JPS63210157A - Curable resin composition - Google Patents

Abstract

PURPOSE:To provide the title compsn. having excellent weather resistance inherent to said compsn. as well as excellent solvent resistance and adhesion, by blending a fluoroolefin polymer with a polymer having a COOH group and a polyepoxy compd. and/or a compd. having epoxy and hydrolyzable silyl group. CONSTITUTION:The title compsn. is obtd. by blending a fluoroolefin polymer (A) (e.g., a polymer of vinylidene fluoride, etc.) with a vinyl polymer (B) having a COOH group (e.g., a copolymer of methacrylic acid with other vinyl monomer copolymerizable therewith) and a polyepoxy compd. (C) (e.g., sorbitol polyglycidyl ether) and/or a compd. (D) having both epoxy and hydrolyzable silyl groups (e.g., gamma-glycidoxypropylisoproenyloxysilane, etc.) and optionally, a catalyst (E) for the hydrolysis and condensation of said silyl group (e.g., dibutyltin acetate). The compsn. has excellent solvent resistance and adhesion and can be used as paints for household appliance, enamel paints for automobiles, surface-protective films for glass, etc.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a novel and useful curable resin composition,
More specifically, it contains a fluoroolefin polymer, a xyl group-containing vinyl polymer, a polyepoxy compound and/or a compound having both an epoxy group and a hydrolyzable silyl group as essential components. The present invention relates to a resin composition comprising:

Curable resin compositions with such specific configurations have excellent solvent resistance, adhesion, and weather resistance, so they can be used as paints for home appliances, buildings, roof tiles, or precoated metal/I/(PCM).
) and other exterior paints, and for automobiles, especially as enamel paints, metallic paste paints, or clear paints, as surface protective films for glass and ceramic products, as films and sheets, or as sealants and It is widely used as an adhesive.

[Prior art and problems to be solved by the invention] Conventionally, as a highly weather-resistant coating resin that is soluble in solvents and forms a continuous coating film at room temperature, tetrafluorocarbon resin has been used as a non-crosslinked resin. Ethylene-7-fuvinylidene copolymer, hexafluoropropylene-vinylidene fluoride copolymer, tetrafluoroethylene-vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride homopolymer, chlorotrifluoroethylene homopolymer , chlorotrifluoroethylene-cycloalkyl vinyl ether-alkyl vinyl ether copolymers, etc., and crosslinked types such as vinylidene fluoride copolymers and hexafluoropropylene copolymers containing hydroxyl groups, epoxy groups, etc. are known. There is.

However, coating films obtained from such non-crosslinked resins have insufficient solvent resistance and adhesion to substrates.
Furthermore, coating films obtained from cross-linked resins have insufficient adhesion to substrates, and their uses are inherently limited.

[Means for solving problems]

However, the present inventors have conducted extensive studies in view of the various drawbacks in the prior art as described above, and have found that a fluoroolefin polymer containing a carxyl group-containing polymer, a polyepoxy compound, and/or a polyepoxy compound and/or By blending the compound with a compound having both an epoxy group and a hydrolyzable silyl group, it improves adhesion to various substrates, etc.
The present invention was completed by discovering that a curable resin composition having excellent solvent resistance can be obtained.

That is, the present invention provides a fluoroolefin polymer (A)
and 1. A caroxyl group-containing vinyl polymer (B) excluding this fluoroolefin polymer (A), a polyepoxy compound (C) and/or an epoxy group and a hydrolyzable silyl group in one molecule. It also contains the compound (D) as an essential component, and if necessary,
The catalyst for hydrolysis-condensation of the hydrolyzable silyl group described above (
6).sb.

Hereinafter, the configuration of the present invention will be explained in detail.

