JP2009286954A - Photo-curable composition and ink composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photo-curable composition being cured at high sensitivity and capable of suppressing coloring caused from a sensitization pigment. <P>SOLUTION: The photo-curable composition contains a polymerizable compound, a compound represented by general formula (I), and a compound represented by general formula (II). (Wherein, X represents O, S or NR<SP>5</SP>, R<SP>5</SP>represents a hydrogen atom, an alkyl group or an acyl group, n represents 0-2, R<SP>1</SP>-R<SP>4</SP>and Z<SP>1</SP>-Z<SP>4</SP>each independently represents a hydrogen atom or a monovalent substituent, R<SP>1</SP>-R<SP>4</SP>may form a ring by bonding two adjacent members to each other respectively, X<SP>a</SP>represents a hydrogen atom or a monovalent substituent, R<SP>1a</SP>-R<SP>5a</SP>each independently represents a hydrogen atom or a monovalent substituent, and R<SP>4a</SP>and R<SP>5a</SP>may be linked to each other to form a ring). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a photocurable composition containing a novel compound useful as a sensitizing dye, and an ink composition using the same.

As an image recording method for forming an image on a recording medium such as paper based on an image data signal, there are an electrophotographic method, a sublimation type and a melt type thermal transfer method, an ink jet method and the like. The electrophotographic system requires a process of forming an electrostatic latent image on a photosensitive drum by charging and exposure, and there is a problem that the system becomes complicated and consequently the manufacturing cost becomes high. In addition, although the thermal transfer system is inexpensive, there are problems such as high running costs and waste materials due to the use of ink ribbons.
On the other hand, the ink jet method is an inexpensive device and ejects ink only to a required image portion to form an image directly on a recording medium. Therefore, the ink can be used efficiently and the running cost is low. Furthermore, there is little noise and it is excellent as an image recording method.

  Ink compositions that can be cured by irradiation with actinic radiation such as ultraviolet rays (radiation curable ink compositions), such as ink compositions for ink jet recording, can be cured with high sensitivity and form high-quality images. It has been demanded. By achieving high sensitivity, high curability is imparted by irradiation with actinic radiation, so that sufficient curing is achieved in addition to reducing power consumption and extending life by reducing the load on the actinic radiation generator. As a result, there are various advantages such as suppression of volatilization of uncured low molecular weight substances and reduction in the strength of the formed image.

  The curable inkjet method using ultraviolet light has been attracting attention in recent years because it has a relatively low odor and can record on a recording medium having no quick drying and no ink absorption. In particular, benzyl, benzoin, benzoin ethyl ether, Michler's ketone, anthraquinone, acridine, phenazine, benzophenone, 2-ethylanthraquinone and the like have been generally used as photopolymerization initiators (see, for example, Non-Patent Document 1). However, when these photopolymerization initiators are used, it takes a long time for image exposure in image formation because the photopolymerizable composition has low curing sensitivity. For this reason, in the case of a fine image, if there is a slight vibration in the operation, an image with good image quality cannot be reproduced, and further, the amount of energy emitted from the light source of the exposure must be increased. It was necessary to consider radiation. In addition, ink used in the ink jet recording system requires various characteristics such as no change in physical properties or precipitation due to storage (solution stability), no clogging of the nozzle (ejection stability), etc. It is.

In general, as a method for increasing the sensitivity to radiation in a radiation curable polymerizable compound, use of various polymerization initiation systems is disclosed (for example, see Non-Patent Document 1 and Patent Documents 1 to 4). However, there is no example in which an ink for ink jet recording employs a polymerization initiating system satisfying sufficient sensitivity for scanning exposure, storage stability, and ejection stability.
For this reason, ink that can be cured with high sensitivity to low-output radiation, can form high-quality images, and has good storage stability and ejection stability, and is suitably used for inkjet recording. Compositions are anxious.

  Conventionally, iodonium salts and sulfonium salts have been widely used as photoinitiators for cationic polymerization. Of these, the sulfonium salt can directly cure the cationically polymerizable compound by irradiation with UV at 366 nm, and thus the necessity of a sensitizer has not been particularly demanded. On the other hand, since iodonium salts have a low absorption wavelength of around 250 nm, thioxanthone derivatives and dialkoxyanthracene derivatives having UV absorption around 380 nm to 400 nm have been used in order to match with UV light from a high-pressure mercury lamp or the like.

However, this dialkoxyanthracene derivative is expensive, and a more effective sensitization method using a cheaper group of compounds is desired for cost reduction.
Bruce M. Monroe et al., Chemical Reviews, Vol. 93, (1993), p. 435-448. U.S. Pat. No. 4,134,813 JP-A-1-253731 JP-A-6-308727 EP1616922A1 specification JP 2001-106648 A

An object of the present invention is to provide a photocurable composition that contains a novel compound useful as a sensitizing dye, is cured with high sensitivity by irradiation, and can suppress coloring derived from the sensitizing dye.
Furthermore, an object of the present invention is to form a high-quality image by curing with high sensitivity even when irradiated with low-output radiation, and even when used for inkjet recording, It is an object of the present invention to provide an ink composition that is less likely to cause ink.

In order to solve the above problems, the present inventors have intensively studied to complete the present invention. That is, the means for solving the above problems are as follows.
<1> A photocurable composition comprising a polymerizable compound, a compound represented by the following general formula (I), and a compound represented by the following general formula (II).

(In general formula (I), X represents O, S, NR ⁵ , R ⁵ represents a hydrogen atom, an alkyl group or an acyl group. N represents an integer of 0 to 2. R ^{1 to} R ⁴ , Z ^{1 to} Z ⁴ each independently represent a hydrogen atom or a monovalent substituent, and R ^{1 to} R ⁴ may be bonded to each other to form a ring.

(In the general formula (II), ^{X a} represents a hydrogen atom or a monovalent each .R ^1a to R ^5a representing a substituent independently a hydrogen atom or a monovalent substituent, ^{R 4a} and ^{R 5a} are connected to each other To form a ring)

<2> The photocurable composition according to <1>, wherein the compound represented by the general formula (II) is a compound represented by the following general formula (III).

(In the general formula (III), ^Xb is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted R ^1b represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl, and represents a substituted aryloxycarbonyl group or a substituted or unsubstituted carbamoyl group. Oxy group, amino group, substituted or unsubstituted acyl group, substituted or unsubstituted acylamino group, substituted or unsubstituted alkyl and arylsulfonylamino group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxy A carbonyl group or a substituted or unsubstituted .R ^2b is hydrogen atom representing a Bamoiru group, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic oxy group, a substituted Alternatively, it represents an unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted acyloxy group, a substituted or unsubstituted alkoxycarbonyl group, or a substituted or unsubstituted aryloxycarbonyl group, R ^3b and R ^4b represents a hydrogen atom or a monovalent substituent, and R ^3b and R ^4b may be linked to each other to form a condensed ring.

<3> The photocurable composition according to <2>, wherein the compound represented by the general formula (III) is a compound represented by the following general formula (IV).

(In the general formula (IV), ^Xc is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted R ^1c represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl, or a substituted aryloxycarbonyl group or a substituted or unsubstituted carbamoyl group. Oxy group, amino group, substituted or unsubstituted acyl group, substituted or unsubstituted acylamino group, substituted or unsubstituted alkyl and arylsulfonylamino group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxy Carbonyl group or substituted or unsubstituted carbon R ^2c represents a hydrogen atom, halogen atom, substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted acyloxy group, a substituted or unsubstituted alkoxycarbonyl group, or,, .R ^3c to R representing a substituted or unsubstituted aryloxycarbonyl group ^6c represents a hydrogen atom or a monovalent substituent.)

<4> The photocurable composition according to any one of <1> to <3>, wherein the polymerizable compound is a cationic polymerizable compound.
<5> The photocurable composition according to any one of <1> to <4>, further containing a photoacid generator.
<6> The photocurable composition according to <5>, wherein the photoacid generator is a sulfonium salt compound.

<7> An ink composition comprising the photocurable composition according to any one of <1> to <6>.
<8> The ink composition according to claim 7, which is for inkjet recording.

  ADVANTAGE OF THE INVENTION According to this invention, the photocurable composition which contains a novel compound useful as a sensitizing dye, hardens | cures with high sensitivity by irradiation, and can suppress the coloring derived from a sensitizing dye can be provided. Furthermore, according to the present invention, it is possible to form a high-quality image by curing with high sensitivity even when irradiated with low-output radiation, and even when used for inkjet recording, Can be provided.

<Photocuring composition>
The photocurable composition of the present invention includes at least one polymerizable compound, at least one compound represented by the following general formula (I), and at least one compound represented by the following general formula (II). And other components as necessary.
By containing a compound represented by the following general formula (I) and a compound represented by the following general formula (II), it can be cured with high sensitivity by irradiation with radiation, and its photocurability is suppressed from being colored. A composition can be constructed.

(Compound represented by formula (I))
The compound represented by the general formula (I) (hereinafter also referred to as “specific sensitizing dye”) is a useful compound that can be contained in a curable composition containing a polymerization initiator and a polymerizable compound. By containing the specific sensitizing dye in the present invention, the curable composition has improved curability and sensitivity.
In addition, the specific sensitizing dye has higher solubility and lower crystallinity than a commonly used thioxanthone compound. For example, when the sensitizing dye is contained in the ink composition, the ink composition is stable as a solution. It is considered that excellent ejection stability can be obtained when an ink composition containing the same is used for inkjet recording.
Hereinafter, the compound represented by formula (I) will be described.

In general formula (I), X represents O, S, NR ⁵ , and R ⁵ represents a hydrogen atom, an alkyl group, or an acyl group. n represents 0-2. R ^{1 to} R ⁴ and Z ^{1 to} Z ⁴ each independently represent a hydrogen atom or a monovalent substituent. Two adjacent R ^{1 to} R ⁴ may be bonded to each other to form a ring.

X represents an oxygen atom, a sulfur atom, or NR ⁵ , and R ⁵ is preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acyl group, and more preferably a hydrogen atom, a methyl group, or an acetyl group. X is preferably an oxygen atom or a sulfur atom, and more preferably a sulfur atom.

n represents an integer of 0 to 2. Here, when n is 0, there is no carbon atom bonded to Z ² and Z ^4, and X containing a hetero atom and a carbon atom bonded to Z ¹ and Z ³ are directly bonded to form X. A 5-membered heterocycle containing it. When n is 1, a 6-membered heterocycle containing one carbon atom bonded to Z ² and Z ⁴ and X is formed. Further, when n is 2, a 7-membered heterocycle containing two carbon atoms bonded to Z ² and Z ⁴ and X is formed. When n is 2, Z ² and Z ⁴ each having two may be the same as or different from each other.
R ^{1 to} R ⁴ and Z ^{1 to} Z ⁴ each independently represent a hydrogen atom or a monovalent substituent.

  Examples of the monovalent substituent include a halogen atom, alkyl group, cycloalkyl group, aralkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, hydroxy group, alkoxy group, aryloxy group, Silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (alkylamino group, arylamino group), acylamino group (amide group), aminocarbonylamino group ( (Ureido group), alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, alkyl Rufinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, silyl group And an imide group, and each monovalent substituent may further have a substituent. The monovalent substituent will be described in more detail below.

  The halogen atom is preferably a chlorine atom, a bromine atom, or an iodine atom. Of these, a chlorine atom or a bromine atom is preferable, and a chlorine atom is particularly preferable.

  The alkyl group includes a substituted alkyl group and an unsubstituted alkyl group. The substituted or unsubstituted alkyl group is preferably an alkyl group having 1 to 30 carbon atoms. Examples of the substituent in the substituted alkyl group include a linear or branched alkyl group having 1 to 12 carbon atoms (for example, methyl, ethyl, propyl, isopropyl, sec-butyl, t-butyl, 2-ethylhexyl, 2-methylsulfonyl). Ethyl, 3-phenoxypropyl, trifluoromethyl), a linear or branched aralkyl group having 7 to 18 carbon atoms, a linear or branched alkenyl group having 2 to 12 carbon atoms, a linear or branched group having 2 to 12 carbon atoms. Chain alkynyl group, linear or branched cycloalkyl group having 3 to 12 carbon atoms (for example, cyclopentyl), linear or branched chain cycloalkenyl group having 3 to 12 carbon atoms, halogen atom (for example, chlorine atom, bromine atom) An aryl group (for example, phenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl), a heterocyclic group (for example, imida Ryl, pyrazolyl, triazolyl, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxyl group, nitro group, amino group, alkyloxy group (eg, methoxy, ethoxy, 2-methoxyethoxy, 2-methylsulfonylethoxy), aryloxy group (for example, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbonylphenoxy, 3-methoxycarbonylphenyloxy, acylamino group (Eg, acetamide, benzamide, 4- (3-tert-butyl-4-hydroxyphenoxy) butanamide), alkylamino groups (eg, methylamino, butylamino, diethylamino, methylbutylamino), arylamino groups (eg , Phenylamino, 2-chloroanilino), ureido group (for example, phenylureido, methylureido, N, N-dibutylureido), sulfamoylamino group (for example, N, N-dipropylsulfamoylamino), alkylthio group ( For example, methylthio, octylthio, 2-phenoxyethylthio), arylthio group (for example, phenylthio, 2-butoxy-5-t-octylphenylthio, 2-carboxyphenylthio), alkyloxycarbonylamino group (for example, methoxycarbonylamino) ), Alkylsulfonylamino group (eg, methylsulfonylamino), arylsulfonylamino group (eg, phenylsulfonylamino, p-toluenesulfonylamino), carbamoyl group (eg, N-ethylcarbamoyl, N, N) -Dibutylcarbamoyl), sulfamoyl groups (eg N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N-phenylsulfamoyl), alkyl and arylsulfonyl groups (eg methylsulfonyl, octylsulfonyl, phenylsulfonyl) P-toluenesulfonyl), alkyloxycarbonyl groups (for example, methoxycarbonyl, butyloxycarbonyl), heterocyclic oxy groups (for example, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), alkyl and arylazo groups (For example, phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo), acyloxy group (for example, acetoxy), carbamoyloxy group ( For example, N-methylcarbamoyloxy, N-phenylcarbamoyloxy), silyloxy groups (for example, trimethylsilyloxy, dibutylmethylsilyloxy), aryloxycarbonylamino groups (for example, phenoxycarbonylamino), imide groups (for example, N-succinimide) N-phthalimido), heterocyclic thio groups (eg, 2-benzothiazolylthio, 2,4-di-phenoxy-1,3,5-triazole-6-thio, 2-pyridylthio), alkyl and arylsulfinyl groups (Eg 3-phenoxypropylsulfinyl), phosphonyl groups (eg phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), aryloxycarbonyl groups (eg phenoxycarbonyl), acyl groups (eg aceto Le, 3-phenylpropanoyl, benzoyl), ionic hydrophilic groups (e.g., carboxy group, a sulfo group, a phosphono group and a quaternary ammonium group).

The cycloalkyl group includes a substituted cycloalkyl group and an unsubstituted cycloalkyl group. The substituted or unsubstituted cycloalkyl group is preferably a cycloalkyl group having 5 to 30 carbon atoms. As an example of a substituent, the same thing as the substituent which was mentioned as a substituent in the above-mentioned substituted alkyl group is mentioned.
Examples of the cycloalkyl group may include cyclohexyl, cyclopentyl, or 4-n-dodecylcyclohexyl.

Aralkyl groups include substituted aralkyl groups and unsubstituted aralkyl groups. As the substituted or unsubstituted aralkyl group, an aralkyl group having 7 to 30 carbon atoms is preferable. As an example of a substituent, the same thing as the substituent which was mentioned as a substituent in the above-mentioned substituted alkyl group is mentioned.
Examples of the aralkyl group include benzyl and 2-phenethyl.

The alkenyl group represents a linear, branched, or cyclic substituted or unsubstituted alkenyl group. Preferably it is a C2-C30 substituted or unsubstituted alkenyl group.
Examples of alkenyl groups include vinyl, allyl, prenyl, geranyl, oleyl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl and the like.

  The alkynyl group is preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, and examples thereof include ethynyl and propargyl.

  The aryl group is preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, or o-hexadecanoylaminophenyl. As an example of a substituent, the same thing as the substituent which was mentioned as a substituent in the above-mentioned substituted alkyl group is mentioned.

The heterocyclic group is a monovalent substituent obtained by removing one hydrogen atom from a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound. The heterocyclic group may be further condensed. Preferably, it is a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. As an example of a substituent, the same thing as the substituent which was mentioned as a substituent in the above-mentioned substituted alkyl group is mentioned.
Examples of the heterocyclic group as a parent heterocyclic compound without limiting the substitution position include pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan , Benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, thiadiazole, isoxazole, benzisoxazole, pyrrolidine, piperidine, piperazine, imidazo Examples include lysine and thiazoline.

The alkoxy group includes a substituted alkoxy group and an unsubstituted alkoxy group. As the substituted or unsubstituted alkoxy group, an alkoxy group having 1 to 30 carbon atoms is preferable. As an example of a substituent, the same thing as the substituent which was mentioned as a substituent in the above-mentioned substituted alkyl group is mentioned.
Examples of the alkoxy group include methoxy, ethoxy, isopropoxy, n-octyloxy, methoxyethoxy, hydroxyethoxy and 3-carboxypropoxy.

The aryloxy group is preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms. As an example of a substituent, the same thing as the substituent which was mentioned as a substituent in the above-mentioned substituted alkyl group is mentioned.
Examples of the aryloxy group include phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy and the like.

  The silyloxy group is preferably a silyloxy group having 3 to 20 carbon atoms, and examples thereof include trimethylsilyloxy and t-butyldimethylsilyloxy.

The heterocyclic oxy group is preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms. As an example of a substituent, the same thing as the substituent which was mentioned as a substituent in the above-mentioned substituted alkyl group is mentioned.
Examples of the heterocyclic oxy group include 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy and the like.

The acyloxy group is preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, or a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms. As an example of a substituent, the same thing as the substituent which was mentioned as a substituent in the above-mentioned substituted alkyl group is mentioned.
Examples of the acyloxy group include formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy and the like.

The carbamoyloxy group is preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms. As an example of a substituent, the same thing as the substituent which was mentioned as a substituent in the above-mentioned substituted alkyl group is mentioned.
Examples of the carbamoyloxy group include, for example, N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyl. Examples include oxy.

The alkoxycarbonyloxy group is preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms. As an example of a substituent, the same thing as the substituent which was mentioned as a substituent in the above-mentioned substituted alkyl group is mentioned.
Examples of the alkoxycarbonyloxy group include methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy and the like.

The aryloxycarbonyloxy group is preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms. As an example of a substituent, the same thing as the substituent which was mentioned as a substituent in the above-mentioned substituted alkyl group is mentioned.
Examples of the aryloxycarbonyloxy group include phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy and the like.

