JP6547110B1 - Active energy ray curable ink composition - Google Patents

Abstract

An object of the present invention is to provide an active energy ray-curable ink composition having excellent specular gloss durability. A binder component (A) containing a cationically polymerizable compound, a metal pigment (B), and an active energy ray acid generator (C), wherein the component (C) contains a carbon atom and a halogen atom. The active energy ray-curable ink composition, which is an onium salt having an anion to be contained as a counter anion, can remarkably improve the specular gloss durability of a cured coating film. Since the specular gloss durability is remarkably improved, the cured coating film is particularly preferably applied to an article used in a wet or wet environment. [Selection figure] None

Description

  The present invention relates to an active energy ray curable ink composition. More specifically, the present invention relates to a metal pigment-containing active energy ray curable ink composition having excellent specular gloss durability of a cured coating film.

  In the inkjet ink composition field, various techniques for imparting metallic gloss to a printed coating film by blending a metal pigment in the composition and improving the design property of a printed matter are known. For example, Patent Document 1 discloses a metal pigment whose average particle diameter is specified in a specific range, and an organic substance whose dispersion term (δD), polar term (δP) and hydrogen bonding term (δH) in a Hansen solubility parameter are specified in a specific range. It is described that a metal pigment-containing ultraviolet-curable inkjet ink containing a solvent, a photopolymerizable compound, and a photopolymerization initiator can form a coating film having a good metallic gloss.

  In addition, Patent Document 2 discloses an inkjet recording including a metal pigment which is a tabular particle having a specific layer laminated and an end surface formed by chemical conversion treatment with a specific chemical oxidizing agent, a cationically polymerizable compound, and a polymerization initiator. It is described that a photocurable ink composition for use can easily form a metallic glossy surface with a good degree of gloss.

  Furthermore, Patent Document 3 discloses a metal particle-containing UV curable ink containing at least metal particles, two or more photopolymerizable compounds, and a photopolymerization initiator, wherein the two or more photopolymerizable compounds are contained. It is described that the metallic gloss of the coating film is compatible with the ink stability (suppression of the change in viscosity during storage in the dark) by the metal particle-containing UV curable ink having a specific composition.

Unexamined-Japanese-Patent No. 2017-2162 JP, 2016-169393, A Unexamined-Japanese-Patent No. 2017-179093

  Regarding any of the compositions of Patent Documents 1 to 3, it is described that a coating film having good metal gloss (hereinafter, good metal gloss is described as mirror gloss) is obtained. There is. However, their specular gloss is only obtained as a characteristic when forming a coating film, and no consideration has been given to its durability. When the present inventors paid attention to the durability of the mirror gloss of the coating film, the gloss value of the cured coating film of the ink composition containing the polymerization initiator as actually used in Patent Documents 1 to 3 over time It was found that the cause of the decrease was due to the corrosion of the aluminum pigment due to moisture such as moisture. That is, the metal pigment-containing ink composition thus far has the property of maintaining the mirror surface glossiness against the environment where water is present (hereinafter referred to as a mirror surface property even if the mirror surface glossiness is obtained well at the time of film formation). It was found that there is a problem with the gloss durability.

  Therefore, the main object of the present invention is to provide an active energy ray curable ink composition having excellent specular gloss durability.

  The present inventors believe that the deterioration of the specular gloss is caused by the corrosion of the metal pigment in the coating film, and as a result of intensive studies, it is an onium salt as a polymerization initiator (active energy ray acid generator) It has been found that the specular gloss durability is remarkably improved when a specific anion is selected as a counter anion with. The present invention has been completed by further studies based on this finding.

That is, the present invention provides the invention of the aspects listed below.
Item 1. A binder component (A) containing a cationically polymerizable compound, a metal pigment (B), and an active energy ray acid generator (C),
An active energy ray curable ink composition, wherein the component (C) is an onium salt having an anion containing a carbon atom and a halogen atom as a counter anion.
Item 2. The anion _{^{is, (R 1) a PF 6}} -a - and ^{_{R 2 b BY 4-b -}} (R 1 represents an alkyl group or at least part of the hydrogen atoms are substituted with fluorine atom alkyl group; R ² represents a phenyl group in which at least a part of hydrogen atoms is substituted by a halogen atom and / or an electron-withdrawing group having a halogen atom; Y represents a halogen atom; a represents an integer of 1 to 6; Item 2. The active energy ray-curable ink composition according to item 1, which is selected from the group consisting of an integer of 1 to 4).
Item 3. 3. The active energy ray curable ink composition according to item 1 or 2, wherein the anion is B (C ₆ F ₅ ) ₄ ^— .
Item 4. The active energy ray curable ink composition according to any one of Items 1 to 3, wherein the onium salt is selected from the group consisting of a sulfonium salt and an iodonium salt.
Item 5. The active energy ray curable ink composition according to any one of Items 1 to 4, wherein the onium salt is a sulfonium salt.
Item 6. Item 6. The active energy ray curable ink composition according to any one of Items 1 to 5, wherein the cationically polymerizable compound is selected from the group consisting of an oxetane compound and an epoxy compound.
Item 7. Item 6. The active energy ray curable ink composition according to any one of Items 1 to 5, wherein the cationically polymerizable compound comprises an oxetane compound and an epoxy compound.
Item 8. 8. The active energy ray curable ink composition according to any one of Items 1 to 7, wherein the cationically polymerizable compound contains at least an oxetane compound having two or more oxetane rings in the molecule.
Item 9. Item 9. The active energy ray curable ink composition according to any one of Items 1 to 8, wherein the component (A) further contains a silane coupling agent.
Item 10. Item 10. The active energy ray curable ink composition according to any one of Items 1 to 9, wherein the component (B) contains aluminum particles.
Item 11. The active energy ray curable ink composition according to any one of Items 1 to 10, wherein the content of the component (B) is 0.1 to 20 parts by mass with respect to 100 parts by mass of the component (A).
Item 12. 12. The active energy ray curable ink composition according to any one of items 1 to 11, wherein the content of the component (C) is 0.5 to 10 parts by mass with respect to 100 parts by mass of the component (A).
Item 13. Item 13. The active energy ray curable ink composition according to any one of Items 1 to 12, which is an ink composition for inkjet.
Item 14. Item 14. A cured coating film of the active energy ray-curable ink composition according to any one of items 1 to 13.
Item 15. An article having the cured coating film according to Item 14.
Item 16. The article according to item 15, which is used in a wet environment or a wet environment.

  According to the present invention, an active energy ray-curable ink composition capable of significantly improving the specular gloss durability of a cured coating film, a cured coating film having the specular gloss durability significantly improved, and the coating film An article having the The cured coating is particularly preferably applied to an article used in a wet environment or in a touch environment because the specular gloss durability is remarkably improved.

<Active energy ray curable ink composition>
The active energy ray-curable ink composition of the present invention comprises a binder component (A) (hereinafter sometimes referred to simply as component (A)), a metal pigment (B) (hereinafter simply referred to as component (B)) And an active energy ray generator (C) (hereinafter, may be simply referred to as component (C)). The component (A) contains a cationically polymerizable compound. The component (C) is an onium salt having an anion containing a carbon atom and a halogen atom as a counter anion. Hereinafter, the active energy ray curable ink composition of the present invention will be described in detail.

<Binder component (A)>
The active energy ray curable ink composition of the present invention contains a cationically polymerizable compound as a binder component (A). By including the cationically polymerizable compound, when using the active energy ray curable ink composition, it is possible to avoid the inhibition of curing by oxygen as observed in the photoradically polymerizable compound, and the shaded portion to which the active energy ray does not reach Even if it is, good curability can be obtained. Further, by including a cationically polymerizable compound, it is possible to avoid curing during several hours in the ink jet head as observed for photo radically polymerizable compounds, and therefore, when used as an ink composition for ink jet recording Excellent inkjet suitability can be obtained.

<Cationically Polymerizable Compound>
The cationically polymerizable compound is not particularly limited, and is not particularly limited as long as it is a compound which initiates a polymerization reaction with an acid generated from an active energy ray acid generator described later to be cured. Specifically, as a cationically polymerizable compound, a compound having an oxetane ring (hereinafter also referred to as an oxetane compound), a compound having an oxirane ring (epoxy ring) (hereinafter referred to as an epoxy compound), a vinyl ether compound, etc. Can be mentioned. These cationically polymerizable compounds can be used singly or in combination of two or more.

  Among these cationically polymerizable compounds, a compound having a cyclic ether structure such as an oxetane compound and an epoxy compound is preferably mentioned from the viewpoint of preferably obtaining durability to specular gloss, curability, and / or viscosity aptitude. From the viewpoint of further enhancing the specular gloss durability and the curability, it is preferable to use an oxetane compound and an epoxy compound in combination. The cationically polymerizable compound may be a monofunctional cationically polymerizable compound or a polyfunctional cationically polymerizable compound, but from the viewpoint of further enhancing the mirror gloss durability, it is preferred to at least a polyfunctional cationically polymerizable compound. It is preferred to include a compound.

