WO2007049488A1 - Composition for coating ceramics - Google Patents

Abstract

Disclosed is a composition for coating ceramics which has remarkably higher curability than conventional coating compositions and is capable of forming a crosslinking-cured coating film which has excellent hardness, chemical resistance and boiling resistance, while being excellent in adhesion to a ceramic surface. Specifically disclosed is a composition for coating ceramics which contains (A) an acrylic resin having a cationically polymerizable functional group at an end and/or in a side chain, (B) a coupling agent, and (C) a cationic photopolymerization initiator having a function of generating an acid when irradiated with an active energy ray.

Description

 Specification

 Ceramic coating composition

 Technical field

 TECHNICAL FIELD [0001] The present invention relates to a coating composition capable of forming a crosslinked cured film exhibiting excellent adhesion, hardness, chemical resistance and boiling resistance on the surface of ceramics such as glass and ceramics by irradiation with active energy rays. .

 Background art

 [0002] As a coating composition used for coating of ceramic products such as glass, that is, for coating and printing, it is required to have strong adhesion to the ceramic substrate. Is used. General-purpose ceramic coating compositions, such as ceramic inks, are baked at a high temperature of around 600 ° C after printing or coating on a substrate, and the ink pattern, display, or coating is fused to the ceramic surface. In addition, it provides a strong adhesion to the substrate. However, with this method, a large amount of energy is required for the baking process, production efficiency is low from the viewpoint of the work environment, installation of a drying furnace and installation of volatile component treatment equipment are required. It has disadvantages such as high costs and high costs. Also, certain ceramic coating compositions contain heavy metals such as lead, cadmium, chromium, and manganese as glass component fusion agents, and require organic volatile components (VOC) as solvents. It is also desirable from an environmental point of view!

 [0003] In general, an ultraviolet (UV) curable coating composition is cured in a short time by irradiating active energy rays such as ultraviolet rays, so that a baking process at a high temperature can be omitted. Furthermore, UV curable coating compositions can be prepared with little or no VOC or other non-aqueous solvents, which is desirable from an environmental, work efficiency, and capital investment perspective. It can be said that. However, when UV curable coating compositions are applied to ceramic product coatings or decorations, it is difficult to achieve adhesion that is equivalent to or acceptable as a ceramic coating composition that requires baking. Met.

[0004] As a method for improving the adhesion to a ceramic substrate, bisphenol A epoxy resin is used. There has been proposed a UV curable composition in which an organic functional silane, a cationic photopolymerization initiator, and a fluorinated surface active agent are blended in a paint as a main component (Japanese Patent Publication No. 2000-507281). However, because this composition has an extremely slow UV curing rate, it is necessary to heat the substrate as a pretreatment, or to heat and cure after light irradiation. The problem is that it is difficult to coat with high-speed coating, especially when using a multi-color printing machine, which is the greatest merit of the system.

 [0005] Further, JP-A-2-289611 discloses a photocrosslinking composition comprising an acrylic resin having an alicyclic epoxy group and a photocationic polymerization initiator as essential components. However, although this composition has higher curability than the conventional light-power thione composition, its interaction with the ceramic substrate (adhesion) is weak, so that it is made of ceramics such as moisture resistance and boiling resistance. The properties required in the environment where the product is used are inferior, and in some cases, the substrate film also has problems such as peeling of the coating.

 Disclosure of the invention

 [0006] The object of the present invention is to have excellent adhesion to the ceramic surface, which is remarkably higher in curability than the above conventional coating composition, and excellent in hardness, chemical resistance and boiling resistance. An object of the present invention is to provide a ceramic coating composition capable of forming a crosslinked cured film.

 [0007] As a result of intensive studies based on the above problems, the present inventors have found that an acrylic resin having a cation polymerizable functional group at the terminal, Z, or side chain in constructing a ceramic coating composition. In order to develop the present invention, the inventors have found that the above-mentioned object can be achieved by blending a coupling agent with a composition containing a coagulant and a photothion polymerization initiator having an acid generation function by irradiation with active energy rays. It came.

 That is, the present invention generates (A) an acrylic resin having a cationic polymerizable functional group at the terminal and Z or side chain, (B) a coupling agent, and (C) an acid upon irradiation with active energy rays. The present invention relates to a ceramic coating composition containing a functional light thione polymerization initiator.

[0009] As the coupling agent (B), a point force silane coupling agent that improves the affinity with the ceramic substrate is preferred, and a point force polymerization that further strengthens the adhesion. Those having functional functional groups may be more specific acrylic resin (A) or ceramic groups. Point power excellent in affinity with the material Particularly preferred is one having an epoxy group and z or oxetal group.

 [0010] The cationic polymerizable functional group possessed by the acrylic resin (A) also includes an epoxy group and

Preferred is Z or an oxetanyl group.

 [0011] Further, the weight average molecular weight of the acrylic resin (A) is preferably 1,000-100,000 because it is excellent in coating (coating and printing) workability! /. .

 [0012] Further, it is preferable that the cationic polymerizable functional group equivalent of the acrylic resin (A) is 100 to 1,500 from the point of rapid curing!

 BEST MODE FOR CARRYING OUT THE INVENTION

 [0013] The ceramic coating composition of the present invention is a coating composition that is cured by causing a cationic polymerization reaction upon irradiation with active energy rays, and (A) a cationically polymerizable functional group at the terminal and Z or side chain. And (B) a coupling agent, and (C) a photothion polymerization initiator having a function of generating an acid upon irradiation with active energy rays.

 [0014] Each component will be specifically described below.

 [0015] (A) Acrylic resin having a cation polymerizable functional group at its terminal and Z or side chain

 The acrylic resin (A) is a polymer or copolymer having an acrylic structural unit and having at least one cationic polymerizable group in the molecule.

 [0016] The cationically polymerizable functional group may be any functional group capable of causing cationic polymerization, such as an epoxy group (including glycidyl group), an oxetal group, a vinyl ether group, and a probe ether group. Examples thereof include cyclic carbonate groups such as bicycloorthoesters and spiroorthocarbonates. Of these, the epoxy group, oxetal group, butyl ether group, etc., which have a high cationic polymerization reaction rate, are preferred, and the epoxy group and oxetanyl group are preferred because of their good affinity with ceramic substrates. Good. The acrylic resin (A) may contain two or more of these functional groups in one molecule, or two or more different acrylic resins having different cationic polymerizable functional groups may be used in combination.

[0017] As a method for introducing a cationically polymerizable functional group into acrylic resin, a conventionally known method, For example, a method of polymerizing or copolymerizing a monomer having a cationic polymerizable functional group (polymerization reaction method), a method of introducing a compound having a cationic polymerizable functional group into a part of an acrylic polymer by post-reaction (polymer reaction) Law).

 In the polymerization reaction method, a cationic polymerizable group-containing polymerizable unsaturated monomer (hereinafter referred to as “cation polymerizable unsaturated monomer”) can be polymerized alone, or, if necessary, a cationic polymerizable unsaturated monomer. Other polymerizable unsaturated monomers (hereinafter referred to as “other unsaturated monomers”) that can be copolymerized with cation polymerizable unsaturated monomers are copolymerized.

 [0019] In the case of a homopolymer, the cationic polymerizable unsaturated monomer is required to be an acrylic monomer. In the case of a copolymer, at least one of the cationic polymerizable unsaturated monomer or the other unsaturated monomer is used. May be an acrylic monomer.

