JPH0558009B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a novel curable resin composition that provides a cured product with little yellowing during curing and excellent weather resistance, and is useful for applications such as paints, adhesives, and sealants. It is. [Prior Art] It has been believed that compositions containing a basic nitrogen-containing vinyl polymer as a base resin and a polyepoxy compound as a curing agent can be cured at room temperature and provide a cured product with excellent weather resistance. It's here (Japanese Patent Application Publication No. 1973)
-76338, patent application No. 57-166795). [Problems to be solved by the present invention] In recent years, there has been a desire to develop maintenance-free outdoor paints, sealants, etc. that have a high degree of weather resistance. In some cases, the gloss and strength decrease significantly after about two years of outdoor exposure, and the weather resistance is insufficient.
The drawback was that the cured product turned yellow when forced drying at relatively high temperatures exceeding 100°C. [Means for Solving the Problem] However, in order to overcome the drawbacks of the prior art as described above, the present inventors developed a hydrolyzable system consisting of a vinyl polymer containing basic nitrogen and a polyepoxy compound. By incorporating a compound containing a silyl group or a silanol compound
No yellowing even when forced drying at temperatures above 100℃.
The present invention was completed by discovering that it is possible to obtain a composition that provides a cured product with significantly improved weather resistance. That is, the present invention comprises (A) a vinyl polymer containing basic nitrogen, (B) a polyepoxy compound, and (C)
A compound containing a hydrolyzable silyl group (C-1) and/or a compound containing a silanol group (C-1)
-2) and, if necessary, (D) the silyl group hydrolysis-condensation catalyst. Here, first, the above-mentioned basic nitrogen-containing vinyl polymer (A) has at least one, preferably two or more, primary amino groups in one molecule,
It refers to a vinyl polymer containing at least one type of amino group selected from the group consisting of a secondary amino group and a tertiary amino group, and a tertiary amino group is particularly preferred from the viewpoint of weather resistance. Such a vinyl polymer (A) is obtained by (co)polymerizing a vinyl monomer containing a primary, secondary or tertiary amino group with another copolymerizable vinyl monomer as necessary. or a vinyl monomer (a-1) containing a carboxylic anhydride group, a group each having an active hydrogen in one molecule that can react with at least one carboxylic anhydride group, and a tertiary amino group. It can be prepared by a known method such as reacting the compound (a-2) with the compound (a-2). Specific examples of the vinyl monomer containing an amino group used in preparing the vinyl polymer (A) by the above method include dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, Dialkylaminoalkyl (meth)acrylates such as dimethylaminopropyl (meth)acrylate, diethylaminopropyl (meth)acrylate; N-dimethylaminoethyl (meth)acrylamide, N-diethylaminoethyl (meth)acrylamide, N-dimethylaminopropyl ( meth)acrylamide,
N-dialkylaminoalkyl (meth)acrylamides such as N-diethylaminopropyl (meth)acrylamide; furthermore t-butylaminoethyl (meth)acrylate, t-butylaminopropyl (meth)acrylate, aziridinylethyl (meth) There are acrylates, pyrrolidinylethyl (meth)acrylate, and piperidinylethyl (meth)acrylate, but from the viewpoint of curability, dialkylaminoalkyl (meth)acrylates and N-dialkylaminoalkyl (meth)acrylamides is particularly preferred. Specific examples of other vinyl monomers that can be copolymerized with the above-mentioned amino group-containing monomers include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, Acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl ( (meth)acrylate, such as benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate; Acrylic acid esters; dimethyl maleate, dibutyl maleate,
Dialkyl esters of unsaturated dibasic acids such as dimethyl fumarate, dibutyl fumarate, dibutyl itaconate; (meth)acrylic acid, monobutyl maleate, monobutyl fumarate, crotonic acid, maleic acid, fumaric acid, itaconic acid monomers containing carboxyl groups such as; monomers containing acid anhydride groups such as maleic anhydride and itaconic anhydride; (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N-alkoxymethyl ( Carboxylic acid amide group-containing monomers such as meth)acrylamide, diacetone (meth)acrylamide, and N-methylol(meth)acrylamide;
p-styrenesulfonamide, N-methyl-p-
Styrene sulfonamide, N,N-dimethyl-p
- Sulfonamide group-containing monomers such as styrene sulfonamide; cyano group-containing monomers such as (meth)acrylonitrile; α, β such as the above-mentioned hydroxyalkyl esters of (meth)acrylic acid;
- Monomers having a phosphoric ester group, which are condensation products of hydroxyalkyl esters of ethylenically unsaturated carboxylic acids and phosphoric acid or phosphoric esters; p-styrenesulfonic acid, 2-acrylamido-2-methyl-propanesulfonic acid Sulfonic acid group-containing monomers such as vinyl acetate, vinyl benzoate, vinyl esters such as "Beoba" (product of Siel, Netherlands); "Viscoat 8F, 8FM,
3F or 3FM” [fluorine-containing (meth)acrylic monomers manufactured by Osaka Organic Chemical Co., Ltd.], perfluorocyclohexyl (meth)acrylate, diperfluorocyclohexyl fumarate or N-isopropyl perfluorooctane sulfonamidoethyl Monomers containing fluoroalkyl or perfluoroalkyl groups such as (meth)acrylate; halogenated olefins such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, and chlorotrifluoroethylene; styrene,
Vinyltoluene, α-methylstyrene, p-t-
There are aromatic vinyl monomers such as butylstyrene. In order to obtain the vinyl polymer (A) used in the present invention from the monomers described above, 0.5 to 100% by weight, preferably 1 to 50% by weight of the amino group-containing monomer is used.