  The oxetane compound is not particularly limited as long as it is a compound having an oxetane ring in the molecule, and any known oxetane compound can be selected and used. In the present invention, examples of the oxetane compound include a compound having one oxetane ring in the molecule (monofunctional oxetane compound) and a compound having two or more oxetane rings in the molecule (polyfunctional oxetane compound).

  As a compound which has one oxetane ring in a molecule | numerator, the compound etc. which are shown by following formula (1) are mentioned.

R ^a1 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, an allyl group, an aryl group, a furyl group or a thienyl group. As an alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group etc. are mentioned, As a fluoroalkyl group, what one of hydrogens of these alkyl groups was substituted by the fluorine atom is mentioned preferably.

R ^a2 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a group having an aromatic ring, an alkyl carbonyl group having 2 to 6 carbon atoms, 2 to 6 carbon atoms And an alkoxycarbonyl group and an N-alkylcarbamoyl group having 2 to 6 carbon atoms. Examples of the alkyl group include methyl group, ethyl group, propyl group and butyl group, and examples of the alkenyl group include 1-propenyl group, 2-propenyl group, 2-methyl-1-propenyl group, 2-methyl-2 -Propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, etc., and examples of the group having an aromatic ring include phenyl group, benzyl group, fluorobenzyl group, methoxybenzyl group, phenoxyethyl group and the like It can be mentioned. As an alkyl carbonyl group, an ethyl carbonyl group, a propyl carbonyl group, a butyl carbonyl group etc. is mentioned, As an alkoxy carbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group etc., As an N-alkyl carbamoyl group, Ethyl carbamoyl group, propyl carbamoyl group, butyl carbamoyl group, pentyl carbamoyl group and the like can be mentioned. R ^a2 may have a substituent, and examples of the substituent include an alkyl group of 1 to 6 and a fluorine atom.

  Examples of monofunctional oxetane compounds that are particularly preferably used in the present invention are listed below in (1-1) to (1-12).

  As commercially available products of the compound represented by the formula (1), OXT-101 (3-ethyl-3-hydroxymethyl oxetane: manufactured by Toagosei Co., Ltd.), OXT-212 (3-ethyl-3- (2-ethyl hex) Siloxymethyl) oxetane: manufactured by Toagosei Co., Ltd.

  From the viewpoint of further enhancing the specular gloss durability, the oxetane compound preferably contains at least a compound having two or more oxetane rings. In the oxetane compound having two or more oxetane rings, the number of oxetane rings in the molecule is preferably 2 to 4, more preferably 2 to 3, and still more preferably 2.

  As a compound which has two oxetane rings in a molecule | numerator, the compound etc. which are shown by following formula (2) and (3) are mentioned. Among these, the compound represented by the following formula (3) is preferable from the viewpoint of further enhancing the specular gloss durability.

R ^a1 has the same ^{meaning as} that in the above formula (1). Two R ^a1 may be the same as or different from each other.

R ^a3 is a linear or branched alkylene group, a linear or branched poly (alkyleneoxy) group, a linear or branched unsaturated hydrocarbon group, a carbonyl group or an alkylene group containing a carbonyl group, a carboxyl group And an alkylene group containing a carbamoyl group. Examples of the alkylene group include ethylene group, propylene group and butylene group, and examples of the poly (alkyleneoxy) group include poly (ethyleneoxy) group and poly (propyleneoxy) group. Examples of the unsaturated hydrocarbon group include propenylene group, methylpropenylene group, butenylene group and the like. In addition, R ^a3 may be a multivalent group represented by (1A) to (1C) below.

When R ^a3 is the above-mentioned multivalent group (1A) to (1C), R ^a4 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a nitro group And a cyano group, a mercapto group, a lower alkyl carboxyl group, a carboxyl group or a carbamoyl group. R ^a5 represents an oxygen atom, a sulfur atom, a methylene group, NH, SO, SO ₂ , C (CF ₃ ) ₂ or C (CH ₃ ) ₂ . R ^a6 represents an alkyl group having 1 to 4 carbon atoms or an aryl group. R ^a6 is preferably a non-aromatic alkyl group having 1 to 4 carbon atoms. N represents an integer of 0 to 2,000. R ^a7 represents an alkyl group having 1 to 4 carbon atoms or an aryl group. R ^a7 is preferably a non-aromatic alkyl group having 1 to 4 carbon atoms, or a monovalent group having a structure of the following formula (1C-A). In the following formula (1C-A), ^Ra8 represents an alkyl group having 1 to 4 carbon atoms or an aryl group. R ^a8 is preferably a non-aromatic alkyl group having 1 to 4 carbon atoms. m represents an integer of 0 to 100.

  As a commercial item of a compound denoted by a formula (2), OXT-121 (1, 4-bis [(3-ethyl -3- oxetanyl methoxy) methyl] benzene: Toagosei Co., Ltd. make) is mentioned. Moreover, as a commercial item of the compound represented by Formula (3), OXT-221 (3-ethyl-3 {[(3-ethyl oxetan-3-yl) methoxy] methyl} oxetane: manufactured by Toagosei Co., Ltd.) It can be mentioned.

  As a compound which has a 3-4 oxetane ring in a molecule | numerator, the compound shown by following formula (4) is mentioned.

In Formula (4), R ^a1 has the same ^{meaning as} that in Formula (1). Moreover, as R ^a9 which is a polyvalent linking group, for example, a branched alkylene group having 1 to 12 carbon atoms such as the groups shown by the following (4A) to (4C), a group shown by the following (4D), etc. And a branched polysiloxy group such as a branched poly (alkyleneoxy) group or a group represented by E below. j (repeating unit) is 3 or 4;

In the above (4A), R ^a10 represents a methyl group, an ethyl group or a propyl group. In the above (4D), p (repeating unit) is an integer of 1 to 10.

  Moreover, as an oxetane compound, the compound shown by following formula (5) which has an oxetane ring in a side chain is also mentioned.

In formula (5), R ^a1 and R ^a8 are as defined in the above formula. R ^a11 is an alkyl group having a carbon number of 1 to 4 such as a methyl group, an ethyl group, a propyl group or a butyl group or a trialkylsilyl group, and r (repetition unit) is 1 to 4.

  Examples of polyfunctional oxetane compounds which are particularly preferably used in the present invention are listed in (2-1) to (2-3) and (3-1) to (3-2) below.

  The epoxy compound is not particularly limited as long as it is a compound having an oxirane ring in the molecule, and a known epoxy compound can be arbitrarily selected and used. Specifically, as the epoxy compound, aromatic epoxide, alicyclic epoxide, aliphatic epoxide and the like can be mentioned. In the case of using an active energy ray curable ink composition as an ink composition for ink jet, in which the viscosity is relatively low, preferred are alicyclic epoxides and aliphatic epoxides, and mirror gloss durability And from the viewpoint of further improving the curability, more preferably alicyclic epoxides.

  Examples of aromatic epoxides include polyhydric phenols having at least one aromatic nucleus or di- or polyglycidyl ethers produced by the reaction of an alkylene oxide adduct thereof with epichlorohydrin, such as bisphenol A or The di- or polyglycidyl ether of the alkylene oxide adduct, the di- or polyglycidyl ether of hydrogenated bisphenol A or its alkylene oxide adduct, and the novolac epoxy resin may, for example, be mentioned. Ethylene oxide, a propylene oxide, etc. are mentioned as alkylene oxide here.

  Cycloaliphatic epoxides are obtained by epoxidizing compounds having a cycloalkane ring such as at least one cyclohexene ring or cyclopentene ring with a suitable oxidizing agent such as hydrogen peroxide, peracid, etc. Preferred are oxides or cyclopentene oxide containing compounds.

  Aliphatic epoxides include aliphatic polyhydric alcohols or di- or polyglycidyl ethers of alkylene oxide adducts thereof, and representative examples thereof include diglycidyl ether of ethylene glycol, diglycidyl ether of propylene glycol or 1,6 -Diglycidyl ether of alkylene glycol such as diglycidyl ether of hexanediol, polyglycidyl ether of polyhydric alcohol such as glycerin or di or triglycidyl ether of its alkylene oxide adduct, diglycidyl of polyethylene glycol or its alkylene oxide adduct Diglycidyl of polyalkylene glycol represented by ether, polypropylene glycol or diglycidyl ether of alkylene oxide adduct thereof Ether and the like. Ethylene oxide, a propylene oxide, etc. are mentioned as alkylene oxide here.