The amino group is preferably a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms and a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms. As an example of a substituent, the same thing as the substituent which was mentioned as a substituent in the above-mentioned substituted alkyl group is mentioned.
Examples of the amino group include, for example, amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino, hydroxyethylamino, carboxyethylamino, sulfoethylamino, 3,5-dicarboxyanilino, etc. Can be mentioned.

The acylamino group is preferably a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, or a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms. As an example of a substituent, the same thing as the substituent which was mentioned as a substituent in the above-mentioned substituted alkyl group is mentioned.
Examples of the acylamino group include formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino, and the like.

The aminocarbonylamino group is preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms. As an example of a substituent, the same thing as the substituent which was mentioned as a substituent in the above-mentioned substituted alkyl group is mentioned.
Examples of the aminocarbonylamino group include carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino and the like.

The alkoxycarbonylamino group is preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms. As an example of a substituent, the same thing as the substituent which was mentioned as a substituent in the above-mentioned substituted alkyl group is mentioned.
Examples of the alkoxycarbonylamino group include methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino and the like.

The aryloxycarbonylamino group is preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms. As an example of a substituent, the same thing as the substituent which was mentioned as a substituent in the above-mentioned substituted alkyl group is mentioned.
Examples of the aryloxycarbonylamino group include phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino and the like.

The sulfamoylamino group is preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms. As an example of a substituent, the same thing as the substituent which was mentioned as a substituent in the above-mentioned substituted alkyl group is mentioned.
Examples of the sulfamoylamino group include sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino and the like.

The alkyl and arylsulfonylamino groups are preferably a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms and a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms. As an example of a substituent, the same thing as the substituent which was mentioned as a substituent in the above-mentioned substituted alkyl group is mentioned.
Examples of the alkylsulfonylamino group and arylsulfonylamino group include, for example, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino and the like. I can do it.

The alkylthio group is preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms. As an example of a substituent, the same thing as the substituent which was mentioned as a substituent in the above-mentioned substituted alkyl group is mentioned.
Examples of the alkylthio group include methylthio, ethylthio, n-hexadecylthio and the like.

The arylthio group is preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms. As an example of a substituent, the same thing as the substituent which was mentioned as a substituent in the above-mentioned substituted alkyl group is mentioned.
Examples of the arylthio group include phenylthio, p-chlorophenylthio, m-methoxyphenylthio and the like.

The heterocyclic thio group is preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms. As an example of a substituent, the same thing as the substituent which was mentioned as a substituent in the above-mentioned substituted alkyl group is mentioned.
Examples of the heterocyclic thio group include 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio and the like.

The sulfamoyl group is preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms. As an example of a substituent, the same thing as the substituent which was mentioned as a substituent in the above-mentioned substituted alkyl group is mentioned.
Examples of the sulfamoyl group include N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl, N -(N'-phenylcarbamoyl) sulfamoyl) and the like.

The alkyl and arylsulfinyl groups are preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms and a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms. As an example of a substituent, the same thing as the substituent which was mentioned as a substituent in the above-mentioned substituted alkyl group is mentioned.
Examples of the alkyl and arylsulfinyl groups include methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl and the like.

The alkyl and arylsulfonyl groups are preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms and a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms. As an example of a substituent, the same thing as the substituent which was mentioned as a substituent in the above-mentioned substituted alkyl group is mentioned.
Examples of the alkyl and arylsulfonyl groups include methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-toluenesulfonyl and the like.

The acyl group is a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, or a substituted or unsubstituted carbon group having 4 to 30 carbon atoms. A heterocyclic carbonyl group bonded to the carbonyl group by an atom is preferred. As an example of a substituent, the same thing as the substituent which was mentioned as a substituent in the above-mentioned substituted alkyl group is mentioned.
Examples of the acyl group include acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl and the like.

The aryloxycarbonyl group is preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms. As an example of a substituent, the same thing as the substituent which was mentioned as a substituent in the above-mentioned substituted alkyl group is mentioned.
Examples of the aryloxycarbonyl group include phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl, and the like.

The alkoxycarbonyl group is preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms. As an example of a substituent, the same thing as the substituent which was mentioned as a substituent in the above-mentioned substituted alkyl group is mentioned.
Examples of the alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl and the like.

The carbamoyl group is preferably a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms. As an example of a substituent, the same thing as the substituent which was mentioned as a substituent in the above-mentioned substituted alkyl group is mentioned.
Examples of the carbamoyl group include carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl and the like.

The phosphino group is preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms. As an example of a substituent, the same thing as the substituent which was mentioned as a substituent in the above-mentioned substituted alkyl group is mentioned.
Examples of the phosphino group include dimethylphosphino, diphenylphosphino, methylphenoxyphosphino and the like.

The phosphinyl group is preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms. As an example of a substituent, the same thing as the substituent which was mentioned as a substituent in the above-mentioned substituted alkyl group is mentioned.
Examples of the phosphinyl group include phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl and the like.

The phosphinyloxy group is preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms. As an example of a substituent, the same thing as the substituent which was mentioned as a substituent in the above-mentioned substituted alkyl group is mentioned.
Examples of the phosphinyloxy group include diphenoxyphosphinyloxy and dioctyloxyphosphinyloxy.

The phosphinylamino group is preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms. As an example of a substituent, the same thing as the substituent which was mentioned as a substituent in the above-mentioned substituted alkyl group is mentioned.
Examples of the phosphinylamino group include dimethoxyphosphinylamino and dimethylaminophosphinylamino.

The silyl group is preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms. As an example of a substituent, the same thing as the substituent which was mentioned as a substituent in the above-mentioned substituted alkyl group is mentioned.
Examples of the silyl group include trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl and the like.

  Examples of the imide group include N-succinimide and N-phthalimide.

Two adjacent R ^{1 to} R ⁴ may be bonded to each other to form a ring. Examples of the ring structure in the case where these form a ring include a 5- to 6-membered aliphatic ring and an aromatic ring, and may be a heterocyclic ring containing an element other than a carbon atom. Further, the formed rings may be further bonded to form a binuclear ring, for example, a condensed ring. Further, these ring structures may further have the substituents exemplified as the monovalent substituents in R ^{1 to} R ⁴ and Z ^{1 to} Z ⁴ . N, O, and S can be mentioned as an example of a hetero atom in case the formed ring structure is a heterocyclic ring.

  The compound represented by the general formula (I) (specific sensitizing dye) is more preferably a compound represented by the following general formula (IA). Hereinafter, Formula (IA) will be described in detail.

In the general formula (IA), X represents O (oxygen atom), S (sulfur atom), or NR ⁵ , and R ⁵ represents an alkyl group or an acyl group.
In the present invention, R ⁵ is preferably a hydrogen atom, a methyl group or an acetyl group. X is preferably an oxygen atom or a sulfur atom, more preferably a sulfur atom, from the viewpoint of sensitivity.

R ^{6 to} R ⁹ and Z ^{5 to} Z ⁸ each independently represent a hydrogen atom or a monovalent substituent. The monovalent substituents represented by R ^{6 to} R ⁹ and Z ^{5 to} Z ⁸ are the same as the monovalent substituents exemplified for R ^{1 to} R ⁴ and Z ^{1 to} Z ⁴ in the general formula (I). It is.
Regarding the general formula (IA) in the present invention, examples of preferable R ^{6 to} R ⁹ and Z ^{5 to} Z ⁸ are shown below.

R ^{6 to} R ⁹ include hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryl Oxycarbonyloxy group, amino group (alkylamino group, arylamino group), acylamino group (amide group), aminocarbonylamino group (ureido group), alkylthio group, arylthio group, sulfamoyl group, acyl group, aryloxycarbonyl group, Alkoxycarbonyl group and carbamoyl group are preferable, hydrogen atom, halogen atom, alkyl group, alkoxy group, amino group (alkylamino group, arylamino group) and acyl group are more preferable, hydrogen atom, halogen atom, alkyl group and alkoxy group. Particularly preferred. Each may further have a substituent.

Two of R ^{6 to} R ⁹ may be bonded to each other to form a ring. Examples of the ring structure in the case where these form a ring include a 5- to 6-membered aliphatic ring and an aromatic ring, and may be a heterocyclic ring containing an element other than a carbon atom, or may be formed. The rings may be further bonded to each other to form a binuclear ring, for example, a condensed ring. Further, these ring structures may further have the substituents exemplified as the monovalent substituents in R ^{1 to} R ⁴ and Z ^{1 to} Z ⁴ . N, O, and S can be mentioned as an example of a hetero atom in case the formed ring structure is a heterocyclic ring.

Z ^{5 to} Z ⁸ are preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a hydroxyl group, an alkoxy group, an aryloxy group, an acyloxy group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, or a carbamoyl group. A hydrogen atom, an alkyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group and a carbamoyl group are more preferable, and a hydrogen atom, an alkyl group, an alkoxycarbonyl group and a carbamoyl group are particularly preferable. Each may further have the substituent exemplified as the monovalent substituent in R ^{1 to} R ⁴ and Z ^{1 to} Z ⁴ . In the present invention, it is more preferable that at least one of Z ⁶ and Z ⁸ is a monovalent substituent.

In the present invention, from the viewpoint of sensitivity, the compound represented by the general formula (I) is such that X is an oxygen atom or a sulfur atom, and R ^{1 to} R ⁴ are a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an amino group. A group (alkylamino group, arylamino group) or an acyl group, wherein n is 1, and Z ^{1 to} Z ⁴ are a hydrogen atom, an alkyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, or It is preferably a carbamoyl group, X is a sulfur atom, R ^{1 to} R ⁴ are a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group, n is 1, and Z ^{1 to} Z ⁴ Is more preferably a hydrogen atom, an alkyl group, an alkoxycarbonyl group, or a carbamoyl group.

  In addition, the compound (specific sensitizing dye) represented by the general formula (I) according to the present invention is, for example, Japanese Patent Application Laid-Open No. 2004-189695, “Tetrahedron” Vol. 49, p939 (1993), “Journal of”. "Organic Chemistry" p893 (1945), "Journal of Organic Chemistry" p4939 (1965), and EP1772774A2, and the like.

  Hereinafter, exemplary compounds (I-1) to (I-108) are shown as specific examples of the specific sensitizing dye, but the present invention is not limited thereto. In addition, the structural formula of the following specific sensitizing dye is described by a simplified structural formula, and in particular, a solid line or the like where no element or substituent is clearly shown represents a hydrocarbon group.

  Among the exemplified compounds (I-1) to (I-108), (I-1) to (I-23), (I-55) to (I-65), and (I-97) in terms of sensitivity. ) To (I-101) are more preferable, (I-14) to (I-19), (I-63) and (I-97) are more preferable, (I-14), (I-17), And (I-19) are particularly preferred.

In the present invention, the content of the compound represented by the general formula (I) (specific sensitizing dye) in the photocurable composition is 0.05% by mass to the total solid content from the viewpoint of sensitivity. It is preferably 30% by mass, and more preferably 0.1% by mass to 20% by mass.
In relation to the polymerization initiator described later, the mass ratio of the polymerization initiator to the specific sensitizing dye is preferably 200: 1 to 1: 200, more preferably 50: 1 to 1:50, and 20 : More preferably, it is contained in an amount of 1-1: 5.
The specific sensitizing dye in the invention has an advantage that there is no concern of affecting the hue of the ink composition because it hardly absorbs in the visible light region.

(Compound represented by formula (II))
The photocurable composition of the present invention contains at least one compound represented by the general formula (II) (hereinafter also referred to as “specific compound”). The compound represented by general formula (II) in the present invention is a useful compound that can be contained in a photocurable composition containing a polymerization initiator and a polymerizable compound together with the specific sensitizing dye. In the present invention, by using a specific compound and a specific sensitizing dye in combination, the curability is improved and the sensitivity is improved in a photocurable composition, particularly a cationic polymerizable photocurable composition.
Hereinafter, the compound represented by formula (II) will be described.

In general formula (II), Xa represents ^a hydrogen atom or a monovalent substituent. R ^{1a to} R ^5a each independently represents a hydrogen atom or a monovalent substituent. R ^4a and R ^5a may be connected to each other to form a ring.

Examples of the monovalent substituent represented by X ^a, is not particularly limited as long as a group capable of substituting for an oxygen atom, for example, an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an acyl group, Examples thereof include an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a silyl group, and the like, and each may further have a substituent.
The X ^a in the present invention, a hydrogen atom, or a substituted or unsubstituted alkyl group, more preferably a hydrogen atom.

The monovalent substituent represented by R ^{1a to} R ^5a is not particularly limited as long as it is a group that can be substituted on the benzene ring. R ^{1a to} R ^5a are preferably hydrogen atoms, halogen atoms, alkyl groups (including cyclic alkyl groups such as cycloalkyl groups and bicycloalkyl groups), and alkenyl groups (cyclic alkenyl groups such as cycloalkenyl groups and bicycloalkenyl groups). Alkynyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, carboxy group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy Group, aryloxycarbonyloxy, amino group (including anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino , Mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and Examples include a heterocyclic azo group, an imide group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, and a silyl group.

R ^4a and R ^5a may be connected to each other to form a ring. When R ^4a and R ^5a are connected to each other to form a ring, R ^4a and R ^5a form a benzene ring together with the carbon atoms to which they are bonded, and the compound represented by the general formula (II) is a naphthol derivative. It is particularly preferred. Moreover, the said naphthol derivative may have the same substituent as the substituent ^{quoted in} the example of said R < ^1a > -R < ^5a >.

In the present invention, R ^1a is preferably a hydrogen atom, a substituted or unsubstituted acylamino group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, or a substituted or unsubstituted carbamoyl group. A substituted acylamino group and a substituted or unsubstituted carbamoyl group are more preferable.
R ^2a is preferably a hydrogen atom. R ^3a is more preferably a halogen atom, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, or a substituted or unsubstituted heterocyclic oxy group. R ^4a and R ^5a are preferably a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group, and it is also preferable that R ^4a and R ^5a are connected to each other to form a benzene ring.
Furthermore, the general formula (II) is preferably the following general formula (III).

In general formula (III), ^Xb is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted An aryloxycarbonyl group, a substituted or unsubstituted carbamoyl group. R ^1b is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, an amino group, a substituted or unsubstituted acyl group, a substituted or unsubstituted An acylamino group, a substituted or unsubstituted alkyl and arylsulfonylamino group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, and a substituted or unsubstituted carbamoyl group are represented. R ^2b is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkylthio A group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted acyloxy group, a substituted or unsubstituted alkoxycarbonyl group, or a substituted or unsubstituted aryloxycarbonyl group; R ^3b and R ^4b represent a hydrogen atom or a monovalent substituent. R ^3b and R ^4b may be connected to each other to form a condensed ring.

In general formula (III), ^Xb is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted An aryloxycarbonyl group, a substituted or unsubstituted carbamoyl group. ^Xb is more preferably a hydrogen atom or a substituted or unsubstituted alkyl group, and further preferably a hydrogen atom.

In general formula (III), R ^1b is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, an amino group, a substituted or unsubstituted acyl Represents a group, a substituted or unsubstituted acylamino group, a substituted or unsubstituted alkyl and arylsulfonylamino group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, a substituted or unsubstituted carbamoyl group . R ^1b is preferably a hydrogen atom, a substituted or unsubstituted acylamino group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, or a substituted or unsubstituted carbamoyl group, and a substituted or unsubstituted acylamino group Further, a substituted or unsubstituted carbamoyl group is more preferable.

R ^2b is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkylthio A group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted acyloxy group, a substituted or unsubstituted alkoxycarbonyl group, or a substituted or unsubstituted aryloxycarbonyl group; R ^2b is more preferably a halogen atom, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, or a substituted or unsubstituted heterocyclic oxy group.

In the general formula (III), the monovalent substituents represented by R ^3b and R ^4b are not particularly limited as long as they can be substituted on the benzene ring, and are listed as R ^{1a to} R ^5a in the general formula (II). A substituent is mentioned. R ^3b and R ^4b are preferably each independently a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group.

R ^3b and R ^4b may be connected to each other to form a ring. When R ^3b and R ^4b are connected to each other to form a ring, the formed ring is preferably a benzene ring, and the compound represented by the general formula (III) is preferably a naphthol derivative.

Regarding the preferred combination of substituents of the compound represented by the general formula (III), a compound in which at least one of various substituents is the above preferred group is preferred, and more various substituents are the above preferred groups. Compounds are more preferred, and compounds in which all substituents are the preferred groups are most preferred.
Specifically, ^Xb is a hydrogen atom, or a substituted or unsubstituted alkyl group, and ^R1b is a hydrogen atom, a substituted or unsubstituted acylamino group, a substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted. An aryloxycarbonyl group or a substituted or unsubstituted carbamoyl group, wherein R ^2b is a halogen atom, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, or a substituted or unsubstituted heterocyclic oxy R ^3b and R ^4b are each independently a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group, or R ^3b and R ^4b are preferably bonded to each other to form a benzene ring. . More preferably, ^Xb is a hydrogen atom, ^R1b is a substituted or unsubstituted acylamino group, or a substituted or unsubstituted carbamoyl group, and ^R2b is a halogen atom, a substituted or unsubstituted alkoxy group, or This is a substituted or unsubstituted aryloxy group in which R ^3b and R ^4b are bonded to each other to form a benzene ring.

  Furthermore, the compound represented by the general formula (III) is preferably a compound represented by the following general formula (IV).

In general formula (IV), ^Xc is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted An aryloxycarbonyl group, a substituted or unsubstituted carbamoyl group. R ^1c is a hydrogen atom, halogen atom, substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, amino group, substituted or unsubstituted acyl group, substituted or unsubstituted An acylamino group, a substituted or unsubstituted alkyl and arylsulfonylamino group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, and a substituted or unsubstituted carbamoyl group are represented. R ^2c is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkylthio A group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted acyloxy group, a substituted or unsubstituted alkoxycarbonyl group, or a substituted or unsubstituted aryloxycarbonyl group; R ^{3c to} R ^6c represent a hydrogen atom or a monovalent substituent.

In the general formula (IV), ^Xc is the same substituent as ^Xb in the general formula (III), and its preferred range is also the same.

In general formula (IV), the substituent represented by R ^1c is the same as R ^1b in general formula (III). R ^1c is preferably a hydrogen atom, a substituted or unsubstituted acylamino group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, a substituted or unsubstituted carbamoyl group, and a substituted or unsubstituted acylamino group Further, a substituted or unsubstituted carbamoyl group is more preferable, and a substituted or unsubstituted carbamoyl group is particularly preferable.