[0020] Among the cationically polymerizable unsaturated monomers, representative examples of the acrylic monomer include, for example, 3, 4 epoxycyclohexenoremethinoleatalylate, 3, 4 epoxycyclohexenoremethymethacrylate, 3,4-epoxy. Cyclohexylmethylated poly-strength prolatataton attalate, 3,4-epoxycyclohexylmethylated polystreptathrate metatalylate, 2,3 Epoxycyclopentenino rare talylate, 2,3 Epoxycyclopentenoylmethacrylate, Glycidyl talylate , Glycidyl metatalylate, methyl daricidyl atylate, methyl daricidyl metatalylate, 2- (1,2 epoxy-1,4,7-methanoperhydroindene-5 (6) -yl) oxetyl atari 2- (1,2 epoxy 4,7—methanoperhydro indene 5 (6) —yl Oxetyl metatalylate, 5,6—Epoxy 1,4,7-Methanopel hydroindene 1—Yel 1 atylate, 5,6 Epoxy 1,4—Methanoperhydroindene 2—Yelume Epoxy group-containing talis such as tartrate, 1,2 epoxy 4,7-methanoperhydroindene 5-yl acrylate, 1,2 epoxy 4,7-methanoperhydroindene -1-5-methacrylate 3—Methyl-3-oxetal methyl acrylate, 3-methyl-3-oxetal methyl methacrylate, 3-ethyl 3-ethyl etherate, 3-ethyl 3-methyl ether Talylate, 2- (3-Ethyl-3-oxeta-lmethoxy) ethyl atylate, 2- (3-Ethyl-3-oxeta-lmethoxy) ethyl metatalylate, 4- (3-Ethyl 3-oxy) Data - Rumeto carboxymethyl) butyl Atari rate, 4 i (3 Echiru 3 Okiseta - Rumetokishi) Buchirumetatari 4——Ethyl-3-oxeta-lmethoxymethyl) benzyl acrylate, 4—

Oxetal group-containing acrylates such as (3-ethylyl-3-oxeta-lmethoxymethyl) benzylmetatalylate; 2-biloxetyl acrylate, 2-bi-loxychetyl methacrylate, 4-vinyloxybutyl attaly 4-vinyloxybutyl methacrylate, 2-methyl-4-bi-hydroxybutyl acrylate, 2-methyl-4-bi-butyl butyl methacrylate, 4-bi-oxymethylcyclohexyl methyl acrylate, 2- (2 , 1-Loxyethoxy) ethyl atylate, 2- (2, -Bi-oxyethoxy) ethyl metatalylate, 4 Vinyloxymethylcyclohexyl methyl metatalylate, 4-vinyloxymethyl benzyl acrylate , 4-bi-roxymethylbenzyl metatalylate, 4-bi-roxybenzyl acrylate, 4-bi-roxy Butyl ether group-containing acrylates such as benzyl methacrylate, polyethylene glycol monobutyl ether, polyethylene glycol monobutyl methacrylate, polypropylene glycol monobutyl ether, and polypropylene glycol monobutyl methacrylate Can be raised. Of these, 3,4-epoxycyclohexylmethyl attalate, 3,4 epoxy cyclohexylmethyl methacrylate, glycidyl acrylate, and glycidyl methacrylate.

It is preferably used from the viewpoint of fast curability. This cation polymerizable functional group-containing acrylic monomer may be polymerized alone or in combination of two or more. Further, the following cationic polymerizable functional group-containing non-acrylic monomer and Z or a cationic polymerizable functional group described later may be copolymerized with one or more of acrylic monomers and non-acrylic monomers. .

Typical examples of the non-acrylic monomer among the cationic polymerizable unsaturated monomers include, for example, 2-aryloxymethyloxysilane, 2- (4-arylphenyloxymethyl) oxysilane, 2- (4-arylcyclohexylmethoxy). Methyl) oxylan, 2- (4-bioxyphenoxymethyl) oxylan, 2- (4-Buhlphenoxymethyl) oxylan, 4-Buhl 1 Dioxyhexene 1, 2 Epoxide, 3, 4 Epoxy 1 Epoxy group-containing monomers such as butene, 1,2 epoxy 5—hexene, 1,2 epoxy 7 otaten, 1,2 epoxy 9-decene; 3-alkyloxymethyl-3-ethyloxetane, 3- (4-arylphenoloxymethyl) 3-Ethyloxetane, 3- (4-Arylcyclohexylmethoxymethyl) 3) -Ethyloxetane, 3-Ethyloxan 3- (4 Bi-Roxyphenoxymethyl) oxetane, 3-Ethyl 3 -— (4-Bulfenoxymethyl) oxetane, 3 -— (3-But-Mouth Oxetal group-containing monomers such as xylmethyl) -3-ethyloxycetane, 3-ethyl-3- (5-hexoxymethyl) oxetane; 1-bi-l- 4-loxybenzene

And butyl ether group-containing monomers such as 1 bul-4 bis-loxymethylcyclohexane. Of these, 2- (4 butylphenoxymethyl) oxysilane and 4 butyl 1-cyclohexene 1,2-epoxide are preferably used from the viewpoint of rapid curing. These non-acrylic monomers are preferably copolymerized with acrylic monomers that are not used in homopolymerization.

 [0022] As the other unsaturated monomer copolymerizable with the cationically polymerizable unsaturated monomer, the obtained acrylic resin (A) is appropriately copolymerized as required according to the intended performance and the like. However, when the cationically polymerizable unsaturated monomer is a non-acrylic monomer, it is necessary to copolymerize the acrylic monomer.

[0023] Representative examples of the acrylic monomer having no cationically polymerizable functional group include, for example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n—, is o or tert butyl Atalylate, n-, iso or tert Butyl metatalylate, Hexyl Atalylate, Hexyl Metatalylate, Octyl Atalylate, Octyl Metatalylate, Lauryl Atalylate, Lauryl Metatalylate, Stearyl Atalylate, Stearyl Metatalylate C1-C24 alkyl esters of acrylic acid or methacrylic acid; Benzylic esters of acrylic acid or methacrylic acid such as benzyl atylate and benzyl metatalylate; Phenoxetyl acrylate, Phenoxetyl metatalylate Such C7-12 phenoxyalkyl esters of acrylic acid or methacrylic acid; C6-24 cycloalkyl esters of acrylic acid or methacrylic acid such as cyclohexyl acrylate and cyclohexyl methacrylate 2 hydroxyethyl acrylate, 2-hydroxy ethynole methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate C1-C8 hydroxyalkyl esters of acrylic acid or methacrylic acid; methoxy-diethylene glycol acrylate, methoxy-diethylene glycol meta Acrylic or methacrylic acid such as talylate, ethoxydiethylene glycol acrylate, ethoxydiethylene glycol methacrylate, methoxy-polyethylene glycol acrylate, methoxy-polyethylene glycol methacrylate, ethoxy polyethylene glycol acrylate, ethoxypolyethylene glycol methacrylate Alkoxypolyethylene glycol esters having 1 to 10 carbon atoms and 1 to 8 carbon atoms of ethylene glycol chain of acid; methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, ethoxydipropylene glycol acrylate, ethoxydi Propylene glycol methacrylate, methoxy monopolypropylene glycol acrylate, methoxy monopolypropyl Alkyl polypropylene glycol esters with 1 to 10 carbon atoms and 1 to 8 carbon atoms in propylene glycol chains of acrylic acid or methacrylic acid such as pyrene glycol metatalylate, ethoxy-polypropylene glycol acrylate, ethoxy polypropylene glycol metatalylate, etc. Phenoxy diethylene glycol acrylate, phenoxy diethylene glycolate methanolate, nonylphenol ethylene ethylene glycolate tallate, noninophenol ethylene glycolate methanolate, crezo monoethylene ethylene glycolate talate, crezo monotale Ethylene glycol nolemethacrylate, phenoxy polyethylene glycol acrylate, phenoxy polyethylene glycol methacrylate Number of ethylene glycol chains of acrylic or methacrylic acid, such as norenoethylene polyethylene glycolenotalylate, nonylphenolene polyethylene glycolenolemethacrylate, cresol monolere polyethylene glycolenore talate, crezo monoreethylene glycol methacrylate 1-10 and C6-C16 aryloxypolyethylene glycol esters; phenoxydipropylene glycol acrylate, phenoxydipropylene glycol metatalylate, nonylphenolate propyleneglycolanolate tallate, nonylphenolate propyleneglycol Noremetatalylate, Cresole Norepropylene Glycol Nore Tarate, Creso Monourere Propylene Glycol Nore Metatalate , Phenoxy Polypropylene Glycol Atallate, Phenoxy Polypropylene Glycol Metatalylate, Nonyl Phenol Polypropylene Glycol Atylate, Norphenol-Polypropylene Glycole Methanolate, Creso Monore Polypropylene Glyconore Taleate, Creso Monore Polypropylene Glycol Metatalylate Propylene of acrylic acid or methacrylic acid such as Examples thereof include aryloxypolypropylene glycol esters having 1 to 10 glycol chains and 6 to 16 carbon atoms; one or more of acrylic acid, methacrylic acid and the like. Others: isobornyl acrylate, isobutyl methacrylate, tetrahydrofluol thiolate, tetrahydro fluorethyl methacrylate, trifluoroethyl acrylate, trifluoroethyl noremetallate, perfunoreoctinorealate, perfnore For example, oloctinoremethacrylate. Of these monomers, methyl methacrylate is particularly suitable because of its high glass transition temperature and good heat resistance.