  As an epoxy compound, the compound (monofunctional epoxy compound) which has one oxirane ring in a molecule | numerator, and the compound (polyfunctional epoxy compound) which has 2 or more of oxirane rings in a molecule | numerator are mentioned.

  Examples of epoxy compounds having one oxirane ring in the molecule include phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide, 3-butadiene monoxide, 1,2-epoxydodecane, epichlorohydrin, 1,2-epoxydecane, styrene oxide, cyclohexene oxide, 3-methacryloyloxymethylcyclohexene oxide, 3-acryloyloxymethylcyclohexene oxide, 3-vinyl A cyclohexene oxide, 4-vinyl cyclohexene oxide, etc. are mentioned.

  It is preferable that an epoxy compound is a compound (multifunctional epoxy compound) which has 2 or more of oxirane rings from a viewpoint of improving mirror gloss durability, curability, etc. further. In the epoxy compound having two or more oxirane rings, the number of oxirane rings in the molecule is preferably two.

  Examples of epoxy compounds having two or more oxirane rings in the molecule include, as aromatic epoxides, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F Diglycidyl ether, brominated bisphenol S diglycidyl ether, epoxy novolac resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether are mentioned; 3 as alicyclic epoxides , 4-Epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-) Propoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ′, 4'-epoxy-6'-methylcyclohexanecarboxylate, methylene bis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylene bis (3,4 -Epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1,2,5,6-diepoxycyclooctane, (4R) -1,2-epoxy-4- ( -Methyloxiranyl) -1-methylcyclohexane (limonene dioxide); as aliphatic epoxides, 1,4-butanediol diglycidyl ether, butyl diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6 -Hexanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ethers, 1, 13-tetradecadiene dioxide, 1, 2, 7, 8- Diepoxy octane and the like can be mentioned.

  Commercially available epoxy compounds include, as monofunctional epoxy compounds, YED series (YED111N, YED111AN, YED122, YED188, etc .: manufactured by Mitsubishi Chemical Corporation), Celoxide Series (Celoxide 2000, manufactured by Daicel Corporation), etc. As multifunctional epoxy compounds, YED series (YED216M, YED216D, etc .: made by Mitsubishi Chemical Corporation), Denacol series (EX-211, EX-212: made by Nagase ChemteX Co., Ltd.), Celoxide Series (Celoxide 2021 P, Celoxide 2081 etc .: manufactured by Daicel Co., Ltd., LDO (manufactured by ARKEMA Co., Ltd.), and the like.

  Examples of polyfunctional epoxy compounds that are particularly preferably used in the present invention are listed in (6-1) to (6-3) below.

  Examples of the vinyl ether compounds include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexane dimethanol divinyl ether, trico Di- or trivinyl ether compounds such as methylolpropane trivinyl ether, ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexane dimethanol monovinyl ether, n-p Pills vinyl ether, isopropyl vinyl ether, isopropenyl vinyl ether, dodecyl vinyl ether, diethylene glycol monovinyl ether, and octadecyl vinyl ether.

  The vinyl ether compounds include monofunctional vinyl ether compounds and polyfunctional vinyl ether compounds. Examples of monofunctional vinyl ether compounds include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, cyclohexylmethyl vinyl ether, 4-methylcyclohexyl Methylvinylether, benzylvinylether, dicyclopentenylvinylether, 2-dicyclopentenoxyethylvinylether, methoxyethylvinylether, ethoxyethylvinylether, butoxyethylvinylether, methoxyethoxyethylvinylether, ethoxyethoxyethylvinylether, methoxypolyethylene glycol vinylether Tetrahydrofurfuryl vinyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxymethyl cyclohexyl methyl vinyl ether, diethylene glycol monovinyl ether, polyethylene glycol vinyl ether, chloroethyl vinyl ether, chlorobutyl vinyl ether, chloroethoxyethyl Vinyl ether, phenylethyl vinyl ether, phenoxy polyethylene glycol vinyl ether and the like can be mentioned.

  Examples of polyfunctional vinyl ether compounds include ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, and bisphenol F alkylene. Divinyl ethers such as oxide divinyl ethers; trimethylolethane trivinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol Hexavinyl ether, ethylene oxide addition trimethylolpropane trivinyl ether, propylene oxide addition trimethylolpropane trivinyl ether, ethylene oxide addition ditrimethylolpropane tetravinyl ether, propylene oxide addition ditrimethylolpropane tetravinyl ether, ethylene oxide addition pentaerythritol tetravinyl ether, propylene oxide Examples include polyfunctional vinyl ethers such as addition pentaerythritol tetravinyl ether, ethylene oxide addition dipentaerythritol hexavinyl ether, and propylene oxide addition dipentaerythritol hexavinyl ether.

  The content of the component (A) in the active energy ray-curable ink composition is a component constituting the active energy ray-curable ink composition from the viewpoint of inkjet suitability and the like, and the total amount of components other than the organic solvent is 100. For example, 70 to 99 parts by mass, preferably 80 to 98 parts by mass, and particularly preferably 85 to 93 parts by mass are included with respect to the parts by mass. The content of the cationically polymerizable compound in the component (A) is preferably 50 to 100 parts by mass, more preferably 90 to 100 parts by mass with respect to 100 parts by mass of the component (A) from the viewpoint of inkjet suitability and the like. It can be mentioned. Further, from the viewpoint of inkjet suitability and the like, it is preferable that the component (A) does not substantially contain a photoradically polymerizable compound. The radical photopolymerizable compound may cause a catalytic action when it coexists with the metal component in the component (B) contained in the active energy ray-curable ink composition, and may cure in several hours even at room temperature, resulting in a decrease in inkjet suitability. Bring The term “does not substantially contain a photoradically polymerizable compound” means that the content of the photoradically polymerizable compound is, for example, 0.1 parts by mass or less, preferably 0.01 parts by mass or less, per 100 parts by mass of the component (A). , Most preferably 0 parts by mass.

  With respect to the cationically polymerizable compound, the content of the oxetane compound in the component (A) is, for example, 0 to 100 parts by mass with respect to 100 parts by mass of the component (A). 10 to 50 parts by mass, more preferably 29 to 45 parts by mass, and still more preferably 30 to 40 parts by mass. The content of the polyfunctional oxetane compound in the component (A) is, for example, 0 to 100 parts by mass, preferably 5 to 40 parts by mass, and more preferably 10 from the viewpoint of durability to mirror gloss and curability. -35 mass parts are mentioned. Further, the content of the epoxy compound in the component (A) is, for example, 0 to 100 parts by mass with respect to 100 parts by mass of the component (A), preferably 50 to 90 from the viewpoint of mirror gloss durability and the like. A mass part, more preferably 54-71 mass parts, still more preferably 60-70 mass parts are mentioned. Furthermore, the total amount of the polyfunctional compound in the component (A) is preferably 65 to 100 parts by mass, more preferably 80 based on 100 parts by mass of the component (A) from the viewpoint of durability to specular gloss and curability. -90 mass parts are mentioned.

<Silane coupling agent>
The component (A) may further contain a silane coupling agent in addition to the above-described cationically polymerizable compound. In the present invention, by including a silane coupling agent in the component (A), adhesion to a substrate (particularly, a glass substrate) can be further enhanced. The silane coupling agent is not particularly limited as long as it is a compound having a hydrolyzable group having affinity or reactivity with the inorganic material and an organic functional group chemically bonded to the organic material, but the following general formula (7) The compounds represented are preferred.

  R represents a methyl group or an ethyl group, s represents 0, 1 or 2, and L is a group represented by the following general formula (8), (9), (10) or (11). L preferably has an oxirane ring or an oxetane ring from the viewpoint of durability to specular gloss and the like, and more preferably has an oxirane ring.

  Y represents an alkylene group having 1 to 3 carbon atoms, Z represents an oxygen atom or a divalent organic group having an organopolysiloxane represented by the following general formula (12), V represents a hydrogen atom, a methyl group, or ethyl And a vinyl group, an allyl group, a (meth) acryloyl group, a glycidyl group, a 3,4-epoxycyclohexyl group or a (3-ethyloxetanyl) methyl group.

  Each Q independently represents an alkoxy group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms, and t represents an integer of 1 to 10.

  Specific examples of the silane coupling agent include 3-glycidyl oxypropyl trimethoxysilane, 3-glycidyl oxypropyl triethoxysilane, 3-glycidyl oxypropyl methyl dimethoxysilane, 3-glycidyl oxypropyl ethyl diethoxysilane, epoxy cyclohexyl ethyl Examples include at least one selected from trimethoxysilane, an alkoxysilane represented by the following general formula (13), and 3-ethyl-3-[[3- (triethoxysilyl) propoxy] methyl] oxetane.

