JP2009108234A - Photocurable composition, ink composition for inkjet recording, and method for inkjet recording - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photocurable composition, providing a cured product having satisfactory color tone and high fastness to light while avoiding the concern of dispersibility deterioration associated with use of pigment. <P>SOLUTION: The photocurable composition contains a polymerizable compound, a polymerization initiator, and a compound represented by the general formula (I). In the general formula (I), R<SP>1</SP>, R<SP>3</SP>and R<SP>4</SP>each represents independently a hydrogen atom or a monovalent substituent, R<SP>2</SP>represents a monovalent substituent, A represents an atom group which forms a hetero ring together with two carbon atoms bonded thereto, and n represents an integer of 0-4. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a photocurable composition that contains a polymerizable compound, a polymerization initiator, and a dye, and is curable by radiation, an ink composition for ink jet recording using the photocurable composition, and an ink jet recording method. About.

  In recent years, a commonly used water-based ink composition has poor water resistance when printed on plain paper or tends to bleed, and when printed on a non-water-absorbing recording medium such as plastic, Due to poor adhesion of ink droplets, image formation could not be performed, and since drying of the solvent was extremely slow, it was necessary to dry without overlaying the recorded material immediately after printing, or the image was likely to bleed. .

Therefore, an ultraviolet curable ink using a polyfunctional monomer excellent in adhesiveness with a recording medium has been proposed as suitable for printing on a non-water-absorbing recording medium (for example, see Patent Document 1). However, since this ultraviolet curable ink is a water-dispersed ink, it dries slowly and is insufficient for forming a full-color image.
In order to solve this drying property, a method using a volatile organic solvent as the solvent of the ink has been used. However, in order to dry quickly, a solvent having a very high volatility such as methyl ethyl ketone and ethanol is mainly used. It was necessary to use it as a component.

  In addition, an ink jet ink that is cured and fixed by radiation rather than volatilization of a solvent in the ink for printing on a non-water-absorbing recording medium has been proposed (for example, see Patent Document 2). However, since this ink uses a pigment dispersion as a coloring component, the nozzle is clogged due to aggregation of the pigment, and it is difficult to stably eject the ink.

Further, when a pigment is used as the coloring component, there is a problem that transparency is inferior and it is difficult to obtain a photographic image quality due to insufficient color tone. As means for solving this problem, an ultraviolet curable ink using a dye as a coloring component has been proposed (for example, see Patent Documents 3 and 4). However, this ink has a problem that an undesirable polymerization reaction tends to occur during storage of the ink and storage stability is not sufficient. In addition, conventionally, dyes used as substitute components for pigments have insufficient light fastness, and have a problem of fading during and after curing. Further, since this ink contains conductive salts, and these salts may have poor solubility in the ink, there is a concern that they may be deposited in a long-term storage state, resulting in poor printing.
Further, as a photosensitive material using a dye, for example, there is one described in the cited document 5, but this photosensitive material also has a problem that light fastness is still insufficient.
JP-T-2001-512777 Japanese Patent Laid-Open No. 5-214279 U.S. Pat. No. 4,303,924 JP 2003-221530 A JP-A-6-19033

Therefore, the present invention aims to solve the above conventional problems and achieve the following objects.
That is, an object of the present invention is to avoid the concern about the deterioration of dispersibility associated with the use of a pigment, and to provide a photocurable composition having a good color tone and high light fastness, and an ink jet using the photocurable composition. It is to provide a recording ink composition and an ink jet recording method.

The present inventors have found that the above-mentioned problem can be solved by using an oil-soluble dye having excellent light resistance as a coloring component instead of a pigment. That is, the means for solving the above problems are as follows.
That is, the photocured neat organism of the present invention is characterized by containing a polymerizable compound, a polymerization initiator, and a compound represented by the following general formula (I).

In the general formula (I), R ¹ , R ³ , and R ⁴ each independently represent a hydrogen atom or a monovalent substituent, and R ² represents a monovalent substituent. A represents an atomic group that forms a heterocycle with two bonded carbon atoms. n represents an integer of 0 to 4.

  Moreover, it is a preferable aspect that the compound represented by the said general formula (I) is a compound represented by the following general formula (II).

In the general formula (II), R ¹¹ , R ¹³ and R ¹⁴ each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. , R ¹² and R ¹⁵ each independently represents a hydrogen atom or a monovalent substituent. Here, R ¹³ and R ¹⁴ may be bonded to each other to form a 5-membered heterocyclic ring or a 6-membered heterocyclic ring. Z ¹ , Z ² , Z ³ , and Z ⁴ each independently represent a hydrogen atom or a monovalent substituent. Here, Z ¹ and Z ² may be bonded to each other to form a 5-membered ring or a 6-membered ring.

The ink composition for ink-jet recording of the present invention is characterized by using the above-described photocurable composition of the present invention.
The inkjet recording method of the present invention includes (i-1) a step of ejecting the ink composition for inkjet recording according to claim 1 onto a recording medium, and (i-2) ejected inkjet recording. And irradiating the ink composition with actinic radiation to cure the ink composition.

ADVANTAGE OF THE INVENTION According to this invention, the concern of the dispersibility deterioration accompanying pigment utilization is avoided, and it is a photocurable composition which has favorable color tone and high light fastness, and inkjet recording using this photocurable composition An ink composition and an ink jet recording method can be provided.
Moreover, according to the photocurable composition of this invention, the hardened | cured material which has a favorable color tone and high light fastness can be obtained.

The photocurable composition of the present invention comprises a polymerizable compound, a polymerization initiator, and a compound represented by the general formula (I).
The photocurable composition of the present invention is a photocurable composition that can be cured by irradiation with radiation. Here, the “radiation” referred to in the present invention is not particularly limited as long as it can impart energy capable of generating an initial species in the composition by irradiation, and widely used as α-ray, γ-ray, X-rays, ultraviolet rays, visible rays, electron beams and the like are included. Among these, from the viewpoints of curing sensitivity and device availability, ultraviolet rays and electron beams are preferable, and ultraviolet rays are particularly preferable. Therefore, the photocurable composition of the present invention is preferably a photocurable composition that can be cured by irradiating ultraviolet rays as radiation.
Hereinafter, various components constituting the photocurable composition of the present invention will be described.

<Compound represented by formula (I) (specific dye)>
The present invention is characterized in that a compound represented by the following general formula (I) (hereinafter, as appropriate, a specific dye), that is, a monomethine dye having a specific structure is used as a coloring component.
Hereinafter, the specific dye will be described in detail.

In the general formula (I), R ¹ , R ³ , and R ⁴ each independently represent a hydrogen atom or a monovalent substituent, and R ² represents a monovalent substituent. A represents an atomic group that forms a heterocycle with two bonded carbon atoms. n represents an integer of 0 to 4.

Examples of the monovalent substituent represented by R ^{1 to} R ⁴ include a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, and a hydroxyl group. , Nitro 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, heterocycle Thio Sulfamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinyl An amino group, a silyl group, an azo group, or an imide group can be mentioned, and each may further have a substituent.
These monovalent substituents will be described in more detail below.

  A halogen atom represents a chlorine atom, a bromine atom, or an iodine atom. Among these, a chlorine atom or a bromine atom is preferable, and a chlorine atom is particularly preferable.

