JPH0238438A - Curable resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition improved in adhesion to various base materials by mixing a fluoroolefin copolymer having basic nitrogen atoms and OH groups with a curing agent and a specified compound. CONSTITUTION:17-70wt.% fluoroolefin (a) (e.g., chlorotrifluoroethylene) is copolymerized with 0.05-10wt.% basic nitrogen monomer (b) (e.g., 2-aminoethyl vinyl ether), 1-30wt.% hydroxy monomer (c) (e.g., 4-hydroxybutyl vinyl ether) and 5-83.5wt.% other monomers (d) copolymerizable therewith to obtain a fluoroolefin copolymer (A) containing 0.003-7g equivalent of basic nitrogen atoms and 0.05-3g equivalent of OH groups each per 1000g of the solid matter of the polymer. 100 pts.wt. component A is mixed with 5-100 pts.wt. curing agent (B) reactive with hydroxyl groups, comprising an aminoaldehyde resin and/or a polyisocyanate compound, and 0.05-50 pts.wt. compound (C) having an epoxy group and a hydrolyzable silyl group in the molecule (e.g., gamma- glycidoxypropyltrimethoxysilane).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel and useful curable resin composition.

[Problems to be solved by conventional techniques and inventions] For objects used outdoors, such as buildings, structures, and transportation vehicles, for the purpose of preserving the base material and imparting cosmetic properties, Various paints have been used.

By the way, in recent years, there has been a demand for longer lifespan of coating films, and in response to this, various attempts have been made in the industry, one of which is the use of solvent-soluble fluororesin and cured A system in which these agents are combined is disclosed in JP-A-57-34107.
It is disclosed in the publication No.

Although it is true that a coating film with excellent weather resistance can be obtained by following this technique, this system lacks adhesion when the substrate is a metal such as a stainless steel plate or an aluminum plate, making it difficult to use in practice. When used as a base coat, it was necessary to apply an undercoat film such as an epoxy resin. When performing a so-called color clear finish, such as a clear finish or dry-colored finish, when an epoxy resin paint is used as an undercoat, the epoxy resin paint film may penetrate through the clear paint film. The problem was that it easily deteriorated due to exposure to ultraviolet rays, resulting in discoloration and even peeling, which were fatal defects.

[Means to Solve the Problem] However, in view of the various drawbacks in the prior art as described above, the present inventors have conducted extensive studies in order to obtain a resin composition that can eliminate all such drawbacks. As a result of repeating
There is a resin composition in which a system of a specific fluoroolefin copolymer and a hydroxyl group-reactive curing agent is further combined with a compound having both an epoxy group and a hydrolyzable silyl group in the molecule. The present inventors have discovered that this material has extremely excellent adhesion to various substrates, and have completed the present invention.

That is, the present invention comprises, as essential components, a solvent-soluble fluoroolefin copolymer (4) having both a basic nitrogen atom and a hydroxyl group, a curing agent capable of reacting with the hydroxyl group, and -
The present invention aims to provide a new and useful curable resin composition comprising a compound (C) having both an epoxy group and a hydrolyzable silyl group in the molecule.

Here, the above-mentioned fluoroolefin copolymer (
A) refers to a substance containing a basic nitrogen atom and a hydroxyl group, and the content of each atomic group is such that the basic nitrogen atom is 1,000% of the solid content of the copolymer (4). g
The hydroxyl groups are within the range of 0.003 to 7 gram equivalents, while the hydroxyl groups are
It is suitable that the amount is within the range of 0.05 to 3 gram equivalents.

If the content of basic nitrogen atoms is less than 0.003 gram equivalent, the adhesion to the coating substrate will decrease, while if it exceeds 7 gram equivalent, the weather resistance of the coating film will decrease. Both of these are not preferable because K decreases the properties of the coating, and if the content of hydroxyl groups is less than 0.05 gram equivalent, the weather resistance of the coating film inevitably decreases. If the equivalent amount is exceeded, the adhesion to the coating substrate will inevitably decrease.
Neither is preferable.

