U.S. patent application number 09/808789 was filed with the patent office on 2001-08-09 for curable organosiloxane composition.
Invention is credited to Amako, Masaaki, Okawa, Tadashi.
Application Number | 20010012881 09/808789 |
Document ID | / |
Family ID | 27467788 |
Filed Date | 2001-08-09 |
United States Patent
Application |
20010012881 |
Kind Code |
A1 |
Amako, Masaaki ; et
al. |
August 9, 2001 |
Curable organosiloxane composition
Abstract
A curable organosiloxane composition comprising: (A) an
organopolysiloxane having at least two silicon atom-bonded alkenyl
groups per molecule; (B) an organopolysiloxane having at least two
silicon atom-bonded hydrogen atoms per molecule; (C) a compound
having an alkenyl group and a phenol residue of the formula: 1
where R.sup.1 is an alkyl group or alkoxy group, a is 1 or 2, and b
is an integer from 0 to 3; and (D) a hydrosilylation reaction
catalyst.
Inventors: |
Amako, Masaaki; (Chiba
Prefecture, JP) ; Okawa, Tadashi; (Chiba Prefecture,
JP) |
Correspondence
Address: |
Dow Corning Corporation
Patent Department - Mail CO1232
P. O. Box 994
Midland
MI
48686-0994
US
|
Family ID: |
27467788 |
Appl. No.: |
09/808789 |
Filed: |
March 15, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09808789 |
Mar 15, 2001 |
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09409810 |
Sep 30, 1999 |
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6252029 |
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Current U.S.
Class: |
528/25 |
Current CPC
Class: |
C08G 77/045 20130101;
C07F 7/0838 20130101 |
Class at
Publication: |
528/25 |
International
Class: |
C08G 077/04 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 30, 1998 |
JP |
10/278538-1998 |
Sep 30, 1998 |
JP |
10/294580-1998 |
Mar 31, 1999 |
JP |
11/090575-1999 |
Jun 17, 1999 |
JP |
11/171113-1999 |
Claims
That which is claimed is:
1. A curable organosiloxane composition comprising: (A) an
organopolysiloxane having at least two silicon atom-bonded alkenyl
groups per molecule; (B) an organopolysiloxane having at least two
silicon atom-bonded hydrogen atoms per molecule; (C) a compound
having an alkenyl group and a phenol residue of the formula:
26where R.sup.1 is an alkyl group or alkoxy group, a is 1 or 2, and
b is an integer from 0 to 3; and (D) a hydrosilylation reaction
catalyst.
2. A composition according to claim 1, wherein component (A) is
selected from the group consisting of a trimethylsiloxy-endblocked
methylvinylpolysiloxane, a trimethylsiloxy-endblocked
dimethylsiloxane-methylvinylsiloxane copolymer, a
trimethylsiloxy-endbloc- ked diphenylsiloxane-methylvinylsiloxane
copolymer, a dimethylvinylsiloxy-endblocked dimethylpolysiloxane, a
dimethylvinylsiloxy-endblocked dimethylsiloxane-methylvinylsiloxane
copolymer, a dimethylvinylsiloxyendblocked
dimethylsiloxane-diphenylsilox- ane copolymer, a cyclic
methylvinylpolysiloxane, an organopolysiloxane comprising of
siloxane units expressed by the formula SiO.sub.4/2 and siloxane
units expressed by the formula CH.sub.2.dbd.CH(CH.sub.3).sub.2Si-
O.sub.1/2, and an organopolysiloxane comprising siloxane units
expressed by the formula SiO.sub.4/2, siloxane units expressed by
the formula (CH.sub.3).sub.3SiO.sub.1/2, and siloxane units
expressed by the formula
CH.sub.2.dbd.CH(CH.sub.3).sub.2SiO.sub.1/2.
3. A composition according to claim 1, wherein component (B) is
selected from the group consisting of a trimethylsiloxy-endblocked
methylhydrogenpolysiloxane, a trimethylsiloxy-endblocked
dimethylsiloxane-methylhydrogensiloxane copolymer, a
trimethylsiloxy-endblocked diphenylsiloxane-methylhydrogensiloxane
copolymer, a dimethylhydrogensiloxy-endblocked
dimethylsiloxane-methylhyd- rogensiloxane copolymer, a cyclic
methylhydrogenpolysiloxane, an organopolysiloxane comprising
siloxane units expressed by the formula SiO.sub.4/2 and siloxane
units expressed by the formula (CH.sub.3).sub.2HSiO.sub.1/2, and an
organopolysiloxane comprising siloxane units expressed by the
formula SiO.sub.4/2, siloxane units expressed by the formula
(CH.sub.3).sub.3SiO.sub.1/2, and siloxane units expressed by the
formula (CH.sub.3).sub.2HSiO.sub.1/2.
4. A composition according to claim 2, wherein component (B) is
selected from the group consisting of a trimethylsiloxy-endblocked
methylhydrogenpolysiloxane, a trimethylsiloxy-endblocked
dimethylsiloxane-methylhydrogensiloxane copolymer, a
trimethylsiloxy-endblocked diphenylsiloxane-methylhydrogensiloxane
copolymer, a dimethylhydrogensiloxy-endblocked
dimethylsiloxane-methylhyd- rogensiloxane copolymer, a cyclic
methylhydrogenpolysiloxane, an organopolysiloxane comprising
siloxane units expressed by the formula SiO.sub.4/2 and siloxane
units expressed by the formula (CH.sub.3).sub.2HSiO.sub.1/2, and an
organopolysiloxane comprising siloxane units expressed by the
formula SiO.sub.4/2, siloxane units expressed by the formula
(CH.sub.3).sub.3SiO.sub.1/2, and siloxane units expressed by the
formula (CH.sub.3).sub.2HSiO.sub.1/2.
5. A composition according to claim 1, wherein component (C) is an
alkenyl group-containing phenol compound.
6. A composition according to claim 1, wherein component (C) is an
organosilicon compound of the formula: 27where X is an alkenyl
group; Z is an oxy group expressed by the formula --O--, a carboxy
group expressed by the formula --C(O)O--, or a phenylene group, A
is a divalent hydrocarbon group, a group expressed by the formula:
--R.sup.4--O--R.sup.4--where the R.sup.4 groups are divalent
hydrocarbon groups, or a group expressed by the formula:
--R.sup.5--O--where R.sup.5 is a substituted or unsubstituted
divalent hydrocarbon group, R.sup.1 is an alkyl group or alkoxy
group, the R.sup.2 groups monovalent hydrocarbon groups having no
aliphatic unsaturated bonds, the R groups are divalent hydrocarbon
groups or groups expressed by the formula: --R.sup.6--O--where
R.sup.6 is a divalent hydrocarbon group, a is 1 or 2, b is an
integer from 0 to 3, m is 0 or 1, n is an integer from 0 to 2, p is
0 or 1, and q is an integer from 0 to 7.
7. A composition according to claim 4, wherein component (C) is an
organosilicon compound of the formula: 28where X is an alkenyl
group; Z is an oxy group expressed by the formula --O--, a carboxy
group expressed by the formula --C(O)O--, or a phenylene group, A
is a divalent hydrocarbon group, a group expressed by the formula:
--R.sup.4--O--R.sup.4--where the R.sup.4 groups are divalent
hydrocarbon groups, or a group expressed by the formula:
--R.sup.5--O--where R.sup.5 is a substituted or unsubstituted
divalent hydrocarbon group, R.sup.1 is an alkyl group or alkoxy
group, the R.sup.2 groups are monovalent hydrocarbon groups having
no aliphatic unsaturated bonds, the R.sup.3 groups are divalent
hydrocarbon groups or groups expressed by the formula:
--R.sup.1--O--where R.sup.6 is a divalent hydrocarbon group, a is 1
or 2, b is an integer from 0 to 3, m is 0 or 1, n is an integer
from 0 to 2, p is 0 or 1, and q is an integer from 0 to 7.
