JPH0339329A - Polysiloxane based oligomer, polysiloxane based resin composition and curable resin composition - Google Patents

Abstract

PURPOSE:To obtain the curable resin composition consisting of a polysiloxane based resin composition obtained by introducing a polysiloxane based oligomer by obtained by reacting a specific silane compound with a specific silane monomer into a resin and curing catalyst and having excellent low-temperature curing properties. CONSTITUTION:A silane compound having a hydroxyl group and/or hydrolyzable group directly coupled to silicon atom is reacted with a silane monomer having hydroxyl group and/or hydrolyzable group directly coupled to a silicon atom and epoxy group to provide the polysiloxane based oligomer having one or more epoxy groups and hydroxyl group and/or hydrolyzable group directly coupled to two or more atoms in the part corresponding to the end. The resultant oligomer is reacted with a resin having a functional group capable of reacting with epoxy group of the oligomer to provide the polysiloxane resin based composition having excellent surface characteristics, etc. The aimed curable resin composition suitable for coating, etc., is obtained from the above- mentioned resin composition and curing reaction catalyst such as an organometallic compound.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel polysiloxane oligomer, a polysiloxane resin composition, and a curable resin composition.

Conventionally, in already known polysiloxanes, compounds having one epoxy group and one hydroxyl group or hydrolyzable group at the end corresponding portion (Si) are added linearly, but reactions of hydroxyl groups, etc. It has the disadvantage that it is difficult to form a crosslinked structure due to its low properties. Compounds that have only one hydroxyl group or hydrolyzable group at both ends and do not contain epoxy groups are polymerized only by condensation. However, they have the disadvantage that they do not have sufficient water resistance, chemical resistance, weather resistance, etc. In addition, compounds that have one epoxy group at both ends tend to gel during addition, making them difficult to handle. The disadvantage is that it cannot be formed.

The present invention aims to eliminate the above-mentioned drawbacks of conventionally known polysiloxanes.

In order to achieve this, the present inventors used specific raw materials to infuse polysiloxane with an average of one epoxy group per molecule and a hydroxyl group and/or hydrolyzable group directly bonded to the silicon atom at the terminal corresponding portion. In the novel polysiloxane-based oligomer obtained by incorporating the oligomer component into the resin, the oligomer component does not gel when introduced into the resin, and can be crosslinked by condensation, and the above purpose can be fully achieved. Based on this heading, the present invention was completed.

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) a silane group, and a silane monomer having an epoxy group (hereinafter referred to as "silane monomer (B)"), and Each molecule contains an average of one or more epoxy groups and an average of two silane groups at the terminal portion.
A polysiloxane-based oligomer characterized by having more than 100% polysiloxane-based oligomers; - A polysiloxane-based resin 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. Composition, (1) The polysiloxane resin composition contains one or more curing reaction catalysts selected from organometallic compounds, Lewis acids, protonic acids, compounds having a 5i-0-AI2 bond, aluminum, and aluminum compounds. The present invention relates to a curable resin composition.

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 the following groups.

-0-R' (1) 4 s / N (5) \ 4 -N-C-R' (
6)4 In the formula, R1 represents a C1-4 alkyl group, and R2-R4, which appear to be the same but are different, represent a C1-8 alkyl group, aryl group, or aralkyl group.

In the general formula, the "C1-8 alkyl group" 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.

Further, in addition to the above-mentioned hydrolyzable groups bonded to silicon atoms, examples of hydrolyzable groups include 5i-H groups.

In the present invention, groups represented by (2) and (3) above and hydroxysilane groups are preferred from the viewpoint of storage stability, curability, etc.

In the present invention, the terminal equivalent portion means one or more silicon atoms located at the terminal 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 epoxy groups are bonded indirectly. It is obtained by reacting the silane compound (A) with the silane monomer (B).

The silane compound (A) has an average of three silane groups in one molecule, and is preferably represented by the general formula (7) (wherein, R6 represents a hydrocarbon group, and R@, R7 and R8 represent a hydrocarbon group). It is a compound represented by ), which indicates a hydroxyl group as a degradable group.

In the above general formula (7), Rv' is preferably an aliphatic hydrocarbon group having 1 to 8 carbon atoms (chain or branched), an aryl group, and an aralkyl group. , more preferably a methyl group and a phenyl group. Examples of aliphatic hydrocarbon groups having 1 to 8 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, etc.
R@, R? and R8 may all be the same and may be different in part or in whole.

Especially preferred as R6, R7 and R6 are methoxy group, ethoxy group, propoxy group, butoxy group, hydroxyl group, acetoxy group and the like. Preferred specific examples of the silane compound (A) include methyltrimethoxysilane, phenyltrimethoxysilane, butyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, phenyltrisilanol, methyltrisilanol, methyltriacetoxysilane, Examples include phenyltriacetoxysilane. Among these, methyltrimethoxysilane, phenyltrimethoxysilane, phenyltrisilanol, methyltriacetoxysilane, phenyltriacetoxysilane, and the like are particularly preferred.