[0024] Representative examples of non-acrylic monomers having no cationically polymerizable functional group include, for example, a, β-ethylenically unsaturated carboxylic acids such as maleic acid, itaconic acid, and crotonic acid; acrylamide, methacrylamide, and methyl Acrylamide or methacrylamide or derivatives thereof such as acrylamide, Νethylmethacrylamide, diacetoneacrylamide, Ν-methylolacrylamide, Ν-methylolmethacrylamide, Ν-methoxymethylacrylamide, Ν-butoxymethylacrylamide; styrene, butyltoluene, _α -Aromatic butyl monomers such as methyl styrene; butyl propionate, butyl acetate, talari-tolyl, meta-tali-tolyl, burbivalate, beroba monomer (trade name: branched chemicals manufactured by Shell Chemical Co., Ltd.) (Bulyl ester of fatty acid), Silaplane FM0711, Silaplane FM0721, Silaplane FM0725 (all of which are polydimethylsiloxane macromonomers having a methacryloyl group at the end, manufactured by Chisso Corporation). One or more can be listed. Of these monomers, styrene is particularly suitable because of its high glass transition temperature and good heat resistance.

 [0025] The acrylic resin (A) is a solution polymerization of a cationically polymerizable unsaturated monomer and, if necessary, a monomer component having other unsaturated monomer power, for example, in the presence or absence of a radical polymerization initiator. It can be obtained by (co) polymerization by a known polymerization method such as bulk polymerization, emulsion polymerization or suspension polymerization.

 [0026] Acrylic resin having a cationically polymerizable functional group at a specific end and Z or side chain

As (A), a homopolymer such as 3,4-epoxycyclohexenoremethinoremethacrylate (ECMMA), glycidylmethacrylate HGMA), 3-ethyl-3-oxeta-methylmethacrylate HOXE MA), etc .; ECMMAZGMA copolymer, ECMMA / OXEMA copolymer Copolymer, GMAZOXEMA copolymer, ECMMAZ methyl methacrylate (MMA) copolymer, ECMMAZMMAZn-butyl acrylate (n-BA) copolymer, ECMMA / MMAZ lauryl acrylate (LA) copolymer, ECMMAZMMAZ cyclohexylene Tacrylate (CMMA) copolymer, ECMMAZMMAZ2-hydroxyethyl methacrylate (HEMA) copolymer, ECMMAZMMAZ methoxydiethylene glycolanolate methacrylate (MDEMA) copolymer, ECMMAZMMAZ isopropanol methacrylate (I BXMA) copolymer Copolymer, ECMMAZMMAZ Styrene (St) Copolymer, ECMMA / St Copolymer, ECMMAZStZn— BA Copolymer, ECMMAZStZLA Copolymer, EC MMAZStZCMMA Copolymer, ECMMAZStZHEMA Copolymer, ECMMA / StZMDEMA Copolymer, ECMMAZStZlBXMA Copolymer Polymer, GMA / MMA / LA copolymer, GMAZMMAZCMMA copolymer, GMAZMMAZHEMA copolymer, GMAZMMAZMDEMA copolymer, GMAZMMAZIBXMA copolymer, G

MAZMMAZSt copolymer, GMAZSt copolymer, GMAZStZn— BA copolymer, GMAZStZLA copolymer, GMAZStZCMMA copolymer, GMA / St / HEM A copolymer, GMAZStZMDEMA copolymer, GMAZStZlBXMA copolymer, E CMMAZGMAZMMAZLA copolymer Polymer, ECMMA / GMA / MMA / CMMA copolymer, ECMMAZGMAZMMAZHEMA copolymer, ECMMA / GMA /

MMAZMDEMA copolymer, ECMMAZGMAZMMAZIBXMA copolymer, E

CMMAZGMAZMMAZSt copolymer, ECMMAZGMAZSt copolymer, ECM MAZGMAZStZn— BA copolymer, ECMMAZGMAZStZLA copolymer, EC MMAZGMAZStZCMMA copolymer, ECMMAZGMAZStZHEMA copolymer, ECMMAZGMAZSt, MDEMA copolymer, ECMMA / GMA / St / The ability to include a copolymer containing one or more cationically polymerizable unsaturated monomers such as a polymer is not limited to these.

Examples of the acrylic resin (A) containing two or more different cationically polymerizable groups in one molecule include, for example, bullcyclohexene dioxide, limonene dioxide, 3, 4-epoxycyclohexyl methyl acrylate or 3 , 4-Epoxycyclohexylmethyl methacrylate and other alicyclic epoxy group-containing ethylenically unsaturated monomers and glycidyl acrylate Containing an alicyclic epoxy group and a glycidyl group obtained by polymerizing a glycidyl group-containing ethylenically unsaturated monomer such as glycidyl methacrylate and other polymerizable unsaturated monomers as necessary. A polymer etc. can be mention | raise | lifted.

 [0028] In the acrylic resin (A), the cation polymerizable functional group equivalent is preferably 100 or more, more preferably 200 or more from the viewpoint of relaxation of the shrinkage of the cation-cured coating film, and fast curing. From the viewpoint of safety, it is preferably 1,500 or less, more preferably 1,000 or less.

 [0029] In the coating composition of the present invention, the acrylic resin (A) plays a role of a binder, and the coating property of the composition, the affinity with the ceramic substrate, and the cationic curing property. For example, the weight average molecular weight of acrylic resin (A) should be 1,000 or more, especially 2,000 or more, and 100,000 or less, especially 50,000 or less. It is.

 [0030] (B) Coupling agent

 The coupling agent which is component (B) of the composition of the present invention increases the affinity of the acrylic resin (A) to the ceramic substrate, and further provides strong adhesion between the ceramic substrate and the cationic coating. Can be expressed.

 [0031] The coupling agent (B) used in the present invention may be any compound that fulfills these functions. Examples of the coupling agent include conventionally known organometallic compounds, such as silane cups. Examples thereof include a ring agent, a titanium coupling agent, an aluminum coupling agent, and a zirconium coupling agent. Of these, silane coupling agents are preferred because they are particularly effective in improving adhesion to ceramic substrates.

 [0032] The silane coupling agent is preferably one having two or more different reactive groups in one molecule. One of the preferred reactive groups is a hydrolyzable alkoxysilane group that can be chemically bonded to the ceramic substrate by hydrolysis after the hydrolysis, and the other is a reactive group that can be chemically bonded to the hardened film. (For example, an amino group, a vinyl group, a hydroxyl group, an isocyanate group, a mercapto group, an alitaroyl group, a methacryloyl group, an oxetanyl group, an alicyclic or aliphatic chain epoxy group, a butyl ether group, etc.).

[0033] Specifically, for example, an amino group-containing alkoxysilane, a bur group-containing alkoxysilane, a hydroxyl group-containing alkoxysilane, an isocyanate group-containing alkoxysilane, a mercapto group-containing alkoxysilane, an taliloyl group or a methacryloyl group-containing alkoxysilane. Hydrolyzable silane coupling agents such as oxetal group-containing alkoxysilanes, alicyclic epoxy group-containing alkoxysilanes, aliphatic epoxy group-containing alkoxysilanes, butyl ether group-containing alkoxysilanes, and partial hydrolysates thereof. can give

. Two or more of these coupling agents may be used simultaneously.

[0034] Among these hydrolyzable silane coupling agents, the compatibility with the acrylic resin (A) is good, and the chemical resin reacts with the acrylic resin (A) when irradiated with active energy rays. In particular, a silane coupling agent containing a cationically polymerizable group such as an oxetal group or an epoxy group is preferable because it has a strong adhesion to a ceramic substrate containing glass.

 [0035] Examples of the silane coupling agent containing a cationically polymerizable group include those represented by the formula (1):

R'SiX (OR ² ) (1)

 P 3-p

(Wherein R ¹ is a cation polymerizable group such as an oxetal group, an alicyclic epoxy group or an aliphatic epoxy group, X is a monovalent hydrocarbon group which may be substituted with a halogen atom, and R ² is Examples thereof include an alkyl group having 1 to 4 carbon atoms, p is 0 or 1), an alkoxysilane containing at least one cationic polymerizable group, and partial hydrolysates thereof.

