JPS627767A - Resin composition for coating compound - Google Patents

Abstract

PURPOSE:The titled composition providing a cured film of coating having improved curing properties and solvent resistance, showing improved weather resistance of film of coating, comprising a vinyl copolymer consisting of a fluoroolefin, etc., and a curing agent having reactivity with hydroxyl group. CONSTITUTION:(A) A vinyl copolymer obtained by copolymerizing a fluoroolefin (e.g., tetrafluoroethylene, etc.) with a carboxylic acid vinyl ester (e.g., cyclohexanecarboxylic acid vinyl ester, etc.), a (hydroxy)alkylvinyl ether and, if necessary, another vinyl monomer, is blended with (B) a curing agent having reactivity with hydroxyl group and (C) optionally a curing catalyst, to give the aimed composition.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a new and useful resin composition for coatings. More specifically, the present invention relates to a composition comprising, as essential components, a solvent-soluble hydroxyl group-containing fluororesin as a pace polymer, and a compound reactive with the hydroxyl groups as a curing agent.

[Conventional technology]

Fluororesins (fluoroolefin polymers) are widely used due to their excellent chemical resistance, heat resistance, abrasion resistance, non-stick properties, and weather resistance. However, it has disadvantages such as requiring melting and baking at high temperatures. In addition, because they are insoluble in solvents, they are currently only used in the form of emulsions and dispersions.

Therefore, it has been extremely difficult to obtain a crosslinked coating film using a curing agent because the form of the coating material is also limited or because the compatibility with the curing agent is poor.

[Problems to be solved by the invention]

In order to eliminate and resolve these shortcomings or deficiencies,
The present inventors have filed a patent application for inventions such as those disclosed in Senju JP-A-59-102961 and No. 102962, but these inventions are based on the combination of a hydroxyl group-containing monomer with a comonomer. This was achieved by discovering that the fluoroolefin polymer obtained by copolymerization as a comonomer reacts with a curing agent to form a crosslinked coating film.

However, it has been confirmed that the coatings obtained according to both of the above inventions have defects in that the curing properties are insufficient and it is not possible to obtain a coating film with good solvent resistance.

[Means for solving problems]

Therefore, the present inventors recognized that the above-mentioned defects were caused by the low copolymerizability of the hydroxyl group-containing monomer and the fluoroolefin monomer, and as a result of extensive studies, the fluoroolefin concerned・As a polymer, a composition consisting of a combination of a copolymer obtained by using specific compounds such as fluoroolefins, carmenic acid vinyl esters, hydroxyalkyl vinyl ethers, and alkyl vinyl ethers as essential monomers and a curing agent can be cured. The inventors have now completed the present invention by discovering that they can provide a cured coating film with excellent properties, especially solvent resistance, and that the resulting coating film also has extremely good weather resistance.

That is, the present invention uses fluoroolefins, carboxylic acid vinyl esters, hydroxyalkyl vinyl ethers, and alkyl vinyl ethers as essential monomers, and if necessary, other vinyl monomers copolymerizable with these monomers. a vinyl-based copolymer obtained by copolymerizing the polymer, and a curing agent (B) that is reactive with hydroxyl groups.
It is an object of the present invention to provide a resin composition for a coating material, which further contains a curing catalyst (C')t- for promoting the crosslinking reaction with the component (A), if necessary.

Ru.

First, typical examples of the above-mentioned fluoroolefins include ethylene fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene,
chlorotrifluoroethylene or hexafluoropropylene, or hafluoroalkyl perfluorovinyl ethers such as trifluoromethyl trifluorovinyl ether or heptafluoropropyl trifluoromethyl vinyl ether, especially,
Preference is given to using tetrafluoroethylene, vinylidene fluoride, chlorotrifluoroethylene or hexafluoroglopyre/. Of course, these fluoroolefins may be used alone or in combination of two or more.

The amount of the fluoroolefin component to be used is 10 to 70 mole, preferably 2 mole, based on the total monomer component.
A range of 0 to 60 molti is suitable.

If it exceeds 70 mol, the gloss of the cured coating will be low, and if it is less than 10 mol, the excellent performance inherent to fluororesins, such as chemical resistance and weather resistance, will be unsatisfactory. You won't get what you should.