To prepare the copolymer, for example, (1) a fluoroolefin, a hydroxyl group-containing monomer, a basic nitrogen atom-containing monomer, and other monomers that can be combined with these are prepared by a conventional method. There is a method of copolymerization, ■ A method of reacting a monoepoxy compound with a pre-prepared fluoroolefin copolymer having both a carboxyl group and an amino group, and ■ A method of reacting a monoepoxy compound with a fluoroolefin copolymer having both a carboxyl group and an amino group. A copolymer containing a basic nitrogen atom-containing monomer as well as a basic nitrogen atom-containing monomer is prepared in advance, and the copolymer is prepared as described in JP-A No. 59-219372. and Japanese Patent Publication No. 60-158209
The method of hydrolysis as disclosed in the above publication may be followed.

Of these, I believe that following method ■ is the simplest.

The copolymer (A) contains 1 fluoroolefin.
5 to 70% by weight, preferably 20 to 60% by weight, and 0.05 to 10% by weight, preferably 0.1 to 101% by weight of basic nitrogen atom-containing monomers, hydroxyl groups. The content of monomers is 1 to 30% by weight, preferably 3 to 20% by weight, and the amount of other copolymerizable monomers is 5% by weight.
Examples include those copolymerized within a range of 83.95% by weight.

If the amount of fluoroolefin used is less than 15% by weight, the durability of the coating film will decrease;
If the amount exceeds the weight percentage, the coating workability inevitably deteriorates, which is not preferable.

The fluoroolefins used in preparing the copolymer (N) include vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene,
fluorine-containing α-olefins such as chlorotrifluoroethylene, promotrifluoroethylene, pentafluoropropylene or hexafluoropropylene; or trifluoromethyl trifluorovinyl tetyl;
Representative examples include fluoroalkyl nosofluorovinyl ethers such as pentafluoroethyl trifluorovinyl ether and heptafluoropropyl trifluorovinyl ether, among others, vinyl fluoride, vinylidene fluoride, and tetrafluoroethylene. ,
Preferably, chlorotrifluoroethylene, hexafluoropropylene, and perfluoroalkyl trifluorovinyl ether having an alkyl group having 1 to 18 carbon atoms are used.