但し、Ｒ^a13はメチル基又はエチル基、ｕは１〜１０の整数を表す。

However, ^Ra13 represents a methyl group or an ethyl group, and u represents an integer of 1 to 10.

  The content of the silane coupling agent in the component (A) is 0 to 15 parts by mass with respect to 100 parts by mass of the component (A), and is preferably 5 from the viewpoint of mirror gloss durability, curability, etc. -10 mass parts are mentioned.

<Metal pigment (B)>
The metallic pigment (B) imparts specular gloss to the cured product of the active energy ray-curable ink composition, and contains metallic particles. Examples of the metal component of the metal particles include aluminum, copper, bronze, silver, gold and the like, and the active energy ray curable ink composition of the present invention is extremely excellent in specular gloss durability in a cured product. Particularly useful when aluminum is inherently susceptible to corrosion. The shape of the particles is not particularly limited, but from the viewpoint of imparting mirror gloss to the cured product of the active energy ray-curable ink composition, it is preferably in the form of a foil or flake.

  The metal particles may be produced by any production method. As a method of producing metal particles, for example, a method of crushing while spreading metal metal, a method of depositing metal on a thin film, a method of making a metal deposited film into powder, creating a foil with good brightness, The method etc. which pulverize precisely are mentioned. In addition, the metal particles at the time of being blended into the active energy ray curable ink composition may be in the form of paste or powder. Examples of the paste-like metal particles include those in which metal particles are dispersed in an organic solvent. Specific examples of the organic solvent will be described in detail in other components described later.

  The metal particles may have been subjected to surface treatment or the like. For example, one in which a fatty acid such as stearic acid is adsorbed on the surface of metal particles can be mentioned. Active energy ray-curable ink compositions containing metal particles adsorbed with fatty acids such as stearic acid tend to have metal particles aligned in parallel on the ink surface when discharged, and obtain cured products with high specularity be able to. The metal particles may also have a surface layer of resin or silicon oxide. The metal particles having such a surface layer can improve adhesion, chemical resistance, weather resistance and the like. However, since the active energy ray curable ink composition of the present invention is extremely excellent in specular gloss durability, it is particularly useful when the metal particles do not have such a surface layer. In addition, when the metal particles do not have such a surface layer, the surface gloss does not interfere with the surface gloss, so that a cured product having a high gloss value can be obtained.

The average particle size (D ₅₀ ) of the metal particles is not particularly limited, but 0.3 to 10 μm is preferably mentioned from the viewpoint of obtaining a cured product having high specular gloss which can be adapted to the nozzle diameter for inkjet. Preferably, 0.4 to 0.8 μm can be mentioned. The average particle diameter (D _50), can be determined using a laser diffraction type particle size distribution measuring apparatus in accordance with the principles of the laser diffraction method, based on the measured particle size distribution is obtained by calculating the volume average.

  The average thickness of the metal particles is not particularly limited, but it is preferably 5 to 25 nm, more preferably 10 to 23 nm, from the viewpoint of obtaining a cured product with high specular gloss. The average thickness can be measured as follows. First, a few drops of metal pigment diluted with acetone are dropped on a glass substrate and allowed to dry naturally. Next, 20 points of metal particles forcibly oriented on the glass substrate are extracted using an atomic force microscope, and the thicknesses of the metal particles are measured by tapping mode. And the average value of the thickness of the remaining 14 points which remove | eliminated thickness of 3 points of each high-order value and low-order value among the measured 20 thickness is calculated | required, and let the average value be average thickness.

  The content of the component (B) in the active energy ray curable ink composition is not particularly limited, but, for example, an amount of 0.1 to 20 parts by mass with respect to 100 parts by mass of the component (A) may be mentioned. Be From the viewpoint of enhancing the gloss value and specular gloss durability of the cured product surface of the active energy ray curable ink composition, the content of the component (B) is preferably 0.5 with respect to 100 parts by mass of the component (A). The amount which becomes -20 mass parts, more preferably 1-20 mass parts is mentioned. Furthermore, as a content of the component (B), from the viewpoint of suppressing a decrease in ink jet suitability and curability resulting from an increase in the amount of metal particles, more preferably 1 to 15 mass with respect to 100 parts by mass of the component (A) The amount is preferably 1 to 10 parts by mass, more preferably 1 to 10 parts by mass.

<Active energy ray acid generator (C)>
The active energy ray acid generator (C) is a compound capable of generating an acid as an active species by irradiation with active energy rays. As an active energy ray which can generate an acid, an ultraviolet-ray, an electron beam, etc. are mentioned, for example.

  In the present invention, an onium salt is used as the active energy ray generating acid generator (C). As the onium salt, a salt of an aromatic onium compound is preferable from the viewpoint of the ability to initiate cationic polymerization and the like. Specific examples of onium salts include diazonium salts, ammonium salts, sulfonium salts, phosphonium salts, iodonium salts and the like. Among these, sulfonium salts and iodonium salts are preferable from the viewpoint of mirror gloss durability, and sulfonium salts are preferable from the viewpoint of storage stability of the active energy ray curable ink composition. These onium salts can be used individually by 1 type or in combination of multiple types.

  Preferred examples of sulfonium salts include compounds represented by the following formula (21), and preferred examples of iodonium salts include compounds represented by the following formula (22).

In formula (21), R ^C1 , R ^C2 and R ^C3 each independently represent an organic group. The carbon number of the organic group is preferably 1 to 30, more preferably 1 to 20. Two of R ^{C1 to} R ^C3 may combine to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. Examples of the group formed by bonding of two of R ^{C1 to} R ^C3 include an alkylene group (for example, a butylene group and a pentylene group). (21) may be an aromatic sulfonium salt in which at least one of R ^{C1 to} R ^C3 is an organic group having an aromatic ring (aryl group), and any one of R ^{C1 to} R ^C3 is aromatic Although it may be a non-aromatic sulfonium salt which is an organic group having no group ring, it is preferably an aromatic sulfonium salt from the viewpoint of the initiation ability of cationic polymerization and the like.

All of R ^{C1 to} R ^C3 in the aromatic sulfonium compound may be an aryl group, and a part of R ^{C1 to} R ^C3 may be an aryl group, and the remaining may be an alkyl group and / or a cycloalkyl group. Preferably, R ^{C1 to} R ^C3 in the aromatic sulfonium compound are all aryl groups. That is, examples of the aromatic sulfonium compound include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, aryldicycloalkylsulfonium compounds and the like, and preferably triarylsulfonium compounds. It can be mentioned.

  The aryl group of the aromatic sulfonium compound is preferably an aryl group such as a phenyl group or a naphthyl group; a heteroaryl group such as an indole residue or a pyrrole residue, more preferably a phenyl group or an indole residue More preferably, a phenyl group is mentioned. When the aromatic sulfonium compound has two or more aryl groups, the two or more aryl groups may be the same as or different from each other.

  As an alkyl group which an aromatic sulfonium compound may have, a C1-C15 linear or branched alkyl group is mentioned, More specifically, a methyl group, an ethyl group, a propyl group, n-butyl group , Sec-butyl group, t-butyl group and the like. As a cycloalkyl group which an aromatic sulfonium compound may have, a C3-C15 cycloalkyl group is mentioned, More specifically, a cyclopropyl group, cyclobutyl group, a cyclohexyl group etc. are mentioned.

The aryl group, alkyl group and cycloalkyl group of R ^{C1 to} R ^C3 may be unsubstituted or may have a substituent. As a substituent, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), an aryl group (for example, 6 to 14 carbon atoms), an alkoxy group (for example, 1 to 15 carbon atoms), A halogen atom, a hydroxyl group, a phenylthio group etc. are mentioned, Preferably, a C1-C12 linear or branched alkyl group, a C3-C12 cycloalkyl group, a C1-C12 linear, branched or branched A cyclic alkoxy group and a phenylthio group are mentioned, More preferably, a C1-C4 alkyl group, a C1-C4 alkoxy group, and a phenylthio group are mentioned. In the case of a triarylsulfonium compound in which R ^{C1 to} R ^C3 are all aryl groups, from the viewpoint of storage stability, as a substituent, an alkyl group (for example, 1 to 15 carbon atoms) or a cycloalkyl group (for example, 3 to 3 carbon atoms) 15), aryl groups (for example, 6 to 14 carbon atoms), alkoxy groups (for example, 1 to 15 carbon atoms), halogen atoms, hydroxyl groups and the like, preferably linear or branched alkyl groups having 1 to 12 carbon atoms And a cycloalkyl group having 3 to 12 carbon atoms and a linear, branched or cyclic alkoxy group having 1 to 12 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms Can be mentioned. The substituent may be substituted on any one of three R ^{C1 to} R ^C3 or may be substituted on all three. Moreover, when a substituent is a substituent of an aryl group, it is preferable to substitute at the p-position of an aryl group. When the substituent is a phenylthio group, the phenylthio group may be unsubstituted, but an alkyl group (for example, 1 to 15 carbon atoms), an alkoxy group (for example, 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, etc. And may have additional substituents.