The silane monomer (B) is a monomer having a silane group and an epoxy group in one molecule. As an epoxy group,
One molecule can preferably contain 1 to 3 silane groups, which can be either aliphatic or alicyclic.

Preferred specific examples of the silane monomer (B) include 3-
Glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-methylglycidoxypropyltrimethoxysilane, 4-glycidoxybutyltriethoxysilane, 3-glycidoxypropyltrisilanol, 3 -glycidoxypropyltriacetoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propylmethyljethoxysilane,
Examples include 2-(3,4-epoxycyclohexyl)ethyltrisilanol and 2-(3,4-epoxycyclohexyl)ethyltriacetoxysilane.

The polysiloxane oligomer of the present invention is obtained by mixing the silane compound (A) and the silane monomer (B) and reacting them. The mixing ratio of both compounds is based on the total amount of the surrounding components. Silane compound (A) is 7
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 group possessed by the surrounding components and the hydroxyl group generated by hydrolysis of the hydrolyzable group,
The desired oligomer is produced. At this time, depending on the reaction conditions, not only dehydration condensation but also partial condensation occurs 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, the reaction can be performed without a solvent, but in an organic solvent that can dissolve both compounds and is inert to both compounds. 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
It is preferable that the amount is 0.0 mole or more, but if it is less than 1 mole, the reaction of both compounds may decrease.

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 in the range of o,oooi to 5% by weight, preferably 0.01 to 0.1% by weight, based on the total amount of the silane compound (A) and silane monomer (B). .

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, which can be added to the water-soluble organic solvent, is effective in 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, a tetraalkoxysilane with a hydrolyzable group bonded thereto, or a dialkyldialkoxysilane with two hydroxyl groups and/or a hydrolyzable group bonded to a silicon atom, for example, may be used in combination; mole%
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 (linear, ladder-like). 1 ladder type and a mixture of these.Among these, those with a ladder-like structure or a mixed type with many ladder-like parts are used for water resistance, heat resistance, and light resistance. These structures, which are preferable from the viewpoint of
It can be arbitrarily selected depending on the mixing ratio with B), the amount of water and acid catalyst, etc.

In particular, the polysiloxane oligomer of the present invention has an average of one epoxy 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.

In addition, the number average molecular weight of the polysiloxane oligomer of the present invention is usually in the range of about 400 to 100,000, but if you try to obtain one with a molecular weight of less than 400, the silane compound (
A) and the silane monomer (B) tend to gel during the reaction, which is undesirable, and those with a molecular weight greater than 100,000 have poor compatibility with the resin when introduced into the resin. The amount of polysiloxane-based oligomer components that do not chemically bond to the resin may increase, resulting in poor coating performance.

The polysiloxane oligomer of the present invention has an average of one epoxy group per molecule and at least two epoxy groups in the terminal portion.
By having more than one hydroxyl group and/or hydrolyzable group, the component can be introduced into other resins using the epoxy group, and by condensation of the hydroxyl group and/or hydrolyzable group, etc. They can also be made into polymers or have a crosslinked structure.

The polysiloxane-based oligomer of the present invention has extremely favorable characteristics such that it does not gel when the oligomer component is introduced into the resin, can form a graft body, and can be easily crosslinked by condensation. This cross-linked product has excellent water resistance, chemical resistance, weather resistance, heat resistance, light resistance, abrasion resistance, water repellency, stain resistance, etc.

The polysiloxane oligomer component of the present invention can be introduced into other resins by utilizing the epoxy group in the molecule. In the resin into which the polysiloxane oligomer component is introduced, a cured resin can be obtained by reacting the functional groups of the hydroxyl group and/or hydrolyzable group directly bonded to the silicon atom derived from the polysiloxane oligomer component. However, from the viewpoint of low-temperature curability, a resin containing the functional group and an epoxy group as essential functional group components is preferred. 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.

Polysiloxane resin compositions include resins containing silane groups and epoxy groups in the same resin (I); resins containing silane groups (H) and resins containing epoxy groups (III);
) can be used.

The types of resins (I) to (III) 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 reacting the epoxy group in the polysiloxane oligomer component with the functional group in the resin. The functional group in the resin may be a group that reacts with the epoxy group in the polysilosane oligomer component;
For example, carboxyl groups, amine groups, mercapto groups, phenolic hydroxyl groups, etc. can be used without particular limitations.

In addition, there are two methods for introducing an epoxy group into a resin, for example, a method in which an epoxy group-containing polymerizable unsaturated monomer is used as a raw material, and a method in which a functional group is introduced into the resin in advance. Next, examples include 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. 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: hydroxyl group/isocyanate group, incyanate group/hydroxyl group, carboxyl group/epoxy group. , amine group/
Preferred examples include epoxy group, mercapto group/epoxy group, and phenolic hydroxyl group/epoxy group.

