JP2009114290A - Photocurable composition, inkjet recording ink composition, and method for inkjet-recording - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photocurable composition avoiding risk of deterioration of dispersibility during utilization of a pigment and having good color tone and high light rigidity. <P>SOLUTION: The photocurable composition contains a polymerizable compound, a polymerization initiator, and a dye represented by general formula I, wherein R<SP>1</SP>, R<SP>2</SP>, R<SP>3</SP>and R<SP>4</SP>are each independently a substituted or unsubstituted alkyl group, aryl group or heteroaryl group, R<SP>3</SP>and R<SP>4</SP>may be bonded to each other to form a ring, Z<SP>1</SP>, Z<SP>2</SP>, Z<SP>3</SP>and Z<SP>4</SP>are each independently a hydrogen atom or a monovalent substituent, and Z<SP>1</SP>and Z<SP>2</SP>, and Z<SP>3</SP>and Z<SP>4</SP>may be bonded to each other to form a ring. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a photocurable composition, an ink composition for ink jet recording using the photocurable composition, and an ink jet recording method.

  A water-based ink composition has poor water resistance when printed on plain paper, and is likely to bleed. In addition, when printed on a non-water-absorbing recording material such as plastic, adhesion of ink droplets is poor. For this reason, image formation could not be performed, and drying of the solvent was extremely slow, so that it was necessary to dry without overlapping the recorded material immediately after printing, and the image was liable to blur.

  As a material suitable for printing on a non-water-absorbing recording material, an ultraviolet curable ink using a polyfunctional monomer excellent in adhesiveness to the recording material has been proposed (for example, see Patent Document 1). However, since this ink is a water-dispersed ink, it dries slowly and is insufficient to form a full-color image. In order to solve the drying property, a method using a volatile organic solvent as an ink solvent has been carried out. However, in order to dry quickly, a highly volatile solvent such as methyl ethyl ketone and ethanol is used as a main component. There was a need.

  In order to solve these problems, an ink jet ink that is cured and fixed by radiation instead of volatilization of the ink solvent has been proposed (see, for example, 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.

On the other hand, when a pigment is used as the colorant, the transparency is inferior and the color tone is insufficient, so that it is difficult to obtain a photographic image quality. As means for solving this problem, an ultraviolet curable ink using a dye as a colorant has been proposed (see Patent Document 3). 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, dye compounds conventionally used as an alternative to pigments have insufficient light fastness and have a problem of fading during or after curing. Furthermore, since conductive salts are contained and the solubility in these inks may be poor, there is a concern of poor printing due to precipitation in a long-term storage state.
JP-T-2001-512777 Japanese Patent Laid-Open No. 5-214279 U.S. Pat. No. 4,303,924

  An object of the present invention is to solve the conventional problems and achieve the following objects. That is, the present invention avoids the concern about deterioration of dispersibility associated with the use of pigments, and has a good color tone and high light fastness, and an ink composition for ink jet recording using the photocurable composition. It is an object to provide a product 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 colorant instead of a pigment. That is, the means for solving the above problems are as follows. That is,
<1>
A photocurable composition comprising a polymerizable compound, a polymerization initiator, and a dye represented by the following general formula (I).

In the formula, R ¹ , R ² , R ³ and R ⁴ each independently represent a substituted or unsubstituted alkyl group, aryl group, or heteroaryl group. R ³ and R ⁴ may combine with each other to form a ring. Z ¹ , Z ² , Z ³ and Z ⁴ each independently represent a hydrogen atom or a monovalent substituent. Z ¹ and Z ² , Z ³ and Z ⁴ may be bonded to each other to form a ring.

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

In the formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom or a monovalent substituent. R ¹⁶ and R ¹⁷ each independently represents an alkyl group, an aryl group, or a heteroaryl group, and may be bonded to each other to form a ring.