R ^{C1 to} R ^C3 in the nonaromatic sulfonium compound are each independently preferably an alkyl group, a cycloalkyl group, an allyl group or a vinyl group, more preferably a linear, branched or cyclic 2-oxoalkyl group, an alkoxy It is preferably a carbonylmethyl group, particularly preferably a linear, branched 2-oxoalkyl group.

The alkyl group as R ^{C1 to} R ^C3 may be linear or branched, and specifically, a linear or branched alkyl group having 1 to 10 carbon atoms (eg, a methyl group) , Ethyl group, propyl group, butyl group, pentyl group), preferably linear, branched 2-oxoalkyl group and alkoxycarbonylmethyl group.

The cycloalkyl group as R ^{C1 to} R ^C3 is preferably a cycloalkyl group having a carbon number of 3 to 10 (cyclopentyl group, cyclohexyl group, norbornyl group), more preferably a cyclic 2-oxoalkyl group Be

Preferred examples of the linear, branched or cyclic 2-oxoalkyl group of R ^{C1 to} R ^C3 include the alkyl group described above and a group having> C = O at the 2-position of the cycloalkyl group. The alkoxy group in the alkoxycarbonylmethyl group as R ^{C1 to} R ^C3 is preferably an alkoxy group having 1 to 5 carbon atoms (a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group). R ^{C1 to} R ^C3 may be unsubstituted or may have a substituent. As a substituent, a halogen atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, a nitro group and the like can be mentioned.

The sulfonium salt may be a compound having a plurality of structures represented by Formula (21). For example, any one of R ^{C1 to} R ^C3 of one compound represented by the formula (21) directly or a linking group with any one of R ^{C1 to} R ^C3 of the other compound represented by the formula (21) It may be a compound having a structure linked via

Examples of particularly preferred sulfonium salts in the present invention include the following (21-1) and (21-2). In the following formula (21-2), R ^{c11 to} R ^c13 each independently represent an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), or an aryl group (for example, 6 carbon atoms) To 14), an alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, and a hydroxyl group.

In formula (22), R ^C4 and R ^C5 each independently represent an organic group. The carbon number of the organic group is preferably 1 to 30, more preferably 1 to 20. R ^C4 and R ^C5 may be bonded to each other to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. Examples of the group and R ^C4 and R ^C5 is formed by bonding, an alkylene group (e.g., butylene group, pentylene group). In addition, (22) may be an aromatic iodonium salt in which at least one of R ^C4 and R ^C5 is an organic group having an aromatic ring (aryl group), and any one of R ^C4 and R ^C5 is Although it may be a non-aromatic iodonium salt which is an organic group having no aromatic ring, it is preferably an aromatic iodonium salt from the viewpoint of the ability to initiate cationic polymerization and the like.

^Examples of R ^C4 and R ^C5 include an aryl group, an alkyl group and a cycloalkyl group. As an aryl group of ^RC4 and ^RC5 , Preferably a phenyl group and a naphthyl group are mentioned, More preferably, a phenyl group is mentioned. The alkyl group as R ^C4 and R ^C5 may be linear or branched, and is preferably a linear or branched alkyl group having 1 to 10 carbon atoms (eg, methyl group, ethyl) Group, a propyl group, a butyl group, a pentyl group). The cycloalkyl group as R ^{C4 to} R ^C5 is preferably a cycloalkyl group having a carbon number of 3 to 10 (a cyclopentyl group, a cyclohexyl group, a norbornyl group).

R ^C4 and R ^C5 may be unsubstituted or may have a substituent. As the substituent, for example, alkyl group (for example, 1 to 15 carbon atoms), cycloalkyl group (for example, 3 to 15 carbon atoms), aryl group (for example, 6 to 15 carbon atoms), alkoxy group (for example, 1 to 15 carbon atoms) And halogen atoms, hydroxyl groups and phenylthio groups. Moreover, when a substituent is a substituent of an aryl group, it is preferable to substitute at the p-position of an aryl group.

The iodonium salt may be a compound having a plurality of structures represented by Formula (22). For example, a structure in which R ^C4 or R ^C5 of one compound represented by the formula (22) is directly or via a linking group bonded to R ^C4 or R ^C5 of the other compound represented by the formula (22) And the like.

  Examples of particularly preferred iodonium salts in the present invention include the following (22-1). In the following formula (22-1), n represents an integer of 1 to 15.

The anion X ^- is a non-nucleophilic anion that constitutes the counter anion of the onium salt. The anion X ⁻ is not particularly limited as long as it is an anion containing a carbon atom and a halogen atom. By using an anion containing a carbon atom and a halogen atom as the anion X ⁻ , excellent curability can be obtained regardless of the presence of metal particles in the component (B). Furthermore, by using an anion containing a carbon atom and a halogen atom as the anion X ⁻ , the corrosion of the metal pigment in the cured coating of the active energy ray curable ink composition can be suppressed. The specular gloss durability can be remarkably enhanced. The reason why the specular gloss durability of the cured coating film is remarkably enhanced by using an onium salt having an anion containing a carbon atom and a halogen atom as a counter ion as an active energy ray acid generator is as follows. It is considered that the extremely stable ions suppress the generation of corrosion factors of metal pigments such as hydrogen halide (especially hydrogen fluoride). In addition, as a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, etc. are mentioned, Preferably a fluorine atom is mentioned.

Anion X ^- include specific examples _{^{of, (R 1) a PF 6}} -a -, R 2 b BY 4-b -, R 2 b GaY 4-b -, RfSO 3 -, (RfSO 2) 3 C - or (RfSO _{2) 2} N ^- 1 monovalent polyatomic anion represented by like. Among these anions, (R ¹ ) _a PF _6-a ^- and R ² _b BY _4-b ^- are preferable, and R ² _b BY _4-b ^- is more preferable, from the viewpoint of further enhancing the specular gloss durability. Alternatively, among these anions, (R ¹ ) _a PF _6-a ^- is more preferable from the viewpoint of storage stability. These anions can be used singly or in combination of two or more.

_{^{(R 1) a PF 6-}} a - in anion represented by, P is phosphorus atom, R ¹ represents an alkyl group, or at least a portion of the hydrogen atoms are substituted with fluorine atom alkyl group. a represents an integer of 1 to 6, preferably 1 to 5, more preferably 2 to 4, and further preferably 2 to 3. The a R ^{1 s} may be identical to or different from ^one another. The carbon number of the alkyl group and the fluorine-substituted alkyl group are all those having 1 to 8 carbon atoms, and specifically, straight-chain alkyl groups (methyl, ethyl, propyl, butyl, pentyl, octyl and the like) And branched alkyl groups (such as isopropyl, isobutyl, sec-butyl and tert-butyl) and cycloalkyl groups (such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl). Specific examples of the anion when R ¹ is an alkyl group, for example _{(C 2 H 5) 3 PF} 3 - , and the like. In an alkyl group in which at least a part of hydrogen atoms is substituted with a fluorine atom, a ratio in which a hydrogen atom of the alkyl group is substituted with a fluorine atom is the number of moles of hydrogen atoms of the unsubstituted alkyl group. When it is%, it is preferably 80 mol% or more, more preferably 90% or more, and particularly preferably 100% from the viewpoint of making the photosensitivity of the component (C) good. More specific examples of the alkyl group in which at least a part of hydrogen atoms are substituted by fluorine atoms include CF _3- , CF ₃ CF _2- , (CF ₃ ) ₂ CF-, CF ₃ CF ₂ CF _2- , _{CF 3 CF 2 CF 2 CF 2} -, (CF 3) 2 CFCF 2 -, CF 3 CF 2 (CF 3) CF- and (CF _{3) 3} C-, and the like. Specific examples of the anion when R ¹ is an alkyl group in which at least a portion of the hydrogen atoms are substituted with fluorine atoms, for example _{(CF 3 CF 2) 3 PF} 3 - , and the like.

From the viewpoint of specular gloss ^{_{durability, (R 1) a PF 6}} -a - commercially available as a particularly preferred example of represented by anionic, CPI-200K, CPI-210S , and CPI-400 pg (manufactured by San-Apro Ltd.) And the anion of the active energy ray acid generator. In addition, the anion of CPI-200K, CPI-210S, and CPI-400PG is a product introduction (https://www.san-apro.co.jp/products/detail04.php) by its manufacturer San Apro Ltd. _{"(Rf) n PF 6-n} - " have been labeled, SciFinder provided by chemical information Association ^{(JAICI) (R)} database (https://www.jaici.or.jp/SCIFINDER/index. According to php), for example the anion of the CPI-200K CAS Registry Number: in _{1632315-11-7 (C 2 H 5) 3} PF 3 -, the anion of the CPI-210S CAS Registry Number: in 870681-07-5 ( CF ₃ CF ₂ ) ₃ PF ₃ ^- is listed.

