U.S. patent application number 15/769335 was filed with the patent office on 2020-02-13 for active energy ray curable hot melt silicone composition, cured product thereof, and method of producing film.
The applicant listed for this patent is Dow Corning Toray Co., Ltd.. Invention is credited to Ryota DOGEN, Haruna YAMAZAKI, Shin YOSHIDA, Makoto YOSHITAKE.
Application Number | 20200048463 15/769335 |
Document ID | / |
Family ID | 58556884 |
Filed Date | 2020-02-13 |
United States Patent
Application |
20200048463 |
Kind Code |
A9 |
DOGEN; Ryota ; et
al. |
February 13, 2020 |
ACTIVE ENERGY RAY CURABLE HOT MELT SILICONE COMPOSITION, CURED
PRODUCT THEREOF, AND METHOD OF PRODUCING FILM
Abstract
Disclosed is an active energy ray curable hot melt silicone
composition that is non-flowable at 25.degree. C. and has a
viscosity of 1,000 Pas or less at 100.degree. C. The active energy
ray curable hot melt silicone composition comprises: (A) a mixture
of (A1) an organopolysiloxane having an aliphatic unsaturated
bond-containing organic group and (A2) an organopolysiloxane
optionally having an aliphatic unsaturated bond-containing organic
group, (B) a compound having at least two mercapto groups in a
molecule, and (C) a photoradical initiator. A cured product and a
method of making a film are also disclosed.
Inventors: |
DOGEN; Ryota; (Chiba,
JP) ; YAMAZAKI; Haruna; (Chiba, JP) ; YOSHIDA;
Shin; (Chiba, JP) ; YOSHITAKE; Makoto; (Chiba,
JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Dow Corning Toray Co., Ltd. |
Tokyo |
|
JP |
|
|
Prior
Publication: |
|
Document Identifier |
Publication Date |
|
US 20180305547 A1 |
October 25, 2018 |
|
|
Family ID: |
58556884 |
Appl. No.: |
15/769335 |
Filed: |
October 12, 2016 |
PCT Filed: |
October 12, 2016 |
PCT NO: |
PCT/JP2016/004557 PCKC 00 |
371 Date: |
April 18, 2018 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
B29K 2083/00 20130101;
B29C 2035/0827 20130101; C08J 5/18 20130101; B29K 2105/0097
20130101; C08G 77/28 20130101; C08G 75/045 20130101; C09J 183/04
20130101; C08L 83/08 20130101; B29C 43/30 20130101; C08G 77/16
20130101; B29C 35/0805 20130101; C08G 81/00 20130101; B29C 43/305
20130101; C08J 2483/08 20130101; C08K 5/0025 20130101; C08G 77/20
20130101; C08J 2383/04 20130101; C08L 83/00 20130101; C09J 183/04
20130101; C08K 5/0025 20130101; C08L 83/00 20130101; C08L 83/00
20130101 |
International
Class: |
C08L 83/08 20060101
C08L083/08; C08J 5/18 20060101 C08J005/18; B29C 43/30 20060101
B29C043/30; B29C 35/08 20060101 B29C035/08 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 19, 2015 |
JP |
2015-205945 |
Claims
1. An active energy ray curable hot melt silicone composition that
is non-flowable at 25.degree. C. and has a viscosity of 1,000 Pas
or less at 100.degree. C., comprising: (A) 100 parts by mass of an
organopolysiloxane mixture containing from 10 to 50% by mass of
component (A-1) below and from 50 to 90% by mass of component
(A-2): (A-1) an organopolysiloxane represented by the following
average unit formula:
(R.sup.1.sub.3SiO.sub.1/2).sub.a(R.sup.1.sub.2SiO.sub.2/2).sub.b(R.sup.1S-
iO.sub.3/2).sub.c(SiO.sub.4/2).sub.d wherein, each R.sup.1
independently is a methyl group, a phenyl group, or an organic
group having an aliphatic unsaturated bond, with the proviso that
from 0.01 to 1 mol % of all R.sup.1 are organic groups having an
aliphatic unsaturated bond and 90 mol % or greater of the other
R.sup.1 are methyl groups, a is a number from 0 to 0.05, b is a
number from 0.9 to 1, c is a number from 0 to 0.03, d is a number
from 0 to 0.03, and the sum of a to d is 1, (A-2) an
organopolysiloxane represented by the following average unit
formula:
(R.sup.2.sub.3SiO.sub.1/2).sub.e(R.sup.2.sub.2SiO.sub.2/2).sub.f(R.sup.2S-
iO.sub.3/2).sub.g(SiO.sub.4/2).sub.h(HO.sub.1/2).sub.i wherein,
each R.sup.2 independently is a methyl group, a phenyl group, or an
organic group having an aliphatic unsaturated bond, with the
proviso that from 0 to 10 mol % of all R.sup.2 are organic groups
having an aliphatic unsaturated bond and 90 mol % or greater of the
other R.sup.2 are methyl groups, e is a number from 0.3 to 0.7, f
is a number from 0 to 0.05, g is a number from 0 to 0.05, h is a
number from 0.3 to 0.7, i is a number from 0 to 0.05, and the sum
of e to h is 1; (B) a compound having at least two mercapto groups
in a molecule, in an amount such that an amount of the mercapto
groups in component (B) is from 0.5 to 5.0 mol per 1 mol of the
total of the organic groups having an aliphatic unsaturated bond in
component (A); and (C) a photoradical initiator in an amount that
accelerates curing of the composition by an active energy ray.
2. The active energy ray curable hot melt silicone composition
according to claim 1, wherein the organic group having an aliphatic
unsaturated bond in component (A) is an alkenyl group, an
alkenyloxyalkyl group, an acryloxyalkyl group, or a
methacryloxyalkyl group.
3. The active energy ray curable hot melt silicone composition
according to claim 1, wherein component (B) is an
organopolysiloxane having at least two mercapto groups in a
molecule.
4. The active energy ray curable hot melt silicone composition
according to claim 1, further comprising (D) a radical scavenger in
an amount of from 0.0001 to 1 part(s) by mass per 100 parts by mass
of the total amount of components (A) to (C).
5. The active energy ray curable hot melt silicone composition
according to claim 1, further comprising (E) a compound containing
at least one type of metal atom selected from the group consisting
of V, Ta, Nb, and Ce in an amount so that the metal atom in this
component is from 5 to 2,000 ppm in terms of mass units relative to
the total amount of components (A) to (C).
6. A cured product formed by curing the active energy ray curable
hot melt silicone composition of claim 1.
7. The cured product according to claim 6, wherein the cured
product is in a film form.
8. The cured product according to claim 6, wherein a surface
thereof is adhesive.
9. A method of producing a film comprising: sandwiching the active
energy ray curable hot melt silicone composition described in claim
1 in between two releasable transparent resin films, forming to a
fixed thickness by thermal compression or heating roller, and then
irradiating the composition with an active energy ray to produce
the film.
10. A film formed in accordance with the method of claim 9.
11. The film according to claim 10 having a thickness of from 5
.mu.m to 5 mm.
12. The cured product according to claim 7 having a thickness of
from 5 .mu.m to 5 mm.
13. The active energy ray curable hot melt silicone composition
according to claim 5, wherein component (E) comprises an
organopolysiloxane containing at least one type of metal atom
selected from the group consisting of V, Ta, Nb, and Ce.
