JP2007254585A - Resin composition for active energy ray curable powder coating - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition for an active energy ray curable powder coating capable of supplying a powder coating that can obtain a coating film with good smoothness, adhesion property and water resistance. <P>SOLUTION: This resin composition for an active energy ray curable powder coating comprises a phosphorus compound modified resin having ethylenic unsaturated group that is obtained by reacting a resin having ethylenic unsaturated group with a phosphorous compound, preferably a phosphorus compound-modified resin having ethylenic unsaturated group with a content of 0.05-1 wt.% of a phosphorus compound derived component. For example, the resin composition comprises a phosphorus compound modified polyester resin having ethylenic unsaturated, a phosphorus compound modified ethylenic epoxy resin having unsaturated group, a phosphorus compound modified acrylic resin having ethylenic unsaturated group-containing and a phosphorus compound modified epoxy polyester resin having ethylenic unsaturated group, etc. , wherein the contents of the phosphorus compound derived component are each 0.05-1 wt.%. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a novel and useful active energy ray-curable resin composition for powder coatings. More specifically, an active energy ray-curable resin composition for a powder coating containing a phosphorus compound-modified ethylenically unsaturated group-containing resin obtained by reacting an ethylenically unsaturated group-containing resin with a phosphorus compound, In particular, the present invention relates to an active energy ray-curable resin composition for powder coatings that can provide a coating having excellent smoothness, adhesion, and water resistance.

  Powder coatings are widely used in general metal coatings as environmentally friendly coatings that do not volatilize organic solvents into the atmosphere during coating.

  Among powder coatings, active energy ray-curable powder coatings can be cured by irradiation with active energy rays after being melted at low temperatures, so they can be cured at low temperatures and for short periods of time compared to conventional thermosetting powder coatings. It has been attracting attention as a coating method that can save energy and shorten processes.

  Furthermore, since the powder coating can be cured at a low temperature by irradiation with active energy rays, a thick metal that requires a long time to raise the temperature of the substrate in a baking furnace, a temperature sensitive substrate, For example, painting on wood or the like is effective (for example, see Patent Document 1).

  However, conventional active energy ray-curable powder coatings cannot be said to have sufficient adhesion to substrates such as metals.

  As a method for improving adhesion to a metal substrate, a method of adding a phosphorus-containing compound has been proposed (see, for example, Patent Document 2), but a relatively large amount of phosphorus compound (0.5 to 20.0% by weight). , Preferably 1 to 10.0% by weight) is incorporated into the paint, and there is a concern about a decrease in water resistance.

  As described above, compared to conventional powder paints, it is energy-saving and process shortening, and it is a highly useful active energy ray-curable powder paint that can be used for materials that could not be applied until now. The coating film properties such as water resistance cannot be said to be sufficient, and an active energy ray-curable resin composition for powder coatings that satisfies this requirement is required.

JP 50-34036 A Special table 2004-535507 gazette

  The problem to be solved by the present invention is to provide an active energy ray-curable resin composition for powder coatings that can provide a powder coating that can provide a coating film with good smoothness, adhesion and water resistance. It is in.

  As a result of intensive studies to solve the above-described problems, the present inventors have reacted an ethylenically unsaturated group-containing resin and a phosphorus compound in place of a mixture of the ethylenically unsaturated group-containing resin and the phosphorus compound. When the resin composition for an active energy ray-curable powder coating containing a phosphorus compound-modified ethylenically unsaturated group-containing resin obtained in this way is used as an essential component, for example, the phosphorus compound-derived component content is 0.05. It has been found that even if it is as low as ˜1% by weight, a powder coating material that forms not only excellent smoothness and adhesion but also excellent water resistance can be easily provided, and the present invention has been completed. .

  That is, the present invention includes an active energy ray-curable powder coating resin characterized by containing a phosphorus compound-modified ethylenically unsaturated group-containing resin obtained by reacting an ethylenically unsaturated group-containing resin with a phosphorus compound A composition.

  The resin composition for an active energy ray-curable powder coating according to the present invention can provide a powder coating that forms not only excellent smoothness and adhesion but also a coating film excellent in water resistance.

Details of the present invention will be specifically described below.
First, phosphorus used in a phosphorus compound-modified ethylenically unsaturated group-containing resin (hereinafter abbreviated as phosphorus compound-modified ethylenically unsaturated group-containing resin) obtained by reacting an ethylenically unsaturated group-containing resin with a phosphorus compound. The compound will be described.

  The phosphorus compound used for modification of the ethylenically unsaturated group-containing resin refers to a phosphorus-containing compound capable of reacting with the ethylenically unsaturated group-containing resin. For example, phosphoric acid, phosphorous acid, hypophosphorous acid, It is a compound having an organic substituent in a part thereof, and a functional group such as an acidic group or acryloyl group that reacts with a polar group such as a hydroxyl group, an epoxy group, an acryloyl group, or a silanol group in an ethylenically unsaturated group-containing resin. And the like. Furthermore, phosphoric acid ester, phosphorous acid ester, hypophosphorous acid ester and the like may be used.

  Among these phosphorus compounds, phosphate esters and / or phosphites are preferable. In particular, phosphoric acid monoesters, phosphoric acid diesters, acryloyl group-containing phosphoric acid triesters can be easily modified with ethylenically unsaturated group-containing resins, and phosphorus compound-modified ethylenically unsaturated group-containing resins with excellent storage stability. Since it is obtained, it is preferable.

  Examples of phosphoric acid monoesters include monomethyl phosphate, monobutyl phosphate, monooctyl phosphate, mono 2-ethylhexyl phosphate, monoisodecyl phosphate, monolauryl phosphate, modiphenyl phosphate, mononaphthyl phosphate , Monocresyl phosphate, 2-methacryloyloxyalkyl phosphate, and the like.

  Examples of the phosphoric acid diester include dimethyl phosphate, dibutyl phosphate, dioctyl phosphate, di-2-ethylhexyl phosphate, dilauryl phosphate, diphenyl phosphate, dinaphthyl phosphate, dicresyl phosphate, di (nonylphenyl). ) Phosphate, methyl octyl phosphate, cetylphenyl phosphate, diisodecyl phosphate and the like, and particularly preferred is dibutyl phosphate or di-2-ethylhexyl phosphate, which is a normal phosphoric acid dialkyl ester having 4 or more carbon atoms. .