8. A composition according to claim 1, wherein component (C) is an
organosilicon compound of the formula: 29where A is a divalent
hydrocarbon group, a group expressed by the formula:
--R.sup.4--O--R.sup.4--where the R.sup.4 groups are divalent
hydrocarbon groups, or a group expressed by the formula:
--R.sup.5--O--where R.sup.5 is a substituted or unsubstituted
divalent hydrocarbon group, R.sup.1 is an alkyl group or alkoxy
group, the R.sup.2 groups are monovalent hydrocarbon groups having
no aliphatic unsaturated bonds, the R.sup.3 groups are divalent
hydrocarbon groups or groups expressed by the formula:
--R.sup.6--O--where R.sup.6 is a divalent hydrocarbon group, a is 1
or 2, b is an integer from 0 to 3, n is an integer from 0 to 2, and
q is an integer from 0 to 7.
9. A composition according to claim 4, wherein component (C) is an
organosilicon compound of the formula: 30where A is a divalent
hydrocarbon group, a group expressed by the formula:
--R.sup.4--O--R.sup.4--where the R.sup.4 groups are divalent
hydrocarbon groups, or a group expressed by the formula:
--R.sup.5--O--where R.sup.5 is a substituted or unsubstituted
divalent hydrocarbon group, R.sup.1 is an alkyl group or alkoxy
group, the R.sup.2 groups are monovalent hydrocarbon groups having
no aliphatic unsaturated bonds, the R.sup.3 groups are divalent
hydrocarbon groups or groups expressed by the formula:
--R.sup.6--O--where R.sup.6 is a divalent hydrocarbon group, a is 1
or 2, b is an integer from 0 to 3, n is an integer from 0 to 2, and
q is an integer from 0 to 7.
10. A composition according to claim 1, wherein component (C) is an
organosilicon compound of the formula: 31where X is an alkenyl
group, A is a divalent hydrocarbon group, a group having the
formula: --R.sup.4--O--R.sup.4--where the R.sup.4 groups are
divalent hydrocarbon groups, or a group expressed by the formula:
--R.sup.5--O--where R.sup.5 is a substituted or unsubstituted
divalent hydrocarbon group; R.sup.1 is an alkyl group or alkoxy
group, the R.sup.2 groups are monovalent hydrocarbon groups having
no aliphatic unsaturated bonds, the R.sup.3 groups are divalent
hydrocarbon groups or groups expressed by the formula:
--R.sup.6--O--where R.sup.6 is a divalent hydrocarbon group, a is 1
or 2, b is an integer from 0 to 3, m is 0 or 1, and n is an integer
from 0 to 2.
11. A curable organosiloxane composition according to claim 4,
wherein component (C) is an organosilicon compound of the formula:
32where X is an alkenyl group, A is a divalent hydrocarbon group, a
group having the formula: --R.sup.4--O--R.sup.4--where the R.sup.4
groups are divalent hydrocarbon groups, or a group expressed by the
formula: --R.sup.5--O--where R is a substituted or unsubstituted
divalent hydrocarbon group; R.sup.1 is an alkyl group or alkoxy
group, the R.sup.2 groups are monovalent hydrocarbon groups having
no aliphatic unsaturated bonds, the R.sup.3 groups are divalent
hydrocarbon groups or groups expressed by the formula:
--R.sup.6--O--where R.sup.6 is a divalent hydrocarbon group, a is 1
or 2, b is an integer from 0 to 3, m is 0 or 1, and n is an integer
from 0 to 2.
12. A curable organosiloxane composition according to claim 1,
where in (C) is selected from the group consisting of 33
13. A curable organosiloxane composition according to claim 4,
where in (C) is selected from the group consisting of: 34
14. A curable organosiloxane composition according to claim 1,
wherein (D) is selected from the group consisting of
chloroplantinic acid, an alcohol solution of chloroplantinic acid,
an olefin complex of platinum, a diketone complex of platinum, an
acetyl acetate complex of platinum, and a vinyl group-containing
siloxane complex of platinum.
15. A curable organosiloxane composition according to claim 13,
wherein (D) is selected from the group consisting of
chloroplantinic acid, an alcohol solution of chloroplantinic acid,
an olefin complex of platinum, a diketone complex of platinum, an
acetyl acetate complex of platinum, and a vinyl group-containing
siloxane complex of platinum.
16. A curable organosiloxane composition according to claim 1,
wherein the composition further comprises at least one ingredient
selected from the group consisting of a hydrosilylation reaction
inhibitor, an adhesion promoter, a pigment, a reinforcing filler, a
plasticizer, an additive for improving thermal conductivity, and a
filler to increase electrical conductivity.
17. A curable organosiloxane composition according to claim 15,
wherein the composition further comprises at least one ingredient
selected from the group consisting of a hydrosilylation reaction
inhibitor, an adhesion promoter, a pigment, a reinforcing filler, a
plasticizer, an additive for improving thermal conductivity, and a
filler to increase electrical conductivity.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present application is a division of application Ser.
Nos. 09/409,810 filed Sep. 30, 1999, entitled "Hydroxyphenyl
Group-Containing Organosilicon Compound, and Method for
Manufacturing Same."
FIELD OF THE INVENTION
[0002] The present invention relates to a novel organosilicon
compound containing hydroxyphenyl groups and aliphatic unsaturated
bonds within the same molecules, and to a method for manufacturing
this compound.
[0003] The present invention also relates to a curable
organosiloxane composition, and more particularly relates to a
curable organosiloxane composition which can be cured through a
hydrosilylation reaction to form a cured product which will adhere
well to a variety of thermosetting organic resins.
BACKGROUND OF THE INVENTION
[0004] Silicone compounds whose main components are an alkenyl
group-containing organosiloxane and an organohydrogenpolysiloxane
and which cure in the presence of a platinum-based catalyst are
called addition reaction-curing silicone compositions, and are used
in many different fields of industry. However, when this type of
silicone composition cures, the surface thereof becomes inert,
which makes it extremely difficult to bond an epoxy resin, phenol
resin, or any of various other organic resins to this cured
material. Various attempts have therefore been made at bonding
these materials together, such as subjecting the surface of a cured
product of an addition reaction-curing silicone composition to an
ozone treatment, then bringing one of various organic resins into
contact with this ozone-treated surface and curing it. This method,
however, is not satisfactory for practical purposes because of its
drawback in that adhesion decreases over time. Accordingly, there
is a need for an adhesion imparter for bonding various organic
resins to the cured product of an addition reaction-curing silicone
composition. It is believed that an organosilicon compound
containing hydroxyphenyl groups (as functional groups for enhancing
adhesion with an organic resin) and alkenyl groups (as functional
groups incorporated into the addition reaction cured product) in
the same molecules would be effective as this adhesion
imparter.
BRIEF DESCRIPTION OF THE DRAWINGS
[0005] FIG. 1 is a nuclear magnetic resonance analysis chart of the
hydroxyphenyl group-containing methacrylic functional organosilicon
compound synthesized in Working Example 1;
[0006] FIG. 2 is an infrared spectroscopic analysis chart of the
hydroxphenyl group-containing methacrylic functional organosilicon
compound synthesized in Working Example 1;
[0007] FIG. 3 is a nuclear magnetic resonance analysis chart of the
hydroxphenyl group-containing methacrylic functional organosilicon
compound synthesized in Working Example 2;
[0008] FIG. 4 is an infrared spectroscopic analysis chart of the
hydroxyphenyl group-containing methacrylic functional organosilicon
compound synthesized in Working Example 2;
[0009] FIG. 5 is a nuclear magnetic resonance analysis chart of the
hydroxyphenyl group-containing methacrylic functional organosilicon
compound synthesized in Working Example 3; and
[0010] FIG. 6 is an infrared spectroscopic analysis chart of the
hydroxyphenyl group-containing methacrylic functional organosilicon
compound synthesized in Working Example 3.
