U.S. patent application number 15/525533 was filed with the patent office on 2018-10-11 for interlayer film for laminated glass 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 | 20180290437 15/525533 |
Document ID | / |
Family ID | 55954419 |
Filed Date | 2018-10-11 |
United States Patent
Application |
20180290437 |
Kind Code |
A1 |
KOBAYASHI; Takuya ; et
al. |
October 11, 2018 |
INTERLAYER FILM FOR LAMINATED GLASS AND LAMINATED GLASS
Abstract
An object of the present invention is to provide an interlayer
film for laminated glass which has excellent sound insulating
properties and which even when used for a long period of time in a
high-temperature and high-humidity environment, is able to keep a
haze good and is also able to suppress whitening from an edge side
thereof. The present invention is concerned with an interlayer film
for laminated glass including a sound insulating layer (layer A)
and thermoplastic resin layers containing a thermoplastic resin
(layers B), the sound insulating layer (layer A) being located
between at least two of the thermoplastic resin layers (layers B),
wherein with respect to a laminated glass obtained by interposing
the interlayer film for laminated glass by two sheets of float
glass and a laminated glass obtained by holding the laminated glass
under conditions at 80.degree. C. and at a relative humidity of 95%
for 1,000 hours, when a haze of a central portion of the laminated
glass in accordance with JIS K 7105 is measured, an increase of the
haze of the laminated glass after holding relative to the haze of
the laminated glass before holding is 2% or less, and a distance of
whitening from an edge side of the laminated glass after holding is
4 mm or less.
Inventors: |
KOBAYASHI; Takuya;
(Kurashiki-shi, JP) ; KUSUDOU; Takeshi;
(Kurashiki-shi, JP) ; YUI; Taiga; (Kurashiki-shi,
JP) ; ISOUE; Koichiro; (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.: |
15/525533 |
Filed: |
November 10, 2015 |
PCT Filed: |
November 10, 2015 |
PCT NO: |
PCT/JP2015/081668 |
371 Date: |
May 9, 2017 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
B32B 2307/30 20130101;
B32B 2307/412 20130101; B32B 17/1077 20130101; B32B 17/10788
20130101; B32B 2309/105 20130101; B60J 1/001 20130101; B32B
17/10559 20130101; B32B 17/10724 20130101; B32B 2307/542 20130101;
B32B 2307/734 20130101; B32B 2605/006 20130101; B60J 7/043
20130101; E06B 3/6707 20130101; B32B 2307/102 20130101; B60J 1/02
20130101; B32B 17/10761 20130101; B32B 17/10678 20130101; B32B
25/08 20130101; B32B 17/10633 20130101; B32B 17/10605 20130101;
B60J 1/08 20130101; B32B 17/10577 20130101; B32B 17/10743 20130101;
B32B 17/10587 20130101; E06B 3/66 20130101; B32B 17/10165 20130101;
B32B 25/042 20130101; E06B 3/6715 20130101; B60J 1/18 20130101;
B32B 17/10036 20130101; B32B 17/1055 20130101 |
International
Class: |
B32B 17/10 20060101
B32B017/10; E06B 3/67 20060101 E06B003/67 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 10, 2014 |
JP |
2014-228354 |
Dec 5, 2014 |
JP |
2014-246710 |
Claims
1: An interlayer film for laminated glass, comprising a sound
insulating layer (layer A) and thermoplastic resin layers
containing a thermoplastic resin (layers B), the sound insulating
layer (layer A) being located between at least two of the
thermoplastic resin layers (layers B), wherein with respect to a
laminated glass obtained by interposing the interlayer film for
laminated glass between two sheets of float glass and a laminated
glass obtained by holding the laminated glass under conditions at
80.degree. C. and at a relative humidity of 95% for 1,000 hours,
when a haze of a central portion of the laminated glass in
accordance with JIS K 7105 is measured, an increase of the haze of
the laminated glass after holding relative to the haze of the
laminated glass before holding is 2% or less, and a distance of
whitening from an edge side of the laminated glass after holding is
4 mm or less.
2: The interlayer film for laminated glass according to claim 1,
wherein with respect to a laminated glass obtained by interposing
the interlayer film for laminated glass between two sheets of float
glass and a laminated glass obtained by holding the laminated glass
under conditions at 80.degree. C. and at a relative humidity of 95%
for 1,000 hours, when a loss factor at a tertiary resonance
frequency is measured at 20.degree. C. by a central exciting
method, the loss factor of the laminated glass before holding is
0.2 or more, and a decrease of the loss factor of the laminated
glass after holding relative to the loss factor of the laminated
glass before holding is 0.05 or less.
3: The interlayer film for laminated glass according to claim 1,
wherein with respect to a laminated glass obtained by interposing
the interlayer film for laminated glass between two sheets of float
glass, in a state where the laminated glass is placed such that in
a positional relation in which a plane of the laminated glass
including the center in a longitudinal direction thereof includes
the center in a width direction of a cylindrical xenon lamp, and a
plane of the laminated glass including the center in a thickness
direction thereof includes the center in a length direction of the
cylindrical xenon lamp, its shortest distance to the cylindrical
xenon lamp is 29 cm, when the laminated glass is held for 1,000
hours while irradiating an edge portion thereof with ultraviolet
rays at a luminance of the xenon lamp of 180 W/m.sup.2 under
conditions at a relative humidity of 50% and a black panel
temperature of 63.degree. C., in measuring an YI (yellow index) of
the laminated glass before holding and an YI of the laminated glass
after holding on the basis of JIS K 7373, an increase of the YI of
the laminated glass after holding relative to the YI of the
laminated glass before holding is 3 or less.
4: The interlayer film for laminated glass according to claim 1,
wherein with respect to a laminated glass having the interlayer
film for laminated glass interposed by two sheets of float glass, a
loss factor at a tertiary resonance frequency as measured at
20.degree. C. by a central exciting method is 0.2 or more.
5: The interlayer film for laminated glass according to claim 1,
wherein the sound insulating layer (layer A) is a layer containing
a thermoplastic elastomer.
6: The interlayer film for laminated glass according to claim 5,
wherein the thermoplastic elastomer is a block copolymer.
7: The interlayer film for laminated glass according to claim 6,
wherein the block copolymer has an aromatic vinyl polymer block and
an aliphatic unsaturated hydrocarbon polymer block.
8: The interlayer film for laminated glass according to claim 1,
wherein the thermoplastic elastomer is a hydrogenated product of a
block copolymer having an aromatic vinyl polymer block containing
60 mol % or more of an aromatic vinyl monomer unit and an aliphatic
unsaturated hydrocarbon polymer block containing 60 mol % or more
of a conjugated diene monomer unit, the aliphatic unsaturated
hydrocarbon polymer block has an isoprene unit and a butadiene unit
in an amount of 50 mol % or more in total as the conjugated diene
monomer unit, and a residual amount of a carbon-to-carbon double
bond derived from the conjugated diene monomer unit is 2 to 40 mol
%.
9: The interlayer film for laminated glass according to claim 1,
wherein the thermoplastic resin is a polyvinyl acetal resin or an
ionomer resin.
10: The interlayer film for laminated glass according to claim 9,
wherein a content of a plasticizer is 50 parts by mass or less
based on 100 parts by mass of the polyvinyl acetal resin.
11: The interlayer film for laminated glass according to claim 1,
wherein when preparing a laminated glass by interposing the
interlayer film for laminated glass between two sheets of float
glass, a transmittance of a near infrared light having a wavelength
of 1,500 nm is 50% or less.
12: The interlayer film for laminated glass according to claim 1,
wherein at least one of the sound insulating layer (layer A) and
the thermoplastic resin layers (layers B) contains a heat
insulating material.
13: The interlayer film for laminated glass according to claim 1,
wherein one or more members selected from the group consisting of
tin-doped indium oxide, antimony-doped tin oxide, aluminum-doped
zinc oxide, zinc antimonate, lanthanum hexaboride, a metal-doped
tungsten oxide, a phthalocyanine compound, and a naphthalocyanine
compound are contained as the heat insulating material.
14: A laminated glass comprising the interlayer film for laminated
glass according to claim 1 disposed between at least two sheets of
glass.
Description
TECHNICAL FIELD
[0001] The present invention relates to an interlayer film for
laminated glass and a laminated glass, each of which has excellent
sound insulating properties and which even when used in a
high-temperature and high-humidity environment for a long period of
time, is able to keep a haze good and is also able to suppress
whitening from an edge side thereof. In addition, the present
invention relates to an interlayer film for laminated glass and a
laminated glass, each of which has excellent sound insulating
properties and which even when used for a long period of time under
sunlight, is able to suppress yellowing of an edge portion
thereof.
BACKGROUND ART
[0002] Polyvinyl acetal resins 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 resin 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 the laminated glass are
improved by a damping performance of the interlayer film and a
performance of the interlayer film of converting vibration energy
into heat energy.
[0006] As for a method of improving sound insulating properties,
there is, for example, proposed an interlayer film in which a
copolymer of polystyrene and a rubber-based resin is laminated by a
plasticized polyvinyl acetal-based resin (see, for example, Patent
Literature 1).
[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).
[0008] Meanwhile, as an interlayer film with improved sound
insulating properties, there are proposed an interlayer film
composed of a three-layer constitution of ionomer/EVA/ionomer (see,
for example, Patent Literature 3), an interlayer film composed of a
three-layer constitution of ionomer/ethylene acid copolymer/ionomer
(see, for example, Patent Literature 4), and the like.
[0009] In addition, in order to not only suppress the generation of
acetic acid or yellowing but also suppress a lowering of
transparency or adhesive force in a moist heat environment, it is
proposed to use an ethylene.vinyl acetate copolymer sheet
containing a repeating unit of a monomer derived from glycidyl
(meth)acrylate as an interlayer film for laminated glass (see, for
example, Patent Literature 5). In addition, in order to not only
reveal excellent transparency and mechanical strength but also not
impair an initial optical quality even after a durability test,
there is also proposed an interlayer film for laminated glass in
which when irradiated with ultraviolet rays at an intensity of 100
mW/cm.sup.2 and at a wavelength of 295 to 450 nm for 300 hours, a
lowering of transmittance of visible light of the laminated glass
after irradiation with ultraviolet rays is 1.0% or less (see, for
example, Patent Literature 6). In addition to the above, in order
to regulate the transmittance of ultraviolet rays at a wavelength
of 400 nm to 1% or less, thereby improving light fastness, there is
also proposed an interlayer film for laminated glass containing a
specified amount of each of two kinds of ultraviolet absorbers
having a specified structure (see, for example, Patent Literature
7). Furthermore, in order to improve transparency, heat insulating
properties, electromagnetic wave permeability, and weather
resistance, there is also proposed an interlayer film for laminated
glass in which when formed into a laminated glass, an
electromagnetic shielding performance at frequencies at 0.1 to 10
MHz and 2 to 26.5 GHz is 10 dB or less, a haze is 1.0% or less, a
transmittance of visible light is 70% or more, and a transmittance
of solar radiation in a wavelength region of 300 nm to 2,100 nm is
85% or less of the transmittance of visible light (see, for
example, Patent Literature 8).
CITATION LIST
Patent Literature
[0010] Patent Literature 1: JP 2007-91491A
[0011] Patent Literature 2: WO 2005/018969A
[0012] Patent Literature 3: WO 2015/013242A
[0013] Patent Literature 4: WO 2015/085165A
[0014] Patent Literature 5: JP 2014-015544A
[0015] Patent Literature 6: JP 2003-327455A
[0016] Patent Literature 7: WO 2012/023616A
[0017] Patent Literature 8: WO 2003/018502A
SUMMARY OF INVENTION
Technical Problem
[0018] However, in the above-described conventional interlayer
films, there was a concern that when the use environment of the
laminated glass is a high-temperature and high-humidity
environment, discoloration of the interlayer film in a stripped
portion is generated, or when the laminated glass is used in a
high-temperature and high-humidity environment for a long period of
time, the sound insulating properties of the laminated glass are
lowered. Alternatively, there was involved such a problem that
though whitening of the periphery is improved, the sound insulating
properties are not sufficient.
