JP2005239877A - Composition of agent generating acid by active energy ray, active energy ray-curable composition, ink composition for inkjet, and image-forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition of an agent generating an acid by an active energy ray, having excellent preservability; to provide an active energy ray-curable composition having excellent preservability even in a state mixed with a cationically polymerizable monomer; to provide an ink composition for inkjet, excellently prevented from being thickened even after a long term preservation, having excellent ink curability and adhesion to a base material, and providing an image having high quality without bleeding; and to provide an image-forming method by using the ink composition. <P>SOLUTION: The composition of the agent generating the acid by the active energy ray contains a compound represented by general formula (a): Q<SP>n+</SP>(Y<SP>m-</SP>)<SB>n/m</SB>and a compound represented by general formula (b). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an active energy ray acid generator composition containing a triarylsulfonium salt compound and a specific ionic compound, an active energy ray curable composition containing the same, and an ink-jet ink composition and image using the same. Regarding the formation method, in detail, an active energy ray curable composition containing an active energy ray acid generator composition containing a triarylsulfonium salt compound and a specific ionic compound is used, and a high-reactivity and high-quality image is obtained. The present invention relates to a photocurable ink composition for inkjet and an image forming method.

  In recent years, the inkjet recording method can create images easily and inexpensively, and thus has been applied to various printing fields such as photographs, various printing, marking, and special printing such as color filters. In particular, recording devices that emit and control fine dots, ink with improved color reproduction gamut, durability, emission suitability, etc., and improved ink absorbency, color development, surface gloss, etc. It is also possible to obtain image quality comparable to silver halide photography using special paper. The image quality improvement of today's ink jet recording system is achieved only when all of the recording apparatus, ink, and special paper are available.

  However, in an inkjet system that requires dedicated paper, the recording medium is limited, and the cost of the recording medium increases. Therefore, many attempts have been made to record on a transfer medium different from dedicated paper by an ink jet method. Specifically, a phase change ink jet method using a wax ink that is solid at room temperature, a solvent ink jet method using an ink mainly composed of a fast-drying organic solvent, a UV ink jet method that is crosslinked by ultraviolet (UV) light after recording, etc. It is.

  Among these, the UV inkjet method has been attracting attention in recent years because it has a relatively low odor compared to the solvent-based inkjet method, and can be recorded on a recording medium having no quick drying and no ink absorption. Discloses an ultraviolet curable ink-jet ink.

  Generally, as the ultraviolet curable ink, a radical polymerization type ink is well known and put into practical use. On the other hand, the cationic polymerization type ink does not inhibit the polymerization caused by oxygen as seen in radical polymerization type inks, can use a light source with low illuminance, has no odor of acrylic monomers, and has low irritation. Although there are advantages such as being there, it has not yet been put into practical use.

One reason for this is the property that the sensitivity decreases significantly under high humidity, the property that the sensitivity depends on temperature, and the increase in the viscosity of the ink during long-term storage. Environment-dependent inks have the essential problem that their image quality depends on the environment.
JP-A-6-200204 Special Table 2000-504778

  The present invention has been made in view of the above problems, and its purpose is to provide an active energy ray acid generator composition having excellent storage stability, and also to storage stability even when mixed with a cationic polymerizable monomer. Providing an active energy ray curable composition that is excellent and highly curable, and also has excellent suppression of thickening even when stored for a long period of time, excellent ink curability and substrate adhesion, and high-quality images without bleeding. An object of the present invention is to provide an inkjet ink composition and an image forming method using the same.

  The above object of the present invention can be achieved by the following constitution.

(Claim 1)
An active energy ray acid generator composition comprising a compound represented by the following general formula (a) and a compound represented by the following general formula (b).

Formula (a) Q ^{n +} (Y ^m− ) _{n / m}
(In the formula, Q ^{n +} is an n-valent cation, Y ^m− is an ^m- valent cation whose pKa value of the conjugate acid is larger than the pKa of the X ^B− conjugate acid in the following general formula (b)). Represents an anion, and n and m each represent an integer of 1 to 3.)

(In the formula, R ^{B1 to} R ^B3 represent substituents, and X ^B- represents a counter ion.)
(Claim 2)
The active energy ray according to claim 1, wherein the compound represented by the general formula (b) is at least one compound selected from the following general formulas (I-1) to (I-3). Acid generator composition.

(In the formula, R ₁₁ , R ₁₂ and R ₁₃ represent substituents, m, n and p each represents an integer of 0 to 5, and X ₁₁ ⁻ represents a counter ion.)

(Wherein R ₁₄ represents a substituent, and q represents an integer of 0 to 2. R ₁₅ and R ₁₆ represent a substituted, unsubstituted alkyl group, a substituted, unsubstituted alkenyl group, a substituted, unsubstituted alkynyl group. or substituted, .X ₁₂ representing the unsubstituted aryl group ^- represents a counter ion).

(Wherein R ₁₇ represents a substituent, r represents an integer of 0 to 3. R ₁₈ represents a hydrogen atom or a substituted or unsubstituted alkyl group, and R ₁₉ and R ₂₀ represent a substituted or unsubstituted alkyl group. , substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group or a substituted, .X ₁₃ representing the unsubstituted aryl group ^- represents a counter ion).
(Claim 3)
The active energy ray acid generator composition according to claim 2, wherein the compound represented by the general formula (I-1) is a compound represented by the following general formula (T-1).

(Wherein R ^T11 and R ^T12 represent an alkyl group or an aromatic group, Z ^T1 represents an oxygen atom or a sulfur atom, and R ^T13 and R ^T14 represent an alkyl group, an aromatic group, an alkoxy group, and an aryloxy group, respectively. , An alkylthio group and an arylthio group, m ^t1 represents an integer of 0 to 4, n ^t1 and p ^t1 each represent an integer of 1 to 5, and X ^T1 represents a counter anion.)
(Claim 4)
The active energy ray acid according to any one of claims 1 to 3, wherein Q ^{n +} in the general formula (a) is a cation having any one of N ⁺ , S ⁺ , and P ^+. Generator composition.

(Claim 5)
The active energy ray acid generator composition according to claim 4, wherein the Q ^{n +} is a quaternary ammonium cation or a pyridinium cation.

(Claim 6)
Y ^m− in the general formula (a) is Cl ⁻ , Br ⁻ , I ⁻ , R ⁶⁰¹ —SO ₃ ⁻ , SO ₄ ²⁻ , NO ₃ ⁻ , R ⁶⁰² —COO ⁻ , AlO ₂ ⁻ , ClO _{4. ^{-, PO 4 3-, B (}} C 6 H 5) 4 -, R 603 -O - at least one anion selected from, X in the general formula (b) ^B- is, PF ₆ ^-, BF _{4 ^{-, SbF 6 -, GaF 6}} -, AsF 6 -, B (C 6 F 5) 4 - , wherein the at least one anion selected from ^{_{-, C n F (2n +}} 1) SO 3 The active energy ray acid generator composition of any one of Claims 1-5.
However, n is an integer of 1 to 30, R ⁶⁰¹ and R ⁶⁰² are each independently an aliphatic group having 1 to 30 carbon atoms or an aromatic group having 6 to 20 carbon atoms, and R ⁶⁰³ is an alkyl group having 6 to 20 carbon atoms. Represents an aromatic group.

(Claim 7)
An active energy ray curable composition comprising an epoxy compound and the active energy ray acid generator composition according to any one of claims 1 to 6.

(Claim 8)
The active energy ray-curable composition according to claim 7, wherein the epoxy compound is an alicyclic epoxy compound represented by the following general formula (A).

(In the formula, R ₁₀₀ represents a substituent, m 0 represents an integer of 0 to 2, r ₀ represents an integer of 1 to 3. L ₀ has 1 to 15 carbon atoms which may contain an oxygen atom or a sulfur atom in the main chain. Represents an r0 + 1-valent linking group or a single bond.)
(Claim 9)
The active energy ray-curable composition according to claim 7 or 8, wherein the epoxy compound is at least one of alicyclic epoxy compounds represented by the following general formulas (1) to (6).

(Wherein the R ₁₀₁ are substituents, .P1 which m1 is an integer of 0 to 2, q1 and each 0 or 1, r1 is .L ₁ represents an integer of 1 to 3 oxygen atoms or in the main chain (It represents a C1-C15 r1 + 1 valent linking group or single bond which may contain a sulfur atom.)

(Wherein the R ₁₀₂ are substituents, .P2 which m2 represents an integer of 0 to 2, q2 and each 0 or 1, r2 is .L ₂ represents an integer of 1 to 3 oxygen atoms or in the main chain (It represents a C1-15 r2 + 1 valent linking group or single bond which may contain a sulfur atom.)

(In the formula, R ₁₀₃ represents a substituent, m3 represents an integer of 0 to 2. p3 represents 0 or 1. L ₃ has 1 to 8 carbon atoms which may contain an oxygen atom or a sulfur atom in the main chain. Represents a divalent linking group or a single bond.)

(In the formula, R ₁₀₄ represents a substituent, m4 represents an integer of 0 to 2. p4 represents 0 or 1. L ₄ has 1 to 8 carbon atoms which may contain an oxygen atom or a sulfur atom in the main chain. Represents a divalent linking group or a single bond.)

(In the formula, R ₁₀₅ represents a substituent, and m5 represents 1 or 2.)

(In the formula, R ₁₀₆ represents a substituent, and m6 represents an integer of 0 to 2.)
(Claim 10)
The active energy ray-curable composition according to claim 7, comprising an oxetane compound.

(Claim 11)
The active energy ray-curable composition according to any one of claims 7 to 10, wherein the active energy ray of the active energy ray acid generator composition is an ultraviolet ray.

(Claim 12)
An ink composition for ink jet, comprising the active energy ray-curable composition according to any one of claims 7 to 11.

(Claim 13)
The inkjet ink composition according to claim 12 is ejected onto a recording material by a recording head having at least one nozzle capable of selectively controlling ejection of the ink droplet, and the ink droplet is landed. Thereafter, the ink is cured by irradiating with an active energy ray.

  According to the present invention, an active energy ray acid generator composition having excellent storage stability is provided, and an active energy ray curable composition having excellent storage stability and high curability even when mixed with a cationic polymerizable monomer is provided. Ink jet ink composition that is excellent in suppressing thickening even when stored for a long period of time, has excellent ink curability and substrate adhesion, and can produce a high-quality image without bleeding, and an image forming method using the same Can be provided.

  As a result of intensive studies in view of the above problems, the present inventor obtained an active energy linear acid generating composition excellent in preservability by using a specific sulfonium salt compound and a specific ionic compound in combination. By using a specific cationic polymerizable monomer for this, an active energy ray curable composition having excellent storage stability and high curability can be obtained. When this active energy ray curable composition is used in an inkjet ink, it is long. Even when stored for a long period of time, it has been found that the suppression of thickening of the ink liquid is very excellent, and as soon as the present invention has been achieved.

  The present invention will be described in detail below.

In the general formula (a), Q ^{n +} represents an n-valent cation, n represents an integer of 1 to 3, and Q ^{n +} is not particularly limited as long as it is a cation, but examples include metal ions, N Mention may be made of cations containing ⁺ , S ⁺ , O ⁺ or P ⁺ .

The metal ions are preferably Li ⁺ , Na ⁺ , K ⁺ , Be ²⁺ , Mg ²⁺ , Ca ²⁺ , Fe ²⁺ , Fe ³⁺ , Ru ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ⁺ , Cu ²⁺ , Ag ⁺ , Zn ²⁺ , Al ³⁺ , more preferably Li ⁺ , Na ⁺ , K ⁺ , Mg ²⁺ , Ca ²⁺ , Zn ²⁺ , Al ³⁺ , most preferably Na ⁺ , K ⁺ and Ca ²⁺ .

Examples of the cation containing N ⁺ include compounds represented by the following general formula (a-1) and general formula (a-2).

In General Formula (a-1), R ^A11 represents a hydrogen atom or an alkyl group, an alkenyl group, an alkynyl group, an aromatic hydrocarbon group, or a heteroaromatic group, and R ^{A12 to} R ^A14 each independently represents an alkyl group, an alkenyl group, Group, alkynyl group, aromatic hydrocarbon group, heteroaromatic group, examples include alkyl groups (eg, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group) Group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (eg, vinyl group, allyl group, etc.), alkynyl group (eg, ethynyl group, propargyl group, etc.), aromatic Hydrocarbon group (eg, phenyl group, naphthyl group, etc.), heteroaromatic group (eg, furyl group, thienyl group, pyridi) Group, pyridazyl group, pyrimidyl group, pyrazyl group, triazyl group, imidazolyl group, pyrazolyl group, thiazolyl group, benzoimidazolyl group, benzoxazolyl group, quinazolyl group, phthalazyl group, etc.), heterocyclic group (for example, pyrrolidyl group, Imidazolidyl group, morpholyl group, oxazolidyl group, etc.), and these R ^{A11 to} R ^A14 may further have a substituent and can be substituted with the substituent represented by R ^{A11 to} R ^A14. Examples of the alkyl group, the alkenyl group, the alkynyl group, the aromatic hydrocarbon group, the heteroaromatic group, the heterocyclic group, and the alkoxy group (for example, methoxy group, ethoxy group, propyloxy group, pentyl). Oxy group, hexyloxy group, octyloxy group, dodecyloxy group, etc.), cycloalkoxy group (for example, cyclopentyl) Xy group, cyclohexyloxy group, etc.), aryloxy group (for example, phenoxy group, naphthyloxy group, etc.), alkylthio group (for example, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc. ), Cycloalkylthio group (for example, cyclopentylthio group, cyclohexylthio group, etc.), arylthio group (for example, phenylthio group, naphthylthio group, etc.), alkoxycarbonyl group (for example, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl) Group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfamoyl group (eg, Minosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2 -Pyridylaminosulfonyl group, etc.), acyl groups (for example, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthyl) Carbonyl group, pyridylcarbonyl group, etc.), acyloxy group (for example, acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy) Group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), amide group (for example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexyl group) Carbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl) Group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexyl Aminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido) Group, dodecylureido group, phenylureido group, naphthylureido group, 2-pyridylaminoureido group, etc.), sulfinyl group (for example, methylsulfinyl group, ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecyl) Sulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-pyridylsulfinyl group, etc.), alkylsulfonyl group (for example, methylsulfonyl group, Acetylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl group (phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (for example, amino Group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, etc.), halogen atom (for example, fluorine atom, Chlorine atom, bromine atom, etc.), fluorinated hydrocarbon group (eg, fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, pentafluorophenyl group, etc.), cyano group, nitro group, hydroxy group, mercapto group, silyl Group (for example, , Trimethylsilyl group, triisopropylsilyl group, triphenylsilyl group, phenyldiethylsilyl group, etc.), hydroxyl group, nitro group, carboxyl group and the like. These substituents are substituents represented by R ^{A11 to} R ^A14. The substituent may be further substituted with a group having the same meaning as the example of the substitutable group, and a plurality of these substituents may be bonded to each other to form a ring. R ^{A11 to} R ^A14 are preferably an alkyl group having 1 to 30 carbon atoms or an alkyl group substituted with an aromatic hydrocarbon, and more preferably an alkyl group having 1 to 18 carbon atoms.