DETAILED DESCRIPTION OF THE INVENTION
[0011] The present invention relates to a hydroxyphenyl
group-containing organosilicon compound expressed by the general
formula: 2
[0012] where X is an alkenyl group; Z is a phenylene group or a
carbonyloxy group expressed by --C(O)O--; Y is a substituted or
unsubstituted hydroxyphenyl group; R.sup.1 is a hydrocarbon group
with two or more carbon atoms, with the various groups being the
same or different; R is a monovalent hydrocarbon group containing
no aliphatic unsaturated bonds, with the various groups being the
same or different; A is a divalent hydrocarbon group with one or
more carbon atoms or a group expressed by the formula
--R.sup.2--O--R.sup.2-- (where R.sup.2 is a divalent hydrocarbon
group); m and p are each independently 0 or 1; n is a number from 0
to 2; and q is an integer from 0 to 7, and to a method for
manufacturing this compound.
[0013] The hydroxyphenyl group-containing organosilicon compound of
the present invention is a compound expressed by the general
formula given above, containing hydroxyphenyl groups and aliphatic
unsaturated bond-containing monovalent hydrocarbon groups in its
molecules. In the above formula, X is an alkenyl group, examples of
which include the vinyl group, allyl group, isopropenyl group, and
hexenyl group. Z is a phenylene group or a carbonyloxy group
expressed by --C(O)O--. Examples of phenylene groups include the
o-phenylene group, m-phenylene group, and p-phenylene group. Y is a
substituted or unsubstituted hydroxyphenyl group, examples of which
include an alkyl group-substituted hydroxyphenyl group and an
alkoxy group-substituted hydroxyphenyl group. There are no
particular restrictions on the substitution position of the alkyl
group or alkoxy group. Examples of the alkyl group include the
methyl group, ethyl group, propyl group, and butyl group, and
examples of the alkoxy group include the methoxy group, ethoxy
group, propoxy group, and butoxy group. Examples of substituted or
unsubstituted hydroxyphenyl groups include the 2-hydroxyphenyl
group, 4-hydroxyphenyl group, 3,4-dihydroxyphenyl group,
3,5-dihydroxyphenyl group, and other such hydroxyphenyl groups; the
3,5-di-tert-butyl-4-hydroxyphenyl group, 3-methyl-4-hydroxyphenyl
group, and other such alkyl group-substituted hydroxyphenyl groups;
and the 4-hydroxy-3-methoxyphenyl group,
3,5-dimethoxy-4-hydroxyphenyl group, and other such alkoxy
group-substituted hydroxyphenyl groups, but in terms of ready
availability it is preferable for Y to be the 2-hydroxyphenyl group
or 4-hydroxy-3-methoxyphenyl group. R.sup.1 is a hydrocarbon group
with two or more carbon atoms, with the various groups being the
same or different, examples of which include the ethylene group,
propylene group, butylene group, hexylene group, and other such
alkylene groups, and the phenylene group and other such arylene
groups. R is a monovalent hydrocarbon group containing no aliphatic
unsaturated bonds, with the various groups being the same or
different, examples of which include the methyl group, ethyl group,
butyl group, pentyl group, hexyl group, and other such alkyl
groups; the phenyl group, tolyl group, xylyl group, and other such
aryl group; and the benzyl group, phenethyl group, and other such
aralkyl groups. A is a divalent hydrocarbon group with one or more
carbon atoms or a group expressed by the formula
--R.sup.2--O--R.sup.2-- (where R.sup.2 is a divalent hydrocarbon
group; examples include the alkylene groups and arylene groups
listed above), examples of which include the ethylene group,
propylene group, butylene group, hexylene group, and an
ethyleneoxypropylene group. m and p are each independently 0 or 1.
n is a number from 0 to 2, and q is an integer from 0 to 7.
[0014] The compounds listed below are examples of the hydroxyphenyl
group-containing organosilicon compound of the present invention.
3
[0015] The method for manufacturing the hydroxyphenyl
group-containing organosilicon compound of the present invention
will also be described herein.
[0016] The hydroxphenyl group-containing organosilicon compound
manufacturing method of the present invention is a method for
manufacturing a hydroxphenyl group-containing organosilicon
compound comprising reacting:
[0017] (A) a silicon atom-bonded hydrogen atom-containing
organosilicon compound expressed by the general formula: 4
[0018] where X is an alkenyl group; Z is a phenylene group or a
carbonyloxy group expressed by --C(O)O--; R is a monovalent
hydrocarbon group containing no aliphatic unsaturated bonds, with
the various groups being the same or different; A is a divalent
hydrocarbon group with one or more carbon atoms or a group
expressed by the formula --R.sup.2--O--R.sup.2-- where R.sup.2 is a
divalent hydrocarbon group; m and p are 0 or 1; n is a number from
0 to 2; and q is an integer from 0 to 7 and
[0019] (B) an aliphatic unsaturated bond-containing compound
expressed by the general formula:
R.sup.3--Y
[0020] where R.sup.3 is an aliphatic unsaturated bond-containing
monovalent hydrocarbon group, and Y.sup.1 is a substituted or
unsubstituted hydroxyphenyl group in the presence of a
hydrosilylation catalyst.
[0021] Another method for manufacturing a hydroxyphenyl
group-containing organosilicon compound comprises
[0022] (I) reacting:
[0023] (A) a silicon atom-bonded hydrogen atom-containing
organosilicon compound expressed by the general formula: 5
[0024] where X is an alkenyl group; Z is a phenylene group or a
carbonyloxy group expressed by --C(O)O--; R is a monovalent
hydrocarbon group containing no aliphatic unsaturated bonds, with
the various groups being the same or different; A is a divalent
hydrocarbon group with one or more carbon atoms or a group
expressed by the formula --R.sup.2--O--R.sup.2-- where R is a
divalent hydrocarbon group; m and p are 0 or 1; n is a number from
0 to 2; and q is an integer from 0 to 7 and
[0025] (B) an aliphatic unsaturated bond-containing compound
expressed by the general formula:
R.sup.3--Y.sup.2
[0026] where R.sup.3 is an aliphatic unsaturated bond-containing
monovalent hydrocarbon group, and Y.sup.2 is a triorganosiloxified
substituted or unsubstituted hydroxyphenyl group in the presence of
a hydrosilylation catalyst, and
[0027] (II) desilylating the product of (I).
[0028] In the above-noted methods, the silicon atom-bonded hydrogen
atom-containing organosilicon compound of component (A) is such
that X, Z, A, R, n, m, and p in the above formulas are the same as
given above. These organosilicon compounds can be manufactured by a
conventional method. For instance, it is known that a silicon
atom-bonded hydrogen atom-containing organosilicon compound
expressed by the formula
CH.sub.2.dbd.C(CH.sub.3)COO(CH.sub.2).sub.3Si{OSi(CH.sub.3).sub.2H}.sub.3
can be produced by the dropwise addition of a silane expressed by
the formula H(CH.sub.3).sub.2SiCl to a silane expressed by the
formula
CH.sub.2.dbd.C(CH.sub.3)COO(CH.sub.2).sub.3Si(OCH.sub.3).sub.3 in
the presence of a mixed solvent comprising water and ether (see
U.S. Pat. No. 3,398,017). This compound can also be manufactured by
subjecting a methacrylic functional group containing chlorosilane
to hydrolysis in the presence of 1,1,3,3-tetramethyldisiloxane, or
subjecting a methacrylic functional group containing chlorosilane
to hydrolysis to produce silanol, and then subjecting this product
to a reaction with a diorganochlorosilane. Here, it is preferable
to use triethylamine, pyridine, or another such amine as a
scavenger for the hydrogen chloride that is produced so as to
suppress the condensation of the silanol groups. The above compound
can also be synthesized by allowing 1,1,3,3-tetramethyldisiloxane
to react with a silane expressed by the formula
(CH.sub.2.dbd.C(CH.sub.3)COO(CH.sub.2).sub.3Si(OCH.sub.3).sub.3 in
the presence of a strong acid and a carboxylic acid.