14. The cured product according to claim 6 as a layer in an image
display device, solar cell module, or touchscreen.
Description
TECHNICAL FIELD
[0001] The present invention relates to an active energy ray
curable hot melt silicone com-position, cured product of the
composition, and a method of producing a film formed from the cured
product.
BACKGROUND ART
[0002] Heat curable, moisture curable, or active energy ray curable
silicone compositions have been used in a wide range of industrial
fields since these silicone compositions cure to form cured
products having excellent heat resistance, cold resistance,
electrical insulating properties, weather resistance, water
repellency, and transparency. In particular, the cured products
thereof are less likely to be discolored compared to other organic
materials, and the cured products cause less degradation of
physical properties. Therefore, the cured products are suitable as
optical materials.
[0003] In recent years, transparent materials have been used in
image display devices, solar cell modules, touchscreens, and the
like. For example, in an image display device, use of transparent
resins, such as acrylic resins, epoxy resins, urethane resins, and
silicone resins, in an intermediate layer arranged in between an
image display part and a protective part has been proposed to
prevent unevenness of display and lowering of brightness due to
light reflection caused in between the image display part and the
protective part (see Patent Document 1). As such silicone resins,
for example, curable silicone compositions in liquid or film form
having a pressure sensitive adhesion have been proposed (see Patent
Documents 2 and 3).
[0004] The film having pressure sensitive adhesion is produced by
coating with a liquid curable silicone composition and then curing;
however, there are problems in that a thick film is difficult to
produce and that a film having a uniform thickness is difficult to
produce.
CITATION LIST
Patent Literature
[0005] Patent Document 1: Japanese Unexamined Patent Application
Publication No. 2003-029644A
[0006] Patent Document 2: Japanese Unexamined Patent Application
Publication No. 2006-290960A
[0007] Patent Document 3: Japanese Unexamined Patent Application
Publication No. 2013-253179A
SUMMARY OF INVENTION
Technical Problem
[0008] An object of the present invention is to provide an active
energy ray curable hot melt silicone composition that is
non-flowable at room temperature, that melts by heating, that can
be formed into a desired shape, and that is cured by an active
energy ray, such as an ultraviolet ray, while the shape is
maintained. Furthermore, another object of the present invention is
to provide a cured product having excellent heat resistance and
light resistance, and to provide a method of producing a film
having such characteristics.
Solution to Problem
[0009] The active energy ray curable hot melt silicone composition
of the present invention is non-flowable at 25.degree. C. and has a
viscosity of 1,000 Pas or less at 100.degree. C., and
comprises:
[0010] (A) 100 parts by mass of an organopolysiloxane mixture
containing from 10 to 50% by mass of component (A-1) below and from
50 to 90% by mass of component (A-2) below:
[0011] (A-1) an organopolysiloxane represented by the following
average unit formula:
(R.sup.1.sub.3SiO.sub.1/2).sub.a(R.sup.1.sub.2SiO.sub.2/2).sub.b(R.sup.1-
SiO.sub.3/2).sub.c(SiO.sub.4/2).sub.d
[0012] wherein, each R.sup.1 is a methyl group, phenyl group, or
organic group having an aliphatic unsaturated bond, from 0.01 to 1
mol % of all R.sup.1 are the organic groups and 90 mol % or greater
of the other R.sup.1 are the methyl groups, a is a number from 0 to
0.05, b is a number from 0.9 to 1, c is a number from 0 to 0.03, d
is a number from 0 to 0.03, and a total of a to d is 1,
[0013] (A-2) an organopolysiloxane represented by the following
average unit formula:
(R.sup.2.sub.3SiO.sub.1/2).sub.e(R.sup.2.sub.2SiO.sub.2/2).sub.f(R.sup.2-
SiO.sub.3/2).sub.g(SiO.sub.4/2).sub.h(HO.sub.1/2).sub.i
[0014] wherein, each R.sup.2 is a methyl group, phenyl group, or
organic group having an aliphatic unsaturated bond, from 0 to 10
mol % of all R.sup.2 are the organic groups and 90 mol % or greater
of the other R.sup.2 are the methyl groups, e is a number from 0.3
to 0.7, f is a number from 0 to 0.05, g is a number from 0 to 0.05,
h is a number from 0.3 to 0.7, i is a number from 0 to 0.05, and a
total of e to h is 1;
[0015] (B) a compound having at least two mercapto groups in a
molecule, in an amount such that an amount of the mercapto group in
this component is from 0.5 to 5.0 mol per 1 mol total of the
organic group having an aliphatic unsaturated bond in component
(A); and
[0016] (C) a photoradical initiator in an amount that accelerates
curing of the composition by an active energy ray.
[0017] The organic group having an aliphatic unsaturated bond in
component (A) is preferably an alkenyl group, alkenyloxyalkyl
group, acryloxyalkyl group, or methacryloxyalkyl group.
[0018] Component (B) is preferably an organopolysiloxane having at
least two mercapto groups in a molecule.
[0019] The present composition preferably further comprises (D) a
radical scavenger in an amount of 0.0001 to 1 part by mass per 100
parts by mass total of components (A) to (C).
[0020] The present composition preferably further comprises (E) a
compound containing at least one type of metal atom selected from
the group consisting of V, Ta, Nb, and Ce, in an amount such that
the metal atom in this component is from 5 to 2,000 ppm in terms of
mass units relative to the total amount of components (A) to
(C).
[0021] The cured product of the present invention is formed by
curing the composition described above, and may be in a film form,
and the surface thereof may be adhesive.
[0022] The method of producing a film of the present invention
comprises: sandwiching the composition described above in between
two releasable transparent resin films, forming to a fixed
thickness by thermal compression or heating roller, and then
irradiating the composition with an active energy ray.
Effect of Invention
[0023] The active energy ray curable hot melt silicone composition
of the present invention can be formed into a desired shape when
being melted by heating, and rapidly cures by irradiating with a
high energy ray, such as an ultraviolet ray, while the shape is
maintained. Furthermore, the cured product of the present invention
exhibits excellent heat resistance and light resistance.
Furthermore, the method of producing the film of the present
invention can produce a film having a precisely controlled film
thickness and having excellent transferability.
DETAILED DESCRIPTION OF THE INVENTION
Active Energy Ray Curable Hot Melt Silicone Composition
[0024] Component (A) is a base compound of the present composition
and is an organopolysiloxane mixture containing from 10 to 50% by
mass of component (A-1) below and from 50 to 90% by mass of
component (A-2) below.
[0025] Component (A-1) is an organopolysiloxane represented by the
following average unit formula:
(R.sup.1.sub.3SiO.sub.1/2).sub.a(R.sup.1.sub.2SiO.sub.2/2).sub.b(R.sup.1-
SiO.sub.3/2).sub.c(SiO.sub.4/2).sub.d
[0026] In the formula, each R.sup.1 is a methyl group, phenyl
group, or organic group having an aliphatic unsaturated bond.