The fluoroolefin polymer (A) component used in the present invention includes vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, difluoroethylene, chlorotrifluoroethylene, pentafluoropropylene, and hexafluoroethylene. Fluoroolefin monomer selected from the group consisting of fluoropropylene and per-fluoroalkyl trifluorovinyl ether [However, the number of carbon atoms in the (](-)7/L/oloalkyl group part is 1 to 18)] The amount of such fluoroolefins used is 5 to 100% by weight of the total monomer, preferably 1
A range of 0 to 100 weight is appropriate. In the present invention, a polymer (A
) Other copolymerizable monomers can be used in preparing the component.

Such copolymerizable monomers include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl piperate, vinyl casilonate, vinyl caprate, vinyl caprylate, vinyl persate, vinyl laurate, or stearate. Vinyl ester of linear or branched aliphatic carboxylic acid such as vinyl; cyclohexane kg
Vinyl benzoate/I/: Vinyl benzoate,
Aromatic carboxylic acid vinyl esters such as pt-butylbenzoic acid vinyl ester or salicylic acid vinyl ester; hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether, hydroxypropyl vinyl ether or hahydroxybutyl vinyl ether; methyl vinyl ether, ethyl vinyl ether , linear or branched aliphatic or alicyclic vinyl ethers such as fluorobyl vinyl ether, n-butyl vinyl ether, l-butyl vinyl ether, -butyl vinyl ether, or cyclohexyl vinyl ether; glycidyl vinyl ether, glycidyl (meth) Monomers having epoxy groups such as acrylate; acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, monoethyl maleate,
Caroxyl group-containing monomers such as motuptil maleate, monobutyl fumarate, monobutyl itaconate, monovinyl adipate, monovinyl sepacate; dimethylaminoethyl vinyl ether, dimethylaminopropyl vinyl ether, N-dimethylaminopropyl (meth) ) Basic nitrogen-containing vinyl monomers such as acrylamide and dimethylaminoethyl (meth)acrylate; α-olefins such as ethylene, propylene, butene-1 or hexene-1; vinyl chloride or vinylidene chloride. , excluding the above-mentioned fluoroolefin monomers, /10 olefins; aromatic vinyl monomers such as styrene, α-methylstyrene or vinyltoluene; methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylic acid esters such as (meth)acrylate, cyclohexy/I/(meth)acrylate, β-hydroxyethyl (meth)acrylate or phosphate ester of β-hydroxyethyl (meth)acrylate; Acrylonitrile, (meth)acrylamide, N-methylol (
Monomers such as meth)acrylamide or N-butoxymethyl(meth)acrylamide; vinyltrimethoxysilane, vinyltrimethoxysilane, and hydrolyzable silyl groups such as γ-(meth)acryloyloxypropyltrimethoxysilane. There are monomers it contains.

Polymerization is carried out in the presence of the above-mentioned monomers using a radical polymerization initiator using known techniques such as bulk polymerization, solution polymerization, and emulsion polymerization in a batch, semi-continuous, or continuous manner. That's fine.

Such radical polymerization initiators include diacyl peroxides such as acetylhydro-oxide or benzoyl peroxide; ketone peroxides such as methyl ethyl ketone peroxide or cyclohexanone peroxide; hydrogen peroxide, t-butyl hydro-oxide or Hydroperoxides such as cumene hydroperoxide; di-t-butyl peroxide or dicumyl/'I? -Dialkyl peroxides such as oxide; t-butyl/#
azo initiators such as azobisisobutyronitrile or azobisisovaleronitrile; or ammonium persulfate or potassium persulfate. Inorganic reducing agents such as sodium hydrogen sulfite or sodium pyrosulfite, or organic reducing agents such as cobalt naphthenate or dimethylaniline are also used if necessary.

Examples of solvents used in the polymerization reaction include hydrocarbons such as toluene, xylene, cyclohexane, n-hexane, and octane; esters such as methyl acetate, ethyl acetate, and butyl acetate; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and methyl. Ketones such as amylketone Amides such as dimethylformamide or dimethylacetamide; methanol, ethanol, i-7'roΔnol, n--1
An alcoholic solvent such as 〇-butanol, i-tutanol, 11eC-butanol, ethylene glycol monoalkyl ether, or a mixture thereof is used.