[0019] In the light of the above, in the conventional interlayer
films, it was difficult to not only exhibit high sound insulating
properties but also make both properties of keeping the haze good
and properties of suppressing whitening from the edge side
compatible with each other in a high-temperature and high-humidity
environment.
[0020] In addition, in the case where the above-described
interlayer films for laminated glass are used for a laminated glass
in which the edge portion of the laminated glass is stripped
without being sealed with a resin or rubber, as in laminated
glasses for building or side laminated glasses for automobile,
there was a concern that when used under sunlight, the interlayer
film in a stripped portion is yellowed. In addition, in the
above-described interlayer films for laminated glass, there was
also involved such a problem that the sound insulating properties
are not sufficient.
[0021] In the light of the above, in the conventional interlayer
films, both properties that the edge portion of the stripped part
is hardly yellowed under sunlight and properties that the sound
insulating properties are high could not be made compatible with
each other.
[0022] The present invention is to solve the above-described
problems. Specifically, a first object of the present invention is
to provide an interlayer film for laminated glass which when used
as an interlayer film for laminated glass, has excellent sound
insulating properties and which even when used in a
high-temperature and high-humidity environment for a long period of
time, is able to keep a haze good and is also able to suppress
whitening from an edge side thereof.
[0023] In addition, a second object of the present invention is to
provide an interlayer film for laminated glass which when used as
an interlayer film for laminated glass, has excellent sound
insulating properties and which even when used for a long period of
time under sunlight, is able to suppress yellowing of an edge
portion thereof.
Solution to Problem
[0024] The objects of the present invention are achieved by
providing the following.
[1] An interlayer film for laminated glass comprising a sound
insulating layer (layer A) and thermoplastic resin layers
containing a thermoplastic resin (layers B), the sound insulating
layer (layer A) being located between at least two of the
thermoplastic resin layers (layers B), wherein
[0025] with respect to a laminated glass obtained by interposing
the interlayer film for laminated glass by two sheets of float
glass and a laminated glass obtained by holding the laminated glass
under conditions at 80.degree. C. and at a relative humidity of 95%
for 1,000 hours, when a haze of a central portion of the laminated
glass in accordance with JIS K 7105 is measured, an increase of the
haze of the laminated glass after holding relative to the haze of
the laminated glass before holding is 2% or less, and a distance of
whitening from an edge side of the laminated glass after holding is
4 mm or less;
[2] The interlayer film for laminated glass as set forth in [1],
wherein with respect to a laminated glass obtained by interposing
the interlayer film for laminated glass by two sheets of float
glass and a laminated glass obtained by holding the laminated glass
under conditions at 80.degree. C. and at a relative humidity of 95%
for 1,000 hours, when a loss factor at a tertiary resonance
frequency is measured at 20.degree. C. by a central exciting
method, the loss factor of the laminated glass before holding is
0.2 or more, and a decrease of the loss factor of the laminated
glass after holding relative to the loss factor of the laminated
glass before holding is 0.05 or less; [3] The interlayer film for
laminated glass as set forth in [1] or [2], wherein
[0026] with respect to a laminated glass obtained by interposing
the interlayer film for laminated glass by two sheets of float
glass,
[0027] in a state where the laminated glass is placed such that in
a positional relation in which a plane of the laminated glass
including the center in a longitudinal direction thereof includes
the center in a width direction of a cylindrical xenon lamp, and a
plane of the laminated glass including the center in a thickness
direction thereof includes the center in a length direction of the
cylindrical xenon lamp, its shortest distance to the cylindrical
xenon lamp is 29 cm,
[0028] when the laminated glass is held for 1,000 hours while
irradiating an edge portion thereof with ultraviolet rays at a
luminance of the xenon lamp of 180 W/m.sup.2 under conditions at a
relative humidity of 50% and a black panel temperature of
63.degree. C.,
[0029] in measuring a YI (yellow index) of the laminated glass
before holding and a YI of the laminated glass after holding on the
basis of JIS K 7373, an increase of the YI of the laminated glass
after holding relative to the YI of the laminated glass before
holding is 3 or less;
[4] The interlayer film for laminated glass as set forth in any of
[1] to [3], wherein with respect to a laminated glass having the
interlayer film for laminated glass interposed by two sheets of
float glass, a loss factor at a tertiary resonance frequency as
measured at 20.degree. C. by a central exciting method is 0.2 or
more; [5] The interlayer film for laminated glass as set forth in
any of [1] to [4], wherein the sound insulating layer (layer A) is
a layer containing a thermoplastic elastomer; [6] The interlayer
film for laminated glass as set forth in [5], wherein the
thermoplastic elastomer is a block copolymer; [7] The interlayer
film for laminated glass as set forth in [6], wherein the block
copolymer has an aromatic vinyl polymer block and an aliphatic
unsaturated hydrocarbon polymer block; [8] The interlayer film for
laminated glass as set forth in any of [5] to [7], wherein
[0030] the thermoplastic elastomer is a hydrogenated product of a
block copolymer having an aromatic vinyl polymer block containing
60 mol % or more of an aromatic vinyl monomer unit and an aliphatic
unsaturated hydrocarbon polymer block containing 60 mol % or more
of a conjugated diene monomer unit,
[0031] the aliphatic unsaturated hydrocarbon polymer block has an
isoprene unit and a butadiene unit in an amount of 50 mol % or more
in total as the conjugated diene monomer unit, and
[0032] a residual amount of a carbon-to-carbon double bond derived
from the conjugated diene monomer unit is 2 to 40 mol %;
[9] The interlayer film for laminated glass as set forth in any of
[1] to [8], wherein the thermoplastic resin is a polyvinyl acetal
resin or an ionomer resin; [10] The interlayer film for laminated
glass as set forth in [9], wherein a content of a plasticizer is 50
parts by mass or less based on 100 parts by mass of the polyvinyl
acetal resin; [11] The interlayer film for laminated glass as set
forth in any of [1] to [10], wherein when preparing a laminated
glass by interposing the interlayer film for laminated glass by two
sheets of float glass, a transmittance of a near infrared light
having a wavelength of 1,500 nm is 50% or less; [12] The interlayer
film for laminated glass as set forth in any of [1] to [11],
wherein at least one of the sound insulating layer (layer A) and
the thermoplastic resin layers (layers B) contains a heat
insulating material; [13] The interlayer film for laminated glass
as set forth in any of [1] to [12], wherein one or more members
selected from the group consisting of tin-doped indium oxide,
antimony-doped tin oxide, aluminum-doped zinc oxide, zinc
antimonate, lanthanum hexaboride, a metal-doped tungsten oxide, a
phthalocyanine compound, and a naphthalocyanine compound are
contained as the heat insulating material; and [14] A laminated
glass comprising the interlayer film for laminated glass as set
forth in any of [1] to [13] disposed between at least two sheets of
glass.
Advantageous Effects of Invention
[0033] According to the present invention, as a first effect, it is
possible to provide an interlayer film for laminated glass and a
laminated glass, each of which has excellent sound insulating
properties and which even when used in a high-temperature and
high-humidity environment for a long period of time, is able to
keep a haze good and is also able to suppress whitening from an
edge side thereof.
[0034] In addition, according to the present invention, as a second
effect, it is possible to provide an interlayer film for laminated
glass and a laminated glass, each of which has excellent sound
insulating properties and which even when used for a long period of
time under sunlight, is able to suppress yellowing of an edge
portion thereof.
BRIEF DESCRIPTION OF DRAWINGS
[0035] FIG. 1 is an example of a cross-sectional view of a
constitution of an interlayer film for laminated glass of the
present invention.
[0036] FIG. 2 is a schematic view exhibiting a positional relation
between a laminated glass and a xenon lamp in a weather resistance
test.
[0037] FIG. 3 is an example of a schematic view of a laminated
glass to be used for evaluation of thermal creep resistance.
[0038] FIG. 4 is an example of a schematic view in the case of
sticking an iron plate onto a laminated glass to be used for
evaluation of thermal creep resistance.
[0039] FIG. 5 is an example of a schematic view in the case of
leaning a laminated glass having an iron plate stuck thereonto
against a stand for the purpose of evaluation of thermal creep
resistance.
DESCRIPTION OF EMBODIMENTS
[0040] Embodiments of the present invention are hereunder
described, but it should not be construed that the present
invention is limited to the present embodiments.
[Layer A]
[0041] The interlayer film for laminated glass of the present
invention is constituted of at least a layer A and a plurality of
layers B, and it is an interlayer film for laminated glass having a
sound insulating layer (layer A) and thermoplastic resin layers
(layers B) containing a thermoplastic resin, the sound insulating
layer (layer A) being located between the at least two layers
B.
[0042] 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 8. 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..
[0043] From the viewpoint of improving the sound insulating
properties, the layer A which is used in the present invention has
a peak (temperature at a peak top) 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 preferably 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. is maximum is present at 30.degree. C. or lower, the sound
insulating properties tend 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. is maximum is present at -40.degree. C. or
higher, the sound insulating properties in a high-frequency region
tend to be improved. Specifically, the above-described tan .delta.
is measured by the method described in the Examples as described
later.
[0044] In addition, in the layer A, 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 more improving the sound insulating properties, 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. When the height of the peak of tan .delta.
under the above-described condition is less than 0.5, the sound
insulating properties of the resulting interlayer film for
laminated glass tend to become low.
[0045] From the viewpoint of improving the sound insulating
properties, the sound insulating layer constituting the layer A is
preferably a layer containing a thermoplastic elastomer.
[0046] The thermoplastic elastomer 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 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 thermoplastic
elastomer has a peak at which the tan .delta. is maximum preferably
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. is maximum is present at higher than
30.degree. C., the sound insulating properties tend to be hardly
exhibited in a temperature region where the layer A is used as a
laminated glass. When the peak at which the tan .delta. is maximum
is present at lower than -40.degree. C., there is a tendency that
the shear storage modulus is lowered, and the sound insulating
properties in a high-frequency region are lowered. Specifically,
the above-described tan .delta. is measured by the method described
in the Examples as described later. As a method of adjusting the
peak temperature at which the tan .delta. is maximum to -40 to
30.degree. C., there is, for example, exemplified a method of using
a suitable thermoplastic elastomer, especially a block copolymer as
described later, or the like.
[0047] From the viewpoint of much more improving the sound
insulating properties, the glass transition temperature of the
thermoplastic elastomer 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 thermoplastic elastomer is not
particularly limited, and the glass transition temperature of the
thermoplastic elastomer 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.
[0048] In the thermoplastic elastomer, 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 more improving the sound insulating
properties, 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. When the height of the peak of
tan .delta. under the above-described condition is less than 0.5,
the sound insulating properties of the resulting interlayer film
for laminated glass tend to become low. As a method of adjusting
the height of the peak of tan .delta. to 0.5 or more, there is, for
example, exemplified a method of using a suitable thermoplastic
elastomer, especially a block copolymer as described later, or the
like.
(Thermoplastic Elastomer)
[0049] The thermoplastic elastomer as referred to in the present
specification means a polymer compound which when heated, is
softened to exhibit plasticity, whereas when cooled, is solidified
to exhibit rubber elasticity, and is distinguished from a
thermoplastic resin. In addition, the thermoplastic elastomer
refers to a polymer compound having a hard segment and a soft
segment. In view of the fact that the layer A serving as an
internal layer contains the thermoplastic elastomer, the sound
insulating properties are improved. Furthermore, when a hydrophobic
polymer compound with low polarity, such as a thermoplastic
elastomer, is used as an internal layer of the interlayer film for
laminated glass, water, such as moisture, etc., hardly penetrates
from the edge side of the laminated glass into the inside of the
interlayer film for laminated glass. For that reason, the edge side
of the laminated glass is hardly whitened even in a moist heat
environment.
