JPH03100022A - Polysiloxane oligomer, polisiloxane resin composition and curable resin composition - Google Patents

Abstract

PURPOSE:To improve the crosslinkability, compatibility, and resistance to water, chemicals, and weathering by reacting a specific silane compd. with a silane monomer. CONSTITUTION:70-99.99mol% silane compd. having a hydroxy and/or hydrolyzable group directly attached to Si (e.g. methyltrimethoxysilane) is reacted with 30-0.001mol% silane monomer having a hydroxyl and/or hydrolyzable group directly attached to Si and an NH2 and/or NH group [e.g. H5C2NHC3H6Si(OCH3)3] in the presence of an acidic or alkaline catalyst to give a polysiloxane oligomer having a number-average mol.wt. of 400-100000, on an average at least one NH2 and/or NH group in the molecule, and at least two hydroxyl and/or hydrolyzable groups directly attached to Si at the terminal of the molecule. Amino groups of the resulting oligomer are subjected to addition or condensation reaction with functional groups of a resin having silane groups and epoxy groups to give a polysiloxane resin compsn. having a number-average mol.wt. of 3000-200000, and hydroxyl and/or hydrolyzable groups and epoxy groups at the essential functional groups.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to novel polysiloxane oligomers, polysiloxane resin compositions, and curable resin compositions.

2. Prior Art Conventionally, in already known polysiloxanes, -NH,
Compounds having one group and one hydroxyl group or hydrolyzable group at the terminal equivalent portion (Si) have a drawback that it is difficult to form a crosslinked structure due to low reactivity. or having only a hydrolyzable group, -
Compounds that do not contain NH2 groups have the disadvantage that they do not have sufficient water resistance, chemical resistance, weather resistance, etc. because they are polymerized only by condensation, and they also have one -N8 group at both ends.
Compounds having two groups tend to gel during addition, making them difficult to handle and having the drawback of not being able to form grafts.

Problems to be Solved by the Invention The present invention aims to eliminate the above-mentioned drawbacks of conventionally known polysiloxanes.

Means for Solving the Problems The present inventor has developed polysiloxane using specific raw materials.
An average of one -NH2 and/or -NH- group per molecule, and a hydroxyl group and/or directly bonded to the silicon atom at the terminal corresponding portion.
In the novel polysiloxane-based oligomer obtained by having a hydrolyzable group or a hydrolyzable group, the oligomer component does not gel when introduced into the resin, and can be crosslinked by condensation, thereby achieving the above-mentioned purpose. It was discovered that the following can be fully achieved, and the present invention was completed based on this finding.

That is, the present invention provides: [1] (A) A silane compound (hereinafter referred to as "silane group") having a hydroxyl group and/or a hydrolyzable group (hereinafter, these groups may be abbreviated as "silane group") directly bonded to a silicon atom. , referred to as "silane compound (A)") and (B) silane group, -N) (2 and/or -NH- group C
Hereinafter, these groups may be abbreviated as "amine groups."

) (hereinafter referred to as "silane monomer (B))", and each molecule has an average of 1 or more amino groups and an average of 2 silane groups at the terminal portion. (1) a polysiloxane-based resin composition in which the resin contains a silane group and an epoxy group as essential functional group components, and the silane group is introduced by the polysiloxane-based oligomer; (2) the aforementioned polysiloxane-based oligomer; The present invention relates to a curable resin composition containing a polysiloxane resin composition and one or more curing reaction catalysts selected from organometallic compounds, Lewis acids, protonic acids, and aluminum compounds.

In this specification, a hydrolyzable group directly bonded to a silicon atom is a group that is hydrolyzed by water or moisture to produce a hydroxysilane group. Examples of the group include those represented by the following general formula.

-0-R' (1)-
oc-R2(2) 3/-0-N=C(3) \4 3/-0-N
(4)\4 3 / -N
(5)\4-N-c-R3(6)4 In the formula, R1 is a C8-4 alkyl group, and R2-R4 are the same or different and represent a C1-8 alkyl group, aryl group, or aralkyl group.

In the general formula, the "alkyl group of 01 to 8" is
For example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secbutyl, te
Examples include rt-butyl, n-pentyl, iso-pentyl, n-octyl, iso-octyl and the like. "
Examples of the "aryl group" include phenyl, tolyl, xylyl, and the like. Also, "aralkyl group"
Examples include benzyl and phenethyl.

Moreover, in addition to the above-mentioned hydrolyzable groups bonded to the silicon atom, a -)S i -H group can be mentioned as a hydrolyzable group.

In the present invention, groups represented by the above general formulas (1) and (2) and hydroxysilane groups are preferred from the viewpoint of storage stability, curability, etc.

In this specification, the term "terminus-equivalent portion" means one or more silicon atoms located at the end of the polysiloxane oligomer.

The polysiloxane oligomer of the present invention has a main skeleton composed of siloxane bonds, and hydrocarbon groups, hydroxyl groups, hydrolyzable groups, etc. are directly bonded to the silicon atoms of this main skeleton, and amino groups are bonded indirectly. It is obtained by reacting the silane compound (A) with the silane monomer CB).

The silane compound (A) has an average of three silane groups in one molecule, and preferably has the general formula (7) % formula % (7) (wherein R6 is a hydrocarbon group, R8, R? and Ra represent a hydrolyzable group or a hydroxyl group.

In the above general formula (7), R6 is preferably an aliphatic hydrocarbon group having 1 to 8 carbon atoms (linear or branched), an aralkyl group, and an aryl group. , more preferably a methyl group and a phenyl group. Examples of the aliphatic hydrocarbon group having 1 to 8 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and the like. R
6, R7 and R'' may all be the same or may be partially or completely different.

As R6, R7 and R'', methoxy, ethoxy, propoxy, butoxy, hydroxyl, acetoxy and the like are particularly preferred.

Preferred specific examples of the silane compound (A) include methyltrimethoxysilane, phenyltrimethoxysilane, butyltrimethoxysilane, methyltriethoxysilane,
Methyltributoxysilane, phenyltrisilanol,
Examples include methyltrisilanol, methyltriacetoxysilane, phenyltonoacetoxysilane, and the like. Among these, methyltrimethoxysilane, phenyltrimethoxysilane, phenyltrisilanol, methyltonoacetoxysilane, phenyltriacetoxysilane, and the like are particularly preferred.

The silane monomer (B) is a monomer having a silane group and an amine group in one molecule. As the silane group, one having 1 to 3 silane groups in one molecule is preferable. As the amine group, one having 1 to 5, preferably 1 to 3 amine groups in one molecule is desirable.

