U.S. patent application number 10/270069 was filed with the patent office on 2003-07-31 for thermoplastic elastomer composition, insulating glass using the composition, process for producing the insulating glass and nozzle for producing the insulating glass.
Invention is credited to Koizumi, Yukio, Serizawa, Toru, Takeyama, Hidekazu, Watanabe, Jiro, Yamauchi, Shigeru.
Application Number | 20030143387 10/270069 |
Document ID | / |
Family ID | 29587437 |
Filed Date | 2003-07-31 |
United States Patent
Application |
20030143387 |
Kind Code |
A1 |
Koizumi, Yukio ; et
al. |
July 31, 2003 |
Thermoplastic elastomer composition, insulating glass using the
composition, process for producing the insulating glass and nozzle
for producing the insulating glass
Abstract
A thermoplastic elastomer composition produced from a
thermoplastic resin and rubber and having a dispersion phase formed
of a rubber composition at least part of which is dynamically
crosslinked in the continuous phase of the thermoplastic resin,
insulating glass using the thermoplastic elastomer composition as a
sealing material and spacer, a process for producing the insulating
glass using a sealing material made from the thermoplastic
elastomer composition, comprising the steps of inserting the
leading end of a charging nozzle into a space between the
peripheral portions of a plurality of glass sheets, discharging the
sealing material from the leading end of the nozzle body at a
predetermined rate, and moving the glass sheets or the nozzle body
relative to each other to charge the sealing material made from the
thermoplastic elastomer composition into the space between the
peripheral portions of the glass sheets, and a nozzle used in this
process.
Inventors: |
Koizumi, Yukio; (Kanagawa,
JP) ; Watanabe, Jiro; (Kanagawa, JP) ;
Takeyama, Hidekazu; (Kanagawa, JP) ; Yamauchi,
Shigeru; (Kanagawa, JP) ; Serizawa, Toru;
(Kanagawa, JP) |
Correspondence
Address: |
RADER, FISHMAN & GRAUER, PLLC
Suite 501
1233 20th Street
Washington
DC
20036
US
|
Family ID: |
29587437 |
Appl. No.: |
10/270069 |
Filed: |
October 15, 2002 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
10270069 |
Oct 15, 2002 |
|
|
|
09639889 |
Aug 17, 2000 |
|
|
|
Current U.S.
Class: |
428/304.4 ;
156/106; 428/192; 428/431; 428/76 |
Current CPC
Class: |
C03C 27/10 20130101;
C08L 2666/04 20130101; Y10T 428/239 20150115; C08L 23/0853
20130101; C08L 23/283 20130101; Y10T 428/249953 20150401; E06B
3/66328 20130101; C09J 123/22 20130101; C08L 23/283 20130101; C09J
123/22 20130101; C08L 2666/04 20130101; Y10T 428/3162 20150401;
C08L 23/22 20130101; C08L 93/04 20130101; C08L 2205/22 20130101;
Y10T 428/24777 20150115; E06B 3/6733 20130101; C08L 23/06 20130101;
C08L 23/22 20130101; C08L 2666/04 20130101; C08L 2666/04
20130101 |
Class at
Publication: |
428/304.4 ;
428/76; 428/192; 428/431; 156/106 |
International
Class: |
C03C 027/00; B32B
017/00 |
Claims
What is claimed is:
1. A thermoplastic elastomer composition produced from a
thermoplastic resin having a water vapor permeability of 100
g/m.sup.2.multidot.24 h or less (30 .mu.m in thickness) and rubber
having a water vapor permeability of 300 g/m.sup.2.multidot.24 h or
less (30 .mu.m in thickness) when crosslinked, said composition
having a dispersion phase formed of a rubber composition at least
part of which is dynamically crosslinked in the continuous phase of
the thermoplastic resin.
2. The thermoplastic resin composition according to claim 1,
wherein said composition further contains a moisture absorbent.
3. The thermoplastic resin composition according to claim 1,
wherein the thermoplastic resin has a heat distortion temperature
of 50.degree. C. or more.
4. The thermoplastic resin composition according to claim 1,
wherein said composition further contains a barrier resin against
steam permeation.
5. Insulating glass which uses the thermoplastic elastomer
composition of claim 1 as a sealing material and spacer.
6. The insulating glass according to claim 5, wherein said
insulating glass has an adhesive layer between the thermoplastic
elastomer composition as the sealing material and spacer and glass
sheets.
7. The insulating glass according to claim 6, wherein the adhesive
layer is formed of an olefin/vinyl acetate copolymer.
8. A process for producing insulating glass by charging a sealing
material having a predetermined width into a space between the
peripheral portions of at least two glass sheets which are opposed
to each other in parallel at a predetermined interval to isolate a
hollow layer from the outside air, the process comprising the steps
of: inserting in advance the leading end of a charging nozzle into
the space between the peripheral portions of a plurality of glass
sheets; contacting a slide plate provided at the top of the leading
end portion of the nozzle to the peripheral portions of the
plurality of glass sheets; discharging the sealing material from
the leading end of the nozzle body at a predetermined rate; and
moving at least one of the glass sheets and the nozzle body
relative to the other to charge the sealing material into the space
between the peripheral portions of the glass sheets from the
leading end of the nozzle.
9. The process for producing insulating glass according to claim 8,
wherein the sealing material at the peripheral portions of the
plurality of glass sheets is leveled by the slide plate provided at
the top of the leading end portion of the nozzle body and the lower
side of the sealing material in the space between the plurality of
glass sheets is leveled by a guide plate provided at a lower end
portion at the leading end of the nozzle body when the sealing
material is charged into the space between the peripheral portions
of the glass sheets.
10. A process for producing insulating glass which uses the
thermoplastic elastomer composition of claim 1 as a sealing
material and spacer.
11. A nozzle for producing insulating glass by inserting the
leading end portion of a nozzle into a space between the peripheral
portions of at least two glass sheets which are opposed to each
other in parallel at a predetermined interval and charging a
sealing material from the leading end portion of the nozzle into
the space between the peripheral portions of the glass sheets while
moving at least one of the glass sheets and the nozzle body
relative to the other, wherein the leading end of the nozzle body
has a width for positioning the interval between the plurality of
glass sheets and a slide plate which slides along the peripheral
portions of the plurality of glass sheets at the top of the leading
end portion.
12. The nozzle for producing insulating glass according to claim
11, wherein the slide plate provided at the top of the leading end
portion of the nozzle body projects along the discharge direction
of the sealing material.
13. The nozzle for producing insulating glass according to claim 11
or 12, wherein a guide plate is formed at the lower end portion at
the leading end of the nozzle body inserted into the space between
the plurality of glass sheets in such a manner that the guide plate
projects parallel to the slide plate and along the discharge
direction of the sealing material.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a thermoplastic elastomer
composition having excellent steam permeation resistance and heat
distortion resistance, insulating glass using the composition as a
sealing material and spacer, a process for producing the insulating
glass and a nozzle for producing the insulating glass.
[0003] 2. Prior Art
[0004] Heretofore, there has been known insulating glass
constituted such that a sealing material having a predetermined
width is charged into a space between the peripheral portions of at
least two glass sheets which are opposed to each other in parallel
and the hollow layer between the glass sheets is isolated from the
outside air for the purpose of an improvement of heat insulating
properties, dew condensation prevention properties and the
like.
[0005] This insulating glass has been produced as follows, for
example. As shown in FIG. 7, an aluminum spacer 73 filled with a
desiccating agent 72 is placed in a space between the peripheral
portions of two glass sheets 71a and 71b which are opposed to each
other in parallel and held by a jig or the like to fix a
predetermined interval between the glass sheets. Thereafter, a
primary sealing material 74 is charged into spaces between the both
side surfaces of the spacer 73 and the glass sheets 71a and 71b,
and a two-liquid mixing and normal temperature curable type
secondary sealing material 75, for example by a polysulfide- or
silicone-based sealing material, is charged into a space between
the spacer 73 and the opening side of the glass sheets 71 and
71b.