The alkyl group includes a substituted or unsubstituted alkyl group. The substituted or unsubstituted alkyl group is preferably an alkyl group having 1 to 30 carbon atoms. In the present specification, “carbon number” or “total carbon number” is a numerical value including the number of carbon atoms in a substituent in the case of a group having a substituent.
Examples of the substituent in the case of a substituted alkyl group include a linear or branched alkyl group having 1 to 12 carbon atoms, a linear or branched aralkyl group having 7 to 18 carbon atoms, and a linear chain having 2 to 12 carbon atoms. Or a branched alkenyl group, a linear or branched alkynyl group having 2 to 12 carbon atoms, a linear or branched cycloalkyl group having 3 to 12 carbon atoms, a linear or branched cycloalkenyl group having 3 to 12 carbon atoms ( Each of the above groups is preferably a group having a branched chain for the purpose of improving the solubility of the dye and the stability of the composition, and particularly preferably a group having an asymmetric carbon, such as a methyl group, an ethyl group, a propyl group, Examples include isopropyl group, sec-butyl group, t-butyl group, 2-ethylhexyl group, 2-methylsulfonylethyl group, 3-phenoxypropyl group, trifluoromethyl group, and cyclopentyl group. , Halogen atoms (eg, chlorine atom, bromine atom), aryl groups (eg, phenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl), heterocyclic groups (eg, imidazolyl, pyrazolyl, triazolyl) , 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxyl group, nitro group, amino group, alkyloxy group (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-methylsulfonylethoxy) ), An aryloxy group (for example, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbonylphenoxy, 3-methoxycarbonylphenyloxy, acylamino group (for example, acetamide, Benzamide, 4- (3-t-bu 4-hydroxyphenoxy) butanamide), alkylamino groups (eg methylamino, butylamino, diethylamino, methylbutylamino), arylamino groups (eg phenylamino, 2-chloroanilino), ureido groups (eg phenylureido) , Methylureido, N, N-dibutylureido), sulfamoylamino group (eg, N, N-dipropylsulfamoylamino), alkylthio group (eg, methylthio, octylthio, 2-phenoxyethylthio), arylthio group ( For example, phenylthio, 2-butoxy-5-t-octylphenylthio, 2-carboxyphenylthio), alkyloxycarbonylamino group (for example, methoxycarbonylamino), alkylsulfonylamino group, and arylsulfonyl Amino group (for example, methylsulfonylamino, phenylsulfonylamino, p-toluenesulfonylamino), carbamoyl group (for example, N-ethylcarbamoyl, N, N-dibutylcarbamoyl), sulfamoyl group (for example, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N-phenylsulfamoyl), sulfonyl group (eg, methylsulfonyl, octylsulfonyl, phenylsulfonyl, p-toluenesulfonyl), alkyloxycarbonyl group (eg, methoxycarbonyl, butyloxycarbonyl) ), A heterocyclic oxy group (for example, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), an azo group (for example, phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenyl) Zo, 2-hydroxy-4-propanoylphenylazo), acyloxy group (for example, acetoxy), carbamoyloxy group (for example, N-methylcarbamoyloxy, N-phenylcarbamoyloxy), silyloxy group (for example, trimethylsilyloxy, dibutyl) Methylsilyloxy), aryloxycarbonylamino group (for example, phenoxycarbonylamino), imide group (for example, N-succinimide, N-phthalimide), heterocyclic thio group (for example, 2-benzothiazolylthio, 2,4- Di-phenoxy-1,3,5-triazole-6-thio, 2-pyridylthio), sulfinyl group (eg 3-phenoxypropylsulfinyl), phosphonyl group (eg phenoxyphosphonyl, octyloxyphosphonyl, phenylphospho) Phonyl), aryloxycarbonyl groups (eg, phenoxycarbonyl), acyl groups (eg, acetyl, 3-phenylpropanoyl, benzoyl), ionic hydrophilic groups (eg, carboxyl group, sulfo group, phosphono group, and quaternary) Ammonium group).

The cycloalkyl group includes a substituted or unsubstituted cycloalkyl group.
As the substituted or unsubstituted cycloalkyl group, a cycloalkyl group having 5 to 30 carbon atoms is preferable. Examples of the substituent in the case of the substituted cycloalkyl group include the same ones as those exemplified as the substituent in the case of the aforementioned substituent alkyl group.
Examples of the cycloalkyl group include cyclohexyl, cyclopentyl, and 4-n-dodecylcyclohexyl.

Aralkyl groups include substituted or unsubstituted aralkyl groups.
As the substituted or unsubstituted aralkyl group, an aralkyl group having 7 to 30 carbon atoms is preferable. Examples of the substituent in the case of the substituted aralkyl group are the same as those described as the substituent in the case of the above-described substituent alkyl group.
Examples of the aralkyl group include benzyl and 2-phenethyl.

  An alkenyl group represents a linear, branched, or cyclic substituted or unsubstituted alkenyl group. Preferably, it is a C2-C30 substituted or unsubstituted alkenyl group, for example, vinyl group, allyl group, prenyl group, geranyl group, oleyl group, 2-cyclopenten-1-yl group, 2-cyclohexene-1 -An yl group etc. can be mentioned.

  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, and examples of the substituent in the case of the substituted aryl group are the substituents in the case of the above-described substituent alkyl group. The same thing is mentioned.
Examples of the aryl group include a phenyl group, a p-tolyl group, a naphthyl group, an m-chlorophenyl group, and an o-hexadecanoylaminophenyl group.

A heterocyclic group is a monovalent group obtained by removing one hydrogen atom from a 5-membered or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, and these are further condensed. Also good. More preferably, it is a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. Examples of the substituent in the case of the substituted heterocyclic group are the same as those described as the substituent in the case of the aforementioned substituent alkyl group.
Examples of the heterocyclic group include, but are not limited to, the substitution position, pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzo Groups such as thiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, thiadiazole, isoxazole, benzisoxazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline Is mentioned.

The alkoxy group includes a substituted or unsubstituted alkoxy group.
As a substituted or unsubstituted alkoxy group, a C1-C30 alkoxy group is preferable. Examples of the substituent in the case of the substituted alkoxy group include the same ones as those exemplified as the substituent in the case of the above-described substituent alkyl group.
Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, an n-octyloxy group, a methoxyethoxy group, a hydroxyethoxy group, and a 3-carboxypropoxy group.

The aryloxy group is preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms. Examples of the substituent in the case of a substituted aryloxy group are the same as those described as the substituent in the case of the above-described substituent alkyl group.
Examples of the aryloxy group include phenoxy group, 2-methylphenoxy group, 4-t-butylphenoxy group, 3-nitrophenoxy group, 2-tetradecanoylaminophenoxy group and the like.

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

The heterocyclic oxy group is preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms. Examples of the substituent in the case of the substituted heterocyclic oxy group include the same as those mentioned as the substituent in the case of the aforementioned substituent alkyl group.
Examples of the heterocyclic oxy group include 1-phenyltetrazol-5-oxy group, 2-tetrahydropyranyloxy group 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, and a substituent that can be introduced into these groups. Examples of are the same as those mentioned as the substituent in the case of the aforementioned substituent alkyl group.
Examples of the acyloxy group include formyloxy group, acetyloxy group, pivaloyloxy group, stearoyloxy group, benzoyloxy group, p-methoxyphenylcarbonyloxy group and the like.

The carbamoyloxy group is preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, and examples of the substituent in the case of the substituted carbamoyloxy group are the substituents in the case of the aforementioned substituent alkyl group. The same thing is mentioned.
Examples of the carbamoyloxy group include N, N-dimethylcarbamoyloxy group, N, N-diethylcarbamoyloxy group, morpholinocarbonyloxy group, N, N-di-n-octylaminocarbonyloxy group, Nn-octyl A carbamoyloxy group can be exemplified.

The alkoxycarbonyloxy group is preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms. Examples of the substituent in the case of the substituted alkoxycarbonyloxy group include the substituent in the case of the above-described substituent alkyl group. The same ones are listed.
Examples of the alkoxycarbonyloxy group include groups such as a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a t-butoxycarbonyloxy group, and an n-octylcarbonyloxy group.

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

The amino group is preferably a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, or a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms. The same thing as what was mentioned as a substituent in the case of a substituent alkyl group is mentioned.
Examples of amino groups include amino groups, methylamino groups, dimethylamino groups, anilino groups, N-methyl-anilino groups, diphenylamino groups, hydroxyethylamino groups, carboxyethylamino groups, sulfoethylamino groups, 3, 5-dicarboxyanilino group 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. Examples are the same as those mentioned as the substituent in the case of the aforementioned substituent alkyl group.
Examples of the acylamino group include formylamino group, acetylamino group, pivaloylamino group, lauroylamino group, benzoylamino group, 3,4,5-tri-n-octyloxyphenylcarbonylamino group, and the like.

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

The alkoxycarbonylamino group is preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms. Examples of the substituent in the case of the substituted alkoxycarbonylamino group include the substituent in the case of the above-described substituent alkyl group. The same ones are listed.
Examples of the alkoxycarbonylamino group include methoxycarbonylamino group, ethoxycarbonylamino group, t-butoxycarbonylamino group, n-octadecyloxycarbonylamino group, N-methyl-methoxycarbonylamino group and the like.

