JPH0352976A - Resin composition for coating - Google Patents

Abstract

PURPOSE:To obtain the subject composition, containing a specific hydroxyl group-containing fluorinated copolymer, specific vinyl copolymer without containing fluorine and polyisocyanate compound, excellent in weather and fouling resistance, gloss and processability and useful for coating metal plates for bending, etc. CONSTITUTION:The objective composition obtained by blending (A) a hydroxyl group-containing fluorinated copolymer with 5-50wt.% fluorine content with (B) a hydroxyl group-containing vinyl copolymer without containing fluorine composed of 81-98wt.% alkyl acrylate and/or alkyl methacrylate having a 2-4C alkyl group, 2-19wt.% hydroxyl group-containing vinyl monomer and 0-17wt.% other copolymerizable monomers at (30-95)/(70-5) weight ratio (A/B) and (C) a polyisocyanate compound at 0.8-100 equiv. ratio (-OH/-NCO).

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 particularly relates to a method that includes a specific hydroxyl group-containing fluorine-containing copolymer, a specific fluorine-free vinyl copolymer, and a polyisocyanate compound as essential ingredients. This invention relates to a resin composite for paints which has extremely excellent weather resistance and has excellent gloss, workability, and stain resistance, and which can be used as a paint useful for painting metal plates and the like.

[Conventional technology]

Conventionally, painted metal materials that have been painted in advance before processing, such as forming or assembling steel materials, are more economical than methods that involve painting after processing the metal materials. It is widely used mainly for various building materials such as roofing materials, exterior wall materials, and duct shutters because it is advantageous in terms of performance, labor saving, and pollution prevention.

In recent years, there has been an increasing demand for long-term weather resistance for this type of coated metal material.

In this regard, in order to meet these requirements, paints using polyvinylidene butylene as a binder have been used, but although such paints themselves can satisfy weather resistance and flexibility, Regarding the shape of the paint film, it is necessary to heat it at a high temperature for several minutes or more, resulting in poor coating productivity.Furthermore, the gloss of the paint film is insufficient, making it difficult to achieve a cosmetic finish. Things that are difficult to even do, etc.
It has various problems.

(Problems to be Solved by the Invention) Therefore, the object of the present invention is to solve all of the various problems in the prior art as described above, and to provide extremely high weather resistance as well as gloss and flexibility. Our goal is to provide excellent paint resins.

Further objects of the invention may be obtained from the description below.

[Means to solve the problem]

Therefore, as a result of intensive studies in accordance with the purpose of the present invention as described above, the present inventors found that a specific hydroxyl group-containing fluorine-containing copolymer, a specific hydroxyl group-containing fluorine-free vinyl copolymer, and a polyisocyanate. It was discovered that by using a certain coating resin composition that contains a compound as an essential precept, a coated product with excellent not only gloss and weather resistance but also processability and stain resistance can be obtained. As a result, we have completed the present invention. That is, the present invention has as essential components a specific hydroxyl group-containing fluorine-containing copolymer (A) having a fluorine content of 5 to 50% by weight, and a C2 to C4 alkyl group (meth).
Hydroxyl group-containing, fluorine-free product obtained by copolymerizing 81 to 98% by weight of an acrylic acid alkyl ester, 19 to 2% by weight of a hydroxyl group-containing vinyl monomer, and 0 to 17% by weight of other copolymerizable monomers. vinyl copolymer (B
) is blended with a polyisocyanate compound (C) in a specific ratio to provide a certain type of resin composition for paints. Here, first, the above-mentioned hydroxyl group-containing fluorine-containing copolymer (A) is abbreviated as fluoroolefin (a-1) hereinafter, fluorine-containing vinyl monomer (a-1) C. ] and hydroxyl group-containing vinyl monomer (a-2) as essential monomer components, and if necessary, these fluoroolefins (a-2)
-1) and hydroxyl group-containing vinyl monomer (a-2)
Among copolymers of copolymerizable monomer (a-3) with other monomers (a-3), it is particularly desirable to use copolymers with a fluorine content of 5 to 50% by weight; -1) To exemplify only typical examples, such as vinyl fluoride, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, promotrifluoroethylene, pentafluorobrobylene or hexafluoropropylene, Fluorine-containing α-olefins; or compounds having a fluorine atom in the main chain, such as perfluoroalkyl perfluorovinyl ethers, such as trifluoromethyl trifluorovinyl ether, pentafluoroethyl trifluorovinyl ether, or heptafluoropropyl trifluorovinyl ether However, it is particularly desirable to use fluorinated vinyl, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, or perfluoroalkyl trifluorovinyl ether in which the alkyl group has 1 to 18 carbon atoms.

