U.S. patent application number 13/253837 was filed with the patent office on 2012-02-02 for base material for adhesion and silicone rubber-adhered article using thereof.
This patent application is currently assigned to ASAHI RUBBER INC.. Invention is credited to Kunio MORI, Kazuhisa TAKAGI.
Application Number | 20120028042 13/253837 |
Document ID | / |
Family ID | 41265915 |
Filed Date | 2012-02-02 |
United States Patent
Application |
20120028042 |
Kind Code |
A1 |
MORI; Kunio ; et
al. |
February 2, 2012 |
BASE MATERIAL FOR ADHESION AND SILICONE RUBBER-ADHERED ARTICLE
USING THEREOF
Abstract
A base material for adhesion to be adhered to a solid body
includes a substrate made from metal, polymer resin, glass or
ceramics whose surface is adhesive to the solid body by
silyl-ether-linkage that at least one active silyl group selected
from the group consisting of a hydrosilyl-containing silyl group, a
vinyl-containing silyl group, an alkoxysilyl-containing silyl group
and a hydrolytic group-containing silyl group having reactivity
with a reactive group on the surface of the solid body is bound to
a dehydrogenated residue of hydroxyl group on the surface of the
substrate.
Inventors: |
MORI; Kunio; (Morioka-shi,
JP) ; TAKAGI; Kazuhisa; (Saitama-shi, JP) |
Assignee: |
ASAHI RUBBER INC.
Saitama-shi
JP
|
Family ID: |
41265915 |
Appl. No.: |
13/253837 |
Filed: |
October 5, 2011 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
12149673 |
May 6, 2008 |
8062466 |
|
|
13253837 |
|
|
|
|
Current U.S.
Class: |
428/354 ;
428/355R; 501/11; 525/445; 525/446; 525/477; 556/173 |
Current CPC
Class: |
C09J 2483/00 20130101;
Y10T 428/2848 20150115; Y10T 428/2852 20150115; C09J 7/35
20180101 |
Class at
Publication: |
428/354 ;
525/446; 525/445; 525/477; 501/11; 556/173; 428/355.R |
International
Class: |
B32B 7/12 20060101
B32B007/12; C09J 7/02 20060101 C09J007/02; C03C 3/00 20060101
C03C003/00; C07F 19/00 20060101 C07F019/00; C08G 63/91 20060101
C08G063/91; C08G 77/38 20060101 C08G077/38 |
Claims
1. A base material for adhesion to be adhered to a solid body
comprising: a substrate made from metal, polymer resin, glass or
ceramics whose surface is adhesive to the solid body by
silyl-ether-linkage that at least one active silyl group selected
from the group consisting of a hydrosilyl-containing silyl group, a
vinyl-containing silyl group, an alkoxysilyl-containing silyl group
and a hydrolytic group-containing silyl group having reactivity
with a reactive group on the surface of the solid body is bound to
a dehydrogenated residue of hydroxyl group on the surface of the
substrate.
2. The base material for adhesion according to claim 1, wherein the
hydroxyl group is an inherent hydroxyl group on the surface of the
substrate, or a generated hydroxyl group on the surface of the
substrate by corona discharge treatment, atmospheric-pressure
plasma treatment or ultraviolet irradiation treatment, and is bound
to the active silyl group from an alkoxysilyl group of an
alkoxysilane compound through the silyl-ether-linkage.
3. The base material for adhesion according to claim 2, wherein the
surface of the solid body has hydroxyl group by oxidation and said
hydroxyl group is bound to the active silyl group from the
alkoxysilyl group through the silyl-ether-linkage.
4. The base material for adhesion according to claim 3, wherein the
silyl-ether-linkage from the alkoxysilane compound constitutes a
monomolecular layer.
5. The base material for adhesion according to claim 1, wherein the
active silyl group is; the hydrosilyl-containing silyl group
selected from a monohydrosilyl-containing silyl group and a
dihydrosilyl-containing silyl group; the vinyl-containing silyl
group as a vinylsilyl-containing silyl group; the
alkoxysilyl-containing silyl group selected from a
terminal-trialkoxysilyl-containing silyl group and a
terminal-dialkoxysilyl-containing silyl group; the hydrolytic
group-containing silyl group having a hydrolysable functional group
selected from an acyloxysilyl group, an alkenyloxysilyl group, an
alkaniminooxy group, an alkyloxysilyl group, an alkylaminosilyl
group, a dialkylaminosilyl group, a nitrogenous heterocyclic
substituted silyl group and a arylaminosilyl group.
6. The base material for adhesion according to claim 5, wherein the
active silyl group is the hydrosilyl-containing silyl group having
--SiH(R.sup.1).sub.2 group or --SiH.sub.2(R.sup.2) group on the
terminal thereof in which R.sup.1 and R.sup.2 are an alkyl group
having 1 to 4 carbon atoms, or --SiH-- group between both terminals
thereof.
7. The base material for adhesion according to claim 5, wherein the
active silyl group is the vinylsilyl-containing silyl group having
--Si--R.sup.3 group on the terminal thereof in which R.sup.3 is a
vinyl-containing group, or --Si(R.sup.4)-- group between both
terminals thereof in which R.sup.4 is a vinyl-containing group.
8. The base material for adhesion according to claim 5, wherein the
active silyl group is the terminal-alkoxysilyl-containing silyl
group having --Si(OR.sup.5).sub.2R.sup.6 group on the terminal
thereof in which R.sup.5 and R.sup.6 are an alkyl group having 1 to
4 carbon atoms, or --Si(OR.sup.7).sub.3 group on the terminal
thereof in which R.sup.7 is alkyl group having 1 to 4 carbon
atoms.
9. The base material for adhesion according to claim 5, wherein the
active silyl group is the hydrolytic group-containing silyl group
having the hydrolysable functional group represented by
--Si(R.sup.8).sub.a(R.sup.9).sub.3-a group in which R.sup.8 is
selected from hydrogen atom; a halogen atom; an alkyl group that
respectively have 1 to 12 carbon atoms; an aralkyl group; and aryl
group, R.sup.9 is selected from an acyloxy group, alkenyloxy group,
an alkaniminooxy group, an alkyloxy group, an alkylamino group and
a dialkylamino group that respectively have 1 to 12 carbon atoms; a
nitrogenous heterocyclic group and an arylamino group, and a is a
number of 0 to 3.
10. The base material for adhesion according to claim 1, wherein
the reactive group is at least one selected from the group
consisting of hydrosilyl, vinylsilyl, hydroxysilyl, alkyloxysilyl,
alkenyloxysilyl, acyloxysilyl, iminooxysilyl and
alkylaminosilyl.
11. The base material for adhesion according to claim 1, wherein
the active silyl group is the vinyl-containing silyl group, a
platinum-containing catalyst or a rhodium-containing catalyst is
applied on the surface of the substrate that exposes the active
silyl group, and the reactive group is hydrosilyl.
12. The base material for adhesion according to claim 11, wherein
the platinum-containing catalyst is a platinum complex, and the
rhodium-containing catalyst is a rhodium complex.
13. The base material for adhesion according to claim 11, wherein
the platinum-containing catalyst or the rhodium-containing catalyst
is applied to the surface of the substrate by coating or immersing
with a solution or a suspension including thereof.
14. The base material for adhesion according to claim 11, wherein
platinum atom of the platinum-containing catalyst or rhodium atom
of the rhodium-containing catalyst coordinates with plural groups
of the vinyl-containing silyl group.
15. The base material for adhesion according to claim 11, wherein
the vinyl-containing silyl group is derived from a vinyl-containing
silyl compound selected from
(CH.sub.2.dbd.CH--)(CH.sub.3O--).sub.2Si--O--[(CH.sub.2.dbd.CH--)(CH.sub.-
3O--)Si--O].sub.b1--Si(--OCH.sub.3).sub.2(--CH.dbd.CH.sub.2) in
which b1 is a number of 0 to 100,
(CH.sub.2.dbd.CH--)(C.sub.2H.sub.5O--).sub.2Si--O--[(CH.sub.2.dbd.CH--)(C-
.sub.2H.sub.5O--)Si--O].sub.b2--Si(--OC.sub.2H.sub.5).sub.2(--CH.dbd.CH.su-
b.2) in which b2 is a number of 0 to 100, or
(CH.sub.2.dbd.CH--)(C.sub.3H.sub.7O--).sub.2Si--O--[(CH.sub.2.dbd.CH--)(C-
.sub.3H.sub.7O--)Si--O].sub.b3--Si(--OC.sub.3H.sub.7).sub.2(--CH.dbd.CH.su-
b.2) in which b3 is a number of 1 to 100.
16. The base material for adhesion according to claim 1, wherein
the solid body is made from silicone rubber or silicone resin.
17. A silicone rubber-adhered article comprising; the base material
for adhesion according to claim 1, and an adhesive silicone rubber
blanket made from polysiloxane, vinyl silicone and/or silanol
silicone that is adhered to the surface of the substrate of the
base material for adhesion.
18. The silicone rubber-adhered article according to claim 17,
wherein plural of the base material for adhesion are adhered
through the adhesive silicone rubber blanket which is granular,
textile, membranous, filmy or plate-like.
19. The silicone rubber adhered article according to claim 17,
wherein the polysiloxane is represented by
H(CH.sub.3).sub.2SiO[SiH(CH.sub.3)O].sub.c[Si(R.sup.11)R.sup.12O].sub.dSi-
(CH.sub.3).sub.2H in which R.sup.11 and R.sup.12 are an alkyl
group, an alkenyl group, an alkyloxy group or a fluoro-substituted
alkyl group that respectively have 1 to 12 carbon atoms; an aralkyl
group; an aryl group; or HSi(CH.sub.3).sub.2O--, c is a number of 1
to 80, and d is a number of 0 to 80, the vinyl silicone is
represented by
CH.sub.2.dbd.CH(CH.sub.3).sub.2SiO[SiCH.dbd.CH.sub.2(CH.sub.3)O].sub.e[Si-
(R.sup.13)R.sup.14O].sub.fSi(CH.sub.3).sub.2CH.dbd.CH.sub.2 in
which R.sup.13 and R.sup.14 are an alkyl group, an alkenyl group,
an alkyloxy group or a fluoro-substituted alkyl group that
respectively have 1 to 12 carbon atoms; an aralkyl group; or an
aryl group, e is a number of 1 to 80, and f is a number of 0 to 80,
the silanol silicone is represented by
A-(CH.sub.3).sub.2SiO[Si(CH.sub.3).sub.2O].sub.g
[Si(R.sup.15)R.sup.16O].sub.hSi(CH.sub.3)--.sub.2-A in which
R.sup.15 and R.sup.16 are an alkyl group, an alkenyl group, an
alkyloxy group or a fluoro-substituted alkyl group that
respectively have 1 to 12 carbon atoms; and aralkyl group; or an
aryl group, A is hydroxyl group, an alkyloxy group, an alkenyloxy
group, an aryloxy group, an acyloxy group that respectively have 1
to 4 carbon atoms, an iminooxy group, or an amino group, g is a
number of 1 to 80, and h is a number of 0 to 80.
Description
[0001] This application is a divisional application of application
Ser. No. 12/149,673 filed May 6, 2008. The entire disclosure of the
prior application is incorporated herein by reference.
TECHNICAL FIELD
[0002] The present invention relates to a substrate made from
metal, polymer resin, glass or ceramics whose surface is prepared
to be adhesive to silicone rubber, and an adhesive article of the
substrate and the silicone rubber.
BACKGROUND ART
[0003] For adhering an adherend material made from a hard raw
material such as metal or ceramics and an adhesive material made
from a soft raw material such as silicone rubber, physical adhesion
by molecular interaction on the adhesive interface of the materials
or chemical adhesion by formation of chemical bond thereon is
performed.
[0004] As such physical adhensive method, a mechanical adhesive
method in which the texture of the surface of an adherend material
is roughened in order to increase its contacting area to an
adhesive material is known. As such chemical adhesive method, an
adhesive method using an adhesive agent in which a heat-hardening
adhesive agent is applied to an adherend material and then an
adhesive material is pressed against the adherend material is
known. A surface treatment method in which a reactive group is
introduced onto the surface of an adherend material by the surface
treatment and then the adherend material binds chemically to the
surface molecule of an adhesive material is also known as another
chemical adhesive method. Also, Japanese Patent Provisional
Publication No. 2006-198797 discloses another method of improving
the reactivity of vinyl group with silicone rubber by a treatment
of applying a vinyl compound to the surface of metal. In addition,
it is also known as another method that liquid composition for
silicone rubber of vinyl group-containing polysiloxane, hydrosilyl
group-containing polysiloxane and a silane coupling agent such as
platinum catalyst suspension is applied to the surface of platy a
metal, which is washed with detergent, in order to harden the
liquid composition to generate thereof as silicone rubber and
simultaneously the silicone rubber is adhered to the metal.
[0005] An adhesive article prepared by the mechanical adhesive
method comes unstuck easily. Adhesive strength of an adhesive
article prepared by the adhesive method using the adhesive agent
decreases due to deterioration of the adhesive agent caused by hard
heat cycle or elapse of long time because the adherend material and
the adhesive material are not chemically-bound on the interface
thereof directly. While an adhesive article prepared by the surface
treatment method is generally able to accomplish relatively strong
adhesive strength by the formation of only two to four chemical
bonds per 10,000 atoms on the surface of the adherend material and
also the adhesive strength thereof does not receive environmental
influence by temperature or solvent, it is difficult to
definitively form chemical bond on the interface of the adherend
material and the adhesive material and therefore a choise of a raw
material for these materials is highly limited. Consequently, the
surface treatment method lucks versatility.
[0006] In these conventional adhesive methods, if the adhesive
material is made from silicone rubber, not only the intensity
thereof is weak, but also adhering an adherend material and the
adhesive material is difficult and, even if the materials are
adherend, the adhesive strength thereof is weak. This is because
the reactivity or the interaction of the silicone rubber with the
surface of the adherend material on the interface thereof is poor.
Therefore, it is necessary to adhere the silicone rubber of the
adhesive material and the surface of the adherend material by an
adhesive agent that well interacts with silicone rubber. However,
the adhesive strength thereof is still not so sufficient.
[0007] Moreover, since thickness of the adhesive layer of the
above-mentioned case is generally several .mu.m to hundreds .mu.m,
the adhesive layer is capable of dispersing the stress from being
pulled or bent but incapable of accomplishing sufficient adhesive
strength as the amount of the adhesive agent thereof is too small.
However, if the amount of the adhesive agent is increased to make
the adhesive layer thicker, it results in strain concentration due
to the stress that causes detachment of the materials, and the
adhesive strength thereof decreases. It is difficult to balance the
dispersion and concentration of stress by conditioning the amount
of the adhesive agent in case of using an adhensive base material
made from silicone rubber.
[0008] Furthermore, it is difficult to mutually adhere very small
materials by the adhesive method using an adhesive agent.
SUMMARY OF THE INVENTION
[0009] The present invention has been developed to solve the
foregoing problems. It is an object of the present invention to
provide a simple base material for adhesion to prepare a silicone
rubber-adhered article that does not come unstuck easily or split
off even being pulled or bent, by firmly adhering an adhesive base
blanket made from silicone rubber and a substrate made from metal,
polymer resin, glass or ceramics without any thick adhesive
layer.
[0010] A base material for adhesion to be adhered to a solid body
of the present invention developed for accomplishing the foregoing
objects comprises a substrate made from metal, polymer resin, glass
or ceramics whose surface is adhesive to the solid body by
silyl-ether-linkage that at least one active silyl group selected
from the group consisting of a hydrosilyl-containing silyl group, a
vinyl-containing silyl group, an alkoxysilyl-containing silyl group
and a hydrolytic group-containing silyl group having reactivity
with a reactive group on the surface of the solid body is bound to
a dehydrogenated residue of hydroxyl group on the surface of the
substrate.
[0011] The hydroxyl group of the base material for adhesion is
inherent hydroxyl group on the surface of the substrate or a
generated hydroxyl group thereon by corona discharge treatment,
atomospheric-pressure plasma treatment or ultraviolet irradiation
treatment, and is bound to the active silyl group from an
alkoxysilyl group of an alkoxysilane compound through the
silyl-ether-linkage.
[0012] The surface of the solid body toward the base material for
adhesion has hydroxyl group by oxidation, and said hydroxyl group
is bound to the active silyl group from the alkoxysilyl group
through the silyl-ether-linkage.
[0013] The silyl-ether-linkage from the alkoxysilane compound of
the base material for adhesion constitutes a monomolecular
layer.
[0014] The active silyl group of the base material for adhesion
is;
[0015] the hydrosilyl-containing silyl group selected from a
monohydrosilyl-containing silyl group and a dihydrosilyl-containing
silyl group;
[0016] the vinyl-containing silyl group as a vinylsilyl-containing
silyl group;
[0017] the alkoxysilyl-containing silyl group selected from a
terminal-trialkoxysilyl-containing silyl group and a
terminal-dialkoxysilyl-containing silyl group; or
[0018] the hydrolytic group-containing silyl group having a
hydrolysable functional group selected from an acyloxysilyl group,
an alkenyloxysilyl group, an alkaniminooxysilyl group, an
alkyloxysilyl group, an alkylaminosilyl group, a dialkylaminosilyl
group, a nitrogenous heterocyclic substituted silyl group and an
arylaminosilyl group.
[0019] The active silyl group of the base material for adhesion is
the hydrosilyl-containing silyl group having --SiH(R.sup.1).sub.2
group or --SiH.sub.2(R.sup.2) group on the terminal thereof in
which R.sup.1 and R.sup.2 are an alkyl group having 1 to 4 carbon
atoms, or --SiH-- group between both terminals thereof.
[0020] The active silyl group of the base material for adhesion may
be the vinylsilyl-containing silyl group having --Si--R.sup.3 group
on the terminal thereof in which R.sup.3 is a vinyl-containing
group, or --Si(R.sup.4)-- group between both terminals thereof in
which R.sup.4 is a vinyl-containing group.
[0021] The active silyl group of the base material for adhesion may
be the terminal-alkoxysilyl-containing silyl group having
--Si(OR.sup.5).sub.2R.sup.6 group on the terminal thereof in which
R.sup.5 and R.sup.6 are a alkyl group having 1 to 4 carbon atoms,
or --Si(OR.sup.7).sub.3 group on the terminal thereof in which
R.sup.7 is a alkyl group having 1 to 4 carbon atoms.
[0022] The active silyl group of the base material for adhesion may
be the hydrolytic group-containing silyl group having the
hydrolysable functional group represented by
--Si(R.sup.8).sub.a(R.sup.9).sub.3-a group in which R.sup.8 is
selected from hydrogen atom; a halogen atom; an alkyl group, an
alkenyl group, an alkyloxy group and a fluoro-substituted alkyl
group that respectively have 1 to 12 carbon atoms; an aralkyl
group; and aryl group, R.sup.9 is selected from an acyloxy group,
an alkenyloxy group, an alkaniminooxy group, an alkyloxy group, an
alkylamino group and a dialkylamino group that respectively have 1
to 12 carbon atoms; a nitrogenous heterocyclic group and an
arylamino group, and a is a number of 0 to 3.