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

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

The alkylsulfonylamino group and the arylsulfonylamino group 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, and can be introduced into these groups. As an example of a substituent, the same thing as what was mentioned as a substituent in the case of the above-mentioned substituent alkyl group is mentioned.
Examples of alkylsulfonylamino groups and arylsulfonylamino groups include methylsulfonylamino group, butylsulfonylamino group, phenylsulfonylamino group, 2,3,5-trichlorophenylsulfonylamino group, p-methylphenylsulfonylamino group, and the like. Can be mentioned.

The alkylthio group is preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, and examples of the substituent in the case of the substituted alkylthio group are the same as those mentioned as the substituent in the case of the above-described substituent alkyl group. Things.
Examples of the alkylthio group include a methylthio group, an ethylthio group, and an n-hexadecylthio group.

The arylthio group is preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, and examples of the substituent in the case of the substituted arylthio group are the same as those described as the substituent in the case of the above-described substituent alkyl group. Things.
Examples of the arylthio group include a phenylthio group, a p-chlorophenylthio group, and an m-methoxyphenylthio group.

The heterocyclic thio group is preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms. Examples of the substituent in the case of the substituted heterocyclic thio group include the substituent in the case of the above-described substituent alkyl group. The same as those mentioned above.
Examples of the heterocyclic thio group include a 2-benzothiazolylthio group and a 1-phenyltetrazol-5-ylthio group.

The sulfamoyl group is preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms. Examples of the substituent in the case of the substituted sulfamoyl group are the same as those mentioned as the substituent in the case of the above-described substituent alkyl group. Things.
Examples of the sulfamoyl group include N-ethylsulfamoyl group, N- (3-dodecyloxypropyl) sulfamoyl group, N, N-dimethylsulfamoyl group, N-acetylsulfamoyl group, N-benzoylsulfa A moyl group, an N- (N′-phenylcarbamoyl) sulfamoyl) group, and the like.

The alkylsulfinyl group and arylsulfinyl group 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. The same as those mentioned as the substituent in the case of the above-mentioned substituent alkyl group.
Examples of the alkylsulfinyl group and the arylsulfinyl group include a methylsulfinyl group, an ethylsulfinyl group, a phenylsulfinyl group, and a p-methylphenylsulfinyl group.

The alkylsulfonyl group and the arylsulfonyl group 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. The same as those mentioned as the substituent in the case of the above-mentioned substituent alkyl group.
Examples of the alkylsulfonyl group and the arylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, a phenylsulfonyl group, and a p-toluenesulfonyl group.

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, a substituted or unsubstituted carbon atom having 4 to 30 carbon atoms. A heterocyclic carbonyl group bonded to a carbonyl group is preferable, and examples of the substituent that can be introduced into these are the same as those mentioned as the substituent in the case of the aforementioned substituent alkyl group.
Examples of acyl groups include acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl and the like. Can do.

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

The alkoxycarbonyl group is preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms. Examples of the substituent in the case of the substituted alkoxycarbonyl group include those listed as the substituents in the case of the above-described substituent alkyl group. The same thing is mentioned.
Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a t-butoxycarbonyl group, and an n-octadecyloxycarbonyl group.

The carbamoyl group is preferably a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms. Examples of the substituent in the case of the substituted carbamoyl group are the same as those described above as the substituent in the case of the substituent alkyl group. Things.
Examples of the carbamoyl group include a carbamoyl group, an N-methylcarbamoyl group, an N, N-dimethylcarbamoyl group, an N, N-di-n-octylcarbamoyl group, and an N- (methylsulfonyl) carbamoyl group.

The phosphino group is preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, and examples of the substituent in the case of the substituted phosphino group are the same as those exemplified as the substituent in the case of the above-described substituent alkyl group. Things.
Examples of the phosphino group include a dimethylphosphino group, a diphenylphosphino group, and a methylphenoxyphosphino group.

The phosphinyl group is preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, and examples of the substituent in the case of the substituted phosphinyl group are the same as those mentioned as the substituent in the case of the above-described substituent alkyl group. Things.
Examples of the phosphinyl group include a phosphinyl group, a dioctyloxyphosphinyl group, a diethoxyphosphinyl group, and the like.

The phosphinyloxy group is preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms. Examples of the substituent in the case of the substituted phosphinyl group include the substituent in the case of the above-described substituent alkyl group. The same as those mentioned above.
Examples of the phosphinyloxy group include a diphenoxyphosphinyloxy group and a dioctyloxyphosphinyloxy group.

The phosphinylamino group is preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms. Examples of the substituent in the case of the substituted phosphinyl group include the substituent in the case of the above-described substituent alkyl group. The same as those mentioned above.
Examples of the phosphinylamino group include a dimethoxyphosphinylamino group and a dimethylaminophosphinylamino group.

The silyl group is preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms, and examples of the substituent in the case of the substituted silyl group are the same as those described above as the substituent in the case of the substituent alkyl group. Things.
Examples of the silyl group include a trimethylsilyl group, a t-butyldimethylsilyl group, and a phenyldimethylsilyl group.

  Examples of the azo group include phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo, and the like.

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

Hereinafter, preferable examples of R ^{1 to} R ⁴ , A, and n in the compound represented by the general formula (I) are shown.
In general formula (I), R ¹ is preferably a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms from the viewpoint of availability of synthetic raw materials and light fastness, and more Preferably it is a hydrogen atom.

In general formula (I), R ² is preferably a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, substituted or unsubstituted carbon, from the viewpoint of the availability of synthetic raw materials and light fastness. It is a C1-C6 alkoxy group or a halogen atom.

In general formula (I), R ³ and R ⁴ are each independently preferably a hydrogen atom, a substituted or unsubstituted alkyl group, substituted or unsubstituted, from the viewpoint of the availability of synthetic raw materials, color tone, and light fastness. A substituted alkenyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, more preferably a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. .

  In general formula (I), A represents an atomic group that forms a heterocycle with two bonded carbon atoms. Examples of the heterocycle formed include imidazolone, pyrazolone, oxazolone, isoxazolone, thiazolone, isothiazolone, indrone, and the like. From the viewpoint of color tone and light fastness, an acidic nucleus is preferable. Here, the acidic nucleus is preferably substituted or unsubstituted 2-pyrazolin-5-one.

  In the general formula (I), n represents an integer of 0 to 4, and is preferably an integer of 0 to 2, more preferably an integer of 0 to 1, from the viewpoint of availability of synthetic raw materials and light fastness. is there.

Regarding the preferred combination of R ^{1 to} R ⁴ , A, and n in the compound represented by the general formula (I), at least one of R ^{1 to} R ⁴ , A, and n is the preferred example described above. It is more preferable that two or more are the above preferable examples, and it is most preferable that all are the above preferable examples.

More specifically, A is 2-pyrazolin-5-one having a substituent, R ¹ is a hydrogen atom, R ² is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or substituted or unsubstituted. An alkoxy group having 1 to 6 carbon atoms, R ³ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, R ⁴ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, n = 0 to 2 A combination that is an integer.
More preferable examples of the combination include A-substituted 3-alkoxy-2-pyrazolin-5-one, R ¹ is a hydrogen atom, R ² is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or A substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, R ³ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, R ⁴ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, n = A combination that is an integer of 0 to 1.

Of the compounds represented by the general formula (I), a compound represented by the following general formula (II) is preferable.
Hereinafter, the compound represented by formula (II) will be described.

In the general formula (II), R ¹¹ , R ¹³ and R ¹⁴ each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. , R ¹² and R ¹⁵ each independently represents a hydrogen atom or a monovalent substituent. Here, R ¹³ and R ¹⁴ may be bonded to each other to form a 5-membered heterocyclic ring or a 6-membered heterocyclic ring. Z ¹ , Z ² , Z ³ , and Z ⁴ each independently represent a hydrogen atom or a monovalent substituent. Here, Z ¹ and Z ² may be bonded to each other to form a 5-membered ring or a 6-membered ring.
Here, examples of monovalent substituents represented by R ¹² , R ¹⁵ , Z ¹ , Z ² , Z ³ , and Z ⁴ are represented by R ^{1 to} R ⁴ in the general formula (I). And the same as the monovalent substituent.