Preferred specific examples of the silane monomer (B) include:
i (OC3Hs) 3H2NC3H8Si 0C4
H913HJCJs 5i (OCCHi) x H2NGSH65i (OHI s Hs HJCsHs 5i (QC:Hz)2 HJC48a Si [0CH1l 5HJCJs 5
ilOCtHsls HaNCJ4NHCaHa Si (OCRs) 5C
H1 H2NC2H4N)ICs)la 5i(OCRs)t
HJCJJHCtHJHCsHe 5ifOCHsls
H-NCONHCJs 5l(OCJa)s etc.-
Compounds having NH2 group or -N Hz group and -NH group: -NH such as HaC2NHCJs SlfOCHslm
Compounds having groups can be mentioned.

Among the above, the former -NH, group or -NH.

Compounds having a group and an -NH group are preferred.

The polysiloxane oligomer of the present invention can be obtained by mixing the silane compound (A) and the silane monomer (B) and reacting them. The mixing ratio of the silane compound (A) is based on the total amount of both components.
0 to 99.999 mol%, preferably 90 to 99.9 mol%, more preferably 95 to 99 mol%, silane monomer (B) 30 to 0.001 mol%, preferably 10
-0.1 mol%, more preferably 5-1 mol%. When the silane compound (A) is less than 70 mol%, gelation tends to occur easily;
If it exceeds mol%, it is not preferable because when it is used, polymerization mainly occurs through condensation, resulting in deterioration in water resistance, chemical resistance, weather resistance, etc.

The reaction between the silane compound (A) and the silane monomer (B) is carried out by dehydration condensation of the hydroxyl groups possessed by both components and the hydroxyl groups generated by hydrolysis of the hydrolyzable groups,
The desired oligomer is produced. At this time, depending on the reaction conditions, not only dehydration condensation may occur (but also some condensation due to elimination of hydrolyzable groups).

When the silane compound (A) and the silane monomer (B) both have a hydroxyl group directly bonded to the silicon atom, they can react without a solvent, but in an organic solvent that can dissolve the compound and is inert to the compound. It is preferable to carry out the dehydration condensation reaction under heating and stirring.

Organic solvents include hydrocarbon, ester, ketone,
Various alcohol-based solvents can be used.

When the silane compound (A) and/or the silane monomer (B) have a hydrolyzable group directly bonded to a silicon atom, it is preferable to hydrolyze it prior to condensation, usually by heating and stirring in the presence of water and a catalyst. By doing so, hydrolysis and condensation can be carried out. The amount of water used in this case is
Although not particularly limited, 0.1 per mole of hydrolyzable group
The amount is preferably mol or more; if it is less than 0.1 mol, the reaction of the compound may be reduced.

As a catalyst, an acid catalyst or an alkali catalyst can be used. Specifically, as an acid catalyst, hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, acrylic acid, methacrylic acid, etc. can be used, and as an alkali catalyst, hydroxide catalyst can be used. Sodium, triethylamine, ammonia, etc. can be used. The amount of the catalyst added is suitably within the range of 0.0001 to 5% by weight, preferably 0 and 1 to 0.1% by weight, based on the total amount of the silane compound (A) and silane monomer (B). There is.

The reaction temperature for the above reaction is usually about 20 to 180°C, preferably 50 to 120°C. Moreover, it is appropriate that the reaction time is usually about 1 to 40 hours.

In this reaction system, a water-soluble organic solvent may be added.The water-soluble organic solvent is effective for homogenizing the reaction system when an alcohol that is sparingly soluble in water is produced by condensation. Ester-based, ether-based, ketone-based, etc. can be preferably used.

In addition, in the production of the polysiloxane oligomer of the present invention, the silane compound (A) and the silane monomer (B)
In addition, four hydroxyl groups and/or
Alternatively, it may be used in combination with a tetraalkoxysilane to which a hydrolyzable group is bonded, or a dialkyldialkoxysilane to which two hydroxyl groups and/or hydrolyzable groups are bonded to a silicon atom. 20 mol%
Can be used together below.

The main skeleton of the polysiloxane oligomer of the present invention obtained by the reaction of the silane compound (A) and the silane monomer (B) is composed of siloxane bonds, and the structure of the main skeleton is mainly linear, Examples include a ladder (1 adder) type and a mixed type thereof. Among these, it is preferable to use one with a ladder-like structure or a mixed system with many ladder-like parts from the viewpoint of water resistance, heat resistance, light resistance, etc. Compound (A) and silane monomer = (
It can be arbitrarily selected depending on the mixing ratio with B) and the amount of water and acid catalyst.

In particular, the polysiloxane oligomer of the present invention has an average of one amine group per molecule, and an average of at least two or more hydroxyl groups and hydrolyzable groups bonded to the terminal portion. Naturally, the above-mentioned functional group may be bonded to a portion other than the terminal portion of the polysiloxane oligomer.

Further, the number average molecular weight of the polysiloxane oligomer of the present invention is usually in the range of about 400 to 100,000.
If you try to obtain a product with a molecular weight of less than 400, it tends to gel during the reaction between the silane compound (A) and the silane monomer (B), which is undesirable. When introduced into a resin, since the compatibility with the resin is poor, the amount of polysiloxane-based oligomer components that do not chemically bond with the resin increases, leading to a risk of poor coating performance.

The polysiloxane oligomer of the present invention has an average of one amino group per molecule and at least two or more hydroxyl groups and/or hydrolyzable groups in the terminal portion, so that the polysiloxane oligomer of the present invention utilizes the amino group to The component can be incorporated into other resins.

Furthermore, polymerization or a crosslinked structure can be obtained by condensation of hydroxyl groups and/or hydrolyzable groups.

The polysiloxane-based oligomer of the present invention has extremely favorable properties such as not gelling when the oligomer component is introduced into the resin, being able to form a graft body, and being easily crosslinked by condensation. The crosslinked product has excellent water resistance, chemical resistance, weather resistance, heat resistance, light resistance, abrasion resistance, water repellency, stain resistance, etc.

The polysiloxane oligomer of the present invention can introduce the polysiloxane oligomer component into other resins by utilizing the amino group in the molecule.

The resin into which the polysiloxane oligomer component is introduced is
A cured resin can be obtained by reacting functional groups of hydroxyl groups and/or hydrolyzable groups directly bonded to silicon atoms derived from the polysiloxane oligomer component, but preferably from the viewpoint of low temperature curability. It is a resin containing a functional group and an epoxy group as essential functional group components. As the epoxy group, an alicyclic epoxy group is preferable since a coating film with further excellent curability can be formed.