R ² _b BY _4-b ^- in anion represented by, B is a boron atom, phenyl R ² is at least a part of the hydrogen atoms are substituted with an electron withdrawing group having a halogen atom and / or halogen atom Represents a group. Examples of the halogen atom in R ^2, a fluorine atom, a chlorine atom and a bromine atom and the like, preferably a fluorine atom. The electron withdrawing group having a halogen atom includes a trifluoromethyl group and the like. Among these R ² , preferred is a phenyl group in which all hydrogen atoms are substituted with halogen atoms. Y represents a halogen atom. As a halogen atom which comprises Y, a fluorine atom, a chlorine atom, a bromine atom, etc. are mentioned, Preferably a fluorine atom is mentioned. b represents an integer of 1 to 4 and preferably 4 (that is, the anion is represented by BR ² ₄ ). The b R ^{2 s} may be identical to or different from one another.

From the viewpoint of specular gloss ^{_{durability, R 2 b BY 4-b}} - as particularly preferred examples of the anion represented _{by, B (C 6 F 5)} 4 - and the like. _{B (C 6 F 5) 4} - Commercially available actinic Sensan generator having as anions, WPI-124 (Fuji Film manufactured by Wako Pure Chemical Industries, Ltd.), include the like CPI-310B (manufactured by San-Apro Ltd.) Be

In an anion represented, Ga is gallium atom, R ^2, Y and b are the aforementioned _{^{R 2 b BY 4-b -}} - R 2 b GaY 4-b R 2 in the anion represented by, Y And b.

In the anions represented by RfSO ₃ ⁻ , (RfSO ₂ ) ₃ C ⁻ , and (RfSO ₂ ) ₂ N ⁻ , S represents a sulfur atom, O represents an oxygen atom, C represents a carbon atom, and N represents a nitrogen atom, Rf Represents a C 1-20 perfluoroalkyl group. The perfluoroalkyl group may be linear, branched or cyclic.

RfSO ₃ ^- as the anion represented by, trifluoromethanesulfonic acid anion, pentafluoroethanesulfonate anion, heptafluoropropanesulfonate acid anion, nonafluorobutanesulfonic acid anion, pentafluorophenyl sulfonate anion, p- toluenesulfonic acid Anions, benzenesulfonic acid anions, camphorsulfonic acid anions, methanesulfonic acid anions, ethanesulfonic acid anions, propanesulfonic acid anions, butanesulfonic acid anions and the like can be mentioned. Among these, trifluoromethanesulfonic acid anion, nonafluorobutanesulfonic acid anion, methanesulfonic acid anion, butanesulfonic acid anion, camphorsulfonic acid anion, benzenesulfonic acid anion and p-toluenesulfonic acid anion are preferable.

The anion represented _{by, (CF 3 SO 2) 3} C - - (RfSO 2) 3 C, (C 2 F 5 SO 2) 3 C -, (C 3 F 7 SO 2) 3 C - and ( _{C 4 F 9 SO 2) 3} C - anion such as represented and the like.

As the anion represented by (RfSO ₂ ) ₂ N ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , (C ₂ F ₅ SO ₂ ) ₂ N ⁻ , (C ₃ F ₇ SO ₂ ) ₂ N ⁻ and (C ₃ F ₇ SO ₂ ) _{C 4 F 9 SO 2) 2} N - anion such as represented and the like.

  Commercially available products of component (C) include WPI-124 (Fuji Film Wako Pure Chemical Industries, Ltd.), CPI-310B (San Apro Corporation), CPI-200 K (San Apro Corporation) and CPI-210 S (San Apro shares) And CPI-400PG (manufactured by San-Apro Co., Ltd.).

  As content of (C) component in an active energy ray curable ink composition, 0.5-10 mass parts is mentioned with respect to 100 mass parts of (A) components. From the viewpoint of enhancing the curability and specular gloss resistance, the content of the component (C) is preferably 1.3 to 10 parts by mass, and more preferably 1.5 to 10 parts by mass with respect to 100 parts by mass of the component (A). 10 parts by mass, more preferably 2.0 to 10 parts by mass, more preferably 2.5 to 10 parts by mass, particularly preferably 3.0 to 10 parts by mass.

<Other ingredients>
In the active energy ray curable ink composition, in addition to the components described above, a dispersant, a pigment other than the component (B), a surfactant, a sensitizing dye, a storage stabilizer, a polymerization inhibitor, an ultraviolet absorber, oxidation One or more of an inhibitor, an antifading agent, a conductive salt, an organic solvent, a polymer compound and the like can be included. Each component illustrated below can be used individually by 1 type or in combination of multiple types.

  Examples of the dispersant include acidic dispersants (polymer compounds having an acidic pigment hydrophilic group at least at one end of the main chain due to a block or graft structure). Examples of the acidic pigment hydrophilic group include a carboxyl group, a sulfonic acid group and a phosphoric acid group. Examples of the polymer compound include polyacrylates, polyurethanes, polyesters, and modified products thereof.

  As pigments other than the above component (B), generally available organic pigments and inorganic pigments which are commercially available; those obtained by dispersing a pigment in an insoluble resin as a dispersion medium; those obtained by grafting a resin on the pigment surface; resin particles And those dyed with a dye.

  As surfactants, anionic surfactants such as dialkyl sulfosuccinates, alkyl naphthalene sulfonates, fatty acid salts, etc .; polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, acetylene glycols, polyoxyethylene. Nonionic surfactants such as polyoxypropylene block copolymers; and cationic surfactants such as alkylamine salts and quaternary ammonium salts.

  A sensitizing dye can be added for the purpose of improving the sensitivity of the active energy ray acid generator, and those having an absorption wavelength in the wavelength range of 350 nm to 450 nm can be mentioned. Specifically, polynuclear aromatics such as pyrene, perylene, triphenylene, 2-ethyl-9,10-dimethoxyanthracene; fluoresceins, eosin, erythrosine, rhodamine B, xanthenes such as rose bengal; Cyanines such as oxacarbocyanines; merocyanines such as merocyanines and carbomerocyanines; thiazines such as thionine, methylene blue and toluidine blue; acridines such as acridine orange, chloroflavin and acriflavine; anthraquinones; (For example, squalium such as 7-diethylamino-4-methylcoumarin and the like can be mentioned.

  As a storage stabilizer, amine compounds such as triethanolamine, triisopropanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like; 2-mercaptobenzothiazole, 2-mercaptobenzoxazole Thiol compounds such as 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene and their sulfide compounds or disulfide compounds; Amino acid compounds such as N-phenylglycine; Organometallics such as tributyltin acetate Compounds; hydrogen donors; sulfur compounds such as trithiane; and phosphorus compounds such as diethyl phosphite. The content of the storage stabilizer is, for example, 0.03 to 0.15 parts by mass, preferably 0.05 to 0.12 parts by mass, per 100 parts by mass of the component (A).

  Examples of polymerization inhibitors include phenolic hydroxyl group-containing compounds, quinones, N-oxide compounds, piperidine-1-oxyl free radical compounds, pyrrolidine-1-oxyl free radical compounds, N-nitrosophenylhydroxylamines, And cationic dyes.

  An ultraviolet absorber can be added for the purpose of weatherability improvement and discoloration prevention. Specifically, benzotriazole compounds, benzophenone compounds, cinnamic acid compounds, triazine compounds, stilbene compounds, benzoxazole compounds and the like can be mentioned.

  Examples of the antioxidant include phenol-based antioxidants, amine-based antioxidants, sulfur-based antioxidants, and phosphorus-based antioxidants.

  Examples of antifading agents include organic and metal complex antifading agents, and examples of organic antifading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, and the like. Indans, chromans, alkoxy anilines, heterocycles, etc. are mentioned; As an antifading agent of metal complex type, a nickel complex, a zinc complex, etc. are mentioned.

  The conductive salts can be added for the purpose of controlling the ejection properties. Specifically, potassium thiocyanate, lithium nitrate, ammonium thiocyanate, dimethylamine hydrochloride and the like can be mentioned.

