like can be used. These
glasses may be any of colorless, colored, transparent, or
non-transparent glasses. These glasses may be used solely, or may
be used in combination of two or more thereof.
EXAMPLES
[0251] The present invention is hereunder specifically described by
reference to Examples and Comparative Examples, but it should not
be construed that the present invention is limited to these
Examples.
[0252] It is to be noted that in the following Examples and
Comparative Examples, as a used polyvinyl butyral resin (PVB), one
obtained by acetalizing polyvinyl alcohol having a viscosity
average polymerization degree the same as the targeted viscosity
average polymerization degree (viscosity average polymerization
degree as measured in accordance with the "Testing Methods for
Polyvinyl Alcohol" of JIS K 6726) with n-butyl aldehyde in the
presence of a hydrochloric acid catalyst was used.
[0253] The following physical properties evaluations (1 to 5) were
conducted with respect to the layers A, layers B, laminates, or
laminated glasses obtained in the following Examples 1 to 14 and
Comparative Examples 1 to 7.
1. Physical Properties Evaluation (Shear Storage Modulus of
Laminate, Shear Storage Modulus of Layer B, and Peak Height and
Peak Temperature of Tan .delta. of Elastomer in Layer A)
[0254] A strain control type dynamic viscoelasticity instrument
(manufactured by Rheomix, ARES) having a diameter of a disk of 8 mm
was used as a parallel-plate oscillatory rheometer in accordance
with JIS K 7244-10. Laminates (thickness: 0.76 mm), single-layered
sheets of layer A (thickness: 0.76 mm), and single-layered sheets
of layer B (thickness: 0.76 mm) obtained in the following Examples
and Comparative Examples were each used as a disk-shaped test
sheet. It is to be noted that each of the above-described sheets
after storing at a temperature 20.degree. C. and at a humidity of
60% RH for 24 hours or more was used. A gap between two flat plates
was completely filled by the test sheet. A vibration with a strain
amount of 1.0% was given to the test sheet at a frequency of 1 Hz,
and a measurement temperature was increased at a constant rate of
1.degree. C./min from -40.degree. C. to 100.degree. C. The
temperatures of the test sheet and the disk were kept until
measured values of shear loss modulus and shear storage modulus did
not change. The results of shear storage modulus of the laminate,
shear storage modulus of the layer B, and peak height and peak
temperature of tan .delta. of elastomer in the layer A as measured
are shown in Tables 1, 2, and 3.
2. Physical Properties Evaluation (Lamination Aptitude of
Laminate)
[0255] Each of the laminates obtained in the Examples and
Comparative Examples was interposed by two sheets of commercially
available float glass (1,100 mm in length.times.1,300 mm in
width.times.3.2 mm in thickness), and a laminated glass was
prepared by using a vacuum laminator (manufactured by Nisshinbo
Mechatronics Inc., 1522N) under the following conditions. The
lamination aptitude of the used laminate was judged according to
the following criteria. The evaluation results of the lamination
aptitude are shown in Tables 1, 2, and 3.
<Conditions>
[0256] Hot plate temperature: 165.degree. C.
[0257] Evacuation time: 12 minutes
[0258] Pressing pressure: 50 kPa
[0259] Pressing time: 17 minutes
<Judgement Criteria>
[0260] A: Defects, such as bubbling, etc., are not observed on the
appearance, and adherence is good.
[0261] B: Though defects, such as bubbling, etc., are slightly
observed on the appearance, but there is no problem in
adherence.
[0262] C: Though defects, such as bubbling, etc., are observed on
the appearance, but there is no problem in adherence.
[0263] D: Defects, such as bubbling, etc., are observed on the
appearance, and adherence is bad.
[0264] E: Defects, such as bubbling, etc., are observed over the
entirety of the laminated glass on the appearance, and adherence is
bad.
3. Physical Properties Evaluation (Maximum Loss Factor of Laminated
Glass)
[0265] Each of the laminates obtained in the Examples and
Comparative Examples was interposed between two sheets of
commercially available float glass (50 mm in length.times.300 mm in
width.times.2.8 mm in thickness), and a laminated glass was
prepared by a vacuum bagging method (condition: the temperature was
increased from 30.degree. C. to 160.degree. C. for 60 minutes,
followed by holding at 160.degree. C. for 30 minutes). Thereafter,
the center of the laminated glass was fixed to a tip portion of an
exciting force detector built in an impedance head of an exciter
(power amplifier/model 371-A) of a mechanical impedance instrument
(manufactured by Ono Sokki Co., Ltd., mass cancel amplifier:
MA-5500, channel data station: DS-2100). A vibration was given to
the center of the laminated glass at a frequency in the range of
from 0 to 8,000 Hz, and an exciting force and an acceleration
waveform at this point were detected, thereby conducting a damping
test of the laminated glass by a central exciting method. A
mechanical impedance at an exciting point (the center of the
laminated glass to which a vibration was given) was determined on
the basis of the obtained exciting force and a speed signal
obtained by integrating an acceleration single; and in an impedance
curve obtained by setting the frequency on the abscissa and the
mechanical impedance on the ordinate, respectively, a loss factor
of the laminated glass was determined from a frequency expressing a
peak and a half-width value. In the damping measurement by the
central exciting method, a value of the loss factor relative to the
frequency at a fixed temperature is obtained. In order to obtain a
maximum loss factor, the measurement was carried out by varying the
temperature to 0, 10, 20, 30, 40, and 50.degree. C., respectively,
and a linear form of the loss factor relative to the temperature at
a fixed frequency was obtained from the obtained values. The
measurement results of the maximum loss factor are shown in Tables
1, 2, and 3.
4. Physical Properties Evaluation (Breaking Strength of Laminated
Glass)
[0266] Each of the laminates obtained in the Examples and
Comparative Examples was interposed between two sheets of
commercially available float glass (26 mm in length.times.76 mm in
width.times.2.8 mm in thickness), and a laminated glass was
prepared by a vacuum bagging method (condition: the temperature was
increased from 30.degree. C. to 160.degree. C. for 60 minutes,
followed by holding at 160.degree. C. for 30 minutes). Thereafter,
a three-point bending test of the laminated glass was carried out
by using an autograph AG-5000B, and a breaking strength of the
laminated glass at a temperature of 20.degree. C. and at a film
inter-fulcrum distance of 55 mm was measured. It is to be noted
that the measurement was conducted at a test speed of 0.25 mm/min.
The measurement results of the breaking strength are shown in
Tables 1, 2, and 3.
5. Physical Properties Evaluation (Evaluation of Heat Insulating
Performance of Laminated Glass)
[0267] Each of the laminates obtained in the Examples and
Comparative Examples was interposed between two sheets of
commercially available float glass (26 mm in length.times.76 mm in
width.times.2.8 mm in thickness), and a laminated glass was
prepared by a vacuum bagging method (condition: the temperature was
increased from 30.degree. C. to 160.degree. C. for 60 minutes,
followed by holding at 160.degree. C. for 30 minutes). Thereafter,
a wavelength transmittance in ultraviolet, visible, and
near-infrared regions was measured by using a spectral photometer
U-4100 (manufactured by Hitachi High-Tech Science Corporation). It
is to be noted that the measurement was conducted at a temperature
of 20.degree. C. The measurement results of the transmittance at a
wavelength of 1,500 nm are shown in Tables 1, 2, and 3.
Example 1
[0268] A linear hydrogenated styrene.isoprene.styrene triblock
copolymer (completely hydrogenated product) composed of 12% by mass
of a styrene unit and 88% by mass of an isoprene unit and having a
temperature of a peak at which a peak height of tan .delta. was
maximum of -22.6.degree. C. (a value in the case of giving a
vibration at a frequency of 1 Hz and increasing a measurement
temperature at a constant rate of 1.degree. C./min from -40.degree.
C. to 100.degree. C.) was used for the layer A, and polyvinyl
butyral having a viscosity average polymerization degree of about
1,000, a degree of acetalization of 70 mol %, and a content of a
vinyl acetate unit of 0.9 mol % was used for the layer B. These
resins were molded into the layer B having a thickness of 300 .mu.m
and the layer A having a thickness of 160 .mu.m, respectively by an
extrusion molding method. The layer A was interposed between two
layers of the layer B and press molded at 150.degree. C., thereby
preparing a laminate made of a composite film of a three-layer
constitution and having a thickness of 0.76 mm. The results of the
above-described physical properties evaluations are shown in Table
1. In addition, a temperature transition of each of a shear storage
modulus 10 and a tan .delta. 11 of the resulting laminate is shown
in FIG. 2. It is to be noted that graduations of the left-side
ordinate represent a shear storage modulus of the laminate, and
graduations of the right-side ordinate represent a loss tangent
(tan .delta.).
Examples 2 to 5
[0269] Laminates were prepared by using the same method as in
Example 1, except that 3GO (triethylene glycol
di(2-ethylhexanoate)) was used as a plasticizer for the layer B in
an amount shown in Table 1 based on 100 parts by mass of the
polyvinyl butyral resin having a viscosity average polymerization
degree of about 1,000, a degree of acetalization of 70 mol %, and a
content of a vinyl acetate unit of 0.9 mol %, and then subjected to
the physical properties evaluations. The results of the physical
properties evaluations are shown in Table 1.
Example 6
[0270] A laminate was prepared by using the same method as in
Example 1, except that the film thickness of the layer A was
changed to 50 .mu.m, and that the film thickness of the layer B was
changed to 355 .mu.m, and then subjected to the physical properties
evaluations. The results of the physical properties evaluations are
shown in Table 1.
Example 7
[0271] A laminate was prepared by using the same method as in
Example 1, except that the film thickness of the layer A was
changed to 300 .mu.m, and that the film thickness of the layer B
was changed to 230 .mu.m, and then subjected to the physical
properties evaluations. The results of the physical properties
evaluations are shown in Table 1.
Example 8
[0272] A laminate was prepared by using the same method as in
Example 1, except that a linear hydrogenated
styrene.isoprene.styrene triblock copolymer composed of 20% by mass
of a styrene unit and 80% by mass of an isoprene unit and having a
temperature of a peak at which a peak height of tan .delta. was
maximum of -5.2.degree. C. (a value in the case of giving a
vibration at a frequency of 1 Hz and increasing a measurement
temperature at a constant rate of 1.degree. C./min from -40.degree.
C. to 100.degree. C.) was used as an elastomer for the layer A, and
then subjected to the physical properties evaluations. The results
of the physical properties evaluations are shown in Table 1.
