JP2964562B2 - Resin composition - Google Patents

Description

The present invention relates to a novel and useful resin composition. More specifically, respectively, a hydroxyl group-containing fluoroolefin copolymer resin having a hydroxyl value of 30 to 200 mg KOH / g,
A carboxyl group-containing resin as an essential base resin component, and an epoxy group-containing compound and an amino resin as essential curing agent components.
The present invention relates to an extremely useful resin composition suitable for a so-called multilayer coating top clear paint such as a bake method and a three-coat two-bake method.

And, the resin composition of the present invention is extremely useful especially for coating an automobile body.

[Conventional technology]

Up to now, acrylic resin / melamine resin (acryl melamine) based paint has been generally used as such a top clear paint.

Such acrylic melamine-based paints are widely used as automotive top clear paints because their coating films have excellent physical properties such as gloss, weather resistance and scratch resistance.

However, in recent years, problems such as easy occurrence of stains have come to the fore with respect to acid rain, which has become important in recent years.

This is nothing but the use of a melamine resin, which is sensitive to acid, as a curing agent component in the first place.

Although studies on hardener components to replace melamine resins are also being made at a rapid pace, they are facing a new unsolved problem that only resin compositions with insufficient scratch resistance can be obtained. Is the actual situation.

[Problems to be solved by the invention]

As described above, it is actually difficult to obtain a resin composition that satisfies both acid resistance and abrasion resistance at the same time as long as the conventional technique described above is followed.

For this purpose, the present inventors have sought a highly useful laminated coating composition that can secure specific performances such as acid resistance and abrasion resistance while maintaining performances such as gloss and weather resistance. I started my research diligently.

Therefore, the problem to be solved by the present invention is, on the one hand, a novel resin composition having excellent properties such as acid resistance and abrasion resistance while maintaining properties such as gloss and weather resistance. To provide.

[Means for solving the problem]

Thus, the present inventors have focused on the problems to be solved by the invention as described above, and as a result of intensive studies, as a result, a fluoroolefin copolymer resin having a specific polar functional group called a hydroxyl group and a carboxyl group And a resin having a specific polar functional group as an essential base resin component,
On the other hand, a composition comprising an epoxy group-containing compound and an amino resin as essential curing agent components has excellent gloss resistance and weather resistance as well as excellent acid resistance and abrasion resistance. The present invention has been completed by finding that it is worthwhile.

That is, the present invention, as an essential component,
A hydroxyl group-containing fluoroolefin copolymer resin having a hydroxyl value of ~ 200 mgKOH / g (hereinafter abbreviated as "hydroxyl group-containing fluoroolefin copolymer resin") and a carboxyl group-containing resin, while an epoxy group-containing compound and an amino acid And a resin composition comprising a resin. Particularly, the composition of the present invention is particularly suitable for a so-called two-coat one-bake system or a three-coat two-bake system for laminating coating. It is.

That is, the present invention first applies a crosslinkable basecoat paint in the form of a mixture of a luminous agent and / or a color pigment on an object to be coated (substrate), and then applies a thermosetting clear coat on the basecoat coated surface. A coating method using a so-called two-coat one-bake method in which a paint (clear paint I) is applied and cross-linked, or a thermosetting clear coat paint (clear paint II) is further applied on the thus-obtained laminated paint. Suitable for use as a top clear paint in various laminated coatings, such as the so-called three-coat two-bake coating method of coating and cross-linking, various properties such as gloss, weather resistance, acid resistance, and scratch resistance. It is an object of the present invention to provide an extremely useful resin composition having excellent, excellent, and well-balanced performance.

According to the above-described various coating methods, for example, when coating the body of an automobile, there is almost no such thing as directly coating the base material with a base coat paint or a clear coat paint. Usually, it goes through several steps such as film formation, electrodeposition coating and / or intermediate coating of the object to be coated.
It goes without saying that the conventional method can be applied as it is.

Next, as a base coat paint, a paint using an ordinary acrylic resin and an amino resin as a crosslinking agent, especially a melamine resin is used.

In some cases, a polyester resin can also be used, and further, a cellulose derivative can be combined with these base resin components.

As a crosslinking agent, of course, an isocyanate resin (isocyanate prepolymer) can also be used.

Further, as the base coat paint, of course, a form containing a glitter or a coloring pigment is used, and among them, first, only a particularly typical one as a glitter is exemplified. Metal powder such as aluminum powder, or mica, or titanium oxide-coated mica.

Next, as typical examples of the coloring pigments, only inorganic pigments such as titanium oxide or carbon black, or various organic pigments such as phthalocyanine blue, phthalocyanine green or quinacridone red are exemplified.

Furthermore, as the two-coat one-bake clear coating in the three-coat two-bake coating, a thermosetting coating such as a normal acrylic resin or a melamine resin is generally used, and therefore, the resin composition of the present invention includes: In the three-coat two-bake coating, it is effective to use the subsequent three-coat two-bake clear, that is, the top clear.