99.5 to 0% by weight of other copolymerizable monomers,
Preferably, 99 to 50% by weight may be (co)polymerized. In addition, the vinyl polymer (A) can be produced by using together the above-mentioned carboxyl group- or phosphate group-containing monomers as copolymerizable monomers.
A carboxyl group or a phosphoric acid ester group can be introduced therein, which is preferable from the viewpoint of further improving the curability of the composition of the present invention. To prepare the vinyl polymer (A) from such monomers, any conventionally known polymerization method can be applied, but solution radical polymerization is the simplest method. Typical solvents used in this case include toluene, xylene, cyclohexane, n-
Hydrocarbon solvents such as hexane and octane; methanol, ethanol, i-propanol, n-butanol, i-butanol, sec-butanol,
Alcohol solvents such as ethylene glycol monomethyl ether; ester solvents such as methyl acetate, ethyl acetate, n-butyl acetate, and amyl acetate;
Examples include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, and cyclohexanone, and any mixtures thereof may of course be used. Solution radical polymerization may be carried out by a conventional method using the solvent and various radical polymerization initiators such as azo type or peroxide type. Chain transfer agents such as lauryl mercaptan, octyl mercaptan, 2-mercaptoethanol, octyl thioglycolate, 3-mercaptopropionic acid or α-methylstyrene dimer can also be used. Vinyl polymer (a-1) containing a carboxylic acid anhydride group used in preparing the vinyl polymer (A) containing basic nitrogen by the following method
In this method, a monomer having a carboxylic acid anhydride group such as maleic anhydride or itaconic anhydride, and monomers copolymerizable with these are radical-treated in the above-mentioned solvents excluding alcohols. It can be prepared by polymerization. Monomers copolymerizable with the monomer having a carboxylic anhydride group used in preparing the vinyl polymer (a-1) containing the carboxylic anhydride group include amino group-containing monomers as described above. Among the vinyl monomers copolymerizable with the monomers mentioned above, any vinyl monomers other than those containing hydroxyl groups can be used. The amount of the monomer containing the above-mentioned carboxylic acid anhydride group to be used is determined from the viewpoint of weather resistance, alkali resistance, etc.