The resin (I) has an average of 2 or more silane groups in one molecule, preferably an average of 4 or more silane groups, and an average of 1 or more silane groups in one molecule.
or more, preferably an average of 2 or more epoxy groups,
It is desirable that the number average molecular weight is between 3,000 and 200,000, preferably between 5.000 and so, ooo.If the number of the above-mentioned functional groups is below the above-mentioned range, the curability tends to be poor, so it is preferable. If the number average molecular weight is less than 3.000, weather resistance, curability, chemical resistance, etc. tend to deteriorate; on the other hand, if it is greater than 200,000,
This is not preferable because the viscosity of the resin composition becomes high and handling becomes difficult.

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

(1) A resin obtained by reacting a carboxyl group-containing resin with a polysiloxane oligomer and a hydroxyl group-containing epoxy compound (or polyepoxy compound).

Examples of carboxyl group-containing resins include the following.

■ Carboxyl group-containing polymerizable unsaturated monomers [e.g.
meth)acrylic acid, 2-carboxyethyl (meth)acrylate, 5-carboxypentyl (meth)acrylate, (anhydrous) maleic acid, (anhydrous) itaconic acid, fumaric acid, crotonic acid, etc.] or the carboxyl group thereof Containing polymerizable unsaturated monomers and other polymerizable unsaturated monomers [e.g., methyl acrylate, 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, methacrylic acid C1-18 alkyl esters of acrylic acid or methacrylic acid such as octyl, lauryl methacrylate, etc.; for example, methoxybutyl acrylate, methoxybutyl methacrylate, methoxyethyl acrylate,
Alkoxyalkyl esters of acrylic acid or methacrylic acid having 2 to 18 carbon atoms, such as methoxyethyl methacrylate, ethoxybutyl acrylate, ethoxybutyl methacrylate, etc.; for example, styrene, α-methylstyrene, vinyltoluene, p-chlorostyrene, etc. Vinyl aromatic compounds such as; (meth)acrylonitrile compounds such as acrylonitrile, methacrylaterile, etc.; Olefinic compounds such as ethylene, propylene, butylene, isoprene, chlorobrene, etc.; such as ethyl vinyl ether, propyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether , tert-butyl vinyl ether, pentyl vinyl ether, hexyl vinyl ether, isohexyl vinyl ether, octyl vinyl ether, chain alkyl vinyl ethers such as 4-methyl-1-pentyl vinyl ether, cycloalkyl vinyl ethers such as cyclopentyl vinyl ether, cyclohexyl vinyl ether, phenyl vinyl ether Vinyl ethers and allyl ether compounds such as aryl vinyl ethers such as , 〇-m+, p-trivinyl ether, aralkyl vinyl ethers such as benzyl vinyl ether and phenethyl vinyl ether; for example, vinyl acetate, vinyl lactate, vinyl butyrate, vinyl isobutyrate, caproic acid Vinyl esters and propenyl ester compounds such as vinyl, vinyl esters such as vinyl isocaproate, vinyl bivaric acid, vinyl caprate, and propenyl esters such as isopropenyl acetate and isopropenyl propionate; for example, CFa"CFi, CHF=CC1, CC1 =CC1
, CH,=CHF , CGIP=CF+, CICC(:
Fz, CC1, = CF,, CGIF = CGIF, CH
F=CC1,,CH! =CGIP, CC11=CCIF
.

cFscF=cFi, CF2CF=CF,
CF,CH=CF, ,CF,CF=CH,,CH
F2CF=CHF, CH,CF=CF, ,CH
=CHCH3, CF, CC1=CC1, CF, CC1=
CF,,CF2CF=CFC1,CF,CICC1=C
F! , CI'aCICF=CFCI.

cpct*cp=ct"*, CF2CC1=C
CIF, CF, CC1=CC12, CC11hC
F”CGlz, CC1aCF”CFa, CF2ClCC
l=CC1,,CFCl,CC1=CC1,,CF,C
C=CC1, CHF2CC=CC1゜CF, CC1=C
lCl, CHF2CC1=CC1,, CF21C
F=CG1! ,CF,'CICC1=ClCl,
CC1, CC=CC1, CF21CF=CF, CF2
1CF=CFi, CFsCBr=CHBr, C
FaCICBr: CHa, CHF2CF=CHF, ,C
F, CBr"CH,, CF2Cl"CHBr, CF, B
rCH=CHF %CF2BrCF=CF, , C
F,CF,CF2CF,,CFsCF”CFCFs,
CFsCH:CFCFs, CF2:CC1=ClC
l, CFaCFaCF"CHa, CH=CHCHCF
3. CF,=CFCF,C1,, CFt=CFCI
ICHI, CF, CH, CH=CH,, CF, CH=C
HCH3,CF,=CHCH1CH8,CH3CF,C
H=CH,, CHFCF=CHFH,, CHsChCH
:CHx, CH*=CFCH*CH*, CFa (CF
al acF=cFt, CF= (CFa)-CF:C
Fluoroolefins such as F-; for example, perfluoroalkyl (meth)acrylates such as perfluorobutylethyl methacrylate, perfluoroisononylethyl methacrylate, perfluorooctyl methacrylate, and the like. These monomers can be used alone or in combination of two or more. ] Copolymer with.