[0023] The reactive group of the base material for adhesion is at
least one selected from the group consisting of hydrosilyl,
vinylsilyl, hydroxysilyl, alkyloxysilyl, alkenyloxysilyl,
acyloxysilyl, iminooxysilyl and alkylaminosilyl.
[0024] The active silyl group is the vinyl-containing silyl group,
a platinum-containing catalyst or a rhodium-containing catalyst
that is applied on the surface of the substrate which exposes the
active silyl group, and the reactive group of hydrosilyl.
[0025] The platinum-containing catalyst is a platinum complex and
the rhodium-containing catalyst of a rhodium complex.
[0026] The platinum-containing catalyst or the rhodium-containing
catalyst is applied on the surface of the substrate by coating or
immersing with a solution or a suspension including thereof.
[0027] Platinum atom of the platinum-containing catalyst or rhodium
atom of the rhodium-containing catalyst coordinates with plural
groups of the vinyl-containing silyl group.
[0028] The vinyl-containing silyl group that is derived from a
vinyl-containing silyl compound selected from
(CH.sub.2.dbd.CH--)(CH.sub.3O--).sub.2Si--O--[(CH.sub.2.dbd.CH--)(CH.sub.-
3O--)Si--O].sub.b1--Si(--OCH.sub.3).sub.2(--CH.dbd.CH.sub.2) in
which b1 is a number of 0 to 100,
(CH.sub.2.dbd.CH--)(C.sub.2H.sub.5O--).sub.2Si--O--[(CH.sub.2
CH--)(C.sub.2H.sub.5O--)Si--O].sub.b2--Si(--OC.sub.2H.sub.5).sub.2(--CH.d-
bd.CH.sub.2) in which b2 is a number of 0 to 100, or
(CH.sub.2.dbd.CH--)(C.sub.3H.sub.7O--).sub.2Si--O--[(CH.sub.2.dbd.CH--)(C-
.sub.3H.sub.7O--)Si--O].sub.b3--Si(--OC.sub.3H.sub.7).sub.2(--CH.dbd.CH.su-
b.2) in which b3 is a number of 1 to 100.
[0029] The solid body is made from silicone rubber or silicone
resin.
[0030] A silicone rubber-adhered article comprises;
[0031] the above-mentioned base material for adhesion and
[0032] an adhesive silicone rubber blanket made from polysiloxane,
vinyl silicone and/or silanol silicone that is adhered to the
surface of the substrate of the adhesive base material.
[0033] The silicone rubber-adhered article comprises plural base
materials for adhesion that are adhered through the adhesive
silicone rubber blanket which is granular, textile, membranous,
filmy or plate-like.
[0034] The silicone rubber-adhered article comprises;
[0035] the polysiloxane represented by
H(CH.sub.3).sub.2SiO[SiH(CH.sub.3)O].sub.c[Si(R.sup.11)R.sup.12O].sub.dSi-
(CH.sub.3).sub.2H in which R.sup.11 and R.sup.12 are an alkyl
group, an alkenyl group, an alkyloxy group or a fluoro-substituted
alkyl group that respectively have 1 to 12 carbon atoms; an aralkyl
group; an aryl group; or HSi(CH.sub.3).sub.2O--, c is a number of 1
to 80, and d is a number of 0 to 80,
[0036] the vinyl silicone represented by
CH.sub.2.dbd.CH(CH.sub.3).sub.2SiO[SiCH.dbd.CH.sub.2(CH.sub.3)O].sub.e[Si-
(R.sup.13)R.sup.14O].sub.fSi(CH.sub.3).sub.2CH.dbd.CH.sub.2 in
which R.sup.13 and R.sup.14 are an alkyl group, an alkenyl group,
an alkyloxy group or a fluoro-substituted alkyl group that
respectively have 1 to 12 carbon atoms; an aralkyl group; or an
aryl group, e is a number of 1 to 80, and f is a number of 0 to
80,
[0037] the silanol silicone represented by
A-(CH.sub.3).sub.2SiO[Si(CH.sub.3).sub.2O].sub.g[Si(R.sup.15)R.sup.16O].s-
ub.hSi(CH.sub.3).sub.2-A in which R.sup.15 and R.sup.16 are an
alkyl group, an alkenyl group, an alkyloxy group or a
fluoro-substituted alkyl group that respectively have 1 to 12
carbon atoms; an aralkyl group; or an aryl group, A is hydroxyl
group, an alkyloxy group, an alkenyloxy group, an aryloxy group, an
acyloxy group that respectively have 1 to 4 carbon atoms, an
iminooxy group, or an amino group, g is a number of 1 to 80, and h
is a number of 0 to 80.
[0038] A method for manufacturing the silicone rubber-adhered
article comprising steps of:
[0039] applying a composition including silicone rubber component
of polysiloxane, vinyl silicone and/or silanol silicone to the
surface of the substrate of the base material for adhesion,
[0040] hardening the composition at room temperature or by heating
to form an adhesive silicone rubber blanket and to adhere the
surface of the substrate with the adhesive silicone rubber
blanket.
[0041] In the method for manufacturing the silicone rubber-adhered
article, the composition includes a cross-linking agent and/or a
cross-linking catalyst.
[0042] By introducing hydroxyl group onto the surface of a
substrate made from metal, polymer resin, glass or ceramics to
chemically bind the hydroxyl group and an active silyl group
derived from an alkoxysilane compound through silyl-ether-linkage,
the base material for adhesion of the present invention easily and
firmly adheres to the silicone rubber blanket through
crosslinkage.
[0043] By the silyl-ether-linkage, an infinitely thin monomolecular
layer of a silyl ether is constituted on the substrate. The layer
is chemically stable, and despite of its thinness, the surface
thereof is modified to be adhered firmly to silicone rubber.
Moreover, the layer is stable for a long period of time, and by the
crosslinkage with silicone rubber or the interaction therewith, a
solid silicone rubber-adhered article that does not come unstuck
easily can be obtained through the layer.
[0044] Especially, when the base material for adhesion comprises a
substrate, of which a vinyl-containing silyl group of an active
silyl group is bound to the surface through the
silyl-ether-linkage, and a platinum-containing catalyst or a
rhodium-containing catalyst is applied thereto, a silicone
rubber-adhered article that the base material for adhesion and an
adhesive hydrosilyl-containing silicone rubber blanket are firmly
adhered can be obtained.
BRIEF EXPLANATION OF THE DRAWINGS
[0045] FIG. 1 is a chart of the surface analysis of the base
material for adhesion, to which the present invention is applied,
measured by X-ray photoelectron spectroscopy (XPS analysis).
[0046] FIG. 2 is a graph of the correlation of the concentration of
vinylmethoxysiloxane, in which the base material for adhesion is
immersed at the time of manufacturing a silicone rubber-adhered
article, and peeling strength of the obtained silicone
rubber-adhered article.
[0047] FIG. 3 is a graph of the correlation of immersion time of a
platinum-containing catalyst suspension, in which the base material
for adhesion is immersed at the time of manufacturing a silicone
rubber-adhered article, and peeling strength of the obtained
silicone rubber-adhered article.
[0048] FIG. 4 is a graph of the correlation chart of the
concentration of a platinum-containing catalyst suspension, in
which the base material for adhesion is immersed at the time of
manufacturing a silicone rubber-adhered article, and peeling
strength of the obtained silicone rubber-adhered article.
DETAILED EXPLANATION OF THE INVENTION
[0049] According to the method for manufacturing such silicone
rubber-adhered article, despite of its size, the silicone
rubber-adhered article can be mass-produced with simple
procedures.
[0050] Hereunder, embodiments of the present invention are
explained in detail. The present invention is not intended to be
limited.
[0051] A base material for adhesion of the present invention such
as the silicone rubber-adhesive base material is manufactured as
follows.
[0052] The surface of a substrate of a base material for adhesion
made from metal is treated by corona discharge treatment to
generate hydroxyl group derived from a metal oxide molecule on the
surface thereof, and the surface with crosslinking-reactivity to
silicone rubber is obtained. When any impurity such as an organic
substance is attached onto the surface thereof, the impurity is
oxidized by corona discharge treatment, and carboxyl group derived
from the organic substance is generated on the surface thereof. As
a result, the surface with crosslinking-reactivity to silicone
rubber on which hydroxyl group generated from the arboxyl group is
obtained.
[0053] Meanwhile, mixture of a solvent and a functional alkoxysilyl
compound such as
HSi(CH.sub.3).sub.2OSi(CH.sub.3).sub.2CH.sub.2CH.sub.2CH.sub.2Si(OC.sub.2-
H.sub.5).sub.3 that reacts with the hydroxyl group and generates a
silyl ether is applied onto the surface of the substrate on which
the hydroxyl group is already generated, and then the surface
thereof is dried and heated. Triethoxysilyl group of the functional
alkoxysilyl compound reacts with the hydroxyl group on the surface
of the substrate to be the active silyl group and generates a
chemically strong silyl-ether-linkage with a dehydrogenated residue
of hydroxyl group. By the alkoxysilyl compound, a silicone
rubber-adhesive base material that is coated by a monomolecular
layer of a silyl ether to which silyl group such as a
hydrosilyl-containing silyl group is bound through
ether-linkage.
[0054] Such monomolecular layer is constituted by a molecular chain
that does not exceed the base unit of the first silyl compound.
[0055] After a composition including silicone rubber component is
applied onto the surface of the silicone rubber-adhesive base
material and hardened thereof to form an adhesive silicone rubber
blanket thereon, a silicone rubber-adhered article that the
adhesive silicone rubber blanket is adhered to a monomolecular
layer of a silyl ether on the surface of the silicone
rubber-adhesive base material by cross-linkage is obtained. The
silyl ether molecule on the surface thereof and the adhesive
silicone rubber blanket are firmly adhered because the silyl ether
molecule and the silicone rubber component are crosslinked by
covalent-bond, or each of the silyl group thereof is attracted and
intracted each other, and crosslinked electrochemically. This
allows us to assume that the silicone rubber-adhered article of the
above has sufficient adhesive strength and does not come unstuck
easily.
[0056] Examples of the silicone rubber-adhesive base material that
the silyl group such as a hydrosilyl-containing silyl group is
bound to the surface thereof through silyl-ether-linkage were
explained above. The surface of the base material can be the
surface to which an active silyl group of a vinly-containing silyl
group, a terminal-alkoxylsilyl-containing silyl group or a
hydrolyzable group-containing silyl group which are respectively
represented by a vinylsilyl-containing silyl group are bound
through silyl-ether-linkage.
[0057] Each of such active silyl group is generated by the reaction
of the alkoxysilyl group of the functional alkoxylsilyl compound
with the hydroxyl group on the surface of the substrate of the base
material for adhesion.
[0058] The silyl-ether-linkage generated on the surface of the
substrate (ie. Sub.) of the base material for adhesion by the
hydrosilyl-containing silyl group is represented by the following
chemical formula (1).
Sub.-O--SiR.sup.20 (1)
In the chemical formula (1), R.sup.20 in the hydrosilyl-containing
silyl group --SiR.sup.20 has --SiH(R.sup.1).sub.2 group or
--SiH.sub.2(R.sup.2) group on the terminal thereof in which R.sup.1
and R.sup.2 are an alkyl group having 1 to 4 carbon atoms, or
--SiH-- group between both terminals thereof. R.sup.20 can be
polysiloxy group.
[0059] Concretely, --SiR.sup.20 is represented by the group
consisting of [0060]
--(C.sub.2H.sub.5O).sub.2SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).su-
b.2H, [0061]
--(CH.sub.3O).sub.2SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub.2H,
[0062]
-(i-C.sub.3H.sub.7O).sub.2SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3)H.sub.2,
[0063]
-(n-C.sub.3H.sub.7O).sub.2SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).s-
ub.2OSi(CH.sub.3).sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub.2Si(CH.sub.3).sub.-
2H, [0064]
-(n-C.sub.4H.sub.9O).sub.2SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3-
).sub.2OSi(CH.sub.3).sub.2H, [0065]
-(t-C.sub.4H.sub.9O).sub.2SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub.2OSi-
(CH.sub.3).sub.2H, [0066]
--(C.sub.2H.sub.5O)CH.sub.3SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub.2OS-
i(CH.sub.3).sub.2H, [0067]
--(CH.sub.3O)CH.sub.3SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub.2OSi(CH.s-