In this polymerization, various chain transfer agents such as lauryl mercaptan, octyl mercaptan, 2-mercaptoethanol or α-methylstyrene dimer can also be used as molecular weight regulators.

The reaction temperature during the polymerization reaction is -20°C to 130°C.
The pressure at the initial stage of the reaction is preferably within the range of 1 to 100 kg/cm", preferably 5.
~60 kli/cm'' is suitable.

The number average molecular weight (Mn) of the 7/l/Oa olefin polymer thus obtained is 1.000 to 300.0
00, preferably s, o o o to 200,000.

Next, the caroxyl group-containing vinyl polymer (B) used in the present invention refers to the carboxylic group-containing vinyl polymer (B) that contains in one molecule, excluding the above-mentioned α-type fukamine-based polymers (A). At least one, preferably two or more Cal? For example, (1) the carboxyl group-containing vinyl monomer (co-polymer) as described below may be used to refer to a vinyl polymer having a xyl group. ) superposition, or (ii) force y
, y acid anhydride group (hereinafter abbreviated as acid anhydride group)
It can be prepared by a known and commonly used method, such as ring-opening a vinyl polymer having the following with water and/or an alcohol.

Among them, the force kyl? used in preparing the polymer Φ) by the method (1). Typical examples of xyl group-containing vinyl monomers include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, itaconic acid, maleic acid, fumaric acid, mono-n-butyl maleate, and mono-n-butyl fumarate. Can be mentioned.

In addition, these carboxyl group-containing vinyl monomers can be copolymerized with other vinyl monomers that can be copolymerized with the monomers, and as such other vinyl monomers, Typical examples include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate,
n-butyl (meth)acrylate, isobutyl (meth)
Acrylate, t-butyl (meth)acrylate, 2-
Ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, benz/I/(meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxyzolopyl (meth)acrylate, 2-hydroxybutyl /I/(meth)acrylate or 4-hydroxybuty/I/(
Meta) Each one like acrylate! (meth)acrylic acid esters; dialkyl esters of unsaturated dibasic acids such as dimethyl maleate, dimethyl fumarate, dibutyl fumarate or dibutyl itacoester; dimethy/L/
Aminoethyl (meth)acrylate, diethylamine ethyl (meth)acrylate, dimethylaminopropyl N (
meth)acrylate or diethylaminozolovir (
Various dialkylaminoalky N(meth)acrylates such as meth)acrylate, N,N-dimethylaminoethyl(meth)acrylamide, N,N-diethylaminoethyl(meth)acrylamide, N,N-
N,N-dialkylaminoalky A/(meth)acrylamides such as dimethylaminopropyl (meth)acrylamide or N,N-diethylaminopropyl (meth)acrylamide, or t-butylaminoethyl (meth)acrylate, t-butylamino Basic nitrogen-containing vinyl monomers such as propylene (meth)acrylate, aziridinylethyl (meth)acrylate, pyrrolidinylethyl (meth)acrylate or piperidinylethyl (meth)acrylate; p-styrene sulfone Various sulfonate (acid)amide group-containing vinyl monomers such as (acid)amide, N-methyl-p-styrenesulfonate (acid)amide, or N,N-dimethyl-p-styrenesulfonate (acid)amide; Cyano group-containing vinyl monomers such as meth)acrylonitrile; various α such as hydroxyalkyl esters of (meth)acrylic acid as listed above;
, β-ethylenically unsaturated cal? Various phosphoric acid ester bond-containing vinyl monomers which are condensation products with hydroxyalkyl esters of phosphoric acid, phosphoric acid or phosphoric acid esters; vinyl acetate, vinyl benzoate or "Peopa 9"
Various vinyl esters such as (manufactured by Shell in the Netherlands, vinyl esters of branched fatty acids): "Visbu" 8
F, 8FM, 3F or 3FM JI
: Fluorine-containing (meth)acrylic monomer manufactured by Osaka Organic Kagaku ) acrylate-like () arm-)
Vinyl monomers containing a ciba(per)fluorocycloalkyl group without a fluoroalkyl group; and each fluoroolefin monomer used in the synthesis of the various fluoroolefin polymers (A) as listed above. Halodanated olefins such as vinyl chloride or vinylidene chloride; or aromatic vinyl monomers such as styrene, α-methylstyrene, pt-butylstyrene, or vinyltoluene.