The amount of the copolymerizable monomer is preferably 0.5 to 50% by weight, more preferably 1 to 20% by weight, and the amount of the other copolymerizable monomer used is preferably 99.5 to 50% by weight, more preferably 99 to 80% by weight. In addition, the combined use of a monomer containing a carboxyl group or a phosphoric acid/ester group as described above as a component of the copolymerizable monomer can shorten the reaction time in the reaction with (a-2) described below. , is preferable in that it greatly improves the curability of the composition of the present invention. Next, the compound (a-2) having both a group having an active hydrogen that can react with the carboxylic acid anhydride group (hereinafter abbreviated as an active hydrogen-containing group) and a tertiary amino group is It refers to compounds containing groups such as a hydroxyl group, a primary or secondary amino group, or a thiol group, and among these, the most preferred compounds include alcohols and alcohols containing a tertiary amino group. Examples include primary or secondary amines having a tertiary amino group. Of these, typical alcohols with a tertiary amino group include adducts of secondary amines and epoxy compounds, but typical secondary amines used here include dimethylamine. , diethylamine, dipropylamine,
dibutylamine, ethyleneimine, morpholine,
These include piperazine, piperidine, and pyrrolidine, as well as secondary amino group-containing amino alcohols obtained by adding primary amines such as methylamine, ethylamine, and butylamine to mono- or polyepoxy compounds. On the other hand, typical epoxy compounds include ethylene oxide, propylene oxide, butylene oxide, dodecene oxide, styrene oxide, cyclohexene oxide, butyl glycidyl ether or phenyl glycidyl ether;
- Monoepoxy compounds such as t-butylbenzoic acid glycidyl ester or "Carduura E-10" (glycidyl ester of branched fatty acids manufactured by Siel, Netherlands); or ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, Polyglycidyl ethers of polyhydric alcohols such as 6-hexanediol diglycidyl ether, diglycidyl ether of bisphenol A or triglycidyl ether of glycerin; diglycidyl ester of phthalic acid, diglycidyl ester of isophthalic acid or diglycidyl ester of adipic acid. Polyglycidyl esters of polyhydric carboxylic acids such as glycidyl esters; or polyepoxy compounds such as various epoxy resins such as diglycidyl ether type epoxy resins of bisphenol A or bisphenol F, novolak type epoxy resins, or hydantoin ring-containing epoxy resins. In addition, there are glycidyl ester ethers of p-oxybenzoic acid and various vinyl polymers having epoxy groups in their side chains. Typical alcohols containing tertiary amino groups obtained by reacting secondary amines with epoxy compounds include dimethylaminoethanol, diethylaminoethanol, di-n-propylaminoethanol, diisopropylaminoethanol, and di-n-propylaminoethanol. -butylaminoethanol, N-(2
-hydroxyethyl)morpholine, N-(2-hydroxyethyl)piperidine, N-(2-hydroxyethyl)pyrrolidine, N-(2-hydroxyethyl)aziridine, N,N-dimethyl-2-hydroxypropylamine, N, N-diethyl-2
-Hydroxypropylamine, triethanolamine or tripropanolamine, etc. In addition to those listed above, the tertiary amino group-containing alcohols include amino alcohols such as ethanolamine and propanolamine. , dimethylaminoethyl (meth)
Acrylate, having a tertiary amino group such as diethylaminoethyl (meth)acrylate (meth)
Adduct with acrylate monomer or said 3
A tertiary amino group and a hydroxyl group are added to the side chain obtained by copolymerizing a tertiary amino group-containing (meth)acrylate monomer with a hydroxyl group-containing monomer such as β-hydroxyethyl (meth)acrylate. Vinyl-based polymers can also be used. In addition, typical examples of the above-mentioned primary or secondary amines containing a tertiary amino group include N,N-
Dimethyl-1,3-propylenediamine, N,N
- N,N-dialkyl-1,3-propylene diamines such as diethyl-1,3-propylene diamine; N,N-dimethyl-1,4-tetramethylene diamine, N,N-diethyl-1,4-tetra N,N-dialkyl- such as methylene diamine
1,4-tetramethylenediamine; N,N-dimethyl-1,6-hexamethylenediamine, N,
N,N-dialkyl-1,6-hexamethylene diamines such as N-diethyl-1,6-hexamethylene diamine; or N-methylpiperazine;
N-alkylpiperazines such as N-ethylpiperazine; or the above-mentioned tertiary amino group-containing (meth)
Examples include adducts of acrylate monomers with ethylenediamine, propylenediamine, hexamethylenediamine, piperazine, methylamine, ethylamine, butylamine, or ammonia. From the viewpoint of curability, N,N-dialkylaminoethanol and N,N-dialkylalkylenediamine are particularly preferred compounds (a-2)
It is mentioned as. In order to obtain the polymer (A), which is the base resin component in the composition of the present invention, from the above-mentioned compound (a-1) and compound (a-2), compound (a-
Compound (a-
2) Mix both compounds at a ratio such that the active hydrogen-containing group in the mixture is about 0.5 to 3 equivalents, and heat from room temperature.