Next, representative examples of the above-mentioned basic nitrogen atom-containing monomers include 2-aminoethyl vinyl ether, 3-
Aminozolobyl vinyl ether, 4-aminobutyl vinyl ether, 5-amine pentyl vinyl ether, 6-
Aminoethyl vinyl ether, 8-aminooctyl vinyl ether, 1-methyl-2-aminoethyl vinyl ether, 1-methylaminopropyl vinyl ether, p-
Monomers containing primary amine groups such as amine ethyl styrene or allyl amine; N-methylaminoethyl vinyl ether, N-ethylaminoethyl vinyl ether, N-
Ni'robylaminoethyl vinyl ether, N-butylaminoethyl vinyl ether, N-cyclohexylaminoethyl vinyl ether, 2-piperazinylaminoethyl vinyl ether, N-methylaminozolobyl vinyl ether, N-methylaminopropyl vinyl ether, N-cyclohexylaminoethyl vinyl ether,
-Propylaminozolobyl vinyl ether, N-methylaminozolobyl vinyl ether, N-methylaminobutyl vinyl ether, N-ethylaminobutyl vinyl ether, N-methylaminopentyl vinyl ether, N-
Ethylaminoethyl vinyl ether, N-methylaminehexyl vinyl ether, N-ethylaminohexyl vinyl ether, N-methylaminooctyl vinyl ether, N-ethylaminooctyl vinyl ether, N-t
ert-butylaminoethyl (meth)acrylate, N
-Methylallylamine, N-ethylallylamine, p-
(2-methylaminoethyl)styrene or p-(2
-ethylaminoethyl) styrene and other secondary amino group-containing monomers: N,N-dimethylaminoethyl vinyl ether, N,N-diethylaminoethyl vinyl ether, 2
-morpholinoethyl vinyl ether, 2-aziridinoethyl vinyl ether, N,N-dipropylaminoethyl vinyl ether, N,N-dibutylaminoethyl vinyl ether, N,N-nomethylamineglopyruvinyl ether, N,N -diethylamine zolobyl vinyl ether, N,N-sopropylaminoglobinyl vinyl ether, N,N-dimethylaminobutyl vinyl ether,
N,N-noethylaminobutyl vinyl ether k,N
sN-dipropylaminoethyl vinyl ether, N,N
-dibutylaminoptervinyl ether/l/, N, N
-trimethylaminotervinylethe/l/, N
, N-'): r-f aminopentyl vinyl ether, N,N-dipropylaminoethyl vinyl ether,
NlN-trimethylaminehexyl vinyl ether, N,N
-diethylaminohexyl vinyl ether, N, N-
Dipropylaminoethyl vinyl ether, N,N-dibutylaminohexyl vinyl ether, N,N-tumethylaminooctyl vinyl ether, N,N-diethylaminooctyl vinyl ether, N,N-soprobylamine octyl vinyl ether, aziridinoethyl (meth)acrylate, Dimethylaminoethyl (meth)acrylate, soethylaminoethyl (meth)acrylate, trimethylaminopropyl (meth)acrylate, nomethylaminobutyl (meth)acrylate, dimethylaminohexyl (meth)acrylate, N-dimethylaminoethyl (
meth)acrylamide, N-diethylaminoethyl (meth)acrylamide, N-tumethylaminopropyl (meth)acrylamide, N-dimethylaminobutyl (meth)acrylamide, N-dimethylaminohexyl (meth)acrylamide, p-(2-dimethyl aminoethyl)
Examples include tertiary amino group-containing monomers such as styrene, p-(2-diethylaminoethyl)styrene, p-(2-diethylaminoethyl)styrene, or p-azirisonylaminoethylstyrene; More than one species may be used in combination.

In addition, as the above-mentioned hydroxyl group-containing monomer, K
is 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 2-hydroxybutyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 5- Hydroxyl group-containing vinyl ethers such as hydroxypentyl vinyl ether or 6-hydroxyethyl vinyl ether; addition reaction products of hydroxyl group-containing vinyl ethers such as depleted hydroxyl group-containing vinyl ethers and ε-caprolactone: 2-hydroxyethyl (meth)allyl ether, 3-hydroxypropyl (meth)allyl ether, 2
-Hydroxypropyl (meth)allyl ether, 4-hydroxybutyl (meth)allyl ether, 3-hydroxybutyl (meth)allyl ether, 2-hydroxybutyl (meth)allyl ether, 2-hydroxy-2-methylzorobyl (meth)allyl Ether, hydroxyl group-containing allyl ethers such as 5-hydroxypentyl (meth)allyl ether modi or 6-hydroxyhexyl (meth)allyl ether; or addition reaction products of hydroxyl group-containing allyl ether and ε-caprolactone, etc. These can be used alone or in combination of two or more.

Furthermore, the other copolymerizable monomers mentioned above include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isozolobyl vinyl ether, n-
-butyl vinyl ether, inbutyl vinyl ether,
tert-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, 2-ethylhexyl vinyl ether,
Alkyl vinyl ethers or substituted alkyl vinyl ethers, such as chloromethyl vinyl ether, chloroethyl vinyl ether, benzyl vinyl ether, or phenyl vinyl ether; cycloalkyl vinyl ethers, such as cyclopentyl vinyl ether, cyclohexyl vinyl ether, and cyclohexyl vinyl ether; ; vinyl-2,2-dimethylpronoate, vinyl-2,2-dimethylbutanoate,
Vinyl-2,2-dimethylpentanoate, vinyl-2
, 2-methylhexanoate, vinyl-2,2-diethylbutanoate, vinyl-2-ethyl-2-methylbutanoate, vinyl-2-ethyl-2-methylbentanoate, vinyl-3- Chloro-2,2-dimethylgropanoate, tlk vinyl vinegar, vinyl globionate, n-
vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl caprate, vinyl caprate, vinyl laurate,
Branched aliphatic vinyl caprate having an alkyl group of C9, branched aliphatic vinyl caprate having an alkyl group of C10, branched aliphatic vinyl caprate having an alkyl group of C11, vinyl stearate, vinyl cyclohexanecarboxylate , methylcyclohexanecal M
7m vinyl, vinyl benzoate or p-tert-
Carboxylic acid vinyl esters such as vinyl butyl benzoate; methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate Acrylate, te+r
Such as t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, dibromozorovir (meth)acrylate or alkoxyalkyl (meth)acrylate Acrylic monomer; 2-hydroxyethyl (meth)
Acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-chloro -2-hydroxyethyl (meth)acrylate, di-2-hydroxyethyl fumarate, mono-2-hydroxyethyl-monobutyl fumarate, polyethylene glycol- or polypropylene glycol mono(meth)acrylate or [Zolaxel y or FAJ [Daicel Chemical (
α, β-ethylenically unsaturated Cal? In addition to hydroxyl group-containing monomers other than the above-mentioned hydroxyl group-containing vinyl or esteryl ethers, such as hydroxyalkyl esters of carbonic acid or addition reaction products of these with ε-caprolactone,
meth)acrylate, β-methylglycidyl (meth)acrylate or (meth)allyl (monobutane-containing monobuttons such as glycidyl ether; unsaturated dicarnic acid such as fumaric acid or itaconic acid and monohydric alcohol) Diesters: (meth)acrylic acid, maleic acid, fumaric acid or itaconic acid, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3
-Hydroxybutyl (meth)acrylate or 4-
Acid anhydrides which are adducts of hydroxyl group-containing (meth)acrylic acid esters such as hydroxybutyl (meth)acrylate and polycarboxylic acid anhydrides such as maleic anhydride, succinic anhydride, phthalic anhydride or hexahydrophthalic anhydride. Group-containing monomer: styrene, α-methylstyrene, p
Aromatic vinyl monomers such as -tert-butylstyrene or vinyltoluene; or olefins other than suspended fluoroolefins such as (meth)acrylonitrile, vinyl chloride or vinylidene chloride; or vinyltrimethoxysilane, vinyltrifluoride, etc. Ethoxysilane, vinyltriethoxysilane, vinylmethyljethoxysilane, vinyltris(β-methoxyethoxy)silane, allyltrimethoxysilane, trimethoxysilylethyl vinyl ether, triethoxysilylethyl vinyl ether, methyldimethoxysilylethyl vinyl ether, trimethoxysilylzolo Bilbinyl ether, triethoxysilyl vinyl ether, methyldimethoxysilylzolobyl vinyl ether, γ-(meth)acryloyloxyzolobyltrimethoxysilane, γ-(meth)acryloyloxyzolobyltriethoxysilane or γ-
Typical examples include hydrolyzable silyl group-containing monomers such as (meth)acryloyloxyzorobylmethyldimethoxysilane, which may be used alone or in combination of two or more.

Among these, those selected from the group consisting of alkyl vinyl ethers, cycloalkyl vinyl ethers, and carboxylic acid vinyl esters are preferable.

For each vertebra monomer listed above, each single component and its usage amount should be determined appropriately from the viewpoint of copolymerizability, coating performance such as painting workability and weather resistance. Bye.

To prepare the fluoroolefin copolymer (N,
Known one-polymerization methods such as bulk polymerization method, solution (pressure) polymerization method, suspension one-polymerization method or emulsion polymerization method can be applied, but among them,
Solution radical polymerization is the simplest method.