[0006] Japanese Patent Application Laid-Open No. Hei 10-158041
discloses a insulating glass production process and apparatus. In
the process and apparatus, a plurality of glass sheets are held in
a perpendicular direction so that the plurality of glass sheets can
be simultaneously moved in the same direction at the same speed,
the glass sheets and a die are moved in different unidirections
which are perpendicular to each other, the glass sheets and the die
are moved relative to each other alternately such that the glass
sheets are stopped when the die is moved, and vice versa, and a
resin material is extruded onto the peripheral portions of the
glass sheets opposed to each other by moving the glass sheets and
the die alternately for each side of the glass sheets.
[0007] However, since the former production process is carried out
by using a jig, spacer and the like, the work becomes complicated
and takes much time and labor. On the other hand, the latter
process has such a problem that it is difficult to obtain
insulating glass having good appearance because the resin material
cannot be paved nicely when it is extruded.
[0008] In the insulating glass using the normal temperature curable
sealing material in the prior art processes, it takes time to cure
the sealing material and a final product cannot be promptly
shipped. Especially in winter, the sealing material must be placed
in a heating chamber for curing.
[0009] Therefore, it is desired to improve productivity by
simplifying the process for producing insulating glass and
shortening the cure time.
[0010] In contrast to this, Japanese Patent Application Laid-Open
Nos. Hei 10-110072, Hei 10-114551, Hei 10-114552 and the like
propose an invention in which a resin containing a desiccating
agent as required is used as a spacer and sealing material in place
of the aluminum spacer. The spacer/sealing material proposed in
these publications is a composition containing butyl-based rubber
and crystalline polyolefin which are preferably mixed at a high
temperature.
[0011] In insulating glass using this composition, the composition
serves as a resin spacer and a sealing material. Insulating glass
can be produced in which the peripheral portions of the glass
sheets are sealed up by paving the composition on the peripheral
portions of two glass sheets opposed to each other with a spacer
therebetween. Thus, the production process is simplified. However,
in this insulating glass, the glass sheets are not dislocated each
other when a load is placed upon the glass sheets at normal
temperature but the glass sheets are dislocated each other while a
high-temperature sealing material is paved and cured especially
when the insulating glass is produced or when the temperature of
the outside air rises in summer or by sunlight after the insulating
glass is formed into a construction material or the like because
the composition which serves as a sealing material and resin spacer
contains a small amount of a resin in rubber and hence, is easily
deformed at high temperatures.
SUMMARY OF THE INVENTION
[0012] It is a first object of the present invention to provide a
thermoplastic elastomer composition which has excellent steam
permeation resistance and heat distortion resistance and is
suitable for use as a sealing material and spacer for insulating
glass.
[0013] It is a second object of the present invention to provide
insulating glass which uses the thermoplastic elastomer composition
as a sealing material and spacer, is produced easily, has excellent
steam permeation resistance and is not deformed in the entire shape
by the dislocation of the glass sheets when it is allowed to cool
after the sealing material and spacer is paved, or after processing
or at high temperatures in summer or the like.
[0014] It is a third object of the present invention to provide a
process for producing insulating glass which enables a sealing
material to be efficiently paved in a space between the peripheral
portions of glass sheets and leveled to obtain good appearance and
reduces the number of working steps to carry out efficient
work.
[0015] It is a fourth object of the present invention to provide a
nozzle for producing insulating glass which can be advantageously
used in the above process for producing insulating glass.
[0016] The inventor of the present invention has conducted
intensive studies to solve the above problems and have found that
the above objects can be attained by a thermoplastic elastomer
composition containing a continuous phase formed of a thermoplastic
resin having a water vapor permeability below a predetermined value
and a dispersion phase formed by dynamically crosslinking a rubber
component having a water vapor permeability below a predetermined
value after crosslinking, and insulating glass using the
composition as a sealing material and spacer. Thus, the present
invention has been accomplished based on this finding.
[0017] To attain the first object, the present invention provides a
thermoplastic elastomer composition which is produced from a
thermoplastic resin having a water vapor permeability of 100
g/m.sup.2.multidot.24 h or less (30 .mu.m in thickness) and rubber
having a water vapor permeability of 300 g/m.sup.2.multidot.24 h or
less (30 .mu.m in thickness) when crosslinked and which has a
dispersion phase formed of a rubber composition at least part of
which is dynamically crosslinked in the continuous phase of the
thermoplastic resin.
[0018] To attain the second object, the present invention provides
insulating glass which uses the thermoplastic elastomer composition
as a sealing material and spacer.
[0019] To attain the third object, the present invention provides a
process for producing insulating glass by charging a sealing
material having a predetermined width into a space between the
peripheral portions of at least two glass sheets which are opposed
to each other in parallel at a predetermined interval to isolate
the hollow layer from the outside air, the process comprising the
steps of inserting in advance the leading end of a charging nozzle
into a space between the peripheral portions of a plurality of
glass sheets, contacting a slide plate provided at the top of the
leading end portion of the nozzle to the peripheral portions of the
plurality of glass sheets, discharging a sealing material from the
leading end of the nozzle body at a predetermined rate, and moving
at least one of the glass sheets and the nozzle body relative to
the other to charge the sealing material from the leading end
portion of the nozzle into the space between the peripheral
portions of the glass sheets.
[0020] To attain the fourth object, the present invention provides
a nozzle for producing insulating glass by inserting the leading
end portion of the nozzle into a space between the peripheral
portions of at least two glass sheets which are opposed to each
other in parallel at a predetermined interval, and charging a
sealing material from the leading end portion of the nozzle into
the space between the peripheral portions of the glass sheets while
at least one of the glass sheets and the nozzle body is moved
relative to the other, wherein the leading end of the nozzle body
has a width for positioning the interval between the plurality of
glass sheets, and a slide plate which slides along the peripheral
portions of the plurality of glass sheets and is provided at the
top of the leading end portion.
BRIEF DESCRIPTION OF THE DRAWINGS
[0021] These and further features of the present invention will be
apparent with reference to the following description and drawings,
wherein:
[0022] FIGS. 1(a) and (b) are schematic sectional views of
insulating glass according to an embodiment of the present
invention;
[0023] FIG. 2 is a perspective view of a nozzle for producing
insulating glass of the present invention;
[0024] FIG. 3 is a side view of the nozzle for producing insulating
glass of the present invention;
[0025] FIG. 4 is a plan view of the nozzle for producing insulating
glass of the present invention;
[0026] FIG. 5 is a perspective view showing that a sealing material
is charged into a space between the peripheral portions of two
glass sheets;
[0027] FIG. 6 is a sectional view of a cup for measuring water
vapor permeability; and
[0028] FIG. 7 is a diagram for explaining the insulating glass
production process of the prior art.
DETAILED DESCRIPTION OF THE INVENTION
[0029] The present invention will be described in detail
hereinunder.
[0030] The thermoplastic elastomer composition of the present
invention (to be referred to as "composition of the present
invention" hereinafter) is suitable for use as a sealing material
and spacer for insulating glass and has a continuous phase formed
of a thermoplastic resin and a dispersion phase formed of a rubber
composition at least part of which is dynamically crosslinked. The
dispersion phase is uniformly dispersed in the continuous
phase.
[0031] A thermoplastic resin having a water vapor permeability of
100 g/m.sup.2.multidot.24 h or less when a sheet having a thickness
of 30 .mu.m is formed from the thermoplastic resin alone is used as
the thermoplastic resin which is one of the components of the
composition of the present invention.
[0032] Illustrative examples of the thermoplastic resin include
polyolefin-based resins such as high-density polyethylene (HDPE),
low-density polyethylene (LDPE), ultra high molecular weight
polyethylene (UHMWPE), isotactic polypropylene, syndiotactic
polypropylene and ethylene-propylene copolymer resins;
polyamide-based resins such as nylon 6 (N6), nylon 66 (N66), nylon
46 (N46), nylon 11 (Nil), nylon 12 (N12), nylon 610 (N610), nylon
612 (N612), nylon 6/66 copolymer (N6/66), nylon 6/66/610 copolymer
(N6/66/610), nylon MXD6 (MXD6), nylon 6T, nylon 6/6T copolymer,
nylon 66/PP copolymer and nylon 66/PPS copolymer; polyester-based
resins such as aromatic polyesters exemplified by polybutylene
terephthalate (PBT) and polyethylene terephthalate (PET);
polyether-based resins such as polyphenylene oxide (PPO), modified
polyphenylene oxide (modified PPO), polysulfone (PSF) and polyether
ether ketone (PEEK); polymethacrylate-based resins such as methyl
polymethacrylate (PMMA) and ethyl polymethacrylate; polyvinyl-based
resins such as a vinyl alcohol/ethylene copolymer (EVOH),
polyvinylidene chloride (PVDC) and vinylidene chloride/methyl
acrylate copolymer; fluororesins such as polyvinylidene fluoride
(PVDF), polychlorofluoroethylene (PCTFE) and polyacrylonitrile
resin (PAN); and the like.