Example 9
[0273] A laminate was prepared by using the same method as in
Example 1, except that a polyvinyl butyral resin having a viscosity
average polymerization degree of 600, a degree of acetalization of
70 mol %, and a content of a vinyl acetate unit of 0.9 mol % was
used for the layer B in place of the polyvinyl butyral resin having
a viscosity average polymerization degree of about 1,000, and then
subjected to the physical properties evaluations. The results of
the physical properties evaluations are shown in Table 1.
Example 10
[0274] A laminate was prepared by using the same method as in
Example 1, except that a polyvinyl butyral resin having a viscosity
average polymerization degree of 1,700, a degree of acetalization
of 70 mol %, and a content of a vinyl acetate unit of 0.9 mol % was
used for the layer B in place of the polyvinyl butyral resin having
a viscosity average polymerization degree of about 1,000, and then
subjected to the physical properties evaluations. The results of
the physical properties evaluations are shown in Table 1.
Example 11
[0275] A laminate was prepared by using the same method as in
Example 1, except that an ionomer film (manufactured by E. I. du
Pont de Nemours and Company, SentryGlas.RTM. Interlayer, thickness:
300 .mu.m) was used for the layer B, and then subjected to the
physical properties evaluations. The results of the physical
properties evaluations are shown in Table 1.
Example 12
[0276] A laminate was prepared by using the same method as in
Example 1, except that cesium-containing composite tungsten oxide
was added to the layer A in an amount of 1.2% by weight relative to
the linear hydrogenated styrene.isoprene.styrene triblock copolymer
(completely hydrogenated product), and then subjected to the
physical properties evaluations. The results of the physical
properties evaluations are shown in Table 1. It is to be noted that
YMDS-874, manufactured by Sumitomo Metal Mining Co., Ltd. was used
as the cesium-containing composite tungsten oxide.
Example 13
[0277] A laminated glass was prepared by using the same method as
in Example 1, except that two sheets of commercially available
float glass (26 mm in length.times.76 mm in width.times.1.6 mm in
thickness) were used in place of the two sheets of commercially
available float glass having a thickness of 2.8 mm, and then
subjected to the physical properties evaluations. The results of
the physical properties evaluations are shown in Table 3.
Example 14
[0278] A laminated glass was prepared by using the same method as
in Example 1, except that one sheet of commercially available float
glass (26 mm in length.times.76 mm in width.times.2.1 mm in
thickness) and one sheet of commercially available float glass (26
mm in length.times.76 mm in width.times.1.3 mm in thickness) were
used in place of the two sheets of commercially available float
glass having a thickness of 2.8 mm, and then subjected to the
physical properties evaluations. The results of the physical
properties evaluations are shown in Table 3.
Comparative Example 1
[0279] A laminate was prepared by using the same method as in
Example 1, except that 30 parts by mass of 3GO was added based on
100 parts by mass of the polyvinyl acetal resin serving as the
layer B, and then subjected to the physical properties evaluations.
The results of the physical properties evaluations are shown in
Table 2.
Comparative Example 2
[0280] A laminate was prepared by using the same method as in
Example 1, except that a urethane resin (manufactured by Kuraray
Co., Ltd., KURAMIRON U1780) was used for the layer A in place of
the linear hydrogenated styrene-isoprene-styrene triblock
copolymer, and then subjected to the physical properties
evaluations. The results of the physical properties evaluations are
shown in Table 2.
Comparative Example 3
[0281] A laminate was prepared by using the same method as in
Example 1, except that a styrene-based elastomer (manufactured by
Kuraray Co., Ltd., SEPTON 8007) was used for the layer A in place
of the linear hydrogenated styrene.isoprene.styrene triblock
copolymer, and then subjected to the physical properties
evaluations. The results of the physical properties evaluations are
shown in Table 2.
Comparative Example 4
[0282] A laminate was prepared by using the same method as in
Example 1, except that the film thickness of the layer A was
changed to 500 .mu.m, and that the film thickness of the layer B
was changed to 130 .mu.m, and then subjected to the physical
properties evaluations. The results of the physical properties
evaluations are shown in Table 2.
Comparative Example 5
[0283] A laminate was prepared by using the same method as in
Example 1, except that a layer composed of a composition containing
3GO in an amount of 60 parts by mass based on 100 parts by mass of
polyvinyl butyral having a viscosity average polymerization degree
of 1,700, a degree of acetalization of 75 mol %, and a content of a
vinyl acetate unit of 0.9 mol % was used as the layer A in place of
the linear hydrogenated styrene.isoprene.styrene copolymer, and
that 3GO in an amount of 37.9 parts by mass based on 100 parts by
mass of polyvinyl butyral having a viscosity average polymerization
degree of 1,700 was used for the layer B in place of the polyvinyl
butyral resin having a viscosity average polymerization degree of
about 1,000, and then subjected to the physical properties
evaluations. The results of the physical properties evaluations are
shown in Table 2.
Comparative Example 6
[0284] A laminate was prepared by using the same method as in
Example 1, except that the film thickness of the layer A was
changed to 600 .mu.m, that the film thickness of the layer B was
changed to 160 .mu.m, and that the layers A and B were superimposed
to form a pair of two-layer films, and then subjected to the
physical properties evaluations. The results of the physical
properties evaluations are shown in Table 2.
[0285] A laminated glass was prepared by using the same method as
in Comparative Example 5, except that two sheets of commercially
available float glass (26 mm in length.times.76 mm in
width.times.2.1 mm in thickness) were used in place of the
commercially available float glass having a thickness of 2.8 mm,
and then subjected to the physical properties evaluations. The
results of the physical properties evaluations are shown in Table
3.
TABLE-US-00001 TABLE 1 Example 1 Example 2 Example 3 Example 4
Example 5 Example 6 Layer B Viscosity average polymerization degree
1000 1000 1000 1000 1000 1000 Degree of acetalization (mol %) 70 70
70 70 70 70 Content of plasticizer (parts by mass)* 0 2 5 10 20 0
Shear storage modulus [at 25.degree. C.] (MPa) 97.9 86.8 84.9 70.1
57.2 97.9 Layer A Styrene content (% by mass)** 12 12 12 12 12 12
Peak temperature of tan .delta. (.degree. C.) -22.6 -22.6 -22.6
-22.6 -22.6 -22.6 Peak height of tan .delta. 1.92 1.92 1.92 1.92
1.92 1.92 Laminate Shear storage modulus [at 25.degree. C.] (MPa)
4.78 4.53 4.17 3.57 2.36 5.78 Shear storage modulus [at 50.degree.
C.] (MPa) 2.84 2.64 2.4 1.98 1.15 3.82 Maximum loss factor [at
2,000 Hz, 1 to 50.degree. C.] 0.32 0.31 0.31 0.32 0.33 0.32
(Thickness of layer A)/(total thickness of layer B) 1/3.75 1/3.75
1/3.75 1/3.75 1/3.75 1/14 Breaking strength [at 25.degree. C.] (kN)
0.65 0.64 0.56 0.57 0.34 0.63 Lamination aptitude A A A B C A
Transmittance (at 1,500 nm) 76 76 76 76 76 78 Example Example
Example Example 7 Example 8 Example 9 10 11 12 Layer B Viscosity
average polymerization degree 1000 1000 600 1700 -- 1000 Degree of
acetalization (mol %) 70 70 70 70 -- 70 Content of plasticizer
(parts by mass)* 0 0 0 0 0 0 Shear storage modulus [at 25.degree.
C.] (MPa) 97.9 97.9 77.3 127.4 43.2 97.9 Layer A Styrene content (%
by mass)** 12 20 12 12 12 12 Peak temperature of tan .delta.
(.degree. C.) -22.6 -5.2 -22.6 -22.6 -22.6 -22.6 Peak height of tan
.delta. 1.92 1.89 1.92 1.92 1.92 1.92 Laminate Shear storage
modulus [at 25.degree. C.] (MPa) 3.45 3.55 3.59 6.1 15.8 4.78 Shear
storage modulus [at 50.degree. C.] (MPa) 2.01 2.89 2.46 3.21 3.9
2.84 Maximum loss factor [at 2,000 Hz, 1 to 50.degree. C.] 0.39
0.33 0.33 0.32 0.25 0.32 (Thickness of layer A)/(total thickness of
layer B) 1/1.53 1/3.75 1/3.75 1/3.75 1/3.75 1/3.75 Breaking
strength [at 25.degree. C.] (kN) 0.36 0.57 0.49 0.52 0.75 0.65
Lamination aptitude A B C C C A Transmittance (at 1,500 nm) 74 71
76 76 79 39 *Expressing parts by mass based on 100 parts by mass of
polyvinyl butyral used for the layer B **Expressing % by mass in
the elastomer
TABLE-US-00002 TABLE 2 Comparative Comparative Comparative
Comparative Comparative Comparative Example 1 Example 2 Example 3
Example 4 Example 5 Example 6 Layer B Viscosity average
polymerization degree 1000 1000 1000 1000 1700 1000 Degree of
acetalization (mol %) 70 70 70 70 70 70 Content of plasticizer
(parts by mass)* 30 0 0 0 38 0 Shear storage modulus [at 25.degree.
C.] (MPa) 0.70 97.9 97.9 97.9 2.83 97.9 Layer A Styrene content (%
by mass)** 12 -- 33 12 -- 12 Peak temperature of tan .delta.
(.degree. C.) -22.6 <-40 <-40 -22.6 -16.1 -22.6 Peak height
of tan .delta. 1.92 Not detected Not detected 1.92 0.80 1.92
Laminate Shear storage modulus [at 25.degree. C.] (MPa) 0.63 37.3
27.9 1.28 2.19 4.78 Shear storage modulus [at 50.degree. C.] (MPa)
0.21 33.0 22.8 1.13 0.32 2.74 Maximum loss factor [at 2,000 Hz, 1
to 50.degree. C.] 0.32 0.18 0.15 0.38 0.34 0.32 (Thickness of layer
A)/(total thickness of layer B) 1/3.75 1/3.75 1/3.75 1/0.52 1/3.75
1/3.75 Breaking strength [at 25.degree. C.] (kN) 0.23 0.66 0.66
0.29 0.28 0.36 Lamination aptitude C B B E A E Transmittance (at
1,500 nm) 76 76 76 74 76 76 *Expressing parts by mass based on 100
parts by mass of polyvinyl butyral used for the layer B
**Expressing % by mass in the elastomer
TABLE-US-00003 TABLE 3 Comparative Example 13 Example 14 Example 7
Layer B Viscosity average polymerization degree 1000 1000 1700
Degree of acetalization (mol %) 70 70 70 Content of plasticizer
(parts by mass)* 0 0 38 Shear storage modulus [at 25.degree. C.]