Examples of this organic group include alkenyl groups, such as a
vinyl group, allyl group, butenyl group, pentenyl group, and
hexenyl group; alkenyloxyalkyl groups, such as an allyloxymethyl
group and 3-allyloxypropyl group; acryloxyalkyl groups or
methacryloxyalkyl groups, such as a methacryloxymethyl group,
3-methacryloxypropyl group, acryloxymethyl group, and
3-acryloxypropyl group; and nitrogen atom-containing organic
groups, such as N-allylamino propyl group, 3-acrylamido propyl
group, and 3-methacrylamido propyl group. The organic group is
preferably an alkenyl group, alkenyloxyalkyl group, acryloxyalkyl
group, or methacryloxyalkyl group. Furthermore, from 0.01 to 1 mol
%, and preferably from 0.05 to 0.5 mol %, of all R.sup.1 in
component (A-1) are the organic groups. This is because curing can
be performed sufficiently by irradiating the obtained composition
with an active energy ray when the proportion of the organic group
is greater than or equal to the lower limit of the range described
above, and meanwhile, mechanical strength of the resulting cured
product is enhanced when the proportion is less than or equal to
the upper limit of the range described above. Furthermore, 90 mol %
or greater, and preferably 95 mol % or greater, of R.sup.1 other
than the organic groups described above are methyl groups. This is
because coloration of the cured product is less likely to
occur.
[0027] In the formula, a is a number from 0 to 0.05, b is a number
from 0.9 to 1, c is a number from 0 to 0.03, d is a number from 0
to 0.03, and a total of a to d is 1; and preferably a is a number
from 0 to 0.03, b is a number from 0.97 to 1, c is a number from 0
to 0.02, d is a number from 0 to 0.02, and a total of a to d is 1.
This is because when a to d are within the range described above,
the mechanical strength of the resulting cured product is
enhanced.
[0028] Examples of component (A-1) include organopolysiloxanes
represented by the following average unit formulas. Note that, in
the formulas, Me represents a methyl group, Ph represents a phenyl
group, Vi represents a vinyl group, and Map represents a
3-methacryloxypropyl group.
(Me.sub.2ViSiO.sub.1/2).sub.0.012(Me.sub.2SiO.sub.2/2).sub.0.988
(Me.sub.2ViSiO.sub.1/2).sub.0.007(Me.sub.2SiO.sub.2/2).sub.0.993
(Me.sub.2ViSiO.sub.1/2).sub.0.004(Me.sub.2SiO.sub.2/2).sub.0.996
(Me.sub.2MapSiO.sub.1/2).sub.0.012(Me.sub.2SiO.sub.2/2).sub.0.988
(Me.sub.2MapSiO.sub.1/2).sub.0.007(Me.sub.2SiO.sub.2/2).sub.0.993
(Me.sub.2MapSiO.sub.1/2).sub.0.004(Me.sub.2SiO.sub.2/2).sub.0.996
Me.sub.3SiO.sub.1/2).sub.0.007(Me.sub.2SiO.sub.2/2).sub.0.983(MeViSiO.sub-
.2/2).sub.0.010
(Me.sub.3SiO.sub.1/2).sub.0.01(Me.sub.2SiO.sub.2/2).sub.0.96(MeViSiO.sub.-
2/2).sub.0.01(MeSiO.sub.3/2).sub.0.02
(Me.sub.2ViSiO.sub.1/2).sub.0.005(Me.sub.2SiO.sub.2/2).sub.0.895(MePhSiO.-
sub.2/2).sub.0.100
Me.sub.3SiO.sub.1/2).sub.0.007(Me.sub.2SiO.sub.2/2).sub.0.983(MeMapSiO.su-
b.2/2).sub.0.010
[0029] Furthermore, examples of component (A-1) include
organopolysiloxanes represented by the following formulas. Note
that, in the formulas, Me, Vi, and Map are as described above.
(MeViSiO.sub.2/2).sub.3 (MeViSiO.sub.2/2).sub.4
(MeViSiO.sub.2/2).sub.5 (MeMapSiO.sub.2/2).sub.4
[0030] Component (A-2) is an organopolysiloxane represented by the
following average unit formula:
(R.sup.2.sub.3SiO.sub.1/2).sub.e(R.sup.2.sub.2SiO.sub.2/2).sub.f(R.sup.2-
SiO.sub.3/2).sub.g(SiO.sub.4/2).sub.h(HO.sub.1/2).sub.i.
[0031] In the formula, each R.sup.2 is a methyl group, phenyl
group, or organic group having an aliphatic unsaturated bond.
Examples of the organic group include the same organic groups
exemplified for R.sup.1 above. The organic group is preferably an
alkenyl group, alkenyloxyalkyl group, acryloxyalkyl group, or
methacryloxyalkyl group. Furthermore, from 0 to 10 mol %, and
preferably from 0.05 to 5 mol %, of all R.sup.2 in component (A-2)
are the organic groups. This is because curing can be performed
sufficiently by irradiating the obtained composition with an active
energy ray when the proportion of the organic group is greater than
or equal to the lower limit of the range described above, and
meanwhile, mechanical strength of the resulting cured product is
enhanced when the proportion is less than or equal to the upper
limit of the range described above. Furthermore, 90 mol % or
greater, and preferably 95 mol % or greater, of R.sup.2 other than
the organic groups described above are methyl groups. This is
because coloration of the cured product is less likely to
occur.
[0032] In the formula, e is a number from 0.3 to 0.7, f is a number
from 0 to 0.05, g is a number from 0 to 0.05, h is a number from
0.3 to 0.7, i is a number from 0 to 0.05, and a total of e to h is
1; and preferably e is a number from 0.4 to 0.6, f is a number from
0 to 0.03, g is a number from 0 to 0.03, h is a number from 0 to
0.03, i is a number from 0 to 0.03, and a total of e to h is 1.
This is because when e to i are within the range described above,
the mechanical strength of the resulting cured product is
enhanced.
[0033] Examples of component (A-2) include organopolysiloxanes
represented by the following average unit formulas. Note that, in
the formulas, Me, Ph, Vi, and Map are as described above.
(Me.sub.2ViSiO.sub.1/2).sub.0.02(Me.sub.3SiO.sub.1/2).sub.0.43(SiO.sub.4/-
2).sub.0.55(HO.sub.1/2).sub.0.01
(MeViPhSiO.sub.1/2).sub.0.05(Me.sub.3SiO.sub.1/2).sub.0.40(SiO.sub.4/2).s-
ub.0.55(HO.sub.1/2).sub.0.02
(Me.sub.2MapSiO.sub.1/2).sub.0.02(Me.sub.3SiO.sub.1/2).sub.0.43(SiO.sub.4-
/2).sub.0.55(HO.sub.1/2).sub.0.01
(Me.sub.2ViSiO.sub.1/2).sub.0.06(Me.sub.3SiO.sub.1/2).sub.0.44(SiO.sub.4/-
2).sub.0.50(HO.sub.1/2).sub.0.01
(Me.sub.2ViSiO.sub.1/2).sub.0.06(Me.sub.3SiO.sub.1/2).sub.0.44(SiO.sub.4/-
2).sub.0.50(HO.sub.1/2).sub.0.01
(Me.sub.2ViSiO.sub.1/2).sub.0.10(Me.sub.3SiO.sub.1/2).sub.0.40(SiO.sub.4/-
2).sub.0.50(HO.sub.1/2).sub.0.01
(Me.sub.2MapSiO.sub.1/2).sub.0.02(Me.sub.3SiO.sub.1/2).sub.0.40(Me.sub.2S-
iO.sub.2/2).sub.0.05(SiO.sub.4/2).sub.0.53(HO.sub.1/2).sub.0.01
(Me.sub.2ViSiO.sub.1/2).sub.0.01(Me.sub.3SiO.sub.1/2).sub.0.44(PhSiO.sub.-
3/2).sub.0.05(SiO.sub.4/2).sub.0.50(HO.sub.1/2).sub.0.01
[0034] In component (A), the content of component (A-1) is from 10
to 50% by mass, and preferably from 15 to 45% by mass or from 20 to
40% by mass. This is because, when the content of component (A-1)
is within the range described above, excellent hot melt properties
of the obtained composition is achieved, and mechanical strength of
the resulting cured product is enhanced.