<3>
An ink composition for inkjet recording, wherein the photocurable composition according to <1> or <2> is used.
<4>
(I-1) A step of ejecting the ink composition for ink jet recording according to <3> above onto a recording medium; and (i-2) irradiating the ejected ink composition for ink jet recording with active radiation. And a step of curing the ink composition.

  ADVANTAGE OF THE INVENTION According to this invention, the photocurable composition which avoids the concern of the dispersibility deterioration accompanying use of a pigment, and has a favorable color tone and high light fastness, and the ink composition for inkjet recording using this photocurable composition Product and an ink jet recording method can be provided.

The photocurable composition of the present invention comprises a polymerizable compound, a polymerization initiator, and a dye represented by the following general formula (I).
The photocurable composition of the present invention avoids the concern of deterioration of dispersibility associated with the use of a pigment, and has a good color tone and high light fastness.

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 viewpoint 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.

<Dye>
The dye used in the present invention is an azomethine dye represented by the following general formula (I).
Hereinafter, the dye represented by formula (I) will be described in detail.

In the general formula (I), R ¹ , R ² , R ³ and R ⁴ each independently represent a substituted or unsubstituted alkyl group, aryl group, or heteroaryl group. R ³ and R ⁴ may combine with each other to form a ring. Z ¹ , Z ² , Z ³ and Z ⁴ each independently represent a hydrogen atom or a monovalent substituent. Z ¹ and Z ² , Z ³ and Z ⁴ may be bonded to each other to form a ring.

In the general formula (I), the substituted or unsubstituted alkyl group represented by R ^{1 to} R ⁴ is a straight chain having 1 to 30 carbon atoms, a branched chain having 3 to 30 carbon atoms, or 3 to 30 carbon atoms. And more preferably a linear alkyl group having 2 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, and a cyclic alkyl group having 3 to 20 carbon atoms, more preferably carbon. A linear alkyl group having 2 to 12 carbon atoms, a branched chain having 3 to 12 carbon atoms, and a cyclic alkyl group having 3 to 12 carbon atoms.

  Specific examples include methyl, ethyl, propyl, isopropyl, sec-butyl, t-butyl, hexyl, octyl, 2-ethylhexyl, dodecyl, cyclopentyl, cyclohexyl, cyclodecyl, and ethyl, isopropyl, sec-butyl, t-butyl. Hexyl, 2-ethylhexyl and cyclohexyl are more preferable, and ethyl, isopropyl, t-butyl, hexyl, 2-ethylhexyl and cyclohexyl are more preferable.

  The alkyl group may further have a substituent, and examples of the substituent that can be introduced 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, and a cyano group. Group, 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) Group), acylamino group (amide group), aminocarbonylamino group (ureido group), alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkylthio group, Thiol group, heterocyclic thio group, sulfamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, phosphino group, phosphinyl group, phosphini Examples include a ruoxy group, a phosphinylamino group, a silyl group, an azo group, or an imide group, a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, and an alkoxy group. Group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, amino group (alkylamino group, arylamino group), acylamino group (amide group), aminocarbonylamino group (ureido group), sulfamoylamino , Alkylsulfonylamino group, arylsulfonylamino group, alkylthio group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, silyl group are more preferable, halogen atom, alkyl group, aryl Group, heterocyclic group, cyano group, hydroxyl group, alkoxy group, silyloxy group, acyloxy group, amino group (alkylamino group, arylamino group), acylamino group (amide group), sulfamoylamino group, alkylthio group, sulfamoyl group More preferably a group, an alkylsulfonyl group, an acyl group, or an alkoxycarbonyl group.

Examples of the substituted or unsubstituted aryl group represented by R ^{1 to} R ⁴ include an aryl group having 6 to 30 carbon atoms, more preferably an aryl group having 6 to 18 carbon atoms, and an aryl having 6 to 12 carbon atoms. More preferred are groups.
As a number, 6-14 is mentioned, 6-10 are more preferable, and 6 is still more preferable.
1-5 are mentioned as a ring number, 1-3 are more preferable, and 1-2 are more preferable. Further, it may be a single ring or a condensed ring.