[0036] X in the formula (1) is, for example, an alkyl group having about 1 to 12 carbon atoms such as methyl, ethyl, propyl, butyl, amyl, hexyl, octyl, decyl, dodecyl; alkenyl groups such as bur and allyl ; Aryl groups such as phenyl, tolyl and xylyl; aralkyl groups such as 13 phenyl, β-phenylpropyl; halogen atoms such as fluorine and chlorine such as γ-chloropropyl, 3, 3, 3-trifluoropropyl; And substituted hydrocarbon groups. Of these, methyl is preferred because of its high hydrolyzability in the sol-gel reaction. Examples of R ¹ include an oxetal group, an alicyclic epoxy group, an aliphatic epoxy group, and a benzyl ether group. Among them, an alicyclic epoxy group, an aliphatic epoxy group, and particularly an alicyclic epoxy group. However, point power with good cationic polymerizability is also suitable. Examples of R ² include alkyl groups having about 1 to 4 carbon atoms such as methyl, ethyl, propyl, and butyl. Among them, methyl is preferable because of its high hydrolyzability in the sol-gel reaction. In addition, ρ is 0 or 1, and among them, 0 is a point power with high sol-gel reactivity. Specific examples of the cationically polymerizable group-containing alkoxysilane represented by the formula (1) include 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylene. Norethinoresin methoxysilane, 3-glycidoxypropylpropyldimethoxysilane, 3-glycidoxypropylphenyldimethoxysilane, 3-xysilane, 3 glycidoxypropinoletriethoxysilane, 3 glycidoxypropyltripropoxysilane, 4- Glycidoxybutyltrimethoxysilane, 5-glycidoxyhexyltriethoxysilane, 2- (3, 4 epoxycyclohexenole) ethinoresin methinole methoxysilane, 2-((3, 4 epoxycyclohexenole) ethynole Methinoresimethoxysilane, 2— (3, 4 Epoxy Chlorohexenole) ethinoreethinoresimethoxymethoxysilane, 2- (3,4 epoxy cyclohexylenole) ethenorepropinoresimethoxymethoxysilane, 2- (3,4 epoxycyclohexenole) ethenolefe ninoresimethoxysilane, 2- (3, 4 epoxycyclohexenole) ethynolecyclohexinoresin methoxysilane, 2-— (3, 4 epoxycyclohexenole) ethynoletrimethoxysilane, 2-— (3,4 epoxy cyclohexylenore) ethinoretriethoxysilane, 2— (3,4 epoxycyclohexyl) ethyltripropoxysilane, 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, 4 (3,4-epoxycyclohexyleno) butynoletrimethoxysilane, etc. Epoxy group-containing silane coupling agent; 3 (3-ethyl 3-methoxy-propyl) dimethyldimethyl Sisilane, 3- (3-Ethyl-3-oxeta-methoxy) propylmethyldimethoxysilane, 3- (3-Ethyl-3-oxeta-methoxy) propylethyldimethoxysilane, 3- (3-Ethyl-3-oxeta-methoxy) Propylpropyldimethoxysilane, 3— (3-Ethyl-3-oxeta-lmethoxy) propylphenyldimethoxysilane, 3 -— (3-Ethyl-3-oxeta-lmethoxy) propyl cyclohexyldimethoxysilane, 3-— (3 —Ethyl 3-oxeta-lmethoxy) propyltrimethoxysilane, 3— (3-Ethyl-1-oxeta-lmethoxy) propyltriethoxysilane, 3 -— (3-Ethyl-3-oxetanylmethoxy) propyltripropoxysilane, 4— (3-Ethyl-3-Oxetanylmethoxy) butyltrimethoxysilane, 5 -— (3-Ethyl 3-Oxetanylmethoxy) Hexyl group-containing silane coupling agents such as hexyltriethoxysilane; 3-Binyloxypropyldimethylmethoxysilane, 3-Vinyloxypropylmethyldimethoxysila 3-vinyloxypropylethyldimethoxysilane, 3-vinyloxypropylpropyl dimethoxysilane, 3-vinyloxypropylphenyldimethoxysilane, 3-vinyloxypropyl pinolecyclohexenoresimethoxysilane, 3-vinyloxypropyltrimethoxy Bulether group-containing silane coupling agents such as silane, 3-vinyloxypropyltriethoxysilane, 3-vinyloxypropyltripropoxysilane, 4-vinyloxybutyltrimethoxysilane, 5-vinyloxyhexyltriethoxysilane; Examples include hydrolysates. Among them, 3 glycidoxypropyltrimethoxysilane, 2- (3,4 epoxy cyclohexyl) ethylmethoxysilane, or its partial hydrolyzate power Cationic polymerization

In view of good sol-gel reactivity, it is preferable.

[0038] Further, as the silane coupling agent represented by the formula (1), two or more kinds of cationically polymerizable group-containing alkoxysilanes or partial hydrolysates thereof may be used in combination without impairing performance. A coupling agent other than the cationically polymerizable group-containing alkoxysilane may be used in combination.

[0039] Examples of silane coupling agents other than cationically polymerizable group-containing alkoxysilanes include N-3- (aminoethyl) 3-aminopropyltriethoxysilane and N-3- (aminoethyl) 3-amino. Propyltrimethoxysilane, 3-Aminopropyltriethoxysilane, 3-Aminopropyltrimethoxysilane, 3-Aminopropylmethyljetoxysilane, 3-Aminopropylmethyldimethoxysilane, 3-Aminopropylphenyljetoxy Silane, 2-amino-1-methylethyltriethoxysilane, N-methyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-butyl 3-aminopropylmethylethoxysilane, 3 —Ureidopropyltrimethoxysilane, 3-mercaptopropyltrimethoate Sisilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3 —Methacryloxypropyltriethoxysilane, 3-Atalyloxypropyltrimethoxysilane, 3-Atalyloxypropyltriethoxysilane, N Polyoxyethylenepropyltrimethoxysilane, N Polyoxyethylenepropyltriethoxysilane, N Polyoxypropylene Propyltrimethoxysilane, N Polyoxypropylenepropyltriethoxysilane, 3 —Hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 4-hydroxybutyltrimethoxysilane, 4-hydroxybutyltriethoxysilane, 3-phenoxypropyltrimethoxysilane, 3-phenoxypropyltriethoxysilane, etc. Is given.

[0040] As coupling agents other than silane coupling agents, for example, isopropyl triisostearoyl titanate, isopropyl tridodecyl benzene sulfo titanate, isopropyl tri (dioctyl pyrophosphate) titanate, tetraisopropyl bis (diotyl phosphate) Phyto) titanate, tetraoctylbis (ditridecylphosphite) titanate, tetra (2,2-diallyloxymethyl 1-butyl) monobis (ditridecylphosphite) titanate, bis (dioctylpyrophosphate) alkoxy acetate titanate, bis (di-O Chi le pyrophosphate) titanate coupling agents such as ethylene titanate; aluminum - © beam isopropylate, mono _sec - butoxy aluminum diisopropylate, aluminum se c-butylate, aluminum ethylate, acetate alkoxy aluminum diisopropylate, ethyl acetate acetate aluminum diisopropylate, aluminum tris (ethyl acetate acetate), alkyl acetate acetate aluminum diisopropylate, aluminum- Aluminum coupling agents such as um monocetylacetonate bis (ethylacetoacetate), aluminum tris (acetylacetonate), cyclic aluminum oxide isopropylate; tetrapropylzirconate, tetrabutylzirconate, tetrakis (acetylacetonate) ) Zirconium, monobutoxy tris (acetyl acetonate) zirconium, dibutoxy bis (acetinoreacetonate) dinoleconium, tributoxyse Noreacetonate zirconium, tetra (ethenoreacetinoleacetate) dinorecum, monobutoxytris (ethenoreacetinoleacetate) dinorecoum, dibutoxybis (ethenoreacetinoreacetate) zirconium, tetrakis (ethyl) Ratatonate) Zirconium, Bis (bisacetylacetonate) Bis (ethylacetylacetonate) Zirconium, Monoacetylacetonate Tris (Ethylacetylacetonate) Zirconium, Monobutoxy monoacetylethylate bis (Ethylacetyl acetate) Zirconium coupling agents such as zirconium can be exemplified.

[0041] The blending amount of the coupling agent (B) is 1 part by mass or more with respect to 100 parts by mass of the acrylic resin (A). Above, preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and 100 parts by mass or less, preferably 50 parts by mass or less, more preferably 30 parts by mass or less. If the amount of the coupling agent (B) is too small, the adhesion to the ceramic substrate tends to be lowered, and if too much, the cationic polymerization reactivity (curability) tends to be lowered.

[0042] (C) Photoactive thione polymerization initiator having a function of generating an acid upon irradiation with an active energy ray The photoactive thione polymerization initiator (C) used in the present invention is an acid generated by irradiation with an active energy ray. A cationically polymerizable component that is generated and contained in the coating composition (such as the above talyl resin (A), a coupling agent having a cationically polymerizable functional group, or a cationically polymerizable compound (D) described later). One or more compounds that act on the cationically polymerizable functional group (for example, epoxy group or oxetanyl group) to initiate cationic polymerization. Examples of active energy rays include ultraviolet rays, electron beams, and radiation (j8 rays, γ rays).

 [0043] As such a light-powered thione polymerization initiator (C), in general, sulfo-um salt, iodine salt, meta-octane compound, benzoin tosylate, etc. are known, and many compounds Is commercially available. In the present invention, such a commercially available photopower thione polymerization initiator can be used.

 [0044] Commercially available products include, for example, Cyracure UVI-6970, Cyracure UVI-6974, Cyracure UVI-6990 (all of which are manufactured by Union Carbite, Inc., US trade name); Irgacure 264 (manufactured by Ciba Geigy Co., Ltd.). CIT-1682 (manufactured by Nippon Soda Co., Ltd., trade name) can be given as a representative example.

 [0045] The compounding amount of the light-power thione polymerization initiator (C) is 0.1 parts by mass or more, preferably 1 with respect to 100 parts by mass of the cationically polymerizable component contained in the coating composition of the present invention. The amount is preferably not less than 3 parts by mass, more preferably not less than 3 parts by mass, not more than 20 parts by mass, preferably not more than 15 parts by mass, and more preferably not more than 10 parts by mass. If the photopower thione polymerization initiator (C) is too small, the polymerization will not start or the polymerization rate tends to be slow, and if it is too large, it tends to precipitate (separate) from the composition.

[0046] In the ceramic coating composition of the present invention, in addition to the essential components (A), (Β) and (C), other than the above (Α) to (Β), if necessary. A cationically polymerizable compound of Sensitizers, non-cationic polymerizable components, colored pigments to improve design, pigments such as extender pigments, pigment dispersants, fluidity modifiers, antifoaming to improve paint workability Agents, leveling agents, light stabilizers, antioxidants, waxes, solvents, etc.

[0047] Hereinafter, some of these optional components will be specifically described.

 [0048] (D) Other cationically polymerizable compounds other than the above (A) to (B)

 In the present invention, if necessary, a cationically polymerizable compound (D) other than the above (A) to (B) may be added for the purpose of adjusting the viscosity of the coating composition and improving the physical properties of the cured coating film. Can be used together. Examples of the other cationically polymerizable compound (D) include the following compounds (D1), (D2), (D3), (D4), (D5) and the like.

 [0049] (D1) Epoxy compound (other than acrylic resin (A) and coupling agent (B))

 An epoxy compound having one or more epoxy groups in one molecule and having an epoxy equivalent of 70 to 5,000, preferably 80 to 3,000 can be used suitably.

 [0050] By blending the epoxy compound (D1), the viscosity of the coating composition can be adjusted, so that the coating property can be improved, and the hardness of the coating film can be further increased by cationic polymerization. .

 [0051] The epoxy group of this epoxy compound (D1) may be an alicyclic epoxy group having a cyclohexene oxide or cyclopentene oxide structure; an aliphatic epoxy group such as a glycidyl group may be shifted 1 Both epoxy groups may be mixed in the molecule! /.

[0052] Examples of the epoxy compound containing an alicyclic epoxy group include dicyclopentadiene dioxide, (3,4 epoxycyclohexyl) methyl-3,4-epoxycyclohexanecarboxylate, bis ( 2,3 epoxycyclopentyl) ether, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, (3,4 epoxy-6-methylcyclohexyl) methyl-3 4 Epoxy-6-methylcyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) acetal, bis (3,4-epoxycyclohexyl) ether of ethylene glycol, 3,4-epoxycyclohexane of ethylene glycol carboxylic acid In addition to diesters, commercially available products such as Epolide GT300 (Trifunctional alicyclic epoxy resin manufactured by Daicel Chemical Industries, Ltd., trade name) and Epolide GT400 (Tetrafunctional alicyclic manufactured by Daicel Chemical Industries, Ltd.) Epoxy resin (trade name), EHPE (polyfunctional alicyclic epoxy resin manufactured by Daicel Chemical Industries, Ltd., trade name), and the like.

[0053] Examples of the epoxy compound containing an aliphatic epoxy group include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and 1,4 butanediol diglycidyl. Ether, neopentyl glycol diglycidyl ether, 1,6 hexanediol diglycidyl ether, glycerin diglycidyl ether, diglycerin tetraglycidinoate ethere, trimethylololepropane triglycidino ether, spiroglycol diglycidyl ether 2, 6 Diglycidyl ether, Sonorbitonore Polyglycidino oleate, Triglycidino lysocyanurate, Bisphenol A Jill ether, butadiene dioxide, diglycidyl phthalate, bis-phenol type epoxy榭脂, _epsilon - force Purorataton modified bisphenol type epoxy榭脂, phenol novolak type epoxy榭脂, cresol one novolac-type epoxy榭脂Nadogaa up It is done.

 [0054] (D2) Bicycloorthoester compound

 For example, 1-phenyl 4-ethyl 2, 6, 7 trioxabicyclo [2, 2, 2] -octane, 1-ethyl 4-hydroxymethyl 1, 6, 6, trioxabicyclo [2, 2, 2] Can give octane.

[0055] By blending the bicycloorthoester compound (D2), the viscosity of the coating composition can be adjusted, so that the coating property can be improved, and the hardness of the coating film can be further increased by cationic polymerization. Can be increased.

[0056] (D3) Spiro orthocarbonate compound

 For example, 1, 5, 7, 11-tetraoxaspiro [5, 5] -undecane, 3, 9-dibenz leu 1, 5, 7, 11-tetraoxaspiro [5, 5] -undecane, 1, 4, 6 Trioxaspirone [4, 4] -nonane, 2-methynole 1, 4, 6 Trioxaspirone [4, 4] -nonane, 1

, 4, 6-trioxaspiro [4, 5] -decane. [0057] By blending the spiro orthocarbonate compound (D3), the viscosity of the coating composition can be adjusted, so that the coating property can be improved, and the hardness of the coating film can be further increased by cationic polymerization. Can be increased.

 [0058] (D4) Oxetane compound

 Formula (D4):

 [0059] [Chemical 1]

 A compound containing at least one oxetane ring represented by 0— in the molecule, and examples thereof include compounds represented by the following formulas (D4-1) to (D4-4).

 Formula (D4-1):

[0060] [Chemical 2]

(In the formula, R ³ is an alkyl group having 1 to 6 carbon atoms; R ⁴ may be substituted with a hydrogen atom or a hydroxyl group, or may be substituted with an alkyl group having 1 to 6 carbon atoms or a hydroxyl group; An alkoxyalkyl group having 2 to 10 carbon atoms, an aryl group having 7 to 12 carbon atoms which may be substituted with a hydroxyl group, an aralkyl group having 7 to 12 carbon atoms, or a hydroxyl group which may be substituted with a hydroxyl group Or an oxetane compound represented by 7-7 carbon aryloxyalkyl group.

 Formula (D4-2):

[0061] [Chemical 3]

(Wherein R ³ is the same as in formula (D4-1)). Formula (D4-3)

[0062] [Chemical 4]

(D 4-3}

(Wherein R ³ is the same as formula (D4-1); R ⁵ is an alkylene group having 1 to 6 carbon atoms, a cycloalkylene group, a phenylene group, a xylylene group, or a polyalkylene group having 4 to 30 carbon atoms) An oxetane compound represented by

 Formula (D4-4):

[0063] [Chemical 5]

 Three

 (Wherein R or the same as in formula (D4-1); is a hydrogen atom or methyl).

 [0064] Representative examples of the oxetane compound represented by the above formula (D4-1) include 3-ethyl-3-methoxymethyloxetane, 3-ethyl-3-ethoxymethyloxetane, 3-ethyl-3- Butoxymethyloxetane, 3-Ethyl-3-hexyloxymethyloxetane, 3-Methyl 3-Hydroxymethyloxetane, 3-Ethyl 3-Hydroxymethyloxetane, 3-Ethyl-3 aralkyloxymethyl Xetane, 3-ethyl-3- (2, -hydroxichetil) oxymethyloxetane, 3-ethyl-3- (2'-hydroxy 3'-phenoxypropyl) oxymethyloxetane, 3-ethyl-3- (2, -hydroxy-3 , Monobutoxypropyl) oxymethyloxetane, 3 ethyl 3— [2 '— (2 “-ethoxyethyl) oxymethyl] oxetane, 3 ethyl 3— (2 ′ butoxych ) Okishimechiruo Kisetan, 3- Echiru 3 base Nji Ruo carboxymethyl O xenon Tan, 3- Echiru 3- (4 tert-butylbenzyl O carboxymethyl) Okisetan and the like.