[0050] From the viewpoint of making both the moldability and the
sound insulating properties compatible with each other, 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 or
polyester/hard segment: polyurethane), a polyester-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. These thermoplastic elastomers may be used solely or may be
used in combination of two or more thereof.
[0051] 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 10% by mass or more, yet still more
preferably 14% by mass or more, even yet still more preferably 15%
by mass or more, and most preferably 17% 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 25% by mass or less, and
especially preferably 20% 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, or the height of the peak of
tan .delta. is small. In addition, there is a tendency that the
bending rigidity of the interlayer film for laminated glass is
small, so that 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 edge portion of the
interlayer film for laminated glass is liable to be yellowed, or
the characteristics as the thermoplastic elastomer are hardly
exhibited.
[0052] 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 75% by mass or more, and yet still more
preferably 80% 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 93% by mass or
less, still more preferably 90% by mass or less, yet still more
preferably 86% by mass or less, even yet still more preferably 85%
by mass or less, and most preferably 83% 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, or the height of the peak of tan .delta. is small. In
addition, there is a tendency that the bending rigidity of the
interlayer film for laminated glass is small, so that the sound
insulating properties in a high-frequency region are lowered.
[0053] 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 more improving the sound insulating properties, it is
preferred to use a polystyrene-based elastomer.
[0054] In addition, rubbers, such as 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.
[0055] 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 thermoplastic elastomer is
preferably a block copolymer having an aromatic vinyl polymer block
(hereinafter also referred to as "polymer block (a)") and an
aliphatic unsaturated hydrocarbon polymer block (hereinafter also
referred to as "polymer block (b)"), for example, a
polystyrene-based elastomer.
[0056] 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.
[0057] 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.
[0058] 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.
[0059] 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 10% by mass or more, yet still
more preferably 14% by mass or more, especially preferably 15% by
mass or more, and most preferably 17% 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, and especially preferably 20% by mass or less
relative to the whole of the monomer units of the block copolymer.
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, or the height of the peak of
tan .delta. is small. In addition, there is a tendency that the
bending rigidity of the interlayer film for laminated glass is
small, so that 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, the
characteristics as the thermoplastic elastomer tend to be hardly
exhibited. 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 aliphatic unsaturated hydrocarbon monomer unit in the block
copolymer is considered as an average value of the mixture.
[0060] A content 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.
[0061] 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.
[0062] In addition, in the aromatic vinyl polymer block, a monomer
other than the aromatic vinyl polymer monomer may be copolymerized.
Examples of the monomer other than the aromatic vinyl monomer
include unsaturated monomers, such as 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, norbornene, acetylene, etc.;
(meth)acrylate-based monomers, such as methyl acrylate, methyl
methacrylate, etc.; conjugated dienes, such as butadiene,
1,3-pentadiene, 1,3-hexadiene, isoprene, cyclopentadiene,
1,3-cyclohexadiene, 1,3-octadiene, 1,3-cyclooctadiene, etc.; and
the like. A content of the monomer other than the aromatic vinyl
monomer is preferably 20% by mass or less, more preferably 5% by
mass or less, and still more preferably 2% by mass or less relative
to the whole of the monomer units in the aromatic vinyl polymer
block.
[0063] 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, and especially preferably 80% 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 93% by
mass or less, still more preferably 90% by mass or less, and
especially preferably 86% by mass or less relative to the whole of
the monomer units of the block copolymer. Furthermore, from the
viewpoint of much more improving the moldability of the layer A or
much more enhancing the height of the peak of tan .delta., the
content of the aliphatic unsaturated hydrocarbon monomer unit in
the block copolymer is more preferably 85% by mass or less, still
more preferably 84% by mass or less, especially preferably 83% by
mass or less, and most preferably 82% by mass or less relative to
the whole of the monomer units of the block copolymer. When the
content of the aliphatic unsaturated hydrocarbon monomer unit in
the block copolymer is less than 60% by mass, the characteristics
as the thermoplastic elastomer tend to be hardly exhibited. 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, or the
height of the peak of tan .delta. is small. In addition, there is a
tendency that the bending rigidity of the interlayer film for
laminated glass is small, so that the sound insulating properties
in a high-frequency region are lowered. 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.
[0064] 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.
[0065] 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.
[0066] 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. Of those, it
is preferred to use a conjugated diene, and it is more preferred to
use butadiene, isoprene, and a combination of butadiene and
isoprene.
[0067] 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. A proportion of the conjugated diene unit in the
aliphatic saturated 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. 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 60 mol % or more, more preferably
70 mol % or more, still more preferably 75 mol % or more, and
especially preferably 80 mol % 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.
[0068] There are included plural binding forms of the conjugated
diene in the aliphatic unsaturated hydrocarbon polymer block. For
example, the isoprene unit includes a 1,4-bond, a 1,2-bond, and a
3,4-bond, and the butadiene unit includes a 1,4-bond and a
1,2-bond. A sum total of contents of the 1,2-bond and the 3,4-bond
of the isoprene unit and a content of the 1,2-bond of the butadiene
unit is preferably 20 mol % or more, more preferably 30 mol % or
more, and still more preferably 40 mol % or more relative to the
total amount of the conjugated diene units (total amount of the
isoprene unit and the butadiene unit) in the aliphatic unsaturated
hydrocarbon polymer block. In addition, the above-described sum
total is preferably 100 mol % or less, more preferably 95 mol % or
less, and still more preferably 90 mol % or less. In the case where
the isoprene unit is contained in the polymer block (b), the
above-described sum total is preferably 85 mol % or less, and more
preferably 75 mol % or less. When the above-described sum total
falls within the foregoing range, there is a tendency that the peak
temperature of tan .delta. is made suitable, so that a maximum
value of tan .delta. becomes high.
[0069] In the case where not only the conjugated diene is contained
in the aliphatic unsaturated hydrocarbon polymer block, but also
the isoprene unit is contained in an amount of 90 mol % or more in
the conjugated diene unit, a monomer other than the conjugated
diene monomer is not contained, and in the case where 90 mol % or
more of the isoprene unit is contained, a sum total of the contents
of the 1,2-bond and the 3,4-bond of the isoprene unit is preferably
30 mol % or more, and more preferably 40 mol % or more. In
addition, the above-described sum total is preferably 75 mol % or
less, and more preferably 60 mol % or less. When the
above-described sum total falls within the foregoing range, there
is a tendency that the peak temperature of tan .delta. is made
suitable, so that a maximum value of tan .delta. becomes high.
[0070] In the case where not only the conjugated diene is contained
in the aliphatic unsaturated hydrocarbon polymer block, but also
the butadiene unit is contained in an amount of 90 mol % or more in
the conjugated diene unit, a content of the 1,2-bond of the
butadiene unit is preferably 65 mol % or more, and more preferably
80 mol % or more. In addition, the above-described content is
preferably 100 mol % or less. When the above-described content
falls within the foregoing range, there is a tendency that the peak
temperature of tan .delta. is made suitable, so that a maximum
value of tan .delta. becomes high.
[0071] In the case where not only the conjugated diene is contained
in the aliphatic unsaturated hydrocarbon polymer block, but also
the butadiene unit is contained in an amount of 90 mol % or more in
the conjugated diene unit, a content of the 1,2-bond of the
butadiene unit is preferably 20 mol % or more, and more preferably
65 mol % or more. In addition, the above-described content is
preferably 100 mol % or less. When the above-described content
falls within the foregoing range, there is a tendency that the peak
temperature of tan .delta. is made suitable, so that a maximum
value of tan .delta. becomes high.
[0072] In the case where not only the conjugated diene is contained
in the aliphatic unsaturated hydrocarbon polymer block, but also a
total content of the isoprene unit and the butadiene unit in the
conjugated diene unit is 90 mol % or more, and a mass ratio of the
isoprene unit and the butadiene unit is 10/90 to 90/10, a sum total
of the contents of the 1,2-bond and the 3,4-bond of the isoprene
unit and the butadiene unit is preferably 20 mol % or more, more
preferably 40 mol % or more, and still more preferably 50 mol % or
more. In addition, the above-described sum total is preferably 95
mol % or less, and more preferably 85 mol % or less. When the
above-described sum total falls within the foregoing range, there
is a tendency that the peak temperature of tan .delta. is made
suitable, so that a maximum value of tan .delta. becomes high.
[0073] It is to be noted that the sum total of the contents of the
1,2-bond and the 3,4-bond in the isoprene unit and the content of
the 1,2-bond in the butadiene unit do not change before and after
the hydrogenation. That is, the 1,2-bond in the isoprene unit is a
structure of (R.sup.1, R.sup.2).dbd.(CH.sub.3, H) in a structural
unit (A) and a structural unit (B) in the following chemical
formula (1). In addition, the 3,4-bond in the isoprene unit is a
structure of (R.sup.1, R.sup.2).dbd.(H, CH.sub.3) in a structural
unit (A) and a structural unit (B) in the following chemical
formula (1). Furthermore, the 1,2-bond in the butadiene unit is a
structure of (R.sup.1, R.sup.2).dbd.(H, H) in a structural unit (A)
and a structural unit (B) in the following chemical formula
(1).
##STR00001##
[0074] In the present invention, as described above, from the
viewpoints of easiness of availability and handling properties as
well as easiness of synthesis, the conjugated diene monomer is
used. Then, in the present invention, from the viewpoint of
improving the thermal creep resistance, such as heat stability,
etc., or the weather resistance, such as change in color
difference, etc., a hydrogenated product resulting from
hydrogenating a part of the aliphatic unsaturated hydrocarbon
polymer block containing a conjugated diene monomer unit is used.
By hydrogenating the aliphatic unsaturated hydrocarbon polymer
block, a residual amount of a carbon-to-carbon double bond derived
from the conjugated diene monomer unit can be adjusted.
[0075] The residual amount of the carbon-to-carbon double bond
derived from the conjugated diene monomer unit is preferably 2 mol
% or more, more preferably 3 mol % or more, still more preferably 4
mol % or more, and especially preferably 5 mol % or more. When the
residual amount of the carbon-to-carbon double bond derived from
the conjugated diene monomer unit is 2 mol % or more, the thermal
creep resistance of the interlayer film for laminated glass tends
to become high.
[0076] The residual amount of the carbon-to-carbon double bond
derived from the conjugated diene monomer unit is preferably 40 mol
% or less, more preferably 35 mol % or less, still more preferably
30 mol % or less, and especially preferably 25 mol % or less. When
the residual amount of the carbon-to-carbon double bond derived
from the conjugated diene monomer unit is 40 mol % or less, even in
the case of using the laminated glass over a long period of time,
there is a tendency that the change in color difference is
suppressed, so that the weather resistance is not lowered.
[0077] 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.
[0078] 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:
[0079] (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;
[0080] (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;
[0081] (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.
[0082] 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.
[0083] 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.
[0084] 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.
[0085] 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)
[0086] In the layer A, a heat insulating material, an antioxidant,
an ultraviolet ray absorber, a photostabilizer, an antiblocking
agent, a pigment, a dye, and the like may be added as other
components, if desired.
(Heat Insulating Material)
[0087] The interlayer film 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 an organic heat insulating compound
each having an infrared absorption ability) into the layer A.
Examples of the inorganic heat insulating fine particle include
tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO),
aluminum-doped zinc oxide (AZO), a metal-doped tungsten oxide
represented by the 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-doped tungsten oxide are more preferred. Examples of the
metal element represented by M in the metal-doped tungsten oxide
include Cs, Ti, 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.