ub.3).sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub.2Si(CH.sub.3).sub.2H,
[0068]
--(CH.sub.3).sub.2SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub.2OSi(CH.sub.-
3).sub.2H, [0069]
--(C.sub.2H.sub.5O).sub.2SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub.2OSi(-
CH.sub.3).sub.2H, [0070]
-(n-C.sub.3H.sub.7).sub.2SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub.2OSi(-
CH.sub.3).sub.2H, [0071]
-(i-C.sub.3H.sub.7O).sub.2SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub.2OSi-
(CH.sub.3).sub.2H, [0072]
-(n-C.sub.4H.sub.9).sub.2SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub.2OSi(-
CH.sub.3).sub.2H, [0073]
-(t-C.sub.4H.sub.9O).sub.2SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub.2OSi-
(CH.sub.3).sub.2H, [0074]
--[(--O)(-)SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub.2OSi(CH.sub.3).sub.-
2H].sub.k1, [0075]
--[(--O)(-)SiCH.sub.2CH.sub.2Si(CH.sub.3).sub.2OSi(CH.sub.3).sub.2H].sub.-
k2, [0076]
--[(--O)(-)SiCH.sub.2CH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub.2-
OSi(CH.sub.3).sub.2H].sub.k3, [0077]
--[(--O)(-)SiCH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3)-
.sub.2OSi(CH.sub.3).sub.2H].sub.k4, [0078]
--[(--O)(-)SiCH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.s-
ub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub.2OSi(CH.sub.3).sub.2H].sub.k5,
[0079] --(CH.sub.3O).sub.2
SiCH.sub.2C.sub.6H.sub.4--CH.sub.2CH.sub.2Si(CH.sub.3).sub.2C.sub.6H.sub.-
4Si(CH.sub.3).sub.2H, [0080]
--(CH.sub.3O)CH.sub.3SiCH.sub.2C.sub.6H.sub.4--CH.sub.2CH.sub.2Si(CH.sub.-
3).sub.2C.sub.6H.sub.4Si(CH.sub.3).sub.2H, [0081]
--(CH.sub.3).sub.2SiCH.sub.2C.sub.6H.sub.4--CH.sub.2CH.sub.2Si(CH.sub.3).-
sub.2C.sub.6H.sub.4Si(CH.sub.3).sub.2H, [0082]
--[(--O)(-)SiCH.sub.2C.sub.6H.sub.4--CH.sub.2CH.sub.2Si(CH.sub.3).sub.2C.-
sub.6H.sub.4Si(CH.sub.3).sub.2H].sub.k6, [0083]
--[(--O)(-)SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub.2C.sub.6H.sub.4OC.s-
ub.6H.sub.4Si(CH.sub.3).sub.2H].sub.k7, [0084]
--[(--O)(-)SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub.2C.sub.2H.sub.4Si(C-
H.sub.3).sub.2H].sub.k8, [0085]
--(C.sub.2H.sub.5O).sub.2SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub.2O[Si-
(CH.sub.3).sub.2O].sub.m1Si(CH.sub.3).sub.2H, [0086]
--(C.sub.2H.sub.5).sub.2SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub.2O[Si(-
CH.sub.3).sub.2O].sub.m2Si(C.sub.2H.sub.5).sub.2H, [0087]
--(C.sub.2H.sub.5O)CH.sub.3SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub.2O[-
Si(CH.sub.3).sub.2O].sub.m3Si(CH.sub.3).sub.2H, [0088]
(CH.sub.3).sub.3SiO[--Si(CH.sub.3)]O[SiH(CH.sub.3)O].sub.m4Si(CH.sub.3).s-
ub.3, [0089]
(CH.sub.3).sub.3SiO[(--Si(CH.sub.3)CH.sub.2CH.sub.2CH.sub.2)(-)SiCH.sub.3-
]O[SiH(CH.sub.3)O].sub.m5Si(CH.sub.3).sub.3, [0090]
(CH.sub.3).sub.3SiO[(--Si(OCH.sub.3)CH.sub.2CH.sub.2CH.sub.2)(-)SiCH.sub.-
3]O[SiH(CH.sub.3)O].sub.m6Si(CH.sub.3).sub.3, [0091]
(CH.sub.3).sub.3SiO[(--Si(CH.sub.3)CH.sub.2CH.sub.2CH.sub.2)(-)SiCH.sub.3-
]O[SiH(CH.sub.3)O].sub.m7Si(CH.sub.3).sub.3, [0092]
(CH.sub.3).sub.3SiO[(--Si(O--)CH.sub.2CH.sub.2CH.sub.2)SiCH.sub.3]O[SiH(C-
H.sub.3)O].sub.m8Si(CH.sub.3).sub.3, [0093]
(CH.sub.3).sub.3SiO[(--Si(CH.sub.3)O[SiH(CH.sub.3)O].sub.m9[Si(CH.sub.3).-
sub.2O].sub.n1Si(CH.sub.3).sub.3, [0094]
(CH.sub.3).sub.3SiO[(--Si(CH.sub.3)CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub-
.2CH.sub.2)(-)Si(CH.sub.3)O][SiH(CH.sub.3)O].sub.m10[Si
(CH.sub.3).sub.2O].sub.n2Si(CH.sub.3).sub.3, [0095]
(CH.sub.3).sub.3SiO[(--Si(OCH.sub.3)CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.su-
b.2CH.sub.2)(-)Si(CH.sub.3)O][SiH(CH.sub.3)O].sub.m11[Si(CH.sub.3).sub.2O]-
.sub.n3Si(CH.sub.3).sub.3, [0096]
(CH.sub.3).sub.3SiO[(--Si(O--)CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.-
sub.2)Si(CH.sub.3)O][SiH(CH.sub.3)O].sub.m12[Si(CH.sub.3).sub.2O].sub.n4Si-
(CH.sub.3).sub.3, [0097]
(CH.sub.3).sub.3SiO[(--Si(OCH.sub.3)CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.su-
b.2CH.sub.2)(-)Si(CH.sub.3)O][SiH(CH.sub.3)O].sub.m13[Si(CH.sub.3).sub.2O]-
.sub.n5Si(CH.sub.3).sub.3, [0098]
(CH.sub.3).sub.3SiO[--Si(C.sub.2H.sub.5)O][SiH(C.sub.2H.sub.5)O].sub.m14S-
i(CH.sub.3).sub.3, [0099]
(CH.sub.3).sub.3SiO[(--Si(O--)CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.-
sub.2)Si(C.sub.2H.sub.5)]O[SiH(C.sub.2H.sub.5)O].sub.m15Si
(CH.sub.3).sub.3, [0100]
(CH.sub.3).sub.3SiO[(--Si(CH.sub.3)CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub-
.2CH.sub.2)(-)Si(C.sub.2H.sub.5)]O[SiH(C.sub.2H.sub.5)O].sub.m16Si(CH.sub.-
3).sub.3, [0101]
--Si(CH.sub.3).sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2(CH.s-
ub.3).sub.2SiO[HSi(CH.sub.3).sub.2OSiC.sub.6H.sub.5O].sub.m17Si
(CH.sub.3).sub.2H, [0102]
--Si(OCH.sub.3).sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2(CH.-
sub.3).sub.2SiO[HSi(CH.sub.3).sub.2OSiC.sub.6H.sub.5O].sub.m18Si
(CH.sub.3).sub.2H, [0103]
--Si(O--)CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2(CH.sub.3).sub.2-
SiO[HSi(CH.sub.3).sub.2OSiC.sub.6H.sub.5O].sub.m19Si(CH.sub.3).sub.2H,
[0104]
H(CH.sub.3).sub.2SiO[(--Si(CH.sub.3).sub.2CH.sub.2CH.sub.2CH.sub.2-
)Si(CH.sub.3)O][HSiCH.sub.3O].sub.m20Si(CH.sub.3).sub.2H, [0105]
H(CH.sub.3).sub.2SiO[(--Si(CH.sub.3).sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.-
2)Si(CH.sub.3)O][HSiCH.sub.3O].sub.m21Si(CH.sub.3).sub.2H, [0106]
H(CH.sub.3).sub.2SiO[(--Si(CH.sub.3).sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.-
2CH.sub.2CH.sub.2)Si(CH.sub.3)O][HSiCH.sub.3O].sub.m22Si
(CH.sub.3).sub.2H, [0107]
H(CH.sub.3).sub.2SiO[(--Si(CH.sub.3).sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.-
2CH.sub.2CH.sub.2CH.sub.2CH.sub.2)Si(CH.sub.3)O][HSiCH.sub.3O].sub.m23Si(C-
H.sub.3).sub.2H, [0108]
H(CH.sub.3).sub.2SiO[(--Si(CH.sub.3).sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.-
2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2)Si(CH.sub.3)O][HSiCH.sub-
.3O].sub.m24Si(CH.sub.3).sub.2H, [0109]
H(CH.sub.3).sub.2SiO[(--Si(OCH.sub.3).sub.2CH.sub.2CH.sub.2C.sub.6H.sub.4-
--CH.sub.2CH.sub.2)Si(CH.sub.3)O][HSiCH.sub.3O].sub.m25Si
(CH.sub.3).sub.2H, [0110]
H(CH.sub.3).sub.2SiO[(--Si(OCH.sub.3).sub.2CH.sub.2C.sub.6H.sub.4--CH.sub-
.2CH.sub.2CH.sub.2)Si(CH.sub.3)O][HSiCH.sub.3O].sub.m26Si
(CH.sub.3).sub.2H, [0111]
H(CH.sub.3).sub.2SiO[(--Si(OCH.sub.3).sub.2CH.sub.2C.sub.6H.sub.4--CH.sub-
.2CH.sub.2)Si(CH.sub.3)O][HSiCH.sub.3O].sub.m27Si(CH.sub.3).sub.2H
[0112]
H(CH.sub.3).sub.2SiO[(--Si(OCH.sub.3).sub.2C.sub.6H.sub.4--CH.sub.2CH.sub-
.2)Si(CH.sub.3)O][HSiCH.sub.3O].sub.m28Si(CH.sub.3).sub.2H, [0113]
H(CH.sub.3).sub.2SiO[(--Si(OCH.sub.3).sub.2CH.sub.2CH.sub.2CH.sub.2)Si(CH-
.sub.3)O][HSiCH.sub.3O].sub.m29Si(CH.sub.3).sub.2H, [0114]
H(CH.sub.3).sub.2SiO[(--Si(OCH.sub.3).sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub-
.2)Si(CH.sub.3)O][HSiCH.sub.3O].sub.m30Si(CH.sub.3).sub.2H, [0115]
H(CH.sub.3).sub.2SiO[(--Si(OCH.sub.3).sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub-
.2CH.sub.2CH.sub.2)Si(CH.sub.3)O][HSiCH.sub.3O].sub.m31Si(CH.sub.3).sub.2H-
, [0116]
H(CH.sub.3).sub.2SiO[(--Si(OCH.sub.3).sub.2CH.sub.2CH.sub.2CH.sub-
.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2)Si(CH.sub.3)O][HSiCH.sub.3O].su-
b.m32Si(CH.sub.3).sub.2H, [0117]
H(CH.sub.3).sub.2SiO[(--Si(OCH.sub.3).sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub-
.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2)Si(CH.sub.3)O][HSiCH.su-
b.3O].sub.m33Si(CH.sub.3).sub.2H, [0118]
H(CH.sub.3).sub.2SiO[(--Si(OCH.sub.3).sub.2CH.sub.2CH.sub.2C.sub.6H.sub.4-
--CH.sub.2CH.sub.2)Si(CH.sub.3)O][HSiCH.sub.3O].sub.m34Si
(CH.sub.3).sub.2H, [0119]
H(CH.sub.3).sub.2SiO[(--Si(OCH.sub.3).sub.2CH.sub.2C.sub.6H.sub.4--CH.sub-
.2CH.sub.2CH.sub.2)Si(CH.sub.3)O][HSiCH.sub.3O].sub.m35Si
(CH.sub.3).sub.2H, [0120]
H(CH.sub.3).sub.2SiO[(--Si(OCH.sub.3).sub.2CH.sub.2C.sub.6H.sub.4--CH.sub-
.2CH.sub.2)Si(CH.sub.3)O][HSiCH.sub.3O].sub.m36Si(CH.sub.3).sub.2H,
[0121]
H(CH.sub.3).sub.2SiO[(--Si(OCH.sub.3).sub.2C.sub.6H.sub.4--CH.sub.2CH.sub-
.2)Si(CH.sub.3)O][HSiCH.sub.3O].sub.m37Si(CH.sub.3).sub.2H, [0122]
H(CH.sub.3).sub.2SiO[(--Si(O--)CH.sub.2CH.sub.2C.sub.6H.sub.4--CH.sub.2CH-
.sub.2)Si(CH.sub.3)O][HSiCH.sub.3O].sub.m38Si(CH.sub.3).sub.2H
[0123]
H(CH.sub.3).sub.2SiO[(--Si(O--)CH.sub.2C.sub.6H.sub.4--CH.sub.2CH.sub.2CH-
.sub.2)Si(CH.sub.3)O][HSiCH.sub.3O].sub.m39Si(CH.sub.3).sub.2H,
[0124]
H(CH.sub.3).sub.2SiO[(--Si(O--)CH.sub.2C.sub.6H.sub.4--CH.sub.2CH.sub.2)S-
i(CH.sub.3)O][HSiCH.sub.3O].sub.m40Si(CH.sub.3).sub.2H, [0125]
H(CH.sub.3).sub.2SiO[(--Si(O--)C.sub.6H.sub.4--CH.sub.2CH.sub.2)Si(CH.sub-
.3)O][HSiCH.sub.3O].sub.m41Si(CH.sub.3).sub.2H, [0126]
H(CH.sub.3).sub.2SiO[(--Si(O--)CH.sub.2CH.sub.2CH.sub.2)Si(CH.sub.3)O][HS-
iCH.sub.3O].sub.m42Si(CH.sub.3).sub.2H, [0127]
H(CH.sub.3).sub.2SiO[(--Si(O--)CH.sub.2CH.sub.2CH.sub.2CH.sub.2)Si(CH.sub-
.3)O][HSiCH.sub.3O].sub.m43Si(CH.sub.3).sub.2H, [0128]
H(CH.sub.3).sub.2SiO[(--Si(O--)CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH-
.sub.2)Si(CH.sub.3)O][HSiCH.sub.3O].sub.m44Si (CH.sub.3).sub.2H,
[0129]
H(CH.sub.3).sub.2SiO[(--Si(O--)CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH-
.sub.2CH.sub.2CH.sub.2)Si(CH.sub.3)O][HSiCH.sub.3O].sub.m45Si(CH.sub.3).su-
b.2H, [0130]
H(CH.sub.3).sub.2SiO[(--Si(O--)CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH-
.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2)Si(CH.sub.3)O][HSiCH.sub.3O].sub.m4-
6Si(CH.sub.3).sub.2H, [0131]
H(CH.sub.3).sub.2SiO[(--Si(O--)CH.sub.2CH.sub.2C.sub.6H.sub.4--CH.sub.2CH-
.sub.2)Si(CH.sub.3)O][HSiCH.sub.3O].sub.m47Si(CH.sub.3).sub.2H
[0132]
H(CH.sub.3).sub.2SiO[(--Si(O--)CH.sub.2C.sub.6H.sub.4--CH.sub.2CH.s-
ub.2CH.sub.2)Si(CH.sub.3)O][HSiCH.sub.3O].sub.m48Si(CH.sub.3).sub.2H
[0133]
H(CH.sub.3).sub.2SiO[(--Si(O--)CH.sub.2C.sub.6H.sub.4--CH.sub.2CH.-
sub.2)Si(CH.sub.3)O][HSiCH.sub.3O].sub.m49Si(CH.sub.3).sub.2H,
[0134]
H(CH.sub.3).sub.2SiO[(--Si(O--)C.sub.6H.sub.4--CH.sub.2CH.sub.2)Si(CH.sub-
.3)O][HSiCH.sub.3O].sub.m50Si(CH.sub.3).sub.2H, [0135]
H(CH.sub.3).sub.2SiO[(-)Si(CH.sub.3)CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.su-
b.2CH.sub.2Si(CH.sub.3).sub.2OSiC.sub.6H.sub.5O].sub.m51[HSi(CH.sub.3).sub-
.2OSiC.sub.6H.sub.5O].sub.n6Si(CH.sub.3).sub.2H, [0136]
H(CH.sub.3).sub.2SiO[(-)Si(OCH.sub.3)CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.s-
ub.2CH.sub.2Si(CH.sub.3).sub.2OSiC.sub.6H.sub.5O].sub.m52 [0137]
[HSi(CH.sub.3).sub.2OSiC.sub.6H.sub.5O].sub.n7Si(CH.sub.3).sub.2H,
[0138]
H(CH.sub.3).sub.2SiO[(-)Si(O--)CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH-
.sub.2Si(CH.sub.3).sub.2OSiC.sub.6H.sub.5O].sub.m53[HSi(CH.sub.3).sub.2OSi-
C.sub.6H.sub.5O].sub.n8Si(CH.sub.3).sub.2H, [0139]
--(CH.sub.3).sub.2SiO[SiH(CH.sub.3)O].sub.m54[SiCH.sub.3(C.sub.6H.sub.5)O-
].sub.n9Si(CH.sub.3).sub.2H, [0140]
--Si(OC.sub.2H.sub.5).sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub-
.2(CH.sub.3).sub.2SiO[SiH(CH.sub.3)O].sub.m55[SiCH.sub.3(C.sub.6H.sub.5)O]-
.sub.n10Si(CH.sub.3).sub.2H, [0141]
--Si(O--)CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2(CH.sub.3).sub.2-
SiO[SiH(CH.sub.3)O].sub.m56[SiCH.sub.3(C.sub.6H.sub.5)O].sub.n11Si(CH.sub.-
3).sub.2H, [0142]
--Si(CH.sub.3).sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2(CH.s-
ub.3).sub.2SiO[SiH(CH.sub.3)O].sub.m57[SiCH.sub.3(C.sub.6H.sub.5)O].sub.n1-
2Si(CH.sub.3).sub.2H [0143]
H(CH.sub.3).sub.2SiO(-)Si(CH.sub.3)O[SiH(CH.sub.3)O].sub.m58[SiCH.sub.3(C-
.sub.6H.sub.5)O].sub.n13Si(CH.sub.3).sub.2H, [0144]
H(CH.sub.3).sub.2SiO[(-)Si(OC.sub.2H.sub.5).sub.2CH.sub.2CH.sub.2CH.sub.2-
Si(CH.sub.3)]O[SiH(CH.sub.3)O].sub.m59[SiCH.sub.3(C.sub.6H.sub.5)O].sub.n1-
4Si(CH.sub.3).sub.2H, [0145]
H(CH.sub.3).sub.2SiO[(-)Si(O--)CH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3)]O[SiH-
(CH.sub.3)O].sub.m60[SiCH.sub.3(C.sub.6H.sub.5)O].sub.n15Si(CH.sub.3).sub.-
2H, and [0146]
H(CH.sub.3).sub.2SiO[(-)Si(CH.sub.3).sub.2CH.sub.2CH.sub.2CH.sub.2Si(CH.s-
ub.3)]O[SiH(CH.sub.3)O].sub.m61[SiCH.sub.3(C.sub.6H.sub.5)O].sub.n16Si(CH.-
sub.3).sub.2H. In the above-mentioned groups, k1 to k8, m1 to m61,
and n1 to n16 are a number of 1 to 100. It is preferable that one
group thereof has 1 to 99 hydrosilyl groups (i.e. SiH groups).
[0147] Examples of the functional alkoxysilyl compound that
generates the hydrosilyl-containing silyl group are as follows.