■ Polybasic acids [e.g. (anhydrous) phthalic acid, isophthalic acid, terephthalic acid, azelaic acid, etc.] and polyhydric alcohols [e.g. ethylene glycol, neopentyl glycol, 1,6-hexanediol, pentaerythritol,
polyester (or alkyd) resin obtained by reacting monobasic acid, -hydric alcohol, etc. to have a carboxyl group.

As a hydroxyl group-containing epoxy compound, the following - maximum (8)
Compounds represented by (18) can be mentioned.

9 9 In each formula, R9 is a hydrogen atom or a methyl group, 71 (10 is C
i=a divalent hydrocarbon group, R11 is the same or different divalent hydrocarbon group 01-2°, n! ;t l~
Indicates an integer of 10.

The divalent hydrocarbon group may be linear or hexabranched. As a basis for these, example construction! f-C)f
, -5-C1(2CH2-1-CH,CH,CH2-1
-CH, -CH-CH, -1CH.

C.I.

-CHa-CHz-C-CHg-CHa-1-CaH+
5-1-cIo-Hzo-1CH.

general formula (8) % formula %18) of the compound represented by As a specific example, for example C1, -C-CH, -OH \1 can be mentioned.

As a polyepoxy compound, below - maximum % formula % (26) List the compounds represented by be able to.

aC where R', R'' and R10 have the same meanings as above,
R11, R11 and RI (l may be the same or different. R+i are the same or different, hydrogen atom, C
1-4 alkyl group, W represents 0 and an integer of 1-10.

General formula (19) (26) Compound represented by As a specific example, for example H,C C xC 0 people etc. can be mentioned.

Also, In addition to the above, For example, the following is used can.

etc,. & CH* Adducts of OH and the following polyisocyanate compounds (Polyisocyanate compounds that can be used include, for example, aliphatic diisocyanates such as hexamethylene diisocyanate or trimethylhexamethylene diisocyanate; hydrogenated xylylene diisocyanate, such as isophorone diisocyanate) Organic diisocyanates such as cycloaliphatic diisocyanates such as nitrilene diisocyanate or aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate, or each of these organic diisocyanates and polyhydric alcohols, water etc. for low molecular weight polyester resins. Examples of typical commercially available products include "Parnock D-750, -800,
DN-950, -970 or l5-455" [
The above are Dainippon Ink & Chemical Industry ■ products], "Desmodule L, NHL, IL or N3390J [West German Bayer product 1," Takenate D-102, -2
02, -11ON or 123NJ [Narita Pharmaceutical ■Products] "Coronate L, HL, EH 2
03J [Nippon Polyurethane Kogyo ■ product] or "Duranate 24A-90CXJ [Musei Kogyo ■ product] etc.); adduct with polybasic acid; ester having an unsaturated group in the molecule, such as Examples include chino, which is obtained by oxidizing a chemical compound (for example, an esterified product with a number average molecular weight of 900 obtained by esterifying tetrahydro anophthalic acid, trimethylolpropane, 1,4-butanediol, etc.) with peracetic acid, etc. It will be done.

(2) A resin obtained by reacting a phenolic hydroxyl group-containing resin with a polysiloxane oligomer and a polyepoxy compound.

As the phenolic hydroxyl group-containing resin, the following ■~■'
I can list things.

■ Phenol or cresol type resin (for example, phenol type novolac resin, phenol type resol resin, cresol type novolac resin, etc.).

(2) A polymer containing a phenolic hydroxyl group-containing polymerizable unsaturated monomer (for example, P-vinylphenol, etc.) as an essential monomer component.

■ A resin obtained by adjusting an epoxy group-containing resin and a polyhydric phenol compound (for example, catechol, resorcinol, hydroquinone, pyrogallol, hydroxyhydroquinone, etc.) so that the polyhydric phenol compound is in excess.

■ A resin obtained by reacting an epoxy group-containing resin with a phenolic hydroxyl group-containing compound (eg, hydroxybenzoic acid, etc.).

In addition to methods (1) and (2) described above, resin 6 obtained by reacting a conventionally known amino group- or mercapto group-containing resin with a polysiloxane oligomer and a polyepoxy compound can 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 3.0 and has an average of 2 or more silane groups, preferably an average of about 4 or more silane groups in one molecule.
000-200,000, preferably about 5.000-s
o, ooo. If the number of silane groups is less than about 2 on average, curability tends to be poor, which is not preferred.

Furthermore, when the number average molecular weight is less than about 3,000, weather resistance, curability, chemical resistance, etc. tend to decrease;
If it is larger than .000, the viscosity of the resin composition becomes high, making it difficult to handle, and the compatibility with the resin (II) tends to decrease, which is not preferable.

Resin (II) has a polysiloxane oligomer component in the resin. The component can be introduced by the method described above, for example, by reacting a resin having a functional group such as a carboxyl group, an amino group, or a mercapto group with a polysiloxane oligomer component such that a silane group remains. can.