[0088] In the case where the inorganic heat insulating fine
particle is contained, its content 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 resins used in the layer constituting the
interlayer film for laminated glass (the thermoplastic elastomer
and thermoplastic resin, and the like in every layer; hereinafter
the same). In addition, the content of the inorganic heat
insulating fine particle is preferably 5% by mass or less, and more
preferably 3% by mass or less. When the content of the inorganic
heat insulating fine particle is more than 5% by mass, there is a
concern that the transmittance of visible rays is influenced. An
average particle diameter of the inorganic heat insulating fine
particle is preferably 100 nm or less, and more preferably 50 nm or
less from the viewpoint of transparency. It is to be noted that the
average particle diameter of the inorganic heat insulating fine
particle as referred to herein means one measured by a laser
diffraction instrument.
[0089] Examples of the organic heat insulating material include
phthalocyanine compounds, naphthalocyanine compounds, and the like.
From the viewpoint of more improving the heat insulating
properties, it is preferred that the organic heat insulating
material 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.
[0090] A content of the organic heat insulating material 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 resins used in the layer constituting the interlayer film
for laminated glass (the thermoplastic elastomer and thermoplastic
resin, and the like in every layer; hereinafter the same). In
addition, the content of the organic heat insulating material 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.
(Ultraviolet Ray Absorber)
[0091] 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-(5-chloro-2-benzotriazolyl)-6-tert-butyl-p-cresol,
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)benzotriazole, 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 resins used in the layer constituting the
interlayer film for laminated glass. 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 resins used in the layer constituting the
interlayer film for laminated glass. 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.
(Antioxidant)
[0092] 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.
[0093] 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]undecan e,
1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane,
1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,-
6-(1H,3H,5H)-trione,
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.
[0094] 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,
tris(2,4-di-t-butylphenyl) phosphate,
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.
[0095] 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.
[0096] 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 resins used
in the layer constituting the interlayer film for laminated glass.
In addition, the compounding amount of the antioxidant is
preferably 5 parts by mass or less, more preferably 4 parts by mass
or less, and still more preferably 3 parts by mass or less based on
100 parts by mass of the resins used in the layer constituting the
interlayer film for laminated glass. 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.
(Photostabilizer)
[0097] 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.
(Adhesive Force Adjustor)
[0098] In order to adjust an adhesive force between the layer A and
the layer B as described later, an adhesive force adjustor may be
added to the layer A or the layer B. Examples of the adhesive force
adjustor include polyolefins having an adhesive functional group,
such as a carboxyl group, a derivative group of a carboxyl group,
an epoxy group, a boronic acid group, a derivative group of a
boronic acid group, an alkoxyl group, a derivative group of an
alkoxyl group, etc.
[0099] In particular, in the case of using a polyvinyl acetal resin
for the layer B, by adding a polyolefin having an adhesive
functional group to the layer A and undergoing coextrusion molding
between the layer A and the layer B, the adhesive force between the
layer A and the layer B can be suitably adjusted. An addition
amount of the polyolefin having an adhesive functional group is
preferably 20 parts by mass or less, more preferably 15 parts by
mass or less, and still more preferably 10 parts by mass or less
based on 100 parts by mass of the thermoplastic elastomer of the
layer A. When the addition amount of the polyolefin having an
adhesive functional group is more than 20 parts by mass, on the
occasion of preparing a laminated glass, there is a concern that
the haze is deteriorated. As the polyolefin having an adhesive
functional group, among the above-described polyolefins,
polypropylene containing a carboxyl group is suitable from the
viewpoints of easiness of availability, easiness of adjustment of
the adhesion, and easiness of adjustment of the haze.
[Layer B]
[0100] As described above, the interlayer film for laminated glass
of the present invention is an interlayer film for laminated glass
having a sound insulting layer (layer A) and thermoplastic resin
layers containing a thermoplastic resin (layers B), the sound
insulating layer (layer A) being located between at least two of
the thermoplastic resin layers (layers B).
[0101] From the viewpoint of improving the strength of the
interlayer film for laminated glass or improving the adhesion to a
glass, the thermoplastic resin to be used for an external layer is
preferably a polyvinyl acetal resin or an ionomer resin. A
constitution of the layer B is hereunder described in detail.
[0102] In the thermoplastic resin which is used for the layer B 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 10.0 MPa or more, more preferably 12.0 MPa or more,
still more preferably 20.0 MPa or more, yet 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 laminated 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 40 parts by mass or less based on 100 parts by mass
of the polyvinyl acetal resin. 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 interlayer film for
laminated glass.
(Thermoplastic Resin)
[0103] The thermoplastic resin as referred to in the present
specification means a polymer compound which when heated, is
softened to exhibit plasticity, whereas when cooled, is solidified,
and is distinguished from a thermoplastic elastomer. In view of the
fact that the layer B serving as an external layer contains the
thermoplastic resin, there is a tendency that the moist heat
resistance, weather resistance, or strength of the interlayer film
for laminated glass is improved, or when formed into a laminated
glass, the bending strength or penetration resistance is
improved.
[0104] In general, when interlaminar separation occurs in the
interlayer film for laminated glass serving as an interlayer film
for laminated glass, water, such as moisture, etc., penetrates into
a gap between the separated layers, and the edge side of the
laminated glass is liable to be whitened. In addition, even in the
case where the adhesion between the interlayer film for laminated
glass and the glass is not sufficient, water, such as moisture,
etc., penetrates into a gap between the interlayer film for
laminated glass and the glass, so that the edge side of the
laminated glass is liable to be whitened. In addition to the above,
in the case where a content of the plasticizer in the interlayer
film for laminated glass is high, or in the case where a
plasticizer with low compatibility with the thermoplastic resin is
used, on the occasion of absorbing water, the edge side of the
laminated glass is liable to be whitened.
[0105] Meanwhile, in the case where the plasticizer is not
contained, or a thermoplastic resin layer with a small content of
the plasticizer is used as an external layer, not only even when
water is absorbed, the edge side is hardly whitened, but also even
when water is absorbed, the migration of the plasticizer hardly
occurs, and hence, the sound insulating properties tend to hardly
change. In addition, in the case of using a plasticizer with high
compatibility with the thermoplastic resin, even when water is
absorbed, the whitening from the edge side tends to be
suppressed.
[0106] Though the kind of the thermoplastic resin is not
particularly limited, examples thereof include a polyvinyl acetal
resin, an ionomer resin, a vinyl chloride resin, a urethane resin,
a polyamide resin, and the like.
[0107] 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, such as a
polyvinyl acetal resin, etc., in a content 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 composed of only the thermoplastic resin, such as a
polyvinyl acetal resin, etc. When the content of the thermoplastic
resin, such as a polyvinyl acetal resin, etc., is less than 40% by
mass, it becomes difficult to obtain the desired shear storage
modulus.
(Polyvinyl Acetal Resin)
[0108] 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.
[0109] An average content of the vinyl acetate unit of the
polyvinyl acetal resin is preferably 30 mol % or less. When the
average 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 average content of the vinyl acetate unit is more preferably 20
mol % or less.
[0110] An average content of the vinyl alcohol unit of the
polyvinyl acetal resin is preferably 15 mol % or more, more
preferably 20 mol % or more, and still more preferably 25 mol % or
more. The average content of the vinyl alcohol unit of the
polyvinyl acetal resin is preferably 50 mol % or less, more
preferably 45 mol % or less, and still more preferably 40 mol % or
less. When the average content of the vinyl alcohol unit is less
than 15 mol %, the adhesion to a glass tends to be lowered, whereas
when the average content of the vinyl alcohol unit is more than 50
mol %, the water resistance tends to be lowered.
[0111] 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).
[0112] 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.
[0113] 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.
[0114] 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,
especially preferably 700 or more, and most preferably 750 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, particularly creep resistance 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 the layer B is
difficult.
[0115] 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.
[0116] 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.
[0117] It is preferred to set the average content of 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.
[0118] 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.
[0119] 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.
[0120] 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 relative to the
total amount of the aldehyde used.
[0121] The polyvinyl acetal resin is most preferably polyvinyl
butyral. As the polyvinyl butyral resin, a modified polyvinyl
butyral resin 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 used.
Here, examples of the other monomer include .alpha.-olefins, such
as ethylene, propylene, 1-butene, isobutene, 1-hexene, etc.;
carboxylic acids or derivatives thereof, such as fumaric acid,
maleic acid, itaconic acid, maleic anhydride, itaconic anhydride,
etc.; acrylic acid or salts thereof; acrylate esters, such as
methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl
acrylate, etc.; methacrylic acid or salts thereof; methacrylate
esters, such as methyl methacrylate, ethyl methacrylate, n-propyl
methacrylate, isopropyl methacrylate, etc.; acrylamide derivatives,
such as acrylamide, N-methylacrylamide, N-ethylacrylamide, etc.;
methacrylamide derivatives, such as methacrylamide,
N-methylmethacrylamide, N-ethylmethacrylamide, etc.; vinyl ethers,
such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl
ether, isopropyl vinyl ether, n-butyl vinyl ether, etc.; hydroxyl
group-containing vinyl ethers, such as ethylene glycol vinyl ether,
1,3-propanediol vinyl ether, 1,4-butanediol vinyl ether, etc.;
allyl ethers, such as allyl acetate, propyl allyl ether, butyl
allyl ether, hexyl allyl ether, etc.; monomers having an
oxyalkylene group; hydroxyl group-containing .alpha.-olefins, such
as isopropenyl acetate, 3-buten-1-ol, 4-penten-1-ol, 5-hexen-1-ol,
7-octen-1-ol, 9-decen-1-ol, 3-methyl-3-buten-1-ol, etc.; monomers
having a sulfonic acid group, such as ethylene sulfonic acid,
allylsulfonic acid, methallylsulfonic acid,
2-acrylamide-2-methylpropanesulfonic acid, etc.; monomers having a
cationic group, such as vinyloxyethyltrimethylammonium chloride,
vinyloxybutyltrimethylammonium chloride,
vinyloxyethyldimethylamine, vinyloxymethyldiethylamine,
N-acrylamidomethyltrimethylammonium chloride,
N-acrylamidoethyltrimethylammonium chloride,
N-acrylamidodimethylamine, allyltrimethylammonium chloride,
methallyltrimethylammonium chloride, dimethylallylamine,
allylethylamine, etc.; monomers having a silyl group, such as
vinyltrimethoxysilane, vinylmethyldimethoxysilane,
vinyldimethylmethoxysilane, vinyltriethoxysilane,
vinylmethyldiethoxysilane, vinyldimethylethoxysilane,
3-(meth)acrylamido-propyltrimethoxysilane,
3-(meth)acrylamide-propyltriethoxysilane, etc.; and the like. On
the occasion of copolymerizing the vinyl ester with other monomer,
though a use amount of the other monomer varies with the use
purpose and application and the like, in general, it is preferably
20 mol % or less, and more preferably 10 mol % or less in terms of
a proportion on the basis of the whole of the monomers to be used
for the copolymerization.
(Ionomer)
[0122] 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.
[0123] 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.
[0124] 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
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), an adhesive force adjustor and/or an additive of every
kind for adjusting the adhesion, and the like may also be further
added, if desired. Examples of the ultraviolet ray absorber, the
antioxidant, the photostabilizer, and the like include those
contained in the layer A as described above.
(Plasticizer)
[0125] 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.
[0126] 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.
[0127] 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.
[0128] 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.
[0129] 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) such as
an aliphatic hydroxycarboxylic acid, e.g., 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, and a
hydroxycarboxylic acid having an aromatic ring, e.g.,
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.
[0130] 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-heptanediol, 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.
[0131] 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.
[0132] 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-hydroxybutyric 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(l-(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.
[0133] In the present invention, these plasticizers may be used
solely or may be used in combination of two or more thereof.
[0134] 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
other 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.).