[0035] Component (B) is a curing agent of the present composition,
and is a compound having at least two mercapto groups in a
molecule. Examples of component (B) include o-, m-, or
p-xylenedithiol, ethyleneglycol bisthioglycolate, butanediol
bisthioglycolate, hexanediol bisthioglycolate, ethyleneglycol
bisthiopropionate, butanediol bisthiopropionate, trimethylolpropane
tristhiopropionate, pentaerythritol tetrakisthiopropionate,
trihydroxyethyl triisocyanuric acid tristhiopropionate, and
mercapto group-containing organopolysiloxanes. From the perspective
of exhibiting excellent miscibility with component (A) as well as
from the perspective of enhancing heat resistance and light
resistance of the resulting cured product, a mercapto
group-containing organopolysiloxane is preferable. Examples of the
mercapto group in this organopolysiloxane include mercaptoalkyl
groups, such as a mercaptopropyl group and mercaptobutyl group.
Furthermore, examples of the groups other than the mercaptoalkyl
group in this organopolysiloxane include alkyl groups, such as a
methyl group, ethyl group, and propyl group; aryl groups, such as a
phenyl group, tolyl group, and xylyl group; aralkyl groups, such as
a benzyl group and phenethyl group.
[0036] Examples of the mercapto group-containing organopolysiloxane
include straight-chain organopolysiloxanes represented by the
following general formula:
R.sup.3.sub.3SiO(R.sup.3.sub.2SiO).sub.mSiR.sup.3.sub.3
[0037] or cyclic organopolysiloxanes represented by the following
general formula:
(R.sup.3.sub.2SiO).sub.n
[0038] In the formulas, R.sup.3 may be the same or different and
represent an alkyl group, aryl group, aralkyl group, or
mercaptoalkyl group; however, at least two of R.sup.3 in a molecule
represent the mercaptoalkyl groups. Examples of the alkyl group of
R.sup.3 include a methyl group, ethyl group, and propyl group.
Examples of the aryl group of R.sup.3 include a phenyl group, tolyl
group, and xylyl group. Examples of the aralkyl group of R.sup.3
include a benzyl group and phenethyl group. Furthermore, examples
of the mercaptoalkyl group of R.sup.3 include a mercaptopropyl
group and mercaptobutyl group.
[0039] Furthermore, in the formula, m is an integer of 1 or
greater, and preferably an integer of 5 to 100 or an integer of 5
to 50. This is because excellent hot melt properties of the
obtained composition is achieved, and mechanical strength of the
resulting cured product is enhanced.
[0040] Furthermore, in the formula, n is an integer of 3 or
greater, and preferably an integer of 4 to 20. This is because
excellent hot melt properties of the obtained composition is
achieved, and mechanical strength of the resulting cured product is
enhanced.
[0041] Examples of the organopolysiloxane of component (B) include
organopolysiloxanes represented by the following formulas. Note
that, in the formulas, Me is as described above.
Me.sub.2(HSC.sub.3H.sub.6)SiO(Me.sub.2SiO).sub.10SiMe.sub.2(C.sub.3H.sub.-
6SH) [Me(HSC.sub.3H.sub.6)SiO].sub.4
Me.sub.3SiO(Me.sub.2SiO).sub.5[Me(HSC.sub.3H.sub.6)SiO].sub.5SiMe.sub.3
[0042] The content of component (B) is an amount so that an amount
of the mercapto groups in this component is from 0.5 to 5.0 mol,
and preferably from 0.8 to 2.0 mol, per 1 mol of the total of
organic groups having an aliphatic unsaturated bond in component
(A). This is because curing can be performed sufficiently by
irradiating the obtained composition with an active energy ray when
the content of component (B) is greater than or equal to the lower
limit of the range described above, and meanwhile, mechanical
strength of the resulting cured product is enhanced when the
content is less than or equal to the upper limit of the range
described above.
[0043] Component (C) is a photoradical initiator to initiate curing
reaction by irradiating the present composition with an active
energy ray. Examples of component (C) include acetophenone,
propiophenone, benzophenone, 2-hydroxy-2-methylpropiophenone,
2,2-dimethoxy-1,2-diphenylethan-1-one,
1-hydroxycyclohexylphenylketone,
1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one,
2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl--
propan-1-one,
2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one,
2-benzyl-2-dimethylamino-(4-morpholinophenyl)-butanone-1,
2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]--
1-butano ne, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide,
bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 1,2-octanedione,
1-[4-(phenylthio)-2-(O-benzoyloxime)]ethanone,
1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime),
ethyl-4-dimethylaminobenzoate,
2-ethylhexyl-4-dimethylaminobenzoate,
bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide,
benzoyl peroxide, cumene peroxide, and mixtures of two or more
types of these.
[0044] The content of component (C) is an amount that accelerates
curing performed by irradiating the present composition with an
active energy ray, and is preferably from 0.1 to 15 parts by mass
or from 0.1 to 10 parts by mass per 100 parts by mass of the total
amount of components (A) and (B). This is because the obtained
composition can be cured sufficiently when the content of component
(C) is greater than or equal to the lower limit of the range
described above, and meanwhile, heat resistance and light
resistance of the resulting cured product is enhanced when the
content is less than or equal to the upper limit of the range
described above.
[0045] The present composition may comprise, as an optional
component, (D) a radical scavenger and (E) a compound containing at
least one type of metal atom selected from the group consisting of
V, Ta, Nb, and Ce as long as the object of the present invention is
not impaired.
[0046] The radical scavenger of component (D) is effective to
enhance storage stability of the present composition, and examples
thereof include quinones, such as hydroquinone, hydroquinone
monomethyl ether, benzoquinone, p-tert-butylcatechol,
2,6-di-tert-butyl-4-methylphenol, and pyrogallol. The content of
component (D) is not limited in the present composition, however,
the content is preferably from 0.0001 to 1 part by mass per 100
parts by mass of total components (A) to (C).
[0047] Examples of the compound containing at least one type of
metal atom selected from the group consisting of V, Ta, Nb, and Ce
of component (E) include carboxylic acid salts of the metals
described above and organopolysiloxanes containing the metal atoms
described above, and Ce-containing organopolysiloxanes are
preferable. The Ce-containing organopolysiloxane is a substance
where Ce is bonded through an oxygen atom to a silicon atom of a
straight-chain or branched organopolysiloxane. Examples of the
organic group of the silicon atom include alkyl group, aryl group,
aralkyl group, and alkenyl group, however, the organic group of the
silicon atom is preferably a methyl group or phenyl group. The
content of component (E) is not limited, however, the content is
preferably an amount so that the metal atom in component (E) is
from 5 to 2,000 ppm in terms of mass units relative to the amount
of the present composition.