(MPa) 97.9 97.9 2.83 Layer A Styrene content (% by mass)** 12 12 --
Peak temperature of tan .delta. (.degree. C.) -22.6 -22.6 -16.1
Peak height of tan .delta. 1.92 1.92 0.80 Laminate Shear storage
modulus [at 25.degree. C.] (MPa) 4.78 4.78 2.19 Shear storage
modulus [at 50.degree. C.] (MPa) 2.84 2.84 0.32 Maximum loss factor
[at 2,000 Hz, 1 to 50.degree. C.] 0.32 0.32 0.34 (Thickness of
layer A)/(total thickness of layer B) 1/3.75 1/3.75 1/3.75 Breaking
strength [at 25.degree. C.] (kN) 0.22 0.23 0.19 Lamination aptitude
A A A Transmittance (at 1,500 nm) 76 76 76 Glass thickness
(top/bottom) (mm) 1.6/1.6 2.1/1.3 2.1/2.1 *Expressing parts by mass
based on 100 parts by mass of polyvinyl butyral used for the layer
B **Expressing % by mass in the elastomer
[0286] The following physical properties evaluations (6 to 11) were
conducted with respect to the layers A, layers B, laminates, or
laminated glasses obtained in the following Examples 15 to 25 and
Comparative Examples 8 to 11.
6. Physical Properties Evaluation (Shear Storage Modulus of Layer
B, Shear Storage Modulus and Peak Height and Peak Temperature of
Tan .delta. of Layer A (Resin Composition Constituting of Layer A),
and Shear Storage Modulus of Laminate)
[0287] A strain control type dynamic viscoelasticity instrument
(manufactured by Rheomix, ARES) having a diameter of a disk of 8 mm
was used as a parallel-plate oscillatory rheometer in accordance
with JIS K 7244-10 was used. Laminates, single-layered sheets of
layer A (thickness: 0.76 mm), and single-layered sheets of layer B
(thickness: 0.76 mm) obtained in the following Examples and
Comparative Examples were each used as a disk-shaped test sheet. It
is to be noted that each of the above-described test sheets after
storing at a temperature 20.degree. C. and at a humidity of 60% RH
for 24 hours or more was used. A gap between two flat plates was
completely filled by the test sheet. A vibration with a strain
amount of 1.0% was given to the test sheet at a frequency of 1 Hz,
and a measurement temperature was increased at a constant rate of
1.degree. C./min from -40.degree. C. to 100.degree. C. The
temperatures of the test sheet and the disk were kept until
measured values of shear loss modulus and shear storage modulus did
not change. The results of shear storage modulus of each of the
laminate, the layer A, and the layer B, and peak height and peak
temperature of tan .delta. of the resin composition constituting
the layer A (elastomer in the layer A) as measured are shown in
Tables 4 and 5.
7. Physical Properties Evaluation (Quaternary Resonance Frequency,
Loss Factor and Bending Rigidity at Quaternary Resonance Frequency,
and Acoustic Transmission Loss at Each of 6,300 Hz, 8,000 Hz, and
10,000 Hz of Laminated Glass)
[0288] Each of the laminates obtained in the Examples and
Comparative Examples was interposed between two sheets of
commercially available float glass (300 mm in length.times.25 mm in
width.times.1.9 mm in thickness), and a laminated glass was
prepared by a vacuum bagging method (condition: the temperature was
increased from 30.degree. C. to 160.degree. C. for 60 minutes,
followed by holding at 160.degree. C. for 30 minutes). Thereafter,
the center of the laminated glass was fixed to a tip portion of an
exciting force detector built in an impedance head of an exciter
(power amplifier/model 371-A) of a mechanical impedance instrument
(manufactured by Ono Sokki Co., Ltd., mass cancel amplifier:
MA-5500, channel data station: DS-2100). A vibration was given at
20.degree. C. to the center of the laminated glass at a frequency
in the range of from 0 to 10,000 Hz, and an exciting force and an
acceleration waveform at this point were detected, thereby
conducting a damping test of the laminated glass by a central
exciting method. A mechanical impedance at an exciting point (the
center of the laminated glass to which a vibration was given) was
determined on the basis of the obtained exciting force and a speed
signal obtained by integrating an acceleration single; and in an
impedance curve obtained by setting the frequency on the abscissa
and the mechanical impedance on the ordinate, respectively, a loss
factor of the laminated glass was determined from a frequency
expressing a peak and a half-width value. Furthermore, by using a
quaternary resonance frequency and a loss factor at the quaternary
resonance frequency, a bending rigidity at the quaternary resonance
frequency was calculated in accordance with ISO 16940 (2008). In
addition, by using the loss factor and the bending rigidity at the
quaternary resonance frequency, an acoustic transmission loss at
each of 6,300 Hz, 8,000 Hz, and 10,000 Hz was calculated in
accordance with ISO 16940 (2008). The measurement results of the
quaternary resonance frequency and the loss factor at the
quaternary resonance frequency, and the calculation results of the
bending rigidity at the quaternary resonance frequency and the
acoustic transmission loss at each of 6,300 Hz, 8,000 Hz, and
10,000 Hz are shown in Table 4.
8. Physical Properties Evaluation (Evaluation of Heat Insulating
Performance of Laminated Glass)
[0289] Each of the laminates obtained in the Examples and
Comparative Examples was interposed between two sheets of
commercially available float glass (26 mm in length.times.76 mm in
width.times.2.8 mm in thickness), and a laminated glass was
prepared by a vacuum bagging method (condition: the temperature was
increased from 30.degree. C. to 160.degree. C. for 60 minutes,
followed by holding at 160.degree. C. for 30 minutes). Thereafter,
a wavelength transmittance in ultraviolet, visible, and
near-infrared regions was measured by using a spectral photometer
U-4100 (manufactured by Hitachi High-Tech Science Corporation). It
is to be noted that the measurement was conducted at a temperature
of 20.degree. C. The measurement results of the transmittance at a
wavelength of 1,500 nm are shown in Tables 4 and 5.
9. Physical Properties Evaluation (Lamination Aptitude of
Laminate)
[0290] Each of the laminates obtained in the Examples and
Comparative Examples was interposed between two sheets of
commercially available float glass (1,100 mm in length.times.1,300
mm in width.times.3.2 mm in thickness), and a laminated glass was
prepared by using a vacuum laminator (manufactured by Nisshinbo
Mechatronics Inc., 1522N) under the following conditions. The
lamination aptitude of the used laminate was judged according to
the following criteria. The evaluation results of the lamination
aptitude are shown in Tables 4 and 5.
<Conditions>
[0291] Hot plate temperature: 165.degree. C.
[0292] Evacuation time: 12 minutes
[0293] Pressing pressure: 50 kPa
[0294] Pressing time: 17 minutes
<Judgement Criteria>
[0295] A: Defects, such as bubbling, etc., are not observed on the
appearance, and adherence is good.
[0296] B: Though defects, such as bubbling, etc., are slightly
observed on the appearance, but there is no problem in
adherence.
[0297] C: Though defects, such as bubbling, etc., are observed on
the appearance, but there is no problem in adherence.
[0298] D: Defects, such as bubbling, etc., are observed on the
appearance, and adherence is bad.
[0299] E: Defects, such as bubbling, etc., are observed over the
entirety of the laminated glass on the appearance, and adherence is
bad.
10. Physical Properties Evaluation (Maximum Loss Factor of
Laminated Glass)
[0300] Each of the laminates obtained in the Examples and
Comparative Examples was interposed between two sheets of
commercially available float glass (50 mm in length.times.300 mm in
width.times.2.8 mm in thickness), and a laminated glass was
prepared by a vacuum bagging method (condition: the temperature was
increased from 30.degree. C. to 160.degree. C. for 60 minutes,
followed by holding at 160.degree. C. for 30 minutes). Thereafter,
the center of the laminated glass was fixed to a tip portion of an
exciting force detector built in an impedance head of an exciter
(power amplifier/model 371-A) of a mechanical impedance instrument
(manufactured by Ono Sokki Co., Ltd., mass cancel amplifier:
MA-5500, channel data station: DS-2100). A vibration was given to
the center of the laminated glass at a frequency in the range of
from 0 to 8,000 Hz, and an exciting force and an acceleration
waveform at this point were detected, thereby conducting a damping
test of the laminated glass by a central exciting method. A
mechanical impedance at an exciting point (the center of the
laminated glass to which a vibration was given) was determined on
the basis of the obtained exciting force and a speed signal
obtained by integrating an acceleration single; and in an impedance
curve obtained by setting the frequency on the abscissa and the
mechanical impedance on the ordinate, respectively, a loss factor
of the laminated glass was determined from a frequency expressing a
peak and a half-width value. In the damping measurement by the
central exciting method, a value of the loss factor relative to the
frequency at a fixed temperature is obtained. In order to obtain a
maximum loss factor, the measurement was carried out by varying the
temperature to 0.degree. C., 10.degree. C., 20.degree. C.,
30.degree. C., 40.degree. C., and 50.degree. C., respectively, and
a linear form of the loss factor relative to the temperature at a
fixed frequency was obtained from the obtained values. In this
linear form, a maximum point was defined as a maximum loss factor.
The measurement results of the maximum loss factor are shown in
Tables 4 and 5.
11. Physical Properties Evaluation (Breaking Strength of Laminated
Glass)
[0301] Each of the laminates obtained in the Examples and
Comparative Examples was interposed between two sheets of
commercially available float glass (26 mm in length.times.76 mm in
width.times.2.8 mm in thickness), and a laminated glass was
prepared by a vacuum bagging method (condition: the temperature was
increased from 30.degree. C. to 160.degree. C. for 60 minutes,
followed by holding at 160.degree. C. for 30 minutes). Thereafter,
a three-point bending test of the laminated glass was carried out
by using an autograph AG-5000B, and a breaking strength of the
laminated glass at a temperature of 20.degree. C. and a film
inter-fulcrum distance of 55 mm was measured. It is to be noted
that the measurement was conducted at a test speed of 0.25 mm/min.
The measurement results of the breaking strength are shown in
Tables 4 and 5.