Next, typical examples of the above-mentioned vinyl carginate esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl piperate, vinyl casylonate, vinyl caprylate, vinyl caprate, Vinyl esters of linear or branched aliphatic carginic acids, such as vinyl persate, vinyl laurate or vinyl stearate, as well as vinyl esters of cyclohexanecarboxylic acid. These include vinyl esters of aromatic carboxylic acids such as vinyl esters of phosphoric acid, vinyl esters of benzoic acid, vinyl esters of p-tert-butylbenzoate, and vinyl esters of aromatic carboxylic acids such as vinyl salicylate. From the point of view of the compatibility of C5 to C18 linear or branched aliphatic monocarboxylic acids, vinyl cyclohexanecarboxylate, vinyl benzoate, or p-tert- The use of butyl benzoic acid vinyl ester is preferred.

Among aliphatic calgeneic acid vinyl esters, cal? Ru having a xyl group, 05-C4
Vinyl esters of 8-narcarboxylic acid, more preferably vinyl esters of C8 carboxylic acid, are particularly recommended from the viewpoint of coating film hardness.

The amount of the carboxylic acid vinyl ester component to be used is suitably within the range of 5 to 70 mol, preferably 10 to 60 mol, based on the total monomer components. Of course, these may be used alone or in combination of two or more.

ifc, representative hydroxyalkyl vinyl ethers mentioned above include hydroxyethyl vinyl k Z
-dal, 2-hydroxypropyl vinyl ether, 3-
Hydroxypropyl vinyl ether, 3-hydroxybutyl vinyl ether, 4-hydroxybutyl vinyl ether, 2-hydroxy-2-)dalpropyl vinyl ether, 5-hydroxypentyl vinyl ether or 6
-Hydroxy akyl vinyl ether, etc., these may be used alone or in combination of two or more types, and the amount of the monomer component used is 3.5 to 30 moles based on the total monomer components, preferably 5 to 30 moles. A range of 25 moles is suitable.

If it is less than 3.5 mol%, it will increase the crosslinking curing time and reduce the stain resistance of the coating film, and if it exceeds 30-mol%, it will reduce the dulling time when mixed with a curing agent. As a result, the workability (coating workability) of the paint begins to deteriorate.

Furthermore, typical examples of the alkyl vinyl ethers mentioned above include methyl vinyl ether, ethyl vinyl ether, n-7'-pyru vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, inbutyl vinyl ether, tert-phthyl vinyl ether,
Examples include n-pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, and 2-ethylhexyl vinyl ether, and it goes without saying that these may be used alone or in combination of two or more types.

The amount of alkyl vinyl ether used is 5 to 70 moles, preferably 7 to 70 moles, based on the total monomer components.
A range of 60 moles is suitable.

If it is less than 5 mol%, the conversion rate of fluoroolefins during the preparation of the vinyl copolymer tends to be low, and conversely, if it exceeds 70 mol%, the fluorine content in the vinyl copolymer ( This is not preferable because the performance decreases as a result of a decrease in the fluorine content.

Furthermore, other typical vinyl monomers copolymerizable with the monomer components listed above that can be used within a range that does not impair the characteristics of the present invention include ethylene, α-olefins such as propylene or butene-1; various halodanated olefins other than fluoroolefins such as vinyl chloride or vinylidene chloride; aromatic vinyl compounds such as styrene, α-methylstyrene or vinyltoluene; or aromatic vinyl ethers, allyl group-containing compounds such as allyl alcohol or allyl glycidyl ether; di- or monoesters of unsaturated polybasic acids such as fumaric acid or maleic acid: (
unsaturated polybasic acids or their anhydrides such as (anhydrous) maleic acid or (anhydrous) itaconic acid; or (meth)
Acrylonitrile, (meth)acrylamide, N-methylol (meth)acrylamide, N-butoxymethyl (
Examples include meth)acrylamide and (meth)acrylic acid esters.