[0029] In the aliphatic unsaturated bond-containing phenol compound
of component (B), R.sup.3 in the above formula is an aliphatic
unsaturated bond-containing monovalent hydrocarbon group, examples
of which include the vinyl group, allyl group, isopropenyl group,
and hexenyl group. Of these, an allyl group is preferred. Y.sup.1
is a substituted or -unsubstituted hydroxyphenyl group. Examples of
Y.sup.1 are the same hydroxyphenyl groups listed as examples for Y
above. Y.sup.2 is a triorganosiloxified substituted or
unsubstituted hydroxyphenyl group. Examples of this organic group
include groups in which the hydroxyl groups of the hydroxyphenyl
groups listed as examples of Y above have been trimethylsiloxified.
It is particularly favorable for component (B) to be 2-allylphenol,
eugenol, or a trimethylsilyl ether of these. Because phenolic
hydroxyl groups undergo a dehydration condensation reaction with
silicon atom-bonded hydrogen atoms in the presence of a
hydrosilylation reaction catalyst, when a product of particularly
high purity is required, it is preferable for component (B) to be
an aliphatic unsaturated bond-containing compound in which the
phenolic hydroxyl groups have been triorganosiloxified.
[0030] Examples of hydrosilylation catalysts include transition
metal complex catalysts from Group 8 of the Periodic Table. Of
these, a platinum-based catalyst is particularly effective. Such
favorable catalysts include chloroplatinic acid and alcohol
solutions thereof, olefin complexes of platinum, complexes of
platinum and a vinyl group-containing siloxane, and other such
platinum compounds.
[0031] A method in which component (B) and the hydrosilylation
catalyst are pre-mixed, and component (A) is then slowly added
dropwise to this mixture, is preferred in order to suppress the
addition reaction velocity between the silicon atom-bonded hydrogen
atoms and the alkenyl groups in component (A). The ratio between
the amount of component (A) and the amount of component (B) is
usually such that the ratio of the equivalents of aliphatic
unsaturated bonds in component (B) with respect to the equivalents
of silicon atom-bonded hydrogen atoms in component (B) is at least
0.8. A range of 0.8 to 2.00 is preferred, and a range of 0.9 to 1.5
is particularly preferred. This reaction can be conducted without a
solvent, although it is preferable for it to be conducted in the
presence of an organic solvent. Solvents that can be used include
benzene, toluene, xylene, and other aromatics; pentane, hexane,
heptane, octane, decane, and other aliphatics; tetrahydrofuran,
diethyl ether, dibutyl ether, and other ethers; acetone, methyl
ethyl ketone, and other ketones; ethyl acetate, butyl acetate, and
other esters; and carbon tetrachloride, trichloroethane,
dichloromethylene, chloroform, and other chlorinated hydrocarbons.
The reaction can be conducted at room temperature, but it is
usually preferable for it to be conducted at a temperature between
50 and 200.degree. C. The reaction solution can be analyzed during
the reaction by gas chromatography analysis (GLC) or infrared
spectroscopic analysis (IR), and the reaction is considered to be
concluded at the point when the characteristic absorption of the
silicon atom-bonded hydrogen atom-containing organosiloxane in
component (A) disappears. Upon conclusion of the reaction, the
aliphatic unsaturated bond- and hydroxyphenyl group-containing
organosilicon compound of the present invention is obtained by
removing any unreacted component (B) or low-boiling matter such as
an organic solvent by distillation under heating and reduced
pressure.
[0032] When an aliphatic unsaturated bond compound in which the
phenolic hydroxyl groups have been triorganosiloxified is used as
component (B), an adduct in which the phenolic hydroxyl groups have
been triorganosiloxified will be obtained, and therefore these
triorganosilyl groups shall be removed and the hydroxyphenyl groups
regenerated. A conventional method can be used for this
desilylation, but a preferable method is one in which a
triorganosiloxified adduct is desilylated in the presence of a
protic solvent using an amine compound or ammonia as a catalyst;
with this method, there are no side reactions, and the targeted
hydroxyphenyl group-containing organosilicon compound is obtained
at a high yield.
[0033] Because this hydroxyphenyl group-containing organosilicon
compound of the present invention contains an aliphatic unsaturated
bond-containing monovalent hydrocarbon group in each molecule, it
is miscible in addition reaction-curing silicone compositions, and
will cure upon reaction with the organohydrogenpolysiloxanes in
these addition reaction-curing silicone compositions. Also, because
it contains hydroxyphenyl groups in its molecules, the cured
product of an addition reaction-curing silicone composition that
contains this organosilicon compound will become a cured silicone
having hydroxyphenyl groups on its surface, and will have the
characteristic of adhering to epoxy resins, phenol resins, and
various other organic resins. Therefore, the hydroxyphenyl
group-containing organosilicon compound of the present invention is
useful as an adhesion imparter in applications where this
characteristic is needed, such as the bonding of addition
reaction-curing silicone compositions to various substrates.
[0034] This invention further relates to a curable organosiloxane
composition comprising:
[0035] (A) an organopolysiloxane having at least two silicon
atom-bonded alkenyl groups per molecule;
[0036] (B) an organopolysiloxane having at least two silicon
atom-bonded hydrogen atoms per molecule;
[0037] (C) a compound having an alkenyl group and a phenol residue
expressed by the general formula: 6
[0038] where R.sup.1 is an alkyl group or alkoxy group, a is 1 or
2, and b is an integer from 0 to 3 in an amount of 0.1 to 50 weight
parts per 100 weight parts of component (A); and
[0039] (D) a hydrosilylation reaction catalyst.
[0040] Component (A) is an organopolysiloxane having at least two
silicon atom-bonded alkenyl groups per molecule. Examples of the
molecular structure of component (A) include linear, linear with
some branches, branched, cyclic, and reticulated, but linear or
branched is preferred for the purpose of the cured product of this
composition exhibiting an elastomeric form such as a gel. There are
no restrictions on the viscosity of component (A), and component
(A) can be anything from a low-viscosity organopolysiloxane
oligomer to a high-viscosity organopolysiloxane raw rubber.
However, a viscosity at 25.degree. C. within the range of 100 to
1,000,000 mm.sup.2/s is preferred because this composition will be
easier to prepare and to handle. Examples of the silicon
atom-bonded alkenyl groups in component (A) include the vinyl
group, allyl group, isopropenyl group, butenyl group, pentenyl
group, hexenyl group, heptenyl group, octenyl group, nonenyl group,
and decenyl group, with the vinyl group being particularly
preferred. Enhanced hydrosilylation reactivity will be exhibited if
the carbon-carbon double bonds in these alkenyl groups are located
at the terminals on the opposite end from the silicon atoms to
which the alkenyl groups are bonded. Examples of groups that can be
bonded to the silicon atoms besides the alkenyl groups in component
(A) include the methyl group, ethyl group, propyl group, butyl
group, pentyl group, hexyl group, and other such alkyl groups; the
phenyl group, tolyl group, xylyl group, and other such aryl groups;
the benzyl group, phenethyl group, and other such aralkyl groups;
and other monovalent hydrocarbon groups having no aliphatic
unsaturated bonds. Furthermore, a small amount of hydroxyl groups,
alkoxy groups, haloalkyl groups, or the like may also be included.
It is preferable for at least half of the groups bonded to the
silicon atoms in component (A) to be methyl groups.
[0041] Examples of the organopolysiloxane of component (A) include
a trimethylsiloxy-endblocked methylvinylpolysiloxane, a
trimethylsiloxy-endblocked dimethylsiloxane-methylvinylsiloxane
copolymer, a trimethylsiloxy-endblocked
diphenylsiloxane-methylvinylsilox- ane copolymer, a
dimethylvinylsiloxy-endblocked dimethylpolysiloxane, a
dimethylvinylsiloxy-endblocked dimethylsiloxane-methylvinylsiloxane
copolymer, a dimethylvinylsiloxy-endblocked
dimethylsiloxane-diphenylsilo- xane copolymer, a cyclic
methylvinylpolysiloxane, an organopolysiloxane comprising siloxane
units expressed by the formula SiO.sub.4/2 and siloxane units
expressed by the formula CH.sub.2.dbd.CH(CH.sub.3).sub.2Si-
O.sub.1/2, and an organopolysiloxane comprising siloxane units
expressed by the formula SiO.sub.4/2, siloxane units expressed by
the formula (CH.sub.3).sub.3SiO.sub.1/2, and siloxane units
expressed by the formula
CH.sub.2.dbd.CH(CH.sub.3).sub.2SiO.sub.1/2.