Of course, these fluoroolefins listed above may be used alone or in combination of two or more.

Typical examples of the hydroxyl group-containing vinyl monomer (a-2) include 2-hydroxyethyl vinyl ether, 2
-Hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 2-hydroxybutyl vinyl ether,
Hydroxy-2-methylbrobyl vinyl ether, 5-
Hydroxyl group-containing vinyl ethers such as hydroxydipentyl vinyl ether or 6-hydroxyhexyl vinyl ether; addition reaction products of the various vinyl ethers listed above and ε-cabrolactone; 2-hydroxyethyl (meth)allyl ether, 3-hydroxyl vinyl ether; building(
meth)allyl ether, 2-hydroxybutyl (meth)allyl ether, 4-hydroxybutyl (meth)allyl ether, 3-hydroxybutyl (meth)allyl ether, 2-hydroxy-2-methylpropyl (meth)allyl ether , hydroxyl group-containing allyl ethers such as 5-hydroxybentyl (meth)allyl ether or 6-hydroxyhexyl (meth)allyl ether; or addition reaction raw materials of various allyl ethers listed above and ε-cabrolactone. and so on.

In addition, typical monomers (a-3) copolymerizable with the above-mentioned fluoroolefins include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-
butyl vinyl ether, isobutyl vinyl ether, t
Alkyl vinyl ethers or substituted alkyls such as ert-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, 2-ethylhexyl vinyl ether, chloromethyl vinyl ether, chloroethyl vinyl ether, penzyl vinyl ether or phenylethyl vinyl ether Vinyl ethers; cycloalkyl vinyl ethers such as cyclopentyl vinyl ether, cyclohexyl vinyl ether or methylcyclohexyl vinyl ether; vinyl-2,2-dimethylbutypanoate, vinyl-2,2-dimethylbutanoate, vinyl 2,2-dimethylbentanoate; Vinyl-2,2-dimethylhexanoate, Vinyl-2-ethyl-2-methylptanoate, Vinyl-2-ethyl-2-methylpentanoate, Vinyl-3-chloro-2,2-dimethylbutypanoate, Acetic acid vinyl, vinyl propionate, vinyl butyrate, vinyl isoacetate, vinyl caproate, vinyl cabrylate, vinyl cabrate, vinyl laurate, C9 branched aliphatic vinyl carboxylate, CIO branched aliphatic vinyl carboxylate, C.I. branched aliphatic vinyl carboxylates such as branched aliphatic vinyl carboxylates or vinyl stearate; vinyl cyclohexanecarboxylate, vinyl methylcyclohexanecarboxylate, vinyl benzoate or p-
Vinyl esters of carboxylic acids having a cyclic structure such as vinyl tert-butylbenzoate; α-olefins such as ethylene, propylene or butene-1; excluding fluoroolefins such as vinyl chloride or vinylidene chloride <various halogenated olefins Class; styrene, α
- aromatic vinyl compounds such as methylstyrene or vinyltoluene; acrylic esters such as methyl acrylate, ethyl acrylate, butyl acrylate or cyclohexyl acrylate; methyl methacrylate, ethyl methacrylate, butyl methacrylate;
Methacrylic acid esters such as cyclohexyl methacrylate or pendyl methacrylate; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinylmethyldiethoxysilane, vinyltris(β-methoxyethoxy)silane, allyltrimethoxysilane, Trimethoxysilylethyl vinyl ether, triethoxysilylethyl vinyl ether, methyldimethoxysilylethyl vinyl ether, trimethoxysilylpropyl vinyl ether, triethoxysilylbrobyl vinyl ether, methyldiethoxysilylbrobyl vinyl ether, γ-(meth)acryloyloxybutyl vinyl ether 1-rimethoxysilane, γ-(meth)acryloyloxyprobyltriethoxysilane or r-
Monomers containing hydrolyzable silyl groups, such as (meth)acryloyloxybutylmethyldimethoxysilane;
N-dimethylaminoethyl (meth)acrylamide, N
- Adan group-containing amide unsaturated monomers such as diethyla tert-
Butylaminoethyl (meth)acrylate, tert-
An amino group-containing monomer such as ptylaminopyr (meth)acrylate, aziridinylethyl (meth)acrylate, pyrrolidinylethyl (meth)acrylate or piperidinylethyl (meth)acrylate: or (
Examples include carboxyl group-containing monomers such as meth)acrylic acid, crotonic acid, itaconic acid, maleic acid or fumaric acid.