[0048] Furthermore, the present composition may comprise an
adhesion-imparting agent. Preferred adhesion-imparting agents are
organosilicon compounds having at least one alkoxy group bonded to
a silicon atom in a molecule. This alkoxy group is exemplified by a
methoxy group, an ethoxy group, a propoxy group, a butoxy group,
and a methoxyethoxy group; and the methoxy group is particularly
preferred. Furthermore, examples of other groups, excluding the
alkoxy group bonded to the silicon atom, of the organosilicon
compound include halogen-substituted or unsubstituted monovalent
hydrocarbon groups, such as an alkyl group, alkenyl group, aryl
group, aralkyl group, and halogenated alkyl group; glycidoxyalkyl
groups, such as a 3-glycidoxypropyl group and 4-glycidoxybutyl
group; epoxycyclohexylalkyl groups, such as a
2-(3,4-epoxycyclohexyl)ethyl group and
3-(3,4-epoxycyclohexyl)propyl group; epoxyalkyl groups, such as a
3,4-epoxybutyl group and 7,8-epoxyoctyl group; acrylic
group-containing monovalent organic groups, such as a
3-methacryloxypropyl group; and a hydrogen atom. The organosilicon
compound preferably has a group that can react with an alkenyl
group or silicon atom-bonded hydrogen atom in the present
composition. Specifically, the organosilicon compound preferably
has a silicon atom-bonded hydrogen atom or alkenyl group. Moreover,
due to the ability to impart good adhesion with respect to various
types of substrates, this organosilicon compound preferably has at
least one epoxy group-containing monovalent organic group in a
molecule. This type of organosilicon compound is exemplified by
organosilane compounds, organosiloxane oligomers, and alkyl
silicates. Examples of the molecular structure of the
organosiloxane oligomer or alkyl silicate include a straight
structure, partially branched straight structure, branched chain
structure, ring-shaped structure, and net-shaped structure. A
straight chain structure, branched chain structure, and net-shaped
structure are particularly preferred. Examples of this type of
organosilicon compound include silane compounds such as
3-glycidoxypropyltrimethoxysilane,
2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and
3-methacryloxypropyltrimethoxysilane; siloxane compounds having at
least one of silicon-bonded alkenyl groups and silicon-bonded
hydrogen atoms, and at least one silicon-bonded alkoxy group in a
molecule; mixtures of a silane compound or siloxane compound having
at least one silicon-bonded alkoxy group and a siloxane compound
having at least one silicon-bonded hydroxyl group and at least one
silicon-bonded alkenyl group in a molecule; and methyl
polysilicate, ethyl polysilicate, and epoxy group-containing ethyl
polysilicate. The content of the adhesion-imparting agent is not
limited, however, the content is preferably in a range of 0.01 to
10 parts by mass per 100 parts by mass of total amount of the
present composition.
[0049] Furthermore, the present composition may comprise an
inorganic filler, such as silica, titanium oxide, glass, alumina,
or zinc oxide; an organic resin fine powder of polymethacrylate
resin, silicone resin, or the like; as well as a pigment, a
fluorescent substance, or the like, as long as the object of the
present invention is not impaired.
[0050] To form the present composition into a thin film or to coat
the present composition in a desired pattern by printing, a solvent
may be added in the present composition. The solvent that can be
used is not limited as long as the solvent can dissolve the present
composition to form a uniform solution. Specific examples thereof
include aliphatic hydrocarbons, such as normal hexane, normal
pentane, normal octane, isooctane, and decalin; aromatic
hydrocarbons, such as toluene, xylene, and mesitylene; ethers, such
as diisopropyl ether, dibutyl ether, and tetrahydrofuran; esters,
such as ethyl acetate and butyl acetate; and glycol esters, such as
propylene glycol monomethylether acetate and dipropylene glycol
monomethylether acetate.
[0051] The present composition is non-flowable at 25.degree. C. and
has a viscosity of 1,000 Pas or less, and preferably 500 Pas or
less, at 100.degree. C. Note that "non-flowable" means not flowing
when no load is applied, and indicates the condition at lower than
the softening point measured by a testing method for the softening
point by the Ring-and-ball method of a hot melt adhesive agent
stipulated in JIS K 6863-1994, "Testing methods for the softening
point of hot melt adhesives". That is, in order to be non-flowable
at 25.degree. C., the softening point needs to be higher than
25.degree. C. This is because excellent shape retention properties
are achieved at the temperature if the composition is non-flowable
at 25.degree. C. Furthermore, if the melt viscosity at 100.degree.
C. is within the range described above, processing into various
forms is facilitated.
[0052] Since the present composition is non-flowable at 25.degree.
C., the present composition can be processed into various forms,
and for example, can be made into a sheet having a thickness of 5
.mu.m to 5 mm, powder form, or tablet form.
[0053] Examples of the active energy ray used to cure the present
composition include an ultraviolet ray, electron beam, and radial
ray, and an ultraviolet ray is preferable. Examples of a device
that emits the ultraviolet ray include high-pressure mercury lamps,
medium-pressure mercury lamps, and ultraviolet LEDs.
Cured Product
[0054] The cured product of the present invention is obtained by
irradiating the active energy ray curable hot melt silicone
composition described above with the active energy ray. Note that a
cured product having a form of the composition before curing can be
obtained if the irradiation with the active energy ray is performed
at a temperature that the present composition does not exhibit
flowability.
[0055] The form of this cured product is not limited; however, the
form is preferably a film form. Furthermore, the surface of the
cured product may be adhesive. The cured product having such an
adhesive surface can be applied to adhesive films, optical adhesive
films, and the like. The adhesion is not particularly limited;
however, the peel strength of bonded SUS steel plate measured by
the method stipulated in JIS K 6854 is preferably from 1 gf/inch to
10 kgf/inch, and more preferably from 10 gf/inch to 5 kgf/inch.
Method of Producing Film
[0056] The method of producing a film of the present invention
includes: sandwiching the active energy ray curable hot melt
silicone composition described above in between two releasable
transparent resin films, forming to a fixed thickness by thermal
compression or heating roller, and then irradiating the composition
with an active energy ray. The irradiation with active energy ray
may be performed through a transparent resin film or the
composition may be directly irradiated after the transparent resin
film is peeled off.
[0057] The releasable transparent resin film that can be used in
this method include a resin film in which the releasability is
exhibited by itself and a film obtained by adding or applying a
releasing agent to a resin film having low releasability. Examples
of the resin film having releasability include polyacrylate resin
films or polyolefin resin films that are grafted with silicone, and
fluorinated polyolefin resin films. Examples of the resin film, to
which a releasing agent is added or applied, include polyester
resin films and polyolefin resin films.
EXAMPLES
[0058] The active energy ray curable hot melt silicone composition,
the cured product thereof, and the method of producing a film of
the present invention will be described in detail using practical
examples and comparative examples. Note that, in the formulas, Me
represents a methyl group, Vi represents a vinyl group, and Map
represents a 3-methacryloxypropyl group.