Example 15
[0302] A linear hydrogenated styrene.isoprene.styrene triblock
copolymer (hydrogenation ratio: 88%, weight average molecular
weight: 112,000) composed of 20% by mass of a styrene unit and 80%
by mass of an isoprene unit and having a temperature of a peak at
which a peak height of tan .delta. was maximum of -5.2.degree. C.
(a value in the case of giving a vibration at a frequency of 1 Hz
and increasing a measurement temperature at a constant rate of
1.degree. C./min from -40.degree. C. to 100.degree. C.) was used
for the layer A, and a composition composed of 100 parts by mass of
a polyvinyl butyral resin having a viscosity average polymerization
degree of about 1,700, a degree of acetalization of 70 mol %, and a
content of a vinyl acetate unit of 0.9 mol % and 15 parts by mass
of, as a plasticizer, a polyester polyol "KURARAY POLYOL P-510",
manufactured by Kuraray Co., Ltd. was used for the layer B.
[0303] These resins (or resin compositions) were molded into the
layer B having a thickness of 0.76 mm and the layer A having a
thickness of 0.76 mm, respectively by an extrusion molding method.
By using a single-layer sheet of each of the resulting layer A and
layer B, the shear storage modulus of the layer B, and the shear
storage modulus and the peak height and peak temperature of tan
.delta. of the layer A were measured according to the
above-described evaluation methods.
[0304] In addition, these resins (or resin compositions) were
molded into the layer B having a thickness of 250 .mu.m and the
layer A having a thickness of 250 .mu.m, respectively by an
extrusion molding method. The layer A was interposed between two
layers of the layer B and press molded at 150.degree. C., thereby
preparing a laminate made of a composite film of a three-layer
constitution and having a thickness of 0.75 mm. The quaternary
resonance frequency, the loss factor at the quaternary resonance
frequency, and the bending rigidity at the quaternary resonance
frequency, and the acoustic transmission loss at each of 6,300 Hz,
8,000 Hz, and 10,000 Hz of the laminated glass were calculated
according to the above-described evaluation methods. In addition,
the heat insulating performance of the laminated glass was
evaluated by using the resulting laminate. The results of the
physical properties evaluations are shown in Table 4. It is to be
noted that the content of the plasticizer of each of the layers B
in Tables 4 to 5 expresses an amount based on 100 parts by mass of
the resin in the layer B.
Examples 16 and 17
[0305] Single-sheets and laminates were prepared by using the same
method as in Example 15, except that the content of the plasticizer
"KURARAY POLYOL P-510" in the layer B was changed as shown in Table
4, and then subjected to the physical properties evaluations. The
results of the physical properties evaluations are shown in Table
4.
Example 18
[0306] A laminate was prepared by using the same method as in
Example 15, except that the film thickness of the layer A was
changed to 100 .mu.m, and that the film thickness of the layer B
was changed to 325 .mu.m, and then subjected to the physical
properties evaluations. The results of the physical properties
evaluations are shown in Table 4.
Example 19
[0307] A laminate was prepared by using the same method as in
Example 15, except that the film thickness of the layer A was
changed to 380 win, and that the film thickness of the layer B was
changed to 190 .mu.m, and then subjected to the physical properties
evaluations. The results of the physical properties evaluations are
shown in Table 4.
Example 20
[0308] A single-layer sheet and a laminate were prepared by using
the same method as in Example 15, except that in the layer A, a
linear hydrogenated styrene.isoprene/butadiene.styrene triblock
copolymer (hydrogenation ratio: 89%, weight average molecular
weight: 121, 500) composed of 18% by mass of a styrene unit and 82%
by mass of an isoprene unit and a butadiene unit
(isoprene/butadiene (mass ratio)=89/11) and having a temperature of
a peak at which a peak height of tan .delta. was maximum of
-10.3.degree. C. (a value in the case of giving a vibration at a
frequency of 1 Hz and increasing a measurement temperature at a
constant rate of 1.degree. C./min from -40.degree. C. to
100.degree. C.) was used as an elastomer in place of the linear
hydrogenated styrene.isoprene.styrene triblock copolymer as used in
Example 15, and then subjected to the physical properties
evaluations. The results of the physical properties evaluations are
shown in Table 4.
Example 21
[0309] A single-layer sheet and a laminate were prepared by using
the same method as in Example 15, except that in the layer A, a
linear hydrogenated styrene.isoprene.styrene triblock copolymer
(hydrogenation ratio: 90%, weight average molecular weight:
131,000) composed of 16% by mass of a styrene unit and an isoprene
unit and a butadiene unit (isoprene/butadiene (mass ratio)=78/22)
and having a temperature of a peak at which a peak height of tan
.delta. was maximum of -15.2.degree. C. (a value in the case of
giving a vibration at a frequency of 1 Hz and increasing a
measurement temperature at a constant rate of 1.degree. C./min from
-40.degree. C. to 100.degree. C.) was used as an elastomer in place
of the linear hydrogenated styrene.isoprene.styrene triblock
copolymer as used in Example 15, and then subjected to the physical
properties evaluations. The results of the physical properties
evaluations are shown in Table 4.
Examples 22 and 23
[0310] Single-layer sheets and laminates were prepared by using the
same method as in Example 15, except that the content of the
plasticizer "KURARAY POLYOL P-510" in the layer B was changed as
shown in Table 4, that the film thickness of the layer A was
changed to 100 .mu.m, and that the film thickness of the layer B
was changed to 325 .mu.m, and then subjected to the physical
properties evaluations. The results of the physical properties
evaluations are shown in Table 4.
Example 24
[0311] A single-layer sheet and a laminate were prepared by using
the same method as in Example 15, except that an ionomer film
(manufactured by E. I. du Pont de Nemours and Company,
SentryGlas.RTM. Interlayer) was used for the layer B, that the film
thickness of the layer A was changed to 100 .mu.m, and that the
film thickness of the layer B was changed to 325 .mu.m, and then
subjected to the physical properties evaluations. The results of
the physical properties evaluations are shown in Table 4.
Example 25
[0312] A single-layer sheet and a laminate were prepared by using
the same method as in Example 15, except that 0.75 parts by mass of
cesium-containing composite tungsten oxide was added to 100 parts
by mass of the linear hydrogenated styrene.isoprene.styrene
triblock copolymer to mold the layer A, and then subjected to the
physical properties evaluations. The results of the physical
properties evaluations are shown in Table 4. It is to be noted that
YMDS-874, manufactured by Sumitomo Metal Mining Co., Ltd. was used
as the cesium-containing composite tungsten oxide.
TABLE-US-00004 TABLE 4 Example Example Example Example Example
Example 15 16 17 18 19 20 Layer B Thickness (.mu.m) 250 250 250 325
190 250 Kind of resin PVB PVB PVB PVB PVB PVB Viscosity average
polymerization degree 1700 1700 1700 1700 1700 1700 Degree of
acetalization (mol %) 70 70 70 70 70 70 Content of plasticizer
(parts by mass) 15 5 25 15 15 15 Shear storage modulus [at
25.degree. C.] (MPa) 82.0 120.3 62.1 82.0 82.0 82.0 Layer A
Thickness (.mu.m) 250 250 250 100 380 250 Styrene content (% by
mass) 20 20 20 20 20 18 Peak temperature of tan .delta. (.degree.
C.) -5.2 -5.2 -5.2 -5.2 -5.2 -10.3 Peak height of tan .delta. 1.89
1.89 1.89 1.89 1.89 1.90 Shear storage modulus [at 25.degree. C.]
(MPa) 1.31 1.31 1.31 1.31 1.31 1.13 Evaluation Quaternary resonance
frequency (Hz) 3916 4020 3764 4867 3627 3697 results Loss factor at
quaternary resonance frequency 0.63 0.56 0.64 0.22 0.69 0.51
Bending rigidity at quaternary resonance frequency 206 218 195 322
181 182 (N m) Acoustic transmission loss at 6,300 Hz (dB) 48.1 47.8
47.6 47.6 47.5 45.4 Acoustic transmission loss at 8,000 Hz (dB)
54.8 54.7 54.3 54.5 54.1 52.4 Acoustic transmission loss at 10,000
Hz (dB) 60.9 60.8 60.4 60.6 60.1 58.7 (Thickness of layer A)/(total
thickness of layer B) 1/2 1/2 1/2 1/6.5 1/1 1/2 Transmittance [at
1,500 nm] (%) 75 77 76 75 74 75 Shear storage modulus [at
25.degree. C.] (MPa) 2.61 3.85 1.85 7.03 1.52 1.55 Maximum loss
factor of laminated glass 0.38 0.36 0.43 0.35 0.39 0.36 Breaking
strength of laminated glass [at 25.degree. C.] (kN) 0.44 0.48 0.31
0.82 0.27 0.29 Lamination aptitude A A B A B A Example Example
Example Example Example 21 22 23 24 25 Layer B Thickness (.mu.m)
250 325 325 325 250 Kind of resin PVB PVB PVB Ionomer PVB Viscosity
average polymerization degree 1700 1700 1700 -- 1700 Degree of
acetalization (mol %) 70 70 70 -- 70 Content of plasticizer (parts
by mass) 15 25 40 -- 15 Shear storage modulus [at 25.degree. C.]