Among these copolymerizable monomers, from the viewpoint of increasing the polymerization yield of the copolymer (A), and from the viewpoint of increasing the polymerization yield of the copolymer (A),
) From the viewpoint of increasing the solubility of the kaibun in organic solvents, it is desirable to use alkyl vinyl ethers, cycloalkyl vinyl ethers, and carboxylic acid vinyl esters.

When preparing the copolymer (A) from the above-mentioned fluoroolefins and other monomers copolymerizable with them, the fluorine content is 5 to 50% by weight, preferably 1.
It should be controlled within a range of 0 to 30% by weight.

If it is less than 5% by weight, the weather resistance of the resulting coating film will decrease, while if it exceeds 50% by weight, the solubility of the copolymer (A) in organic solvents will decrease. Both are unfavorable as they result in a decrease in

In addition, in preparing the hydroxyl group-containing fluorine-containing copolymer (A), the hydroxyl group-containing vinyl monomer (a-2)
should be used in an amount necessary for the copolymer (A) to contain on average at least two hydroxyl groups in one molecule, and the amount used is 2.
A range of 19% to 19% by weight, preferably 5 to 19% by weight, is suitable.

After all, if the usage amount of the hydroxyl group-containing vinyl monomer (a-2) is less than 2%, the solvent resistance and durability of the coating film will decrease; In such cases, the flexibility of the coating film will be reduced, which is undesirable.

The above-mentioned copolymerizable monomer (a-3) can be used by appropriately determining the type and amount of the monomer from the viewpoint of copolymerizability, coating workability, and coating performance such as weather resistance. good.

Therefore, in order to prepare the fluorine-containing copolymer (A), which is one of the essential components of the coating resin composition of the present invention,
Solution (pressure) polymerization, bulk polymerization or 'S4. Any known method such as turbidity polymerization can be followed, inter alia,
Solution polymerization is the simplest method.

The radical polymerization initiators used in this case include acetyl peroxide, penzoyl peroxide, lauroyl peroxide, methyl ethyl peroxide, cyclohexanone peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, and di-tert- Peroxides such as butyl peroxide, diruver oxide, tert-butylperoxyacetate or tert-butylperoxypiparate; or azo compounds such as azobisisobutyronitrile or azobisisovaleronitrile, etc. It is listed as a typical example.

In addition, the solvents used during such polymerization include hydrocarbons such as toluene, xylene, cyclohexane, n-hexane or octane; methyl acetate, ethyl acetate,
Ester systems such as butyl acetate or ethylene glycol monoethylene ether acetate; ketone systems such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone or cyclohexanone; dimethyl formamide, dimethyl acetate or N-
Amides such as methylpyrrolidone; or methanol,
Typical examples include alcoholic solvents such as ethanol, n-propanol, iso-probanol, n-butanol, isobutanol, sec-butanol, tert-butanol, or ethylene glycol monoalkyl ether, or mixtures thereof. .

Additionally, chain transfer agents such as lauryl mercabutane, 2-mercaptoethanol or α-methylstyrene dimer can also be used in the polymerization.