  The organic solvent is added for the purpose of dispersing the metal particles of the component (B), the purpose of improving the adhesion to the object forming the cured coating film, etc., and the components such as the component (C) What is used as a solvent is mentioned. Specific examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone and diethyl ketone; alcohol solvents such as methanol, ethanol, 2-propanol, 1-propanol, 1-butanol and tert-butanol; chloroform and chloride Chlorinated solvents such as methylene; aromatic solvents such as benzene and toluene; ester solvents such as ethyl acetate, butyl acetate and isopropyl acetate; ether solvents such as diethyl ether, tetrahydrofuran and dioxane; ethylene glycol monomethyl ether, ethylene glycol Examples include glycol ether solvents such as dimethyl ether and propylene glycol monomethyl ether; cyclic carbonate solvents such as ethylene carbonate and propylene carbonate.

  The polymer compound can be added for the purpose of adjusting the film physical properties. Specifically, acrylic polymers, polyvinyl butyral resin, polyurethane resin, polyamide resin, polyester resin, epoxy resin, phenol resin, polycarbonate resin, polyvinyl butyral resin, polyvinyl formal resin, shellac, vinyl resin, acrylic resin, Rubber-based resins, waxes, other natural resins, etc. may be mentioned.

<Use>
The active energy ray curable ink composition of the present invention can be used, for example, as an inkjet ink composition. In this case, the viscosity at 25 ° C. is, for example, 5 to 40 mPa from the viewpoint of improving the ejectability from the ink jet head and from the viewpoint of obtaining good printing characteristics by suppressing penetration to the recording paper when printing on recording paper.・ S is mentioned. The viscosity is a value measured under the conditions of 100 rpm using an E-type viscometer according to JIS K7117-1.

  Further, the active energy ray curable ink composition of the present invention can be used as an optional paint ink composition other than the ink composition for inkjet. When used in any paint ink composition other than the inkjet ink composition, the viscosity at 25 ° C. may exceed the above viscosity range. Furthermore, since the active energy ray-curable ink composition of the invention is excellent in the specular gloss durability of the cured coating film, the cured coating film is formed on the surface of an article used in a wet environment or a wet environment described later. It is preferably used in the following applications.

<Production of Active Energy Ray-Curable Ink Composition>
The active energy ray curable ink composition of the present invention can be prepared by dispersing the above-mentioned component (A), the above component (B) and the above component (C), and, if necessary, other components in a non-aqueous system. it can. These components may be simultaneously mixed and dispersed, or the component (B) may be prepared by first preparing a dispersion with a high concentration of metal particles, and then adding and diluting the component (A) and the component (C). You can also.

  Dispersion can be performed using, for example, a dispersion apparatus such as a ball mill, sand mill, attritor, roll mill, jet mill, homogenizer, paint shaker, kneader, agitator, Henschel mixer, colloid mill, ultrasonic homogenizer, pearl mill, wet jet mill, etc. .

  The active energy ray-curable ink composition can be prepared such that the total amount of components other than the organic solvent is 20 to 100% by mass, preferably 40 to 95% by mass.

<Cured coating>
The cured coating film of the present invention is obtained by forming a coating film on the surface of an object by inkjet or coating, and curing by irradiation with active energy rays. As an active energy ray, an ultraviolet ray, an electron beam, etc. are mentioned. When using an ultraviolet ray as an active energy ray, a mercury lamp, a metal halide lamp, etc. can be used, and an integral light quantity can be made into 100-10000 mJ / cm < ² >, for example. When an electron beam is used as the active energy ray, the acceleration voltage can be, for example, 150 to 250 keV, and the irradiation amount can be 1 to 20 Mrad.

  The cured coating exhibits excellent mirror gloss. The 60 ° gloss value of the cured coating film is, for example, 250 or more, preferably 300 or more, more preferably 350 or more, still more preferably 390 or more, particularly preferably 400 or more.

<Articles>
The articles of the present invention have the cured coating described above. In an article having a cured coating, the cured coating may be provided on the surface of the article directly or through a subbing layer. Moreover, the surface of the said cured coating film may be exposed so that external air may be contacted, and also the transparent layer may be laminated | stacked.

  The article on which the cured coating film is provided is not particularly limited, and examples of the material of the article include metal, glass, resin, rubber, stone material, and concrete. Moreover, since the active energy ray-curable ink composition of the present invention is excellent in specular gloss durability of a cured coating film, it is particularly preferable to be an article used in a wet environment or a wet environment. Here, the wet environment means an environment with a humidity of 40% or more, and the wet environment means an environment in which water is constantly or occasionally contacted. Examples of articles used in a wet environment or in a wet environment include, for example, fishing rods, umbrellas, tents, bicycles, helmets, golf clubs, skis, snowboard boards, leisure equipment such as floats, and so on; bathtubs, Indoor watering articles such as ceiling panels, wall panels, floor pans, doors, water faucets, mirrors, sinks, toilets, handwashers, humidifiers, etc .; buildings, signs, guide plates, portals, gates, shutters, mail receivers, handrails, etc. Outdoor structures.

  EXAMPLES The present invention will be more specifically described below by showing Examples and Comparative Examples, but the present invention is not limited thereto. The reagent etc. which were used in the Example and the comparative example are shown below.

(A) Binder component-oxetane compound OXT-221: manufactured by Toagosei Co., Ltd. 3-ethyl-3 {[(3-ethyloxetan-3-yl) methoxy] methyl} oxetane OXT-101: Toagosei Co., Ltd. Made, 3-ethyl-3-hydroxymethyl oxetane (oxetane alcohol)
OXT-212: manufactured by Toagosei Co., Ltd., 3-ethyl-3-[(2-ethylhexyloxy) methyl] oxetane

(A) Binder component-epoxy compound · celloxide 2021 P: manufactured by Daicel, 3 ', 4'- epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate LDO: manufactured by ARKEMA Co., (4R) -1, 2 -Epoxy-4- (2-methyloxiranyl) -1-methylcyclohexane (limonene dioxide)
YED-216M: manufactured by Mitsubishi Chemical Corporation, 1,6-hexanediol diglycidyl ether

(A) Binder component-Silane coupling agent-Dynasilane GLYMO: manufactured by Evonik Japan, 3-glycidyl oxypropyl trimethoxysilane

(B) Metal pigment / aluminum pigment dispersion (The aluminum pigment having an average particle diameter of 0.5 μm and an average thickness of 0.02 μm dispersed in propylene glycol monomethyl ether. The contained amount of aluminum pigment is 10% by mass.)

(C) Active energy ray acid generator WPI-124: 50% by mass propylene carbonate solution of bis [4- (alkyl C10 to C13) phenyl] iodonium tetrakis pentafluorophenyl borate manufactured by Fuji Film Wako Pure Chemical Industries, Ltd. CPI-310B: San-Apro Co., Ltd., triarylsulfonium borate salt CPI-200K: San-Apro Co., Ltd., 50% by mass propylene carbonate solution of triarylsulfonium phosphate salt WPI-116: Fujifilm Wako Pure Chemical Industries, Ltd. 50% by mass propylene carbonate solution of bis [4-alkyl (C10 to C13) phenyl] iodonium hexafluoroantimonate • CPI-101A: 50% by mass of triarylsulfonium hexafluoroantimonate manufactured by San-Apro Co., Ltd. Acid propylene solution · CPI-100P: 50% by mass propylene carbonate solution of triarylsulfonium hexafluorophosphate salt in propylene carbonate solution · WPI-113: Fuji Film Wako Pure Chemical Industries, Ltd., bis [4- n 50% by mass propylene carbonate solution of alkyl (C10-13) phenyl] iodonium hexafluorophosphate salt OMNICAT 250: manufactured by IGM, (4-methylphenyl) [4- (2-methylpropyl) phenyl] iodonium hexafluorophosphate 75 mass% propylene carbonate solution of salt

Storage stabilizer TIPA: triisopropanolamine

[Test Example 1]
Active energy ray-curable ink compositions (Examples 1 to 14 and Comparative Examples 1 to 6) having the compositions described in Tables 1 to 3 were prepared. Specifically, the active energy ray curable ink composition was prepared by mixing the components in the amounts described in Tables 1 to 3. The active energy ray curable ink composition is prepared as an ink composition for inkjet. In addition, the unit of the numerical value which shows the quantity of each component of Table 1-Table 3 is a mass part.
Moreover, the quantity of each component is shown as a quantity of components other than the organic solvent. For example, in the component (C), for CPI-200K, which is a 50% by mass solution of an active energy ray acid generator, converted to the amount of the active energy ray acid generator in the reagent instead of the amount of the CPI-200K reagent Described. As for the component (B), not the amount of the aluminum pigment dispersion but the amount of the aluminum pigment contained in the dispersion is described (in accordance with this, not the aluminum pigment dispersion but the “aluminum pigment” Described).
The obtained active energy ray curable ink composition was subjected to the following evaluation test. The results are shown in Tables 1 to 3.