In General Formula (II), R ¹¹ is an unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, or R ¹¹ from the viewpoint of solvent solubility and color tone, or A substituted or unsubstituted heterocyclic group having 4 to 12 carbon atoms is preferable, and among them, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, or a substituted or unsubstituted heterocyclic group having 4 to 12 carbon atoms in total. A cyclic group is preferable, and a substituted or unsubstituted benzene ring is particularly preferable.

In the general formula (II), R ¹² is preferably an electron-withdrawing group among monovalent substituents from the viewpoint of color tone and molar absorbance. The electron-withdrawing group herein is preferably an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more. The upper limit is 1.0 or less electron withdrawing group.
Here, Hammett's substituent constant σp value used in the present specification will be described briefly. Hammett's rule was published in 1935, in order to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. P. A rule of thumb proposed by Hammett, which is widely accepted today. Substituent constants determined by Hammett's rule include a σp value and a σm value, and these values can be found in many general books. A. Dean, “Lange's Handbook of Chemistry”, 12th edition, 1979 (Mc Graw-Hill) and “Areas of Chemistry” special edition, 122, 96-103, 1979 (Nankodo). In the present invention, the electron-withdrawing group is limited or explained by Hammett's substituent constant σp, but this is limited to only a substituent having a known value that can be found in the above-mentioned book. Needless to say, it also includes substituents that would be included in the range when measured based on Hammett's rule even if the value is unknown. In the present invention, the compound represented by the general formula (II) is not a benzene derivative, but the σp value is used as a scale indicating the electronic effect of the substituent regardless of the substitution position. In the present invention, the σp value will be used in this sense.

  Specific examples of the electron-withdrawing group having a σp value of 0.20 or more include acyl group, acyloxy group, carbamoyl group, alkyloxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, dialkylphosphono group, diarylphospho group Group, diarylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, halogenated alkyl group, halogenated alkoxy Group, halogenated aryloxy group, halogenated alkylamino group, halogenated alkylthio group, aryl group substituted with other electron-withdrawing group having σp value of 0.20 or more, heterocyclic group, halogen atom, azo group, Or the selenocyanate group Can be mentioned.

Preferred examples of R ¹² include an acyl group having 2 to 12 carbon atoms, an acyloxy group having 2 to 12 carbon atoms, a carbamoyl group having 1 to 12 carbon atoms, an alkyloxycarbonyl group having 2 to 12 carbon atoms, and 7 to 7 carbon atoms. 18 aryloxycarbonyl group, cyano group, nitro group, alkylsulfinyl group having 1 to 12 carbon atoms, arylsulfinyl group having 6 to 18 carbon atoms, alkylsulfonyl group having 1 to 12 carbon atoms, aryl having 6 to 18 carbon atoms Sulfonyl group, C 0-12 sulfamoyl group, C 1-12 halogenated alkyl group, C 1-12 halogenated alkyloxy group, C 1-12 halogenated alkylthio group, C 7-7 18 halogenated aryloxy groups, and aryl groups having 7 to 18 carbon atoms substituted with two or more other electron-withdrawing groups having σp of 0.20 or more And, a nitrogen atom, an oxygen atom, or a 5-membered ring to 8-membered ring having a sulfur atom can be exemplified heterocyclic group having 1 to 18 carbon atoms.

R ¹² is more preferably an acyl group having 2 to 12 carbon atoms, an acyloxy group having 2 to 12 carbon atoms, a carbamoyl group having 1 to 12 carbon atoms, an alkyloxycarbonyl group having 2 to 12 carbon atoms, or 7 to 18 carbon atoms. Aryloxycarbonyl group, cyano group, C1-C12 alkylsulfinyl group, C6-C18 arylsulfinyl group, C1-C12 alkylsulfonyl group, C6-C18 arylsulfonyl group, carbon A sulfamoyl group having 0 to 12 carbon atoms, a halogenated alkyl group having 1 to 12 carbon atoms, and a halogenated alkyloxy group having 1 to 12 carbon atoms.

Particularly preferred as R ¹² is an acyl group having 2 to 12 carbon atoms, an acyloxy group having 2 to 12 carbon atoms, a carbamoyl group having 1 to 12 carbon atoms, an alkyloxycarbonyl group having 2 to 12 carbon atoms, or 7 to 7 carbon atoms. 18 aryloxycarbonyl group, cyano group, alkylsulfonyl group having 1 to 12 carbon atoms, arylsulfonyl group having 6 to 18 carbon atoms, sulfamoyl group having 0 to 12 carbon atoms, and most preferred are those having 2 to 2 carbon atoms. 12 alkyloxycarbonyl groups, and aryloxycarbonyl groups having 7 to 18 carbon atoms.

In the general formula (II), R ¹³ and R ¹⁴ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group from the viewpoint of the availability of synthetic raw materials, color tone, and light fastness. , A substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group is preferable.
R ¹³ and R ¹⁴ may be bonded to each other to form a 5-membered heterocyclic ring or a 6-membered heterocyclic ring. Examples of the 5-membered or 6-membered heterocyclic ring formed include pyrrolidine, piperidine, piperazine, morpholine and the like.

In the general formula (II), R ¹⁵ is preferably a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms in view of the availability of synthetic raw materials and light fastness. A hydrogen atom, a linear alkyl group having 1 to 8 carbon atoms or a branched alkyl group having 1 to 8 carbon atoms is preferable, and a hydrogen atom is most preferable.

In general formula (II), Z ¹ , Z ² , Z ³ , and Z ⁴ are each independently a hydrogen atom, a substituted or unsubstituted total carbon number from the viewpoint of availability of synthetic raw materials and light fastness. An alkyl group having 1 to 12 alkyl groups, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms in total, or a substituted or unsubstituted heterocyclic group having 4 to 12 carbon atoms in total is preferable. Among them, a hydrogen atom or a total A linear alkyl group having 1 to 8 carbon atoms or a branched alkyl group having 1 to 8 carbon atoms in total is preferable, and a hydrogen atom is particularly preferable.
Z ¹ and Z ² may be bonded to each other to form a 5-membered ring or a 6-membered ring. Examples of the 5-membered or 6-membered ring formed include naphthalene, benzothiazole, quinoline, and isoquinoline.

With respect to a preferred combination of R ^{11 to} R ¹⁵ and Z ^{1 to} Z ^{4 in} the compound represented by the general formula (II), at least one of R ^{11 to} R ¹⁵ and Z ^{1 to} Z ⁴ is the preferred example described above. It is preferable that two or more are the above preferable examples, and it is most preferable that all are the above preferable examples.

  Specific examples (exemplary dyes DYE-1 to 25) of the compounds represented by the general formula (I) are shown below, but the present invention is not limited to the following examples.

  Among the above exemplified dyes, DYE-1, DYE-2, DYE-6, DYE-7, DYE-11, DYE-12, DYE-20, DYE-22 are more preferable, and DYE-1, DYE-2, DYE. -12 is more preferable.

  In addition, 0.05-20 mass% is preferable in the photocurable composition whole quantity, and, as for content of the dye represented by the said general formula (I), 0.1-15 mass% is more preferable, 0.2 -6 mass% is still more preferable.

  In addition, in the range which does not prevent the effect of this invention, dyes other than specific dye can be used together for the purpose of hue adjustment. In this case, the other dye is preferably 50% by mass or less, and more preferably 30% by mass or less with respect to the total content of the dye (specific dye + other dye).

<Polymerizable compound>
It is essential that the photocurable composition of the present invention contains a polymerizable compound such as a cationic polymerizable compound or a radical polymerizable compound.

