U.S. patent application number 11/579635 was filed with the patent office on 2007-12-13 for curable composition.
Invention is credited to Masato Kusakabe, Toshihiko Okamoto, Katsuyu Wakabayashi.
Application Number | 20070287780 11/579635 |
Document ID | / |
Family ID | 35320211 |
Filed Date | 2007-12-13 |
United States Patent
Application |
20070287780 |
Kind Code |
A1 |
Wakabayashi; Katsuyu ; et
al. |
December 13, 2007 |
Curable Composition
Abstract
[Problem] There is provided a curable composition having
satisfactory curability and adhesion by use of a non-tin curing
catalyst, and minimizing lowering of mechanical properties of a
cured article obtained after storing. [Means to Solve] A
one-component type curable composition comprising (A) a
polyoxyalkylene polymer (a1) having a silicon-containing group
being capable of crosslinking by forming siloxane bonds and/or a
(meth)acrylate polymer (a2) having a silicon-containing group being
capable of crosslinking by forming siloxane bonds, (B) a chelate
type methyl titanate (b1) and/or a chelate type ethyl titanate
(b2), and (C) a compound having, in its molecule, a hydrolyzable
silicon group and a nitrogen-substituted group.
Inventors: |
Wakabayashi; Katsuyu;
(Osaka, JP) ; Okamoto; Toshihiko; (Hyogo, JP)
; Kusakabe; Masato; (Osaka, JP) |
Correspondence
Address: |
SUGHRUE MION, PLLC
2100 PENNSYLVANIA AVENUE, N.W.
SUITE 800
WASHINGTON
DC
20037
US
|
Family ID: |
35320211 |
Appl. No.: |
11/579635 |
Filed: |
April 25, 2005 |
PCT Filed: |
April 25, 2005 |
PCT NO: |
PCT/JP05/07799 |
371 Date: |
July 27, 2007 |
Current U.S.
Class: |
524/188 |
Current CPC
Class: |
C08G 65/336 20130101;
C08K 3/014 20180101; C08L 101/10 20130101; C08L 101/10 20130101;
C08L 71/02 20130101; C08K 5/0091 20130101; C08K 5/0091 20130101;
C08K 5/544 20130101; C09K 3/10 20130101; C09J 171/02 20130101; C08K
3/014 20180101; C08K 5/544 20130101; C09D 171/02 20130101 |
Class at
Publication: |
524/188 |
International
Class: |
C08L 71/02 20060101
C08L071/02; C08K 5/04 20060101 C08K005/04; C08L 23/00 20060101
C08L023/00 |
Foreign Application Data
Date |
Code |
Application Number |
May 7, 2004 |
JP |
2004-139110 |
May 7, 2004 |
JP |
2004-139111 |
May 17, 2004 |
JP |
2004-146972 |
May 17, 2004 |
JP |
2004-146973 |
May 17, 2004 |
JP |
2004-146974 |
May 17, 2004 |
JP |
2004-146976 |
May 17, 2004 |
JP |
2004-146977 |
Claims
1. A one-component type curable composition comprising, as
components, (A) a polyoxyalkylene polymer (a1) having a
silicon-containing group being capable of crosslinking by forming
siloxane bonds and/or a (meth)acrylate polymer (a2) having a
silicon-containing group being capable of crosslinking by forming
siloxane bonds, (B) a chelate type methyl titanate (b 1)
represented by the general formula (1): ##STR5## wherein each of
(4-n) R.sup.1s is independently hydrogen atom or a substituted or
unsubstituted hydrocarbon group having 1 to 20 carbon atoms, each
of (4-n) A.sup.1s and (4-n) A.sup.2s is independently --R.sup.2 or
--OR.sup.2 where R.sup.2 is a substituted or unsubstituted
hydrocarbon group having 1 to 20 carbon atoms, n is 1, 2 or 3,
and/or a chelate type ethyl titanate (b2) represented by the
general formula (2): ##STR6## wherein R.sup.1, A.sup.1, A.sup.2 and
n are the same as defined above, and (C) a compound having, in its
molecule, a hydrolyzable silicon group and a nitrogen-substituted
group represented by the general formula (3): --NHR.sup.2 (3)
wherein R.sup.3 is hydrogen atom or a substituted or unsubstituted
hydrocarbon group having 1 to 20 carbon atoms, or the general
formula (4): --N.dbd.R.sup.4 (4) wherein R.sup.4 is CO or a
substituted or unsubstituted divalent hydrocarbon group having 1 to
20 carbon atoms and is bonded to a nitrogen atom by double
bonding.
2. The one-component type curable composition according to claim 1
wherein said polyoxyalkylene polymer (a1) is a polyoxypropylene
polymer.
3. The one-component type curable composition according to claim 1,
wherein said component (B) is a chelate type methyl titanate (b1)
represented by the general formula (1).
4. The one-component type curable composition according to claim 1,
wherein said silicon-containing group contained in the component
(A) and said hydrolyzable silicon group contained in the component
(C) are groups represented by the following general formula (5) and
the general formula (6), respectively:
--SiR.sup.5.sub.3-a(OR.sup.6).sub.a (5) . . . silicon-containing
group of the component (A) --SiR.sup.7.sub.3-b(OR.sup.8).sub.b (6)
. . . hydrolyzable silicon group of the component (C) wherein each
of R.sup.5 and R.sup.7 is independently a substituted or
unsubstituted hydrocarbon group having 1 to 20 carbon atoms or a
triorganosiloxy group represented by (R').sub.3SiO-- where each of
R's is independently a substituted or unsubstituted hydrocarbon
group having 1 to 20 carbon atoms, R.sup.6 is an alkyl group having
1 to 4 carbon atoms, R.sup.8 is an alkyl group having 1 to 4 carbon
atoms, a is 1, 2 or 3, b is 1, 2 or 3, and R.sup.6 is an alkyl
group having the number of carbon atoms equal to or more than the
number of carbon atoms of R.sup.8.
5. The one-component type curable composition according to claim 1,
wherein said hydrolyzable silicon group contained in the component
(C) is a methoxysilyl group represented by the general formula (7):
--SiR.sup.7.sub.3-b(OCH.sub.3).sub.b (7) wherein each of R.sup.7s
is independently a substituted or unsubstituted hydrocarbon group
having 1 to 20 carbon atoms or a triorganosiloxy group represented
by (R').sub.3SiO-- where each of R's is independently a substituted
or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, b
is 1, 2 or 3.
6. A sealant comprising said one-component type curable composition
according to claim 1.
7. An adhesive comprising said one-component type curable
composition according to claim 1.
8. The one-component type curable composition according to claim 2,
wherein said component (B) is a chelate type methyl titanate (b 1)
represented by the general formula (1).
9. The one-component type curable composition according to claim 2,
wherein said silicon-containing group contained in the component
(A) and said hydrolyzable silicon group contained in the component
(C) are groups represented by the following general formula (5) and
the general formula (6), respectively:
--SiR.sup.5.sub.3.sub.--.sub.a(OR.sup.6).sub.a (5) . . .
silicon-containing group of the component (A)
--SiR.sup.7.sub.3.sub.--.sub.b(OR.sup.8).sub.b (6) . . .
hydrolyzable silicon group of the component (C) wherein each of
R.sup.5 and R.sup.7 is independently a substituted or unsubstituted
hydrocarbon group having 1 to 20 carbon atoms or a triorganosiloxy
group represented by (R').sub.3SiO-- where each of R's is
independently a substituted or unsubstituted hydrocarbon group
having 1 to 20 carbon atoms, R.sup.6 is an alkyl group having 1 to
4 carbon atoms, R.sup.8 is an alkyl group having 1 to 4 carbon
atoms, a is 1, 2 or 3, b is 1, 2 or 3, and R.sup.6 is an alkyl
group having the number of carbon atoms equal to or more than the
number of carbon atoms of R.sup.8.
10. The one-component type curable composition according to claim
3, wherein said silicon-containing group contained in the component
(A) and said hydrolyzable silicon group contained in the component
(C) are groups represented by the following general formula (5) and
the general formula (6), respectively:
--SiR.sup.5.sub.3.sub.--.sub.a(OR.sup.6).sub.a (5) . . .
silicon-containing group of the component (A)
--SiR.sup.7.sub.3.sub.--.sub.b(OR.sup.8).sub.b (6) . . .
hydrolyzable silicon group of the component (C) wherein each of
R.sup.5 and R.sup.7 is independently a substituted or unsubstituted
hydrocarbon group having 1 to 20 carbon atoms or a triorganosiloxy
group represented by (R').sub.3SiO-- where each of R's is
independently a substituted or unsubstituted hydrocarbon group
having 1 to 20 carbon atoms, R.sup.6 is an alkyl group having 1 to
4 carbon atoms, R.sup.8 is an alkyl group having 1 to 4 carbon
atoms, a is 1, 2 or 3, b is 1, 2 or 3, and R.sup.6 is an alkyl
group having the number of carbon atoms equal to or more than the
number of carbon atoms of R.sup.8.
11. The one-component type curable composition according to claim
8, wherein said silicon-containing group contained in the component
(A) and said hydrolyzable silicon group contained in the component
(C) are groups represented by the following general formula (5) and
the general formula (6), respectively:
--SiR.sup.5.sub.3-a(OR.sup.6).sub.a (5) . . . silicon-containing
group of the component (A) --SiR.sup.7.sub.3-b(OR.sup.8).sub.b (6)
. . . hydrolyzable silicon group of the component (C) wherein each
of R.sup.5 and R.sup.7 is independently a substituted or
unsubstituted hydrocarbon group having 1 to 20 carbon atoms or a
triorganosiloxy group represented by (R').sub.3SiO-- where each of
R's is independently a substituted or unsubstituted hydrocarbon
group having 1 to 20 carbon atoms, R.sup.6 is an alkyl group having
1 to 4 carbon atoms, R.sup.8 is an alkyl group having 1 to 4 carbon
atoms, a is 1, 2 or 3, b is 1, 2 or 3, and R.sup.6 is an alkyl
group having the number of carbon atoms equal to or more than the
number of carbon atoms of R.sup.8.
12. The one-component type curable composition according to claim
2, wherein said hydrolyzable silicon group contained in the
component (C) is a methoxysilyl group represented by the general
formula (7): --SiR.sup.7.sub.3-b(OCH.sub.3).sub.b (7) wherein each
of R.sup.7s is independently a substituted or unsubstituted
hydrocarbon group having 1 to 20 carbon atoms or a triorganosiloxy
group represented by (R').sub.3SiO-- where each of R's is
independently a substituted or unsubstituted hydrocarbon group
having 1 to 20 carbon atoms, b is 1, 2 or 3.
13. The one-component type curable composition according to claim
3, wherein said hydrolyzable silicon group contained in the
component (C) is a methoxysilyl group represented by the general
formula (7): --SiR.sup.7.sub.3-b(OCH.sup.3).sub.b (7) wherein each
of R.sup.7s is independently a substituted or unsubstituted
hydrocarbon group having 1 to 20 carbon atoms or a triorganosiloxy
group represented by (R').sub.3SiO-- where each of R's is
independently a substituted or unsubstituted hydrocarbon group
having 1 to 20 carbon atoms, b is 1, 2 or 3.
14. The one-component type curable composition according to claim
8, wherein said hydrolyzable silicon group contained in the
component (C) is a methoxysilyl group represented by the general
formula (7): --SiR.sup.7.sub.3-b(OCH.sub.3).sub.b (7) wherein each
of R.sup.7s is independently a substituted or unsubstituted
hydrocarbon group having 1 to 20 carbon atoms or a triorganosiloxy
group represented by (R').sub.3SiO-- where each of R's is
independently a substituted or unsubstituted hydrocarbon group
having 1 to 20 carbon atoms, b is 1, 2 or 3.
15. A sealant comprising said one-component type curable
composition according to claim 2.
16. A sealant comprising said one-component type curable
composition according to claim 3.
17. A sealant comprising said one-component type curable
composition according to claim 8.
18. An adhesive comprising said one-component type curable
composition according to claim 2.
19. An adhesive comprising said one-component type curable
composition according to claim 3.
20. An adhesive comprising said one-component type curable
composition according to claim 8.
Description
TECHNICAL FIELD
[0001] The present invention relates to a curable composition
comprising an organic polymer containing a silicon-containing group
(hereinafter referred to as a "reactive silicon group") which has
hydroxyl group or a hydrolyzable group bonded to the silicon atom
and which is capable of crosslinking by forming siloxane bonds.
BACKGROUND ART
[0002] It is known that an organic polymer having at least one
reactive silicon group in the molecule undergoes crosslinking by
formation of siloxane bonds accompanying a hydrolysis reaction of
the reactive silicon group with moisture or the like even at room
temperature, and a rubber-like cured article can be obtained.
[0003] Among the polymers having a reactive silicon group, organic
polymers in which the main chain skeleton is a polyoxyalkylene
polymer or a (meth)acrylate polymer are disclosed in (Patent
Document 1), (Patent Document 2) and the like. Those polymers have
already been industrially produced, and are widely used in
applications to sealants, adhesives, coatings and the like.
[0004] Curable compositions comprising the above described organic
polymers having a reactive silicon group are cured by using silanol
condensation catalysts, and usually organotin catalysts having a
carbon-tin bond such as dibutyltin bis(acetylacetonate) are widely
used. However, in recent years, toxicity of organotin catalysts is
pointed out, and development of non-organotin catalysts are
demanded.
[0005] With respect to curable silicone compositions prepared using
a titanium compound as a non-organotin curing catalyst, so far many
investigations have been made, and are disclosed in (Patent
Document 3) and the like. At an initial stage of the
investigations, when a titanium compound was used as a curing
catalyst, there were many problems with curability, storage
stability, an extreme increase in viscosity when silicone came into
contact with a titanium catalyst, and the like. As described in
(Patent Document 4), (Patent Document 5), (Patent Document 6),
(Patent Document 7) and the like, as a result of various
investigations made, improvement methods such as modification of a
silicone-terminated structure, use of a chelate type titanium
compound, and the like have been found, and at the present time,
dealcoholization type silicone compositions using titanium
catalysts are widely used in a variety of applications.
Additionally, in (Patent Document 8), a technique for improving
curability by using a chelate type methyl titanium is
disclosed.
[0006] However there are relatively few examples of adding a
titanium catalyst to a reactive silicon group-containing organic
polymer. Those examples are disclosed in (Patent Document 9),
(Patent Document 10), (Patent Document 11), (Patent Document 12),
(Patent Document 13), (Patent Document 14), (Patent Document 15),
(Patent Document 16), (Patent Document 17) and (Patent Document
18).
[0007] On the other hand, various properties such as curability,
adhesion and mechanical properties such as a modulus, a strength,
an elongation and the like are demanded for curable compositions
used for a sealant, an adhesive, a coating and the like and
rubber-like cured articles obtained by curing the compositions.
Also with respect to organic polymers having a reactive silicon
group, so far many investigations have been made. As a result, it
is already known that a strong adhesion to various articles to be
adhered can be imparted by blending a silane coupling agent such as
amino silane as proposed in (Patent Document 19).
Patent Document 1: JP-52-73998A
Patent Document 2: JP-59-74149A
Patent Document 3: JP-39-27643B (U.S. Pat. No. 3,175,993)
Patent Document 4: U.S. Pat. No. 3,334,067
Patent Document 5: JP-56-14701B
Patent Document 6: JP-55-43119A
Patent Document 7: JP-2-133490A
Patent Document 8: JP-2001-302934A
Patent Document 9: JP-58-17154A
Patent Document 10: JP-11-209538A
Patent Document 11: JP-5-311063A
Patent Document 12: JP-2001-302929A
Patent Document 13: JP-2001-302930A
Patent Document 14: JP-2001-302931A
Patent Document 15: JP-2001-302934A
Patent Document 16: JP-2001-348528A
Patent Document 17: JP-2002-249672A
Patent Document 18: JP-2003-165916A
Patent Document 19: JP-62-35421B
DISCLOSURE OF INVENTION
Problem to be Solved by the Invention
[0008] In order to obtain a one-component type curable composition
having practical curability and sufficient adhesion, the present
inventors have investigated a one-component type curable
composition which comprises a reactive silicon group-containing
organic polymer as a main component, is prepared using a titanium
catalyst as a non-tin curing catalyst and contains an amino silane
as an adhesion-imparting agent, and have found that mechanical
properties of a cured article obtained from the composition having
been stored for a given period of time are remarkably lowered as
compared with a cured article obtained from the composition before
storing.
[0009] It is an object of the present invention to provide a
one-component type curable composition which comprises a reactive
silicon group-containing organic polymer as a main component, has
practical curability and good adhesion by use of a non-tin curing
catalyst, and minimizes lowering of mechanical properties of a
cured article after storing.
Means to Solve the Problem
[0010] As a result of a diligent investigation to solve such
problems, the present inventors perfected the present invention by
discovering that a curable composition having practical curability
and good adhesion and minimizing lowering of mechanical properties
of a cured article after storing can be obtained by use of a silane
compound having a nitrogen-substituted group as an
adhesion-imparting agent and a chelate type methyl titanate (b1)
and/or a chelate type ethyl titanate (b2) as a curing catalyst for
the polymer although the catalyst concerned is a non-tin curing
catalyst.
[0011] Namely, the present invention relates to a one-component
type curable composition characterized by comprising, as
components,
[0012] (A) a polyoxyalkylene polymer (a1) having a
silicon-containing group being capable of crosslinking by forming
siloxane bonds and/or a (meth)acrylate polymer (a2) having a
silicon-containing group being capable of crosslinking by forming
siloxane bonds, (B) a chelate type methyl titanate (b 1)
represented by the general formula (1): ##STR1## wherein each of
(4-n) R.sup.1s is independently hydrogen atom or a substituted or
unsubstituted hydrocarbon group having 1 to 20 carbon atoms, each
of (4-n) A.sup.1s and (4-n) A.sup.2s is independently --R.sup.2 or
--OR.sup.2 where R.sup.2 is a substituted or unsubstituted
hydrocarbon group having 1 to 20 carbon atoms, n is 1, 2 or 3,
and/or a chelate type ethyl titanate (b2) represented by the
general formula (2): ##STR2## wherein R.sup.1, A.sup.1, A.sup.2 and
n are the same as defined above, and (C) a compound having, in its
molecule, a hydrolyzable silicon group and a nitrogen-substituted
group represented by the general formula (3): --NHR.sup.3 (3)
wherein R.sup.3 is hydrogen atom or a substituted or unsubstituted
hydrocarbon group having 1 to 20 carbon atoms, or the general
formula (4): --N.dbd.R.sup.4 (4) wherein R.sup.4 is CO or a
substituted or unsubstituted divalent hydrocarbon group having 1 to
20 carbon atoms and is bonded to a nitrogen atom by double
bonding.
[0013] The polyoxyalkylene polymer (al) is preferably a
polyoxypropylene polymer.
[0014] As the component (B), the chelate type methyl titanate (b1)
represented by the general formula (1) is preferable.
[0015] Additionally, it is preferable that the silicon-containing
group contained in the component (A) and the hydrolyzable silicon
group contained in the component (C) are groups represented by the
following general formula (5) and the general formula (6),
respectively: --SiR.sup.5.sub.3-a(OR.sup.6).sub.a (5) . . .
silicon-containing group of the component (A)
--SiR.sup.7.sub.3-b(OR.sup.8).sub.b (6) . . . hydrolyzable silicon
group of the component (C) wherein each of R.sup.5 and R.sup.7 is
independently a substituted or unsubstituted hydrocarbon group
having 1 to 20 carbon atoms or a triorganosiloxy group represented
by (R).sub.3SiO-- where each of R's is independently a substituted
or unsubstituted hydrocarbon group having 1 to 20 carbon atoms,
R.sup.6 is an alkyl group having 1 to 4 carbon atoms, R.sup.8 is an
alkyl group having 1 to 4 carbon atoms, a is 1, 2 or 3, b is 1, 2
or 3, and R.sup.6 is an alkyl group having the number of carbon
atoms equal to or more than the number of carbon atoms of
R.sup.8.