Practical Example 1
[0059] An active energy ray curable hot melt silicone composition
was prepared by mixing, in xylene, 20.0 parts by mass of
organopolysiloxane represented by the following average unit
formula:
(Me.sub.2ViSiO.sub.1/2).sub.0.0025(Me.sub.2SiO.sub.2/2).sub.0.9975
[0060] 79.5 parts by mass of organopolysiloxane represented by the
following average unit formula:
(Me.sub.3SiO.sub.1/2).sub.0.50(SiO.sub.4/2).sub.0.50(HO.sub.1/2).sub.0.0-
1
[0061] 0.5 parts by mass (an amount so that an amount of
3-mercaptopropyl groups was 0.83 mol per 1 mol of vinyl groups in
the organopolysiloxane described above) of 3-mercaptopropyl
group-containing organopolysiloxane represented by the following
formula:
Me.sub.3SiO(Me.sub.2SiO).sub.29[Me(HSC.sub.3H.sub.6)SiO].sub.3SiMe.sub.3
[0062] 0.1 parts by mass of
bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and 0.01 parts
by mass of 2,6-di-tert-butyl-4-methylphenol until the mixture was
uniform, and then removing the xylene by heating under reduced
pressure.
[0063] This composition was a solid with no flowability at
25.degree. C. and had a viscosity of 270 Pas at 100.degree. C. This
composition was sandwiched between fluorosilicone-treated
polyethylene terephthalate films (FL3-01, manufactured by Takara
Inc. Co., Ltd.) having a thickness of 50 .mu.m, and heated and
compressed at 130.degree. C. to form a film having a thickness of
500 .mu.m. Thereafter, the film was irradiated through the
polyethylene terephthalate film with an ultraviolet ray using a
high-pressure mercury lamp in a manner that the ultraviolet
radiation dose was 500 mJ/cm.sup.2 to produce a film-like cured
product. The release film was peeled off from one face of the
film-like cured product, and this film-like cured product was
adhered to an untreated-polyethylene terephthalate film having a
thickness of 50 .mu.m. Thereafter, the other release film on the
other face was peeled off, and the film-like cured product was
adhered to a SUS steel plate. The peel strength was measured by the
method stipulated in JIS K 6854, and the peel strength was 680
gf/25 mm.
Practical Example 2
[0064] An active energy ray curable hot melt silicone composition
was prepared by mixing, in xylene, 40.0 parts by mass of
organopolysiloxane represented by the following average unit
formula:
(Me.sub.2MapSiO.sub.1/2).sub.0.0025(Me.sub.2SiO.sub.2/2).sub.0.9975
[0065] 59.1 parts by mass of organopolysiloxane represented by the
following average unit formula:
(Me.sub.3SiO.sub.1/2).sub.0.44(Si.sup.O.sub.4/2).sub.0.56(HO.sub.1/2).su-
b.0.01
[0066] 0.9 parts by mass (an amount so that an amount of
3-mercaptopropyl group was 0.74 mol per 1 mol of
3-methacryloxypropyl groups in the organopolysiloxane described
above) of 3-mercaptopropyl group-containing organopolysiloxane
represented by the following formula:
Me.sub.3SiO(Me.sub.2SiO).sub.29[Me(HSC.sub.3H.sub.6)SiO].sub.3SiMe.sub.3
[0067] 0.1 parts by mass of 2-hydroxy-2-methylpropiophenone, and
0.01 parts by mass of 2,6-di-tert-butyl-4-methylphenol until the
mixture was uniform, and then removing the xylene by heating under
reduced pressure.
[0068] This composition was a solid with no flowability at
25.degree. C. and had a viscosity of 110 Pas at 100.degree. C. This
composition was sandwiched between fluorosilicone-treated
polyethylene terephthalate films (FL3-01, manufactured by Takara
Inc. Co., Ltd.) having a thickness of 50 .mu.m, and heated and
compressed at 130.degree. C. to form a film having a thickness of
500 .mu.m. Thereafter, the film was irradiated through the
polyethylene terephthalate film with an ultraviolet ray using a
high-pressure mercury lamp in a manner that the ultraviolet
radiation dose was 500 mJ/cm.sup.2 to produce a film-like cured
product. The release film was peeled off from one face of the cured
product, and this cured product was adhered to an
untreated-polyethylene terephthalate film having a thickness of 50
.mu.m. Thereafter, the other release film on the other face was
peeled off, and the cured product was adhered to a SUS steel plate.
The peel strength was measured by the method stipulated in JIS K
6854, and the peel strength was 430 gf/25 mm.
Practical Example 3
[0069] An active energy ray curable hot melt silicone composition
was prepared by mixing, in xylene, 30.0 parts by mass of
organopolysiloxane represented by the following average unit
formula:
(Me.sub.2ViSiO.sub.1/2).sub.0.0025(Me.sub.2SiO.sub.2/2).sub.0.9975
[0070] 68.0 parts by mass of organopolysiloxane represented by the
following average unit formula:
(Me.sub.2ViSiO.sub.1/2).sub.0.007(Me.sub.3SiO.sub.1/2).sub.0.433(Si.sup.-
O.sub.4/2).sub.0.560(HO.sub.1/2).sub.0.01
[0071] 2.0 parts by mass (an amount so that an amount of
3-mercaptopropyl groups was 0.86 mol per 1 mol of the total of
vinyl groups in the two types of the organopolysiloxanes described
above) of 3-mercaptopropyl group-containing organopolysiloxane
represented by the following formula:
Me.sub.3SiO(Me.sub.2SiO).sub.20[Me(HSC.sub.3H.sub.6)SiO].sub.10SiMe.sub.-
3
[0072] 0.1 parts by mass of 2-hydroxy-2-methylpropiophenone, and
0.01 parts by mass of 2,6-di-tert-butyl-4-methylphenol until the
mixture was uniform, and then removing the xylene by heating under
reduced pressure.
[0073] This composition was a solid with no flowability at
25.degree. C. and had a viscosity of 1100 Pas at 100.degree. C.
This composition was sandwiched between fluorosilicone-treated
polyethylene terephthalate films (FL3-01, manufactured by Takara
Inc. Co., Ltd.) having a thickness of 50 .mu.m, and heated and
compressed at 130.degree. C. to form a film having a thickness of
500 .mu.m. Thereafter, the film was irradiated through the
polyethylene terephthalate film with an ultraviolet ray using a
high-pressure mercury lamp in a manner that the ultraviolet
radiation dose was 500 mJ/cm.sup.2 to produce a film-like cured
product. The release film was peeled off from one face of the cured
product, and this cured product was adhered to an
untreated-polyethylene terephthalate film having a thickness of 50
.mu.m. Thereafter, the other release film on the other face was
peeled off, and the cured product was adhered to a SUS steel plate.
The peel strength was measured by the method stipulated in JIS K
6854, and the peel strength was 1.2 kgf/25 mm.