  In the case of a substituted aryl group, the substituents that can be introduced include halogen atoms, alkyl groups, cycloalkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, cyano groups, hydroxyl groups, nitro groups. , 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, hete Ring thio group, sulfamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, phosphino group, phosphinyl group, phosphinyloxy group, Examples include a phosphinylamino group, a silyl group, an azo group, or an imide group. A halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, an alkoxy group, and an aryloxy group. Group, silyloxy group, acyloxy group, carbamoyloxy group, amino group (alkylamino group, arylamino group), acylamino group (amide group), aminocarbonylamino group (ureido group), sulfamoylamino group, alkylsulfo More preferred are a ruamino group, an arylsulfonylamino group, an alkylthio group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, and a silyl group, and a halogen atom, an alkyl group, an aryl group, a hetero group Ring group, cyano group, hydroxyl group, alkoxy group, silyloxy group, acyloxy group, amino group (alkylamino group, arylamino group), acylamino group (amide group), sulfamoylamino group, alkylthio group, sulfamoyl group, alkyl More preferred are a sulfonyl group, an acyl group, and an alkoxycarbonyl group.

The substituted or unsubstituted heteroaryl group represented by R ¹ to R ^4, include 5 to 30 carbon atoms, more preferably 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms.
As a member, 5-14 is mentioned, 6-10 are more preferable, and 6 is still more preferable.
1-5 are mentioned as a ring number, 1-3 are more preferable, and 1-2 are more preferable. Further, it may be a single ring or a condensed ring.
Examples of the hetero atom include an oxygen atom, a nitrogen atom, and a sulfur atom.

  Specific examples of the heteroaryl group include nitrogen-containing aromatic ring groups such as triazole residues, imidazolyl residues, and pyridinyl residues, sulfur-containing aromatic ring groups such as thiophene residues and thiazole residues, and furan residues. And oxygen-containing aromatic ring groups such as oxazole residues.

  In the case of a substituted heteroaryl group, the substituents that can be introduced include halogen atoms, alkyl groups, cycloalkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, cyano groups, hydroxyl groups, nitro groups. Group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (alkylamino group, arylamino group), acylamino group ( Amide group), aminocarbonylamino group (ureido group), alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkylthio group, arylthio group Heterocyclic thio group, sulfamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, phosphino group, phosphinyl group, phosphinyloxy group Phosphinylamino group, silyl group, azo group or imide group, halogen atom, alkyl group, cycloalkyl group, aralkyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, alkoxy group, aryl Oxy group, silyloxy group, acyloxy group, carbamoyloxy group, amino group (alkylamino group, arylamino group), acylamino group (amide group), aminocarbonylamino group (ureido group), sulfamoylamino group, alkyl A sulfonylamino group, an arylsulfonylamino group, an alkylthio group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, and a silyl group are more preferable, and a halogen atom, an alkyl group, an aryl group, and a hetero group are preferred. Ring group, cyano group, hydroxyl group, alkoxy group, silyloxy group, acyloxy group, amino group (alkylamino group, arylamino group), acylamino group (amide group), sulfamoylamino group, alkylthio group, sulfamoyl group, alkyl More preferred are a sulfonyl group, an acyl group, and an alkoxycarbonyl group.

R ³ and R ⁴ in the general formula (I) can be bonded to each other to form a ring. In this case, the ring that can be formed is preferably a 5-membered ring or a 6-membered ring.

Next, the monovalent substituent represented by Z ^{1 to} Z ⁴ will be described in detail.
Monovalent substituents include halogen atoms, alkyl groups, cycloalkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, cyano groups, hydroxyl groups, nitro groups, alkoxy groups, aryloxy groups, Silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (alkylamino group, arylamino group), acylamino group (amide group), aminocarbonylamino group ( (Ureido group), alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, al Rusulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, silyl A group, an azo group, or an imide group, each of which may further have a substituent.

