JPS63196644A - Curable resin composition - Google Patents

Abstract

PURPOSE:To form a curable resin composition excellent in adhesion to bases and solvent resistance, by using a fluoroolefin polymer, a basic nitrogen- containing vinyl polymer, a polyepoxy compound and/or a compound having both epoxy hydrolyzable silyl groups as essential components. CONSTITUTION:This curable resin composition comprises a fluoro-olefin polymer (A), a basic nitrogen-containing vinyl polymer (B), a polyepoxy compound (D) and/or a compound having both epoxy and hydrolyzable silyl groups in the molecule and optionally contains at least one member selected from among a compound (E) having a silyl group, a hydrolyzable silyl compound (F) other than said compound (D) and a catalyst (G) for hydrolyzing and condensing said hydrolyzable silyl groups.

Description

Detailed Description of the Invention [Object of the Invention] (Industrial Field of Application) The present invention relates to a resin composition containing a fluoroolefin polymer, and more specifically, a resin composition containing a fluoroolefin polymer (
A) and a vinyl polymer containing a basic nitrogen atom (B)
and a polyepoxy compound (C) and/or a compound having both an epoxy group and a hydrolyzable silyl group in one molecule (
The present invention relates to a curable resin composition comprising D) as an essential component.

(Prior art) Non-crosslinked tetrafluoroethylene-vinylidene fluoride copolymer and hexafluoropropylene-vinylidene fluoride copolymer have been used as highly weather-resistant paint resins that are soluble in solvents and form a continuous coating film at room temperature. Vinylidene fluoride copolymer, tetrafluoroethylene-vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride homopolymer, chlorotrifluoroethylene homopolymer, chlorotrifluoroethylene-cycloalkyl vinyl ether-alkyl vinyl ether copolymer Also known are crosslinked polymers such as vinylidene fluoride copolymers, hexafluoropropylene copolymers, and chlorotrifluoroethylene copolymers containing hydroxyl groups, epoxy groups, etc.

(Problems to be Solved by the Invention) However, coating films obtained from non-crosslinked resins have insufficient solvent resistance and adhesion to substrates, and coating films obtained from crosslinked resins are based on It has insufficient adhesion to materials, and its uses are inherently limited.

In view of the shortcomings of the prior art described above, the present inventors made extensive studies and found that the above-mentioned fluoroolefin polymer contains a vinyl polymer containing a basic nitrogen atom, and a polyepoxy compound and/or The present inventors have discovered that a curable resin composition with excellent adhesion to substrates and solvent resistance can be obtained by blending a compound having both an epoxy group and a hydrolyzable silyl group with a compound having both an epoxy group and a hydrolyzable silyl group. [Structure of the Invention] (Means for Solving the Problems) To summarize the present invention, the present invention comprises a fluoroolefin polymer (A) and a vinyl polymer containing a basic nitrogen atom (B). ), a polyepoxy compound (C) and/or a compound (D) having both an epoxy group and a hydrolyzable silyl group in one molecule as essential components, and further containing a silanol group as necessary ( E), the above (D
) Compounds containing a hydrolyzable silyl group excluding CF),
The present invention provides a curable resin composition comprising at least one compound selected from the above-mentioned catalysts for hydrolysis and condensation of hydrolyzable silyl groups (CG). Hereinafter, the configuration of the present invention will be explained in detail.

The fluoroolefin polymers (A) used in the present invention include vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, pentafluoropropylene, hexafluoropropylene, and (per)fluoroallyl trifluoride. It is a polymer obtained by polymerizing at least one type selected from the group consisting of fluorovinyl ether [however, the number of carbon atoms in the (per)fluoroalkyl group is 1 to 18], and the amount of such fluoroolefins used is 1 to 18. A suitable range is 5 to 100% by weight, preferably 10 to 100% by weight.

In the present invention, other copolymerizable monomers can be used together with the fluoroolefin monomer.

Such monomers include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl caproate, vinyl caprate, vinyl caprylate, vinyl persate, vinyl laurate or vinyl stearate. Vinyl esters of linear or branched aliphatic carboxylic acids; alicyclic carboxylic acid vinyl esters such as cyclohexanecarboxylic acid vinyl ester; such as benzoic acid vinyl ester, pt-butylbenzoic acid vinyl ester or salicylic acid vinyl ester Aromatic carboxylic acid vinyl esters; hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether, hydroxypropyl vinyl ether or hydroxybutyl vinyl ether; methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl ether or cyclohexyl vinyl ether Linear or branched aliphatic or alicyclic vinyl ethers such as; monomers having epoxy groups such as glycidyl vinyl ether and glycidyl (meth)acrylate; nialic acid, methacrylic acid, maleic acid, maleic anhydride , itaconic acid, itaconic anhydride, fumaric acid, monoethyl maleate, monobutyl maleate, monobutyl fumarate, monobutyl itaconate, monovinyl adipate, monovinyl sebacate; monomers having a carboxyl group; dimethylaminoethyl vinyl ether; Vinyl monomers containing basic nitrogen such as dimethylaminopropyl vinyl ether, N-dimethylaminopropyl (meth)acrylamide, dimethylaminoethyl (meth)acrylate; such as ethylene, propylene, butene-1 or hexene-1 α-olefins; halogenated olefins other than the above-mentioned fluoroolefins, such as vinyl chloride or vinylidene chloride; aromatic vinyl monomers, such as styrene, α-methylstyrene, or vinyltoluene; methyl (meth)acrylate, ethyl (meth)acrylic acid esters such as (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, β-hydroxyethyl (meth)acrylate or phosphate ester of β-hydroxyethyl (meth)acrylate; (meta)
Acrylonitrile, (meth)acrylamide.