[0148]
(CH.sub.3O).sub.3SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub.2OSi(CH.sub.3-
).sub.2H, [0149]
(C.sub.2H.sub.5O).sub.3SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub.2OSi(CH-
.sub.3).sub.2H, [0150]
(CH.sub.3O).sub.3SiCH.sub.2CH.sub.2CH.sub.2Si(OCH.sub.3).sub.2OSi(OCH.sub-
.3).sub.3, [0151]
(C.sub.2H.sub.5O).sub.3SiCH.sub.2CH.sub.2CH.sub.2Si(OCH.sub.3).sub.2OSi(O-
CH.sub.3).sub.3, [0152]
(C.sub.2H.sub.5O).sub.3SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub.2H,
[0153]
(CH.sub.3O).sub.3SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub.2H,
[0154]
(i-C.sub.3H.sub.7O).sub.3SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3)H.s-
ub.2, [0155]
(n-C.sub.3H.sub.7O).sub.3SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub.2OSi(-
CH.sub.3).sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub.2Si(CH.sub.3).sub.2H,
[0156]
(n-C.sub.4H.sub.9O).sub.3SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).su-
b.2OSi(CH.sub.3).sub.2H, [0157]
(t-C.sub.4H.sub.9O).sub.3SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub.2OSi(-
CH.sub.3).sub.2H, [0158]
(C.sub.2H.sub.5O).sub.2CH.sub.3SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub-
.2OSi(CH.sub.3).sub.2H, [0159]
(CH.sub.3O).sub.2CH.sub.3SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub.2OSi(-
CH.sub.3).sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub.2Si(CH.sub.3).sub.2H,
[0160]
CH.sub.3O(CH.sub.3).sub.2SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).su-
b.2OSi(CH.sub.3).sub.2H, [0161]
(C.sub.2H.sub.5O).sub.3SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub.2OSi(CH-
.sub.3).sub.2H, [0162]
(n-C.sub.3H.sub.7).sub.3SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub.2OSi(C-
H.sub.3).sub.2H, [0163]
(i-C.sub.3H.sub.7O).sub.3SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub.2OSi(-
CH.sub.3).sub.2H, [0164]
(n-C.sub.4H.sub.9).sub.3SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub.2OSi(C-
H.sub.3).sub.2H, [0165]
(t-C.sub.4H.sub.9O).sub.3SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub.2OSi(-
CH.sub.3).sub.2H, [0166]
(C.sub.2H.sub.5O).sub.3SiCH.sub.2CH.sub.2Si(CH.sub.3).sub.2OSi(CH.sub.3).-
sub.2H, [0167]
(C.sub.2H.sub.5O).sub.3SiCH.sub.2CH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub-
.2OSi(CH.sub.3).sub.2H, [0168]
(C.sub.2H.sub.5O).sub.3SiCH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2-
Si(CH.sub.3).sub.2OSi(CH.sub.3).sub.2H, [0169]
(C.sub.2H.sub.5O).sub.3SiCH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2-
CH.sub.2CH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub.2OSi(CH.sub.3).sub.2H,
[0170]
(CH.sub.3O).sub.3SiCH.sub.2C.sub.6H.sub.4CH.sub.2CH.sub.2Si(CH.sub-
.3).sub.2C.sub.6H.sub.4Si(CH.sub.3).sub.2H, [0171]
(CH.sub.3O).sub.2CH.sub.3SiCH.sub.2C.sub.6H.sub.4CH.sub.2CH.sub.2Si(CH.su-
b.3).sub.2C.sub.6H.sub.4Si(CH.sub.3).sub.2H, [0172]
CH.sub.3O(CH.sub.3).sub.2SiCH.sub.2C.sub.6H.sub.4CH.sub.2CH.sub.2Si(CH.su-
b.3).sub.2C.sub.6H.sub.4Si(CH.sub.3).sub.2H, [0173]
(C.sub.2H.sub.5O).sub.3SiCH.sub.2C.sub.6H.sub.4CH.sub.2CH.sub.2Si(CH.sub.-
3).sub.2C.sub.6H.sub.4Si(CH.sub.3).sub.2H, [0174]
(C.sub.2H.sub.5O).sub.3SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub.2C.sub.-
6H.sub.4OC.sub.6H.sub.4Si(CH.sub.3).sub.2H, [0175]
(C.sub.2H.sub.5O).sub.3SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub.2C.sub.-
2H.sub.4Si(CH.sub.3).sub.2H, [0176]
(C.sub.2H.sub.5O).sub.3SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub.2O[Si(C-
H.sub.3).sub.2O].sub.p1Si(CH.sub.3).sub.2H, [0177]
C.sub.2H.sub.5O(CH.sub.3).sub.2SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub-
.2O[Si(CH.sub.3).sub.2O].sub.p2Si(C.sub.2H.sub.5).sub.2H, [0178]
(C.sub.2H.sub.5O).sub.2CH.sub.3SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub-
.2O[Si(CH.sub.3).sub.2O].sub.p3Si(CH.sub.3).sub.2H, [0179]
(CH.sub.3).sub.3SiOSiH(CH.sub.3)O[SiH(CH.sub.3)O].sub.p4Si(CH.sub.3).sub.-
3, [0180]
(CH.sub.3).sub.3SiO[(C.sub.2H.sub.5OSi(CH.sub.3)CH.sub.2CH.sub.2-
CH.sub.2)SiCH.sub.3]O[SiH(CH.sub.3)O].sub.p5Si(CH.sub.3).sub.3,
[0181]
(CH.sub.3).sub.3SiO[(C.sub.2H.sub.5OSiOCH.sub.3CH.sub.2CH.sub.2CH.sub.2)S-
iCH.sub.3]O[SiH(CH.sub.3)O].sub.p6Si(CH.sub.3).sub.3, [0182]
(CH.sub.3).sub.3SiO[(C.sub.2H.sub.5OSi(CH.sub.3)CH.sub.2CH.sub.2CH.sub.2)-
SiCH.sub.3]O[SiH(CH.sub.3)O].sub.p7Si(CH.sub.3).sub.3, [0183]
(CH.sub.3).sub.3SiO[(Si(OC.sub.2H.sub.5).sub.2CH.sub.2CH.sub.2CH.sub.2)Si-
CH.sub.3]O[SiH(CH.sub.3)O].sub.p8Si(CH.sub.3).sub.3, [0184]
(CH.sub.3).sub.3SiOSi(OC.sub.2H.sub.5).sub.2O[SiH(CH.sub.3)O].sub.p9[Si(C-
H.sub.3).sub.2].sub.q1Si(CH.sub.3).sub.3, [0185]
(CH.sub.3).sub.3SiO[(C.sub.2H.sub.5Osi(CH.sub.3)CH.sub.2CH.sub.2CH.sub.2C-
H.sub.2CH.sub.2CH.sub.2)Si(CH.sub.3)O][SiH(CH.sub.3)O].sub.p10[Si(CH.sub.3-
).sub.2O].sub.q2Si(CH.sub.3).sub.3, [0186]
(CH.sub.3).sub.3SiO[(Si(OCH.sub.3).sub.3CH.sub.2CH.sub.2CH.sub.2CH.sub.2C-
H.sub.2CH.sub.2)Si(CH.sub.3)O][SiH(CH.sub.3)O].sub.P11 [0187]
[Si(CH.sub.3).sub.2O].sub.q3Si(CH.sub.3).sub.3, [0188]
(CH.sub.3).sub.3SiOSi(OC.sub.2H.sub.5).sub.2O[SiH(C.sub.2H.sub.5)O].sub.p-
12 Si(CH.sub.3).sub.3, [0189]
(CH.sub.3).sub.3SiO[(Si(OC.sub.2H.sub.5).sub.2CH.sub.2CH.sub.2CH.sub.2CH.-
sub.2CH.sub.2CH.sub.2)Si(C.sub.2H.sub.5)]O[SiH(C.sub.2H.sub.5)O].sub.p13Si-
(CH.sub.3).sub.3, [0190]
(CH.sub.3).sub.3SiO[(C.sub.2H.sub.5OSi(CH.sub.3)CH.sub.2CH.sub.2CH.sub.2C-
H.sub.2CH.sub.2CH.sub.2)Si(C.sub.2H.sub.5)]O
[SiH(C.sub.2H.sub.5)O].sub.p14Si(CH.sub.3).sub.3, [0191]
C.sub.2H.sub.5OSi(CH.sub.3).sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2-
CH.sub.2(CH.sub.3).sub.2SiO[(HSi(CH.sub.3).sub.2OSiC.sub.6H.sub.5O].sub.p1-
5Si(CH.sub.3).sub.2H, [0192]
Si(OCH.sub.3).sub.3CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2(CH.su-
b.3).sub.2SiO[HSi(CH.sub.3).sub.2OSiC.sub.6H.sub.5O].sub.p16Si(CH.sub.3).s-
ub.2H, [0193]
H(CH.sub.3).sub.2SiO[(C.sub.2H.sub.5OSi(CH.sub.3).sub.2CH.sub.2CH.sub.2CH-
.sub.2)Si(CH.sub.3)O][HSiCH.sub.3O].sub.p17Si(CH.sub.3).sub.2H,
[0194]
H(CH.sub.3).sub.2SiO[(C.sub.2H.sub.5OSi(CH.sub.3).sub.2CH.sub.2CH.sub.2CH-
.sub.2CH.sub.2)Si(CH.sub.3)O][HSiCH.sub.3O].sub.p18Si(CH.sub.3).sub.2H,
[0195]
H(CH.sub.3).sub.2SiO[(C.sub.2H.sub.5OSi(CH.sub.3).sub.2CH.sub.2CH.-
sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2)Si(CH.sub.3)O] [0196]
[HSiCH.sub.3O].sub.p19Si(CH.sub.3).sub.2H, [0197]
H(CH.sub.3).sub.2SiO[(C.sub.2H.sub.5OSi(CH.sub.3).sub.2CH.sub.2CH.sub.2CH-
.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2)Si(CH.sub.3)O]
[0198] [HSiCH.sub.3O].sub.p20Si(CH.sub.3).sub.2H, [0199]
H(CH.sub.3).sub.2SiO[(C.sub.2H.sub.5OSi(CH.sub.3).sub.2CH.sub.2CH.sub.2CH-
.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2)Si
[0200] (CH.sub.3)O][HSiCH.sub.3O].sub.p21Si(CH.sub.3).sub.2H,
[0201]
H(CH.sub.3).sub.2SiO[(Si(OCH.sub.3).sub.3CH.sub.2CH.sub.2C.sub.6H.sub.4---
CH.sub.2CH.sub.2)Si(CH.sub.3)O][HSiCH.sub.3O].sub.p22Si(CH.sub.3).sub.2H,
[0202]
H(CH.sub.3).sub.2SiO[(Si(OCH.sub.3).sub.3CH.sub.2C.sub.6H.sub.4--C-
H.sub.2CH.sub.2CH.sub.2)Si(CH.sub.3)O][HSiCH.sub.3O].sub.p23Si
(CH.sub.3).sub.2H, [0203]
H(CH.sub.3).sub.2SiO[(Si(OCH.sub.3).sub.3CH.sub.2C.sub.6H.sub.4--CH.sub.2-
CH.sub.2)Si(CH.sub.3)O][HSiCH.sub.3O].sub.p24Si(CH.sub.3).sub.2H,
[0204]
H(CH.sub.3).sub.2SiO[(Si(OCH.sub.3).sub.3C.sub.6H.sub.4--CH.sub.2CH.sub.2-
)Si(CH.sub.3)O][HSiCH.sub.3O].sub.p25Si(CH.sub.3).sub.2H, [0205]
H(CH.sub.3).sub.2SiO[(Si(OCH.sub.3).sub.3CH.sub.2CH.sub.2CH.sub.2)Si(CH.s-
ub.3)O][HSiCH.sub.3O].sub.p26Si(CH.sub.3).sub.2H, [0206]
H(CH.sub.3).sub.2SiO[(Si(OCH.sub.3).sub.3CH.sub.2CH.sub.2CH.sub.2CH.sub.2-
)Si(CH.sub.3)O][HSiCH.sub.3O].sub.p27Si(CH.sub.3).sub.2H, [0207]
H(CH.sub.3).sub.2SiO[(Si(OCH.sub.3).sub.3CH.sub.2CH.sub.2CH.sub.2CH.sub.2-
CH.sub.2CH.sub.2)Si(CH.sub.3)O][HSiCH.sub.3O].sub.p28Si
(CH.sub.3).sub.2H, [0208]
H(CH.sub.3).sub.2SiO[(Si(OCH.sub.3).sub.3CH.sub.2CH.sub.2CH.sub.2C-
H.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2)Si(CH.sub.3)O][HSiCH.sub.3O].sub.p-
29Si(CH.sub.3).sub.2H, [0209]
H(CH.sub.3).sub.2SiO[(Si(OCH.sub.3).sub.3CH.sub.2CH.sub.2CH.sub.2CH.sub.2-
CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2)Si(CH.sub.3)O][HSiCH.sub.-
3O].sub.p30Si(CH.sub.3).sub.2H, [0210]
H(CH.sub.3).sub.2SiO[(Si(OCH.sub.3).sub.3CH.sub.2CH.sub.2C.sub.6H.sub.4---
CH.sub.2CH.sub.2)Si(CH.sub.3)O][HSiCH.sub.3O].sub.p31Si
(CH.sub.3).sub.2H, [0211]
H(CH.sub.3).sub.2SiO[(Si(OCH.sub.3).sub.3CH.sub.2C.sub.6H.sub.4--C-
H.sub.2CH.sub.2CH.sub.2)Si(CH.sub.3)O][HSiCH.sub.3O].sub.p32Si
(CH.sub.3).sub.2H, [0212]
H(CH.sub.3).sub.2SiO[(Si(OCH.sub.3).sub.3CH.sub.2C.sub.6H.sub.4--CH.sub.2-
CH.sub.2)Si(CH.sub.3)O][HSiCH.sub.3O].sub.p33Si(CH.sub.3).sub.2H,
[0213]
H(CH.sub.3).sub.2SiO[(Si(OCH.sub.3).sub.3C.sub.6H.sub.4--CH.sub.2CH.sub.2-
)Si(CH.sub.3)O][HSiCH.sub.3O].sub.p34Si(CH.sub.3).sub.2H, [0214]
H(CH.sub.3).sub.2SiO[(Si(OCH.sub.3).sub.3CH.sub.2CH.sub.2C.sub.6H.sub.4---
CH.sub.2CH.sub.2)Si(CH.sub.3)O][HSiCH.sub.3O].sub.p35Si
(CH.sub.3).sub.2H, [0215]
H(CH.sub.3).sub.2SiO[(CH.sub.3O)Si(CH.sub.3)CH.sub.2CH.sub.2CH.sub-
.2CH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub.2OSiC.sub.6H.sub.5O].sub.p36
[0216]
[HSi(CH.sub.3).sub.2OSiC.sub.6H.sub.5O].sub.q4Si(CH.sub.3).sub.2H,
[0217]
H(CH.sub.3).sub.2SiO[Si(OCH.sub.3).sub.2CH.sub.2CH.sub.2CH.sub.2CH-
.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub.2OSiC.sub.6H.sub.5O].sub.p37
[0218]
[HSi(CH.sub.3).sub.2OSiC.sub.6H.sub.5O].sub.g5Si(CH.sub.3).sub.2H,
[0219]
C.sub.2H.sub.5O(CH.sub.3).sub.2SiO[SiH(CH.sub.3)O].sub.p38[SiCH.su-
b.3(C.sub.6H.sub.5)O].sub.c6Si(CH.sub.3).sub.2H, [0220]
Si(OC.sub.2H.sub.5).sub.3CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2-
(CH.sub.3).sub.2SiO[SiH(CH.sub.3)O].sub.p39[SiCH.sub.3(C.sub.6H.sub.5)O].s-
ub.q7Si(CH.sub.3).sub.2H, [0221]
C.sub.2H.sub.5OSi(CH.sub.3).sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2-
CH.sub.2(CH.sub.3).sub.2SiO[SiH(CH.sub.3)O].sub.p40[SiCH.sub.3(C.sub.6H.su-
b.5)O].sub.q8Si(CH.sub.3).sub.2H, [0222]
H(CH.sub.3).sub.2SiO(C.sub.2H.sub.5O)Si(CH.sub.3)O[SiH(CH.sub.3)O].sub.p4-
1[SiCH.sub.3(C.sub.6H.sub.5)O].sub.q9Si(CH.sub.3).sub.2H, and
[0223]
H(CH.sub.3).sub.2SiO[Si(OC.sub.2H.sub.5).sub.3CH.sub.2CH.sub.2CH.sub.2Si(-
CH.sub.3)]O[SiH(CH.sub.3)O].sub.p42[SiCH.sub.3(C.sub.6H.sub.5)O].sub.q10Si-
(CH.sub.3).sub.2H. In the above-mentioned groups, p1 to p42 and q1
to q10 are a number of 1 to 100. It is preferable that one molecule
thereof has 1 to 99 hydrosilyl groups.
[0224] The silyl-ether linkage generated on the surface of the
substrate (i.e. Sub.) of the base material for adhesion by the
vinylsilyl-containing silyl group is represented by the following
chemical formula (2).
Sub.-O--SiR.sup.21 (2)
In the chemical formula (2), R.sup.21 of the vinylsilyl-containing
silyl group-SiR.sup.21 has --Si--R.sup.3 group on the terminal
thereof in which R.sup.3 is a vinyl-containing group, or
--Si(R.sup.4)-- group between both terminals thereof in which
R.sup.4 is a vinyl-containing group.
[0225] Concretely, --SiR.sup.21 is represented by the group
consisting of [0226]
--(C.sub.2H.sub.5O).sub.2SiCH.sub.2--CH.dbd.CH.sub.2, [0227]
--(C.sub.2H.sub.5O).sub.2SiCH.sub.2CH.sub.2--CH.dbd.CH.sub.2,
[0228]
--(C.sub.2H.sub.5O).sub.2SiCH.sub.2CH.sub.2CH.sub.2CH.sub.2--CH--CH.sub.2-
, [0229]
--(C.sub.2H.sub.5O).sub.2SiCH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub-
.2CH.sub.2--CH.dbd.CH.sub.2, [0230]
--C.sub.2H.sub.5OSi(CH.dbd.CH.sub.2)OSi(OC.sub.2H.sub.5)--CH.dbd.CH.sub.2-
, [0231]
--(CH.sub.3O).sub.2SiCH.sub.2CH.sub.2C.sub.6H.sub.4--CH.dbd.CH.su-
b.2, [0232]
--(CH.sub.3O)Si(CH.dbd.CH.sub.2)O[SiOCH.sub.3(CH.dbd.CH.sub.2)O].sub.r1Si-
(OCH.sub.3).sub.2--CH.dbd.CH.sub.2, [0233]
--(C.sub.2H.sub.5O)Si(CH.dbd.CH.sub.2)O[SiOC.sub.2H.sub.5(CH.dbd.CH.sub.2-
)O].sub.r2Si(OC.sub.2H.sub.5).sub.2--CH.dbd.CH.sub.2, [0234]
--(C.sub.2H.sub.5O).sub.2SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub.2OSi(-
CH.sub.3).sub.2CH.sub.2CH.sub.2[Si(CH.sub.3).sub.2O].sub.r3--CH.dbd.CH.sub-
.2, [0235]
--(CH.sub.3O).sub.2SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub.2-
OSi(CH.sub.3).sub.2CH.sub.2CH.sub.2[Si(CH.sub.3).sub.2O].sub.r4--CH.dbd.CH-
.sub.2, [0236]
--(CH.sub.3).sub.2SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub.2OSi(CH.sub.-
3).sub.2CH.sub.2CH.sub.2[Si(CH.sub.3).sub.2O].sub.r5--CH.dbd.CH.sub.2,
[0237]
--(C.sub.2H.sub.5O)CH.sub.3SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).-
sub.2OSi(CH.sub.3).sub.2CH.sub.2CH.sub.2[Si(CH.sub.3).sub.2O].sub.r6--CH.d-
bd.CH.sub.2, [0238]
--(--O)SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub.2OSi(CH.sub.3).sub.2CH.-
sub.2CH.sub.2[Si(CH.sub.3).sub.2O].sub.r7--CH.dbd.CH.sub.2, [0239]
--(C.sub.2H.sub.5O).sub.2SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub.2OSi(-
CH.sub.3).sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub.3O)Si(CH.sub.3)O[Si
CH.sub.3(-)O].sub.s1Si(CH.sub.3).sub.3, [0240]
--(C.sub.2H.sub.5O).sub.2SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub.2OSi(-
CH.sub.3).sub.2CH.sub.2CH.sub.2(Si(CH.sub.3).sub.3O)Si(CH.sub.3)O[Si
CH.sub.3(-)O].sub.s2[Si(CH.sub.3).sub.2O].sub.r8Si(CH.sub.3).sub.3,
[0241]
--C.sub.2H.sub.5OSi(CH.dbd.CH.sub.2)O[SiCH.sub.3(-)O].sub.s3Si(OC.-
sub.2H.sub.5).sub.2CH.dbd.CH.sub.2, [0242]
--C.sub.2H.sub.5OSi(CH.dbd.CH.sub.2)O[SiCH.sub.3(-)O].sub.s4Si(CH.dbd.CH.-
sub.2)OC.sub.2H.sub.5--CH.dbd.CH.sub.2, [0243]
--(--O)Si(CH.dbd.CH.sub.2)O[SiCH.sub.3(-)O].sub.s5Si(OC.sub.2H.sub.5).sub-
.2CH.dbd.CH.sub.2, [0244]
--(--O)Si(CH.dbd.CH.sub.2)O[SiCH.sub.3(-)O].sub.s6Si(CH.dbd.CH.sub.2)(O---
)--CH.dbd.CH.sub.2, [0245]
--(--O)Si(CH.dbd.CH.sub.2)O[SiCH.sub.3(-)(O--)].sub.s7Si(CH.dbd.CH.sub.2)-
(O--)--CH.dbd.CH.sub.2, [0246]
--Si(CH.dbd.CH.sub.2)O[Si(-)OC.sub.2H.sub.5].sub.s8[Si(O--)CH.dbd.CH.sub.-
2].sub.2, [0247]
--Si(CH.dbd.CH.sub.2)O[Si(O--)].sub.r9[Si(-)OC.sub.2H.sub.5].sub.s9[Si(OC-
.sub.2H.sub.5).sub.2CH.dbd.CH.sub.2].sub.2, and [0248]
--Si(CH.dbd.CH.sub.2)O[Si(-)(O--)].sub.s10[Si(O--)CH.dbd.CH.sub.2].sub.2.
In the above-mentioned groups, r1 to r9 and s1 to s10 are a number
of 1 to 30. It is preferable that one group thereof has 1 to 30
vinyl groups (i.e. CH.dbd.CH.sub.2 groups).
[0249] Examples of the functional alkoxysilyl compound that
generates the vinylsilyl-containing silyl group are as follows.