[0016] Additionally, the hydrolyzable silicon group contained in
the component (C) is preferably a methoxysilyl group represented by
the general formula (7): --SiR.sup.7.sub.3-b(OCH.sub.3).sub.b (7)
wherein each of R.sup.7s is independently a substituted or
unsubstituted hydrocarbon group having 1 to 20 carbon atoms or a
triorganosiloxy group represented by (R').sub.3SiO-- where each of
R's is independently a substituted or unsubstituted hydrocarbon
group having 1 to 20 carbon atoms, b is 1, 2 or 3.
[0017] Additionally, preferred embodiments of the curable
composition of the present invention are sealants or adhesives
comprising any of the above described one-component type curable
compositions.
EFFECT OF THE INVENTION
[0018] The curable composition of the present invention is
excellent in curability and adhesion by use of a non-tin curing
catalyst, and lowering of mechanical properties of a cured article
obtained after storing is minimized.
BEST MODE FOR CARRYING OUT THE INVENTION
[0019] The present invention is then explained below in detail.
[0020] In the present invention, the polyoxyalkylene polymer (a1)
having a reactive silicon group and/or the (meth)acrylate polymer
(a2) having a reactive silicon group (hereinafter referred to as
"organic polymer") are used as the component (A). By using the
polyoxyalkylene polymer and/or the (meth)acrylate polymer as a main
chain skeleton of the polymer of the component (A), a satisfactory
adhesion can be achieved. Additionally, when a curable composition
is prepared using a titanium catalyst as the component (B) of the
present invention, there is a tendency that deep-part curability of
the obtained composition is lowered depending on an added amount
thereof. Accordingly, a polyoxyalkylene polymer and a
(meth)acrylate polymer as used for the component (A) of the present
invention are preferable because they are high in moisture
permeability and excellent in deep-part curability in the case of a
one-component type composition.
[0021] No particular constraint is imposed on the glass transition
temperature of the organic polymer of the component (A). The glass
transition temperature is preferably not more than 20.degree. C.,
more preferably not more than 0.degree. C., particularly preferably
not more than -20.degree. C. If the glass transition temperature is
higher than 20.degree. C., in some cases, a viscosity increases and
workability is lowered in wintertime or at a cold district or
flexibility and elongation of the cured article are degraded. The
above described glass transition temperature denotes values
measured by DSC.
[0022] The reactive silicon group contained in the polyoxyalkylene
polymer (a1) having a reactive silicon group and the (meth)acrylate
polymer (a2) having a reactive silicon group is a group which has a
hydroxyl group or a hydrolyzable group bonded to a silicon atom,
and is capable of cross-linking through a reaction accelerated by a
curing catalyst. Examples of the reactive silicon groups include
groups represented by the general formula (8):
--(SiR.sup.9.sub.2-cX.sub.cO).sub.m--SiR.sup.10.sub.3-dX.sub.d (8)
wherein each of R.sup.9 and R.sup.10 is independently a substituted
or unsubstituted hydrocarbon group having 1 to 20 carbon atoms or a
triorganosiloxy group represented by (R').sub.3SiO--, where R' is
independently a substituted or unsubstituted hydrocarbon group
having 1 to 20 carbon atoms, each of Xs is independently hydroxyl
group or a hydrolyzable group, c is 0, 1 or 2, d is 0, 1, 2 or 3, c
and d are not 0 at the same time, m is 0 or an integer of 1 to
19.
[0023] No particular constraint is imposed on the hydrolyzable
group, and the hydrolyzable group may be a hydrolyzable group well
known in the art. More specifically, examples of the hydrolyzable
group include, for instance, hydrogen atom, a halogen atom, an
alkoxy group, an acyloxy group, a ketoximate group, an amino group,
an amide group, an acid amide group, an aminooxy group, a mercapto
group, an alkenyloxy group and the like. Among these groups,
hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate
group, an amino group, an amide group, an aminooxy group, a
mercapto group and an alkenyloxy group are preferable and an alkoxy
group is particularly preferable from the viewpoint that an alkoxy
group is moderately hydrolyzable and easily handled.
[0024] One to three hydrolyzable groups and hydroxyl groups can
bond to one silicon atom, and (a+.SIGMA.c) is preferably within a
range from 1 to 5. When two or more hydrolyzable groups and
hydroxyl groups are bonded in the reactive silicon group, they may
be the same or different.
[0025] The number of silicon atoms forming the reactive silicon
group is one or more, and is preferably not more than 20 in the
case of the silicon atoms connected by siloxane bonds.
[0026] Particularly reactive silicon groups represented by the
general formula (9): --SiR.sup.10.sub.3-eX.sub.e (9) wherein
R.sup.10 and X are the same as defined above, e is an integer of 1
to 3, are preferable because they are easily available.
[0027] Examples of R.sup.9 and R.sup.10 in the above described
general formulae (8) and (9) include alkyl groups such as a methyl
group and an ethyl group, cycloalkyl groups such as a cyclohexyl
group, aryl groups such as a phenyl group, aralkyl groups such as a
benzyl group, a triorganosiloxy group represented by
(R').sub.3SiO-- where R' is a methyl group, a phenyl group or the
like and the like group. Of these groups, a methyl group is
particularly preferable.
[0028] More specific examples of the reactive silicon group include
a trimethoxysilyl group, a triethoxysilyl group, a
triisopropoxysilyl group, a dimethoxymethylsilyl group, a
diethoxymethylsilyl group and a diisopropoxymethylsilyl group. A
trimethoxysilyl group, a triethoxysilyl group and a
dimethoxymethylsilyl group are more preferable and a
trimethoxysilyl group is particularly preferable because these
groups are high in activity and satisfactory curability can be
obtained. Also from the viewpoint of storage stability, a
dimethoxymethylsilyl group is particularly preferable.
Additionally, a triethoxysilyl group is particularly preferable
because the alcohol produced by the hydrolysis reaction of the
reactive silicon group is ethanol and hence a triethoxysilyl group
has a high safety. Additionally, a trimethoxysilyl group and a
triethoxysilyl group are preferable because lowering of physical
properties of a cured article after storing is relatively
small.
[0029] The introduction of the reactive silicon group can be
carried out by methods well known in the art. More specifically,
examples of such methods include the followings.
[0030] (a) With an organic polymer having in the molecule
functional groups such as hydroxy groups, an organic compound
having both an active group exhibiting reactivity to the functional
groups and an unsaturated group is reacted, to yield an unsaturated
group-containing organic polymer. Alternatively, an unsaturated
group-containing organic polymer is obtained by copolymerization of
an epoxy compound having an unsaturated group with an organic
polymer having in the molecule functional groups such as hydroxy
groups. Then, a reactive silicon group-containing hydrosilane is
reacted with the reaction product to be hydrosilylated.
[0031] (b) With an unsaturated group-containing organic polymer
obtained similarly to the method described in (a), a mercapto
group- and reactive silicon group-containing compound is
reacted.
[0032] (c) With an organic polymer having in the molecule
functional groups such as hydroxy groups, epoxy groups and
isocyanate groups, a compound having a functional group exhibiting
reactivity to the functional groups and a reactive silicon group is
reacted.
[0033] Among the above methods, the method described in (a) or the
method described in (c) in which a hydroxy group-terminated polymer
is reacted with an isocyanate group- and reactive silicon
group-containing compound is preferable because the method provides
a high conversion rate at a relatively short reaction time.
Additionally, the method described in (a) is particularly
preferable because the reactive silicon group-containing organic
polymer obtained by the method described in (a) is lower in
viscosity and more satisfactory in workability than an organic
polymer obtained by the method described in (c), and an organic
polymer obtained by the method described in (b) is strong in odor
due to mercaptosilane.
[0034] Examples of the hydrosilane compound used in the method
described in (a) include halogenated silanes such as
trichlorosilane, methyldichlorosilane, dimethylchlorosilane and
phenyldichlorosilane; alkoxysilanes such as trimethoxysilane,
triethoxysilane, methyldiethoxysilane, methyldimethoxysilane and
phenyldimethoxysilane; acyloxysilanes such as methyldiacetoxysilane
and phenyldiacetoxysilane; ketoximate silanes such as
bis(dimethylketoximate)methylsilane and
bis(cyclohexylketoximate)methylsilane and the like. However, the
hydrosilane compound used in the method described in (a) is not
limited to these compounds. Of these compounds, halogenated silanes
and alkoxysilanes are preferable and in particular, alkoxysilanes
are most preferable because the obtained curable compositions are
moderately hydrolyzable and easily handled. Of the alkoxysilanes,
methyldimethoxysilane is particularly preferable because it is
easily available and curability, storage stability, elongation
property and tensile strength of the curable composition containing
the obtained organic polymer are high.
[0035] Examples of the synthesis method described in (b) include a
method in which a mercapto group- and reactive silicon
group-containing compound is introduced into the sites on the
unsaturated bonds of an organic polymer by means of a radical
addition reaction in the presence of a radical initiator and/or a
radical generating source; however, the synthesis method concerned
is not limited to these methods. Examples of the above described
mercapto group- and reactive silicon group-containing compound
include .gamma.-mercaptopropyltrimethoxysilane,
.gamma.-mercaptopropylmethyldimethoxysilane,
.gamma.-mercaptopropyltriethoxysilane,
.gamma.-mercaptopropylmethyldiethoxysilane,
mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane and
the like; however, the mercapto group- and reactive silicon
group-containing compound is not limited to these compounds.
[0036] Examples of the method, of the methods described in (c), in
which a hydroxy-terminated polymer is reacted with an isocyanate
group- and reactive silicon group-containing compound include a
method disclosed in Japanese Patent Laid-Open No. 3-47825; however,
the method concerned is not limited to these methods. Examples of
the above described isocyanate group- and reactive silicon
group-containing compound include
.gamma.-isocyanatopropyltrimethoxysilane,
.gamma.-isocyanatopropylmethyldimethoxysilane,
.gamma.-isocyanatopropyltriethoxysilane,
.gamma.-isocyanatopropylmethyldiethoxysilane,
isocyanatomethyltrimethoxysilane, isocyanatomethyltriethoxysilane,
isocyanatomethyldimethoxymethylsilane,
isocyanatomethyldiethoxymethylsilane and the like; however, the
compound concerned is not limited to these compounds.
[0037] In the case of silane compounds such as trimethoxysilane in
which three hydrolyzable groups are bonded to one silicon atom, in
some cases, disproportionation reaction proceeds. If
disproportionation reaction proceeds, a very dangerous compound
like dimethoxysilane is generated. However in the cases of
.gamma.-mercaptopropyltrimethoxysilane and
.gamma.-isocyanatepropyltrimethoxysilane, such a disproportionation
reaction does not proceed. Accordingly, when using, as a
silicon-containing group, a group such as a trimethoxysilyl group
in which three hydrolyzable groups are bonded to one silicon atom,
it is preferable to employ the synthesis method of (b) or (c).
[0038] The reactive silicon group-containing organic polymer may be
a straight chain or may have branches, and the number average
molecular weight thereof, measured by GPC relative to polystyrene
standard, is preferably of the order of 500 to 100,000, more
preferably 1,000 to 50,000, particularly preferably 3,000 to
30,000. When the number average molecular weight is less than 500,
it tends to be disadvantageous from the viewpoint of an elongation
property of the cured article, while when the number average
molecular weight exceeds 100,000, it tends to be disadvantageous
from the viewpoint of workability because the viscosity becomes
high.
[0039] For the purpose of obtaining a rubber-like cured article
having a high strength, a high elongation property and a low
elastic modulus, it is recommended that the number of reactive
silicon groups contained in the organic polymer is, on average in
one polymer molecule, at least one, and preferably 1.1 to 5. When
the average number of reactive silicon groups contained in the
molecule is less than 1, the curability becomes insufficient, and
hence a satisfactory rubber elasticity behavior can hardly be
exhibited. The reactive silicon group may be located at the
terminal of the main chain or at the terminal of the side chain, or
at the both in the organic polymer molecule chain. In particular,
when the reactive silicon group is located only at the terminal of
the main chain, the effective network content in the organic
polymer component contained in the finally formed cured article
becomes large, so that it becomes easier to obtain a rubber-like
cured article having a high strength, a high elongation property
and a low elastic modulus.
[0040] The polyoxyalkylene polymer (a1) is essentially a polymer
having the repeating units represented by the general formula (10):
--R.sup.11--O-- (10) wherein R.sup.11 is a linear or branched
alkylene group having 1 to 14 carbon atoms. In the general formula
(10), R.sup.11 is preferably a linear or branched alkylene group
having 1 to 14 carbon atoms, and more preferably 2 to 4 carbon
atoms. Examples of the repeating units represented by the general
formula (10) include: --CH.sub.2O--, --CH.sub.2CH.sub.2O--,
--CH.sub.2CH(CH.sub.3)O--, --CH.sub.2CH(C.sub.2H.sub.5)O--,
--CH.sub.2C(CH.sub.3).sub.2O--,
--CH.sub.2CH.sub.2CH.sub.2CH.sub.2O--, and the like. The main chain
skeleton of the polyoxyalkylene polymer may be formed of either
only one type of repeating unit or two or more types of repeating
units. In particular, in the case where the polymer is used for a
sealant and the like, it is preferable that the main chain skeleton
is formed of a polymer containing as the main component a
propyleneoxide polymer because a polymer having such a main chain
skeleton is amorphous and relatively low in viscosity.
[0041] Examples of the synthesis method of the polyoxyalkylene
polymer include a polymerization method in the presence of an
alkaline catalyst such as KOH; a polymerization method in the
presence of a transition metal compound-porphyrin complex catalyst
prepared by reacting an organoaluminum compound with porphyrin,
disclosed in Japanese Patent Laid-Open No. 61-215623;
polymerization methods in the presence of composite metal cyanide
complex catalysts, disclosed in Japanese Patent Examined
Publication Nos. 46-27250 and 59-15336, and U.S. Pat. Nos.
3,278,457, 3,278,458, 3,278,459, 3,427,256, 3,427,334, 3,427,335
and the like; a polymerization method in the presence of a catalyst
composed of a polyphosphazene salt disclosed in Japanese Patent
Laid-Open No. 10-273512, and a polymerization method in the
presence of a catalyst composed of a phosphazene compound disclosed
in Japanese Patent Laid-Open No. 11-060722. However, the method
concerned is not limited to these methods.
[0042] Examples of the preparation method of the reactive silicon
group-containing polyoxyalkylene polymer (a1) of the present
invention include the methods disclosed in Japanese Patent Examined
Publication Nos. 45-36319 and 46-12154, Japanese Patent Laid-Open
Nos. 50-156599, 54-6096, 55-13767, 55-13468 and 57-164123, Japanese
Patent Examined Publication No. 3-2450, and U.S. Pat. Nos.
3,632,557, 4,345,053, 4,366,307 and 4,960,844; and the methods of
preparing polyoxyalkylene polymers each having a high molecular
weight such that the number average molecular weight is not less
than 6,000 and a narrow molecular weight distribution such that the
Mw/Mn value is not more than 1.6, disclosed in Japanese Patent
Laid-Open Nos. 61-197631, 61-215622, 61-215623, 61-218632, 3-72527,
3-47825 and 8-231707. However, the method concerned is not limited
to these methods.
[0043] The above described reactive silicon group-containing
polyoxyalkylene polymers (a1) may be used either each alone or in
combinations of two or more thereof.
[0044] On the other hand, no particular constraint is imposed on
the (meth)acrylate monomers constituting the main chains of the
above described (meth)acrylate polymers (a2), and various types can
be used. Examples of the monomers concerned include (meth)acrylic
acid monomers such as (meth)acrylic acid, methyl (meth)acrylate,
ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl
(meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate,
tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl
(meth)acrylate, cyclohexyl (meth)acrylate, n-heptyl (meth)acrylate,
n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl
(meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate,
phenyl (meth)acrylate, tolyl (meth)acrylate, benzyl (meth)acrylate,
2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate,
2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate,
stearyl (meth)acrylate, glycidyl (meth)acrylate, 2-aminoethyl
(meth)acrylate, .gamma.-(methacryloyloxypropyl)trimethoxysilane,
.gamma.-(methacryloyloxypropyl)dimethoxymethylsilane,
methacryloyloxymethyltrimethoxysilane,
methacryloyloxymethyltriethoxysilane,
methacryloyloxymethyldimethoxymethylsilane,
methacryloyloxymethyldiethoxymethylsilane, ethylene oxide adduct of
(meth)acrylate, trifluoromethylmethyl (meth)acrylate,
2-trifluoromethylethyl (meth)acrylate, 2-perfluoroethylethyl
(meth)acrylate,
2-perfluoroethyl-2-perfluorobutylethyl(meth)acrylate,
perfluoroethyl(meth)acrylate, trifluoromethyl(meth)acrylate,
bis(trifluoromethlymethyl)(meth)acrylate,
2-trifluoromethyl-2-perfluoroethylethyl(meth)acrylate,
2-perfluorohexylethyl(meth)acrylate, 2-perfluorodecylethyl
(meth)acrylate and 2-perfluorohexadecylethyl(meth)acrylate. For the
above described (meth)acrylate polymers, (meth)acrylate monomers
can be copolymerized with the following vinyl monomers. Examples of
the vinyl monomers concerned include styrene monomers such as
styrene, vinyltoluene, .alpha.-methylstyrene, chlorostyrene,
styrenesulfonic acid and the salts thereof; fluorine-containing
vinyl monomers such as perfluoroethylene, perfluoropropylene and
fluorinated vinylidene; silicon-containing vinyl monomers such as
vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride,
maleic acid, and monoalkyl esters and dialkyl esters of maleic
acid; fumaric acid, and monoalkyl esters and dialkyl esters of
fumaric acid; maleimide monomers such as maleimide,
methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide,
hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide,
phenylmaleimide and cyclohexylmaleimide; nitrile group-containing
vinyl monomers such as acrylonitrile and methacrylonitrile; amide
group-containing vinyl monomers such as acrylamide and
methacrylamide; vinyl esters such as vinyl acetate, vinyl
propionate, vinyl pivalate, vinyl benzoate and vinyl cinnamate;
alkenes such as ethylene and propylene; conjugated dienes such as
butadiene and isoprene; and vinyl chloride, vinylidene chloride,
allyl chloride and allyl alcohol. These monomers may be used each
alone or two or more of these monomers may be copolymerized. Among
these, from the viewpoint of the physical properties of the
products, polymers formed of styrene monomers and (meth)acrylic
acid monomers are preferable. More preferable are the (meth)acryl
polymers formed of acrylate monomers and methacrylate monomers, and
particularly preferable are the acryl polymers formed of acrylate
monomers. For general construction applications, the butyl acrylate
monomers are further preferable because compositions concerned each
are required to have physical properties including a low viscosity,
and the cured articles each are required to have physical
properties including a low modulus, a high elongation property, a
weather resistance and a heat resistance. On the other hand, for
applications to vehicles and the like where oil resistance is
required, copolymers made of ethyl acrylate as the main material
are further preferable. The copolymers made of ethyl acrylate as
the main material are excellent in oil resistance, but slightly
tend to be poor in low-temperature property (low-temperature
resistance); for the purpose of improving the low-temperature
property thereof, a part of ethyl acrylates can be replaced with
butyl acrylate. However, with the increase of the ratio of butyl
acrylate, the satisfactory oil resistance comes to be degraded, so
that for the application to the use requiring oil resistance, the
ratio of butyl acrylate is set preferably to not more than 40%, and
more preferably to not more than 30%. Additionally, it is also
preferable to use 2-methoxyethyl acrylate and 2-ethoxyethyl
acrylate which have side chain alkyl groups containing oxygen atoms
introduced for the purpose of improving the low-temperature
property and the like without degrading the oil resistance; in this
connection, it is to be noted that the introduction of alkoxy
groups having an ether bond in the side chains tends to degrade the
heat resistance, so that the ratio of such an acrylate is
preferably not more than 40% when heat resistance is required. It
is possible to obtain appropriate polymers by varying the ratio in
consideration of required physical properties such as oil
resistance, heat resistance and low-temperature property according
to the various applications and the required objectives. Examples
of the polymers excellent in the balance between the physical
properties including the oil resistance, heat resistance,
low-temperature property and the like include a copolymer of ethyl
acrylate/butyl acrylate/2-methoxyethyl acrylate (40 to 50/20 to
30/30 to 20 in a ratio by weight), this copolymer imposing no
constraint on the polymers concerned. In the present invention,
these preferable monomers can be copolymerized with other monomers,
and moreover, block copolymerized with other monomers. In such
cases, it is preferable that the preferable monomers are contained
in an amount of not less than 40% in a ratio by weight.