The resin (III) has an average of about 1 or more epoxy groups, preferably an average of about 1 to 40 epoxy groups in one molecule, and a number average molecular weight of about 400 to 200,000, preferably about 400 to 40.
It can have a range of so, ooo. If the number of epoxy groups is less than about 1 on average, the curability tends to decrease, which is undesirable.In addition, those with a number average molecular weight of less than about 400 are difficult to obtain;
If it is larger than 0, it may become difficult to handle, so it is not preferable.

The resin (III) 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, novolac type, etc.; resins having functional groups (e.g., incyanate groups, hydroxyl groups, carboxyl groups, etc.); and resins that are complementary to the functional groups. Reaction product of a functional group that reacts with the compound (e.g., hydroxyl group, isocyanate group, epoxy group, etc.) and a compound having an epoxy group: Examples include polymers containing the following epoxy group-containing polymerizable unsaturated monomer as an essential component. be able to.

The epoxy group-containing polymerizable unsaturated monomer is a compound having an epoxy group and a radically polymerizable unsaturated group in one molecule. The epoxy group may be alicyclic or aliphatic. The radically polymerizable unsaturated group is CH2=C(R"l COO- e.g. CH2=C(R") CC- CH,=C(R'1C-N- 1 CH2=CHCH2-0- CH,=CHO - CH2=CH- In the formula, R9 has the same meaning as above.

etc. can be mentioned.

The radically polymerizable unsaturated group is CHI・C(R'1COO-
Examples of the epoxy group-containing polymerizable unsaturated monomer include compounds represented by the following formulas (27) to (39), where R9, 10 R'', R'!, and W has the same meaning as above.

As a specific example represented by the general formula (27) (39), for example, the radial force is the combined unsaturated radical force 5CHa・CfR9)C-N
In each formula, R9, R1G and RI2 have the same meanings as above.

-M As specific examples of the compounds represented by formulas (40) to (42), for example, as the boxy group-containing polymerizable unsaturated monomer, for example, compounds represented by the following general formulas (46) to (48) are used. can be mentioned.

In each formula, R@ and RIG have the same meanings as above.

-a Specific examples of the compounds represented by formulas (46) to (48) include the following.

The radically polymerizable unsaturated group is CH, ・C(R'l C-N
-Procedure 1 Examples of the boxy group-containing polymerizable unsaturated monomer include compounds represented by the following general formulas (49) to (54).

In each formula, R", R", F(11 have similar meanings.

General formulas (49) to (54) As a specific example, for example, RI2 and W are as above. Compound represented by can be mentioned.

Examples of the epoxy group-containing polymerizable unsaturated monomer in which the radically polymerizable unsaturated group is CH2=CHCH20- include compounds represented by the following general formulas (55) to (58).

R@ In each formula, R9 and RIG have the same meanings as above.

Specific examples of the compounds represented by the general formulas (55) to (58) include, for example, 口RaG+, =t)lcl! , 0-(L-C-Q(2\1).

Examples of the epoxy group-containing unsaturated monomer whose radically polymerizable unsaturated group is CH, CHO- include the following general formula (59
) to (61) can be mentioned.

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

Specific examples of compounds represented by general formulas (59) to (61) include CHf010- ((](a) s-C→*\1).

Examples of the epoxy group-containing unsaturated monomer whose radically polymerizable unsaturated group is CH2/CH- include the following general formula (62):
Compounds represented by (64) can be mentioned.

R・ In each formula, 0 and R10 have the same meaning as above. have

General formula (62) (64) Compound represented by As a specific example, for example CHf0l-(7) “(7)-(7).

\1 can be mentioned.

As the epoxy group-containing unsaturated monomer whose radically polymerizable unsaturated group is CH, .C(R')+, for example, the following - maximum (
Compounds represented by (65) to (69) can be mentioned.

In each formula, R@, R" and R" have the same meanings as above.

-R9 Specific examples of the compounds represented by formulas (65) to (69) include the following.

In the mixed resin, resins (II) and (III) are desirably blended so that the ratio of silane groups in resin (II) to epoxy groups in resin (III) is approximately 1.

In the polysiloxane resin composition of the present invention, the resin (I) or resin (II) (and/or) resin (III)
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 of any type, such as a solution type using an organic solvent as a medium, a dispersion type, a non-aqueous dispersion type, and a solution type and a single dispersion type using water as a medium.