Practical Example 4
[0074] 35.0 parts by mass of organopolysiloxane represented by the
following average unit formula:
(Me.sub.2ViSiO.sub.1/2).sub.0.0025(Me.sub.2SiO.sub.2/2).sub.0.9975
[0075] 64.4 parts by mass of organopolysiloxane represented by the
following average unit formula:
(Me.sub.3SiO.sub.1/2).sub.0.44(SiO.sub.4/2).sub.0.56(HO.sub.1/2).sub.0.0-
1
[0076] 0.6 parts by mass (an amount so that an amount of
3-mercaptopropyl groups was 1.72 mol per 1 mol of vinyl groups in
the organopolysiloxane described above) of 3-mercaptopropyl
group-containing organopolysiloxane represented by the following
formula:
Me.sub.3SiO(Me.sub.2SiO).sub.20[Me(HSC.sub.3H.sub.6)SiO].sub.10SiMe.sub.-
3
[0077] 0.1 parts by mass of 1-hydroxycyclohexylphenylketone, 0.01
parts by mass of 2,6-di-tert-butyl-4-methylphenol, and 25 parts by
mass of xylene were mixed until the mixture was uniform.
[0078] This solution was applied on a polyethylene terephthalate
film having a thickness of 100 .mu.m so that the thickness of the
solution layer was 100 .mu.m. The xylene was volatilized in an oven
at 110.degree. C. to produce a film having a thickness of 90 .mu.m
formed from the active energy ray curable hot melt silicone
composition. This film was a solid with no flowability at
25.degree. C. and had a viscosity of 820 Pas at 100.degree. C. This
film was sandwiched between fluorosilicone-treated polyethylene
terephthalate films (FL3-01, manufactured by Takara Inc. Co., Ltd.)
having a thickness of 50 .mu.m, and heated and compressed at
130.degree. C. to form the film having a thickness of 500 .mu.m.
Thereafter, the film was irradiated through the polyethylene
terephthalate film with an ultraviolet ray using a high-pressure
mercury lamp in a manner that the ultraviolet radiation dose was
500 mJ/cm.sup.2 to produce a film-like cured product. The release
film was peeled off from one face of the cured product, and this
cured product was adhered to an untreated-polyethylene
terephthalate film having a thickness of 50 .mu.m. Thereafter, the
other release film on the other face was peeled off, and the cured
product was adhered to a SUS steel plate. The peel strength was
measured by the method stipulated in JIS K 6854, and the peel
strength was 780 gf/25 mm.
Practical Example 5
[0079] 20.0 parts by mass of organopolysiloxane represented by the
following average unit formula:
(Me.sub.2ViSiO.sub.1/2).sub.0.0025(Me.sub.2SiO.sub.2/2).sub.0.9975
[0080] 78.0 parts by mass of organopolysiloxane represented by the
following average unit formula:
(Me.sub.2ViSiO.sub.1/2).sub.0.007(Me.sub.3SiO.sub.1/2).sub.0.503(SiO.sub-
.4/2).sub.0.490(HO.sub.1/2).sub.0.02
[0081] 2.0 parts by mass (an amount so that an amount of
3-mercaptopropyl groups was 0.79 mol per 1 mol of the total of
vinyl groups in the two types of the organopolysiloxanes described
above) of 3-mercaptopropyl group-containing organopolysiloxane
represented by the following formula:
Me.sub.3SiO(Me.sub.2SiO).sub.20[Me(HSC.sub.3H.sub.6)SiO].sub.10SiMe.sub.-
3
[0082] 0.1 parts by mass of 1-hydroxycyclohexylphenylketone, 0.01
parts by mass of 2,6-di-tert-butyl-4-methylphenol, and 25 parts by
mass of xylene were mixed until the mixture was uniform.
[0083] This solution was applied on a polyethylene terephthalate
film having a thickness of 100 .mu.m so that the thickness of the
solution layer was 100 .mu.m. The xylene was volatilized in an oven
at 110.degree. C. to produce a film having a thickness of 90 .mu.m
formed from the active energy ray curable hot melt silicone
composition. This film was a solid with no flowability at
25.degree. C. and had a viscosity of 900 Pas at 100.degree. C. This
film was sandwiched between fluorosilicone-treated polyethylene
terephthalate films (FL3-01, manufactured by Takara Inc. Co., Ltd.)
having a thickness of 50 .mu.m, and heated and compressed at
130.degree. C. to form the film having a thickness of 500 .mu.m.
Thereafter, the film was irradiated through the polyethylene
terephthalate film with an ultraviolet ray using a high-pressure
mercury lamp in a manner that the ultraviolet radiation dose was
500 mJ/cm.sup.2 to produce a film-like cured product. The release
film was peeled off from one face of the cured product, and this
cured product was adhered to an untreated-polyethylene
terephthalate film having a thickness of 50 .mu.m. Thereafter, the
other release film on the other face was peeled off, and the cured
product was adhered to a SUS steel plate. The peel strength was
measured by the method stipulated in JIS K 6854, and the peel
strength was 1.1 kgf/25 mm.
Practical Example 6
[0084] An active energy ray curable hot melt silicone composition
was prepared by mixing, in xylene, 32.0 parts by mass of
organopolysiloxane represented by the following average unit
formula:
(Me.sub.2ViSiO.sub.1/2).sub.0.0025(Me.sub.2SiO.sub.2/2).sub.0.9975
[0085] 66.0 parts by mass of organopolysiloxane represented by the
following average unit formula:
(Me.sub.2ViSiO.sub.1/2).sub.0.007(Me.sub.3SiO.sub.1/2).sub.0.433(SiO.sub-
.4/2).sub.0.560(HO.sub.1/2).sub.0.01
[0086] 2.0 parts by mass (an amount so that an amount of
3-mercaptopropyl groups was 0.87 mol per 1 mol of the total of
vinyl groups in the two types of the organopolysiloxanes described
above) of 3-mercaptopropyl group-containing organopolysiloxane
represented by the following formula:
Me.sub.3SiO(Me.sub.2SiO).sub.20[Me(HSC.sub.3H.sub.6)SiO].sub.10SiMe.sub.-
3
[0087] 0.1 parts by mass of 2-hydroxy-2-methylpropiophenone, 0.5
parts by mass of cerium-containing dimethylpolysiloxane (content of
cerium=0.5% by mass), and 0.01 parts by mass of
2,6-di-tert-butyl-4-methylphenol until the mixture was uniform, and
then removing the xylene by heating under reduced pressure.
[0088] This composition was a solid with no flowability at
25.degree. C. and had a viscosity of 520 Pas at 100.degree. C. This
composition was sandwiched between fluorosilicone-treated
polyethylene terephthalate films (FL3-01, manufactured by Takara
Inc. Co., Ltd.) having a thickness of 50 .mu.m, and heated and
compressed at 130.degree. C. to form a film having a thickness of
500 .mu.m. Thereafter, the film was irradiated through the
polyethylene terephthalate film with an ultraviolet ray using a
high-pressure mercury lamp in a manner that the ultraviolet
radiation dose was 500 mJ/cm.sup.2 to produce a film-like cured
product. The release film was peeled off from one face of the cured
product, and this cured product was adhered to an
untreated-polyethylene terephthalate film having a thickness of 50
.mu.m. Thereafter, the other release film on the other face was
peeled off, and the cured product was adhered to a SUS steel plate.
The peel strength was measured by the method stipulated in JIS K
6854, and the peel strength was 0.9 kgf/25 mm.