Incidentally, it is to be noted that in the above form of
presentation, for example, "(meth)acrylic acid" means acrylic acid
and/or methacrylic acid.
[0045] No particular constraint is imposed on the synthesis methods
of the (meth)acrylate polymers, and the methods well known in the
art can be applied. However, polymers obtained by the usual free
radical polymerization methods using azo compounds and peroxides as
polymerization initiators have a problem such that the molecular
weight distribution values of the polymers are generally as large
as not less than 2 and the viscosities of the polymers are high.
Accordingly, it is preferable to apply living radical
polymerization methods for the purpose of obtaining (meth)acrylate
polymers being narrow in molecular weight distribution and low in
viscosity, and moreover, having cross-linking functional groups at
the molecular chain terminals in a high ratio.
[0046] Among "the living radical polymerization methods," "the atom
transfer radical polymerization method" in which (meth)acrylate
monomers are polymerized by use of an organic halogenated compound
or a halogenated sulfonyl compound as an initiator and a transition
metal complex as a catalyst has, in addition to the features of the
above described "living radical polymerization methods," features
such that the obtained polymer has halogen atoms at the terminals
relatively favorable for the functional group conversion reaction
and freedom for designing the initiator and the catalyst is wide,
so that the atom transfer radical polymerization method is further
preferable as a method for preparing (meth)acrylate polymers having
particular functional groups. Examples of the atom transfer radical
polymerization method include the method reported by Matyjaszewski
et al. in Journal of the American Chemical Society (J. Am. Chem.
Soc.), Vol. 117, p. 5614 (1995).
[0047] As a preparation method of a reactive silicon
group-containing (meth)acrylate polymer (a2), for example, Japanese
Patent Examined Publication Nos. 3-14068 and 4-55444, and Japanese
Patent Laid-Open No. 6-211922 and the like disclose preparation
methods according to the free radical polymerization methods by
using chain transfer agents. Additionally, Japanese Patent
Laid-Open No. 9-272714 and the like disclose a preparation method
according to the atom transfer radical polymerization method.
However, the preparation method concerned is not limited to these
methods.
[0048] The above described reactive silicon group-containing
(meth)acrylate polymers (a2) may be used either each alone or in
combinations of two or more thereof.
[0049] The preparation methods of the organic polymers formed by
blending the reactive silicon group-containing polyoxyalkylene
polymers (a1) with the reactive silicon group-containing
(meth)acrylate polymers (a2) are proposed in Japanese Patent
Laid-Open Nos. 59-122541, 63-112642, 6-172631, 11-116763 and the
like. However, the preparation method concerned is not limited to
these methods.
[0050] From the viewpoint of compatibility of (a1) with (a2) and
adhesion of an obtained cured article, with respect to a preferable
specific example of the component (a2), there is a preparation
method in which a reactive silicon group-containing polyoxyalkylene
polymer is blended with a copolymer formed of two (meth)acrylate
monomer units: one (meth)acrylate monomer unit has the reactive
silicon groups and alkyl groups having 1 to 8 carbon atoms, and the
molecular chain is substantially represented by the following
general formula (11): --CH.sub.2--C(R.sup.12)(COOR.sup.13)-- (11)
wherein R.sup.12 represents hydrogen atom or a methyl group, and
R.sup.13 represents an alkyl group having 1 to 8 carbon atoms; and
the other (meth)acrylate monomer unit has alkyl groups having 10 or
more carbon atoms and is represented by the following general
formula (12): --CH.sub.2--C(R.sup.12)(COOR.sup.14)-- (12) wherein
R.sup.12 is the same as defined above, and R.sup.14 represents an
alkyl group having 10 or more carbon atoms.
[0051] In the above general formula (11), examples of R.sup.13
include alkyl groups having 1 to 8 carbon atoms, preferably 1 to 4
carbon atoms and further preferably 1 to 2 carbon atoms such as a
methyl group, an ethyl group, a propyl group, a n-butyl group, a
t-butyl group and a 2-ethylhexyl group. It is also to be noted that
the alkyl group of R.sup.13 may represent either one type or
admixtures of two or more types.
[0052] In the above general formula (12), examples of R.sup.14
include long chain alkyl groups having 10 or more carbon atoms,
usually 10 to 30 carbon atoms, and preferably 10 to 20 carbon atoms
such as a lauryl group, a tridecyl group, a cetyl group, a stearyl
group and a behenyl group. It is also to be noted that the alkyl
group of R.sup.14 may represent, similarly to R.sup.13, either one
type or admixtures of two or more types.
[0053] The molecular chains of the above described (meth)acrylate
copolymers are substantially formed of the monomer units
represented by formulas (11) and (12): "substantially" as referred
to here means that in the copolymer concerned, the sum content of
the monomer unit of formula (11) and the monomer unit of formula
(12) exceeds 50 wt %. The sum content of the monomer units of
formulas (11) and (12) is preferably not less than 70 wt %.
[0054] Additionally, the abundance ratio by weight of the monomer
unit of formula (11) to the monomer unit of formula (12) is
preferably 95:5 to 40:60, and further preferably 90:10 to
60:40.
[0055] Examples of the monomer units other than the monomer units
of formulas (11) and (12) which may be contained in the above
described copolymer include acrylic acids such as acrylic acid and
methacrylic acid; monomers containing amide groups such as
acrylamide, methacrylamide, N-methylolacrylamide and
N-methylolmethacrylamide, monomers containing epoxy groups such as
glycidylacrylate and glycidylmethacrylate, and monomers containing
amino groups such as diethylaminoethyl acrylate, diethylaminoethyl
methacrylate and aminoethyl vinyl ether; and monomer units derived
from acrylonitrile, styrene, .alpha.-methylstyrene, alkyl vinyl
ethers, vinyl chloride, vinyl acetate, vinyl propionate and
ethylene.
[0056] Moreover, for the preparation method of the organic polymers
formed by blending the (meth)acrylate polymers having the reactive
silicon functional groups, there can be used additional methods in
which (meth)acrylate monomers are polymerized in the presence of a
reactive silicon group-containing polyoxyalkylene polymer. These
methods are disclosed specifically in Japanese Patent Laid-Open
Nos. 59-78223, 60-228516, 60-228517 and the like. However, the
method concerned is not limited to these methods.
[0057] The main chain skeleton of the organic polymer of the
present invention may include other components such as binding
urethane components as far as such inclusion does not largely
impair the effect of the invention.
[0058] No particular constraint is imposed on the binding urethane
components. Examples thereof include groups (hereinafter referred
to as amide segments) formed by a reaction of an isocyanate group
with an active hydrogen group.
[0059] The above described amide segments are groups represented by
the general formula (13): --NR.sup.15--C(.dbd.O)-- (13) wherein
R.sup.15 represents hydrogen atom or a substituted or unsubstituted
organic group.
[0060] Examples of the above described amide segments include a
urethane group formed by a reaction of an isocyanate group with
hydroxyl group; a urea group formed by a reaction of an isocyanate
group with an amino group; a thiourethane group formed by a
reaction of an isocyanate group with a mercapto group; and the
like. Additionally, in the present invention, groups formed by
further reaction of an active hydrogen in the urethane group, urea
group or thiourethane group with an isocyanate group are included
in the groups of the general formula (13).
[0061] Example of an industrially easy method of preparing an
organic polymer having both of an amide segment and a reactive
silicon group is a method in which after or at the same time of
reacting an organic polymer having an active hydrogen-containing
group at the terminal with an excessive amount of polyisocyanate
compound to yield a polymer having isocyanate groups at the
terminals of polyurethane main chains, a part or the whole of
isocyanate groups are reacted with a W group of the silicon
compound represented by the general formula (14):
W--R.sup.16--SiR.sup.10.sub.3-eX.sub.e (14) wherein R.sup.10, X and
e are the same as defined above; R.sup.16 is a divalent organic
group, more preferably a substituted or unsubstituted divalent
hydrocarbon group having 1 to 20 carbon atoms; W is an active
hydrogen-containing group selected from hydroxyl group, a carboxyl
group, a mercapto group and an amino group (unsubstituted or
mono-substituted). Known methods of preparing organic polymers in
relation to this preparation method are disclosed in Japanese
Patent Examined Publication No. 46-12154 (U.S. Pat. No. 3,632,557),
Japanese Patent Laid-Open Nos. 58-109529 (U.S. Pat. No. 4,374,237),
62-13430 (U.S. Pat. No. 4,645,816), 8-53528 (EP Patent No.
0676403), and 10-204144 (EP Patent No. 0831108), Japanese Patent
Laid-Open No. 2003-508561 (U.S. Pat. No. 6,197,912), Japanese
Patent Laid-Open Nos. 6-211879 (U.S. Pat. No. 5,364,955), 10-53637
(U.S. Pat. No. 5,756,751), 11-100427, 2000-169544, 2000-169545, and
2002-212415, Japanese Patent No. 3313360, U.S. Pat. No. 4,067,844,
U.S. Pat. No. 3,711,445, Japanese Patent Laid-Open No. 2001-323040
and the like.
[0062] Additionally, there are methods of preparation by reacting
an organic polymer having an active hydrogen-containing group at
the terminal (oxyalkylene polymer (polyether polyol) having
hydroxyl group at the terminal, polyacryl polyol and the like) with
a reactive silicon group-containing isocyanate compound represented
by the general formula (15):
O.dbd.C.dbd.N--R.sup.16--SiR.sup.10.sub.3-eX.sub.e (15) wherein
R.sup.10, R.sup.16, X and e are the same as defined above. Known
methods of preparing organic polymers in relation to this
preparation method are disclosed in Japanese Patent Laid-Open Nos.
11-279249 (U.S. Pat. No. 5,990,257), 2000-119365 (U.S. Pat. No.
6,046,270), 58-29818 (U.S. Pat. No. 4,345,053), 3-47825 (U.S. Pat.
No. 5,068,304), 11-60724, 2002-155145, 2002-249538, WO03/018658,
WO03/059981 and the like.
[0063] Polyether polyols prepared by any of preparation methods can
be used, and preferred are polyether polyols having at least 0.7
hydroxyl group per a molecular terminal on average of the whole
molecules. Specifically, examples thereof are oxyalkylene polymers
prepared by using conventional alkali metal catalysts, oxyalkylene
polymers prepared by reacting an initiator such as a polyhydroxy
compound having at least two hydroxyl groups with alkylene oxide in
the presence of a composite metal cyanide complex and cesium, and
the like.
[0064] Of the above described polymerization methods, the method
using a composite metal cyanide complex is preferable because
oxyalkylene polymers having a lower degree of unsaturation, a
narrow Mw/Mn, a lower viscosity and high acid resistance and
weather resistance can be obtained.
[0065] Examples of the above described polyacryl polyols include
polyols having an alkyl (meth)acrylate (co)polymer skeleton and
containing hydroxy groups in the molecule. As the synthesis method
to produce these polymers, the living radical polymerization method
is preferable because this method can lead to narrow molecular
weight distributions and low viscosities, and the atom transfer
radical polymerization method is further preferable. Additionally,
it is preferable to use a polymer based on the so-called SGO
process which is obtained by continuously block-polymerizing an
alkyl acrylate monomer at a high temperature under a high pressure,
as described in Japanese Patent Laid-Open No. 2001-207157.
Specifically, examples thereof include UH-2000 produced by Toagosei
Co., Ltd., and the like.
[0066] Examples of the polyisocyanate compound include aromatic
polyisocyanates such as toluene (tolylene) diisocyanate,
diphenylmethane diisocyanate and xylylene diisocyanate; and
aliphatic polyisocyanates such as isophorone diisocyanate and
hexamethylene diisocyanate.
[0067] No particular constraint is imposed on the silicon compound
of the general formula (14). Specifically, examples thereof include
silanes having amino group such as
.gamma.-aminopropyltrimethoxysilane,
N-(.beta.-aminoethyl)-.gamma.-aminopropyltrimethoxysilane,
.gamma.-(N-phenyl)aminopropyltrimethoxysilane,
N-ethylaminoisobutyltrimethoxysilane,
N-cyclohexylaminomethyltriethoxysilane,
N-cyclohexylaminomethyldiethoxymethylsilane and
N-phenylaminomethyltrimethoxysilane; silanes having hydroxy group
such as .gamma.-hydroxypropyltrimethoxysilane; silanes having
mercapto group such as .gamma.-mercaptopropyltrimethoxysilane; and
the like. Additionally, as described in Japanese Patent Laid-Open
Nos. 6-211879 (U.S. Pat. No. 5,364,955), 10-53637 (U.S. Pat. No.
5,756,751), 10-204144 (EP Patent No. 0831108), 2000-169544 and
2000-169545, there can be used Michael addition reaction products
of various .alpha.,.beta.-unsaturated carbonyl compounds and
primary amino group-containing silanes and Michael addition
reaction products of various (meth)acryloyl group-containing
silanes and primary amino group-containing compounds as the silicon
compounds of the general formula (14).
[0068] No particular constraint is imposed on the reactive silicon
group-containing isocyanate compound of the general formula (15).
Specifically, examples thereof include
.gamma.-trimethoxysilylpropylisocyanate,
.gamma.-triethoxysilylpropylisocyanate,
.gamma.-methyldimethoxysilylpropylisocyanate,
.gamma.-methyldiethoxysilylpropylisocyanate,
trimethoxysilylmethylisocyanate,
diethoxymethylsilylmethylisocyanate,
dimethoxymethylsilylmethylisocyanate,
diethoxymethylsilylmethylisocyanate and the like. Additionally, as
described in Japanese Patent Laid-Open No. 2000-119365 (U.S. Pat.
No. 6,046,270), a compound obtained by reacting the silicon
compound of the general formula (14) with an excessive amount of
the above described polyisocyanate compound can be used as the
reactive silicon group-containing isocyanate compound of the
general formula (15).
[0069] When amide segments contained in the main chain skeleton of
the organic polymer of the present invention are abundant, the
viscosity of the organic polymer becomes high and forms a
composition poor in workability as the case may be. On the other
hand, curability of the composition of the present invention tends
to be enhanced by the amide segments contained in the main chain
skeleton of the organic polymer. When the organic polymer having
amide segments in its main skeleton is used as the component (A),
the composition prepared in a combination of the polymer with the
component (B) is preferable because the composition has a quicker
curability by use of a non-organotin catalyst. Accordingly, when
the amide segments are contained in the main chain skeleton of the
organic polymer, the average number of amide segments per molecule
is preferably from 1 to 10, more preferably from 1.5 to 7,
particularly preferably from 2 to 5. When the number of amide
segments is less than 1, in some cases, curability becomes
insufficient, and when the number of amide segments is more than
10, the viscosity of the organic polymer becomes high and forms a
composition poor in workability.
[0070] In the present invention, the chelate type methyl titanate
(b1) represented by the general formula (1): ##STR3## wherein each
of (4-n) R.sup.1s is independently hydrogen atom or a substituted
or unsubstituted hydrocarbon group having 1 to 20 carbon atoms,
each of (4-n) A.sup.1s and (4-n) A.sup.2s is independently
--R.sup.2 or --OR.sup.2 where R.sup.2 is a substituted or
unsubstituted hydrocarbon group having 1 to 20 carbon atoms, n is
1, 2 or 3, and/or the chelate type ethyl titanate (b2) represented
by the general formula (2): ##STR4## wherein R.sup.1, A.sup.1,
A.sup.2 and n are the same as defined above, are used as the
component (B).
[0071] These components (B) function as a curing catalyst for the
organic polymer of the component (A). Organotin compounds such as
dibutyltin dilaurate and dibutyltin bis(acetylacetonate) which have
a fear of having an influence on environment have been so far used
as a curing catalyst for the reactive silicon group-containing
organic polymer of the component (A), but by using the titanium
catalysts of the component (B) of the present invention, a load on
environment is small and a curable composition having practical
curing properties can be obtained. Further as compared with the
case of using other curing catalysts such as organotin catalysts,
adhesion to articles to be hardly adhered such as acrylic resins
can be enhanced.
[0072] Tetraalkoxy titanium, halogenated titanium, titanium chelate
and the like are known as a titanium catalyst, and particularly
when titanium chelate is used, there is a tendency that quick
curability can be obtained.
[0073] However, like the present invention, when a one-component
type curable composition is prepared using a silane compound having
a nitrogen-substituted group like the component (C) as an
adhesion-imparting agent and a commonly used titanium
diisopropoxidebis(ethylacetoacetate) as a titanium catalyst, there
is a tendency that mechanical properties such as a modulus and a
strength of a cured article obtained from the stored composition
are significantly lowered as compared with mechanical properties
before storing. The reason for this is not obvious, but it is
presumed that when a silane compound having a nitrogen-substituted
group like the component (C) is present, during the storing, an
alkoxy group constituting the reactive silicon group of the
component (A) and an isopropoxy group of titanium
diisopropoxidebis(ethylacetoacetate) are exchanged with each other
by any mechanism, and as a result, inherent curability of the
component (A) is lowered and a crosslinking reaction does not
proceed sufficiently. Namely, for example, when the reactive
silicon group of the component (A) is a dimethoxymethylsilyl group,
a part or the whole of methoxy groups on silicon are converted to
isopropoxy groups, and the reactive silicon group becomes a group
having a lower reactivity.
[0074] Accordingly, when a titanium chelate in which an
alkoxy-substituted group is limited to a methoxy group or an ethoxy
group is used as a titanium catalyst like the component (B) of the
present invention, lowering of mechanical properties of a cured
article after storing can be inhibited. Namely, even if during the
storing, an alkoxy group on the reactive silicon group of the
component (A) and a methoxy group or an ethoxy group in the
component (B) are exchanged with each other by the same mechanism
as above, the converted reactive silicon group of the component (A)
is a relatively active methoxy group or ethoxy group, and therefore
it can be considered that a crosslinking reaction proceeds
sufficiently.
[0075] Examples of the chelate type methyl titanate (b1) include
titanium dimethoxidebis(acetylacetonate), titanium
dimethoxidebis(3-methylacetylacetonate), titanium
dimethoxidebis(methylacetoacetate), titanium
dimethoxidebis(ethylacetoacetate), titanium
dimethoxidebis(ethyl-2-methylacetoacetate), titanium
dimethoxidebis(ethyl-2-ethylacetoacetate), titanium
dimethoxidebis(t-butylacetoacetate), titanium
dimethoxidebis(allylacetoacetate), titanium
dimethoxidebis(methyl-3-oxo-4,4-dimethylhexanoate), titanium
dimethoxidebis(ethyl-3-oxo-4,4,4-trifluorobutanoate), titanium
dimethoxidebis(2,2,6,6-tetramethyl-3,5-heptanedionate), titanium
trimethoxide(acetylacetonate), titanium
trimethoxide(ethylacetoacetate), titanium
trimethoxide(allylacetoacetate), titanium
trimethoxide(diethylmalonate), titanium
trimethoxide(methacryloxyethylacetoacetate), and the like. Of these
chelates, titanium dimethoxidebis(ethylacetoacetate), titanium
dimethoxidebis(ethyl-2-methylacetoacetate) and titanium
dimethoxidebis(acetylacetonate) are preferable from the viewpoint
of catalytic activity, and titanium
dimethoxidebis(ethylacetoacetate) and titanium
dimethoxidebis(ethyl-2-methylacetoacetate) are especially
preferable.
[0076] Additionally, examples of the chelate type ethyl titanate
(b2) include titanium diethoxidebis(acetylacetonate), titanium
diethoxidebis(3-methylacetylacetonate), titanium
diethoxidebis(methylacetoacetate), titanium
diethoxidebis(ethylacetoacetate), titanium
diethoxidebis(ethyl-2-methylacetoacetate), titanium
diethoxidebis(ethyl-2-ethylacetoacetate), titanium
diethoxidebis(t-butylacetoacetate), titanium
diethoxidebis(allylacetoacetate), titanium
diethoxidebis(methyl-3-oxo-4,4-dimethylhexanoate), titanium
diethoxidebis(ethyl-3-oxo-4,4,4-trifluorobutanoate), titanium
diethoxidebis(2,2,6,6-tetramethyl-3,5-heptanedionate), titanium
triethoxide(acetylacetonate), titanium
triethoxide(ethylacetoacetate), titanium
triethoxide(allylacetoacetate), titanium
triethoxide(diethylmalonate), titanium
triethoxide(methacryloxyethylacetoacetate), and the like. Of these
chelates, titanium diethoxidebis(ethylacetoacetate), titanium
diethoxidebis(ethyl-2-methylacetoacetate) and titanium
diethoxidebis(acetylacetonate) are preferable from the viewpoint of
catalytic activity, and titanium dimethoxidebis(ethylacetoacetate)
and titanium dimethoxidebis(ethyl-2-methylacetoacetate) are
especially preferable.
[0077] It is preferable to use the chelate type methyl titanate
(b1) as the component (B) from the point that the effect of the
present invention, i.e. an effect of inhibiting lowering of
physical properties after storing is higher. Additionally, it is
preferable to use the chelate type methyl titanate (b1) from the
point that higher curability can be obtained. On the other hand,
use of the chelate type ethyl titanate (b2) is preferable because a
by-product derived from the titanate is ethanol which has less
effect on environment. Additionally, also when the reactive silicon
group of the component (A) is an ethoxysilyl group such as a
triethoxysilyl group, it is preferable to use the chelate type
ethyl titanate (b2) from the viewpoint of storage stability.
Further use of the chelate type ethyl titanate (b2) is preferable
because good adhesion can be obtained.
[0078] Preferred examples of the chelating agents capable of
forming chelate ligands of the above described component (B)
include .beta.-diketones such as acetylacetone,
3-methylacetylacetone and 2,2,4,4-tetramethyl-3,5-heptanedion;
.beta.-ketoesters such as methyl acetoacetate, ethyl acetoacetate,
t-butyl acetoacetate, allyl acetoacetate,
(2-methacryloxyethyl)acetoacetate, methyl
3-oxo-4,4-dimethylhexanoate, ethyl 3-oxo-4,4,4-trifluorobutanoate,
3-methylacetylacetone, ethyl 2-methylacetoacetate and ethyl
2-ethylacetoacetate; .beta.-diesters such as dimethyl malonate and
diethyl malonate; cyclic dicarbonyl compounds such as
2-acetylbutyrolactone; and the like from the viewpoint of
curability. .beta.-Diketones and .beta.-ketoesters are more
preferred from the viewpoint of curability and storage stability,
and .beta.-ketoesters are particularly preferred. Specifically
acetylacetone, methyl acetoacetate, ethyl acetoacetate and ethyl
2-methylacetoacetate are more preferred from the viewpoint of
curability and storage stability and because those compounds are
easily available, and ethyl acetoacetate and ethyl
2-methylacetoacetate are particularly preferable. Also when two or
more chelate ligands are present, those chelate ligands may be the
same or different.
[0079] The component (B) may be used either each alone or in
combinations of two or more thereof.
[0080] The used amount of the component (B) is preferably from 0.1
to 20 parts by weight, and more preferably from 0.5 to 15 parts by
weight, especially preferably from 1 to 10 parts by weight with
respect to 100 parts by weight of the component (A). When the
blended amount of the component (B) is less than the above
described ranges, sometimes the practical curing rate cannot be
obtained, and the curing reaction hardly proceeds to a sufficient
extent. On the other hand, when the blended amount of the component
(B) exceeds the above described ranges, sometimes the work life
becomes too short, and the workability is degraded.
[0081] In the present invention, a titanium catalyst other than the
component (B) can be used to an extent not to degrade the effect of
the present invention. Examples thereof include titanium chelates
such as titanium diisopropoxidebis(ethylacetoacetate), titanium
diisopropoxidebis(methylacetoacetate), titanium
diisopropoxidebis(t-butylacetoacetate), titanium
diisopropoxidebis(methyl-3-oxo-4,4-dimethylhexanoate), titanium
diisopropoxidebis(ethyl-3-oxo-4,4,4-trifluoropentanoate), titanium
diisopropoxidebis(acetylacetonate), titanium
diisopropoxidebis(2,2,6,6-tetramethyl-3,5-heptanedionate), titanium
di-n-butoxidebis(ethylacetoacetate), titanium
di-t-butoxidebis(ethylacetoacetate), titanium
di-2-ethylhexoxidebis(ethylacetoacetate),
1,2-dioxyethanetitaniumbis(ethylacetoacetate),
1,3-dioxypropanetitaniumbis(ethylacetoacetate),
2,4-dimethyl-2,4-dioxypentanetitaniumbis(ethylacetoacetate),
titanium diisopropoxidebis(triethanolaminate), titanium
bis(trimethylsiloxy)bis(ethylacetoacetate), titanium
bis(trimethylsiloxy)bis(acetylacetonate), titanium
tetrakis(ethylacetoacetate) and titanium tetrakis(acetylacetonate);
titanium alkoxides such as titanium tetramethoxide, titanium
tetraethoxide, titanium tetraallyloxide, titanium
tetraisopropoxide, titanium tetra-n-butoxide, titanium
tetra-t-butoxide, titanium tetracyclohexyloxide, titanium
tetrabenzyloxide, titanium tetraoctyloxide, titanium
tetrakis(2-ethylhexyloxide), titanium tetrabutoxide dimer, titanium
tetrakis(8-hydroxyoctyloxide), titanium
tetrakis(trimethylsilyloxide), titanium
diisopropoxidebis(2-ethyl-1,3-hexanediolate), titanium
tetrakis(2-chloroethoxide), titanium tetrakis(2-methoxyethoxide),
titanium tetraphenoxide, titanium tetrakis(o-chlorophenoxide) and
titanium tetrakis(m-nitrophenoxide); titanium acylates such as
titanium acrylate triisopropoxide, titanium methacrylate
triisopropoxide, titanium dimethacrylate diisopropoxide, titanium
trimethacrylate isopropoxide, titanium hexanoate triisopropoxide
and titanium stearate triisopropoxide; halogenated titanates such
as titanium chloride triisopropoxide, titanium dichloride
diisopropoxide, titanium isopropoxide trichloride, titanium bromide
triisopropoxide, titanium fluoride triisopropoxide, titanium
chloride triethoxide and titanium chloride tributoxide; other
titanates such as titanium tris(dioctylphosphate)isopropoxide,
titanium tris(dodecylbenzenesulfonate)isopropoxide and
dihydroxytitaniumbislactate; and the like.
[0082] In the present invention, the compound having, in its
molecule, a hydrolyzable silicon group and a nitrogen-substituted
group represented by the general formula (3): --NHR.sup.3 (3)
wherein R.sup.3 is hydrogen atom or a substituted or unsubstituted
hydrocarbon group having 1 to 20 carbon atoms, or the general
formula (4): --N.dbd.R.sup.4 (4) wherein R.sup.4 is CO or a
substituted or unsubstituted divalent hydrocarbon group having 1 to
20 carbon atoms and is bonded to a nitrogen atom by double bonding,
is used. The component (C) of the present invention is a kind of
so-called silane coupling agent, and acts as an adhesion-imparting
agent.
[0083] By use of the component (C), a marked effect of improving
adhesion is exhibited under a non-primer condition or under a
condition of treating with a primer when the composition is used on
various articles to be adhered, namely, inorganic substrates such
as glass, aluminum, stainless steel, zinc, copper and mortar and
organic substrates such as polyvinyl chloride, acryl, polyester,
polyethylene, polypropylene and polycarbonate. In the case of use
under the non-primer condition, an effect of improving adhesion to
various articles to be adhered is exhibited markedly.
[0084] Examples of the hydrolyzable silicon groups of the component
(C) are the groups represented by the general formula (8) in which
X is a hydrolyzable group. Specifically there are groups
exemplified supra as a hydrolyzable group, and a methoxy group and
an ethoxy group are preferable from the viewpoint of a hydrolyzing
rate. The number of hydrolyzable groups is preferably not less than
2, particularly not less than 3.
[0085] In claims of the instant patent application, the reactive
silicon group contained in the component (A) is described as "a
silicon-containing group being crosslinkable by forming siloxane
bonds", and the reactive silicon group contained in the component
(C) is described as "a hydrolyzable silicon group", and the both
are substantially the same kind of reactive silicon groups.
Representative examples of those reactive silicon groups are
reactive silicon groups represented by the following general
formulae (5) and (6), respectively. Those groups have an alkoxy
group having 1 to 4 carbon atoms as a hydrolyzable group.
SiR.sup.5.sub.3-a(OR.sup.6).sub.a (5) . . . Silicon-containing
group of the component (A) --SiR.sup.7.sub.3-b(OR.sup.8).sub.b (6)
. . . Hydrolyzable silicon group of the component (C) wherein each
of R.sup.5 and R.sup.7 is independently a substituted or
unsubstituted hydrocarbon group having 1 to 20 carbon atoms or a
triorganosiloxy group represented by (R').sub.3SiO-- where each of
R's is independently a substituted or unsubstituted hydrocarbon
group having 1 to 20 carbon atoms, R.sup.6 is an alkyl group having
1 to 4 carbon atoms, R.sup.8 is an alkyl group having 1 to 4 carbon
atoms, a is 1, 2 or 3, b is 1, 2 or 3.
[0086] It is preferable that R.sup.6 is an alkyl group having the
number of carbon atoms more than the number of carbon atoms of
R.sup.8, from the viewpoint of curability. This is because when
R.sup.6 is an alkyl group having the number of carbon atoms less
than that of R.sup.8, it is presumed that in some cases, inherent
curability of the component (A) is lowered.
[0087] Supplementary explanation of the above described presumption
is as follows.
[0088] In the results of experiments explained infra, when a
polyoxypropylene polymer having a methyldimethoxy group is used as
the component (A) and
.gamma.-(2-aminoethyl)aminopropyltriethoxysilane and
N-(1,3-dimethylbutylidene)-3-(triethoxysilyl)-1-propaneamine are
used as the component (C), a tack-free time is extremely long.
Though the reason for this is not obvious, it can be considered
that this is because an exchange reaction of an alkoxy group occurs
between the reactive silicon group of the component (A) and the
reactive silicon group of the component (C) and a part of methoxy
groups of the component (A) are replaced by ethoxy groups which
contain more carbon atoms and have moderate hydrolyzability.
[0089] Accordingly, from the point that the reactive silicon group
of the component (A) is selected from a wider range, the
hydrolyzable silicon group of the component (C) is preferably a
methoxysilyl group represented by the general formula (7):
--SiR.sup.7.sub.3-b(OCH.sub.3).sub.b (7) wherein each of R.sup.7s
is independently a substituted or unsubstituted hydrocarbon group
having 1 to 20 carbon atoms or a triorganosiloxy group represented
by (R').sub.3SiO-- where each of R's is independently a substituted
or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, b
is 1, 2 or 3.
[0090] Specific examples of the methoxysilyl group are a
methoxydimethylsilyl group, a methoxydiphenylsilyl group, a
methoxybistrimethylsiloxysilyl group, a dimethoxymethylsilyl group,
an ethyldimethoxysilyl group, a dimethoxyphenylsilyl group, a
dimethoxytrimethylsiloxysilyl group, a trimethoxysilyl group and
the like. The methoxysilyl group is not limited to them. From the
viewpoint of curability of the obtained curable composition, a
dimethoxymethylsilyl group and a trimethoxysilyl group are
preferable and a trimethoxysilyl group is particularly
preferable.
[0091] Additionally, since the component (C) has the
nitrogen-substituted group of the above described general formula
(3) or (4), a higher adhesion can be obtained. Since an effect of
imparting adhesion is higher, the substituent represented by the
general formula (3) is preferable, and an amino group is
particularly preferable.
[0092] Specific examples of the component (C) include amino
group-containing silanes such as
.gamma.-aminopropyltrimethoxysilane,
.gamma.-aminopropylmethyldimethoxysilane,
.gamma.-aminopropyltriethoxysilane,
.gamma.-aminopropylmethyldiethoxysilane,
.gamma.-aminopropyltriisopropoxysilane,
.gamma.-(methylamino)propyltrimethoxysilane,
.gamma.-(2-aminoethyl)aminopropyltrimethoxysilane,
.gamma.-(2-aminoethyl)aminopropylmethyldimethoxysilane,
.gamma.-(2-aminoethyl)aminopropyltriethoxysilane,
.gamma.-(2-aminoethyl)aminopropylmethyldiethoxysilane,
.gamma.-(2-aminoethyl)aminopropyltriisopropoxysilane,
.gamma.-(2-(2-aminoethyl)aminoethyl)aminopropyltrimethoxysilane,
.gamma.-(6-aminohexyl)aminopropyltrimethoxysilane,
3-(N-ethylamino)-2-methylpropyltrimethoxysilane,
4-amino-3,3-dimethylbutyltrimethoxysilane,
4-amino-3,3-dimethylbutyldimethoxymethylsilane,
.gamma.-ureidopropyltrimethoxysilane,
.gamma.-ureidopropyltriethoxysilane,
N-phenyl-.gamma.-aminopropyltrimethoxysilane,
N-benzyl-.gamma.-aminopropyltrimethoxysilane,
N-vinylbenzyl-.gamma.-aminopropyltriethoxysilane,
N-phenylaminomethyltrimethoxysilane,
N-cyclohexylaminomethyltriethoxysilane,
N-cyclohexylaminomethyldiethoxymethylsilane,
(2-aminoethyl)aminomethyltrimethoxysilane and
N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine; isocyanate
group-containing silanes such as
.gamma.-isocyanatepropyltrimethoxysilane,
.gamma.-isocyanatepropyltriethoxysilane,
.gamma.-isocyanatepropylmethyldiethoxysilane,
.gamma.-isocyanatepropylmethyldimethoxysilane,
(isocyanatemethyl)trimethoxysilane,
(isocyanatemethyl)dimethoxymethylsilane,
isocyanatemethyltriethoxysilane, and
isocyanatemethyldiethoxymethylsilane; ketimine type silanes such as
N-(1,3-dimethylbutylidene)-3-(trimethoxysilyl)-1-propaneamine and
N-(1,3-dimethylbutylidene)-3-(triethoxysilyl)-1-propaneamine; and
the like. Additionally, partially condensed products of the above
described silanes can be used. Further the following derivatives
obtained by modifying these compounds can be used as the component
(C): amino-modified silylpolymer, silylated aminopolymer,
unsaturated aminosilane complex, phenylamino-long chain alkylsilane
and aminosilylated silicone. It is to be noted that as described
above, when the reactive silicon group of the component (A) is a
methoxysilyl group represented by the general formula (5), it is
essential to use the component (C) having a methoxysilyl group
among those described above.
[0093] The above described component (C) may be used alone or in a
mixture of two or more kinds thereof.
[0094] In the present invention, the used amount of the component
(C) is preferably of the order of 0.1 to 20 parts by weight, and
more preferably of the order of 0.5 to 10 parts by weight,
especially preferably of the order of 2 to 7 parts by weight with
respect to 100 parts by weight of the component (A). When the
blended amount of the component (C) is less than the above
described ranges, sometimes sufficient adhesion cannot be obtained.
On the other hand, when the blended amount of the component (C)
exceeds the above described ranges, sometimes the practical curing
rate cannot be obtained, and the curing reaction hardly proceeds to
a sufficient extent.
[0095] In the present invention, a silane coupling agent other than
the component (C) can be used to an extent not to degrade the
effect of the present invention. Examples of these silane coupling
agents are di-substituted amino group-containing silanes such as
.gamma.-(dimethylamino)propyltrimethoxysilane; mercapto
group-containing silanes such as
.gamma.-mercaptopropyltrimethoxysilane,
.gamma.-mercaptopropyltriethoxysilane,
.gamma.-mercaptopropylmethyldimethoxysilane,
.gamma.-mercaptopropylmethyldiethoxysilane,
mercaptomethyltrimethoxysilane and mercaptomethyltriethoxysilane;
epoxy group-containing silanes such as
.gamma.-glycidoxypropyltrimethoxysilane,
.gamma.-glycidoxypropyltriethoxysilane,
.gamma.-glycidoxypropylmethyldimethoxysilane,
.beta.-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and
.beta.-(3,4-epoxycyclohexyl)ethyltriethoxysilane; carboxysilanes
such as .beta.-carboxyethyltriethoxysilane,
.beta.-carboxyethylphenylbis(2-methoxyethoxy)silane and
N-.beta.-(carboxymethyl)aminoethyl-.gamma.-aminopropyltrimethoxysilane;
vinyl-type unsaturated group-containing silanes such as
vinyltrimethoxysilane, vinyltriethoxysilane,
.gamma.-methacryloyloxypropylmethyldimethoxysilane,
.gamma.-acryloyloxypropyltriethoxysilane and
methacryloyloxymethyltrimethoxysilane; halogen-containing silanes
such as .gamma.-chloropropyltrimethoxysilane; isocyanurate silanes
such as tris(3-trimethoxysilylpropyl)isocyanurate, and the like.
Additionally, compounds (for example, a compound of epoxysilane and
aminosilane, a compound of isocyanatesilane and aminosilane, and
the like) obtained by reacting the above described silane coupling
agents with each other can be used.
[0096] In addition to the above described component (C) and other
silane coupling agents, for example, epoxy resins, phenolic resins,
sulfur, alkyl titanates, aromatic polyisocyanates and the like can
be used as an adhesion-imparting agent. The adhesion-imparting
agent is not limited particularly to them. The above described
adhesion-imparting agents may be used alone or in a mixture of two
or more thereof.
[0097] In the present invention, as the curing catalyst, the
component (B) is used, and other curing catalysts can be
simultaneously used to an extent not to degrade the effect of the
present invention. Examples of the curing catalyst include metal
salts of carboxylic acids such as tin 2-ethylhexanoate, tin
versatate and bismuth 2-ethylhexanoate; tetravalent organotin
compounds such as dibutyltin dilaurate, dibutyltin maleate,
dibutyltin phthalate, dibutyltin dioctanoate, dibutyltin
bis(2-ethylhexanoate), dibutyltin bis(methylmaleate), dibutyltin
bis(ethylmaleate), dibutyltin bis(butylmaleate), dibutyltin
bis(octylmaleate), dibutyltin bis(tridecylmaleate), dibutyltin
bis(benzylmaleate), dibutyltin diacetate, dioctyltin
bis(ethylmaleate), dioctyltin bis(octylmaleate), dibutyltin
dimethoxide, dibutyltin bis(nonylphenoxide), dibutyltin oxide,
dibutenyltin oxide, dibutyltin bis(acetylacetonate), dibutyltin
bis(ethylacetoacetate), a reaction product of dibutyltin oxide and
a silicate compound, and a reaction product of dibutyltin oxide and
a phthalic acid ester; organoaluminum compounds such as aluminum
tris(acetylacetonate), aluminum tris(ethylacetoacetate) and
diisopropoxyaluminumethylacetoacetate; and zirconium compounds such
as zirconium tetrakis(acetylacetonate). However, depending on an
adding amount of the organotin compound, there is a case where
toxicity of the obtained curing composition becomes strong.
[0098] A filler can be added to the composition of the present
invention. Examples of the fillers include reinforcing fillers such
as fumed silica, precipitated silica, crystalline silica, fused
silica, dolomite, anhydrous silicic acid, hydrous silicic acid and
carbon black; fillers such as ground calcium carbonate,
precipitated calcium carbonate, magnesium carbonate, diatomite,
sintered clay, clay, talc, titanium oxide, bentonite, organic
bentonite, ferric oxide, aluminum fine powder, flint powder, zinc
oxide, active zinc white, shirasu balloon, glass microballoon,
organic microballoons of phenolic resin and vinylidene chloride
resin, and resin powders such as PVC powder and PMMA powder; and
fibrous fillers such as asbestos, glass fiber and glass filament.