The vinyl copolymer (4) of the present invention can be obtained by copolymerizing each of the monomer components listed above. Particularly desirable are copolymers obtained from

0.7 (b+c)≦a+d<3.5 (b+e)
CI ) [However, in the formula, a is the molar ratio of the fluoroolefin, b is the molar ratio of the vinyl ether that does not contain a hydroxyl group, and c is the molar ratio of the hydroxyalkyl vinyl ether. and d represent the molar ratio of the carboxylic acid vinyl ester. ] f-/xb, the sum of a (mol%) of the fluoroolefin and d (mole percentage) of the carboxylic acid vinyl ester (7)
+d) is smaller than 0.7 times the sum (b+c) of hydroxyl group-free vinyl ether b (mol 1) and hydroxyalkyl vinyl ether C (mol 2), then the vinyl copolymer of hydroxyl group-containing vinyl ether (4 ), the curability of the composition of the present invention tends to decrease, and the solvent resistance of the cured coating film tends to decrease. Both are undesirable because the olefin conversion rate becomes low and the original excellent characteristics of the fluororesin are impaired.

Vinyl copolymer GA) using each monomer component listed above? , by known methods such as bulk polymerization, solution (pressure) polymerization, suspension polymerization or emulsion polymerization in the presence of a radical polymerization initiator, either batchwise, semi-continuously or continuously. Polymerization may be carried out by the following procedure.

At this time, the above-mentioned radical polymerization initiators include noacyl 4-oxides such as acetyl peroxide and benzoyl peroxide; methyl ethyl ketone J?
-Oxides, ketone-based oxides such as cyclohexanone peroxide: hydrogen peroxide, tert-
Hydroperoxides such as butyl hydroperoxide; dialkyl peroxides such as di-tert-butyl peroxide, dicumyl peroxide: tert-butyl peroxyacetate, te
Alkyl oxyesters such as rt-butylperoxyester (14 L/-); or azo compounds such as azobisisobutyronitrile and azobisisovaleronitrile; or persulfates such as ammonium persulfate and potassium persulfate. Typical examples include hydrogen sulfite (hydrogen sulfite), as required.
It may be used in combination with an inorganic reducing agent such as sodium pyrosulfite, or a thin organic reducing agent such as cobalt naphthenate or dimethylaniline.

As a copolymerization reaction method, among the various methods mentioned above, the solution polymerization method is the simplest. Typical solvents used in this case include hydrocarbons such as toluene, xylene, cyclohexane, n-hexane/octane; esters such as methyl acetate, ethyl acetate, and butyl acetate; acetone, meth2ethylketone, Ketones such as methyl isobutyl ketone and cyclohexanone; amides such as dimethylformamide and dimethylacetamide;
or methanol, ethanol, insolonol,
Alcohol solvents such as n-butanol, inbutanol, 81110-butanol, ethylene glycol monoalkyl ether, or mixtures thereof may be used.

However, when a (block) polyisocyanate compound as listed below is used as the curing agent (B), the use of alcoholic solvents as listed above should be avoided.

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

During the copolymerization reaction, the reaction temperature is -20~
A range of 130°C is appropriate, and the reaction pressure is 1 to 100 kg7 cm, preferably 5 to 60 kg.
A range of 9/cm" is appropriate.

The vinyl copolymer (4) thus obtained preferably has a number average molecular weight of 1,000 to 100,000, and a hydroxyl value of 17 to 200.

Next, representative examples of the curing agent (B) mentioned above, which is reactive with the hydroxyl groups in the divinyl copolymer (1), include aminoplast, (block) polyisocyanate compounds, and polybasic acids (anhydrous). things) etc.

Among them, typical aminoplasts include amine group-containing compound components such as melamine, urea, acetoguanamine, benzoguanamine, steroguanamine, or spiroguanamine, and formaldehyde, no! Examples include condensates obtained by reacting an aldehyde compound component such as formaldehyde, acetaldehyde or glyoxal by a known and commonly used method, or those obtained by etherifying each of these condensates with t-flucols. Of course, any material that is normally used for paints can be used.

Among them, those partially or completely etherified with C1 to C4 alcohols are preferable.
Specific examples of such aminogellasts include hexamethyl etherified methylol melamine, hexabutyl etherified methylol melamine, methylbutyl mixed etherified methylol melamine, methyl etherified methylol melamine, butyl etherified methylol melamine or isobutyl etherified methylol melamine, or condensates thereof. Examples include.

In particular, it is desirable to use methyl etherified methylolmelamine from the viewpoint of compatibility with the vinyl copolymerization motive force.