[0135] 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, and especially preferably 20
parts by mass or less 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., the shear storage modulus tends to be
lowered. In addition, two or more plasticizers may also be used in
combination.
[0136] 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 in the layer B is preferably 50% by mass or more, more
preferably 70% by mass or more, and still more preferably 90% by
mass or more. The compound having a hydroxyl group has high
compatibility with the polyvinyl acetal resin and is low in
migration properties into other resin layer, and hence, the
compound having a hydroxyl group can be suitably used.
[0137] In addition, in order to control the adhesion of the
interlayer film for laminated glass to a glass or the like, an
adhesive force adjustor and/or an additive of every kind for
adjusting the adhesion may also be added, if desired.
[0138] As the adhesive force adjustor and/or the additive of every
kind for adjusting the adhesion, 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.
[0139] Though an optimal addition amount of the adhesive force
adjustor and/or the additive of every kind for adjusting the
adhesion varies with the additive to be used, it is preferably
adjusted in such a manner that an adhesive force of the resulting
interlayer film for laminated glass 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
adhesive force adjustor and/or the additive of every kind for
adjusting the adhesion 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 adhesive force adjustor and/or
the additive of every kind for adjusting the adhesion 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 force adjustor is not added.
[Interlayer Film for Laminated Glass]
[0140] As described above, the interlayer film for laminated glass
of the present invention is an interlayer film for laminated glass
having a sound insulting layer (layer A) and thermoplastic resin
layers containing a thermoplastic resin (layers B), the sound
insulating layer (layer A) being located between at least two of
the thermoplastic resin layers (layers B).
[0141] In general, in the edge side of the laminated glass, when
water, such as moisture, etc., penetrates into an interface between
the external layer and the glass, the edge side of the laminated
glass is whitened. Meanwhile, when the interlayer film for
laminated glass having a three-layer constitution, in which a
thermoplastic resin layer with high adhesion to a glass is an
external layer, is used as an interlayer film for laminated glass,
the adhesion between the interlayer film for laminated glass and
the glass becomes good, so that the whitening in the edge side of
the laminated glass can be suppressed. The interlayer film for
laminated glass of the present invention is hereunder described in
detail.
[0142] A film thickness of the layer A is preferably 20 .mu.m or
more, more preferably 30 .mu.m or more, and still more preferably
50 .mu.m or more. In addition, the film thickness of the layer A is
preferably 400 .mu.m or less, more preferably 350 .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 interlayer film for laminated glass of the present
invention, it is preferred that a total thickness of the entirety
of the layer A satisfies the foregoing range.
[0143] 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
750 .mu.m or less, more preferably 650 .mu.m or less, and still
more preferably 550 .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 interlayer film for laminated glass 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 750 .mu.m, the sound insulating properties tend to be
lowered regardless of the frequency region.
[0144] 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 1/1.5 or less, and still more preferably 1/2 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 1/8 or more, and
especially preferably 1/6.5 or more. When the above-described ratio
is smaller than 1/30, the sound insulating effect of the interlayer
film for laminated glass 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 interlayer film for
laminated glass becomes small, so that the sound insulating
properties in a high-frequency region are lowered.
[0145] As shown in FIG. 1, the interlayer film for laminated glass
in the present embodiment has a lamination constitution in which a
layer A 1 is interposed by a layer B 2a and a layer B 2b. Though
the lamination constitution in the interlayer film for laminated
glass 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 lamination constitution 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. It is to be noted that it is preferred
that at least one of the outermost layers is the layer B; and that
it is more preferred that both of the outermost layers are the
layer B.
[0146] One or more layers may also be included as other layer
(referred to as "layer C") 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. It
is to be noted that it is preferred that at least one of the
outermost layers is the layer B; and that it is more preferred that
both of the outermost layers are the layer B.
[0147] 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 adhesive force adjustor and/or an additive of
every kind for adjusting the adhesion, 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. As those additives, the
same materials which may be contained in the layer A or the layer B
are used.
[0148] A production method of the interlayer film for laminated
glass of the present invention is not particularly limited, the
interlayer film for laminated glass 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 calendar method, a pressing
method, a casting method, an inflation method, etc., the layer A is
prepared with the elastomer by the same method, 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.
[0149] Among the known film formation methods, in particular, a
method of producing an interlayer film for laminated glass 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.
[0150] 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 interlayer film for laminated glass 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.
[0151] In addition, a total film thickness of the interlayer film
for laminated glass is preferably 20 .mu.m or more, and more
preferably 100 .mu.m or more. In addition, the total film thickness
of the interlayer film for laminated glass is preferably 10,000
.mu.m or less, and more preferably 3,000 .mu.m or less. When the
film thickness of the interlayer film for laminated glass is too
thin, there is a concern that in preparing a laminated glass,
lamination cannot be achieved well. What the film thickness of the
interlayer film for laminated glass is too thick results in an
increase of the costs, and hence, such is not preferred.
[Laminated Glass]
[0152] By using the interlayer film for laminated glass of the
present invention, a laminated glass which is excellent in sound
insulating properties, particularly sound insulating properties in
a high-frequency region can be obtained. In addition, by using the
interlayer film for laminated glass of the present invention, a
laminated glass which has excellent sound insulating properties and
which even when used for a long period of time under sunlight, is
able to suppress yellowing of an edge portion thereof can be
obtained. For that reason, the interlayer film for laminated glass
of the present invention can be suitably used 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, and the
like. In the case where the laminated glass including the
constitution of the interlayer film for laminated glass of the
present invention in the inside thereof is applied to a glass for
head-up display, a cross-sectional shape of the interlayer film for
laminated glass 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.
[0153] 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 interlayer film for laminated glass 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.
[0154] In a laminated glass obtained by interposing the interlayer
film for laminated glass of the present invention by two sheets of
float glass and a laminated glass after a moist heat resistance
test (test of holding a test sample for 1,000 hours under
conditions at 80.degree. C. and at a relative humidity of 95%), in
the case of measuring a haze of a central portion of the laminated
glass in accordance with JIS K 7105, an increase of the haze after
the moist heat resistance test relative to the haze before the
moist heat resistance test is 2% or less, preferably 1.5% or less,
and more preferably 1.3% or less. In a product in which the
increase of the haze after the moist heat resistance test relative
to the haze before the moist heat resistance test is more than 2%,
when allowed to stand in a moist heat environment for a long period
of time, the appearance becomes inferior, and hence, such is not
preferred. It is to be noted that in the test of the present
invention, a float glass having a length of 50 mm, a width of 50
mm, and a thickness of 1.9 mm is in general used as the
above-described float glass.
[0155] As a method of preparing an interlayer film for laminated
glass in which the increase of the haze after the moist heat
resistance test relative to the haze before the moist heat
resistance test is 2% or less, there is, for example, exemplified a
method of using an interlayer film for laminated glass in which a
sound insulating layer is interposed between two thermoplastic
resin layers, or the like. In addition, as a more preferred method,
there is exemplified a method of using an interlayer film for
laminated glass in which a sound insulating layer using a
thermoplastic elastomer having an aromatic vinyl polymer block and
an aliphatic unsaturated hydrocarbon polymer block is interposed
between two thermoplastic resin layers using a polyvinyl acetal
resin or an ionomer.
[0156] Furthermore, in the laminated glass after the moist heat
resistance test, a distance of whitening from the edge side is 4 mm
or less, preferably 3.5 mm or less, and more preferably 3 mm or
less. In the laminated glass after the moist heat resistance test,
in a product in which the distance of whitening from the edge side
is more than 4 mm, when allowed to stand in a moist heat
environment for a long period of time, the edge side is whitened,
and hence, such is not preferred.
[0157] In the laminated glass after the moist heat rest, as a
method of preparing an interlayer film for laminated glass in which
the distance of whitening from the edge side is 4 mm or less, there
is, for example, exemplified a method of using an interlayer film
for laminated glass in which a sound insulating layer is interposed
between two thermoplastic resin layers. In addition, more
preferably, there is exemplified a method of using an interlayer
film for laminated glass in which a sound insulating layer using a
thermoplastic elastomer having an aromatic vinyl polymer block and
an aliphatic unsaturated hydrocarbon polymer block is interposed
between two thermoplastic resin layers using a polyvinyl acetal
resin or an ionomer.
[0158] In the interlayer film for laminated glass of the present
invention, with respect to a laminated glass obtained by
interposing the interlayer film for laminated glass by two sheets
of float glass, in a state where the laminated glass is placed such
that in a positional relation in which a plane of the laminated
glass including the center in a longitudinal direction thereof
includes the center in a width direction of a cylindrical xenon
lamp, and a plane of the laminated glass including the center in a
thickness direction thereof includes the center in a length
direction of the cylindrical xenon lamp, its shortest distance to
the cylindrical xenon lamp is 29 cm, when a weather resistance test
of holding the laminated glass for 1,000 hours is conducted while
irradiating an edge portion thereof with ultraviolet rays at a
luminance of the xenon lamp of 180 W/m.sup.2 under conditions at a
relative humidity of 50% and a black panel temperature of
63.degree. C., in measuring a YI (yellow index) of the laminated
glass before holding and a YI of the laminated glass after holding
on the basis of JIS K 7373, an increase of the YI of the laminated
glass after holding relative to the YI of the laminated glass
before holding is preferably 3 or less, more preferably 2.85 or
less, and still more preferably 2.7 or less. In a product in which
the increase of the YI of the laminated glass after the weather
resistance test relative to the YI of the laminated glass before
the weather resistance test is more than 3, there is a tendency
that when allowed to stand for a long period of time under
sunlight, the edge portion is liable to be yellowed. It is to be
noted that in the above-described test to be carried out with
respect to the present invention, a float glass having a length of
70 mm, a width of 5 mm, and a thickness of 1.9 mm is in general
used as the above-described float glass.
[0159] As a method of preparing an interlayer film for laminated
glass in which the increase of the YI of the laminated glass after
the weather resistance test relative to the YI of the laminated
glass before the weather resistance test is 3 or less, there is,
for example, exemplified a method of using an interlayer film for
laminated glass in which a sound insulating layer is interposed
between tow thermoplastic resin layers. In addition, as a more
preferred method, there is exemplified a method of using an
interlayer film for laminated glass in which a sound insulating
layer using a thermoplastic elastomer having an aromatic vinyl
polymer block and an aliphatic unsaturated hydrocarbon polymer
block is interposed between two thermoplastic resin layers using a
polyvinyl acetal resin or an ionomer. As a still more preferred
method, there is 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 for the layer A.
[0160] Here, a positional relation between a laminated glass 10 and
a xenon lamp 20 in a weather resistance test is shown in FIG. 2. As
described above, the laminated glass 10 is constituted so as to
interpose an interlayer film 11 for laminated glass by two sheets
of glasses 12 and 13.
[0161] The center in a longitudinal direction of the laminated
glass 10 means a cross section including a middle point (point of
35 mm from the transverse side) in the longitudinal direction of
the laminated glass 10 and vertical to the laminated glass 10. The
center in a width direction of the cylindrical xenon lamp 20 means
a center line extending in a length direction of the xenon lamp 20.
The center in a thickness direction of the laminated glass 10 means
a cross section including a middle point (center in a thickness
direction of the sound insulating layer) in a thickness direction
of the laminated glass 10 and parallel to the laminated glass 10.
The center in a length direction of the cylindrical xenon lamp 20
means a circular cross section to be divided by a middle point in a
length direction of the xenon lamp 20.
[0162] In FIG. 2, a shortest distance to the cylindrical xenon lamp
20 means a length of a line segment joining an edge point 14 of the
laminated glass 10 and an edge point 21 of the xenon lamp 20. The
edge point 14 of the laminated glass 10 is a point closest to the
xenon lamp 20 in the line segment including the center in a
longitudinal direction and the center in a thickness direction of
the laminated glass 10. The edge point 21 of the xenon lamp 20 is a
point closest to the laminated glass 10 in the circular cross
section corresponding to the center in a length direction of the
xenon lamp 20.