The reaction may be carried out in a temperature range up to about 120°C. In addition, when using a compound having both a tertiary amino group and a primary amino group such as N,N-dimethyl-1,3 propylene diamine as compound (a-2), these compounds (a-1) and Compound (a
-2), first of all, a polymer [] having a carboxyl group and an N-monosubstituted amide group is obtained as shown in the following reaction formula. The obtained polymer [] can be used as it is in the present invention, but for applications that require stain resistance and alkali resistance of cured coatings, such a polymer [] can be used as is. 70~
It is preferable to convert the polymer into an imide ring-containing polymer [] by dehydrating and ring-closing it at a temperature of about 150° C., and use it as the base resin component (A) of the composition of the present invention. Next, the polyepoxy compound (B), which is the curing agent component of the composition of the present invention, is a compound containing at least two epoxy groups in one molecule, and alcohols having a tertiary amino group as described above. Any polyepoxy compound used in the preparation can be used. Among these, vinyl polymers having an epoxy group in the side chain, such as polyglycidyl ether of aliphatic polyhydric alcohol and glycidyl (meth)acrylate copolymer, are preferred from the viewpoint of weather resistance. The compound (C-1) containing a hydrolyzable silyl group, which is one of the components (C) of the present invention, has the general formula [However, R ¹ in the formula is a hydrogen atom or an alkyl group,
A monovalent organic group such as an aryl group or an aralkyl group, R ² is a halogen atom or an alkoxyl group,
represents an acyloxy group, phenoxy group, iminooxy group or alkenyloxy group, and n
is an integer of 0, 1, or 2. ] Halosilyl group, alkoxysilyl group represented by
It refers to low molecular weight compounds or resins containing reactive groups that are easily hydrolyzed, such as acyloxysilyl groups, phenoxysilyl groups, iminosilyl groups, or alkenyloxysilyl groups. Representative examples of the compound (C-1) containing such a hydrolyzable silyl group include tetramethoxysilane, trimethoxysilane, tetraethoxysilane, triethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetraoctoxysilane, Tetrakis(2-methoxyethoxy)silane, tetrabenzyloxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, phenyltriethoxysilane, dimethyldiethoxysilane, diphenyldiethoxysilane, γ-chloropropyl Trimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-isocyanatopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane , γ-aminopropyltrimethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane; tetraisopropenyloxysilane;
Phenyltriisopropenyloxysilane, γ-
glycidoxypropyltriisopropenyloxysilane, γ-isocyanatopropyltriisopropenyloxysilane, γ-methacryloxypropyltriisopropenyloxysilane, γ-mercaptopropyltriisopropenyloxysilane, tetrabutenyloxysilane, γ- Alkenyloxysilanes such as glycidoxypropyltributenyloxysilane; tetraacetoxysilane, methyltriacetoxysilane, γ-mercaptopropyltriacetoxysilane, tetrapropionyloxysilane, phenyltripropionyloxysilane, γ-glycidoxypropyl Acyloxysilanes such as triacetoxysilane and vinyltriacetoxysilane; tetrachlorosilane,
Halosilanes such as methyltetrachlorosilane, phenyltrichlorosilane, tetrabromosilane, benzyltribromosilane; tetrakis(dimethyliminooxy)silane, methyltris(dimethyliminooxy)silane, tetrakis(methyl-ethyliminooxy)silane, γ - Iminoxysilanes such as methacryloxypropyltris(dimethyliminooxy)silane and γ-mercaptopropyltris(dimethyliminooxy)silane; Containing siloxane oligomers: Siloxane oligomers containing an alkenyloxy group obtained by partial hydrolytic condensation of the above-mentioned alkenyloxysilanes; γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxy described above Homopolymers of vinyl monomers containing hydrolyzable silyl groups such as silane, vinyltriethoxysilane, and vinyltriacetoxysilane, or copolymers with monomers copolymerizable with these monomers. Coalescence: Using a mercaptan containing a hydrolyzable silyl group such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriisopropenyloxysilane, and γ-mercaptopropyltriacetoxysilane as a chain transfer agent, as necessary. A vinyl polymer containing a hydrolyzable silyl group at the terminal obtained by (co)polymerizing a vinyl monomer containing a vinyl monomer having a hydrolyzable silyl group as described above; a polyhydric alcohol hydroxyl group-containing acrylic resins, hydroxyl group-containing alkyd resins, hydroxyl group-containing polyester resins,