[0065] As a typical example of the oxetane compound represented by the formula (D4-2), a compound in which V and both R ^{3 in} the formula (D4-2) are both methyl or ethyl Can give. [0066] As a typical example of the oxetane compound represented by the formula (D4-3), in the formula (D4-3), both R ³ are ethyl, R ⁵ is methylene, ethylene. , Propylene, butylene, cyclohexylene, phenylene, xylylene, poly (ethyleneoxy), poly (propyleneoxy), and the like.

 [0067] As representative examples of the oxetane compound represented by the formula (D4-4), 3-methyl-3-oxeta-methylmethyl acrylate, 3-methyl-3-oxeta-methyl methacrylate, 3 Examples include ethyl 3-oxetanyl methyl atallylate, 3-ethyl 3-oxetanyl methyl methacrylate, and the like.

 [0068] (D5) Probe ether compound

 For example, 1- (2-probe-mouth xymethylenoethoxy) propene, 1- (2,2 bis-probe-methyl-butoxy) propene, 1-methyl-3- (1 methyl—1 -Probe-Kuchichtil) 7-Oxabicyclo [4. 1. 0] heptane.

 [0069] By blending the probe ether compound (D5), the viscosity of the coating composition can be adjusted, so that the coating property can be improved, and the hardness of the coating film can be improved by cationic polymerization. It can be further increased.

 [0070] As these cationically polymerizable compounds (D), epoxy compounds (D1) and oxetane compounds (D4) are suitable, and among them epoxy compounds (D1), especially alicyclic compounds. A compound having an epoxy group is suitable for point strength with good coating properties such as high viscosity and curability with high compatibility and dispersibility with acrylic resin (A).

 [0071] In the composition of the present invention, the component having cationic polymerizability may consist only of acrylic resin (A). However, when other cationically polymerizable compound (D) is blended, In general, acrylic resin (A) Z Other cation polymerizable compound (D) compounding ratio (mass) force 10Z90 ~ 90 ZlO, preferably in the range of 20 ~ 80 ~ 80 ~ 20 It is suitable because it is easy to adjust the properties.

 [0072] (ii) Sensitizer

The sensitizer is blended for the purpose of further improving the cationic polymerization reactivity (curability) by active energy rays such as ultraviolet rays. [0073] Specific examples include pyrene, perylene, atalidine orange, thixanthone, 2-chlorothiaxanthone, benzoflavine, 9, 10 bis (2-ethylhexyloxy) anthracene, 9, 10 bis (n— Dodecyloxy) anthracene, 2 ethyl 9, 10-jetoxyanthracene, and the like.

 [0074] The blending amount of the sensitizer is 100 parts by mass with respect to 100 parts by mass of the acrylic resin (A) (when the cationic polymerizable compound (D) is used in combination) (A) and (D)) Usually, it is used within the range of 10 parts by mass or less, preferably 5 parts by mass or less. In addition, when a silane coupling agent having a cationic polymerizable functional group such as an epoxy group or a oxetal group is used as the coupling agent (B), the coupling agent (B) has an acrylic resin (A) and a cationic polymerizable functional group. Total of silane coupling agent (B) (when using cation-polymerizable compound (D) in combination, total of (A), (B) and (D)) 10 parts by mass or less, preferably 100 parts by mass Is used within the range of 5 parts by mass or less. If the amount is too large, precipitation (separation) from the composition may occur.

 [0075] (F) Component having no cationic polymerizability

The soot component may be blended for the purpose of adjusting the viscosity of the composition and improving the physical properties and adhesion of the resulting cured product.

 Specific examples include, for example, acrylic resins other than the acrylic resin (A) having cationic polymerization properties, polyester resins, rosin-modified phenol resins, rosin-modified alkyd resins, and ketone resins. The blending amount is within a range not inhibiting the cationic polymerization reactivity (curability) of the composition.

 [0077] (G) Pigment

 The pigment may be a colored pigment or an extender pigment. None of these are particularly limited, and pigments commonly used in the coating and printing fields can be used.

[0078] Examples of the coloring pigment include white pigments such as titanium white and zinc white; blue pigments such as cyanine blue and indanthrene blue; green pigments such as cyanine green and patina; organic reds such as azo and quinacridone Inorganic red pigments such as Bengala; organic yellow pigments such as benzimidazoline, isoindolinone, isoindoline, and quinophthalone; inorganic yellow pigments such as titanium yellow and yellow lead; carbon black, graphite, pine smoke Black pigments such as; aluminum powder, copper powder, nickel powder, acid-titanium-coated my powder, iron oxide-coated my powder, Examples include glitter pigments such as glitter graphite.

 [0079] Examples of extender pigments include titanium oxide, silicon oxide, calcium carbonate, calcium sulfate, barium sulfate, and alumina white.

 [0080] The pigment is preferably a neutral or acidic pigment because it does not inhibit the cationic polymerization reaction. Even if the pigment surface is treated neutral or acidic.

 [0081] In the ceramic coating composition of the present invention, a solvent is basically unnecessary, but an appropriate amount may be used in some cases in order to adjust the viscosity of the composition and improve coating properties.

 [0082] The ceramic coating composition of the present invention may be in the form of a printing ink or a coating for coating. As a method for preparing the coating composition, a conventional method for preparing a UV curable coating composition can be applied. For example, it can be prepared by mixing each component, heating as necessary (for example, about 50 ° C), and stirring with a stirrer such as a dissolver, for example, for about 30 minutes. . In the case of dispersing pigment (coloring, constitution), disperser such as bead mill or attritor is used to mix acrylic resin (A) with pigment and other components as required, for example, known pigment dispersant. Can be used for dispersion mixing. A ceramic coating composition in which the pigment is dispersed can be obtained by mixing the obtained pigment dispersion with the remaining components as necessary.

 [0083] Examples of the ceramic substrate to which the ceramic coating composition of the present invention is applied include glass, ceramics, porcelain, cement, and the like, and the form is not particularly limited. Containers, decorative objects, decorative figurines , Vases, windows, tiles and more.

 [0084] The method for coating or printing the ceramic coating composition of the present invention is not particularly limited, for example, roller coating, brush coating, roll coating coating, bar coating coating, dipping coating, spray coating, electrostatic coating, silk printing. , Offset printing, gravure printing, etc. can be selected and used as appropriate.

[0085] The coating film may be cured by applying an active energy ray at 0 to: LOO ° C, for example, room temperature after coating. The active energy ray to be used is not particularly limited, and examples thereof include an ultraviolet ray, an electron beam, and radiation (j8 ray, X ray). Also, the energy source of the active energy line is not particularly limited. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, a gallium lamp, an electrodeless lamp, a xenon lamp, Examples thereof include ultraviolet lamps such as a xymer lamp, scanning type and non-scanning type electron beam irradiation apparatuses. An active energy ray irradiation device that can irradiate the surface of a three-dimensional object as uniformly as possible is preferable. The irradiation conditions can be changed as appropriate according to the type and thickness of the coated ceramic coating composition. Good.

[0086] The irradiation amount of the active energy ray necessary for curing the coating film is lower limit of 100 mj / cm ^{2 in} the case of ultraviolet rays, and lower limit of 1 in the case of an electron beam whose upper limit is preferably 10,000 mj / cm ^2.

Mrad, with an upper limit of 50 Mrad being preferred.

[0087] Further, if necessary, preheating may be performed before irradiation with active energy rays, or heating may be performed after irradiation with active energy rays.

[0088] The preheating is preferably performed under a condition of 30 to: LOO ° C from the viewpoint of improving the wettability with respect to the ceramic substrate.

[0089] Further, post-heating after the irradiation can reduce the amount of unreacted substances in the coating film, and can reduce the distortion of the coating film caused by the curing of the coating film by irradiation with active energy rays. In addition, follow-up heating may improve the hardness and adhesion of the coating film. The follow-up heating is preferably performed at an ambient temperature of 100 to 250 ° C for 1 to 30 minutes.

 [0090] The film obtained by curing using the coating composition of the present invention is excellent in hardness, chemical resistance and boiling resistance, and has a particularly improved adhesion to the ceramic substrate.

Example

 [0091] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In the following examples, parts and% mean mass parts and mass%, respectively. The weight average molecular weight and the cationic polymerizable functional group (epoxy group and oxetal group) equivalent were calculated by the following methods.