[Ink jet suitability]
An ink jet head is filled with an active energy ray curable ink composition using an ink jet printer equipped with a piezo type ink jet head (Konica Minolta Co., Ltd., KM 1024 L, ink droplet volume 40 pl), and a nozzle at a head temperature of 40 ° C. Perform check pattern printing, confirm that the ink is ejected from all the nozzles, and print an image of 70 mm × 70 mm on a PET film (Cosmo Shine ^(R) A4300 thickness 100 μm) with resolution of 720 × 720 dpi. We performed (solid printing). Then, after standing still for 30 minutes with the power on, nozzle check pattern printing was performed on a PET film (Cosmo Shine ^(R) A4300 thickness 100 μm manufactured by Toyobo Co., Ltd. ⁾ . The defect state of the check pattern was ranked into five levels as follows according to the print defect rate with respect to the total number of nozzles, and the inkjet suitability was evaluated. The larger the number, the better the inkjet suitability.

5 ... When the print defect rate is less than 1% of the total nozzle number 4 ... When the print defect rate is 1% or more and less than 5% of the total nozzle number 3 ... 5 print defect rate is 5 of the total nozzle number % Or more and less than 20% 2 ... when the print defect rate is 20% or more and less than 50% of the total number of nozzles 1 ... when the print loss rate is 50% or more of the total number of nozzles

[Curable]
The active energy ray-curable ink composition was coated on a PET film (Cosmo Shine ^(R) A4300 thickness 100 μm) using a 1-mil applicator. The coated material obtained was subjected to ultraviolet irradiation with an integrated light quantity of 500 mJ / cm 2 using a high pressure mercury lamp (UB 041-5 A / B 60 Hz manufactured by I-Graphics Co., Ltd.). The cured state of the coating film after the ultraviolet irradiation was evaluated according to the following evaluation criteria by the finger tack of the coating film surface. The larger the number, the better the curability is evaluated.

5 ・ ・ ・ Sufficiently cured, no tackiness 4 ・ ・ ・ Tackiness, but no fingerprints left even when touched with fingers 3 ・ ・ ・ There is tackiness, fingerprints remain when touched with fingers While stick coating component touches the coating film 2 ... fingers on the finger, thickening (hardening) 1 ... not cured at all that is [specular glossiness -60 ° gloss value
Piezo type inkjet head (Konica Minolta Co., KM1024L, ink droplet volume 40 pl) using an inkjet printer equipped with a head temperature of 40 ° C., resolution 720 × 720 dpi, in the conditions, PET films (Toyobo Cosmo Shine ^{(R )} A4300 thickness 100 μm) The active energy ray curable ink composition is discharged to print an image of 70 mm × 70 mm (solid printing), and immediately thereafter, the active energy ray curable property is printed by irradiating ultraviolet rays. The ink composition was cured. The cured PET film was heat-treated at 120 ° C. for 3 minutes to obtain a sample for evaluation. In addition, the ultraviolet irradiation to the ink composition after solid printing was performed by irradiating an ultraviolet-ray on the conditions of 500 mJ / cm < ² > of irradiation doses about 10 seconds after ink discharge using the said inkjet printer attachment apparatus. The 60 ° gloss value of the coating film surface in the obtained evaluation sample was measured using a gloss meter “micro-gloss” manufactured by BYK-Gardner GmbH.

[Surface gloss durability-gloss change rate]
The above-mentioned sample for evaluation was immersed in water at 50 ° C. for 3 days (72 hours) by a method according to the procedure of liquid resistance (water immersion method) of JIS K5600-6-2. The change rate (gloss change rate) of the 60 ° gloss value of the coating film surface in the evaluation sample before and after immersion was calculated based on the following equation. The measurement method of the 60 ° gloss value is the same as the measurement method of the gloss value in the above-mentioned gloss test. The smaller the rate of change in gloss, the less the corrosion of the aluminum, and the better the specular gloss durability.
Gloss change rate (%) = (Gloss value before test−Gloss value after test) / (Gloss value before test) × 100

[Mirror surface gloss durability-change amount of total light transmittance]
The above-mentioned evaluation sample was immersed in water under the same conditions as Durability Evaluation 1. The amount of change in total light transmittance of the samples before and during the immersion evaluation was calculated based on the following equation. The total light transmittance was measured using a haze meter NDH4000 manufactured by Nippon Denshoku Industries Co., Ltd. The smaller the amount of change in the total light transmittance, the less the corrosion of aluminum and the better the specular gloss durability.
Amount of change in total light transmittance = initial total light transmittance-total light transmittance after test

  From Tables 1 to 3, in Comparative Examples 2 to 6 in which the anion of the onium salt which is the active energy ray acid generator (C) does not contain both a carbon atom and a halogen atom, the gloss change rate and the total light transmittance change amount In Examples 1 to 14 in which the anion contains a carbon atom and a halogen atom, the gloss change rate and the total light transmittance change amount are very small, whereas the mirror gloss is extremely large. It was found that the durability was remarkably improved. Moreover, the said anion contains a carbon atom and a halogen atom from the comparison with Comparative Examples 2-6 and Examples 1-3 whose conditions other than an active energy ray acid generator (C) are the same. It was also found that the curability was good. In the active energy ray curable ink compositions of Examples 1 to 14 exhibiting such excellent specular gloss durability and curability, the specular gloss itself is also good, and when not cured (Comparative Example 1), It also had almost the same good inkjet suitability.

[Test Example 2]
The following storage stability evaluations were performed on the active energy ray curable ink compositions of Examples 1 to 3. The results are shown in Table 4.

[Storage stability]
The storage stability of the active energy ray-curable ink composition was evaluated in accordance with the normal temperature storage stability operation of JIS K5600-2-7. Specifically, 30 ml of an active energy ray curable ink composition was filled in a sealed / lightproof glass container having a volume of about 50 ml, and allowed to stand at 40 ° C. for 7 days. From the viscosities of the active energy ray-curable ink composition before and after standing, the thickening ratio was calculated based on the following equation. The viscosity was measured according to JIS K 7117-1 using an E-type viscometer (RE-85 viscometer manufactured by Toki Sangyo Co., Ltd.) under the condition of 100 rpm.
Viscosity ratio (%) = (viscosity after test-viscosity before test) / (viscosity before test) x 100

  As shown in Table 4, in Examples 2 and 3 in which a sulfonium salt was used as an active energy ray acid generator (C), as compared with Example 1 in which an iodonium salt was used as an active energy ray acid generator (C). It was found that the thickening rate was very low, and also had excellent storage stability.

Claims (13)

A binder component (A) containing a cationically polymerizable compound, a metal pigment (B), and an active energy ray acid generator (C),
The component (C) is an onium salt in which an anion containing a carbon atom and a halogen atom is a counter anion,
The cationically polymerizable compound contains an oxetane compound and an epoxy compound, and the content of the epoxy compound is 54 to 71 parts by weight with respect to 100 parts by mass of the cationically polymerizable compound,
The ^{_{anion, R 1 a PF 6-a}} - and ^{_{R 2 b BY 4-b -}} (R 1 represents an alkyl group or at least part of the hydrogen atoms are substituted with fluorine atom alkyl group; R ² is At least a part of hydrogen atoms is a halogen atom and / or a phenyl group substituted by an electron-withdrawing group having a halogen atom; Y is a halogen atom; a is an integer of 1 to 6; An active energy ray-curable ink composition selected from the group consisting of: an integer of 4). The active energy ray curable ink composition according to claim 1, wherein the anion is B (C ₆ F ₅ ) ₄ ^— . The active energy ray curable ink composition according to claim 1 or 2 , wherein the onium salt is selected from the group consisting of a sulfonium salt and an iodonium salt. The active energy ray curable ink composition according to any one of claims 1 to 3 , wherein the onium salt is a sulfonium salt. The active energy ray curable ink composition according to any one of claims 1 to 4 , wherein the cationically polymerizable compound contains at least an oxetane compound having two or more oxetane rings in the molecule. The active energy ray curable ink composition according to any one of claims 1 to 5 , wherein the component (A) further contains a silane coupling agent. The active energy ray curable ink composition according to any one of claims 1 to 6 , wherein the component (B) contains aluminum particles. The active energy ray curable ink composition according to any one of claims 1 to 7 , wherein the content of the component (B) is 0.1 to 20 parts by mass with respect to 100 parts by mass of the component (A). object. The active energy ray curable ink composition according to any one of claims 1 to 8 , wherein the content of the component (C) is 0.5 to 10 parts by mass with respect to 100 parts by mass of the component (A). object. The active energy ray curable ink composition according to any one of claims 1 to 9 , which is an ink composition for inkjet. A cured coating film of the active energy ray curable ink composition according to any one of claims 1 to 10 . An article having the cured coating film according to claim 11 . The article according to claim 12 , which is used in a wet environment or a wet environment.