The radical polymerization initiators used in this case include acetyl peroxide, benzoyl) J? oxide,
lauroyl peroxide, methyl ethyl ketone monooxide, cyclohexanone monooxide, t
art-bunalhydro/f-oxide, cumenehydrono and monooxide, g-tert-butylnoJ? −
Oxide, dicumyl peroxide, tert-zotylno! -peroxides such as oxybenzoate, tert-butylno-oxyoctoate, tert-butylperoxyacetate or tert-7''oxypivalate; or azo-based compounds such as azobisisobutyronitrile or azobisisovaleronitrile. Typical examples include compounds.

In addition, the solvents used in the first reaction include various hydrocarbons such as toluene, xylene, cyclohexane, n-hexane, and mono-octane; methyl acetate, ethyl acetate, n-butyl acetate, or ethylene glycol monoethyl ether acetate. Ester series such as; acetone,
Ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone or cyclohexanone; amide systems such as dimethylformamide, dimethylacetamide or N-methylpyrrolidone; or methanol, ethanol, n-propanol, isozolopanol, lobutanol, imbutanol, 5eC Typical examples include alcohol-based organic solvents such as -butanol, tert-butanol, and ethylene glycol monoalkyl ether, or mixtures thereof.

Furthermore, during polymerization, lauryl mercaptan, 2-
Chain transfer agents such as mercazotoethanol or α-methylstyrene dimer can also be used.

The fluoroolefin copolymer thus obtained (the weight average molecular weight of N is 7,000 to 300,000,
Preferably, it is within the range of s, o o o to 200,000. If it is less than 7,000, the durability of the coating film will inevitably decrease;
Exceeding this value is unpractical and undesirable, as coating workability is likely to be poor.

In the above, we have mainly explained the method for preparing the copolymer (A) in a solvent-soluble type, but a non-aqueous dispersion method in which the copolymer (A) is dispersed in a solvent It is a matter of opinion that it may be of a type, or even of a form containing partially fluorinated particles.

Typical curing agents (B) that can react with the hydroxyl groups mentioned above include incyanate compounds and aminoaldehyde resins, among which in7anate compounds include tetramethylene diincyanate and hexamethylene. Aliphatic diynes such as diynoanoate or trimethylhexamethylene diincyanate 7
or inphorone diinnoanate, methylfuclohexane-2,4- or -2,6-diinzoane), 4,4'-methylenebis(cyclohexyl incyanate) or 1,3-di(incyanatemethyl)cyclohexane. Cycloaliphatic diincyanates such as;
Alternatively, adducts of each of these diincyanates and polyhydric alcohols or low-molecular-weight hydroxyl group-containing polymers, and reaction products of the various diincyanates listed above with water or a biuret forming agent (beeret) or trimers (incanulates) of the various diincyanates listed above; A typical example is one blocked with a known blocking agent, and the amino aldehyde resin may contain one or more amino compounds such as melamine, acetoguanamine, benzoguanamine, or urea. Typical examples include a condensate obtained by reacting with a formaldehyde supplying substance such as formalin, paraformaldehyde or hexamethylenetetramine, or an etherified product obtained by reacting such a condensate with a C4 to C4 lower alcohol. However, in terms of weather resistance, melamine
The use of formaldehyde resin is preferred.

The amount of the curing agent (B) to be used is within the range of 5 to 100 parts by weight, preferably 10 to 80 parts by weight, based on 100 parts by weight of the aforementioned fluoroolefin copolymer (A). is appropriate.

If it is less than 5 parts by weight, the fluoroolefin copolymer (A) will inevitably be insufficiently crosslinked, resulting in poor weather resistance and poor film hardness and solvent resistance. On the other hand, if it exceeds 100 parts by weight, the mechanical properties inevitably deteriorate, which is not preferable.

In addition, as the above-mentioned compound (C) having both an epoxy group and a hydrolyzed silyl group in one molecule, a polymer having both of these types of reactive groups (functional groups) and a 7-rank polymer containing an epoxy group can be used. A typical example is a ring agent.