In order to prepare the vinyl polymer using the various monomers listed above, 0.5 to 100 weight percent of the caryloxyl group-containing vinyl monomer, preferably 1 to 50
The weight ratio and O to 99.5% by weight, preferably 50 to 99% by weight of another vinyl monomer copolymerizable with the carboxyl group-containing vinyl monomer are mixed in a conventional manner. ) All you have to do is to superimpose them.

In addition, when using the above-mentioned basic nitrogen atom-containing vinyl monomers as other vinyl monomers copolymerizable with the carboxyl group-containing vinyl monomer,
This is particularly desirable since it is possible to introduce such basic nitrogen atoms into the vinyl-based polymer (B), thereby further improving the curability of the composition of the present invention.

To prepare the vinyl polymer (B)'ir from the various monomers listed above, any conventionally known polymerization method can be applied, but solution radical polymerization is the simplest method.

At that time, polymerization initiators, solvents, chain transfer agents, etc.
Of course, those used in the preparation of the fluoroolefin polymer (6) can be used as they are.

Next, the acid anhydride group-containing vinyl polymer used in preparing the vinyl polymer (B) by the above-mentioned method (11) is an acid anhydride group-containing vinyl polymer such as maleic anhydride or itaconic anhydride. The containing monomer and another monomer copolymerizable with the nucleic acid anhydride group-containing monomer may be radically copolymerized in various solvents as listed above, excluding alcohols. .

The ring-opening reaction of the acid anhydride group in the acid anhydride group-containing vinyl polymer with water and/or alcohol can also be carried out during the copolymerization reaction when preparing the acid anhydride group-containing polymer. It is also possible to carry out the process again after once obtaining the acid anhydride group-containing polymer.

Here, other copolymerizable monomers used in the preparation of the acid anhydride group-containing vinyl-y-based polymer include cal-oxysilane, such as those used in the method (1) above. Among other vinyl monomers copolymerizable with the group-containing vinyl monomer, any other vinyl monomer other than the hydroxyl group-containing monomer can be used.

In terms of weather resistance and alkali resistance, the amount of the acid anhydride group-containing monomer mentioned above should be 0.5 to 0.
A suitable range is 60 parts by weight, preferably 1 to 30 parts by weight, while the amount of other copolymerizable monomers used is 99.5 to 40 parts by weight, preferably 99 to 70 parts by weight. It is appropriate to fall within this range.

At this time, as a component of other copolymerizable W and mer,
It is particularly desirable to use an amino group-containing vinyl monomer as described above in combination, since the curability of the composition of the present invention can be further improved.

Cal obtained in this way is a xyl group-containing vinyl polymer (
B) is 1,000 to 1,000 aoo, o
oo, preferably within the range of 3,000 to 100,000.

Furthermore, the polyethylene oxy compound (C
) refers to a compound containing at least two epoxy groups in one molecule, among which representative examples include ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexane. Polyglycidyl ethers of polyhydric alcohols such as thiol diglycidyl ether, sorbitol tetraglycidyl ether, diglycidyl ether of bispheno-/I/A or triglycidyl ether of glycerin; diglycidyl ester of 7-talic acid, diglycidyl isophthalic acid Polyglycidyl esters of polyhydric carginic acids such as esters or diglycidyl esters of adipic acid: or bispheno-A/human or bispheno-A.
/l/F diglycidyl ether type epoxy resin, )R
Examples include various epoxy resins such as lac type epoxy resins and hydantoin ring-containing epoxy resins, and furthermore, glycidyl ester ethers of p-oxybenzoic acid and various vinyl polymers having epoxy groups in their side chains.