The weight average molecular weight of the hydroxyl group-containing fluorine-containing copolymer (A) is preferably within the range of 7,000 to 300,000, and if it is less than 7.000, the durability of the coating film will inevitably deteriorate. On the other hand, 3
00. If it becomes too large, exceeding 000, the coating workability tends to deteriorate, making it impractical, and both are unfavorable.

Next, as the above-mentioned hydroxyl group-containing fluorine-free vinyl copolymer (B), it is particularly desirable to use one containing, for example, a specific (meth)acrylic acid alkyl ester and a hydroxyl group-containing vinyl monomer as essential components.

In particular, an acrylic acid alkyl ester and/or a methacrylic acid alkyl ester having 2 to 4 carbon atoms [hereinafter abbreviated as (meth)acrylic ester (b-1). ] and a hydroxyl group-containing vinyl monomer (b-2) as essential components, and further using another copolymerizable monomer (b-3) as an optional component. is desirable.

Among them, the (meth)acrylic ester (b-1) having 2 to 4 carbon atoms includes ethyl acrylate, n-propylacrylate, isopropylacrylate, n-
Typical examples include butyl acrylate, isobutyl acrylate, or tert-butyl acrylate, or ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, or tert-butyl methacrylate. Among them, the use of ethyl methacrylate is most preferred.

The amount of the (meth)acrylic acid ester (b-1) used is within the range of 81 to 98% by weight, preferably,
A range of 81 to 95% by weight is suitable.

If it is less than 81% by weight, the stain resistance will inevitably decrease, while if it exceeds 98% by weight, the weather resistance will inevitably decrease. Undesirable.

Among these (meth)acrylic esters (b-1), the amount of ethyl methacrylate used is 5 to 8.
It is desirable to maintain the content within a range of 0% by weight.

If the amount of ethyl methacrylate used is less than 5% by weight, stain resistance will inevitably decrease, while if it exceeds 80% by weight, processability will decrease. , both are unfavorable.

Particularly typical examples of the hydroxyl group-containing vinyl monomer (b-2) include 2-hydroxyethyl (meth)acrylate, 2-hydroxybubutyr (meth)acrylate, and 3-hydroxybutyr (meth)acrylate. meth)acrylate, 2-hydroxybutyl(meth)acrylate, 3-hydroxybutyl(meth)acrylate, 4-
Hydroxybutyl (meth)acrylate, 3-chloro-
2 = Hydroxypyl (meth)acrylate, G2
-Hydroxyethyl fumarate, mono-2hydroxyethyl-monobutyl fumarate or polyethylene glycol- or polypropylene glycol-mono (
meth)acrylate, or α. These include hydroxyalkyl esters of β-ethylenically unsaturated carboxylic acids, and adducts of these with ε-cabrolactone.

The amount of the hydroxyl group-containing vinyl monomer (b-2) used is within the range of 2 to 19%, preferably 5%.
A range of 19% by weight is suitable.

If it is less than 2% by weight, the stain resistance inevitably decreases, while if it exceeds 19% by weight, the processability inevitably decreases, so either case is preferable. do not have.