  Examples of the acryloyl group-containing phosphoric acid triester include dialkyl-2- (meth) acryloyloxyethyl phosphate, diphenyl-2- (meth) acryloyloxyethyl phosphate, and the like.

  Examples of phosphorous acid diesters include dimethyl phosphite, dibutyl phosphite, dioctyl phosphite, di-2-ethylhexyl phosphite, dilauryl phosphite, and diphenyl phosphite.

  Next, the ethylenically unsaturated group-containing resin used for the phosphorus compound-modified ethylenically unsaturated group-containing resin will be described.

  The ethylenically unsaturated group-containing resin is a resin having an ethylenically unsaturated double bond in the molecule, for example, an ethylenically unsaturated group-containing polyester resin, an ethylenically unsaturated group-containing epoxy resin, Examples thereof include group-containing epoxy / polyester resins, ethylenically unsaturated group-containing acrylic resins, ethylenically unsaturated group-containing polyurethane resins, and ethylenically unsaturated group-containing polyamide resins.

  Among these ethylenically unsaturated group-containing resins, since a powder coating excellent in smoothness and adhesion can be obtained, an ethylenically unsaturated group-containing polyester resin, an ethylenically unsaturated group-containing epoxy resin, an ethylenically unsaturated group Preferred are epoxy-containing polyester resins and acrylic resins containing ethylenically unsaturated groups.

  The ethylenically unsaturated group-containing resin is solidified and can flow even at a low temperature to form a smooth coating film, and can prevent blocking in the course of storage, and therefore has a softening point temperature of 70 to 120 ° C. Is preferred.

  The number average molecular weight of the ethylenically unsaturated group-containing resin is preferably in the range of 1,000 to 10,000, since it is difficult to block during storage and a powder coating having excellent smoothness is obtained. More preferably, it is 000-7,000.

  In addition, the ethylenically unsaturated group equivalent of the ethylenically unsaturated group-containing resin is preferably in the range of 300 to 5,000 because a powder coating having high coating strength and good adhesion is obtained. A range of ˜3,000 is more preferable.

Hereinafter, details of the following resins preferable as the ethylenically unsaturated group-containing resin will be described.
Ethylenically unsaturated group-containing polyester resin Ethylenically unsaturated group-containing epoxy resin Ethylenically unsaturated group-containing epoxy / polyester resin Ethylenically unsaturated group-containing acrylic resin Ethylenically unsaturated group-containing polyurethane resin

  The ethylenically unsaturated polyester resin is a condensate of a polyol and a polybasic acid or an anhydride thereof, and uses a polyol having an ethylenically unsaturated group and / or a polybasic acid having an ethylenically unsaturated group, It can be obtained by adding a compound having an ethylenically unsaturated group to a polyester resin which is a condensate.

  Various types of polyol can be used as the constituent component of the ethylenically unsaturated polyester resin. Among them, typical examples of the polyol having an ethylenically unsaturated group include allyl ether group-containing compounds. Various compounds can be used as the allyl ether group-containing compound, but typical examples include allyl alcohol, ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, triethylene glycol monoallyl ether, polyethylene. Glycol monoallyl ether, propylene glycol monoallyl ether, dipropylene glycol monoallyl ether, tripropylene glycol monoallyl ether, polypropylene glycol monoallyl ether, 1,2-butylene glycol monoallyl ether, 1,3-butylene glycol monoallyl ether Hexylene glycol monoallyl ether, octylene glycol monoallyl ether, trimethylolpropane monoallyl ether , Trimethylolpropane diallyl ether, glyceryl monoallyl ether, glyceryl diallyl ether, pentaerythritol monoallyl ether, pentaerythritol diallyl ether, pentaerythritol triallyl ether, etc., allyl ether compounds of polyhydric alcohols; And allyl ether compounds having an oxirane ring.

  Typical examples of polyols other than the polyol having an ethylenically unsaturated group include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, and dipropylene. Glycol, tripropylene glycol, polypropylene glycol, neopentyl glycol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 2,2,4-trimethyl-1,3-pentanediol, 3-methyl-1,5-pentanediol, dichloroneopentyl glycol, dibromoneopentylglycol , Hydroxypivalic acid neopentyl glycol ester, cyclohexane dimethylol, 1,4-cyclohexanediol, ethylene oxide or propylene oxide adduct of hydroquinone, ethylene oxide or propylene oxide adduct of trimethylol ethane or trimethylol ethane, trimethylol propane, Ethylene oxide or propylene oxide adduct of trimethylolpropane, glycerin, ethylene oxide or propylene oxide adduct of glycerin, 3-methylpentane-1,3,5-triol, pentaerythritol, spiroglycol, tricyclodecane dimethylol, water Bisphenol A, "New Coal PM-8701L, BA-E4, BA-E8, BA-P6" [Japan Examples thereof include carbonate diols such as bisphenol A ethylene oxide or propylene oxide adducts manufactured by Emulsifier Co., Ltd., or “carbodiol” [product of Toagosei Chemical Co., Ltd.].

  Further, representative examples of polybasic acids having an ethylenically unsaturated group or anhydrides thereof include α, β-unsaturated polybasic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, and chlorinated maleic acid. Examples include acids or their anhydrides.

  Typical examples of the polybasic acid having an ethylenically unsaturated group or a polybasic acid other than the anhydride thereof include oxalic acid, (anhydrous) succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanediate. Acids, aliphatic dibasic acids such as eicosan diacid, terephthalic acid, isophthalic acid, (anhydrous) phthalic acid, aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3 -Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, hexahydrophthalic anhydride and tetrahydrophthalic anhydride. Also included are trivalent or higher carboxylic acids such as (anhydrous) trimellitic acid and (anhydrous) pyromellitic acid, and hydroxycarboxylic acids such as P-oxybenzoic acid and tartaric acid.

  Moreover, unsaturated fatty acids such as linseed oil fatty acid, potato oil fatty acid, safflower oil fatty acid, soybean oil fatty acid, rice bran fatty acid, coconut oil fatty acid, castor oil fatty acid, cottonseed oil fatty acid and tall oil fatty acid may be used in combination.

  Various methods can be applied to the preparation of the polyester resin. For example, an esterification method in which dehydration condensation is performed on a polyol and a polybasic acid, and optionally an ethylenically unsaturated group-containing compound at a high temperature can be used.