Next, the compound (D) used in the present invention refers to a compound having both an epoxy group and a hydrolyzable silyl group in one molecule as described above, and representative examples of the compound include: Examples include epoxy group-containing silane cassilling agents and vinyl polymers having both of the above types of reactive groups (functional groups).

Here, the hydrolyzable silyl group is a general formula [where R4 is a hydrogen atom or a monovalent organic group such as an alkyl group, an aryl group, or an aralkyl group, and R2 is a halogen atom or an alkoxy group, an acyloxy group, or a phenoxy group. group, iminooxy group or alkenyloxy group, and a is an integer of 0.1 or 2. ] A herrosilyl group, an alkoxysilyl group,
It refers to a reactive group (functional group) that is easily hydrolyzed, such as an acyloxysilyl group, a phenoxysilyl group, an iminooxysilyl group, or an alkenyloxysilyl group.

Representative examples of the above-mentioned epoxy group-containing silane cassilling agents include r-glycidoxypropyltrimethoxysilane, γ-glycidoxysolopyltriethoxysilane, and γ-glycidoxyzolopylmethyljethoxysilane. Silane, γ-glycidoxypropyltriisogropenyloxysilane or γ-glycidoxypropyltriiminooxysilane; or γ-isocyanatozolopyltriisozolopenyloxysilane or γ-isocyanatopropyltrimethoxysilane and glycidol (2,3-epoxy-1-propanol); or adducts of r-aminozolopyltrimethoxysilane and various known jepoxy compounds; Among the silane cassilling agents contained, r-glycidoxypropyltrimethoxysilane or γ-glycidoxypropyltriisogropenyloxysilane is particularly preferred in terms of curability and economical efficiency.

On the other hand, vinyl polymers having both types of reactive groups (functional groups), epoxy groups and hydrolyzable silyl groups, as described above,
For example, hydrolyzable silyl group-containing vinyl monomers such as γ-(meth)acryloyloxyzolobyltrimethoxysilane and vinyltrimethoxysilane, and epoxy group-containing monomers such as (β-methyl)glycidyl (meth)acrylate. It can be obtained by a known and commonly used method such as copolymerizing vinyl monomers and gold, or even monomers copolymerizable with monomers of both types.

In preparing the curable resin composition of the present invention, a reactive functional group such as a hydroxyl group other than a xyl group is contained in the polymer serving as the above-mentioned carrier component or component (B). If such functional groups are present, a curing agent that can react with these functional groups, such as a polyisocyanate compound or aminoplast when these functional groups are hydroxyl groups, is added to further increase the crosslinking density of the coating film, thereby improving solvent resistance. etc. can be completely improved.

By the way, although the composition of the present invention has good curability even without the use of a curing catalyst, if it is desired to further improve this curability, hydrolysis of various hydrolyzable silyl groups as mentioned above can be used. There is no hindrance to adding and blending the hydrolysis-condensation catalyst (E) as a catalyst for hydrolysis and condensation.

Typical examples of the catalyst (6) include n-butylamine, di-n-butylamine, t-butylamine, hexylamine, ethylenediamine, triethylamine, isophoronediamine, imidazole, lithium hydroxide, sodium hydroxide, potassium hydroxide, or Basic compounds such as sodium methylate; tetrasilopyr titanate;
Such as tetrabutyl titanate, tin octylate, lead octylate, cobalt octylate, calcium octylate, zinc octylate, lead naphthenate, cobalt naphthenate, diptyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate, dibutyltin malate. Metal-containing compounds; or acidic compounds such as p-toluenesulfonic acid, trichloroacetic acid, phosphoric acid, monoalkyl phosphoric acid, dialkyl phosphoric acid, phosphate ester of β-hydroxyethyl (meth)acrylate, monoalkyl phosphorous acid, dialkyl phosphorous acid, etc. .