In the general formula (a-2), R ^A21 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aromatic hydrocarbon group or a heteroaromatic group, preferably an alkyl group, more preferably 1 carbon atom. -30 alkyl group or an alkyl group substituted by an aromatic hydrocarbon, more preferably an alkyl group having 1-18 carbon atoms. Q ^A2 represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing aromatic ring together with the nitrogen cation and X ^A2 , X ^A2 represents carbon, nitrogen, sulfur, and oxygen, and the nitrogen cation and X ^A2 Examples of 5-membered or 6-membered rings formed by imidazole ring, pyrazole ring, thiazole ring, isothiazole ring, oxazole ring, isoxazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring Preferably, it is an imidazole ring, a pyrazole ring or a pyridine ring, and more preferably a pyridine ring. R ^A22 each independently represents a hydrogen atom or a substituent which can be substituted at any position of a 5-membered or 6-membered ring formed by Q ^A2 , a nitrogen cation and X ^A2 , and n ^A2 represents an integer of 1 to 5 As examples of R ^A22 , the same substituents as the examples of the groups that can be substituted for the substituents represented by R ^{A11 to} R ^A14 described above can be given. These substituents may be further substituted with substituents having the same meanings as the examples of the groups that can be substituted for the substituents represented by R ^{A1 to} R ^A3 described above. It may combine to form a ring. A plurality of R ^A22 may be optionally bonded to each other to form a ring.

Examples of cations containing S ⁺ include thiopyrylium cation, thiochromenium cation, isothiochromenilium cation, thioxanthine thyllium cation, and in general formula (b) described later.

And cations having the same meaning. Preferably, the thiopyrylium cation, in the general formula (b) described later

Of the compound represented by Q ^{n +} and general formula (b).

Are cations having the same structure.

An example of a cation containing O ⁺ is a pyrylium cation.

As an example of the cation containing P ⁺ , a compound represented by the following general formula (a-3) can be given.

In the formula, R ^{A31 to} R ^A34 each independently represent a substituent having the same ^meaning as the example of the substituent represented by R ^{A12 to} R ^A14 in the general formula (a-1). R ^{A31 to} R ^A34 are preferably an alkyl group having 1 to 30 carbon atoms or an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an alkyl group having 1 to 18 carbon atoms or an alkyl group having 6 to 18 carbon atoms. It is an aromatic hydrocarbon group.

Q ^{n +} in the general formula (a) is preferably a cation containing N ⁺ , S ⁺ or P ⁺ , more preferably a cation containing S ⁺ , a general formula (a-1), a general formula (a− 2) or a cation represented by formula (a-3), most preferably a cation represented by formula (a-1), formula (a-2) or formula (a-3). is there.

Y ^m− represents an m-valent anion in which the pKa value of the conjugate acid is larger than the pKa of the X ^B− conjugate acid in the general formula (b), and m represents an integer of 1 to 3. Y ^m− is its conjugate acid (H) There is no particular limitation as long as pKa _{Y of m} Y satisfies pKa _Y > pKa _XB with respect to pKa _{XB of} HX ^B which is a conjugate acid of X ^B− , m There first stage of pKa _Y of two or more if H _m Y is, relative pKa _XB of X ^B- is a conjugate acid HX ^B, should satisfy pKa _Y> pKa _XB. Preferred examples of Y ^m- include halogen ions, sulfonate ions, SO ₄ ²⁻ , NO ₃ ⁻ , carboxylate ions, AlO ₂ ⁻ , ClO ₄ ⁻ , PO ₄ ³⁻ , SCN ⁻ , CN ⁻ , B (C ₆ H ₅ ) ₄ ⁻ , phenoxaodo ion, more preferably Cl ⁻ , Br ⁻ , I ⁻ , R ⁶⁰¹ —SO ₃ ⁻ , SO ₄ ²⁻ , NO ₃ ⁻ , R ⁶⁰² —COO ⁻ , AlO _{2. ^{-, ClO 4 -, PO 4}} 3-, B (C 6 H 5) 4 -, R 603 -O - a is (wherein, R ^601, R ⁶⁰² are each independently an aliphatic group having from 1 to 30 carbon atoms Or an aromatic group having 6 to 20 carbon atoms, R ⁶⁰³ represents an aromatic group having 6 to 20 carbon atoms, and R ⁶⁰¹ , R ⁶⁰² , and R ⁶⁰³ are the substituents represented by R ^{A11 to} R ^A14 described above. And may be further substituted with a substituent having the same meaning as the example of the substitutable group. More preferable examples of Y include Cl ⁻ , Br ⁻ , I ⁻ , CH ₃ —SO ₃ ⁻ , p—CH ₃ —C ₆ H ₄ —SO ₄ ²⁻ , NO ₃ ⁻ , R ⁶⁰² —COO ⁻ , AlO. ₂ ⁻ , PO ₄ ³⁻ , B (C ₆ H ₅ ) ₄ ⁻ , R ⁶⁰³ —O ⁻ , most preferably Cl ⁻ , Br ⁻ , I ⁻ , CH ₃ —SO ₃ ⁻ , p—CH ₃ —. C ₆ H ₄ —SO ₄ ²⁻ , R ⁶⁰² —COO ⁻ , AlO ₂ ⁻ , PO ₄ ³⁻ , B (C ₆ H ₅ ) ₄ ⁻ , R ⁶⁰³ —O ⁻ . When Q ^{n +} is a quaternary ammonium cation, Y ^m− is particularly Cl ⁻ , Br ⁻ , I ⁻ , AlO ₂ ⁻ , PO ₄ ³⁻ , B (C ₆ H ₅ ) ₄ ⁻ , R ⁶⁰³ −. O ^- it is preferred that.

  Although the specific example of a compound represented by general formula (a) is shown, this invention is not limited to these.

  It is preferable to contain the compound represented by general formula (a) of this invention in the ratio of 0.001-20 mass parts with respect to 100 mass parts of compounds which have cationic polymerizability. When the compound represented by the general formula (a) is less than 0.001 part by mass, it is difficult to obtain sufficient storage stability, and even if the compound is contained exceeding 20 parts by mass, there is no further effect of improving storage stability. . The content is more preferably 0.005 to 10 parts by mass, and most preferably 0.01 to 5 parts by mass. These compounds represented by the general formula (a) of the present invention can be used alone or in combination of two or more.

Next, the compound represented by formula (b) will be described. In the general formula (b), R ^{B1 to} R ^B3 each represents a substituent, and each may be the same or different, and the substituent is not particularly limited, but examples include an alkyl group (methyl group, ethyl group). Propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (for example, vinyl group, allyl group) Group), alkynyl group (eg ethynyl group, propargyl group etc.), aromatic hydrocarbon group (eg phenyl group, naphthyl group etc.), heteroaromatic group (eg furyl group, thienyl group, pyridyl group, pyridazyl) Group, pyrimidyl group, pyrazyl group, triazyl group, imidazolyl group, pyrazolyl group, thiazolyl group, benzimidazole Zolyl group, benzoxazolyl group, quinazolyl group, phthalazyl group, etc.), heterocyclic groups (for example, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.) and the like, and these are represented by R ^{B1 to} R ^B3 . The substituent to be substituted may further have a substituent, and examples of the group that can be substituted with the substituent represented by R ^{B1 to} R ^B3 include the above-described alkyl group, alkenyl group, alkynyl group, and aromatic group. In addition to hydrocarbon groups, heteroaromatic groups, and heterocyclic groups, alkoxy groups (eg, methoxy, ethoxy, propyloxy, pentyloxy, hexyloxy, octyloxy, dodecyloxy, etc.), cyclo An alkoxy group (eg, cyclopentyloxy group, cyclohexyloxy group, etc.), an aryloxy group (eg, phenoxy group, naphthyloxy group, etc.), Kirthio group (for example, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio group (for example, cyclopentylthio group, cyclohexylthio group, etc.), arylthio group (for example, phenylthio group) Group, naphthylthio group, etc.), alkoxycarbonyl group (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenyloxycarbonyl) Group, naphthyloxycarbonyl group, etc.), sulfamoyl group (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexyl group) A silaminosulfonyl group, a cyclohexylaminosulfonyl group, an octylaminosulfonyl group, a dodecylaminosulfonyl group, a phenylaminosulfonyl group, a naphthylaminosulfonyl group, a 2-pyridylaminosulfonyl group, etc.), an acyl group (for example, an acetyl group, an ethylcarbonyl group, Propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy group (for example, acetyloxy group, ethyl group) Carbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), amide group ( For example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino group, dodecylcarbonylamino group, phenyl Carbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl 2-pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group, naphthylureido group, 2-pyridylaminoureido Group), sulfinyl group (for example, methylsulfinyl group, ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-pyridylsulfinyl group, etc.) Alkylsulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dode Silsulfonyl group etc.), arylsulfonyl group (phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group etc.), amino group (for example, amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, etc.), halogen atom (eg, fluorine atom, chlorine atom, bromine atom etc.), fluorinated hydrocarbon group (eg, fluoromethyl) Group, trifluoromethyl group, pentafluoroethyl group, pentafluorophenyl group, etc.), cyano group, nitro group, hydroxy group, mercapto group, silyl group (for example, trimethylsilyl group, triisopropylsilyl group, triphenylsilyl group, phenyl) Diethylsilyl group), water Group, nitro group, carboxyl group, etc., and these substituents may be further substituted by the above-mentioned substituents, and these substituents are bonded to each other to form a ring. Also good. R ^{B1 to} R ^B3 may be optionally bonded to each other to form a ring. R ^{B1 to} R ^B3 are preferably an alkyl group or an aromatic hydrocarbon group, which may further have a substituent, and the substituent is a substituent represented by R ^{B1 to} R ^B3 described above. Examples of substitutable groups can be given.

X ^B- represents a counter ion, which includes halogen ions such as F ⁻ , Cl ⁻ , Br ⁻ , BF ₄ ⁻ , B (C ₆ F ₅ ) ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF. ₆ ⁻ , GaF ₆ ⁻ , complex ions such as benzene sulfonate (eg, p-CH ₃ C ₆ H ₄ SO ₃ ⁻ , C ₆ H ₅ SO ₃ ⁻ ), alkyl sulfonate (eg, CH ₃ SO ₃ ⁻ , C ₂ H ₅ SO ₃ ⁻ ), fluorinated alkyl sulfonate ions (for example, CF ₃ SO ₃ ⁻ , C ₂ F ₅ SO ₃ ⁻ , C ₉ F ₁₉ SO ₃ ⁻ ), fluorinated alkyl benzene sulfonate ions (Eg, p-CF ₃ —C ₆ H ₄ SO ₃ ⁻ , p-CF ₃ —C ₆ F ₄ SO ₃ ⁻ ), fluorinated benzenesulfonate ion (eg, p-F—C ₆ H ₄ SO ₃ ⁻ And sulfonate ions such as C ₆ F ₅ SO ₃ ⁻ ). Counter ions include PF ₆ ⁻ , BF ₄ ⁻ , SbF ₆ ⁻ , GaF ₆ ⁻ , AsF ₆ ⁻ , B (C ₆ F ₅ ) ₄ ⁻ , fluorinated alkyl sulfonate ions (for example, CF ₃ SO ₃ ⁻ , C ₂ F ₅ SO ₃ ⁻ and C ₉ F ₁₉ SO ₃ ⁻ ) are more preferable, and BF ₄ ⁻ , B (C ₆ F ₅ ) ₄ ⁻ and PF ₆ ⁻ are most preferable.

  Furthermore, the sulfonium salt represented by general formula (I-1), (I-2), (I-3) is demonstrated.