In general formula (IV), the substituent represented by R ^2c is the same as R ^2b in general formula (III). R ^2c is preferably a halogen atom, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy Groups are more preferred.

In general formula (IV), the substituents represented by R ^{3c to} R ^6c are each independently the same substituents as R ^3b and R ^4b in general formula (III), and preferred ranges thereof are also the same. is there.

As for the preferred combination of substituents of the compound represented by the general formula (IV), a compound in which at least one of various substituents is the above preferred group is preferred, and more various substituents are the above preferred groups. Compounds are more preferred, and compounds in which all substituents are the preferred groups are most preferred.
Specifically, ^Xc is a hydrogen atom or a substituted or unsubstituted alkyl group, and ^R1c is a hydrogen atom, a substituted or unsubstituted acylamino group, a substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted. An aryloxycarbonyl group or a substituted or unsubstituted carbamoyl group, wherein R ^2c is a halogen atom, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, or a substituted or unsubstituted heterocyclic oxy It is preferable that R ^{3c to} R ^6c are each independently a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group. More preferably, ^Xc is a hydrogen atom, ^R1b is a substituted or unsubstituted acylamino group, or a substituted carbamoyl group, and ^R2c is a halogen atom, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted group In which R ^{3cb to} R ^46c are hydrogen atoms.

As the compound represented by the general formula (II) in the present invention, a commercially available compound may be used, or a compound appropriately synthesized by a conventional method may be used.
Hereinafter, exemplary compounds (A-1) to (A-68) are shown as preferred specific examples of the compound represented by the general formula (II) in the present invention, but the present invention is not limited thereto.

  Among the exemplary compounds (A-1) to (A-68), in terms of sensitivity, (A-2), (A-4), (A-9), (A-16), (A-28) ), (A-37), (A-48), (A-59), (A-62), (A-64) are more preferred, and (A-4), (A-9), (A- 28), (A-37), and (A-48) are more preferable, and (A-4) and (A-48) are particularly preferable.

In the present invention, the content of the compound (specific compound) represented by the general formula (II) in the photocurable composition is from 0.1% by mass to 10% by mass with respect to the total solid content in terms of sensitivity. It is preferably 0.0% by mass, and more preferably 1.0% by mass to 5.0% by mass.
The mass ratio of the specific compound to the specific sensitizing dye is preferably 1:10 to 10: 1 by mass ratio of the specific sensitizing dye to the specific compound, and is preferably 1: 2 to 5: 1. More preferably, the mass ratio is 1: 1 to 3: 1.

(Polymerizable compound)
The photocurable composition of the present invention contains at least one polymerizable compound. Examples of the polymerizable compound include a cationic polymerizable compound and a radical polymerizable compound.

-Cationically polymerizable compound-
As the cationically polymerizable compound that can be used in the present invention, a compound that can be cured by initiating a polymerization reaction with an acid generated from a compound that generates an acid upon irradiation with radiation (a photoacid generator) described later is preferable. For example, various known cationically polymerizable monomers known as photocationically polymerizable compounds can be used. Examples of the cationic polymerizable compound include JP-A-6-9714, JP-A-2001-31892, JP-A-2001-40068, JP-A-2001-55507, JP-A-2001-310938, JP-A-2001-310937, and JP-A-2001-2001. Examples thereof include epoxy compounds, vinyl ether compounds, oxetane compounds and the like described in each publication such as No. 220526.

Examples of the epoxy compound include aromatic epoxides and alicyclic epoxides. The epoxy compound may be monofunctional or polyfunctional.
Examples of the polyfunctional aromatic epoxide include di- or polyglycidyl ethers 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 Examples thereof include di- or polyglycidyl ethers of the alkylene oxide adducts, hydrogenated bisphenol A or di- or polyglycidyl ethers of the alkylene oxide adducts, and novolak-type epoxy resins. Here, examples of the alkylene oxide include ethylene oxide and propylene oxide.

As the alicyclic epoxide, cyclohexene oxide 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. Or a cyclopentene oxide containing compound is mentioned preferably.
Examples of polyfunctional aliphatic epoxides include dihydric polyhydridyl 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 alkylene oxide adduct thereof, polyethylene glycol or adduct of alkylene oxide thereof Diglycidyl ether, polypropylene glycol or diglycidyl of polyalkylene glycol represented by diglycidyl ether of alkylene oxide adducts thereof Ether and the like. Here, examples of the alkylene oxide include ethylene oxide and propylene oxide.

Below, the monofunctional and polyfunctional epoxy compound which can be used for this invention is illustrated.
Examples of monofunctional epoxy compounds include, for example, phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide, 1,3-butadiene. Monooxide, 1,2-epoxydodecane, epichlorohydrin, 1,2-epoxydecane, styrene oxide, cyclohexene oxide, 3-methacryloyloxymethylcyclohexene oxide, 3-acryloyloxymethylcyclohexene oxide, 3-vinylcyclohexene oxide, etc. Is mentioned.

  Examples of polyfunctional epoxy compounds include, for example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, and brominated bisphenol. S diglycidyl ether, epoxy novolac resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxy 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxy Hexylmethyl) adipate, vinylcyclohexene oxide, 4-vinylepoxycyclohexane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ', 4'-epoxy- 6'-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di (3,4-epoxycyclohexylmethyl) ether, ethylenebis (3,4-epoxycyclohexanecarboxylate) ), Dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl Ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ethers, 1,1,3-tetradecadiene dioxide, limonene dioxide, 1,2,7,8 -Diepoxyoctane, 1,2,5,6-diepoxycyclooctane and the like.

Among these epoxy compounds, aromatic epoxides and alicyclic epoxides are preferable from the viewpoint of excellent curing speed, and alicyclic epoxides are particularly preferable.
Moreover, a monofunctional epoxy compound is preferable from the viewpoint of curability, and a monofunctional alicyclic epoxy compound is more preferable.

The vinyl ether compound may be a monofunctional vinyl ether compound or a polyfunctional vinyl ether compound.
Examples of monofunctional vinyl ethers and polyfunctional vinyl ethers are given below.

  Examples of monofunctional vinyl ethers include, for example, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether, isopropenyl ether-O-propylene carbonate, n-butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, cyclohexyl methyl vinyl ether, 4-methylcyclohexyl methyl vinyl ether, cyclohexane dimethanol monovinyl ether, benzyl vinyl ether, dicyclopentenyl vinyl ether, 2-dicyclopenteno Xylethyl vinyl ether, methoxyethyl vinyl ether Ter, ethoxyethyl vinyl ether, butoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, ethoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether, tetrahydrofurfuryl vinyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4- Examples thereof include hydroxymethylcyclohexyl methyl vinyl ether, diethylene glycol monovinyl ether, polyethylene glycol vinyl ether, chloroethyl vinyl ether, chlorobutyl vinyl ether, chloroethoxyethyl vinyl ether, phenylethyl vinyl ether, phenoxy polyethylene glycol vinyl ether and the like.

Examples of the polyfunctional vinyl ether include, for example, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol. Divinyl ethers such as divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether; trimethylol ethane trivinyl ether, trimethylol propane trivinyl ether, ditrimethylol propane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetra Nyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether, propylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether, propylene oxide-added ditrimethylolpropane tetravinyl ether, Polyfunctional vinyl ethers such as ethylene oxide-added pentaerythritol tetravinyl ether, propylene oxide-added pentaerythritol tetravinyl ether, ethylene oxide-added dipentaerythritol hexavinyl ether, propylene oxide-added dipentaerythritol hexavinyl ether, etc. It is below.
As the vinyl ether compound, a di- or trivinyl ether compound is preferable from the viewpoints of curability, adhesion to a recording medium, surface hardness of the formed image, and the like, and a divinyl ether compound is particularly preferable.

As the oxetane compound, a known oxetane compound (compound having an oxetane ring) can be arbitrarily selected as described in JP-A Nos. 2001-220526, 2001-310937, and 2003-341217. Can be used.
As the compound having an oxetane ring that can be used in the photocurable composition of the present invention, a compound having 1 to 4 oxetane rings in its structure is preferable. By using such a compound, it becomes easy to maintain the viscosity of the composition in a favorable range of handling properties.

  Examples of the compound having 1 to 2 oxetane rings in the molecule used in the ink composition of the present invention include oxetane compounds represented by the following formulas (1) to (3).

R ^a1 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, an allyl group, an aryl group, a furyl group, or a thienyl group. When two R ^a1 are present in the molecule, they may be the same or different.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. Preferred examples of the fluoroalkyl group include those in which at least one hydrogen atom of the alkyl group is substituted with a fluorine atom.

R ^a2 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a group having an aromatic ring, an alkylcarbonyl group having 2 to 6 carbon atoms, or 2 to 6 carbon atoms. Represents an alkoxycarbonyl group, and an N-alkylcarbamoyl group having 2 to 6 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the alkenyl group include a 1-propenyl group, a 2-propenyl group, a 2-methyl-1-propenyl group, and 2-methyl-2. -Propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group and the like. Examples of the group having an aromatic ring include phenyl group, benzyl group, fluorobenzyl group, methoxybenzyl group, phenoxyethyl group and the like. Can be mentioned. As the alkylcarbonyl group, an ethylcarbonyl group, a propylcarbonyl group, a butylcarbonyl group, etc., as an alkoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, etc., as an N-alkylcarbamoyl group, Examples thereof include an ethylcarbamoyl group, a propylcarbamoyl group, a butylcarbamoyl group, and a pentylcarbamoyl group. R ^a2 may further have a substituent, and examples of the substituent include an alkyl group of 1 to 6 and a fluorine atom.

R ^a3 is a linear or branched alkylene group having 1 to 15 carbon atoms (for example, an ethylene group, a propylene group, a butylene group, etc.), a linear or branched divalent unsaturated hydrocarbon group (for example, Propenylene group, methylpropenylene group, butenylene group, etc.), carbonyl group or alkylene group containing carbonyl group, alkylene group containing carboxyl group, alkylene group containing carbamoyl group, poly (alkyleneoxy) group (for example, poly (ethyleneoxy) ) Group, poly (propyleneoxy) group, etc.) or the following groups.

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

  Specific examples of the oxetane compound represented by the formula (1) include 3-ethyl-3-hydroxymethyloxetane (OXT-101: manufactured by Toagosei Co., Ltd.), 3-ethyl-3- (2-ethylhexane). And siloxymethyl) oxetane (OXT-212: manufactured by Toagosei Co., Ltd.) and 3-ethyl-3-phenoxymethyloxetane (OXT-211: manufactured by Toagosei Co., Ltd.). Examples of the oxetane compound represented by the formula (2) include 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene (OXT-121: Toagosei Co., Ltd.). Examples of the oxetane compound represented by the formula (3) include bis (3-ethyl-3-oxetanylmethyl) ether (OXT-221: Toagosei Co., Ltd.).

  Further, examples of the oxetane compound having 3 to 4 oxetane rings include compounds represented by the following formula (4).

In the above formula (4), R ^a1 has the same ^{meaning as} in the above formula (1). Moreover, as R ^a9 which is a polyvalent linking group, for example, a group derived from a branched alkane having 1 to 12 carbon atoms represented by the following formulas A to C, a branched polyalkyleneoxy compound represented by the following D Or a group derived from a branched disiloxane compound represented by E below. J is 3 or 4.

In the above formula A, R ^a10 represents a methyl group, an ethyl group or a propyl group. Moreover, in the said Formula D, p represents the integer of 1-10.

  Moreover, the polysiloxane derivative shown by following formula (5) which has an oxetane ring in a side chain as another aspect of the oxetane compound which can be used suitably for this invention can also be mentioned.

In said formula (5), R ^{<a1 >} is synonymous with the thing in the said Formula (1), and R ^<a8> is a C1-C4 alkyl group or an aryl group. R ^a11 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.

The compounds having such an oxetane ring are described in detail in JP-A No. 2003-341217, paragraph numbers [0021] to [0084], and the compounds described therein can be suitably used in the present invention.
Oxetane compounds described in JP-A-2004-91556 can also be used in the present invention. The compounds are described in detail in paragraph numbers [0022] to [0058] of the publication.
Among the other oxetane compounds used in combination with the present invention, it is preferable to use a compound having one oxetane ring from the viewpoint of the viscosity and adhesiveness of the composition.

When a cationic polymerizable compound is contained as the polymerizable compound in the photocurable composition of the present invention, the content of the cationic polymerizable compound with respect to the total solid content of the photocurable composition is 60% by mass or more. Is preferable, and it is more preferable that it is 70 mass% or more. In addition, as an upper limit of the content rate of a cationically polymerizable compound, it is preferable that it is 95 mass% or less.
Furthermore, it is preferable to contain 50 mass% or more of cation polymerizable monofunctional monomers among the cationic polymerizable compounds, and it is more preferable to contain 60 mass% or more. By containing the cationic polymerizable monofunctional monomer in the above range, an effect of improving the flexibility of the cured film can be obtained.

-Radically polymerizable compounds-
The radically polymerizable compound that can be used in the photocurable composition of the present invention is a compound having a radically polymerizable ethylenically unsaturated bond, and at least one radically polymerizable ethylenically unsaturated bond in the molecule. Any compound may be used as long as it has a chemical form such as a monomer, oligomer, or polymer. Only one kind of radically polymerizable compound may be used, or two or more kinds thereof may be used in combination at an arbitrary ratio in order to improve desired properties. It is preferable to use two or more kinds in combination for controlling performance such as reactivity and physical properties.

  Examples of the polymerizable compound having an ethylenically unsaturated bond capable of radical polymerization include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid and maleic acid, and salts, esters and amides thereof. And the like, radically polymerizable compounds such as anhydrides having an ethylenically unsaturated bond, acrylonitrile, styrene, various unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, and unsaturated urethanes.

  Specifically, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, butoxyethyl acrylate, carbitol acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, bis (4-acryloxypolyethoxyphenyl) propane, neopentyl glycol Diacrylate, 1,6-hexanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, pentaerythritol triacrylate, pentaerythritol Tetraacrylate, dipentaery Acrylic acid derivatives such as lithol tetraacrylate, trimethylolpropane triacrylate, oligoester acrylate, N-methylol acrylamide, diacetone acrylamide, epoxy acrylate, methyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, allyl methacrylate Glycidyl methacrylate, benzyl methacrylate, dimethylaminomethyl methacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylolethane trimethacrylate, trimethylol The Methacryl derivatives such as pantrimethacrylate, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane, and other derivatives of allyl compounds such as allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, etc. Specifically, Shinzo Yamashita, “Cross-linking agent handbook” (1981 Taiseisha); Kato Kiyomi ed., “UV / EB curing handbook (raw material)” (1985, Polymer publication society); Edition, “Application and Market of UV / EB Curing Technology”, p. 79, (1989, CMC); Eiichiro Takiyama, “Polyester Resin Handbook”, (1988, Nikkan Kogyo Shimbun), etc. Alternatively, radically polymerizable or crosslinkable monomers, oligomers, and polymers known in the industry can be used. .

  Examples of the radical polymerizable compound include those disclosed in JP-A-7-159983, JP-B-7-31399, JP-A-8-224982, JP-A-10-863, JP-A-9-134011, and the like. Photocurable polymerizable compound materials used for the described photopolymerizable compositions are known and can also be applied to the photocurable compositions of the present invention.

Furthermore, it is also preferable to use a vinyl ether compound as the radical polymerizable compound. As the vinyl ether compound, the vinyl ether compounds mentioned in the description of the photopolymerizable compound can be preferably used.
A vinyl ether compound may be used individually by 1 type, and may be used in combination of 2 or more type as appropriate.

  When a radically polymerizable compound is contained as a polymerizable compound in the photocurable composition of the present invention, the content of the radically polymerizable compound in the total solid content of the photocurable composition is 60% by mass or more. Is preferable, and it is more preferable that it is 70 mass% or more. In addition, as an upper limit of the content rate of a radically polymerizable compound, it is preferable that it is 95 mass% or less.

<Polymerization initiator>
The photocurable composition of the present invention preferably contains at least one polymerization initiator.
The polymerization initiator may be a compound that absorbs external energy and generates a polymerization initiating species, and may be appropriately selected according to the type of the polymerizable compound contained in the photocurable composition of the present invention. it can.
As a polymerization initiator that can be used in the photocurable composition of the present invention, a photopolymerization initiator for photocationic polymerization, a photopolymerization initiator for photoradical polymerization, a photodecolorant for dyes, a photochromic agent, or , Light (400 nm to 200 nm ultraviolet light, far ultraviolet light, particularly preferably g-line, h-line, i-line, KrF excimer laser beam), ArF excimer laser beam, electron beam, X-ray, Alternatively, a compound that generates an acid upon irradiation with a molecular beam ion beam or the like can be appropriately selected and used.

-Photoacid generator-
In the present invention, for example, when a cationic polymerizable compound is used as the polymerizable compound, it is preferable to use a compound that generates an acid upon irradiation with actinic rays or radiation, that is, a photoacid generator, as the polymerization initiator. By using such a polymerization initiator, a polymerization reaction of the cationic polymerizable compound is caused by an acid generated by irradiation with actinic rays or radiation, and the photocurable composition can be cured.

  Examples of such a polymerization initiator include an onium salt compound such as diazonium salt, phosphonium salt, sulfonium salt, iodonium salt, imide sulfonate, oxime sulfonate, diazodisulfone, which decomposes upon irradiation with actinic rays or radiation to generate an acid. Examples thereof include sulfonate compounds such as disulfone and o-nitrobenzyl sulfonate.

  Examples of other compounds that generate acid upon irradiation with actinic rays or radiation include S.I. I. Schlesinger, Photogr. Sci. Eng. 18, 387 (1974), T .; S. Diazonium salts described in Bal etal, Polymer, 21, 423 (1980), U.S. Pat. Nos. 4,069,055, 4,069,056, Re27,992, and JP-A-3-140140. Ammonium salts described in the above, and the like. C. Necker et al., Macromolecules, 17, 2468 (1984), C.I. S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), U.S. Pat. Nos. 4,069,055 and 4,069,056, and the like. V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), Chem. & Eng. News, Nov. 28, p31 (1988), European Patent Nos. 104,143, 339,049, 410,201, JP-A-2-150848, JP-A-2-296514, etc. Iodonium salt,

  J. et al. V. Crivello et al, Polymer J. et al. 17, 73 (1985), J. Am. V. Crivello et al. J. et al. Org. Chem. 43, 3055 (1978); R. Watt et al. Polymer Sci. , Polymer Chem. Ed. , 22, 1789 (1984), J. Am. V. Crivello et al., Polymer Bull. 14, 279 (1985), J. Am. V. Crivello et al, Macromolecules, 14 (5), 1141 (1981), J. MoI. V. Crivello et al. PolymerSci. , Polymer Chem. Ed. 17, 2877 (1979), European Patent Nos. 370,693, 161,811, 410,201, 339,049, 233,567, 297,443, and 297,442. U.S. Pat.Nos. 3,902,114, 4,933,377, 4,760,013, 4,734,444, 2,833,827, German Patent 2, Nos. 904, 626, 3,604, 580, 3,604, 581, JP-A-7-28237, and 8-27102, etc.