Here, examples of the above-mentioned hydroxyl group-containing fluoroolefin copolymer resin, which is one of the essential components constituting the resin composition of the present invention, include, for example, a copolymer resin containing a fluoroolefin and a hydroxyl group-containing monomer as essential components. Can be

Examples of the fluoroolefin include vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, bromotrifluoroethylene, pentafluoropropylene or hexafluoropropylene, or trifluoromethyl trifluorovinyl ether, pentafluoro Representative examples thereof include perfluoroalkyl perfluorovinyl ether such as ethyl trifluorovinyl ether or heptafluoropropyl trifluorovinyl ether, among which tetrafluoroethylene, vinylidene fluoride, chlorotrifluoroethylene, or hexafluoroethylene. The use of fluoropropylene is preferred. These fluoroolefin monomers may be used alone or in combination of two or more.

As the hydroxyl group-containing monomer, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 5-hydroxypentyl Vinyl ethers containing a hydroxyl group such as vinyl ether or 6-hydroxyhexyl vinyl ether, or hydroxyalkyl vinyl ether to which ε-caprolactone has been added or hydroxyalkyl allyl ether to which ε-caprolactone has been added.

The constituent monomers other than the fluoroolefin and the hydroxyl group-containing monomer include vinyl 2,2 which is a monocarboxylic acid vinyl ester having a C _{1 to} C ₁₈ hydrocarbon group.
-Dimethylpropanoate, vinyl 2,2-dimethylbutanoate, vinyl 2,2-dimethylpentanoate, vinyl 2,2-dimethylhexanoate, vinyl 2,2-dimethylbutanoate, vinyl 2-ethyl -2-methylbutanoate, vinyl 2-ethyl-2-methylventanoate,
Vinyl 3-chloro-2,2-dimethyl propanoate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, branched aliphatic C ₉ vinyl carboxylic acids, branched fatty carboxylic acid vinyl, fatty acid vinyl esters such as branched fatty acids or vinyl stearate, the C ₁₁ of the C _10; or cyclohexanecarboxylic acid, vinyl cyclohexanecarboxylate, vinyl benzoate or There are vinyl carboxylate esters having a cyclic structure such as vinyl p-tert-butyl benzoate.

Other copolymerizable monomers include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, n
-Alkyl vinyl ethers or substituted alkyl vinyl ethers such as hexyl vinyl ether, n-octyl vinyl ether, 2-ethylhexyl vinyl ether, chloromethyl vinyl ether, chloroethyl vinyl ether, benzyl vinyl ether or phenylethyl vinyl ether; cycloalkyls such as cyclopentyl vinyl ether, cyclohexyl vinyl ether or methylcyclohexyl vinyl ether Alkyl vinyl ethers: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinylmethyldiethoxysilane, vinyltris (β-methoxyethoxy)
Silane, allyltrimethoxysilane, trimethoxysilylethyl vinyl ether, triethoxysilylethyl vinyl ether, methyldimethoxysilylethyl vinyl ether, trimethoxysilylpropyl vinyl ether,
Triethoxysilylpropyl vinyl ether, methyldimethoxysilylpropyl vinyl ether, γ- (meth)
Acryloyloxypropyltrimethoxysilane, γ-
Monomers containing a hydrolyzable silyl group such as (meth) acryloyloxypropyltriethoxysilane or γ- (meth) acryloyloxypropylmethyldimethoxysilane; ethylene, propylene or butene-1
Α-olefins such as vinyl chloride or vinylidene chloride; various halogenated olefins other than fluoroolefins; aromatic vinyl compounds such as styrene, α-methylstyrene or vinyltoluene; methyl methacrylate, ethyl methacrylate And methacrylates such as butyl methacrylate and cyclohexyl methacrylate; and acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate and cyclohexyl acrylate.

Further, a carboxyl group-containing monomer such as (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monoethyl malate, mono-n-butyl fumarate or mono-n-butyl itaconate can be used.

To prepare the hydroxyl group-containing fluoroolefin copolymer resin, JP-A-61-275311, and JP-B-60-21
A method such as that disclosed in JP-A-686 or the like may be used.

And the hydroxyl value of the copolymer resin is 30 to 200 mg KOH
/ g, preferably 60
150150 mgKOH / g.

If it is less than 30 mg KOH / g, it will not be possible to secure good scratch resistance (scratch resistance) as a composite cured system, while if it exceeds 200 mg KOH / g, In any case, the viscosity of the coating material tends to be high, and the workability tends to decrease, and furthermore, the appearance of the coating film is impaired.

Next, as the above-mentioned carboxyl group-containing resin which is one of the essential components constituting the resin composition of the present invention, for example, a resin represented by a carboxyl group-containing vinyl copolymer resin, particularly (meth) Examples thereof include an acryloyloxy group-containing vinyl resin (hereinafter, also referred to as a carboxyl group-containing acrylic resin) and a carboxyl group-containing polyester resin.

First, if only a particularly typical example of the above-mentioned carboxyl group-containing vinyl copolymer resin is exemplified, a carboxyl group-containing monomer as an essential component as described later is used as an essential component, and further described below. Examples thereof include those obtained by using various copolymerizable other monomers and hydroxyl group-containing vinyl monomers.

The acid value of the carboxyl group-containing vinyl copolymer resin is suitably from 30 to 150, preferably from 50 to 120.