[0163] That is, the weather resistance test is conducted in a
positional relation such that the laminated glass 10 and the
cylindrical xenon lamp 20 are orthogonal to each other in a twisted
positional relation, and that the line segment orthogonal to the
edge portion of the laminated glass 10 and the cylindrical xenon
lamp 20 is a segment joining the edge point 14 of the laminated
glass 10 and the edge point 21 of the xenon lamp 20 in FIG. 2.
[0164] The loss factor at a tertiary resonance frequency can be,
for example, measured by the following method. The interlayer film
for laminated glass is interposed by two sheets of commercially
available float glass, 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, a central portion 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 central portion
of the laminated glass at 20.degree. C. and 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
central portion 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 tertiary
resonance frequency can be determined from a frequency expressing a
peak of the tertiary mode and a half-width value. It is to be noted
that in the test of the present invention, a float glass having a
length of 300 mm, a width of 25 mm, and a thickness of 1.9 mm is in
general used as the above-described float glass.
[0165] In the interlayer film for laminated glass of the present
invention, when the interlayer film for laminated glass is
interposed by two sheets of float glass to prepare a laminated
glass, a loss factor at a tertiary resonance frequency as measured
at 20.degree. C. by a central exciting method is preferably 0.2 or
more, more preferably 0.3 or more, still more preferably 0.4 or
more, and especially preferably 0.5 or more. When the loss factor
at a tertiary resonance frequency is less than 0.2, the sound
insulating properties of the laminated glass tend to be
lowered.
[0166] As a method of preparing a laminated glass in which the loss
factor restricted under the above-described conditions is 0.2 or
more, there is, for example, exemplified a method of using an
interlayer film for laminated glass in which a sound insulating
layer is interposed between two thermoplastic resin layers. In
addition, as a more preferred method, there is exemplified a method
of using an interlayer film for laminated glass in which a sound
insulating layer using a thermoplastic elastomer having an aromatic
vinyl polymer block and an aliphatic unsaturated hydrocarbon
polymer block is interposed between two thermoplastic resin layers
using a polyvinyl acetal resin or an ionomer. Besides, as a
preferred 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, 5% by mass or more, 10%
by mass or more, 14% by mass or more, 15% by mass or more, or 17%
by mass or more) relative to the thermoplastic elastomer
constituting the sound insulating layer and regulating a ratio of
the total thickness of the sound insulating layer (layer A) to the
total thickness of the protective layer (layer B) of the interlayer
film for laminated glass to a prescribed portion or more (for
example, 1/30 or more, 1/15 or more, 1/8 or more or 1/6.5 or more),
or other method.
[0167] In a laminated glass obtained by interposing the interlayer
film for laminated glass of the present invention by two sheets of
float glass and a laminated glass after a moist heat resistance
test (test of holding a test sample for 1,000 hours under
conditions at 80.degree. C. and at a relative humidity of 95%), in
the case of measuring a loss factor at a tertiary resonance
frequency at 20.degree. C. by a central exciting method, a decrease
of the loss factor after the moist heat resistance test relative to
the loss factor before the moist heat resistance test is preferably
0.05 or less, more preferably 0.04 or less, and still more
preferably 0.03 or less. When the decrease of the loss factor after
the moist heat resistance test relative to the loss factor before
the moist heat resistance test is more than 0.05, in the case of
using the laminated glass in a moist heat environment for a long
period of time, the sound insulating properties tend to be lowered.
In the above-described moist heat resistance test, a float glass
having a length of 300 mm, a width of 25 mm, and a thickness of 1.9
mm is in general used, too.
[0168] As a method of preparing a laminated glass in which the
decrease of the loss factor after the moist heat resistance test
relative to the loss factor before the moist heat resistance test
is 0.05 or less, there is, for example, exemplified a method of
using, as the interlayer film for laminated glass, an interlayer
film for laminated glass in which a sound insulating layer using a
thermoplastic elastomer having an aromatic vinyl polymer block and
an aliphatic unsaturated hydrocarbon polymer block is interposed
between two thermoplastic resin layers using a polyvinyl acetal
resin or an ionomer. In addition, as a more preferred method, there
are exemplified a method of using a material in which the 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 sound insulating layer and regulating a
ratio of the total thickness of the sound insulating layer (layer
A) to the total thickness of the protective layer (layer B) of the
interlayer film for laminated glass to a prescribed proportion or
more (for example, 1/6.5 or more); a method of regulating a ratio
of the total thickness of the sound insulating layer to the total
thickness of the thermoplastic resin to a prescribed proportion or
more (for example, 1/6.5 or more); and the like.
[0169] In the interlayer film for laminated glass of the present
invention, the tertiary resonance frequency is preferably 1,250 Hz
or more, more preferably 1,500 Hz or more, and still more
preferably 1,750 Hz or more. When the tertiary resonance frequency
of the interlayer film for laminated glass is less than 1,250 Hz, a
coincidence phenomenon is liable to be generated in a
high-frequency region, so that the sound insulating properties in a
high-frequency region tends to be lowered. In the interlayer film
for laminated glass of the present invention, the tertiary
resonance frequency is preferably 3,000 Hz or less, more preferably
2,750 Hz or less, and still more preferably 2,500 Hz or less. When
the tertiary resonance frequency of the interlayer film for
laminated glass is more than 3,000 Hz, a coincidence phenomenon is
liable to be generated in a low-frequency region, so that the sound
insulating properties in a low-frequency region tends to be
lowered.
[0170] As a method of regulating the tertiary resonance frequency
of the interlayer film for laminated glass to 1,250 Hz or more and
3,000 Hz or less, there is, for example, exemplified a method of
using an interlayer film for laminated glass in which a sound
insulating layer is interposed between two thermoplastic resin
layers. In addition, more preferably, there is exemplified a method
of using an interlayer film for laminated glass in which a sound
insulating layer using a thermoplastic elastomer having an aromatic
vinyl polymer block and an aliphatic unsaturated hydrocarbon
polymer block is interposed between two thermoplastic resin layers
using a polyvinyl acetal resin or an ionomer.
[0171] In the case where the laminated glass obtained by
interposing the interlayer film for laminated glass of the present
invention by two sheets of float glass contains a heat insulating
material, a transmittance of a near infrared light having a
wavelength of 1,500 nm is preferably 50% or less, and more
preferably 20% or less. When the transmittance of a near infrared
light having 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 a
heat insulating performance of the laminated glass is improved. In
the present invention, the float glass having a thickness of 1.9 mm
per single sheet is in general used.
[0172] In the laminated glass of the present invention, a haze when
the interlayer film for laminated glass is laminated between two
sheets of float glass having a thickness of 2 mm is preferably less
than 5, more preferably less than 3, and still more preferably less
than 1.
[Production Method of Laminated Glass]
[0173] 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.
[0174] 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.
[0175] 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.
[0176] 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
interlayer film for laminated glass of the present invention is
included in the inside of the laminated glass.
[0177] 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.
[0178] 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
[0179] 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.
[0180] 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.
Example 1
(Preparation of Layer A)
[0181] In a pressure-resistant vessel which had been purged with
nitrogen and dried, 50 kg of cyclohexane as a solvent and 130 g of
sec-butyllithium as an anionic polymerization initiator were
charged, and 290 g of tetrahydrofuran as a Lewis base was charged
(since the sec-butyllithium contains a 10.5% by mass cyclohexane
solution, a substantial addition amount of sec-butyllithium is 13.9
g). After increasing the temperature within the pressure-resistant
vessel to 50.degree. C., 1.8 kg of styrene was added, and
polymerization was conducted for one hour. Subsequently, 13.2 kg of
isoprene was added, and polymerization was conducted for 2 hours;
and 1.8 kg of styrene was further added, and polymerization was
conducted for one hour, thereby obtaining a reaction solution
containing a polystyrene-polyisoprene-polystyrene triblock
copolymer.
[0182] To the reaction solution, a Ziegler-based hydrogenation
catalyst formed of nickel octylate and trimethylaluminum was added
in a hydrogen atmosphere, and the contents were allowed to react
under conditions at a hydrogen pressure of 1 MPa and at 80.degree.
C. for 5 hours. After allowing the resulting reaction solution to
stand for cooling and pressure discharge, the catalyst was removed
by water washing and dried in vacuo, thereby obtaining a
hydrogenated product of a polystyrene-polyisoprene-polystyrene
triblock copolymer (hereinafter referred to as "TPE-2"). 100 parts
by mass of the resulting TPE-2 and 5 parts by mass of maleic
anhydride-modified polypropylene (manufactured by Sanyo Chemical
Industries, Ltd., UMEX 1010) as an adhesive force adjustor to a
layer B were mixed and molded into a layer A having a thickness of
250 .mu.m by an extrusion molding method.
(Preparation of Layer B)
[0183] As for a layer B, a composition in which 100 parts by mass
of a polyvinyl butyral resin having a viscosity average
polymerization degree of about 1,700, an average degree of
acetalization of 70 mol %, and an average content of a vinyl
acetate unit of 0.9 mol % (hereafter referred to as "PVB-a") was
compounded with 15 parts by mass of a polyester polyol
(manufactured by Kuraray Co., Ltd., KURARAY POLYOL P-510:
poly[(3-methyl-1,5-pentanediol)-alt-(adipic acid)]) was molded into
the layer B having a thickness of 250 .mu.m by an extrusion molding
method.
(Preparation of Interlayer Film for Laminated Glass)
[0184] The layer A was interposed between two layers of the layer B
and press molded at 150.degree. C., thereby preparing an interlayer
film for laminated glass composed of a composite film of a
three-layer constitution and having a thickness of 0.75 mm.
1. Physical Properties Evaluation (Calculation of Residual Amount
of Double Bond Derived from Conjugated Diene Monomer Unit)
[0185] An iodine value of the block copolymer obtained in Example 1
before and after the hydrogenation was measured, and the residual
amount of the double bond was calculated from a measured value
thereof. The calculation results of the residual amount of the
double bond are shown in Table 1.
2. Physical Properties Evaluation (Calculation of Total Value of
Contents of 1,2-Bond and 3,4-Bond in Isoprene Unit and Content of
1,2-Bond in Butadiene Unit)
[0186] 50 mg of each of TPE-1 to TPE-4 obtained in the Examples was
dissolved in deuterated chloroform and subjected to .sup.1H-NMR
measurement. The contents of the 1,2-bond and the 3,4-bond in the
isoprene unit and the content of the 1,2-bond in the butadiene unit
were measured, respectively from peaks derived from the 1,2-bond
and the 3,4-bond in the isoprene unit and a peak derived from the
1,2-bond in the butadiene unit in the resulting spectra.
[0187] The contents of the 1,2-bond and the 3,4-bond in the
resulting isoprene unit and the content of the 1,2-bond in the
resulting butadiene unit were totalized, thereby calculating a
total value of the contents of the 1,2-bond and the 3,4-bond. The
calculation results are shown in Table 1 or Table 2.
3. Physical Properties Evaluation (Peak Temperature and Peak Height
of Tan .delta. of Layer a (Thermoplastic Elastomer))
[0188] 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. The hydrogenated product of a
polystyrene-polyisoprene-polystyrene triblock copolymer (TPE-2) as
used in Example 1 was formed into a single-layer sheet (thickness:
0.76 mm) by an extrusion molding method. The single-layer sheet was
cut out in a disk shape and used as a test sheet. A gap between two
sheets of flat plate was completely filled by the test sheet, and
the resultant was held at a temperature of 20.degree. C. and at a
humidity of 60% RH for 24 hours or more. 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 measurement results of a peak temperature and a
peak height of tan .delta. of the layer A (thermoplastic elastomer)
are shown in Table 1.