  J. et al. V. Crivello et al., Macromolecules, 10 (6), 1307 (1977), J. MoI. V. Crivello et al. Polymer Sci. , Polymer Chem. Ed. , 17, 1047 (1979), etc., selenonium salts, C.I. S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988) and other onium salts such as arsonium salts, US Pat. No. 3,905,815, Japanese Examined Patent Publication No. 46-4605, Japanese Unexamined Patent Publication No. 48-36281, Japanese Unexamined Patent Publication No. 55-55. -32070, JP-A-60-239736, JP-A-61-169835, JP-A-61-169837, JP-A-62-58241, JP-A-62-212401, JP-A-63-70243 Organic halogen compounds described in JP-A 63-298339 and the like; Meier et al, J.A. Rad. Curing, 13 (4), 26 (1986), T.A. P. Gill et al, Inorg. Chem. , 19, 3007 (1980), D.M. Astruc, Acc. Chem. Res. , 19 (12), 377 (1986), JP-A-2-161445, etc.

  S. Hayase et al. Polymer Sci. 25, 753 (1987), E.I. Reichmanis et al. Polymer Sci. , Polymer Chem. Ed. , 23, 1 (1985), Q.M. Q. Zhu etal, J. et al. Photochem. 36, 85, 39, 317 (1987), B.R. Amit etal, Tetrahedron Lett. , (24) 2205 (1973), D.M. H. R. Barton et al. Chem. Soc. , 3571 (1965), p. M.M. Collins et al. Chem. Soc. Perkin I, 1695 (1975), M .; Rudinstein et al., Tetrahedron Lett. , (17), 1445 (1975), J. MoI. W. Walker et al. Am. Chem. Soc. 110, 7170 (1988), S.A. C. Busman et al. Imaging Technol. 11 (4), 191 (1985), H. et al. M.M. Houlihan et al, Macormolecules, 21, 2001 (1988), p. M.M. Collins et al. Chem. Soc. , Chem. Commun. 532 (1972), S.A. Hayase et al., Macromolecules, 18, 1799 (1985), E.I. Reichmanis et al. Electrochem. Soc. , Solid State Sci. Technol. , 130 (6), F.M. M.M. Houlihan et al, Macromolecules, 21, 2001 (1988), European Patent Nos. 0290,750, 046,083, 156,535, 271,851, 0,388,343, US Patent No. 3 , 901,710, 4,181,531, JP-A-60-198538, JP-A-53-133022 and the like, and a polymerization initiator having an O-nitrobenzyl type protecting group,

  M.M. TUNOOKA et al, Polymer Preprints Japan, 35 (8), G.M. Berner et al. Rad. Curing, 13 (4), W.M. J. et al. Mijs et al, Coating Technol. , 55 (697), 45 (1983), Akzo, H .; Adachi et al, Polymer Preprints, Japan, 37 (3), European Patent No. 0199,672, No. 84515, No. 044,115, No. 618,564, No. 0101,122, US Pat. No. 4,371 , 605, 4,431,774, Japanese Patent Application Laid-Open No. 64-18143, Japanese Patent Application Laid-Open No. 2-245756, Japanese Patent Application Laid-Open No. 3-140109, etc. Compounds that decompose to generate sulfonic acid, disulfone compounds described in JP-A Nos. 61-166544 and 2-71270, JP-A-3-103854, JP-A-3-103856, and JP-A-210960 And diazoketosulfone and diazodisulfone compounds described in the above publications.

  Further, a group in which an acid is generated by the light, or a compound in which a compound is introduced into the main chain or side chain of the polymer, for example, E. Woodhouse et al. Am. Chem. Soc. 104, 5586 (1982), S .; P. Pappas et al. Imaging Sci. , 30 (5), 218 (1986), S .; Kondo et al, Makromol. Chem. , Rapid Commun. , 9, 625 (1988), Y. et al. Yamada et al, Makromol. Chem. 152, 153, 163 (1972), J. Am. V. Crivello et al. PolymerSci. , Polymer Chem. Ed. 17, 3845 (1979), U.S. Pat. No. 3,849,137, German Patent No. 3,914,407, JP-A 63-26653, JP-A 55-164824, JP-A 62- 69263, JP-A 63-146038, JP-A 63-163452, JP-A 62-153853, JP-A 63-146029, and the like can be used. For example, diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, onium salts such as arsonium salts, organic halogen compounds, organic metal / organic halides, polymerization initiators having o-nitrobenzyl type protecting groups And compounds capable of generating a sulfonic acid by photolysis, such as iminosulfonate, disulfone compounds, diazoketosulfones, and diazodisulfone compounds.

  Furthermore, V. N. R. Pillai, Synthesis, (1), 1 (1980), A.M. Abad et al., Tetrahedron Lett. , (47) 4555 (1971), D.M. H. R. Barton et al. Chem. Soc. , (C), 329 (1970), U.S. Pat. No. 3,779,778, European Patent No. 126,712, etc., compounds that generate an acid by light can also be used.

  Preferred examples of the polymerization initiator that can be used in the present invention include compounds represented by the following formulas (b1), (b2), and (b3).

In the above formulas (b1), (b2), and (b3), R ²⁰¹ , R ²⁰² and R ²⁰³ each independently represents an organic group. R ²⁰⁴ , R ²⁰⁵ , R ²⁰⁶ , and R ²⁰⁷ each independently represents an aryl group, an alkyl group, or a cycloalkyl group.
X ⁻ represents a non-nucleophilic anion, preferably a sulfonate anion, a carboxylate anion, a bis (alkylsulfonyl) amide anion, a tris (alkylsulfonyl) methide anion, BF ⁴⁻ , PF ⁶⁻ , SbF ⁶⁻ or the following The organic anion which has a carbon atom is preferable.

  Preferable organic anions include organic anions represented by the following formula.

In the above formula, R ^c1 represents an organic group. ^Examples of R ^c1 include an organic group having 1 to 30 carbon atoms. Preferably, an alkyl group, a cycloalkyl group, an aryl group, or two or more groups selected from these are each a single bond, —O—, —CO. _{2 -, - S -, -} SO 3 -, - SO 2 N (R d1) - can be a group formed by linking a linking group such as. R ^d1 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

R ^c3 , R ^c4 and R ^c5 each independently represents an organic group. Preferred examples of the organic group for R ^c3 , R ^c4 , and R ^c5 include the same organic groups as those for R ^c1 , and most preferred is a perfluoroalkyl group having 1 to 4 carbon atoms.
R ^c3 and R ^c4 may be bonded to form a ring. ^{Examples of the} group formed by combining R ^c3 and R ^c4 include an alkylene group and an arylene group. Preferably it is a C2-C4 perfluoroalkylene group.

The organic group of R ^c1 and R ^{c3 to} R ^c5 is most preferably an alkyl group substituted at the 1-position with a fluorine atom or a fluoroalkyl group, or a phenyl group substituted with a fluorine atom or a fluoroalkyl group. By having a fluorine atom or a fluoroalkyl group, the acidity of the acid generated by light irradiation is increased and the sensitivity is improved.

In the formula ^(b1), the carbon number of the organic groups represented by R ^{201, R 202} and ^{R 203} are generally from 1 to 30, preferably 1 to 20. Two of R ^{201 to} R ²⁰³ may be bonded to form a ring structure, and the formed ring structure may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. . If two of R ²⁰¹ to R ²⁰³ is to form a ring structure, preferably a 5- to 6-membered aliphatic ring.

Specific examples of the organic group represented by R ²⁰¹ , R ²⁰² and R ²⁰³ include corresponding groups in the compounds (b1-1), (b1-2) and (b1-3) described later.

The compound represented by the formula (b1) may be a compound having a plurality of structures represented by the formula (b1) in the molecule. For example, at least one of ^R 201 ^{to R 203} of a compound represented by formula (b1), at least one direct ^R 201 ^{to R 203} of another compound represented by formula (b1), or a linking group It may be a compound having a structure bonded via There is no particular limitation on the linking group, a single _{bond, -O -, - CO 2 -} , - S -, - SO 3 -, - SO 2 N (R d1) - and the like. R ^d1 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

  Further preferred compounds represented by formula (b1) include compounds (b1-1), (b1-2), and (b1-3) described below.

Compound (b1-1) is at least one ^R 201 ^{to R 203} in the compound represented by the formula (b1) is an arylsulfonium compound is an aryl group, namely, compounds containing an arylsulfonium as a cation.

In the arylsulfonium compound, all of R ^{201 to} R ²⁰³ may be an aryl group, or at least one of R ^{201 to} R ²⁰³ may be an aryl group, and the rest may be an alkyl group or a cycloalkyl group.

  Examples of the arylsulfonium compound include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, aryldicycloalkylsulfonium compounds, and the like.

  The aryl group of the arylsulfonium compound is preferably an aryl group such as a phenyl group or a naphthyl group, or a heteroaryl group such as an indole residue or a pyrrole residue, more preferably a phenyl group or an indole residue. When the arylsulfonium compound has two or more aryl groups, the two or more aryl groups may be the same or different.

As the alkyl group that the arylsulfonium compound has as necessary, a linear or branched alkyl group having 1 to 15 carbon atoms is preferable, for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, A sec-butyl group, a t-butyl group, etc. can be mentioned.
Moreover, as a cycloalkyl group which an aryl sulfonium compound has as needed, a C3-C15 cycloalkyl group is preferable, For example, a cyclopropyl group, a cyclobutyl group, a cyclohexyl group etc. can be mentioned.

In the compound (b1-1), the aryl group, alkyl group, and cycloalkyl group represented by R ^{201 to} R ²⁰³ may further have a substituent. As all good substituents, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), an aryl group (for example, 6 to 14 carbon atoms), an alkoxy group (for example, 1 to 15 carbon atoms) ), Halogen atoms, hydroxyl groups, and phenylthio groups.
Preferred substituents are linear or branched alkyl groups having 1 to 12 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms, and linear, branched or cyclic alkoxy groups having 1 to 12 carbon atoms, and most preferred. Is an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms.
The substituent may be substituted with any one of the three R ^{201 to} R ²⁰³ , or may be substituted with all three. When R ^{201 to} R ²⁰³ are an aryl group, the substituent is preferably substituted at the p-position of the aryl group.

Next, the compound (b1-2) will be described.
The compound (b1-2) is a compound when R ^{201 to} R ²⁰³ in the formula (b1) each independently represents an organic group that does not contain an aromatic ring. Here, the aromatic ring includes a heteroaromatic ring containing a hetero atom.
The organic group not containing an aromatic ring as R ^{201 to} R ²⁰³ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
R ^{201 to} R ²⁰³ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear, branched, or cyclic 2-oxoalkyl group, alkoxycarbonylmethyl. Group, particularly preferably a linear or branched 2-oxoalkyl group.

The alkyl group represented by ^R 201 ^{to R 203} in the compound (b1-2) is a linear, it may be either branched, preferably a straight-chain or branched alkyl group having 1 to 10 carbon atoms ( Examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group, and a linear or branched 2-oxoalkyl group or an alkoxycarbonylmethyl group is more preferable.

Cycloalkyl groups represented by ^R 201 ^{to R 203} in the compound (b1-2) can preferably be mentioned a cycloalkyl group having 3 to 10 carbon atoms (a cyclopentyl group, a cyclohexyl group, a norbornyl group), cyclic The 2-oxoalkyl group is more preferable.

Compound (b1-2) in ^R 201 ^{to R 203} is linear, the case of 2-oxoalkyl group branched, or cyclic, preferably have a carbonyl group at the 2-position of the above-described alkyl or cycloalkyl group The group can be mentioned.
Further, the alkoxy group in the ^R 201 ^{to R 203} in the compound (b1-2) is an alkoxycarbonylmethyl group is preferably an alkoxy group (methoxy group of 1 to 5 carbon atoms, an ethoxy group, a propoxy group, a butoxy group, Pentoxy group).
R ^{201 to} R ²⁰³ in the compound (b1-2) may be further substituted with a halogen atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

  The compound (b1-3) is a compound represented by the following formula (b1-3) and is a compound having a phenacylsulfonium salt structure.

In the above formula (b1-3), R ^{1d to} R ^5d each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, or a halogen atom.
R ^6d and R ^7d each independently represents a hydrogen atom, an alkyl group or a cycloalkyl group.
R ^x and R ^y each independently represents an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group.
At least two selected from R ^{1d to} R ^5d , R ^6d and R ^7d , and R ^x and R ^y may be bonded to each other to form a ring structure.
Zc ^- represents a non-nucleophilic anion, in X in Formula (b1) ^- may be the same as the non-nucleophilic anion.

In the above formula (b1-3), the alkyl group represented by R ^{1d to} R ^7d may be linear or branched. For example, the alkyl group has 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms. And linear and branched alkyl groups (for example, methyl group, ethyl group, linear or branched propyl group, linear or branched butyl group, linear or branched pentyl group).

Preferred examples of the cycloalkyl group represented by R ^{1d to} R ^7d in the above formula (b1-3) include cycloalkyl groups having 3 to 8 carbon atoms (for example, a cyclopentyl group and a cyclohexyl group).

In the above formula (b1-3), the alkyl part of the alkoxy group represented by R ^{1d to} R ^5d may be linear, branched or cyclic, for example, an alkoxy group having 1 to 10 carbon atoms, preferably Are linear and branched alkoxy groups having 1 to 5 carbon atoms (for example, methoxy group, ethoxy group, linear or branched propoxy group, linear or branched butoxy group, linear or branched pentoxy group), and 3 to 8 carbon atoms. And a cyclic alkoxy group (for example, cyclopentyloxy group, cyclohexyloxy group).

In the above formula (b1-3), when at least two selected from R ^{1d to} R ^5d , R ^6d and R ^7d , and R ^x and R ^y are bonded to form a ring structure, a 5- to 6-membered ring is formed. It is preferably formed, and this ring structure may contain an oxygen atom, a sulfur atom, an ester bond, or an amide bond.

Preferably any one of R ^{1d to} R ^5d is a linear or branched alkyl group, a cycloalkyl group, or a linear, branched or cyclic alkoxy group, and more preferably the sum of the carbon number of R ^1d to R ^5d is 2-15. This is preferable because solvent solubility is further improved and generation of particles is suppressed during storage.

Examples of the alkyl group and cycloalkyl group represented by R ^x and R ^y include the same alkyl groups and cycloalkyl groups represented by R ^{1d to} R ^7d above.
R ^x and R ^y are preferably a 2-oxoalkyl group or an alkoxycarbonylmethyl group.
Examples of the 2-oxoalkyl group include a group having a carbonyl group at the 2-position of the alkyl group or cycloalkyl group represented by R ^{1d to} R ^5d .
About the alkoxy group in an alkoxycarbonylmethyl group, the thing similar to the alkoxy group represented by R ^{< 1d} > -R <^5d> can be mentioned.

R ^x and R ^y are preferably an alkyl group or cycloalkyl group having 4 or more carbon atoms, more preferably 6 or more, and still more preferably 8 or more alkyl groups or cycloalkyl groups.

In the above formulas (b2) and (b3), R ^{204 to} R ²⁰⁷ each independently represents an aryl group, an alkyl group, or a cycloalkyl group. X ⁻ represents a non-nucleophilic anion, and examples thereof include the same non-nucleophilic anion as X ^{− in} formula (b1).

The aryl group represented by R ^{204 to} R ²⁰⁷ is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.
The alkyl group represented by R ²⁰⁴ to R ²⁰⁷ may be linear, it may be either branched, preferably a straight-chain or branched alkyl group (e.g., methyl group having 1 to 10 carbon atoms, an ethyl group Propyl group, butyl group, pentyl group). The cycloalkyl group as R204 to R207 preferably includes a cycloalkyl group having 3 to 10 carbon atoms (cyclopentyl group, cyclohexyl group, norbornyl group).
The aryl group, alkyl group or cycloalkyl group represented by R ^{204 to} R ²⁰⁷ may further have a substituent. Examples of the substituent include an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), an aryl group (for example, 6 to 15 carbon atoms), an alkoxy group (for example, 1 to 1 carbon atoms). 15), halogen atoms, hydroxyl groups, phenylthio groups and the like.

  Examples of the compound capable of generating an acid upon irradiation with actinic rays or radiation that can be used in the present invention include compounds represented by the following formulas (b4), (b5), and (b6).

In the above formulas (b4) to (b6), Ar ³ and Ar ⁴ each independently represents an aryl group.
R ²⁰⁸ , R ²⁰⁹ and R ²¹⁰ each independently represent an alkyl group having 1 to 16 carbon atoms, a cycloalkyl group or an aryl group. A represents an alkylene group, an alkenylene group or an arylene group.

In the present invention, the compounds represented by the above formulas (b1) to (b3) are preferable among the compounds that generate an acid upon irradiation with radiation. Among these, those having a sulfonium salt structure are preferable, those having a triarylsulfonium salt structure are more preferable, and those having a tri (chlorophenyl) sulfonium salt structure are particularly preferable. Examples of the polymerization initiator having a tri (chlorophenyl) sulfonium salt structure include compound examples (b-37) to (b-40) listed below as preferred compound examples of the polymerization initiator.
Preferable compound examples [(b-1) to (b-96)] of compounds (photoacid generators) that generate an acid upon irradiation with radiation as a polymerization initiator that can be used in the present invention are listed below. The invention is not limited to these examples.

In the present invention, oxazole derivatives and s-triazine derivatives described in JP-A No. 2002-122994, paragraphs [0029] to [0030] are also preferably used.
Furthermore, onium salt compounds and sulfonate compounds exemplified in JP-A No. 2002-122994, paragraphs [0037] to [0063] can also be suitably used in the present invention.

-Radical polymerization initiator-
In the present invention, for example, when a radical polymerizable compound is used as the polymerizable compound, it is preferable to use a conventionally known radical polymerization initiator as shown below. By using these compounds, the polymerization reaction of the radical polymerizable compound described above is caused by radicals generated from the radical polymerization initiator, and the photocurable composition can be cured.