Monomers such as N-methylol (meth)acrylamide or N-butoxymethyl (meth)acrylamide,
Alternatively, there are monomers containing a hydrolyzable silyl group such as vinyltrimethoxysilane and γ-(meth)acryloyloxypropyltrimethoxysilane.

In order to obtain the fluoroolefin polymer (A) from the monomers, bulk polymerization, solution polymerization,
The polymerization may be carried out in a batch, semi-continuous or continuous manner by making full use of known techniques such as emulsion polymerization.

Such radical initiators include diacyl peroxides such as acetyl peroxide or benzoyl peroxide; ketone peroxides such as methyl ethyl ketone peroxide or cyclohexanone peroxide; hydrogen peroxide, t-butyl hydroperoxide or cumene hydroperoxide. Hydroperoxides such as; dialkyl peroxides such as di-t-butyl peroxide or dicumyl peroxide; alkyl peroxy esters such as t-butyl peroxy acetate or t-butyl peroxy pivalate; azobis Azo initiators such as isobutyronitrile or azobisisovaleronitrile; or persulfates such as ammonium persulfate or potassium persulfate are used, and if necessary, inorganic initiators such as sodium bisulfite or sodium pyrosulfite are used. or organic reducing agents such as cobalt naphthenate or dimethylaniline may also be used; solvents used in the polymerization reaction include hydrocarbons such as toluene, xylene, cyclohexane, n-hexane or octane; methyl acetate; Ester systems such as ethyl acetate or butyl acetate; ketone systems such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone or methyl amyl ketone; amide systems such as dimethylformamide or dimethylacetamide;
Alcoholic solvents such as methanol, ethanol, i-propertool, n-butanol, i-butanol, 5ec-butanol or ethylene glycol monoalkyl ether or mixtures thereof are used.

In addition, during polymerization, lauryl mercaptan, octyl mercaptan, 2-mercaptoethanol, γ-mercaptopropyltrimethoxysilane,
Various chain transfer agents such as gamma-mercaptopropylmethyldimethoxysilane or alpha-methylstyrene dimer can also be used.

The reaction temperature during the polymerization reaction is -20°C to 130°C.
℃, and the initial pressure of the reaction is preferably 1 to 100 kg/cd, preferably 5 to 60 kg/cd.

The number average molecular fi (Mn) of the fluoroolefin polymer thus obtained is 1,000 to 300,000, from the viewpoint of film forming properties and solvent solubility of the polymer.
Preferably, it is from s, ooo to 200,000.

The vinyl polymer (B) containing a basic nitrogen atom used in the present invention has at least one, preferably at least two, basic nitrogen atoms in one molecule, that is, a -class amino group, a secondary amino group, and It refers to a vinyl polymer containing at least one type of amino group selected from the group consisting of tertiary amino groups.

Such a polymer (B) is composed of (1) a vinyl monomer containing any of the above-mentioned amino groups [hereinafter also referred to as vinyl monomer (b-1); ] or with another vinyl monomer (b-2) copolymerizable with these, or () carboxylic acid anhydride group (hereinafter referred to as acid anhydride group) Containing vinyl polymer [hereinafter referred to as polymer (b-
Also called 3). ], and a compound having at least one active hydrogen-containing group capable of reacting with this acid anhydride group and a tertiary amino group in one molecule [hereinafter referred to as compound (b-
4). ] It can be prepared by a known method such as reacting with.

Among them, dimethylaminoethyl (meth) is a typical amino group-containing vinyl monomer (b-1) used in preparing the vinyl polymer (B) by the method of Doraage (2). Acrylate, diethylaminoethyl (
meth)acrylate, dimethylaminopropyl(meth)
Acrylate or diethylaminopropyl (meth)
Various dialkylaminoalkyl (meth)acrylates such as acrylates: N-dimethylaminoethyl (meth)acrylamide, N-diethylaminoethyl (meth)
Acrylamide, N-dimethylaminopropyl (meth)
Acrylamide or N-diethylaminopropyl (
N-dialkylaminoalkyl (meth)acrylamides such as meth)acrylamide; or t-butylaminoethyl (meth)acrylate, t-butylaminopropyl (meth)acrylate, aziridinylethyl (meth)acrylate, pyrrolidinylethyl Examples include (meth)acrylate and piperidinylethyl (meth)acrylate, but from the viewpoint of curability, dialkylaminoalkyl (meth)acrylates and N-
Particularly preferred are dialkylaminoalkyl (meth)acrylamides.