Next, a polysiloxane resin composition containing a silane group and an epoxy group will be explained.

Examples of polysiloxane resin compositions include a resin containing a silane group and an epoxy group in the same resin (■), a resin containing a dirane group (II), and a resin containing an epoxy group (IL+).
) can be used.

The types of resins (I) to (II+) may be appropriately selected from conventional resins without any particular limitations, such as vinyl resins, fluorine resins, polyester resins, alkyd resins, silicone resins, Examples include urethane resins, polyether resins, epoxy resins, and modified products thereof.

The polysiloxane oligomer component can be introduced into the resin by subjecting the amino groups in the polysiloxane oligomer component and the functional groups in the resin to an addition reaction or condensation reaction. The functional group in the resin is not particularly limited as long as it reacts with the amine group in the polysiloxane oligomer component, and for example, incyanate groups, carboxyl groups, epoxy groups, etc. can be used.

In addition, methods for introducing epoxy groups into resins include, for example, methods in which an epoxy group-containing polymerizable unsaturated monomer is used as a raw material to introduce them into the resin, and methods in which functional groups are introduced into the resin in advance. Next, a method of introducing an epoxy group by reacting an epoxy compound having an epoxy group with a complementary functional group that reacts with the functional group in the resin can be mentioned. In the latter method, functional groups in the resin and
Combinations with complementary functional groups in the epoxy compound include combinations of functional groups in the resin and complementary functional groups in the epoxy compound, such as hydroxyl group/isocyanate group, incyanate group/hydroxyl group, carboxyl group/epoxy group. This can be cited as a preferable example.

Resin (I) has an average number of silane groups or more, preferably an average of two or more silane groups in one molecule.1. In addition, it has an average of 1 or more epoxy groups, preferably an average of 2 or more epoxy groups in one molecule, and has a number average molecular weight of 3.000 to 200,000, preferably 5.000 to so, ooo. Desirably, if the number of the above-mentioned functional groups is less than the above-mentioned range, curability tends to be poor, which is undesirable.If the number average molecular weight is less than 3.000, weather resistance, chemical resistance, curability, etc. tend to decrease. On the other hand, if it is larger than 200.000, the viscosity of the resin composition becomes high and handling becomes difficult, which is not preferable.

Examples of the resin (1) include those listed below (1) and (2).

(1) An epoxy group-containing polymer obtained by polymerizing an epoxy group-containing polymerizable unsaturated monomer (a') and, if necessary, another polymerizable unsaturated monomer (b); A resin obtained by reacting a portion of the epoxy groups in the coalescence with a polysiloxane oligomer.

As the epoxy group-containing polymerizable unsaturated monomer (a), 1
Examples of zero polymerizable unsaturated groups, which are compounds having an epoxy group and a polymerizable unsaturated group in the molecule, include CH,=(1: (R') COO- CH2=CfRllll CC- 1 CH,=C( R') C-N-1CH,=CHCH, -0-CH,=CHO-CH2=CH- (in the formula, R9 represents a hydrogen atom or a methyl group), and the like.

Examples of the epoxy group-containing polymerizable unsaturated monomer having a polymerizable unsaturated group of CH2.C(RglCOO-) include compounds represented by the following general formulas (8) to (20).

(19) In each formula, R' has the same meaning as above, and R'' is 01 to
8 divalent hydrocarbon group, RII is CI-2° divalent hydrocarbon group, R'2 represents C1-4 hydrocarbon group or hydrogen atom, W represents 0 and an integer from 1 to 10. .

Examples of the above divalent hydrocarbon groups include -CH2-CH2CI+, -, -C11, -f; H, -CH2-
CH3 -CH5-CH-(:Ha-1-CH2-CH, -C-
CH2-CH2-CH, CH.

-(:611.,-,-C,,H,,-1-CIJ2
Examples include 4-5-C+-H5s-5,
R9, RIo, RI 1 and R1 may be the same or different.

-8 Specific examples expressed by formulas (8) to (20) are:
For example, as a polymerizable unsaturated monomer, for example, the following general formula (2
Those represented by 1) to (23) can be mentioned.

In each formula, R9, RIo and R12 have the same meanings as above.

As specific examples of the compounds represented by the general formulas (21) to (23), for example, as the polymerizable unsaturated monomer, for example, the following general formula (2
Compounds represented by 4) to (26) can be mentioned.

In each formula, R9 and RIo have the same meanings as above.

Specific examples of the compounds represented by formulas (24) to (26) include the following.

Examples of the epoxy-containing 1 polymerizable unsaturated monomer in which the polymerizable unsaturated group is CH2=CfR'l C-N- include the following general formula (2
Compounds represented by 7) to (32) can be mentioned.

In each formula, R", R", R", have similar meanings.

General formulas (27) to (32) As a specific example, for example, R1″ and W are as above. Compound represented by can be mentioned.

As the epoxy group-containing polymerizable unsaturated monomer in which the polymerizable unsaturated group is CH2=CHCHtO-, for example, the following -Ki formula (
Compounds represented by 33) to (36) can be mentioned.

In each formula, R9 and R1G have the same meanings as above.

Specific examples of compounds represented by general formulas (33) to (36) include CH3CH,=CH(:H2O-CH2-C-CH2\/).

Examples of the epoxy group-containing unsaturated monomer whose polymerizable unsaturated group is CH2/CHO- include the following general formulas (37) to (3).
Examples include compounds represented by 9).

In each formula, R9 and R10 have the same meanings as above.

Specific examples of the compounds represented by formulas (37) to (39) include the following.

Examples of epoxy group-containing unsaturated monomers in which the polymerizable unsaturated group is CH2/CH- include the following general formulas (40) to (42).
) can be mentioned.

can be mentioned.

Ru.

As specific examples of the compounds represented by the general formulas (40) to (42), for example, as the unsaturated monomer containing an xyl group, for example, the following - general formula (
Compounds represented by 43) to (47) can be mentioned.

(45) In each formula, R9, RIO and R have the same meanings as above.

Specific examples of the compounds represented by formulas (43) to (47) include the following.

Other polymerizable unsaturated monomers (b) that can be copolymerized with monomer (a) as necessary include (b-1) esters of acrylic acid or methacrylic acid: for example, methyl acrylate, acrylic Ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate , octyl methacrylate,
C1-18 alkyl esters of acrylic acid or methacrylic acid such as lauryl methacrylate: methoxybutyl acrylate, methoxybutyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate, ethoxybutyl acrylate, ethoxybutyl methacrylate, etc. C2-C18 alkoxyalkyl esters of acrylic acid or methacrylic acid, etc.