As radical polymerization initiators, α-aminoketones, acylphosphine oxides, acetophenone derivatives, benzophenone derivatives, benzyl derivatives, benzoin derivatives, benzoin ether derivatives, benzyldialkyl ketal derivatives, thioxanthone derivatives, acylphosphine oxide derivatives, metal complexes, p -Dialkylaminobenzoic acid, azo compounds, peroxide compounds, etc. are generally known, among which α-aminoketones, acylphosphine oxides, acetophenone derivatives, benzyl derivatives, benzoin ether derivatives, benzyldialkyl ketal derivatives, thioxanthone derivatives, acyl Phosphine oxide derivatives are preferred, acetophenone derivatives, benzoin ether derivatives, benzyl dialkyl ketal derivatives, acyl A phosphine oxide derivative is more preferable.
In particular, the radical polymerization initiator that can be most suitably used in relation to the specific compound of the present invention includes a radical polymerization initiator selected from the group consisting of α-aminoketones and acylphosphine oxides.

  Examples of radical polymerization initiators include acetophenone, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, p-dimethylaminopropiophenone, benzophenone, p, p'-dichlorobenzophenone, p, p'-bisdiethylamino. Benzophenone, Michler's ketone, benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin-n-propyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, 1-hydroxy-cyclohexyl phenyl ketone, tetramethylthiuram monosulfide, thioxanthone, 2-chloro Thioxanthone, 2,4-dimethylthioxanthone, 2,2-dimethylpropioyl diphenylphosphine oxide, 2-methyl-2- Ethylhexanoyl diphenylphosphine oxide, 2,6-dimethylbenzoyl diphenylphosphine oxide, 2,6-dimethoxybenzoyl diphenylphosphine oxide, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2 , 4,4-trimethylpentylphosphine oxide, 2,3,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,3,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethoxybenzoyl-diphenyl Phosphine oxide, 2,4,6-trichlorobenzoyl diphenylphosphine oxide, 2,4,6-trimethylbenzoyl naphthyl phosphonate, bis (η5- , 4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -finyl) titanium, p-dimethylaminobenzoic acid, p-diethylaminobenzoic acid, azobis Examples include isobutyronitrile, 1,1′-azobis (1-acetoxy-1-phenylethane), benzoin peroxide, and di-tert-butyl peroxide.

A radical polymerization initiator (hereinafter also referred to as “specific polymerization initiator”) selected from the group consisting of α-aminoketones and acylphosphine oxides particularly preferably used in the present invention will be described.
The α-aminoketone compound which is a specific polymerization initiator is preferably a compound represented by the following general formula (11).

In the general formula (11), Ar is a phenyl group substituted with —SR ^13r or —N (R ^11r ) (R ^12r ), where R ^13r represents a hydrogen atom or an alkyl group.
R ^1r and R ^2r are each independently an alkyl group having 1 to 8 carbon atoms. R ^1r and R ^2r may be bonded to each other to form an alkylene group having 2 to 9 carbon atoms. R ^3r and R ^4r are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy-substituted alkyl group having 2 to 4 carbon atoms, or an alkenyl group having 3 to 5 carbon atoms. Represents a group. Here, R ^3r and R ^4r may be bonded to each other to form an alkylene group having 3 to 7 carbon atoms, and the alkylene group is —O— or —N (R ^14r ) — in the alkylene chain. Wherein R ^14r represents an alkyl group having 1 to 4 carbon atoms.
R ^11r and R ^12r are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy-substituted alkyl group having 2 to 4 carbon atoms, or an alkenyl group having 3 to 5 carbon atoms. Represents a group. Here, R ^11r and R ^12r may be bonded to each other to form an alkylene group having 3 to 7 carbon atoms, and the alkylene group is —O— or —N (R ^14r ) — in the alkylene chain. May be included. Here, R ^14r has the same ^{meaning as} described above.

  Examples of compounds included in the α-amino ketones include 2-methyl-1-phenyl-2-morpholinopropan-1-one, 2-methyl-1- [4- (hexyl) phenyl] -2-morpholino. Propan-1-one, 2-ethyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, and the like. Further, Irgacure series manufactured by Ciba Geigy, such as Irgacure 907, Irgacure 369, Irgacure 379, etc., are also available as commercial products, and these are also compounds included in α-aminoketones, and are suitable for the present invention. Can be used.

  The compound included in the acylphosphine oxides is a compound represented by the following general formula (12) or general formula (13).

In the general formula (12), R ^5r and R ^6r each independently represent an aliphatic group, an aromatic group, an aliphatic oxy group, an aromatic oxy group, or a heterocyclic group, and R ^7r represents an aliphatic group, Represents an aromatic group or a heterocyclic group.

Examples of the aliphatic group represented by R ^5r , R ^6r, or R ^7r include an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aralkyl group, and a substituted aralkyl group. Among them, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aralkyl group, or a substituted aralkyl group is preferable, and an alkyl group and a substituted alkyl group are particularly preferable. The aliphatic group may be a cyclic aliphatic group or a chain aliphatic group. The chain aliphatic group may have a branch.

  Examples of the alkyl group include linear, branched, and cyclic alkyl groups, and the number of carbon atoms of the alkyl group is preferably 1 to 30, and more preferably 1 to 20. The preferred range of the number of carbon atoms in the alkyl part of the substituted alkyl group is the same as in the case of the alkyl group. Further, the alkyl group may be either a substituted alkyl group or an unsubstituted alkyl group. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, octadecyl, cyclohexyl, cyclopentyl, neopentyl, An isopropyl group, an isobutyl group, etc. are mentioned.

  Examples of the substituent of the substituted alkyl group include a carboxy group, a sulfo group, a cyano group, a halogen atom (for example, fluorine atom, chlorine atom, bromine atom), a hydroxy group, and an alkoxycarbonyl group having 30 or less carbon atoms (for example, methoxycarbonyl). Group, ethoxycarbonyl group, benzyloxycarbonyl group), alkylsulfonylaminocarbonyl group having 30 or less carbon atoms, arylsulfonylaminocarbonyl group, alkylsulfonyl group, arylsulfonyl group, acylaminosulfonyl group having 30 or less carbon atoms, carbon number 30 The following alkoxy groups (for example, methoxy group, ethoxy group, benzyloxy group, phenoxyethoxy group, phenethyloxy group, etc.), alkylthio groups having 30 or less carbon atoms (for example, methylthio group, ethylthio group, methylthioethylthioethyl group, etc.) Aryloxy group having 30 or less carbon atoms (for example, phenoxy group, p-tolyloxy group, 1-naphthoxy group, 2-naphthoxy group, etc.), nitro group, alkyl group having 30 or less carbon atoms, alkoxycarbonyloxy group, aryloxycarbonyl An oxy group,

  Acyloxy group having 30 or less carbon atoms (for example, acetyloxy group, propionyloxy group, etc.), Acyl group having 30 or less carbon atoms (for example, acetyl group, propionyl group, benzoyl group, etc.), carbamoyl group (for example, carbamoyl group, N , N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group, etc.), sulfamoyl group (for example, sulfamoyl group, N, N-dimethylsulfamoyl group, morpholinosulfonyl group, piperidinosulfonyl group, etc.), carbon An aryl group having a number of 30 or less (for example, phenyl group, 4-chlorophenyl group, 4-methylphenyl group, α-naphthyl group, etc.), substituted amino group (for example, amino group, alkylamino group, dialkylamino group, arylamino group) , Diarylamino group, acylamino group, etc.), substituted urea De group, a substituted phosphono group, and a heterocyclic group. Here, the carboxyl group, the sulfo group, the hydroxy group, and the phosphono group may be in a salt state. At that time, examples of the cation forming the salt include alkali metal ions and ammonium ions.

  Examples of the alkenyl group include linear, branched, and cyclic alkenyl groups. The number of carbon atoms of the alkenyl group is preferably 2 to 30, and more preferably 2 to 20. The alkenyl group may be a substituted alkenyl group having a substituent or an unsubstituted alkenyl group, and the preferred range of the number of carbon atoms in the alkenyl part of the substituted alkenyl group is the same as that of the alkenyl group. . Examples of the substituent of the substituted alkenyl group include the same substituents as those of the substituted alkyl group.

  Examples of the alkynyl group include linear, branched, and cyclic alkynyl groups, and the number of carbon atoms of the alkynyl group is preferably 2 to 30, and more preferably 2 to 20. The alkynyl group may be a substituted alkynyl group having a substituent or an unsubstituted alkynyl group, and the preferred range of the number of carbon atoms in the alkynyl part of the substituted alkynyl group is the same as in the case of the alkynyl group. . Examples of the substituent for the substituted alkynyl group include the same substituents as those for the substituted alkyl group.

  Examples of the aralkyl group include linear, branched, and cyclic aralkyl groups. The number of carbon atoms in the aralkyl group is preferably 7 to 35, and more preferably 7 to 25. The aralkyl group may be a substituted aralkyl group having a substituent or an unsubstituted aralkyl group, and the preferred range of the number of carbon atoms in the aralkyl part of the substituted aralkyl group is the same as in the case of the aralkyl group. . Examples of the substituent for the substituted aralkyl group include the same substituents as those for the substituted alkyl group.

Examples of the aromatic group represented by R ^5r , R ^6r or R ^7r include an aryl group and a substituted aryl group. As a carbon atom number of an aryl group, 6-30 are preferable and 6-20 are more preferable. The preferable range of the number of carbon atoms in the aryl part of the substituted aryl group is the same as that of the aryl group. Examples of the aryl group include a phenyl group, an α-naphthyl group, a β-naphthyl group, and the like. Examples of the substituent for the substituted aryl group include the same substituents as those for the substituted alkyl group.

The aliphatic oxy group represented by R ^5r or R ^6r is preferably an alkoxy group having 1 to 30 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a butoxy group, an octyloxy group, and a phenoxyethoxy group. . However, it is not limited to these.

The aromatic oxy group represented by R ^5r or R ^6r is preferably an aryloxy group having 6 to 30 carbon atoms, such as a phenoxy group, a methylphenyloxy group, a chlorophenyloxy group, a methoxyphenyloxy group, and an octyloxy group. A phenyloxy group etc. are mentioned. However, it is not limited to these.

The heterocyclic group represented by R ^5r , R ^6r or R ^7r is preferably a heterocyclic group containing an N, O or S atom, for example, a pyridyl group, a furyl group, a thienyl group, an imidazolyl group, a pyrrolyl group or the like. Is mentioned.

R ^8r and R ^10r in the general formula (13) each independently represents an alkyl group, an aryl group, or a heterocyclic group, and R ^9r represents an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a heterocyclic group. Represents. The alkyl group, aryl group, heterocyclic group, alkoxy group and aryloxy group represented by R ^8r , R ^9r or R ^10r may have a substituent. The same substituents as in the formula (12) can be mentioned.

  The alkyl group, aryl group, heterocyclic group, alkoxy group and aryloxy group in the general formula (13) have the same meaning as in the general formula (12).

  Examples of the acylphosphine oxide compounds represented by the general formula (12) or (13) include, for example, Japanese Patent Publication No. 63-40799, Japanese Patent Publication No. 5-29234, Japanese Patent Application Laid-Open No. 10-95788, Japanese Patent Application Laid-Open No. Examples thereof include compounds described in JP-A No. 10-29997.

  Specific examples of the acylphosphine oxide compound include the following compounds (Exemplary compounds (P-1) to (P-26)), but the present invention is not limited to these. .

  Among the exemplified compounds, for example, (P-2) [2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide] is available under the trade name of Darocur TPO (manufactured by Ciba Specialty Chemicals). , (P-19) [Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide] is available under the trade name Irgacure 819 (manufactured by Ciba Specialty Chemicals).

  The content of the specific polymerization initiator in the photocurable composition of the present invention is preferably in the range of 0.1 to 30% by mass and in the range of 0.2 to 20% by mass in terms of solid content. It is more preferable.

Furthermore, other examples of radical polymerization initiators include photopolymerization initiators described on pages 65 to 148 of “UV Curing System” written by Kayo Kiyomi (General Technology Center Co., Ltd .: 1989). Can be mentioned.
These photopolymerization initiators can be used alone or in combination of two or more, and may be used in combination with a sensitizer described later.

  Moreover, it is preferable that a photoinitiator does not raise | generate a thermal decomposition to 80 degreeC. Use of an initiator that causes thermal decomposition at 80 ° C. or lower is not preferable because there is a problem in product storage.

In the photocurable composition of the present invention, the polymerization initiator can be used alone or in combination of two or more.
The content of the polymerization initiator in the photocurable composition is preferably 0.1% by mass to 25% by mass, more preferably 0.5% by mass to 20% by mass, in terms of the total solid content of the ink composition. More preferably, it is 1 mass%-18 mass%.

<Other ingredients>
The various additives that can be used in the present invention as necessary are described below.
-UV absorber-
In the present invention, an ultraviolet absorber can be used from the viewpoint of improving the weather resistance of the resulting cured product and preventing discoloration.
Examples of the ultraviolet absorber are described in JP-A-58-185679, JP-A-61-190537, JP-A-2-782, JP-A-5-97075, JP-A-9-34057, and the like. Benzotriazole compounds, benzophenone compounds described in JP-A No. 46-2784, JP-A No. 5-194843, US Pat. No. 3,214,463, etc., JP-B Nos. 48-30492 and 56-21141 Cinnamic acid compounds described in JP-A-10-88106, JP-A-4-298503, JP-A-8-53427, JP-A-8-239368, JP-A-10-182621, JP The triazine compounds described in JP-A-8-501291, Research Disclosure No. Examples thereof include compounds described in No. 24239, compounds that emit ultraviolet light by absorbing ultraviolet rays typified by stilbene and benzoxazole compounds, so-called fluorescent brighteners, and the like.
The addition amount is appropriately selected according to the purpose, but generally it is preferably 0.5% by mass to 15% by mass in terms of solid content.

-Sensitizer-
The sensitizer is not activated by light irradiation when used alone, but is more effective when used together with the polymerization initiator than when used alone. In the case where the photocurable composition of the present invention contains, for example, a radical polymerizable compound, amines are generally used.
The reason why the curing rate is increased by the addition of amines is to supply hydrogen to the polymerization initiator first by the hydrogen abstraction action, and secondly, the generated radicals react with oxygen molecules in the atmosphere to react. This is because the amine has an action of trapping oxygen dissolved in the composition, whereas the property is deteriorated.

  Specific examples of the sensitizer include amine compounds (aliphatic amines, amines containing aromatic groups, piperidine, reaction products of epoxy resins and amines, triethanolamine triacrylate, etc.), urea compounds (allylthiourea, o -Tolylthiourea, etc.), sulfur compounds (sodium diethyldithiophosphate, soluble salts of aromatic sulfinic acid, etc.), nitrile compounds (N, N-diethyl-p-aminobenzonitrile, etc.), phosphorus compounds (tri-n-butyl, etc.) Phosphine, sodium diethyldithiophosphide, etc.), nitrogen compounds (Michler ketone, N-nitrisohydroxylamine derivatives, oxazolidine compounds, tetrahydro-1,3-oxazine compounds, formaldehyde or condensates of acetaldehyde and diamines), chlorine compounds (four Carbon, hexachloroethane, etc.) and the like.

The amount of the sensitizer used can be appropriately selected from the selection and combination of the polymerization initiator and the sensitizer, the polymerizable compound to be used, and the like. Generally, 0 to 10% by mass is preferable based on the photocurable composition. 1-10 mass% is more preferable, and 0.2-5 mass% is especially preferable.
[Other sensitizing dyes]
In the present invention, a known sensitizing dye can be used in combination with the specific sensitizing dye as long as the effects of the present invention are not impaired. The other sensitizing dye is 1: 5 to 100: 1, preferably 1: 1 to 100: 1, more preferably, in a mass ratio of the specific sensitizing dye to the other sensitizing dye with respect to the specific sensitizing dye. Can be added in an amount of 2: 1 to 100: 1.
Examples of known sensitizing dyes that can be used in combination include benzophenone, thioxanthone (particularly isopropylthioxanthone), anthraquinone and 3-acylcoumarin derivatives, terphenyl, styryl ketone and 3- (aroylmethylene) thiazoline, camphorquinone, eosin, Examples include rhodamine and erythrosine.

The further example of the photosensitizer which can be used together is as follows.
(1) Thioxanthone Thioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-dodecylthioxanthone, 2,4-di-ethylthioxanthone, 2,4-dimethylthioxanthone, 1-methoxycarbonylthioxanthone, 2-ethoxycarbonylthioxanthone, 3 -(2-methoxyethoxycarbonyl) thioxanthone, 4-butoxycarbonylthioxanthone, 3-butoxycarbonyl-7-methylthioxanthone, 1-cyano-3-chlorothioxanthone, 1-ethoxycarbonyl-3-chlorothioxanthone, 1-ethoxycarbonyl- 3-ethoxythioxanthone, 1-ethoxycarbonyl-3-aminothioxanthone, 1-ethoxycarbonyl-3-phenylsulfurylthioxanthone, 3,4- Bis- [2- (2-methoxyethoxy) ethoxycarbonyl] thioxanthone, 1-ethoxycarbonyl-3- (1-methyl-1-morpholinoethyl) thioxanthone, 2-methyl-6-dimethoxymethylthioxanthone, 2-methyl-6 -(1,1-dimethoxybenzyl) thioxanthone, 2-morpholinomethylthioxanthone, 2-methyl-6-morpholinomethylthioxanthone, n-allylthioxanthone-3,4-dicarboximide, n-octylthioxanthone-3,4-di Carboximide, N- (1,1,3,3-tetramethylbutyl) thioxanthone-3,4-dicarboximide, 1-phenoxythioxanthone, 6-ethoxycarbonyl-2-methoxythioxanthone, 6-ethoxycarbonyl-2- Methylthioxan , Thioxanthone-2-polyethylene glycol ester, 2-hydroxy-3- (3,4-dimethyl-9-oxo-9H-thioxanthone-2-yloxy) -N, N, N-trimethyl-1-propanaminium chloride ;

(2) Benzophenone Benzophenone, 4-phenylbenzophenone, 4-methoxybenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-dimethylbenzophenone, 4,4′-dichlorobenzophenone, 4,4′-dimethylaminobenzophenone, 4 , 4'-diethylaminobenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4- (4-methylthiophenyl) benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, methyl-2-benzoylbenzoate 4- (2-hydroxyethylthio) benzophenone, 4- (4-tolylthio) benzophenone, 4-benzoyl-N, N, N-trimethylbenzenemethanaminium chloride, 2-hydroxy-3- (4-benzoylphenoxy) ) -N, N, N-trimethyl-1-propanaminium chloride monohydrate, 4- (13-acryloyl-1,4,7,10,13-pentaoxatridecyl) benzophenone, 4-benzoyl-N , N-dimethyl-N- [2- (1-oxo-2-propenyl) oxy] ethylbenzenemethanaminium chloride;

(3) 3-acylcoumarin 3-benzoylcoumarin, 3-benzoyl-7-methoxycoumarin, 3-benzoyl-5,7-di (propoxy) coumarin, 3-benzoyl-6,8-dichlorocoumarin, 3-benzoyl- 6-chlorocoumarin, 3,3′-carbonylbis [5,7-di (propoxy) coumarin], 3,3′-carbonylbis (7-methoxycoumarin), 3,3′-carbonylbis (7-diethylaminocoumarin) ), 3-isobutyroylcoumarin, 3-benzoyl-5,7-dimethoxycoumarin, 3-benzoyl-5,7-diethoxycoumarin, 3-benzoyl-5,7-dibutoxycoumarin, 3-benzoyl-5 7-bis (methoxyethoxy) coumarin, 3-benzoyl-5,7-di (allyloxy) coumarin, 3-benzoyl-7 -Dimethylaminocoumarin, 3-benzoyl-7-diethylaminocoumarin, 3-isobutyroyl-7-dimethylaminocoumarin, 5,7-dimethoxy-3- (1-naphthoyl) coumarin, 5,7-dimethoxy-3- (1- Naphthoyl) coumarin, 3-benzoylbenzo [f] coumarin, 7-diethylamino-3-thienoylcoumarin, 3- (4-cyanobenzoyl) -5,7-dimethoxycoumarin;

(4) 3- (Aroylmethylene) thiazoline 3-methyl-2-benzoylmethylene-β-naphthothiazoline, 3-methyl-2-benzoylmethylenebenzothiazoline, 3-ethyl-2-propionylmethylene-β-naphthothiazoline;

(5) Anthracene 9,10-dimethoxy-anthracene, 9,10-diethoxy-anthracene, 9,10-dimethoxy-2-ethyl-anthracene,

(6) Other carbonyl compounds Acetophenone, 3-methoxyacetophenone, 4-phenylacetophenone, benzyl, 2-acetylnaphthalene, 2-naphthaldehyde, 9,10-naphtholaquinone, 9-fluorenone, dibenzosuberone, xanthone, 2,5 -Bis (4-diethylaminobenzylidene) cyclopentanone, α- (para-dimethylaminobenzylidene) ketone, such as 2- (4-dimethylaminobenzylidene) indan-1-one or 3- (4-dimethylaminophenyl)- 1-Indan-5-ylpropenone, 3-phenylthiophthalimide, N-methyl-3,5-di (ethylthio) phthalimide.