4. Physical Properties Evaluation (Tertiary Resonance Frequency,
Loss Factor at Tertiary Resonance Frequency, and Loss Factor after
Moist Heat Resistance Test of Laminated Glass)
[0189] The interlayer film for laminated glass obtained in Example
1 was interposed by 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, a central portion 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 central portion of the laminated glass at a
frequency in the range of from 0 to 10,000 Hz. An exciting force
and an acceleration waveform in the central portion of this
laminated glass 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 tertiary resonance frequency and a
loss factor at a tertiary resonance frequency of the laminated
glass were obtained from a frequency expressing a peak and a
half-width value. In addition, the laminated glass was subjected to
a moist heat resistance test (test of holding a test sample for
1,000 hours under conditions at a temperature of 80.degree. C. and
at a relative humidity of 95%). Immediately after the moist heat
resistance test, the above-described damping test was conducted,
thereby obtaining a tertiary resonance frequency and a loss factor
at a tertiary resonance frequency of the laminated glass. The
measurement results of a tertiary resonance frequency, a loss
factor before the moist heat resistance test, a loss factor after
the moist heat resistance test, and a decrease of the loss factor
are shown in Table 1.
5. Physical Properties Evaluation (Evaluation of Heat Insulating
Properties of Laminated Glass)
[0190] The interlayer film for laminated glass obtained in Example
1 was interposed by two sheets of commercially available float
glass (50 mm in length.times.50 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, 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 a transmittance of a near-infrared light
having a wavelength of 1,500 nm are shown in Table 1.
6. Physical Properties Evaluation (Evaluation of Haze and Distance
of Whitening of Laminated Glass)
[0191] The interlayer film for laminated glass obtained in Example
1 was interposed by two sheets of commercially available float
glass (50 mm in length.times.50 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, a haze of a central
portion of the laminated glass was measured by using a haze meter
HZ-1 (manufactured by Suga Test Instruments Co., Ltd.) in
accordance with JIS K 7105. It is to be noted that the measurement
was conducted at a temperature of 20.degree. C. In addition, the
laminated glass was subjected to a moist heat resistance test (test
of holding a test sample for 1,000 hours under conditions at a
temperature of 80.degree. C. and at a relative humidity of 95%).
Immediately after the moist heat resistance test, a haze in the
central portion of the laminated glass was measured by the same
method as described above. Furthermore, a whitened state in the
edge side of the laminated glass was also visually confirmed,
thereby measuring a distance of whitening from the edge side of the
laminated glass. The measurement results of a haze before the moist
heat resistance test, a haze after the moist heat resistance test,
an increase of the haze, and a distance of whitening after the
moist heat resistance test are shown in Table 1.
7. Physical Properties Evaluation (Evaluation of YI of Laminated
Glass)
[0192] The interlayer film for laminated glass obtained in Example
1 was interposed by two sheets of commercially available float
glass (70 mm in length.times.5 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, a YI of the laminated
glass was measured at 20.degree. C. by using a color meter
(manufactured by Suga Test Instruments Co., Ltd.) according to a
transmittance measurement method in accordance with JIS K 7373.
[0193] As shown in FIG. 2, a laminated glass 10 was placed in a
super xenon weather meter SX75 (manufactured by Suga Test
Instruments Co., Ltd.) in such a manner that in a positional
relation in which a plane of the laminated glass 10 including the
center in a longitudinal direction thereof includes the center in a
width direction of a cylindrical xenon lamp 20, and a plane of the
laminated glass 10 including the center in a thickness direction
thereof includes the center in a length direction of the
cylindrical xenon lamp 20, its shortest distance to the cylindrical
xenon lamp 20 (length of a line segment joining an edge point 14
and an edge point 21) is 29 cm.
[0194] Thereafter, a weather resistance test of holding the
laminated glass for 1,000 hours was conducted while irradiating an
edge portion thereof with ultraviolet rays at a luminance of the
xenon lamp of 180 W/m.sup.2 under conditions at a relative humidity
of 50% and a black panel temperature of 63.degree. C. Immediately
after the weather resistance test, a YI of the laminated glass was
measured by the same method as described above. The measurement
results of a YI of the laminated glass before and after the weather
resistance test and an increase of the YI are shown in Table 1.
8. Physical Properties Evaluation (Evaluation of Thermal Creep
Resistance of Laminated Glass)
[0195] As shown in FIG. 3, an interlayer film 73 for laminated
glass obtained in Example 1 was interposed by float glasses 71 and
72 each having a length of 300 mm, a width of 100 mm, and a
thickness of 3 mm, and a laminated glass 70 was prepared by using a
vacuum laminator (manufactured by Nisshinbo Mechatronics Inc.,
1522N) under conditions of hot plate temperature: 165.degree. C.,
evacuation time: 12 minutes, pressing pressure: 50 kPa, and
pressing time: 17 minutes.
[0196] As shown in FIG. 4, a laminated glass 80 having an iron
plate stuck thereonto was prepared by sticking an iron plate 81
having a weight of 1 kg onto one side of the glass 72 by using an
instant adhesive.
[0197] As shown in FIG. 5, the laminated glass 80 was leaned
against a stand 91 and allowed to stand within a chamber at
100.degree. C. for one week. After standing, a distance at which
the glass 72 slipped down was measured, the distance was evaluated
according to the following criteria, and the evaluation was made as
an evaluation of thermal creep resistance. The evaluation results
are shown in Table 1.
<Evaluation Criteria>
[0198] A: The slip down distance of the glass 72 is 1 mm or
less.
[0199] B: The slip down distance of the glass 72 is more than 1
mm.
Example 2
[0200] An interlayer film for laminated glass and a laminated glass
were prepared by the same method as in Example 1, except that in
the layer B, the polyester polyol was used in an amount of 25 parts
by mass in place of 15 parts by mass, and then subjected to the
various physical properties evaluations. The results of the various
physical properties evaluations are shown in Table 1.
Example 3
[0201] An interlayer film for laminated glass and a laminated glass
were prepared by the same method as in Example 1, except that in
the layer B, the polyester polyol was used in an amount of 40 parts
by mass in place of 15 parts by mass, and then subjected to the
various physical properties evaluations. The results of the various
physical properties evaluations are shown in Table 1.
Example 4
[0202] In a pressure-resistant vessel which had been purged with
nitrogen and dried, 50 kg of cyclohexane as a solvent and 76 g of
sec-butyllithium as an anionic polymerization initiator were
charged, and 313 g of tetrahydrofuran as a Lewis base was charged
(since the sec-butyllithium contains a 10.5% by mass cyclohexane
solution, a substantial addition amount of sec-butyllithium is 8.0
g). After increasing the temperature within the pressure-resistant
vessel to 50.degree. C., 0.5 kg of styrene was added, and
polymerization was conducted for one hour. Subsequently, a mixed
solution composed of 8.2 kg of isoprene and 6.5 kg of butadiene was
added, and polymerization was conducted for 2 hours; and 1.5 kg of
styrene was further added, and polymerization was conducted for one
hour, thereby obtaining a reaction solution containing a
polystyrene-poly(isoprene/butadiene)-polystyrene triblock
copolymer.
[0203] To the reaction solution, a Ziegler-based hydrogenation
catalyst formed of nickel octylate and trimethylaluminum was added
in a hydrogen atmosphere, and the contents were allowed to react
under conditions at a hydrogen pressure of 1 MPa and at 80.degree.
C. for 5 hours. After allowing the resulting reaction solution to
stand for cooling and pressure discharge, the catalyst was removed
by water washing and dried in vacuo, thereby obtaining a
hydrogenated product of the
polystyrene-poly(isoprene/butadiene)-polystyrene triblock copolymer
(hereinafter referred to as "TPE-1"). Subsequently, TPE-1 and TPE-2
were melt kneaded in a mass ratio of 1/1 at 200.degree. C., thereby
obtaining TPE-3.
[0204] An interlayer film for laminated glass and a laminated glass
were prepared by the same method as in Example 1, except that as
the layer A, TPE-3 was used in place of TPE-2, and then subjected
to the various physical properties evaluations. The results of the
various physical properties evaluations are shown in Table 1.
Example 5
[0205] An interlayer film for laminated glass and a laminated glass
were prepared by the same method as in Example 4, 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 various physical properties evaluations. The
results of the various physical properties evaluations are shown in
Table 1.
Example 6
[0206] An interlayer film for laminated glass and a laminated glass
were prepared by the same method as in Example 1, except that as
the layer A, TPE-1 was used in place of TPE-2, and then subjected
to the various physical properties evaluations. The results of the
various physical properties evaluations are shown in Table 1.
Example 7
[0207] An interlayer film for laminated glass and a laminated glass
were prepared by the same method as in Example 6, 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 various physical properties evaluations. The
results of the various physical properties evaluations are shown in
Table 1.
Example 8
[0208] An interlayer film for laminated glass and a laminated glass
were prepared by the same method as in Example 1, except that the
film thickness of the layer A was changed to 380 .mu.m, and that
the film thickness of the layer B was changed to 190 m, and then
subjected to the various physical properties evaluations. The
results of the various physical properties evaluations are shown in
Table 1.
Example 9
[0209] An interlayer film for laminated glass and a laminated glass
were prepared by the same method as in Example 6, except that in
the hydrogenation treatment on the block copolymer to be used for
the layer A, the hydrogen pressure was changed to 10 MPa in place
of setting the hydrogen pressure to 1 MPa, thereby obtaining a
hydrogenated product having a residual amount of the double bond of
1 mol % (hereinafter referred to as "TPE-4"), and then subjected to
the various physical properties evaluations. The results of the
various physical properties evaluations are shown in Table 1.
TABLE-US-00001 TABLE 1 Exam- Exam- Exam- Exam- Exam- Exam- Exam-
Exam- Exam- ple 1 ple 2 ple 3 ple 4 ple 5 ple 6 ple 7 ple 8 ple 9
Layer A Kind TPE-2 TPE-2 TPE-2 TPE-3 TPE-3 TPE-1 TPE-1 TPE-2 TPE-4
Content of polymer block (a) (% by mass) 20 20 20 16 16 12 12 20 12
Content of polymer block (b) (% by mass) 80 80 80 84 84 88 88 80 88
Mass ratio of monomer of polymer block (b) Ip = Ip = Ip = Ip:Bd =
Ip:Bd = Ip:Bd = Ip:Bd = Ip = Ip:Bd = 100 100 100 77.5:22.5
77.5:22.5 55:45 55:45 100 55:45 Sum total of 1,2-bond and 3,4-bond
(mol %) 55 55 55 57.5 57.5 60 60 55 60 Residual amount of double
bond (mol %) 12.0 12.0 12.0 10.3 10.3 8.5 8.5 12.0 1 Peak
temperature of tan .delta. (.degree. C.) -5.2 -5.2 -5.2 -15.2 -15.2
-22.6 -22.6 -5.2 -22.6 Peak height of tan .delta. 1.89 1.89 1.89
1.91 1.91 1.92 1.92 1.89 1.92 Content of adhesive force adjuster
(parts 5 5 5 5 5 5 5 5 5 by mass) Layer B Kind PVB-a PVB-a PVB-a
PVB-a PVB-a PVB-a PVB-a PVB-a PVB-a Viscosity average
polymerization degree 1700 1700 1700 1700 1700 1700 1700 1700 1700
Average degree of acetalization (mol %) 70 70 70 70 70 70 70 70 70
Kind of plasticizer P-510 P-510 P-510 P-510 P-510 P-510 P-510 P-510
P-510 Content of plasticizer (parts by mass) 15 25 40 15 15 15 15
15 15 Laminated Sum total of thickness of layer A and 1/2 1/2 1/2
1/2 1/6.5 1/2 1/6.5 1/1 1/2 glass thickness of layer B B/A/B
Transmittance [at 1,500 nm] (%) 75 76 75 76 75 76 74 77 76 Tertiary
resonance frequency (Hz) 2106 1816 1821 1895 2254 1355 1821 1995
1352 Loss factor before moist heat resistance test 0.46 0.57 0.52
0.33 0.26 0.29 0.28 0.40 0.28 Loss factor after moist heat
resistance test 0.45 0.54 0.48 0.29 0.21 0.27 0.25 0.35 0.27
Decrease of loss factor 0.01 0.03 0.04 0.04 0.05 0.02 0.03 0.05
0.01 Haze before moist heat resistance test [%] 0.9 0.9 0.8 0.9 1.0
0.8 1.1 0.6 0.8 Haze after moist heat resistance test [%] 2.0 1.6
1.5 1.8 2.2 1.9 2.3 1.4 2.0 Increase of haze 1.1 0.7 0.7 0.9 1.2
1.1 1.2 0.8 1.2 Distance of whitening after moist heat 3 1 1 3 2 2
4 3 2 resistance test [mm] YI before weather resistance test 1.20
1.08 0.99 1.18 1.43 1.17 1.35 0.92 1.08 YI after weather resistance
test 3.92 3.92 3.88 3.71 4.38 3.73 4.26 3.65 1.93 Increase of YI
2.72 2.84 2.89 2.53 2.95 2.56 2.91 2.73 0.85 Thermal creep
resistance A A A A A A A A B * Ip: Isoprene unit, Bd: Butadiene
unit * P-510: Polyester polyol * The content of the adhesive force
adjuster expresses an amount based on 100 parts by mass of the
thermoplastic elastomer, and the content of the plasticizer
expresses an amount based on 100 parts by mass of polyvinyl
butyral.