(b-2) Vinyl aromatic compound: for example, styrene, α
-Methylstyrene, vinyltoluene, p-chlorostyrene, etc.

(b-3) Others: acrylonitrile, meccrylonitrile, etc.

(b-4) Olefin compounds: for example, ethylene, propylene, butylene, isoprene, chlorobrene, etc.

(b-5) Vinyl ether and allyl ether; for example, ethyl vinyl ether, propyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether, te
Chain alkyl vinyl ethers such as rt-butyl vinyl ether, pentyl vinyl ether, hexyl vinyl ether, isohexyl vinyl ether, octyl vinyl ether, 4-methyl-1-pentyl vinyl ether,
Cycloalkyl vinyl ethers such as cyclopentyl vinyl ether and cyclohexyl vinyl ether, aryl vinyl ethers such as phenyl vinyl ether, 0-m-, p-1-rivinyl ether, and aralkyl vinyl ethers such as benzyl vinyl ether and phenethyl vinyl ether.

(b-6) Vinyl esters and propenyl esters - Vinyl esters such as vinyl acetate, vinyl lactate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl isocaproate, vinyl bivaric acid, vinyl caprate, and impropenyl acetate propionic acid Propenyl esters such as impropenil.

(b-7) In the general formula CL"CLI, X is the same or different and represents H, C1, Br, F, an alkyl group or a haloalkyl group, provided that at least one F in the formula
Contains. ): For example, CFa"CFa, CHF"CFa, CH2=CF
, , CH2=CHF , CCIF=(:F2,C
HCl=CF2,CCL,=CF,,(1:cIF=c
cIF, CHF=C(:12, CI(,=CGIF
, CC12=CCIF CF, CF=CF, , CF, CF=CHF, C
F, CH=CH2, CF, CF=CH,, CHF, CF
=CHF, (:H, CH=CH2, CH2CF=CH
2, CFa (:ICF”CFa, CFsCCCCF
i, CHCl=CFC1, (:F2CIC(:1=cF
l, CF2CC1=CCIFCFC12CF:CFg
, CF2CC1=CCIF , CFsCCl”CG
la, CCIF2(:F”CGlz, CC1, CF=C
F,,CFICICCI=CG12,CFCl2CCl
=CC1,,CF,CF=C)IC1,CCIF,CF
=CHC1,CF,CC1=CHC1,CI(F,CC
1=CC1,, CH2=CF"CCl2, CFClCC
F= to l=CC1, CC1, CF=CHC1, CF21
CF, CFJrCH'CF*, CFsCBr=
CHBr, CFzCICBr"CH2, CHJr
CF”CGla, CFaCBr”CHi, CFzC)l
;cIIBr, CFJrCH=CHF, CF2B
rCF=CFa, CF-CF2(:F”CFi, C
FsCF”CFCFs, CFnCH”CFCFs
, CF2''CC1=CHC1, CFsCFaCF=C
Hg, CFz=CFCHgC)Ia, CFsCHzC
H=CHx.

CFsCH=CHCHm, CFt=CHCHzCH
s, CH3CF2CH=CH2, CFHtCH=CHC
FHi, CHa=CFCHzCHs, CFs (CF
a) icF=cF*, CFsfCF2) sc:F=
CFa et al.

(b-8) Perfluoroalkyl (meth)acrylate; Examples include perfluorobutylethyl methacrylate, perfluoroisononylethyl methacrylate, and perfluorotetraoctylethyl meccrylate. These monomers can be used singly or in combination of two or more.

(2) A resin having an average of two or more carboxyl groups in one molecule is reacted with an epoxy compound and a polysiloxane oligomer having a functional group (e.g., hydroxyl group, epoxy group, etc.) that reacts with the carboxyl group. resin.

As the resin having a carboxyl group, a carboxyl group-containing polymerizable unsaturated monomer [e.g. (meth)acrylic acid,
Homopolymers of (anhydrous) maleic acid, crotonic acid, (anhydrous) ichonic acid, etc.] or copolymers of these monomers with other polymerizable unsaturated monomers (b): Polybasic acids [e.g. (anhydrous) phthalic acid, isophthalic acid, terephthalic acid, azelaic acid, etc.], a polyhydric alcohol [e.g., ethylene glycol, neopentyl glycol 1,6-hexanediol, pentaerythritol, glycerin, etc.] and, if necessary, a monobase. Typical examples include polyester (or alkyd) resins obtained by reacting acids, -hydric alcohols, etc. so as to have carboxyl groups.

As the hydroxyl group-containing epoxy compound, the following general formula (48) is used.
Compounds represented by (58) can be mentioned.

CH2-C-R"OH \1 \1 \1 \1 (48) In each formula, R9, RIG, R11, R12 and W have the same meanings as above.

Specific examples of compounds represented by general formulas (48) to (58) include CH, -C-CH, -OH\1CH.

R9 C of\/\ ON O can be mentioned.

As polyepoxy compounds, the following general formulas (59) to (6) are used.
Examples include compounds represented by 6).

In the formula, R6, R@, RIo, R'' and W have the same meanings as above.

Specific examples of the compounds represented by formulas (59) to (66) include (63) N 0 2C C C1 (s CHa) and the like.

In addition to the above, for example, the following can be used.

Adducts with anate compounds (Polyisocyanate compounds that can be used include, for example, aliphatic diisocyanates such as hexamethylene diisocyanate or trimethylhexamethylene diisocyanate; cycloaliphatic diisocyanates such as hydrogenated xylylene diisocyanate or isophorone diisocyanate; Organic diisocyanates themselves such as isocyanates or aromatic diisocyanates such as 4.4'-diphenylmethane diisocyanate, or adducts of these organic diisocyanates with polyhydric alcohols, low molecular weight polyester resins, water, etc., or each of the above-mentioned Examples include polymers of organic diisocyanates and isocyanate biuret bodies, and typical commercially available products include "Parnock D-750, -
800, DN-950, -970 or 15-455
J [The above, Dainippon Ink and Chemicals (meat products), “Desmodule L, NHL, IL or N3390J
[Product of Bayer AG, West Germany] “Fuquenate D-1
02, -202, -11ON or -123NJ
[Takeda Pharmaceutical ■Products] “Coronate L, HL, EH
or 203” [Japan Polyurethane Industries (meat products) or “Duranate 24A-90CXJ [Asahi Kasei Kogyo (11 products] etc.)”: adduct with polybasic acid; having an unsaturated group in the molecule, such as Esterified products (for example, number average molecular weight 90 obtained by esterifying tetrahydrophthalic anhydride, trimethylolpropane, 1,4-butanediol, etc.)
Examples include those obtained by oxidizing an esterified product of 0) with peracetic acid or the like.

In addition to the above-mentioned resins (1) and (2), there are also hydroxyl group-containing resins [e.g., vinyl resins, polyester resins, alkyd resins, polyether polyol resins, silicone resins, fluorine resins, etc.], and polyisocyanates. Resin obtained by reacting the hydroxyl group-containing epoxy resin and polysiloxane oligomer with the incyanate group-containing resin obtained by reacting the inocyanate group-containing resin with a compound such that isocyanate groups remain: Isocyanate ethyl acrylate, α, α
- A polymer of incyanate group-containing polymerizable unsaturated monomers such as dimethyl-m-impropenyl benzyl isocyanate, or this and other polymerizable unsaturated monomers (b
) etc., and a resin obtained by reacting a hydroxyl group-containing epoxy resin and a polysiloxane oligomer, etc. can also be used.

Next, a mixed resin of resin (II) having a silane group and resin (III) having an epoxy group will be described.

The resin (II) has a number average molecular weight of about 3, and has an average number of silane groups or more, preferably an average of about 2 or more silane groups in one molecule.
000-200,000 preferably about 5,000-so
, ooo. If the number of silane groups is less than the average number, curability tends to be poor, which is not preferable. In addition, when the number average molecular weight is less than about 3,000, weather resistance, curability, etc. tend to decrease;
If it is larger than 0.000, the viscosity of the resin composition becomes high, making it difficult to handle, and 1. The compatibility with the resin (nl) tends to decrease, which is not preferable.

The resin (H) has a polysiloxane oligomer component in the resin. The method for introducing this component is as described above, for example, by reacting a resin having a functional group such as an incyanate group, a carboxyl group, or an epoxy group with a polysiloxane oligomer component such that a silane group remains; Polysiloxane oligomers can be introduced into resins by using them as raw materials for resins, alkyd resins, and polyurethane resins.

The resin (m) has a number average molecular weight of about 250 to 200,000, preferably about 250 to so, and has an average of about 1 or more, preferably about 2 to 40, epoxy groups in one molecule.
It can have a range of ooo. If the number of epoxy groups is less than about 2 on average, curability tends to decrease, which is not preferred. Moreover, those with a number average molecular weight of less than about 250 are difficult to obtain, while those with a number average molecular weight of more than 200,000 are undesirable because they may become difficult to handle.

The resin (I) can be appropriately selected from conventionally known epoxy group-containing resins or compounds. Typical examples of these include the above-mentioned polyepoxy compounds; epoxy resins such as bisphenol epichlorohydrin type, novolak type, etc.; polymers containing the epoxy group-containing polymerizable unsaturated monomer (a) as an essential monomer component: Functional groups (e.g. isocyanate group, hydroxyl group,
A resin having a carboxyl group, etc.) and a functional group (such as a hydroxyl group, an isocyanate group, etc.) that reacts complementary to the functional group.
epoxy group, etc.) and a compound having an epoxy group.

The mixed resin includes resins (II) and (III), and resin (
It is desirable that the ratio of the silane groups in II) to the epoxy groups in the resin (III) be about 1.

In the polysiloxane resin composition of the present invention, the resin (I) or resin (II) (and/or) resin (II+
It is preferable to use a resin containing a hydroxyl group and/or a carboxyl group in ) because the curability of the coating can be further improved.

The polysiloxane resin composition of the present invention may be any of the solution type, dispersion type, and non-aqueous dispersion type using an organic solvent as a medium, and the solution type and dispersion type using water as a medium.

The above-mentioned non-aqueous dispersion type polysiloxane resin composition is
Using resin (1) or resin (II) or (II) as a dispersion stabilizer, one or more radically polymerizable unsaturated monomers and a polymerization initiator are added to the monomer in the presence of the dispersion stabilizer. A non-aqueous dispersion can be produced by adding the monomer and dispersion stabilizer to an organic solvent in which the monomer and the dispersion stabilizer are dissolved, but in which the polymer particles obtained from the monomer are not dissolved, and a polymerization reaction is carried out. All of the monomers described above can be used to form the polymer that is the particle component of the non-aqueous dispersion. Preferably, the polymer forming the particle component must not be soluble in the organic solvent used.
It is a copolymer containing a large amount of highly polar monomers. Namely, methyl (meth)acrylate, ethyl (meth)acrylate, (meth)acrylonitrile, 2-hydroxy (meth)acrylate, hydroxypropyl (meth)acrylate, (meth)acrylamide, acrylic acid, methacrylic acid, itaconic acid, styrene, vinyl. Toluene, α-
It is preferable that the particles contain a large amount of monomers such as methylstyrene and N-methylol (meth)acrylamide, and the particles of the non-aqueous dispersion can be crosslinked as necessary.An example of a method for crosslinking the inside of the particles. This can be achieved by copolymerizing polyfunctional monomers such as divinylbenzene and ethylene glycol dimethacrylate.

Although the dispersed polymer particles produced by the polymerization are not substantially dissolved in the organic solvent used for the non-aqueous dispersion, it is a good solvent for the dispersion stabilizer and the radically polymerizable unsaturated monomer. things are included. Examples of organic liquids that can be used include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, mineral spirits, and naphtha; aromatic hydrocarbons such as benzene, toluene, and xylene; alcohols, ethers, esters, and ketone solvent,
For example, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, octyl alcohol, cellosolve, butyl cellosolve, diethylene glycol monobutyl ether, methyl isobutyl ketone, diisobutyl ketone, ethyl acyl ketone, methyl hexyl ketone,
Examples include ethyl butyl ketone, ethyl acetate, isobutyl acetate, acyl acetate, 2-ethylhexyl acetate, etc. Each of these can be used alone or in a mixture of two or more, but - generally, Preferably, the solvent is mainly composed of aliphatic hydrocarbons, in combination with aromatic hydrocarbons or alcohol-based, ether-based, ester-based, or ketone-based solvents such as those mentioned above. Furthermore, trichlorotrifluoroethane, metaxylene hexafluoride, tetrachlorohexafluorobucne, etc. can also be used if necessary.

The polymerization of the above monomers is carried out using a radical polymerization initiator.6 Usable radical polymerization initiators include, for example, 2,2-azoisobutyronitrile, 2,2'-azobis(2゜4- Azo initiators such as dimethylvaleronitrile; benzoyl peroxide, lauryl peroxide,
Examples include suitable oxide initiators such as tert-butyl peroctoate, and these polymerization initiators are generally used in an amount of 0.2 to 10 parts by weight per 100 parts by weight of monomers to be subjected to polymerization. I can do it. The formulation of the dispersion stabilizer resin to be present during the above polymerization can be selected from a wide range depending on the type of the resin, but -M contains a radically polymerizable unsaturated monomer based on 100 parts by weight of the resin. Appropriately, the amount is about 3 to 240 parts by weight, or 5 to 82 parts by weight.

In the present invention, by combining a dispersion stabilizer resin and polymer particles, the storage stability of a non-aqueous dispersion is improved, and a cured film with excellent transparency, smoothness, and mechanical properties is formed. A method for bonding the dispersion stabilizer resin and polymer particles, which can be carried out, is by polymerizing a radically polymerizable unsaturated monomer in the presence of a dispersion stabilizer having a polymerizable double bond. can.

A method for introducing a polymerizable double bond is to add α,β-ethylenically unsaturated monocarboxylic acid such as acrylic acid, methacrylic acid, or iconic acid to a part of the oxirane group in the resin. Although most convenient, other methods include adding an isocyanate group-containing monomer such as isocyanoethyl methacrylate to a hydroxyl group that has been previously incorporated into the resin.

Furthermore, as a method for bonding the dispersant stabilizer and the polymerizable particles, in addition to the method described above, monomer components forming the polymer particles may be used, such as γ-methacryloxypropyltrimethoxysilane and γ-methacryloxybrobyl. Triethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-methacryloxybutyltriethoxysilane, γ-
Attachment can be achieved by using reactive monomers such as acryloxypropyltrisilanol.

The non-aqueous dispersion resin composition described above is a non-aqueous dispersion in which a solid phase, which is a polymer particle formed by polymerizing a radically polymerizable unsaturated monomer, is stably dispersed in a liquid phase in which a dispersion stabilizer resin is dissolved in an organic solvent. It is a dispersion liquid that can significantly increase the solid content during coating, and also increases the viscosity after coating, so it does not cause sagging,
It is possible to form a film with excellent finished appearance and no run-off. Furthermore, the formed film is a photo- and chemically stable film in which the continuous phase of the film has a siloxane bond, and the polymer particle component in the film is stabilized by the continuous phase, and the film is stabilized by the particles. Since it is reinforced by the component, it is possible to form a film that has excellent optical and chemical properties as well as mechanical properties such as impact resistance.

The polysiloxane resin composition of the present invention may optionally contain an inorganic pigment, an organic pigment, a metallic pigment (for example, aluminum powder, mica powder, etc.), a silane compound [for example, the above-mentioned silane compound (A)], and a hydroxyl group-containing resin. , a carboxyl group-containing resin, an epoxy resin, a coating surface conditioner, etc. can be added.

The curable resin composition of the present invention is obtained by blending the above-mentioned polysiloxane resin composition with an organic metal compound such as a Lewis acid, a protonic acid, and an aluminum compound as a curing reaction catalyst.

(1) Organometallic compounds such as metal alkoxide compounds, metal chelate compounds,
Examples include metal alkyl compounds.

[Metal Alkoxide Compound] Examples include compounds in which an alkoxy group is bonded to metals such as aluminum, titanium, zirconium, calcium, and barium. These compounds may be associated; among them, aluminum alkoxide, titanium alkoxide and zirconium alkoxide are preferred. Examples of these preferred metal alkoxide compounds are shown below.

Aluminum alkoxide has, for example, the general formula %) [wherein R1! are the same or different and have 1 to 2 carbon atoms
0 alkyl group or alkenyl group] can be mentioned.

Examples of alkyl groups having 1 to 20 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, heptyl, octyl,
Examples of the alkenyl group include undecyl, dodecyl, tridecyl, tetradecyl, and octadecyl groups, and examples of the alkenyl group include vinyl and allyl groups.

-M The aluminum alcoholades represented by formula (67) include aluminum trimethoxide, aluminum triethoxide, aluminum tri-n-propoxide, aluminum triisopropoxide, aluminum tri-n-butoxide, aluminum triisobutoxide, Aluminum tri-5eC-butoxide, aluminum tri-tert-butoxide, etc., especially aluminum triisopropoxide, aluminum tri-5eC-butoxide, etc.
Preferably, ee-butoxide, aluminum tri-n-butoxide, etc. are used.

The titanium chelate compound has, for example, the general formula [wherein, W
and R+s have the same meanings as above.

- Chikunates represented by the J1 formula (68) are:
When W is 1, tetramethyl titanate, tetraethyl titanate, tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetraisobutyl titanate, tetra-ter
Examples include t-butyl titanate, tetra-n-pentyl titanate, tetra-n-hexyl titanate, tetra-isooctyl titanate, tetra-n-lauryl titanate, and especially tetra-isopropyl titanate, tetra-n-
Suitable results are obtained using butyl titanate, tetraisobutyltichnate, tetra-tert-butyl titanate, and the like. In addition, for those where W is 1 or more, tetraisopropyl titanate, tetra-n-butyl titanate, tetra-isobutyl titanate, etra-tert
- butyl ticunate dimer to 11-mer (general formula (6)
9) where w=1 to 10) gives suitable results.

Examples of zirconium chelate compounds include zirconates represented by the general formula (1), in which W and R13 have the same meanings as above.
Examples of the zirconates represented by 69) include tetraethyl zirconate, tetra-n-propyl titanate,
Tetraisopropyl zirconate, tetra-n-butyl zirconate, tetra-5ec-butyl zirconate,
Tetra-tert-butylzirconate, tetra-n-
Pentyl zirconate, tetra-tert-pentyl zirconate, tetra-tert-hexyl zirconate, tetra-n-hebutyl zirconate, tetra-n-octyl zirconate, tetra-n-stearyl zirconate, etc. Tetraisopropyl zirconate,
Tetra-n-propyl zirconate, tetra-isobutyl zirconate, tetra-n-butyl zirconate, tetra-5ee-butyl zirconate, tetra-tert-
Suitable results are obtained using butyl zirconate and the like.

In addition, for those where W is 1 or more, tetraisopropyl zirconate, tetra-n-propyl zirconate,
11 from the dimer of tetra-n-butylzirconate, tetraisobutylzirconate, tetra-3ec-butylzirconate, and tetra-tert-butylzirconate
mer (W=1 to 10 in general formula (69)) gives preferable results. Further, it may contain a structural unit in which these zirconates are associated.