[0250] (C.sub.2H.sub.5O).sub.3SiCH.sub.2CH.dbd.CH.sub.2, [0251]
(CH.sub.3O).sub.3SiCH.sub.2CH.sub.2CH.dbd.CH.sub.2, [0252]
(C.sub.2H.sub.5O).sub.3SiCH.sub.2CH.sub.2CH.dbd.CH.sub.2, [0253]
(CH.sub.3O).sub.3SiCH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.dbd.CH.sub.2,
[0254]
(C.sub.2H.sub.5O).sub.3SiCH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.dbd.CH-
.sub.2, [0255]
(C.sub.2H.sub.5O).sub.3SiCH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2-
CH.dbd.CH.sub.2, [0256]
(CH.sub.3O).sub.3SiCH.sub.2(CH.sub.2).sub.2CH.dbd.CH.sub.2, [0257]
(C.sub.2H.sub.5O).sub.2Si(CH.dbd.CH.sub.2)OSi(OCH.sub.2H.sub.5)CH.dbd.CH.-
sub.2, [0258]
(CH.sub.3O).sub.3SiCH.sub.2CH.sub.2C.sub.6H.sub.4--CH.dbd.CH.sub.2,
[0259]
(CH.sub.3O).sub.2Si(CH.dbd.CH.sub.2)O[SiOCH.sub.3(CH.dbd.CH.sub.2)-
O].sub.t1Si(OCH.sub.3).sub.2CH.dbd.CH.sub.2, [0260]
(C.sub.2H.sub.5O).sub.2Si(CH.dbd.CH.sub.2)O[SiOC.sub.2H.sub.5(CH.dbd.CH.s-
ub.2)O].sub.t2Si(OC.sub.2H.sub.5).sub.3, [0261]
(C.sub.2H.sub.5O).sub.3SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub.2OSi(CH-
.sub.3).sub.2CH.sub.2CH.sub.2[Si(CH.sub.3).sub.2O].sub.t3CH.dbd.CH.sub.2,
[0262]
(CH.sub.3O).sub.3SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub.2OSi(C-
H.sub.3).sub.2CH.sub.2CH.sub.2[Si(CH.sub.3).sub.2O].sub.t4--CH.dbd.CH.sub.-
2, [0263]
CH.sub.3O(CH.sub.3).sub.2SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).-
sub.2OSi(CH.sub.3).sub.2CH.sub.2CH.sub.2[Si(CH.sub.3).sub.2O].sub.t5CH.dbd-
.CH.sub.2, [0264]
(C.sub.2H.sub.5O).sub.2CH.sub.3SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub-
.2OSi(CH.sub.3).sub.2CH.sub.2CH.sub.2[Si(CH.sub.3).sub.2O].sub.t6CH.dbd.CH-
, [0265]
(C.sub.2H.sub.5O).sub.3SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub-
.2OSi(CH.sub.3).sub.2CH.sub.2CH.sub.2[Si(CH.sub.3).sub.2O].sub.t7CH.dbd.CH-
, [0266]
(C.sub.2H.sub.5O).sub.3SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub-
.2OSi(CH.sub.3).sub.2CH.sub.2CH.sub.2(Si(CH.sub.3).sub.3O)Si(CH.sub.3)O[Si
CH.sub.3(-)O].sub.u1Si(CH.sub.3).sub.3CH.dbd.CH.sub.2, [0267]
(C.sub.2H.sub.5O).sub.3SiCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.3).sub.2OSi(CH-
.sub.3).sub.2CH.sub.2CH.sub.2(Si(CH.sub.3).sub.3O)Si(CH.sub.3)O[Si
CH.sub.3(-)O].sub.u2[Si(CH.sub.3).sub.2O].sub.t8Si(CH.sub.3).sub.3CH.dbd.-
CH.sub.2, [0268]
(C.sub.2H.sub.5O).sub.2Si(CH.dbd.CH.sub.2)O[SiCH.sub.3(OC.sub.2H.sub.5)O]-
.sub.u3Si(OC.sub.2H.sub.5).sub.2CH.dbd.CH.sub.2, [0269]
(C.sub.2H.sub.5O).sub.2Si(CH.dbd.CH.sub.2)O[Si(OC.sub.2H.sub.5).sub.2O].s-
ub.u4Si(OC.sub.2H.sub.5).sub.2CH.dbd.CH.sub.2, and [0270]
(C.sub.2H.sub.5O).sub.2Si(CH.dbd.CH.sub.2)O[Si(OC.sub.2H.sub.5).sub.2O].s-
ub.u5Si(OC.sub.2H.sub.5).sub.2CH.dbd.CH.sub.2 In the
above-mentioned groups, t1 to t8 and u1 to u5 are a number of 1 to
30. It is preferable that one molecule thereof has 1 to 30 vinyl
groups.
[0271] The silyl-ether-linkage generated on the surface of the
substrate (i.e. Sub.) of the base material for adhesion by the
terminal-alkoxysilyl-containing silyl group is represented by the
following chemical formula (3).
Sub.-O--SiR.sup.22 (3)
In the chemical formula (3), R.sup.22 in the
terminal-alkoxysilyl-containing silyl group --SiR.sup.22 has
--Si(OR.sup.5).sub.2R.sup.6 group on the terminal thereof in which
R.sup.5 and R.sup.6 are an alkyl group having 1 to 4 carbon atoms,
or --Si(OR.sup.7).sub.3 group on the terminal thereof in which
R.sup.7 is an alkyl group having 1 to 4 carbon atoms. Concretely,
--SiR.sup.22 is represented from the group consisting of [0272]
--(C.sub.2H.sub.5O).sub.2SiCH.sub.2CH.sub.2Si(OC.sub.2H.sub.5).sub.3,
[0273]
--(C.sub.2H.sub.5O)CH.sub.3SiCH.sub.2CH.sub.2Si(OC.sub.2H.sub.5).s-
ub.3, [0274]
--(C.sub.2H.sub.5O).sub.2SiCH.dbd.CHSi(OC.sub.2H.sub.5).sub.3,
[0275] --(CH.sub.3O).sub.2SiCH.sub.2CH.sub.2Si(OCH.sub.3).sub.3,
[0276]
--(CH.sub.3O).sub.2SiCH.sub.2CH.sub.2C.sub.6H.sub.4--CH.sub.2CH.sub.2Si(O-
CH.sub.3).sub.3, [0277]
--(CH.sub.3O).sub.2Si[CH.sub.2CH.sub.2].sub.3Si(OCH.sub.3).sub.3,
[0278]
--(CH.sub.3O).sub.2Si[CH.sub.2CH.sub.2].sub.4Si(OCH.sub.3).sub.3,
[0279]
--(CH.sub.3O)CH.sub.3SiCH.sub.2CH.sub.2Si(OCH.sub.3).sub.2CH.sub.3,
[0280]
--(C.sub.2H.sub.5O)CH.sub.3SiOSi(OC.sub.2H.sub.5).sub.2CH.sub.3,
and [0281] --(C.sub.2H.sub.5O)Si(OC.sub.2H.sub.5).sub.2
[0282] Examples of the functional alkoxysilyl compound that
generates the terminal-alkoxysilyl-containing silyl group are as
follows. [0283]
(C.sub.2H.sub.5O).sub.3SiCH.sub.2CH.sub.2Si(OC.sub.2H.sub.5).sub.3,
[0284]
(C.sub.2H.sub.5O).sub.2CH.sub.3SiCH.sub.2CH.sub.2Si(OC.sub.2H.sub.-
5).sub.3, [0285]
(C.sub.2H.sub.5O).sub.3SiCH.dbd.CHSi(OC.sub.2H.sub.5).sub.3, [0286]
(CH.sub.3O).sub.3SiCH.sub.2CH.sub.2Si(OCH.sub.3).sub.3(CH.sub.3O).sub.3Si-
CH.sub.2CH.sub.2C.sub.6H.sub.4--CH.sub.2CH.sub.2Si(OCH.sub.3).sub.3,
[0287]
(CH.sub.3O).sub.3Si[CH.sub.2CH.sub.2].sub.3Si(OCH.sub.3).sub.3,
[0288]
(CH.sub.3O).sub.2Si[CH.sub.2CH.sub.2].sub.4Si(OCH.sub.3).sub.3,
[0289] (C.sub.2H.sub.5O).sub.2Si(OC.sub.2H.sub.5).sub.2, [0290]
(CH.sub.3O).sub.2CH.sub.3SiCH.sub.2CH.sub.2Si(OCH.sub.3).sub.2CH.sub.3,
[0291]
(C.sub.2H.sub.5O).sub.2CH.sub.3SiOSi(OC.sub.2H.sub.5).sub.2CH.sub.-
3, [0292] (CH.sub.3O).sub.3SiO[Si(OCH.sub.3).sub.2O].sub.v1
Si(OCH.sub.3).sub.3, [0293]
(C.sub.2H.sub.5O).sub.3SiO[Si(OC.sub.2H.sub.5).sub.2O].sub.v2Si(OC.sub.2H-
.sub.5).sub.3, and [0294]
(C.sub.3H.sub.7O).sub.3SiO[Si(OC.sub.3H.sub.7).sub.2O].sub.v3Si(OC.sub.3H-
.sub.7).sub.3. In the above-mentioned groups, v1 to v3 are a number
of 0 to 30.
[0295] The silyl-ether-linkage generated on the surface of the
substrate (i.e. Sub.) of the base material for adhesion by the
hydrolytic group-containing silyl group is represented by the
following chemical formula (4).
Sub.-O--Si(R.sup.8).sub.a(R.sup.9).sub.3-a (4)
In the chemical formula (4), R.sup.8 is selected from the group
consisting of hydrogen atom; a halogen atom; an alkyl group, an
alkenyl group, an alkyloxy group and a fluoro-substituted alkyl
group that respectively have 1 to 12 carbon atoms; an aralkyl
group; and aryl group. R.sup.9 is selected from the group
consisting of an acyloxy group, an alkenyloxy group, an
alkaniminooxy group, an alkyloxy group, an alkylamino group and a
dialkylamino group that respectively have 1 to 12 carbon atoms; a
nitrogenous heterocyclic group and an arylamino group. a is a
number of 0 to 3. Concretely, R.sup.8 in the hydrolytic
group-containing silyl group: --Si(R.sup.8).sub.a(R.sup.9).sub.3-a
is represented by H--, F--, CH.sub.3--, C.sub.2H.sub.5--,
CH.sub.2.dbd.CH--, n-C.sub.3H.sub.7--, i-C.sub.3H.sub.7--,
CH.sub.2--CHCH.sub.2--, C.sub.4H.sub.9--, C.sub.6H.sub.13--,
C.sub.8H.sub.7--, C.sub.6H.sub.5--, CH.sub.3C.sub.6H.sub.4--,
C.sub.6H.sub.5CH.sub.2--, CF.sub.3CF.sub.2CH.sub.2CH.sub.2--,
CF.sub.3CF.sub.2CF.sub.2CH.sub.2CH.sub.2--,
CF.sub.3CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2CH.sub.2--
-, CH.sub.3O-- or C.sub.2H.sub.5O--. R.sup.9 therein is represented
by CH.sub.3COO--, CH.sub.2.dbd.C(CH.sub.3)O--,
C.sub.2H.sub.5(CH.sub.3)C.dbd.NO--, CH.sub.3O--,
(CH.sub.3).sub.2N--, (C.sub.2H.sub.5).sub.2N--,
(i-C.sub.3H.sub.7).sub.2N--, O(CH.sub.2CH.sub.2).sub.2N--,
(CH.sub.3).sub.3CNH--, C.sub.6H.sub.10NH-- or
C.sub.6H.sub.5NH--.
[0296] Examples of the functional alkoxysilyl compound that
generates the hydrolytic group-containing silyl group is a
hydrolysable organosilane such as CH.sub.3Si(OCOCH.sub.3).sub.3,
(CH.sub.3).sub.2Si(OCOCH.sub.3).sub.2,
n-C.sub.3H.sub.7Si(OCOCH.sub.3).sub.3,
CH.sub.2.dbd.CHCH.sub.2Si(OCOCH.sub.3).sub.3,
C.sub.6H.sub.5Si(OCOCH.sub.3).sub.3,
CF.sub.3CF.sub.2CH.sub.2CH.sub.2Si(OCOCH.sub.3).sub.3,
CH.sub.2.dbd.CHCH.sub.2Si(OCOCH.sub.3).sub.3,
CH.sub.3OSi(OCOCH.sub.3).sub.3,
C.sub.2H.sub.5OSi(OCOCH.sub.3).sub.3,
CH.sub.3Si(OCOC.sub.3H.sub.7).sub.3,
CH.sub.3Si[OC(CH.sub.3)--CH.sub.2].sub.3,
(CH.sub.3).sub.2Si[OC(CH.sub.3)--CH.sub.2]n-C.sub.3H.sub.7Si[OC(CH.sub.3)-
.dbd.CH.sub.2].sub.3,
CH.sub.2.dbd.CHCH.sub.2Si[OC(CH.sub.3).dbd.CH.sub.2].sub.3,
C.sub.6H.sub.5Si[OC(CH.sub.3).dbd.CH.sub.2].sub.3,
CF.sub.3CF.sub.2CH.sub.2CH.sub.2Si[OC(CH.sub.3).dbd.CH.sub.2].sub.3,
CH.sub.2.dbd.CHCH.sub.2Si[OC(CH.sub.3).dbd.CH.sub.2].sub.3,
CH.sub.3OSi[OC(CH.sub.3).dbd.CH.sub.2].sub.3,
C.sub.2H.sub.5OSi[OC(CH.sub.3).dbd.CH.sub.2].sub.3,
CH.sub.3Si[ON.dbd.C(CH.sub.3)C.sub.2H.sub.5].sub.3,
(CH.sub.3).sub.2Si[ON.dbd.C(CH.sub.3)C.sub.2H.sub.5].sub.2,
n-C.sub.3H.sub.7Si[ON.dbd.C(CH.sub.3)C.sub.2H.sub.5].sub.3,
CH.sub.2.dbd.CHCH.sub.2Si[ON.dbd.C(CH.sub.3)C.sub.2H.sub.5].sub.3,
C.sub.6H.sub.5Si[ON.dbd.C(CH.sub.3)C.sub.2H.sub.5].sub.3,
CF.sub.3CF.sub.2CH.sub.2CH.sub.2Si[ON.dbd.C(CH.sub.3)C.sub.2H.sub.5].sub.-
3,
CH.sub.2.dbd.CHCH.sub.2Si[ON.dbd.C(CH.sub.3)C.sub.2H.sub.5].sub.3,
CH.sub.3OSi[ON.dbd.C(CH.sub.3)C.sub.2H.sub.5].sub.3,
C.sub.2H.sub.5OSi[ON.dbd.C(CH.sub.3)C.sub.2H.sub.5]].sub.3,
CH.sub.3Si[ON.dbd.C(CH.sub.3)C.sub.2H.sub.5].sub.3,
CH.sub.3Si[N(CH.sub.3)].sub.3,
(CH.sub.3).sub.2Si[N(CH.sub.3)].sub.2,
n-C.sub.3H.sub.7Si[N(CH.sub.3)].sub.3,
CH.sub.2.dbd.CHCH.sub.2Si[N(CH.sub.3)].sub.3,
C.sub.6H.sub.5Si[N(CH.sub.3)].sub.3,
CF.sub.3CF.sub.2CH.sub.2CH.sub.2Si[N(CH.sub.3)].sub.3,
CH.sub.2.dbd.CHCH.sub.2Si[N(CH.sub.3)].sub.3,
CH.sub.3OSi[N(CH.sub.3)].sub.3,
C.sub.2H.sub.5OSi[N(CH.sub.3)].sub.3 and
CH.sub.3Si[N(CH.sub.3)].sub.3.
[0297] The functional alkoxysilyl compound is used by being
dissolved in water; alcohols such as methanol, ethanol,
isopropanol, ethylene glycol; ketones such as acetone and methyl
ethyl ketone; esters such as ethyl acetate; halide such as
methylene chloride; hydrocarbons such as butane and hexane; ethers
such as tetrahydrofuran and butyl ether; aromatics such as benzene
and toluene; amides such as dimethylformamide and
methylpyrrolidone; and a mixed solvent thereof.
[0298] It is preferable that an additive amount of the functional
alkoxysilyl compound is approximately 0.001 g to 5 g per 100 g of
the before-mentioned solvent. If the additive amount thereof is
less than 0.001 g, the adhesion is insufficient. Also, it is not
preferable if the additive amount is more than 5 g because it
results in generating a multilayered thin layer even if the
condition is controlled.
[0299] While examples of the substrate of the base material for
adhesion made from metal was explained above, a substrate made from
polymer resin, glass or ceramics can be used as well.
[0300] The hydroxyl group can be general hydroxyl group derived
from metal oxide on the surface of the metal, a polymer having
hydroxyl group, or hydroxyl group of ceramics.
[0301] Examples of the metal are a metallic material such as Mg,
Ti, Be, Ca, Li, Al, Mn, Zn, Cr, Ga, Fe, Cd, In, Ta, Co, Ni, Sn, Sb,
Bi, Pb, Cu, Ag, Pt, Pd and Au; a binary alloy, a ternary alloy and
a multi alloy of these metallic material. Examples of the alloy are
Mg-alloy, Al-alloy, Fe--Cr--Ni-alloy, Ni-alloy, Co-alloy,
Cu--Zn-alloy, Cu--Sn-alloy, Cu--Ni-alloy and Ag-alloy. Each of the
substrate made from the metal or the alloy generates an oxide layer
on the surface thereof for introducing the hydroxyl group
thereto.
[0302] Examples of the polymer resin are a polymer material of a
cellulose derivative (ex. cellulose, hydroxyethyl cellulose, starch
and cellulose diacetate), vinyl acetate resin saponify partially on
the surface thereof, low-density polyethylene, high-density
polyethylene, i-polypropylene, petroleum resin, polystyrene,
s-polystyrene, chromane-indene resin, terpene resin,
styrene-divinylbenzene compolymer, acrylonitrile-butadiene-styrene
resin (ABS resin), polymethyl acrylate, polyethyl acrylate,
polyacrylonitrile, polymethyl methacrylate, polyethyl methacrylate,
polycyanoacrylate, polyvinyl acetate, polyvinyl alcohol, polyvinyl
formal, polyvinyl acetal, polyvinyl chloride, vinyl chloride-vinyl
acetate copolymer, vinyl chloride-ethylene copolymer,
polyvinylidene-fluoride, vinylidene fluoride-ethylene copolymer,
vinylidene fluoride-propylene copolymer, 1,4-trans-polybutadiene,
polyoxymethylene, polyethyleneglycol, polypropylene glycol,
phenol-formaline resin, cresol-formaline resin, resorcin resin,
melamine resin, xylene resin, toluene resin, glyptal resin,
modified glyptal resin, polyethylene terephthalate, polybutylene
terephthalate, unsaturated polyester resin, allyl ester resin,
polycarbonate, 6-nylon, 6'6-Nylon, 6'10-nylon (nylon is a
registered trademark), polyimide, polyamide, polybenzimidazole,
polyamideimide, silicon-containing resin(ex. silicone rubber,
silicone resin), fran resin, polyurethane resin, epoxide resin,
polyphenylene oxide, polydimethylphenylene oxide, polyxylene,
polyphenylene sulfide (PPS), polysulfone (PSF), polyether sulfone
(PES), polyether ether ketone (PEEK), polyimide (PPI, ex. kapton),
liquid crystal resin, Kevlar fiber, mixture of carbon fiber and
pulural thereof, polytetrafluoroethylene (PTFE) and so on; a rubber
material such as natural rubber, 1,4-cis-butadiene rubber, isoprene
rubber, polychloroprene rubber, styrene-butadiene copolymer rubber,
hydrogenated styrene-butadiene copolymer rubber,
acrylonitrile-butadiene copolymer rubber, hydrogenated
acrylonitrile-butadiene copolymer rubber, polybutene,
polyisobutylene, ethylene-propylene rubber, ethylene-propylene
terpolymer, chlorinated polyethylene, chlorsulfonated polyethylene,
alkylated chlorsulfonated polyethylene, chloroprene rubber,
chlorinated acrylic rubber, brominated acrylic rubber,
fluoro-rubber, epichlorohydrin and the copolymer rubber,
chlorinated ethylene-propylene rubber, chlorinated butyl rubber,
brominated butyl rubber and so on. The plural polymer resin may be
mixed or crosslinked.