  In that case, when using an ethylenically unsaturated group containing compound, it is necessary to adjust reaction temperature so that the polymerization reaction of ethylenically unsaturated groups may be prevented during reaction.

  Furthermore, an ethylenically unsaturated group-containing polyester resin can be obtained by addition-reacting an unsaturated monoglycidyl compound to a polyester resin containing a carboxyl group at the molecular end.

  Examples of the unsaturated monoglycidyl compound include glycidyl esters of unsaturated monobasic acids such as acrylic acid and methacrylic acid such as glycidyl (meth) acrylate; allyl alcohols such as allyl glycidyl ether and methallyl glycidyl ether; Examples thereof include glycidyl ethers of unsaturated alcohols such as methallyl alcohol, and the epoxy group-containing vinyl monomers described below can be exemplified as typical examples.

Next, the ethylenically unsaturated group-containing epoxy resin will be described.
The ethylenically unsaturated group-containing epoxy resin can be obtained, for example, by adding an unsaturated group-containing carboxylic acid compound such as (meth) acrylic acid to the epoxy resin.

  The epoxy resin can be produced using, for example, a compound having a divalent or higher hydroxyl group and epihalohydrin. More specifically, an epoxy resin can be produced by reacting a compound having a divalent or higher hydroxyl group with epihalohydrin in the presence of a catalyst. A so-called one-step process for producing a resin, or a compound having a divalent or higher hydroxyl group and an epihalohydrin are reacted in the presence of a catalyst to obtain a low molecular weight epoxy resin. There is a so-called two-stage method in which an epoxy resin is produced by increasing the molecular weight by reaction.

  Examples of the compound having a divalent or higher hydroxyl group include bisphenols such as bisphenol A, bisphenol F, bisphenol S, bisphenol AD, and bisphenol Z, diphenol acid, 1,5-dioxynaphthalene, and 1,6-di- Examples include naphthols such as oxynaphthalene, dihydroxybenzenes such as hydroquinone, resorcin, and catechol, biphenols, phenol formaldehyde resins, and orthocresol formaldehyde resins, and bisphenols and dihydroxybenzenes are preferably used. It is more preferable to use bisphenols. These can be used alone or in combination of two or more. In addition, among the compounds having a divalent or higher hydroxyl group, those having an aromatic ring are such that the hydrogen on the aromatic ring is substituted at one or more positions by a linear or branched alkyl group or halogen having 1 to 9 carbon atoms. May be.

  As the epihalohydrin, for example, epichlorohydrin or methyl epichlorohydrin is preferably used, and epichlorohydrin is more preferable because of good reactivity.

  Examples of the unsaturated group-containing carboxylic acid compound include various carboxyl group-containing ethylenically unsaturated monomers such as (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid.

Next, the ethylenically unsaturated group-containing epoxy polyester resin will be described.
Here, the ethylenically unsaturated group-containing epoxy-polyester resin can be obtained, for example, by adding an unsaturated group-containing compound to a reaction product of the above-described epoxy resin and the above-described polyester resin.

  For example, when a carboxyl group-containing polyester resin is reacted with an epoxy resin, 1) an epoxy-polyester resin reaction product having a carboxyl group so that the carboxyl group is in excess of the epoxy group, and then the unsaturated monoglycidyl described above An epoxy-polyester resin containing an ethylenically unsaturated group is obtained by addition reaction of the compound. 2) After making an epoxy-polyester resin reaction product having an epoxy group so that the epoxy group is in excess of the carboxyl group, Examples thereof include an addition reaction of a saturated group-containing carboxylic acid compound to obtain an ethylenically unsaturated group-containing epoxy-polyester resin. The ethylenically unsaturated group-containing epoxy-polyester resin has an advantage that adhesion derived from the polyester resin and solvent resistance derived from the epoxy resin can be obtained at the same time.

Next, the ethylenically unsaturated group-containing acrylic resin will be described.
Examples of the ethylenically unsaturated group-containing acrylic resin include 1) an addition reaction of an unsaturated monoglycidyl compound such as an epoxy group-containing vinyl monomer to a carboxyl group-containing acrylic resin, and 2) the unsaturated group described above for an epoxy group-containing acrylic resin. It can be obtained by a method such as addition reaction of a group-containing carboxylic acid compound and 3) addition reaction of an unsaturated group-containing isocyanate compound with a hydroxyl group-containing acrylic resin.

  Functional group-containing acrylic resins such as carboxyl group-containing acrylic resins, epoxy group-containing acrylic resins, hydroxyl group-containing acrylic resins, unsaturated monoglycidyl compounds, unsaturated group-containing carboxylic acid compounds, unsaturated group-containing isocyanate compounds, etc. The addition reaction of the ethylenically unsaturated group-containing compound can usually be carried out in an organic solvent at 40 to 160 ° C. using a catalyst as necessary. The addition reaction can be carried out by melting the functional group-containing acrylic resin, but the former is preferred from the viewpoint of ease of production.

  Subsequently, the unsaturated monoglycidyl compound, the unsaturated group-containing carboxylic acid compound, and the unsaturated group-containing isocyanate compound used in the addition reaction will be described.

  As the unsaturated monoglycidyl compound, epoxy group-containing vinyl monomers are typical, for example, epoxy groups such as glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, glycidyl vinyl ether, allyl glycidyl ether, etc. Containing monomers; (2-oxo-1,3-oxolane) group-containing vinyl monomers such as (meth) acrylic acid (2-oxo-1,3-oxolane) methyl; (meth) acrylic acid 3 , 4-epoxycyclohexyl, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, and the like.

  As the unsaturated group-containing carboxylic acid compound, a carboxyl group-containing vinyl monomer is representative, and examples thereof include monocarboxylic acids such as (meth) acrylic acid, crotonic acid, and isocrotonic acid, maleic acid, fumaric acid, and itaconic acid. , Α, β-unsaturated dicarboxylic acids such as citraconic acid and chlorinated maleic acid or their half esters.

  Examples of the unsaturated group-containing isocyanate compound include those obtained by reacting a part of the isocyanate of a polyvalent isocyanate described later with a hydroxyl group-containing ethylenically unsaturated compound. Representative examples of the hydroxyl group-containing ethylenically unsaturated compound include hydroxyl group-containing vinyl monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate. , 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropyne glycol mono (meth) acrylate, pentaerythritol tri (meth) acrylate, and (meth) acrylate compounds and ring-opening reaction products with ε-caprolactones.