-Cationically polymerizable compound-
The cationically polymerizable compound that can be used in the present invention is preferably a compound that initiates a polymerization reaction with an acid generated from a compound that generates an acid upon irradiation with radiation and cures, and is known as a photocationically polymerizable compound. A known cationic polymerizable monomer 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.
Aromatic epoxides include di- or polyglycidyl ethers produced by the reaction of polyphenols having at least one aromatic nucleus or their alkylene oxide adducts and epichlorohydrin, such as bisphenol A or its alkylene oxides. Examples thereof include di- or polyglycidyl ethers of adducts, di- or polyglycidyl ethers of hydrogenated bisphenol A or its 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 the aliphatic epoxide include dihydric polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof. Typical examples thereof include diglycidyl ether of ethylene glycol, diglycidyl ether of propylene glycol, or 1,6. -Diglycidyl ether of alkylene glycol such as diglycidyl ether of hexanediol, diglycidyl ether of polyhydric alcohol such as di- or triglycidyl ether of glycerin or its alkylene oxide adduct, diglycidyl of polyethylene glycol or its alkylene oxide adduct Diglycidyl ethers of polyalkylene glycols typified by diglycidyl ethers of ethers, polypropylene glycols or alkylene oxide adducts thereof And the like. Here, examples of the alkylene oxide include ethylene oxide and propylene oxide.

The monofunctional and polyfunctional epoxy compounds that can be used in the present invention are exemplified in detail.
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.

  Examples of the vinyl ether compound include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexanedimethanol divinyl ether, and trimethylol. Di- or trivinyl ether compounds such as propane trivinyl ether, ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexane dimethanol monovinyl ether, n-pro Vinyl ether, isopropyl vinyl ether, isopropenyl ether -O- propylene carbonate, dodecyl vinyl ether, diethylene glycol monovinyl ether, and octadecyl vinyl ether.

Below, monofunctional vinyl ether and polyfunctional vinyl ether are illustrated in detail.
Examples of monofunctional vinyl ethers include, for example, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, cyclohexyl methyl vinyl ether, 4 -Methylcyclohexyl methyl vinyl ether, benzyl vinyl ether, dicyclopentenyl vinyl ether, 2-dicyclopentenoxyethyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, butoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, ethoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl D Ter, tetrahydrofurfuryl vinyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxymethylcyclohexyl methyl vinyl ether, diethylene glycol monovinyl ether, polyethylene glycol vinyl ether, chloroethyl vinyl ether, chlorobutyl vinyl ether, chloro Examples thereof include ethoxyethyl 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, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, and bisphenol F. Divinyl ethers such as alkylene oxide divinyl ether; trimethylolethane trivinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl 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, ethylene oxide-added pentaerythritol tetravinyl ether, propylene oxide addition Examples thereof include polyfunctional vinyl ethers such as pentaerythritol tetravinyl ether, ethylene oxide-added dipentaerythritol hexavinyl ether, and propylene oxide-added dipentaerythritol hexavinyl ether.
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 that can be used in the present invention, a known oxetane compound can be arbitrarily selected and used as described in JP-A Nos. 2001-220526, 2001-310937, and 2003-341217. 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 photocurable composition of the present invention include 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 any hydrogen of these alkyl groups 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 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, a linear or branched unsaturated hydrocarbon group, an alkylene group containing a carbonyl group or a carbonyl group, an alkylene group containing a carboxyl group, an alkylene group containing a carbamoyl group, or Represents a group shown below.
Examples of the alkylene group include an ethylene group, a propylene group, and a butylene group. Examples of the poly (alkyleneoxy) group include a poly (ethyleneoxy) group and a poly (propyleneoxy) group. Examples of the unsaturated hydrocarbon group include a propenylene group, a methylpropenylene group, and a butenylene group.

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 group 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.

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

  Examples of the compound having 3 to 4 oxetane rings include a compound represented by the following formula (4).

In the formula ^{(4), R a1} is synonymous with ^{R a1} in the formula (1).
In addition, examples of R ^a9 that is a polyvalent linking group include branched alkylene groups having 1 to 12 carbon atoms such as groups represented by A to C below, and branched poly ( An alkyleneoxy) group, or a branched polysiloxy group such as a group represented by E below. j is 3 or 4.

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

  Another embodiment of the oxetane compound that can be suitably used in the present invention includes a compound represented by the following formula (5) having an oxetane ring in the side chain.

In the formula ^{(5), R a1} has the same meaning as ^{R a1} in Formula ^{(1), R a8} has the same meaning as ^{R a8} in the above formula. 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 cationically polymerizable compound is used in the photocurable composition of the present invention, it is preferably contained in an amount of 60% by mass or more, more preferably 70% by mass or more based on the total solid content of the photocurable composition. . In addition, as an upper limit of the addition amount 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. And any compound having 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, maleic acid, and salts thereof, Examples thereof include radically polymerizable compounds such as anhydrides having a saturated group, 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, tetramethylolmethane tetraacrylate, 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, trimethylol Methacryl derivatives such as tan trimethacrylate, trimethylolpropane trimethacrylate, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane, and other derivatives of allyl compounds such as allyl glycidyl ether, diallyl phthalate, triallyl trimellitate More specifically, Shinzo Yamashita, “Cross-linking agent handbook”, (1981 Taiseisha); Kato Kiyomi, “UV / EB curing handbook (raw material)” (1985, Polymer publication) ); Rad-Tech Study Group, “Application and Market of UV / EB Curing Technology”, p. 79, (1989, CMC); Eiichiro Takiyama, “Polyester Resin Handbook”, (1988, Nikkan Kogyo Shimbun) Commercially available products described in the above, or radically polymerizable or crosslinkable monomers known in the industry, Ligomers and polymers 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. Suitable vinyl ether compounds include, for example, ethylene glycol divinyl ether, ethylene glycol monovinyl ether, diethylene glycol divinyl ether, triethylene glycol monovinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol. Di- or trivinyl ether compounds such as divinyl ether, hexanediol divinyl ether, cyclohexanedimethanol divinyl ether, hydroxyethyl monovinyl ether, hydroxynonyl monovinyl ether, trimethylolpropane trivinyl ether, ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octade Monovinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexanedimethanol monovinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, isopropenyl ether-O-propylene carbonate, dodecyl vinyl ether, diethylene glycol monovinyl ether, octadecyl vinyl ether, etc. Examples include vinyl ether compounds.
Of these vinyl ether compounds, divinyl ether compounds and trivinyl ether compounds are preferable from the viewpoints of curability, adhesion, and surface hardness, and divinyl ether compounds are particularly preferable. 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 used in the photocurable composition of the present invention, the radically polymerizable compound is preferably contained in an amount of 60% by mass or more in the total solid content of the photocurable composition, and 70% by mass or more. Is more preferable. In addition, as an upper limit of the addition amount of a radically polymerizable compound, it is preferable that it is 95 mass% or less.

<Polymerization initiator>
It is essential that the photocurable composition of the present invention contains a polymerization initiator.
The polymerization initiator to be used may be a compound that absorbs external energy and generates a polymerization initiating species, and can be appropriately selected according to the type of the polymerizable compound to be used in combination.
Examples of the polymerization initiator that can be used in the photocurable composition of the present invention include 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, deep ultraviolet light, particularly preferably g-line, h-line, i-line, KrF excimer laser beam), ArF excimer laser beam, electron beam, X-ray, molecule A compound that generates an acid upon irradiation with a line or an ion beam can be appropriately selected and used.

-Compounds that generate acid upon irradiation-
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 radiation as the polymerization initiator. By using these compounds, the polymerization reaction of the cationically polymerizable compound described above is caused by the acid generated by the irradiation of radiation and is cured.

  Examples of such a polymerization initiator include an onium salt compound such as a diazonium salt, a phosphonium salt, a sulfonium salt, and an iodonium salt, which decomposes upon irradiation with radiation, an imide sulfonate, an oxime sulfonate, a diazodisulfone, a disulfone, o -Sulfonate compounds, such as nitrobenzyl sulfonate, etc. can be mentioned.

  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. For example, diazonium salts described in Bal etal, Polymer, 21, 423 (1980), U.S. Pat. Nos. 4,069,055, 4,069,056, Re27,992, JP-A-3-140140, etc. Ammonium salts as described, D. 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, 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 and the like,

  J. et al. V. Crivello et al, Polymer J. et al. 17, 73 (1985), J. MoI. V. Crivello et al. J. et al. Org. Chem. 43, 3055 (1978); R. Watt et al. PolymerSci. , 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, 8-27102 and the like,

  J. et al. V. Crivello et al., Macromolecules, 10 (6), 1307 (1977), J. MoI. V. Crivello et al. PolymerSci. , 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), and organometallic / organic halides described in 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, J.A. 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, 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, JP-A 64-18143, JP-A-2-245756, JP-A-3-140109, etc. Compounds generating an acid, disulfone compounds described in JP-A-61-1166544 and JP-A-2-71270, diazo compounds described in JP-A-3-103854, JP-A-3-103856, and JP-A-4-210960 Examples thereof include ketosulfone and diazodisulfone compounds.