[0303] Examples of ceramics are a sintered body of metallic
material such as Mg, Ti, Be, Ca, Li, Al, Mn, Zn, Cr, Ga, Fe, Cd,
In, Ta, Co, Ni, Sn, Sb, Bi, Pb, Cu and Ag, a sintered body of oxide
of binary metal alloy thereof, a sintered body of oxide of ternary
metal alloy, and a sintered body of oxide of multi metal alloy.
[0304] The substrate of the base material for adhesion is not
intended to be limited unless it is made from the metal, the
polymer resin, the glass or the ceramics, and it can be a particle.
The substrate can be a film, a plate or a fabric in a shape of
rectangle, square, polygon and so on, while it also can be in a
product of a tube, macaroni yarn, a hose or a net. The substrate
can be in a shape of sphere or oval sphere.
[0305] The example of introducing the hydroxyl group to the surface
of the substrate by the corona discharge treatment was explained
above. Also, the hydroxyl group can be introduced thereto by
atomospheric-pressure plasma treatment or ultraviolet irradiation
treatment.
[0306] Corona discharge treatment was proceeded according to the
instruction indicated in Corona Discharge Treatment by The Adhesion
Society of Japan, Vol. 36, No. 3, p. 126 (2000).
Atomospheric-pressure plasma treatment was proceeded according to
the instruction indicated in Plasma Treatment by The Adhesion
society of Japan, Vol. 41, No. 1, p. 4 (2005). Ultraviolet
irradiation treatment was proceeded by an exposure of ultraviolet
ray. As it is mentioned in L. J. Gerenser: J. Adhesion Sci.
Technol. Vol. 7, p. 1019 (1997), by these procedures, hydroxyl
group, calboxyl group, or calbonyl group is generated or appeared
on the surface of the substrate made from metal, polymer resin,
glass or ceramics.
[0307] Not every polymer resin originally has hydroxyl group. Even
if the surface of the substrate made from the polymer resin does
not have hydroxyl group thereon, hydroxyl group is efficiently
generated on the surface thereof by corona discharge treatment,
atmospheric-pressure plasma treatment or ultraviolet irradiation
treatment.
[0308] Although the preferable treatment condition differs
depending on the material of a type or course on the surface of the
substrate, it is important that the treatment is treated
continually until the surface tension thereof goes up to 55 kJ/m or
more in order to achieve sufficient adhesive strength.
[0309] Concretely, the corona discharge treatment on the surface of
the substrate made from the resin or the resin composition is
proceeded by a surface reforming instrument such as Corona Master
that is available from Shinko electric & Instrumentation Co.,
Ltd. The treatment is proceeded at 0 to 60 degrees centigrade for
0.1 to 60 seconds under the condition of output power: AC100V,
output voltage: 0 to 20 kV and oscillation frequency: 0 to 40
kHz
[0310] The atomospheric-pressure plasma treatment on the surface of
the substrate made from the resin or the resin composition is
proceeded by an atmospheric-pressure plasma generator such as
Aiplasuma that is available from Matsushita Electric Works, Ltd.
The treatment is proceeded under the condition of plasma processing
rate: 10 to 100 mm/s, output power: 200 or 220V AC (30 A),
compression air: 0.5 MPa (1 NL/min) and 10 kHz/300 W-5 GHz,
electrical power: 100 W to 400 W and irradiating time: 0.1 to 60
seconds.
[0311] The ultraviolet irradiation treatment of the surface of the
substrate made from the resin or the resin composition is proceeded
by ultraviolet ray light emitting diodes (UV-LED) irradiating
instrument such as ZUV-C30H that is available from Omron
Corporation. The treatment is proceeded under the condition of
wavelength: 200 to 400 nm, output power: 100V AC, peak illumination
intensity of the light source: 400 to 3000 mW/cm.sup.2 and
irradiating time: 1 to 60 seconds.
[0312] The surface of the base material for adhesion on which the
hydroxyl group is generated by a pretreatment such as the corona
discharge treatment can be in contact with the functional
alkoxysilyl compound of a molecular adhesive agent by soaking the
surface thereof or spraying the compound thereto. The time of
soaking thereof or spraying the compound thereto is not limited,
and it is important that the surface of the base material for
adhesion is uniformly wet.
[0313] The base material for adhesion of which the functional
alkocysilyl compound is applied to the surface is dried by heating
thereof in an oven, with a dryer or by irradiating high frequency.
The procedure of heating and drying the base material is proceeded
in temperature range of 50 degrees centigrade to 250 degrees
centigrade for 1 to 60 minutes. If the temperature is lower than 50
degrees centigrade, the reaction time of the hydroxyl group
generated on the surface of the base material for adhesion and the
functional alkoxysilyl compound takes too long, and as a result it
results in decreasing productivity and increasing in cost. If the
temperature is higher than 250 degrees centigrade, the surface
thereof is deformed or the functional alkoxyl compound is
decomposed, even if the time of heating and drying is short. If the
procedural time is less than 1 minute, the heat conduction is not
enough and therefore the binding of the hydroxyl group on the
surface thereof and the functional alkoxysilyl compound is
insufficient. If the procedural time is more than 60 minutes, the
productivity decreases.
[0314] If the reaction of the hydroxyl group on the surface of the
base material for adhesion and the functional alkoxysilyl compound
is insufficient, the above-mentioned procedures of immersing and
drying the surface thereof can be repeated for 1 to 5 times because
repeating procedures shortens the time of immersing and drying the
surface thereof per procedure and therefore accelerates the
reaction.
[0315] Moreover, by mixing the functional alkoxysilyl compound and
the silane compound, a silyl ether having the crosslinking
reactivity to silicone rubber crosslinkage can be generated on the
surface of the base material for adhesion.
[0316] For example, the silane compound used for the following
procedure is selected from the group consisting of; [0317]
HSi(CH.sub.3).sub.2C.sub.6H.sub.4Si(CH.sub.3).sub.2H, [0318]
HSi(CH.sub.3).sub.2C.sub.6H.sub.4OC.sub.6H.sub.4Si(CH.sub.3).sub.2H,
[0319] CH.sub.3 Si(H).sub.2C.sub.2H.sub.4Si(H).sub.2CH.sub.3,
[0320] HSi(CH.sub.3).sub.2C.sub.2H.sub.4Si(CH.sub.3).sub.2H, [0321]
HSi(CH.sub.3).sub.2OSi(CH.sub.3).sub.2H, [0322]
HSi(CH.sub.3).sub.2O[Si(CH.sub.3).sub.2O].sub.x1Si(CH.sub.3).sub.2H(x1=1--
840), [0323]
(CH.sub.3).sub.3SiO[SiH(R.sup.17)O].sub.x2[Si(CH.sub.3).sub.2O].sub.y1Si(-
CH.sub.3).sub.3(R.sup.17.dbd.CH.sub.3--, C.sub.2H.sub.5--,
C.sub.6H.sub.5--; y1=1-50; x2=0-50), [0324]
HSi(CH.sub.3).sub.2O[SiC.sub.6H.sub.5(OSi(CH.sub.3).sub.2H)].sub.oSi(CH.s-
ub.3).sub.2H(x3=1-5) and [0325]
HSi(CH.sub.3).sub.2O[SiCH.sub.3(H)O].sub.x4[SiCH.sub.3(C.sub.6H.sub.5)O].-
sub.y2Si(CH.sub.3).sub.2H(x4=1-10, y2=1-10). After reacting the
hydroxyl group on the surface of the substrate with the functional
alkoxysilyl compound, the substrate is immsered into alcohol
solution of 0.01% to 5% of the silane compound. Then it is heated
at 0 to 200 degrees centigrade for 1 to 60 minutes to obtain a
silicone rubber-adhesive base material. If the concentration of the
silane compound in the alcohol solution is less than 0.01%, the
reacting time takes too long. If the concentration thereof is more
than 5%, the cost for cleaning and collecting unreacted silane
compound increases. If the reaction time is less than 1 minute, the
reaction may be completed, and if it is more than 60 minutes, the
productivity decreases.
[0326] Similarly, the silicone rubber-adhesive base material also
can be obtained by the following procedures. Unsaturated
alkoxysilane compound used for the following procedure is for
example selected from the group consisting of; [0327]
CH.sub.2.dbd.CHCH.sub.2Si(OC.sub.2H.sub.5).sub.3, [0328]
CH.sub.2.dbd.CHCH.sub.2CH.sub.2Si(OC.sub.2H.sub.5).sub.3, [0329]
CH.sub.2.dbd.CHCH.sub.2CH.sub.2CH.sub.2CH.sub.2Si(OC.sub.2H.sub.5).sub.3,
[0330]
CH.sub.2.dbd.CHCH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2Si(-
OCH.sub.3).sub.3, [0331]
CH.sub.2.dbd.CHSi(OC.sub.2H.sub.5).sub.2OSi(OC.sub.2H.sub.5).sub.2CH.dbd.-
CH.sub.2, [0332]
CH.sub.2.dbd.CHC.sub.6H.sub.4--CH.sub.2CH.sub.2Si(OCH.sub.3).sub.3,
[0333]
CH.sub.2.dbd.CHSi(OCH.sub.3).sub.2O[SiOCH.sub.3(CH.dbd.CH.sub.2)O]-
.sub.x5Si(OCH.sub.3).sub.2CH.dbd.CH.sub.2 in which x5 is 1 to 30,
[0334]
CH.sub.2.dbd.CHSi(CH.sub.3).sub.2O[Si(CH.sub.3).sub.2O].sub.y3[Si(R.sup.1-
8).sub.2O].sub.x6Si(CH.sub.3).sub.2CH.dbd.CH.sub.2 in which
R.sup.18 is CH.sub.3--, C.sub.2H.sub.5--, C.sub.6H.sub.5-- or
CF.sub.3CH.sub.2CH.sub.3--, x6 is 0 to 2100 and y3 is 0 to 2100,
[0335]
(CH.sub.3).sub.3SiO[Si(CH.sub.3).sub.2O].sub.y4[SiCH.sub.3(CH.dbd.CH.sub.-
2)O].sub.x7Si(CH.sub.3).sub.3 in which x7 is 0 to 2100 and y4 is 0
to 2100, and [0336]
(CH.sub.3).sub.3SiO[Si(CH.sub.3).sub.2O].sub.y5[SiCH.sub.3(CH.dbd.CH.sub.-
2)O].sub.x8[SiCH.sub.3(R.sup.19)O].sub.z1Si(CH.sub.3).sub.3 in
which R.sup.19 is CH.sub.3--, C.sub.2H.sub.5--, C.sub.6H.sub.5-- or
CF.sub.3CH.sub.2CH.sub.3--, x8 is 0 to 2100, y5 is 0 to 2100 and z1
is 0 to 2100. After the hydroxyl group on the surface of the
substrate with the unsaturated alkoxysilane compound, the substrate
is immsered into suspension of the mixture of 0.01% to 5% of the
silane compound and 10 to 1000 ppm of platinum catalyst. It is
heated at 0 to 200 degrees centigrade for 1 to 60 minutes to obtain
a silicone rubber-adhesive base material.
[0337] If the concentration of the silane compound is less than
0.01%, the reacting time takes too long. If the concentration
thereof is more than 5%, the cost for cleaning and collecting
unreacted silane compound increases. If the concentration of the
platinum catalyst is less than 10 ppm, the reacting speed is too
slow. If the concentration thereof is more than 1000 ppm, the cost
increases. If the temperature is lower than 0 degrees centigrade,
the reactivity is low and therefore the productivity is low. If the
temperature is higher than 200 degrees centigrade, SiH group is
oxided and therefore the quality of the silicone rubber-adhesive
base material is poor. If the reaction time is less than 1 minute,
the reaction may be completed, and if it is more than 60 minutes,
the productivity decreases.
[0338] A silicone rubber-adhesive base material also can be
obtained by the following procedures. After the hydroxyl group on
the surface of the substrate is reacted with the functional
polyalkoxysilane, the substrate is immsered into methanol solution
of 0.01 to 5% of terminal-silanol siloxan such as
HOSi(CH.sub.3).sub.2O[Si(CH.sub.3).sub.2O].sub.2Si(CH.sub.3).sub.2OH.
It is heated at 0 to 200 degrees centigrade for 1 to 60 minutes to
obtain a silicone rubber-adhesive base material having the silanol
group on the surface thereof.
[0339] If the concentration of terminal-silanol siloxane is less
than 0.01%, the reaction time takes too long. If the concentration
thereof is more than 5%, the cost for cleaning and collecting
unreacted terminal-silanol siloxane increases. If the reaction
temperature is lower than 0 degrees centigrade, the reactivity and
productivity are low. If the temperature is higher than 200 degrees
centigrade, a multilayered silicone rubber-adhesive base material
can be obtained. If the reaction time is less than 1 minute, the
reaction may not be completed, and if it is more than 60 minutes,
the productivity decreases.
[0340] The silicone rubber-adhesive base material, which is
obtained by the procedure of introducing the crosslinkage reactive
group such as the hydrosilyl (SiH) group, the unsaturated group and
the silanol (SiOH) group to the surface thereof, and a composition
including a silicone rubber component are contacted, and by keeping
thereof or heating thereof, they are adhered through crosslinkage.
This is further explained hereunder.
[0341] After contacting the silicone rubber-adhesive base material
and the composition including silicone rubber component, they are
heated at 0 to 200 degrees centigrade for 1 to 240 minutes under
the atmospheric pressure to the pressure of 100 kg/cm.sup.2 to
obtain a silicone rubber-adhered article.
[0342] If the temperature is lower than 0 degrees centigrade, the
crosslinkage reaction rate is too slow and the productivity is low.
If the temperature is higher than 200 degrees centigrade, heating
spoils thermal stability of the used polymer resin is not
preferable. If the reaction time is less than 1 minute, the
crosslinkage reaction is insufficient, and most of the time the
silicone rubber-adhesive base material and the composition are not
adhered. If the reaction time is more than 240 minutes, the
productivity is low. Except for manufacturing a foam blanket the
strength of silicone rubber under the atmospheric pressure is low.
Also, there is no any significant advantage of controlling the
pressure in the procedure more than 100 kg/cm.sup.2.
[0343] Examples of the silicone rubber component are;
poly-H-siloxane selected from the group represented by the
following chemical formula (5)
H(CH.sub.3).sub.2SiO[SiH(CH.sub.3)O].sub.c[Si(R.sup.11)R.sup.12O].sub.dS-
i(CH.sub.3).sub.2H (5)
(in the chemical formula (5), R.sup.11 and R.sup.12 are more
concretely represented by the group consisting of CH.sub.3--,
C.sub.2H.sub.5--, CH.sub.2CH.dbd.CH.sub.2--, n-C.sub.3H.sub.7--,
n-C.sub.6H.sub.13--, n-C.sub.8H.sub.17--, C.sub.6H.sub.5--,
C.sub.6H.sub.5CH.sub.2--, C.sub.6H.sub.5CH.sub.2CH.sub.2--,
C.sub.10H.sub.7--, CF.sub.3CH.sub.2CH.sub.2--,
CF.sub.3CF.sub.2CH.sub.2CH.sub.2--,
CF.sub.3CF.sub.2CF.sub.2CH.sub.2CH.sub.2--,
CF.sub.3CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2CH.sub.2--,
CF.sub.3CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2CH.sub.2--,
CF.sub.3CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2C-
H.sub.2--,
CF.sub.3CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.-
2CF.sub.2CF.sub.2CH.sub.2CH.sub.2--, and HSi(CH.sub.3).sub.2O--. c
is a number of 1 to 80 and d is a number of 0 to 80), vinyl
silicone selected from the group represented by the following
chemical formula (6)
CH.sub.2.dbd.CH(CH.sub.3).sub.2SiO[SiCH.dbd.CH.sub.2(CH.sub.3)O].sub.e[S-
i(R.sup.13)R.sup.14O].sub.fSi(CH.sub.3).sub.2CH.dbd.CH.sub.2
(6)
(in the chemical formula (6), R.sup.13 and R.sup.14 are more
concretely represented by the group consisting of CH.sub.3--,
C.sub.2H.sub.5, CH.sub.2.dbd.CH--, CH.sub.2.dbd.CHCH.sub.2--,
n-C.sub.3H.sub.7--, i-C.sub.3H.sub.7--, n-C.sub.6H.sub.13--,
n-C.sub.8H.sub.17--, C.sub.6H.sub.5--,
CH.sub.2--CHC.sub.6H.sub.4--,
CH.sub.2--CHC.sub.6H.sub.4--CH.sub.2--,
C.sub.6H.sub.5CH.sub.2CH.sub.2--, C.sub.10H.sub.7--,
CF.sub.3CH.sub.2CH.sub.2--, CF.sub.3CF.sub.2CH.sub.2CH.sub.2--,
CF.sub.3CF.sub.2CF.sub.2CH.sub.2CH.sub.2--,
CF.sub.3CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2CH.sub.2--,
CF.sub.3CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2CH.sub.2--,
CF.sub.3CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2C-
H.sub.2--,
CF.sub.3CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.-
2CF.sub.2CF.sub.2CH.sub.2CH.sub.2--, and HSi(CH.sub.3).sub.2O--. e
is a number of 1 to 80 and f is a number of 0 to 80.) or silanol
silicone derivative selected from the group represented by the
following chemical formula (7)
A-(CH.sub.3).sub.2SiO[Si(CH.sub.3).sub.2O].sub.g[Si(R.sup.15)R.sup.16O].-
sub.hSi(CH.sub.3).sub.2-A (7)
(in the chemical formula, R.sup.15 and R.sup.16 are more concretely
represented by the group consisting of CH.sub.3--,
C.sub.2H.sub.5--, CH.sub.2.dbd.CH--, CH.sub.2.dbd.CHCH.sub.2--,
n-C.sub.3H.sub.7--, i-C.sub.3H.sub.7--, n-C.sub.6H.sub.13--,
n-C.sub.8H.sub.17--, C.sub.6H.sub.5--,
CH.sub.2.dbd.CHC.sub.6H.sub.4--,
CH.sub.2.dbd.CHC.sub.6H.sub.4--CH.sub.2--,
C.sub.6H.sub.5CH.sub.2CH.sub.2--, C.sub.10H.sub.7--,
CF.sub.3CH.sub.2CH.sub.2--, CF.sub.3CF.sub.2CH.sub.2CH.sub.2--,
CF.sub.3CF.sub.2CF.sub.2CH.sub.2CH.sub.2--,
CF.sub.3CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2CH.sub.2--,
CF.sub.3CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2CH.sub.2--,
CF.sub.3CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2C-
H.sub.2--, and
CF.sub.3CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2C-
F.sub.2CH.sub.2CH.sub.2--. A is represented by the group consisting
of HO--, CH.sub.3O--, C.sub.2H.sub.5O--, n-C.sub.3H.sub.7O--,
i-C.sub.3H.sub.7O--, C.sub.6H.sub.5O--, CH.sub.3COO--,
CH.sub.2.dbd.C(CH.sub.3)O--, C.sub.2H.sub.5(CH.sub.3)C.dbd.NO--,
and (CH.sub.3).sub.2N-- and (C.sub.2H.sub.5).sub.2N--. g is a
number of 1 to 80, h is a number of 0 to 80.)