Alternatively, it can be obtained by reacting a polyhydroxy compound such as a polyether polyol with a compound containing a hydrolyzable silyl group such as the above-mentioned alkoxysilanes by the method disclosed in Japanese Patent Application No. 57-51183. Compounds; low molecular weight polyallyl compounds such as diallyl succinate, triallyl trimellitate, diallyl phthalate, unsaturated compounds such as unsaturated group-containing vinyl polymers, unsaturated group-containing polyester resins or unsaturated group-containing alkyd resins; Adducts with hydrosilanes containing hydrolyzable silyl groups such as trimethoxysilane and triethoxysilane; compounds containing epoxy groups such as vinyl polymers and epoxy resins containing epoxy groups and the above-mentioned mercaptosilanes adduct; obtained by reacting the above polyhydroxy compound with a hydrolyzable silyl group-containing compound having an isocyanate group such as γ-isocyanatopropyltrimethoxysilane or γ-isocyanatopropyltriisopropenyloxysilane Resins containing urethane bonds; and silicone resins having a hydrolyzable silyl group at the end of the molecule. Next, specific examples of the compound (C-2) containing a silanol group, which is one of the components (C) of the present invention, include methyltrichlorosilane, phenyltrichlorosilane, ethyltrichlorosilane, dimethyldichlorosilane, Silanol compounds such as those obtained by almost complete hydrolysis of halosilanes such as silane and diphenyldichlorosilane; Polysiloxanes having silanol groups obtained by further dehydration condensation of the silanol compounds; Alkoxysilanes listed above polysiloxanes containing silanol groups obtained by hydrolyzing and condensing compounds such as alkenyloxysilanes; silicone resins having silanol groups at the ends; and Toray silicone.
There are silanol compounds having a cyclic siloxane structure, such as SH-6018 (manufactured by Toray Silincon Co., Ltd.). (C-1) component and (C-2) listed above
Each of the components can be used alone or as a mixture of two or more. Of component (C-1) and component (C-2), component (C-1) is more preferred from the viewpoint of the pot life of the composition and the smoothness of the resulting cured product. Among the components (C-1), from the point of view of economy or smoothness of the cured product, tetra(substituted) alkoxysilanes, partially hydrolyzed condensates of tetra(substituted) alkoxysilanes, tetraalkenyloxysilanes, tetra A partially hydrolyzed condensate of alkenyloxysilanes, a compound obtained by reacting a polyhydroxy compound with a compound having at least two (substituted) alkoxy or alkenyloxy groups bonded to a silicon atom in one molecule, a (substituted) ) Alkyd resin containing an alkoxysilyl group or alkenyloxysilyl group, polyester resin containing a (substituted) alkoxysilyl group or alkenyloxysilyl group, vinyl polymer containing a (substituted) alkoxysilyl group or alkenyloxysilyl group Among them, from the viewpoint of curability, γ-glycidoxypropyltrimethoxysilane,
A vinyl polymer obtained by polymerizing a monomer mixture containing γ-glycidoxypropyltriisopropenyloxysilane or glycidyl (meth)acrylate and γ-methacryloxypropyltrimethoxysilane as essential monomer components. Particularly preferred are compounds having both an epoxy group and a hydrolyzable silyl group. The composition of the present invention has good curability even without the addition of a curing catalyst, but if it is desired to further improve the curability, a silyl group hydrolysis-condensation catalyst (D) can be added. Specific examples of such catalysts (D) include basic compounds such as sodium hydroxide, lithium hydroxide, potassium hydroxide, and sodium methylate; tetraisopropyl titanate, tetrabutyl titanate,
Metal-containing compounds such as tin octylate, lead octylate, cobalt octylate, zinc octylate, calcium octylate, lead naphthenate, cobalt naphthenate, dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin dimaleate; p - Acidic compounds such as toluenesulfonic acid, trichloroacetic acid, phosphoric acid, monoalkylphosphoric acid, dialkylphosphoric acid, monoalkylphosphorous acid, and dialkylphosphorous acid. In order to obtain the resin composition of the present invention from the components (A) to (D) listed above, one of the reactive functional groups (amino group, carboxyl group and/or phosphoric acid ester group) of component (A) is required. The epoxy group of component (B) is
Both components (A) and (B) are used in a ratio such that the amount is about 0.2 to 5 equivalents, more preferably about 0.5 to 3 equivalents, and (A), (B)
0.5 to 0.5 parts of component (C) per 100 parts by weight of both components
1000 parts by weight, more preferably about 2 to 500 parts by weight, and if necessary, component (D).