-Antioxidant-
An antioxidant can be added to improve the stability of the composition. Examples of the antioxidant include European Published Patent Nos. 223739, 309401, 309402, 310551, 310552, 457416, and German Patent No. 3435443. JP-A-54-48535, JP-A-62-262047, JP-A-63-113536, JP-A-63-163351, JP-A-2-262654, JP-A-2-71262, and JP-A-3 No. 112449, JP-A-5-61166, JP-A-5-119449, US Pat. No. 4,814,262, US Pat. No. 4,980,275, and the like.
Although the addition amount is appropriately selected according to the purpose, it is preferably 0.1% by mass to 8% by mass in terms of solid content.

-Anti-fading agent-
In the present invention, various organic and metal complex anti-fading agents can be used. Examples of the organic anti-fading agent include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, and heterocycles. Examples of the metal complex anti-fading agent include nickel complexes and zinc complexes. No. 17643, No. VII, I to J, ibid. 15162, ibid. No. 18716, page 650, left column, ibid. No. 36544, page 527, ibid. No. 307105, page 872, ibid. The compounds described in the patent cited in No. 15162 and the compounds included in the general formulas and compound examples of representative compounds described in JP-A-62-215272, pages 127 to 137 can be used. .
Although the addition amount is appropriately selected according to the purpose, it is preferably 0.1% by mass to 8% by mass in terms of solid content.

-Conductive salts-
Conductive salts are solid compounds that can improve conductivity by dissolving in a photocurable composition. When the photocurable composition of the present invention is used as, for example, an ink composition for ink jet recording, it is preferably added for the purpose of controlling ejection properties. In the present invention, it is preferable not to use the ink composition substantially because it is likely to precipitate during storage of the ink composition, but it is highly soluble in the liquid component of the ink composition or the solubility of the conductive salt is increased. If the solubility is good by using, an appropriate amount may be added. Examples of conductive salts include potassium thiocyanate, lithium nitrate, ammonium thiocyanate, dimethylamine hydrochloride and the like.

-Solvent-
When the photocurable composition of the present invention is used, for example, as an ink composition for ink jet recording, it is also effective to add a trace amount of an organic solvent in order to improve the adhesion to a recording medium.
Examples of the solvent include ketone solvents such as acetone, methyl ethyl ketone, and diethyl ketone, alcohol solvents such as methanol, ethanol, 2-propanol, 1-propanol, 1-butanol, and tert-butanol, and chlorine such as chloroform and methylene chloride. Solvents, aromatic solvents such as benzene and toluene, ester solvents such as ethyl acetate, butyl acetate and isopropyl acetate, ether solvents such as diethyl ether, tetrahydrofuran and dioxane, glycols such as ethylene glycol monomethyl ether and ethylene glycol dimethyl ether Examples include ether solvents.
In this case, from the viewpoint of solvent resistance and solvent volatility, the amount of the solvent added is preferably 5% by mass or less, more preferably 3% by mass or less, and no solvent is contained with respect to the entire photocurable composition. Further preferred.

-Polymer compound-
Various polymer compounds can be added to the photocurable composition of the present invention in order to adjust film physical properties.
High molecular compounds include acrylic polymers, polyvinyl butyral resins, polyurethane resins, polyamide resins, polyester resins, epoxy resins, phenol resins, polycarbonate resins, polyvinyl butyral resins, polyvinyl formal resins, shellacs, vinyl resins, acrylic resins. Rubber resins, waxes and other natural resins can be used. Two or more of these may be used in combination. Of these, vinyl copolymer obtained by copolymerization of acrylic monomers is preferred. Furthermore, a copolymer containing “carboxyl group-containing monomer”, “methacrylic acid alkyl ester”, or “acrylic acid alkyl ester” as a structural unit is also preferably used as the copolymer composition of the polymer binder.

-Surfactant-
A surfactant may be added to the photocurable composition of the present invention.
Examples of the surfactant include those described in JP-A Nos. 62-173463 and 62-183457. For example, anionic surfactants such as dialkylsulfosuccinates, alkylnaphthalenesulfonates, fatty acid salts, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, acetylene glycols, polyoxyethylene / polyoxypropylene blocks Nonionic surfactants such as copolymers, and cationic surfactants such as alkylamine salts and quaternary ammonium salts. An organic fluoro compound may be used in place of the surfactant. The organic fluoro compound is preferably hydrophobic. Examples of the organic fluoro compounds include fluorine surfactants, oily fluorine compounds (eg, fluorine oil) and solid fluorine compound resins (eg, tetrafluoroethylene resin). No. (columns 8 to 17) and those described in JP-A Nos. 62-135826.

-Storage stabilizer-
The photocurable composition of the present invention may contain a storage stabilizer.
The storage stabilizer is used to suppress undesired polymerization during storage of the photocurable composition, and a storage stabilizer that can be dissolved in the photocurable composition is used. Examples include quaternary ammonium salts, hydroxyamines, cyclic amides, nitriles, substituted ureas, heterocyclic compounds, organic acids, hydroquinones, hydroquinone monoethers, organic phosphines, copper compounds, etc. Specific examples include benzyltrimethylammonium chloride, diethylhydroxylamine, benzothiazole, 4-amino-2,2,6,6-tetramethylpiperidine, citric acid, hydroquinone monomethyl ether, hydroquinone monobutyl ether, and copper naphthenate.

  The amount of the storage stabilizer used is preferably adjusted as appropriate based on the activity of the polymerization initiator used, the polymerizability of the polymerizable compound, and the type of the storage stabilizer, but is 0.005 to 1% by mass in the ink composition. Preferably, 0.01 to 0.5 mass% is more preferable, and 0.01 to 0.2 mass% is still more preferable. If the addition amount is small, the storage stability is inferior, and if the addition amount is large, there is a problem that curing is difficult to occur.

In addition to this, if necessary, for example, a pH adjusting agent, a leveling additive, a matting agent, an antifoaming agent, waxes for adjusting film physical properties, and adhesion to a recording medium such as polyolefin and PET. In order to improve, a tackifier or the like that does not inhibit the polymerization can be contained.
As the tackifier, specifically, a high molecular weight adhesive polymer described in JP-A-2001-49200, 5-6p (for example, (meth) acrylic acid and an alkyl group having 1 to 20 carbon atoms). An ester with an alcohol having, an ester of (meth) acrylic acid with an alicyclic alcohol having 3 to 14 carbon atoms, a copolymer comprising an ester of (meth) acrylic acid with an aromatic alcohol having 6 to 14 carbon atoms) And a low molecular weight tackifying resin having a polymerizable unsaturated bond.

<Colorant>
For example, when the photocurable composition of the present invention is applied as an ink composition to an application such as formation of an image portion of a lithographic printing plate, it is not essential to form a colored image. In this application, a colorant is not particularly necessary. However, in order to improve the visibility of the image portion formed by the ink composition, or when a colored image is to be formed using the ink composition, the colorant is used. Can be contained.

  The colorant that can be used in the present invention is not particularly limited, and is selected from any known colorant such as (1) pigment, (2) oil-soluble dye, (3) disperse dye, and soluble dye. Can be used. Of these, (1) pigments and (2) oil-soluble dyes that are excellent in weather resistance and rich in color reproducibility are preferable. In the present invention, the colorant that can be suitably used in the ink composition or the ink composition for inkjet recording functions as a polymerization inhibitor in a polymerization reaction that is a curing reaction from the viewpoint of not reducing the sensitivity of the curing reaction by actinic radiation. It is preferred to select compounds that do not.

(1) Pigment The pigment that can be used in the present invention is not particularly limited. For example, organic or inorganic pigments having the following numbers described in the color index can be used.
Examples of the red or magenta pigment include Pigment Red 3, 5, 19, 22, 31, 38, 43, 48: 1, 48: 2, 48: 3, 48: 4, 48: 5, 49: 1, and 53. : 1, 57: 1, 57: 2, 58: 4, 63: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 88, 104, 108, 112, 122, 123, 144 146, 149, 166, 168, 169, 170, 177, 178, 179, 184, 185, 208, 216, 226, 257, Pigment Violet 3, 19, 23, 29, 30, 37, 50, 88, Pigment Orange 13, 16, 20, 36, and the like.
Examples of the blue or cyan pigment include Pigment Blue 1, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17-1, 22, 27, 28, 29, 36. , 60, and the like.
Examples of the green pigment include Pigment Green 7, 26, 36, 50, and party.
Examples of the yellow pigment include Pigment Yellow 1, 3, 12, 13, 14, 17, 34, 35, 37, 55, 74, 81, 83, 93, 94, 95, 97, 108, 109, 110, and 137. 138, 139, 153, 154, 155, 157, 166, 167, 168, 180, 185, 193, and the like.
Examples of the black pigment include Pigment Black 7, 28, 26, and the like.
Examples of the white pigment include Pigment White 6, 18, 21, and the like.
These pigments can be appropriately selected and used according to the purpose.

(2) Oil-soluble dye The oil-soluble dye that can be used in the present invention is described below.
The oil-soluble dye that can be used in the present invention means a dye that is substantially insoluble in water. Specifically, the solubility in water at 25 ° C. (the mass of the dye that can be dissolved in 100 g of water) is 1 g or less, preferably 0.5 g or less, more preferably 0.1 g or less. Accordingly, the oil-soluble dye means a so-called water-insoluble pigment or oil-soluble dye, and among these, an oil-soluble dye is preferable.

  Among the oil-soluble dyes that can be used in the present invention, any yellow dye can be used. For example, phenols, naphthols, anilines, pyrazolones, pyridones, aryl or heteryl azo dyes having open-chain active methylene compounds as coupling components; for example, azomethine dyes having open-chain active methylene compounds as coupling components; Examples include methine dyes such as benzylidene dyes and monomethine oxonol dyes; quinone dyes such as naphthoquinone dyes and anthraquinone dyes; and other dye species such as quinophthalone dyes, nitro / nitroso dyes, Examples include acridine dyes and acridinone dyes.

  Among the oil-soluble dyes that can be used in the present invention, any magenta dye can be used. For example, aryl or heteryl azo dyes having phenols, naphthols, anilines as coupling components; for example, azomethine dyes having pyrazolones, pyrazolotriazoles as coupling components; for example arylidene dyes, styryl dyes, merocyanine dyes, oxonol dyes Methine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes; quinone dyes such as naphthoquinone, anthraquinone, anthrapyridone; condensed polycyclic dyes such as dioxazine dyes, etc. Can be mentioned.

  Of the oil-soluble dyes applicable to the present invention, any cyan dye can be used. For example, indoaniline dyes, indophenol dyes or azomethine dyes having pyrrolotriazoles as coupling components; polymethine dyes such as cyanine dyes, oxonol dyes, merocyanine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes Phthalocyanine dyes; anthraquinone dyes; for example, aryl or heteryl azo dyes having phenols, naphthols and anilines as coupling components; indigo / thioindigo dyes;

  Each of the above dyes may exhibit yellow, magenta, and cyan colors only after a part of chromophore (chromogenic atomic group) is dissociated. In this case, the counter cation may be an alkali metal or ammonium. Such inorganic cations may be used, and organic cations such as pyridinium and quaternary ammonium salts may be used, and furthermore, polymer cations having such a structure may be used.

Although not limited to the following, preferred specific examples include C.I. I. Solvent Black 3, 7, 27, 29 and 34; C.I. I. Solvent Yellow 14, 16, 19, 29, 30, 56, 82, 93 and 162; C.I. I. Solvent Red 1, 3, 8, 18, 24, 27, 43, 49, 51, 72, 73, 109, 122, 132 and 218; C.I. I. Solvent Violet 3; C.I. I. Solvent Blue 2, 11, 25, 35, 38, 67 and 70; C.I. I. Solvent Green 3 and 7; I. Solvent orange 2; and the like.
Particularly preferred among these are: Nubian Black PC-0850, Oil Black HBB, Oil Yellow 129, Oil Yellow 105, Oil Pink 312, Oil Red 5B, Oil Scallet 308, Vali Fast Blue chemistry 2606e B2 (Manufactured by Co., Ltd.), Aizen Spiron Blue GNH (manufactured by Hodogaya Chemical Co., Ltd.), Neopen Yellow 075, Neopen Magenta SE1378, Neopen Blue 808, Neopen Blue FF4012, and Neo42 Cy FF4012.

In the present invention, the oil-soluble dye may be used alone or in combination of several kinds.
Further, when an oil-soluble dye is used as a colorant, other water-soluble dyes, disperse dyes, pigments, and other colorants can be used in combination as long as the effects of the present invention are not impaired. .

(3) Disperse dye In the present invention, a disperse dye may be used as long as it is soluble in a water-immiscible organic solvent. The disperse dye generally includes a water-soluble dye, but in the present invention, the disperse dye is preferably used as long as it is soluble in a water-immiscible organic solvent. Preferable specific examples of the disperse dye include C.I. I. Disperse Yellow 5, 42, 54, 64, 79, 82, 83, 93, 99, 100, 119, 122, 124, 126, 160, 184: 1, 186, 198, 199, 201, 204, 224 and 237 C. I. Disperse Orange 13, 29, 31: 1, 33, 49, 54, 55, 66, 73, 118, 119 and 163; C.I. I. Disperse Red 54, 60, 72, 73, 86, 88, 91, 92, 93, 111, 126, 127, 134, 135, 143, 145, 152, 153, 154, 159, 164, 167: 1, 177 , 181, 204, 206, 207, 221, 239, 240, 258, 277, 278, 283, 311, 323, 343, 348, 356 and 362; I. Disperse Violet 33; C.I. I. Disperse Blue 56, 60, 73, 87, 113, 128, 143, 148, 154, 158, 165, 165: 1, 165: 2, 176, 183, 185, 197, 198, 201, 214, 224, 225 257, 266, 267, 287, 354, 358, 365 and 368; I. Disperse Green 6: 1 and 9;

  It is preferable that the colorant that can be used in the present invention is appropriately dispersed in the ink after being added to the ink composition of the present invention or the ink composition for inkjet recording. For dispersing the colorant, for example, a dispersion device such as a ball mill, a sand mill, an attritor, a roll mill, an agitator, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, a pearl mill, a wet jet mill, or a paint shaker can be used.

  It is also possible to add a dispersant when dispersing the colorant. The type of the dispersant is not particularly limited, but a polymer dispersant is preferably used. Examples of the polymer dispersant include Solsperse series manufactured by Nippon Lubrizol. Moreover, it is also possible to use a synergist according to various pigments as a dispersion aid. In the present invention, these dispersant and dispersion aid are preferably added in an amount of 1 to 50 parts by mass with respect to 100 parts by mass of the colorant.

  In preparing the ink composition of the present invention, the colorant may be added by adding directly with each component. However, in order to improve dispersibility, a solvent or a specific monofunctional (meth) acrylic acid derivative according to the present invention is used in advance. Alternatively, it may be added to a dispersion medium such as other polymerizable compound used in combination as desired, and uniformly dispersed or dissolved, and then blended.

  In the present invention, in order to avoid the problem of deterioration of the solvent resistance of the image area over time and the problem of VOC (Volatile Organic Compound) of the remaining solvent, which is a concern when the solvent remains in the cured image. The colorant is preferably added in advance to any one of a polymerizable compound containing a specific monofunctional (meth) acrylic acid derivative or a mixture thereof and blended. In consideration of only dispersibility, it is preferable to select a monomer having the lowest viscosity as the polymerizable compound used for the addition of the colorant.

One or more colorants may be appropriately selected and used depending on the purpose of use of the photocurable composition.
In the photocurable composition of the present invention, when using a colorant such as a pigment that remains in a solid state, the average particle diameter of the colorant particles is preferably 0.005 to 0.5 μm. It is preferable to set the colorant, the dispersant, the dispersion medium, the dispersion conditions, and the filtration conditions so that the thickness is preferably 0.01 to 0.45 μm, and more preferably 0.015 to 0.4 μm. By controlling the particle size, when the photocurable composition of the present invention is used as an ink composition for inkjet, clogging of the head nozzle is suppressed, and ink storage stability, ink transparency, and curing sensitivity are maintained. Is preferable.

  The content of the colorant in the photocurable composition of the present invention is appropriately selected depending on the purpose of use. For example, when used as an ink composition, generally considering the ink physical properties and colorability, The content is preferably 1 to 10% by mass and more preferably 2 to 8% by mass with respect to the total mass of the ink composition.