When a filler is used, the used amount thereof is 1 to 250 parts by
weight, and preferably 10 to 200 parts by weight with respect to
100 parts by weight of the polymer of the component (A).
[0099] As described in Japanese Patent Laid-Open No. 2001-181532,
it is possible to homogeneously mix the above described filler with
a dehydrating agent such as oxidized calcium, put the mixture in a
bag made of an air-tight material to be sealed and then allow to
stand for a proper period of time to dehydrate and dry previously.
The use of this low molecular weight filler makes it possible to
improve storage stability particularly in the case of one-component
type composition.
[0100] Additionally, when preparing a highly transparent
composition, as described in Japanese Patent Laid-Open No.
11-302527, it is possible to use, as a filler, a polymer powder
prepared by using a polymer such as methyl methacrylate as a
starting material or a non-crystalline silica. Also as described in
Japanese Patent Laid-Open No. 2000-38560, a highly transparent
composition can be obtained by using, as a filler, a hydrophobic
silica which is a fine powder of silicon dioxide having hydrophobic
groups bonded to the surface thereof. The surface of a fine powder
of silicon dioxide has generally silanol groups (--SiOH), but can
be formed into a hydrophobic silica by reacting those silanol
groups with halides of organosilicon or alcohols to produce --SiO--
hydrophobic group. Specifically, the hydrophobic silica is obtained
by reacting silanol groups being present in the surface of the fine
powder of silicon dioxide with dimethylsiloxane,
hexamethyldisilazane, dimethyldichlorosilane,
trimethoxyoctylsilane, trimethylsilane or the like. A fine powder
of silicon dioxide in which the surface thereof is formed by
silanol groups (--SiOH) is called a hydrophilic fine powder of
silica.
[0101] When it is desired to obtain a cured article high in
strength by use of these fillers, preferable is a filler mainly
selected from fumed silica, precipitated silica, crystalline
silica, fused silica, dolomite, anhydrous silicic acid, hydrous
silicic acid, carbon black, surface treated fine calcium carbonate,
sintered clay, clay and active zinc white; a desirable effect is
obtained when such a filler is used within a range from 1 to 200
parts by weight with respect to 100 parts by weight of the reactive
silicone group-containing organic polymer (A). Additionally, when
it is desired to obtain a cured article low in tensile strength and
large in elongation at break, a desirable effect is obtained by use
of a filler mainly selected from titanium oxide, calcium carbonate
such as ground calcium carbonate and magnesium carbonate, talc,
ferric oxide, zinc oxide and shirasu balloon within a range from 5
to 200 parts by weight with respect to 100 parts by weight of the
reactive silicone group-containing organic polymer (A). It is to be
noted that in general, the calcium carbonate exhibits, with
increasing specific surface area value thereof, an increasing
improvement effect of the tensile strength at break, elongation at
break and adhesion of the cured article. Needless to say, these
fillers may be used either each alone or in admixtures of two or
more thereof. When calcium carbonate is used, it is desirable to
use surface treated fine calcium carbonate in combination with
calcium carbonate larger in particle size such as ground calcium
carbonate. The particle size of surface treated fine calcium
carbonate is preferably not more than 0.5 .mu.m, and the surface
treatment is preferably carried out by treating with a fatty acid
or a fatty acid salt. The calcium carbonate larger in particle size
is preferably not less than 1 .mu.m in particle size, and can be
used without being subjected to surface treatment.
[0102] For the purpose of improving the workability (cutting
property, etc) of the composition and deglossing the surface of the
cured article, organic balloons and inorganic balloons are
preferably added. Such fillers can be subjected to surface
treatment, and may be used each alone or can be used in admixtures
of two or more thereof. For the purpose of improving the
workability (cutting property, etc), the particle sizes of these
balloons are preferably not more than 0.1 mm. For the purpose of
deglossing the surface of the cured article, the particle sizes are
preferably 5 to 300 .mu.m.
[0103] On the grounds that the cured article of the composition of
the present invention is satisfactory in chemical resistance and
the like, the composition of present invention is suitably used for
joints of housing exterior wall such as sizing boards, in
particular, ceramic sizing boards, for an adhesive for exterior
wall tiles, for an adhesive for exterior wall tiles remaining in
the joints and for the like purposes; in this connection, it is
desirable that the design of the exterior wall and the design of
the sealant are in harmony with each other. Particularly, posh
exterior walls have come to be used by virtue of sputter coating
and mixing colored aggregates. When the composition of the present
invention is blended with a scale-like or granulated material
having a diameter of not less than 0.1 mm, preferably of the order
of 0.1 to 5.0 mm, the cured article comes to be in harmony with
such posh exterior walls, and is excellent in chemical resistance,
so that the composition concerned comes to be an excellent
composition in the sense that the exterior appearance of the cured
article remains unchanged over a long period of time. Use of a
granulated material provides a dispersed sand-like or
sandstone-like surface with a rough texture, while use of a
scale-like material provides an irregular surface based on the
scale-like shape of the material.
[0104] The preferable diameter, blended amount and materials for
the scale-like or granulated material are described in Japanese
Patent Laid-Open No. 9-53063 as follows.
[0105] The diameter is not less than 0.1 mm, preferably of the
order of 0.1 to 5.0 mm, and there is used a material having an
appropriate size in conformity with the material quality and
pattern of exterior wall. Materials having a diameter of the order
of 0.2 mm to 5.0 mm and materials having a diameter of the order of
0.5 mm to 5.0 mm can also be used. In the case of a scale-like
material, the thickness is set to be as thin as the order of 1/10
to 1/5 the diameter (the order of 0.01 to 1.00 mm). The scale-like
or granulated material is transported to the construction site as a
sealant on condition that the material is beforehand mixed in the
main component of the sealant, or is mixed in the main component of
the sealant at the construction site when the sealant is used.
[0106] The scale-like or granulated material is blended in a
content of the order of 1 to 200 parts by weight with respect to
100 parts by weight of a composition such as a sealant composition
and an adhesive composition. The blended amount is appropriately
selected depending on the size of the scale-like or granulated
material, and the material quality and pattern of exterior
wall.
[0107] As the scale-like or granulated material, natural products
such as silica sand and mica, synthetic rubbers, synthetic resins
and inorganic substances such as alumina are used. The material is
colored in an appropriate color so as to match the material quality
and pattern of exterior wall to heighten the design quality when
filled in the joints.
[0108] A preferable finishing method and the like are described in
Japanese Patent Laid-Open No. 9-53063.
[0109] Additionally, when a balloon (preferably the mean particle
size thereof is not less than 0.1 mm) is used for a similar
purpose, the surface is formed to have a dispersed sand-like or
sandstone-like surface with a rough texture, and a reduction of
weight can be achieved. The preferable diameter, blended amount and
materials for the balloon are described in Japanese Patent
Laid-Open No. 10-251618 as follows.
[0110] The balloon is a sphere-shaped material with a hollow
interior. Examples of the material for such a balloon include
inorganic materials such as glass, shirasu and silica; and organic
materials such as phenolic resin, urea resin, polystyrene and
Saran.TM.; however, the material concerned is not limited to these
examples; an inorganic material and an organic material can be
compounded, or can be laminated to form multiple layers. An
inorganic balloon, an organic balloon, a balloon made of a
compounded inorganic-organic material or the like can be used.
Additionally, as a balloon to be used, either a type of balloon or
an admixture of multiple types of balloons can be used. Moreover, a
balloon with the processed surface thereof or with the coated
surface thereof can be used, and additionally, a balloon with the
surface thereof subjected to treatment with various surface
treatment agents can also be used. More specifically, examples are
an organic balloon coated with calcium carbonate, talc, titanium
oxide and the like, and an inorganic balloon subjected to surface
treatment with a silane coupling agent.
[0111] For the purpose of obtaining a dispersed sand-like or
sandstone-like surface with a rough texture, the particle size of
the balloon is preferably not less than 0.1 mm. A balloon of a
particle size of the order of 0.2 mm to 5.0 mm or a balloon of a
particle size of the order of 0.5 mm to 5.0 mm can also be used.
Use of a balloon of a particle size of less than 0.1 mm sometimes
only increases the viscosity of the composition, and yields no
rough texture, even when the used amount of the balloon is large.
The blended amount of the balloon can be easily determined in
conformity with the desired degree of the dispersed sand-like or
sandstone-like rough texture. Usually, it is desirable that a
balloon of not less than 0.1 mm in particle size is blended in a
ratio of 5 to 25 vol % in terms of the volume concentration in the
composition. When the volume concentration of the balloon is less
than 5 vol %, no rough texture can be obtained, while when the
volume concentration of the balloon exceeds 25 vol %, the viscosity
of the sealant and that of the adhesive tend to become high to
degrade the workability, and the modulus of the cured article
becomes high, so that the basic performance of the sealant and that
of the adhesive tend to be impaired. The preferable volume
concentration to balance with the basic performance of the sealant
is 8 to 22 vol %.
[0112] When a balloon is used, there can be added an antislip agent
described in Japanese Patent Laid-Open No. 2000-154368 and an amine
compound to make irregular and degloss the surface of the cured
article as described in Japanese Patent Laid-Open No. 2001-164237,
in particular, a primary amine and/or a secondary amine having a
melting point of not less than 35.degree. C.
[0113] Specific examples of the balloon are described in the
following publications: Japanese Patent Laid-Open Nos. 2-129262,
4-8788, 4-173867, 5-1225, 7-113073, 9-53063, 10-251618, 2000-154368
and 2001-164237, and WO97/05201 pamphlet.
[0114] Additionally, thermally expandable fine hollow particles
disclosed in Japanese Patent Laid-Open No. 2004-51701 or 2004-66749
can be used. The thermally expandable fine hollow particles are
plastic spherical particulates produced by surrounding a low
boiling point compound such as a hydrocarbon having 1 to 5 carbon
atoms with a high molecular weight shell material (vinylidene
chloride copolymer, acrylonitrile copolymer or vinylidene
chloride-acrylonitrile copolymer). When the adhered portion
obtained by using the composition of the present invention is
heated, gas pressure inside the shell of the thermally expandable
fine hollow particles is increased and the high molecular weight
shell material is softened to markedly expand its volume and
functions to cause peeling at the adhesion interface. By the
addition of the thermally expandable fine hollow particles, it is
possible to obtain an adhesive composition which can be peeled
easily only by heating without breakage of material when adhesion
becomes unnecessary and also can be peeled by heating without using
an organic solvent.
[0115] When the composition of the present invention includes the
particles of the cured article derived from a sealant, the cured
article can make irregularities on the surface to improve the
design quality. The preferable diameter, blended amount and
materials of the cured article particle material derived from a
sealant is described in Japanese Patent Laid-Open No. 2001-115142
as follows. The diameter is preferably of the order of 0.1 mm to 1
mm, and further preferably of the order of 0.2 to 0.5 mm. The
blended amount is preferably 5 to 100 wt %, and further preferably
20 to 50 wt % in the curable composition. Examples of the materials
include urethane resin, silicone, modified silicone and polysulfide
rubber. No constraint is imposed on the materials as long as the
materials can be used as sealants; however, modified silicone
sealants are preferable.
[0116] To the composition of the present invention can be added an
adhesion-imparting agent. No particular constraint is imposed on
the adhesion-imparting resins, and usual adhesion-imparting resins
can be used irrespective of solid form or liquid form at ordinary
temperature. Specific examples of such adhesion-imparting resins
include styrene block copolymers, hydrogenated products thereof,
phenolic resins, modified phenolic resins (for example, cashew
oil-modified phenolic resins, tall oil-modified phenolic resins and
the like), terpene phenolic resins, xylene-phenol resins,
cyclopentadiene-phenol resins, cumarone-indene resins, rosin
resins, rosin ester resins, hydrogenated rosin ester resins, xylene
resins, low molecular weight polystyrene resins, styrene copolymer
resins, petroleum resins (for example, C5 hydrocarbon resin, C9
hydrocarbon resin, C5C9 hydrocarbon copolymer resin and the like),
hydrogenated petroleum resins, terpene resins, DCPD resin-petroleum
resin and the like. Those resins may be used either each alone or
in combinations of two or more thereof. Examples of the styrene
block copolymers and hydrogenated products thereof include
styrene-butadiene-styrene block copolymer (SBS),
styrene-isoprene-styrene block copolymer (SIS),
styrene-ethylenebutylene-styrene block copolymer (SEBS),
styrene-ethylenepropylene-styrene block copolymer (SEPS),
styrene-isobutylene-styrene block copolymer (SIBS) and the like.
The above described adhesion-imparting resins may be used either
each alone or in combinations of two or more thereof.
[0117] The adhesion-imparting resins are used within a range from 5
to 1,000 parts by weight, preferably from 10 to 100 parts by weight
with respect to 100 parts by weight of the organic polymer (A).
[0118] To the composition of the present invention can be added a
solvent or a diluent. No particular constraint is imposed on the
solvent or the diluent, and aliphatic hydrocarbon, aromatic
hydrocarbon, alicyclic hydrocarbon, halogenated hydrocarbon,
alcohol, ester, ketone, ether and the like can be used. When a
solvent or a diluent is used, the boiling point of the solvent is
preferably not less than 150.degree. C., more preferably not less
than 200.degree. C., particularly preferably not less than
250.degree. C. from the viewpoint of a problem with contamination
to the air when the composition is used indoor. These solvents or
diluents may be used either each alone or in combinations of two or
more thereof.
[0119] A plasticizer can be added to the composition of the present
invention. Addition of a plasticizer makes it possible to adjust
the viscosity and slump property of the curable composition and the
mechanical properties such as tensile strength and elongation of
the cured article obtained by curing the composition. Examples of
the plasticizer include phthalates such as dibutyl phthalate,
diheptyl phthalate, bis(2-ethylhexyl)phthalate, diisodecy
phthalate, diundecyl phthalate and butyl benzyl phthalate;
non-aromatic dibasic acid esters such as dioctyl adipate, dioctyl
sebacate, dibutyl sebacate and diisodecyl succinate; aliphatic
esters such as butyl oleate and methyl acetyl recinolate;
phosphates such as tricresyl phosphate and tributyl phosphate;
trimellitates; chlorinated paraffins; hydrocarbon oils such as
alkyldiphenyls and partially hydrogenated terphenyls; process oils;
epoxy plasticizers such as epoxidized soybean oil and benzyl
epoxystearate.
[0120] Additionally, a polymer plasticizer can be used. When a
polymer plasticizer is used, there can be obtained effects of
hardly causing curing retardation and improving drying property
(also referred to as coating property) in the case of coating of an
alkyd coating material on the cured article as compared with the
case of using a low molecular weight plasticizer containing no
polymer component in the molecule. Examples of the polymer
plasticizer include vinyl polymers obtained by polymerizing vinyl
monomers by means of various methods; polyalkylene glycol esters
such as diethylene glycol dibenzoate, triethylene glycol dibenzoate
and pentaerythritol ester; polyester plasticizers obtained from
dibasic acids such as sebacic acid, adipic acid, azelaic acid and
phthalic acid and dihydric alcohols such as ethylene glycol,
diethylene glycol, triethylene glycol, propylene glycol and
dipropylene glycol; polyethers including polyether polyols each
having a molecular weight of not less than 500, additionally not
less than 1,000 such as polyethylene glycol, polyprolpylene glycol
and polytetramethylene glycol, and the derivatives of these
polyether polyols in which the hydroxy groups in these polyether
polyols are substituted with acyl groups such as acetoxy groups,
alkoxy groups such as methoxy groups, ethoxy groups, butoxy groups
and allyloxy groups and the like; polystyrenes such as polystyrene
and poly-.alpha.-methylstyrene; and polybutadiene, polybutene,
polyisobutylene, butadiene-acrylonitrile and polychloroprene.
However, the polymer plasticizer concerned is not limited to these
examples.
[0121] Of these polymer plasticizers, the polymer plasticizers
which are compatible with the polymer of component (A) are
preferable. In this regard, polyethers and vinyl polymers are
preferable. Additionally, when polyethers are used as plasticizers,
the surface curability, deep-part curability and adhesion are
improved, and no curing retardation after storage occurs, and hence
polyethers are preferable; of polyethers, polypropylene glycol is
more preferable. Also it is preferable to use polymer plasticizers;
polyether polyols such as polyethylene glycol and polypropylene
glycol in which hydroxyl groups thereof are converted to alkoxy
groups or the like because storage stability is increased.
Additionally, from the viewpoint of the compatibility, weather
resistance and heat resistance, vinyl polymers are preferable. Of
the vinyl polymers, acryl polymers and/or methacryl polymers are
preferable, and acryl polymers such as polyalkylacrylate are
further preferable. As the polymerization method to produce acryl
polymers, the living radical polymerization method is preferable
because this method can lead to narrow molecular weight
distributions and low viscosities, and the atom transfer radical
polymerization method is further preferable. Additionally, it is
preferable to use a polymer based on the so-called SGO process
which is obtained by continuously block-polymerizing an alkyl
acrylate monomer at a high temperature under a high pressure, as
described in Japanese Patent Laid-Open No. 2001-207157.
[0122] The number average molecular weight of the polymer
plasticizer is preferably 500 to 15,000, more preferably 800 to
10,000, further preferably 1,000 to 8,000, particularly preferably
1,000 to 5,000, and most preferably 1,000 to 3,000. When the
molecular weight is too low, the plasticizer is removed with time
due to heat and by rainfall, and hence it is made impossible to
maintain the initial physical properties over a long period of
time, contamination is caused due to cohesion of dusts, and the
coating property with an alkyd coating material cannot be improved.
On the other hand, when the molecular weight is too high, the
viscosity becomes high and the workability is degraded. No
particular constraint is imposed on the molecular weight
distribution of the polymer plasticizer. However, it is preferable
that the molecular weight distribution is narrow; the molecular
weight distribution is preferably less than 1.80, more preferably
not more than 1.70, further preferably not more than 1.60, yet
further preferably not more than 1.50, particularly preferably not
more than 1.40 and most preferably not more than 1.30.
[0123] The number average molecular weight of a polyether polymer
is measured with the terminal group analysis method, and that of
other polymers is measured with the GPC method. Additionally, the
molecular weight distribution (Mw/Mn) is measured with the GPC
method (relative to polystyrene standard).
[0124] Additionally, the polymer plasticizer either may have no
reactive silicon group or may have a reactive silicon group. When
the polymer plasticizer has a reactive silicon group, the polymer
plasticizer acts as a reactive plasticizer, and can prevent the
migration of the plasticizer from the cured article. When the
polymer plasticizer has a reactive silicon group, the average
number of reactive silicon groups per molecule is not more than 1,
and preferably not more than 0.8. When the reactive silicon
group-containing plasticizer, in particular, a reactive silicon
group-containing oxyalkylene polymer is used, it is necessary that
the number average molecular weight thereof is lower than that of
the organic polymer (A).
[0125] The plasticizers may be used either each alone or in
combinations of two or more thereof. Additionally, a low molecular
weight plasticizer and a polymer plasticizer may be used in
combination. It is to be noted that these plasticizers can also be
blended when the polymer is produced.
[0126] The used amount of the plasticizer is 5 to 150 parts by
weight, preferably 10 to 120 parts by weight, and further
preferably 20 to 100 parts by weight, with respect to 100 parts by
weight of the polymer of the component (A). When the used amount is
less than 5 parts by weight, the effect as the plasticizer is not
exhibited, while when the used amount exceeds 150 parts by weight,
the mechanical strength of the cured article is insufficient.
[0127] To the curable composition of the present invention,
according to need, a physical properties-regulating agent for
adjusting tensile properties of a produced cured article may be
added. No particular constraint is imposed on the physical
properties-regulating agent. Examples thereof include
tetraalkoxysilanes (tetraalkylsilicates) such as
tetramethoxysilane, tetraethoxysilane, ethoxytrimethoxysilane,
dimethoxydiethoxysilane, methoxytriethoxysilane,
tetra-n-propoxysilane, tetra-1-propoxysilane, tetra-n-butoxysilane,
tetra-1-butoxysilane and tetra-t-butoxysilane; trialkoxysilanes
such as methyltrimethoxysilane, methyltriethoxysilane,
methyltriisopropoxysilane, methyltriphenoxysilane,
ethyltrimethoxysilane, butyltrimethoxysilane and
phenyltrimethoxysilane; dialkoxysilanes such as
dimethyldimethoxysilane, diethyldimethoxysilane and
diphenyldimethoxysilane; monoalkoxysilanes such as
trimethylmethoxysilane and triphenylmethoxysilane;
alkylisopropenoxysilanes such as dimethyldiisopropenoxysilane and
methyltriisopropenoxysilane; the partially hydrolyzed condensates
of these silanes; silicone varnishes; polysiloxanes; and the like.