[0033] Out of these, polyolefin-based resins, polyester-based
resin, polyether-based resin and fluororesins having a heat
distortion temperature of 50.degree. C. or more are preferred
because the composition of the present invention obtained therefrom
has excellent moldability and excellent heat distortion resistance
against the temperature of the outside air or the like when it is
used as a sealing material and spacer for insulating glass which
will be described hereinafter, so that a reduction in water vapor
permeability caused by water absorption can be minimized.
[0034] The dispersion phase dispersed in the continuous phase of
the composition of the present invention is formed of a rubber
composition at least part of which is dynamically crosslinked.
Rubber having a water vapor permeability of 300
g/m.sup.2.multidot.24 h or less when a sheet having a thickness of
30 .mu.m is produced by crosslinking only a rubber component is
used as a rubber component which is the main constituent ingredient
of this dispersion phase. Illustrative examples of the rubber
component include cyclic NR, ethylene propylene rubber (EPDM, EPM),
polyisobutylene, IIR, Br-IIR, CI-IIR, halide of a paramethyl
styrene-polyisobutylene copolymer (X-IPMS), ethylene-vinyl acetate
rubber (EVA), chlorinated polyethylene, chlorosulfonated
polyethylene, acrylonitrile butadiene rubber and hydride thereof,
hydrin rubber and the like. Out of these, ethylene propylene
rubber, IIR, Br-IIR and X-IPMS are preferred from the viewpoints of
heat resistance at the time of kneading with a resin, low water
vapor permeability and crosslinking reactivity.
[0035] Further, a reinforcement, filler, softening agent,
crosslinking agent, age resistor, processing aid and the like which
are generally blended to improve the dispersibility, heat
resistance and the like of the rubber composition and for other
purposes may be suitably blended into the rubber composition
forming the dispersion phase.
[0036] A combination of a thermoplastic resin forming the
continuous phase and rubber which is the main constituent
ingredient of the dispersion phase of the composition of the
present invention is not particularly limited and at least one
thermoplastic resin selected from the above thermoplastic resins
and at least one rubber selected from the above rubbers may be used
in combination.
[0037] The weight ratio of the thermoplastic resin composition to
the rubber composition constituting the composition of the present
invention is not particularly limited but preferably 85/15 to
15/85, more preferably 50/50 to 30/70.
[0038] The criticality of this ratio is dependent upon the volume
ratio and viscosity ratio of the thermoplastic resin composition to
the rubber composition.
[0039] The rubber composition is the dispersion phase and the
thermoplastic resin composition is the continuous phase of the
composition of the present invention. Even when the both components
are simply kneaded together while they are molten, a thermoplastic
elastomer composition having a dispersion structure of interest is
not always obtained. The relationship between the melt viscosity of
the thermoplastic resin composition to the melt viscosity of the
rubber component at their kneading temperature is adjusted by
controlling the volume ratio of the both components to be blended
so that the value of .alpha..sub.1 obtained from the following
equation should become less than 1.
.alpha..sub.1=(.phi..sub.R/.phi..sub.P).times.(.eta..sub.P/.eta..sub.R)
[0040] where .PHI..sub.R is the volume fraction of the rubber
composition, .phi..sub.P is the volume fraction of the
thermoplastic resin composition, .eta..sub.P is the melt viscosity
(poise) of the rubber composition at a temperature and a shearing
speed at which the thermoplastic resin composition and the rubber
composition are kneaded together, and .eta..sub.R is the melt
viscosity (poise) of the thermoplastic resin composition at a
temperature and a shearing speed at which the thermoplastic resin
composition and the rubber composition are kneaded together.
[0041] When the value of .alpha..sub.1 is 1 or more, the dispersion
structure of the composition of the present invention may be
inverted and the rubber composition may be the continuous phase of
the composition.
[0042] 0.5.ltoreq..eta..sub.R/.eta..sub.P.ltoreq.3.0 is preferred.
Within this range, the rubber composition is dispersed in the
thermoplastic resin as particles having a size of about 0.1 .mu.m
to several tens of .mu.m.
[0043] In the present invention, the term "melt viscosity" means
the melt viscosity of each component at an arbitrary temperature
when it is kneaded. Since the melt viscosity of a polymer component
changes according to temperature, shearing speed (sec.sup.-1) and
shearing stress, it is obtained from the following equation by
flowing the polymer component in a molten state in a thin tube at
an arbitrary temperature at which the component is molten,
particularly at a temperature range at the time of kneading and
measuring stress and shearing speed.
.eta.=.sigma./{dot over (.gamma.)}
[0044] where .sigma. is a shearing stress and {dot over (.gamma.)}
is a shearing speed.
[0045] The capillary rheometer capillograph 1C of Toyo Seiki Co.,
Ltd. may be used as an example for the measurement of melt
viscosity.
[0046] The composition of the present invention may contain a
moisture absorbent. When the composition of the present invention
is used as a sealing material or spacer for insulating glass,
particularly a sealing material and spacer, it preferably contains
a moisture absorbent.
[0047] The expression "sealing material and spacer" means that the
composition of the present invention is used as a spacer arranged
in a space between the peripheral portions of the opposed glass
sheets of insulating glass to ensure the thickness of an air layer
for the insulating glass and that the spacer is press-contacted to
the glass sheets without paving a sealing material between the
spacer and the glass sheets so that the composition of the present
invention is used as a sealing material for isolating the air layer
from the outside air. That is, when the composition of the present
invention is used as a sealing material and spacer, it serves as a
spacer and a sealing material at the same time.
[0048] The composition of the present invention may be used as a
sealing material for insulating glass and used in combination with
other spacer, or may be used as a spacer and used in combination
with other sealing material.
[0049] The composition of the present invention preferably contains
a moisture absorbent. When the composition of the present invention
is used as a sealing material and spacer for insulating glass, it
is effective because it can absorb moisture contained in the air
layer formed between the two glass sheets, dry the air layer,
absorb water entering from the outside of the insulating glass and
prevent a rise in the dew point of air sealed in the air layer. The
expression "dew point in the insulating glass" means the highest
temperature at which dew condensation on the inner surface of the
insulating glass is visually observed.
[0050] A moisture absorbent which is generally charged in the metal
spacer or the like of insulating glass may be used as the moisture
absorbent, as exemplified by synthetic zeolite, silica gel, alumina
and the like.
[0051] The amount of the moisture absorbent is preferably 10 to 70
parts by weight based on 100 parts by weight of the total of
polymer components (a thermoplastic resin and rubber) of the
present invention. Within this range, a composition having
excellent hygroscopicity can be obtained.
[0052] Further, the composition of the present invention preferably
contains a steam permeable barrier resin (to be referred to as
"barrier resin" hereinafter). The composition of the present
invention has excellent steam permeation resistance because the
thermoplastic resin which is the continuous phase of the
composition and rubber which is the main constituent ingredient of
the dispersion phase have a water vapor permeability below
respective predetermined values. However, when the composition of
the present invention contains a barrier resin, the steam
permeation resistance of the obtained composition of the present
invention is further improved.
[0053] The term "barrier resin" used herein means a resin which has
a smaller water vapor permeability than that of the thermoplastic
resin which is the continuous phase, can be a barrier by increasing
its crystallinity even if it is the same type of a resin as the
thermoplastic resin of the continuous phase, which is preferably
kneaded into the continuous phase in layers in a lamellar form when
it is kneaded into the thermoplastic elastomer composition of the
present invention and which is desirably lamellar in shape with an
aspect ratio of 10 to 500 (aspect ratio: a/b where a is the length
of a long axis and b is the length of a short axis).