On the other hand, typical examples of polyincyanate compounds include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; cycloaliphatic diisocyanates such as xylylene diisocyanate and inphorone diisocyanate; or tolylene diisocyanate; Organic diisocyanates such as aromatic diisocyanates such as 4'-diphenylmethane diisocyanate, or adducts of these organic diisocyanates with polyhydric alcohols, low molecular weight polyester resins, or water, and polymers of the above-mentioned organic diisocyanates. Examples of typical commercially available polyinocyanate compounds include "Bernock D-750, -800, DN-950, -970, -
980, -981 or 15-455 J [Dainippon Ink Chemical Industry ■Product], "Desmosil L, N, HL
or LL j (manufactured by Bayer AG, West Germany), [Takenate D-102, -202, -11ON4 or -11
23NJ [Takeda Pharmaceutical Co., Ltd.], “Coronate L, H
L, EH or 203'' [Japan Polyurethane Industries ■Iwahin] or ``Puranate 24A-90EX JC Mukasei Kogyo ■Nashihin''.

In addition, representative examples of blocked polyisocyanate compounds refer to those obtained by blocking the various polyisocyanate compounds listed above with known and commonly used blocking agents, and representative commercially available block polyisocyanate compounds. An example of a product is [Parnock D-5]
50J C Dainippon Ink Chemical Co., Ltd. product], [Takene] B-815-N J [Takeda Pharmaceutical Co., Ltd. product], "Azoitol (ADDITOL) VXL -80J
C H*st Synthesis Product] or “Coronate 2507
Jl: Nippon Polyurethane Industries ■Product].

Among these (block) polyisocyanate compounds, in terms of compatibility with the vinyl copolymer (4),
In particular, it is desirable to use a compound having an isocyanuric ring in the molecule, such as "Coronate 2507 or EHj" or "Burnock DN-980 or ~981".

Furthermore, representative examples of the above-mentioned polybasic acid curing agents include -acrylic resins having two or more carboxyl groups in the molecule, -polyester resins having two or more carboxyl groups in the molecule, or pyromellitic acid. It is something like that. Typical polybasic acid anhydride curing agents include acrylic resins containing two or more acid anhydride groups in the molecule, trimellitic anhydride, pyromellitic anhydride, and the like.

The ratio of the above-mentioned vinyl copolymer particles and curing agent (B), which are essential components constituting the composition of the present invention, is based on 50 to 99 parts by weight of the recovered material.
A suitable range is 50 to 1 part by weight of each component (all components are based on solid content).

Next, when a (block) polyisocyanate compound is used as the curing agent (B) component, typical examples of the curing catalyst (C) include diptyltin noacetate, dibutyltin dioctate, dibutyltin nolaurate, triethylamine or When using aminoplast as the curing agent (B), p-toluenesulfonic acid, phosphoric acid or alkyl ester of phosphoric acid, or [Beccamin P-198
J [Dainippon Ink & Chemicals Product] or [Necure 155.2500X, X-49-110,5225
or dinonylnaphthalenedisulfonic acid, dodecylbenzenesulfonic acid, or organic amine block compounds thereof, typified by 3525 J (manufactured by King Company, USA).

The amount of the curing catalyst (C) to be added is within a range of 0 to 10 parts by weight based on the total solid weight of the above-mentioned copolymer (g) component and curing agent (B) component, respectively. The amount of component (C) to be added is appropriately determined mainly by the curing temperature and curing time.

In the present invention, an acid anhydride group-containing compound such as maleic anhydride or itaconic anhydride is added to the hydroxyl group in the vinyl copolymer (4) to form an acid in the copolymer (4). groups pendant, thereby curing the curing agent (B).
It can also serve as a latent catalyst during the curing reaction with components.

The thus obtained composition of the present invention may further contain pigments, various resins, solvents, flow regulators,
It is a matter of course that various known and commonly used additives can be added, such as color separation inhibitors, antioxidants, ultraviolet absorbers, silane coupling agents, and the like.

Specific examples of pigments include inorganic pigments such as titanium oxide and carbon black, organic pigments such as quinacridone and azo pigments, and metal powders such as aluminum powder, copper powder, and zinc powder.

In addition, representative resins include nitrocellulose, cellulose resins such as cellulose acetate butyrate, vinyl chloride-vinyl acetate copolymer resins, ketone resins,
Examples include petroleum resins, (meth)acrylic resins that may contain styrene, oil-free alkyd resins, alkyd resins, and epoxy resins.