Furthermore, the other copolymerizable heptanomer (b-3) described above
Of course, each (meta) as listed above
If the monomer is copolymerizable with the acrylic ester (b-1) and the hydroxyl group-containing vinyl monomer (b-2),
Any of them can be used, but the most representative ones are methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, and cyclohexyl (meth)acrylate. , benzyl (meth)acrylate, alkoxyalkyl (meth)acrylate or dibromopvir (meth)acrylate, other than the above-mentioned (meth)acrylic ester (b-1).
Acrylate neck; styrene, α-methylstyrene, p
Aromatic vinyl monomers such as -tert-butylstyrene or vinyltoluene; epoxy group-containing monomers such as glycidyl (meth)acrylate, (β-monomethyl)glycidyl (meth)acrylate or (meth)allyl glycidyl ether; fumaric acid or Diesters of unsaturated dicarboxylic acids such as itaconic acid and monohydric alcohols; (meth)acrylic acid, maleic acid, fumaric acid, itaconic acid, as well as 2-hydroxyethyl (meth)acrylate, 2-hydroxybutipyr (meth) Acrylate, 3-hydroxypropyl (meth)acrylate, 2
- Anhydrides of hydroxyl-containing monomers such as hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxybrobyl vinyl ether or 4-hydroxybutyl vinyl ether and polycarboxylic acids such as maleic acid, succinic acid, phthalic acid or hexahydrophthalic acid. Acid group-containing monomers such as adducts with compounds; acid anhydride group-containing heptanomers such as vinyl esters of maleic anhydride, itaconic anhydride or trimethyl anhydride;
or olefins other than fluoroolefins such as (meth)acrylic nitrile, vinyl chloride or vinylidene chloride; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriproxysilane, vinylmethyldiethoxysilane, vinyltris(β-methoxy ethoxy)silane, allyltrimethoxysilane, trimethoxysilylethyl vinyl ether, triethoxysilylethyl vinyl ether, methyldimethoxysilylethyl vinyl ether, trimethoxysilylvinyl ether, triethoxysilylpropyl vinyl ether, methyldimethoxysilylvinyl ether, γ one(
meth)acryloyloxypyltrimethoxycin,
Vinyl monomers containing a hydrolyzable silyl group such as r-(meth)acryloyloxypyltriethoxysilane or r(meth)acryloyloxypylmethyldimethoxysilane; N-dimethylanoethyl (
Acrylic radical-containing ado-based unsaturations such as meth)acrylamide, N-diethylaminoethyl (meth)acrylamide, N-dimethylanopyl(meth)acrylamide or N-diethylaminopropyl(meth)acrylamide. Monomer; dialkyl acinoalkyl (meth)acrylates such as dimethyl acinoethyl (meth)acrylate or diethyl 7minoethyl (meth)acrylate; tert-butylaminoethyl (meth)acrylate, tert-butylaminobutyl (meth)acrylate;
Amino group-containing monomers such as acrylate, aziridinylethyl (meth)acrylate, pyrrolidinylethyl (meth)acrylate or biperidinylethyl (meth)acrylate; or (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid Or carboxyl group-containing monomers such as fumaric acid.

The amount of the other copolymerizable monomer (b-3) to be used is suitably within the range of 0 to 17 percent.

When using an excessively large amount exceeding 17% by weight based on the total amount (100% by weight) of the above-mentioned (meth)acrylic acid ester (b-1) and hydroxyl group-containing vinyl heptanomer (b-2), After all, in order to prepare the hydroxyl group-containing fluorine-free vinyl copolymer (B), known and commonly used copolymerization reaction methods can be employed, but solution polymerization, particularly solution radical polymerization, is the simplest method. It is.

The radical polymerization initiators used in this case include acetyl peroxide, penzoyl peroxide, lauroyl peroxide, methyl ethyl peroxide, cyclohexanone peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, and G-jerk-butyl peroxide. oxide, peroxides such as dicumyl peroxide, tert-butyl peroxyoctoate, tert-butyl peroxy acetate or tert-butyl peroxypiparate; or abbis isoptylonitrile or azobisisovaleronitrile. Typical examples include azo compounds such as

In addition, the solvents used during such polymerization include hydrocarbon solvents such as toluene, xylene, cyclohexane, n-hexane, or n-octane; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, or ethylene glycol monoethyl ether acetate; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone or cyclohexanone; dimethyl formamide, dimethyl acetate or N
- Amides such as methylpyrrolidone; or methanol, ethanol, n-probanol, isoprobanol,
Alcohols such as n-butanol, isobutanol, see-butanol, tert-butanol or ethylene glycol monoalkyl ether are typical.

The weight average molecular weight of the hydroxyl group-containing fluorine-free vinyl copolymer (B) is suitably within the range of 7,000 to 300,000, and if the molecular weight is smaller than this, the durability will inevitably deteriorate. It will start to decline,
On the other hand, if the number exceeds 300,000,
Either case is unfavorable because painting workability deteriorates.