[0054] In insulating glass which uses the composition of the
present invention as a sealing material and spacer which will be
described hereinafter, the barrier resin is preferably existent in
the continuous phase of the composition of the present invention
and dispersed as a lamellar product parallel to the peripheral
surfaces of the insulating glass. The barrier resin dispersed in
layers is effective in preventing the permeation of steam and
reducing water vapor permeability.
[0055] Illustrative examples of a resin component constituting the
barrier resin include polyolefins such as high-density polyethylene
(HDPE) and ultra high molecular weight polyethylene (UHMWPE),
polyamide resins such as nylon 6, nylon 66 and aromatic nylon
(MXD6), polyester resins such as polyethylene terephthalate (PET),
polyvinyl resins such as ethylene-vinyl alcohol (EVOH), polyvinyl
chloride resins, polyvinylidene chloride (PVDC) resins and the
like. In the present invention, these barrier resins may be used
alone or in combination of two or more.
[0056] When the composition of the present invention contains a
barrier resin, the content of the barrier resin is suitably
determined such that the melt viscosities and volume fractions of
the thermoplastic elastomer composition which is the composition of
the present invention excluding the barrier resin, and the barrier
resin should satisfy the following expressions (1) and (2). The
weight ratio of the above thermoplastic elastomer composition to
the barrier resin is generally 90/10 to 50/50, particularly
preferably 90/10 to 70/30.
.eta..sub.d/.eta..sub.m.gtoreq.2.0 (1)
.alpha..sub.2=.PHI..sub.d/.PHI..sub.m.times..eta..sub.m/.eta..sub.d<1.0
(2)
[0057] where .eta..sub.d is the melt viscosity (poise) of the
barrier resin, .eta..sub.m is the melt viscosity (poise) of the
thermoplastic elastomer composition, .PHI..sub.d is the volume
fraction of the barrier resin, and .PHI..sub.m is the volume
fraction of the thermoplastic elastomer composition.
[0058] In the expression (1), when the value of
.eta..sub.d/.eta..sub.m is less than 2, the barrier resin is finely
dispersed in the thermoplastic elastomer composition while it is
molten and kneaded and its function as a barrier becomes reduced.
The value of .eta..sub.d/.eta..sub.m is preferably 3 or more. In
the expression (2), when .alpha..sub.2 is less than 1, the barrier
resin can be existent as a dispersion phase in the continuous phase
formed of the thermoplastic elastomer composition, more
specifically, in the thermoplastic resin composition forming the
continuous phase of the thermoplastic elastomer composition.
[0059] A filler such as talc, calcium carbonate, mica or carbon
black, tackifier such as rosin ester and coumarone resin, age
resistor, thermal stabilizer, antioxidant, softening agent,
processing aid agent and other additives may be added to the
composition of the present invention in limits that do not impair
the object of the present invention in order to improve fluidity,
heat resistance, physical strength, cost performance and the like.
Further, an inorganic pigment and organic pigment may be blended
into the thermoplastic resin composition for coloration.
[0060] Moreover, an adhesion promoter may be added to the
composition of the present invention to improve adhesion to glass.
The adhesion promoter is a silane coupling agent such as
vinylsilane, methacrylsilane, aminosilane, epoxysilane or
mercaptosilane, or a polymer having a maleic acid group, carboxylic
acid group, hydroxyl group or epoxy group. Specific examples of the
adhesion promoter include maleic acid modified polyethylene, maleic
acid modified polypropylene, maleic acid modified ethylene ethyl
acrylate, epoxy modified styrene-butadiene copolymer, epoxy
modified ethylene-vinyl acetate copolymer, ethylene-vinyl acetate
copolymer and saponified products thereof.
[0061] When the chemical compatibilities of the above specific
thermoplastic resin composition and rubber composition are
different from each other, an appropriate compatibilizing agent is
preferably used as a third component to compatibilize the both
materials. The interfacial tension between the thermoplastic resin
composition and the rubber composition is reduced by mixing a
compatibilizing agent, with the result that the characteristic
properties of the both compositions are developed more effectively
as the particle diameter of the rubber composition forming the
dispersion phase becomes very small. The compatibilizing agent is
generally a copolymer having both structures of a resin component
and a rubber component or either one of them, or a copolymer having
an epoxy group, carboxyl group, carbonyl group, halogen group,
amino group, oxazoline group or hydroxyl group which can react with
a resin component or rubber component. They can be selected
according to the types of the resin component and the rubber
component to be mixed together.
[0062] General-purpose compatibilizing agents include a
styrene-ethylene-butylene-styrene-based block copolymer (SEBS) and
maleic acid modified product thereof, EPDM, EPM and maleic acid
modified products thereof, EPDM/styrene and EPDM/acrylonitrile
graft copolymer and maleic acid modified products thereof,
styrene/maleic acid copolymer, reactive phenoxthine and the
like.
[0063] When a compatibilizing agent is blended into the composition
of the present invention, its amount is not particularly limited
but preferably 0.5 to 20 parts by weight based on 100 parts by
weight of the total of polymer components (the thermoplastic resin
and rubber).
[0064] In the present invention, a vulcanizing agent, vulcanizing
accelerator, vulcanization conditions (temperature and time) and
the like used for the dynamic crosslinking of the rubber
composition may be suitably determined according to the composition
of the rubber composition used and are not particularly limited. A
general rubber vulcanizing agent (crosslinking agent) may be used
as the vulcanizing agent.
[0065] Illustrative examples of sulfur-based vulcanizing agents
used as the rubber vulcanizing agent include powdery sulfur,
precipitating sulfur, highly dispersible sulfur, surface treated
sulfur, insoluble sulfur, dimorpholine sulfide, alkylphenol
disulfide and the like.
[0066] When this sulfur-based vulcanizing agent is used, its amount
is preferably 0.5 to 4 phr (parts by weight based on 100 parts by
weight of the rubber component, this shall apply thereafter).
[0067] Organic peroxide-based vulcanizing agents include benzoyl
peroxide, t-butylhydro peroxide, 2,4-dichlorobenzoyl peroxide,
2,5-dimethyl-2,5-di(t-butylperoxy)hexane and
2,5-dimethylhexane-2,5-di(pe- roxybenzoate).
[0068] When this organic peroxide-based vulcanizing agent is used,
its amount is preferably 1 to 15 phr.
[0069] Further, phenol resin-based vulcanizing agents include
bromides of alkylphenol resins, mixed crosslinking vulcanizing
agents containing a halogen doner such as tin chloride or
chloroprene and an alkylphenol resin.
[0070] When this phenol resin-based vulcanizing agent is used, its
amount is preferably 1 to 20 phr.
[0071] Other vulcanizing agents include zinc oxide (about 5 phr),
magnesium oxide (about 4 phr), litharge (about 10 to 20 phr),
p-quinone dioxime, p-dibenzoylquinone dioxime,
tetrachloro-p-benzoquinone, poly-p-dinitrosobenzene (about 2 to 10
phr) and methylindianiline (about 0.2 to 10 phr).
[0072] The composition of the present invention may contain a
vulcanizing accelerator as required. A general vulcanizing
accelerator such as aldehyde-ammonia-based, guanidine-based,
thiazole-based, sulfenamide-based, thiuram-based, dithionate-based
or thiourea-based general vulcanizing accelerator may be used in an
amount of about 0.5 to 2 phr.
[0073] Illustrative examples of the vulcanizing accelerator include
hexamethylenetetramine as the aldehyde-ammonia-based vulcanizing
accelerator, diphenylguanidine as the guanidine-based vulcanizing
accelerator, dibenzothiazyldisulfide (DM), 2-mercaptobenzothiazole
and Zn salts and cyclohexylamine salts thereof as the
thiazole-based vulcanizing accelerator, cyclohexylbenzothiazyl
sulfenamide (CBS), N-oxydiethylenebenzothiazyl-2-sulfenamide,
N-t-butyl-2-benzothiazole sulfenamide and
2-(thymolpolynildithio)benzothiazole as the sulfenamide-based
vulcanizing accelerator, tetramethylthiuram disulfide (TMTD),
tetraethylthiuram disulfide, tetramethylthiuram monosulfide (TMTM)
and dipentamethylenethiuram tetrasulfide as the thiuram-based
vulcanizing accelerator, Zn-dimethyl dithiocarbamate, Zn-diethyl
dithiocarbamate, Zn-di-n-butyl dithiocarbamate, Zn-ethylphenyl
dithiocarbamate, Tc-diethyl dithiocarbamate, Cu-dimethyl
dithiocarbamate, Fe-dimethyl dithiocarbamate and
pipecolinepipecolyl dithiocarbamate as the dithionate-based
vulcanizing accelerator, and ethylene thiourea and diethyl thiourea
as the thiourea-based vulcanizing accelerator.