  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., J. MoI. 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, J.A. 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, J.A. Chem. Soc. , (C), 329 (1970), U.S. Pat. No. 3,779,778, European Patent No. 126,712, and the like, 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 formula (b1), (b2), or (b3).

In the formula (b1), R ²⁰¹ , R ²⁰² and R ²⁰³ each independently represents an organic 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 ⁻ , The following groups are exemplified, and an organic anion having a carbon atom is preferable.

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

Rc ¹ represents an organic group.
Examples of the organic group for Rc ¹ include those having 1 to 30 carbon atoms, preferably an alkyl group, a cycloalkyl group, an aryl group, or a plurality of these are a single bond, —O—, —CO ₂ —, —S—. , —SO ₃ —, —SO ₂ N (Rd ¹ ) — and the like.
Rd ¹ represents a hydrogen atom or an alkyl group.

Rc ³ , Rc ⁴ and Rc ⁵ each independently represents an organic group.
Examples of the organic group represented by Rc ³ , Rc ⁴ , and Rc ⁵ are preferably the same as the preferable organic group in Rc ¹ , and most preferably a perfluoroalkyl group having 1 to 4 carbon atoms.
Rc ³ and Rc ⁴ may be bonded to form a ring.
Examples of the group formed by combining Rc ³ and Rc ⁴ include an alkylene group and an arylene group. Preferably, it is a C2-C4 perfluoroalkylene group.

As the organic groups of Rc ¹ and Rc ^{3 to} Rc ⁵ , the most preferred is 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.

The carbon number of the organic group as R ²⁰¹ , R ²⁰² and R ²⁰³ is generally 1 to 30, preferably 1 to 20.
Two of R ^{201 to} R ²⁰³ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. Examples of the group formed by combining two of R ^{201 to} R ²⁰³ include an alkylene group (eg, butylene group, pentylene group).

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

In addition, the compound which has two or more structures represented by the said formula (b1) may be sufficient. For example, at least one of ^R 201 ^{to R 203} of a compound represented by the formula (b1) is at least one directly with ^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

  Further preferred examples of the component (b1) include compounds (b1-1), (b1-2), and (b1-3) described below.

Compound (b1-1) is in which at least one aryl group ^R 201 ^{to R 203} in formula (b1), arylsulfonium compound, i.e., a compound having arylsulfonium as a cation.

In the arylsulfonium compound, all of R ^{201 to} R ²⁰³ may be an aryl group, or a part 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, sec -A butyl group, a t-butyl group, etc. can be mentioned.
The cycloalkyl group that the arylsulfonium compound has as necessary is preferably a cycloalkyl group having 3 to 15 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group.

The aryl group, alkyl group and cycloalkyl group of R ^{201 to} R ²⁰³ are 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, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, or a phenylthio group may be substituted. 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 an aromatic 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, cyclic 2-oxoalkyl group, or an alkoxycarbonylmethyl group, particularly preferably Is a linear, branched 2-oxoalkyl group.

The alkyl group as R ^{201 to} R ²⁰³ may be either linear or branched, and is preferably a linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group). Group, a butyl group, a pentyl group), and a linear, branched 2-oxoalkyl group, and an alkoxycarbonylmethyl group are more preferable.

The cycloalkyl group as R ^{201 to} R ²⁰³ preferably includes a cycloalkyl group having 3 to 10 carbon atoms (cyclopentyl group, cyclohexyl group, norbornyl group), and a cyclic 2-oxoalkyl group is more preferable.

Preferred examples of the linear, branched and cyclic 2-oxoalkyl group represented by R ^{201 to} R ²⁰³ include a group having> C═O at the 2-position of the above alkyl group or cycloalkyl group.
The alkoxy group in the alkoxycarbonylmethyl group as R ^{201 to} R ²⁰³ is preferably an alkoxy group having 1 to 5 carbon atoms (methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group).
R ^{201 to} R ²⁰³ may be further substituted with a halogen atom, an alkoxy group (eg, 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 ^{1c to} R ^5c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, or a halogen atom.
R ^6c and R ^7c 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.
Any two or more of R ^{1c to} R ^5c , R ^6c and R ^7c , and R ^x and R ^y may be bonded to each other to form a ring structure.
Zc ⁻ represents a non-nucleophilic anion, and examples thereof include the same as the non-nucleophilic anion of X ⁻ in formula (b1).

The alkyl group as R ^{1c to} R ^7c may be either linear or branched, and for example, a linear and branched alkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms (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 ^{1c to} R ^7c include cycloalkyl groups having 3 to 8 carbon atoms (for example, a cyclopentyl group and a cyclohexyl group).

The alkoxy group as R ^{1c to} R ^{5c may} be linear, branched or cyclic, for example, an alkoxy group having 1 to 10 carbon atoms, preferably a linear or branched alkoxy group 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), C3-C8 cyclic alkoxy group (for example, cyclopentyloxy group, cyclohexyloxy group) ).

Examples of the group formed by combining any two or more of R ^{1c to} R ^5c , R ^6c and R ^7c , and R ^x and R ^y include a butylene group and a pentylene group. This ring structure may contain an oxygen atom, a sulfur atom, an ester bond, or an amide bond.

Preferably, any one of R ^{1c to} R ^5c 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 ^1c to R ^5c 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 as R ^x and R ^y include the same alkyl groups and cycloalkyl groups as R ^{1c to} R ^7c .
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> C═O at the 2-position of the alkyl group or cycloalkyl group as R ^{1c to} R ^5c .
The alkoxy group in the alkoxycarbonylmethyl group may be the same as the alkoxy group as R ^1c to R ^5c.

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

In 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 as the non-nucleophilic anion of X ⁻ in formula (b1).

The aryl group of R ²⁰⁴ to R ^207, a phenyl group, a naphthyl group, more preferably a phenyl group.
The alkyl group as R ^{204 to} R ²⁰⁷ may be either linear or branched, and is preferably a linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group). Group, butyl group, pentyl group). The cycloalkyl group as R ²⁰⁴ to R ²⁰⁷ is preferably, and a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, norbornyl).
Examples of the substituent that R ^{204 to} R ²⁰⁷ may have include, for example, an alkyl group (eg, having 1 to 15 carbon atoms), a cycloalkyl group (eg, having 3 to 15 carbon atoms), an aryl group (eg, carbon (Chemical formula 6-15), an alkoxy group (for example, C1-C15), a halogen atom, a hydroxyl group, a phenylthio group etc. can be mentioned.

  Examples of the compound that generates an acid upon irradiation with actinic rays or radiation further include compounds represented by the following formulas (b4), (b5), and (b6).

In formulas (b4) to (b6), Ar ³ and Ar ⁴ each independently represent an aryl group.
R ²⁰⁶ , R ²⁰⁷ and R ²⁰⁸ each independently represents an alkyl group, a cycloalkyl group, or an aryl group.
A represents an alkylene group, an alkenylene group, or an arylene group.

  Among the compounds that generate an acid upon irradiation with radiation, preferred are compounds represented by formulas (b1) to (b3). 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 polymerization initiators (compounds that generate an acid upon irradiation with radiation) that can be used in the present invention are listed below, but the present invention is limited to these. Is not to be done.

Further, oxazole derivatives and s-triazine derivatives described in JP-A No. 2002-122994, paragraph numbers [0029] to [0030] are also preferably used.
The onium salt compounds and sulfonate compounds exemplified in JP-A-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 radically polymerizable compound described above is caused by the radicals generated from the radical polymerization initiator, and is cured.