(MPa) 82.0 62.1 13.6 43.2 82.0 Layer A Thickness (.mu.m) 250 100
100 100 250 Styrene content (% by mass) 16 20 20 20 20 Peak
temperature of tan .delta. (.degree. C.) -15.2 -5.2 -5.2 -5.2 -5.5
Peak height of tan .delta. 1.91 1.89 1.89 1.89 1.88 Shear storage
modulus [at 25.degree. C.] (MPa) 0.95 1.31 1.31 1.31 1.31
Evaluation Quaternary resonance frequency (Hz) 3951 4625 4377 4497
3903 results Loss factor at quaternary resonance frequency 0.31
0.25 0.23 0.23 0.62 Bending rigidity at quaternary resonance
frequency 208 290 259 272 205 (N m) Acoustic transmission loss at
6,300 Hz (dB) 44.9 47.0 45.3 45.9 47.9 Acoustic transmission loss
at 8,000 Hz (dB) 52.3 54.1 52.6 53.1 54.7 Acoustic transmission
loss at 10,000 Hz (dB) 58.6 60.2 58.9 59.3 60.8 (Thickness of layer
A)/(total thickness of layer B) 1/6.5 1/6.5 1/6.5 1/6.5 1/2
Transmittance [at 1,500 nm] (%) 76 76 75 78 40 Shear storage
modulus [at 25.degree. C.] (MPa) 3.35 6.71 5.82 6.16 2.59 Maximum
loss factor of laminated glass 0.35 0.36 0.40 0.38 0.38 Breaking
strength of laminated glass [at 25.degree. C.] (kN) 0.40 0.79 0.61
0.69 0.42 Lamination aptitude A B C A A
Comparative Example 8
[0313] A single-layer sheet and a laminate were prepared by using
the same method as in Example 15, except that in the layer A, a
linear hydrogenated styrene.isoprene/butadiene.styrene triblock
copolymer (hydrogenation ratio: 92%, weight average molecular
weight: 150,000) composed of 12% by mass of a styrene unit and 88%
by mass of an isoprene unit and a butadiene unit
(isoprene/butadiene (molar ratio)=55/45) and having a temperature
of a peak at which a peak height of tan .delta. was maximum of
-22.6.degree. C. (a value in the case of giving a vibration at a
frequency of 1 Hz and increasing a measurement temperature at a
constant rate of 1.degree. C./min from -40.degree. C. to
100.degree. C.) was used as an elastomer in place of the linear
hydrogenated styrene.isoprene.styrene triblock copolymer as used in
Example 15, and then subjected to the physical properties
evaluations. The results of the physical properties evaluations are
shown in Table 5.
Comparative Example 9
[0314] A single-layer sheet and a laminate were prepared by using
the same method as in Example 15, except that in the layer A, a
linear hydrogenated styrene.isoprene.styrene triblock copolymer
(hydrogenation ratio: 92%, weight average molecular weight:
150,000) composed of 12% by mass of a styrene unit and 88% by mass
of an isoprene unit and a butadiene unit (isoprene/butadiene (molar
ratio)=55/45) and having a temperature of a peak at which a peak
height of tan .delta. was maximum of -22.6.degree. C. (a value in
the case of giving a vibration at a frequency of 1 Hz and
increasing a measurement temperature at a constant rate of
1.degree. C./min from -40.degree. C. to 100.degree. C.) was used as
an elastomer in place of the linear hydrogenated
styrene.isoprene.styrene triblock copolymer as used in Example 15,
that the film thickness of the layer A was changed to 100 .mu.m,
and that the film thickness of the layer B was changed to 325
.mu.m, and then subjected to the physical properties evaluations.
The results of the physical properties evaluations are shown in
Table 5.
Comparative Example 10
[0315] A single-layer sheet and a laminate were prepared by using
the same method as in Example 15, except that a layer composed of a
composition containing a polyvinyl butyral resin having a viscosity
average polymerization degree of 1,700, a degree of acetalization
of 70 mol %, and a content of a vinyl acetate unit of 0.9 mol % and
"KURARAY POLYOL P-510" in an amount of 60 parts by mass based on
100 parts by mass of the polyvinyl butyral resin was used for the
layer A in place of the linear hydrogenated styrene.isoprene block
copolymer, and that a layer composed of a composition containing a
polyvinyl butyral resin having a viscosity average polymerization
degree of 1,700, a degree of acetalization of 70 mol %, and a
content of a vinyl acetate unit of 0.9 mol % and "KURARAY POLYOL
P-510" in an amount of 60 parts by mass based on 100 parts by mass
of the polyvinyl butyral resin was used for the layer B, and then
subjected to the physical properties evaluations. The results of
the physical properties evaluations are shown in Table 5.
Comparative Example 11
[0316] A single-layer sheet and a laminate were prepared by using
the same method as in Example 15, except that a layer composed of a
composition containing a polyvinyl butyral resin having a viscosity
average polymerization degree of 1,700, a degree of acetalization
of 70 mol %, and a content of a vinyl acetate unit of 0.9 mol % and
"KURARAY POLYOL P-510" in an amount of 15 parts by mass based on
100 parts by mass of the polyvinyl butyral resin was used for the
layer A in place of the linear hydrogenated styrene.isoprene block
copolymer, and that a layer composed of a composition containing a
polyvinyl butyral resin having a viscosity average polymerization
degree of 1,700, a degree of acetalization of 70 mol %, and a
content of a vinyl acetate unit of 0.9 mol % and "KURARAY POLYOL
P-510" in an amount of 15 parts by mass based on 100 parts by mass
of the polyvinyl butyral resin was used for the layer B, and then
subjected to the physical properties evaluations. The results of
the physical properties evaluations are shown in Table 5.
TABLE-US-00005 TABLE 5 Comparative Comparative Comparative
Comparative Example 8 Example 9 Example 10 Example 11 Layer B
Thickness (.mu.m) 250 325 250 250 Kind of resin PVB PVB PVB PVB
Viscosity average polymerization degree 1700 1700 1700 1700 Degree
of acetalization (mol %) 70 70 70 70 Content of plasticizer (parts
by mass) 15 15 60 15 Shear storage modulus [at 25.degree. C.] (MPa)
82.0 82.0 6.2 82.0 Layer A Thickness (.mu.m) 250 100 250 250
Styrene content (% by mass) 12 12 -- -- Peak temperature of tan
.delta. (.degree. C.) -22.6 -22.6 0.7 35.2 Peak height of tan
.delta. 1.92 1.92 0.79 0.76 Shear storage modulus [at 25.degree.
C.] (MPa) 0.51 0.51 0.37 82.0 Evaluation Quaternary resonance
frequency (Hz) 2544 3063 2827 4990 results Loss factor at
quaternary resonance 0.23 0.36 0.44 0.037 frequency Bending
rigidity at quaternary resonance 88 128 109 339 frequency (N m)
Acoustic transmission loss at 6,300 Hz 41.4 40.0 42.6 41.7 (dB)
Acoustic transmission loss at 8,000 Hz 39.2 46.5 48.5 48.4 (dB)
Acoustic transmission loss at 10,000 Hz 47.3 53.5 55.1 54.4 (dB)
(Thickness of layer A)/(total thickness of 1/2 1/6.5 1/2 1/2 layer
B) Transmittance [at 1,500 nm] (%) 74 75 76 77 Shear storage
modulus [at 25.degree. C.] (MPa) 0.31 0.77 0.55 7.71 Maximum loss
factor of laminated glass 0.37 0.40 0.35 0.09 Breaking strength of
laminated glass [at 0.15 0.17 0.15 1.04 25.degree. C.] (kN)
Lamination aptitude B A D B
[0317] The following physical properties evaluations (12 to 15)
were conducted with respect to the layers A, layers B, laminates,
or laminated glasses obtained in the following Examples 26 to 37
and Reference Examples 12 to 13.
12. Physical Properties Evaluation (Shear Storage Modulus of
Laminate, Shear Storage Modulus of Layer B (Adhesive Layer), and
Shear Storage Modulus and Peak Height and Peak Temperature of Tan
.delta. of Layer A (Sound Insulating Layer))
[0318] A strain control type dynamic viscoelasticity instrument
(manufactured by Rheomix, ARES) having a diameter of a disk of 8 mm
was used as a parallel-plate oscillatory rheometer in accordance
with JIS K 7244-10. Laminates (thickness: 0.76 mm), single-layered
sheets of layer A (thickness: 0.76 mm), and single-layered sheets
of layer B (thickness: 0.76 mm) obtained in the following Examples
and Comparative Examples were each used as a disk-shaped test
sheet. It is to be noted that each of the above-described test
sheets after storing at a temperature 20.degree. C. and at a
humidity of 60% RH for 24 hours or more was used. A gap between two
flat plates was completely filled by the test sheet. A vibration
with a strain amount of 1.0% was given to the test sheet at a
frequency of 1 Hz, and a measurement temperature was increased at a
constant rate of 1.degree. C./min from -40.degree. C. to
100.degree. C. The temperatures of the test sheet and the disk were
kept until measured values of shear loss modulus and shear storage
modulus did not change. The results of shear storage modulus of
each of the laminate and the layer B at 25.degree. C., and peak
height and peak temperature of tan .delta. of the layer A
(elastomer in the layer A) as measured are shown in Tables 6 and
8.
13. Physical Properties Evaluation (Loss Factor and Maximum Loss
Factor of Laminated Glass)
[0319] Each of the laminates obtained in the Examples and
Comparative Examples was interposed between two sheets of
commercially available float glass (26 mm in length.times.76 mm in
width.times.2.8 mm in thickness), and a laminated glass was
prepared by a vacuum bagging method (condition: the temperature was
increased from 20.degree. C. to 140.degree. C. for 30 minutes,
followed by holding at 140.degree. C. and at a pressure of 1 MPa
for 60 minutes). Thereafter, the center of the laminated glass was
fixed to a tip portion of an exciting force detector built in an
impedance head of an exciter (power amplifier/model 371-A) of a
mechanical impedance instrument (manufactured by Ono Sokki Co.,
Ltd., mass cancel amplifier: MA-5500, channel data station:
DS-2100). A vibration was given at 20.degree. C. to the center of
the laminated glass at a frequency in the range of from 0 to 10,000
Hz, and an exciting force and an acceleration waveform at this
point were detected, thereby conducting a damping test of the
laminated glass by a central exciting method. A mechanical
impedance at an exciting point (the center of the laminated glass
to which a vibration was given) was determined on the basis of the
obtained exciting force and a speed signal obtained by integrating
an acceleration single; and in an impedance curve obtained by
setting the frequency on the abscissa and the mechanical impedance
on the ordinate, respectively, a loss factor at each resonance
point frequency was determined from a frequency expressing a peak
and a half-width value, and a loss factor .alpha. of the laminated
glass at 20.degree. C. and 2,000 Hz through proportional
calculation from the resonance point frequency at about 2,000 Hz
and a value of the loss factor at that resonance point frequency.
Furthermore, the laminated glass after the above-described
measurement was held at 18.degree. C. for one month. With respect
to the laminated glass after lapsing one month, a loss factor
.beta. was determined under the same conditions as described for
.alpha.. In addition, with respect to the laminated glass after
lapsing one month, a highest value among the loss factors at a
temperature 20.degree. C. and at primary to quantic modes was
determined as the maximum loss factor. With respect to a laminated
glass obtained after holding a laminated glass at 18.degree. C. for
one month and further heat treating at 100.degree. C. for 24 hours,
a loss factor .alpha. was determined under the same conditions as
described for a. The loss factor immediately after preparation of
the laminated glass, the loss factor after preparation of the
laminated glass and further lapsing one month, the loss factor
after the heat treatment, and the maximum loss factor at 20.degree.