Comparative Example 1
[0089] An active energy ray curable silicone composition was
prepared by mixing, in xylene, 5.0 parts by mass of
organopolysiloxane represented by the following average unit
formula:
(Me.sub.2ViSiO.sub.1/2).sub.0.0025(Me.sub.2SiO.sub.2/2).sub.0.9975
[0090] 94.8 parts by mass of organopolysiloxane represented by the
following average unit formula:
(Me.sub.3SiO.sub.1/2).sub.0.50(SiO.sub.4/2).sub.0.50(HO.sub.1/2).sub.0.0-
1
[0091] 0.2 parts by mass (an amount so that an amount of
3-mercaptopropyl groups was 1.33 mol per 1 mol of vinyl groups in
the organopolysiloxane described above) of 3-mercaptopropyl
group-containing organopolysiloxane represented by the following
formula:
Me.sub.3SiO(Me.sub.2SiO).sub.29[Me(HSC.sub.3H.sub.6)SiO].sub.3SiMe.sub.3
[0092] 0.1 parts by mass of
bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and 0.01 parts
by mass of 2,6-di-tert-butyl-4-methylphenol until the mixture was
uniform, and then removing the xylene by heating under reduced
pressure. This composition was a solid with no flowability at
25.degree. C. and at 100.degree. C., and did not have hot melt
properties.
Comparative Example 2
[0093] An active energy ray curable silicone composition was
prepared by mixing, in xylene, 45.0 parts by mass of
organopolysiloxane represented by the following average unit
formula:
(Me.sub.2MapSiO.sub.1/2).sub.0.0025(Me.sub.2SiO.sub.2/2).sub.0.9975
[0094] 53.5 parts by mass of organopolysiloxane represented by the
following average unit formula:
(Me.sub.3SiO.sub.1/2).sub.0.44(SiO.sub.4/2).sub.0.56(HO.sub.1/2).sub.0.0-
1
[0095] 1.5 parts by mass (an amount so that an amount of
3-mercaptopropyl groups was 1.10 mol per 1 mol of
3-methacryloxypropyl groups in the organopolysiloxane described
above) of 3-mercaptopropyl group-containing organopolysiloxane
rep-resented by the following formula:
Me.sub.3SiO(Me.sub.2SiO).sub.29[Me(HSC.sub.3H.sub.6)SiO].sub.3SiMe.sub.3
[0096] 0.1 parts by mass of 2-hydroxy-2-methylpropiophenone, and
0.01 parts by mass of 2,6-di-tert-butyl-4-methylphenol until the
mixture was uniform, and then removing the xylene by heating under
reduced pressure. This composition had a viscosity of 390 Pas at
25.degree. C. and a viscosity of 23 Pas at 100.degree. C. and did
not have hot melt properties.
Comparative Example 3
[0097] An active energy ray curable hot melt silicone composition
was prepared by mixing, in xylene, 30.0 parts by mass of
organopolysiloxane represented by the following average unit
formula:
(Me.sub.2ViSiO.sub.1/2).sub.0.0025(Me.sub.2SiO.sub.2/2).sub.0.9975
[0098] 69.7 parts by mass of organopolysiloxane represented by the
following average unit formula:
(Me.sub.2ViSiO.sub.1/2).sub.0.007(Me.sub.3SiO.sub.1/2).sub.0.433(Si.sup.-
O.sub.4/2).sub.0.560(HO.sub.1/2).sub.0.01
[0099] 0.3 parts by mass (an amount so that an amount of
3-mercaptopropyl groups was 0.13 mol per 1 mol of the total of
vinyl groups in the two types of the organopolysiloxanes described
above) of 3-mercaptopropyl group-containing organopolysiloxane
represented by the following formula:
Me.sub.3SiO(Me.sub.2SiO).sub.20[Me(HSC.sub.3H.sub.6)SiO].sub.10SiMe.sub.-
3
[0100] 0.1 parts by mass of 2-hydroxy-2-methylpropiophenone, and
0.01 parts by mass of 2,6-di-tert-butyl-4-methylphenol until the
mixture was uniform, and then removing the xylene by heating under
reduced pressure.
[0101] This composition was a solid with no flowability at
25.degree. C. and had a viscosity of 1100 Pas at 100.degree. C.
This composition was sandwiched between fluorosilicone-treated
polyethylene terephthalate films (FL3-01, manufactured by Takara
Inc. Co., Ltd.) having a thickness of 50 .mu.m, and heated and
compressed at 130.degree. C. to form a film having a thickness of
500 .mu.m. Thereafter, the film was irradiated through the
polyethylene terephthalate film with an ultraviolet ray using a
high-pressure mercury lamp in a manner that the ultraviolet
radiation dose was 500 mJ/cm.sup.2. However, a cured product was
not obtained and the composition had flowability at 100.degree.
C.
Comparative Example 4
[0102] 35.0 parts by mass of organopolysiloxane represented by the
following average unit formula:
(Me.sub.2ViSiO.sub.1/2).sub.0.0025(Me.sub.2SiO.sub.2/2).sub.0.9975
[0103] 64.9 parts by mass of organopolysiloxane represented by the
following average unit formula:
(Me.sub.3SiO.sub.1/2).sub.0.44(Si.sup.O.sub.4/2).sub.0.56(HO.sub.1/2).su-
b.0.01
[0104] 1.8 parts by mass (an amount so that an amount of
3-mercaptopropyl groups was 5.17 mol per 1 mol of vinyl groups in
the organopolysiloxane described above) of 3-mercaptopropyl
group-containing organopolysiloxane represented by the following
formula:
Me.sub.3SiO(Me.sub.2SiO).sub.20[Me(HSC.sub.3H.sub.6)SiO].sub.10SiMe.sub.-
3
[0105] 0.1 parts by mass of 1-hydroxycyclohexylphenylketone, 0.01
parts by mass of 2,6-di-tert-butyl-4-methylphenol, and 25 parts by
mass of xylene were mixed until the mixture was uniform.
[0106] This solution was applied on a polyethylene terephthalate
film having a thickness of 100 .mu.m and the thickness of the
coated film was 100 .mu.m. The xylene was volatilized in an oven at
110.degree. C. to produce a film having a thickness of 90 .mu.m
formed from the active energy ray curable hot melt silicone
composition. This film was a solid with no flowability at
25.degree. C. and had a viscosity of 930 Pas at 100.degree. C. This
film was sandwiched between fluorosilicone-treated polyethylene
terephthalate films (FL3-01, manufactured by Takara Inc. Co., Ltd.)
having a thickness of 50 .mu.m, and heated and compressed at
130.degree. C. to form a film having a thickness of 500 .mu.m.
Thereafter, the film was irradiated through the polyethylene
terephthalate film with an ultraviolet ray using a high-pressure
mercury lamp in a manner that the ultraviolet radiation dose was
500 mJ/cm2. However, a cured product was not obtained and the
composition had flowability at 100.degree. C.
INDUSTRIAL APPLICABILITY
[0107] Since the active energy ray curable hot melt silicone
composition of the present invention is non-flowable at room
temperature, melts by heating, can be formed into a desired shape,
such as a sheet, and cures when irradiated with an active energy
ray, such as an ultraviolet ray, while the shape is maintained, the
active energy ray curable hot melt silicone composition is suitable
for forming intermediate layers or surface protection layers of
image display devices, solar cell modules, touchscreens, and the
like. Furthermore, since the cured product of the present invention
has excellent heat resistance and light resistance, the cured
product is suitable for image display devices, solar cell modules,
touchscreens, and the like.
* * * * *