[0074] A general rubber auxiliary such as zinc oxide (about 5 phr),
stearic acid, oleic acid or Zn salt thereof (about 2 to 4 phr) may
also be used as the vulcanizing accelerator.
[0075] The composition of the present invention is prepared by
previously supplying a thermoplastic resin component and an
unvulcanized rubber composition to a kneader such as a double-screw
kneader to melt and knead these compositions and dispersing the
rubber composition in the thermoplastic resin composition forming a
continuous phase (matrix phase) as a dispersion phase (domain).
Thereafter, a thermoplastic elastomer composition can be produced
by adding a vulcanizing agent under kneading to dynamically
crosslink the rubber composition. The addition of compounding
additives to the thermoplastic resin composition or rubber
composition may be carried out during kneading but preferably
carried out before kneading. A vulcanizing agent is mixed into the
rubber composition in advance so that the rubber composition can be
crosslinked while the thermoplastic resin composition and the
rubber composition are kneaded together.
[0076] The kneader used for the kneading of the thermoplastic resin
composition and the rubber composition is not particularly limited
and a screw extruder, kneader, Banbury mixer, double-screw kneading
extruder and the like may be used. Particularly for the kneading of
the thermoplastic resin composition and the rubber composition and
the dynamic crosslinking of the rubber composition, a double-screw
kneading extruder is preferably used. Two or more kneaders may be
used to knead these compositions sequentially.
[0077] As for melt kneading conditions, the temperature may be
higher than the melting temperature of the thermoplastic resin.
When a barrier resin is blended, the temperature may be higher than
the melting temperature of the thermoplastic resin and lower than
the heat distortion temperature of the barrier resin. The shearing
speed at the time of kneading is preferably 500 to 7,500
sec.sup.-1. The total kneading time is 30 seconds to 10 minutes and
the vulcanizing time after addition is preferably 15 seconds to 5
minutes.
[0078] The prepared thermoplastic elastomer composition is then
extruded into a strand form from the kneading extruder, cooled with
water or the like, pelletized by a pelletizer for resins and then
may be molded. The high-temperature thermoplastic elastomer
composition thus prepared may be directly paved and charged into a
space surrounded by the peripheral portions of the glass sheets of
the insulating glass and a previously installed spacer as a sealing
material for the insulating glass.
[0079] Alternatively, the prepared thermoplastic elastomer
composition may be molded into the form of a spacer by extrusion
molding, injection molding or the like. In this case, when the
high-temperature thermoplastic elastomer composition discharged
from a molding machine is used, adhesion to the glass sheets and
the spacer is advantageously increased.
[0080] When the composition of the present invention contains a
barrier resin, pellets obtained by molding the thermoplastic
elastomer composition prepared as described above and the pellets
of the above barrier resin are mixed in a predetermined ratio. The
mixing of the pellets is carried out by dry blending with a
commonly used blender or the like, or by supplying the pellets into
a kneader from independent feeders in a predetermined ratio.
[0081] The mixture of the both pellets is melt kneaded at a low
shearing speed (for example, 30 sec.sup.-1 or more and less than
300 sec.sup.-1), such that the thermoplastic elastomer composition
and the barrier resin are melt kneaded in a single-screw extruder
and the resulting mixture is extruded from the end of the extruder
or injection molded, and the resulting melt kneaded product is
directly supplied into a molding machine to produce a sealing
material and spacer. Alternatively, the kneaded product may be
extruded into a strand form from the end of the extruder,
pelletized and molded.
[0082] When the composition of the present invention is used as a
sealing material, spacer, or a sealing material and spacer, the
barrier resin is preferably aligned in lamellar layers parallel to
the peripheral surfaces of the insulating glass. In order to align
the barrier resin like this, it is effective to make flat the shape
of the nozzle for extruding the composition of the present
invention for injection or to set the shearing speed at the outlet
of the extruder at 30 to 300 s.sup.-1.
[0083] In the composition of the present invention obtained from
the above components and by the above production process, the
dynamically crosslinked rubber composition forms a dispersion phase
in the thermoplastic resin composition forming a continuous phase.
That is, in the above production process, the crosslinking of the
rubber composition proceeds while the thermoplastic resin
composition and the rubber composition are kneaded together so that
the obtained composition contains the crosslinked rubber as a
dispersion phase finely dispersed in the resin composition as a
continuous phase.
[0084] In a composition obtained merely by kneading the
thermoplastic resin with rubber, rubber is dispersed as fine
particles immediately after they are kneaded and provided with
large shearing force but rubber turns back to a large mass when
kneading is stopped with the result that the rubber may form a
continuous phase and the thermoplastic resin may be dispersed in
the rubber. A composition having this structure has low heat
distortion resistance because the rubber forms a continuous
phase.
[0085] The composition of the present invention has excellent steam
permeation resistance. The composition of the present invention in
which rubber is finely dispersed in the thermoplastic resin has
also excellent heat distortion resistance.
[0086] The composition of the present invention containing a
moisture absorbent has excellent hygroscopicity.
[0087] The composition of the present invention comprising a
thermoplastic resin having a heat distortion temperature of
70.degree. C. or more as a continuous phase is excellent in heat
distortion resistance and also processability when the composition
of the present invention is processed into a sealing material or
the like.
[0088] Further, the composition of the present invention containing
a steam permeable barrier resin is more superior in steam
permeation resistance.
[0089] A description is subsequently given of insulating glass
which uses the composition of the present invention as a sealing
material and spacer.
[0090] FIGS. 1(a) and 1(b) are schematic sectional views in a
direction perpendicular to glass sheets of the insulating glass of
the present invention. In the insulating glass 10 shown in FIGS.
1(a) and 1(b), a spacer 3 for determining the interval between two
opposed glass sheets 1a and 1b is installed between the two glass
sheets 1a and 1b to form an air layer 2 having a predetermined
volume therebetween. This spacer 3 may be made from a metal such as
aluminum and a sealing material made from the composition of the
present invention may be installed as a separate unit, but the
spacer 3 is preferably made from the composition of the present
invention. The hardness of the spacer made from the composition of
the present invention is 25 to 90 in terms of JIS A hardness.
Within this range, even when stress is applied to the adhesive
surfaces between the glass sheets and the spacer by a rise in the
temperature of the air layer 2, it can be avoided that the glass is
broken if bonding strength is high and the glass sheets and the
spacer are separated from each other if bonding strength is
insufficient. Further, within this range, the insulating glass is
not deformed by the weight of the glass sheets.
[0091] The interval between the glass sheets 1a and 1b is generally
about 6 mm or about 12 mm. The insulating glass 10 shown in FIGS.
1(a) and 1(b) comprises two glass sheets. The number of the glass
sheets is not limited to two but two or more glass sheets may be
used and the number of the glass sheets can be selected as
required.
[0092] In the insulating glass of the present invention shown in
FIGS. 1(a) and 1(b), the spacer 3 also serves as a sealing material
for sealing up the space between the two glass sheets 1a and 1b
from the outside air and holding the glass sheets. The spacer 3
prevents water from entering from the outside without using a
primary sealing material, a secondary sealing material and the like
and serves as a spacer and sealing material for holding the two
glass sheets 1a and 1b at a predetermined interval.
[0093] The insulating glass of the present invention may have
adhesive layers 4 between the spacer 3 which also serves as a
sealing material and the glass sheets 1a and 1b as shown in FIG.
1(b). When the insulating glass of the present invention has the
adhesive layers 4, adhesion between the spacer 3 and the glass
sheet 1a or 1b can be improved, the entry of water from the outside
of the insulating glass can be prevented, and a rise in the dew
point of the air layer 2 can be suppressed.