 [0092] (1) Weight average molecular weight

 Equipment: HLC-8220 manufactured by Tosoh Corporation

 Detector: HLC-8220 built-in RI * UV-8220

Measurement conditions: eluent black mouth form, 40 ° C Column used: TSK GEL SUPER AW3000 X 1 + 2500 X 3

 Standard material: polystyrene

 [0093] (2) Cationic polymerizable functional group equivalent

 For the cation polymerizable functional group (epoxy group and oxetal group) equivalent, the theoretical value in which the composition specific power of the monomer as a raw material was also calculated was described. In general, the cation polymerizable functional group (epoxy group and oxetal group) equivalent is determined by the method described in JIS K-7236. This is done by dissolving the sample in 10 mL of chloroform, adding 20 mL of acetic anhydride and 10 mL of 20% tetraethylammonium bromide acetic acid solution, and using a potentiometric titrator, 0.1 mol ZL perchlorate standard solution. It is the calculation method which titrates with.

 Production Example (Production of Acrylic Resin (A) Having Cationic Polymerizable Functional Group)

 In a polymerization apparatus that can be heated and cooled, 300 parts of deionized water and 0.5 parts of polyvinyl alcohol (80% of the degree of polymerization, 1,700 degree of polymerization) are covered, and the polybulu alcohol is completely dissolved. Until stirred. Add 25 parts of glycidyl methacrylate (GMA), 75 parts of methyl methacrylate (MMA), 1.0 part of 2,2, -azobisisobutyric-tolyl, and 0.5 part of n-dodecyl mercaptan. The temperature was raised to 80 ° C. and held at this temperature for 1 hour, and then heated to 90 ° C. and kept at this temperature for 1 hour to complete the polymerization of the monomer. The obtained aqueous suspension was filtered through a filter cloth having a mesh size of 10 μm, and the filtrate was washed and dried in an electric oven at 50 ° C. under reduced pressure to obtain a cationic polymerizable functional group equivalent weight of 540 (theoretical value). ) Granular epoxy group-containing acrylic resin (al). The weight average molecular weight of the obtained acrylic resin was 10,000.

 [0095] In the following, examination was performed using the acrylic resin (A) shown in Table 1. In Table 1, ECMM A means 3,4-epoxycyclohexylmethyl metatalylate, OXEMA means 3-ethyl-1-oxomethyl methyl methacrylate, and St means styrene. Atalyl resin numbers a15 and a16 are comparative acrylic resin having no cationically polymerizable functional group. The amount of each component in Table 1 is expressed in parts by mass.

[0096] [Table 1] table 1

Example 1

As other cationically polymerizable compound (D), 3,4-epoxycyclohexylene 3,4-epoxycyclohexanecarboxylate (cationic polymerizable compound dl-1) 25 parts, the above formula (D4-1) In which R ³ is ethyl and R ⁴ is a hydrogen atom (cation-polymerizable compound dl—2) 5 parts 1,4 bis [(3 ethyl 3-oxetal) methoxy] benzene (force thione polymerization) Dl— 3) Use 10 parts of this compound, mix 40 parts of epoxy group-containing acrylic resin (al) as acrylic resin (A), and maintain at 60 ° C for 5 hours. As a result, an acrylic resin solution was obtained. After 80 parts of the resulting solution was cooled to 25 ° C, the coupling agent (B) and Cycure UVI—6992 (trade name, force thione polymerization initiator cl) 8 parts, BYK—022 (hydrophobic solid and antifoaming poly in polydarlicol made by BYK Chemie) as initiator (C) A mixture of siloxanes (trade name) 2 parts was blended and kept at 25 ° C and stirred for 10 minutes to obtain a ceramic coating composition of the present invention.

 [0098] This ceramic coating composition was subjected to the following test. The results are shown in Table 2.

 [0099] (1) Preparation of test coating plate

A commercially available hard glass plate (100 × 150 × 2 mm) was washed with methanol and then dried in an oven at 80 ° C. The ceramic coating composition obtained in Example 1 was applied to the surface of this hard glass plate by bar coater coating so that the film thickness was 10 m. Next, the coated glass plate was irradiated with ultraviolet rays using a condensing metal halide lamp (160W / cm) (distance to the coated glass plate 11cm; energy dose 100mJ / cm ² and 500mJ / cm ² ) Cured to obtain a test coated plate.

 [0100] The following characteristics were examined for each of the obtained test coated plates. All tests were conducted at 20 ° C. The results are shown in Tables 2-5.

[0101] (2) Test method

In accordance with JIS K-5400 8.5.2 (cross-cut tape method), apply 100 Omm squares to the cured coating on the surface of the test coating plate using a knife and adhere to the surface. After applying the tape and peeling it off instantaneously, the condition of the squares is evaluated according to the following criteria. A practical surface strength of C or higher is desired.

 A: No peeling at all!

 B: The border of the grid is slightly peeled off.

 C: The borders of the cells are slightly peeled off and adhered! /, The number of cells is 90Z100 or more. D: The borders of the squares peeled and adhered! /, The number of squares is 80-89Z100

 E: The borders of the squares peeled and adhered! / The number of squares is 30 to 79 ZlOO.

 F: The number of cells in close contact is less than 30Z100.

[0102] Lead hardness: The pencil pulling force test specified in JIS K-5400 8.4.2 (hand force method) is performed, and the evaluation is performed by the tear method. From a practical aspect, 3H or higher is desired.

[0103] Surface curability:

 30 seconds and 1 minute after UV irradiation, press the surface of the cured coating film with your index finger, and evaluate the coating surface condition according to the following criteria. A practical surface strength of C or higher is desired. A: Even after 30 seconds of irradiation, there is no change in the paint surface! /.

 B: After 1 minute of irradiation, no change is observed on the painted surface.

 C: After 1 minute of irradiation, a slight trace of fingerprints is observed on the paint surface, but the paint does not transfer to the fingers.

 D: After 1 minute of irradiation, a marked trace of fingerprints is observed on the coated surface, and the coating material is slightly transferred to the finger.

 E: The coating surface falls off after 1 minute of irradiation, and the coating material transfers significantly to the finger.

[0104] Boiling resistance:

 After immersing the test coating in hot water at 90 ° C for 5, 15, and 30 minutes, remove the test coating from the hot water, dry with a waste cloth, and remove the adhesive coating on the coating surface 1 minute later. Adhere and peel off instantly to visually evaluate the adhesion and the appearance of the cured coating. The evaluation is based on the following criteria. A practical surface strength of C or higher is desired.

 A: Even if it is immersed in hot water for 30 minutes, no change is observed.

 B: No change even when immersed in hot water for 15 minutes.

 C: No change is observed even when immersed in hot water for 5 minutes.

 D: Even if immersed in hot water for 5 minutes, the coating film has smoothness and gloss, but slight water bubbles are observed, and after the adhesion test, the part with water bubbles peels off (residual area, 90% or more) To do.

 E: Even if immersed in hot water for 5 minutes, the coating film is smooth and glossy, but water bubbles are remarkably observed, and peeling (remaining area, 30 to 90%) is observed after the adhesion test.

 F: After dipping in hot water for 5 minutes, the smoothness or glossiness of the coating disappears. Or, after the adhesion test, the remaining area will be less than 30%.

[0105] Solvent resistance:

Lightly rub the cured coating surface of the test coating with a cotton swab impregnated with methyl ethyl ketone. The glossiness of the coating surface is evaluated according to the following criteria. B or higher is desired for practical use.

 A: Even after 30 reciprocations, there is no change in the gloss of the coated surface.

 B: Even after 30 reciprocations, there is almost no change in the gloss of the coated surface.

 C: There is a considerable change in the gloss of the coated surface at 30 round trips, but there is almost no change in the gloss at 10 round trips.

 D: Force with a significant change in the gloss of the coated surface after 10 reciprocations. There is almost no change in the gloss with 3 reciprocations.

 E: A significant change in the gloss of the coated surface is observed in one round trip.

[0106] Leveling:

 After coating each ceramic coating composition with a bar coater, the surface condition of the coated surface is visually evaluated. Evaluation is performed according to the following criteria. A practical surface strength of B or higher is desired.

 A: The coating surface is smooth.

 B: Traces painted with a bar coater remain slightly.

 C: Marks painted with a bar coater remain clearly.

 D: Cannot be painted with a bar coater.

[0107] Examples 2 to 5 and Comparative Example 1

 For various acrylic resins using GMA as an acrylic monomer containing a cationically polymerizable functional group, the same operation as in Example 1 was carried out except that the components shown in Table 2 were used! ヽ Each ceramic coating composition I got a thing. The acrylic resin (al5) used in Comparative Example 1 is an acrylic resin having no cationic polymerizable functional group.

[0108] These ceramic coating compositions were subjected to the same tests as in Example 1. Table the results

Shown in 2.