C. are shown in Tables 6 and 8.
14. Physical Properties Evaluation (Haze of Laminated Glass)
[0320] A haze of a laminated glass after preparation of the
laminated glass and further lapsing one month was measured by using
a haze meter (manufactured by Suga Test Instruments Co., Ltd.). The
results are shown in Tables 6 and 8.
15. Physical Properties Evaluation (Lamination Aptitude of
Laminate)
[0321] Each of the laminates obtained in the Examples and
Comparative Examples was interposed between two sheets of
commercially available float glass (1,100 mm in length.times.1,300
mm in width.times.3.2 mm in thickness), and a laminated glass was
prepared by using a vacuum laminator (manufactured by Nisshinbo
Mechatronics Inc., 1522N) under the following conditions. The
lamination aptitude of the used laminate was judged according to
the following criteria. The evaluation results of the lamination
aptitude are shown in Tables 6 and 8.
<Conditions>
[0322] Hot plate temperature: 165.degree. C.
[0323] Evacuation time: 12 minutes
[0324] Pressing pressure: 50 kPa
[0325] Pressing time: 17 minutes
<Judgement Criteria>
[0326] A: Defects, such as bubbling, etc., are not observed on the
appearance, and adherence is good.
[0327] B: Though defects, such as bubbling, etc., are slightly
observed on the appearance, but there is no problem in
adherence.
[0328] C: Though defects, such as bubbling, etc., are observed on
the appearance, but there is no problem in adherence.
[0329] D: Defects, such as bubbling, etc., are observed on the
appearance, and adherence is bad.
[0330] E: Defects, such as bubbling, etc., are observed over the
entirety of the laminated glass on the appearance, and adherence is
bad.
Example 26
[0331] A linear hydrogenated styrene.isoprene/butadiene.styrene
triblock copolymer (weight average molecular weight: 100,000)
composed of 12% by mass of a styrene unit and 88% by mass of an
isoprene unit and a butadiene unit (isoprene/butadiene (molar
ratio)=89/11) and having a temperature of a peak at which a peak
height of tan .delta. was maximum of -22.6.degree. C. (a value in
the case of giving a vibration at a frequency of 1 Hz and
increasing a measurement temperature at a constant rate of
1.degree. C./min from -40.degree. C. to 100.degree. C.) was used
for the layer A. A polyvinyl butyral resin having a viscosity
average polymerization degree of about 1,700, a degree of
acetalization of 70 mol %, and a content of a vinyl acetate unit of
0.9 mol % was used for the layer B.
[0332] These resins were molded into the layer B having a thickness
of 330 .mu.m and the layer A having a thickness of 100 .mu.m,
respectively by an extrusion molding method. By using a
single-layer sheet of each of the resulting layer A and layer B,
the shear storage modulus of the layer B, and the peak height and
peak temperature of tan .delta. of the layer A were measured
according to the above-described evaluation methods.
[0333] Subsequently, the layer A was interposed between two layers
of the layer B and press molded at 150.degree. C., thereby
preparing a laminate made of a composite film of a three-layer
constitution and having a thickness of 0.76 mm. By using the
resulting laminate, the shear storage modulus of the laminate, the
loss factor after preparation of the laminated glass, the loss
factor after lapsing one month after preparation of the laminated
glass, the maximum loss factor of the laminated glass, the
lamination aptitude, and the haze of the laminated glass were
measured according to the above-described evaluation methods. The
results of the physical properties evaluations are shown in Table
6.
Examples 27 to 30
[0334] The layer A, the layer B, and the laminate were prepared by
using the same method as in Example 26, except that the layer B was
molded with a polyvinyl butyral resin composition in which KURARAY
POLYOL P-510 (manufactured by Kuraray Co., Ltd., polyester polyol
having a freezing point of -20.degree. C. or lower, a hydroxyl
value of 213 mgKOH/g, and a number average molecular weight per two
hydroxyl groups of 500, polyester diol composed of
3-methyl-1,5-pentanediol and adipic acid) was added as a
plasticizer in an amount as shown in Table 6 based on 100 parts by
mass of a polyvinyl butyral resin having a viscosity average
polymerization degree of about 1,700, a degree of acetalization of
70 mol %, and a content of a vinyl acetate unit of 0.9 mol %, and
then subjected to the physical properties evaluations. The results
of the physical properties evaluations are shown in Table 6.
[0335] In addition, in a laminated glass prepared by using the
laminate of Example 27, with respect to the loss factor immediately
after preparation of the laminated glass and the loss factor after
lapsing one month after preparation of the laminated glass, a loss
factor at each of frequencies obtained from the results of the
above-described damping test carried out at 20.degree. C. and at a
frequency in the range of from 0 to 10,000 Hz is shown in Table 7.
Similarly, in a laminated glass prepared by using the laminate of
Example 27, with respect to the loss factor immediately after
preparation of the laminated glass and the loss factor after
lapsing one month after preparation of the laminated glass, a loss
factor at each of frequencies obtained from the results of the
above-described damping test carried out at 30.degree. C. and at a
frequency in the range of from 0 to 10,000 Hz is shown in Table 7.
A graph showing a relation between the frequency and the loss
factor in the case of conducting the measurement at 20.degree. C.
as shown in Table 7 is shown in FIG. 2. In FIG. 2, the graph of a
solid line expresses the loss factor at each frequency immediately
after preparation of the laminated glass, and the graph of a dotted
line expresses the loss factor at each frequency after lapsing one
month after preparation of the laminated glass.
Example 31
[0336] The layer A, the layer B, and the laminate were prepared by
using the same method as in Example 27, except that a polyvinyl
butyral resin having a viscosity average polymerization degree of
about 1,000 was used in place of the polyvinyl butyral resin having
a viscosity average polymerization degree of about 1,700, and then
subjected to the physical properties evaluations. The results of
the physical properties evaluations are shown in Table 6.
Example 32
[0337] The layer A, the layer B, and the laminate were prepared by
using the same method as in Example 26, except that the layer B was
molded in a thickness of 253 .mu.m, and that the layer A was molded
in a thickness of 253 .mu.m, and then subjected to the physical
properties evaluations. The results of the physical properties
evaluations are shown in Table 6.
TABLE-US-00006 TABLE 6 Example Example Example Example Example
Example Example 26 27 28 29 30 31 32 Layer B Viscosity average
polymerization degree 1700 1700 1700 1700 1700 1000 1700 Degree of
acetalization (mol %) 70 70 70 70 70 70 70 Plasticizer -- A A A A A
-- Content of plasticizer (parts by mass) 0 5 15 25 40 5 0 Shear
storage modulus [at 25.degree. C.] (MPa) 127.4 100.6 71.3 50.2 34.7
84.9 127.4 Layer A Styrene content (% by mass) 12 12 12 12 12 12 12
Peak temperature of tan .delta. (.degree. C.) -22.6 -22.6 -22.6
-22.6 -22.6 -22.6 -22.6 Peak height of tan .delta. 1.92 1.92 1.92
1.92 1.92 1.92 1.92 Laminate Thickness [(layer B)/(layer A)/(layer
B)] (.mu.m) 330/100/ 330/100/ 330/100/ 330/100/ 330/100/ 330/100/
253/253/ 330 330 330 330 330 330 253 Loss factor .alpha.
immediately after preparation of 0.33 0.34 0.30 0.30 0.33 0.27 0.28
laminated glass [at 2,000 Hz and 20.degree. C.] Loss factor .beta.
after lapsing one month after preparation 0.33 0.32 0.28 0.32 0.35
0.25 0.28 of laminated glass [at 2,000 Hz and 20.degree. C.] (Loss
factor .beta.)/(loss factor .alpha.) 1 0.94 0.93 1.06 1.07 0.93 1
Loss factor .gamma. after heat treatment [at 2,000 Hz and 0.31 0.3
0.27 0.29 0.31 0.24 0.25 20.degree. C.] (Loss factor .gamma.)/(loss
factor .beta.) 0.93 0.93 0.96 0.90 0.88 0.96 0.89 Shear storage
modulus [at 25.degree. C.] (MPa) 6.1 5.5 4.8 3.6 3 3.55 5 Maximum
loss factor [at 20.degree. C.] 0.35 0.34 0.31 0.32 0.38 0.33 0.29
Haze 0.5 0.4 0.3 0.3 0.2 0.5 0.5 Lamination aptitude C B B A A A c
*The content of plasticizer in the table expresses a content based
on 100 parts by mass of the polyvinyl butyral resin. *Plasticizer
A: KURARAY POLYOL P-510 (manufactured by Kuraray Co., Ltd.)
TABLE-US-00007 TABLE 7 Measurement Measurement temperature:
20.degree. C. temperature: 30.degree. C. Hz Loss factor Hz Loss
factor Example 27 146.641 0.12343021 140.938 0.10514655
[Immediately after 690.781 0.22666067 660.547 0.16500056
preparation of 1660.469 0.32214686 1592.656 0.24094285 laminated
glass] 2950.781 0.37720704 2833.594 0.25291634 4592.969 0.36264682
4464.063 0.2206839 6536.719 0.34909666 6265.625 0.2012313 8953.906
0.3031235 8694.922 0.16430253 Example 27 146.25 0.13214622 139.531
0.10234539 [After lapsing one 687.109 0.24197893 650.547 0.16478501
month after 1660.391 0.3064782 1578.984 0.25061136 preparation of
2977.734 0.33963957 2818.75 0.25594711 laminated glass] 4641.797
0.3192904 4448.047 0.21662763 6692.578 0.3153483 6252.734
0.19007754 -- -- 8702.344 0.16414237
Examples 33 to 35
[0338] The layer A, the layer B, and the laminate were prepared by
using the same method as in Example 26, except that the layer B was
molded with a polyvinyl butyral resin composition in which KURARAY
POLYOL P-510 (manufactured by Kuraray Co., Ltd.) was added as a
plasticizer in an amount as shown in Table 8 based on 100 parts by
mass of a polyvinyl butyral resin having a viscosity average
polymerization degree of about 1,700, a degree of acetalization of
70 mol %, and a content of a vinyl acetate unit of 0.9 mol %, that
the layer B was molded in a thickness of 253 .mu.m, and that the
layer A was molded in a thickness of 253 .mu.m, and then subjected
to the physical properties evaluations. The results of the physical
properties evaluations are shown in Table 8.