[0094] A glass sheet for use in construction materials, vehicles or
the like can be used as the glass sheet of the insulating glass of
the present invention, as exemplified by glass which is generally
used in windows, reinforced glass, wire-net glass, heat absorbing
glass, heat reflecting glass, organic glass and the like. The
thickness of the glass sheet is suitably determined.
[0095] An adhesive used in the adhesive layer 4 is a silane
coupling agent such as vinylsilane, methacrylsilane, aminosilane,
epoxysilane or mercaptosilane, or a polymer having a maleic acid
group, carboxylic acid group, hydroxyl group, epoxy group or the
like. Illustrative examples of the adhesive include maleic acid
modified polyethylene, maleic acid modified polypropylene, maleic
acid modified ethylene ethyl acrylate, epoxy modified
styrene-butadiene copolymer, epoxy modified ethylene-vinyl acetate
copolymer, ethylene-vinyl acetate copolymer and saponified products
thereof. Out of these, olefin-vinyl acetate copolymers are
preferred. Illustrative examples of the olefin include ethylene,
propylene, butene and the like. Out of these, an ethylene-vinyl
acetate copolymer is preferred from the viewpoint of adhesion to
glass and water resistance. The above olefin-vinyl acetate
copolymer is preferably saponified because the saponified product
has high reactivity and improved adhesion.
[0096] The insulating glass of the present invention can be
basically produced by extruding the composition of the present
invention through a nozzle or the like connected to an extruder
into a space between two fixed parallel glass sheets and bonding it
to the glass sheets. The inner sides of the peripheral portions of
the glass sheets 1a and 1b to which the spacer 3 is bonded can be
coated with a primer as required and further an adhesive as
required. As the case may be, the composition of the present
invention is extruded onto the inner side of the peripheral portion
of one of the two glass sheets and the other glass sheet is
press-bonded to the composition of the present invention before the
composition does not become cool. To coat the primer and the
adhesive, they may be coated manually with an applicator or the
like, or automatically using a robot for extruding the primer and
the adhesive.
[0097] Particularly, the composition of the present invention and
the adhesive are co-extruded by an extruder such that the adhesive
forms an outer layer and the composition of the present inventor
forms an inner layer and then molded into a spacer having a
predetermined shape. Alternatively, the extruded composition of the
present invention and the extruded adhesive may be directly
discharged into the space between the peripheral portions of the
glass sheets.
[0098] The composition of the present invention for forming a
spacer, which has a high temperature after kneading, is preferably
used even when it is molded into a spacer and installed between the
glass sheets and even when it is directly discharged into the space
between the glass sheets from an extruder. This is because strong
adhesion between the spacer and the glass sheets can be
obtained.
[0099] The insulating glass of the present invention constituted as
described above is produced very easily because the number of
production steps is greatly reduced compared with conventional
insulating glass which is produced using a metal spacer and a
sealing material.
[0100] Since the composition of the present invention is used as a
sealing material and spacer, it does not take long to cure it
unlike the conventional two-liquid type sealing material and hence,
productivity is high. Since the composition of the present
invention has excellent steam permeation resistance as described
above, the insulating glass of the present invention has a low dew
point. Further, since the composition of the present invention has
excellent heat distortion resistance, even when the temperature of
the glass sheets becomes high due to the temperature of the outside
air or the like, the insulating glass is not deformed by the
dislocation of the glass sheets.
[0101] In the insulating glass which uses the composition of the
present invention containing a moisture absorbent and a barrier
resin, the air layer can be held while it is dry, the entry of
water from the outside can be prevented, and the dew point is
maintained at a low level.
[0102] Further, out of the above processes for producing the
insulating glass of the present invention, preferred is a process
which comprises the steps of inserting in advance the leading end
of the charging nozzle into the space between the peripheral
portions of a plurality of glass sheets, contacting a slide plate
provided at the top of the leading end portion of the nozzle to the
peripheral portions of the plurality of glass sheets, discharging a
sealing material from the leading end of the nozzle body at a
predetermined speed, and moving at least either one of the glass
sheets and the nozzle body relative to the other to charge the
sealing material into the space between the peripheral portions of
the glass sheets from the leading end of the nozzle. According to
this process, the sealing material can be efficiently paved in the
space between the peripheral portions of the glass sheets and the
sealing material can be leveled to obtain good appearance, and
efficient work can be carried out by reducing the number of working
steps.
[0103] Further, a production nozzle having a width for positioning
the interval between the plurality of glass sheets at the leading
end of the nozzle body and having a slide plate which slides along
the peripheral portions of the plurality of glass sheets at the top
of the leading end portion is preferably used in this process.
[0104] This process will be described hereinunder with reference to
FIGS. 2 to 6.
[0105] FIG. 2 is a perspective view of a nozzle 20 for producing
insulating glass which is inserted between the peripheral portions
of two glass sheets 1a and 1b which are opposed to each other in
parallel and held by an unshown jig or the like, FIG. 3 is a side
view of the production nozzle 20 and FIG. 4 is a plan view of the
production nozzle 20.
[0106] The production nozzle 20 has a passage 12 for discharging a
sealing material W in a nozzle body 11 having an L-shaped section,
at least the leading end portion 11a of the nozzle 20 has a width H
for positioning the interval h between a plurality of glass sheets
1a and 1b, and a slide plate 13 which slides along the peripheral
portions lx of the plurality of glass sheets 1a and 1b is
integrally provided on the upper surface of the leading end portion
11a.
[0107] The slide plate 13 projects along the discharge direction
(direction shown by an arrow Q) of the sealing material W, and a
guide plate 14 is formed at a lower end portion at the leading end
of the nozzle body 20 in such a manner that the guide plate 14 is
substantially parallel to the slide plate 13 and projects along the
discharge direction of the sealing material W. The rear end portion
11b of the nozzle body 11 is connected to an unshown sealing
material W feeder.
[0108] In the process for producing the insulating glass using this
production nozzle 20, as shown in FIG. 2, the leading end portion
11a of the nozzle body 11 is first inserted into the space between
the peripheral portions of two glass sheets 1a and 1b which are
opposed to each other in parallel at a predetermined interval and
held by an unshown jig or the like, and the sealing material W is
charged into the space between the peripheral portions of the glass
sheets from the leading end portion 11a of the nozzle at a
predetermined delivery pressure (for example, 15 MPa) or a
predetermined delivery rate (for example, 2,000 g/min) while at
least one of the glass sheets 1a and 1b and the nozzle body 11 is
moved relative to the other.
[0109] That is, the nozzle body 11 is moved along the peripheral
portions lx of the glass sheets 1a and 1b while the glass sheets 1a
and 1b are fixed at predetermined positions, or the glass sheets 1a
and 1b are moved at a predetermined speed while the nozzle body 11
is fixed. Or the nozzle body 11 and the glass sheets 1a and 1b are
moved in opposite directions at the same speed, while the sealing
material W is supplied into the discharge passage 12 in the nozzle
body 11 from the sealing material W feeder and charged into the
space between the peripheral portions of the glass sheets 1a and
1b.
[0110] When the sealing material W is charged while at least one of
the glass sheets 1a and 1b and the nozzle body 11 is moved relative
to the other, the slide plate 13 provided at the top of the leading
end portion of the nozzle body 11 is contacted to the peripheral
portions 1x of the plurality of glass sheets 1a and 1b and slid
(the sealing material Q is flatly pressed with a so-called knife),
whereby the sealing material W at the peripheral portions 1x of the
glass sheets 1a and 1b can be leveled, and at the same time, the
lower side of the sealing material in the space between the glass
sheets 1a and 1b can be leveled by the guide plate 14 provided at
the low end portion at the leading end of the nozzle body 11 as
shown in FIG. 5.
[0111] The sealing material used in this process preferably has an
MFR (melt flow rate) of 20 to 500 g/10 min.
[0112] According to the above process, the sealing material W can
be efficiently paved in the space between the peripheral portions
of the glass sheets 1a and 1b by charging the sealing material W
into the space between the peripheral portions of the glass sheets
1a and 1b from the leading end of the nozzle body 11 and leveled to
obtain good appearance, and efficient work can be carried out by
reducing the number of working steps.
[0113] In the above process, the method of charging the sealing
material W into the space between the two glass sheets 1a and 1b
has been described. However, the sealing material W can be charged
into spaces among two or more glass sheets by transforming and
processing the nozzle body 11.