  As radical polymerization initiators, acetophenone derivatives, benzophenone derivatives, benzyl derivatives, benzoin derivatives, benzoin ether derivatives, benzyldialkyl ketal derivatives, thioxanthone derivatives, acylphosphine oxide derivatives, metal complexes, p-dialkylaminobenzoic acids, azo compounds, Peroxide compounds are generally known, among which acetophenone derivatives, benzyl derivatives, benzoin ether derivatives, benzyl dialkyl ketal derivatives, thioxanthone derivatives, acylphosphine oxide derivatives are preferred, acetophenone derivatives, benzoin ether derivatives, benzyl dialkyl ketal derivatives, Acylphosphine oxide derivatives are particularly preferred.

  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-diphenylphosphine oxide, 2,4,6-trichlorobenzoyl diphenylphosphine oxide, 2,4,6-trimethylbenzoyl naphthylphospho Bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -finyl) titanium, p-dimethylaminobenzoic acid, Examples include p-diethylaminobenzoic acid, azobisisobutyronitrile, 1,1′-azobis (1-acetoxy-1-phenylethane), benzoin peroxide, di-tert-butyl peroxide, and the like.

Furthermore, other examples of radical polymerization initiators include photopolymerization initiators described on pages 65 to 148 of "UV Curing System" written by Kiyotsugu Kato (published by 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.

A polymerization initiator can be used individually by 1 type or in combination of 2 or more types.
The content of the polymerization initiator in the photocurable composition is preferably 0.1% by mass to 20% by mass, more preferably 0.5% by mass to 10% by mass in terms of the total solid content of the photocurable composition. %, More preferably 1% by mass to 7% by 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-
Sensitizers are not activated by light irradiation alone, but are more effective when used together with a polymerization initiator than when used alone, and 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 salt Carbon, hexachloroethane, etc.) and the like.

  In the present invention, a sensitizer may be added as necessary for the purpose of improving the acid generation efficiency of the polymerization initiator and increasing the photosensitive wavelength. Any sensitizer may be used as long as it sensitizes the polymerization initiator by an electron transfer mechanism or an energy transfer mechanism. Preferably, aromatic polycondensed compounds such as anthracene, 9,10-dialkoxyanthracene, pyrene and perylene, aromatic ketone compounds such as acetophenone, benzophenone, thioxanthone and Michlerketone, heterocyclic compounds such as phenothiazine and N-aryloxazolidinone Is mentioned.

  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 with respect to the photocurable composition. 1-10 mass% is more preferable, and 0.2-5 mass% is especially preferable.

-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 an ink composition for inkjet recording, it is preferably added for the purpose of controlling ejected physical properties. In the present invention, it is preferable not to use substantially because there is a great concern that the photocurable composition is deposited during storage, but it is possible to increase the solubility of conductive salts or dissolve in the liquid component of the photocurable composition. If the solubility is good by using a highly soluble material, 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 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 adhesion with 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, it is effective to add the solvent within a range that does not cause the problem of solvent resistance and VOC. It is in the range of 1% by mass to 3% by mass.

-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 mass in the photocurable composition. % Is preferable, 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.

The photocurable composition of the present invention uses an oil-soluble dye (specific dye) instead of a pigment as a coloring component, so there is no need to consider the deterioration of dispersibility associated with the use of the pigment, and the photocurable composition More dye can be contained in the inside. Moreover, since the specific dye has high light fastness, the photocurable composition containing the specific dye has a good color tone and high light fastness.
A cured product obtained from such a photocurable composition of the present invention is cured by irradiation with ultraviolet rays or the like, has excellent strength, has high light fastness, and is bright even with a thin film thickness. Color development is obtained. Therefore, the photocurable composition of the present invention is used for various applications such as an ink composition for image formation, formation of an ink receiving layer (image portion) of a lithographic printing plate, a coating material, a sealing material, and an elastomer. Can be applied.
Among these, since the obtained cured product is excellent in color developability and light fastness, it is preferably used as an ink composition, particularly an ink composition for ink jet recording.

  When the photocurable composition of the present invention is used as an ink composition, an image can be formed by applying it to a known recording method (printing method), printing apparatus or the like. The viscosity of the photocurable 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, and more preferably 10 to 80 mPa · s. Is more preferable. Moreover, as surface tension, 20-60 mN / m is preferable and 30-50 mN / m is more preferable.

  The photocurable composition of the present invention is cured with high sensitivity by irradiation with radiation, and the obtained cured product is excellent in color development and light fastness, and can form high-quality images. It is preferable to be used as a composition. Thus, when the photocurable composition of the present invention is used as an ink composition for inkjet recording, the photocurable composition is ejected onto a recording medium by an inkjet printer, and then the ejected photocurable composition is used. Recording is performed by irradiating the composition with radiation to cure.

  In addition, when using the photocurable composition of this invention as an ink composition for inkjet recording, the temperature at the time of discharge (for example, 40 ° C. to 80 ° C., preferably 25 ° C. to 30 ° C., considering discharge properties). ), The viscosity is preferably 7 mPa · s to 30 mPa · s, more preferably 7 mPa · s to 20 mPa · s. For example, the viscosity at room temperature (25 ° C. to 30 ° C.) of the photocurable composition of the present invention 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 photocurable 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.

  When the photocurable composition of the present invention is used as an ink composition for inkjet recording, the surface tension is preferably 20 mN / m to 30 mN / m, more preferably 23 mN / m to 28 mN / m. is there. 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 photocurable composition of the present invention is preferably applied (the ink jet recording method of the present invention) will be described below.
The ink jet recording method of the present invention includes the following two steps.
That is, using the photocurable composition of the present invention as an ink composition for ink jet recording, and discharging the composition onto a recording medium (support, recording material, etc.), and the discharged photocurable composition It is a step of irradiating actinic radiation to cure the photocurable composition. The cured product obtained through these steps becomes an image.

The recording medium applicable to the ink jet recording method of the present invention is not particularly limited, and various non-absorbing 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)
The ink jet recording apparatus applicable to the ink jet recording method of the present invention is not particularly limited, and a commercially available ink jet recording apparatus 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.
The ink supply system includes, for example, an original tank containing the photocurable composition of the present invention (ink composition for inkjet recording of the present invention), a supply pipe, an ink supply tank immediately before the inkjet head, a filter, and a piezo-type inkjet head. The thing which becomes. 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 photocurable composition of the present invention (ink jet recording ink composition of the present invention), preferably has a constant temperature for the ejected ink. Until then, it is preferable that heat insulation and heating can be performed. 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 of the present invention will be described below, but the present invention is not limited to these examples. In the following, “parts” and “%” represent “parts by mass” and “% by mass” unless otherwise specified.

(Example 1-1)
-Preparation of ink 1-1-
The following components were stirred with a high-speed water-cooled stirrer to obtain a yellow UV inkjet ink (ink 1-1).

(Yellow ink)
-Actilane 421 55.8 parts (Akcros acrylate monomer)
・ Photomer 2017 (manufactured by EChem, UV diluent) 20.0 parts ・ Specific dye (previously exemplified dye DYE-1) 3.6 parts ・ Genorad 16 (manufactured by Rahn, stabilizer) 0.05 part ・ Rapi-Cure 4.0 parts of DVE-3 (manufactured by ISP Europe, vinyl ether)
・ Lucirin TPO (manufactured by BASF, photopolymerization initiator) 8.5 parts ・ Benzophenone (photopolymerization initiator) 4.0 parts ・ Irgacure 184 4.0 parts (manufactured by Ciba Specialty Chemicals, photopolymerization initiator)
・ Byk 307 (by anti-foaming agent manufactured by BYK Chemie) 0.05 parts

  The produced yellow ink 1-1 is printed on a PET sheet, and the ink is irradiated by passing it under the light of an iron-doped ultraviolet lamp (power 120 W / cm) at a speed of 40 m / min. Was cured to obtain a printed matter.

(Evaluation of ink)
Regarding the ejection stability and storage stability of the ink 1-1 (photocurable composition) obtained as described above, and the curability and light resistance of the printed matter obtained as described above, Evaluation was performed as follows.

(Curable)
Curability was evaluated by palpation of the image area after the printed material was cured with this ink 1-1.
The evaluation index is as follows.
A: Curability is good (no stickiness).
B: Curability Acceptable (Slightly sticky but not so much as to contaminate the contacted object).
C: Hardness is poor (stickiness is remarkable).