It may be added in an amount of about 0.01 to 10 parts by weight per 100 parts by weight of the total amount of (A), (B), and (C). The composition of the present invention may further contain organic or inorganic pigments as necessary; various additives such as known and commonly used flow regulators, color separation inhibitors, ultraviolet absorbers, and antioxidants; Cellulose derivatives such as nitrocellulose and cellulose acetate butyrate; various resins such as chlorinated polyethylene, chlorinated polypropylene, petroleum resin, and chlorinated rubber can be added. Further, the composition of the present invention can be used as a solvent-free composition or as a solution-type composition by adding a solvent. [Effects of the Invention] The composition of the present invention thus obtained can be applied to various substrates by a conventional method and then dried at room temperature for several days to obtain a cured product with excellent weather resistance. Even when cured at temperatures exceeding ℃, a cured product with little yellowing can be obtained, so it can be used as a coating for automobile repair, woodworking, architecture, building materials, and various plastic products, as well as as a sealant or Can be used as an adhesive. [Example] Next, the present invention will be specifically explained using reference examples, examples, and comparative examples, and unless otherwise specified, all parts and percentages are based on weight. Reference Example 1 [Preparation example of basic nitrogen-containing polymers (A)] 392 parts of toluene and 408 parts of isobutanol were charged into a reactor equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a reflux condenser, and nitrogen was added. 80℃ under atmosphere
At elevated temperature to was added dropwise over 3 hours. After keeping at the same temperature for 2 hours
5 parts AIBN, 448 parts toluene and isobutanol
A mixture consisting of 37 parts was added dropwise over the course of 1 hour. It is then kept at the same temperature for 12 hours to remove non-volatile content (NV).
A solution of a tertiary amino group-containing vinyl polymer (A) having a number average molecular weight (n) of 12,000 at 40% was obtained. below,
This polymer solution is abbreviated as polymer (A-1). Reference Examples 2 to 5 [Same as above] In place of 900 parts of methyl methacrylate and 100 parts of dimethylaminoethyl methacrylate,
Solutions of tertiary amino group-containing vinyl polymers (A-2) to (A-5) with an NV of 40% were obtained in the same manner as in Reference Example 1 except that the monomers listed in the table were used. .
Hereinafter, these polymer solutions were added to polymers (A-2) to
It is abbreviated as (A-5).

[Table] Reference Example 6 [Same as above] 300 parts of toluene and 400 parts of butyl acetate were charged into the same reactor as in Reference Example 1, and the mixture was heated to 110 parts under a nitrogen atmosphere.
The temperature was raised to ℃. Next, 100 parts of styrene, 400 parts of methyl methacrylate, 300 parts of n-butyl methacrylate, 130 parts of n-butyl acrylate, 30 parts of acrylic acid, 40 parts of maleic anhydride, 10 parts of AIBN,
A mixture consisting of 5 parts of TBPO, 5 parts of t-butyl peroxybenzoate (TBPB) and 300 parts of toluene was added dropwise over 3 hours and then kept at the same temperature for 15 hours to continue the reaction until the NV was 50%.
A solution of a vinyl polymer (a-1) having an acid anhydride group and a carboxyl group with Mn of 10,000 was obtained.
Hereinafter, this solution was added to vinyl polymer (a-1-1).
It is abbreviated as Next, this vinyl polymer (a-1-1)
After the temperature was lowered to 70°C, 40 parts of N,N-dimethylaminoethanol was added to it, and then the temperature was lowered to 55°C.
The mixture was maintained for a period of time, and 270 parts of n-butanol was further added to obtain a solution of the polymer (A) containing tertiary amino groups and carboxyl groups with an NV of 45%. Hereinafter, this polymer solution will be abbreviated as polymer (A-6). Reference Example 7 [Same as above] A polymer containing a tertiary amino group and a carboxyl group with an NV of 45 was prepared in the same manner as Reference Example 6, except that the same amount of itaconic anhydride was used instead of maleic anhydride. A solution of coalescence (A) was obtained. below,
This polymer solution is abbreviated as polymer (A-7). Reference Example 8 [Same as above] 1000 parts of the vinyl polymer (a-1-1) having an acid anhydride group and a carboxyl group obtained in Reference Example 6 was heated to 90°C under a nitrogen stream and heated to N, 20.8 parts of N-dimethyl-1,3-propylene diamine was added and the mixture was maintained at the same temperature for 6 hours to carry out a dehydration reaction. During this period, the acid value was 22.7 at the beginning of the reaction, but it decreased to 12.5 at the end of the reaction. From this, it is clear that about 90 mol% of the amide groups once generated were converted to imide rings. Furthermore, according to IR spectrum analysis, the absorption of the amide group disappeared, and instead, an absorption at 1700 cm ^-1 due to the imide ring was confirmed. 135 parts of n-butanol was added to the imide ring-containing polymer solution obtained in this way to obtain NV.