In the general formula (I-1), R ₁₁ , R ₁₂ and R ₁₃ each represent a substituent. Examples of the substituent include a halogen atom (for example, chlorine atom, bromine atom, fluorine atom, etc.), an alkyl group having 1 to 6 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, etc.) ), A cycloalkyl group having 3 to 6 carbon atoms (for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc.), an alkenyl group having 1 to 6 carbon atoms (for example, vinyl group, 1-propenyl group, 2-propenyl group, 2-butenyl group, etc.), C1-C6 alkynyl groups (for example, acetylenyl group, 1-propynyl group, 2-propynyl group, 2-butynyl group, etc.), C1-C1 6 alkoxy groups (for example, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, tert-butoxy group, etc.), having 1 to 6 carbon atoms Alkylthio group (for example, methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, tert-butylthio group, etc.), aryl group having 6 to 14 carbon atoms (for example, phenyl group, naphthyl group, anthracenyl group) Group), an aryloxy group having 6 to 10 carbon atoms (eg, phenoxy group, naphthoxy group, etc.), an arylthio group having 6 to 10 carbon atoms (eg, phenylthio group, naphthylthio group, etc.), an acyl group (eg, acetyl group, propionyl). Group, trifluoroacetyl group, benzoyl group, etc.), acyloxy group (for example, acetoxy group, propionyloxy group, trifluoroacetoxy group, benzoyloxy group, etc.), alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl) Group) Heteroatom-containing aromatic Hajime Tamaki having 4 to 8 carbon atoms (such as furyl group, a thienyl group, etc.), a nitro group, a cyano group, and the like.
Preferred examples of the substituent include a halogen atom, an alkyl group, an alkyloxy group, an aryl group, an aryloxy group, an arylthio group, and an acyl group. Of these substituents, possible ones may be further substituted.

m, n and p each represents an integer of 0 to 5, and each is preferably 1 or more.
X ₁₁ ⁻ represents a counter anion. Counter anions include complex ions such as halogen ions such as F ⁻ , Cl ⁻ and Br ⁻ , BF ₄ ⁻ , B (C ₆ F ₅ ) ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ and GaF ₆ ^−. Ions, benzenesulfonate ions (eg, p-CH ₃ C ₆ H ₄ SO ₃ ⁻ , C ₆ H ₅ SO ₃ ⁻ ), alkylsulfonate ions (eg, CH ₃ SO ₃ ⁻ , C ₂ H ₅ SO ₃ ⁻⁾ ), Fluorinated alkyl sulfonate ions (for example, CF ₃ SO ₃ ⁻ , C ₂ F ₅ SO ₃ ⁻ , C ₉ F ₁₉ SO ₃ ⁻ ), fluorinated alkyl benzene sulfonate ions (for example, p-CF ₃ —C _6). H ₄ SO ₃ ⁻ , p-CF ₃ —C ₆ F ₄ SO ₃ ⁻ ), fluorinated benzene sulfonate ions (eg, p-F—C ₆ H ₄ SO ₃ ⁻ , C ₆ F ₅ SO ₃ ⁻ ), etc. The sulfonate ion can be mentioned. Counter anions include PF ₆ ⁻ , BF ₄ ⁻ , SbF ₆ ⁻ , GaF ₆ ⁻ , AsF ₆ ⁻ , B (C ₆ F ₅ ) ₄ ⁻ , fluorinated alkyl sulfonate ions (for example, CF ₃ SO ₃ ⁻ , C ₂ F ₅ SO ₃ ⁻ and C ₉ F ₁₉ SO ₃ ⁻ ) are more preferable, and BF ₄ ⁻ , B (C ₆ F ₅ ) ₄ ⁻ and PF ₆ ⁻ are most preferable.

In the general formula (I-2), R ₁₄ represents a substituent. Examples of the substituent include a halogen atom (for example, chlorine atom, bromine atom, fluorine atom, etc.), an alkyl group having 1 to 6 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, etc.) ), A cycloalkyl group having 3 to 6 carbon atoms (for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc.), an alkenyl group having 1 to 6 carbon atoms (for example, vinyl group, 1-propenyl group, 2-propenyl group, 2-butenyl group, etc.), C1-C6 alkynyl groups (for example, acetylenyl group, 1-propynyl group, 2-propynyl group, 2-butynyl group, etc.), C1-C1 6 alkoxy groups (for example, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, tert-butoxy group, etc.), having 1 to 6 carbon atoms Alkylthio group (for example, methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, tert-butylthio group, etc.), aryl group having 6 to 14 carbon atoms (for example, phenyl group, naphthyl group, anthracenyl group) Group), an aryloxy group having 6 to 10 carbon atoms (eg, phenoxy group, naphthoxy group, etc.), an arylthio group having 6 to 10 carbon atoms (eg, phenylthio group, naphthylthio group, etc.), an acyl group (eg, acetyl group, propionyl). Group, trifluoroacetyl group, benzoyl group, etc.), acyloxy group (for example, acetoxy group, propionyloxy group, trifluoroacetoxy group, benzoyloxy group, etc.), alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl) Group) Heteroatom-containing aromatic Hajime Tamaki having 4 to 8 carbon atoms (such as furyl group, a thienyl group, etc.), a nitro group, a cyano group, and the like. Preferably, they are a halogen atom, an alkyl group, an aryl group, an alkoxy group, and an aryloxy group. Of these substituents, possible ones may be further substituted.

q represents an integer of 0 to 2, preferably 1 or more, and more preferably 2. R ₁₅ and R _{16 each} represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted aryl group.

  Examples of the substituent include a halogen atom (eg, chlorine atom, bromine atom, fluorine atom, etc.), an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group, isopropyl group, butyl group). Etc.), a cycloalkyl group having 3 to 6 carbon atoms (eg, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc.), an alkenyl group having 1 to 6 carbon atoms (eg, vinyl group, 1-propenyl group). , 2-propenyl group, 2-butenyl group, etc.), C1-C6 alkynyl groups (for example, acetylenyl group, 1-propynyl group, 2-propynyl group, 2-butynyl group, etc.), carbon number 1 -6 alkoxy groups (for example, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, tert-butoxy group, etc.), 1 to 6 carbon atoms An alkylthio group (eg, methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, tert-butylthio group, etc.), aryl group having 6 to 14 carbon atoms (eg, phenyl group, naphthyl group, Anthracenyl group, etc.), C6-C10 aryloxy groups (e.g., phenoxy group, naphthoxy group, etc.), C6-C10 arylthio groups (e.g., phenylthio group, naphthylthio group, etc.), acyl groups (e.g., Acetyl group, propionyl group, trifluoroacetyl group, benzoyl group, etc.), acyloxy group (eg, acetoxy group, propionyloxy group, trifluoroacetoxy group, benzoyloxy group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxy) Carbonyl group, tert-but Aryloxycarbonyl group), hetero atom-containing aromatic Hajime Tamaki having 4 to 8 carbon atoms (e.g., furyl group, a thienyl group, etc.), a nitro group, a cyano group, and a hydroxyl group. Preferred are a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, and an acyl group.

R ₁₅ and R ₁₆ are preferably a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and the substituent is preferably a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, An acyl group and a hydroxyl group.

X ₁₂ ⁻ represents a counter anion. Counter anions include complex ions such as halogen ions such as F ⁻ , Cl ⁻ and Br ⁻ , BF ₄ ⁻ , B (C ₆ F ₅ ) ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ and GaF ₆ ^−. Ions, benzenesulfonate ions (eg, p-CH ₃ C ₆ H ₄ SO ₃ ⁻ , C ₆ H ₅ SO ₃ ⁻ ), alkylsulfonate ions (eg, CH ₃ SO ₃ ⁻ , C ₂ H ₅ SO ₃ ⁻⁾ ), Fluorinated alkyl sulfonate ions (for example, CF ₃ SO ₃ ⁻ , C ₂ F ₅ SO ₃ ⁻ , C ₉ F ₁₉ SO ₃ ⁻ ), fluorinated alkyl benzene sulfonate ions (for example, p-CF ₃ —C _6). H ₄ SO ₃ ⁻ , p-CF ₃ —C ₆ F ₄ SO ₃ ⁻ ), fluorinated benzene sulfonate ions (eg, p-F—C ₆ H ₄ SO ₃ ⁻ , C ₆ F ₅ SO ₃ ⁻ ), etc. The sulfonate ion can be mentioned. Counter anions include PF ₆ ⁻ , BF ₄ ⁻ , SbF ₆ ⁻ , GaF ₆ ⁻ , AsF ₆ ⁻ , B (C ₆ F ₅ ) ₄ ⁻ , fluorinated alkyl sulfonate ions (for example, CF ₃ SO ₃ ⁻ , C ₂ F ₅ SO ₃ ⁻ and C ₉ F ₁₉ SO ₃ ⁻ ) are more preferable, and BF ₄ ⁻ , B (C ₆ F ₅ ) ₄ ⁻ and PF ₆ ⁻ are most preferable.

In the general formula (I-3), R ₁₇ represents a substituent. Examples of the substituent include a halogen atom (for example, chlorine atom, bromine atom, fluorine atom, etc.), an alkyl group having 1 to 6 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, etc.) ), A cycloalkyl group having 3 to 6 carbon atoms (for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc.), an alkenyl group having 1 to 6 carbon atoms (for example, vinyl group, 1-propenyl group, 2-propenyl group, 2-butenyl group, etc.), C1-C6 alkynyl groups (for example, acetylenyl group, 1-propynyl group, 2-propynyl group, 2-butynyl group, etc.), C1-C1 6 alkoxy groups (for example, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, tert-butoxy group, etc.), having 6 to 14 carbon atoms Reel group (for example, phenyl group, naphthyl group, anthracenyl group, etc.), acyl group (for example, acetyl group, propionyl group, trifluoroacetyl group, benzoyl group, etc.), acyloxy group (for example, acetoxy group, propionyloxy group, trifluoro) An acetoxy group, a benzoyloxy group, etc.), an alkoxycarbonyl group (eg, a methoxycarbonyl group, an ethoxycarbonyl group, a tert-butoxycarbonyl group, etc.), an aryl group having 6 to 10 carbon atoms (eg, a phenyl group, a naphthyl group, an anthracenyl group). Etc.), a C4-C8 heteroatom-containing aromatic ring group (for example, a furyl group, a thienyl group, etc.), a nitro group, a cyano group, and the like. Preferably, they are a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, and an acyl group.

r represents an integer of 0 to 3, preferably 1 or more, and more preferably 2. R ₁₈ represents a hydrogen atom or a substituted or unsubstituted alkyl group, and R ₁₉ and R ₂₀ represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted group. Represents a substituted aryl group.

  Examples of the substituent include a halogen atom (for example, chlorine atom, bromine atom, fluorine atom, etc.), an alkyl group having 1 to 6 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, etc.) ), A cycloalkyl group having 3 to 6 carbon atoms (for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc.), an alkenyl group having 1 to 6 carbon atoms (for example, vinyl group, 1-propenyl group, 2-propenyl group, 2-butenyl group, etc.), C1-C6 alkynyl groups (for example, acetylenyl group, 1-propynyl group, 2-propynyl group, 2-butynyl group, etc.), C1-C1 6 alkoxy groups (for example, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, tert-butoxy group, etc.), having 6 to 14 carbon atoms Reel group (for example, phenyl group, naphthyl group, anthracenyl group, etc.), acyl group (for example, acetyl group, propionyl group, trifluoroacetyl group, benzoyl group, etc.), acyloxy group (for example, acetoxy group, propionyloxy group, trifluoroacetoxy group) Group, benzoyloxy group, etc.), alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl group, etc.), aryl group having 6 to 10 carbon atoms (eg, phenyl group, naphthyl group, anthracenyl group, etc.), carbon Examples thereof include hetero atom-containing aromatic ring groups of 4 to 8 (for example, furyl group, thienyl group, etc.), nitro group, cyano group and the like. Preferably, they are a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, and an acyl group.

R ₁₈ is preferably a hydrogen atom or an unsubstituted lower alkyl group (methyl group, ethyl group, propyl group), and R ₁₉ and R ₂₀ are preferably a substituted, unsubstituted alkyl group, or substituted, unsubstituted. The substituent is preferably a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, or an acyl group.

X ₁₃ ^- is a counter anion. Counter anions include complex ions such as halogen ions such as F ⁻ , Cl ⁻ and Br ⁻ , BF ₄ ⁻ , B (C ₆ F ₅ ) ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ and GaF ₆ ^−. Ions, benzenesulfonate ions (eg, p-CH ₃ C ₆ H ₄ SO ₃ ⁻ , C ₆ H ₅ SO ₃ ⁻ ), alkylsulfonate ions (eg, CH ₃ SO ₃ ⁻ , C ₂ H ₅ SO ₃ ⁻⁾ ), Fluorinated alkyl sulfonate ions (for example, CF ₃ SO ₃ ⁻ , C ₂ F ₅ SO ₃ ⁻ , C ₉ F ₁₉ SO ₃ ⁻ ), fluorinated alkyl benzene sulfonate ions (for example, p-CF ₃ —C _6). H ₄ SO ₃ ⁻ , p-CF ₃ —C ₆ F ₄ SO ₃ ⁻ ), fluorinated benzene sulfonate ions (eg, p-F—C ₆ H ₄ SO ₃ ⁻ , C ₆ F ₅ SO ₃ ⁻ ), etc. The sulfonate ion can be mentioned. Counter anions include PF ₆ ⁻ , BF ₄ ⁻ , SbF ₆ ⁻ , GaF ₆ ⁻ , AsF ₆ ⁻ , B (C ₆ F ₅ ) ₄ ⁻ , fluorinated alkyl sulfonate ions (for example, CF ₃ SO ₃ ⁻ , C ₂ F ₅ SO ₃ ⁻ and C ₉ F ₁₉ SO ₃ ⁻ ) are more preferable, and BF ₄ ⁻ , B (C ₆ F ₅ ) ₄ ⁻ and PF ₆ ⁻ are most preferable.

  Specific examples of the sulfonium salt represented by the general formulas (b), (I-1), (I-2) and (I-3) are shown below, but the present invention is not limited thereto.

In the general formula (T-1), R ^T11 and R ^T12 each represents an alkyl group or an aromatic group. The alkyl group may be linear, branched or cyclic, for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, Examples include dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, cyclopentyl group, cyclohexyl group, and the aromatic group may be an aromatic hydrocarbon ring group or an aromatic heterocyclic group, and has a condensed ring. Examples include aromatic hydrocarbon groups (for example, phenyl group, naphthyl group, etc.), aromatic heterocyclic groups (for example, furyl group, thienyl group, pyridyl group, pyridazyl group, pyrimidyl group, pyrazyl group, triazyl group). Imidazolyl group, pyrazolyl group, thiazolyl group, benzimidazolyl group, benzoxazolyl group, quinazolyl group, phthalazyl group, etc.) And the like. The alkyl group or aromatic group described above may further have a substituent, and a plurality of these substituents may be bonded to each other to form a ring, or may have a condensed ring. Examples of the substituent include, in addition to the alkyl group described above, an alkenyl group (for example, vinyl group, allyl group, etc.), an alkynyl group (for example, ethynyl group, propargyl group, etc.), an aromatic hydrocarbon group (for example, Phenyl group, naphthyl group, etc.), heteroaromatic group (for example, furyl group, thienyl group, pyridyl group, pyridazyl group, pyrimidyl group, pyrazyl group, triazyl group, imidazolyl group, pyrazolyl group, thiazolyl group, benzoimidazolyl group, benzooxa Zolyl group, quinazolyl group, phthalazyl group, etc.), heterocyclic group (for example, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group) ), Alkoxy groups (for example, methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group, etc.), cycloalkoxy groups (for example, cyclopentyloxy group, cyclohexyloxy group, etc.) , Aryloxy groups (for example, phenoxy group, naphthyloxy group, etc.), alkylthio groups (for example, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio groups (for example, Cyclopentylthio group, cyclohexylthio group, etc.), arylthio group (for example, phenylthio group, naphthylthio group, etc.), alkoxycarbonyl group (for example, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarboni) Group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfamoyl group (eg, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl) Group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), acyl group (for example, Acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl Group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy group (for example, acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, Phenylcarbonyloxy group, etc.), amide groups (for example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octyl) Carbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, Tylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl Group, 2-pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group, naphthylureido group, 2-pyridylamino group) Ureido group), sulfinyl group (for example, methylsulfinyl group, ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group, -Ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-pyridylsulfinyl group, etc.), alkylsulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexyl) Sulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl group (phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (for example, amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentyl) Amino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, etc.), halogen atom (for example, fluorine atom, chlorine atom, bromine atom, etc.) ), Fluorinated hydrocarbon group (eg, fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, pentafluorophenyl group, etc.), cyano group, nitro group, hydroxy group, mercapto group, silyl group (eg, trimethylsilyl group) , Triisopropylsilyl group, triphenylsilyl group, phenyldiethylsilyl group, etc.), and these substituents may be further substituted with the above-mentioned substituents. They may be bonded to each other to form a ring. The alkyl group or aromatic group represented by R ^T11 or R ^T12 may or may not further have a substituent, but is preferably an unsubstituted alkyl group or aromatic group. Or an alkyl group substituted with a halogen atom, or an aromatic group substituted with an alkoxy group, more preferably an unsubstituted alkyl group or an aromatic group, or an alkyl group substituted with a fluorine atom, or Examples of the alkyl group substituted with an alkoxy group and substituted with a fluorine atom include a fluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, and a pentafluorophenyl group.

Z ^T1 represents an oxygen atom or a sulfur atom, and Z ^T1 is preferably bonded to the ortho-position or para-position, and more preferably bonded to the para-position, with respect to the benzene ring to which the sulfonium ion is bonded. R ^T13 and R ^T14 each represent an alkyl group, an aromatic group, an alkoxy group, an aryloxy group, an alkylthio group, and an arylthio group, and the alkyl group and the aromatic group represent the same groups as R ^T11 and R ^T12 described above, The alkoxy group and the aryloxy group are groups in which a group having the same meaning as R ^T11 and R ^T12 described above is bonded to an oxygen atom at one position, and examples include an alkoxy group (for example, a methoxy group, an ethoxy group, a propyloxy group, Pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group, fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, pentafluorophenyl group, etc.), cycloalkoxy group (for example, cyclopentyloxy group, cyclohexyloxy group) Etc.), aryloxy groups (for example, phenoxy group, naphthyloxy group, etc.) Are, alkylthio group, arylthio group, an R ^T11 described above to a sulfur atom, R ^T12 synonymous groups attached thereto one location group, examples, alkylthio group (e.g., methylthio group, ethylthio group, propylthio group Pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio group (eg, cyclopentylthio group, cyclohexylthio group, etc.), arylthio group (eg, phenylthio group, naphthylthio group, etc.) and the like. The aromatic group, aryloxy group, and arylthio group described above may have a condensed ring. The alkyl group, aromatic group, alkoxy group, aryloxy group, alkylthio group, and arylthio group described above may further have a substituent, and a plurality of these substituents are bonded to each other to form a ring. And may have a condensed ring, and examples of the substituent include the same groups as the examples of the substituent of R ^T11 described above. These substituents may be substituted, or a plurality of these substituents may be bonded to each other to form a ring. The alkyl group, aromatic group, alkoxy group, aryloxy group, alkylthio group and arylthio group represented by R ^T13 and R ^T14 may or may not have a substituent, but preferably , An unsubstituted alkyl group, an aromatic group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, or an alkyl group substituted with a halogen atom or an aromatic group substituted with an alkoxy group, more preferably An unsubstituted alkyl group, an aromatic group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyl group substituted with a fluorine atom, or an aromatic group substituted with an alkoxy group, and the fluorine atom Examples of substituted alkyl groups include fluoromethyl, trifluoromethyl, pentafluoroethyl, pen Fluorophenyl group and the like.

m ^t1 represents an integer of 0 to 4, preferably 0 to 3, more preferably 0 to 2, and n ^t1 and p ^t1 each represents an integer of 1 to 5, preferably 1 to 3, respectively. More preferably, it is 1-2 respectively. A plurality of R ^T12, R ^T13, R ^T14, respectively, which may be the same or different, may be R ^T11 and R ^T12, or a plurality of R ^T12 each other combine to form a ring, R ^T12 and R ^T13 or a plurality of R ^T13 may combine to form a ring, R ^T12 and R ^T14 or a plurality of R ^T14 may combine to form a ring, and R ^T12 and R ^T14 may They may combine to form a ring. At least one of R ^T13 is preferably bonded to the ortho position or the para position, and more preferably bonded to the para position, with respect to the benzene ring to which the sulfonium ion is bonded. At least one of R ^T14 is preferably bonded to the ortho or para position, and more preferably bonded to the para position, with respect to the benzene ring to which the sulfonium ion is bonded. X ^T1 represents a counter anion. Examples of the counter anion include halogen ions such as F ⁻ , Cl ⁻ and Br ⁻ , BF ₄ ⁻ , B (C ₆ F ₅ ) ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ and SbF _6. ^-, GaF ₆ ^- like of the complex ion, benzenesulfonate ion _{(e.g., p-CH 3 C 6 H} 4 SO 3 -, C 6 H 5 SO 3 -), alkyl sulfonate ion (e.g., CH ₃ SO ₃ ^- , C ₂ H ₅ SO ₃ ⁻ ), fluorinated alkyl sulfonate ions (for example, CF ₃ SO ₃ ⁻ , C ₂ F ₅ SO ₃ ⁻ , C ₉ F ₁₉ SO ₃ ⁻ ), fluorinated alkyl benzene sulfonate ions (for example, P-CF ₃ —C ₆ H ₄ SO ₃ ⁻ , p-CF ₃ —C ₆ F ₄ SO ₃ ⁻ ), fluorinated benzenesulfonate ions (for example, p-F—C ₆ H ₄ SO ₃ ⁻ , C _And sulfonate ions such as ₆ F ₅ SO ₃ ⁻ ). Counter anions include PF ₆ ⁻ , BF ₄ ⁻ , SbF ₆ ⁻ , GaF ₆ ⁻ , AsF ₆ ⁻ , B (C ₆ F ₅ ) ₄ ⁻ , fluorinated alkyl sulfonate ions (for example, CF ₃ SO ₃ ⁻ , C ₂ F ₅ SO ₃ ⁻ and C ₉ F ₁₉ SO ₃ ⁻ ) are more preferable, and BF ₄ ⁻ , B (C ₆ F ₅ ) ₄ ⁻ and PF ₆ ⁻ are most preferable.

Specific examples of the compound represented by formula (T-1) are shown below, but the present invention is not limited thereto.

  It is preferable to contain the sulfonium salt based on this invention in the ratio of 0.2-20 mass parts with respect to 100 mass parts of compounds which have cationic polymerizability. If the content of the polymerization initiator is less than 0.2 parts by mass, it is difficult to obtain a cured product, and even if the content exceeds 20 parts by mass, there is no further effect of improving curability. These sulfonium salts of the present invention can be used alone or in combination of two or more.

  Moreover, in the active energy ray hardening composition of this invention, it is preferable to contain an epoxy compound further. An aromatic epoxide and an alicyclic epoxide are used as the epoxy compound.

  A preferable aromatic epoxide is a di- or polyglycidyl ether produced by the reaction of a polyhydric phenol having at least one aromatic nucleus or an alkylene oxide adduct thereof and epichlorohydrin, such as bisphenol A or an alkylene oxide thereof. Examples thereof include di- or polyglycidyl ethers of adducts, di- or polyglycidyl ethers of hydrogenated bisphenol A or alkylene oxide adducts thereof, and novolak type epoxy resins. Here, examples of the alkylene oxide include ethylene oxide and propylene oxide.

  The alicyclic epoxide can be obtained by epoxidizing a compound having at least one cycloalkane ring such as cyclohexene or cyclopentene ring with a suitable oxidizing agent such as hydrogen peroxide or peracid. Cyclohexene oxide or cyclopentene oxide-containing compounds are preferred.

  Preferred aliphatic epoxides include di- or polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, and typical examples thereof include diglycidyl ether of ethylene glycol, diglycidyl ether of propylene glycol or Diglycidyl ether of alkylene glycol such as diglycidyl ether of 1,6-hexanediol, polyglycidyl ether of polyhydric alcohol such as di- or triglycidyl ether of glycerin or its alkylene oxide adduct, polyethylene glycol or its alkylene oxide adduct Of polyalkylene glycols such as diglycidyl ether, polypropylene glycol or diglycidyl ether of its alkylene oxide adduct Glycidyl ether, and the like. Here, examples of the alkylene oxide include ethylene oxide and propylene oxide.

  Among these epoxides, in view of rapid curability, aromatic epoxides and alicyclic epoxides are preferable, and alicyclic epoxides are particularly preferable. In the present invention, one of the epoxides may be used alone, or two or more may be used in appropriate combination.

  Particularly preferred as the alicyclic epoxide are compounds represented by the following general formulas (A) and (1) to (6).

Formula (A), representing the (1) in _{~ (6), R 100,} R 101, R 102, R 103, R 104, R 105, R 106 are each a substituent. Examples of the substituent include a halogen atom (for example, chlorine atom, bromine atom, fluorine atom, etc.), an alkyl group having 1 to 6 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, etc.) ), An alkoxy group having 1 to 6 carbon atoms (for example, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, tert-butoxy group, etc.), acyl group (for example, acetyl group, Propionyl group, trifluoroacetyl group, etc.), acyloxy group (eg, acetoxy group, propionyloxy group, trifluoroacetoxy group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl group, etc.) Etc. Among the above substituents, an alkyl group, an alkoxy group, or an alkoxycarbonyl group is preferable.

  In the general formulas (A) and (1) to (6), m0, m1, m2, m3, m4, and m6 each represents an integer of 0 to 2, and 0 or 1 is preferable. M5 represents 1 or 2.

In formula (A), L ₀ is the main chain of r0 + 1 valent connecting group or a single bond oxygen atoms or from 1 to 15 carbon atoms which may contain a sulfur atom, the general formula (1), L ₁ Is an R1 + 1 valent linking group or single bond having 1 to 15 carbon atoms which may contain an oxygen atom or a sulfur atom in the main chain. In the general formula (2), L ₂ contains an oxygen atom or a sulfur atom in the main chain. In the general formula (3) and the general formula (4), L ₃ and L ₄ may each contain an oxygen atom or a sulfur atom in the main chain. Or a divalent linking group having a carbon number of 8 or a single bond.

  Examples of the divalent linking group that may contain an oxygen atom or a sulfur atom in the main chain include the following groups, and these groups and —O— group, —S— group, —CO— group, —CS -The group formed by combining a plurality of groups can be mentioned.

A methylene group [—CH ₂ —],
An ethylidene group [> CHCH ₃ ],
Isopropylidene [> C (CH ₃ ) ₂ ],
1,2-ethylene group [—CH ₂ CH ₂ —],
1,2-propylene group [—CH (CH ₃ ) CH ₂ —],
1,3-propanediyl group [—CH ₂ CH ₂ CH ₂ —],
2,2-dimethyl-1,3-propanediyl group [—CH ₂ C (CH ₃ ) ₂ CH ₂ —],
2,2-dimethoxy-1,3-propanediyl group [—CH ₂ C (OCH ₃ ) ₂ CH ₂ —],
2,2-dimethoxymethyl-1,3-propanediyl group [—CH ₂ C (CH ₂ OCH ₃ ) ₂ CH ₂ —],
1-methyl-1,3-propanediyl group [—CH (CH ₃ ) CH ₂ CH ₂ —],
1,4-butanediyl group [—CH ₂ CH ₂ CH ₂ CH ₂ —],
1,5-pentanediyl group [—CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ —],
An oxydiethylene group [—CH ₂ CH ₂ OCH ₂ CH ₂ —],
A thiodiethylene group [—CH ₂ CH ₂ SCH ₂ CH ₂ —],
3-oxothiodiethylene group [—CH ₂ CH ₂ SOCH ₂ CH ₂ —],
3,3-dioxothiodiethylene group [—CH ₂ CH ₂ SO ₂ CH ₂ CH ₂ —],
1,4-dimethyl-3-oxa-1,5-pentanediyl group [—CH (CH ₃ ) CH ₂ OCH (CH ₃ ) CH ₂ —],
3-oxopentanediyl group [—CH ₂ CH ₂ COCH ₂ CH ₂ —],
1,5-dioxo-3-oxapentanediyl group [—COCH ₂ OCH ₂ CO—],
4-oxa-1,7-heptanediyl group [—CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ —],
3,6-dioxa-1,8-octanediyl group [—CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ —],
1,4,7-trimethyl-3,6-dioxa-1,8-octanediyl group [—CH (CH ₃ ) CH ₂ OCH (CH ₃ ) CH ₂ OCH (CH ₃ ) CH ₂ —],
5,5-dimethyl-3,7-dioxa-1,9-nonanediyl group [—CH ₂ CH ₂ OCH ₂ C (CH ₃ ) ₂ CH ₂ OCH ₂ CH ₂ —],
5,5-dimethoxy-3,7-dioxa-1,9-nonanediyl group [—CH ₂ CH ₂ OCH ₂ C (OCH ₃ ) ₂ CH ₂ OCH ₂ CH ₂ —],
5,5-dimethoxymethyl-3,7-dioxa-1,9-nonanediyl group [—CH ₂ CH ₂ OCH ₂ C (CH ₂ OCH ₃ ) ₂ CH ₂ OCH ₂ CH ₂ —],
4,7-dioxo-3,8-dioxa-1,10-decandiyl group [—CH ₂ CH ₂ O—COCH ₂ CH ₂ CO—OCH ₂ CH ₂ —],
3,8-dioxo-4,7-dioxa-1,10-decandiyl group [—CH ₂ CH ₂ CO—OCH ₂ CH ₂ O—COCH ₂ CH ₂ —],
1,3-cyclopentanediyl group [-1,3-C ₅ H ₈ —],
1,2-cyclohexanediyl group [-1,2-C ₆ H _10- ],
1,3-cyclohexanediyl group [-1,3-C ₆ H _10- ],
1,4-cyclohexanediyl group [-1,4-C ₆ H _10- ],
2,5-tetrahydrofurandiyl group [2,5-C ₄ H ₆ O—]
p- phenylene _{[-p-C 6 H 4 -} ],
m- phenylene group _{[-m-C 6 H 4 -} ],
α, α′-o-xylylene group [—o—CH ₂ —C ₆ H ₄ —CH ₂ —],
α, α′-m-xylylene group [—m—CH ₂ —C ₆ H ₄ —CH ₂ —],
α, α'-p- xylylene group _{[-p-CH 2 -C 6 H} 4 -CH 2 -],
Furan-2,5-diyl - bismethylene group _{[2,5-CH 2 -C 4 H} 2 O-CH 2 -],
A thiophene-2,5-diyl-bismethylene group [2,5-CH ₂ —C ₄ H ₂ S—CH ₂ —],
Isopropylidenebis -p- phenylene group _{[-p-C 6 H 4 -C} (CH 3) 2 -p-C 6 H 4 -]
Examples of the trivalent or higher valent linking group include the divalent linking groups listed above to groups formed by removing hydrogen atoms at arbitrary positions as necessary, and those with —O— group, —S— group, —CO—. And a group formed by combining a plurality of groups and -CS- groups.

L ₀ , L ₁ , L ₂ , L ₃ and L ₄ may each have a substituent. Examples of the substituent include a halogen atom (for example, chlorine atom, bromine atom, fluorine atom, etc.), an alkyl group having 1 to 6 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, etc.) ), An alkoxy group having 1 to 6 carbon atoms (for example, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, tert-butoxy group, etc.), acyl group (for example, acetyl group, Propionyl group, trifluoroacetyl group, etc.), acyloxy group (eg, acetoxy group, propionyloxy group, trifluoroacetoxy group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl group, etc.) Etc. Preferred as a substituent is an alkyl group, an alkoxy group, or an alkoxycarbonyl group.

L ₀ , L ₁ and L ₂ are preferably divalent linking groups having 1 to 8 carbon atoms which may contain an oxygen atom or a sulfur atom in the main chain, or L ₀ , L ₁ , L ₂ , L ₃ , L ₄ is more preferably a divalent linking group having 1 to 5 carbon atoms, each having a main chain consisting of only carbon.

  p1 and q1 each represents 0 or 1, and p1 + q1 is preferably 1 or more. p2 and q2 each represents 0 or 1, and 1 is preferable for each. p3 and p4 each represents 0 or 1.

  Specific examples of preferable alicyclic epoxides are shown below, but the present invention is not limited thereto.

  In each of the above alicyclic epoxide compounds according to the present invention, a value obtained by dividing the molecular weight by the total number of epoxy groups in the molecule is preferably 160 to 300.

  The synthesis of the alicyclic epoxide compounds represented by the general formulas (A) and (1) to (6) can be performed, for example, according to the methods described in the patent specifications listed below.

A: US Pat. No. 2,745,847 B: US Pat. No. 2,750,395 C: US Pat. No. 2,853,498 D: US Pat. No. 2,853,499 E: US Pat. No. 2,863,881 In the following, examples of the synthesis of the above exemplified compounds are shown below according to the methods described in the above patent specifications, but the present invention is not limited thereto. is not.

[Synthesis Example 1]
Example Compound EP-9: Synthesis of Ethylglycol-bis- (4-methyl-3,4-epoxy-cyclohexanecarboxylate) <Synthesis of Methyl- (4-methyl-3-cyclohexanecarboxylate)>
Methyl- (4-methyl-3-cyclohexanecarboxylate) was synthesized from isoprene and methyl acrylate as raw materials by a known Diels-Alder reaction. Reactions are described in the literature (J. Organomet. Chem., 285, 1985, 333-342, J. Phys. Chem., 95, 5, 1992, 2293-2297, Acta. Chem. Scand., 47, 6, 1993, 581-591) or reaction conditions according to the conditions described in US Pat. No. 1,944,731, etc., and the desired compound was obtained in high yield.

<Synthesis of Ethyleneglycol-bis- (4-methyl-3-cyclohexenecarboxylate)>
1 g of toluenesulfonic acid monohydrate was added to 340 g (2 mol) of Methyl- (4-methyl-3-cyclohexanecarboxylate) and 62 g (1 mol) of ethylene glycol, and reacted at 80 to 90 ° C. for 8 hours. The reaction solution was washed with aqueous sodium bicarbonate and then distilled under reduced pressure to obtain the target compound. The yield was 92%.

<Synthesis of Exemplified Compound EP-9>
306 g (1 mol) of ethylglycol-bis- (4-methyl-3-cyclohexanecarbylate) is placed in a 2 L three-headed flask, and an acetone solution having a peracetic acid content of 25% by mass while maintaining the internal temperature at 35 to 40 ° C. 770 g (192 g (2.5 mol) peracetic acid) was added dropwise over 4 hours. After completion of the dropwise addition, the reaction was carried out after 4 hours at the same temperature. The reaction solution was stored at −11 ° C. overnight, and then the remaining amount of peracetic acid was examined to confirm that 98% or more of the theoretical amount had reacted.

  Next, the reaction solution was diluted with 1 L of toluene, heated to 50 ° C. under reduced pressure using a water aspirator, and the low boiling point components were distilled off and removed until the distillate disappeared. The remaining reaction composition was distilled under reduced pressure to obtain the target exemplified compound EP-9. The yield was 78%.

  The structure of the obtained exemplary compound EP-9 was confirmed by NMR and MASS analysis.

1H NMR (CDCl ₃ ) δ (ppm): 1.31 (s, 6H, CH ₃ —), 1.45 to 2.50 (m, 14H, cyclohexane ring), 3.10 (m, 2H, epoxy root) ), 4.10 (s, 4H, —CH ₂ —O—)
[Synthesis Example 2]
Example Compound EP-12: Synthesis of Propane-1,2-diol-bis- (4-methyl-3,4-epoxy-cyclohexanecarboxylate) <Propane-1,2-diol-bis- (4-methyl-3-cyclohexanecarbylate) )
1 g of toluenesulfonic acid monohydrate was added to 340 g (2 mol) of Methyl- (4-methyl-3-cyclohexanecarboxylate) and 76 g (1 mol) of Propane-1,2-diol at 80 to 90 ° C. for 8 hours. Reacted. The reaction solution was washed with aqueous sodium bicarbonate, and then distilled under reduced pressure to obtain the target compound. The yield was 90%.

<Synthesis of Exemplified Compound EP-12>
Propane-1,2-diol-bis- (4-methyl-3-cyclohexenecarboxylate) 320 g (1 mol) was placed in a 2 L three-headed flask, and the peracetic acid content was kept at 35-40 ° C. while maintaining the internal temperature at 35-40 ° C. 770 g of a 25 mass% acetone solution (192 g (2.5 mol) of peracetic acid) was added dropwise over 4 hours. After completion of the dropwise addition, the reaction was carried out after 4 hours at the same temperature. The reaction solution was stored at −11 ° C. overnight, and then the remaining amount of peracetic acid was examined to confirm that 98% or more of the theoretical amount had reacted.

  Next, the reaction solution was diluted with 1 L of toluene, heated to 50 ° C. under reduced pressure using a water aspirator, and the low boiling point components were distilled off and removed until the distillate disappeared.

  The remaining reaction composition was distilled under reduced pressure to obtain the target exemplified compound EP-12. The yield was 75%.

  The structure of the obtained exemplary compound EP-12 was confirmed by NMR and MASS analysis.

1H NMR (CDCl ₃ ) δ (ppm): 1.23 (d, 3H, CH ₃ —), 1.31 (s, 6H, CH ₃ —), 1.45 to 2.50 (m, 14H, cyclohexane) Ring), 3.15 (m, 2H, epoxy root), 4.03 (m, 1H, —O—CH ₂ —), 4.18 (m, 1H, —O—CH ₂ —), 5.15 (M, 1H,> CH-O-)
[Synthesis Example 3]
Synthesis of Exemplary Compound EP-17: 2,2-Dimethyl-propane-1,3-diol-bis- (4-methyl-3,4-epoxy-cyclohexanecarboxylate) <2,2-Dimethyl-propane-1,3- Synthesis of diol-bis- (4-methyl-3-cyclohexenecarboxylate)>
1 g of toluenesulfonic acid monohydrate was added to 340 g (2 mol) of methyl- (4-methyl-3-cyclohexanecarboxylate) and 104 g (1 mol) of 2,2-dimethyl-propane-1,3-diol. It reacted at 80-90 degreeC for 12 hours. The reaction solution was washed with aqueous sodium bicarbonate, and then distilled under reduced pressure to obtain the target compound. The yield was 86%.

<Synthesis of Exemplified Compound EP-17>
348 g (1 mol) of 2,2-Dimethyl-propane-1,3-diol-bis- (4-methyl-3-cyclohexenecarboxylate) was placed in a 2 L three-headed flask, and the internal temperature was kept at 40 ° C. 770 g of an acetone solution having an acetic acid content of 25% by mass (192 g (2.5 mol) of peracetic acid) was added dropwise over 4 hours. After completion of the dropwise addition, the reaction was carried out after 4 hours at the same temperature. The reaction solution was stored at −11 ° C. overnight, and then the remaining amount of peracetic acid was examined to confirm that 98% or more of the theoretical amount had reacted.

  Next, the reaction solution was diluted with 1 L of toluene, heated to 50 ° C. under reduced pressure using a water aspirator, and the low boiling point components were distilled off and removed until the distillate disappeared.

  The remaining reaction composition was distilled under reduced pressure to obtain the target exemplified compound EP-17. The yield was 70%.

  The structure of exemplary compound EP-17 was confirmed by NMR and MASS analysis.

1H NMR (CDCl ₃ ) δ (ppm): 0.96 (s, 6H, CH ₃ —), 1.31 (s, 6H, CH ₃ —), 1.45 to 2.50 (m, 14H, cyclohexane) Ring), 3.00 (m, 2H, epoxy root), 3.87 (s, 4H, —O—CH ₂ —)
[Synthesis Example 4]
Synthesis of Exemplified Compound EP-31: 1,3-Bis- (4-methyl-3,4-epoxy-cyclohexylmethyl) -2-propanol <Synthesis of 4-Methyl-3-cyclohexenylmethyl>
4-Methyl-3-cyclohexenyl aldehyde was synthesized from isoprene and acrolein by known Diels-Alder reactions. The reaction was performed under the reaction conditions according to the conditions described in the literature (J. Amer. Chem. Soc., 119, 15, 1997, 3507-3512, Tetrahedron Lett., 40, 32, 1999, 5817-5822). The target compound was obtained in high yield. Subsequently, 4-methyl-3-cyclohexenyl methanol was synthesized in a high yield by reducing this compound.

<Synthesis of 1,2-Bis- (4-methyl-3-cyclohexylmethyl) -2-propanol>
305 g (2.2 mol) of potassium carbonate was added to 1 L of acetone containing 284 g (2 mol) of 4-methyl-3-cyclohexenylethanol and 92 g (1 mol) of epichlorohydrin, and reacted at 50 ° C. for 8 hours. The precipitated salt was removed by filtration, the reaction solution was concentrated under reduced pressure, and the remaining crude product was distilled under reduced pressure to obtain the desired compound. The yield was 90%.

<Synthesis of Exemplified Compound EP-31>
308 g (1 mol) of 1,2-Bis- (4-methyl-3-cyclomethylyloxy) -2-propanol was placed in a 2 L three-headed flask, and the peracetic acid content was maintained while maintaining the internal temperature at 35-40 ° C. 770 g of a 25 mass% acetone solution (192 g (2.5 mol) of peracetic acid) was added dropwise over 4 hours. After completion of the dropwise addition, the reaction was carried out after 4 hours at the same temperature. The reaction solution was stored at −11 ° C. overnight, and then the remaining amount of peracetic acid was examined to confirm that 98% or more of the theoretical amount had reacted.

  Next, the reaction solution was diluted with 1 L of toluene, heated to 50 ° C. under reduced pressure using a water aspirator, and the low boiling point components were distilled off and removed until the distillate disappeared.

  The remaining reaction composition was distilled under reduced pressure to obtain the target exemplified compound EP-31. The yield was 83%.

  The structure of exemplary compound EP-31 was confirmed by NMR and MASS analysis.

1H NMR (CDCl ₃ ) δ (ppm): 1.31 (s, 6H, CH ₃ —), 1.4 to 2.0 (m, 14H, cyclohexane ring), 2.7 (s, 1H, —OH) ), 3.10 (m, 2H, epoxy base), 3.45 (d, 4H, -CH 2 -O -), 3.50 (m, 4H, -CH 2 -O -), 3.92 ( m, 1H,> CH-)
[Synthesis Example 5]
Exemplary Compound EP-35: Synthesis of Bis- (4-methyl-3,4-epoxy-cyclohexylmethyl) oxalate <Synthesis of Bis- (4-methyl-3-cyclomethylethyl) succinate>
To a 1 L toluene solution containing 284 g (2 mol) of 4-methyl-3-cyclohexenyl methanol and 100 g (1 mol) of succinic anhydride, 5 g of toluenesulfonic acid monohydrate was added, and water produced was separated with a water separator. The reaction was carried out at 110 to 120 ° C. for 8 hours while removing. The reaction solution was washed with an aqueous sodium bicarbonate solution, and toluene was distilled off by concentration under reduced pressure. The remaining crude product was distilled under reduced pressure to obtain the target compound. The yield was 90%.

<Synthesis of Exemplified Compound EP-35>
335 g (1 mol) of Bis- (4-methyl-3-cyclohexylmethyl) succinate was put into a 2 L three-headed flask, and 770 g of an acetone solution having a peracetic acid content of 25% by mass while maintaining the internal temperature at 35 to 40 ° C. (192 g (2.5 mol) of peracetic acid) was added dropwise over 4 hours. After completion of the dropwise addition, the reaction was carried out after 4 hours at the same temperature. The reaction solution was stored at −11 ° C. overnight, and then the remaining amount of peracetic acid was examined to confirm that 98% or more of the theoretical amount had reacted.

  Next, the reaction solution was diluted with 1 L of toluene, heated to 50 ° C. under reduced pressure using a water aspirator, and low boiling point components were distilled off and removed until the distillate disappeared.

  The remaining reaction composition was distilled under reduced pressure to obtain Exemplified Compound EP-35. The yield was 75%.

  The structure of exemplary compound EP-35 was confirmed by NMR and MASS analysis.

1H NMR (CDCl3) δ (ppm): 1.31 (s, 6H, CH ₃ —), 1.4 to 2.0 (m, 14H, cyclohexane ring), 3.10 (m, 2H, epoxy base) 2.62 (s, 4H, —CH ₂ —CO—), 4.05 (d, 4H, —CH ₂ —O—)
Other alicyclic epoxide compounds according to the present invention listed above can also be synthesized in a high yield in the same manner as in the above method.

  The active energy ray-curable composition of the present invention contains an oxetane compound together with the alicyclic epoxide compound represented by the general formulas (A) and (1) to (6) according to the present invention described above. Is preferred. As the oxetane compound, a conventionally known oxetane compound can be used. Particularly, an oxetane compound which is not substituted at the 2-position is preferably used because an effect of improving the sensitivity or an effect of improving the physical properties of the cured film can be obtained.

  Hereinafter, the oxetane compound in which the 2-position is not substituted will be described.

  As an example of the oxetane compound in which the 2-position is not substituted, a compound represented by the following general formula (101) can be given.

In General Formula (101), R ¹ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group, a fluoroalkyl group having 1 to 6 carbon atoms, an allyl group or an aryl group. , Furyl group or thienyl group. R ² is an alkyl group having 1 to 6 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, 1-propenyl group, 2-propenyl group, 2-methyl-1-propenyl group, 2-methyl-2. -Alkenyl groups having 2 to 6 carbon atoms such as propenyl group, 1-butenyl group, 2-butenyl group and 3-butenyl group, aromatic groups such as phenyl group, benzyl group, fluorobenzyl group, methoxybenzyl group and phenoxyethyl group A group having a ring, an alkylcarbonyl group having 2 to 6 carbon atoms such as an ethylcarbonyl group, a propylcarbonyl group and a butylcarbonyl group, an alkoxy having 2 to 6 carbon atoms such as an ethoxycarbonyl group, a propoxycarbonyl group and a butoxycarbonyl group Carbonyl group, ethylcarbamoyl group, propylcarbamoyl group, butylcarbamoyl group, pentylcarbamoyl group Number 2-6 carbons of an N- alkylcarbamoyl group. As the oxetane compound used in the present invention, it is particularly preferable to use a compound having one oxetane ring because the resulting composition has excellent tackiness, low viscosity and excellent workability.

  An example of a compound having two oxetane rings includes a compound represented by the following general formula (102).

In the general formula (102), R ¹ is the same group as that in the general formula (101). R ³ is, for example, a linear or branched alkylene group such as an ethylene group, a propylene group or a butylene group, a linear or branched poly (alkyleneoxy) such as a poly (ethyleneoxy) group or a poly (propyleneoxy) group. ) Group, propenylene group, methylpropenylene group, butenylene group or other linear or branched unsaturated hydrocarbon group, alkylene group containing carbonyl group or carbonyl group, alkylene group containing carboxyl group, alkylene containing carbamoyl group Group.

Moreover, as R < ³ >, the polyvalent group selected from the group shown by the following general formula (103), (104) and (105) can also be mentioned.

In the general formula (103), R ⁴ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group, or a carbon such as a methoxy group, an ethoxy group, a propoxy group, or a butoxy group. A C 1-4 alkoxy group, a halogen atom such as a chlorine atom or a bromine atom, a nitro group, a cyano group, a mercapto group, a lower alkyl carboxyl group, a carboxyl group, or a carbamoyl group.

In the general formula (104), R ⁵ represents an oxygen atom, a sulfur atom, a methylene group, NH, SO, SO ₂ , C (CF ₃ ) ₂ , or C (CH ₃ ) ₂ .

In General Formula (105), R ⁶ is an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group, or an aryl group. n is an integer of 0-2000. R ⁷ is a methyl group, an ethyl group, a propyl group, a butyl group having 1 to 4 carbon atoms, or an aryl group. Examples of R ^{7 also} include a group represented by the following general formula (106) to a selected group.

In General Formula (106), R ⁸ is an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group, or an aryl group. m is an integer of 0-100.

  Specific examples of the compound having two oxetane rings include the following compounds.

Exemplary compound 11 is a compound in which R ¹ is an ethyl group and R ³ is a carboxyl group in the general formula (102). The exemplified compound 12 is a compound in which R ¹ is an ethyl group, R ³ is the general formula (105), R ⁶ and R ⁷ are methyl groups, and n is 1 in the general formula (102).

  In the compound having two oxetane rings, a preferred example other than the above compound is a compound represented by the following general formula (107).

In formula (107), R ¹ has the same meaning as R ¹ in the general formula (101).

  Moreover, as an example of a compound having 3 to 4 oxetane rings, a compound represented by the following general formula (108) can be given.

In formula (108), R ¹ has the same meaning as R ¹ in the general formula (101). As R ⁹ , for example, a branched alkylene group having 1 to 12 carbon atoms such as groups represented by the following A to C, a branched poly (alkyleneoxy) group such as a group represented by the following D, or the following E And branched polysiloxy groups such as those shown. j is 3 or 4.

In the above A, R ¹⁰ is a lower alkyl group such as a methyl group, an ethyl group or a propyl group. Moreover, in said D, p is an integer of 1-10.

  Illustrative compound 13 is an example of a compound having 3 to 4 oxetane rings.

  Furthermore, examples of the compound having 1 to 4 oxetane rings other than those described above include compounds represented by the following general formula (109).

In formula (109), R ⁸ has the same meaning as R ⁸ in the general formula (106). R ¹¹ is an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group or a trialkylsilyl group, and r is 1 to 4.

  Preferable specific examples of the oxetane compound used in the present invention include the following compounds.

  The production method of each compound having an oxetane ring described above is not particularly limited, and may be a conventionally known method, for example, Pattisson (DB Pattison, J. Am. Chem. Soc., 3455, 79). (1957)) discloses a method for synthesizing an oxetane ring from a diol.

  An oxetane compound represented by the following general formula (I), (II), (III), (IV) or (V) in order to obtain a further sensitivity improving effect, an effect film physical property improving effect or an environmental humidity fluctuation resistance improving effect May be contained.

In the general formula (I), R ₁₀₁ ~R ₁₀₄ represents a hydrogen atom or a substituent. R ₁₀₅ represents a substituted or unsubstituted alkoxy group or a substituted or unsubstituted aryloxy group, and m1 represents 0, 1 or 2. R ₁₀₆ represents a substituent, and n1 represents 0 to 3.

In formula (II), R ₂₀₁ ~R ₂₀₄ represents a hydrogen atom or a substituent. _R205 represents a substituted or unsubstituted alkoxy group or a substituted or unsubstituted aryloxy group, and m2 represents 0, 1 or 2. R ₂₀₆ represents a substituent, and n2 represents 0 to 3.

In the general formula (III), R ₃₀₁ ~R ₃₀₄ represents a hydrogen atom or a substituent. R ₃₀₅ and R ₃₀₆ represent a substituent, and m3 and n3 represent 0 to 4.

In the general formula (IV), R _{401 to} R ₄₀₄ represent a hydrogen atom or a substituent. R ₄₀₅ represents a substituent, and m4 represents 0 to 4. L ₁ represents a C 1-15 divalent linking group that may contain an oxygen atom or a sulfur atom in the main chain.

In formula (V), R ₅₀₁ ~R ₅₀₄ represents a hydrogen atom or a substituent. R ₅₀₅ represents a substituted or unsubstituted alkyl group. R ₅₀₆ represents a substituent, and m5 represents 0 to 3. L ₂ represents a C 1-15 divalent linking group which may contain an oxygen atom or a sulfur atom in the main chain, or an oxygen atom.

R _{101 to} R _{104 of} the general formula (I), R _{201 to} R _{204 of} the general formula (II), R _{301 to} R _{304 of} the general formula (III), R _{401 to} R _{405 of} the general formula (IV), Examples of the substituent represented by R _{501 to} R ₅₀₄ in (V) include a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom, etc.), an alkyl group having 1 to 6 carbon atoms (for example, a methyl group) , Ethyl group, propyl group, isopropyl group, butyl group, etc.), cycloalkyl group having 3 to 6 carbon atoms (for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc.), 1 to 6 carbon atoms An alkenyl group (for example, vinyl group, 1-propenyl group, 2-propenyl group, 2-butenyl group, etc.), alkynyl group having 1 to 6 carbon atoms (for example, acetylenyl group, 1-propynyl group, 2-propynyl group, 2-butynyl group, etc.), carbon number 1 Alkoxy groups (for example, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, tert-butoxy group, etc.), acyl groups (for example, acetyl group, propionyl group, trifluoroacetyl group) Etc.), acyloxy groups (for example, acetoxy group, propionyloxy group, trifluoroacetoxy group, etc.), alkoxycarbonyl groups (for example, methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl group, etc.), aryloxycarbonyl groups, etc. Can be mentioned.

R ₁₀₁ and R _102, R ₁₀₃ and R _104, R ₂₀₁ and R _202, R ₂₀₃ and R _204, R ₃₀₁ and R _302, R ₃₀₃ and R _304, R ₄₀₁ and R _402, R ₄₀₃ and R _404, R ₅₀₁ And R ₅₀₂ , R _503, and R ₅₀₄ , two substituents on the same carbon may be bonded to each other at a terminal to form a divalent group to form a ring.

  These groups may further have a substituent. Examples of the substituent include a halogen atom (for example, chlorine atom, bromine atom, fluorine atom, etc.), an alkoxy group having 1 to 6 carbon atoms (for example, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n -Butoxy group, tert-butoxy group etc.), acyl group (eg acetyl group, propionyl group, trifluoroacetyl group etc.), acyloxy group (eg acetoxy group, propionyloxy group, trifluoroacetoxy group etc.), alkoxycarbonyl Examples thereof include a group (for example, methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl group), aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, cyano group, nitro group and the like. As the substituent, a halogen atom, an alkoxy group, an acyloxy group, and an alkoxycarbonyl group are preferable.

  These oxetane compounds preferably have one or more substituents at the 3-position of the oxetane ring. Preferred substituents include alkyl groups having 1 to 6 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, etc.), and cycloalkyl groups having 3 to 6 carbon atoms (for example, cyclopropyl group). Group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc.), alkoxy group having 1 to 6 carbon atoms (for example, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, tert-butoxy group) Etc.), acyl groups (eg acetyl group, propionyl group, trifluoroacetyl group etc.), acyloxy groups (eg acetoxy group, propionyloxy group, trifluoroacetoxy group etc.), alkoxycarbonyl groups (eg methoxycarbonyl group, Ethoxycarbonyl group, tert-butoxycarbonyl group, etc.) That. These may be further substituted, and preferred as a substituent are a halogen atom, an alkoxy group, an acyloxy group, and an alkoxycarbonyl group.

  In these oxetane compounds, a substituted or unsubstituted alkyl group is preferably substituted at the 3-position, and it is more preferable that the 3-position of the oxetane becomes a tertiary carbon by substitution with two alkyl groups. . Preferred as a substituent for the alkyl group are a halogen atom, an alkoxy group, an acyloxy group, and an alkoxycarbonyl group.

These oxetane compounds can be made more reactive by substituting an electron-withdrawing group at the 4-position. The electron withdrawing group is a substituent having a positive Hammett substituent constant σp. Specific examples of the electron withdrawing group include —NO ₂ , —CN, —SO ₂ —Alkyl, —SO ₂ -Aryl, -CO-Alkyl, -CO-Aryl, -CO-O-Alkyl, -CO-O-Aryl, and halogen atoms (fluorine atom, chlorine atom, bromine atom). In the oxetane compound of the present invention, a preferable electron-withdrawing group as a substituent at the 4-position is an alkyl group in which the above-mentioned electron-withdrawing group is substituted on the carbon atom at the α to γ positions, particularly an alkyl substituted with a fluorine atom. Groups are preferred.

  The active energy ray-curable composition of the present invention may further contain a vinyl ether compound.

  Examples of the vinyl ether compound 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, cyclohexanedimethanol divinyl ether, 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- B pills vinyl ether, isopropyl vinyl ether, isopropenyl ether -O- propylene carbonate, dodecyl vinyl ether, diethylene glycol monovinyl ether, and octadecyl vinyl ether.

  Among these vinyl ether compounds, in consideration of curability, adhesion, and surface hardness, di- or trivinyl ether compounds are preferable, and divinyl ether compounds are particularly preferable. In the present invention, one of the above vinyl ether compounds may be used alone, or two or more thereof may be used in appropriate combination.

  In the active energy ray-curable composition of the present invention, a photoacid generator may be used in combination. For example, a chemical amplification type photoresist or a compound used for photocationic polymerization is used (see Organic Electronics Materials Research Group, “Organic Materials for Imaging”, Bunshin Publishing (1993), pages 187 to 192). Examples of compounds suitable for the present invention are listed below.

First, B (C ₆ F ₅ ) ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , p-CH ₃ C ₆ H ₄ of aromatic onium compounds such as diazonium, ammonium, iodonium, sulfonium, and phosphonium. SO ₃ ^- salt, CF ₃ SO ₃ ^- and sulfonic acid salts such as salts. Those having a borate compound as a counter anion and PF ₆ ^- salt acid generation capability higher preferred.

  Specific examples of the onium compound are shown below.

  Secondly, sulfonated products that generate sulfonic acid can be mentioned. Specific compounds are exemplified below.

  Thirdly, a halide that generates hydrogen halide can also be used. Specific compounds are exemplified below.

  Fourthly, an iron allene complex can be mentioned.

  Examples of the photopolymerization accelerator include anthracene, anthracene derivatives (for example, Adekaoptomer SP-100 manufactured by Asahi Denka Kogyo Co., Ltd.), phenothiazine (10H-phenothiazine), phenothiazine derivatives (for example, 10-methylphenothiazine, 10-ethylphenothiazine, 10-decylphenothiazine, 10-acetylphenothiazine, 10-decylphenothiazine-5-oxide, 10-decylphenothiazine-5,5-dioxide, 10-acetylphenothiazine-5,5-dioxide, etc.). These photopolymerization accelerators can be used alone or in combination.

  In addition to the components described above, various additives can be used in the inkjet ink composition of the present invention.

  As the coloring material used in the inkjet ink composition of the present invention, a coloring material that can be dissolved or dispersed in the main component of the polymerizable compound can be used, but a pigment is preferred from the viewpoint of weather resistance.

  The pigments that can be preferably used in the present invention are listed below.

C. I. Pigment Yellow-1, 3, 12, 13, 14, 17, 81, 83, 87, 95, 109, 42,
C. I. Pigment Orange-16, 36, 38,
C. I. Pigment Red-5, 22, 38, 48: 1, 48: 2, 48: 4, 49: 1, 53: 1, 57: 1, 63: 1, 144, 146, 185, 101,
C. I. Pigment Violet-19, 23,
C. I. Pigment Blue-15: 1, 15: 3, 15: 4, 18, 60, 27, 29,
C. I. Pigment Green-7, 36,
C. I. Pigment White-6, 18, 21,
C. I. Pigment Black-7
For the dispersion of the pigment, for example, a ball mill, sand mill, attritor, roll mill, agitator, Henschel mixer, colloid mill, ultrasonic homogenizer, pearl mill, wet jet mill, paint shaker, or the like can be used. It is also possible to add a dispersant when dispersing the pigment. As the dispersant, a polymer dispersant is preferably used, and examples of the polymer dispersant include Solsperse series manufactured by Avecia. Moreover, it is also possible to use a synergist according to various pigments as a dispersion aid. These dispersants and dispersion aids are preferably added in an amount of 1 to 50 parts by mass with respect to 100 parts by mass of the pigment. The dispersion medium is used using a solvent or a polymerizable compound. In the ink composition for inkjet according to the present invention, it is preferable that the ink is non-solvent because it is reacted and cured immediately after ink landing. If the solvent remains in the cured image, the solvent resistance deteriorates and the VOC of the remaining solvent arises. Therefore, it is preferable in view of dispersibility that the dispersion medium is not a solvent but a polymerizable compound, and among them, a monomer having the lowest viscosity is selected.

  The pigment is preferably dispersed so that the average particle diameter of the pigment particles is 0.08 to 0.5 μm, and the maximum particle diameter is 0.3 to 10 μm, preferably 0.3 to 3 μm. The selection of the dispersion medium, the dispersion conditions, and the filtration conditions are appropriately set. By controlling the particle size, clogging of the head nozzle can be suppressed, and ink storage stability, ink transparency, and curing sensitivity can be maintained.

  In the inkjet ink composition of the present invention, the colorant concentration is preferably 1 to 10% by mass of the total ink.

  In the present invention, a thermal base generator can also be used for the purpose of improving ejection stability and storage stability.

  Examples of the thermal base generator include compounds that release amines by decomposition by reactions such as organic acid and base salts that are decomposed by decarboxylation by heating, intramolecular nucleophilic substitution reaction, Rossen rearrangement, Beckmann rearrangement, etc. Those which cause some kind of reaction by heating and release a base are preferably used. Specifically, the salt of trichloroacetic acid described in British Patent No. 998,949, the salt of alpha-sulfonylacetic acid described in US Pat. No. 4,060,420, and the propionic acids described in JP-A-59-157737 Salts, 2-carboxycarboxamide derivatives, salts with a base component described in JP-A-59-168440 and a thermally decomposable acid using an alkali metal or an alkaline earth metal in addition to an organic base, JP-A-59-180537 Hydroxam carbamates utilizing the Lossen rearrangement described in No. 5, and aldoxime carbamates described in JP-A No. 59-195237 that generate nitriles by heating. In addition, British Patent No. 998,945, US Pat. No. 3,220,846, British Patent No. 279,480, Japanese Patent Laid-Open Nos. 50-22625, 61-32844, 61-51139, 61 The thermal base generators described in Nos. -52638, 61-51140, 61-53634, 61-53640, 61-55644, 61-55645 and the like are useful. More specifically, guanidine trichloroacetate, methylguanidine trichloroacetate, potassium trichloroacetate, guanidine phenylsulfonylacetate, guanidine p-chlorophenylsulfonylacetate, guanidine p-methanesulfonylphenylsulfonylacetate, potassium phenylpropiolate, phenylpropiool Examples include acid guanidine, cesium phenylpropiolate, guanidine p-chlorophenylpropiolate, guanidine p-phenylene-bis-phenylpropiolate, tetramethylammonium phenylsulfonylacetate, and tetramethylammonium phenylpropiolate. The thermal base generator can be used in a wide range.

  The ink-jet ink composition of the present invention includes an acid proliferating agent that newly generates an acid by an acid generated by irradiation of actinic rays, which is already known, such as those disclosed in JP-A-8-248561 and 9-34106. It is also possible to contain.

  The ink-jet ink composition of the present invention is produced by well dispersing the pigment together with an active energy ray-curable composition and a pigment dispersant using an ordinary dispersing machine such as a sand mill. It is preferable to prepare a concentrated solution having a high pigment concentration in advance and dilute with an active energy ray-curable composition. Sufficient dispersion is possible even with dispersion by a normal disperser, so it does not take excessive dispersion energy and does not require a great amount of dispersion time. Ink excellent in the quality is prepared. The ink is preferably filtered through a filter having a pore diameter of 3 μm or less, more preferably 1 μm or less.

  The ink composition for inkjet according to the present invention is preferably adjusted so that the viscosity at 25 ° C. is as high as 5 to 50 mPa · s. An ink having a viscosity of 5 to 50 mPa · s at 25 ° C. exhibits stable ejection characteristics even from a head having a normal frequency of 4 to 10 KHz to a head having a high frequency of 10 to 50 KHz. When the viscosity is less than 5 mPa · s, a decrease in the followability of the discharge is recognized in the high-frequency head, and when it exceeds 50 mPa · s, the discharge characteristic itself even if a mechanism for reducing the viscosity by heating is incorporated in the head. Drop, the stability of the discharge becomes poor, and it becomes impossible to discharge at all.

  In addition, the ink-jet ink composition of the present invention preferably has an electrical conductivity of 10 μS / cm or less and no electrical corrosion inside the head in a piezo head. Further, in the continuous type, it is necessary to adjust the electric conductivity by the electrolyte. In this case, it is necessary to adjust the electric conductivity to 0.5 mS / cm or more.

  In the present invention, the surface tension of the inkjet ink composition at 25 ° C. is preferably in the range of 25 to 40 mN / m. If the surface tension of the inkjet ink composition at 25 ° C. is less than 25 mN / m, stable emission is difficult to obtain, and if it exceeds 40 mN / m, a desired dot diameter cannot be obtained. Outside the range of 25 to 40 mN / m, uniform isot diameter on various supports, even when emitted and irradiated with light while controlling the viscosity and water content of the ink-jet ink composition as in the present invention. It becomes difficult to obtain.

  In order to adjust the surface tension, a surfactant may be contained as necessary. Examples of the surfactant preferably used in the ink according to the present invention include anionic surfactants such as dialkylsulfosuccinates, alkylnaphthalenesulfonates, and fatty acid salts, polyoxyethylene alkyl ethers, and polyoxyethylene alkyl. Nonionic surfactants such as allyl ethers, acetylene glycols, polyoxyethylene / polyoxypropylene block copolymers, cationic surfactants such as alkylamine salts and quaternary ammonium salts, and surfactants having a polymerizable group Compounds and the like. Of these, particularly preferred are surface active compounds having a polymerizable group such as an unsaturated bond, oxirane, or oxetane ring, such as silicone-modified acrylate, fluorine-modified acrylate, silicone-modified epoxy, fluorine-modified epoxy, silicone-modified oxetane, and fluorine-modified oxetane. .

  Various additives other than those described above can be used in the inkjet ink composition of the present invention. For example, leveling additives, matting agents, polyester resins for adjusting film properties, polyurethane resins, vinyl resins, acrylic resins, rubber resins, and waxes can be added. In order to improve the adhesion with the recording medium, it is also effective to add a trace amount of organic solvent. In this case, it is effective to add in the range where the solvent resistance and VOC problems do not occur, and the amount used is in the range of 0.1 to 5%, preferably 0.1 to 3%. It is also possible to combine a radically polymerizable monomer and an initiator into a radical / cation hybrid type curable ink.

  In the image forming method of the present invention, an ink jet ink composition is ejected onto a recording material by a recording head having at least one nozzle capable of selectively controlling the ejection of the ink droplets. After landing, the ink is cured by irradiating with active energy rays.

  In the image forming method of the present invention, it is preferable that the ink is heated together with the ink jet nozzles during ink ejection so that the ink liquid has a low viscosity. As heating temperature, it is 30-80 degreeC, Preferably it is 35-60 degreeC.

  In the present invention, the total ink film thickness after the ink has landed and cured by irradiation with actinic rays is preferably 2 to 20 μm. In image formation in the screen printing field, the total ink film thickness currently exceeds 20 μm, but in the flexible packaging printing field, where the recording material is often a thin plastic material, the problem of curling and wrinkling of the recording material Not only that, but there is a problem that the texture and texture of the entire printed matter will change. Moreover, in this invention, it is preferable that the amount of droplets discharged from each nozzle is 2 to 15 pl.

  In the present invention, in order to form a high-definition image, the irradiation timing is preferably as early as possible, but it is preferable to start the light irradiation at a timing at which the viscosity or moisture content of the ink is favorable. Specifically, as the irradiation condition of the generated light, actinic light irradiation is preferably started within 0.001 to 2.0 seconds after ink landing, and more preferably 0.001 to 0.4 seconds. Also, it is preferable to terminate the light irradiation after 0.1 to 3 seconds, preferably within 0.2 to 1 second, until the ink fluidity is lost. By setting it as the above condition, enlargement of the dot diameter and bleeding between the dots can be prevented.

  As a method for irradiating actinic rays, the basic method is disclosed in JP-A-60-132767. According to this, the light source is provided on both sides of the recording head unit, and the recording head and the light source are scanned by the shuttle method. Irradiation is performed after a certain period of time after ink landing. Further, the curing is completed by another light source that is not driven. In US Pat. No. 6,145,979, as an irradiation method, a method using an optical fiber or a method of applying a collimated light source to a mirror surface provided on the side surface of a recording head unit and irradiating the recording unit with UV light is disclosed. ing. Any of these irradiation methods can be used in the image forming method of the present invention.

  In addition, irradiation with actinic rays is divided into two stages. First, actinic rays are irradiated by the above-described method within 0.001 to 2.0 seconds after ink landing, and further, actinic rays are irradiated after all printing is completed. The method is also a preferred embodiment. By dividing the irradiation of actinic rays into two stages, it is possible to further suppress the shrinkage of the recording material that occurs during ink curing.

Examples of light sources used in actinic ray irradiation include mercury arc lamps, xenon arc lamps, fluorescent lamps, carbon arc lamps, tungsten-halogen copying lamps, high pressure mercury lamps, metal halide lamps, electrodeless UV lamps, low pressure mercury lamps, and UV lasers. , Xenon flash lamps, insect traps, black lights, germicidal lamps, cold cathode tubes, LEDs, and the like, but are not limited to these. Among these, fluorescent tubes are preferred because of their low energy and low cost. A light source having a light emission wavelength peak at 250 to 370 nm, preferably 270 to 320 nm is preferable in terms of sensitivity. The illuminance is 1 to 3000 mW / cm ² , preferably 1 to 200 mW / cm ² . In addition, in the case of curing with an electron beam, the curing is usually performed with an electron beam having an energy of 300 eV or less, but it is also possible to cure instantaneously with an irradiation amount of 1 to 5 Mrad.

  The inkjet ink composition of the present invention is used to print an image on a recording medium. As the recording medium, all of a wide range of conventional synthetic resins used in various applications can be used. Examples include polyester, polyvinyl chloride, polyethylene, polyurethane, polypropylene, acrylic resin, polycarbonate, polystyrene, acrylonitrile-butadiene-styrene copolymer, polyethylene terephthalate, polybutadiene terephthalate, and the like. The shape is not limited at all.

  As a base material that can be used in the present invention, a non-absorbent support can be used in addition to normal uncoated paper, coated paper, etc. Among them, a non-absorbable support is used as the base material. It is preferable.

  In the present invention, various non-absorbing plastics and films thereof can be used as the non-absorbing support. Examples of the various plastic films include PET film, OPS film, OPP film, ONy film, and PVC film. , PE film, and TAC film. As other plastics, polycarbonate, acrylic resin, ABS, polyacetal, PVA, rubbers and the like can be used. Moreover, it is applicable also to metals and glass. Among these recording materials, the structure of the present invention is effective particularly when an image is formed on a PET film, an OPS film, an OPP film, an ONy film, or a PVC film that can be shrunk by heat. These base materials are not only susceptible to curling and deformation of the film due to curing shrinkage of the ink and heat generated during the curing reaction, but also the ink film is difficult to follow the shrinkage of the base material.

  The surface energies of these various plastic films differ greatly, and it has been a problem in the past that the dot diameter after ink landing varies depending on the recording material. The constitution of the present invention includes an OPP film having a low surface energy, an OPS film, and a PET having a relatively large surface energy, but the substrate preferably has a wetting index of 40 to 60 mN / m.

  In the present invention, it is more advantageous to use a long (web) recording material in terms of the cost of the recording material such as packaging cost and production cost, the efficiency of creating the print, and the ability to cope with printing of various sizes. is there.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, the embodiment of this invention is not limited to these.

Example 1
<< Preparation of Active Energy Ray Curing Composition >>
An active energy ray-curable composition 101 having the following composition was prepared under light shielding.

Sulfonium salt compound: TAS-1 (solid content mass 50% propylene carbonate solution)
5 parts by mass Epoxy compound: EP-17 30 parts by mass Oxetane compound: Aron oxetane OXT-221 70 parts by mass In the preparation of the active energy ray-curable composition 101, the types of sulfonium salt compounds and epoxy compounds are as shown in Tables 1 and 2 The active energy ray-curable compositions 102 to 108 were prepared by changing to

  In the preparation of the active energy ray-curable composition 101, the types and addition amounts of sulfonium salt compounds and epoxy compounds are changed as shown in Tables 1 and 2, and ionic compounds are added as shown in Tables 1 and 2 to obtain active energy. Line curable compositions 109-159 were prepared.

  Details of symbols abbreviated in Tables 1 and 2 are shown below.

UVI 6990: Triphenylsulfonium salt (Syracure UVI 6990, manufactured by Union Carbide)
S-1: Alicyclic epoxy compound (Celoxide 3000, manufactured by Daicel UCB)
<< Evaluation of Active Energy Ray Curing Composition >>
(Viscosity change)
20 ml of the active energy ray curable composition was put into a glass container with a screw cap, the lid was closed, and the viscosity change of the active energy ray curable composition after storage for 1 month in a thermostatic bath at 70 ° C. was then examined. The change in viscosity was evaluated based on the following criteria based on the tactile sensation by touching the active energy ray curable composition stored at 70 ° C. with a metal spatula, based on the active energy ray curable composition stored at room temperature for 1 month under light shielding.

5: No significant difference was found in the tactile sensation of the active energy ray curable composition 4: There was a slight difference in the viscosity of the active energy ray curable composition 3: The viscosity of the active energy ray curable composition was clearly increased 2: The active energy ray-curable composition became a gel. 1: The active energy ray-curable composition became a solid.

(UV curable)
1 ml of active energy ray-curable composition stored in a thermostatic chamber at 70 ° C. for 1 month under light shielding is applied to a 157 cm ² PET film and heated to 30 ° C., using a high-pressure mercury lamp, and an irradiation energy of 10 mJ / cm ^2. Was irradiated for 20 seconds, and the curability of the coating film was touched with a metal spatula.

3: The coating film was solidified 2: The coating film was gelled 1: The coating film was not cured 2 or more is a composition suitable for practical use with respect to curability.

  The results of evaluation are shown in Tables 1 and 2.

  As is clear from Tables 1 and 2, the active energy ray photoacid generator composition of the present invention, the active energy ray curable composition comprising an epoxy compound and an oxetane compound does not impair the curing performance even when stored at a high temperature. It can be seen that it can be stored stably.

Example 2
<Preparation of magenta ink>
Magenta ink 1 having the following composition was prepared. The magenta ink 1 was prepared by dispersing each composition excluding the active energy ray photoacid generator composition for 4 hours using a sand grinder, adding the active energy ray photoacid generator composition, and adding a 0.8 μm membrane. After filtration through a filter, it was prepared by dehydration under reduced pressure while heating to 50 ° C.

Pigment: C.I. I. Pigment Red 184 3 parts by weight Dispersant: Solsperse 24000 (manufactured by Avecia) 1 part by weight Oxetane compound: Aron oxetane OXT-221 70 parts by weight Epoxy compound: EP-17 30 parts by weight Active energy ray photoacid generator composition: sulfonium Salt compound, TAS-1 (solid content 50% propylene carbonate solution) 5 parts by weight In the preparation of magenta ink 1, the types and amounts of pigment, oxetane compound, epoxy compound and active energy ray acid generator composition are shown in Table 3. 4, magenta inks 102 to 159 were prepared.

  Details of symbols abbreviated in Tables 3 and 4 are shown below.

<Pigment>
P0: C.I. I. Pigment Red 184
P1: 250 parts of crude copper phthalocyanine (“Copper phthalocyanine” manufactured by Toyo Ink Manufacturing Co., Ltd.), 2500 parts of sodium chloride and 160 parts of polyethylene glycol (“Polyethylene glycol 300” manufactured by Tokyo Chemical Industry Co., Ltd.), 4.55 L (1 gallon) made of styrene And kneaded for 3 hours. Next, this mixture is poured into 2.5 L of warm water, heated to about 80 ° C. and stirred for about 1 hour with a high speed mixer to form a slurry, followed by filtration and washing 5 times to remove sodium chloride and solvent. Then, the mixture was spray dried and dried to obtain Pigment P1.

  P2: 250 parts of quinacridone red pigment (“Cincacia Magenta RT-355-D” manufactured by Ciba Specialty Chemicals), 2500 parts of sodium chloride, and 160 parts of “polyethylene glycol 300”, 4.55 L (1 gallon) kneader made of styrene In the same manner as in P1, pigment P2 was obtained.

<Epoxy compound>
S-1: Alicyclic epoxy compound (Celoxide 3000, manufactured by Daicel UCB)
<Photoacid generator>
UVI 6990: Triphenylsulfonium salt (Syracure UVI 6990, manufactured by Union Carbide)
<Oxetane compound>
OXT-221: Di [1-ethyl (3-oxetanyl)] methyl ether (manufactured by Toagosei Co., Ltd.)

<< Inkjet image recording and evaluation >>
Using the magenta inks prepared as described above, images obtained by image recording were evaluated according to the following methods. Each of the prepared magenta inks was stored in a thermostatic chamber at 70 ° C. for 1 week under light shielding, and then the same evaluation was performed.

[Image Evaluation A]
(Image recording)
Piezo-type inkjet nozzles (nozzle pitch 360 dpi, dpi as used in the present invention represents the number of dots per 2.54 cm) for each magenta ink obtained to obtain a droplet size of 7 pl, and the nozzle portion at 50 ° C. A polyethylene terephthalate film subjected to heating control and subjected to corona treatment was emitted as a base material, and a magenta solid image and a 6-point MS Mincho font were printed. As the light source, a fluorescent tube having a main peak at 308 nm is used. Under the condition that the illuminance of the substrate surface is 10 mW / cm ² directly under the light source, the exposure starts 0.3 seconds after landing and the exposure ends after 0.8 seconds. I let you. The exposure energy was 5 mJ / cm ² . This image printing was performed in a low humidity environment (35 ° C., 20% RH) and a high humidity environment (35 ° C., 80% RH).

(Image evaluation)
The following evaluation was performed on each image obtained as described above.

<Ink curing>
For the printed images formed under each environment, the ink curability was evaluated according to the following criteria.

○: The image has no tackiness even when touched immediately after the exposure is finished. Δ: The image has a slight tackiness when touched immediately after the exposure is finished, but the tackiness disappears after one minute. X: The tackiness remains even after one minute after the exposure. Material adhesion>
A solid tape (R) with a width of 25 mm is applied on the solid image formed in each environment and strongly pressed, and then quickly peeled off at a peeling angle of 90 degrees. The state of the image after isolation is visually observed, and the following The substrate adhesion was evaluated according to the standard.

○: The image is not peeled even when the tape is peeled △: The image is peeled off partly by the tape peeling ×: The whole image is peeled off by the tape peeling
The 6-point MS Mincho characters formed under each environment were observed with a loupe, the state of adjacent dots was observed, and image blur resistance was evaluated according to the following criteria.

◯: Almost no bleeding between 2 dots Δ: Slight bleeding between 2 dots is observed X: The dots are greatly blurred The results obtained as described above are shown in Tables 5-8.

  In Table 5, the inks 201 to 208 could not be evaluated for ejection after being stored at 70 ° C. for 1 week due to the significant increase in viscosity of the ink liquid.

[Image Evaluation B]
In the image evaluation A, image recording and evaluation were performed in the same manner except that the exposure irradiation start time after printing the ink was changed to 0.5 seconds and the exposure irradiation end time was changed after 1.0 seconds. . The exposure time and exposure energy were 5 mJ / cm 2 for 0.5 seconds, respectively, as in image evaluation A. The obtained results are shown in Tables 9-12.

  In Table 9, the inks 201 to 208 could not be evaluated for ejection after being stored at 70 ° C. for 1 week due to the significant increase in viscosity of the ink liquid.

  As is clear from Tables 5 to 12, the ink containing the active energy ray curable composition of the present invention containing the active energy ray acid generator composition of the present invention is different from the comparative example in a high humidity environment and various inks. It can be seen that even in an exposure environment, excellent ink curability and substrate adhesion can be obtained, and a high-quality image without bleeding can be obtained. Further, it can be seen that even when the ink of the present invention is stored at a high temperature, the ink characteristics are not deteriorated and an ink having high storage stability can be obtained.

Claims (13)

An active energy ray acid generator composition comprising a compound represented by the following general formula (a) and a compound represented by the following general formula (b).
Formula (a) Q ^{n +} (Y ^m− ) _{n / m}
(In the formula, Q ^{n +} is an n-valent cation, Y ^m− is an ^m- valent cation whose pKa value of the conjugate acid is larger than the pKa of the X ^B− conjugate acid in the following general formula (b)). Represents an anion, and n and m each represent an integer of 1 to 3.)

(In the formula, R ^{B1 to} R ^B3 represent substituents, and X ^B- represents a counter ion.) The active energy ray according to claim 1, wherein the compound represented by the general formula (b) is at least one compound selected from the following general formulas (I-1) to (I-3). Acid generator composition.

(In the formula, R ₁₁ , R ₁₂ and R ₁₃ represent substituents, m, n and p each represents an integer of 0 to 5, and X ₁₁ ⁻ represents a counter ion.)

(Wherein R ₁₄ represents a substituent, and q represents an integer of 0 to 2. R ₁₅ and R ₁₆ represent a substituted, unsubstituted alkyl group, a substituted, unsubstituted alkenyl group, a substituted, unsubstituted alkynyl group. or substituted, .X ₁₂ representing the unsubstituted aryl group ^- represents a counter ion).

(Wherein R ₁₇ represents a substituent, r represents an integer of 0 to 3. R ₁₈ represents a hydrogen atom or a substituted or unsubstituted alkyl group, and R ₁₉ and R ₂₀ represent a substituted or unsubstituted alkyl group. , substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group or a substituted, .X ₁₃ representing the unsubstituted aryl group ^- represents a counter ion). The active energy ray acid generator composition according to claim 2, wherein the compound represented by the general formula (I-1) is a compound represented by the following general formula (T-1).

(Wherein R ^T11 and R ^T12 represent an alkyl group or an aromatic group, Z ^T1 represents an oxygen atom or a sulfur atom, and R ^T13 and R ^T14 represent an alkyl group, an aromatic group, an alkoxy group, and an aryloxy group, respectively. , An alkylthio group and an arylthio group, m ^t1 represents an integer of 0 to 4, n ^t1 and p ^t1 each represent an integer of 1 to 5, and X ^T1 represents a counter anion.) The active energy ray acid according to any one of claims 1 to 3, wherein Q ^{n +} in the general formula (a) is a cation having any one of N ⁺ , S ⁺ , and P ^+. Generator composition. The active energy ray acid generator composition according to claim 4, wherein the Q ^{n +} is a quaternary ammonium cation or a pyridinium cation. Y ^m− in the general formula (a) is Cl ⁻ , Br ⁻ , I ⁻ , R ⁶⁰¹ —SO ₃ ⁻ , SO ₄ ²⁻ , NO ₃ ⁻ , R ⁶⁰² —COO ⁻ , AlO ₂ ⁻ , ClO _{4. ^{-, PO 4 3-, B (}} C 6 H 5) 4 -, R 603 -O - at least one anion selected from, X in the general formula (b) ^B- is, PF ₆ ^-, BF _{4 ^{-, SbF 6 -, GaF 6}} -, AsF 6 -, B (C 6 F 5) 4 - , wherein the at least one anion selected from ^{_{-, C n F (2n +}} 1) SO 3 The active energy ray acid generator composition of any one of Claims 1-5.
However, n is an integer of 1 to 30, R ⁶⁰¹ and R ⁶⁰² are each independently an aliphatic group having 1 to 30 carbon atoms or an aromatic group having 6 to 20 carbon atoms, and R ⁶⁰³ is an alkyl group having 6 to 20 carbon atoms. Represents an aromatic group. An active energy ray curable composition comprising an epoxy compound and the active energy ray acid generator composition according to any one of claims 1 to 6. The active energy ray-curable composition according to claim 7, wherein the epoxy compound is an alicyclic epoxy compound represented by the following general formula (A).

(In the formula, R ₁₀₀ represents a substituent, m 0 represents an integer of 0 to 2, r ₀ represents an integer of 1 to 3. L ₀ has 1 to 15 carbon atoms which may contain an oxygen atom or a sulfur atom in the main chain. Represents an r0 + 1-valent linking group or a single bond.) The active energy ray-curable composition according to claim 7 or 8, wherein the epoxy compound is at least one of alicyclic epoxy compounds represented by the following general formulas (1) to (6).

(Wherein the R ₁₀₁ are substituents, .P1 which m1 is an integer of 0 to 2, q1 and each 0 or 1, r1 is .L ₁ represents an integer of 1 to 3 oxygen atoms or in the main chain (It represents a C1-C15 r1 + 1 valent linking group or single bond which may contain a sulfur atom.)

(Wherein the R ₁₀₂ are substituents, .P2 which m2 represents an integer of 0 to 2, q2 and each 0 or 1, r2 is .L ₂ represents an integer of 1 to 3 oxygen atoms or in the main chain (It represents a C1-15 r2 + 1 valent linking group or single bond which may contain a sulfur atom.)

(In the formula, R ₁₀₃ represents a substituent, m3 represents an integer of 0 to 2. p3 represents 0 or 1. L ₃ has 1 to 8 carbon atoms which may contain an oxygen atom or a sulfur atom in the main chain. Represents a divalent linking group or a single bond.)

(In the formula, R ₁₀₄ represents a substituent, m4 represents an integer of 0 to 2. p4 represents 0 or 1. L ₄ has 1 to 8 carbon atoms which may contain an oxygen atom or a sulfur atom in the main chain. Represents a divalent linking group or a single bond.)

(In the formula, R ₁₀₅ represents a substituent, and m5 represents 1 or 2.)

(In the formula, R ₁₀₆ represents a substituent, and m6 represents an integer of 0 to 2.) The active energy ray-curable composition according to claim 7, comprising an oxetane compound. The active energy ray-curable composition according to any one of claims 7 to 10, wherein the active energy ray of the active energy ray acid generator composition is an ultraviolet ray. An ink composition for ink jet, comprising the active energy ray-curable composition according to any one of claims 7 to 11. The inkjet ink composition according to claim 12 is ejected onto a recording material by a recording head having at least one nozzle capable of selectively controlling ejection of the ink droplet, and the ink droplet is landed. Thereafter, the ink is cured by irradiating with an active energy ray.