(Light resistance)
The image portion of the printed matter obtained as described above was irradiated with xenon light (140000 lx) for 14 days using a weather meter (Atlas C.I65), and the image density before and after the xenon irradiation was measured using a reflection densitometer (X -Rite310TR), and the dye residual ratio was evaluated.
The evaluation index is as follows.
A: Light resistance is good (dye residual ratio> 80%).
B: Light resistance acceptable (dye residual ratio 40-80%).
C: Poor light resistance (dye residual ratio <40%).

(Discharge stability)
After the ink 1-1 obtained as described above is continuously ejected for 30 minutes using the ink jet printer described below, defects due to nozzle clogging (the presence or absence of unprinted parts) on the printed matter and the setting around the printing dots are set. The presence or absence of minute dots (satellite) that were not observed was visually evaluated.
As an inkjet printer, three shear mode piezo heads (KM512SH manufactured by Konica Minolta, minimum droplet volume 4 pL, nozzle number 512, nozzle density 360 nozzles / 25.4 mm) are arranged as a head, and the nozzles are arranged in a staggered manner. Mounted with 15 sets of one-pass head units (recording width of 542 mm) so that the nozzle density of 1080 dpi head units arranged in the moving direction of the recording medium can be printed in the width direction of the recording medium. It is.
The evaluation index is as follows.
A: No nozzle defect or satellite is generated.
B: Nozzle defects or satellites are slightly generated.
C: Nozzle defects or satellites are remarkably generated.

(Storage stability)
After the ink 1-1 obtained as described above was stored at 75% RH and 60 ° C. for 3 days, the ink viscosity at the discharge temperature (45 ° C.) was measured, and the increase in the ink viscosity was determined as the viscosity ratio. It was evaluated as (ratio of viscosity after storage / viscosity before storage). If the viscosity does not change and is close to 1.0, the storage stability is good, and if it exceeds 1.5, clogging may occur at the time of injection, which is not preferable.
Specific evaluation indexes are as follows.
A: Storage stability is good (viscosity ratio is 1 or more and less than 1.2).
B: Storage stability acceptable (viscosity ratio is 1.2 or more and less than 1.5).
C: Storage stability is poor (viscosity ratio is 1.5 or more).

(Examples 1-2 to 1-5 and Comparative Examples 1-1 to 1-4)
<Preparation of Inks 1-2 to 1-9>
In the preparation of the ink 1-1, except that the specific dye (exemplary dye DYE-1) is replaced with the specific dye, pigment, or comparative dye described below, and other compositions are changed as necessary. In the same manner as in the preparation of the ink 1-1, inks 1-2 to 1-9 were prepared and evaluated.

(Example 1-2)
<Ink 1-2>
Ink 1-2 was prepared using the exemplified dye DYE-6 instead of the exemplified dye DYE-1 as a dye.

(Example 1-3)
<Ink 1-3>
Ink 1-3 was prepared using the exemplified dye DYE-8 instead of the exemplified dye DYE-1 as a dye.

(Example 1-4)
<Ink 1-4>
Ink 1-4 was prepared using the exemplified dye DYE-16 instead of the exemplified dye DYE-1 as a dye.

(Example 1-5)
<Ink 1-5>
Ink 1-5 was prepared using the exemplified dye DYE-22 in place of the exemplified dye DYE-1.

(Comparative Example 1-1)
<Ink 1-6>
Instead of the specific dye (Exemplary dye DYE-1), Chromophthal Yellow LA (Ciba Specialty Chemicals, pigment) is used, and 0.4 part of Solsperse 32000 (Noveon) is added as a dispersant. Ink 1-6 was prepared by changing Actilane 421 (Akcros, acrylate monomer) to 55.4 parts.

(Comparative Example 1-2)
<Ink 1-7>
Ink 1-7 was prepared using Comparative Compound 1 (Comparative Dye) having the following structure instead of Illustrative Dye DYE-1 as a dye.

(Comparative Example 1-3)
<Ink 1-8>
Ink 1-8 was prepared using Comparative Compound 2 (Comparative Dye) having the following structure instead of Illustrative Dye DYE-1 as a dye.

(Comparative Example 1-4)
<Ink 1-9>
Ink 1-9 was prepared using Comparative Compound 3 (Comparative Dye) having the following structure instead of Illustrative Dye DYE-1 as a dye.

  The evaluation results in Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-4 are summarized in Table 1 below.

As is clear from the results in Table 1, the inks (inks 1-1 to 1-5) containing the compound represented by the general formula (I) are compared with the inks using conventional pigments (inks 1-6). It can be seen that the ejection stability, which was a problem, has been greatly improved while the curability, light resistance and storage stability are equivalent.
In addition, it can be seen that light resistance and storage stability are greatly improved as compared with inks using conventional dyes (inks 1-7 to 1-9).

(Examples 2-1 to 2-5 and Comparative Examples 2-1 to 2-4)
-Preparation of inks 2-1 to 2-9-
In the same manner as in Example 1-1, the following components were stirred using a high-speed water-cooled stirrer to obtain yellow UV inkjet inks (inks 2-1 to 2-9).
Note that the coloring components used in the inks 2-1 to 2-9 were the same as those used for the inks 1-1 to 1-9. The used coloring components are shown in Table 2 below.

(Yellow ink)
・ Light acrylate LA 15.4 parts (manufactured by Kyoeisha Chemical Co., Ltd., acrylate monomer)
-Actilane 421 36.4 parts (Akcros acrylate monomer)
・ Photomer 2017 (made by EChem, UV diluent) 20.0 parts ・ Specific dye, pigment, or comparative dye 3.6 parts ・ Genorad 16 (made by Rahn, stabilizer) 0.05 parts ・ Rapi-Cure DVE -3 8.0 parts (made by ISP Europe, vinyl ether)
・ Lucirin TPO (manufactured by BASF, photopolymerization initiator) 8.5 parts ・ Benzophenone (photopolymerization initiator) 4.0 parts ・ Irgacure 184 4.0 parts (manufactured by Ciba Specialty Chemicals, photopolymerization initiator)
-Byk 307 (BYK Chemie company make, antifoamer) 0.05 part The said light acrylate LA is acrylic acid lauryl ester (monofunctional acrylate).

  Ink 2-6 was prepared by adding 0.4 part of Solsperse 32000 (manufactured by Noveon) as a dispersant, and further changing Actilane 421 (manufactured by Akcros, acrylate monomer) to 36.0 parts. .

  The obtained inks 2-1 to 2-9 are evaluated in the same manner as in Example 1-1, and the results are shown in Table 2 below.

As is apparent from the results in Table 2, even when the ink composition is changed, the inks (inks 2-1 to 2-5) containing the compound represented by the general formula (I) are inks using conventional pigments. Compared with (Ink 2-6), it can be seen that the ejection stability was greatly improved.
In addition, as in Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-4, inks 2-1 to 2-5 and conventional dyes (inks 2-7 to 2-9) were used. It can be seen that light resistance and storage stability are greatly improved.

Claims (4)

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

(In general formula (I), R ¹ , R ³ , and R ⁴ each independently represents a hydrogen atom or a monovalent substituent, and R ² represents a monovalent substituent. Represents an atomic group that forms a heterocycle with two carbon atoms in which n represents an integer of 0 to 4.) The photocurable composition according to claim 1, wherein the compound represented by the general formula (I) is a compound represented by the following general formula (II).

(In the general formula (II), R ¹¹ , R ¹³ and R ¹⁴ each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. , R ¹² and R ¹⁵ each independently represents a hydrogen atom or a monovalent substituent, wherein R ¹³ and R ¹⁴ may be bonded to each other to form a 5-membered heterocyclic ring or a 6-membered heterocyclic ring. Z ¹ , Z ² , Z ³ , and Z ⁴ each independently represent a hydrogen atom or a monovalent substituent, wherein Z ¹ and Z ² are bonded to each other to form a 5-membered ring or 6 A member ring may be formed.)   An ink composition for ink-jet recording, wherein the photocurable composition according to claim 1 or 2 is used. (I-1) a step of discharging the ink composition for ink jet recording according to claim 3 onto a recording medium; and
(I-2) a step of irradiating the discharged ink composition for inkjet recording with active radiation to cure the ink composition;
An ink jet recording method comprising: