U.S. patent application number 10/822768 was filed with the patent office on 2004-09-30 for one-part, room temperature moisture curable resin composition.
This patent application is currently assigned to The Yokohama Rubber Co., Ltd.. Invention is credited to Adachi, Naoya, Ishikawa, Kazunori, Kotani, Yo, Okuhira, Hiroyuki, Takeda, Toshimitsu.
Application Number | 20040192873 10/822768 |
Document ID | / |
Family ID | 27455007 |
Filed Date | 2004-09-30 |
United States Patent
Application |
20040192873 |
Kind Code |
A1 |
Okuhira, Hiroyuki ; et
al. |
September 30, 2004 |
One-part, room temperature moisture curable resin composition
Abstract
This invention provides a one-part, room temperature moisture
curable resin composition which comprises a ketimine prepared by
reacting a ketone having a substituent at .alpha. position and a
polyamine having at least two amino groups within its molecule
wherein .alpha. position is methylene, and a main polymer which is
an epoxy resin and/or a modified silicone having at least two
hydrolyzable alkoxysilyl groups in its molecule, and which exhibits
good shelf stability and high curing rate once taken out of the
container, and which may further exhibit flexibility; a one-part,
room temperature moisture curable resin composition which exhibits
good shelf stability and curability as well as wet surface adhesion
or initial thixotropic properties; a silicon containing compound
having ketimine group whose reaction with the epoxy resin during
the storage is prevented by the presence of a bulky alkyl group
near the ketimine group and which exhibits good shelf stability and
curability, and its production method; a one-part, room temperature
moisture curable resin composition containing said silicon
containing compound adapted as a latent curing agent which exhibits
good shelf stability and short curing period once taken out of the
container; and a novel method of ketimine synthesis.
Inventors: |
Okuhira, Hiroyuki; (Oiwake
Hiratsuka City, JP) ; Adachi, Naoya; (Oiwake
Hiratsuka City, JP) ; Ishikawa, Kazunori; (Oiwake
Hiratsuka City, JP) ; Takeda, Toshimitsu; (Oiwake
Hiratsuka City, JP) ; Kotani, Yo; (Oiwake Hiratsuka
City, JP) |
Correspondence
Address: |
FINNEGAN, HENDERSON, FARABOW, GARRETT & DUNNER
LLP
1300 I STREET, NW
WASHINGTON
DC
20005
US
|
Assignee: |
The Yokohama Rubber Co.,
Ltd.
|
Family ID: |
27455007 |
Appl. No.: |
10/822768 |
Filed: |
April 13, 2004 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10822768 |
Apr 13, 2004 |
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10291601 |
Nov 12, 2002 |
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6756466 |
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10291601 |
Nov 12, 2002 |
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09155097 |
Mar 30, 1999 |
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6525159 |
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09155097 |
Mar 30, 1999 |
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PCT/JP98/00220 |
Jan 21, 1998 |
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Current U.S.
Class: |
528/25 |
Current CPC
Class: |
C08L 63/00 20130101;
C08G 59/4042 20130101; C08K 5/29 20130101; C08G 77/18 20130101;
C09D 183/08 20130101; C08L 83/04 20130101; C08K 5/29 20130101; C08L
63/00 20130101; C08K 5/29 20130101; C08L 83/04 20130101; C08L 63/00
20130101; C08L 83/00 20130101; C08L 83/04 20130101; C08L 2666/44
20130101; C08L 83/04 20130101; C08L 83/00 20130101 |
Class at
Publication: |
528/025 |
International
Class: |
C08G 077/04 |
Foreign Application Data
Date |
Code |
Application Number |
Jan 21, 1997 |
JP |
9-008714 |
Jul 23, 1997 |
JP |
9-197085 |
Sep 4, 1997 |
JP |
9-239586 |
Nov 11, 1997 |
JP |
9-308227 |
Claims
1-19. (Cancelled).
20. A method for producing a ketimine compound comprising reacting
a ketone with a polyamine, and then adding an isocyanate
group-containing compound represented by the following formula:
27wherein R.sup.4 is an organic group (which may be a group
containing O, S or N).
21. A method for producing a ketimine compound according to claim
20 wherein said ketimine is synthesized from the ketone represented
by the following formula (1): 28wherein R.sup.1 is a member
selected from the group consisting of alkyl groups containing 1 to
6 carbon atoms, R.sup.2 is methyl group or ethyl group, and R.sup.3
is hydrogen atom, methyl group, or ethyl group and the polyamine by
the following formula (2): 29wherein R.sup.4 is an organic group
(which may be a group containing O, S or N), and n is an integer of
at least 2.
22. (Cancelled).
Description
TECHNICAL FIELD
[0001] This invention relates to a one-part, room temperature
moisture curable resin composition adapted for use as an adhesive
or a sealant in the field of civil engineering and architecture
which exhibits good shelf stability and fast curing rate once taken
out of the container, and which may further exhibit flexibility; a
one-part, room temperature moisture curable resin composition which
exhibits good shelf stability and curability as well as wet surface
adhesion or initial thixotropic properties; a silicon containing
compound adapted for use as a latent curing agent -or a latent
catalyst for an adhesive or a sealant in the field of civil
engineering and architecture and as a coupling agent for various
adhesives which exhibits good shelf stability and curability, and
its production method; a one-part, room temperature moisture
curable resin composition containing said silicon containing
compound adapted for use as an adhesive or a sealant in the field
of civil engineering and architecture which exhibits good shelf
stability and curability; and a novel method of ketimine
synthesis.
BACKGROUND ART
[0002] Epoxy resins have been widely used as adhesives, sealants
and coating compositions in the fields of civil engineering,
architecture, electronic equipment and the like in view of their
favorable properties including the excellent adhesion and
strength.
[0003] Epoxy resins are highly reactive, and when an epoxy resin is
mixed with an amine component, it easily reacts with the amine
component to cure. Therefore, most epoxy resins have been used in
two-part form.
[0004] Under such situation, various attempts have been made to
develop one-part resin compositions by using a ketimine compound or
the like as a latent curing agent. However, no system have been so
far been developed that exhibits well balanced shelf stability and
curability.
[0005] For example, JP-A 5-132541 discloses a technique wherein
reactivity during the storage is reduced by using a long chain
polyoxylene for the skeleton of the ketimine compound to thereby
improve shelf stability. This resin, however, slowly cures when it
is taken out of the container and is not a one-part epoxy resin
composition of practical level.
[0006] In addition, the resin compositions comprising an epoxy
resin and a ketimine compound also suffer from the drawback of poor
flexibility of the cured product.
[0007] On the other hand, organosilicon compounds having ketimine
structure are known, and various process of their synthesis and
various techniques of their use as a tackifier or a curing agent to
be blended in the resin composition are also known. Number of the
ketimine group in the molecule of such known compounds are one or
two, and in most cases one.
[0008] The ketimine compound are synthesized, for example, by a
process wherein an alkoxysilane having amino group is reacted with
a ketone in the presence of anhydrous sulfate or a molecular sieve
(see JP-A 3-263421 and JP-A 7-247295), a process wherein an
alkoxysilane having amino group is gradually introduced into a
ketone by heating (see JP-A 7-247294), or a process wherein an
organic unsaturated compound having ketimine group is reacted with
hydroalkoxysilane in the presence of a transition metal catalyst
(see JP-A 4-83439). Many of the processes for synthesizing
organosilicon compound having ketimine structure attempts to obtain
the product in monomer form by suppressing the side reaction,
namely, polymerization of the alkoxysilane moiety, for example, by
using a dehydrating agent which removes the water generated by the
reaction between the amine and the ketone.
[0009] There is also disclosed a process wherein a compound having
secondary amino group in the molecular skeleton is reacted with an
alkoxysilane having a halogen atom to produce a silane coupling
agent having two ketimine group in the molecule (see JP-A
8-27167).
[0010] With regard to the techniques wherein an organosilane
compound having ketimine structure is used as a component to be
blended in a composition, there are disclosed a technique wherein
an organosilane compound having ketimine structure is used as an
additive for imparting adhesive properties and heat resistance to
the one-part chloroprene-based adhesive (JP-A 8-27447), a technique
wherein an organosilane compound having ketimine structure is used
as a curing agent for hot melt epoxy resin which is solid at room
temperature (JP-B 57-11582), a technique wherein a
.beta.-dicarbonyl compound is reacted with a silane coupling agent
with stirring at room temperature for use as a tackifier for a
polyurethane or a modified silicone (JP-B 2-19866).
[0011] The organosilane compounds having ketimine structure in the
disclosed techniques, however, all suffered from insufficient shelf
stability and, for example, experienced viscosity increase or
gelation with lapse of time when the organosilane compound was
mixed with an epoxy resin or a polyurethane resin and stored in
sealed condition since nitrogen atom in the imine moiety had high
nucleophilicity. Conventional organosilane compounds having
ketimine group which have been used as a curing agent for an epoxy
resin have been mostly bifunctional, and such bifunctional
organosilane compounds have suffered from insufficient shelf
stability, and the situation has been worse in the case of
multifunctional organosilane compounds having ketimine group.
[0012] A plurality of inventions attempting to improve the shelf
stability of the one-part, room temperature moisture curable resin
compositions have been disclosed. The shelf stability in these
inventions, however, have all been improved in the sacrifice of the
reactivity itself, and the one-part, room temperature moisture
curable resin compositions of such inventions have been far from
being practical. For example, a composition prepared by mixing an
epoxy resin having an increased molecular weight and a long chain
polyether for the skeleton with a ketimine compound is disclosed
(See JP-A 5-230182). This composition, however, does not have a
curing speed adapted for use in a one-part, epoxy resin
composition.
[0013] A technology wherein a sterically hindered compound wherein
an amine or a thiol is capped with a trialkylsilyl group is used
for a latent curing agent is also disclosed (JP-A 1-138221,
JP-A2-36220). This curing agent sensitively reacts with a minute
amount of moisture, and undergoes gelation during its storage by
contact with a minute amount of moisture.
[0014] In addition, epoxy resins have the drawback of low wet
surface adhesion in spite of its strong adhesion to a wide variety
of materials. In view of such situation, improvement of the wet
surface adhesion has been attempted by using a polyamine or a
polyamideamine curing agent. Such conventional known attempts have
so far failed to develop one-part adhesive because of the
insufficient shelf stability.
[0015] Improvements in the wet surface adhesion by using a silane
coupling agent has been also proposed. The one-part epoxy resin
compositions which have so far been proposed have confronted with
the difficulty in balancing the shelf stability and the curing
rate.
[0016] In the meanwhile, one-part curable resin compositions of
modified silicone series have suffered from insufficient adhesion
to concretes and mortars, and required simultaneous use of an epoxy
resin and a latent curing agent for an epoxy resin.
[0017] One-part sealants employing the one-part curable resin
compositions of modified silicone series have used tin compounds
for the curing catalyst, and such sealants have been highly
reactive and sensitive to moisture. Therefore, a dehydrating agent
such as vinylsilane had to be blended in such sealants to thereby
remove the water of a minute amount in the system and maintain the
shelf stability. Although the shelf stability has been improved by
such means to some extent, the curing rate of the sealant once it
is taken out of the container are yet to be improved, and there is
a demand for a latent curing agent with better shelf stability.
Because of the difficulty in balancing the shelf stability and the
curing rate, a one-part sealant adapted for an industrial scale
production which is excellent in both the shelf stability and the
curing rate has not been so far developed.
[0018] In view of such situation, an object of the present
invention is to provide a one-part, room temperature moisture
curable resin composition which exhibits good shelf stability and
fast curing rate once taken out of the container, and which may
further exhibit flexibility; a one-part, room temperature moisture
curable resin composition which exhibits good shelf stability and
curability as well as wet surface adhesion or initial thixotropic
properties; a silicon containing compound having ketimine group
whose reaction with the epoxy resin during the storage is prevented
by the presence of a bulky alkyl group near the ketimine group and
which exhibits good shelf stability and curability, and its
production method; a one-part, room temperature moisture curable
resin composition containing said silicon containing compound
adapted as a latent curing agent which exhibits good shelf
stability and short curing period once taken out of the container;
and a novel method of ketimine synthesis.
SUMMARY OF THE INVENTION
[0019] In order to solve the problems as described above, the
present invention provides
[0020] a one-part, room temperature moisture curable resin
composition comprising a ketimine prepared by reacting a ketone
having a substituent at .alpha. position and a polyamine having at
least two amino groups within its molecule wherein .alpha. position
is methylene; and a main polymer which is an epoxy resin and/or a
modified silicone having at least two hydrolyzable alkoxysilyl
groups in its molecule.
[0021] The ketone is preferably a compound represented by the
following formula (1): 1
[0022] wherein R.sup.1 is a member selected from the group
consisting of alkyl groups containing 1 to 6 carbon atoms,
[0023] R.sup.2 is methyl group or ethyl group, and
[0024] R.sup.3 is hydrogen atom, methyl group, or ethyl group;
and
[0025] the polyamine is a compound represented by the following
formula (2): 2
[0026] wherein R.sup.4 is an organic group (which may be a group
containing O, S or N), and
[0027] n is an integer of at least 2.
[0028] The polyamine is most preferably norbornane diamine,
1,3-bisaminomethylcyclohexane, metaxylylenediamine, or
polyamideamine.
[0029] The composition may contain a phosphorous ester as a curing
accelerator at a content of at least 0.005 mol % of the main
functional group of said main polymer.
[0030] The present invention also provides a one-part, room
temperature moisture curable resin wherein the composition contains
a silane coupling agent at a content of 0.1 to 20 parts by weight
per 100 parts by weight of said main polymer.
[0031] The silane coupling agent is preferably
trimethoxy-vinylsilane or 3-glycidoxypropyltrimethoxysilane.
[0032] The present invention also provides a one-part, room
temperature moisture curable resin composition wherein said
composition contains a compound having a silyl ester group
represented by the following formula (3) at a content of 0.05 to 10
parts by weight per 100 parts by weight of said main polymer. 3
[0033] The present invention also provides a one-part, room
temperature moisture curable resin composition wherein the
composition contains a surface treated calcium carbonate, and the
ketimine is a ketimine represented by the following formula (4):
4
[0034] wherein R.sup.9 is an organic group including at least one
of O, S, N and an aromatic ring, and/or the following formula (5):
5
[0035] wherein R.sup.4 is an organic group (which may be a group
containing O, S or N).
[0036] The concentration of said ketimine in the one-part, room
temperature moisture curable resin composition is up to 1.6
[mmol/g].
[0037] The epoxy resin preferably contains sulfur atom in its
skeleton.
[0038] The present invention also provides, as a silicon containing
compound, a silicone compound having in its backbone the structure
shown in the following formula (9): 6
[0039] wherein R.sup.1 is a member selected from the group
consisting of alkyl groups containing 1 to 6 carbon atoms,
[0040] R.sup.2 is methyl group or ethyl group,
[0041] R.sup.3 is hydrogen atom, methyl group, or ethyl group,
[0042] R.sup.5 is an alkyl group containing 1 to 6 carbon atoms, an
alkoxy group containing 1 to 6 carbon atoms, or a monovalent
siloxane derivative,
[0043] R.sup.6 is a divalent hydrocarbon group containing or not
containing nitrogen atom,
[0044] R.sup.7 is methyl group, ethyl group or isopropyl group,
and
[0045] l is an integer of at least 1.
[0046] The present invention also provides, as a silicon containing
compound, a silicon compound comprising the structure as shown in
the following formula (10): 7
[0047] wherein R.sup.1 is a member selected from the group
consisting of alkyl groups containing 1 to 6 carbon atoms,
[0048] R.sup.2 is methyl group or ethyl group,
[0049] R.sup.3 is hydrogen atom, methyl group, or ethyl group,
[0050] R.sup.5 is an alkyl group containing 1 to 6 carbon atoms, an
alkoxy group containing 1 to 6 carbon atoms, or a monovalent
siloxane derivative,
[0051] R.sup.6 is a divalent hydrocarbon group containing or not
containing nitrogen atom,
[0052] R.sup.7 is methyl group, ethyl group or isopropyl group,
[0053] R.sup.8 is a monovalent siloxane derivative, and m is an
integer of 1 to 3.
[0054] Said R.sup.1, said R.sup.2 and said R.sup.7 are preferably
methyl group, and said R.sup.3 is preferably hydrogen atom or
methyl group.
[0055] The present invention also provides a one-part, room
temperature moisture curable resin composition containing the
silicon containing compound as described above; and an epoxy resin
and/or a modified silicone having at least two hydrolyzable
alkoxysilyl groups in its molecule. The resin composition may
contain either one silicon containing compound or two or more
silicon containing compounds.
[0056] The present invention also provides a method for producing
said silicon containing compound characterized in that said
compound is obtained by heating and stirring a compound containing
an alkoxysilyl group having amino group in its molecule and a
ketone represented by formula (1) as described above.
[0057] The present invention also provides a method for producing a
silicone compound having epoxy group, a ketimine group, and an
alkoxysilyl group in its molecule characterized in that said
compound is produced by heating and stirring an alkoxysilane having
epoxy group in its molecule, an alkoxysilane having amino group in
its molecule, and a ketone; and the silicone compound obtained by
such production method.
[0058] The ketone is preferably the one represented by said formula
(1).
[0059] The present invention also provides a one-part, room
temperature moisture curable resin composition comprising a
silicone compound as described above; and an epoxy resin and/or a
modified silicone having at least two hydrolyzable alkoxysilyl
groups in it molecule.
[0060] The present invention also provides a method for producing a
ketimine compound characterized in that said compound is produced
by reacting a ketone with a polyamide, and then adding an
isocyanate group-containing compound represented by the following
formula: 8
[0061] wherein R.sup.4 is an organic group (which may be a group
containing O, S or N).
[0062] In the production method of the ketimine compound, the
ketimine is preferably synthesized from the ketone represented by
said formula (1) and the polyamide represented by said formula
(2).
[0063] The present invention also provides a method for producing a
ketimine compound characterized in that said compound is produced
by reacting a ketone and a polyamide, and then adding a silane
coupling agent as a dehydration agent.
[0064] Preferred Embodiments for Carrying Out the Invention
[0065] Next, the present invention is described in further
detail.
[0066] The present invention provides a one-part, room temperature
moisture curable resin composition which exhibits good shelf
stability and quickly cures once taken out of the container, or
which exhibits excellent flexibility as well as wet surface
adhesion, and a silicon-containing compound which has a particular
structure which prevents the compound from undergoing a reaction
with the epoxy resin or the like during its storage. The present
invention includes first to fourth aspects as described below.
[0067] First aspect of the present invention is a one-part, room
temperature moisture curable resin composition which comprises a
ketimine prepared by reacting a ketone having a substituent at
.alpha. position and a polyamine having at least two amino groups
within its molecule wherein .alpha. position is methylene; and an
epoxy resin and/or a modified silicone having hydrolyzable
alkoxysilyl groups within its molecule; and which may further
comprise particular curing agent, silane coupling agent, a compound
containing silyl ester group, or surface-treated calcium carbonate.
The resin composition has the properties as described above.
[0068] Second aspect of the present invention is directed to a
silicon containing compound of a particular type; its production
process; and a one-part, room temperature moisture curable resin
composition which comprises such silicon containing compound, and
an epoxy resin and/or a modified silicone having hydrolyzable
alkoxysilyl groups within its molecule. The resin composition has
the properties as described above.
[0069] Third aspect of the present invention is directed to a
method for producing a silicone compound having a ketimine group,
epoxy group, and an alkoxysilyl group in its molecule from an
alkoxysilyl group-containing compound having epoxy group and amino
group in its molecule and a ketone, and a one-part, room
temperature moisture curable resin composition which comprises the
silicone compound produced by such production method and an epoxy
resin and/or a modified silicone having hydrolyzable alkoxysilyl
groups within its molecule.
[0070] Fourth aspect of the present invention is a novel method of
ketimine synthesis.
[0071] Next, the ketone having a substituent at .alpha. position
and the compound having at least two amino groups within its
molecule wherein .alpha. position is methylene which are used as
starting materials for producing the ketimine compound used in the
first aspect of the present invention are described.
[0072] The ketone having a substituent at .alpha. position used in
the present invention is a ketone having a substituent at .alpha.
position counted from the carbonyl group, and exemplary such
ketones include methyl t-butyl ketone, diisopropyl ketone, methyl
isopropyl ketone and the like as well as propiophenone,
benzophenone and the like. Among such ketones, the preferred are
the compounds represented by formula (1) as mentioned above
including methyl isopropyl ketone and methyl t-butyl ketone in view
of the well balanced shelf stability and curablity of the
composition prepared by blending the ketimine synthesized by using
such ketone and an epoxy resin.
[0073] The polyamine having at least two amino groups within its
molecule wherein .alpha. position is methylene used in the present
invention is preferably a compounds represented by formula (2) as
mentioned above. Exemplary such compounds represented by formula
(2) include ethylenediamine, propylenediamine, butylenediamine,
diethylenetriamine, triethylenetetramine, tetraethylenepentamine,
pentaethylenehexamine, hexamethylenediamine,
trimethylhexamethylenediamine, N-aminoethylpiperadine,
1,2-diaminopropane, iminobispropylamine, methyliminobispropylamine,
diamines having polyether skeleton as typically exemplified by
JEFFAMINE EDR-148 manufactured by Sun Technochemical Inc.,
aliphatic polyamines such as MPMD manufactured by DuPont Japan,
isophorone diamine, 1,3-bisaminomethylcyclohexane,
1-cyclohexylamino-3-aminopropane,
3-aminomethyl-3,3,5-trimethylcyclohexyl- amine, diamines having
norbornane skeleton as typically exemplified by NBDA manufactured
by Mitsui Toatsu Chemicals K.K.; metaxylylenediamine, and polyamide
amines having amino group on a terminal of the polyamide molecule.
Among these, the preferred are 1,3-bisaminomethylcyclohexane,
norbornane diamine, metaxylylenediamine, and polyamide amine since
the composition comprising the ketimine synthesized by using such
polyamine and an epoxy resin has good shelf stability as well as
excellent curability.
[0074] Preferable examples of the ketimine compounds used in the
present invention are ketimine compound obtained by using a
combination of the polyamine as mentioned above and a ketone
selected from methyl t-butyl ketone, diisopropyl ketone, methyl
isopropyl ketone, propiophenone, benzophenone and the like
[0075] Among such ketimine compounds, the ketimine compounds
synthesized from the polyamine as mentioned above and methyl
isopropyl ketone or methyl t-butyl ketone exhibit particularly good
balance between the curing rate and the shelf stability.
[0076] The ketimine compounds synthesized from the ketone as
mentioned above and 1,3-bisaminomethylcyclohexane, a norbornane
diamine, methaxylylene diamine, or apolyamide amine also exhibit
particularly good balance between the curing rate and the shelf
stability, and such ketimine compounds exhibit particularly
excellent curability.
[0077] Exemplary ketimine compounds include those prepared from
JEFFAMINE EDR-148 which is a diamine having polyether skeleton
manufactured by Sun Technochemical Inc. and methyl isopropyl
ketone; those prepared from JEFFAMINE EDR-148 and methyl t-butyl
ketone; those prepared from 1,3-bisaminomethylcyclohexane and
methyl t-butyl ketone; those prepared from NBDA manufactured by
Mitsui Toatsu Chemicals K.K. and methyl isopropyl ketone; those
prepared from 1,3-bisaminomethylcyclohexane and methyl isopropyl
ketone; those prepared from NBDA and methyl t-butyl ketone; those
prepared from MXDA manufactured by Mitsubishi Gas Chemical Company,
Inc. and methyl isopropyl ketone; those prepared from MXDA
manufactured by Mitsubishi Gas Chemical Company, Inc. and methyl
t-butyl ketone; those prepared from X2000 manufactured by SANWA
CHEMICAL PRODUCT LTD. and methyl isopropyl ketone; those prepared
from X2000 manufactured by SANWA CHEMICAL PRODUCT LTD. and methyl
t-butyl ketone; and the like.
[0078] Among these, those prepared from NBDA manufactured by Mitsui
Toatsu Chemicals K.K. and methyl isopropyl ketone; those prepared
from NBDA and methyl t-butyl ketone; and those prepared from
1,3-bisaminomethylcyclohex- ane and methyl isopropyl ketone exhibit
excellent curability.
[0079] Those prepared from X2000 and methyl isopropyl ketone; those
prepared from X2000 and methyl t-butyl ketone exhibit excellent wet
surface adhesion.
[0080] The ketimine compound prepared by reacting a ketone having a
substituent at .alpha. position and a polyamine having at least two
amino groups within its molecule wherein ax position is methylene
has a bulky group near the double bond of the ketimine group, and
therefore, the compound fulfills contradictory requirements of fast
curing rate and shelf stability. When the ketimine compound is
synthesized by using a universal ketone commonly used in the prior
art such as methyl isobutyl ketone (MIBK) or methyl ethyl ketone
(MEK) which has no substituent at the .alpha. position, nitrogen of
the ketimine is exposed, and the ketimine compound exhibits strong
basicity. When such ketimine compound is blended with an epoxy
resin, the resulting composition suffers from gelation and the like
to detract from shelf stability. In contrast, in the ketimine
compound prepared by using methyl isopropyl ketone, methyl t-butyl
ketone, or the like which has a substituent at the .alpha. position
for the starting material, nitrogen of the ketimine is protected by
the substituent, and such steric hindrance strongly weaken the
basicity of the compound. As a consequence, the composition
prepared by blending the ketimine compound with an epoxy resin is
not influenced by the ketimine compound, and the composition
remains stable.
[0081] In the meanwhile, when the epoxy resin composition
containing such ketimine compound is taken out into the air,
moisture, namely, water molecules of small size readily attack the
nitrogen of the ketimine without being hindered by the substrate,
and hydrolysis is readily promoted. Therefore, the epoxy resin
composition cures in a short period.
[0082] The ketimine compound used in the present invention is
produced by heating the ketone and the polyamine as mentioned above
under reflux in the absence of a solvent or in the presence of a
solvent such as benzene, toluene, xylene or the like and removing
the released water by azeotropic distillation.
[0083] The resin composition of the present invention contains an
epoxy resin and/or a modified silicone having at least two
hydrolyzable alkoxysilyl groups as its main polymer, and the amount
of the ketimine compound added to such resin composition in terms
of the equivalent ratio of (imino group of the ketimine
compound)/(main reaction group of the main polymer) is in the range
of 0.01 to 1, and preferably 0.1 to 0.5. The amount outside such
range results in poor curability.
[0084] The term "main reaction group of the main polymer" used
herein designates epoxy group in the case of an epoxy resin, and a
hydrolyzable alkoxysilyl group in the case of a modified
silicone.
[0085] The concentration of the ketimine group added in the resin
composition of the present invention is preferably up to 1.6
(mmol/g), and more preferably in the range of 0.2 to 1.5 (mmol/g).
The concentration in such range results in improved curing
properties as well as storage stability.
[0086] The epoxy resin which is one main polymer used in the
present invention is not limited to any particular type as long as
the epoxy resin is a polyepoxy compound which has at least two
epoxy groups in one molecule.
[0087] Exemplary such epoxy resins include bisphenol A-glycidyl
ether epoxy resins, glycerin-glycidyl ether epoxy resins,
polyalkylene oxide-glycidyl ether epoxy resins, phenol
novolak-glycidyl ether epoxy resins, dimeric acid-glycidyl ether
epoxy resins, bisphenol F-glycidyl ether epoxy resins, and epoxy
resins including sulfur atoms in its skeleton as typically
exemplified by Flep 10 manufactured by Toray Thiokol K.K. Among
these, a bisphenol A-glycidyl ether epoxy resin is preferable as a
universal epoxy resin, and an epoxy resin including sulfur atoms in
its skeleton is preferable since the resulting resin composition of
the present invention exhibits excellent wet surface adhesion.
[0088] The epoxy resin including sulfur atom in its skeleton used
in the present invention is an epoxy resin which has sulfur atoms
in its backbone. Exemplary such epoxy resin includes Flep series
manufactured by Toray Thiokol K.K.
[0089] The modified silicone which is another main polymer used in
the present invention is, for example, a silicone resin having a
functional group such as amino group, phenyl group or alkoxy group
introduced therein. The resin which is preferable for use is a
silicone resin which has bonded thereto at least one alkoxy group
having a hydrocarbon group containing 1 to 6 carbon atoms, and
which has on its terminal a hydrolyzable silicon functional group
including silicon atom which may have a hydrocarbon group
containing 1 to 12. carbon atoms bonded thereto.
[0090] Exemplary such modified silicones include modified silicones
having a dimethoxysilyl group or the like in its terminal such as
poly(methyldimethoxysilyl ethyl ether). The modified silicone may
be used alone or in combination of two or more.
[0091] Use of such modified silicone is important for imparting
flexibility with the cured product of the epoxy resin composition.
The modified silicone also contributes for the improvement of the
shelf stability of the epoxy resin composition.
[0092] The modified silicone and the epoxy resin may be used at any
ratio. When the modified silicone is used with no epoxy resin, the
resulting composition will exhibit particularly improved shelf
stability. When the content of the modified silicone is in excess
of 300 parts by weight, the product will exhibit poor adhesion.
[0093] Conventional one-part sealants containing a modified
silicone have used a tin compound for the curing catalyst, and a
dehydrating agent such as vinylsilane had to be blended in such
sealants to thereby remove the moisture of a minute amount in the
system and maintain the shelf stability since the tin compound is
highly reactive and sensitive to moisture. However, use of the
ketimine compound with severe steric hindrance as described above
for the latent catalyst enabled to realize excellent shelf
stability as well as high curing rate of the resin composition in
the absence of vinylsilane or other dehydrating agent.
[0094] The one-part, room temperature moisture curable resin
composition of the present invention can be prepared by mixing the
main polymer and the ketimine compound as described above in
nitrogen atmosphere, and in optional presence of a curing
accelerator.
[0095] Use of a phosphorous ester for the curing accelerator is
most effective since phosphorous esters do not induce unfavorable
effects such as viscosity increase in the epoxy resin composition
during its storage.
[0096] Exemplary phosphorous esters which may be used in the
present invention include triphenyl phosphite, tris(nonylphenyl)
phosphite, triethyl phosphite, tributyl phosphite,
tris(2-ethylhexyl) phosphite, tridecyl phosphite, tris(tridecyl)
phosphite, diphenylmono(2-ethylhexyl) phosphite,
diphenyl-monodecylphosphite, diphenylmono(tridecyl) phosphite,
tetraphenyl dipropylene glycol diphosphite,
tetraphenyl-tetra(tridecyl)pe- ntaerythritol tetraphosphite,
trilauryl trithiophosphite, bis(tridecyl)pentaerythritol
diphosphite, bis(nonylphenyl) pentaerythritol diphosphite,
tristearyl phosphite, distearyl pentaerythritol diphosphite,
tris(2,4-di-t-butylphenyl) phosphite, hydrogenated bisphenol
A-pentaerythritol phosphite polymer, and other triesters. The di-
and mono-esters prepared by partial hydrolysis of such triester are
also examples of the phosphorous esters. Among these
tetraphenyltetra(tridecyl)pentaerythritol tetraphosphite,
bis(tridecyl)pentaerythritol diphosphite, bis(nonylphenyl)
pentaerythritol diphosphite, distearyl pentaerythritol diphosphite,
hydrogenated bisphenol A-pentaerythritol phosphite polymer and the
like exhibit particularly high acceleration effects, and use of
such phosphites are preferable. of these phosphites, triesters may
be added in an amount of at least 0.005 mol %, and preferably 0.005
to 1.0 mol % in relation to the main functional group of the main
polymer. The main functional group of the main polymer is the same
as the main functional group of the main polymer as described
above. When di- or monoester prepared by partial hydrolysis of the
triester is used, such di- or monoester may be added in an amount
of 0.005 to 50 mol %, and preferably 0.005 to 10 mol % in relation
to the main functional group of the main polymer. The di- or
monoester added in an amount less than 0.005 mol % is not effective
as an accelerator, and the diester added in an amount more than 50
mol % will adversely affect the shelf stability.
[0097] It should be noted that the one-part, room temperature
moisture curable resin composition of the present invention may
contain an accelerator other than phosphites.
[0098] The one-part, room temperature moisture curable resin
composition may further contain a silane coupling agent. Addition
of a particular amount of silane coupling agent enables production
of a one-part, room temperature moisture curable resin composition
which exhibits well balanced shelf stability and curing rate
simultaneously with favorable wet surface adhesion.
[0099] The silane coupling agent used in the present invention is
not limited to any particular type, and any silane coupling agent
generally blended in an epoxy resin can be used. Exemplary such
silane coupling agents include, chloropropyltrimethoxy silane,
vinyltrichlorosilane, trimethoxyvinylsilane, vinyl-triethoxysilane,
vinyltris(2-methoxyethoxy)s- ilane,
.gamma.-methacryloxypropyltrimethoxysilane, and
3-glycidoxypropyl-trimethoxysilane. Among these preferred are
trimethoxyvinylsilane and 3-glycidoxypropyltrimethoxysilane in view
of their high effectivity in improving the wet surface adhesion and
universality.
[0100] The silane coupling agent is added in an amount of 0.1 to 20
parts by weight, and preferably 0.5 to 10 parts by weight per 100
parts by weight of the main polymer. Use in such amount is
preferable since the wet surface adhered by using the resulting
resin composition exhibits high shear stress upon breakage and
matrix damage of approximately 100%.
[0101] The one-part, room temperature moisture curable resin
composition of the present invention may contain a compound having
a silyl ester group represented by the following formula (3).
Presence of such compound having a silyl ester group in the
one-part, room temperature moisture curable resin composition in a
particular amount contributes for the shortening of the curing time
without detracting from the shelf stability of the resin
composition. 9
[0102] In the formula, R represents hydrogen atom or a hydrocarbon
group containing 1 to 20 carbon atoms. Exemplary hydrocarbon groups
include straight-chain hydrocarbon groups such as methyl group,
ethyl group, vinyl group, propyl group, octyl group, lauryl group,
palmityl group, stearyl group, allyl group, and eicosyl group;
branched hydrocarbon groups such as isopropyl group and isobutyl
group; aliphatic hydrocarbon groups such as hexamethyl group; and
aromatic groups such as phenyl group and benzyl group.
[0103] R is most preferably a hydrocarbon group containing 1 to 17
carbon atoms since the resulting products exhibits good shelf
stability and accelerated curing reaction. When R is hydrogen atom,
the shelf stability is not so favorable, and when R is a
hydrocarbon group containing 18 or more carbon atoms, the curing
reaction is not so much accelerated.
[0104] The compound having a silyl ester group which may be used in
the present invention is not particularly limited as long as its
silyl ester group is represented by formula (3) as described above.
The compound may have the silyl ester group in the intermediate
portion or at the terminal of its backbone, or in its side chain,
and the compound may have either one, or two or more silyl ester
groups. When the compound has two or more silyl ester groups
represented by formula (3), the silyl ester groups may comprise
either the same type or different types of silyl ester groups. The
backbone of the compound having the silyl ester group mainly
comprises Si-O bond, and the backbone may comprise either single
type or different types. When the silyl ester group represented by
formula (3) is present in the backbone, the Si in the silyl ester
group is the Si in the backbone.
[0105] Examples of the compounds having the silyl ester group
include the compounds represented by the following formulae. 10
11
[0106] In formulae (6) to (8), the number of recurrent units m of
the silyl ester group is an integer of at least 1.
[0107] The compound having the silyl ester group as described above
may be prepared by a process wherein a polyhydrogen siloxane having
Si-H group such as poly(methyl hydrogen) siloxane is reacted with a
straight-chain saturated fatty acid such as formic acid and stearic
acid, unsaturated fatty acid such as caproleic acid, or a
carboxylic acid such as an aromatic carboxylic acid such as benzoic
acid, or an alicyclic carboxylic acid such as naphtoic acid, or
alternatively, a copolymer of the polyhydrogen siloxane as
described above and an alkene is reacted with the carboxylic acid
as described above for dehydration condensation by using Pt, Ru or
other transition metal of Group VIII in the form of a simple
substance or a metal chloride as a catalyst.
[0108] The one-part, room temperature moisture curable resin
composition of the present invention may preferably contain the
compound having the silyl ester group as described above in an
amount of 0.05 to 10 parts by weight per 100 parts by weight of the
main polymer as described above since the curing time can be
reduced without detracting from the shelf stability when the
content is within such range. A content at 0.1 to 8.0 parts by
weight is most preferable.
[0109] The one-part, room temperature moisture curable resin
composition of the present invention may also contain calcium
carbonate at a content which does not adversely affect the object
of the present invention. In particular, addition of a
surface-treated calcium carbonate enables adjustment of the
viscosity as well as realization of good initial thixdtropic
properties and shelf stability.
[0110] Examples of such calcium carbonates which may be used
include conventional known surface-treated calcium carbonates
surface treated with a fatty acid, a resin acid or a fatty acid
ester. Exemplary preferable calcium carbonates surface treated with
a fatty acid include Calfine 200 (manufactured by Maruo Calcium
K.K.), and Whitein 305 (ground calcium carbonate, manufactured by
Shiraishi Calcium K.K.); and exemplary preferable calcium
carbonates surface treated with a fatty acid ester include Sealet
200 (manufactured by Maruo Calcium K.K.).
[0111] The one-part, room temperature moisture curable resin
composition wherein a surface-treated calcium carbonate is used for
the calcium carbonate exhibits particularly improved thixotropic
properties and shelf stability when the ketimine used is a compound
represented by the following formula (4) or (5): 12
[0112] wherein R.sup.9 is an organic group which has at least one
of O, S, N and an aromatic ring; 13
[0113] wherein R.sup.4 is an organic group (which may be a group
containing O, S or N).
[0114] The surface-treated calcium carbonate has low surface
polarity. Therefore, use of a ketimine with low polarity will
invite wetting and the resulting product will suffer from poor
thixotropic properties. Use of a ketimine with a relatively high
polarity is preferable for the purpose of preventing such
wetting.
[0115] In the ketimine represented by the formula (5), the
substituents near the imine moiety are methyl group and isopropyl
group, which are too small to reduce the polarity of the imine
portion with high polarity. Therefore, good thixotropic properties
and the shelf stability can be maintained without being influenced
by the ketimine skeleton (R.sup.4).
[0116] On the other hand, in the ketimine represented by the
formula (4), polarity of the imine moiety is reduced by the methyl
group and t-butyl group. Therefore, the ketimine skeleton (R.sup.9)
should have a high polarity.
[0117] Examples of such ketimine of relatively high polarity
include ketimines synthesized from a diamine having polyether
skeleton as typically exemplified by JEFFAMINE EDR-148 manufactured
by Sun Technochemical Inc. or a diamine having xylylene skeleton as
typically exemplified by MXDA manufactured by Mitsubishi Gas
Chemical Company, Inc. and methyl isopropyl ketone or methyl
t-butyl ketone; and ketimines synthesized from a diamine having
norbornane skeleton as typically exemplified by NBDA manufactured
by Mitsui Toatsu Chemicals K. K. or a diamine having cyclohexane
skeleton as typically exemplified by 1,3-BAC manufactured by
Mitsubishi Gas Chemical Company, Inc. and methyl isopropyl ketone
or methyl t-butyl ketone.
[0118] The calcium carbonate is added preferably in an amount of 30
to 300 parts by weight, and more preferably, 80 to 200 parts by
weight per 100 parts by weight of the main polymer. At a content of
less than 30 parts by weight, the resulting product will not have
adequate initial thixotropic properties and handling convenience.
At a content in excess of 300 parts by weight, the resulting
product will exhibit viscosity increase to detract from handling
convenience.
[0119] Next, the silicon containing compounds having ketimine
group; its production process; and the one-part, room temperature
moisture curable resin compositions which comprises such silicon
containing compound according to the second aspect of the present
invention are described.
[0120] The silicon containing compounds having ketimine group of
the present invention is the compounds represented by the following
formula (9) or (10). 14
[0121] In formula (9), R.sup.5 represents an alkyl group containing
1 to 6 carbon atoms, an alkoxy group containing 1 to 6 carbon
atoms, or a monovalent siloxane derivative. Exemplary alkyl groups
containing 1 to 6 carbon atoms include, methyl group, ethyl group,
and propyl group; exemplary alkoxy groups containing 1 to 6 carbon
atoms include methoxy group, ethoxy group and propyloxy group; and
exemplary monovalent siloxane derivatives include silyloxy group.
Among these, the preferred are methyl group, methoxy group and
ethoxy group.
[0122] R.sup.6 represents a divalent hydrocarbon group containing
nitrogen atom, or a divalent hydrocarbon group containing no
nitrogen atom. Such hydrocarbon groups are preferably those
containing 1 to 6 carbon atoms. Exemplary divalent hydrocarbon
groups containing no nitrogen atom include methylene group ethylene
group, and propylene group and exemplary divalent hydrocarbon
groups containing nitrogen atom include those mentioned above for
the divalent hydrocarbon group containing no nitrogen atom which
also contain imino group. Among such groups, the preferred are
propyl group and ethylpropylamino group.
[0123] R.sup.7 represents methyl group, ethyl group or isopropyl
group.
[0124] R.sup.1 represents a alkyl group containing 1 to 6 carbon
atoms such as methyl group, ethyl group or propyl groups, and
R.sup.1 is the same as the groups defined by R.sup.1 in the first
aspect of the present invention.
[0125] R.sup.2 represents methyl group or ethyl group, and R.sup.2
is the same as the groups defined by R.sup.2 in the first aspect of
the present invention.
[0126] R.sup.3 represents hydrogen atom, methyl group or ethyl
group, and R.sup.3 is the same as the groups defined by R.sup.3 in
the first aspect of the present invention.
[0127] Q represents an integer of at least 1, and preferably, an
integer of 1 to 50.
[0128] In the silicone compound of the present invention having the
structure represented by formula (9) in the backbone, the siloxane
bond constituting the backbone may have in its terminal hydrogen
atom; an alkyl group containing 1 to 6 carbon atoms such as methyl
group, ethyl group, or propyl group; an alkoxy group containing 1
to 6 carbon atoms such as methoxy group, ethoxy group, or propioxy
group; or a monovalent siloxane derivative such as silyloxy
group.
[0129] In formula (10), R.sup.1 to R.sup.3 and R.sup.5 to R.sup.7
are the same as R.sup.1 to R.sup.3 and R.sup.5 to R.sup.1 defined
for formula (7). R.sup.8 is a monovalent siloxane derivative. An
example of such monovalent siloxane derivative is silyloxy group.
Among these, the preferred are methyl group, methoxy group and
ethoxy group. m is an integer of 1 to 3.
[0130] Of the silicon containing compounds having ketimine group
represented by the formula (9) or (10), the silicon containing
compounds wherein R.sup.1, R.sup.2 and R.sup.7 are methyl group and
R.sup.3 is hydrogen atom or methyl group are preferable in view of
the well balanced shelf stability and curability of the one-part,
room temperature moisture curable resin composition prepared by
blending such compound with an epoxy resin.
[0131] The silicon containing compound having ketimine group
represented by the formula (9) or (10) is prepared by mixing a
silicon compound having amino group represented by formula (9) as
shown below with a ketone represented by formula (12) as shown
below; or alternatively, by mixing a silicon compound having no
amino group as described below in addition to the silicon compound
having amino group represented by formula (11), and stirring the
mixture under heating. The reaction temperature is preferably 50 to
150.degree. C., and the reaction time is preferably 2 to 24 hours.
15
[0132] In formula (11), R.sup.5, R.sup.6 and m are the same as the
R.sup.5, R.sup.6 and m defined for formula (9). R.sup.5 may be the
same or different with each other.
[0133] In formula (12), R.sup.1, R.sup.2, R.sup.3 and R.sup.7 are
the same as the R.sup.1, R.sup.2, R.sup.3 and R.sup.7 defined for
formula (9).
[0134] More illustratively, when equimolar amounts of the silicon
compound having amino group represented by formula (11) and the
ketone represented by formula (12) are stirred under heating, the
silicon compound having ketimine group of the present invention
represented by formula (10) is formed through dehydration reaction.
16
[0135] Next, the released water hydrolyzes the alkoxysilyl group,
and the hydrolyzed alkoxysilyl group polymerizes to form the
silicone composition of the present invention having the structure
shown by formula (9) as its backbone skeleton. 17
[0136] The silicon compound represented by formula (11) may
comprise any silicon compound having amino group in its molecule,
and use of a silicon compound having both amino group and
alkoxysilyl group is preferable. Exemplary such silicon compounds
include the compound represented by formulae (13) to (20). 18
[0137] Among these, the silicon compounds represented by formulae
(13) to (16) are universal silane coupling agents which are
favorably used, and use of such silicon compounds is
preferable.
[0138] In the reaction between the silicon compound represented by
formula (11) and the ketone represented by formula, (12), an
alkoxysilane having no amino group may also be added to the
reaction system for simultaneous reaction. Although such
alkoxysilane having no amino group may be added in any amount,
addition in a molar amount of up to 5 times, and preferably up to 2
times the amount of the silicon compound represented by formula
(11) is preferred in view of the physical properties of the cured
product.
[0139] Any silicon compound having an alkoxysilyl group may be used
for the alkoxysilane having no amino group. Exemplary silicon
compounds include the compounds represented by the following
formula. 19
[0140] Examples of the ketone represented by formula (12) include
methyl isopropyl ketone, methyl t-butyl ketone, and diisopropyl
ketone. Among these, methyl isopropyl ketone and methyl t-butyl
ketone are most preferable since they are easily converted into
ketimine in the reaction with the silicon compound represented by
formula (11) and the thus formed ketimine group is easily
hydrolyzed, and the resulting product has excellent curability and
shelf stability.
[0141] Such ketone reacts with the silicon compound represented by
formula (11), and imparts bulkiness to the ketimine group formed by
the reaction near its nitrogen atom, and the reaction of the
nitrogen atom of the ketimine group and the epoxy compound is
prevented by the steric hindrance effects of the bulky group.
[0142] Therefore, when the silicon containing compound having such
molecular structure is stored after mixing with the epoxy resin,
the resulting product exhibits high curability once taken out of
the container as well as excellent shelf stability.
[0143] In the sealants wherein a modified silicone is blended, use
of a dehydrating agent such as vinylsilane has been required for
the purpose of maintaining the shelf stability as described for the
first aspect of the present invention. Use of the silicon
containing compound as described above for the latent catalyst
enables the production of a resin composition which exhibits good
shelf stability as well as high curing rate without blending the
dehydrating agent such as vinylsilane.
[0144] In the conventional reaction for synthesizing an
organosilicon compound having ketimine group, polymerization of the
alkoxysilyl group induced by the water released upon ketimine
formation has been suppressed by using a dehydrating agent. In
contrast, in the above-described method for producing the silicon
containing compound of the present invention represented by
formulae (9) and (10), the water generated is utilized in the
hydrolysis of the alkoxysilane moiety of the molecule. As a
consequence, in the production of the silicon containing compound
according to the present invention, the resulting silicon
containing compound having the ketimine group does not undergo
gelation, and a polyfunctional ketimine is readily produced.
[0145] Next, the one-part, room temperature moisture curable resin
composition containing the silicon containing compound having the
ketimine as described above and an epoxy resin and/or a modified
silicone having at least two hydrolyzable alkoxysilyl groups in its
molecule (hereinafter referred to as the resin composition
according to second aspect of the present invention) is
described.
[0146] In the present invention, either or both of the silicone
compound represented by the formula (9) and the silicon compound
represented by the formula (10) may be used.
[0147] The epoxy resin used in the second aspect of the present
invention is not particularly limited as long as it is an epoxy
resin having at least two epoxy groups in its molecule, and an
epoxy resin the same as the one used in the first aspect of the
present invention may be used.
[0148] The modified silicone used in the second aspect of the
present invention is not particularly limited as long as it is a
silicone resin having at least two hydrolyzable alkoxysilyl groups
in its molecule, and a modified silicone the same as the one used
in the first aspect of the present invention may be used.
[0149] The epoxy resin and the modified silicone resin are
hereinafter referred to as the main polymer. Such main polymer is
the same as the main polymer described in the first aspect of the
present invention. The main functional group of the main polymer is
the epoxy group in the case of the epoxy resin, and the alkoxysilyl
group in the case of the modified silicone. The main functional
group of the main polymer is also the same as the one in the first
aspect of the present invention.
[0150] The silicon containing compound according to the second
aspect of the present invention may be added in the epoxy resin
composition according to the second aspect of the present invention
in an equivalent ratio of (imino group in the silicon containing
compound) : (the main functional group of the main polymer) of 0.01
to 1, and preferably, 0.1 to 0.5. Addition in an amount outside
such range results in poor curability.
[0151] The resin composition according to the second aspect of the
present invention can be prepared by mixing the main polymer and
the silicon containing compound having ketimine group according to
the second aspect of the present invention in nitrogen atmosphere,
and as in the case of the first aspect of the present invention,
the resin composition may be prepared by incorporating optional
curing accelerator such as a phosphorous ester.
[0152] Next, the method for producing a silicone compound having
epoxy group, a ketimine group, and an alkoxysilyl group in its
molecule from an alkoxysilane having epoxy group in its molecule
and alkoxysilane having amino group in its molecule and a ketone;
and a one-part, room temperature moisture curable resin composition
which comprises the silicone compound produced by such production
method and an epoxy resin and/or a modified silicone having
hydrolyzable alkoxysilyl groups within its molecule according to
the third aspect of the present invention are described.
[0153] In the method for producing a silicone compound according to
the third aspect of the present invention, an alkoxysilane having
epoxy group in its molecule, an alkoxysilane having amino group in
its molecule, and a ketone is mixed and the mixture is stirred
under heating. The ketone is added in an amount such that the
ketone is present at the same equivalent with or in excess of the
amino group, and more preferably, in an amount of at least 1.2
equivalents of the amino group. The reaction temperature is
preferably 50 to 150.degree. C., and more preferably, 70 to
110.degree. C. The reaction time is preferably 2 to 24 hours, and
more preferably, 2 to 5 hours. The excessive ketone and the
methanol generated are then removed under reduced pressure to
obtain the product of interest.
[0154] It should be noted that the alkoxysilane having the epoxy
group and the alkoxysilane having the amino group, are the
alkoxysilanes which may be used for silane coupling agents.
[0155] The reaction which is estimated to take place in the
silicone compound production method as described above is as
described below. When equimolar amounts of the silicon compound
having amino group and the ketone are mixed and stirred with
heating, an alkoxysilane having ketimine group and hydrolyzable
alkoxysilyl group is first generated by dehydration reaction. The
water released then hydrolyzes the alkoxysilyl group of the
alkoxysilane having ketimine group and hydrolyzable alkoxysilyl
group, and the alkoxysilyl group of the alkoxysilane having epoxy
group, and the hydrolyzed alkoxysilyl groups undergo
polymerization.
[0156] As a consequence, a silicone compound having epoxy group,
ketimine group, and an alkoxysilyl group in the same molecule is
produced in the silicone compound production method according to
the third aspect of the invention.
[0157] The alkoxysilane having epoxy group used in the silicone
compound production method according to the third aspect of the
invention is a compound having epoxy group and a hydrolyzable
alkoxysilyl group at the terminals of the molecule. The backbone of
the compound is an organic group mainly comprising a hydrocarbon
groups such as methylene group or ethylene group and also includes
a group containing O, S, or N.
[0158] The hydrolyzable alkoxysilyl group present at the terminal
of the molecule is a reactive silicon group wherein an alkoxy group
such as methoxy group or ethoxy group is bonded to the silicon
atom, and which may also have hydrogen atom, or an alkyl group such
as methyl group or ethyl group bonded thereto. The alkoxy group is
preferably methoxy group in view of its mild hydrolyzability and
handling convenience.
[0159] An exemplary alkokysilane is the one represented by the
following formula. 20
[0160] The alkoxysilane having amino group in its molecule used in
the production of the silicone compound according to the third
aspect of the present invention is a compound which has amino group
and a hydrolyzable alkoxysilyl group in the terminals of the
molecule. The backbone may comprise an organic group which may
contain N, such as an alkylene group such as an ethylene group or a
propenylene group. Exemplary such alkoxysilanes include those
represented by formulae (13) to (20) mentioned for the second
aspect of the present invention.
[0161] An exemplary silicone compound produced by the production
method of the silicone compound according to the third aspect of
the present invention is the one represented by the following
formula (21). 21
[0162] Epoxy group and amino group readily undergo reaction with
each other, and copresence of such functional groups in unreacted
states in the same reaction system has been impossible. In view of
such situation, an attempt has been made wherein the amino group
has been converted into ketimine for copresence with the epoxy
group. The epoxy resin composition containing such compound,
however, suffered from poor shelf stability, and there has been so
far no compound wherein both functional groups are included at the
same time.
[0163] In the silicone compound according to the third aspect of
the present invention, epoxy group, ketimine group, and alkoxysilyl
group are copresent in the same molecule in a stable condition.
Therefore, when such silicone compound is used for the curing
agents, the resulting resin composition exhibits fast curing and
good shelf stability, and such resin composition is favorable for
use as an adhesive.
[0164] In particular, the silicone compound obtained by using the
ketone of severe steric hindrance as shown in the formula (1) for
the material of ketimine group synthesis is preferable for use as a
curing agent, and when used as a curing agent, it realizes
remarkably favorable balance between the shelf stability and the
curability.
[0165] Next, the one-part curable resin composition containing a
silicone compound according to third aspect of the present
invention is described.
[0166] This resin composition is a one-part, room temperature
moisture curable resin composition containing epoxy resin and/or a
modified silicone containing at least two hydrolyzable alkoxysilyl
group in the molecule; and the silicone compound as described
above.
[0167] The epoxy resin or the modified silicone contained in the
one-part curable resin composition containing a silicone compound
according to the third aspect of the present invention may be the
same as the epoxy resin and the modified silicone used in the first
and second aspects of the present invention.
[0168] The silicone compound may be blended in an equivalent ratio
of (imino group in the silicon compound): (the main functional
group of the main polymer and the silicone compound) of 0.01 to 1,
and preferably, 0.1 to 0.5. Addition in an amount outside such
range results in poor curability.
[0169] The one-part curable resin composition according to the
third aspect of the present invention can be prepared by mixing the
epoxy resin and/or the modified silicone with the silicone compound
having epoxy group, ketimine group, and alkoxysilyl group in the
same molecule in nitrogen atmosphere.
[0170] The one-part curable resin composition containing a silicone
compound as a latent catalyst according to the third aspect of the
invention exhibits good shelf stability, and in particular, the
composition having epoxy resin and a modified silicone blended
thereto exhibits improved adhesion compared to conventional
one-part curable resin composition of modified silicone type which
suffered from poor adhesion to concrete and mortar. Since the resin
composition has a modified silicone blended therein, the resin
composition has a flexibility higher than the resin composition
solely containing the epoxy resin. In addition, in the one-part
sealant employing a modified silicone, a dehydrating agent such as
vinylsilane has been necessary for the purpose of maintaining the
shelf stability as described for the first aspect of the present
invention. Use of the silicone compound as described above for the
latent catalyst enables the production of a resin composition which
exhibits good shelf stability as well as high curing rate without
blending the dehydrating agent such as vinylsilane.
[0171] In addition to the critical compounds as described above,
the resin compositions according to the first to the third aspects
of the present invention may have blended therewith a filler, a
plasticizer, a thixotropic agent, a pigment, a dye, an anti-aging
agent, an antioxidant, an antistatic agent, a flame retardant, a
tackifier, a dispersing agent, a solvent, and the like in an amount
that does not hinder the objects of the present invention,
[0172] Exemplary fillers which may be used in the present invention
include organic and inorganic fillers of various forms such as
fumed silica, calcined silica, precipitated silica, powdered
silica, and molten silica; diatomaceous earth; iron oxide, zinc
oxide, titanium oxide, barium oxide, and magnesium oxide; calcium
carbonate, magnesium carbonate and zinc carbonate; talc clay,
kaolin clay, and calcined clay; carbon black; and any of the
foregoing treated by a fatty acid, a resin acid, a fatty acid ester
and the like.
[0173] The filler may be blended in all of the first to the third
aspect of the present invention in an amount of 30 to 300 parts by
weight, and preferably 80 to 200 parts by weight per 100 parts by
weight of the main polymer in consideration of the physical
properties of the cured product produced after the curing of the
resin composition of the present invention.
[0174] Exemplary plasticizers which may be used in the present
invention include dioctyl phthalate (DOP) dibutyl phthalate (DBP);
dioctyl adipate isodecyl malonate; diethylene glycol dibenzoate,
pentaerythritol ester; butyl oleate, methyl acetylricinoleate;
tricresyl phosphate and trioctyl phosphate; polypropylene glycol
adipate and polybutylene glycol adipate; and the like. These
plasticizers may be used alone or in combination of two or
more.
[0175] The plasticizer may be blended in all of the first to the
third aspect of the present invention in an amount of up to 100
parts by weight, and preferably up to 50 parts by weight per 100
parts by weight of the main polymer in consideration of the
physical properties of the cured product and handling
convenience.
[0176] Exemplary thixotropic agents which may be used in the
present invention include Aerosil (manufactured by Nippon Aerosil
K.K.) and Disparon (manufactured by Kusumoto Kasei K.K.), and
exemplary antistatic agents include common antistatic agents such
as quaternary ammonium salts, polyglycols, ethylene oxide
derivatives and other hydrophilic agents.
[0177] Both inorganic and organic pigments may be used in the
present invention. Exemplary inorganic pigments include titanium
dioxide, zinc oxide, ultramarine, red iron oxide, lithopone, lead,
cadmium, iron, cobalt, aluminum, hydrochloride, sulfate.
[0178] Exemplary organic pigments which may be used in the present
invention include azo pigments and copper phthalocyanine
pigments.
[0179] Exemplary anti-aging agents which may be used in the present
invention include hindered phenol-based compounds.
[0180] Exemplary antioxidants which may be used in the present
invention include butylated hydroxytoluene (BHT) and butylated
hydroxy anisole (BHA).
[0181] Exemplary flame retardants which may be used in the present
invention include chloroalkyl phosphate, dimethyl
methylphosphonate, bromine-phosphorus compounds, ammonium
polyphosphate, neopentylbromide polyether, and brominated
polyether.
[0182] Exemplary tackifier which may be used in the present
invention include terpene resin, phenol resin, terpene-phenol
resin, rosin resin, and xylene resin.
[0183] The method for producing the one-part, room temperature
moisture curable resin composition according to first to third
aspects of the present invention is not particularly limited.
However, the epoxy resin composition is preferably produced by
fully kneading the components as described above under reduced
pressure, and in particular, in nitrogen atmosphere of reduced
pressure by using an agitator such as a mixer to thereby uniformly
disperse the components.
[0184] Next, the method of ketimine synthesis according to the
fourth aspect of the present invention is described.
[0185] A ketimine compound is produced by a dehydration reaction
from an amine and a ketone. This reaction, however, is an
equilibrium reaction, and promotion of the reaction in the final
stage and completion of the reaction has been difficult. Therefore,
the amine which failed to react remained, and the one-part moisture
curable resin composition which employed the ketimine compound
containing the unreacted amine for the latent curing agent suffered
from the drawback of poor shelf stability.
[0186] The method of ketimine synthesis according to fourth aspect
of the present invention is a production method which has obviated
such problem.
[0187] The method of ketimine synthesis according to fourth aspect
of the present invention include two exemplary processes. The first
process is the process of ketimine compound synthesis characterized
in that a ketone and a polyamide are reacted, and then, an
isocyanate group-containing compound represented by the following
formula: 22
[0188] wherein R.sup.4 is an organic group (including the group
having O, S and N) is added.
[0189] In this first process, a compound having an isocyanate group
with severe steric hindrance is added to the reaction system in the
final step so that the amine which failed to react remaining after
the reaction of the ketone with the polyamide is capped by the
isocyanate compound. As a consequence, the resin compositions
having blended therein the ketimine compound produced by this
production process exhibit good shelf stability and curability.
[0190] Preferable examples of the isocyanate group-containing
compound represented by the above-mentioned formula employed in the
first process include TMXDI, TMI, Scisen and the like manufacture
by Mitsui Scitech K.K.
[0191] The isocyanate group-containing compound is preferably
blended in an amount such that equivalent of the isocyanate group
will be the same as the unreacted amino group.
[0192] The second process is the process of ketimine compound
synthesis characterized in that a ketone and a polyamide are
reacted, and then, a silane coupling agent is added as a
dehydrating agent. More illustratively, in the equilibrium reaction
wherein the polyamine and the ketone are reacted to produce the
ketimine, the water generated in the dehydration reaction between
the polyamine and the ketone is dehydrated and removed by the
silane coupling agent to thereby shift the equilibrium to the
direction of ketimine synthesis and complete the reaction.
[0193] The silane coupling agent used in this second process may be
the same as the one used for the first aspect of the present
invention.
[0194] The silane coupling agent may be blended at an amount of 1
to 3 times the molar amount of the unreacted amine. The silane
coupling agent of the amount within such range is capable of
effectively dehydrating and removing the water in the system.
[0195] The first and the second processes as described above may be
carried out at once. That is, the ketone and the polyamine may be
reacted to induce the dehydration reaction, and the silane coupling
agent may be added as a dehydrating agent for the removal of the
water in the reaction system to thereby shift the equilibrium to
the direction of ketimine synthesis and the reaction completion.
Then, the compound having an isocyanate group with severe steric
hindrance may be added to the reaction system so that the amine
which failed to react remaining in the reaction system can be
capped by such isocyanate compound.
[0196] In the first and the second processes as described above,
the ketone and the polyamine used in the ketimine production are
preferably the ketone represented by the above formula (1) with a
severe steric hindrance having a substituent at the .alpha.
position and the polyamine represented by the formula (2) having at
least two amino groups in its molecule wherein the .alpha. position
is methylene, respectively. The ketimine produced by the ketimine
production process as described above using such ketone and such
polyamine will be favorably used as a latent curing agent having
excellent shelf stability and curability.
[0197] Industrial Utility Field
[0198] As evident from the above description, the one-part, room
temperature moisture curable resin compositions according to first
to third aspect of the present invention are compositions which
exhibit good shelf stability, quick curing once taken out of the
container, well balanced properties, and in some cases,
flexibility, and are effective for use as adhesives for concretes,
woods, metals and the like, and as sealants. The resin composition
containing a ketimine synthesized from a polyamide amine, the resin
composition containing an epoxy resin including sulfur atom in its
skeleton, and a one-part, room temperature moisture curable resin
composition containing a silane coupling agent which are within the
scope of the first aspect of the present invention exhibit not only
the excellent shelf stability and curability but also excellent wet
surface adhesion, and therefore, these composition can be favorably
used as adhesives for a wide variety of materials such as
concretes, woods and metals irrespective of whether the surface to
be adhered is wet or dry. The resin composition containing surface
treated calcium carbonated and a ketimine of low polarity exhibits
not only the excellent shelf stability and curability but also
excellent initial thixotropy properties, and therefore, such resin
composition is excellent for use as an adhesive.
[0199] The silicon containing compound according to second aspect
of the present invention renders excellent shelf stability and high
curing rate when it is used as a latent curing agent or a latent
catalyst for a one-part epoxy resin or a modified silicone. In
particular, the silicon containing compound of the present
invention synthesized by using a ketone with severe steric
hindrance is especially useful as a latent curing agent for fast
curing of a one-part epoxy resin and as a latent catalyst for a
modified silicone. Therefore, the silicon containing compound of
the present invention is useful as a latent curing agent of an
epoxy based adhesive or a sealant in the field of civil engineering
and architecture, and as a coupling agent for various
adhesives.
[0200] The method for producing a silicone compound according to
third aspect of the present invention is capable of readily
producing a compound which has epoxy group, a ketimine group, and
an alkoxysilyl group in one molecule. The resin composition
containing the silicone compound according to the third aspect of
the present invention as the curing agent exhibits high curing rate
and excellent shelf stability, and therefore, favorable for use as
an adhesive and the like.
[0201] In the method for synthesizing a ketimine according to
fourth aspect of the present invention, a ketone and a polyamine
used for the ketimine synthesis react with each other to enable the
synthesis of a ketimine of high shelf stability at a high
efficiency.
EXAMPLES
[0202] Next, the present invention is described in further detail
by referring to Examples which by no means limit the scope of the
present invention.
[0203] <Synthesis of Ketimine Compounds>
[0204] (Synthesis 1)
[0205] A flask was charged with 100 g of a diamine having polyether
skeleton (JEFFAMINE EDR148*.sup.1, manufactured by Sun
Technochemical Inc.), 189 g of methyl isopropyl ketone (3.6
equivalents of the diamine), and 200 g of toluene, and the water
produced was removed by azeotropic distillation. The reaction was
allowed to take place for 20 hours to obtain ketimine compound
A.
[0206] (Synthesis 2)
[0207] The procedure of the Synthesis 1 was repeated except that
220 g of methyl t-butyl ketone was used for the ketone, and
ketimine compound B was obtained after 50 hours.
[0208] (Synthesis 3)
[0209] The procedure of the Synthesis 1 was repeated except that
100 g of 1,3-bisaminomethylcyclohexane (1,3-BAC, manufactured by
Mitsubishi Gas Chemical Company, Inc.) was used for the amine, and
254 g of methyl isobutyl ketone was used for the ketone, and
ketimine compound D was obtained after 24 hours.
[0210] (Synthesis 4)
[0211] The procedure of the Synthesis 1 was repeated except that
100 g of a diamine having PPG skeleton (JEFFAMINE D230*.sup.3,
manufactured by Sun Technochemical Inc.) was used for the amine,
and 157 g of methyl isobutyl ketone was used for the ketone, and
ketimine compound E was obtained after 50 hours.
[0212] (Synthesis 5)
[0213] The procedure of the Synthesis 1 was repeated except that
100 g of a diamine having norbornane skeleton (NBDA*.sup.4,
manufactured by Mitsui Toatsu Chemicals K.K.) was used for the
amine, and 200 g of methyl isopropyl ketone was used for the
ketone, and ketimine compound F was obtained after 20 hours.
[0214] (Synthesis 6)
[0215] The procedure of the Synthesis 1 was repeated except that
100 g of 1,3-bisaminomethylcyclohexane (1,3-BAC*.sup.2,
manufactured by Mitsubishi Gas Chemical Company, Inc.) was used for
the amine, and 200 g of methyl isopropyl ketone was used for the
ketone, and ketimine compound G was obtained after 20 hours.