  Next, functional group-containing acrylic resins such as the carboxyl group-containing acrylic resin, epoxy group-containing acrylic resin, and hydroxyl group-containing acrylic resin will be described.

  Various methods can be applied to prepare the functional group-containing acrylic resin. The above-mentioned carboxyl group-containing vinyl monomer, epoxy group-containing vinyl monomer or hydroxyl group-containing vinyl monomer, and other vinyls can be used. A method of copolymerizing a monomer in an organic solvent is recommended because it is the simplest. Various kinds of polymerization initiators and organic solvents can be used. In preparing the carboxyl group-containing acrylic resin, an epoxy group-containing vinyl monomer and a hydroxyl group-containing vinyl monomer are used. In preparing an epoxy group-containing acrylic resin, a carboxyl group-containing vinyl monomer and a hydroxyl group-containing vinyl monomer are used. In the preparation of the hydroxyl group-containing acrylic resin, the epoxy group-containing vinyl monomer and the hydroxyl group-containing vinyl monomer are both handled as other vinyl monomers. However, when the carboxyl group-containing vinyl monomer is used as the other vinyl monomer, the amount used is limited to a small amount because the reaction becomes difficult due to thickening during the preparation of the acrylic resin.

  Typical examples of the other vinyl monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) N-butyl acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate or n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) N-octyl acrylate, isooctyl (meth) acrylate, 2-ethyloctyl (meth) acrylate, dodecyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate (Meth) acrylic acid alkyl esters such as;

(Meth) acrylic acid alkyl carbitols such as benzyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ethyl carbitol (meth) acrylate; Other (meth) acrylic esters such as isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate;

hydrolyzable silyl group-containing monomers such as γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, γ- (meth) acryloyloxypropylmethyldimethoxysilane;

Fluorine-containing α-olefins such as vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, bromotrifluoroethylene, pentafluoropropylene, hexafluoropropylene;

Perfluoroalkyl perfluorovinyl ether such as trifluoromethyl trifluorovinyl ether, pentafluoroethyl trifluorovinyl ether, heptafluoropropyl trifluorovinyl ether or (per) fluoroalkyl vinyl ether (wherein the alkyl group has 1 to 18 carbon atoms) Fluorine-containing vinyl monomers such as fumaric acid, maleic acid, itaconic acid, etc., and monovalent monomers having 1 to 18 carbon atoms, such as various polyvalent carboxyl group-containing monomers represented by Mono- or diesters with alkyl alcohols; aromatic vinyl compounds such as styrene, vinyltoluene, α-methylstyrene, p-tert-butylstyrene;

(Meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, Nn-propyl (meth) acrylamide, N-iso-propyl (meth) acrylamide, Nn-butyl (meth) acrylamide N-iso-butyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N-amyl (meth) acrylamide, N- (meth) acrylamide, N-hexyl (meth) acrylamide, N-heptyl (meth) Acrylamide, N-2-ethylhexyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N -Ethoxymethyl (meth) Kurylamide, Nn-propoxymethyl (meth) acrylamide, N-iso-propoxymethyl (meth) acrylamide, Nn-butoxymethyl (meth) acrylamide, N-iso-butoxymethyl (meth) acrylamide, N-tert- Butoxymethyl (meth) acrylamide, N-amyloxymethyl acrylamide, N-hexyloxy (meth) acrylamide, N-heptyloxymethyl (meth) acrylamide, N-octyloxymethyl (meth) acrylamide, N-2-ethyl-hex Amino group-containing amide vinyl monomers such as siloxymethyl (meth) acrylamide and diacetone (meth) acrylamide;

(Meth) acrylic acid dialkylaminoalkyls such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate; tert-butylaminoethyl (meth) acrylate, tert-butylaminopropyl (meth) acrylate, Aziridinylethyl (meth) acrylate, pyrrolidinylethyl (meth) acrylate, piperidinylethyl (meth) acrylate, (meth) acryloylmorpholine, N-vinyl-2-pyrrolidone, N-vinylcaprolactam, Nitrogen-containing vinyl monomers such as N-vinyloxazoline and (meth) acrylonitrile;

Vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, branched (branched) vinyl aliphatic carboxylate having 9 carbon atoms, carbon number 10 A branched (branched) aliphatic carboxylate, an aliphatic vinyl carboxylate such as a branched (branched) aliphatic carboxylate having 11 carbon atoms, and vinyl stearate;

Vinyl esters of carboxylic acids having a cyclic structure such as vinyl cyclohexanecarboxylate, vinyl methylcyclohexanecarboxylate, vinyl benzoate, vinyl p-tert-butylbenzoate;

Alkyl vinyl ethers such as ethyl vinyl ether, hydroxyethyl vinyl ether, hydroxy n-butyl vinyl ether, hydroxyisobutyl vinyl ether, cyclohexyl vinyl ether, lauryl vinyl ether;

Halogenated olefins other than the above-mentioned fluoroolefins such as vinyl chloride and vinylidene chloride; α-olefins such as ethylene, propylene, and butene-1.

  Illustrative examples of radical polymerization initiators used in the preparation of functional group-containing acrylic resins such as carboxyl group-containing acrylic resins, epoxy group-containing acrylic resins, and hydroxyl group-containing acrylic resins include 2,2′- Azobisisobutyronitrile, 2,2'-azobis-methylbutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobis-cyclohexanecarbonitrile, dimethyl-2,2 '-Azobisisobutyrate, 4,4'-azobis-4-cyanovaleric acid, 2,2'-azobis- (2-amidinopropene) dihydrochloride, 2-tert-butylazo-2-cyanopropane, 2 , 2'-azobis (2-methyl-propionamide) dihydrate, 2,2'-azobis [2- (2-imidazolin-2-yl) propyl Pen], 2,2'-azobis (2,2,4-trimethylpentane) and other azo compounds; benzoyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, potassium persulfate, tert-butylperoxyneodecanoate , Tert-butylperoxypivalate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxyisobutyrate, 1,1-bis-tert-butylperoxy-3,3,5-trimethyl Such as cyclohexane, tert-butyl peroxy-laurate, tert-butyl peroxyisophthalate, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, dicumyl peroxide, di-tert-butyl peroxide Npaokishido like; peroxy ketals; hydroperoxide oxides; dialkyl peroxides such; diacyl peroxides like; peroxy esters; peroxydicarbonates like; hydrogen peroxide and the like.