Here, the hydrolyzable silyl group has the general formula % (1) and is a natural number equal to 2. " is a reactive group that is easily hydrolyzed, such as a halosilyl group, an alkoxysilyl group, an acyloxynoryl group, a phenoxysilyl group, an iminooxysilyl group, or an alkenyloxysilyl group.

Any known method can be applied to prepare a polymer having specific bireactive groups such as those mentioned above. Meta) Acrylic Oki 77
``Pyrmethyldimethoxy77rane, γ-(meth)acryloyloxy7probyltriingropenylox7silane, γ-(meth)acryloyloxypropyliminooxy77rane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyl (Tris-β-methoxy7ethoxy)
silane, vinyltriethoxysilane or vinyltrichlor7-containing vinyl monomer, and (β-methyl)glycidyl (meth)azilylate,
Allyl glinosyl ether and cy(β-methyl)glycidyl flate are combined with an epoxy group-containing monomer such as cy(β-methyl)glycidyl fumarate and, if necessary, with a fluoroolefin copolymer (A). Solution radical polymerization may also be carried out using various other copolymerizable monomers already listed as monomers that can be used in the preparation of γ-mercazotoglozolotrimerine. 77ran, γ-mercadetogzolortriethoxy 7rane, γ-mercaptozolopylmethyldimethoxysilane, γmercazotopropyl triimpene penyloxysilane 7
In the presence of a chain transfer agent such as silane or r-merkanotozolopyltriiminookine silane, a monomer mixture containing an epoxy group-containing monomer as described above is subjected to solution radical (co)polymerization, etc. This method is cited as a simple method.

In addition, in order to prepare a polymer having both an epoxy group and a hydrolyzable silyl group according to the above-mentioned method (1), a hydrolyzable silyl group-containing vinyl monomer as described above can also be used in combination. Of course.

Next, representative examples of the above-mentioned epoxy group-containing 7-run coupling agents include γ-glycidoxypropyltrilinoxy 7-run, r-glycidoxypropyltriethoxy/
oran, γ-glycidokingzololmethyldimethoxy7norane, γ-gly/doki7propyltriinzopenyloxy7noranmoshi, or γ-glycidocane/propyltriiminoki7norane; or in7anatonoropyl Examples include adducts of triinglo (niloquinolane or γ-yne/anetopropyltrimethoquinosilane, etc., with grindol; or adducts of γ-aminozolobil trilinqui77ran, etc., with jepoxy compounds, etc.).
In particular, γ-gly7doxyprobyl triinzolopenyl 77ran or γ-glytoxyprobyl triinzolopenyl 77ran is preferred from the viewpoint of curability and economical efficiency.

The lid for use of the compound (C) is in a range of 0.05 to 50 parts by weight, preferably 0.1 to 40 parts by weight, based on 100 parts by weight of the fluoroolefin copolymer (A). The inside is appropriate.

If the amount is less than 0.05 parts by weight, the adhesion will inevitably decrease, and if it exceeds 50 parts by weight, the water resistance of the coating will inevitably decrease.
Neither is preferable.

In order to prepare the curable resin composition of the present invention using each of the essential components as described above, they may be mixed in a conventional manner.

The thus obtained composition of the present invention may further contain colored pigments and/or metal powders, if necessary.

In addition, the curable resin composition of the present invention may further contain various resins and solvents, flow regulators, color separation inhibitors, curing accelerators, antioxidants, ultraviolet absorbers, or Of course, various known and commonly used additives such as light stabilizers can also be added.

Among these, typical resins include cellulose resins such as nitrocellulose and cellulose acetate, vinyl chloride-vinyl acetate copolymer resins, ketone resins, petroleum resins, acrylic resins, There are polyester resins, alkyd resins or epoxy/resins, etc.
Furthermore, as solvents, those that can be used in preparing the inside of the fluoroolefin copolymer as listed above can be used as is, but when using a (block) innoanate compound as the curing agent (B) component listed above, It goes without saying that the use of compounds that react with innoanate groups should be avoided as the solvents.