Thus, 81 to 98% by weight of acrylic acid alkyl ester and/or methacrylic acid alkyl ester (b-1) having an alkyl group having 2 to 4 carbon atoms, and 19
~2% by weight of a hydroxyl group-containing vinyl monomer (b-2),
0 to 17% by weight of other copolymerizable heptanomers (b-3)
copolymer (B) with a weight average molecular weight of 7.
000-300. By using the copolymer 000 (8), a resin composition for paints having excellent weather resistance, gloss, processability, stain resistance, etc. can be obtained.

Therefore, the mixing ratio of both essential components of the hydroxyl group-containing fluorine-containing copolymer (A) and the hydroxyl group-containing fluorine-free vinyl copolymer (B) is (A)/(B) = 30. ~9 5
/7 0 to 5 (weight ratio) is preferably within the range of
A range of 30-8 0/7 0-20 (same as above) is appropriate.

(A) If the mixing amount of the precepts is less than this, the weather resistance will inevitably decrease; on the other hand, if it is used in an excessively large amount exceeding this, the stain resistance will inevitably decrease. Both of these are undesirable.

Next, as the polyisocyanate compound (C), aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, or trimethylhexamethylene diisocyanate; or isophorone diisocyanate, methylcyclohexane- 2.4- or -2.6-diisocyanate, 4.4'-methylenebis(cyclohexyl isocyanate) or 1.
Alicyclic diisocyanates such as 3-di(isocyanatomethyl)cyclohexane; or adducts of each of these diisocyanates with polyhydric alcohols or low molecular weight hydroxyl group-containing polymers; diisocyanates such as those listed above; Water, a reaction product with a buretizing agent (buretate form), a sankei form (isocyanurate form) of diisocyanates such as those listed above, or addition of polyester polyol and/or polycaprolactone polyol with various diisocyanates such as those listed above. These include reaction products, and furthermore, they include those obtained by blocking the various polyisocyanates mentioned above with known blocking agents such as methyl ethyl ketoxime and caprolactam.

The blending amount of the polyisocyanate compound (C) is the hydroxyl group in the hydroxyl group-containing fluorine-containing copolymer (A) and the hydroxyl group-containing fluorine-free vinyl copolymer (B), respectively, and the compound. Equivalent ratio of (C) to isocyanate group: -OH/-NCO=0.8 to 10
A range of 0, preferably a range of 1.0 to 80 is appropriate.

If the blending amount of the polyisocyanate (C) is less than this, stain resistance etc. will decrease,
On the other hand, if the amount is more than this, the processability and weather resistance will inevitably deteriorate, so both cases are unfavorable. In the preparation, it is preferable to use a known and commonly used curing catalyst, if necessary.

Particularly representative curing catalysts include various organometallic compounds such as dibutyltin dilaurate, dibutyltin diacetate, dioctyl atin or cobalt naphthenate;
or 1,4-diazabisic-(2.2.2)
monooctane or 1,8-diazabicyclo-(5
．． 4.0) Various amine compounds such as undecene-7 can be mentioned.

The product of the present invention thus obtained is usually used with the addition of a pigment, but of course, it is also possible to use it without any colorant.

Typical examples of such pigments include titanium oxide, zinc white, carbon plaque, iron black, copper chrome black, and copper.
Iron/manganese black, yellow lead, cadmium yellow, ocher, titanium yellow zinc chromate, Bengara, zinc/iron brown, cadmium red, chrome vermilion, manganese violet, navy blue, ultramarine blue, cobalt blue, chrome green, chromium oxide Green, titanium/cobalt/nickel/zinc green, viridian, cobalt green, emerald green, kaolin, bentonite, silica white, alkuna white, gypsum, chalk,
Inorganic pigments such as precipitated barium sulfate, precipitated calcium carbonate or barite; β-naphthol type, β-oxynaphthoic acid type, naphthol AS type, pyrazolone type,
Organic pigments such as acetoacetanilide, acetoacetate, phthalocyanine, anthraquinone, indigo, berylene, perinone, dioxazine, quinacridone, isoindolinone, metal complex, fluorobin, or quinophthalone. ; metal powders such as brass powder, silver powder, gold powder, aluminum powder, or copper powder; or scaly mica treated with titanium oxide.

The composition of the present invention may further contain various resins and solvents, flow regulators, color separation inhibitors, matting agents, antioxidants, ultraviolet absorbers, light stabilizers, or silanes, as necessary. Of course, various known and commonly used additives such as coupling agents can be added.

Among such additive components, representative resins include cellulose resins such as nitrocellulose and cellulose acetate butyrate; vinyl chloride/vinyl acetate copolymer resins, petroleum resins, ketone resins, and oil-fluid alkyds. Examples include resin or epoxy resin.

Furthermore, as solvents, those already listed as melting agents for preparing the solvent-soluble fluoroolefin copolymer (A) or vinyl copolymer (B),
and mixtures thereof are used.

The resin composition for coatings of the present invention can be applied to various materials or processed products such as metal, wood, inorganic base materials, or plastics by a known and commonly used method such as spray coating, brush coating, roll coating, or impregnation coating. By applying the coating and drying it for several tens of seconds to several days at a temperature ranging from room temperature to about 300° C., a cured coating film with excellent performance can be formed.

〔Effect of the invention〕

The resin composition for paint of the present invention has excellent properties such as flexibility and weather resistance, as well as gloss, processability, and stain resistance. It is extremely useful for coating metal plates that can be bent.

Moreover, since the composition of the present invention has excellent overall durability, it can be used both for outdoor use and for pre-coated metal (PCM).

〔Example〕

Next, the present invention will be specifically explained using reference examples, examples, applied examples, and comparative applied examples. In the following, parts and percentages are all based on weight unless otherwise specified.

Reference Example 1 [Example of preparation of hydroxyl group-containing fluorine-containing copolymer (A)] "Beoba 9" (manufactured by Shell in the Netherlands, C
, a vinyl ester of a branched aliphatic monocarboxylic acid)
200 parts of 4-hydroxybutyl vinyl ether, 1 part of 4-hydroxybutyl vinyl ether
50 parts, 150 parts of ethyl vinyl ether, 430 parts of 101-butyl acetate, 10 parts of azobisisobutylonitrile
parts, 10 of tert-butyl peroxyoctoate
part and 1, 2, 2, 6. After charging 3 parts of 6-pentamethylpiperidine, 500 parts of the liquefied chlorotrifluoroethylene was added to the mixture, and while stirring,
The reaction was carried out at 60°C for 15 hours to remove the non-volatile content (N
When V) reached 67%, it was cooled to room temperature and 318 parts of xylene was added to obtain a mixture with the objective of having a Nv of 55%, a fluorine content of 24%, and a weight average molecular weight of 30,000. A solution of polymer (8) was obtained. Hereinafter, this will be abbreviated as copolymer (A-1).

Reference Example 2 (same as above) The monomer composition was as follows: Vinyl p-tert-butylbenzoate 100 parts Cyclohexyl vinyl ether 150 4-hydroxybutyl vinyl ether 100 Ethyl vinyl ether
150〃 and chlorotrifluoroethylene 500〃, the same procedure as in Reference Example 1 was carried out, and when the NV reached 68%, it was cooled to room temperature, 60 parts of xylene was added, and the NV was 55%. %, a fluorine content of 24% and a weight average molecular weight of 31,000 was obtained. Hereinafter, this will be abbreviated as copolymer (A-2).

Reference Example 3 [Hydroxyl group-containing fluorine-free vinyl copolymer (B
) Preparation example] In a four-piece flask equipped with a stirrer, a thermometer, and a nitrogen gas inlet tube, 700 parts of xylene and 3 parts of n-butyl acetate were added.
At the same temperature, 700 parts of ethyl methacrylate and 1 part of n-butyl acrylate were charged.
50 parts, 150 parts of β-hydroxyethyl methacrylate
parts, 20 of tert-7' tyl peroxyoctoate
A mixture of IO parts and azobisisobutyronitrile was added dropwise over 4 hours, and even after the dropwise addition was completed, the reaction was continued by maintaining the same temperature for about 15 hours, achieving the goal of achieving an NV of 50%. A solution of polymer (B) was obtained. Hereinafter, this will be abbreviated as copolymer (B-1).

Reference example 4 (same as above) Reference example except that the monomer composition was changed to 650 parts of ethyl meccrylate, 70 parts of 2-ethylhexyl methacrylate, 180 parts of n-butyl methacrylate, and 100 parts of β-hydroxyethyl methacrylate. Same as 3, NV is 50%
A solution of the desired copolymer (B) was obtained.

Hereinafter, this will be abbreviated as copolymer (B-2).

Example 1 100 parts of the copolymer (A-1) obtained in Reference Example 1,
80 parts of the copolymer (B-2) obtained in Reference Example 3 and
30 of Parnock DN-980J (terminal isocyanate group-containing prebolymer manufactured by Dainippon Ink & Chemicals)
i.e. -OH/-NGO=1/1
(equivalent ratio), and further add 2 parts of "Tinuvin 900" (ultraviolet absorber manufactured by Ciba-Geigy, Switzerland) and 2 parts of "Sanol LS-765J (light stabilizer manufactured by Sankyo Specialty)". A clear paint was obtained by mixing the two parts.

Example 2 100 parts of the copolymer (B-2) obtained in Reference Example 4,
A mixture with 100 parts of TYPEQ CR-93J (rutile titanium oxide manufactured by Ishihara Sangyo ■) was subjected to pigment dispersion using a sand mill for 1 hour. 100 parts of Polymer (A-2), 36 parts of Burnosoku B7-887J [polyisocyanate compound manufactured by Dainippon Ink & Chemicals Ltd.], and G-n-
Mix 0.5 parts of butyltin dilaurate, i.e.
A white paint was obtained by mixing -OH/-NGO = 1.25/1 (equivalent ratio).

Application example 1 The clear paint obtained in Example 1 was
Dilute with J (petroleum-based solvent manufactured by Exxon, USA),
On a pre-coated zinc steel sheet with a thickness of 0.3 mm, which had been previously coated with a commercially available polyester-melon-based baked coating, it was coated with a roll coater so that the dry film thickness was 10 microns. Forced drying was performed at 80° C. for 30 minutes.

Application Example 2 The white paint obtained in Example 2 was coated with “Solbefuso 150” (
(same as above) and coated with a roll coater to a dry film thickness of 10. Paint it so that it looks like a clone, 2
Baking was performed at 20° C. for 30 seconds.

Various performances of the coating films of the coated steel sheets obtained in each of the above application examples were evaluated. The results are summarized in Table 1.

For comparison, Comparative Application Example 1 uses a commercially available brecoat zinc steel sheet coated with a vinylidene fluoride coating film, and Comparative Application Example 2 uses a commercially available zinc steel sheet coated with a commercially available vinylidene fluoride coating film. The same table also includes the case where a precoated zinc steel sheet itself coated with a polyester-melamine baked coating is used.

As described above, the resin composition for coatings of the present invention has, in particular,
It can be seen that it has a good balance of processability, stain resistance, weather resistance, and gloss.

Claims (1)

[Scope of Claims] 1. A hydroxyl group-containing fluorine-containing copolymer (A) having a fluorine content of 5 to 50% by weight, and an acrylic acid alkyl ester and/or methacrylic acid having an alkyl group having 2 to 4 carbon atoms. Fluorine-free vinyl containing hydroxyl groups obtained by copolymerizing 81 to 98% by weight of an acid alkyl ester, 19 to 2% by weight of a hydroxyl group-containing vinyl monomer, and 0 to 17% by weight of other copolymerizable monomers A mixture of the copolymer (B) and the copolymer (A) and the copolymer (B) at a weight mixing ratio of (A)/(B)=30-95/70-5, - A resin composition for a coating material, comprising a polyisocyanate compound (C) blended at an equivalent ratio of OH/-NCO=0.8 to 100. 2. The alkyl acrylate and/or alkyl methacrylate having an alkyl group having 2 to 4 carbon atoms are 5 to 80 carbon atoms of ethyl methacrylate.
% by weight, and 95 to 20% by weight of an acrylic acid alkyl ester and/or a methacrylic acid alkyl ester having an alkyl group having 2 to 4 carbon atoms, excluding the ethyl methacrylate. The resin composition for paint according to.