  Examples of typical organic solvents used in the preparation of the functional group-containing acrylic resin include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, and tert-butanol. Alkyl alcohols such as n-pentanol and isopentanol;

Glycol ethers such as methyl cellosolve, ethyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether;

Aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; Exon Aromatic Naphtha No. Mixed hydrocarbons containing aromatic hydrocarbons such as 2 (made by Exxon USA); aliphatic hydrocarbons such as n-pentane, n-hexane and n-octane; Isopar C, Isopar E, Exol DSP 100/140 , Exol D30 (all manufactured by Exxon, USA), IP Solvent 1016 [Idemitsu Petrochemical Co., Ltd.] and other mixed hydrocarbons containing aliphatic hydrocarbons; cyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, etc. Alicyclic hydrocarbons;

Ethers such as tetrahydrofuran, dioxane, diisopropyl ether, di-n-butyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate And esters such as n-amyl acetate, isoamyl acetate, hexyl acetate, ethyl propionate and butyl propionate. A small amount of water can be used in combination with these organic solvents.

  Furthermore, in the preparation of the acrylic resin, a chain transfer agent can be used as required. Typical examples among them include dodecyl mercaptan, lauryl mercaptan, thioglycolic acid ester, mercaptoethanol. , Α-methylstyrene dimer, and the like.

  Examples of the method for solidifying the functional group-containing acrylic resin solution thus obtained include 1) removing the solvent used in the reaction under reduced pressure, and 2) using the spray drying method for the reaction. For example, the solvent may be evaporated and scattered.

Next, the ethylenically unsaturated group-containing polyurethane resin will be described.
Examples of the ethylenically unsaturated group-containing polyurethane resin include 1) reacting a polyol compound such as polyether polyol, polyester polyol, alkylene polyol, polycarbonate polyol, etc., preferably a polyol compound having a molecular weight of 100 to 5,000, and a polyvalent isocyanate compound. 2) adding an unsaturated group-containing hydroxy compound, 2) reacting the above-described polyol compound, polyvalent isocyanate compound, and unsaturated group-containing hydroxy compound simultaneously, 3) polyvalent isocyanate compound, and unsaturated group It can be obtained by a method of reacting the containing hydroxy compound.

  Examples of typical polyvalent isocyanate compounds include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylene diisocyanate, (tetramethylxylene diisocyanate), diphenylmethane-4,4. A diisocyanate compound having an aromatic ring such as diisocyanate, 3-methyl-diphenylmethane diisocyanate or 1,5-naphthalene diisocyanate; a diisocyanate compound having an aliphatic ring such as dicyclohexylmethane diisocyanate or isophorone diisocyanate;

Aliphatic diisocyanate compounds such as hexamethylene diisocyanate and lysine diisocyanate; compounds obtained by hydrogenating the above-mentioned various aromatic ring-containing diisocyanate compounds, such as hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane-4,4-diisocyanate, etc. A bifunctional diisocyanate compound obtained by reacting the above diisocyanate compound with water; a trifunctional isocyanate compound such as 2-isocyanatoethyl-2,6-diisocyanatohexanoate; Examples include multimers obtained by converting a diisocyanate compound to isocyanurate.

  Examples of the unsaturated group-containing hydroxy compound include the aforementioned unsaturated group-containing polyols and the aforementioned hydroxyl group-containing (meth) acrylic acid esters.

  The phosphorus compound-modified ethylenically unsaturated group-containing resin used in the present invention may be any resin obtained by reacting an ethylenically unsaturated group-containing resin with a phosphorus compound. For example, the phosphorus compound-derived component content is 0.00. A powder coating material that forms a coating film that not only has excellent smoothness and adhesion, but also has excellent water resistance, even if the phosphorus compound-derived component content is low. Since the characteristics of the present invention that can be provided can be fully utilized, the phosphorus compound-derived component content is preferably in the range of 0.05 to 1% by weight, and preferably 0.1 to 0.45% by weight. Is more preferable. Although the content of the phosphorus compound-derived component may exceed 1% by weight, an improvement in the effect of easily providing a powder coating material that forms a coating film excellent in smoothness, adhesion, and water resistance can be expected. Therefore, it is preferably 10% by weight or less.

  Examples of the modification method of the ethylenically unsaturated group-containing resin in which the ethylenically unsaturated group-containing resin and the phosphorus compound are reacted include, for example: 2) A method of charging and reacting a compound in the process of producing an ethylenically unsaturated group-containing resin and a phosphorus compound during the production process of the ethylenically unsaturated group-containing resin. 3) An ethylenically unsaturated solution or in a molten state. Examples thereof include a method in which a phosphorus compound is charged and reacted in a saturated group-containing resin.

  Among the above modification methods, a method in which a phosphorus compound is charged and reacted in an ethylenically unsaturated group-containing resin in a solution or in a molten state is preferable from the viewpoint of ease of production. As such modification conditions, a phosphorus compound-modified ethylenically unsaturated group-containing resin that is sufficiently modified with a phosphorus compound and has a high effect of improving water resistance is obtained, so that the ethylenically unsaturated group-containing resin and the phosphorus compound are 1200 to 200. A method of reacting at a temperature of 1 ° C. for 1 to 10 hours is preferable because it can be modified with phosphorus without impairing the resin properties and characteristics of the ethylenically unsaturated group-containing resin.

  As the phosphorus compound-modified ethylenically unsaturated group-containing resin used in the present invention, the total amount is preferably obtained by reacting an ethylenically unsaturated group-containing resin with a phosphorus compound. An unmodified ethylenically unsaturated group-containing resin was mixed with a phosphorus compound-modified ethylenically unsaturated group-containing resin having a high content of phosphorus compound-derived components obtained by reacting a group-containing resin with a relatively large amount of a phosphorus compound. It may be a thing. In this case, the dilution ratio with the unmodified ethylenically unsaturated group-containing resin is preferably 5 times by weight or less, and more preferably 3 times by weight or less.

  Moreover, the said phosphorus compound modified ethylenically unsaturated group containing resin may use together a polymerizable unsaturated oligomer depending on the case in the range which does not impair the storage stability of a powder coating material.