[0042] Component (B) is the curing agent of this composition, and
is an organopolysiloxane having at least two silicon atom-bonded
hydrogen atoms per molecule. Examples of the molecular structure of
component (B) include linear, linear with some branches, branched,
cyclic, reticulated, and star-shaped. There are no restrictions on
the viscosity of component (B), and component (B) may vary from a
low-viscosity organopolysiloxane oligomer to a high-viscosity
organopolysiloxane raw rubber. However, a viscosity at 25.degree.
C. within the range of 1 to 100,000 mm.sup.2/s is preferred because
this composition will be easier to handle. Examples of groups that
can be bonded to the silicon atoms besides the hydrogen atoms in
component (B) include the methyl group, ethyl group, propyl group,
butyl group, pentyl group, hexyl group, and other such alkyl
groups; the phenyl group, tolyl group, xylyl group, and other such
aryl groups; the benzyl group, phenethyl group, and other such
aralkyl groups; and other monovalent hydrocarbon groups having no
aliphatic unsaturated bonds. Furthermore, to the extent that the
object of the present invention is not compromised, a small amount
of hydroxyl groups, alkoxy groups, haloalkyl groups, or the like
may also be included. It is preferable for at least half of the
groups bonded to the silicon atoms in component (B) to be methyl
groups.
[0043] Examples of the organopolysiloxane of component (B) include
a trimethylsiloxy-endblocked methylhydrogenpolysiloxane, a
trimethylsiloxy-endblocked dimethylsiloxane-methylhydrogensiloxane
copolymer, a trimethylsiloxy-endblocked
diphenylsiloxane-methylhydrogensi- loxane copolymer, a
dimethylhydrogensiloxy-endblocked
dimethylsiloxane-methylhydrogensiloxane copolymer, a cyclic
methylhydrogenpolysiloxane, an organopolysiloxane comprising
siloxane units expressed by the formula SiO.sub.4/2 and siloxane
units expressed by the formula (CH.sub.3).sub.2HSiO.sub.1/2, and an
organopolysiloxane comprising siloxane units expressed by the
formula SiO.sub.4/2, siloxane units expressed by the formula
(CH.sub.3).sub.3SiO.sub.1/2, and siloxane units expressed by the
formula (CH.sub.3).sub.2HSiO.sub.1/2.
[0044] The amount of component (B) contained in this composition is
an amount large enough to cure this composition; from 0.5 to 20 mol
of silicon atom-bonded hydrogen atoms in this component per mole of
total alkenyl groups in components (A) and (C). It is preferred
that this amount be such that the range is from 0.5 to 10 mol, and
more particularly, from 1.0 to 5 mol. Note that a composition will
tend not to cure adequately if the content of component (B) is less
than the lower end of the above range, but if the upper end of the
above range is exceeded, the composition will tend to foam during
curing, or the physical properties of the cured product that is
obtained will tend to suffer.
[0045] Component (C) is a compound having an alkenyl group and a
phenol residue expressed by the general formula: 7
[0046] This component serves to enhance the adhesion of a variety
of thermosetting organic resins to the cured product obtained by
curing this composition. Examples of the alkenyl group in component
(C) include the vinyl group, allyl group, isopropenyl group,
butenyl group, pentenyl group, hexenyl group, heptenyl group,
octenyl group, nonenyl group, and decenyl group. In the phenol
residue in component (C), R.sup.1 in the formula is an alkyl group
or alkoxy group. Examples of this alkyl group include the methyl
group, ethyl group, n-propyl group, 1-propyl group, n-butyl group,
1-butyl group, and t-butyl group. Examples of this alkoxy include
the methoxy group, ethoxy group, and propoxy group. Also, in the
phenol residue in component (C), a in the formula is 1 or 2, and
preferably 1, and b is an integer from 0 to 3, and preferably 0 to
2. Examples of this phenol residue include the 2-hydroxyphenyl
group, 4-hydroxyphenyl group, 3,4-dihydroxyphenyl group,
3,5-dihydroxyphenyl group, 3,5-di-t-butyl-4-hydroxyphenyl group,
3-methyl-4-hydroxyphenyl group, 4-hydroxy-3-methoxyphenyl group,
and 3,5-dimethoxy-4-hydroxyphenyl group. In terms of ready
availability, the 2-hydroxyphenyl group and the
4-hydroxy-3-methoxyphenyl group are preferred.
[0047] Examples of the compound of component (C) include
2-allylphenol, eugenol, -ortho-eugenol,
4-allyl-2,6-dimethoxyphenol, and other such alkenyl
group-containing phenol compounds, and organosilicon compounds
expressed by the general formula: 8
[0048] As to the organosilicon compound of component (C), X in the
formula is an alkenyl group, examples of which include the vinyl
group, allyl group, isopropenyl group, and butenyl group, with the
allyl group and isopropenyl group being particularly preferred. Z
in the formula is an oxy group expressed by the formula --O--, a
carboxy group expressed by the formula --C(O)O--, or a phenylene
group. Examples of this phenylene group include an o-phenylene
group, m-phenylene group, and p-phenylene group. A in the formula
is a divalent hydrocarbon group, a group expressed by the
formula:
--R.sup.4--O--R.sup.4--,
[0049] or a group expressed by the formula:
--R.sup.5--O--.
[0050] Examples of the divalent hydrocarbon group of A include the
methylene group, ethylene group, propylene group, and other such
alkylene groups; and the methylenephenylene group,
ethylenephenylene group, and other such alkylenearylene groups. The
R.sup.4 groups in the above formula are the same or different
divalent hydrocarbon groups, examples of which include the
methylene group, ethylene group, propylene group, and other such
alkylene groups; and the methylenephenylene group,
ethylenephenylene group, and other such alkylenearylene groups.
R.sup.5 in the above formula is a substituted or unsubstituted
divalent hydrocarbon group, examples of which include the methylene
group, ethylene group, propylene group, and other such alkylene
groups, the methylenephenylene group, ethylenephenylene group, and
other such alkylenearylene groups, and other unsubstituted divalent
hydrocarbon groups, or the hydroxyethylene group, hydroxypropylene
group, and other hydroxy group-substituted divalent hydrocarbon
groups. It is preferable for this A to be an alkylene group, or a
methyleneoxyethylene group, methyleneoxypropylene group,
ethyleneoxypropylene group, propyleneoxypropylene group, or other
such alkyleneoxyalkylene group, with an alkylene group being
particularly preferred. R.sup.1 in the formula is an alkyl group or
alkoxy group, examples of which are the same as those listed above.
The R.sup.2 groups in the formula are the same or different
monovalent hydrocarbon groups having no aliphatic unsaturated
bonds, examples of which include the methyl group, ethyl group,
propyl group, butyl group, pentyl group, hexyl group, and other
such alkyl groups; the phenyl group, tolyl group, xylyl group, and
other such aryl groups; and the benzyl group, phenethyl group, and
other such aralkyl groups, with the methyl group being particularly
favorable. The R.sup.3 groups in the formula are the same or
different divalent hydrocarbon groups or groups expressed by the
formula:
--R.sup.6--O--
[0051] Examples of the divalent hydrocarbon group of R.sup.3
include the methylene group, ethylene group, propylene group, and
other such alkylene groups; and the methylenephenylene group,
ethylenephenylene group, and other such alkylenearylene groups. It
is preferred that these R.sup.3 groups be alkylene groups. a in the
formula is 1 or 2, and preferably 1. b in the formula is an integer
from 0 to 3, and preferably an integer from 0 to 2. m in the
formula is 0 or 1. n in the formula is an integer from 0 to 2. p in
the formula is 0 or 1. q in the formula is an integer from 0 to 7,
and preferably 0 or 1. It is particularly preferred that the
organosilicon compound of component (C) be an organosilicon
compound in which X in the general formula given above is an
isopropenyl group, Z is a carboxy group expressed by the formula
--C(O)O--, p is 1, and m is 1, or more specifically, an
organosilicon compound expressed by the general formula: 9
[0052] or an organosilicon compound in which Z in the general
formula given above is an oxy group expressed by the formula --O--,
p is 1, and q is 1, or more specifically, an organosilicon compound
expressed by the general formula: 10
[0053] The following compounds of this organosilicon compound of
components (C). 11
[0054] The amount of component (C) which is contained in this
composition is between 0.1 and 50 weight parts, with 1 and 20
weight parts preferred, and between 1 and 10 weight parts, per 100
weight parts of component A particularly preferred
[0055] Component (D) is a hydrosilylation reaction catalyst that
serves to promote the curing of this composition. A conventional
catalyst can be used as this component (D), specific examples of
which include chloroplatinic acid, an alcohol solution of
chloroplatinic acid, an olefin complex of platinum, a diketone
complex of platinum, an acetyl acetate complex of platinum, a vinyl
group-containing siloxane complex of platinum, and other
platinum-based catalysts; a triphenylphosphine complex of rhodium
and other rhodium-based catalysts; a tetrakis(triphenylphosphine)
palladium complex and other palladium-based catalysts; compounds of
ruthenium, iridium, iron, cobalt, manganese, zinc, lead, aluminum,
nickel, and the like; and peroxides, azo compounds, and other
radical generators. Of these, a platinum-based catalyst is
preferred because it promotes a hydrosilylation reaction especially
well. Two or more types of the above catalysts may also be used
together as needed for this hydrosilylation reaction catalyst.
[0056] The amount of component (D) which is contained in this
composition is an amount large enough to promote the curing of this
composition, and when a platinum-based catalyst is used as
component (D), it is preferred for the platinum metal in component
(D) to be contained in this composition in an amount between 0.01
and 1000 ppm (weight units), with an amount between 0.1 to 500 ppm
being particularly preferred, and an amount between 0.1 to 100 ppm
being most preferred.
[0057] This composition is prepared by mixing the above-mentioned
components (A) to (D). A hydrosilylation reaction inhibitor may
also be added as an optional component for enhancing the storage
stability of this composition. Examples of this hydrosilylation
reaction inhibitor include triphenylphosphine and other phosphorus
compounds, tributylamine, tetramethylethylenediamine,
benzotriazole, and other nitrogen-containing compounds,
sulfur-containing compounds, acetylene-based compounds, compounds
having two or more alkenyl groups, compounds containing alkynyl
groups, hydroperoxy compounds, maleic acid derivatives, and other
such known compounds, with compounds having two or more alkynyl
groups being preferred, and compounds having at least two alkynyl
groups per molecule, compounds having an alkynyl group and an
alcoholic hydroxyl group per molecule,
1,3-divinyl-1,1,3,3-tetramethyldisiloxane, and maleic diesters
being particularly preferred.
[0058] There are no particular restrictions on the amount in which
this hydrosilylation reaction inhibitor is contained in this
composition, but the hydrosilylation reaction inhibition effect
will be inadequate if this amount is too small, and curing will be
far slower if the amount is too large, so it is preferable for this
inhibitor to be contained in this composition in an amount between
0.1 and 50,000 ppm (weight units).
[0059] A known adhesion promoter can also be added to this
composition as another optional component in order to improve
adhesion with metal, glass, and other inorganic substances. A
pigment can also be contained for coloring, a reinforcing filler to
increase strength, a plasticizer to enhance melting under heating
and to make the composition easier to work with, an additive for
improving thermal conductivity, or a filler to increase electrical
conductivity, for example.
[0060] The curable organosiloxane composition of the present
invention cures quickly at room temperature or under heating and
can be molded into a cured product in the form of a resin or in an
elastomeric form such as a gel or rubber. A characteristic of the
present invention is that epoxy resins, phenol resins, melamine
resins, urea resins, polyurethane resins, polyimide resins, and
other such thermosetting organic resins adhere well to this cured
product, so it can be used favorably as a silicone rubber
composition for compound molding, or as a silicone-type die bonding
agent.
[0061] The organosilicon compound and curable organosiloxane
composition of the present invention will now be described in
further detail through working examples. The viscosity mentioned in
these examples is the value measured at 25.degree. C.
EXAMPLES
Reference Example 1
[0062] 73.7 g of 1,1,3,3-tetramethyldisiloxane, 18 g of ice, 100 g
of water, and 50 g of concentrated hydrochloric acid were added to
a flask equipped with an agitator, a thermometer, a condenser, and
a dropping funnel. 215.7 g of
methacryloxypropyldimethylchlorosilane was added dropwise to the
flask while the system was cooled in an ice bath so that the
reaction temperature did not exceed 10.degree. C. Upon completion
of the dropping, the flask was allowed to stand so as to separate
the aqueous layer, and the organic layer thus obtained was washed
twice with water. This organic layer was then washed twice with a
5% aqueous solution of sodium hydrogencarbonate, and washed two
more times with water. After the removal of the aqueous layer,
sodium sulfate was added to the organic layer to dry it, after
which the sodium sulfate was filtered off. 0.6 g of phenothiazine
was then added to this product, and the system was distilled under
reduced pressure, which yielded 198 g of a fraction of 71 to
80.degree. C./1 mmHg. This fraction was analyzed by nuclear
magnetic resonance (hereinafter referred to as NMR) and infrared
spectroscopic analysis (hereinafter referred to as IR), which
revealed it to be a disiloxane expressed by the following formula
1: 12
Working Example 1
[0063] 28.66 g of the compound expressed by the following formula
2, 0.030 g of a polymerization inhibitor expressed by the following
formula 3, and 17 .mu.L of a toluene solution of a complex of
chloroplatinic acid and 1,3-divinyltetramethyl-disiloxane (platinum
metal concentration: 2 wt %) were added to a 100 mL three-necked
flask to which a thermometer and a dropping funnel had been
attached. The system was then heated to 80.degree. C., and 4.02 g
of the trisiloxane expressed by the following formula 7 was added
dropwise. Upon completion of this dropping, the system was agitated
for 40 minutes at 80.degree. C., the reaction solution was analyzed
by GLC and IR, and the reaction was concluded at the point when the
signal representing the disiloxane in the raw material had
disappeared according to GLC and the signal representing the
silicon atom-bonded hydrogen atoms had disappeared according to IR.
The unreacted compounds expressed by the following formulae (2 and
3) were distilled off from the reaction solution under heating and
reduced pressure, which yielded 54.54 g of residue. 13
[0064] 53.90 g of this residue, 45.0 g of methanol, 30.0 g of
tetrahydrofuran, 1.24 g of diethylamine, and a rotator were then
placed in a 200 mL four-necked flask to which a reflux condenser
and a thermometer had been attached, and the system was heated to
reflux for 2 hours at 60.degree. C. The low-boiling matter was then
distilled off, which yielded 46.73 g of residue. This was analyzed
by NMR and IR, which revealed it to be a hydroxyphenyl
group-containing methacrylic functional organosilicon compound
expressed by the following formula 4. GLC revealed the purity of
this organosilicon compound to be 93.9%. 14
Reference Example 2
[0065] As noted above, 73.7 g of 1,1,3,3-tetramethyldisiloxane, 18
g of ice, 100 g of water, and 50 g of concentrated hydrochloric
acid were placed in a 1 L flask equipped with an agitator, a
thermometer, a cooling pipe, and a dropping funnel. 215.7 g (1 mol)
of 3-methacryloxypropyldimet- hylchlorosilane was added dropwise to
this flask while the system was cooled in an ice bath so that the
reaction temperature would not exceed 10.degree. C. Upon completion
of this dropping, the flask was allowed to stand so as to separate
the aqueous layer, and the organic layer thus obtained was washed
twice with water. This organic layer was washed twice with a 5%
sodium hydrogencarbonate aqueous solution, and then washed two more
times with water. After the removal of the aqueous layer, sodium
sulfate was added to the resulting organic layer to dry it, after
which the sodium sulfate was filtered off. 0.6 g of phenothiazine
was then added to this product, and the system was distilled under
reduced pressure, which yielded 198 g of a fraction of 71 to
80.degree. C./1 mmHg. This fraction was analyzed by nuclear
magnetic resonance (hereinafter referred to as NMR) and infrared
spectroscopic analysis (hereinafter referred to as IR), which
revealed it to be a disiloxane expressed by the following formula.
15
[0066] This disiloxane was analyzed by gas chromatography
(hereinafter referred to as GLC), which revealed the purity to be
99%.
Reference Example 3
[0067] A rotor, 28.66 g of the compound expressed by the formula:
16
[0068] 0.030 g of a polymerization inhibitor expressed by the
formula: 17
[0069] and 17 .mu.L of a toluene solution of a complex prepared
from chloroplatinic acid and 1,3-divinyltetramethyldisiloxane
(platinum metal concentration: 2 wt %) were placed in a 100 mL
three-necked flask to which a reflux condenser, a thermometer, and
a dropping funnel had been attached. The system was then heated to
80.degree. C., and 30.03 g of the disiloxane synthesized in
Reference Example 2 was added dropwise. Upon completion of this
dropping, the system was agitated for 40 minutes at 80.degree. C.,
and the reaction solution was analyzed by GLC and IR, wherein GLC
revealed that the signal representing the disiloxane in the raw
material had disappeared, and IR that the signal representing the
silicon atom-bonded hydrogen atoms had disappeared. The unreacted
compounds were distilled off from the reaction solution under
heating and reduced pressure, which yielded 54.54 g of residue.
[0070] 53.90 g of this residue, 45.0 g of methanol, 30.0 g of
tetrahydrofuran, 1.24 g of diethylamine, and a rotor were then
placed in a 200 mL flask to which a reflux condenser and a
thermometer had been attached, and the system was heated to reflux
for 2 hours at 60.degree. C. The low-boiling matter was then
distilled off, which yielded 46.73 g of residue. This was analyzed
by NMR and IR, which revealed it to be a phenol group-containing
methacrylic functional organosilicon compound expressed by the
formula: 18
[0071] GLC revealed the purity of this organosilicon compound to be
93.9%.
Reference Example 4
[0072] A rotor, 6.19 g of the compound expressed by the formula:
19
[0073] 0.0048 g of a polymerization inhibitor expressed by the
formula: 20
[0074] and 3 .mu.L of a toluene solution of a platinum
vinylsiloxane complex prepared from chloroplatinic acid and
1,3-divinyltetramethyldisil- oxane (platinum metal concentration: 2
wt %) were placed in a 50 mL two-necked flask to which a
thermometer and a dropping funnel had been attached. The system was
then heated to 80.degree. C., and 4.01 g of the trisiloxane
expressed by the formula: 21
[0075] was added dropwise. Upon completion of this dropping, the
system was agitated for 1 hour at 95.degree. C., and the reaction
solution was analyzed by GLC and IR, wherein GLC revealed that the
signal representing the disiloxane in the raw material had
disappeared, and IR that the signal representing the silicon
atom-bonded hydrogen atoms had disappeared. It was concluded from
this that the reaction had concluded, and the unreacted compounds
were distilled off from the reaction solution under heating and
reduced pressure. A reflux condenser was then attached, 6.00 g of
methanol and 0.15 g of diethylaamine were added, and the system was
heated to reflux for 1 hour at 56.degree. C. The low-boiling matter
was then distilled off, which yielded 7.69 g of residue. This was
analyzed by NMR and IR, which revealed it to be a phenol
group-containing methacrylic functional organosilicon compound
expressed by the formula: 22
[0076] NMR revealed the purity of this organosilicon compound to be
88%.
Reference Example 5
[0077] 100 g of toluene and 50 .mu.L of a toluene solution of a
platinum vinylsiloxane complex prepared from chloroplatinic acid
and 1,3-divinyltetramethyldisiloxane (platinum metal concentration:
2 wt %) were placed in a 300 mL four-necked flask to which a reflux
condenser, a thermometer, a dropping funnel, and an agitator had
been attached. The system was then heated to 90.degree. C., and
113.80 g of the organosilicon compound expressed by the formula:
23
[0078] was added dropwise. Upon completion of this dropping, the
system was agitated for 3 hours at 100.degree. C., and the reaction
solution was analyzed by IR, which revealed that the reaction had
concluded since the signal representing silicon atom-bonded
hydrogen atoms had almost completely disappeared. The above
reaction solution was poured into a 500 mL four-necked flask
equipped with a reflux condenser, a thermometer, an agitator, to
which 101 g of allyl alcohol, 40 g of tetrahydrofuran, and 20 mL of
diethylamine were added, and the system was agitated for 14 hours
at 90.degree. C. Upon completion of this agitation, low-boiling
matter was distilled off from the reaction solution under heating,
which yielded 116.50 g of reaction product. This was analyzed by
NMR and IR, which revealed it to be an organosilicon compound
expressed by the formula: 24
[0079] GLC revealed the purity of this organosilicon compound to be
93.4%.
Working Example 2
[0080] A curable organosiloxane composition was prepared by mixing
10.01 g of a dimethylvinylsiloxy group-capped dimethylpolysiloxane
capped at both ends of the molecular chain and having a viscosity
of 20000 mm.sup.2/s, 0.3754 g of a trimethylsiloxy group-capped
methylhydrogenpolysiloxane capped at both ends of the molecular
chain and having a viscosity of 30 mm.sup.2/s, 0.505 g of eugenol,
0.613 mg of phenylbutynol, and a complex of chloroplatinic acid and
1,3-divinyltetramethyldisiloxane in an amount such that the amount
of platinum metal was 1 ppm with respect to the total amount of the
composition.
[0081] This curable organosiloxane composition was cast onto a
polyfluoroethylene plate and left in a 150.degree. C. oven for 1
hour to cure, which yielded a silicone rubber sheet with a
thickness of 10 mm. A polyfluoroethylene resin sheet with a hole in
its center was placed on the surface of this silicone rubber sheet,
and a commercially available curable epoxy resin was cast into this
hole. A polyfluoroethylene resin sheet was then laid over this, and
a weight placed on top. This test piece was put in a 150.degree. C.
oven and left for 1 hour, which cured the epoxy resin and produced
a molded article in which the epoxy resin was integrated with the
silicone rubber. The epoxy resin was then peeled away from this
molded article, and the failure interface between the epoxy resin
and the silicone rubber was observed visually, which revealed that
this failure interface was cohesive failure, failing entirely in
the silicone rubber layer. This revealed that the epoxy resin and
the silicone rubber were securely bonded together.
[0082] Other than using a phenol/epoxy resin whose main components
were an epoxy resin and a phenol resin instead of the commercially
available epoxy resin used above, the adhesion of a phenol/epoxy
resin to silicone rubber was examined in the same way as above.
This phenol/epoxy resin was prepared by uniformly mixing 100 weight
parts epoxy resin, 10 weight parts phenol resin, 5 weight parts
3-glycidoxy-propyltrimethoxysilane, and 20 weight parts
imidazole-based curing agent. As a result, it was found that the
failure interface was cohesive failure, failing entirely in the
silicone rubber layer.
Working Example 3
[0083] A curable organosiloxane composition was prepared from 10.01
g of a dimethylvinylsiloxy group-capped
dimethylpolysiloxane-diphenylsiloxane copolymer capped at both ends
of the molecular chain and having a viscosity of 2000 mm.sup.2/s,
0.1542 g of a trimethylsiloxy group-capped
methylhydrogenpolysiloxane capped at both ends of the molecular
chain and having a viscosity of 20 mm.sup.2/s, 0.499 mg of
phenylbutynol, and 0.413 g of phenol group-containing methacrylic
functional organosilicon compound prepared in Reference Example
4.
[0084] Next, a complex of chloroplatinic acid and
1,3-divinyltetramethyldi- siloxane was added to this composition in
an amount such that the amount of platinum metal was 1 ppm with
respect to the total amount of the composition, to prepare a
curable organosiloxane composition. This curable organosiloxane
composition was cast onto a polyfluoroethylene plate and left in a
150.degree. C. oven for 1 hour to cure, which produced a silicone
rubber sheet with a thickness of 10 mm. A polyfluoroethylene resin
sheet with hole made in its center was placed on the surface of
this silicone rubber sheet, and a commercially available curable
epoxy resin was cast into this hole. A polyfluoroethylene resin
sheet was then laid over this, and a weight placed on top. This
test piece was placed in a 150.degree. C. oven and left for 1 hour,
which cured the epoxy resin and produced a molded article in which
the epoxy resin was integrated with the silicone rubber. The epoxy
resin was then peeled away from this molded article, and the
failure interface between the epoxy resin and the silicone rubber
was observed visually, which revealed that this failure interface
was cohesive failure, failing entirely in the silicone rubber
layer. This revealed that the epoxy resin and the silicone rubber
were securely bonded together.
[0085] Other than using a phenol/epoxy resin whose main components
were an epoxy resin and a phenol resin instead of the commercially
available epoxy resin used above, the adhesion of a phenol/epoxy
resin to silicone rubber was examined in the same way as above.
This phenol/epoxy resin was prepared by uniformly mixing 100 weight
parts epoxy resin, 10 weight parts phenol resin, 5 weight parts
3-glycidoxypropyltrimethoxysilane, and 20 weight parts
imidazole-based curing agent. As a result, it was found that the
failure interface was cohesive failure, failing entirely in the
silicone rubber layer.
Working Example 4
[0086] An organopolysiloxane composition was prepared from 10.01 g
of a dimethylvinylsiloxy group-capped dimethylpolysiloxane capped
at both ends of the molecular chain and having a viscosity of 2000
mm.sup.2/s, 1.00 g of fumed silica treated with
hexamethyldisilazane, 0.27 g of a trimethylsiloxy group-capped
methylhydrogenpolysiloxane capped at both ends of the molecular
chain and having a viscosity of 20 mm.sup.2/s, 1.014 g of the
phenol group-containing organosilicon compound obtained in
Reference Example 3, 2.81 mg of phenylbutynol, and a complex of
chloroplatinic acid and 1,3-divinyltetramethyldisiloxane in an
amount such that the amount of platinum metal was 1 ppm with
respect to the total amount of the composition. This curable
organosiloxane composition was cast onto a polyfluoroethylene plate
and left in a 150.degree. C. oven for 1 hour to cure, which
produced a silicone rubber sheet with a thickness of 10 mm. A
polyfluoroethylene resin sheet with a hole made in its center was
placed on the surface of this silicone rubber sheet, and a
commercially available curable epoxy resin was cast into this hole.
A polyfluoroethylene resin sheet was then laid over this, and a
weight placed on top. This test piece was put in a 150.degree. C.
oven and left for 1 hour, which cured the epoxy resin and produced
a molded article in which the epoxy resin was integrated with the
silicone rubber. The epoxy resin was then peeled away from this
molded article, and the failure interface between the epoxy resin
and the silicone rubber was observed visually, which revealed that
this failure interface was cohesive failure, failing entirely in
the silicone rubber layer. This revealed that the epoxy resin and
the silicone rubber were securely bonded together.
[0087] Other than using a phenol/epoxy resin whose main components
were an epoxy resin and a phenol resin instead of the commercially
available epoxy resin used above, the adhesion of a phenol/epoxy
resin to silicone rubber was examined in the same way as above.
This phenol/epoxy resin was prepared by uniformly mixing 100 weight
parts epoxy resin, 10 weight parts phenol resin, 5 weight parts
3-glycidoxypropyltrimethoxysilane, and 20 weight parts
imidazole-based curing agent. As a result, it was found that the
failure interface was cohesive failure, failing entirely in the
silicone rubber layer.
Working Example 5
[0088] An organopolysiloxane composition was prepared by mixing
10.01 g of a dimethylvinylsiloxy group-capped dimethylpolysiloxane
capped at both ends of the molecular chain and having a viscosity
of 2000 mm.sup.2/s, 0.2272 g of a trimethylsiloxy group-capped
methylhydrogenpolysiloxane capped at both ends of the molecular
chain and having a viscosity of 30 mm.sup.2/s, 0.499 mg of
phenylbutynol, 0.42 g of the organosilicon compound obtained in
Reference Example 5, and a complex of chloroplatinic acid and
1,3-divinyltetramethyldisiloxane in an amount such that the amount
of platinum metal was 1 ppm with respect to the total amount of the
composition.
[0089] This curable organosiloxane composition was cast onto a
polyfluoroethylene plate and left in a 150.degree. C. oven for 1
hour to cure, which produced a silicone rubber sheet with a
thickness of 10 mm. A polyfluoroethylene resin sheet with a hole
made in its center was placed on the surface of this silicone
rubber sheet, and a commercially available curable epoxy resin was
cast into this hole. A polyfluoroethylene resin sheet was then laid
over this, and a weight placed on top. This test piece was placed
in a 150.degree. C. oven and left for 1 hour, which cured the epoxy
resin and produced a molded article in which the epoxy resin was
integrated with the silicone rubber. The epoxy resin was then
peeled away from this molded article, and the failure interface
between the epoxy resin and the silicone rubber was observed
visually, which revealed that this failure interface was cohesive
failure, failing entirely in the silicone rubber layer. This
revealed that the epoxy resin and the silicone rubber were securely
bonded together.
[0090] Other than using a phenol/epoxy resin whose main components
were an epoxy resin and a phenol resin instead of the commercially
available epoxy resin used above, the adhesion of a phenol/epoxy
resin to silicone rubber was examined in the same way as above.
This phenol/epoxy resin was prepared by uniformly mixing 100 weight
parts epoxy resin, 10 weight parts phenol resin, 5 weight parts
3-glycidoxypropyltrimethoxysilane, and 20 weight parts
imidazole-based curing agent. As a result, it was found that the
failure interface was cohesive failure, failing entirely in the
silicone rubber layer.
Comparative Example 1
[0091] An organopolysiloxane composition was prepared from 10.04 g
of a dimethylvinylsiloxy group-capped dimethylpolysiloxane capped
at both ends of the molecular chain and having a viscosity of 2000
mm.sup.2/s, 0.3620 g of a trimethylsiloxy group-capped
methylhydrogenpolysiloxane capped at both ends of the molecular
chain and having a viscosity of 30 mm.sup.2/s, 0.594 g of the
alicyclic epoxy functional compound expressed by the formula:
25
[0092] 0.538 mg of phenylbutynol, and a complex of chloroplatinic
acid and 1,3-divinyltetramethyldisiloxane in an amount such that
the amount of platinum metal was 1 ppm with respect to the total
amount of the composition.
[0093] This curable organosiloxane composition was cast onto a
polyfluoroethylene plate and left in a 150.degree. C. oven for 1
hour to cure, which produced a silicone rubber sheet with a
thickness of 10 mm. A polyfluoroethylene resin sheet with a hole
made in its center was placed on the surface of this silicone
rubber sheet, and a commercially available curable epoxy resin was
cast into this hole. A polyfluoroethylene resin sheet was then laid
over this, and a weight placed on top. This test piece was placed
in a 150.degree. C. oven and left for 1 hour, which cured the epoxy
resin and produced a molded article in which the epoxy resin was
integrated with the silicone rubber. The epoxy resin was then
peeled away from this molded article, and the failure interface
between the epoxy resin and the silicone rubber was observed
visually, which revealed that this failure interface was peeling at
the interface between the silicone rubber layer and the epoxy resin
layer, and 100% of the interface had peeled.
* * * * *