<Other ingredients>
If necessary, other components can be added to the photocurable composition of the present invention. Examples of other components include a polymerization inhibitor and a solvent.
A polymerization inhibitor may be added from the viewpoint of enhancing the storage stability. In addition, when the photocurable composition of the present invention is used as an ink composition for ink jet recording, it is preferably heated and reduced in viscosity within a range of 40 to 80 ° C. to prevent head clogging due to thermal polymerization. In order to prevent this, it is preferable to add a polymerization inhibitor. The polymerization inhibitor is preferably added in an amount of 200 to 20,000 ppm based on the total amount of the ink composition of the present invention. Examples of the polymerization inhibitor include hydroquinone, benzoquinone, p-methoxyphenol, TEMPO, TEMPOL, and cuperon Al.

  The photocurable composition of the present invention containing the specific sensitizing dye and the specific compound can be used for various applications, but is particularly preferably used for an ink composition.

<Ink composition>
In view of the fact that the ink composition of the present invention is an actinic ray or radiation curable ink composition, it is preferable that the ink composition does not contain a solvent so that it can quickly react and cure immediately after the ink composition has landed. However, a predetermined solvent can be included as long as the curing rate of the ink composition is not affected. In the present invention, an organic solvent or water can be used as the solvent. In particular, an organic solvent can be added in order to improve the adhesion with a recording medium (a support such as paper). When an organic solvent is added, the VOC problem can be avoided by setting the addition amount within a specific range, which is effective.
The amount of the organic solvent is, for example, 0.1 to 5% by mass, preferably 0.1 to 3% by mass with respect to the mass of the entire ink composition of the present invention.

  In addition to this, a known compound can be added to the ink composition of the present invention as necessary. For example, surfactants, leveling additives, matting agents, polyester resins for adjusting film properties, polyurethane resins, vinyl resins, acrylic resins, rubber resins, washes, etc. are appropriately selected and added. be able to. In order to improve the adhesion to a recording medium such as polyolefin or PET, it is also preferable to contain a tackifier that does not inhibit the polymerization. Specifically, a high molecular weight adhesive polymer described in JP-A-2001-49200, pages 5 to 6 (for example, (meth) acrylic acid and an alcohol having an alkyl group having 1 to 20 carbon atoms). An ester, a copolymer of (meth) acrylic acid and an alicyclic alcohol having 3 to 14 carbon atoms, a copolymer of an ester of (meth) acrylic acid and an aromatic alcohol having 6 to 14 carbon atoms), and polymerizability. Examples thereof include a low molecular weight tackifying resin having an unsaturated bond.

  The ink composition of the present invention can form an image by applying it to a known recording method (printing method), printing apparatus or the like. The viscosity of the ink composition of the present invention at the time of forming an image is appropriately determined depending on the recording method and printing apparatus used, but is generally preferably 5 to 100 mPa · s, more preferably 10 to 80 mPa · s. preferable. Moreover, as surface tension, 20-60 mN / m is preferable and 30-50 mN / m is more preferable.

  The ink composition of the present invention is used particularly as an ink for ink jet recording, because it is cured with high sensitivity by radiation irradiation, and the obtained cured product is excellent in color developability and light fastness and can form a high quality image. It is preferred that As described above, when the ink composition of the present invention is used as an ink for inkjet recording, the ink composition is ejected onto a recording medium by an inkjet printer, and then the ejected ink composition is irradiated with radiation. Recording is performed by curing.

  In addition, when using the ink composition of the present invention as an inkjet ink composition, in consideration of dischargeability, at a discharge temperature (for example, 40 ° C. to 80 ° C., preferably 25 ° C. to 30 ° C.), The viscosity is preferably 7 mPa · s to 30 mPa · s, more preferably 7 mPa · s to 20 mPa · s. For example, the viscosity of the ink composition of the present invention at room temperature (25 ° C. to 30 ° C.) is preferably 35 to 500 mPa · s, more preferably 35 mPa · s to 200 mPa · s. It is preferable that the composition ratio of the ink composition of the present invention is appropriately adjusted so that the viscosity is in the above range. By setting the viscosity at room temperature high, even when a porous recording medium is used, ink penetration into the recording medium can be avoided, and uncured polymerizable compounds can be reduced and odors can be reduced. . Further, it is preferable because ink bleeding at the time of ink droplet landing can be suppressed, and as a result, the image quality is improved.

  Moreover, when using the ink composition of this invention as an ink composition for inkjet, the surface tension becomes like this. Preferably it is 20mN / m-30mN / m, More preferably, it is 23mN / m-28mN / m. When recording on various recording media such as polyolefin, PET, coated paper, and non-coated paper, 20 mN / m or more is preferable from the viewpoint of bleeding and penetration, and the wettability is preferably 30 mN / m or less.

<Inkjet recording method>
The ink jet recording method to which the ink composition of the present invention is preferably applied will be described below.
An ink jet recording method to which the ink composition of the present invention is applied includes the following two steps. That is, a step of ejecting the ink composition of the present invention onto a recording medium (support, recording material, etc.) by an ink jet recording apparatus, and irradiating the ejected ink composition with actinic radiation to produce the ink composition. It is a step of curing. The cured product obtained through these steps becomes an image.

The recording medium applicable to the ink jet recording method in the present invention is not particularly limited, and various non-absorbent resin materials used for ordinary non-coated paper, coated paper, and so-called soft packaging, or the like. A resin film formed into a film can be used, and examples of the various plastic films include PET film, OPS film, OPP film, ONy film, PVC film, PE film, and TAC film. In addition, examples of the plastic that can be used as a recording medium material include polycarbonate, acrylic resin, ABS, polyacetal, PVA, and rubbers. Metals and glasses can also be used as the recording medium.
Furthermore, examples of the recording medium applicable to the present invention include a support for a lithographic printing plate.
These recording media can be applied to any printing method regardless of the ink jet recording method.

Examples of the active radiation applied to the ink jet recording method of the present invention include α rays, γ rays, X rays, ultraviolet rays, visible rays, infrared rays, and electron beams. The peak wavelength of the actinic radiation is preferably 200 to 600 nm, more preferably 300 to 450 nm, and still more preferably 350 to 420 nm. The output of active radiation is preferably 2,000 mJ / cm ² or less, more preferably from 10 to 2,000 mJ / cm ^2, more preferably be 20 to 1,000 mJ / cm ² Particularly preferably, it is 50 to 800 mJ / cm ² .
In particular, in the inkjet recording method of the present invention, irradiation with radiation generates ultraviolet rays having an emission wavelength peak of 350 to 420 nm and a maximum illuminance on the surface of the recording medium of 10 to 2,000 mW / cm ^2. Irradiation from a light emitting diode is preferred.
These radiation irradiations can be applied to any printing method regardless of the ink jet recording method.

(Inkjet recording device)
There is no restriction | limiting in particular as an inkjet recording device applicable to the said inkjet recording method, A commercially available inkjet recording device can be used.
Examples of the ink jet recording apparatus include an ink supply system, a temperature sensor, and an apparatus including an active radiation source capable of emitting radiation as described above.
Examples of the ink supply system include an original tank containing the ink composition of the present invention, a supply pipe, an ink supply tank immediately before the inkjet head, a filter, and a piezo inkjet head. The piezo-type inkjet head has a multi-size dot of 1 pl to 100 pl, preferably 8 pl to 30 pl. It can drive so that it can discharge with a resolution of 720 dpi. In the present invention, dpi represents the number of dots per 2.54 cm.

  The radiation curable ink such as the ink composition of the present invention desirably has a constant temperature for the ejected ink. Therefore, heat insulation and heating can be performed from the ink supply tank to the inkjet head portion. preferable. The temperature control method is not particularly limited, but for example, it is preferable to provide a plurality of temperature sensors at each piping site and perform heating control according to the ink flow rate and the environmental temperature. The temperature sensor can be provided near the ink supply tank and the nozzle of the inkjet head. Moreover, it is preferable that the head unit to be heated is thermally shielded or insulated so that the apparatus main body is not affected by the temperature from the outside air. In order to shorten the printer start-up time required for heating or to reduce the loss of heat energy, it is preferable to insulate from other parts and reduce the heat capacity of the entire heating unit.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. “Part” and “%” represent “part by mass” and “% by mass” unless otherwise specified.
The following examples relate to UV ink jet ink compositions for each color.

[Example 1]
The following components were stirred with a high-speed water-cooled stirrer to obtain a white ink composition for UV inkjet.
(White ink composition)
・ Light acrylate LA 18.4 parts [Lauryl acrylate: monofunctional acrylate]
・ Actilane 421 25.0 parts (Akcros acrylate monomer)
[Propoxylated neopentyl glycol diacrylate: bifunctional acrylate]
・ Photomer 2017 (UV diluent made by EChem) 13.0 parts ・ Solsperse 36000 (dispersant made by Noveon) 2.0 parts ・ MICROLITH WHITE R-A 15.0 parts (pigment made by Ciba, Specialty, Chemicals)
-Genorad 16 (stabilizer manufactured by Rahn) 0.05 parts-Rapi-Cure DVE-3 8.0 parts (vinyl ether manufactured by ISP Europe)
Specific sensitizing dye [I-14 (the following structure)] 4.0 parts Specific compound [A-4 (the following structure)] 2.0 parts Darocur TPO [specific polymerization initiator (P-2)] 5 parts (Ciba / Specialty / Chemicals photopolymerization initiator)
Irgacure 907 [specific polymerization initiator] 4.0 parts (Ciba / Specialty / Chemicals photopolymerization initiator)
・ Byk 307 (defoamer manufactured by BYK Chemie) 0.05 parts

<Evaluation of ink>
The white ink composition obtained above was printed on a polyvinyl chloride sheet using the following inkjet recording apparatus. The ink composition was cured by passing it through a light beam of an iron-doped ultraviolet lamp (power 120 W / cm ² ) at a speed of 40 m / min to obtain a printed matter.
The obtained white ink composition and printed matter were evaluated as follows.

-Sensitivity-
The exposure energy in curing was measured with a light quantity integrator (UV PowerMAP manufactured by EIT). As a result, the accumulated exposure amount of ultraviolet rays on the sheet was 270 mJ / cm ² , and it was confirmed that the sheet was cured with high sensitivity.
The image formed at this time had a good white color.

−Discharge stability−
The dots obtained when the obtained white ink composition was stored at room temperature for 2 weeks, recorded on a recording medium using a commercially available inkjet recording apparatus having a piezo-type inkjet nozzle, and continuously printed at room temperature for 48 hours. The presence or absence of omission and ink scattering was visually observed and evaluated according to the following criteria. The results are shown in Table 1 below.
○: Dot drop or ink splatter does not occur or occurs 3 times or less △: Dot drop or ink splatter occurs 4 to 10 times ×: Dot drop or ink splatter occurs 11 times or more

  The ink supply system of the ink jet recording apparatus used for the evaluation consists of the original tank, supply pipe, ink supply tank immediately before the ink jet head, filter, and piezo ink jet head, and heat insulation and heating from the ink supply tank to the ink jet head part are performed. Went. Temperature sensors were provided near the ink supply tank and the nozzles of the inkjet head, respectively, and temperature control was performed so that the nozzle portions were always 70 ° C. ± 2 ° C. The piezo-type inkjet head was driven so that 8 to 30 pl multi-size dots could be ejected at a resolution of 720 × 720 dpi. In the present invention, dpi represents the number of dots per 2.54 cm.

[Example 2]
The following components were stirred with a high-speed water-cooled stirrer to obtain a cyan ink for UV inkjet.
(Cyan ink composition)
・ Light acrylate L-A 21.4 parts ・ Atilane 421 28.0 parts (Acrys acrylate monomer)
・ Photomer 2017 (UV diluent made by EChem) 20.0 parts ・ Solsperse 32000 (dispersant made by Noveon) 0.4 parts ・ Irgalite Blue GLVO 3.6 parts (pigment made by Ciba, Specialty, Chemicals)
・ Genorad 16 (stabilizer manufactured by Rahn) 0.05 part ・ Rapi-Cure DVE-3 (vinyl ether manufactured by ISP Europe) 8.0 part ・ Specific sensitizing dye [I-14 (the above structure)] 4.0 parts Specific compound [A-4 (the above structure)] 2.0 parts Darocur TPO 8.5 parts (Ciba / Specialty / Chemicals photopolymerization initiator)
Irgacure 907 [specific polymerization initiator] 4.0 parts (Ciba / Specialty / Chemicals photopolymerization initiator)
・ Byk 307 (defoamer manufactured by BYK Chemie) 0.05 parts

<Evaluation of ink>
The obtained cyan ink composition was printed on a polyvinyl chloride sheet in the same manner as in Example 1 and 40 m / min under the light of an iron-doped ultraviolet lamp (power 120 W / cm ² ). Irradiation was carried out by passing at a speed of. The printed matter with this ink was evaluated in the same manner as in Example 1. The results are shown in Table 1 below.

Example 3
The following components were stirred with a high-speed water-cooled stirrer to obtain a magenta ink for UV inkjet.
(Magenta ink composition)
・ Light acrylate LA 15.4 parts ・ Atilane 421 34.0 parts (Acrys acrylate monomer)
・ Photomer 2017 (UV diluent manufactured by EChem) 20.0 parts ・ Solsperse 32000 (dispersant made by Noveon) 0.4 part ・ Cinquasia Magenta RT-355 D 3.6 parts (pigment manufactured by Ciba Specialty Chemical)
-Genorad 16 (stabilizer manufactured by Rahn) 0.05 parts-Rapi-Cure DVE-3 8.0 parts (vinyl ether manufactured by ISP Europe)
・ Specific sensitizing dye [I-14 (above structure)] 4.0 parts ・ Specific compound [A-4 (above structure)] 2.0 parts ・ Darocur TPO 8.5 parts (Ciba / Specialty / Chemicals, Inc.) Polymerization initiator)
・ Irgacure 907 [specific polymerization initiator] 4.0 parts (photoinitiator manufactured by Ciba / Specialty / Chemicals)
・ Byk 307 (defoamer manufactured by BYK Chemie) 0.05 parts

<Evaluation of ink>
The obtained magenta ink composition was printed on a polyvinyl chloride sheet in the same manner as in Example 1, and 40 m / min under the light of an iron-doped ultraviolet lamp (power 120 W / cm ² ). Irradiation was carried out by passing at a speed of. The printed matter with this ink was evaluated in the same manner as in Example 1. The results are shown in Table 1 below.

Example 4
The following components were stirred with a high-speed water-cooled stirrer to obtain a yellow UV inkjet ink composition.
(Yellow color ink composition)
Light acrylate L-A 10 parts Actilane 421 43.4 parts (Acrys acrylate monomer)
・ Photomer 2017 (UV diluent manufactured by EChem) 20.0 parts ・ Solsperse 32000 (dispersant made by Noveon) 0.4 part ・ 3.6 parts of Chromophthalal Yellow LA (pigment manufactured by Ciba, Specialty, Chemicals)
-Genorad 16 (stabilizer manufactured by Rahn) 0.05 parts-Rapi-Cure DVE-3 4.0 parts (vinyl ether manufactured by ISP Europe)
・ Specific sensitizing dye [I-14 (the above structure)] 4.0 parts ・ Specific compound [A-48 (the following structure)] 2.0 parts ・ Darocur TPO 8.5 parts (Ciba, Specialty, Chemicals, Inc. Polymerization initiator)
Irgacure 907 [specific polymerization initiator] 4.0 parts (Ciba / Specialty / Chemicals photopolymerization initiator)
・ Byk 307 (defoamer manufactured by BYK Chemie) 0.05 parts

<Evaluation of ink>
The obtained yellow color ink composition was printed on a sheet made of polyvinyl chloride in the same manner as in Example 1, and the integrated exposure amount under the light of an iron-doped ultraviolet lamp (power 120 W / cm ² ). Irradiation was carried out by passing it so as to be 250 mJ / cm ² . The printed matter with this ink was evaluated in the same manner as in Example 1. The results are shown in Table 1 below.

Example 5
The following components were stirred with a high-speed water-cooled stirrer to obtain a black ink composition for UV inkjet.
(Black ink composition)
・ Light acrylate LA 22.4 parts ・ Atilane 421 31.0 parts (Acrys acrylate monomer)
・ Photomer 2017 (UV diluent manufactured by EChem) 20.0 parts ・ Solsperse 32000 (dispersant made by Noveon) 0.4 parts ・ 2.6 parts of Microlith Black C-K (pigment manufactured by Ciba / Specialty / Chemicals)
-Genorad 16 (stabilizer manufactured by Rahn) 0.05 part-Rapi-Cure DVE-3 5.0 parts (vinyl ether manufactured by ISP Europe)
・ Specific sensitizing dye [I-14 (the above structure)] 4.0 parts ・ Specific compound [A-48 (the above structure)] 2.0 parts ・ Darocur TPO 8.5 parts (Ciba / Specialty / Chemicals, Inc.) Polymerization initiator)
Irgacure 907 [specific polymerization initiator] 4.0 parts (Ciba / Specialty / Chemicals photopolymerization initiator)
・ Byk 307 (defoamer manufactured by BYK Chemie) 0.05 parts

<Evaluation of ink>
The obtained black ink composition was printed on a polyvinyl chloride sheet in the same manner as in Example 1, and the integrated exposure amount was reduced under the light of an iron-doped ultraviolet lamp (power 120 W / cm ² ). Irradiation was carried out by passing through 250 mJ / cm ² . The printed matter with this ink was evaluated in the same manner as in Example 1. The results are shown in Table 1 below.

Example 6
The following components were stirred with a high-speed water-cooled stirrer to obtain a white ink composition for UV inkjet.
(White ink composition)
・ Phenoxyethyl acrylate 23.0 parts ・ N-vinylcaprolactam 15.0 parts ・ FA-512A [following structure] 18.4 parts ・ Solsperse 36000 (Noveon's dispersant) 2.0 parts ・ MICROLITH WHITE R-A 15 0.0 part (Ciba, Specialty, Chemicals pigment)
-Genorad 16 (stabilizer manufactured by Rahn) 0.05 parts-Rapi-Cure DVE-3 8.0 parts (vinyl ether manufactured by ISP Europe)
・ Specific sensitizing dye [I-14 (above structure)] 4.0 parts ・ Specific compound [A-4 (above structure)] 2.0 parts ・ Darocur TPO 8.5 parts (Ciba / Specialty / Chemicals, Inc.) Polymerization initiator)
Irgacure 907 [specific polymerization initiator] 4.0 parts (Ciba / Specialty / Chemicals photopolymerization initiator)
・ Byk 307 (defoamer manufactured by BYK Chemie) 0.05 parts

<Evaluation of ink>
The obtained white ink composition was printed on a sheet made of polyvinyl chloride in the same manner as in Example 1, and the integrated exposure amount under the light of an iron-doped ultraviolet lamp (power 120 W / cm ² ). Irradiation was carried out by passing through 270 mJ / cm ² . The printed matter with this ink was evaluated in the same manner as in Example 1. The results are shown in Table 1 below.