EXAMPLE
[0114] The following examples are given to further illustrate the
thermoplastic elastomer composition, insulating glass, a process
for producing the insulating glass and a nozzle of the present
invention.
Examples 1 to 10 and Comparative Examples 1 and 2
[0115] Rubber shown in Table 1 was first pelletized by a rubber
pelletizer at about 100.degree. C., and then rubber, a matrix
resin, age resistor, filler and tackifier were dry blended in
blending ratios for Examples 1 to 10 and Comparative Examples 1 and
2, each of the resulting blends being injected into a double-screw
kneader to be melt kneaded. Thereafter, and a vulcanizing agent was
added from an intermediate injection port to carry out dynamic
vulcanization. At this point, the double-screw kneader was set at a
temperature of 230.degree. C. and a shearing speed of 1,000
s.sup.-1. Further, a moisture absorbent and an adhesive promoter
were injected from a final injection port of the double-screw
kneader.
[0116] A thermoplastic elastomer composition extruded into a strand
form from the double-screw kneader was cooled with water and
pelletized by a resin pelletizer.
[0117] Two square glass sheets having 300 mm per side were fixed in
parallel to each other at an interval of 6 mm, the above material
was paved in a space between the peripheral portions of the two
glass sheets while it was extruded from a nozzle and molded to form
insulating glass. The pellet was molded into a 30 .mu.m-thick film
by press molding as a sample used for the measurement of water
vapor permeability.
[0118] As for Examples 5 and 6, the thermoplastic elastomer
compositions prepared by the above method were dry blended with a
barrier resin immediately before extrusion molding for the
formation of insulating glass to form insulating glass by the same
method as described above.
Comparative Example 3
[0119] Insulating glass was produced in the same manner as in the
above Examples and Comparative Examples except that a vulcanizing
agent for rubber was not added during blending.
[0120] (1) Water Vapor Permeability
[0121] Six liters of water which is half the volume of a stainless
steel cup 60 shown in FIG. 6 is injected into the stainless steel
cup 60. An upper opening in the cup 60 is covered with a sample
sheet 63 (30 .mu.m in thickness) obtained by cutting the sample
sheet obtained in Examples 1 to 10 and Comparative Examples 1 to 3,
a sintered metal plate 64 is placed upon the top of the sample
sheet 63, and they are fastened together with a bolt 66 and a nut
67 through affixing member 65. This cup is left to stand in the
atmosphere at a temperature of 25.degree. C. and the total weight
of the cup is measured after 1 month. A reduction in the weight of
the cup per 24 hours is calculated and water vapor permeability is
calculated from the following expression water vapor permeability
[(g/24 hr.multidot.m.sup.2)]=M/(T.multidot.A) where A is a
permeation area [m.sup.2], T is a test time [day] and M is a weight
reduction [g].
[0122] (2) The Heat Distortion Temperature (Load Deflection
Temperature) of a Thermoplastic Resin used as a Continuous Phase is
Measured at 0.45 MPa in Accordance with JIS K 7207.
[0123] (3) Measurement of Dew Point
[0124] The dew point is measured after the end of the following
tests based on the test standards of classes I to III
(classification by acceleration durability) specified in JIS R
3209.
[0125] class I: 7 days of moisture resistance and light resistance
test +12 cycles of cooling and heating repetition test class II: 14
days of moisture resistance and light resistance test +24 cycles of
cooling and heating repetition test class III: 42 days of moisture
resistance and light resistance test +72 cycles of cooling and
heating repetition test In the table, .largecircle. indicates that
the dew point is -35.degree. C. or less, .DELTA. indicates that the
dew point is more than -35.degree. C. and less than -30.degree. C.
and .times. indicates that the dew point is -30.degree. C. or
more.
[0126] (4) Dislocation at the Time of Processing
[0127] One glass sheet of the insulating glass produced in Examples
and Comparative Examples is fixed and a load of 8 kg is placed upon
the other glass sheet to measure the amount of downward movement of
the glass sheet that is loaded at a temperature of 50.degree. C. A
glass sheet which is moved 0.5 mm or less a day is expressed by
.largecircle. and a glass sheet which is moved more than 0.5 mm is
expressed by .times..
[0128] As a result, the thermoplastic elastomer composition as in
Comparative Examples 1 and 2 which is produced from the rubber or
thermoplastic resin with more water vapor permeability has low
steam permeation resistance, and when such a thermoplastic
elastomer composition is used to form insulating glass, it has a
high dew point due to steam entry into the insulating glass through
the seal.
[0129] Further, in Comparative Example 3, the amount of rubber was
large and the value of .alpha..sub.1 exceeded 1, so that the
continuous phase formed by rubber and the dispersion phase formed
by the resin were constructed into layer. Since the rubber forming
the continues phase has a low heat distortion temperature, the
rubber could not bear the load of glass at the time of processing,
resulting in dislocation.
1TABLE 1 (part 1) Example 1 Example 2 Example 3 Example 4 Example 5
Example 6 Example 7 matrix resin PET HDPE 30 30 30 30 30 30 50 PS
rubber modified butyl rubber 70 70 70 70 70 70 50 (Br-IPMS) EPDM IR
barrier resin HDPE 10 20 vulcanizing system ZnO 3.5 3.5 3.5 3.5 3.5
3.5 2.5 zinc stearate 1.4 1.4 1.4 1.4 1.4 1.4 1 stearic acid 0.7
0.7 0.7 0.7 0.7 0.7 0.5 sulfur NS phenol bromide age resistor RD
1.4 1.4 1.4 1.4 1.4 1.4 1 moisture absorbing filler 50 50 50
zeolite 1 50 50 25 zeolite 2 50 filler tackifier adhesion promoter
(epoxysilane) talc 50 50 50 50 50 50 50 rosin ester 50 50 50 50 50
50 50 silane coupling agent 2 0.5 2 2 2 2 2 steam permeability of
resin*.sup.1 9 9 9 9 9 9 9 steam permeability of rubber*.sup.1 82
82 82 82 82 82 82 heat deformation temperature of 112 112 112 112
112 112 112 matrix resin (.degree. C.) .alpha..sub.1 0.93 0.93 0.93
0.93 0.93 0.93 0.40 .alpha..sub.1 -- -- -- -- 0.003 0.005 --
.eta..sub.d/.eta..sub.m -- -- -- -- 3.8 3.8 -- characteristic
properties of material 38 37 38 38 25 16 24 steam permeability
characteristic properties of multi-layer glass JIS R-3209 class 1
.smallcircle. .smallcircle. .smallcircle. .smallcircle.
.smallcircle. .smallcircle. .smallcircle. class 2 .smallcircle.
.smallcircle. .smallcircle. .smallcircle. .smallcircle.
.smallcircle. .smallcircle. class 3 .smallcircle. .DELTA. .DELTA.
.smallcircle. .smallcircle. .smallcircle. .smallcircle. dislocation
at the .smallcircle. .smallcircle. .smallcircle. .smallcircle.
.smallcircle. .smallcircle. .smallcircle. time of processing (part
2) Comparative Comparative Comparative Example 8 Example 9 Example
10 Example 1 Example 2 Example 3 matrix resin PET 30 HDPE 70 30 30
5 PS 30 rubber modified butyl rubber 30 70 95 (Br-IPMS) EPDM 70 70
70 IR barrier resin HDPE vulcanizing system ZnO 1.5 3.5 3.5 3.5 3.5
zinc stearate 0.6 1.4 0.7 1.4 stearic acid 0.3 0.7 0.7 2.1 0.7
sulfur 1.4 Ns 0.7 phenol bromide 8.4 age resistor RD 0.6 1.4 1.4
1.4 1.4 2 moisture absorbing filler zeolite 1 50 50 50 50 50 50
zeolite 2 filler tackifier adhesion promoter (epoxysilane) talc 50
50 50 50 50 50 rosin ester 50 50 50 50 50 50 silane coupling agent
2 2 2 2 2 2 steam permeability of resin*.sup.1 9 9 10 9 840 9 steam
permeability of rubber*.sup.1 82 157 82 1720 157 82 heat
deformation temperature of 112 112 191 112 88 -- matrix resin
(.degree. C.) .alpha..sub.1 0.03 0.93 0.98 0.90 0.89 7.6
.alpha..sub.1 -- -- -- -- -- -- .eta..sub.d/.eta..sub.m -- -- -- --
-- -- characteristic properties of 16 51 39 100 319 82 material
steam permeability characteristic properties of multi-layer glass
JIS R-3209 class 1 .smallcircle. .smallcircle. .smallcircle.