[Metal chelate compound 1 Aluminum chelate compounds, titanium chelate compounds, and zirconium chelate compounds are preferred; Chelate compounds contained as ligands are preferred.

Compounds that can constitute keto-enol tautomers include β-diketones (acetylacetone, etc.), acetoacetic esters (methyl acetoacetate, etc.), malonic acid esters (ethyl malonate, etc.), and Ketones having a hydroxyl group (such as diaheptone alcohol), aldehydes having a hydroxyl group at the β position (such as salicylaldehyde), esters having a hydroxyl group at the β position (methyl salicylate), and the like can be used. In particular, acetoacetic acid esters, β
- Favorable results are obtained using diketones.

The aluminum chelate compound is preferably prepared by mixing a compound capable of forming the above-mentioned keto enol tautomer at a molar ratio of about 3 moles or less per 1 mole of the aluminum alkoxide, and heating as necessary. It can be prepared. Particularly preferred aluminum chelate compounds include, for example, tris(ethylacetoacetate)aluminum, tris(n-propylacetoacetate)aluminum, tris(isopro and ruacetoacetate)aluminum, tris(n-butylacetoacetate)aluminum, isopropoxy Bis(ethylacetoacetate)aluminum, diisopropoxyethylacetoacetatealuminum, tris(acetylacetonato)aluminum, tris(propionylacetonato)aluminum, diisopropoxypropionylacetonatoaluminum, acetylacetonato bis(propionylacetonato) Examples include aluminum, monoethylacetoacetate bis(acetylacetonato)aluminum, and the like.

The titanium chelate compound is preferably prepared by mixing a compound capable of forming the keto enol tautomer at a molar ratio of about 4 moles or less per mole of the titanium alkoxide, and heating as necessary. Can be adjusted. Particularly preferred titanium chelate compounds include, for example, diisopropoxy bis(ethylacetoacetate) titanium, diisopropoxy bis(acetylacetonato) titanium, and the like.

The zirconium chelate compound is preferably prepared by mixing a compound capable of forming the above-mentioned keto enol tautomer in a molar ratio of about 4 moles or less per 1 mole of the above-mentioned zirconium alkoxide, and heating if necessary. Can be adjusted. Particularly preferred zirconium chelate compounds include, for example, zirconium chelate compounds such as tetrakis(acetylacetonato)zirconium, tetrakis(n-propylacetoacetate)zirconium, and tetrakis(ethylacetoacetate)zirconium.

Any one type of the aluminum chelate compound, zirconium chelate compound, and titanium chelate compound may be used, or two or more types may be used in combination as appropriate.

[Metal alkyl compound] The compound is a metal such as aluminum or zinc with an alkyl group,
Preferably, it is one in which a C3-2° alkyl group is bonded. Specific examples include triethylaluminum, diethylzinc, and the like.

(2) Lewis acid metal halides, compounds in which the metal shares a halogen and other substituents, and complex salts of these compounds can be mentioned. Specifically, for example, AiC, IcFs
, AJFs, /Ll'(C-HslCf-1AI(C
tHsltCj, 5nf4, TiC, TiBr
4. TiF4, ZrCmu, ZrBr4, ZrF4,
SnC, FeC, sbcm, 5bC1s,
PCl5, PCJ's, GaCJ! z, GaFs
, InFi, BC, BBrs, BF, , Wants:
foc*oil z, BF4: [0CJi) -5B
Cmu: (OCJil *, Liver, :NI(,C,H,
, BFs:NH*CJ<0H1BFs:NHCH*C
H*CH*C)l! , PF, S÷◎)3, (CJs)
4PeCHmCOOe (C4H*)3P' CHs (CHsol xPoe
, [CnHsl "Pe(J"'(c4nsl*p, (
Q+r P, C4H9PH2, (C4HIltP)I
, NiC4* [(C*Hs) sP]x, CoBr
* [((3+r Pl *, (0→p, (C4HI1
4PeB e(CJJ4, (11:Jsl 4PeBr
e, (QCs p e CH3I8 etc.) can be enumerated.

(3) Protonic acids The protonic acids include, for example, organic protonic acids such as methanesulfonic acid, exonsulfonic acid, trifluorotothanesulfonic acid, benzenesulfonic acid, and p-tφenesulfonic acid; phosphoric acid; Examples include inorganic protonic acids such as phosphorous phosphinic acid, phosphonic acid, sulfuric acid, and perchloric acid.

(4) Aluminum Compound Examples of the compound include compounds having a 5i-0-AI2 bond, specifically reaction products of aluminum alkoxide and silane alkoxide, and aluminum silicate.

In addition to the above, aluminum oxide and the like can also be used.

Among the above-mentioned curing reaction catalysts, metal chelate compounds are preferably used because they can form a coating film with excellent curability.

(1) to (3) The appropriate amount of the crosslinking reaction curing agent is about 0.01 to 30 parts by weight per 100 parts by weight of the solid content of the resin composition, organic liquid, and aqueous liquid. . If it is less than this range, crosslinking reaction curability tends to decrease, and if it is more than this range, it tends to remain in the cured product and reduce water resistance, which is not preferable.The preferred blending amount is 0.1 to 10 In terms of parts by weight, the preferred amount is 1 to 1.
5 parts by weight.

(4) The amount of the crosslinking reaction curing agent is 1 to 10 parts by weight per 100 parts by weight of the solid content of the resin, organic liquid, and aqueous liquid.
It is appropriate to use about 0 parts by weight. If the amount is less than this range, the crosslinking curability tends to decrease, and if it exceeds this range, the physical properties of the coating film tend to decrease, which is not preferable.

The curable composition of the present invention can be suitably used in paints, adhesives, inks, and the like. As for paint, it ranges from room temperature drying to 60~
Low-temperature baking at 100°C can be applied to a wide range of objects, including molds and high-temperature baking types at 100 to 160°C. The objects to be coated include iron plates, plastic materials, wood, and all other materials that are conventionally coated with paint. Painting of automobile bodies is also an example to which the curable composition of the present invention is suitably applied.

Solid color, metallic color,
It can be applied in the form of clear paint, etc., using a wet-on-wet layering method (so-called 2CIB painting), a monocoat method, or other painting methods.

It can be used as an intermediate coating for automobile bodies, and as a top coating or undercoat for various plastic materials and metal parts used as automobile parts.