  Typical examples of the polymerizable unsaturated oligomer include neopentyl glycol di (meth) acrylate, EO-modified bisphenol A di (meth) acrylate, EO-modified phosphate di (meth) acrylate, triethylene glycol di ( (Meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, hexamethylenediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetrapropylene glycol Bifunctional (meth) acrylates such as di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate; trimethylol proppant (Meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, PO-modified glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate And trifunctional (meth) acrylates. Of course, each of the polymerizable unsaturated oligomers may be used alone or in combination of two or more.

  When curing the phosphorus compound-modified ethylenically unsaturated group-containing resin, various kinds of active energy rays such as α rays, β rays, γ rays, neutron rays, X rays, electron rays, etc. Visible light and the like can be used as well as ionizing radiation and ultraviolet rays. However, when curing by irradiation with ultraviolet rays or visible light, it is necessary to add a photopolymerization initiator in advance.

  Various photopolymerization initiators can be used. Among them, typical examples include 4-phenoxydichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenyl. Propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy 2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2 Acetophenones such as -propyl) ketone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2,2-dimethoxy-2-phenylacetophenone;

Benzoins such as benzoin, benzoin methyl ether, benzoin isoethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl Benzophenones such as diphenyl sulfide and 3,3′-dimethyl-4-methoxybenzophenone;

Thioxanthones such as thioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone; 4,4 Anthraquinones such as' -dimethylaminobenzophenone (also known as Miheraz ketone), 4,4'-diethylaminobenzophenone, α-acyloxime ester, benzyl, methylbenzoylformate (“Bicure 55”), 2-ethylanthraquinone;

Acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide (“Lucirin TPO”); 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone [Nippon Yushi Co., Ltd. "BTTB"], acrylated benzophenone, and the like.

  Typical examples of photopolymerization initiators for visible light curing include camphorquinone, 3-ketocoumarin, anthraquinone, α-naphthyl, acenaphthene, benzyl, p, p′-dimethoxybenzyl, p, p′-dichloro. Dicarbonyl photopolymerization initiators such as benzyl; thioxanthone photopolymerization initiators such as 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dimethylthioxanthone; 2,4,6-trimethyl Acylphosphine oxide photopolymerization initiators such as benzoyldiphenylphosphine oxide ("Lucirin TPO"), 2,6-dimethylbenzoyldiphenylphosphine oxide, benzoyldiethoxyphosphine oxide; α-acyloxime ester ("Cantercure PDO"), etc. Is mentioned.

  These photopolymerization initiators may be used singly or in combination of two or more. However, the amount of the photopolymerization initiator is 0. 0 parts by weight with respect to 100 parts by weight of the phosphorus compound-modified ethylenically unsaturated group-containing resin. 1 to 10 parts by weight is appropriate.

  As a so-called sensitizer used in order to increase the curing efficiency in combination with such a photopolymerization initiator, various sensitizers can be used and applied. First, as amines, triethylamine, triethanolamine, methyldiethanolamine, triisopropanolamine, n-butylamine, N-methyldiethanolamine, diethylaminoethyl (meth) acrylate, 2-dimethylaminoethylbenzoic acid, 4-dimethylaminobenzoate Ethyl acetate, ethyl 4-dimethylaminobenzoate (n-butoxy), isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, polymerizable tertiary amine ("Ubekryl P-104, P-105 or P-115 "), ureas, sulfur-containing Compounds, phosphorus-containing compounds, chlorine-containing compounds, nitriles, and other nitrogen-containing compounds.

  For the active energy ray-curable resin composition for powder coatings of the present invention, a polymerization inhibitor can be used as necessary for the purpose of preventing gelation during storage. As such a polymerization inhibitor, various types can be used, but among them, typical ones are exemplified by 3,5-bismutual butyl-4-hydroxytoluene, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether (methoquinone). ), Para-tert-butyl catechol and the like.

  The method for adding the above-described photopolymerization initiator, sensitizer, and polymerization inhibitor is not particularly limited, but it is recommended that the resin is produced or paint is blended.

  In addition, for example, a solution in which a powder coating material containing the resin composition for an active energy ray-curable powder coating of the present invention, a photopolymerization initiator, a sensitizer, and a polymerization inhibitor is dissolved in a solvent is prepared. The method of spray-drying can also be mentioned. At that time, the photopolymerization initiator, the sensitizer, the polymerization inhibitor and the like are preferably completely dissolved in the organic solvent. If completely dissolved, phosphorus compound-modified ethylenically unsaturated group-containing resin, photopolymerization initiator, sensitizer, polymerization prohibited compared to mixing by melt kneading as is done by conventional production methods This is because a powder coating comprising a resin composition for powder coating, in which the agent is more uniformly mixed and the physical properties of the coating and the appearance of the coating, particularly the sharpness of the coating, is significantly improved can be obtained.

  The thus obtained powder coating comprising the resin composition for active energy ray-curable powder coating of the present invention can be coated by various methods such as electrostatic spraying, triboelectric charging, and fluid immersion. Let the paint substrate be painted. Next, the coated product thus obtained can be heated and melted at a temperature higher than the melting temperature of the powder coating material in an air circulating furnace or by radiant heat such as infrared rays, and then cured by irradiation with active energy rays. it can.

  A powder coating comprising the resin composition for an active energy ray-curable powder coating according to the present invention is used as a top coat in a coating film forming method for forming a single-layer or multi-layer coating on an object to be coated. Can be suitably used, and has particularly excellent smoothness. The active energy ray-curable resin composition for powder coatings of the present invention may be blended with a surface conditioner, leveling agent, antifoaming agent, anti-repelling agent, thixotropy imparting agent, sensitizer, etc., if necessary. Needless to say, it is also possible to use pigments and dyes within a range that does not cause curing inhibition.

  The powder coating composition comprising the resin composition for an active energy ray-curable powder coating composition of the present invention thus obtained can be used for coating woodwork products such as plywood and furniture, or for various substrates including metal coating. Suitable for painting on materials.

  Next, the present invention will be described more specifically with reference examples, examples, and comparative examples, but it is needless to say that the present invention is not limited to these illustrative examples. In the following, unless otherwise specified, “parts” means “parts by weight”.