The above-mentioned non-aqueous dispersion type polysiloxane resin composition is
At least one of resin (I), resin (II) and (III) is used as a dispersion stabilizer, and in the presence of the dispersion stabilizer,
Adding one or more radically polymerizable unsaturated monomers and a polymerization initiator to an organic solvent in which the monomers and the dispersion stabilizer are eluted, but the polymer particles obtained from the monomers are not dissolved. A non-aqueous dispersion can be produced by carrying out a polymerization reaction. (However, resin (I) is used as a dispersion stabilizer.
When only I) or (III) is used, resin (III) or (II) is added to the obtained non-aqueous dispersion, and resin (II) and resin (III) are added to the non-aqueous dispersion. Blend so that the image components are included. ) All of the monomers already described can be used to form the polymer that becomes the particle component of the non-aqueous dispersion. Preferably, the polymer serving as the particle component must not be dissolved in the organic solvent used, so it is preferably a copolymer containing a large amount of highly polar monomers, such as methyl (meth)acrylate, ethyl (meth)acrylate, (meth)acrylonitrile, 2-hydroxy(meth)acrylate, hydroxypropyl(meth)acrylate, (meth)acrylamide, acrylic acid, methacrylic acid, itaconic acid, styrene, vinyltoluene, a-methylstyrene, N-methylol(meth) It is preferable that it contains a large amount of monomers such as acrylamide. Further, the particles of the non-aqueous dispersion can be crosslinked if necessary. An example of a method for crosslinking the inside of the particles is to copolymerize a polyfunctional monomer such as divinylbenzene or 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; alcohol-based, ether-based, ester-based, 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 in general, fatty acids Preferably, the solvent is mainly composed of group hydrocarbons, in combination with aromatic hydrocarbons and alcohol, ether, ester, or ketone solvents such as those mentioned above. Furthermore, trichlorotrifluoroethane, metaxylene hexafluoride, tetrachlorohexafluorobutane, etc. can also be used if necessary.

Polymerization of the above monomers is carried out using a radical polymerization initiator. Usable radical polymerization initiators include, for example, azo initiators such as 2,2-azoisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile); benzoyl peroxide, lauryl peroxide, etc. ,
Examples include peroxide-based initiators such as tert-butyl peroctoate, and these polymerization initiators are generally used within a range 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 polymerization can be selected from a wide range depending on the type of resin, but in general, 3 parts by weight of the radically polymerizable unsaturated monomer are added to 100 parts by weight of the resin. Appropriately, the amount is about 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. be able to. The dispersion stabilizer resin and the polymer particles can be bonded by polymerizing a radically polymerizable unsaturated monomer in the presence of a dispersion stabilizer having a polymerizable double bond.

A method for introducing a polymerizable double bond is to add α,β-ethylenically unsaturated monocarboxylic acid such as acrylic acid, methacrylic acid, or itaconic acid to a part of the oxirane group in the resin. Another convenient method is to add 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 above-mentioned method, as a monomer component forming the polymer particles, for example, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, etc. Ethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-methacryloxybutyltriethoxysilane, γ-
Attachment can be achieved by using reactive monomers such as acryloxypropyltrisilanol.

The resin composition of the non-aqueous dispersion described above is a non-aqueous dispersion in which the same 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 liquid and can significantly increase the solid content during painting, which tends to increase the viscosity after painting and 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 (e.g., aluminum powder, mica powder, etc.), a silane compound (e.g., the silane compound (A)), a hydroxyl group-containing resin, Carboxyl group-containing resins, epoxy resins, coating surface conditioners, etc. can be added.

The curable resin composition of the present invention is obtained by blending an organic metal compound Lewis acid, a protonic acid, a compound having a 5i-0-Al bond, aluminum and an aluminum compound curing reaction catalyst into the polysiloxane resin composition described above. That's what happens.

(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 alkoxides, titanium alkoxides and zirconium alkoxides are preferred. Examples of these preferred metal alkoxide compounds are shown below.

Aluminum alkoxides can be used, for example - up to [wherein R
``indicates an alkyl group or alkenyl group having 1 to 20 carbon atoms, which may or may not be the same.''

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.

Examples of the aluminum alkoxides represented by the general formula (70) include aluminum trimethoxide, aluminum tri-1-oxide, aluminum tri-n-propoxide, aluminum triisopropoxide, aluminum tri-n-butoxide, aluminum triisobutoxide, Aluminum tri-5ee-butoxide, aluminum tri-tert-butoxide, etc., especially aluminum triisopropoxide, aluminum tri-5ee-butoxide, etc.
Preferably, ec-butoxide, aluminum tri-n-butoxide, etc. are used.

The titanium chelate compound is, for example, -max [wherein W
and R1 has the same meaning as above, and titanate represented by 1 can be mentioned.

The titanates represented by -fi formula (71) are:
In those where W is 1, tetramethyltichnate, tetraethyltitanate, tetra-n-propyltitanate, tetraisopropyltichnate, tetra-n-butyltitanate, tetraisobutyltitanate, tetra-ter
Examples include t-butyl titanate, tetra-n-pentyl titanate, tetra-n-hexyl titanate, tetraisooctyl titanate, tetra-n-lauryl titanate, and especially tetraisopropyl titanate, tetra-n
-butyl titanate, tetra-isobutyl titanate, tetra-tert-butyl titanate, etc. give suitable results. In addition, for 6 where W is 1 or more, tetraisopropyl titanate, tetra-n-butyltichnate, tetraisobutyl titanate, tetra-ter
Dimer to decamer of t-butyl titanate (-maximum (
71) with w=1 to 10) gives suitable results.