Ingredients (A) to (9) listed above, or (A)
The composition ratio for obtaining the curable resin composition of the present invention using components (6) to (6) is usually a weight ratio of component (E)/component (6) of 10 to 90/90 to 10. It is suitable within the range of
Furthermore, from the viewpoint of improving adhesion, solvent resistance, and chemical resistance,
It is appropriate to fall within the following range.

Next, each of (Q component and (9) component) is a reactive group (
Component (C) and/or (D ) 0 epoxy groups present in the component
．． It is appropriate to mix them in a proportion of about 2 to 5 equivalents.

Component (E) is suitably used in a proportion of 0 to 10 parts by weight per 100 parts by weight of components (B), (0 and (D)).

Furthermore, the composition of the present invention may optionally contain various known organic and inorganic pigments, various metal powders such as aluminum, copper, brass, gold, silver, and nickel, ultraviolet absorbers, and antioxidants. Additive components and the like can also be added.

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, coating using a roll coater, etc., and is coated at room temperature. A cured coating film is formed by dry curing or by baking at a temperature of 60 to 250°C, preferably 60 to 200°C, for about 5 seconds to 40 minutes.

Thus, the curable resin composition of the present invention can be used as a paint for home appliances, or various exterior paints such as buildings, tiles, or PCM, or various automobiles such as enamel paints, metallic paste paints, or clear paints for automobiles. As a paint for industrial use, as a surface protective film for glass or ceramic products, and as molded products such as films and sheets.
It can be used in a wide range of applications, such as as a sealant or adhesive.

〔Example〕

Next, the present invention will be explained in more detail with reference to Reference Examples, Examples, and Comparative Examples. In the following, parts and qbFi are all based on weight unless otherwise noted.

Reference Example 1 [Preparation example of fluoroolefin polymer (6)] Methyl isobutyl ketone 330I and t-butyl/I/
4.2JF of i-oxypivalate, 84.9 of human axybutyl vinyl ether, and "Beoba 9" (C2
Vinyl ester of branched aliphatic caldic acid) O12
6JF and vinyl cyclohexanecarboxylate 84II were charged, cooled to -70°C in a dry ice/methanol bath, and nitrogen gas was blown to replace the air in the pressure vessel.

In the next step, 12 of the liquefied hexafluoropropylene
69 was prepared and sealed.

Thereafter, this pressure tube was placed in a rotary constant-temperature water bath heated to 60.degree. 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 non-volatile content of 53% and a reaction value of 9,000. Hereinafter, this copolymer solution was mixed with A-
It is abbreviated as 1.

Reference Example 2 [Same as above] A copolymer solution (A-2) was obtained in the same manner as Reference Example 1, except that the types of monomers used and their usage amounts were changed as shown below. .

Chlorotrifluoroethylene 126g Hydroxybutyl vinyl ether v 42F Ethyl vinyl ether 42.9 "Beoba 9J
21011 This copolymer solution (A-2) has a non-volatile content of 53, and a response of 17,
It was 000.

Reference Example 3 [Preparation example of vinyl polymer (B) containing xyl groups] Into a reactor equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube, 1.200 II of butyl acetate was charged and nitrogen gas was added. The temperature was raised to 110°C in an atmosphere, and 430.9. , 42 OL of t-butyl methacrylate, 501 of methacrylic acid, 10 g of azobis impronitri/I/(AIBN), t-butyl methacrylate
10 g of oxyoctoate and 200 g of butyl acetate
(See Table 1)
, then kept at the same temperature for 2 hours, then further AIB
A mixture of 511 N and 100 I of butyl acetate was added dropwise over a period of 1 hour, and the temperature was kept at the same temperature for 12 hours to obtain the desired polymer (with a non-volatile content of 4 (L) and a response of 10.000). A solution of B) was obtained.Hereinafter, this will be abbreviated as polymer (B-1).