Reference Example 1 [Preparation of phosphorus compound-modified ethylenically unsaturated group-containing polyester resin]
A reactor equipped with a stirrer, a thermometer, a rectifying column and a nitrogen gas inlet is charged with 440 parts of neopentyl glycol, 550 parts of terephthalic acid and 0.5 part of dibutyltin oxide while stirring in a nitrogen atmosphere. The temperature was raised to 240 ° C. in 5 hours. After continuing the dehydration condensation reaction at 240 ° C. and confirming that the acid value was 10 mg KOH / g or less, the temperature was lowered to 180 ° C., 140 parts of isophthalic acid and 20 parts of adipic acid were added, and again to 240 ° C. The temperature was increased over 5 hours. The dehydration condensation reaction was continued as it was at 240 ° C. to obtain a polyester resin melt having an acid value of 34 mgKOH / g. Subsequently, 919 parts of the melted polyester resin was cooled to 140 ° C. while stirring, 2 parts of triphenylphosphine and 0.5 part of hydroquinone monomethyl ether were added, and 77 parts of glycidyl methacrylate was heated. Carefully added in 4 portions over 30 minutes. After 3 hours, 4 parts of dibutyl phosphate was added and cooled after 2 hours to obtain the target phosphorus compound-modified ethylenically unsaturated group-containing polyester resin (A-1). The softening point was 93 ° C and the acid value was 3.7 mgKOH / g.

Reference example 2 (same as above)
The reaction was carried out in the same manner as in Reference Example 1 except that the amount of dibutyl phosphate used was changed to 2 parts, thereby obtaining the intended phosphorus compound-modified ethylenically unsaturated polyester resin (A-2). The softening point was 94 ° C and the acid value was 2.9 mgKOH / g.

Reference example 3 (same as above)
A reaction was carried out in the same manner as in Reference Example 1 except that the amount of dibutyl phosphate used was changed to 9 parts to obtain the intended phosphorus compound-modified ethylenically unsaturated polyester resin (A-3). The softening point was 90 ° C. and the acid value was 4.5 mgKOH / g.

Reference example 4 (same as above)
The reaction was conducted in the same manner as in Reference Example 1 except that the temperature at which dibutyl phosphate was added was 110 ° C. and the reaction time after addition was changed to 40 minutes, and the target phosphorus compound-modified ethylenically unsaturated polyester resin (A- 4) was obtained. The softening point was 97 ° C and the acid value was 4.2 mgKOH / g.

Reference example 5 (same as above)
The reaction was conducted in the same manner as in Reference Example 1 except that the amount of dibutyl phosphate used was changed to 2 parts.
The reaction was carried out in the same manner as in Reference Example 1 except that 4 parts of diethyl hydrogen phosphite was used instead of 4 parts of dibutyl phosphate to obtain the target phosphorus compound-modified ethylenically unsaturated polyester resin (A-5). The softening point was 95 ° C and the acid value was 4.3 mgKOH / g.

Reference Example 6 [Preparation of phosphorus compound-modified ethylenically unsaturated group-containing epoxy resin]
A reactor equipped with a stirrer, thermometer, rectification column and nitrogen gas inlet was charged with 1000 parts of Epicron AM-040-P (Epichlorohydrin bisphenol A type epoxy resin manufactured by Dainippon Ink & Chemicals, Inc.) in a nitrogen atmosphere. The temperature was raised in the interior, and after confirmation of melting of the epoxy resin, the temperature was raised to 120 ° C. while stirring. After adding 3 parts of triphenylphosphine and 0.8 part of hydroquinone monomethyl ether, 83 parts of methacrylic acid was added in 4 portions over 30 minutes while paying attention to heat generation. After 3 hours, the temperature was raised to 130 ° C., 4.4 parts of dibutyl phosphate was added, and the mixture was cooled after 2 hours to obtain the target phosphorus compound-modified ethylenically unsaturated epoxy resin (A-6). The softening point was 90 ° C and the acid value was 1.7 mgKOH / g.

Reference Example 7 [Preparation of Phosphorus Compound-Modified Ethylenically Unsaturated Epoxy / Polyester Resin]
A reactor equipped with a stirrer, a thermometer, a rectifying column and a nitrogen gas inlet is charged with 420 parts of neopentyl glycol, 550 parts of terephthalic acid and 0.5 part of dibutyltin oxide while stirring in a nitrogen atmosphere. The temperature was raised to 240 ° C. in 5 hours. The dehydration condensation reaction was continued at 240 ° C., and after confirming that the acid value was 10 mg KOH / g or less, the temperature was lowered to 180 ° C., 120 parts of isophthalic acid and 38 parts of adipic acid were added, and again to 240 ° C. The temperature was increased over 5 hours. The dehydration condensation reaction was continued as it was at 240 ° C. to obtain a polyester resin melt having an acid value of 55 mgKOH / g. Subsequently, 677 parts of this melted polyester resin was charged, the temperature was lowered to 130 ° C. while stirring, 2 parts of triphenylphosphine was added, and then Epicron 850 [Epichlorohydrin bisphenol A type manufactured by Dainippon Ink & Chemicals, Inc.] Epoxy resin] 262 parts were added. After confirming that the acid value was 1 mg KOH / g or less, 0.5 part of hydroquinone monomethyl ether was added, and then 57 parts of methacrylic acid was added in 4 portions over 30 minutes while paying attention to heat generation. After 5 hours, 4 parts of dibutyl phosphate was added, and after 2 hours, it was confirmed that the acid value was 5 mgKOH / g or less, and the mixture was cooled and the desired phosphorus compound-modified ethylenically unsaturated epoxy-polyester resin (A-7 ) The softening point was 95 ° C. and the acid value was 1.2 mgKOH / g.

Reference Example 8 [Preparation of phosphorus compound-modified ethylenically unsaturated acrylic resin]
In a reaction vessel equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen inlet, 500 parts of toluene was placed and heated to 110 ° C. To this, 160 parts of glycidyl methacrylate, 308 parts of n-butyl methacrylate, 2 parts of diphenyl-2- (meth) acryloyloxyethyl phosphate, 280 parts of methyl methacrylate and 250 parts of styrene were started as monomers. A mixture consisting of 60 parts of tert-butyl peroxy 2-ethylhexanoate as an agent was added dropwise over 6 hours. After completion of the dropping, the polymerization reaction was continued by maintaining the same temperature for another 10 hours. Next, after adding 0.5 part of hydroquinone monomethyl ether and 3 parts of triphenylphosphine, 77 parts of acrylic acid was added, 5 hours later, 2.3 parts of dibutyl phosphate was added, and the acid value was 3 mg KOH after 2 hours. / G or less was confirmed. Furthermore, it hold | maintained under 140 degreeC and 20 Torr of pressure reduction, and the solid phosphorus compound modified | denatured ethylenically unsaturated acrylic resin (A-8) was obtained by removing toluene.