Zirconium chelate compounds can be used, for example - up to [In the formula, W and R'' have the same meanings as above.] Zirconate represented by:

-IIU The zirconates represented by formula (72) include tetraethylzirconate, tetra-n-probyl ziconate, tetraisopropylzirconate, tetra-n-butylzirconate, tetra-5ec-butylzirconate, tetra- tert-butyl zirconate,
Tetra-n-pentyl zirconate, tetra-tert
- pentyl zirconate, tetra-tert-hexyl zirconate, tetra-n-hebutyl zirconate, tetra-n-tert-hexyl zirconate, tetra-n-stearyl zirconate, etc., especially tetraisopropyl zirconate, tetra- -n-propyl zirconate, tetraisobutyl zirconate, tetra-n-butyl zirconate, tetra-5ec-butyl zirconate, tetra-tert-butyl zirconate, etc. are used to give suitable results. In addition, for those where W is 1 or more, tetraisopropyl zirconate, tetra-n-propyl zirconate, tetra-n-butyl zirconate, tetra-isobutyl zirconate, tetra-5ec-butyl zirconate, tetra-tert-butyl Zirconate 2
mer to 11-mer (- w = 1 to 1 at maximum (72)
0) gives suitable results. Further, it may contain a constituent unit in which these zirconates are associated.

[Metal chelate compound] Aluminum chelate compounds, titanium chelate compounds, and zirconium chelate compounds are preferable, and among these chelate compounds, compounds capable of forming a keto-enol tautomer are used to form a stable chelate fB. 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 keto enol tautomer at a molar ratio of about 3 moles or less per 1 mole of the aluminum alkoxide, and heating if necessary. It can be prepared as follows. Particularly preferred aluminum chelate compounds include, for example, tris(ethylacetoacetate)aluminum, tris(n-propylacetoacetate)aluminum, tris(isopropylacetoacetate)aluminum, tris(n-butylacetoacetate)aluminum, isopropoxybis( ethyl acetoacetate) aluminum, diisopropoxyethylacetoacetate aluminum, tris(acetylacetonato) aluminum, tris(propionylacetonato) aluminum, diisobroboxybrobionyl acetonato aluminum, acetylacetonato bis(
Propionyl acetonato)aluminum, monoethylacetoacetate bis(acetylacetonato)aluminum, and the like can be mentioned.

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 keto-dinol tautomer with a molar ratio of about 4 moles or less per mole of the zirconium alkoxide, and heating if necessary. can be adjusted to 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, the alkyl group of Cl-20 is bonded. Specific examples include triethylaluminum and diethylzinc.

(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, KLCM, AICFs,
AIF,,AI [C-H5lCfz,AI (C-H
,)'CI.

5nC1, TiCmu, TiBr4, Ti
Fa, ZrCノ4, ZrBr4, ZrF4
．． 5nCI<, FeCl5, 5b(Js, 5
bC7s, PCIs-pcm, GaC, GaF
3, InF*, BCmu, BBrs, BFx.

BFi: (OC*HJ a, BF-: (ociH
i) , acm: (octHsl −.

BFI:NJ(,C,H,,BF,:NH2(,H,0
H1BFs: NHCH, CH, CH2CH2, pps
sQ s.

(C,Ll 4P”CH,COO”, (C4H,l S
P"CH, (CLOI, POo, (C4H9) 4P
@C1e, (c4He)-P, (Q+!P, C4H@
Pi(2°(Q+, p・CH, re, etc.) can be mentioned.

(3) Protonic acids The protonic acids include, for example, organic protonic acids such as methanesulfonic acid, ethanesulfonic acid, trifluoro/thanesulfonic acid, benzenesulfonic acid, and P-toluenesulfonic acid; diphosphoric acid, phosphorous acid; Examples include inorganic protonic acids such as acid phosphinic acid, bosphonic acid, sulfuric acid, and perchloric acid.

(4) Compound having 5i=o-A flood bond Specific examples of the compound include a condensate of an alkoxysilane compound and an aluminum alkoxide compound and aluminum silicate.

(5) Aluminum and aluminum compounds Preferably, the aluminum compounds include alumina and the like.

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 blending amount of the crosslinking reaction curing agent is suitably about 0.01 to 30 parts by weight based on 100 parts by weight of the solid content of the resin composition, organic liquid, and aqueous liquid. If it is less than this range, the 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 amount is 0.1 to 10 parts by weight, and the more preferred amount is 1 to 10 parts by weight.
5 parts by weight.

The amount of the crosslinking reaction curing agent (4) and (5) is preferably about 1 to 100 parts by weight based on 100 parts by weight of the solid content of the resin, organic liquid, and aqueous liquid. 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 widely applied to molds and high-temperature baking at 100-160°C. It can be applied to all kinds of objects that are conventionally coated with paint, such as iron plates, plastic materials, and wood. 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 painted in the form of clear paint, etc., using wet-on-wet layered painting methods (so-called 2CIB painting), monocoat painting methods, and 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.For example, air spray electrostatic air spray, airless spray, Bell electrostatic coating, minibell electrostatic Methods such as painting, roll painting, and brush painting 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.