By the use of the above described physical properties-regulating
agent, when the composition of the present invention is cured, a
hardness can be increased or reversely can be decreased and an
elongation at break can be increased. The above described physical
properties-regulating agent may be used alone or in a mixture of
two or more kinds thereof. Additionally, by adding partially
hydrolyzed condensates of tetraalkoxysilanes and alkoxysilanes,
there can be obtained effects of enhancing water resistant adhesion
of the curable composition and enhancing recovery properties of the
obtained cured article.
[0128] Partially hydrolyzed condensates of organosilicate compounds
are commercially available. Examples of such condensates include
Methyl silicate 51 and Ethyl silicate 40 (both are products of
Colcoat Co., Ltd.).
[0129] The used amount of the physical properties-regulating agent
is preferably 0.1 to 20 parts by weight, and more preferably 0.5 to
10 parts by weight with respect to 100 parts by weight of the
reactive silicon group-containing organic polymer (A).
[0130] To the curable composition of the present invention may be
added, as case demands, a compound to hydrolytically produce a
compound having a monovalent silanol group in the molecule thereof.
This compound has an effect of decreasing the modulus of the cured
article without degrading the stickiness of the surface of the
cured article. Particularly, a compound to produce trimethylsilanol
is preferable. Examples of the compound to hydrolytically produce a
compound having a monovalent silanol group in the molecule thereof
include a compound described in Japanese Patent Laid-Open No.
5-117521. Additionally, examples of such a compound include a
compound which is a derivative of an alkyl alcohol such as hexanol,
octanol or decanol, and produces a silicon compound to
hydrolytically produce R.sub.3SiOH such as trimethylsilanol, and a
compound described in Japanese Patent Laid-Open No. 11-241029 which
is a derivative of a polyhydric alcohol having three or more
hydroxy groups such as trimethylolpropane, glycerin,
pentaerythritol or sorbitol, and produces a silicon compound to
hydrolytically produce R.sub.3SiOH such as trimethylsilanol.
[0131] Additionally, there can be cited such a compound as
described in Japanese Patent Laid-Open No. 7-258534 which is a
derivative of oxypropylene polymer and produces a silicon compound
to hydrolytically produce R.sub.3SiOH such as trimethylsilanol.
Moreover, there can be used a polymer described in Japanese Patent
Laid-Open No. 6-279693 which contains a hydrolyzable
silicon-containing group capable of cross-linking and a
silicon-containing group capable of hydrolytically forming a
monosilanol-containing compound.
[0132] The compound to hydrolytically produce a compound having a
monovalent silanol group in the molecule thereof is used within a
range from 0.1 to 20 parts by weight, and preferably from 0.5 to 10
parts by weight, with respect to 100 parts by weight of the
reactive silicon group-containing organic polymer (A).
[0133] To the curable composition of the present invention,
according to need, a thixotropy providing agent (antisagging agent)
may be added for the purpose of preventing sagging and improving
workability. No particular constraint is imposed on the antisagging
agent; however, examples of the antisagging agent include polyamide
waxes; hydrogenated castor oil derivatives; and metal soaps such as
calcium stearate, aluminum stearate and barium stearate.
Additionally, when a rubber powder having a particle size of 10 to
500 .mu.m as described in Japanese Patent Laid-Open No. 11-349916,
and an organic fiber as described in Japanese Patent Laid-Open No.
2003-155389 are used, a composition having high thixotropy and
satisfactory workability can be obtained. These thixotropy
providing agents (antisagging agents) may be used either each alone
or in combinations of two or more thereof. The thixotropy providing
agents each are used within a range from 0.1 to 20 parts by weight
with respect to 100 parts by weight of the reactive silicon
group-containing organic polymer (A).
[0134] In the composition of the present invention, a compound
containing an epoxy group in one molecule can be used. Use of an
epoxy group-containing compound can increase the recovery
properties of the cured article. Examples of the epoxy
group-containing compound include compounds such as epoxidized
unsaturated oils and fats, epoxidized unsaturated fatty acid
esters, alicyclic epoxy compounds and epichlorohydrin derivatives,
and admixtures of these compounds. More specific examples include
epoxidized soybean oil, epoxidized flaxseed oil,
bis(2-ethylhexyl)-4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS),
epoxyoctyl stearate and epoxybutyl stearate. Of these, E-PS is
particularly preferable. It is recommended that these epoxy
group-containing compounds each are used within a range from 0.5 to
50 parts by weight with respect to 100 parts by weight of the
reactive silicon group-containing organic polymer (A).
[0135] For the composition of the present invention, a photocuring
substance can be used. Use of a photocuring substance forms a
coating film of the photocuring substance on the surface of the
cured article to improve the stickiness and the weather resistance
of the cured article. A photocuring substance means a substance
which undergoes a chemical change, caused by action of light, of
the molecular structure thereof in a fairly short time to result in
changes of the physical properties such as curability. Among such a
large number of compounds known are organic monomers, oligomers,
resins and compositions containing these substances, and any
commercially available substances concerned can optionally be
adopted. As representative photocuring substances, unsaturated
acryl compounds, polyvinyl cinnamates, azidized resins and the like
can be used. The unsaturated acryl compounds are monomers,
oligomers and admixtures of the monomers and the oligomers, the
monomers and oligomers each having one or a few acryl or methacryl
unsaturated groups; examples of the unsaturated acryl compounds
include monomers such as propylene (or butylene, or ethylene)glycol
di(meth)acrylate and neopentylglycol di(meth)acrylate, and
oligoesters of not more than 10,000 in molecular weight related to
these monomers. Specific examples include special acrylates
(bifunctional) such as ARONIX M-210, ARONIX M-215, ARONIX M-220,
ARONIX M-233, ARONIX M-240 and ARONIX M-245; special acrylates
(trifunctional) such as ARONIX M-305, ARONIX M-309, ARONIX M-310,
ARONIX M-315, ARONIX M-320 and ARONIX M-325; and special acrylates
(multifunctional) such as ARONIX M-400. Those compounds which each
have acrylic functional groups are particularly preferable, and
additionally, those compounds which each have, on average, three or
more acrylic functional groups in one molecule are preferable (all
the aforementioned ARONIXs are the products of Toagosei Co.,
Ltd.).
[0136] Examples of the polyvinyl cinnamates include photosensitive
resins having cinnamoyl groups as photosensitive groups, namely,
those compounds obtained by esterification of polyvinyl alcohol
with cinnamic acid; and additionally, a large number of derivatives
of polyvinyl cinnamates. Azidized resins are known as
photosensitive resins having azide groups as photosensitive groups;
common examples of the azidized resins include a rubber
photosensitive solution added with an azide compound as a
photosensitive agent, and additionally, the compounds detailed in
"photosensitive resins" (published by Insatu Gakkai Shuppanbu, Mar.
17, 1972, p. 93, p. 106 and p. 117); and these compounds can be
used each alone or in admixtures thereof, and in combination with
sensitizers to be added according to need. It is to be noted that
addition of sensitizers such as ketones and nitro compounds and
accelerators such as amines sometimes enhances the effect. It is
recommended that the photocuring substance is used within a range
from 0.1 to 20 parts by weight and preferably from 0.5 to 10 parts
by weight with respect to 100 parts by weight of the reactive
silicon group-containing organic polymer (A); when the content of
the photocuring substance is less than 0.1 part by weight, no
effect to increase the weather resistance is displayed, while when
the content exceeds 20 parts by weight, the cured article tends to
be too hard and cracked.
[0137] For the composition of the present invention, an
oxygen-curable substance can be used. Examples of the
oxygen-curable substance include unsaturated compounds reactable
with the oxygen in the air, which react with the oxygen in the air
and form a cured coating film around the surface of the cured
article to act to prevent the surface stickiness and the sticking
of dust and grime to the surface of the cured article and to do the
like. Specific examples of the oxygen-curable substance include
drying oils represented by wood oil, flaxseed oil and the like and
various alkyd resins obtained by modifying these compounds; acryl
polymers, epoxy resins and silicon resins all modified with drying
oils; liquid polymers such as 1,2-polybutadiene and
1,4-polybutadiene obtained by polymerizing or copolymerizing diene
compounds such as butadiene, chloroprene, isoprene and
1,3-pentadiene, and polymers derived from C5 to C8 dienes, liquid
copolymers such as NBR, SBR and the like obtained by copolymerizing
these diene compounds with monomers such as acrylonitrile, styrene
and the like having copolymerizability so as for the diene
compounds to dominate, and various modified substances of these
compounds (maleinized modified substances, boiled oil-modified
substances, and the like). These substances can be used either each
alone or in combinations of two or more thereof. Of these
substances, wood oil and liquid diene polymers are particularly
preferable. Additionally, in some cases, when catalysts to
accelerate the oxidation curing reaction and metal dryers are used
in combination with these substances, the effect is enhanced.
Examples of these catalysts and metal dryers include metal salts
such as cobalt naphthenate, lead naphthenate, zirconium
naphthenate, cobalt octylate and zirconium octylate; and amine
compounds. It is recommended that the oxygen-curing substance is
used within a range from 0.1 to 20 parts by weight and further
preferably from 0.5 to 10 parts by weight with respect to 100 parts
by weight of the reactive silicon group-containing organic polymer
(A); when the used amount is less than 0.1 part by weight,
improvement of stain-proof property becomes insufficient, while
when the used amount exceeds 20 parts by weight, the tensile
property and the like of the cured article tends to be impaired. It
is recommended that the oxygen-curing substance is used in
combination with a photocuring substance as described in Japanese
Patent Laid-Open No. 3-160053.
[0138] For the composition of the present invention, an antioxidant
(antiaging agent) can be used. Use of an antioxidant can increase
the heat resistance of the cured article. Examples of the
antioxidant can include hindered phenol antioxidants, monophenol
antioxidants, bisphenol antioxidants and polyphenol antioxidants,
and hindered phenol antioxidants are particularly preferable.
Similarly, the following hindered amine photostabilizers can also
be used: TINUVIN 622LD, TINUVIN 144; CHIMASSORB944LD and
CHIMASSORB119FL (all produced by Ciba-Geigy Japan Ltd.); MARK
LA-57, MARK LA-62, MARK LA-67, MARK LA-63 and MARK LA-68 (all
produced by Adeka Corporation); and SANOL LS-770, SANOL LS-765,
SANOL LS-292, SANOL LS-2626, SANOL LS-1114 and SANOL LS-744 (all
produced by Sankyo Co., Ltd.). Specific examples of the
antioxidants are described also in Japanese Patent Laid-Open Nos.
4-283259 and 9-194731. It is recommended that the antioxidant is
used within a range from 0.1 to 10 parts by weight and further
preferably from 0.2 to 5 parts by weight with respect to 100 parts
by weight of the reactive silicon group-containing organic polymer
(A).
[0139] For the composition of the present invention, a
photostabilizer can be used. Use of a photostabilizer can prevent
the photooxidation degradation of the cured article. Examples of
the photostabilizer include benzotriazole compounds, hindered amine
compounds, benzoate compounds and the like; hindered amine
compounds are particularly preferable. It is recommended that the
photostabilizer is used within a range from 0.1 to 10 parts by
weight and further preferably from 0.2 to 5 parts by weight with
respect to 100 parts by weight of the reactive silicon
group-containing organic polymer (A). Specific examples of the
photostabilizer are described in Japanese Patent Laid-Open No.
9-194731.
[0140] When the photocuring substance is used for the composition
of the present invention, in particular, when an unsaturated acryl
compound is used, it is preferable to use a tertiary
amine-containing hindered amine photostabilizer as a hindered amine
photostabilizer as described in Japanese Patent Laid-Open No.
5-70531 for the purpose of improving the storage stability of the
composition. Examples of the tertiary amine-containing hindered
amine photostabilizer include TINUVIN 622LD, TINUVIN 144 and
CHIMASSORB119FL (all produced by Ciba-Geigy Japan Ltd.); MARK
LA-57, LA-62, LA-67 and LA-63 (all produced by Adeka Corporation);
and SANOL LS-765, SANOL LS-292, SANOL LS-2626, SANOL LS-1114 and
SANOL LS-744 (all produced by Sankyo Co., Ltd.).
[0141] For the composition of the present invention, an ultraviolet
absorber can be used. Use of an ultraviolet absorber can increase
the surface weather resistance of the cured article. Examples of
the ultraviolet absorber include benzophenone compounds,
benzotriazole compounds, salicylate compounds, substituted tolyl
compounds and metal chelate compounds; benzotriazole compounds are
particularly preferable. The ultraviolet absorber is used within a
range from 0.1 to 10 parts by weight, and further preferably from
0.2 to 5 parts by weight with respect to 100 parts by weight of the
reactive silicon group-containing organic polymer (A). It is
preferable that a phenol antioxidant, a hindered phenol
antioxidant, a hindered amine photostabilizer and a benzotriazole
ultraviolet absorber are used in combination.
[0142] To the composition of the present invention, an epoxy resin
can be added. The composition added with an epoxy resin is
particularly preferable as an adhesive, in particular, an adhesive
for exterior wall tile. Examples of the epoxy resin include
epichlorohydrin-bisphenol A-type epoxy resins,
epichlorohydrin-bisphenol F-type epoxy resins, flame resistant
epoxy resins such as glycidyl ether of tetrabromobisphenol A,
novolac-type epoxy resins, hydrogenated bisphenol A-type epoxy
resins, epoxy resins of the type of glycidyl ether of bisphenol A
propyleneoxide adduct, p-oxybenzoic acid glycidyl ether ester-type
epoxy resins, m-aminophenol epoxy resins, diaminodiphenylmethane
epoxy resins, urethane modified epoxy resins, various alicyclic
epoxy resins, N,N-diglycidylaniline, N,N-diglycidyl-o-toluidine,
triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether,
glycidyl ethers of polyhydric alcohols such as glycerin,
hydantoin-type epoxy resins and epoxidized substances of
unsaturated polymers such as petroleum resins; however the epoxy
resin is not limited to these examples, and commonly used epoxy
resins can be used. Epoxy resins having at least two epoxy groups
in one molecule are preferable because such compositions are high
in reactivity when curing is made, and the cured articles can
easily form three dimensional networks. Examples of further
preferable epoxy resins include bisphenol A-type epoxy resins or
novolac-type epoxy resins. The ratio of the used amount of each of
these epoxy resins to the used amount of the reactive silicon
group-containing organic polymer (A) falls, in terms of weight
ratio, in the range such that organic polymer (A)/epoxy resin=100/1
to 1/100. When the ratio of organic polymer (A)/epoxy resin is less
than 1/100, the effect of improving the impact strength and the
toughness of the cured article of the epoxy resin becomes hardly
obtainable, while when the ratio of organic polymer (A)/epoxy resin
exceeds 100/1, the strength of the cured article of the organic
based polymer becomes insufficient. The preferable ratio of the
used amounts varies depending on the application of the curable
resin composition and hence cannot be unconditionally determined;
for example, when the impact resistance, flexibility, toughness,
peel strength and the like of the cured article of the epoxy resin
are to be improved, it is recommended that with respect to 100
parts by weight of the epoxy resin, 1 to 100 parts by weight of the
component (A), further preferably 5 to 100 parts by weight of the
component (A) is used. On the other hand, when the strength of the
cured article of the component (A) is to be improved, it is
recommended that with respect to 100 parts of the component (A), 1
to 200 parts by weight of the epoxy resin, further preferably 5 to
100 parts by weight of the epoxy resin is used.
[0143] When the epoxy resin is added, as a matter of course, a
curing agent to cure the epoxy resin can be applied together to the
composition of the present invention. No particular constraint is
imposed on the usable epoxy resin-curing agent, and commonly used
epoxy resin-curing agents can be used. Specific examples of the
epoxy resin-curing agent include primary and secondary amines such
as triethylenetetramine, tetraethylenepentamine,
diethylaminopropylamine, N-aminoethylpiperidine, m-xylylenediamine,
m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone,
isophoronediamine, and polyether with amine terminal groups;
tertiary amines such as 2,4,6-tris(dimethylaminomethyl)phenol and
tripropylamine, and salts of those tertiary amines; polyamide
resins; imidazoles; dicyandiamides; borontrifluoride complexes;
carboxylic anhydrides such as phthalic anhydride, hexahydrophthalic
anhydride, tetrahydrophthalic anhydride, dodecynylsuccinic
anhydride, pyromellitic anhydride and chlorendic anhydride;
alcohols; phenols; carboxylic acids; and diketone complexes of
aluminum and zirconium. However, the epoxy resin-curing agent is
not limited to these examples. Additionally, the curing agents may
be used either each alone or in combinations of two or more
thereof.
[0144] When an epoxy resin-curing agent is used, the used amount
thereof falls within a range from 0.1 to 300 parts by weight with
respect to 100 parts by weight of the epoxy resin.
[0145] As an epoxy resin-curing agent, a ketimine can be used. A
ketimine is stable when no moisture is present, but moisture
decomposes the ketimine into a primary amine and a ketone; the thus
produced primary amine acts as a room temperature curable curing
agent to cure the epoxy resin. Use of a ketimine makes it possible
to obtain a one-component type composition. Such a ketimine can be
obtained by condensation reaction of an amine compound and a
carbonyl compound.
[0146] For the synthesis of a ketimine, an amine compound and a
carbonyl compound well known in the art can be used. For example,
the following compounds can be used as such an amine compound:
diamines such as ethylenediamine, propylenediamine,
trimethylenediamine, tetramethylenediamine, 1,3-diaminobutane,
2,3-diaminobutane, pentamethylenediamine, 2,4-diaminopentane,
hexamethylenediamine, p-phenylenediamine and
p,p'-biphenylenediamine; polyvalent amines such as
1,2,3-triaminopropane, triaminobenzene, tris(2-amionoethyl)amine
and tetrakis(aminomethyl)methane; polyalkylenepolyamines such as
diethylenetriamine, triethylenetriamine and tetraethylenepentamine;
polyoxyalkylene polyamines; and aminosilanes such as
.gamma.-aminopropyltriethoxysilane,
N-(.beta.-aminoethyl)-.gamma.-aminopropyltrimethoxysilane and
N-(.beta.-aminoethyl)-.gamma.-aminopropylmethyldimethoxysilane.
Additionally, the following compounds can be used as such a
carbonyl compound: aldehydes such as acetaldehyde, propionaldehyde,
n-butylaldehyde, isobutylaldehyde, diethylacetaldehyde, glyoxal and
benzaldehyde; cyclic ketones such as cyclopentanone,
trimethylcyclopentanone, cyclohexanone and trimethylcyclohexanone;
aliphatic ketones such as acetone, methyl ethyl ketone, methyl
propyl ketone, methyl isopropyl ketone, methyl isobutyl ketone,
diethyl ketone, dipropyl ketone, diisopropyl ketone, dibutyl ketone
and diisobutyl ketone; and .beta.-dicarbonyl compounds such as
acetylacetone, methyl acetoacetate, ethyl acetoacetate, dimethyl
malonate, diethyl malonate, methyl ethyl malonate and
dibenzoylmethane.
[0147] When an imino group is present in the ketimine, the imino
group can be reacted with styrene oxide; glycidyl ethers such as
butyl glycidyl ether and allyl glycidyl ether; and glycidyl esters.
These ketimines may be used either each alone or in combinations of
two or more thereof; these ketimines each are used within a range
from 1 to 100 parts by weight with respect to 100 parts by weight
of the epoxy resin, the used amount of each of the ketimines varies
depending on the type of the epoxy resin and the type of the
ketimine.