Reference Example 9 [Preparation of polyester resin containing ethylenic unsaturation for comparison]
Except that the addition of dibutyl phosphate was omitted, the reaction was conducted in the same manner as in Reference Example 1 to obtain an ethylenically unsaturated polyester resin (a-1). The softening point was 94 ° C and the acid value was 3.2 mgKOH / g.

Examples 1-8 and Comparative Examples 1-3
The phosphorus compound-modified ethylenically unsaturated group-containing polyester resins (A-1) to (A-5) obtained in Reference Examples 1 to 5 and the phosphorus compound-modified ethylenically unsaturated group-containing epoxy resin obtained in Reference Example 6 (A-6), the phosphorus compound-modified ethylenically unsaturated group-containing epoxy polyester resin (A-7) obtained in Reference Example 7, and the phosphorus compound-modified ethylenically unsaturated group-containing acrylic resin obtained in Reference Example 8 (A-8) and each of the comparative ethylenically unsaturated group-containing polyester resins (a-1) obtained in Reference Example 9, a photopolymerization initiator, benzoin, and powder mate 570FL (Troy Chemicals) 8) active energy ray-curable resin composition for powder coating of the present invention and comparative active energy ray curing Three types of resin compositions for mold powder coatings were obtained, and each of the obtained active energy ray-curable resin compositions for powder coatings was used using “MP-2015” (a biaxial kneader manufactured by APV). After being melt-kneaded at a barrel temperature of 80 to 120 ° C., finely pulverized, and further classified with a 140-mesh wire mesh, various powder coatings (P-1) to (P-8) and comparative controls Powder coatings (p-1) to (p-3) were obtained.

  Subsequently, using the obtained powder coating materials (P-1) to (P-8) and the comparative powder coating materials (p-1) to (p-3), the following coating film forming method was used. After producing various coating films, coating film performance tests (smoothness, adhesion, solvent resistance, water resistance) were performed on each coating film.

  As a base material used as a coating object, a 0.8 mm (thickness) × 70 mm × 150 mm zinc phosphate treated steel plate was used.

  The powder coating materials (P-1) to (P-8) and the comparative powder coating materials (p-1) to (p-3) were each placed on a substrate so that the film thickness was about 70 μm. After the electropowder coating was performed, baking was performed at 150 ° C. for 5 minutes, and the mixture was melted, and then irradiated with an ultraviolet ray of 3000 mj / cm 2 with a high-pressure mercury lamp to form a coating film made of a powder coating (hereinafter referred to as “the powder coating”). An article having a powder coating film) was obtained.

  The powder coating film on the coating material thus obtained was evaluated for coating film performance. The results are summarized in Tables 3 to 4.

In addition, the point of evaluation determination is as follows.
・ Smoothness: PCI [(powder coating institute), non-profit organization established in 1981 to promote the spread of powder coatings representing the powder coating industry in North America, and exchanges in the powder coating industry ( Homepage: http://www.powdercoating.org/home.htm))
The smoothness of the powder coating film was determined using a standard plate for visual judgment. The standard plate is No. 1-No. There are 10 sheets up to 10. 1-No. The smoothness becomes good step by step. It was visually judged which standard plate the smoothness of the powder coating film on the obtained object corresponds to.
No. 1: poor smoothness 10: Good smoothness

・ Adhesiveness: Cut the powder coating with a cutter knife on the grid at intervals of 2 mm, create 25 grids, peel off with cellophane tape, and count the number of grids remaining on the coating It was.

-Solvent resistance: After rubbing the powder coating film 30 times with absorbent cotton containing xylene, it was visually judged according to the following criteria.
A: No abnormality is observed at all.
○: A slight decrease in gloss is recognized.
(Triangle | delta): A considerable gloss fall is recognized.
X: The coating film was destroyed by the erosion by the solvent.

Water resistance: An article having a powder coating film was immersed in warm water at 40 ° C. for 5 days, and the adhesion test was performed 1 hour after the pulling up and the determination was made.

<< Legs of Tables 1 and 2 >>
* 1) Irgacure 184: Photoinitiator manufactured by Ciba Geigy.
* 2) Irgacure 2959: Photoinitiator manufactured by Ciba Geigy.
* 3) Benzoin: A reagent manufactured by Tokyo Chemical Industry Co., Ltd.
* 4) Powder Mate 570FL: a surface conditioner manufactured by Troy Chemicals.

Claims (6)

A resin composition for an active energy ray-curable powder coating, comprising a phosphorus compound-modified ethylenically unsaturated group-containing resin obtained by reacting an ethylenically unsaturated group-containing resin with a phosphorus compound. The phosphorus compound-modified ethylenically unsaturated group-containing resin is a phosphorus compound-modified ethylenically unsaturated group-containing polyester resin, a phosphorus compound-modified ethylenically unsaturated group-containing epoxy resin, a phosphorus compound-modified ethylenically unsaturated group-containing acrylic resin and phosphorus 2. The resin for active energy ray-curable powder coating material according to claim 1, wherein the resin is one or more phosphorus compound-modified ethylenically unsaturated group-containing resins selected from the group consisting of compound-modified ethylenically unsaturated group-containing epoxy polyester resins. Composition. The phosphorus compound-modified ethylenically unsaturated group-containing resin is obtained by reacting an ethylenically unsaturated group-containing resin and a phosphorus compound at a temperature of 120 to 200 ° C. for 1 to 10 hours. The resin composition for active energy ray-curable powder coatings according to claim 1. The resin composition for an active energy ray-curable powder coating according to claim 1, wherein the phosphorus compound is a phosphate ester and / or a phosphite ester. The phosphorus compound-modified ethylenically unsaturated group-containing resin is a phosphorus compound-modified ethylenically unsaturated group-containing resin having a phosphorus compound-derived component content of 0.05 to 1% by weight. The resin composition for active energy ray hardening-type powder coating materials of description. The phosphorus compound-modified ethylenically unsaturated group-containing resin is a phosphorus compound-modified ethylenically unsaturated group-containing resin having a phosphorus compound-derived component content of 0.10 to 0.45% by weight. The active energy ray-curable resin composition for powder coatings according to the item.