[0216] (Synthesis 7)
[0217] The procedure of the Synthesis 1 was repeated except that
100 g of a diamine having norbornane skeleton (NBDA*.sup.4,
manufactured by Mitsui Toatsu Chemicals K.K.) was used for the
amine, and 200 g of methyl isobutyl ketone was used for the ketone,
and ketimine compound H was obtained after 20 hours.
[0218] (Synthesis 8)
[0219] The procedure of the Synthesis 1 was repeated except that
100 g of a diamine having norbornane skeleton (NBDA*.sup.4,
manufactured by Mitsui Toatsu Chemicals K.K.) was used for the
amine, and 200 g of methyl t-butyl ketone was used for the ketone,
and ketimine compound I was obtained after 30 hours.
[0220] (Synthesis 9)
[0221] The procedure of the Synthesis 1 was repeated except that
100 g of methaxylylenediamine (MXDA, manufactured by Mitsubishi Gas
Chemical Company, Inc.) was used for the polyamine, and 190 g of
methyl isopropyl ketone was used for the ketone, and ketimine
compound J was obtained after 20 hours.
[0222] (Synthesis 10)
[0223] The procedure of the Synthesis 1 was repeated except that
100 g of methaxylylenediamine (MXDA, manufactured by Mitsubishi Gas
Chemical Company, Inc.) was used for the polyamine, and 216 g of
methyl t-butyl ketone was used for the ketone, and ketimine
compound K was obtained after 30 hours.
[0224] (Synthesis 11)
[0225] The procedure of the Synthesis 1 was repeated except that
100 g of polyamide amine (X2000, manufactured by SANWA CHEMICAL
PRODUCT LTD.) was used for the polyamine, and 180 g of methyl
isopropyl ketone was used for the ketone, and ketimine compound L
was obtained after 20 hours.
[0226] (Synthesis 12)
[0227] The procedure of the Synthesis 1 was repeated except that
100 g of polyamide amine (X2000, manufactured by SANWA CHEMICAL
PRODUCT LTD.) was used for the polyamine, and 200 g of methyl
t-butyl ketone was used for the ketone, and ketimine compound M was
obtained after 40 hours. 23
Examples 1 to 16 and Comparative Examples 1 to 3
[0228] The components were mixed at the blend ratio as shown in
Table 1 to produce the resin composition described in Examples 1 to
16 and Comparative Examples 1 to 3. The resin compositions were
evaluated, and the results of the evaluation are also shown in
Table 1.
1 TABLE 1 Examples 1 2 3 4 5 6 7 8 9 10 Epoxy resin 100 100 100 100
100 100 100 100 100 100 Calcium carbonate 100 100 100 100 100 100
100 50 20 100 Ketimine compound A 40 Ketimine compound B 43 43 43
43 43 Ketimine compound F 36 40 40 Ketimine compound G 32 Ketimine
compound I Ketimine compound D Ketimine compound E Ketimine
compound H Ketimine compound J Ketimine compound K Phosphorous
ester A 1.6 Phosphorous ester B 3.2 Silyl ester A 8.0 Silyl ester B
0.2 Toluene 20 Conc. of ketimine group 1.1 1.08 1.05 1.08 1.07 1.06
1.1 1.38 1.46 1.12 [mmol/g] Tack free time 5 h 15 h 8 h 8 h 11 h 10
h 1.8 h 2.5 h 3.0 h 1.8 h Viscosity increase [times] 1.0 1.0 1.1
1.2 1.2 1.2 1.1 1.5 1.3 1.1 Examples Comparative Examples 11 12 13
14 15 16 1 2 3 Epoxy resin 100 100 70 30 100 100 100 Modified
silicone 30 70 100 100 Calcium carbonate 100 100 100 100 100 100
100 100 100 Ketimine compound A Ketimine compound B Ketimine
compound F 26 13 30 8 Ketimine compound G Ketimine compound I
Ketimine compound D 43 Ketimine compound E 107 Ketimine compound H
33 Ketimine compound J 35 Ketimine compound K 39 Phosphorous ester
A Phosphorous ester B Silyl ester A Silyl ester B Toluene Conc. of
ketimine group 1.1 1.09 0.79 0.42 0.90 0.27 1.08 0.86 1.1 [mmol/g]
Tack free time 4 h 13 h 4 h 5 h 4 h 6 h 1.8 h 5 days 1.8 h
Viscosity increase [times] 1.0 1.0 1.1 1.1 1.1 1.0 >10 1.1
>10 The unit of the compounds in the Table is parts by
weight.
[0229] 1) Tack free time: Time required until polyethylene film no
longer adheres to the surface of the resin composition under the
conditions of 20.degree. C. and humidity of 55%.
[0230] 2) Viscosity increase: The resin composition was stored at
20.degree. C. for 1 day after its blending, and at 70.degree. C.
for another day, and the value determined by dividing the viscosity
after storage at 70.degree. C. by the viscosity after storage at
20.degree. C. for 1 day is designated the viscosity increase.
[0231] <Components in the Table>
[0232] Epoxy resin: ELA128 (manufactured by Sumitomo Chemical
Industry K.K.).
[0233] Modified silicone: MS polymer (manufactured by Kanegafuchi
Chemical K.K.)
[0234] Calcium carbide: Calfine 200 (manufactured by Maruo Calcium
K.K.)
[0235] Phosphorous ester A: JP360 (manufactured by Johoku Chemical
K.K.)
[0236] Phosphorous ester B: JPP31 (manufactured by Johoku Chemical
K.K.)
[0237] Silyl ester A: the compound represented by formula (22)
[0238] Silyl ester B: the compound represented by formula (23)
24
Examples 17 to 28 and Comparative Examples 4 to 6
[0239] The components were mixed at the blend ratio as shown in
Table 2 to produce the resin compositions described in Examples 17
to 28 and Comparative Examples 4 to 6. The resin compositions were
evaluated for their shelf stability and wet surface adhesion by the
procedures as described below. The results of the evaluation are
shown in Table 2.
[0240] 1) Viscosity Increase (Times)
[0241] The viscosity increase was evaluated by the procedure
similar to Examples 1 to 16 and Comparative Examples 1 to 3.
[0242] [Wet Surface Adhesion]
[0243] 2) Shear Stress at Break (kgf/cm.sup.2)
[0244] 2 mortar pieces of 5 cm.times.5 cm.times.2.5 cm were
immersed in water for 24 hours, and water on the surface was wiped
off. One piece of the mortar to an adhesion area of 5 cm.sup.2 was
coated with the resin composition described in Examples 17 to 28 or
Comparative Examples 4 to 6. To this mortar piece was adhered the
other mortar piece with pressure, and the mortar pieces were
secured to each other with a tape. Immediately after such adhesion,
the mortar pieces were again immersed in water such that one mortar
piece of the two mortar pieces was underneath the other, and bottom
half of the piece that is underneath the other piece was immersed
in water. The mortar pieces were allowed to cure for one week under
such condition, and the pair of two mortar pieces were used for the
test piece, which was evaluated for its shear stress at break by
applying shear deformation using biaxial shear tester.
[0245] 3) Matrix Damage (%)
[0246] Area of the test piece matrix that was damaged at break was
measured, and ratio of such area to the total adhesion area was
calculated.
2 TABLE 2 Examples 17 18 19 20 21 22 23 24 25 Epoxy resin A 100 100
100 100 100 100 100 100 100 Calcium carbonate 100 100 100 100 100
100 100 100 100 Ketimine compound A 40 Ketimine compound B Ketimine
compound F 40 40 40 40 40 Ketimine compound G 40 Ketimine compound
I Ketimine compound D Ketimine compound E Ketimine compound H
Ketimine compound L 45 Ketimine compound M 50 Epoxy silane 0.5 3.0
6.0 3.0 3.0 Vinyl silane 3.0 15 Viscosity increase [times] 1.1 1.1
1.1 1.1 1.0 1.1 1.1 1.3 1.2 Wet surface adhesion Shear stress
[kgf/cm.sup.2] 45 50 45 50 41 50 50 45 45 Matrix damage [%] 95 100
95 100 90 100 100 100 100 Examples Comparative Examples 26 27 28 4
5 6 Epoxy resin A 50 100 100 100 Epoxy resin B 50 100 100 Calcium
carbonate 100 100 100 100 100 100 Ketimine compound A Ketimine
compound B 25 Ketimine compound F 30 21 Ketimine compound G
Ketimine compound I Ketimine compound D Ketimine compound E
Ketimine compound H 40 40 40 Ketimine compound L Ketimine compound
M Epoxy silane 3.0 Vinyl silane 25 Viscosity increase [times] 1.1
1.1 1.0 >10 >10 >10 Wet surface adhesion Shear stress
[kgf/cm.sup.2] 45 47 47 50 30 10 Matrix destruction [%] 100 95 95
100 40 15 The unit of the compounds in the Table is parts by
weight.
[0247] <Components in the Table>
[0248] Epoxy resin A: ELA128 (manufactured by Sumitomo Chemical
Industry K.K.)
[0249] Epoxy resin B: Flep 10 (an epoxy resin which contains S in
its skeleton; manufactured by Toray Thiokol K.K.)
[0250] Calcium carbide: Calfine 200 (manufactured by Maruo Calcium
K.K.)
[0251] Epoxy silane: 3-glycidoxypropyltrimethoxysilane
[0252] Vinyl silane: trimethoxyvinylsilane
[0253] Next, Examples of the resin composition containing a
ketimine of low polarity and a surface treated calcium carbonate
are described. The components were mixed at the blend ratio as
shown in Table 3, below, to thereby produce the resin composition
described in Examples 29 to 31 and Comparative Examples 7 to 8. The
resin compositions were evaluated as described below.
3 TABLE 3 Comparative Examples Examples 29 30 31 7 8 Epoxy resin
100 100 100 100 100 Ketimine compound F 38 15 15 Ketimine compound
B 24 41 Ketimine compound I 40 24 Surface treated 100 100 100 100
100 calcium carbonate Initial thixotropy 6.7 7.3 7.5 Separation 5.2
index of curing Viscosity increase 1.2 1.1 1.0 agent 1.5 [times]
The unit of the compounds in the Table is parts by weight.
[0254] 1) Initial Thixotropy Index
[0255] Viscosity (cps) of the resin composition after its
preparation was measured under the condition of 1 rpm by using a BS
type viscometer. Viscosity (cps) of the resin composition after its
preparation was measured under the condition of 10 rpm was also
measure by a similar procedure. The thixotropy index was calculated
by dividing the viscosity at 1 rpm by the viscosity at 10 rpm.
[0256] 2) Viscosity Increase (Times)
[0257] The viscosity increase was evaluated by the procedure
similar to Examples 1 to 16 and Comparative Examples 1 to 3.
[0258] The results are'shown in Table 3.
[0259] Next, synthesis of silicon containing compounds which have a
ketimine group, and Examples of the epoxy resin compositions
containing such silicon containing compound and an epoxy resin are
described.
[0260] <Synthesis of Silicon Containing Compounds which has a
Ketimine Group>
[0261] (Synthesis 13)
[0262] A flask was charged with 100 g of
.gamma.aminopropyltrimethoxysilan- e (manufactured by Nippon Uniker
K.K.) and 96 g of methyl isopropyl ketone (manufactured by Kuraray
K.K.), and the mixture was stirred at 110.degree. C. for 2 hours.
The methanol that was produced and the excessive methyl isopropyl
ketone were removed under reduced pressure to obtain silicon
containing compound A which has a ketimine group.