Further, as the solvent, those mentioned above as a solvent for preparing the vinyl copolymer prisoner, and mixtures thereof can be used, but as the curing agent (B) component, (block) polyisocyanate can be used. It goes without saying that when using compounds, it is necessary to avoid using solvents that react with isocyanate groups.

The composition of the present invention is applied by a known and commonly used method such as spray coating, brush coating, roll coater, etc.
When a polyincyanate compound is used as the curing agent (B), it is baked at a temperature from room temperature to 120°C, and when other curing agents are used, it is baked at a temperature of 60°C to 120°C.
Baked at temperatures up to 250°C for 5 seconds to 40 minutes to give a cured coating.

[Use of invention]

The resin composition for paints of the present invention is suitable for general baking such as home appliances, for exterior use such as coil coating for buildings, tile spanning PCM, etc., and for automobiles, more specifically for automobile enamel paints, metallic It can be applied as a paste paint or clear paint, or as a surface protective film for glass or ceramic products, but is by no means limited to the above range of application.

〔Example〕

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

ε Precedents 1 to 9 [Examination of vinyl copolymer prisoners] Methyl isobutyl ketone (MIBK) 4001 and "Perbutyl PVJ I: NOF ■Pear" were placed in a stainless steel pressure-resistant tube with an internal volume of 1,000 d. Radical polymerization initiator] No. 5
I, ethyl vinyl ether (EVE), inbutyl vinyl ether CIB listed in Table 1
VE), 4-hydroxybutyl vinyl ether (HBV
E), 6-hydroxybutyl vinyl ether (HH
VE), vinyl hyvalate (PIV), C
, Vinyl A/ x Ste/ of tertiary carboxylic acid
l/ (!: Peopa 9J (manufactured by Shell, Netherlands; hereinafter abbreviated as vv-g), vinyl cyclohexylcarboxylate (VCHC), vinyl benzoate (VBZ) or p-tert-butylbenzoic acid Vinyl acid (VPTBZ) was charged and cooled to -70°C in a dry ice/methanol bath, and nitrogen gas was blown into the tube to replace the air in the pressure tube.

In the next step, the liquefied hexafluorozorobiley (R
FP) 1 (fi dichlorlyfluoroethylene (
CTFg) was charged in the amount indicated in the same table, and the tube was sealed. On the other hand, tetrafluoroethylene (TFE:
), use a pressure tube with pulp to charge each raw material in the same manner as described above, and then
This TFE was sealed under pressure from the E&P, and then the valve was closed and weighed.

Afterwards, each of these pressure-resistant tubes was placed in a rotating constant temperature water tank heated to 60°C and reacted for 16 hours.
The contents were taken out to obtain each desired copolymer.

Next, each constant value was measured for each copolymer, and the results shown in the table were obtained.

Reference Example 10 [Example of preparation of vinyl copolymer (A') for comparison] 500 parts of toluene and 500 parts of MI BK were charged into a stainless steel ring autoclave, and dry ice/
It was cooled to -70°C in a methanol bath, and nitrogen gas was introduced to replace the inside of the system with nitrogen. Next, 400 parts of the liquefied CTFE was charged and the temperature was raised to 60°C, and then VV
-9, 150 parts of methyl methacrylate, 50 parts of β-hydroxyethyl methacrylate, and 20 parts of azopisisoparelloni) was added dropwise over 4 hours, and after the completion of the addition, The desired copolymer (A') was obtained by maintaining the same temperature for 15 hours.

When various constant values of this copolymer were measured, the non-volatile □ minute was 50 cm, the hydroxyl value was 10.8, and the glass transition temperature was 25°C.

Examples 1 to 14 Each copolymer (A-1) to (A-
9) were mixed with a curing agent and thinner, and if necessary, a curing catalyst, in the proportions listed in Table 2 to form a paint separately. Then, degreased with petroleum benzine. With a 6 mil applicator, a dry film thickness of 35 to 4
After coating and setting each layer to a thickness of 0 μm, each layer was baked under the conditions listed in the same table and left at room temperature for 7 days to obtain each cured coating.

After that, note 10 in the margin of the same table for each coating film.
Solvent resistance was evaluated by the method described in . The results are summarized in the same table.

Comparative Examples 1 to 3 Except for changing to use the copolymer (A') obtained in Reference Example 10 and following the blending ratio and baking conditions as listed in Table 2, Example 1~
It was made into a paint and formed into a film in the same manner as in No. 14, and this was used as a control sample.

Subsequently, Examples 1 to 14 were also applied to this control coating.
Solvent resistance was evaluated in the same manner as above.

The results are shown in the same table.

Note 1) Incyanate content = 12.5%, solid content =
75 Section 2) Incyanate content = 21.31, solid content = 10
0 coefficient 3) Effective incyanate content = 11.84, solid content =
81 4) Butyl etherified methylol melamine resin manufactured by Dainippon Ink & Chemicals ■; solid content = 60% 5) Hexamethyl etherified methylol melamine resin manufactured by Sumitomo Chemical ■; solid content = 100 t) xylene/toluene/ Ethyl acetate/butyl acetate/cellosolve acetate = 40/20/10/20/10
(Weight ratio) 7) "Swazol 1000 J/butyl acetate/cellosolve acetate 50/30/20 weight ratio); "Swazol 1000 J is a mixture of aromatic hydrocarbons produced by Maruzen Sekiyu.

8) [Swazol 1000 J/n-butanol = 7
0/30 (weight ratio) 9) The composition was coated on a glass plate and baked, and the transparency of the resulting cured coating film was evaluated by visual judgment.

◎...Completely transparent ○...Not completely transparent, but comparable ×...Poor transparency (occurrence of "turbidity") 10) Appearance of the coating film immediately after being immersed in each solvent for 2 hours and pulled up. Judgment was made visually.

◎... There is no softening of the coating film, and no abnormalities such as coloring are observed. ×... When the coating film softens, blisters occur [Effects of the invention] It is clear from the results in Table 2. Therefore, it is known that the coating resin composition of the present invention has excellent compatibility and provides a cured coating film with good solvent resistance.

Agent Patent Attorney Katsutoshi Takahashi Proceeding Amendment Written on May 20, 1986 by the Commissioner of the Patent Office Mr. Michibu Uga t Description of the case 1986 Patent Application No. 48241 2 Name of the invention Resin composition for paints 5 Relationship with the case of the person making the amendment Patent applicant 3-35-58 Sakashita, Itabashi-ku, Tokyo (288) Dainippon Ink Chemical Industry Co., Ltd. Representative Shigeru Kuni Kawamura 4, Agent Address: 3 Nihonbashi, Chuo-ku, Tokyo 103 No. 7-20 Dainippon Ink & Chemicals Co., Ltd. Telephone: Tokyo (03) 272-451'l (main representative)
Contents of amendment (1) The description of the scope of claims is corrected as shown in the attached sheet.

(2) The statement on page 7, lines 9-10 of the specification is corrected as follows.

"Moshik is perfluoroalkyl such as heptafluoropropyl trifluorovinyl ether." (3) The statement "C8 carboxylic acid" on page 9, line 8 of the specification is corrected to "C9 carboxylic acid."

(4) The statement "isocyanuric ring" on page 20, line 2 of the specification is corrected to "incyanurate ring."

(5) The statement on page 25, lines 4 and 5 of the specification is corrected as follows.

"Products from KokuShell Co., Ltd.: hereinafter abbreviated as VV-9), vinyl cyclohexanecarboxylate (VOHO), benzoin"
(6) The statement in the 5th line on page 32 of the specification is corrected as follows.

"3) Blocked incyanate group content = 118
(7) The statement on page 36, line 12 of the specification is corrected as follows.

"×...Selective blisters are generated due to softening of the coating film." The above amended claims (Japanese Patent Application No. 1983-48241) r include a full olefin, a carboxylic acid vinyl ester, a hydroxyalkyl vinyl ether, and an alkyl A vinyl copolymer obtained by copolymerizing vinyl ether as an essential monomer and, if necessary, other vinyl monomers copolymerizable with the above monomers; A coating composition comprising a reactive curing agent as an essential component and, if necessary, a curing catalyst for promoting the crosslinking reaction between component D and each of the above-mentioned components (5). Resin composition.

z The above-mentioned fluoroolefin is at least one compound selected from the group consisting of tetrafluoroethylene, vinylidene fluoride, chlorotrifluoroethylene, and hexafluoropropylene. Compositions as described.