  The halogen atom represents a chlorine atom, a bromine atom, or an iodine atom. Of these, a chlorine atom or a bromine atom is preferable, and a chlorine atom is more 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, more preferably an alkyl group having 1 to 20 carbon atoms, and further preferably an alkyl group having 1 to 12 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a sec-butyl group, a t-butyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, and a dodecyl group.

  Examples of the substituent that can be introduced into the 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 chain 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 preferably has a branched chain because it improves the solubility of the dye and the stability of the ink, and more preferably has an asymmetric carbon, such as methyl, ethyl, propyl, isopropyl, sec-butyl, t-butyl, 2-ethylhexyl, 2-methylsulfonylethyl, 3-phenoxypropyl, trifluoromethyl, cyclopentyl), halogen Child (for example, chlorine atom, bromine atom), aryl group (for example, phenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl), heterocyclic group (for example, 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), Aryloxy groups (for example, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbonylphenoxy, 3-methoxycarbonylphenyloxy, acylamino groups (for example, acetamide, benzamide, 4- (3-tert-butyl-4-butyl Loxyphenoxy) butanamide), alkylamino groups (eg, methylamino, butylamino, diethylamino, methylbutylamino), arylamino groups (eg, phenylamino, 2-chloroanilino), ureido groups (eg, phenylureido, methylureido, N, N-dibutylureido), sulfamoylamino group (for example, N, N-dipropylsulfamoylamino), alkylthio group (for example, methylthio, octylthio, 2-phenoxyethylthio), arylthio group (for example, phenylthio, 2-butoxy-5-t-octylphenylthio, 2-carboxyphenylthio), alkyloxycarbonylamino group (for example, methoxycarbonylamino), alkylsulfonylamino group and arylsulfonylamino 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 groups (eg methylsulfonyl, octylsulfonyl, phenylsulfonyl, p-toluenesulfonyl), alkyloxycarbonyl groups (eg methoxycarbonyl, butyloxycarbonyl), hetero A ring oxy group (for example, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), an azo group (for example, phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2- Droxy-4-propanoylphenylazo), acyloxy group (for example, acetoxy), carbamoyloxy group (for example, N-methylcarbamoyloxy, N-phenylcarbamoyloxy), silyloxy group (for example, trimethylsilyloxy, dibutylmethylsilyloxy) , 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 (for example, 3-phenoxypropylsulfinyl), phosphonyl group (for example, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl) An aryloxycarbonyl group (for example, phenoxycarbonyl), an acyl group (for example, acetyl, 3-phenylpropanoyl, benzoyl), an ionic hydrophilic group (for example, a carboxyl group, a sulfo group, a phosphono group, and a quaternary ammonium group). Can be mentioned.

The cycloalkyl group includes a substituted or unsubstituted cycloalkyl group. The substituted or unsubstituted cycloalkyl group is preferably a cycloalkyl group having 5 to 30 carbon atoms, more preferably a cycloalkyl group having 5 to 20 carbon atoms, and further preferably a cycloalkyl group having 5 to 12 carbon atoms. Specific examples include cyclohexyl, cyclopentyl, cyclooctyl, cyclodecyl, or 4-n-dodecylcyclohexyl. Examples of the substituent include those similar to the substituents exemplified as the substituent that may be introduced when having an alkyl group is further substituted group represented by Z ¹ to Z ⁴ above.

The aralkyl group includes a substituted or unsubstituted aralkyl group. As the substituted or unsubstituted aralkyl group, an aralkyl group having 7 to 30 carbon atoms is preferable, an aralkyl group having 7 to 20 carbon atoms is more preferable, and an aralkyl group having 7 to 12 carbon atoms is more preferable. Specific examples include benzyl and 2-phenethyl. Examples of the substituent include those similar to the substituents exemplified as the substituent that may be introduced when having an alkyl group is further substituted group represented by Z ¹ to Z ⁴ above.