[0344] The composition including silicone rubber component includes
at least one silicone rubber component selected from the above
groups. The silicone rubber component can be an addition reaction
type silicone rubber component of mixture of the group of the
chemical formula (5) and the group of chemical formula (6), a
peroxide silicone rubber component of the group of chemical formula
(6), and a condensation-type silicone rubber component of the group
of chemical formula (7) or a mixture of the group of the chemical
formula (5) and the group of chemical formula (7).
[0345] Besides the above-mentioned silicone rubber component, a
filler, a crosslinkage agent and catalyst can be added to the
composition including silicone rubber component.
[0346] Examples of the filler are wet silica, dry silica, talc,
nipsil, carbon black, metallic oxide, and they are added in the
range of 10 to 100 parts by weight. If the additive amount is less
than 10 parts by weight, the stiffening effect is insufficient, and
if the amount thereof is more than 100 parts by weight, it is
difficult to blend for filling the filler up.
[0347] Silicone rubber is prepared through crosslinking such as
crosslinking type peroxide, additional reaction type crosslinking,
and condenced type crosslinking. The crosslinking of a silicone
rubber-adhesive base material and silicone rubber of the silicone
rubber blanket can be obtained.
[0348] For peroxide type silicone rubber composition, 0.5 to 5
parts by weight of peroxide such as benzoyl peroxide,
t-butylperbenzoate, dicumylperoxide, di-t-butylperoxide,
2,5-dimethyl-2,5-di(t-butylperoxy)hexane,
2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3 and
di(t-dutylperoxyisopropyl)benzene is added into the composition. If
the additive amount of peroxide is less than 0.5 parts by weight,
the crosslinkage is insufficient, and if the amount thereof is more
than 5 parts by weight, the crosslinkage may happen during forming
on ahead preparation.
[0349] An adhesive article, which is prepared by cross-linking the
surface of the silicone rubber-adhesive base material and peroxide
type silicone rubber component of the composition, can be obtained
by heating thereof at 80 to 200 degrees centigrade for 1 to 60
minutes. If the temperature is lower than 80 degrees centigrade, it
is difficult to obtain an adhesive article, and if the temperature
is higher than 200 degrees centigrade, the silicone rubber may turn
yellowish color. If heating time is less than 1 minute, the
crosslinkage is insufficient, and if it is more than 60 minutes,
the productivity is low and the cost is high.
[0350] For the additional reaction type silicone rubber
composition, as catalyst used for the additional reaction type
crosslinkage, chloroplatinic acid, platinum carbonyl
cyclovinylmethylsiloxane complex, platinum divinyl
tetramethyldisiloxane complex, platinum cyclovinylmethylsiloxane
complex, platinum octanal/octanol complex or
tris(dibutylsulfide)rhodiumtrichloride is added into the
composition within the range of 1 to 100 ppm. If the concentration
thereof is less than 1 ppm, the crosslinkage is insufficient, and
if the concentration thereof is more than 100 ppm, the cost
increases.
[0351] The above-mentioned catalyst is used by being added to the
composition including silicone rubber component of the silicone
rubber represented by the chemical formula (5), the silicone rubber
represented by the chemical formula (6) or the mixture of these
silicone rubbers.
[0352] In case of using an ordinary industrial product of rubber
molded article having thickness of less than 10 mm, the composition
including silicone rubber component can be cross-linked to the
substrate by hearing thereof at 0 to 150 degrees centigrade for 1
to 240 minutes. If the temperature is lower than 0 degrees
centigrade, it is difficult to obtain an adhesive article.
Incidentally, there is no sufficient problem if the temperature is
over 150 degrees centigrade. If the heating time is less than 1
minute, the crosslinkage is insufficient. If the heating time is
more than 240 minutes, the productivity is low and the cost
increases. If the thickness of rubber molded article is more than
10 mm, the heat conductivity and cross-linking speed inside the
article decreases. Therefore, it may be necessary to keep the
temperature of a mold in order to proceed a crosslinkage for a
longer time. In this case, the temperature can be changed
accordingly. In case of using a relatively thin industrial product
of rubber molded article, the composition including silicone rubber
component can be cross-linked the substrate by hearing thereof at
room temperature for around the clock. In this case, the rubber
molded article with high dimensional accuracy can be obtained
because differential thermal expansion between high temperature for
crosslinking and room temperature for usage thereof is not broken
out.
[0353] The mixing ratio of the silicone rubber of chemical formula
(5) and the silicone rubber of chemical formula (6) is
approximately equivalent molar ratio of SiH group and
CH.dbd.CH.sub.2, however, generally the mixing ration thereof is
1.3/1 to 4.5/1. If the mixing ratio is less than 1.3/1, the degree
of hardness is lower than the desired hardness. If the mixing ratio
is more than 4.5/1, the degree of hardness tend to be lower than
the desired hardness. The preferable mixing ratio of SiH group and
CH.dbd.CH.sub.2 is selected accordingly because the mixing ratio is
influenced by an additive such as filler.
[0354] Especially, if the concentration of SiH group of the
crosslinking reactive group on the surface of the substrate is
high, adhesive strength increases, even if the mixing ratio of SiH
group and CH.dbd.CH.sub.2 is high. If the concentration of SiH
group is low, adhesive strength decreases, even if the mixing ratio
of SiH group and CH.dbd.CH.sub.2 group is high. However, if the
concentration of CH.dbd.CH.sub.2 of the crosslinking reactive group
on the surface thereof is high, adhesive strength does not increase
unless the mixing ration of SiH group and CH.dbd.CH.sub.2 is
high.
[0355] For condensation-type silicone rubber composition, 0.5 to 10
parts by weight of CH.sub.3Si(OCOCH.sub.3).sub.3,
C.sub.2H.sub.5OSi(OCOCH.sub.3).sub.3,
CH.sub.3Si[OC(CH.sub.3).dbd.CH.sub.2].sub.3,
CH.sub.3Si[ON.dbd.C(CH.sub.3)C.sub.2H.sub.5]].sub.3,
CH.sub.3OSi[ON.dbd.C(CH.sub.3)C.sub.2H.sub.5]].sub.3,
CH.sub.3Si[N(CH.sub.3)].sub.3 and so on are added into the
composition as a condensation-type crosslinking agent. As catalyst,
0.5 to 10 parts by weight of an organic tin compound such as
bis(ethylhexyl)tin, bis(neodecanoate)tin, dibutyllauryl tin; a
metal salt such aszinc octylate and iron octylate, titanate ester,
titanium chelate compounds; amins and so on are added thereto.
[0356] Among the condensation-type silicone rubber composition, the
condensation-type crosslinking agent is added to the silanol
silicone type rubber represented by the chemical formula (7). The
catalyst is used by being added to either H silicone polymer
represented by the chemical formula (5) or the silanol silicone
type rubber represented by the chemical formula (7), or a mixture
thereof.
[0357] Organic titanium compound can be used together therewith. It
is preferable that the organic titanium compound as useful catalyst
for hydrolysis and condensation of alkoxysilyl group is organic
titanium compound having Ti--O--C bond such as alkoxy titan, titan
chelate, titan acylate, composite titanate. Examples of the organic
compound are titanium tetraisopropoxide (ORGATIX TA-10), titanium
diisopropoxy bis(acetylacetonate) (ORGATIX TC-100), wherein ORGATIX
series are available from Matsumoto Trading Co., Ltd. Other
examples of the organic compound are PLENACT series of KR TTS, KR
46B, KR 55, KR 41B, KR 38S, KR 1385, KR 238S, 338.times., KR 44, KR
9SA and KR ET, wherein PLENACT series are available from Ajinomoto
Fine-Techno Co., Inc.
[0358] A base material for adhesion and a silicone rubber-adhered
article prepared by using thereof can be another embodiment as
explained below.
[0359] For example, as a substrate, the surface of a washed
substrate made from metal such as aluminum is treated by corona
discharge treatment in order to generate hydroxyl group thereon.
The substrate is immersed into a solution of vinyl-containing silyl
compound such as
(CH.sub.2.dbd.CH--)(CH.sub.3O--).sub.2Si--O--[(CH.sub.2.dbd.CH--)(CH.sub.-
3O--)Si--O].sub.b1--Si(--OCH.sub.3).sub.2(--CH.dbd.CH.sub.2) and
then heated, and the vinyl-containing silyl compound reacts with
the hydroxyl group on the surface thereof. Then, the substrate is
immersed into hexane solution of platinum catalyst suspension for
example platinum catalyst such as
platinum-tetramethyldivinyldisiloxane complex and dried in order to
obtain a base material for adhesion on which the
platinum-containing catalyst is applied. Although the chemical
structure thereof is still inapparent, it is assumed that platinum
atom of the platinum complex coordinates with several
vinyl-containing silyl groups generated on the surface of the base
material for adhesion.
[0360] The hydrosilyl-containing polysiloxane, or vinyl-containing
polysiloxane, or if necessary a composition including platinum
catalyst suspension is applied onto the base material for adhesion
to harden thereof in order to obtain an adhesive silicone rubber
blanket. As a result, the hydrosilyl group of the
hydrosilyl-containing polysiloxane preferentially reacts with the
double-bond of the vinyl-containing silyl group by the
hydrosilylation reaction rather than the cross-linking
polymerization of the vinly-containing silyl group on the surface
of the substrate, and then it is polymerised. And then, a silicone
rubber-adhered article that the adhesive silicone rubber blanket
made from polysiloxane is applied to the surface thereof is
obtained.
[0361] Examples of platinum-containing catalyst are platinum
complex such as hexane solution of
platinum-tetramethyldivinyldisiloxane complex,
vinylmethylcyclosiloxane solution including 1.85% to 2.1% of
platinum carbonylcyclovinylmethylsiloxane complex such as SIP6829.2
that is available from Gelest Inc., both-terminal-vinyl
polydimethylsiloxane solution including 3% to 3.5% of
platinum-divinyltetramethyldisiloxane complex such as SIP6830.3
that is available from Gelest Inc., xylene solution including 2.1%
to 2.4% of platinum-divinyltetramethyldisiloxane complex such as
SIP6831.2 that is available from Gelest Inc., pale colored xylene
solution including 2.1% to 2.4% of
platinum-divinyltetramethyldisiloxane complex such as SIP6831.2LC
that is available from Gelest Inc., cyclomethylvinylsiloxane
solution of 2% to 2.5% of platinum-cyclic vinylmethylsiloxane
complex such as SIP6832.2 that is available from Gelest Inc.,
octanol solution including 2% to 2.5% of platinum-octanal/octanol
complex such as SIP6833.2 that is available from Gelest Inc.
Instead of platinum-containing catalyst, a rhodium-containing
catalyst for example toluene solution of 3% to 3.5% including
tris(dibutylsulfide)rhodiumtrichloride such as INRH078 that is
available from Gelest Inc. can be used.
[0362] Examples of procedures in which the adhesive silicone rubber
blanket is adhered to singular base material for adhesion were
explained. However, pulural base materials for adhesion for example
two base materials for adhesion can be also used in the procedure.
For example, each of the surface thereof on which
silyl-ether-linkage is generated by the active silyl group is faced
to each other. After applying a silicone rubber composition in
between or sandwitching an adhesive silicone rubber blanket that is
granular, textile, membranous, filmy or plate-like by the base
materials, and if necessary heating thereof, the base materials for
adhesion are adhered. Each of plural base materials for adhesion
can be homogeneous or heterogeneous. Each substrate of plural base
materials can be prepared with the same or different subject
matter.
[0363] Hereunder, examples of manufacturing a base material for
adhesion and a silicone rubber-adhered article are explained in
detail.
Example 1
Reaction of Dimethylsiloxane Having Hydrogen at the Terminal
[0364] HSi(CH.sub.3).sub.2OSi(CH.sub.3).sub.2H, whose boiling point
is at 70 degrees centigrade, and unsaturated silane:
CH.sub.2.dbd.CHCH.sub.2Si(OC.sub.2H.sub.5).sub.3, whose boiling
point is at 176 degrees centigrade:
[0365] 0.5 mol (67 g) of HSi(CH.sub.3).sub.2OSi(CH.sub.3).sub.2H,
0.1 mol (20.4 g) of
CH.sub.2.dbd.CHCH.sub.2Si(OC.sub.2H.sub.5).sub.3 and 0.2 ml of a
solution including platinum-containing catalyst that catalyses at
room temperature of catalog number SIP6830.3 that is available from
Gelest Inc. were added in 200 ml conical flask, and the mixture was
stirred for 24 hours at 50 degrees centigrade under nitrogen gas
stream. After the reaction, the reaction the mixture was distilled
to remove unreacted HSi(CH.sub.3).sub.2OSi(CH.sub.3).sub.2H. Then,
33.8 g of crude
HSi(CH.sub.3).sub.2OSi(CH.sub.3).sub.2CH.sub.2CH.sub.2CH.sub.2Si(OC.sub.2-
H.sub.5).sub.3 was obtained. After the distilution thereof at 82 to
83 degrees centigurade under 10 mmHg of reduced pressure, the
desired pure product was obtained.
[0366] Elemental Analysis Found (Calculated): C, 46.0% (46.10%), H,
8.9% (8.93%)
Example 2
Method (A) for Manufacturing an Adhesive Base Material Having a
Hydrosilyl-Containing Silyl Group on the Surface Thereof
[0367] After treating the surface of substrates such as a
polyethylene terephthalate (PET) resin plate of 30 mm by 50 mm, an
aluminum plate of 30 mm by 50 mm and a glass plate of 30 mm by 50
mm by corona discharge treatment by Corona Master, the substrates
were immersed for two minutes in 0.5 weight % of
HSi(CH.sub.3).sub.2OSi(CH.sub.3).sub.2CH.sub.2CH.sub.2CH.sub.2Si(OC.sub.2-
H.sub.5).sub.3 in methanol-water mixed solution whose ratio is 95/5
by weight. After drying the substrates at room temperature and
heating thereof for 10 minutes at 150 degrees centigrade, an
adhesive base material having a hydrosilyl-containing silyl group
on the surface thereof was obtained.
[0368] By X-ray-induced photoelectron spectroscopy (XPS) using an
equipment of catalog number ESCA-5600 that is available from
Physical Electronics Inc., the obtained adhesive base material
having a hydrosilyl-containing silyl group on the surface thereof
was determined at 350 W of AI output power and 45-degree angle of
acceptance angle. It was determined that each of the PET resin
plate, the aluminum plate and the glass plate has the
hydrosilyl-containing silyl group on the surface thereof because
C1s peak at 184 eV, Sils peak for HS and Sils peak for SiCH.sub.3
were observed by the determination.
Example 3
Method (B) for Manufacturing an Adhesive Base Material Having a
Hydrosilyl-Containing Silyl Group on the Surface Thereof
[0369] After treating the surface of a substrate such as a PET
resin plate of 30 mm by 50 mm, an aluminum plate of 30 mm by 50 mm
and a glass plate of 30 mm by 50 mm by corona discharge treatment
by Corona Master, the substrate was immersed for 2 minutes in 0.2
weight % of
CH.sub.2.dbd.CHCH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2Si(OCH.sub-
.3).sub.3 in methanol solution. After dying the substrate at room
temperature and heating thereof for 10 minutes at 150 degrees
centigrade, an adhesive base material having CH.sub.2.dbd.CH on the
surface thereof was obtained. The obtained adhesive base material
having CH.sub.2.dbd.CH on the surface thereof was immersed in 100
ml of isopropanol solution of 10 g of
HSi(CH.sub.3).sub.2OSi(CH.sub.3).sub.2H and 0.2 ml of solution
including platinum-containing catalyst of catalog number SIP6830.3
that is available from Gelest Inc. for 10 minutes at 70 degrees
centigrade, and an adhesive base material having
hydrosilyl-containing silyl group on the surface thereof was
obtained. By XPS using an equipment of catalog number ESCA-5600
that is available from Physical Electronics Inc., the obtained
adhesive base material having a hydrosilyl-containing silyl group
on the surface thereof were determined at 350 W of AI output power
and 45-degree angle of acceptance angle. It was determined that
each of the PET resin plate, the aluminum plate and the glass plate
has the hydrosilyl-containing silyl group on the surface thereof
because C1s peak at 184 eV, Sils peak for HSi and Sils peak for
SiCH.sub.3 were observed by the determination.
Example 4
Method (C) for Manufacturing an Adhesive Base Material Having
CH.sub.2.dbd.CH on the Surface Thereof
[0370] After treating the surface of substrates such as a PET resin
plate of 30 mm by 50 mm, an aluminum plate of 30 mm by 50 mm and a
glass plate of 30 mm by 50 mm by corona discharge treatment by
Corona Master, the substrates were immersed for two minutes in 0.1
weight % of
CH.sub.2.dbd.CHSi(OCH.sub.3).sub.2O[SiOCH.sub.3(CH.dbd.CH.sub.2)O].sub.2
Si(OCH.sub.3).sub.2CH.dbd.CH.sub.2 in methanol-water mixed solution
whose ratio is 95/5 by weight. After drying the substrates at room
temperature and heating thereof for 5 minutes at 170 degrees
centigrade, an adhesive base material having CH.sub.2.dbd.CH on the
surface thereof was obtained. By XPS using an equipment of catalog
number ESCA-5600 that is available from Physical Electronics Inc.,
the obtained adhesive base material having CH.sub.2.dbd.CH on the
surface thereof was determined at 350 W of AI output power and
45-degree angle of acceptance angle. It was determined that each of
the PET resin plate, the aluminum plate and the glass plate has
CH.sub.2.dbd.CH on the surface thereof because C1s peak for
CH.sub.2.dbd.CH at 184 eV was observed by the determination.
Example 5
Method (D) for Manufacturing an Adhesive Base Material Having
Alkoxysilyl Group on the Surface Thereof
[0371] After treating the surface of substrates such as a
polyethylene terephthalate (PET) resin plate of 30 mm by 50 mm, an
aluminum plate of 30 mm by 50 mm and a glass plate of 30 mm by 50
mm by corona discharge treatment by Corona Master, the substrates
were immersed for 2 minutes in 0.1 weight % of
(C.sub.2H.sub.5O).sub.3SiCH.sub.2CH.sub.2Si(OC.sub.2H.sub.5).sub.3
in ethanol-water mixed solution whose ratio is 95/5 by weight.