The curable resin composition thus obtained can be applied to various materials such as metals, wood, inorganic base materials, and plastics, or processed products, etc., for example, by electrostatic coating, air gray, airless gray electrostatic coating, etc. Painted by conventional methods such as roller painting or brush painting, then
By drying it for a few days in a regular air conditioner, or by drying it for 60~
A hardened film can be formed by forced drying or baking at a temperature of 300° C. for 30 seconds to 60 minutes.

〔Example〕

Next, the present invention will be specifically explained with reference to Reference Examples, Examples, and Comparative Examples. In the following, all parts and parts are based on weight unless otherwise specified.

Reference Example 1 [Example of Preparation of Fluoroolefin Copolymer (A)] 0250 parts of ethyl vinyl ether, 140 parts of 7-chlorohexfulvinyl ether, and 4-hydrocarbon 100 parts of butyl vinyl ether (7) and 1 part of 2-aminoethyl vinyl ether, 424 parts of n-butyl acetate, 15 parts of azobisisovaleronitrile, t
10 parts of art-butyl/4'-oxyoctoate and 1,2,2,6.6--J#! Then, 500 parts of the liquefied and collected chlorotrifluoroethylene was charged into the mixture, and the mixture was reacted at 60°C for 15 hours with stirring, resulting in a solution with a non-volatile content of 67%. Then, the solution was cooled to room temperature, and 175 parts of xyl/lene was added to obtain a solution of the desired copolymer with a nonvolatile content of 60.0% and a fluorine content of 24% in the solid fraction. The weight average molecular weight of this product was so, ooo. Hereinafter, this will be abbreviated as copolymer (A-1).

Reference Examples 2 and 3 (same as above) Except for changing the monomer composition as shown in Table 2,
A solution of the desired copolymer was obtained in the same manner as in Reference Example 1.

Reference Examples 4 and 5 (NI4 production example of fluoroolefin copolymer for control) Except for changing the monomer composition as shown in Table 2,
In the same manner as in Reference Example 1, a basic nitrogen atom-free fluoroolefin copolymer solution was obtained.

/ Examples 1 to 4 and Comparative Examples 1 to 4 Using each fluoroolefin copolymer obtained in each reference example, various curable resin compositions were obtained according to the composition ratios shown in Table 2. .

Next, each resin composition was used as a clear paint.
Each layer was coated on a stainless steel substrate and dried and cured.

Thereafter, the performance of each cured coating film thus obtained was compared and studied.

The results are summarized in the same table.

/ / 〔Effect of the invention〕 As is clear from Table 2, Curability of the present invention The resin composition is It has extremely good adhesion. I know this.

Claims (1)

[Claims] 1. As essential components, (A) a fluoroolefin copolymer having both a basic nitrogen atom and a hydroxyl group, (B) a curing agent capable of reacting with the hydroxyl group, and (C) one molecule A curable resin composition comprising a compound having both an epoxy group and a hydrolyzable silyl group. 2. The fluoroolefin copolymer (A) having both a basic nitrogen atom and a hydroxyl group as described above contains vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, and a carbon alkyl group. The composition according to claim 1, which is a copolymer of at least one compound selected from the group consisting of (per)fluoroalkyl trifluorovinylethers having a number of 1 to 18 and a monomer copolymerizable therewith. thing. 3. The composition according to claim 1, wherein the curing agent (B) capable of reacting with the hydroxyl group described above is an aminoaldehyde resin. 4. The composition according to claim 1, wherein the curing agent (B) capable of reacting with the hydroxyl group described above is a polyisocyanate compound. 5. The composition according to claim 1, wherein the curing agent (B) capable of reacting with the hydroxyl group described above is an aminoaldehyde resin and a polyisocyanate compound.