The alkenyl group represents a linear, branched, or cyclic alkenyl group, and includes a substituted or unsubstituted alkenyl group, respectively. Preferred examples include C2-C30 substituted or unsubstituted alkenyl groups such as vinyl, allyl, prenyl, geranyl, oleyl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl and the like. More preferred is a substituted or unsubstituted alkenyl group having 3 to 20 carbon atoms, and further preferred is a substituted or unsubstituted alkenyl group having 3 to 12 carbon atoms. Examples of the substituent include those similar to the substituents exemplified as the substituent that may be introduced when having an alkyl group is further substituted group represented by Z ¹ to Z ⁴ above.

  The alkynyl group is a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, and examples thereof include ethynyl and propargyl. More preferred is a substituted or unsubstituted alkynyl group having 3 to 18 carbon atoms, and further preferred is a substituted or unsubstituted alkynyl group having 3 to 12 carbon atoms.

The aryl group is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, or o-hexadecanoylaminophenyl. More preferred is a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, and further preferred is a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. Examples of the substituent include those similar to the substituents exemplified as the substituent that may be introduced when having an alkyl group is further substituted group represented by Z ¹ to Z ⁴ above.

The heterocyclic group is a monovalent group obtained by removing one hydrogen atom from a 5- 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 include those similar to the substituents exemplified as the substituent that may be introduced when having an alkyl group is further substituted group represented by Z ¹ to Z ⁴ above.

  Examples of the heterocyclic group include, but are not limited to, substitution positions: pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene Benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, thiadiazole, isoxazole, benzisoxazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline, etc. Can be 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, A C1-C18 alkoxy group is more preferable, A C1-C12 alkoxy group is further more preferable. Examples of the substituent include those similar to the substituents exemplified as the substituent that may be introduced when having an alkyl group is further substituted group represented by Z ¹ to Z ⁴ above. Examples of the alkoxy group include methoxy, ethoxy, isopropoxy, n-octyloxy, methoxyethoxy, hydroxyethoxy and 3-carboxypropoxy.

The aryloxy group is preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, more preferably a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms, and a substituted or unsubstituted group having 6 to 16 carbon atoms. A substituted aryloxy group is more preferred. Examples of the substituent include those similar to the substituents exemplified as the substituent that may be introduced when having an alkyl group is further substituted group represented by Z ¹ to Z ⁴ above. Examples of the aryloxy group include phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy and the like.

  The silyloxy group is preferably a silyloxy group having 3 to 20 carbon atoms, more preferably a silyloxy group having 3 to 16 carbon atoms, and further preferably a silyloxy group having 3 to 9 carbon atoms. Examples thereof include trimethylsilyloxy and t-butyldimethylsilyloxy.

The heterocyclic oxy group is preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, more preferably a substituted or unsubstituted heterocyclic oxy group having 3 to 20 carbon atoms, and 3 to 16 carbon atoms. A substituted or unsubstituted heterocyclic oxy group is more preferable. Examples of the substituent include those similar to the substituents exemplified as the substituent that may be introduced when having an alkyl group is further substituted group represented by Z ¹ to Z ⁴ above.
Examples of the heterocyclic oxy group include 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy and the like.

The acyloxy group is preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, or a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, more preferably 2 carbon atoms. A substituted or unsubstituted alkylcarbonyloxy group having 20 to 20 carbon atoms, and a substituted or unsubstituted arylcarbonyloxy group having 6 to 18 carbon atoms. More preferably, they are a C2-C12 substituted or unsubstituted alkylcarbonyloxy group, and a C6-C12 substituted or unsubstituted arylcarbonyloxy group. Examples of the substituent include those similar to the substituents exemplified as the substituent that may be introduced when having an alkyl group is further substituted group represented by Z ¹ to Z ⁴ above.
Examples of the acyloxy group include formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy and the like.