[0148] To the curable composition of the present invention can be
added a phosphorous-based plasticizer such as polyphosphoric acid
ammonium or tricresyl phosphate and a flame retardant such as
aluminum hydroxide, magnesium hydroxide or thermally expandable
graphite. These flame retardants may be used either each alone or
in combinations of two or more thereof.
[0149] The flame retardant is used within a range from 5 to 200
parts by mass, and preferably from 10 to 100 parts by mass with
respect to 100 parts by weight of the component (A).
[0150] To the curable composition of the present invention, various
additives can be added according to need for the purpose of
regulating the physical properties of the curable composition or
the cured article. Examples of such additives include curing
regulators, radical inhibitors, metal deactivators, antiozonants,
phosphorus-based peroxide decomposers, lubricants, pigments,
foaming agents, ant-proofing agents and mildewproofing agents.
These various additives may be used either each alone or in
combinations of two or more thereof. Specific examples of additives
other than the specific examples cited in the present specification
are described, for example, in Japanese Patent Examined Publication
Nos. 4-69659 and 7-108928, Japanese Patent Laid-Open Nos.
63-254149, 64-22904, 2001-72854 and the like.
[0151] With respect to the method of preparing the one-component
type curable composition of the present invention, all the blended
components are blended together beforehand, so that it is
preferable that the blended components containing moisture are used
after dehydrating and drying, or the components are dehydrated by
reducing pressure or the like while being kneaded for blending. As
for the methods of dehydration and drying, a thermal drying method
is suitable for a powdery solid substance or the like, while a
reduced pressure dehydration method or a dehydration method which
uses a synthetic zeolite, active alumina, silica gel, quick lime or
magnesium oxide is suitable for a liquid substance. Additionally,
there can be adopted a method in which a small amount of an
isocyanate compound is added to make its isocyanate group react
with water for dehydration, or a method in which an oxazolidine
compound such as 3-ethyl-2-methyl-2-(3-methylbutyl)-1,3-oxazolidine
is added to make it react with water for dehydration. In addition
to these dehydration and drying methods, addition of the following
compounds further improves the storage stability: lower alcohols
such as methanol and ethanol; and alkoxysilane compounds such as
n-propyltrimethoxysilane, vinyltrimethoxysilane,
vinylmethyldimethoxysilane, methylsilicate, ethylsilicate,
.gamma.-mercaptopropylmethyldimethoxysilane,
.gamma.-mercaptopropylmethyldiethoxysilane and
.gamma.-glycidoxypropyltrimethoxysilane.
[0152] It is particularly preferable that the used amount of a
dehydrating agent, in particular, a silicon compound capable of
reacting with water such as vinyltrimethoxysilane falls within a
range from 0.1 to 20 parts by weight, and preferably 0.5 to 10
parts by weight with respect to 100 parts by weight of the reactive
silicon group-containing organic polymer (A).
[0153] With respect to the preparation method, the components (A),
(B), (C) and other additives are blended together with a mixer, a
roll or a kneader, and are subjected to complete dehydration by
heating under reduced pressure or the like, so that water content
is decreased to an extent substantially not causing a problem. The
obtained one-component type curable composition is stored in a
moisture-proof sealed vessel.
[0154] In the thus obtained one-component type curable composition
of the present invention, curing does not proceed during the
storing, but when taken out of the vessel and exposed to moisture
in the air, the composition forms three dimensional networks to be
quickly cured from its surface into a solid matter having a
rubber-like elasticity.
[0155] The curable composition of the present invention can be used
as tackifiers, sealants for buildings, ships, vehicles and road,
adhesives, mold forming materials, vibration-proof material,
damping materials, soundproof materials, foaming materials, coating
materials, spraying materials and the like. It is preferable that
the cured article obtained by curing the curable composition of the
present invention is used as a sealant and an adhesive because the
cured article is excellent in flexibility and adhesion.
[0156] Additionally, the curable composition of the present
invention can be used in various applications as liquid sealants to
be used in materials for electric and electronic components such as
backside sealants for solar cells, electric insulating materials
such as insulating coating materials for use in electric wire and
cable, elastic adhesives, contact type adhesives, spray type
sealants, crack repairing materials, adhesives for tiling, powdery
coating materials, casting materials, medical rubber materials,
medical adhesives, medical instrument sealants, food packaging
materials, sealants for joints in exterior materials such as sizing
boards, coating materials, primers, electromagnetic wave shielding
conductive materials, heat conducting materials, hot melt
materials, electric and electronic potting agents, films, gaskets,
various molding materials, antirust and waterproof sealants for
edges (cut portions) of wire glass and laminated glass, vehicle
components, electric appliance components, various machinery
components and the like. Moreover, the curable composition of the
present invention can adhere alone or in combination with a primer
to a wide variety of substrates including glass, porcelain, woods,
metals and molded resin articles, and accordingly, can be used as
various types of sealing and adhesive compositions. Additionally,
the curable composition of the present invention can be used as
adhesives for interior panels, adhesive for exterior panels,
adhesives for tiling, adhesives for stone tiling, adhesives for
finishing ceiling, adhesives for finishing floor, adhesives for
finishing wall, adhesives for vehicle panels, adhesives for
assembling electric, electronic and precision instruments, sealants
for direct glazing, sealants for double glazing, sealants for the
SSG technique and sealants for working joints of buildings.
EXAMPLES
[0157] In the next place, the present invention is specifically
described on the basis of examples and comparative examples, but
the present invention is not limited by these examples and
comparative examples.
Synthesis Example 1
[0158] By use of a polyoxypropylene diol having a molecular weight
of about 2,000 as an initiator and zinc hexacyanocobaltate-glyme
complex as a catalyst, polymerization of propylene oxide was
carried out to yield a polypropylene oxide having a number average
molecular weight of about 25,500 (a molecular weight relative to
polystyrene standard measured by using a HLC-8120 GPC manufactured
by Tosoh Corp. as a liquid delivery system, a column of TSK-GEL
H-type manufactured by Tosoh Corp., and THF as a solvent). Then, a
methanol solution of NaOMe was added in an amount of 1.2
equivalents with respect to the hydroxy group of the above hydroxy
group-terminated polypropylene oxide, the methanol was distilled
off, and allyl chloride was further added to thereby convert the
terminal hydroxy group into an allyl group. The unreacted allyl
chloride was distilled off under reduced pressure. To 100 parts by
weight of the obtained crude allyl-terminated polypropylene oxide,
300 parts by weight of n-hexane and 300 parts by weight of water
were added. The mixture thus obtained was stirred to mix, and then
the water was removed by centrifugal separation. To the hexane
solution thus obtained, 300 parts by weight of water was further
added, the mixture thus obtained was stirred to mix, the water was
again removed by centrifugal separation, and then the hexane was
distilled off under reduced pressure. Thus, an allyl
group-terminated bifunctional polypropylene oxide having a number
average molecular weight of about 25,500 was obtained.
[0159] 100 Parts by weight of the obtained allyl group-terminated
polypropylene oxide and 0.9 part by weight of methyldimethoxysilane
were reacted at 90.degree. C. for five hours by using, as a
catalyst, 150 ppm of isopropanol solution of platinum-vinylsiloxane
complex containing 3 wt % platinum to yield a polyoxypropylene
polymer (A-1) terminated with methyldimethoxysilyl group. By
measurement using .sup.1H-NMR (measured in CDCl.sub.3 as a solvent
by use of a JNM-LA400 manufactured by JEOL Ltd.), the number of
terminal methyldimethoxysilyl groups per molecule was about 1.3 on
average.
Comparative Examples 1 to 8
[0160] The reactive silicon group-containing polyoxyalkylene
polymer (A-1) obtained in Synthesis Example 1 as the component (A),
a filler, a titanium oxide, a plasticizer, an antisagging agent, an
ultraviolet absorber, a photostabilizer, an antioxidant, a
dehydrating agent, an adhesion-imparting agent and titanium
diisopropoxidebis(ethylacetoacetate) as a curing catalyst were
weighed out according to the formulations shown in Table 1, then,
these ingredients were mixed together with a mixer to yield each
one-component type curable composition, and the composition was
charged in an aluminum cartridge. It is to be noted that the added
amount of each adhesion-imparting agent was so set that the number
of silyl groups of the respective adhesion-imparting agents became
equimolar amounts.
[0161] The curable compositions each were extruded from the
cartridge and filled in a molding frame of about 5 mm in thickness
with a spatula; the surface of each of the filled compositions was
fully flattened, and the planarization completion time was set as
the curing starting time. The surface of each of the compositions
was touched every five minutes with a finger wiped with ethanol,
and the tack-free time was measured as the time when the
composition no longer stuck to the finger.
[0162] Further the one-component type curable compositions each
were extruded so that the compositions each were adhered to various
articles to be adhered (anodized aluminum, cold rolled steel sheet,
hard polyvinyl chloride, FRP, polycarbonate, acrylic resin sheet),
and were aged at 23.degree. C. for 7 days. Thereafter, a 90 degree
hand peel test was carried out. The breakdown conditions of the
cured articles were observed and the cohesion failure rates (CF
rate) were measured.
[0163] Also by using a cartridge containing one-component type
curable composition, after storing at a constant temperature of
23.degree. C. for 7 days (before storing) and further after storing
in an oven at 50.degree. C. for 28 days (after storing), a tension
test was carried out under the following conditions, and variations
of physical properties before and after storing were
investigated.
(Tension Test Method 1)
[0164] First, the curable compositions each were filled in a
sheet-like molding frame of about 3 mm in thickness, and the
surface of each of the filled compositions was fully flattened,
followed by aging at 23.degree. C. for 3 days+50.degree. C. for 4
days, to produce sheet-like cured articles. The cured articles were
punched to obtain No. 3 dumbbell type test pieces (JIS K6251), and
a modulus at 50% tension, a strength at break and an elongation at
break (measuring environment: 23.degree. C., tensile speed: 200
mm/min) were measured with an AUTOGRAPH produced by Shimadzu
Corporation.
[0165] Table 1 shows curability, adhesion, mechanical properties
(modulus, strength, elongation) before and after storing and
maintenance factor of physical properties of each curable
composition. In the table, A denotes a CF rate of 100%, B denotes a
CF rate of not less than 50% and less than 100%, C denotes a CF
rate of not less than 10% and less than 50%, and D denotes a CF
rate of less than 10%. TABLE-US-00001 TABLE 1 Comparative Example
Composition (parts by weight) 1 2 3 4 Organic polymer (A) A-1 100
100 100 100 Filler Hakuenka CCR .sup.(1) Shiraishi Kogyo Kaisha,
Ltd. 120 120 120 120 Titanium oxide Tipaque R-820 Ishihara Sangyo
Kaisha, Ltd. 20 20 20 20 Plasticizer DIDP .sup.(2) Kyowa Hakko
Kogyo Co., Ltd. 55 55 55 55 Antisagging agent Disparlon #6500
.sup.(3) Kusumoto Chemicals, Ltd. 2 2 2 2 Ultraviolet absorber
Sumisorb 400 .sup.(4) Sumitomo Chemical Co., Ltd. 1 1 1 1
Photostabilizer Sanol LS-765 .sup.(5) Sankyo Co., Ltd. 1 1 1 1
Antioxidant Irganox 1010 .sup.(6) Ciba-Geigy Japan Ltd. 1 1 1 1
Dehydrating agent A-171 .sup.(7) Nippon Unicar Company Limited 2 2
2 2 Adhesion-imparting A-1120 .sup.(8) Nippon Unicar Company
Limited 3 agent KBE603 .sup.(9) Shin-Etsu Chemical Co., Ltd. 3.57
Y-11597 .sup.(10) Nippon Unicar Company Limited 2.8 A-189 .sup.(11)
Nippon Unicar Company Limited 2.7 A-187 .sup.(12) Nippon Unicar
Company Limited S340 .sup.(13) Chisso Corporation Reaction mixture
of aminosilane and epoxysilane .sup.(14) Titanium catalyst Orgatix
TC-750 .sup.(15) Matsumoto Chemical Industry Co., 7.5 7.5 7.5 7.5
Ltd. Curability Tack-free time (hour) 3.2 9.8 1.5 2.8 Tensile
properties of Modulus at 50% (MPa) 0.3 0.35 0.32 0.25 dumbbell
before tension storing Strength at break (MPa) 1.7 1.79 1.96 1.63
Elongation at break (%) 538 484 479 622 Tensile properties of
Modulus at 50% (MPa) 0.22 0.19 0.32 0.23 dumbbell after tension
storing at 50.degree. C. Strength at break (MPa) 1.13 0.87 1.68
1.52 for four weeks Elongation at break (%) 472 433 437 705
Maintenance factor Modulus at 50% (%) 73% 54% 100% 92% of physical
tension properties Strength at break (%) 66% 49% 86% 93% (after
storing/before Elongation at break (%) 88% 89% 91% 113% storing)
Adhesion Hand peel Anodized aluminum A A A D at 90 degrees Steel
sheet A A D D Hard polyvinyl chloride A A D D FRP A A B C
Polycarbonate A A D D Acrylic resin sheet A A A A Comparative
Example Composition (parts by weight) 5 6 7 8 Organic polymer (A)
A-1 100 100 100 100 Filler Hakuenka CCR .sup.(1) Shiraishi Kogyo
Kaisha, Ltd. 120 120 120 120 Titanium oxide Tipaque R-820 Ishihara
Sangyo Kaisha, Ltd. 20 20 20 20 Plasticizer DIDP .sup.(2) Kyowa
Hakko Kogyo Co., Ltd. 55 55 55 55 Antisagging agent Disparlon #6500
.sup.(3) Kusumoto Chemicals, Ltd. 2 2 2 2 Ultraviolet absorber
Sumisorb 400 .sup.(4) Sumitomo Chemical Co., Ltd. 1 1 1 1
Photostabilizer Sanol LS-765 .sup.(5) Sankyo Co., Ltd. 1 1 1 1
Antioxidant Irganox 1010 .sup.(6) Ciba-Geigy Japan Ltd. 1 1 1 1
Dehydrating agent A-171 .sup.(7) Nippon Unicar Company Limited 2 2
2 2 Adhesion-imparting A-1120 .sup.(8) Nippon Unicar Company
Limited agent KBE603 .sup.(9) Shin-Etsu Chemical Co., Ltd. Y-11597
.sup.(10) Nippon Unicar Company Limited A-189 .sup.(11) Nippon
Unicar Company Limited A-187 .sup.(12) Nippon Unicar Company
Limited 3.9 S340 .sup.(13) Chisso Corporation 4.1 Reaction mixture
of aminosilane and epoxysilane .sup.(14) 3.1 Titanium catalyst
Orgatix TC-750 .sup.(15) Matsumoto Chemical Industry Co., 7.5 7.5
7.5 4 Ltd. Curability Tack-free time (hour) 2.8 >24 2.6 1.7
Tensile properties of Modulus at 50% (MPa) 0.27 0.28 0.28 0.21
dumbbell before tension storing Strength at break (MPa) 1.86 1.59
1.94 1.77 Elongation at break (%) 615 534 579 903 Tensile
properties of Modulus at 50% (MPa) 0.28 0.19 0.28 0.18 dumbbell
after tension storing at 50.degree. C. Strength at break (MPa) 1.69
0.91 1.53 1.33 for four weeks Elongation at break (%) 608 424 468
794 Maintenance factor Modulus at 50% (%) 104% 68% 100% 86% of
physical tension properties Strength at break (%) 91% 57% 79% 75%
(after storing/before Elongation at break (%) 99% 79% 81% 88%
storing) Adhesion Hand peel Anodized aluminum C A A D at 90 degrees
Steel sheet C A C D Hard polyvinyl chloride D D D D FRP C A B D
Polycarbonate D D D D Acrylic resin sheet A A A A .sup.(1)
Colloidal calcium carbonate .sup.(2) Diisodecyl phthalate .sup.(3)
Fatty acid amide wax .sup.(4)
2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate .sup.(5)
Bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate .sup.(6)
Pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propi-
onate] .sup.(7) Trimethoxyvinylsilane .sup.(8)
H.sub.2NC.sub.2H.sub.4NHC.sub.3H.sub.6Si(OMe).sub.3 .sup.(9)
H.sub.2NC.sub.2H.sub.4NHC.sub.3H.sub.6Si(OEt).sub.3 .sup.(10)
1,3,5-N-tris(3-trimethoxysilylpropyl)isocyanurate .sup.(11)
HSC.sub.3H.sub.6Si(OMe).sub.3 .sup.(12)
3-glycidoxypropyltrimethoxysilane .sup.(13)
N-(1,3-dimethylbutylidene)-3-(triethoxysilyl)-1-propaneamine
.sup.(14) a mixture obtained by mixing
.gamma.-aminopropyltrimethoxysilane and
.gamma.-glycidoxypropyltrimethoxysilane at a molar ratio of 1:2 and
allowing to stand under conditions of a room temperature of
23.degree. C. and a humidity of 50% for four weeks .sup.(15)
Diisopropoxytitaniumbis(ethylacetoacetate)
[0166] The curable compositions prepared using titanium
diisopropoxidebis(ethylacetoacetate) as a curing catalyst and
aminosilanes of Comparative Examples 1 and 2 and ketimine silane of
Comparative Example 6 of the component (C) of the present invention
as an adhesion-imparting agent displayed satisfactory adhesion to
various articles to be adhered, but after storing, mechanical
properties of the cured articles were lowered.
[0167] On the other hand, in the case of using silane coupling
agents other than the component (C) as an adhesion-imparting agent
like Comparative Examples 3, 4, 5 and 7 and in the case of adding
no adhesion-imparting agent like Comparative Example 8, lowering of
physical properties was small, but sufficient adhesion could not be
obtained. Also like Comparative Examples 2 and 6, the curable
compositions prepared by using silane coupling agents having
ethoxysilyl groups as a hydrolyzable silicon group exhibited a
tendency that curability was inferior.
Synthesis Example 2
[0168] At 23.degree. C. in nitrogen gas atmosphere, 100 ml of
dehydrated methanol (product of Kanto Chemical Co., Inc.) was
poured in a reaction vessel containing 25.5 g (60 mmol) of Orgatix
TC750 (titanium diisopropoxidebis(ethylacetoacetate)) produced by
Matsumoto Chemical Industry Co., Ltd., followed by stirring for
about 30 minutes. Thereafter methanol and 2-propanol generated by
an alkoxy exchange reaction of methanol and TC750 were subjected to
azeotropic dehydration under reduced pressure. As a result of
measurement of .sup.1HNMR spectrum of the obtained reaction product
(measured in CDCl.sub.3 as a solvent by use of a JNM-LA400
manufactured by JEOL Ltd.), the integrated value of (--OCH).sup.1H
peak (4.7 ppm) of an isopropoxy group of TC750 was decreased and a
peak (4.2 ppm) of a methoxy group (--OCH.sub.3) of the
methoxy-substituted titanium compound appeared. Further 100 ml of
dehydrated methanol was poured to the reaction product, and the
same procedures as above were repeated three times. Lastly, 100 ml
of hexane was added, followed by azeotropic dehydration. As a
result, titanium dimethoxidebis(ethylacetoacetate) (B-1) was
obtained at a purity of not less than 95%. The purity of the
generated product was calculated from a ratio of integrated peak
intensities of TC750 and the product (B-1) based on .sup.1HNMR
spectrum.
[0169] .sup.1HNMR spectrum of TC750:1.0-1.3 ppm (18H), 1.8-2.0 ppm
(6H), 3.9-4.2 ppm (4H), 4.7 ppm (2H), 4.9 ppm (2H); .sup.1HNMR
spectrum of (B-1): 1.0-1.3 ppm (6H), 1.7-2.0 ppm (6H), 3.9-4.1 ppm
(4H), 4.2 ppm (6H), 4.9 ppm (2H)
Synthesis Example 3
[0170] Titanium diethoxidebis(ethylacetoacetate) (B-2) was obtained
at a purity of not less than 95% in the same manner as in Synthesis
Example 2 except that ethanol (produced by Wako Pure Chemicals Co.,
Ltd.) subjected to dehydration treatment with a molecular sieve was
used instead of methanol of Synthesis Example 2.