In addition, these amino group-containing vinyl monomers (b-1
) Typical vinyl monomers (b-2) copolymerizable with methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, 1so-propyl ( meth)acrylate, n
-butyl (meth)acrylate, 1so-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, 2 -Hydroxyethyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxybutyl (
various (meth)acrylic acid esters such as meth)acrylate or 4-hydroxybutyl (meth)acrylate; dialkyl esters of unsaturated dibasic acids such as dimethyl maleate, dimethyl fumarate, dibutyl fumarate or dimethyl itaconate; Carboxyl group-containing vinyl monomers such as (meth)acrylic acid, monobutyl maleate, monobutyl fumarate, crotonic acid, maleic acid, fumaric acid or itaconic acid; acid anhydride groups such as maleic anhydride or itaconic anhydride Containing Vinyl Monomer 1 Various carboxylic acid amides such as (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N-alkoxymethyl (meth)acrylamide, diacetone (meth)acrylamide or N-methylol (meth)acrylamide Group-containing vinyl monomer; p-styrenesulfonamide, N-methyl-p-styrenesulfonamide or N.

Various sulfonamide group-containing vinyl monomers such as N-dimethyl-p-styrene sulfonamide; cyano group-containing vinyl monomers such as (meth)acrylonitrile; hydroxyalkyl esters of (meth)acrylic acid such as Diyang Phosphate bond-containing vinyl monomers that are condensation products of hydroxyalkyl esters of α,β-ethylenically unsaturated carboxylic acids such as phosphoric acid or phosphoric acid esters; p-styrenesulfonic acid or 2-acrylamide- Vinyl monomers containing sulfonic acid groups such as 2-methyl-propanesulfonic acid; various vinyl esters such as vinyl acetate, vinyl benzoate or "Beoba" (vinyl ester manufactured by Shell, Netherlands); -g8
F, 8FM, 3Fmol<Ha3FMJ [fluorine-containing (meth)acrylic monomers manufactured by Osaka Organic Chemical Co., Ltd.] or perfluorocyclohexyl (meth)acrylate, diperfluorocyclohexyl fumarate or N-1so-propyl (per)fluoroalkyl group-containing vinyl monomers such as perfluorooctane sulfonamide ethyl (meth)acrylate; the aforementioned fluoroolefin polymers (A) such as vinyl chloride and vinylidene chloride;
halogenated olefins other than fluoroolefins used in the preparation of olefins; or aromatic vinyl heptamers such as styrene, α-methylstyrene, p-tart-butylstyrene or vinyltoluene.

In order to prepare the vinyl polymer (B) using the various monomers listed above, 0.5 to 100 weight of the amino group-containing vinyl monomer (b-1) is prepared. %, preferably 1 to 70% by weight, and another vinyl monomer (b-2) copolymerizable with the amino group-containing vinyl monomer (b-2).
What is necessary is just to copolymerize 9.5-0 weight%, preferably 99-30 weight%.

Further, as other vinyl monomers (b-2) copolymerizable with the amino group-containing vinyl monomer (b-1), carboxyl group-containing monomers or phosphoric acid ester bond-containing monomers as listed above may be used. By using the polymer in combination, a carboxyl group or a phosphoric acid ester bond can be introduced into the vinyl polymer (B), thereby further improving the curability of the composition of the present invention. Particularly desirable.

To prepare the vinyl polymer (B) from the various monomers listed above, any conventionally known polymerization method can be applied, but solution radical polymerization is the simplest method. In this case, it goes without saying that the polymerization initiator, solvent, and chain transfer agent used when synthesizing the fluoroolefin polymer (A) component can be used.

Next, the acid anhydride group-containing vinyl polymer (b-3) used in preparing the vinyl polymer (B) by the above method It can be prepared by radical copolymerization of monomers containing monomers and monomers copolymerizable with these monomers in a solvent other than alcohols among the solvents listed above. .

Here, such an acid anhydride group-containing vinyl polymer (b
The copolymerizable monomers used in the preparation of -3) include the amino group-containing vinyl monomers (b-1) and Among other possible vinyl monomers (b-2),
Any monomer other than the monomer containing a hydroxyl group can be used.

The amount of the monomer containing an acid anhydride group as mentioned above should be 0.00000000000 from the viewpoint of weather resistance and alkali resistance.
A suitable range is 5 to 50% by weight, preferably 1 to 20% by weight, while the amount of copolymerizable monomer used is 99.5 to 50% by weight, preferably 99 to 80% by weight. It is appropriate to fall within the following range.

In addition, in this case, when a carboxyl group-containing monomer or a phosphoric acid ester bond-containing monomer as listed above is also used as a component of the copolymerizable monomer, an acid anhydride as listed later is used. The reaction time can be shortened when reacting with a compound (b-4) having both a group having an active hydrogen that can react with the group (hereinafter referred to as an active hydrogen-containing group) and a tertiary amino group, This is particularly desirable since it can further improve the curability of the composition of the present invention.

Here, the compound (b-4) refers to a compound having a hydroxyl group, a -class or secondary amino group, or a thiol group as an active hydrogen-containing group present in the compound. However, among these, the most preferred compounds include alcohols having a tertiary amino group, and primary or secondary amines having a tertiary amino group.

Representative examples of the tertiary amino group-containing amino alcohols include dimethylaminoethanol, diethylaminoethanol, di-n-propylaminoethanol, and di-1s.
o-propylaminoethanol, di-n-butylaminoethanol, N-(2-hydroxyethyl)morpholine, N-(2-hydroxyethyl)pyrrolidine, N-(2-hydroxyethyl)morpholine, N-(2-hydroxyethyl)pyrrolidine,
-hydroxyethyl)-aziridine, N,N-dimethyl-2-hydroxypropylamine, N,N-diethyl-
Examples of the tertiary amino group-containing amino alcohols include 2-hydroxypropylamine, triethanolamine, and tripropatulamine. Adducts of amino alcohols and (meth)acrylate monomers having a tertiary amino group such as dimethylaminoethyl (meth)acrylate or diethylaminoethyl (meth)acrylate, or (meth)acrylate monomers containing the tertiary amino group Vinyl copolymers having both tertiary amino groups and hydroxyl groups in the side chains obtained by copolymerizing acrylate monomers with hydroxyl group-containing monomers such as β-hydroxyethyl (meth)acrylate are also used. can.

In addition, typical examples of the above-mentioned primary or secondary amines containing a tertiary amino group include N,N-dimethyl-1,3
-propylene diamine or N,N-diethyl-1,
N,N-dialkyl-1 such as 3-propylene diamine
, 3-propylene diamines; N.

N,N-dialkyl-1,4-tetramethylenediamines such as N-dimethyl-1,4-tetramethylenediamine or N,N-diethyl-1,4-tetramethylenediamine: N,N-dimethyl-1, N,N-dialkyl-1,6-hexamethylene diamines such as 6-hexamethylene diamine or N,N-diethyl-1,6-hexamethylene diamine; N,N,N'-trimethyl-1,3 -Propylenediamine, N,N.

N,N,N'-trialkylalkylene diamines such as N'-triethyl-1,3-propylene diamine or N,N,N'-)-dimethyl-1,6-hexamethylene diamine; or N-methyl N-alkylpiperazines such as piperazine or N-ethylpiperazine; or tertiary amino group-containing (meth)acrylate monomers such as doffed ethylenediamine, propylenediamine, hexamethylenediamine, piperazine, methylamine, ethylamine, Examples include adducts with propylamine or ammonia.

From the viewpoint of curability, N,N-dialkylaminoethanol and N,N-dialkylalkylenediamine are particularly preferred as the compound (b-4).

Then, a basic nitrogen-containing vinyl polymer (B
), the ratio of active hydrogen-containing groups in compound (b-4) to 1 equivalent of acid anhydride group in polymer (b-3) is about 0.5 to 3 equivalents. Both compounds may be mixed and reacted at a temperature range from room temperature to about 150°C. The number average molecular weight (U) of the basic nitrogen-containing vinyl polymer (B) obtained in this way is 1,000 to 30 from the viewpoint of film formability and workability of the polymer.
0,000, preferably 3.000 to ioo, ooo.

The polyepoxy compound (C) used in the present invention is a compound containing at least two epoxy groups in one molecule, and specifically, ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1
, 6-hexanesiol diglycidyl ether, bisphenol A diglycidyl ether or glycerin triglycidyl ether; phthalic acid diglycidyl ester, isophthalic acid diglycidyl ester or adipic acid diglycidyl ether; Polyglycidyl esters of polyvalent carboxylic acids such as glycidyl esters; or various epoxy resins such as diglycidyl ether type epoxy resins of bisphenol A or bisphenol F, novolac type epoxy resins, or hydantoin ring-containing epoxy resins, and further p-oxybenzoic acid. Examples include acid glycidyl ester ethers and various vinyl polymers having epoxy groups in their side chains. Among these, compounds such as polyglycidyl ethers of aliphatic polyhydric alcohols are preferred from the viewpoint of weather resistance.

Next, as the compound (D) having both an epoxy group and a hydrolyzable silyl group in one molecule, a vinyl polymer having both of these types of reactive groups and a silane coupling agent having an epoxy group can be used. etc. are representative examples.

Here, the hydrolyzable silyl group refers to a reactive group having the general formula %() which is easily hydrolyzed, such as an acyloxysilyl group, phenoxysilyl group, iminooxysilyl group, or alkenyloxysilyl group. shall be taken as a thing.

Any known method can be applied to prepare a vinyl polymer having a specific bireactive group as described above, such as a hydrolyzable silyl group such as γ-(meth)acryloyloxypropyltrimethoxysilane. By copolymerizing vinyl monomers having , vinyl monomers having an epoxy group such as (β-methyl)glycidyl (meth)acrylate, and monomers copolymerizable with these. You can get it.

Furthermore, typical examples of the above-mentioned epoxy group-containing silane coupling agents include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyljethoxysilane, There are γ-glycidoxypropyltriisopropenyloxysilane, γ-glycidoxypropyltriiminooxysilane, and addition of γ-isocyanatepropyltriisobropenyloxysilane or γ-isocyanatepropyltrimethoxysilane with glycidol. or adducts of γ-aminopropyltrimethoxysilane and jepoxy compounds, etc.
In particular, γ-glycidoxyprobyltrimethoxysilane or γ-glycidoxyprobyltriisopropenyloxysilane is preferred from the viewpoint of curability and economical efficiency.

This completes the explanation of the essential components constituting the curable resin composition of the present invention. In addition, in the present invention, when component (A) or component (B) contains a reactive functional group other than an amino group such as a hydroxyl group, a curing agent that can react with the functional group such as a hydroxyl group, such as a functional When the group is a hydroxyl group, adding a polyisocyanate compound, aminoplast, etc. can further increase the crosslinking density of the coating film and improve the solvent resistance of the coating film.

Next, other components that can be used in the composition of the present invention will be explained.

The compound (E) having a silanol group used in the present invention is
Methyltrichlorosilane, phenyltrichlorosilane,
Low molecular weight silanol compounds obtained by almost complete hydrolysis of halosilanes such as ethyltrichlorosilane, dimethyldichlorosilane or diphenyldichlorosilane; silanol groups obtained by further dehydration condensation of these silanol compounds; polysiloxanes having silanol groups; silicone resins having silanol groups obtained by hydrolyzing and condensing metal compounds such as various alkoxysilanes and alkenyloxysilanes; There are silanol compounds with a cyclic siloxane structure, such as those typified by products from Co., Ltd.

Further, the compound (F) containing a hydrolyzable silyl group other than the compound (D) used in the present invention has the general formula (
It refers to low molecular weight compounds or resins that contain at least one hydrolyzable silyl group shown in 1) in one molecule, but do not contain an epoxy group.

Typical examples of the compound (F) include tetramethoxysilane, trimethoxysilane, tetraethoxysilane, triethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetraoctoxysilane, and tetrakis(2-methoxyethoxy)silane. , tetrabenzyloxysilane, methyltrimethoxysilane, ethyltrimethoxy.

Silane, methyltriatoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyljethoxysilane, diphenyljethoxysilane, γ-isocyanatepropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-chloropropyltrimethoxy silane, alkoxysilanes such as γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane or γ-(2-aminoethyl)aminopropyltrimethoxysilane; tetraisopropenyloxysilane, phenyltriisopropenyloxysilane, Alkenyloxysilanes such as γ-isocyanatepropyltriisopropenyloxysilane, γ-methacryloxypropyltriisoprobenyloxysilane, γ-mercaptopropyltriisopropenyloxysilane or tetrabutenyloxysilane: tetraacetoxysilane, methyltrioxysilane Acetoxysilane, γ-mercaptopropyltriacetoxysilane,
Acyloxysilanes such as tetrapropionyloxysilane, phenyltripropionyloxysilane or vinyltriacetoxysilane; Halosilanes such as tetrachlorosilane, phenyltrichlorosilane, tetrabromosilane or benzyltribromosilane: tetrakis(dimethyliminooxy)silane , methyltris (
dimethyliminooxy)silane, tetrakis(methyl-
ethyliminooxy)silane, γ-methacryloxypropyltris(dimethyliminooxy)silane or γ
-Mercaptopropyl tris(dimethyliminooxy)
Iminooxysilanes such as silanes; alkoxysilyl group-containing siloxane oligomers obtained by partially hydrolyzing and condensing alkoxysilanes such as detents; alkenyloxy groups obtained by partially hydrolyzing and condensing alkenyloxysilanes such as degentes Containing siloxane oligomers: Various hydrolyzable silyl group-containing vinyl monomers such as γ-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane or γ-methacryloxypropyltriacetoxysilane. Homopolymers or copolymers of monomers copolymerizable with these monomers; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriisopropenyloxysilane, or γ-mercapto A vinyl-based system using a mercaptan containing a hydrolyzable silyl group such as propyltriacetoxysilane as a chain transfer agent, and optionally containing various hydrolyzable silyl group-containing vinyl monomers as listed above. Vinyl polymers containing hydrolyzable silyl groups at the terminals obtained by (co)polymerizing monomers; polyhydric alcohols, hydroxyl group-containing acrylic resins, hydroxyl group-containing alkyd resins, hydroxyl group-containing polyester resins, or polyethers. Various polyhydroxy compounds such as polyols and various hydrolyzable silyl group-containing compounds including the alkoxysilanes listed above are reacted according to the method disclosed in JP-A-58-168625. Resins obtained by the process; low molecular weight polyallyl compounds such as diallyl succinate, triallyl trimellitate or diallyl phthalate, unsaturated bond-containing vinyl polymers, unsaturated bond-containing polyester resins or unsaturated bond-containing alkyd resins. Adducts of various unsaturated compounds and hydrolyzable silyl group-containing hydrosilanes such as trimethoxysilane or triethoxysilane; various epoxy group-containing compounds such as epoxy group-containing vinyl polymers or epoxy resins and the above. adducts with various mercaptosilanes such as; or γ-isocyanatepropyltrimethoxysilane and γ-
Urethane bond-containing resins obtained by reacting various hydrolyzable silyl group-containing compounds with isocyanate groups, such as isocyanate propyltriisopropenyloxysilane, and various polyhydroxy compounds as listed above; There are silicone resins containing a hydrolyzable silyl group at the end.

Although the composition of the present invention has good curability even without the addition of a curing catalyst, if it is desired to further improve the curability, it is necessary to use a method for hydrolyzing the hydrolyzable silyl group in the composition of the present invention. , and there is no hindrance to adding the condensation catalyst (G).

Typical examples of such CG components include bases such as butylamine, dibutylamine, hexylamine, t-butylamine, ethylenediamine, triethylamine, isophoronediamine, imidazole, lithium hydroxide, sodium hydroxide, potassium hydroxide, and sodium methylate. Compounds: Tetrapropyl titanate, tetrabutyl titanate, tin octylate, lead octylate, cobalt octylate, zinc octylate, calcium octylate, lead naphthenate, cobalt naphthenate, dibutyltin diacetate, dibutyltin dioctate, dibutyltin Metal-containing compounds such as dilaurate, dibutyltin malate; α-toluenesulfonic acid, trichloroacetic acid, phosphoric acid, monoalkyl phosphoric acid, dialkyl phosphoric acid, β-hydroxyethyl (meth)
Examples include acidic compounds such as phosphoric esters of acrylates, monoalkyl phosphorous acids, and dialkyl phosphorous acids.

The composition ratio for obtaining the composition of the present invention from the components (A) to (G) listed above is (A) component/CB) + (C)
+(D)+(E)+(F) components usually have a weight ratio of 10/
Within the range of 90 to 90/10, 30/70 is preferred from the viewpoint of improving adhesion, solvent resistance, and chemical resistance without reducing the inherent properties of fluoroolefin polymers such as weather resistance. For the CB)(C)(D) component, which is preferably in the range of ~90/10, 1 equivalent of the reactive groups present in the (B) component, such as an amino group and a carboxyl group and/or a phosphate ester bond, On the other hand, (E) may be blended in such a proportion that the amount of epoxy groups present in components (C) and/or (D) is approximately 0.2 to 5 equivalents.

CF) component may be blended in an amount of 0 to 1,000 parts, preferably 0 to 500 parts, per 100 parts of the total amount of components (B), (C), and (D). B)～(
About 0 to 10 parts may be added to 100 parts of the total weight of component F). Furthermore, the curable resin composition of the present invention may contain known organic or inorganic pigments, metal powders such as aluminum, copper, brass, gold, silver, and nickel, ultraviolet absorbers, antioxidants, etc., as necessary. Various additives and the like can be added.

In order to obtain the curable resin composition of the present invention, the above-mentioned components and additives are mixed and dispersed or dissolved in an organic solvent using a known method, for example, a dispersion mixer such as a glass bead mill or a homodisper. Just let it happen. The nonvolatile content concentration is usually 10 to 80% by weight, preferably 20 to 60% by weight.
is within the range of

When the curable resin composition of the present invention is used as a coating composition, it is applied by a known and commonly used method such as spray coating, brush coating, or roll coater, and left at room temperature for about 1 to 7 days to cure. Alternatively, a cured coating film can be formed by baking at a temperature of 60 to 250°C for 5 seconds to 40 minutes.

The curable resin composition of the present invention is applicable to home appliance paints, exterior paints for buildings, roof tiles, pre-coated metal (PCM), etc., and various automotive paints such as car enamel paints, metallic base paints, and clear paints. Furthermore, it can be used as a surface protective film, film, sealant, adhesive, etc. for glass or ceramic products.

(Examples) Next, the present invention will be explained in more detail using reference examples, examples, and comparative examples, but the present invention is not limited to these examples in any way. Note that all parts and percentages hereinafter are based on weight unless otherwise specified.

Reference Example 1 [Example of Preparation of Fluoroolefin Polymer (A)] In a stainless steel pressure-resistant tube with an internal volume of 1000, 3309 of methyl isobutyl ketone, 4.2 molecules of tert-butyl peroxypivalate, and hydroxyl 849 of butyl vinyl ether, 126 children of Beover 9 (vinyl ester of C9 branched aliphatic carboxylic acid manufactured by Shell, Netherlands) and 84 of vinyl cyclohexane carboxylate
1i and heated to -70℃ in a dry ice/methanol bath.
The tube was cooled to a temperature of 100 mL, and nitrogen gas was blown into the tube to replace the air inside the pressure tube.

126 of the hexafluoropropylene which was then liquefied and collected.
9 was prepared and sealed.

Thereafter, this pressure tube was placed in a rotary constant temperature water bath heated to 60° C., and a reaction was carried out for 16 hours, and then the tube was opened to obtain a copolymer solution. This product had a nonvolatile content of 53% and a number average molecular weight (Mn) of 9,000. Hereinafter, this polymer solution will be abbreviated as A-1.

Reference example [Preparation example of fluoroolefin polymer (A)]
A polymer solution (A-2) was obtained in the same manner as in Reference Example 1, except that the type and amount of the monomers used were changed as described below.

Chlorotrifluoroethylene 126% Hydroxybutyl vinyl ether 429 Ethyl vinyl ether 42 Guveover 9210
This item has a non-volatile content of 53% and a number average content (U) of 17.0.
It was 00.

Reference Example 3 [Preparation example of basic nitrogen-containing vinyl polymer (B)] 800 g of toluene was charged into a reactor equipped with a stirrer, a thermometer, a reflux condenser tube, and a nitrogen introduction tube, and the temperature was heated to 80°C under a nitrogen atmosphere. Methyl methacrylate 509, n at elevated temperature
-butyl methacrylate 850 g dimethylaminoethyl acrylate 1009, azobisisobutyronitrile (AIBN) 5 g, tart-butyl peroxyoctoate (TBPO) 5 leaching and toluene 200
The mixture consisting of the following ingredients was added dropwise over a period of 3 hours.

After dropping, maintain the same temperature for 2 hours and then add AIB.
N5. A mixture of 5007 and toluene was added dropwise over 1 hour. Next, the same temperature was maintained for 12 hours to obtain a tertiary amino group-containing vinyl polymer (B) with a nonvolatile content (NV) of 40% and a number average molecular weight (M n ) of 12,000.
) was obtained. Hereinafter, this will be abbreviated as polymer (B-1).

Reference Example 4 [Preparation example of basic nitrogen-containing vinyl polymer (B)] A polymer solution (B- 2) was obtained.

Cyclohexyl methacrylate 420qTe
rt-butyl methacrylate 420 methacrylic acid 10-dimethylaminoethyl methacrylate 1509 Reference example 5 [Preparation example of basic nitrogen-containing vinyl polymer (B)] The type and amount of the monomer used were changed as shown below. Reference example 3 except that
A polymer solution (B-3) was obtained in the same manner as above.

Methyl methacrylate 840g Methacrylic acid 10g Dimethylaminoethyl methacrylate 150g Reference example 6 [Preparation example of basic nitrogen-containing vinyl polymer (B)] The types and amounts of monomers used and the solvent used are as follows. A superimposed solution (B-4) was obtained in the same manner as in Reference Example 3 except for the following changes.

rMethyl methacrylate 630
1 dimethylaminoethyl methacrylate 350
Leak [Solvent] Toluene/isobutanol = 6/4 Reference Example 7 [Am example of basic nitrogen-containing vinyl polymer (B)] Toluene 3009 and butyl acetate 400 were charged in the same reactor as Reference Example 3. The temperature was raised to 110°C in a nitrogen atmosphere, and 100% styrene and 545% methyl methacrylate were added.
child, n-butyl acrylate 310i, maleic anhydride 45i, AIBNIO9, TBPO5SF, tar
t-Butyl peroxybenzoate (TBPB) 5
A mixture consisting of # and toluene 3009 was added dropwise over 3 hours, and the reaction was continued by maintaining the same temperature for 15 hours even after the dropwise addition was completed, to obtain a solution of acid anhydride group-containing vinyl polymer (b-3). . Next, the temperature of this polymer solution was lowered to 90 DEG C., 46.8 ii of N,N-dimethyl-1,3-propylene diamine was added thereto, and the solution was kept at the same temperature for 6 hours to dehydrate. 46 to the resulting imide ring-containing polymer solution.
．． 814 of n-butanol was added to obtain a polymer solution (B-5) with an NV of 50%.

Examples 1 to 6 Components (A), (B), (C), (D), etc. were mixed in the proportions shown in Table 1 below to obtain curable resin compositions. Next, this resin composition was degreased with toluene on an aluminum plate (A
-5052P) using a doctor blade to give a dry film thickness of 50 μs, and then cured under the conditions shown in Table 1 to obtain a coating film. The resulting coating film was evaluated for adhesion and solvent resistance using the methods described in the footnotes outside the margin of Table 1. These results are also shown in Table 1.

Comparative Examples 1 and 2 Except that component (B), etc. was not used and changes were made to follow the blending ratio and curing conditions as listed in Table 1,
It was made into a paint and formed into a film in the same manner as in the example.

This was used as a comparative sample. The coating film performance of this product is also shown in Table 1.

(Left below) (Footnotes) 1) Polymer A-3: Number average molecular weight (M) 40,000
A solution of a copolymer consisting of 50% by weight of vinylidene fluoride and 50% by weight of tetrafluoroethylene in methyl isobutyl ketone. Non-volatile content 30%.

2) Polymer A-4: Number average molecular weight (in) 30,000
A solution of a copolymer of 45% by weight of vinylidene fluoride, 45% by weight of tetrafluoroethylene and 10% by weight of hexafluoropropylene in methyl isobutyl ketone. Non-volatile content 45%.

3) Bunacol Ex 612: Sorbitol polyglycidyl ether manufactured by Nagase Sangyo Co., Ltd. Epoxy equivalent weight 17
0° 4) Glycerin polyglycidyl ether: Epoxy equivalent: 145 5) Coronate EH: Polyisocyanate having an isocyanate ring, manufactured by Nippon Polyurethane Industry Co., Ltd. Isocyanate content 21.3%, solid content 100%.

6) Cut lines were made in the paint film with a safety razor blade to create 100 goblets with 1-spacing intervals, and after peeling off the cut portions with cellophane tape, the number of goblets adhering to the aluminum plate was shown. The larger this value is, the better the adhesion is.

7) Rubbing tester using xylene as a solvent (load 1
The appearance of the coating after rubbing it 50 times with 50 kg) was visually evaluated.

〔Judgment criteria〕

O No abnormality 0 Slightly decreased gloss Δ Significantly decreased gloss X The coating film completely disappeared [Effects of the Invention] The curable resin composition of the present invention has excellent solvent resistance and adhesion, and is free from fluoroolefins. It has the advantage that the excellent properties inherent to the polymer, such as weather resistance, are maintained. Therefore, the curable resin composition of the present invention can be used as paint for home appliances, exterior paints for buildings, roof tiles, or PCM (pre-coated metal), or for automobiles, especially automobile enamel paints, metallic base paints, or clear paints. Furthermore, it can be applied as a surface protective film, film, sealant, adhesive, etc. for glass and ceramic products, but it is by no means limited to the scope of doffing.

Claims (1)

[Claims] 1. A fluoroolefin polymer (A), a vinyl polymer containing a basic nitrogen atom (B), a polyepoxy compound (C) and/or an epoxy group in one molecule. and a compound (D) having both a hydrolyzable silyl group as an essential component, and optionally a compound (E) containing a silanol group, and a hydrolyzable silyl group other than the above compound (D). A curable resin composition comprising at least one compound selected from the compound (F) and the catalyst (G) for hydrolysis and condensation of hydrolyzable silyl groups. 2. The fluoroolefin polymer (A) is vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, pentafluoropropylene, hexafluoropropylene, and (per)fluoroaryl trifluorovinyl ether [
However, the number of carbon atoms in the (per)fluoroalkyl group is 1 to 18]
The curable resin composition according to claim 1, which is obtained by polymerizing at least one fluoroolefin monomer selected from the group consisting of: 3. The vinyl polymer (B) contains at least one vinyl monomer selected from the group consisting of dialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylate, N-dialkylaminoalkylacrylamide, and N-dialkylaminoalkylmethacrylamide. The curable resin according to claim 1, which is a polymer obtained by copolymerizing the monomer (b-1) and another vinyl monomer (b-2) copolymerizable with these. Composition. 4. The vinyl polymer (B) has a vinyl polymer (b-3) containing a carboxylic acid anhydride group, and at least one active hydrogen in one molecule that can react with the carboxylic acid anhydride group. compound having both a group and a tertiary amino group (b-4
2. The curable resin composition according to claim 1, which is a polymer containing a tertiary amino group obtained by reacting with a tertiary amino group. 5. The vinyl polymer (B) has a carboxyl group and/or
The curable resin composition according to claim 1, which is also a polymer having a phosphate ester bond. 6. Claim 1, wherein the compound (D) having both an epoxy group and a hydrolyzable silyl group is γ-glycidoxypropyltrialkoxysilane and/or γ-glycidoxypropyltriisopropenyloxysilane The curable resin composition described in .