After drying the substrates at room temperature and heating thereof
for 60 minutes at 120 degrees centigrade, an adhesive base material
having C.sub.2H.sub.5OSi on the surface thereof was obtained.
[0372] By XPS using an equipment of catalog number ESCA-5600 that
is available from Physical Electronics Inc., the obtained adhesive
base material having C.sub.2H.sub.5OSi on the surface thereof was
determined at 350 W of AI output power and 45-degree angle of
acceptance angle. It was determined that each of the PET resin
plate, the aluminum plate and the glass plate has C.sub.2H.sub.5OSi
on the surface thereof because C1s peak for C.sub.2H.sub.5OSi at
184 eV, O1s peak for C.sub.2H.sub.5OSi at 184 eV and Sil s peak for
C.sub.2H.sub.5OSi at 184 eV were observed.
Example 6
Method for Manufacturing Adhesive Article from Surface of Base
Material and Silicone Rubber
[0373] Mixture of 100 parts by weight of terminal-vinyl type
silicone of catalog number DMS-V31, whose molecular weight is
28000, that is available from Chisso Corporation, and 30 parts by
weight of hexamethylsilazane-treated silica, and mixture of 3 parts
by weight of methyl-H-siloxane copolymer and 2 ml of 200 ppm of
platinum catalyst suspension of catalog number SIP6830 that is
available from Chisso Corporation are mixed in a mixer in order to
obtain a silicone rubber composition. Each of the base materials
prepared by conventional methods as the comparative example and the
methods (A), (B) and (C) of the present invention was put in a mold
with the surface-side up, and the obtained silicone rubber
composition was poured into the mold up to the thickness of 2 cm
thereof and kept at 40 degrees centigrade to obtain an adhesive
article. After making a cut in the interface between the base
material and the silicone rubber, peeling strength of the adhesive
article was determined at tensile speed of 5 mm per minute. Each
peeling strength of the adhesive articles prepared by the base
material of the present invention to which the unsaturated group or
the hydrosilyl-containing silyl group was introduced was 4 kN/m or
more. After peeling the silicone rubber, the surface of the
fractured silicone rubber was in a state of delamination. The
result shows that the surface of the base material to which the
unsaturated group or the hydroxysilyl-containing silyl group was
introduced easily and firmly adheres to silanol silicone rubber. On
the other hand, comparative examples without using the base
material of the present invention could not obtain adhesive
articles as the base material and the silicone rubber thereof were
unstuck, and therefore each peeling strength thereof was 0
kN/m.
Example 7
Method for Manufacturing Adhesive Article from Surface of Base
Material and Silicone Rubber
[0374] Mixture of 100 parts by weight of silanol silicone group of
catalog number DMS-S33, whose molecular weight is 43500, that is
available from Chisso Corporation, 50 parts by weight of
hexamethylsilazane-treated silica, 4 g of
CH.sub.3Si(OCOCH.sub.3).sub.3 and 0.1 g of dibutyl tin malate were
mixed in order to obtain a silicone rubber composition. Each of the
comparative base materials and the base material of the present
invention whose surface was introduced by the alkoxysilyl group was
put in a mold with the surface-side up, and the obtained silicone
rubber composition was poured into the mold and then heated thereof
at 140 degrees centigrade for 20 minutes to obtain an adhesive
article. After making a cut in the interface between the base
material and the silicone rubber, peeling strength thereof was
determined at tensile speed of 5 mm per minute. Peeling strength of
the adhesive article whose surface was introduced by the
alkoxysilyl group was 5 kN/m or more. After peeling the silicone
rubber, the surface of the fractured silicone rubber was in a state
of delamination. The result shows that the surface of the base
material to which the alkoxysilyl group was introduced easily and
firmly adheres to silanol silicone rubber. On the other hand,
comparative examples without using the base material of the present
invention could not obtain adhesive articles as the base material
and the silicone rubber thereof were unstuck, and therefore each
peeling strength thereof was 0 kN/m.
Example 8
Method for Manufacturing Adhesive Article from Surface of Base
Material and Silicone Rubber
[0375] Mixture of 100 parts by weight of terminal-vinyl type
silicone of catalog number VDF-131 that is available from Chisso
Corporation and 40 parts by weight of hexamethylsilazane-treated
silica, and 4 parts by weight of dicumyl peroxide were mixed in
order to obtain a silicone rubber composition. Each of the
comparative base materials and the base material of the present
invention whose surface was introduced by CH.sub.2.dbd.CH group was
put in a mold with the surface-side up, and the obtained silicone
rubber composition was poured into the mold and then heated thereof
at 150 degrees centigrade for 20 minutes to obtain an adhesive
article. After making a cut in the interface between the base
material and the silicone rubber, peeling strength thereof was
determined at tensile speed of 5 mm per minute. Peeling strength of
the adhesive article whose surface was introduced by
CH.sub.2.dbd.CH group of the unsaturated group was 6 kN/m or more.
After peeling the silicone rubber, the surface of the fractured
silicone rubber was in a state of delamination. The result shows
that the surface of the base material to which CH.sub.2.dbd.CH
group was introduced easily and firmly adheres to the silicone
rubber by peroxide cross-linkage. On the other hand, comparative
examples without using the base material of the present invention
could not obtain adhesive articles as the base material and the
silicone rubber thereof were unstuck, and therefore each peeling
strength thereof was 0 kN/m.
Example 9
Method for Manufacturing Another Base Material for Adhesion and
Silicone Rubber-Adhered Article
(Preparation of Base Material for Adhesion)
[0376] As a substrate, aluminum plate was washed in acetone by 30
minutes of ultrasonic irradiation and then in ion-exchange water by
10 minutes of ultrasonic irradiation twice. The surface of the
substrate was treated by corona discharge treatment under
atmospheric pressure to oxidize the surface thereof and generate
hydroxyl group thereon. Six substrates of such were obtained, and
each substrate was immersed into each ethanol aqueous solution,
whose volume ratio of ethanol and water is 95:5, of 0.1 g/L of
vinylmethoxysiloxane (VMS) represented by
(CH.sub.2.dbd.CH--)(CH.sub.3O--).sub.2Si--O--[(CH.sub.2.dbd.CH--)(CH.sub.-
3O--)Si--O].sub.b1--Si(--OCH.sub.3).sub.2(--CH.dbd.CH.sub.2) in
which b1 is 3.78 and the average molecular weight is 635.6, 0.5 g/L
thereof, 1.0 g/L thereof, 2.0 g/L thereof, 3.0 g/L thereof, 5.0 g/L
thereof and 10 g/L thereof for five minutes. After collecting each
substrate from each aquesous solution, it was heated at 150 degrees
centigrade for 10 minutes. Then, unreacted vinylmethoxysiloxane
(VMS) was washed by ethanol and dried to obtain a base material for
adhesion (VMS-Al). Surface analysis of the washed Al substrate and
the obtained base material was performed by X-ray photoelectron
spectroscopy (XPS analysis). The result thereof is shown in FIG. 1.
Also, the ratio of surface element regarding the washed Al
substrate and the obtained base material was also shown in Table
1.
TABLE-US-00001 TABLE 1 Element C O Si Al Washed Al substrate 19.10%
60.50% -- 19.75% Base Material 22.07% 49.27% 10.76% 17.90% for
Adhesion (VMS-Al)
[0377] As shown in FIG. 1 and Table 1, vinylmethoxysiloxane (VMS)
was introduced to the surface of Al sustrate.
(Preparation of Silicone Rubber-Adhered Article)
[0378] After poly(methylvinylsiloxane) of catalog number KE-1935-A
and poly(methylsiloxane) of catalog number KE-1935-B that are both
available from Shin-Etsu Chemical Co., Ltd., and
platinum-containing catalyst were mixed at required time, any
remaining air therein was evacuated under reduced pressure therein
in order to prepare liquid composition for forming silicone rubber.
The obtained liquid composition was applied onto the base material
for adhesion (VMS-Al) and was hardened by heating thereof at 50
degrees centigrade to prepare an adhesive silicone rubber blanket.
The blanket was reacted with the vinyl group derived from the
vinylmethoxysiloxane (VMS) on the surface of the base material by
crosslinkage, and as a result a silicone rubber-adhered article was
obtained. For each of six ethanol solution with different
concentration of the vinylmethoxysiloxane (VMS), a silicone
rubber-adhered article was obtained. As a comparative example, a
comparative silicone rubber-adhered article was obtained by the
same procedures except for not using the ethanol solution of the
vinylmethoxysiloxane (VMS). Peeling strength of each of the
silicone rubber-adhered article and the comparative silicone
rubber-adhered article was determined by 90 degrees peeling assay
in which the adhesive silicone rubber blanket was peeled off from
the base material for adhesion according to JIS K6256-2:2005. A
correlation chart of the concentration of ethanol solution of the
vinylmethoxysiloxane (VMS) and peeling strength of each silicone
rubber-adhered article is shown in FIG. 2.
[0379] As shown in FIG. 2, when the concentration of the ethanol
solution of vinylmethoxysiloxane (VMS) was 0.1 to 1.0 g/L, peeling
strength of the silicone rubber-adhered article was stronger if the
solution was more concentrated. However, when the concentration
thereof is more than 1.0 g/L, the peeling strength of the silicone
rubber-adhered article plateaus at about 1.0 kN/m. In each case,
peeling strength thereof was stronger compared to the case of
comparative silicone rubber-adhered article whose peeling strength
was 0.4 kN/m that was prepared without the ethanol solution of
vinylmethoxysiloxane (VMS).
Example 10
Method for Manufacturing Another Base Material for Adhesion and a
Silicone Rubber-Adhered Article
(Preparation of Base Material for Adhesion)
[0380] As same as the procedures of Example 9 (preparation of base
material for adhesion), by using the ethanol solution of 1.0 g/L of
vinylmethoxysiloxane (VMS), seven substrates (VMS-Al) were
obtained. Each of the obtained substrates was immered into hexane
solution of 100 ppm of platinum-tetramethyldivinyldisiloxane
complex respectively for 1 minute, 2 minutes, 3 minutes, 4 minutes,
5 minutes, 7 minutes and 10 minutes. After each substrate was
collected and dried, a base material for adhesion (Pt-VMS-AI) of
which a platinum-containing catalyst was applied onto the surface
was obtained respectively.
(Preparation of Silicone Rubber-Adhered Article)
[0381] As same as the procedures of Example 9 (Preparation of
silicone rubber-adhered article), poly(methylvinylsiloxane),
poly(methylsiloxane) and platinum-containing catalyst were mixed at
required time, and then any remaining air therein was evacuated
under reduced pressure in order to prepare liquid composition for
forming silicone rubber. The obtained liquid composition was
applied onto the base material for adhesion (Pt-VMS-AI) and was
hardened by heating thereof at 50 degrees centigrade to prepare an
adhesive silicone rubber blanket. The blanket was reacted and bound
with the vinyl group derived from the vinylmethoxysiloxane (VMS) on
the surface of the base material through crosslinkage, and as a
result each of silicone rubber-adhered articles was obtained. For
each of seven different immersing time of the substrate into hexane
solution of platinum-tetramethyldivinyldisiloxane complex, seven
silicone rubber-adhered articles were obtained. As a comparative
example, a comparative silicone rubber-adhered article was obtained
by the same procedures except for no using the hexane solution of
platinum-tetramethyldivinyldisiloxane complex. As same as Example
9, peeling strength of each of the silicone rubber-adhered article
and the comparative silicone rubber-adhered article was determined
by 90 degrees peeling assay in which the adhesive silicone rubber
blanket was peeled off from the base material for adhesion. A
correlation chart of the immersing time of the substrate into the
hexane solution of platinum-tetramethyldivinyldisiloxane complex
and peeling strength of each silicone rubber-adhered article in
FIG. 3.
[0382] As shown in FIG. 3, when the immersing time of the base
material into hexane solution of
platinum-tetramethyldivinyldisiloxane complex was 1 to 2 minutes,
peeling strength of the silicone rubber-adhered article was
stronger if the immersing time was longer. However, when the
immersing time was longer than 2 minutes, the peeling strength of
the silicone rubber-adhered article plateaus at 4.0 kN/m. In each
case, pleeling strength thereof was stronger compared to the
comparative silicone rubber-article with the peeling strength of
1.0 kN/m that was prepared without using the hexane solution of
platinum-tetramethyldivinyldisiloxane complex and its immersion
time was 0 minute.
Example 11
Method for Manufacturing Another Base Material for Adhesion and
Silicone Rubber-Adhered Article
(Preparation of Base Material for Adhesion)
[0383] As same as a procedures of Example 9 (Preparation of base
material for adhesion), by using the ethanol solution of 1.0 g/L of
vinylmethoxysiloxane (VMS), four substrates (VMS-AI) were obtained.
For 3 minutes, each of the obtained substrates was respectively
immersed into a hexane solution of 20 ppm of
platinum-tetramethyldivinyldisiloxane complex, the hexane solution
of 60 ppm thereof, the hexane solution of 100 ppm thereof, and the
hexane solution of 200 ppm thereof. After each substrate was
collected and dried, a base material for adhesion (Pt-VMS-AI) of
which a platinum-containing catalyst is applied onto the surface
was obtained respectively.
(Preparation of Silicone Rubber-Adhered Article)
[0384] As same as the procedures of Example 9 (Preparation of
silicone rubber-adhered article), poly(methylvinylsiloxane),
poly(methylsiloxane) and platinum-containing catalyst were mixed at
required time, and then any remaining air therein was evacuated
under reduced pressure in order to prepare liquid composition for
forming silicone rubber. The obtained liquid composition was
applied onto the base material for adhesion (Pt-VMS-AI) and was
hardened by heating thereof at 50 degrees centigrade to prepare an
adhesive silicone rubber blanket. The blanket was reacted with the
vinyl group derived from the vinylmethoxysiloxane (VMS) on the
surface of the base material for adhesion by crosslinkage, and as a
result each of silicone rubber-adhered articles was obtained. For
each of four hexane solution with different concentration of the
platinum-tetramethyldivinyldisiloxane complex, silicone
rubber-adhered articles were obtained. As a comparative example, a
comparative silicone rubber-adhered article was obtained by the
same procedures except for not using the hexane solution of the
platinum-tetramethyldivinyldisiloxane complex. As same as Example
9, peeling strength of each of the silicone rubber-adhered article
and the comparative silicone rubber-adhered article was determined
by 90 degrees peeling assay in which the adhesive silicone rubber
blanket was peeled off from the base material for adhesion. A
correlation chart of the concentration of the hexane solution of
platinum-tetramethyldivinyldisiloxane complex and peeling strength
of each silicone rubber-adhered article in FIG. 4.
[0385] As shown in FIG. 4, when the concentration of the hexane
solution of platinum-tetramethyldivinyldisiloxane complex was more
than 200 ppm, the peeling strength of the silicone rubber-adhered
article stayed constant at 4.0 kN/m. Each peeling strength of the
silicone rubber-adhered article of the present invention was
stronger compared to the comparative silicone rubber-adhered
article prepared without the hexane solution of
platinum-tetramethyldivinyldisiloxane complex whose peeling
strength was 1.0 kN/m.
Example 12
Method for Manufacturing Another Base Material for Adhesion and
Silicone Rubber-Adhered Article
[0386] As same as the procedures of Example 9 (preparation of base
material for adhesion) except for using a glass plate instead of
aluminum plate, a substrate (VMS-Glass) instead of VMS-AI was
obtained. The obtained substrate was immersed into hexane solution
of 100 ppm of platinum-tetramethyldivinyldisiloxane complex for 3
minutes. After collecting each substrate therefrom and drying
thereof, a base material for adhesion (Pt-VMS-Glass) of which the
platinum-containing catalyst is applied on the surface was
obtained. Then, as same as the procedures of Example 9 (Preparation
of silicone rubber-adhered article), poly(methylvinylsiloxane),
poly(methylsiloxane) and platinum-containing catalyst were mixed at
required time, and then any remaining air therein was evacuated
under reduced pressure the pressure in order to prepare liquid
composition for forming silicone rubber. The obtained liquid
composition was applied onto the base material for adhesion
(Pt-VMS-Glass) and was hardened by heating thereof at 150 degrees
centigrade to prepare an adhesive silicone rubber blanket. The
blanket was reacted and bound with the vinyl group derived from the
vinylmethoxysiloxane (VMS) on the surface of the base material
through crosslinkage, and as a result the silicone rubber-adhered
article was obtained. As same as Example 9, peeling strength of the
silicone rubber-adhered article was determined by 90 degree peeling
assay in which the adhesive silicone rubber blanket was peeled off
from the base material for adhesion, and peeling strength thereof
was 3.7 kN/m.
Examples 13 to 15
Method for Manufacturing Another Base Material for Adhesion and
Silicone Rubber-Adhered Article
[0387] As same as the procedures of Example 12 except for using a
epoxy resin plate, polypropylene (PP) plate, and polyethylene (PE)
plate, a substrate (Pt-VMS-EpoxyResin), a substrate (Pt-VMS-PP) and
a substrate (Pt-VMS-PE) were obtained, and each silicone
rubber-adhered article prepared using each of the substrates were
obtained. Peeling strength of each silicone rubber-adhered article
was determined by the same peeling assay as Example 12. Peeling
strength of the silicone rubber-adhered article prepared using the
substrate (Pt-VMS-EpoxyResin) was 3.8 kN/m. Peeling strength of the
article prepared using the substrate (Pt-VMS-PP) was 3.2 kN/m, and
that of the article using the substrate (Pt-VMS-PE) was 3.3
kN/m.
[0388] As shown in the Examples, adhesive strength of the silicone
rubber-adhered article prepare by using a base material for
adhesion of the present invention was strong. Especially, adhesive
strength of the silicone rubber-adhered article prepared by
adhering the solid body such as the adhesive silicone rubber
blanket having reactivity to the hydroxy group, and the base
material for adhesion whose substrate surface comprises the
vinyl-containing silyl group and is applied the platinum-containing
catalyst and so on was sufficiently strong as the adhesive silicone
rubber blanket was torn if the article was forced to be peeled.
INDUSTRIAL APPLICABILITY
[0389] A base material for adhesion of the present invention is
prepared by adhering the adhesive silicone rubber article and the
surface of the substrate made from metal, polymer resin, glass or
ceramics in order to protect the substrate and to form elasticity
thereon.
[0390] The silicone rubber-adhered article prepare by adhering the
adhesive silicone rubber blanket and the substrate is used for home
electric appliances, stationery and so on that require elasticity
on the surface thereof. Additionally, because the silicone
rubber-adhered article prepared by sandwitching the adhesive
silicone rubber blanket by the plural substrates and strongly
adhering thereof through chemical bonding, the article is used for
a product that requires strong adhesive strength.
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