.smallcircle. .DELTA. .smallcircle. class 2 .smallcircle.
.smallcircle. .smallcircle. .DELTA. .smallcircle. class 3
.smallcircle. .smallcircle. .smallcircle. x x .smallcircle.
dislocation at the .smallcircle. .smallcircle. .smallcircle.
.smallcircle. .smallcircle. x time of processing *.sup.1(g/m.sub.2
.multidot. 24 h)
Examples 11 and 12
[0130] The thermoplastic elastomer composition of Example 1 as an
inner layer and maleic acid modified EEA or ethylene-vinyl acetate
saponified product as an outer layer were co-extruded at about
200.degree. C. to form a spacer and insulating glass was produced
in the same manner as in Example 1. The thickness of the obtained
adhesive layer was about 20 .mu.m.
[0131] The characteristic properties of the insulating glass were
measured and evaluated in the same manner as in Example 1. Results
are shown in Table 2.
Example 13
[0132] A primer was prepared by dissolving an ethylene-vinyl
acetate saponified product in toluene in a solid content of 10%
This primer was coated on a glass sheet with a brush and left to
stand for 15 minutes and then insulating glass was produced in the
same manner as in Example 1. Thereafter, the characteristic
properties of the insulating glass were evaluated in the same
manner as in Example 1. Results are shown in Table 2.
2 TABLE 2 Example 11 Example 12 Example 13 thermoplastic material
of material of material of elastomer Example 1 Example 1 Example 1
composition layer maleic acid ethylene-vinyl ethylene-vinyl
adhesive layer modified EEA actetate actetate saponified saponified
product product coating of double-layer double-layer primer coating
adhesive coextrusion coextrusion molding molding characteristic
properties of insulating glass JIS R-3209 class 1 .largecircle.
.largecircle. .largecircle. class 2 .largecircle. .largecircle.
.largecircle. class 3 .largecircle. .largecircle. .largecircle.
dislocation .DELTA. .largecircle. .largecircle. at the time of
.largecircle. .largecircle. .largecircle. processing
[0133] <components in tables>
[0134] PET: J125 by Mitsui PET Co., Ltd.
[0135] HDPE (matrix): Hizex 2100J by Mitsui Chemical Co., Ltd.
[0136] PS: Stylon 666 R by Asahi Chemical Industry Co., Ltd.
[0137] modified butyl rubber: Exxpro89-4 by Eccson Co., Ltd.
[0138] EPDM: EPT 3045 by Mitsui Chemical Co., Ltd.
[0139] IR: Nipole 2200 by Nippon Zeon Co., Ltd.
[0140] HDPE (barrier resin): Ryubmer 5000 by Mitsui Chemical Co.,
Ltd.
[0141] ZnO: zinc oxide No. 3 by Seido Kagaku Co., Ltd.
[0142] zinc stearate: zinc stearate by Seido Kagaku Co., Ltd.
[0143] stearic acid: bead stearic acid by NOF Corporation
[0144] sulfur: powdery sulfur by Karuizawa Seirensho Co., Ltd.
[0145] NS: Nokusera NS by Ohuchi Shinko Kagaku Co., Ltd.
[0146] phenol bromide: Tackirol 250-1 by Taoka Kagaku Co., Ltd.
[0147] RD: Antigen-RD-F by Sumitomo Chemical Co., Ltd.
[0148] zeolite 1: Zeoram 4A by Tosoh Corporation
[0149] zeolite 2: Zeoram 3 by Tosoh Corporation
[0150] talc: Talc F by Nippon Talc Co., Ltd.
[0151] rosin ester: Pensel AD by Arakawa Kagaku Co., Ltd.
[0152] silane coupling agent: A-174 by Nippon Unicar Co., Ltd.
[0153] maleic acid modified EEA: AR-201 by Mitsui-Dupont
Polychemical Co., Ltd.
[0154] ethylene-vinyl acetate saponified product: Dumiran C1550 by
Takeda Chemical Industries, Ltd.
Examples 14 to 16 and Comparative Example 4
[0155] A sealing material was produced according to formulations
shown in Table 3 below in the same manner as in Example 1. The
steam permeabilities of the used resin and the used rubber were 9
g/24 hr.multidot.m.sup.2 and 82 g/24 hr.multidot.m, respectively,
and the water vapor permeability of the produced thermoplastic
elastomer composition for sealing the insulating glass was 38 g/24
hr.multidot.m.sup.2.
3 TABLE 3 Example matrix resin HDPE 30 Rubber modified butyl rubber
70 vulcanizing system ZnO 3.5 zinc stearate 1.4 stearic acid 0.7
Age resistor RD 1.4 moisture absorbing filler zeolite 1 50 filler
talc 50 tackifier rosin ester 50 adhesive promoter ethylene-vinyl
acetate 10 copolymer saponified product
[0156] The sealing material produced by the above method had an MFR
at 230.degree. C. of 100 g/min. The produced sealing material
pellets were injected into a simplified extruder, a nozzle was
inserted into a space between two glass sheets at 230.degree. C.,
and the sealing material was charged into the space at a delivery
rate of 2,000 g/min to produce the following insulating glass
production of insulating glass
[0157] size of glass sheet
[0158] thickness of glass sheet
[0159] type of glass sheet float glass
[0160] interval between glass sheets h: 6 mm
[0161] size of nozzle
[0162] H: 5 mm
[0163] L: 15 mm
[0164] l: 5 mm
[0165] S.sub.1: 5 mm
[0166] S.sub.2: 2 mm
[0167] Table 4 below shows experimental results obtained by the
comparison of the leveled surfaces of the sealing material W by the
shape of the discharge port of the nozzle body 11 and adhesion to
the surface of glass between Examples 14, 15 and 16 of the present
invention and the prior art (Comparative Example 4).
[0168] As obvious from the experimental results, it has been found
that the upper and lower leveled surfaces of the sealing material
are better and the adhesion of the sealing material to glass is
better when the slide plate and the guide plate are provided at the
leading end of the nozzle body 11.
4 TABLE 4 Comparative Example 14 Example 15 Example 16 Example 4
shape of discharge port of nozzle no sliding portion upper and
lower upper surface Smooth Smooth almost smooth cut portion of
leveled .circleincircle. .circleincircle. .smallcircle. glass is
not flat surfaces x lower surface Smooth almost smooth almost
smooth becomes wavy .circleincircle. .smallcircle. .smallcircle. x
adhesion to glass surface adhered to almost adhered almost adhered
partly not entire surface to entire to entire adhered
.circleincircle. surface surface .smallcircle. .smallcircle.
.DELTA.
[0169] The thermoplastic elastomer composition of the present
invention has excellent steam permeation resistance and heat
distortion resistance and is suitable for use as the raw material
of a sealing material and spacer for insulating glass when a
thermoplastic resin and rubber having a low water vapor
permeability are used and the thermoplastic resin is used as a
continuous phase.
[0170] The insulating glass of the present invention which uses the
thermoplastic elastomer composition of the present invention as a
sealing material and spacer has excellent heat distortion
resistance and an air layer having a sufficiently low dew point.
Further, the insulating glass of the present invention can be
produced very easily because the number of production steps is much
smaller than that of the conventional insulating glass.
[0171] Further, according to the process of the present invention,
since a sealing material is charged into a space between the
peripheral portions of glass sheets using a production nozzle
having a slide plate which slides along the peripheral portions of
a plurality of glass sheets at the top of the leading end portion
of the nozzle body as described above, the sealing material can be
efficiently paved in the space between the peripheral portions of
the glass sheets and can be directly adhered to the glass sheets,
and the sealing material at the peripheral portions of the glass
sheets can be leveled to obtain good appearance, and efficient work
can be carried out by reducing the number of working steps.
[0172] Further, the production nozzle of the present invention can
be advantageously used in this production process.
* * * * *