Example 7
The following components were stirred with a high-speed water-cooled stirrer to obtain a white ink composition for UV inkjet.
(White ink composition)
・ Phenoxyethyl acrylate 23.0 parts ・ N-vinylcaprolactam 15.0 parts ・ FA-512A [above structure] 18.4 parts ・ Solsperse 36000 (Noveon dispersant) 2.0 parts ・ MICROLITH WHITE R-A 15 0.0 part (Ciba, Specialty, Chemicals pigment)
-Genorad 16 (stabilizer manufactured by Rahn) 0.05 parts-Rapi-Cure DVE-3 8.0 parts (vinyl ether manufactured by ISP Europe)
・ Specific sensitizing dye [I-17 (the following structure)] 4.0 parts ・ Specific compound [A-4 (the above structure)] 2.0 parts ・ Darocur TPO 8.5 parts (Ciba, Specialty, Chemicals, Inc. Polymerization initiator)
Irgacure 907 [specific polymerization initiator] 4.0 parts (Ciba / Specialty / Chemicals photopolymerization initiator)
・ Byk 307 (defoamer manufactured by BYK Chemie) 0.05 parts

<Evaluation of ink>
The obtained white ink composition was printed on a sheet made of polyvinyl chloride in the same manner as in Example 1, and the integrated exposure amount under the light of an iron-doped ultraviolet lamp (power 120 W / cm ² ). Irradiation was carried out by passing through 240 mJ / cm ² . The printed matter with this ink was evaluated in the same manner as in Example 1. The results are shown in Table 1 below.

Example 8
The following components were stirred with a high-speed water-cooled stirrer to obtain a white ink composition for UV inkjet.
(White ink composition)
・ Phenoxyethyl acrylate 23.0 parts ・ N-vinylcaprolactam 15.0 parts ・ FA-512A [above structure] 18.4 parts ・ Solsperse 36000 (Noveon dispersant) 2.0 parts ・ MICROLITH WHITE R-A 15 0.0 part (Ciba, Specialty, Chemicals pigment)
-Genorad 16 (stabilizer manufactured by Rahn) 0.05 parts-Rapi-Cure DVE-3 8.0 parts (vinyl ether manufactured by ISP Europe)
・ Specific sensitizing dye [I-19 (the following structure)] 4.0 parts ・ Specific compound [A-4 (the above structure)] 2.0 parts ・ Darocur TPO 8.5 parts (Ciba, Specialty, Chemicals, Inc.) Polymerization initiator)
Irgacure 907 [specific polymerization initiator] 4.0 parts (Ciba / Specialty / Chemicals photopolymerization initiator)
・ Byk 307 (defoamer manufactured by BYK Chemie) 0.05 parts

<Evaluation of ink>
The obtained white ink composition was printed on a sheet made of polyvinyl chloride in the same manner as in Example 1, and the integrated exposure amount under the light of an iron-doped ultraviolet lamp (power 120 W / cm ² ). Irradiation was carried out by passing through 240 mJ / cm ² . The printed matter with this ink was evaluated in the same manner as in Example 1. The results are shown in Table 1 below.

Example 9
The following components were stirred with a high-speed water-cooled stirrer to obtain a white ink composition for UV inkjet.
(White ink composition)
・ Phenoxyethyl acrylate 23.0 parts ・ N-vinylcaprolactam 15.0 parts ・ FA-512A [above structure] 18.4 parts ・ Solsperse 36000 (Noveon dispersant) 2.0 parts ・ MICROLITH WHITE R-A 15 0.0 part (Ciba, Specialty, Chemicals pigment)
-Genorad 16 (stabilizer manufactured by Rahn) 0.05 parts-Rapi-Cure DVE-3 8.0 parts (vinyl ether manufactured by ISP Europe)
・ Specific sensitizing dye [I-42 (the following structure)] 4.0 parts ・ Specific compound [A-4 (the above structure)] 2.0 parts ・ Darocur TPO 8.5 parts (Ciba, Specialty, Chemicals, Inc. Polymerization initiator)
Irgacure 2959 4.0 parts (Ciba / Specialty / Chemicals photopolymerization initiator)
・ Byk 307 (defoamer manufactured by BYK Chemie) 0.05 parts

<Evaluation of ink>
The obtained white ink composition was printed on a sheet made of polyvinyl chloride in the same manner as in Example 1, and the integrated exposure amount under the light of an iron-doped ultraviolet lamp (power 120 W / cm ² ). Irradiation was carried out by passing through 240 mJ / cm ² . The printed matter with this ink was evaluated in the same manner as in Example 1. The results are shown in Table 1 below.

Example 10
The following components were stirred with a high-speed water-cooled stirrer to obtain a white ink composition for UV inkjet.
・ Phenoxyethyl acrylate 23.0 parts ・ N-vinylcaprolactam 15.0 parts ・ FA-512A [above structure] 18.4 parts ・ Solsperse 36000 (Noveon dispersant) 2.0 parts ・ MICROLITH WHITE R-A 15 0.0 part (Ciba, Specialty, Chemicals pigment)
-Genorad 16 (stabilizer manufactured by Rahn) 0.05 parts-Rapi-Cure DVE-3 8.0 parts (vinyl ether manufactured by ISP Europe)
Specific sensitizing dye [I-63 (the following structure)] 4.0 parts Specific compound [A-4 (the above structure)] 2.0 parts Irgacure 819 [specific polymerization initiator (P-19)] 5 parts (Ciba / Specialty / Chemicals photopolymerization initiator)
Irgacure 2959 4.0 parts (Ciba / Specialty / Chemicals photopolymerization initiator)
・ Byk 307 (defoamer manufactured by BYK Chemie) 0.05 parts

<Evaluation of ink>
The obtained white ink composition was printed on a sheet made of polyvinyl chloride in the same manner as in Example 1, and the integrated exposure amount under the light of an iron-doped ultraviolet lamp (power 120 W / cm ² ). Irradiation was carried out by passing it to 260 mJ / cm ² . The printed matter with this ink was evaluated in the same manner as in Example 1. The results are shown in Table 1 below.

Example 11
The following components were stirred with a high-speed water-cooled stirrer to obtain a white ink composition for UV inkjet.
(White ink composition)
・ Phenoxyethyl acrylate 23.0 parts ・ N-vinylcaprolactam 15.0 parts ・ FA-512A [above structure] 18.4 parts ・ Solsperse 36000 (Noveon dispersant) 2.0 parts ・ MICROLITH WHITE R-A 15 0.0 part (Ciba, Specialty, Chemicals pigment)
-Genorad 16 (stabilizer manufactured by Rahn) 0.05 part-Rapi-Cure DVE-3 8.0 parts (Ciba-Specialty-Chemicals pigment)
・ Specific sensitizing dye [I-97 (the following structure)] 4.0 parts ・ Specific compound [A-4 (the above structure)] 2.0 parts ・ Irgacure 819 8.5 parts (Ciba, Specialty, Chemicals, Inc. Polymerization initiator)
・ Irgacure 369 [specific polymerization initiator] 4.0 parts (Ciba / Specialty / Chemicals photopolymerization initiator)
・ Byk 307 (defoamer manufactured by BYK Chemie) 0.05 parts

<Evaluation of ink>
The obtained white ink composition was printed on a sheet made of polyvinyl chloride in the same manner as in Example 1, and the integrated exposure amount under the light of an iron-doped ultraviolet lamp (power 120 W / cm ² ). Irradiation was carried out by passing it to 260 mJ / cm ² . The printed matter with this ink was evaluated in the same manner as in Example 1. The results are shown in Table 1 below.

Example 12
The following components were stirred with a high-speed water-cooled stirrer to obtain a white ink composition for UV inkjet.
(White ink composition)
・ Phenoxyethyl acrylate 23.0 parts ・ N-vinylcaprolactam 15.0 parts ・ FA-512A [above structure] 18.4 parts ・ Solsperse 36000 (Noveon dispersant) 2.0 parts ・ MICROLITH WHITE R-A 15 0.0 part (Ciba, Specialty, Chemicals pigment)
-Genorad 16 (stabilizer manufactured by Rahn) 0.05 parts-Rapi-Cure DVE-3 (vinyl ether manufactured by ISP Europe) 8.0 parts-Specific sensitizing dye [I-88 (the following structure)] 4.0 parts Specific compound [A-4 (the above structure)] 2.0 parts Irgacure 819 8.5 parts (Ciba, Specialty, Chemicals photopolymerization initiator)
・ Irgacure 369 [specific polymerization initiator] 4.0 parts (Ciba / Specialty / Chemicals photopolymerization initiator)
・ Byk 307 (defoamer manufactured by BYK Chemie) 0.05 parts

<Evaluation of ink>
The obtained white ink composition was printed on a sheet made of polyvinyl chloride in the same manner as in Example 1, and the integrated exposure amount under the light of an iron-doped ultraviolet lamp (power 120 W / cm ² ). Irradiation was carried out by passing it to 260 mJ / cm ² . The printed matter with this ink was evaluated in the same manner as in Example 1. The results are shown in Table 1 below.

(Comparative Example 1)
The following components were stirred with a high-speed water-cooled stirrer to obtain a comparative cyan ink composition for UV inkjet.
(Cyan ink composition)
・ Light acrylate LA 23.4 parts ・ Atilane 421 32.0 parts (Acrys acrylate monomer)
・ Photomer 2017 (UV diluent made by EChem) 20.0 parts ・ Solsperse 32000 (dispersant made by Noveon) 0.4 parts ・ Irgalite Blue GLVO 3.6 parts (pigment made by Ciba, Specialty, Chemicals)
-Genorad 16 (stabilizer manufactured by Rahn) 0.05 part-Rapi-Cure DVE-3 (vinyl ether manufactured by ISP Europe)
8.0 parts Darocur TPO 8.5 parts (Ciba / Specialty / Chemicals photopolymerization initiator)
Irgacure 907 [specific polymerization initiator] 4.0 parts (Ciba / Specialty / Chemicals photopolymerization initiator)
・ Byk 307 (defoamer manufactured by BYK Chemie) 0.05 parts

<Evaluation of ink>
The resulting cyan ink composition, the integrated exposure amount under rays of Example 1 and was printed to on the polyvinyl chloride sheet Similarly, and iron-doped ultraviolet lamp (power 120 W / cm ²⁾ is Irradiation was carried out by passing it to 1000 mJ / cm ² . The printed matter with this ink was evaluated in the same manner as in Example 1. The results are shown in Table 1 below.

(Comparative Example 2)
The following components were stirred with a high-speed water-cooled stirrer to obtain a cyan ink for UV inkjet.
(Cyan ink composition)
・ Light acrylate L-A 21.4 parts ・ Atilane 421 28.0 parts (Acrys acrylate monomer)
・ Photomer 2017 (UV diluent made by EChem) 20.0 parts ・ Solsperse 32000 (dispersant made by Noveon) 0.4 parts ・ Irgalite Blue GLVO 3.6 parts (pigment made by Ciba, Specialty, Chemicals)
-Genorad 16 (stabilizer manufactured by Rahn) 0.05 part-Rapi-Cure DVE-3 (vinyl ether manufactured by ISP Europe)
8.0 parts, 2-chlorothioxanthone [the following structure] 4.0 parts, specific compound [A-4 (the above structure)] 2.0 parts, Darocur TPO 8.5 parts (Photopolymerization manufactured by Ciba, Specialty, Chemicals) Initiator)
Irgacure 907 [specific polymerization initiator] 4.0 parts (Ciba / Specialty / Chemicals photopolymerization initiator)
・ Byk 307 (defoamer manufactured by BYK Chemie) 0.05 parts

<Evaluation of ink>
The obtained cyan ink composition was printed on a sheet made of polyvinyl chloride in the same manner as in Example 1, and the integrated exposure amount under the light of an iron-doped ultraviolet lamp (power 120 W / cm ² ). Irradiation was carried out by passing it so as to be 300 mJ / cm ² . The printed matter with this ink was evaluated in the same manner as in Example 1. The results are shown in Table 1 below.

(Comparative Example 3)
The following components were stirred with a high-speed water-cooled stirrer to obtain a cyan ink composition for UV inkjet.
(Cyan ink composition)
・ Light acrylate L-A 21.4 parts ・ Atilane 421 28.0 parts (Acrys acrylate monomer)
・ Photomer 2017 (UV diluent made by EChem) 20.0 parts ・ Solsperse 32000 (dispersant made by Noveon) 0.4 parts ・ Irgalite Blue GLVO 3.6 parts (pigment made by Ciba, Specialty, Chemicals)
-Genorad 16 (stabilizer manufactured by Rahn) 0.05 part-Rapi-Cure DVE-3 (vinyl ether manufactured by ISP Europe)
8.0 parts 2,4-diethylthioxanthone [the following structure] 4.0 parts specific compound [A-4 (the above structure)] 2.0 parts Darocur TPO 8.5 parts (manufactured by Ciba Specialty Chemicals) Photopolymerization initiator)
Irgacure 907 [specific polymerization initiator] 4.0 parts (Ciba / Specialty / Chemicals photopolymerization initiator)
・ Byk 307 (defoamer manufactured by BYK Chemie) 0.05 parts

<Evaluation of ink>
The obtained cyan ink composition was printed on a sheet made of polyvinyl chloride in the same manner as in Example 1, and the integrated exposure amount under the light of an iron-doped ultraviolet lamp (power 120 W / cm ² ). Irradiation was carried out by passing it so as to be 280 mJ / cm ² . The printed matter with this ink was evaluated in the same manner as in Example 1. The results are shown in Table 1 below.

[Comparative Example 4]
The following components were stirred with a high-speed water-cooled stirrer to obtain a white ink composition for UV inkjet.
(White ink composition)
・ Phenoxyethyl acrylate 23.0 parts ・ N-vinylcaprolactam 15.0 parts ・ FA-512A [above structure] 17.4 parts ・ Solsperse 36000 (Noveon dispersant) 2.0 parts ・ MICROLITH WHITE R-A 15 .0 parts (Ciba, Specialty, Chemicals pigment)
-Genorad 16 (stabilizer manufactured by Rahn) 0.05 parts-Rapi-Cure DVE-3 8.0 parts (vinyl ether manufactured by ISP Europe)
・ 4.0 parts of 2,4-diethylthioxanthone ・ Specific compound [A-4 (the above structure)] 2.0 parts ・ 8.5 parts of Darocur TPO (Photopolymerization initiator manufactured by Ciba, Specialty, Chemicals)
Irgacure 907 [specific polymerization initiator] 4.0 parts (Ciba / Specialty / Chemicals photopolymerization initiator)
・ Byk 307 (defoamer manufactured by BYK Chemie) 0.05 parts

<Evaluation of ink>
The obtained white ink composition was printed on a sheet made of polyvinyl chloride in the same manner as in Example 1, and the integrated exposure amount under the light of an iron-doped ultraviolet lamp (power 120 W / cm ² ). Irradiation was carried out by passing through 280 mJ / cm ² . The printed matter with this ink was evaluated in the same manner as in Example 1. The results are shown in Table 1 below.

As is apparent from Table 1, the ink compositions of Examples 1 to 12 of the present invention were all cured with high sensitivity and excellent ejection stability.
In addition, since the images formed on the printed materials in Examples 1 and 6 to 12 exhibit a good white color, the ink composition of the present invention is excellent in sensitivity and ejection stability, and is also excellent in color reproducibility. It can be seen that a white ink is obtained.
On the other hand, the ink composition of Comparative Example 1 to which neither the specific compound of the present invention nor the sensitizing dye was added had insufficient curability under the condition of an integrated exposure amount of 270 mJ / cm ² equivalent to Example 1. High energy of 1000 mJ / cm ² was required for sufficient curing. In addition, the ink compositions of Comparative Examples 2, 3, and 4 to which a thioxanthone compound other than the specific sensitizing dye of the present invention was added as a sensitizing dye showed good curability, but had insufficient ejection stability. there were. Further, the white ink of Comparative Example 4 was yellow colored due to the sensitizing dye 2,4-diethylthioxanthone, and thus the color reproducibility of the white image was not good.

Claims (8)

A photocurable composition comprising a polymerizable compound, a compound represented by the following general formula (I), and a compound represented by the following general formula (II).

(In general formula (I), X represents O, S, NR ⁵ , R ⁵ represents a hydrogen atom, an alkyl group or an acyl group. N represents an integer of 0 to 2. R ^{1 to} R ⁴ , Z ^{1 to} Z ⁴ each independently represent a hydrogen atom or a monovalent substituent, and R ^{1 to} R ⁴ may be bonded to each other to form a ring.

(In the general formula (II), ^{X a} represents a hydrogen atom or a monovalent each .R ^1a to R ^5a representing a substituent independently a hydrogen atom or a monovalent substituent, ^{R 4a} and ^{R 5a} are connected to each other To form a ring) The photocurable composition according to claim 1, wherein the compound represented by the general formula (II) is a compound represented by the following general formula (III).

(In the general formula (III), ^Xb is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted R ^1b represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl, and represents a substituted aryloxycarbonyl group or a substituted or unsubstituted carbamoyl group. Oxy group, amino group, substituted or unsubstituted acyl group, substituted or unsubstituted acylamino group, substituted or unsubstituted alkyl and arylsulfonylamino group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxy A carbonyl group or a substituted or unsubstituted .R ^2b is hydrogen atom representing a Bamoiru group, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic oxy group, a substituted Alternatively, it represents an unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted acyloxy group, a substituted or unsubstituted alkoxycarbonyl group, or a substituted or unsubstituted aryloxycarbonyl group, R ^3b and R ^4b represents a hydrogen atom or a monovalent substituent, and R ^3b and R ^4b may be linked to each other to form a condensed ring. The photocurable composition according to claim 2, wherein the compound represented by the general formula (III) is a compound represented by the following general formula (IV).

(In the general formula (IV), ^Xc is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted R ^1c represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl, or a substituted aryloxycarbonyl group or a substituted or unsubstituted carbamoyl group. Oxy group, amino group, substituted or unsubstituted acyl group, substituted or unsubstituted acylamino group, substituted or unsubstituted alkyl and arylsulfonylamino group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxy Carbonyl group or substituted or unsubstituted carbon R ^2c represents a hydrogen atom, halogen atom, substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted acyloxy group, a substituted or unsubstituted alkoxycarbonyl group, or,, .R ^3c to R representing a substituted or unsubstituted aryloxycarbonyl group ^6c represents a hydrogen atom or a monovalent substituent.)   The photocurable composition according to any one of claims 1 to 3, wherein the polymerizable compound is a cationic polymerizable compound.   The photocurable composition according to any one of claims 1 to 4, further comprising a photoacid generator.   The photocurable composition according to claim 5, wherein the photoacid generator is a sulfonium salt compound.   The ink composition containing the photocurable composition of any one of Claims 1-6.   The ink composition according to claim 7, which is for inkjet recording.