When it is less than 30, it is difficult to obtain a coating film having both excellent acid resistance and abrasion resistance.On the other hand, when it exceeds 150, the viscosity of the coating material is significantly increased, and Either case is not preferable because the workability deteriorates.

Only typical representative examples of such carboxyl group-containing monomers include (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid,
Monoethyl malate, monoethyl fumarate or mono-n-butyl itaconate.

Only other typical examples of other copolymerizable monomers are exemplified, and 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) Acrylate, 2-hydroxybutyl (meth) acrylate, 3
-Hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, di-2-hydroxyethyl fumarate, mono-2-hydroxyethyl-monobutyl fumarate Or hydroxyalkyl esters of α, β-ethylenically unsaturated carboxylic acids such as polypropylene glycol mono (meth) acrylate, “Placcel FM, FA monomer” (caprolactone-added monomer manufactured by Daicel Chemical Co., Ltd.) or a combination thereof. ε
-Aromatic vinyl monomers such as styrene, α-methylstyrene, p-tert-butylstyrene or vinyltoluene, including hydroxyl group-containing vinyl monomers represented by adducts with caprolactone; ) Acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2 -Ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth)
(Meth) acrylates such as acrylate, benzyl (meth) acrylate, dibromopropyl (meth) acrylate or alkoxyalkyl (meth) acrylate; N-dimethylaminoethyl (meth) acrylamide;
N-diethylaminoethyl (meth) acrylamide, N
-Amino group-containing unsaturated monomers such as -dimethylaminopropyl (meth) acrylamide or N-diethylaminopropyl (meth) acrylamide; dialkylaminoalkyl (meth) such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate ) Acrylates; or tert-butylaminoethyl (meth) acrylate, tert-butylaminopropyl (meth) acrylate, tert-butylaminobutyl (meth) acrylate, aziridinylethyl (meth) acrylate, pyrrolidinylethyl (meth) ) Basic nitrogen atom-containing monomers such as acrylate or piperidinylethyl (meth) acrylate; Dialkyl ((meth) acryloyloxyalkyl) phosphates or (meth) acryloyloxyalkyl acid phosphates represented by the general formula: (R ₁ , R ₂ and R ₃ and A are as described above). Dialkyl ((meth) acryloyloxylalkyl) phosphites; (meth) acryloyloxyalkyl acid phosphites, and Are the above (meth) acryloyloxyalkyl acid phosphates, alkylene oxide adducts of acid phosphites, epoxy group-containing vinyl monomers such as glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate, and phosphoric acid or Phosphorous acid or esters thereof with acidic esters thereof, phosphorus atom-containing monomers such as 3-chloro-2-acidphosphoxypropyl (meth) acrylate; various α, β-ethylenically unsaturated monomers as described above. Saturated carboxylic acid hydroxyalkyl esters, maleic acid, amber Various polycarboxylic acids such as phthalic acid, phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, benzenetricarboxylic acid, benzenetetracarboxylic acid, "Hymic acid" (product of Hitachi Chemical Co., Ltd.), tetrachlorophthalic acid or dodecinylsuccinic acid Carboxyl group-containing monomers other than those mentioned above, such as adducts of acid with anhydride; silicon monomers such as vinylethoxysilane or α-methacryloyloxypropyltrimethoxysilane; glycidyl (meth) acrylate, β- Methyl glycidyl (meth) acrylate or (meth)
Epoxy group-containing monomers such as allyl glycidyl ether; acid anhydride-containing monomers such as vinyl esters of various acid anhydrides (polycarboxylic anhydrides) such as maleic anhydride, itaconic anhydride or trimellitic anhydride Diesters of unsaturated dicarboxylic acids such as fumaric acid or itaconic acid and monohydric alcohols; vinyl acetate, vinyl benzoate, "Veoba" (vinyl ester manufactured by Shell)
Vinyl esters such as "Viscoat 88F, 8FM, 17FM, 3
F or 3FM "[fluorinated acrylic monomer manufactured by Osaka Organic Chemical Co., Ltd.], perfluorocyclohexyl (meth)
Vinyl esters, vinyl ethers, (meth) acrylates or unsaturated polycarboxylic acids containing (per) fluoroalkyl groups such as acrylates, diperfluorocyclohexyl fumarate or N-iso-propylperfluorooctanesulfonamidoethyl (meth) acrylate Fluorine-containing polymerizable compounds such as acid esters; and vinyl monomers free of polar functional groups such as olefins such as (meth) acrylonitrile, vinyl chloride and vinylidene chloride.

Further, if necessary, as a copolymerizable unsaturated bond-containing resin, having copolymerizability with the various monomers listed above, containing an unsaturated bond, oil- or fatty acid-modified, A so-called alkyd resin, an unsaturated bond-containing polyester resin, or an unsaturated bond-containing vinyl resin can also be added to the copolymerizable monomer in the form of a so-called macromonomer.

The preparation of the carboxyl group-containing vinyl copolymer may be performed by a conventional method, for example, by performing radical copolymerization with a polymerization initiator such as a peroxide or an azo compound in an organic solvent.

On the other hand, as the acid component used in preparing the carboxyl group-containing polyester resin, it is preferable to use so-called alicyclic carboxylic acids having a cyclohexane ring in consideration of the weather resistance of the coating film. If only typical examples of the cyclic carboxylic acids are exemplified, 1,1-cyclohexanedicarboxylic acid, hexahydro (anhydride) phthalic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid or Methylhexahydro (anhydride) phthalic acid and the like, and if necessary, a cyclohexane mono- or polycarboxylic acid such as 4-tert-butylcyclohexanemonocarboxylic acid, hexahydrobenzoic acid or hydrogenated trimellitic acid, and further, , These methyl esters can also be used.

Other acid components include (anhydrous) phthalic acid, isophthalic acid, terephthalic acid, benzoic acid, p-tert-butylbenzoic acid or p-methylbenzoic acid, or (anhydrous)
Various aromatic carboxylic acids, such as trimellitic acid or (anhydrous) pyromellitic acid, are used. Further, adipic acid, azelaic acid, sebacic acid, tetrahydro (anhydride) phthalic acid, tetrachloro (anhydride) phthalic acid,
(Anhydrous) hetonic acid, "(anhydride) hymic acid", (anhydrous) maleic acid, fumaric acid, itaconic acid and the like are also used.

If only typical representative examples of polyhydric alcohol components used together with these acid components are given, ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,6-hexanediol, diethylene glycol, dipropylene Glycol, neopentyl glycol, triethylene glycol, cyclohexane dimethanol, hydrogenated bisphenol A, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol or sorbitol.

The oil component can be used as a part of the acid component in preparing the polyester resin, that is, within a range in which the oil length is less than 30% in all the acid components. In view of the above, it is desirable to use coconut oil, hydrogenated coconut oil, "Kajura E" (branched fatty acid monocarboxylic acid, manufactured by Ciel, Netherlands), octenoic acid or isononanoic acid. Rice bran oil fatty acid, tall oil fatty acid, soybean oil, castor oil, dehydrated castor oil and the like can also be used as appropriate.

As the acid value of the various carboxyl group-containing resins as described above, 30 to 150 mg KOH / g, preferably, 50 to 120 mg KOH
The range of / g is appropriate.

If it is less than 30 mg KOH / g, it will be difficult to obtain a coating film having excellent properties of both acid resistance and scratch resistance.
On the other hand, when the amount exceeds 150 mg KOH / g (hereinafter, the unit is omitted), the viscosity of the coating material is inevitably increased, and the workability tends to be impaired.

Then, as the compounding ratio of the hydroxyl group-containing fluoroolefin copolymer resin and the carboxyl group-containing resin described above, the carboxyl group-containing resin / hydroxyl group-containing fluoroolefin copolymer resin = 50/100 in terms of solid content weight ratio.
A range of from 200/100, preferably from 80/100 to 150/100 is appropriate.

On the other hand, the above-mentioned epoxy group-containing compound, which is one of the essential components of the resin composition of the present invention, refers to a compound having substantially two or more epoxy groups (including glycidyl groups) in one molecule. Of course, they can be used as long as they follow this definition.
A compound having both an epoxy group and a hydrolyzable silyl group in one molecule, a compound having both an epoxy group and a hydroxyl group in one molecule, or a compound having an epoxy group, a hydrolyzable silyl group and a hydroxyl group in one molecule The use of compounds having

As the epoxy group-containing compound, first, a compound having at least two epoxy groups in one molecule is exemplified, and ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether,
Polyglycidyl ethers of polyhydric alcohols such as 6-hexanediol diglycidyl ether, diglycidyl ether of bisphenol A or triglycidyl ether of glycerin; diglycidyl ester of phthalic acid, diglycidyl ester of isophthalic acid or diglycidyl of adipic acid Polyglycidyl esters of polycarboxylic acids such as esters; or polyepoxy compounds such as various epoxy resins such as diglycidyl ether type epoxy resin of bisphenol A or bisphenol F, novolak type epoxy resin or epoxy resin containing a hydantoin ring. And glycidyl ester ethers of p-oxybenzoic acid, and various alicyclic epoxy group-containing compounds as described below. That is, Or Next, use of a copolymer resin of an epoxy group-containing vinyl monomer having an epoxy group in a side chain and another copolymerizable monomer as the epoxy resin is, in particular, a coating such as scratch resistance. It is desirable in terms of film properties.

If only typical representative examples of such epoxy group-containing vinyl monomers are given, the general formula Or Alicyclic epoxy group-containing vinyl monomers such as And so-called aliphatic epoxy group-containing vinyl monomers.

Here, as the number of carbon atoms mentioned above is 1-6 divalent aliphatic saturated hydrocarbon group (R _5), straight-chain or branched alkylene group such as methylene, ethylene, propylene, tetramethylene, ethyl ethylene , Pentamethylene or hexamethylene group. Examples of the divalent hydrocarbon group having 1 to 10 carbon atoms (R ₆ ) include methylene, ethylene, propylene, and tetramethylene. , Ethylethylene, pentamethylene, hexamethylene, polymethylene, phenylene, Or And the like.

If only other typical examples of other monomers copolymerizable with these various epoxy group-containing vinyl monomers are exemplified, besides excluding the carboxyl group-containing vinyl monomers, Various monomers as described above, which are used in preparing the above-mentioned hydroxyl-containing vinyl copolymer, are applied as they are.

Next, in one molecule described above, as a compound having both an epoxy group and a hydrolyzable silyl group,
Representative examples thereof include a vinyl polymer having both types of reactive groups and a silane coupling agent having an epoxy group.

Here, such a hydrolyzable silyl group has a general formula And a reactive group which is easily hydrolyzed, such as a halosilyl group, an alkoxysilyl group, an acyloxysilyl group, a phenoxysilyl group, an iminooxysilyl group or an alkenyloxysilyl group.

In order to prepare the vinyl copolymer having both the specific amphoteric groups as described above, any of the known methods can be applied, but γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) Acryloyloxypropylmethyldimethoxysilane, γ- (meth) acryloyloxypropyltriisopropenyloxysilane, γ-
Vinyl having a hydrolyzable silyl group such as (meth) acryloyloxypropyltriiminooxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyl (tris-β-methoxyethoxy) silane, vinyltriacetoxysilane or vinyltrichlorosilane. Monomers and vinyl monomers having an epoxy group such as (β-methyl) glycidyl (meth) acrylate, allyl glycidyl ether, di (β-methyl) glycidyl malate or di (β-methyl) glycidyl fumarate And, if necessary, solution radical copolymerization using various copolymerizable monomers as described above, or γ-mercaptopropyltrimethoxysilane, γ- Mercaptopropyltriethoxysilane, γ-mercaptop In the presence of a chain transfer agent such as pyrmethyldimethoxysilane, γ-mercaptopropyltriisopropenyloxysilane or γ-mercaptopropyltriiminooxysilane, an epoxy group-containing vinyl monomer as described above is an essential component. Methods such as solution radical (co) polymerization of the monomer mixture,
It is mentioned as a simple thing.

Next, typical examples of the epoxy group-containing silane coupling agent described above include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, adducts of glycidol with γ-glycidoxypropyltriisopropenyloxysilane, γ-glycidoxypropyltriiminooxysilane, γ-isocyanatopropyltriisopropenyloxysilane or γ-isocyanatopropyltrimethoxysilane, or Adducts of γ-aminopropyltrimethoxysilane and the like with a diepoxy compound.

Further, a compound having both an epoxy group and a hydroxyl group in one molecule is also effective for enhancing the curability, and if only a particularly desirable example of such a compound is given, the side chain as described above may be used. An epoxy group-containing vinyl monomer having an epoxy group, and a hydroxyl group-containing vinyl monomer, if necessary, further obtained by copolymerizing other copolymerizable monomers. Things.

Further, as one of the epoxy group-containing vinyl copolymers, a compound having an epoxy group, a hydrolyzable silyl group and a hydroxyl group in one molecule can also be used, and for example, these compounds have various polar functional groups. It is obtained by copolymerizing the respective monomers.

As the amount of the epoxy group-containing compound used, the essential four components of the composition of the present invention, that is, the total solid content of the hydroxyl group-containing fluoroolefin copolymer resin, the carboxyl group-containing resin, the epoxy group-containing compound, and the melamine resin (hereinafter, referred to as the total amount) , The total amount of the resin) is 10 to 40% by weight, preferably 15 to 30% by weight.

Next, if the amino resin, which is one of the essential components of the resin composition of the present invention, is only a typical example, it is an alkyl etherified melamine resin. If only typical examples are illustrated, "Super Beckamine L-117-60" (product of Dainippon Ink and Chemicals, Inc.) or "Uban 225" (product of Mitsui Toatsu Chemicals, Inc.) A methoxymethylmelamine resin such as "Symer $ 300 or $ 303" (product of Mitsui Cyanamid Co., Ltd.) or "Sumimal M-100" (product of Sumitomo Chemical Co., Ltd.); ♯1130 ”or“ Sumimar
And Methoxy-butoxy mixed etherified methylmelamine resin such as "M-66B".

The amount of the melamine resin used is appropriately in the range of 5 to 30% by weight, preferably 10 to 25% by weight based on the total amount of the resin.

In order to accelerate the curing of the composition of the present invention, a curing catalyst can be used.However, if only particularly typical examples of such a curing catalyst are exemplified, paratoluenesulfonic acid, dodecylbenzenesulfonic acid, Acid catalysts such as dinonylnaphthalenedisulfonic acid or amine blocked products thereof, half-esterified product of tetrachlorophthalic anhydride and monohydric alcohol, organic acids such as trichloroacetic acid; tetraisopropyl titanate, dibutyltin laurate, dibutyltin acetate, dibutyl Metal-containing compounds such as tin dioctate and cobalt naphthenate;
Alternatively, phosphorus-based acidic compounds such as monoalkylphosphoric acid, dialkylphosphoric acid, monoalkylphosphorous acid, dialkylphosphoric acid, and triphenylphosphine can be used.

The amount of the curing catalyst used is suitably in the range of 0.01 to 10% by weight based on the total amount of the resin.

The resin composition of the present invention thus obtained, which is useful as a top clear coating, is generally not mixed with a pigment, but to the extent that the transparency of the coating film is maintained, that is, deviates from the object of the present invention. As long as the effect of the present invention is not impaired, it may be advisable to incorporate a luminous agent and / or a coloring pigment as described above, which is used for a base coat paint.

The composition of the present invention, if necessary, including various resins and solvents, a flow regulator, a color separation inhibitor,
It goes without saying that various conventional additives such as antioxidants, ultraviolet absorbers, light stabilizers or silane coupling agents can be added.

Representatives of the various resins include cellulose resins such as nitrocellulose or cellulose acetate butyrate, vinyl chloride / vinyl acetate copolymer resins, ketone resins, petroleum resins, polyester resins, or
There is a fluorine resin and the like.

Examples of the solvents include hydrocarbons such as toluene, xylene, cyclohexane, n-hexane and octane; ester systems such as methyl acetate, ethyl acetate, butyl acetate and ethylene glycol monoethyl ether acetate; acetone, methyl ethyl ketone and methyl isobutyl. Ketones such as ketone, methyl amyl ketone or cyclohexanone; amides such as dimethylformamide, dimethylacetamide or N-methylpyrrolidone; or methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-
Representative examples are alcohol solvents such as butanol, sec-butanol, tert-butanol and ethylene glycol monoalkyl ether, and mixtures thereof.

Using the thus obtained resin composition of the present invention, in particular, as a top clear coating, to form a coating film having a high practical effect intended, for example, surface treatment, or, if necessary, In advance, on the surface of the substrate to be coated which has been subjected to a primer or a surfacer, first, a base coat paint is diluted with a diluting solvent, if necessary,
The coated film is applied by a normal method so that the dry coating film has a thickness of 10 to 50 μm, and then the composition of the present invention is applied to a two-coat and one-bake coating by a normal method to obtain a dry film thickness of 5 to 5 μm. 40
μm and then cross-linking under predetermined conditions. In the case of three-coat two-bake coating, coating and cross-linking are performed in the same manner as the two-coat one-bake coating as described above. Furthermore, the composition of the present invention may be applied thereon by a conventional method so as to have a dry film thickness of 5 to 40 μm, and then crosslinked under predetermined conditions.

Usually, each of the above crosslinking conditions is 110 to 1
Suitable at 70 ° C. for 15 to 40 minutes, preferably at 130 to 150 ° C. for 20 to 30 minutes.

Thus, the so-called top coat (top clear coat) obtained using the resin composition of the present invention is, inter alia,
Not only acid resistance and scratch resistance, but also gloss, leveling and sharpness are remarkably excellent, and coating workability is also good.

〔Example〕

Next, the present invention will be described more specifically with reference examples, examples, comparative examples, applied examples, and comparative applied examples. In the following, parts and percentages are by weight unless otherwise specified.

Reference Example 1 (Preparation Agent for Hydroxyl-Containing Fluoroolefin Copolymer Resin) In a stainless steel autoclave sufficiently substituted with nitrogen, 390 parts of p-tert-butyl vinyl benzoate was added.
"VeoVa 9" (before arrival manufactured, 100 parts of a vinyl ester] of C ₉ comprising branched aliphatic monocarboxylic acids, 110 parts of 4-hydroxybutyl vinyl ether, acetate n- butyl 430
Part of 2,2-azobis (2,4-dimethylvaleronitrile)
20 parts and 3 parts of [Sanol LS-765] (an amine compound manufactured by Sankyo) were charged. Then, 400 parts of the liquefied and collected chlorotrifluoroethylene were injected under pressure, and the reaction was carried out at 60 ° C. for 15 hours with stirring to remove non-volatile components.
When the content became 67%, the mixture was cooled to room temperature and 175 parts of xylene was added to obtain a solution of the target copolymer resin having a nonvolatile content of 60%. Hereinafter, this is abbreviated as resin (F-1), and its hydroxyl value is 53 in solid content.

Reference Example 2 (same as above) The composition ratio of the monomers to be used was changed to vinyl benzoate 110 parts 4-hydroxyethyl vinyl 300 parts ether cyclohexyl vinyl ether 190 parts chlorotrifluoroethylene 400 parts, and n-butyl acetate was used. Instead, a solution of the target copolymer resin having a nonvolatile content of 60% was obtained in the same manner as in Reference Example 1, except that 670 parts of xylene was used. Hereinafter, this is abbreviated as resin (F-2), and the solid content of the resin is 145.

Reference Example 3 (Preparation Agent for Hydroxyl-Containing Vinyl Resin for Control) In a four-necked flask equipped with a stirrer, a thermometer, a cooler, and a nitrogen inlet tube, "Solvesso 100" (produced by Exxon, USA) 500 parts of a hydrogen-based solvent mixture) and 200 parts of n-butanol were charged and maintained at 120 ° C.

Then 250 parts of styrene, 300 parts of n-butyl methacrylate, 120 parts of n-butyl acrylate, 320 parts
Part of 2-hydroxyethyl methacrylate and 10 parts of acrylic acid, 30 parts of tert-butylperoxy-2-ethylhexanoate, 10 parts of azobisisobutyronitrile
Parts and 10 parts of -tert-butylperoxybenzoate, 200 parts of "Solvesso 100" and n-butanol
100 parts were added dropwise over 5 hours.

After completion of the dropwise addition, the reaction was continued at the same temperature for 6 hours to continue the reaction. The non-volatile content was 50.2% and the hydroxyl group was 14%.
0 was obtained as the solution of the target resin. Hereinafter, the resin (A ′)
Abbreviated as -1).

Reference Example 4 (Preparation Example of Carboxyl Group-Containing Resin) In the same reaction solution as in Reference Example 3, 5
100 parts and 200 parts of n-butanol were charged and maintained at 120 ° C. Then 250 parts of styrene and 493 parts of n-
Butyl methacrylate, 180 parts of n-butyl acrylate and 77 parts of acrylic acid, 30 parts of tert-butyl peroxy-2-ethylhexanoate, 10 parts of azobisisobutyronitrile and 10 parts of di-tert-butyl 10 parts of oxybenzoate, 200 parts of "Solvesso 100" and 100 parts of n-butanol were added dropwise over 5 hours.

After completion of the dropwise addition, the reaction was continued at the same temperature for 6 hours to obtain a solution of the target resin having a nonvolatile content of 50.1% and an acid value of 60. Hereinafter, this is referred to as resin (A-1)
Abbreviated.

Reference Example 5 (same as above) A solution of the target resin was obtained in the same manner as in Reference Example 1, except that the raw material charging ratio as shown in Table 1 was changed.
The property values are shown in the same table.

Reference Examples 6 to 10 (Preparation Examples of Epoxy Group-Containing Compound) In the same manner as in Reference Example 4, except that the raw material charging ratios were changed as shown in Table 2, solutions of various target compounds were obtained. . The property values of each compound solution are shown in the same table.

Reference Example 11 (Preparation example of carboxyl group-containing polyester resin) In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser equipped with a dehydration trap, and a nitrogen gas inlet tube, 136 parts of trimethylolpropane and 53 parts of neopentyl glycol were placed. Parts and 208 parts of 1,6-hexanediol,
The temperature was raised to ° C.

Then, 289 parts of hexahydrophthalic acid and 410 parts of adipic acid and 0.85 parts of lithium hydroxide were added, and 220 ° C was added.
, And a dehydration-condensation reaction was further performed at this temperature, and the solid content was continued until the acid value reached 70.

After the reaction, cool and add 428 parts of xylene,
A solution of the target resin having a nonvolatile content of 70% and an acid value of the solid content of 70 was obtained. Hereinafter, this is abbreviated as resin (P-1).

Reference Examples 12 and 13 (same as above) A solution of the target resin was obtained in the same manner as in Reference Example 11, except that the raw material charging ratios were changed as shown in Table 3.

 The respective property values are collectively shown in the same table.

The abbreviations in the table have the following meanings.

HHPA: hexahydrophthalic acid IPA: isophthalic acid AA: adipic acid TMP: trimethylolpropane NPG: neopentyl glycol 1,6HD: 1,6-hexanediol Reference Example 14 (Preparation Example of Base Coat Paint) According to the following composition ratio, a mixture prepared and prepared by a usual paint preparation method is used as a diluting solvent, and a Ford cup No. 4 takes 12 to 13 seconds. The desired paint was obtained by adjusting the viscosity as described above. Hereinafter, this is called paint (BC-
Abbreviated as 1).

"Beccolite 57-1054" [hydroxyl-containing polyester resin manufactured by Dainippon Ink and Chemicals, Incorporated; nonvolatile content = 70
%] 72 parts "Super Beckamine L-117-60" (n
-Butylated melamine resin nonvolatile content = 60%] 42 parts "CAB 381-2" (cellulose acetate butyrate manufactured by Eastman Kodaz Company, USA) 25 parts "Epolen N-10" (manufactured by the same company) Wax) 15 parts “Alpaste 1860YL” [Aluminum paste manufactured by Toyo Aluminum Industry Co., Ltd . ; non-volatile content = 65%] 23 parts Total 177 parts Reference Example 15 (same as above) Changed to the one with the following composition ratio A target paint was obtained in the same manner as in Reference Example 14, except that the adjusted viscosity was changed to 13 to 14 seconds in Ford Cup No. 4. Hereinafter, this is abbreviated as paint (BC-2).

"Acridic 47-712" (hydroxyl-containing acrylic resin manufactured by Dainippon Ink and Chemicals, Incorporated; nonvolatile content = 50%) 160 parts "Super Beckamine L-117-60" 33 parts "Aspaste 1860YL" 23 parts "Fast Gen Blue NK" ( Cyanine Blue manufactured by Dainippon Ink and Chemicals, Inc.) 2 parts Total 218 parts Reference Example 16 The same procedures as in Reference Example 14 were carried out except that the composition was changed as shown below. The desired paint was obtained. Hereinafter, this is abbreviated as paint (BC-3).

"Acridic 47-567" (hydroxyl-containing acrylic resin manufactured by former company; non-volatile content = 50%) 100 parts "Barnock DN-950" [Dainippon Ink & Chemicals, Inc.
Polyisocyanate compound; non-volatile content = 75%] 18 parts "Typek CR-93" [rutile type titanium oxide manufactured by Ishihara Sangyo Co., Ltd. ] 60 parts Total 178 parts Example 1 According to the following composition ratio, By the paint preparation method, what was blended and prepared, by the solvent for dilution,
The viscosity was adjusted to 25 seconds with Ford Cup No. 4 to obtain a clear coat paint. Hereafter, paint this (CC
Abbreviated as -1).

Resin (F-1) 85 parts Resin (A-1) 100 parts Resin (E-2) 50 parts "Super Beckamine L-117-60" 60 parts "Tinuvin 900" (ultraviolet light manufactured by Ciba Geigy, Switzerland) Absorbent) 1.5 parts "Tinuvin 440" (radical scavenger manufactured by the same company) 1.5 parts "Nacure 5225" (curing catalyst manufactured by King, USA) 4.5 parts Triphenylphosphine 1 part Dibutyltin dioctate 1 part Implemented Examples 2 to 12 and Comparative Examples 1 and 2 Various clear coat paints were obtained in the same manner as in Example 1 except that the combination of various resins as shown in Table 4 was changed.

Various base coat paints obtained in Application Examples 1 to 15 and Comparative Application Examples 1 to 3 and Reference Examples 14 to 16,
Using the various clear coat paints obtained in Examples 1 to 12 and Comparative Examples 1 and 2, according to the conditions shown in Table 5, a mild steel sheet subjected to a phosphorylation treatment was prepared.
On the coated plate obtained by coating the electrodeposition primer and the intermediate coating surfacer for automobiles, respectively, in the case of 2 coats 1 bake coating, first, by air spray, so that the dry film thickness becomes 15-20 μm, After applying the base coat paint, set it for 3 minutes, then apply the top clear coat paint wet-on-wet so that the dry film thickness becomes 25-30 μm, leave it for 20 minutes, and then put it in an electric hot air dryer. At 140 ° C. for 20 minutes.

On the other hand, in the case of three-coat two-bake coating,
One hour after the coat 1 bake coating, apply an overcoat clear paint so that the dry film thickness becomes 25 to 30 μm, leave it for 10 minutes, and then in an electric hot air drier at 140 ° C.
For 20 minutes.

The coating performance was evaluated for each of the thus-obtained laminated coatings.

 The results are summarized in the same table.

The evaluation of the coating film performance was roughly performed in the following manner.

Mitsuzawa: The value obtained by measuring the 60-degree specular reflectance (%) using a Murakami gloss meter.

Acid resistance: A change in the coated surface after immersion in a 5% aqueous sulfuric acid solution for 24 hours was visually determined.

…: No abnormalities ○: Remarkably good ×: Extremely discolored brown Scratch resistance: Gloss retention (%) of the coated surface after washing the coated surface by reciprocating 50 times with a 5% aqueous solution of polishing powder under a load of 300 g / m ² ) Was displayed.

Weather resistance: A change in the paint surface after 24 months of actual exposure in the suburbs of Bangkok was determined by visual observation.

…: No abnormalities…: Slight discoloration ×: Extremely discolored brown Water resistance: A change in the coating surface after standing for 240 hours in a container at 50 ° C. and 98 RH was visually judged.

◎… No abnormality ×… Slight whitening [Effect of the Invention] The thermosetting laminated coating composition of the present invention obtained as described above is a so-called carboxyl group-containing resin-epoxy group-containing compound curing system, and a hydroxyl group-containing resin-melamine resin curing system. It is extremely useful as a complex curing system. In particular, by using the composition of the present invention as a top clear coat paint or overcoat clear paint, it is excellent in acid resistance and scratch resistance, in other words, glossy In addition, various properties such as weather resistance, acid resistance and abrasion resistance are all excellent, well-balanced and extremely high in practical value.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ identification code FI C09D 163/00 C09D 163/00 (58) Field surveyed (Int.Cl. ⁶ , DB name) C08G 59/42 C08G 59/62 C08G 59/20 C09D 163/00-163/10 C09D 127/00-127/24 C09D 5/00

Claims (6)

(57) [Claims] 1. A resin composition comprising a hydroxyl group-containing fluoroolefin copolymer resin having a hydroxyl value of 30 to 200 mg KOH / g and a carboxyl group-containing resin as a base resin component, and a compound having an epoxy group and an amino resin as a curing agent component. A resin composition, characterized in that: 2. The method according to claim 1, wherein the carboxyl-containing resin is 30 to 15%.
The resin composition according to claim 1, wherein the resin composition has at least one kind selected from the group consisting of a vinyl copolymer resin and a polyester resin, having an acid value of 0 mgKOH / g. 3. The resin composition according to claim 1, wherein the compound having an epoxy group has both an epoxy group and a hydrolyzable silyl group in one molecule. 4. The resin composition according to claim 1, wherein the compound having an epoxy group has both an epoxy group and a hydroxyl group in one molecule. 5. The coating composition according to claim 1, wherein the coating composition is used as the clear coating material in a multilayer coating method in which a base coating material containing a luminous agent and / or a coloring pigment is applied, and a clear coating is further laminated and crosslinked. 3. The resin composition according to item 1. 6. A laminated paint which comprises applying a base paint containing a luminous agent and / or a coloring pigment, coating a clear paint thereon to crosslink, and then further laminating a clear paint thereon to crosslink. The resin composition according to any one of claims 1 to 4, which is used as a clear paint for each of the above.