Polymer (A) with a Gardner color of 45% and a Gardner color of 1 or less
A solution of was obtained. Hereinafter, this polymer solution will be abbreviated as polymer (A-8). Reference Example 9 [Preparation Example of Polyepoxy Compound (B)] 800 parts of toluene and 500 parts of sec-butanol were charged into the same reactor as in Reference Example 1, and the temperature was raised to 105°C under a nitrogen atmosphere to prepare glycidyl methacrylate. 500 parts, n-butyl methacrylate 200 parts, n
- 300 parts of butyl acrylate, 50 parts of TBPO,
A mixture of 5 parts of TBPB and 200 parts of toluene was added dropwise over 8 hours and then heated to the same temperature for 15 minutes.
Vinyl polymer containing epoxy groups with NV of 40% and 4000 when kept for a long time to continue the reaction
A solution (B) was obtained. Hereinafter, this polymer solution will be abbreviated as polymer (B-1). Reference Example 10 [Preparation example of compound (C-1) containing a hydrolyzable silyl group] 500 parts of toluene and 800 parts of n-butanol were charged into the same reactor as in Reference Example 1, and the mixture was heated to 105°C under a nitrogen atmosphere. At elevated temperature, 400 parts of γ-methacryloxypropyltrimethoxysilane, 200 parts of methyl methacrylate, 400 parts of n-butyl acrylate,
NV
A solution of a vinyl polymer (C-1) containing trimethoxysilyl groups of 40% and 4000 was obtained. Hereinafter, a solution of this polymer was added to the polymer (C-1-
It is abbreviated as 1). Reference Example 11 [Same as above] Triisoprobenyloxysilyl was prepared in the same manner as Reference Example 10, except that 500 parts of γ-methacryloxypropyltriisoprobenyloxysilane was used instead of 400 parts of γ-methacryloxypropyltrimethoxysilane. A solution of the group-containing polymer (C-1) was obtained. Hereinafter, a solution of this polymer was added to the polymer (C
-1-2). Reference Example 12 [Same as above] 134 parts (1 mol) of trimethylolpropane, 684 parts (6 mol) of ε-caprolactone, and 0.04 part of tetrabutyl titanate were placed in the same reactor as in Reference Example 1, and the mixture was heated at 180°C under a nitrogen atmosphere. The reaction was carried out for 6 hours to obtain an adduct (polyester resin) in which the molar ratio of trimethylolpropane and ε-caprolactone was 1:6. Next, after raising the temperature to 90°C, 936 parts of tetraethyl silicate (equivalent ratio of tetraethyl silicate to hydroxyl group = 1.5) and 5.3 parts of tetrabutyl titanate were added, and the temperature was raised at 110 to 120°C until the distillation of ethanol stopped (3 time) to obtain a polyester resin (C-1) containing an ethoxysilyl group. Hereinafter, this will be referred to as a polymer (C-1
-3). Reference Example 13 [Same as above] Ethylene glycol was placed in the same reactor as Reference Example 1.
62 parts (1 mol), ε-caprolactone 2280 parts (20
mol) and 0.12 parts of tetrabutyl titanate were charged, the temperature was raised to 180°C under a nitrogen atmosphere, and the temperature was maintained for 6 hours to obtain an adduct with a molar ratio of ethylene glycol and ε-caprolactone of 1:20. Next, after cooling down to 90℃, 1180 parts of butyl acetate,
γ-Isocyanatopropyltrimethoxysilane
410 parts of tin octylate and 0.14 parts of tin octylate were added and kept at the same temperature for 10 hours to obtain a polyester resin (C
-1) was obtained. Hereinafter, this will be referred to as a polymer (C-1-
4). Reference Example 14 [Same as above] 157.4 parts of adipic acid was placed in a reactor equipped with a stirring device, a thermometer, a nitrogen introduction pipe, and a reaction product water distillation pipe
Hexahydrophthalic anhydride 300 parts, trimethylolpropane 203.8 parts, neobentyl glycol 230 parts
and 200 parts of coconut oil fatty acid were charged and the temperature was gradually raised to 230°C over 5 hours under a nitrogen stream until the acid value decreased.