3. The above carboxylic acid vinyl ester is at least selected from the group consisting of cyclohexane carboxylic acid vinyl ester, benzoic acid vinyl ester, p-tert-butylbenzoic acid vinyl ester, and vinyl ester of aliphatic carboxylic acid consisting of C3 to CtS. The composition according to claim 1, which is one type of compound.

4. The above C3-C vinyl ester has a carboxyl group bonded to a tertiary carbon atom.
The composition according to claim 1 or 3, wherein the composition is an ester of an aliphatic carboxylic acid having the following formula: 1.

5. Claims 1 and 3, characterized in that the above-mentioned vinyl Nisder carboxylate is a vinyl ester of the C9 aliphatic carboxylic acid having a carboxyl group bonded to a tertiary carbon atom. Or the composition according to item 4.

B) The above-mentioned hydroxyalkyl vinyl ether is 02
The composition according to claim 1, which is a compound having a hydroxyalkyl group of ~C0.

Z. The composition according to claim 1, wherein the alkyl vinyl ether is a compound having an alkyl group of O, %O.

a. The composition according to claim 1, wherein the curing agent 031 is an aminoplast.

2. Claim 1, wherein the curing agent) is methyl etherified methylolmelamine.
The composition according to item 8 or item 8.

1a The composition according to claim 1, wherein the curing agent (81) is a polyincyanate compound.

1t The composition according to claim 1 or 10, wherein the curing agent Q31 is a polyincyanate compound having an incyanurate ring.

1z The composition according to claim 1, wherein the fecalizing agent (81) is a block polyincyanate compound.

Claims (1)

[Claims] 1. (A) Fluoroolefins, carboxylic acid vinyl esters, hydroxyalkyl vinyl ethers, and alkyl vinyl ethers as essential monomers, and if necessary,
A vinyl copolymer obtained by copolymerizing other vinyl monomers copolymerizable with these above-mentioned monomers, and (B) a curing agent reactive with hydroxyl groups as essential components, The resin composition for coatings further comprises, if necessary, (C) a curing catalyst for promoting the crosslinking reaction between the above-mentioned components (A) and (B). 2. The fluoroolefin described above is at least one compound selected from the group consisting of tetrafluoroethylene, vinylidene fluoride, chlorotrifluoroethylene, and hexafluoropropylene.
A composition according to claim 1. 3. The carboxylic acid vinyl ester described above is at least one selected from the group consisting of cyclohexane carboxylic acid vinyl ester, benzoic acid vinyl ester, p-tert-butylbenzoic acid vinyl ester, and vinyl esters of aliphatic carboxylic acids C_5 to C_1_8. A composition according to claim 1, characterized in that it is a compound of species. 4. The above-mentioned carboxylic acid vinyl ester has a carboxyl group bonded to a tertiary carbon atom, the above-mentioned C_5-
The composition according to claim 1 or 3, characterized in that it is an ester of aliphatic carboxylic acid C_1_8. 5. The above-mentioned carboxylic acid vinyl ester is a vinyl ester of the aliphatic carboxylic acid C_9 having a carboxyl group bonded to a tertiary carbon atom, Claims 1 and 2 The composition according to item 3 or 4. 6. The above-mentioned hydroxyalkyl vinyl ether is C
The composition according to claim 1, which is a compound having a hydroxyalkyl group of _2 to C_6. 7. The above alkyl vinyl ether is C_1 to C_
The composition according to claim 1, which is a compound having an alkyl group of 8. 8. The composition according to claim 1, wherein the curing agent (B) is an aminoplast. 9. The composition according to claim 1 or 8, wherein the curing agent (B) is methyl etherified methylolmelamine. 10. The composition according to claim 1, wherein the curing agent (B) is a polyisocyanate compound. 11. The curing agent (B) described above is a polyisocyanate compound having an isocyanuric ring.
A composition according to claim 1 or claim 10. 12. The composition according to claim 1, wherein the curing agent (B) is a block polyisocyanate compound. 13. The composition according to item 1 or 12, wherein the curing agent (B) is a block polyisocyanate compound having an isocyanuric ring.