[0263] (Synthesis 14)
[0264] The procedure of the Synthesis 13 was repeated except that
100 g of .gamma.-aminopropyltrimethoxysilane (manufactured by
Nippon Uniker K.K.) and 112 g of methyl t-butyl ketone
(manufactured by Shell Japan K.K.) were used to obtain silicon
containing compound B which has a ketimine group.
[0265] (Synthesis 15)
[0266] The procedure of the Synthesis 13 was repeated except that
100 g of .gamma.-aminopropyltrimethoxysilane (manufactured by
Nippon Uniker K.K.), 27.6 g of vinyltrimethoxysilane (manufactured
by Nippon Uniker K.K.), and 96 g of methyl isopropyl ketone
(manufactured by Kuraray K.K.) were used to obtain silicon
containing compound C which has a ketimine group.
[0267] (Synthesis 16)
[0268] The procedure of the Synthesis 13 was repeated except that
100 g of .gamma.-aminopropyltrimethoxysilane (manufactured by
Nippon Uniker K.K.), 46.9 g of tetraethoxysilane (manufactured by
Shin-Etsu Chemical K.K.), and 96 g of methyl isopropyl ketone
(manufactured by Kuraray K.K.) were used to obtain silicon
containing compound D which has a ketimine group.
[0269] (Synthesis 17)
[0270] The procedure of the Synthesis 13 was repeated except that
100 g of .gamma.-aminopropyltrimethoxysilane (manufactured by
Nippon Uniker K.K.) and 112 g of methyl isobutyl ketone were used
to obtain silicon containing compound E which has a ketimine
group.
Examples 32 to 39 and Comparative Examples 9 to 12
[0271] To 100 parts by weight of a main polymer comprising an epoxy
resin (ELA128, manufactured by Sumitomo Chemical Industry K.K.)
and/or a modified silicone (MS polymer, manufactured by Kanegafuchi
Chemical K.K.) was blended the silicon containing compound which
had been synthesized as described above at the proportion as
described in Table 4, below, to produce one-part epoxy resin
compounds. The thus produced resin compounds were evaluated for
their tack free time and shelf stability by the procedure similar
to Examples 1 to 16. It should be noted that the silicon containing
compound F in Table 4 is represented by the following chemical
structural formula.
[0272] The results are shown in Table 4. 25
4 TABLE 4 Comparative Comparative Examples Examples Examples
Examples 32 33 34 35 1 2 36 37 38 39 11 12 Epoxy resin 100 100 100
100 100 100 30 Modified silicone 100 100 100 70 100 100 Si
containing compound A 53 5 20 30 Si containing compound B 57 20 Si
containing compound C 60 Si containing compound D 60 Si containing
compound E 56 Si containing compound F 56 Tin catalyst 2 2 Vinyl
silane 3 Calcium carbonate 100 100 100 100 100 100 Tack free time
[h] 10 13 10 10 10 >24 6 3 3 2 4 4 Viscosity increase [times]
1.1 1.0 1.1 1.1 x*.sup.1 10 1.1 1.2 1.1 1.2 1.2 x*.sup.2 The unit
of the compounds in the Table is parts by weight.
*.sup.1Unmeasurable because of increase in viscosity.
*.sup.2Unmeasurable because of curing.
[0273] <Components in the Table>
[0274] Epoxy resin A: ELA128 (manufactured by Sumitomo Chemical
Industry K.K.)
[0275] Modified silicone: MS polymer (manufactured by Kanegafuchi
Chemical K.K.)
[0276] Tin catalyst: tin dibutyl laurate
[0277] Calcium carbide: Calfine 200 (manufactured by Maruo Calcium
K.K.)
[0278] Vinyl silane: trimethoxyvinylsilane
Examples 40 to 42 and Comparative Examples 13 to 15
[0279] An epoxy resin (ELA128, manufactured by Sumitomo Chemical
Industry K.K.), a modified silicone (MS polymer, manufactured by
Kanegafuchi Chemical K.K.), ketimines X and Y synthesized in the
synthesis examples as described below, ketimine Z represented by
the formula below (H-3, manufactured by Yuka Shell Epoxy K.K.) and
other additives were blended at the proportion as shown in Table 6
to produce the resin compositions. The resin compositions were
evaluated for their tensile strength, mode of breakage, and shelf
stability. The results are shown in Table 5. It should be noted
that the compounds in the Table were the same as those shown in
Table 5.
[0280] (Synthesis 19) A flask was charged with 200 g of
3-glycidoxypropyltrimethoxysilane (A187, manufactured by Nippon
Uniker K.K.), 152 g of .gamma.-aminopropyltrimethoxysilane (A1110,
manufactured by Nippon Uniker K.K.) and 200 g of methyl isopropyl
ketone, and the mixture was stirred at 110.degree. C. for 4 hours.
Excessive methyl isopropyl ketone and methanol were removed to
obtain ketimine X.
[0281] (Synthesis 20)
[0282] The procedure of Synthesis 20 was repeated except that 200 g
of methyl t-butyl ketone was used instead of the 200 g of methyl
isopropyl ketone to produce ketimine Y.
[0283] 1) Tensile Strength
[0284] Tensile strength was evaluated in accordance with the
procedure described in JIS K 6911. The unit is (kg/cm.sup.2).
[0285] 2) Mode of Breakage
[0286] Mode of breakage was evaluated by observing the site of
breakage with naked eye.
[0287] 3) Shelf Stability
[0288] Shelf stability was determined by the procedure similar to
Examples 1 to 16. 26
5 TABLE 5 Compara- tive Comparative Exam- Exam- Examples Examples
ple ple 40 41 13 14 42 15 Modified silicone 100 100 100 100 70 70
Epoxy resin 30 30 Tin catalyst 1.5 1.5 Ketimine X 40 40 Ketimine Y
40 Ketimine Z 40 Vinyl silane 2 Calcium carbonate 100 100 100 100
100 100 Tensile strength 20 20 5 6 35 25 [kg/.sup.2cm.sup.2] Mode
of breakage cf cf af af cf cf Viscosity 1.1 1.1 Cured 1.2 1.2 Cured
increase [times]
[0289] The unit of the compounds in the Table is parts by
weight.
[0290] cf: Breakage of matrix
[0291] af: Delamination at the boundary
[0292] <Components in the Table>
[0293] Epoxy resin: ELA128 (manufactured by Sumitomo Chemical
Industry K.K.)
[0294] Modified silicone: MS polymer (manufactured by Kanegafuchi
Chemical K.K.)
[0295] Tin catalyst: tin dibutyl laurate
[0296] Calcium carbide: Calfine 200 (manufactured by Maruo Calcium
K.K.)
[0297] Vinyl silane: trimethoxyvinylsilane
[0298] Next, synthesis of ketimines prepared by blending isocyanate
group with severe steric hindrance or a silane coupling agent as a
dehydration agent are described. The resulting ketimine was blended
with an epoxy resin (ELA128, manufactured by Sumitomo Chemical
Industry K.K.) to evaluate their shelf stability by the procedure
similar to Examples 1 to 16. The results are shown in Table 6.
[0299] (Synthesis 21)
[0300] A flask was charged with 100 g of a diamine having polyether
skeleton (JEFFAMINE EDR-148, manufactured by Sun Technochemical
Inc.), 189 g of methyl isopropyl ketone (3.6 equivalents of the
diamine), and 200 g of toluene, and the water produced was removed
by azeotropic distillation. The reaction was allowed to take place
for 15 hours to obtain ketimine B.
[0301] (Synthesis 22)
[0302] The procedure of Synthesis 21 was repeated except that,
after the completion of the reaction, the solvent was removed, 5 g
of vinyltrimethoxysilane and 10 g of methyl isopropyl ketone were
added, and the reaction mixture was stirred for another 2 hours at
120.degree. C. to thereby obtain ketimine A.
[0303] (Synthesis 23)
[0304] The procedure of the Synthesis 21 was repeated except that
100 g of a diamine having norbornane skeleton (NBDA, manufactured
by Mitsui Toatsu Chemicals K.K.) was used for the amine, and
ketimine D was obtained after 15 hours.
[0305] (Synthesis 24)
[0306] The procedure of Synthesis 23 was repeated except that,
after the completion of the reaction, the solvent was removed, 5 g
of vinyltrimethoxysilane and 10 g of methyl isopropyl ketone were
added, and the stirring was continued for another 2 hours at
120.degree. C. to thereby obtain ketimine C.
[0307] (Synthesis 25)
[0308] The procedure of Synthesis 23 was repeated except that,
after reacting for 15 hours, 10 g of magnesium sulfate was added,
and the stirring was continued for another 2 hours to thereby
obtain ketimine E.
[0309] (Synthesis 26)
[0310] The procedure of Synthesis 23 was repeated except that,
after reacting for. 15 hours, 10 g of zeolite was added, and the
stirring was continued for another 2 hours to thereby obtain
ketimine F.
[0311] (Synthesis 27)
[0312] The procedure of Synthesis 21 was repeated except that,
after reacting for 15 hours, 3 g of an isocyanate compound (TMXDI,
manufactured by Mitsui Scitech K.K.) was added to thereby obtain
ketimine G.
[0313] (Synthesis 28)
[0314] The procedure of Synthesis 21 was repeated except that,
after reacting for15 hours, 3 g of an isocyanate compound (TMI,
manufactured by Mitsui Scitech K.K.) was added to thereby obtain
ketimine H.
[0315] (Synthesis 29)
[0316] The procedure of Synthesis 21 was repeated except that,
after reacting for 15 hours, 3 g of an isocyanate compound (TDI,
manufactured by Mitsui Scitech K.K.) was added to thereby obtain
ketimine J.
Examples 43 to 46 and Comparative Examples 16 to 20
[0317] An epoxy resin (ELA128, manufactured by Sumitomo Chemical
Industry K.K.) and ketimines A to J synthesized in the synthesis
examples as described above were mixed at the proportion as shown
in Table 7, below, to produce the resin compositions. The resulting
resin compositions were evaluated for their content of unreacted
amine (% by weight) and shelf stability.
[0318] 1) Unreacted Amine (%)
[0319] Unreacted amine and ketimine compound were quantitated by
gas chromatography to calculate the unreacted amine (%). The
unreacted amine (%) is given by:
Unreacted amine (%)=(moles of unreacted amine compound)/(moles of
ketimine compound+moles of unreacted amine compound)
[0320] 2) Viscosity Increase (Times)
[0321] The viscosity increase was measured and evaluated by the
procedure similar to Examples 1 to 16.
6 TABLE 6 E*.sup.1 43 CE*.sup.216 E44 CE17 CE18 CE19 E45 E46 CE20
Ketimine compound Ketimine A Ketimine B Ketimine C Ketimine D
Ketimine E Ketimine F Ketimine G Ketimine H Ketimine I used
(Unreacted (0) (4) (0) (4) (2) (4) (0) (0) (0) amine, %) Epoxy
resin 100 100 100 100 100 100 100 100 100 Ketimine (of 40 40 38 38
38 38 38 38 38 the type as described above) Viscosity 1.1 5.5 2.0
15.0 9.0 20 1.2 1.2 6 increase of the epoxy resin blend [times] The
unit of the compounds in the Table is parts by weight *.sup.1E:
Example *.sup.2CE: Comparative Example
* * * * *