Dehydrated and condensed by holding at the same temperature until the temperature reached 10.
An alkyd resin with a hydroxyl value of 125 was obtained. Then,
After the temperature was lowered to 90°C, 624 parts of butyl acetate, 456 parts of γ-isocyanatopropyltrimethoxysilane and 0.07 parts of tin octylate were added, and the temperature was lowered to 10°C.
After holding for a period of time, an alkyd resin (C-1) containing a trimethoxysilyl group having an NV of 70% was obtained. Hereinafter, this will be abbreviated as polymer (C-1-5). Reference Example 16 [Compound containing silanol group (C
Preparation example of -2)] 534 parts of methyltriethoxysilane, 162 parts of water, and 0.5 g of 0.1N hydrochloric acid were placed in a reactor equipped with a stirrer, a thermometer, and a reflux condenser, and the mixture was heated for 80 minutes while stirring well.
Heated at ℃ for 4 hours. Next, the ethanol was distilled off to obtain a 50% NV solution, and the mixture was further heated under reflux for 20
heated for an hour. Residual ethanol and water were distilled off from the solution obtained in this way under reduced pressure to form a white powdery hydrolyzed condensate of methyltriethoxysilane (C-
2) was obtained. Hereinafter, this will be abbreviated as polymer (C-2-1). Examples 1 to 15 and Comparative Examples 1 to 8 After preparing a white paint of 40% PWC with the blending ratios (parts by weight) shown in Tables 2, 3, and 4, toluene/xylene/n-butanol/ Cellosolve acetate = 40/20/30/10 (weight ratio) diluted to spray viscosity with a mixed solvent, spray painted onto zinc phosphate treated steel plate to a dry film thickness of approximately 50μm, and dried at room temperature for 7 days. A cured coating film was obtained by allowing the mixture to dry or heating at 120° C. for 10 minutes. The weather resistance of each coating film thus obtained was evaluated by exposing it outdoors for two years in Miyazaki Prefecture. In addition, the solvent resistance, smoothness, and degree of coloration of each cured coating film were also evaluated. The results of Examples 1 to 5 and Comparative Examples 1 to 5 were
The results of Examples 6 to 8 and Comparative Examples 6 to 8 are shown in Table 3, and the results of Examples 9 to 16 are shown in Table 4.

【table】

【table】

【table】

【table】

【table】

【table】

Claims (1)

[Claims] 1. (A) a vinyl polymer containing basic nitrogen, (B) a polyepoxy compound, and (C) a compound containing a hydrolyzable silyl group (C-
1) and/or a silanol group-containing compound (C-2); and, if necessary, (D) a silyl group hydrolysis-condensation catalyst. . 2. The vinyl polymer (A) is at least one vinyl monomer selected from the group consisting of dialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylate, N-dialkylaminoalkylacrylamide, and N-dialkylaminoalkylmethacrylamide. The curable resin composition according to claim 1, which is obtained by copolymerizing the above with a vinyl monomer copolymerizable with the above. 3. A group in which the vinyl polymer (A) has an active hydrogen that can react with at least one carboxylic anhydride group in each molecule of the vinyl polymer (a-1) containing a carboxylic acid anhydride group; The curable resin according to claim 1, which is a polymer containing a tertiary amino group obtained by reacting the compound (a-2) with a tertiary amino group. Composition. 4. The curable resin composition according to claim 1, wherein the vinyl polymer (A) also contains a carboxyl group and/or a phosphate ester group. 5 The compound (C-1) containing a hydrolyzable silyl group is a tetra(substituted) alkoxysilane,
Partially hydrolyzed condensates of tetra(substituted) alkoxysilanes, tetraalkenyloxysilanes, partially hydrolyzed condensates of tetraalkenyloxysilanes, bonded to a silicon atom in one molecule (substituted)
A compound obtained by reacting a compound having at least two alkoxy groups or alkenyloxy groups with a polyhydroxy compound, a vinyl polymer containing a hydrolyzable silyl group in the side chain and/or at the end, an epoxy group in one molecule and a hydrolyzable silyl group, alkyd resins containing (substituted) alkoxysilyl groups or alkenyloxysilyl groups, and polyester resins containing (substituted) alkoxysilyl groups or alkenyloxysilyl groups. Claim 1 which is at least one selected compound
The curable resin composition described in 1.