Reference Examples 4 to 7 [Same as above] A solution of the target polymer (B) was prepared in the same manner as in Reference Example 3, except that the proportions of monomers used were changed as shown in Table 1: (B-2 ) to (B-5) were obtained. In the same table, the nonvolatile components are abbreviated as rN, V, and J.

Examples 1-6 (A)-(
A curable resin composition was obtained by mixing component D) or components (A) to (E).

Next, each curable resin composition was applied with a doctor blade to an aluminum plate (JIS A-5052P standard product) degreased with toluene so that the dry film thickness was 50 μm, and heated at 150° C. for 20 minutes. A coating film was obtained by curing.

Thereafter, adhesion and solvent resistance of each cured coating film were evaluated in accordance with the procedures described in the footnotes outside the table. The results are summarized in the same table.

Comparative Examples 1 and 2 Except for completely omitting the use of components (B), (C') and Φ), and making changes to follow the blending ratio and curing conditions as shown in Table 2. Example 1~
Apply the curable resin composition and form a film in the same manner as in 6.
Two control products were obtained. The performance of these coating films is also shown in the same table.

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

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

3) “Dinacol EX-612J: Sorbitol polyglycidyl ether manufactured by Nagashio Sangyo @), epoxy equivalent = 170° 4) Glycerin polyglycidyl ether: Epoxy equivalent = 145° 5) [Coronate EHJ: manufactured by Nippon Polyurethane Industry @) , polyisocyanate having incyanate rings, incyanate content = 21.3%, non-volatile content = 100%.

6) Cut lines were made on the coating film using a safety razor blade, and after peeling off the cut lines with cellophane tape, the number of punctures that remained on 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 film after rubbing it 50 times with a polishing machine (klil) was visually evaluated.

〔Judgment criteria〕

◎No abnormalities ○Slightly reduced gloss △Gloss significantly decreased.

X The coating film completely disappeared [Effect of the invention] The curable resin composition of the present invention has excellent solvent resistance and adhesion, as well as excellent performance such as weather resistance inherent to fluoroolefin polymers. It has the advantage of being retained. For this reason, the curable resin composition of the present invention can be used as paint for home appliances, exterior paints for buildings, tiles, or PCM, or for automobiles, especially as enamel paints, metallic paste paints, or clear paints for automobiles, and even for glass. It can be applied as a surface protective film, film, sealant, adhesive, etc. for ceramic products, but it is by no means limited to the application range of lifting.

Claims (1)

[Claims] 1. As essential components, (A) a fluoroolefin polymer, (B) a vinyl polymer containing a carboxyl group other than the above polymer (A), and (C) a polyester. comprising an epoxy compound and/or (D) a compound having both an epoxy group and a hydrolyzable silyl group in one molecule,
A curable resin composition further comprising (E) the above-mentioned catalyst for hydrolysis-condensation of a hydrolyzable silyl group, if necessary. 2. The fluoroolefin polymer (A) described above is vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, pentafluoropropylene, hexafluoropropylene, and (per)fluoroalkyltrifluoro Vinyl ether [However, the number of carbon atoms in this (per)fluoroalkyl group is 1 to 18. ] The composition according to claim 1, which is obtained by polymerizing at least one fluoroolefin monomer selected from the group consisting of: 3. The above carboxyl group-containing vinyl polymer (B)
is at least one carboxyl group-containing vinyl monomer selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid and maleic acid, and another vinyl monomer copolymerizable with the vinyl monomer. The composition according to claim 1, characterized in that it is a copolymer with a copolymer. 4. The above carboxyl group-containing vinyl polymer (B)
The composition according to claim 1, wherein the composition has both a carboxyl group and a basic nitrogen atom. 5. The composition according to claim 1, wherein the compound (D) is γ-glycidoxypropyltrialkoxysilane. 6. The composition according to claim 1, wherein the above-mentioned compound (D) is γ-glycidoxypropyltriisopropenyloxysilane.