Example 10
[0210] An interlayer film for laminated glass and a laminated glass
were prepared by the same method as in Example 1, except that the
adhesive force adjustor was not used for the layer A, and that an
ionomer film having a thickness of 250 m (manufactured by E. I. du
Pont de Nemours and Company, SentryGlas.RTM. Interlayer) was used
for the layer B in place of the composition of PVB and the
polyester polyol as molded in a thickness of 250 .mu.m, and then
subjected to the various physical properties evaluations. The
results of the various physical properties evaluations are shown in
Table 2.
Example 11
[0211] An interlayer film for laminated glass and a laminated glass
were prepared by the same method as in Example 10, except that as
the layer A, TPE-3 was used in place of TPE-2, and then subjected
to the various physical properties evaluations. The results of the
various physical properties evaluations are shown in Table 2.
Example 12
[0212] An interlayer film for laminated glass and a laminated glass
were prepared by the same method as in Example 11, 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 various physical properties evaluations. The
results of the various physical properties evaluations are shown in
Table 2.
Example 13
[0213] An interlayer film for laminated glass and a laminated glass
were prepared by the same method as in Example 10, except that as
the layer A, TPE-1 was used in place of TPE-2, and then subjected
to the various physical properties evaluations. The results of the
various physical properties evaluations are shown in Table 2.
Example 14
[0214] An interlayer film for laminated glass and a laminated glass
were prepared by the same method as in Example 13, 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 various physical properties evaluations. The
results of the various physical properties evaluations are shown in
Table 2.
Example 15
[0215] An interlayer film for laminated glass and a laminated glass
were prepared by the same method as in Example 10, except that the
film thickness of the layer A was changed to 380 .mu.m, and that
the film thickness of the layer B was changed to 190 .mu.m, and
then subjected to the various physical properties evaluations. The
results of the various physical properties evaluations are shown in
Table 2.
Example 16
[0216] An interlayer film for laminated glass and a laminated glass
were prepared by the same method as in Example 1, except that in
the layer A, 0.75 parts by mass of cesium-doped tungsten oxide
(manufactured by Sumitomo Metal Mining Co., Ltd., YMDS-874) was
added to 100 parts by mass of TPE-2, and then subjected to the
various physical properties evaluations. The results of the various
physical properties evaluations are shown in Table 2.
TABLE-US-00002 TABLE 2 Exam- Exam- Exam- Exam- Exam- Exam- Exam-
ple 10 ple 11 ple 12 ple 13 ple 14 ple 15 ple 16 Layer A Kind TPE-2
TPE-3 TPE-3 TPE-1 TPE-1 TPE-2 TPE-2 Content of polymer block (a) (%
by mass) 20 16 16 12 12 20 20 Content of polymer block (b) (% by
mass) 80 84 84 88 88 80 80 Mass ratio of monomer of polymer block
(b) Ip = Ip:Bd = Ip:Bd = Ip:Bd = Ip:Bd = Ip = Ip = 100 77.5:22.5
77.5:22.5 55:45 55:45 100 100 Sum total of 1,2-bond and 3,4-bond
(mol %) 55 57.5 57.5 60 60 55 55 Residual amount of double bond
(mol %) 12.0 10.3 10.3 8.5 8.5 12.0 12.0 Peak temperature of tan
.delta. (.degree. C.) -5.2 -15.2 -15.2 -22.6 -22.6 -5.2 -5.2 Peak
height of tan .delta. 1.89 1.91 1.91 1.92 1.92 1.89 1.89 Content of
adhesive force adjustor (parts -- -- -- -- -- -- 5 by mass) Layer B
Kind Ionomer Ionomer Ionomer Ionomer Ionomer Ionomer PVB-a
Viscosity average polymerization degree -- -- -- -- -- -- 1700
Average degree of acetalization (mol %) -- -- -- -- -- -- 70 Kind
of plasticizer -- -- -- -- -- -- P-510 Content of plasticizer
(parts by mass) -- -- -- -- -- -- 15 Laminated Sum total of
thickness of layer A and 1/2 1/2 1/6.5 1/2 1/6.5 1/1 1/2 glass
thickness of layer B B/A/B Transmittance [at 1,500 nm] (%) 77 76 78
76 78 76 40 Tertiary resonance frequency (Hz) 2000 1816 2157 1322
1536 1907 2099 Loss factor before moist heat resistance test 0.46
0.35 0.27 0.20 0.36 0.38 0.45 Loss factor after moist heat
resistance test 0.45 0.33 0.27 0.19 0.35 0.36 0.43 Decrease of loss
factor 0.01 0.02 0.00 0.01 0.01 0.02 0.02 Haze before moist heat
resistance test [%] 0.8 0.7 0.6 0.7 0.5 0.9 1.5 Haze after moist
heat resistance test [%] 1.5 1.6 1.5 1.4 1.4 1.9 2.8 Increase of
haze 0.7 0.9 0.9 0.7 0.9 1.0 1.3 Distance of whitening after moist
heat 2 2 1 1 1 3 3 resistance test [mm] YI before weather
resistance test 0.79 0.77 0.88 0.81 0.89 0.79 0.65 YI after weather
resistance test 1.75 1.52 1.49 1.52 1.43 1.68 1.23 Increase of YI
0.96 0.75 0.61 0.71 0.54 0.89 0.58 Thermal creep resistance A A A A
A A A * Ip: Isoprene unit, Bd: Butadiene unit * P-510: Polyester
polyol * The content of the adhesive force adjustor expresses an
amount based on 100 parts by mass of the thermoplastic elastomer,
and the content of the plasticizer expresses an amount based on 100
parts by mass of polyvinyl butyral.
Comparative Example 1
[0217] An interlayer film for laminated glass and a laminated glass
were prepared by the same method as in Example 1, except that as
the layer B, an ethylene.vinyl acetate copolymer saponified product
(EVA saponified product) (manufactured by Tosoh Corporation,
MELTHENE H6051) was used in place of the composition of PVB and the
polyester polyol, and then subjected to the various physical
properties evaluations. The results of the various physical
properties evaluations are shown in Table 3.
Comparative Example 2
[0218] An interlayer film for laminated glass and a laminated glass
were prepared by the same method as in Example 1, except that as
the layer A, an ethylene.vinyl acetate copolymer (EVA)
(manufactured by Tosoh Corporation, ULTRATHENE 635) was used in
place of the hydrogenated product of a
polystyrene-polyisoprene-polystyrene triblock copolymer, and the
adhesive force adjustor was not used, and then subjected to the
various physical properties evaluations. The results of the various
physical properties evaluations are shown in Table 3.
Comparative Example 3
[0219] An interlayer film for laminated glass and a laminated glass
were prepared by the same method as in Example 5, except that as
the layer A, a composition in which 100 parts by mass of a
polyvinyl butyral resin having a viscosity average polymerization
degree of about 1,700, an average degree of acetalization of 64 mol
%, and an average content of a vinyl acetate unit of 12.5 mol %
(hereafter referred to as "PVB-b") was compounded with 60 parts by
mass of triethylene glycol-di(2-ethylhexanoate) (hereinafter
referred to as "3GO") was used in place of the hydrogenated product
of a polystyrene-polyisoprene-polystyrene triblock copolymer and
the adhesive force adjustor, and that in the layer B, 60 parts by
mass of 3GO was used in place of 15 parts by mass of the polyester
polyol, and then subjected to the various physical properties
evaluations. The results of the various physical properties
evaluations are shown in Table 3.
TABLE-US-00003 TABLE 3 Comparative Comparative Comparative Example
1 Example 2 Example 3 Layer A Kind TPE-2 EVA PVB-b Content of
polymer block (a) (% by mass) 20 -- -- Content of polymer block (b)
(% by mass) 80 -- -- Mass ratio of monomer of polymer block (b) Ip
= 100 -- -- Sum total of 1,2-bond and 3,4-bond (mol %) 55 -- --
Residual amount of double bond (mol %) 12.0 -- -- Peak temperature
of tan .delta. (.degree. C.) -5.2 -28.1 0.7 Peak height of tan
.delta. 1.89 0.24 0.79 Kind of plasticizer -- -- 3GO Content of
plasticizer (parts by mass) -- -- 60 Layer B Kind EVA saponified
PVB-a PVB-a product Viscosity average polymerization degree -- 1700
1700 Average degree of acetalization (mol %) -- 70 70 Kind of
plasticizer -- P-510 3GO Content of plasticizer (parts by mass) --
15 60 Laminated Sum total of thickness of layer A and thickness 1/2
1/2 1/6.5 glass of layer B B/A/B Transmittance [at 1,500 nm] (%) 71
72 76 Tertiary resonance frequency (Hz) 2097 1239 2024 Loss factor
before moist heat resistance test 0.43 0.17 0.34 Loss factor after
moist heat resistance test 0.40 0.11 0.27 Decrease of loss factor
0.03 0.06 0.07 Haze before moist heat resistance test [%] 2.2 1.6
0.7 Haze after moist heat resistance test [%] 7.2 4.7 33.3 Increase
of haze 5.0 3.1 32.6 Distance of whitening after moist heat 8 7 25
resistance test [mm] Yl before weather resistance test 1.03 1.49
1.31 Yl after weather resistance test 4.21 5.22 4.71 Increase of Yl
3.18 3.73 3.40 Thermal creep resistance A B A Ip: Isoprene unit
P-510: Polyester polyol 3GO: Triethylene
glycol-di-(2-ethylhexanoate) The content of the plasticizer
expresses an amount based on 100 parts by mass of polyvinyl
butyral.
REFERENCE SIGNS LIST
[0220] 1: Layer A [0221] 2a: Layer B [0222] 2b: Layer B [0223] 10:
Laminated glass [0224] 11: Interlayer film for laminated glass
[0225] 12: Glass [0226] 13: Glass [0227] 14: Edge point [0228] 20:
Xenon lamp [0229] 21: Edge point [0230] 70: Laminated glass [0231]
71: Glass [0232] 72: Glass [0233] 73: Intermediate glass for
laminated glass [0234] 80: Laminated glass [0235] 81: Iron plate
[0236] 91: Stand
* * * * *