[0171] .sup.1HNMR spectrum of (B-2): 1.0-1.3 ppm (12H), 1.8-2.0 ppm
(6H), 3.9-4.1 ppm (4H), 4.3-4.5 ppm (4H), 4.9 ppm (2H)
Examples 1 to 4 and Comparative Examples 9 and 10
[0172] The reactive silicon group-containing polyoxyalkylene
polymer (A-1) obtained in Synthesis Example 1 as the component (A),
a filler, a titanium oxide, a plasticizer, an antisagging agent, an
ultraviolet absorber, a photostabilizer, an antioxidant, a
dehydrating agent, the component (C) as an adhesion-imparting agent
and a titanium catalyst as a curing catalyst were weighed out
according to the formulations shown in Table 2, then, these
ingredients were mixed together with a mixer to yield each
one-component type curable composition, and the composition was
charged in an aluminum cartridge. It is to be noted that the added
amount of each curing catalyst was so set as to became equimolar
amounts.
[0173] The curable compositions each were extruded from the
cartridge and filled in a molding frame of about 5 mm in thickness
with a spatula; the surface of each of the filled compositions was
fully flattened, and the planarization completion time was set as
the curing starting time. The surface of each of the compositions
was touched with a spatula every five minutes, and the skin
formation time was measured as the time when the composition no
longer stuck to the spatula.
[0174] Also by using a cartridge containing one-component type
curable composition, after storing at a constant temperature of
23.degree. C. for 7 days (before storing) and further after storing
in an oven at 50.degree. C. for 28 days (after storing), a tension
test was carried out under the following conditions, and variations
of physical properties before and after storing were
investigated.
(Tension Test Method 2)
[0175] First, the curable compositions each were filled in a
sheet-like molding frame of about 3 mm in thickness, and the
surface of each of the filled compositions was fully flattened,
followed by aging at 23.degree. C. for 3 days+50.degree. C. for 4
days, to produce sheet-like cured articles. The cured articles were
punched to obtain No. 2 (1/3) dumbbell type test pieces (JIS
K7113), and a modulus at 50% tension, a strength at break and an
elongation at break (measuring environment: 23.degree. C., tensile
speed: 200 mm/min) were measured with an AUTOGRAPH produced by
Shimadzu Corporation.
[0176] Also adhesion to various articles to be adhered (anodized
aluminum, polyvinyl chloride-coated steel sheet, FRP,
polycarbonate, acrylic resin sheet) was evaluated in the same
manner as above.
[0177] Mechanical properties (modulus, strength, elongation) and
maintenance factors of physical properties of each curable
composition before and after the storing are shown in Table 2. The
added amounts of each curing catalyst is so set as to be equimolar
amounts. TABLE-US-00002 TABLE 2 Example Composition (parts by
weight) 1 2 3 4 Organic polymer (A) A-1 100 100 100 100 Filler
Hakuenka CCR .sup.(1) Shiraishi Kogyo Kaisha, Ltd. 120 120 120 120
Titanium oxide Tipaque R-820 Ishihara Sangyo Kaisha, Ltd. 20 20 20
20 Plasticizer DIDP .sup.(2) Kyowa Hakko Kogyo Co., Ltd. 55 55 55
Allyl group-terminated PPG.sup.(3) 55 Antisagging agent Disparlon
#6500 .sup.(4) Kusumoto Chemicals, Ltd. 2 2 2 2 Ultraviolet
absorber Sumisorb 400 .sup.(5) Sumitomo Chemical Co., Ltd. 1 1 1 1
Photostabilizer Sanol LS-765 .sup.(6) Sankyo Co., Ltd. 1 1 1 1
Antioxidant Irganox 1010 .sup.(7) Ciba-Geigy Japan Ltd. 1 1 1 1
Dehydrating agent A-171 .sup.(8) Nippon Unicar Company Limited 2 2
2 2 Adhesion-imparting A-1120 .sup.(9) Nippon Unicar Company
Limited 3 3 3 agent KBE603 .sup.(10) Shin-Etsu Chemical Co., Ltd. 3
Chelate type methyl Titanium dimethoxidebis(ethylacetoacetate)
(B-1) 6.5 6.5 6.5 titanate (b1) Chelate type ethyl Titanium
diethoxidebis(ethylacetoacetate) (B-2) 7 titanate (b2) Titanium
catalyst Orgatix TC-750 .sup.(11) Matsumoto Chemical Industry Co.,
Ltd. Curability Skin formation time (hour) 3.5 1.5 8.5 8 Tensile
properties of Modulus at 50% (MPa) 0.4 0.4 0.37 0.38 dumbbell
before tension storing Strength at break (MPa) 1.83 1.83 1.47 1.8
Elongation at break (%) 486 486 411 499 Tensile properties of
Modulus at 50% (MPa) 0.37 0.37 0.32 0.33 dumbbell after tension
storing at 50.degree. C. Strength at break (MPa) 1.47 1.47 1.38
1.31 for four weeks Elongation at break (%) 461 461 432 440
Maintenance factor Modulus at 50% (%) 93% 93% 86% 87% of physical
tension properties Strength at break (%) 80% 80% 94% 73% (after
storing/before Elongation at break (%) 95% 95% 105% 88% storing)
Adhesion Hand peel Anodized aluminum A A A A at 90 degrees
Polyvinyl chloride resin-coated A A A A steel sheet FRP A A A A
Polycarbonate A A A A Acrylic resin sheet A A A A Comparative
Example Composition (parts by weight) 9 10 Organic polymer (A) A-1
100 100 Filler Hakuenka CCR .sup.(1) Shiraishi Kogyo Kaisha, Ltd.
120 120 Titanium oxide Tipaque R-820 Ishihara Sangyo Kaisha, Ltd.
20 20 Plasticizer DIDP .sup.(2) Kyowa Hakko Kogyo Co., Ltd. 55 55
Allyl group-terminated PPG.sup.(3) Antisagging agent Disparlon
#6500 .sup.(4) Kusumoto Chemicals, Ltd. 2 2 Ultraviolet absorber
Sumisorb 400 .sup.(5) Sumitomo Chemical Co., Ltd. 1 1
Photostabilizer Sanol LS-765 .sup.(6) Sankyo Co., Ltd. 1 1
Antioxidant Irganox 1010 .sup.(7) Ciba-Geigy Japan Ltd. 1 1
Dehydrating agent A-171 .sup.(8) Nippon Unicar Company Limited 2 2
Adhesion-imparting A-1120 .sup.(9) Nippon Unicar Company Limited 3
agent KBE603 .sup.(10) Shin-Etsu Chemical Co., Ltd. Chelate type
methyl Titanium dimethoxidebis(ethylacetoacetate) (B-1) 3.47
titanate (b1) Chelate type ethyl Titanium
diethoxidebis(ethylacetoacetate) (B-2) titanate (b2) Titanium
catalyst Orgatix TC-750 .sup.(11) Matsumoto Chemical Industry Co.,
7.5 Ltd. Curability Skin formation time (hour) 2.5 3.7 Tensile
properties of Modulus at 50% (MPa) 0.39 0.28 dumbbell before
tension storing Strength at break (MPa) 1.65 1.95 Elongation at
break (%) 458 775 Tensile properties of Modulus at 50% (MPa) 0.26
0.26 dumbbell after tension storing at 50.degree. C. Strength at
break (MPa) 0.97 1.98 for four weeks Elongation at break (%) 362
808 Maintenance factor Modulus at 50% (%) 67% 93% of physical
tension properties Strength at break (%) 59% 102% (after
storing/before Elongation at break (%) 79% 104% storing) Adhesion
Hand peel Anodized aluminum A D at 90 degrees Polyvinyl chloride
resin-coated D D steel sheet FRP A D Polycarbonate A A Acrylic
resin sheet A A .sup.(1) Colloidal calcium carbonate .sup.(2)
Diisodecyl phthalate .sup.(3) Allyl-terminated PPG prepared by
subjecting terminal hydroxyl group of PPG3000 to allylation
.sup.(4) Fatty acid amide wax .sup.(5)
2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate .sup.(6)
Bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate .sup.(7)
Pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propi-
onate] .sup.(8) Trimethoxyvinylsilane .sup.(9)
H.sub.2NC.sub.2H.sub.4NHC.sub.3H.sub.6Si(OMe).sub.3 .sup.(10)
H.sub.2NC.sub.2H.sub.4NHC.sub.3H.sub.6Si(OEt).sub.3 .sup.(11)
Diisopropoxytitaniumbis(ethylacetoacetate)
[0178] When titanium diisopropxidebis(ethylacetoacetate) was used
as a titanium catalyst like Comparative Example 9, mechanical
properties after storing were lowered considerably. On the
contrary, lowering of various mechanical properties could be
inhibited by using, as a curing catalyst, titanium
dimethoxidebis(ethylacetoacetate) and titanium
diethoxidebis(ethylacetoacetate) of the component (B) of the
present invention.
[0179] Also the composition containing no component (C) like
Comparative Example 10 is insufficient in adhesion to several kinds
of articles to be adhered.
Synthesis Example 4
[0180] Into a reactor containing 42.6 g (150 mmol) of titanium
tetraisopropoxide was added dropwise 43.3 g (300 mmol) of ethyl
2-methylacetoacetate over 30 minutes with stirring. During the
addition, an exothermic reaction proceeded. After completion of the
addition, stirring was carried out further one hour, and then
produced 2-propanol was distilled off under reduced pressure.
Further hexane was added to the reaction product. Then the mixture
was subjected to azeotropic dehydration, and measurement of a
spectrum of .sup.1HNMR was carried out. As a result, titanium
diisopropoxidebis(ethyl-2-methylacetoacetate) (B'-1) was
obtained.
[0181] .sup.1HNMR spectrum of (B'-1): 1.0-1.3 ppm (18H), 1.7 ppm
(6H), 1.8-2.1 ppm (6H), 3.9-4.2 ppm (4H), 4.7-4.8 ppm (2H)
Synthesis Example 5
[0182] Titanium dimethoxidebis(ethyl-2-methylacetoacetate) (B-3) of
a purity of not less than 95% was obtained by the same procedures
as in Synthesis Example 2 except that 27.1 g (60 mmol) of titanium
diisopropoxidebis(ethyl-2-methylacetoacetate) (B'-1) obtained in
Synthesis Example 4 was used instead of TC750 of Synthesis Example
2.
[0183] .sup.1HNMR spectrum of (B-3): 1.1-1.3 ppm (6H), 1.75 ppm
(6H), 2.0 ppm (6H), 3.9-4.2 ppm (4H), 4.2 ppm (6H)
Synthesis Example 6
[0184] Titanium diethoxidebis(ethyl-2-acetoacetate) (B-4) of a
purity of not less than 95% was obtained in the same manner as in
Synthesis Example 5 except that ethanol (produced by Wako Pure
Chemical Industries, Ltd.) subjected to dehydration treatment with
a molecular sieve was used instead of methanol of Synthesis Example
5.
[0185] .sup.1HNMR spectrum of (B-4): 1.1-1.4 ppm (12H), 1.7 ppm
(6H), 2.0 ppm (6H), 3.9-4.2 ppm (4H), 4.3-4.5 ppm (4H)
Examples 5 and 6 and Comparative Example 11
[0186] The reactive silicon group-containing polyoxyalkylene
polymer (A-1) obtained in Synthesis Example 1 as the component (A),
a filler, a titanium oxide, a plasticizer, an antisagging agent, an
ultraviolet absorber, a photostabilizer, an antioxidant, a
dehydrating agent, the component (C) as an adhesion-imparting agent
and a titanium catalyst as a curing catalyst were weighed out
according to the formulations shown in Table 3, then, these
ingredients were mixed together with a mixer to yield each
one-component type curable composition, and the composition was
charged in an aluminum cartridge. It is to be noted that the added
amount of each curing catalyst was so set as to became equimolar
amounts.
[0187] The curable compositions each were extruded from the
cartridge and filled in a molding frame of about 5 mm in thickness
with a spatula; the surface of each of the filled compositions was
fully flattened, and the planarization completion time was set as
the curing starting time. The surface of each of the compositions
was touched with a spatula every five minutes, and the skin
formation time was measured as the time when the composition no
longer stuck to the spatula.
[0188] Also adhesion to various articles to be adhered (anodized
aluminum, polyvinyl chloride-coated steel sheet, FRP,
polycarbonate, acrylic resin sheet) was evaluated in the same
manner as above.
[0189] Mechanical properties before and after storing were measured
by the same test method as the above described (Tension test method
2), and maintenance factors of physical properties were calculated.
The results are shown in Table 3. TABLE-US-00003 TABLE 3
Comparative Example Example Composition (parts by weight) 5 6 11
Organic polymer (A) A-1 100 100 100 Filler Hakuenka CCR .sup.(1)
Shiraishi Kogyo Kaisha, Ltd. 120 120 120 Titanium oxide Tipaque
R-820 Ishihara Sangyo Kaisha, Ltd. 20 20 20 Plasticizer DIDP
.sup.(2) Kyowa Hakko Kogyo Co., Ltd. 55 55 55 Antisagging agent
Disparlon #6500 .sup.(3) Kusumoto Chemicals, Ltd. 2 2 2 Ultraviolet
absorber Sumisorb 400 .sup.(4) Sumitomo Chemical Co., Ltd. 1 1 1
Photostabilizer Sanol LS-765 .sup.(5) Sankyo Co., Ltd. 1 1 1
Antioxidant Irganox 1010 .sup.(6) Ciba-Geigy Japan Ltd. 1 1 1
Dehydrating agent A-171 .sup.(7) Nippon Unicar Company Limited 2 2
2 Adhesion-imparting A-1120 .sup.(8) Nippon Unicar Company Limited
3 3 3 agent Chelate type methyl Titanium
dimethoxidebis(ethyl-2-methylacetoacetate) (B-3) 7 titanate (b1)
Chelate type ethyl Titanium
diethoxidebis(ethyl-2-methylacetoacetate) (B-4) 7.5 titanate (b2)
Titanium catalyst Titanium
diisopropoxidebis(ethyl-2-methylacetoacetate) 8 (B'-1) Curability
Skin formation time (hour) 1.5 4.5 0.8 Tensile properties of
Modulus at 50% (MPa) 0.46 0.4 0.41 dumbbell before tension storing
Strength at break (MPa) 1.7 1.53 1.44 Elongation at break (%) 374
373 349 Tensile properties of Modulus at 50% (MPa) 0.38 0.31 0.26
dumbbell after tension storing at 50.degree. C. Strength at break
(MPa) 1.55 1.3 0.98 for four weeks Elongation at break (%) 482 453
361 Maintenance factor Modulus at 50% (%) 83% 78% 63% of physical
tension properties Strength at break (%) 91% 85% 68% (after
storing/before Elongation at break (%) 129% 121% 103% storing)
Adhesion Hand peel Anodized aluminum A A A at 90 degrees Polyvinyl
chloride-coated A A A steel sheet FRP A A A Polycarbonate A A A
Acrylic resin sheet A A A .sup.(1) Colloidal calcium carbonate
.sup.(2) Diisodecyl phthalate .sup.(3) Fatty acid amide wax
.sup.(4) 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate
.sup.(5) Bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate .sup.(6)
Pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propi-
onate] .sup.(7) Trimethoxyvinylsilane .sup.(8)
H.sub.2NC.sub.2H.sub.4NHC.sub.3H.sub.6Si(OMe).sub.3
[0190] When titanium diisopropxidebis(ethyl-2-methylacetoacetate)
was used like Comparative Example 11 in the same manner as above,
mechanical properties after storing were lowered considerably. On
the contrary, lowering of various mechanical properties could be
inhibited by using, as a curing catalyst, titanium
dimethoxidebis(ethyl-2-methylacetoacetate) and titanium
diethoxidebis(ethyl-2-methylacetoacetate) of the component (B) of
the present invention.
Synthesis Example 7
[0191] A triethoxysilyl group-terminated polyoxypropylene polymer
(A-2) was obtained in the same manner as in Synthesis Example 1
except that 1.3 parts by weight of triethoxysilane was used instead
of methyldimethoxysilane. According to measurement based on
.sup.1H-NMR, the number of terminal triethoxysilyl groups per
molecule was about 1.1 on average.
Example 7 and Comparative Example 12
[0192] The reactive silicon group-containing polyoxyalkylene
polymer (A-2) obtained in Synthesis Example 7 as the component (A),
a filler, a titanium oxide, a plasticizer, an antisagging agent, an
ultraviolet absorber, a photostabilizer, an antioxidant, a
dehydrating agent, the component (C) as an adhesion-imparting agent
and a titanium catalyst as a curing catalyst were weighed out
according to the formulations shown in Table 4, then, these
ingredients were mixed together with a mixer to yield each
one-component type curable composition, and each composition was
charged in an aluminum cartridge. It is to be noted that the added
amount of each curing catalyst was so set as to be equimolar
amounts.
[0193] A skin formation time and adhesion to various articles to be
adhered (anodized aluminum, polyvinyl chloride-coated steel sheet,
FRP, polycarbonate, acrylic resin sheet) were evaluated in the same
manner as above.
[0194] Mechanical properties before and after storing were measured
by the same test method as the above described (Tension test method
2), and maintenance factors of physical properties were calculated.
The results are shown in Table 4. TABLE-US-00004 TABLE 4
Comparative Example Example Composition (parts by weight) 7 12
Organic polymer (A) A-2 100 100 Filler Hakuenka CCR .sup.(1)
Shiraishi Kogyo Kaisha, Ltd. 120 120 Titanium oxide Tipaque R-820
Ishihara Sangyo Kaisha, Ltd. 20 20 Plasticizer DIDP .sup.(2) Kyowa
Hakko Kogyo Co., Ltd. 55 55 Antisagging agent Disparlon #6500
.sup.(3) Kusumoto Chemicals, Ltd. 2 2 Ultraviolet absorber Sumisorb
400 .sup.(4) Sumitomo Chemical Co., Ltd. 1 1 Photostabilizer Sanol
LS-765 .sup.(5) Sankyo Co., Ltd. 1 1 Antioxidant Irganox 1010
.sup.(6) Ciba-Geigy Japan Ltd. 1 1 Dehydrating agent ESi28 .sup.(7)
Colcoat Co., Ltd. 2 2 Adhesion-imparting KBE603 .sup.(8) Shin-Etsu
Chemical Co., Ltd. 3.57 3.57 agent Chelate type ethyl Titanium
diethoxidebis(ethylacetoacetate) (B-2) 7 titanate (b1) Titanium
catalyst Orgatix TC-750 .sup.(9) Matsumoto Chemical Industry Co.,
7.5 Ltd. Curability Skin formation time (hour) 3.3 2.8 Tensile
properties of Modulus at 50% (MPa) 0.45 0.46 dumbbell before
tension storing Strength at break (MPa) 1.83 1.77 Elongation at
break (%) 356 338 Tensile properties of Modulus at 50% (MPa) 0.41
0.34 dumbbell after tension storing at 50.degree. C. Strength at
break (MPa) 1.72 1.44 for four weeks Elongation at break (%) 395
363 Maintenance factor Modulus at 50% (%) 91% 74% of physical
tension properties Strength at break (%) 94% 81% (after
storing/before Elongation at break (%) 111% 107% storing) Adhesion
Hand peel Anodized aluminum A A at 90 degrees Polyvinyl
chloride-coated A B steel sheet FRP A A Polycarbonate A A Acrylic
resin sheet A A .sup.(1) Colloidal calcium carbonate .sup.(2)
Diisodecyl phthalate .sup.(3) Fatty acid amide wax .sup.(4)
2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate .sup.(5)
Bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate .sup.(6)
Pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propi-
onate] .sup.(7) Tetraethoxysilane .sup.(8)
H.sub.2NC.sub.2H.sub.4NHC.sub.3H.sub.6Si(OEt).sub.3 .sup.(9)
Diisopropoxytitaniumbis(ethylacetoacetate)
[0195] When titanium diisopropxidebis(ethylacetoacetate) was used
like Comparative Example 12 in the same manner as above, mechanical
properties after storing were lowered considerably. On the
contrary, lowering of various mechanical properties could be
inhibited by using, as a curing catalyst, titanium
diethoxidebis(ethylacetoacetate) of the component (B) of the
present invention.
* * * * *