Example 36
[0339] The layer A, the layer B, and the laminate were prepared by
using the same method as in Example 27, except that the layer A was
molded by using a linear hydrogenated styrene.isoprene.styrene
triblock copolymer (weight average molecular weight: 100,000)
composed of 20% by mass of a styrene unit and 80% by mass of an
isoprene unit and having a temperature of a peak at which a peak
height of tan .delta. was maximum of -5.2.degree. C. (a value in
the case of giving a vibration at a frequency of 1 Hz and
increasing a measurement temperature at a constant rate of
1.degree. C./min from -40.degree. C. to 100.degree. C.), and then
subjected to the physical properties evaluations. The results of
the physical properties evaluations are shown in Table 8.
Example 37
[0340] The layer A, the layer B, and the laminate were prepared by
using the same method as in Example 30, except that the layer A was
molded by using a linear hydrogenated styrene.isoprene.styrene
triblock copolymer (weight average molecular weight: about 100,000)
composed of 20% by mass of a styrene unit and 80% by mass of an
isoprene unit and having a temperature of a peak at which a peak
height of tan .delta. was maximum of -5.2.degree. C. (a value in
the case of giving a vibration at a frequency of 1 Hz and
increasing a measurement temperature at a constant rate of
1.degree. C./min from -40.degree. C. to 100.degree. C.), and then
subjected to the physical properties evaluations. The results of
the physical properties evaluations are shown in Table 8.
Reference Example 12
[0341] The layer A, the layer B, and the laminate were prepared by
using the same method as in Example 26, except that the layer B was
molded with a polyvinyl butyral resin composition in which KURARAY
POLYOL P-510 (manufactured by Kuraray Co., Ltd.) was added as a
plasticizer in an amount as shown in Table 8 based on 100 parts by
mass of a polyvinyl butyral resin having a viscosity average
polymerization degree of about 1,700, a degree of acetalization of
70 mol %, and a content of a vinyl acetate unit of 0.9 mol %, that
the layer B was molded in a thickness of 253 .mu.m, and that the
layer A was molded in a thickness of 253 .mu.m, and then subjected
to the physical properties evaluations. The results of the physical
properties evaluations are shown in Table 8.
Reference Example 13
[0342] The layer A, the layer B, and the laminate were prepared by
using the same method as in Example 27, except that 3GO
(triethylene glycol di(2-ethylhexanoate)) was used as a plasticizer
to be used for the layer B in an amount shown in Table 8 in place
of the KURARAY POLYOL P-510, and then subjected to the physical
properties evaluations. The results of the physical properties
evaluations are shown in Table 8.
[0343] In addition, in a laminated glass prepared by using the
laminate of Reference Example 12, with respect to the loss factor
immediately after preparation of the laminated glass and the loss
factor after lapsing one month after preparation of the laminated
glass, a loss factor at each of frequencies obtained from the
results of the above-described damping test carried out at
20.degree. C. and at a frequency in the range of from 0 to 10,000
Hz is shown in Table 9. Similarly, in a laminated glass prepared by
using the laminate of Reference Example 12, with respect to the
loss factor immediately after preparation of the laminated glass
and the loss factor after lapsing one month after preparation of
the laminated glass, a loss factor at each of frequencies obtained
from the results of the above-described damping test carried out at
30.degree. C. and at a frequency in the range of from 0 to 10,000
Hz is shown in Table 9. A graph showing a relation between the
frequency and the loss factor in the case of conducting the
measurement at 20.degree. C. shown in Table 9 is shown in FIG. 3.
In FIG. 3, the graph of a solid line expresses the loss factor at
each frequency immediately after preparation of the laminated
glass, and the graph of a dotted line expresses the loss factor at
each frequency after lapsing one month after preparation of the
laminated glass.
TABLE-US-00008 TABLE 8 Example Example Example Example Example
Reference Reference 33 34 35 36 37 Example 1 Example 2 Layer B
Viscosity average polymerization degree 1700 1700 1700 1700 1700
1700 1700 Degree of acetalization (mol %) 70 70 70 70 70 70 70
Plasticizer A A A A A A B Content of plasticizer (parts by mass) 5
15 25 5 40 40 5 Shear storage modulus [at 25.degree. C.] (MPa)
100.6 71.3 50.2 100.6 34.7 34.7 95.2 Layer A Styrene content (% by
mass) 12 12 12 20 20 12 12 Peak temperature of tan .delta.
(.degree. C.) -22.6 -22.6 -22.6 -5.2 -5.2 -22.6 -22.6 Peak height
of tan .delta. 1.92 1.92 1.92 1.89 1.89 1.92 1.92 Laminate
Thickness [(layer B)/(layer A)/(layer B)] (.mu.m) 253/253/ 253/253/
253/253/ 330/100/ 330/100/ 253/253/ 330/100/ 253 253 253 330 330
253 330 Loss factor .alpha. immediately after preparation of 0.28
0.26 0.23 0.22 0.24 0.24 0.28 laminated glass [at 2,000 Hz and
20.degree. C.] Loss factor .beta. after lapsing one month after
preparation 0.20 0.19 0.16 0.29 0.30 0.08 0.1 of laminated glass
[at 2,000 Hz and 20.degree. C.] (Loss factor .beta.)/(loss factor
.alpha.) 0.71 0.73 0.70 1.32 1.25 0.33 0.36 Loss factor .gamma.
after heat treatment [at 2,000 Hz and 0.24 0.23 0.21 0.25 0.26 0.17
0.16 20.degree. C.] (Loss factor .gamma.)/(loss factor .beta.) 1.2
1.21 1.31 0.86 0.86 2.12 1.6 Shear storage modulus [at 25.degree.
C.] (MPa) 4.6 3.9 2.6 5.5 3 1.7 4.9 Maximum loss factor [at
20.degree. C.] 0.23 0.23 0.23 0.32 0.30 0.21 0.29 Haze 0.4 0.4 0.3
0.4 0.3 0.3 2.3 Lamination aptitude B B A B A A C *The content of
plasticizer in the table expresses a content based on 100 parts by
mass of the polyvinyl butyral resin. *Plasticizer A: KURARAY POLYOL
P-510 (manufactured by Kuraray Co., Ltd.), Plasticizer B: 3GO
(triethylene glycol di(2-ethylhexanoate))
TABLE-US-00009 TABLE 9 Measurement Measurement temperature:
20.degree. C. temperature: 30.degree. C. Loss Loss Hz factor Hz
factor Reference Example 12 111.172 0.2379556 105.469 0.1577949
[Immediately after 531.563 0.2554719 506.797 0.1650353 preparation
of laminated 1329.297 0.2761577 1294.844 0.14923 glass] 2510.547
0.207985 2460.156 0.1155404 4056.641 0.1733666 3991.797 0.0935679
5973.438 0.1440492 5891.016 0.0800329 8241.016 0.1310047 8136.719
0.0746555 Reference Example 12 89.844 0.2198277 84.688 0.1277608
[After lapsing one month 462.344 0.1223238 447.422 0.0760299 after
preparation of 1214.531 0.0746864 1187.969 0.0534276 laminated
glass] 2327.734 0.0862531 2266.797 0.0752894 3689.453 0.0925822
3587.891 0.11532 5181.641 0.1041758 4954.688 0.1265927
[0344] The following physical properties evaluations (16 to 18)
were conducted with respect to the layers A, layers B, laminates,
or laminated glasses obtained in the following Examples 38 to 44
and Comparative Examples 14 to 15.
16. Physical Properties Evaluation (Peak Temperature of Tan .delta.
of Elastomer of Layer A and Entirety of Layer A)
[0345] A strain control type dynamic viscoelasticity instrument
(manufactured by Rheomix, ARES) having a diameter of a disk of 8 mm
was used as a parallel-plate oscillatory rheometer in accordance
with JIS K 7244-10. Single-layered sheets of layer A (layer A1 or
layer A2) (thickness: 0.76 mm) obtained in the following Examples
and Comparative Examples were each used as a disk-shaped test
sheet. It is to be noted that each of the above-described test
sheets after storing at a temperature 20.degree. C. and at a
humidity of 60% RH for 24 hours or more was used. A gap between two
flat plates was completely filled by the test sheet. A vibration
with a strain amount of 1.0% was given to the test sheet at a
frequency of 1 Hz, and a measurement temperature was increased at a
constant rate of 1.degree. C./min from -40.degree. C. to
100.degree. C. The temperatures of the test sheet and the disk were
kept until measured values of shear loss modulus and shear storage
modulus did not change. The peak temperature of tan .delta. was
determined from the shear storage modulus of the layer A (layer A1
or layer A2) as measured. The results are shown in Table 10.
17. Physical Properties Evaluation (Loss Factor of Laminated
Glass)
[0346] Each of the laminates obtained in the Examples and
Comparative Examples was interposed between two sheets of
commercially available float glass (50 mm in width.times.300 mm in
length.times.3 mm in thickness), and a laminated glass was prepared
by a vacuum bagging method (condition: the temperature was
increased from 30.degree. C. to 160.degree. C. for 60 minutes,
followed by holding at 160.degree. C. for 30 minutes). Thereafter,
the center of the laminated glass was fixed to a tip portion of an
exciting force detector built in an impedance head of an exciter
(power amplifier/model 371-A) of a mechanical impedance instrument
(manufactured by Ono Sokki Co., Ltd., mass cancel amplifier:
MA-5500, channel data station: DS-2100). A vibration was given to
the center of the laminated glass at a frequency in the range of
from 0 to 8,000 Hz, and an exciting force and an acceleration
waveform at this point were detected, thereby conducting a damping
test of the laminated glass by a central exciting method. A
mechanical impedance at an exciting point (the center of the
laminated glass to which a vibration was given) was determined on
the basis of the obtained exciting force and a speed signal
obtained by integrating an acceleration single; and in an impedance
curve obtained by setting the frequency on the abscissa and the
mechanical impedance on the ordinate, respectively, a loss factor
of the laminated glass was determined from a frequency expressing a
peak of the tertiary mode and a half-width value, and a width of
the temperature range where the loss factor was 0.2 or more was
determined. The calculation results of the width of the temperature
range where the loss factor was 0.2 or more are shown in Table
10.
18. Physical Properties Evaluation (Breaking Strength of Laminated
Glass)
[0347] Each of the laminates obtained in the Examples and
Comparative Examples was interposed between two sheets of
commercially available float glass (26 mm in length.times.76 mm in
width.times.2.8 mm in thickness), and a laminated glass was
prepared by a vacuum bagging method (condition: the temperature was
increased from 30.degree. C. to 160.degree. C. for 60 minutes,
followed by holding at 160.degree. C. for 30 minutes). Thereafter,
a three-point bending test (temperature: 20.degree. C.,
inter-fulcrum distance: 55 mm, test speed: 0.25 mm/min) of the
laminated glass was carried out by using an autograph AG-5000B, and
a breaking strength of the laminated glass was measured. The
measurement results of the breaking strength are shown in Table
10.
Comparative Example 14
[0348] A polyvinyl butyral resin having a viscosity average
polymerization degree of 600, an average degree of acetalization of
70 mol %, and a content of a vinyl acetate unit of 2 mol % and a
polyvinyl butyral resin having a viscosity average polymerization
degree of 1,700, an average degree of acetalization of 70 mol %,
and a content of a vinyl acetate unit of 1 mol % were used in a
mass ratio of 95/5 (hereinafter referred to as "PVB-1"), and a film
having a thickness of 250 .mu.m (PVB-1 film; used as the layer B)
was obtained by an extrusion molding method.
[0349] Subsequently, a coating liquid containing an elastomer X
(solvent: cyclohexane, solid content: 20% by mass) was coated on
one surface of the PVB-1 film such that a film thickness of the
layer A1 containing the elastomer X after drying was 10 .mu.m and
then dried with a warm air at 50 to 60.degree. C. for about
minutes. As the elastomer X, a linear hydrogenated
styrene.isoprene.styrene triblock copolymer (hydrogenation ratio:
90%) containing 12% by mass of a styrene unit and 88% by mass of an
isoprene unit and having a temperature of a peak at which a peak
height of tan .delta. was maximum of -22.6.degree. C. (a value in
the case of giving a vibration at a frequency of 1 Hz and
increasing a measurement temperature at a constant rate of
1.degree. C./min from -40.degree. C. to 100.degree. C.) was used.
It is to be noted that an MFR of the elastomer X as measured at a
temperature of 190.degree. C. and at a load of 2.16 kg was 0.5 g/10
min. In addition, the same PVB-1 film as in the base material was
used as a masking film on the surface having the elastomer X coated
thereon, so as to form a three-layer film after winding up. The
resultant was dried for 48 hours by a vacuum dryer at 50.degree.
C., thereby obtaining a laminate composed of three layers
(interlayer film for laminated glass).
[0350] A laminated glass was prepared by using the resulting
laminate, and a width of the temperature range where the loss
factor of the laminated glass was 0.2 or more by a damping test by
a central exciting method was determined. In addition, a
three-point bending test of the laminated glass was carried out,
thereby measuring a breaking strength of the laminated glass. The
measurement results of the width of the temperature range where the
loss factor was 0.2 or more and the breaking strength are shown in
Table 10.
Example 38
[0351] A laminate was prepared by using the same method as in
Comparative Example 14, except that a coating liquid containing the
elastomer X (solvent: cyclohexane, solid content: 20% by mass) was
coated on one surface of the PVB-1 film such that a film thickness
of the layer A1 containing the elastomer X after drying was 50
.mu.m, and then subjected to the physical evaluations. The
measurement results of the width of the temperature range where the
loss factor was 0.2 or more and the breaking strength are shown in
Table 10.
Comparative Example 15
[0352] A laminate was prepared by using the same method as in
Comparative Example 14, except that a coating liquid containing the
elastomer X (solvent: cyclohexane, solid content: 20% by mass) was
coated on one surface of the PVB-1 film such that a film thickness
of the layer A1 containing the elastomer X after drying was 150
.mu.m, and then subjected to the physical evaluations. The
measurement results of the width of the temperature range where the
loss factor was 0.2 or more and the breaking strength are shown in
Table 10.
Example 39
[0353] A laminate was prepared by using the same method as in
Comparative Example 14, except that a coating liquid containing the
elastomer X and an elastomer Y (solvent: cyclohexane, solid
content: 20% by mass, mass ratio of (elastomer X)/(elastomer Y):
1/1) was coated on one surface of the PVB-1 film such that a film
thickness of the layer A1 containing the elastomer X and the
elastomer Y after drying was 100 .mu.m, and then subjected to the
physical evaluations. The measurement results of the width of the
temperature range where the loss factor was 0.2 or more and the
breaking strength are shown in Table 10. It is to be noted that as
the elastomer Y, a linear hydrogenated styrene.isoprene.styrene
triblock copolymer (hydrogenation ratio: 88%) containing 20% by
mass of a styrene unit and 80% by mass of an isoprene unit and
having a temperature of a peak at which a peak height of tan
.delta. was maximum of -5.2.degree. C. (a value in the case of
giving a vibration at a frequency of 1 Hz and increasing a
measurement temperature at a constant rate of 1.degree. C./min from
-40.degree. C. to 100.degree. C.) was used. It is to be noted that
an MFR of the elastomer Y as measured at a temperature of
190.degree. C. and at a load of 2.16 kg was 0.7 g/10 min.
Example 40
[0354] A laminate was prepared by using the same method as in
Comparative Example 14, except that a coating liquid containing the
elastomer X (solvent: cyclohexane, solid content: 20% by mass) was
coated on one surface of the PVB-1 film such that a film thickness
of the layer A1 containing the elastomer X after drying was 50
.mu.m, followed by drying with a warm air at 50 to 60.degree. C.
for about 10 minutes, and that a coating liquid containing the
elastomer Y (solvent: cyclohexane, solid content: 20% by mass) was
further coated thereon such that a film thickness of the layer A2
containing the elastomer Y after drying was 50 .mu.m, followed by
drying with a warm air at 50 to 60.degree. C. for about 10 minutes,
and then subjected to the physical evaluations. The measurement
results of the width of the temperature range where the loss factor
was 0.2 or more and the breaking strength are shown in Table
10.
Example 41
[0355] A laminate was prepared by using the same method as in
Example 38, except that as the layer B, a film having a thickness
of 250 .mu.m was fabricated by an extrusion molding method by using
95 parts by mass of a polyvinyl butyral resin having a viscosity
average polymerization degree of 600, an average degree of
acetalization of 70 mol %, and a content of a vinyl acetate unit of
2 mol %, 5 parts by mass of a polyvinyl butyral resin having a
viscosity average polymerization degree of 1,700, an average degree
of acetalization of 70 mol %, and a content of a vinyl acetate unit
of 1 mol %, and 100 parts by mass of KURARAY POLYOL P-510
(manufactured by Kuraray Co., Ltd., polyester polyol; polyester
diol composed of 3-methyl-1,5-pentanediol and adipic acid; number
average molecular weight per two hydroxyl groups: 500), and then
subjected to the physical evaluations. The measurement results of
the width of the temperature range where the loss factor was 0.2 or
more and the breaking strength are shown in Table 10.
Example 42
[0356] A laminate was prepared by using the same method as in
Comparative Example 15, except that the coating liquid containing
the elastomer Y was used in place of the coating liquid containing
the elastomer X, and then subjected to the physical evaluations.
The measurement results of the width of the temperature range where
the loss factor was 0.2 or more and the breaking strength are shown
in Table 10.
Example 43
[0357] A laminate was prepared by using the same method as in
Example 39, except that the film thickness of the layer B after
drying was regulated to 100 .mu.m, and that the film thickness of
the layer A1 after drying was regulated to 300 .mu.m, and then
subjected to the physical evaluations. The measurement results of
the width of the temperature range where the loss factor was 0.2 or
more and the breaking strength are shown in Table 10.
Example 44
[0358] A laminate was prepared by using the same method as in
Example 38, except that the coating liquid containing the elastomer
Y was used in place of the coating liquid containing the elastomer
X, and then subjected to the physical evaluations. The measurement
results of the width of the temperature range where the loss factor
was 0.2 or more and the breaking strength are shown in Table
10.
TABLE-US-00010 TABLE 10 Comparative Exam- Comparative Example
Example Example Exam- Example 14 ple 38 Example 15 Example 39 40 41
42 Example 43 ple 44 Layer B Thermoplastic resin PVB-1 PVB-1 PVB-1
PVB-1 PVB-1 PVB-1 PVB-1 PVB-1 PVB-1 Plasticizer -- -- -- -- --
KURARAY -- -- -- POLYOL P-510 (10 phr) Thickness (.mu.m) 250 250
250 250 250 250 250 100 250 Layer A1 Thermoplastic Elastomer X
Elasto- Elastomer X Elastomer X Elastomer Elastomer Elastomer
Elastomer X Elasto- elastomer mer X Elastomer Y X X Y Elastomer Y
mer Y (mass ratio: (mass ratio: 1/1) 1/1) Thickness (.mu.m) 10 50
150 100 50 50 150 300 50 Layer A2 Thermoplastic -- -- -- --
Elastomer -- -- -- -- elastomer Y Thickness (.mu.m) -- -- -- -- 50
-- -- -- -- Layer constitution B/A1/B B/A1/B B/A1/B B/A1/B B/A1/
B/A1/B B/A1/B B/A1/B B/A1/B A2/B Lower limit of temperature range
-- 8 4 13 9 7 18 11 22 where the loss factor is 0.2 or more Upper
limit of temperature range -- 34 18 37 41 35 42 41 41 where the
loss factor is 0.2 or more Width of temperature range where 0 26 14
24 32 28 24 30 19 the loss factor is 0.2 or more (.degree. C.) Loss
factor at 20.degree. C. 0.09 0.28 0.21 0.27 0.28 0.27 0.21 0.3 0.18
Maximum loss factor 0.13 0.28 0.32 0.27 0.29 0.27 0.34 0.31 0.29
Breaking strength of laminated 0.90 0.72 0.52 0.63 0.62 0.64 0.54
0.34 0.74 glass [at 25.degree. C.] (kN) Peak temperature of tan
.delta. of the layer containing the elastomer X: -22.6.degree. C.,
peak top height: 1.92 Peak temperature of tan .delta. of the layer
containing the elastomer Y: -5.2.degree. C., peak top height: 1.89
Peak temperature of tan .delta. of the layer containing the
elastomer X and the elastomer Y in a mass ratio of 1/1:
-12.9.degree. C., peak top height: 1.68
REFERENCE SIGNS LIST
[0359] 1: Layer A [0360] 2a: Layer B [0361] 2b: Layer B [0362] 10:
Shear storage modulus [0363] 11: Loss tangent (tan .delta.)
* * * * *