[0109] [Table 2]

From the results shown in Table 2, the heat resistance of GMA is copolymerized with MMA or styrene, and boiling resistance is hardly lowered with almost no deterioration of the coating properties of the GMA homopolymer (a8) of Example 5. It can be seen that the properties and pencil hardness are improved. In addition, the acrylic resin (al5) having no cationically polymerizable functional group used in Comparative Example 1 significantly deteriorates the coating properties as a whole.

[0111] Examples 6-8

 Each ceramic coating composition was obtained in the same manner as in Example 1 except that the components shown in Table 3 were used for various acrylic resins having different weight average molecular weights (Mw).

[0112] These ceramic coating compositions were subjected to the same tests as in Example 1. Table the results

Shown in 3. For reference, Table 3 also shows the results of Examples 2 and 4.

[0113] [Table 3]

 [0114] From the results shown in Table 3, it is evident that excellent coating properties are expressed at a weight average molecular weight of 2000 to 50000.

[0115] Examples 9 to 10 and Comparative Example 2

ECMMA (Example 9) and OX as acrylic monomers containing cationically polymerizable functional groups For each acrylic resin using EMA (Example 10), the same operations as in Example 1 were carried out except that the components shown in Table 4 were used to obtain respective ceramic coating compositions. The other cationically polymerizable compounds (dl-4) and (dl-5) used in Comparative Example 2 are Dow liquid epoxy resin DER331 and Dow solid epoxy resin DER661 (manufactured by Dow Chemical Co., Ltd.). Product name), which is an epoxy resin mainly composed of bisphenol A epoxy resin.

[0116] These ceramic coating compositions were subjected to the same tests as in Example 1. The results are shown in Table 4. For reference, Table 4 also includes the results of Examples 1, 2, and 5 and Comparative Example 1.

[0117] [Table 4]

From the results shown in Table 4, homopolymers of cationically polymerizable unsaturated monomers, especially the epoxy group-containing acrylic resins (a8) and (al 1), are surface-cured even at low light (100 mj / cm ² )! This proves useful in fields where quick drying is required, such as when using multi-color printers and ink jets. In addition, when talyl resin (al5) and bisphenol A epoxy resin having no cationically polymerizable functional group are used as the main components, such as Comparative Examples 1 and 2, the surface curability is low.

 [0119] Examples 11 to 13 and Comparative Examples 3 to 5

 As in Example 1, except that 3- (3-ethyl-3-oxycetalmethoxy) propyltrimethoxysilane (b2) was used in place of the coupling agent (bl) as a coupling agent and the components shown in Table 5 were used. By performing the above operations, each ceramic coating composition was obtained.

 [0120] These ceramic coating compositions were subjected to the same tests as in Example 1. The results are shown in Table 5. For reference, Table 5 also shows the results of Examples 2, 4, and 5.

[0121] [Table 5]

From the results in Table 5, it can be seen that the use of a force coupling agent having a cationic polymerizable functional group (epoxy group, oxetal group) improves adhesion and exhibits boiling resistance. [0123] Example 14

 Ratio of toluene and methylethylketone 70 parts of S4 to i mixed solvent (toluene Z methylethylketone = 4Zl) and 70 parts of epoxy group-containing acrylic resin (a8), and kept at 50 ° C 3 The mixture was stirred for a time to obtain an acrylic resin solution. After 140 parts of the resulting solution were cooled to 25 ° C, 20 parts of 3-glycidoxypropyltrimethoxysilane (coupling agent bl) as a coupling agent (B) and syracure as a cationic polymerization initiator (C) were added thereto. UVI—6992 (cationic polymerization initiator cl) 8 parts, BYK—022 (BYK Chemi Co., Ltd. Mixture of hydrophobic solid and antifoaming polysiloxane in polydalicol) 2 parts and keep at 25 ° C The mixture was stirred for 10 minutes to obtain the ceramic coating composition of the present invention.

 [0124] This ceramic coating composition was subjected to the same test as in Example 1 (test temperature 20 ° C). However, the test coating plate was produced by the following method.

 [0125] (Preparation of test coating)

A commercially available hard glass plate (100 × 150 × 2 mm) was washed with methanol and then dried in an oven at 80 ° C. After coating the ceramic coating composition obtained in Example 14 on the surface of this hard glass plate with a bar coater to a dry film thickness of 10 m, the solvent was dried in an oven at 100 ° C for 1 minute. . Condensation type metalo, ride lamp (160W / cm) is used V, and ultraviolet rays are applied to the coated glass plate (distance to the painted glass plate 1 lcm; energy dose power SlOOmJ / cm ² and 500mJ / cm ² ) The coating film was cured to obtain a test coated plate.

 [0126] Examples 15 to 16

 The same operation as in Example 14 was carried out except that the components shown in Table 6 were used, and each ceramic coating composition was obtained.

 [0127] These ceramic coating compositions were subjected to the same tests as in Example 1. Table the results

Shown in 6.

[0128] [Table 6]

 [0129] From the results in Table 6, it is evident that excellent coating properties are expressed at a weight average molecular weight of 2000 to 50000.

 [0130] Examples 17 to 21 and Comparative Examples 6 to 7

For each ceramic coating, the same operation as in Example 14 was performed except that the acrylic resin containing cationically polymerizable functional groups shown in Table 7 was used as the acrylic resin (A) and the components shown in Table 7 were used. A composition was obtained. Acrylic rosin (al6) used in Comparative Example 6 is a cationic polymerizable compound. It is an acrylic resin that has no active groups. The other cationically polymerizable compounds (dl-4) and (dl-5) used in Comparative Example 7 are Dow liquid epoxy resin DER331 and Dow solid epoxy resin DER661 (manufactured by Dow Chemical Co., Ltd.). (Trade name) and epoxy resin mainly composed of bisphenol A epoxy resin.

 [0131] These ceramic coating compositions were tested in the same manner as in Example 1. The results are shown in Table 7.

[0132] [Table 7]

Based on the results in Table 7, homopolymers of cationically polymerizable unsaturated monomers, especially epoxy group-containing acrylic resins (a9) and (al ² ), are surface cured even at low light levels (lOOmjZcm ² ). This proves useful in fields where quick drying is required, such as when using multi-color printers and ink jets. In addition, when talyl resin (al6) and bisphenol A epoxy resin having no cationically polymerizable functional group are used as the main components, such as Comparative Examples 6 and 7, surface curability is low.

 [0134] Examples 22 to 23 and Comparative Examples 8 to 9

 Similar to Example 14 except that 3- (3-ethyl-3-oxycetalmethoxy) propyltrimethoxysilane (b2) was used in place of the coupling agent (bl) as a coupling agent, and the components shown in Table 8 were used. The ceramic coating compositions were obtained by performing the above operations.

 [0135] These ceramic coating compositions were tested in the same manner as in Example 1. The results are shown in Table 8. For reference, Table 8 also shows the results of Examples 17 and 19.

[0136] [Table 8]

Table 8

[0137] From the results in Table 8, it can be seen that the use of a force coupling agent having a cationic polymerizable functional group (epoxy group, oxetal group) improves the adhesion and expresses boiling resistance. Industrial applicability

[0138] The ceramic coating composition of the present invention has high curability, and the coating obtained by curing the composition is bonded to the ceramic substrate by forming a chemical bond. In addition, since the coating itself has excellent hardness, chemical resistance and boiling resistance, it is possible to provide a cured film having high practicality in an environment where ceramic products are used.

Claims

The scope of the claims

 [1] (A) Acrylic resin having cationic polymerizable functional groups at the terminal and Z or side chain, (B) Coupling agent, and (C) Photocation polymerization having a function of generating an acid upon irradiation with active energy rays A ceramic coating composition containing an agent.

[2] The composition for coating ceramic according to claim 1, wherein the coupling agent (B) is a silane coupling agent.

[3] The ceramic coating composition according to claim 1 or 2, wherein the coupling agent (B) contains a cationically polymerizable functional group.

[4] The ceramic coating according to any one of claims 1 to 3, wherein the cationic polymerizable functional group of the acrylic resin (A) is an epoxy group and a Z or oxetal group. Composition.

 [5] The ceramic coating composition according to claim 3 or 4, wherein the cationically polymerizable functional group of the coupling agent (B) is an epoxy group and a Z or oxetal group.

 [6] The ceramic coating composition according to any one of [1] to [5], wherein the acrylic resin (A) has a weight average molecular weight of 1,000-100,000.

 [7] The ceramic coating composition according to any one of [1] to [6] above, wherein the acrylic resin (A) has a cationic polymerizable functional group equivalent of 100 to 1,500.