In the present invention, the polysiloxane oligomer can be introduced into various types of resins without gelation and thickening by reacting the epoxy groups in the oligomer with a resin having a functional group that reacts with the epoxy groups. I can do it. Furthermore, 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 the conventional resin having a polysiloxane side chain. Since there are two or more of these, crosslinkability is good and compatibility with other components is also good.

length Examples of the present invention will be shown below.

Production example of polysiloxane oligomer Oligomer (1) Methyltrimethoxysilane 3-glycidoxypropyltrimethoxysilane Deionized water 720g (20mal1 36g (1 mol) 134g 36% hydrochloric acid aqueous solution 2g These mixtures were reacted at 80°C for 5 hours. I let it happen.

The obtained polysiloxane oligomer had a number average molecular weight of 2000, and had on average one epoxy group per molecule and four hydroxyl groups at the terminal portion.

Oligomer (2) Phenyltrisilanol 7aoog (50
mal1 2-(3,4-cyclohexyl)ethyltrisilanol 204g (1mall toluene 45QO [These mixtures were reacted at 117°C for 3 hours and dehydrated. The number average molecular weight of the obtained polysiloxane oligomer was 7
000, each molecule had on average one epoxy group and 5 to 10 hydroxyl groups at the terminal portion.

Oligomer (3) Phenyltriacetoxysilane 6402g F29.1
mol) and 288 g (0.9 mol) of 3-glycidoxybrobyltriacetoxysilane were reacted in the same manner as oligomer (1). The obtained polysiloxane oligomer had a number average molecular weight of about 15,000, and on average had one epoxy group and 5 to 10 acetoxy groups per molecule at the terminal portion.

Production example of resin (a) Trimethylolpropane 137g Neopentyl glycol 945g Phthalic anhydride 444g Adipic acid
1007g of the above mixture
After carrying out the condensation reaction at a reaction temperature of 0°C until the acid value became 2 or less, 54 g of succinic anhydride was added and the reaction temperature was 8°C at 240°C.
The reaction mixture was allowed to react for an hour, and then diluted with xylene to a resin solid content of 50% by weight. The resin had an acid value of 32 and a number average molecular weight of 7.000.

Next, 700g of the above resin solution (50% by weight), 100g of the above oligomer (1) (100% by weight), 100g of methyl isobutyl ketone, and the above mixture was reacted at 140'C for 6 hours.
) solution was obtained. It resin (a) had 3 epoxy groups per molecule and a number average molecular weight of 13.000.

Example of producing resin (b) Add n to 1000 g of equidistant compound of xylene and n-butanol.
-butyl methacrylate-1-618g 2- and a mixture of 160g acrylic acid, 72g styrene, 150g azobisisobutyronitrile, 10g droxyethyl acrylate, iio'
The resin solution was added dropwise over a period of 3 hours at c, and then reacted at the same temperature for 2 hours to obtain a resin solution.

The resin solution has a solid content of 50% by weight and a resin number average molecular weight of 250.
It was 00.

Next, 1000 g of the above resin solution (50% by weight) and 280 g of the above oligomer (2) (100% by weight) were reacted at 110° C. for 5 hours to obtain a resin (b) solution. Resin (b) had 23 epoxy groups per molecule and a number average molecular weight of 45.000.

Production example of resin (c) Isocyanate ethyl methacrylate 155gn-
Butyl methacrylate 819g Styrene 150g2.2'-
Azobis(2,4-dimethylvaleronitrile)
10g of the above mixture was dropped into 1000g of xylene. The reaction was carried out at 100° C. After the completion of the reaction, 7.8 g of 2-mercaptoethanol was added to obtain a mercapto group-containing resin solution (solid content: 50% by weight) having a number average molecular weight of 28,000.

Next, 1000g of the above resin solution (50% by weight) 750g of the above oligomer (3) (100% by weight) 750g of methyl isobutyl ketone The above mixture was reacted at 140°C for 14 hours. ) solution was obtained. Resin (c) had 25 epoxy groups per molecule and a number average molecular fi of 80.000.

Examples 1 to 9 Compositions of Examples were obtained by blending the resin (a) to (c) solutions described above and a curing reaction catalyst (each 1 part by weight per 100 parts by weight of resin solid content) into the resin solution. Ta.

[Coating Film Performance Test] Each of the compositions of Examples 1 to 9 was coated to a dry film thickness of about 50 μ, dried, and subjected to a test.

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

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

Acid resistance: A glass plate was used as the material. The test piece was heated to 40% H2
The appearance of the coating film (
(blurring, whitening, etc.) was observed.

Storage stability: The time during which the viscosity did not increase when the product was 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; A silane monomer having an epoxy group is reacted with the silane monomer, and each molecule contains an average of one or more epoxy groups and a hydroxyl group and/or a hydrolyzable group directly bonded to a silicon atom at the terminal corresponding portion. A polysiloxane oligomer characterized by having two or more oligomers. [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] The polysiloxane resin composition according to claim 2 contains an organometallic compound, a Lewis acid, a protonic acid, a Si-
A curable resin composition comprising one or more curing reaction catalysts selected from a compound having an O-Al bond, aluminum, and an aluminum compound.