When the curable composition of the present invention is used as a coating material, there are no particular limitations on the coating method, and conventional methods can be used as they are. Methods such as painting, roll coating, and heka-coating can be applied.

The curable composition of the present invention can be easily crosslinked and cured at a low temperature of 140°C or lower. For example, when it is cured at room temperature without any heating, it is usually sufficiently cured in about 8 hours to 7 days. Furthermore, when heated to about 40 to 100°C, it can be sufficiently cured in about 5 minutes to 3 hours.

can be introduced into various types of resins without gelation and thickening by reacting the amino groups in the oligomer with a resin having a functional group that reacts with the amino groups. Further, the polysiloxane-containing resin into which the polysiloxane oligomer component is introduced has extremely excellent surface properties due to the presence of side chains having siloxane bonds. In addition, in the polysiloxane-containing resin,
The functional group bonded to Si in the side chain has higher reactivity than the functional group bonded to Si in conventional polysiloxane side chain resins, and since there are two or more such functional groups, It has good crosslinking properties and good compatibility with other components.

1 vassal father-in-law Examples of the present invention will be shown below.

Production Example of Polysiloxane Oligomer Oligomer (1) In the present invention, a polysiloxane oligomer trimethoxysilane (l mol) deionized water 1,134 g 36% hydrochloric acid aqueous solution 2 g A mixture of these was reacted at 80° C. for 5 hours. The obtained polysiloxane oligomer had a number average molecular weight of 2.000, and had on average one amino group per molecule and four hydroxyl groups at the terminal portion.

Oligomer (2) Toluene 4.500g The mixture was reacted at 117°C for 3 hours and dehydrated. The number average molecular weight of the obtained polysiloxane oligomer was 7.0.
00, each molecule had on average one amino group and 5 to 10 hydroxyl groups at the terminal portion.

Oligomer (3) 9.504 g (48 mol) of phenyltriacetoxysilane and 2 mol of 3-aminopropyltriacetoxysilane were reacted in the same manner as oligomer (1). The number average molecular weight of the obtained polysiloxane oligomer was approximately 6.0.
00, each molecule had on average one amine group and 5 to 10 acetoxy groups in the portion corresponding to the end.

Production example of resin (a) Glycidyl methacrylate 142gn-Butyl methacrylate 708g Styrene
A mixture of 150g of azobisisobutyronitrile was added dropwise into 1.000g of xylene.The reaction was carried out at 100°C. The resulting resin solution had a resin solid content of 50% by weight and a resin number average molecular weight of 30.
000. Next, a mixture of 2.000 g of the above resin solution, 1.000 g of the above oligomer (1), and 1,000 g of methyl ethyl ketone was reacted at 120° C. for 3 hours to obtain a resin (a) solution (solid content 50% by weight). .

Resin (a) has 22 epoxy groups per molecule and a number average molecular weight of 44. ．． It was 000.

Production example of resin (b) A mixture of 695 g of n-butyl methacrylate, 150 g of styrene, and 5 g of azobisisobutyronitrile was mixed with 1.0 g of xylene.
6 reactions were carried out at 100°C.

The obtained resin solution had a resin solid content of 50% by weight and a resin number average molecular weight of 32.000.
2.000g of the above oligomer (2)
1,400g. 0 island-04 call, -oζo
A mixture of 285 g and 1.685 g of methyl isobutyl ketone was reacted at 100° C. for 4 hours to obtain a resin (b) solution (solid content: 50% by weight).

Resin (b) has 76 epoxy groups per molecule, number average molecule! It was 95,000.

Production example of resin (c) Trimethylolpropane 137g Neopentyl glycol 945g Phthalic anhydride
444g adipic acid
A condensation reaction was carried out on 1.007 g of the mixture at 220° C. until the acid value became 2 or less.

Next, 120 g of isophorone diisocyanate and 1,500 g of methyl isobutyl ketone were added to the above reaction product, and the mixture was heated to 80°C.
The mixture was reacted for 3 hours to obtain an incyanate group-containing resin solution (solid content: 50% by weight). The isocyanate group-containing resin has an isocyanate value of 20 mg/g and a number average molecular weight of 8.
It was 000.

Furthermore, 1.450 g of the oligomer (3) and 1,731 g of methyl isobutyl ketone were reacted at 140° C. for 6 hours to obtain a resin (c) solution (solid content: 50% by weight). Resin (C) had 38 epoxy groups per molecule and a number average molecular weight of 20,000.

Examples 1 to 9 Compositions of Examples were prepared by blending the resins (a) to (c) i@ liquids described above and a curing reaction catalyst (1 part by weight for each 100 parts by weight of resin solids) into the resin solution. I got it.

[Coating Film Performance Test] Each of the compositions of Examples 1 to 9 was coated to a dry film thickness of 20 μm, dried, and subjected to a test.

Gel fraction: The dried coating film was peeled off from the glass plate and extracted with acetone at reflux temperature using a Soxhlet extractor for 6 hours, and then expressed as the residual weight % of the coating film.

Paint film appearance: The material used was polished mild steel plate. The presence or absence of any abnormalities in the painted surface condition (glossy pockets, smudges, cracks, peeling) was examined.

Acid resistance: A glass plate was used as the material. The test piece was heated to 40% H2
It was immersed in an SO4 aqueous solution (40°C) for 5 hours, and the appearance of the coating film (blurring, whitening, etc.) was observed.

Storage stability: The time during which viscosity does not increase when the product is left in an open container at a temperature of 40°C and a humidity of 70% was measured.

The test results are shown in Table 1.

Claims (1)

[Scope of Claims] [1] (A) a silane compound having a hydroxyl group and/or a hydrolyzable group directly bonded to a silicon atom; and (B) a hydroxyl group and/or a hydrolyzable group directly bonded to a silicon atom; -NH_2 and/or -NH-
and an average of one or more -NH_2 and/or -NH- groups per molecule, and a hydroxyl group and/or directly bonded to the silicon atom at the terminal corresponding portion. A polysiloxane oligomer having an average of two or more hydrolyzable groups. [2] The resin contains a hydroxyl group and/or a hydrolyzable group directly bonded to a silicon atom and an epoxy group as essential functional group components, and the hydroxyl group and/or hydrolyzable group directly bonded to the silicon atom A polysiloxane resin composition, characterized in that it is introduced by the polysiloxane oligomer according to claim 1. [3] Curing properties characterized by containing the polysiloxane resin composition according to claim 2, one or more curing reaction catalysts selected from organometallic compounds, Lewis acids, protonic acids, and aluminum compounds. Resin composition.