The carbamoyloxy group is preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, more preferably a substituted or unsubstituted carbamoyloxy group having 3 to 18 carbon atoms, and a substituted or unsubstituted group having 3 to 12 carbon atoms. A substituted carbamoyloxy group is more preferred. Examples of the substituent include those similar to the substituents exemplified as the substituent that may be introduced when having an alkyl group is further substituted group represented by Z ¹ to Z ⁴ above.
Examples of the carbamoyloxy group include, for example, N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyl. Examples include oxy.

The alkoxycarbonyloxy group is preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, more preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 18 carbon atoms, and 2 to 10 carbon atoms. A substituted or unsubstituted alkoxycarbonyloxy group is more preferable. Examples of the substituent include those similar to the substituents exemplified as the substituent that may be introduced when having an alkyl group is further substituted group represented by Z ¹ to Z ⁴ above.
Examples of the alkoxycarbonyloxy group include methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy and the like.

The aryloxycarbonyloxy group is preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, more preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 18 carbon atoms, and a carbon number of 7 Even more preferred are -12 substituted or unsubstituted aryloxycarbonyloxy groups. Examples of the substituent include those similar to the substituents exemplified as the substituent that may be introduced when having an alkyl group is further substituted group represented by Z ¹ to Z ⁴ above.
Examples of the aryloxycarbonyloxy group include phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy and the like.

The amino group is preferably a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms or a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, more preferably a substituted or unsubstituted group having 1 to 18 carbon atoms. A substituted alkylamino group and a substituted or unsubstituted arylamino group having 6 to 18 carbon atoms. More preferably, they are a C1-C12 substituted or unsubstituted alkylamino group, and a C6-C12 substituted or unsubstituted arylamino group. Examples of the substituent include those similar to the substituents exemplified as the substituent that may be introduced when having an alkyl group is further substituted group represented by Z ¹ to Z ⁴ above.
Examples of the amino group include, for example, amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino, hydroxyethylamino, carboxyethylamino, sulfoethylamino, 3,5-dicarboxyanilino And so on.

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, more preferably 1 carbon atom. A substituted or unsubstituted alkylcarbonylamino group having 20 to 20 carbon atoms, and a substituted or unsubstituted arylcarbonylamino group having 6 to 24 carbon atoms. More preferred are a substituted or unsubstituted alkylcarbonylamino group having 1 to 14 carbon atoms and a substituted or unsubstituted arylcarbonylamino group having 6 to 18 carbon atoms. Examples of the substituent include those similar to the substituents exemplified as the substituent that may be introduced when having an alkyl group is further substituted group represented by Z ¹ to Z ⁴ above.
Examples of the acylamino group include formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino, and the like.

The aminocarbonylamino group is preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, more preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 18 carbon atoms, and 3 to 12 carbon atoms. A substituted or unsubstituted aminocarbonylamino group is more preferred. Examples of the substituent include those similar to the substituents exemplified as the substituent that may be introduced when having an alkyl group is further substituted group represented by Z ¹ to Z ⁴ above.
Examples of the aminocarbonylamino group include carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino and the like.

The alkoxycarbonylamino group is preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, more preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 18 carbon atoms, and a substituted group having 2 to 12 carbon atoms. Or an unsubstituted alkoxycarbonylamino group is more preferable. Examples of the substituent include the same substituent that may be introduced when having an alkyl group is further substituted group represented by Z ¹ to Z ⁴ above.
Examples of the alkoxycarbonylamino group include methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino and the like.

The aryloxycarbonylamino group is preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, more preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 24 carbon atoms, and a carbon number of 7 More preferred are -16 substituted or unsubstituted aryloxycarbonylamino groups. Examples of the substituent include the same substituent that may be introduced when having an alkyl group is further substituted group represented by Z ¹ to Z ⁴ above.
Examples of the aryloxycarbonylamino group include phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino and the like.

The sulfamoylamino group is preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, more preferably a substituted or unsubstituted sulfamoylamino group having 1 to 18 carbon atoms, and 2 carbon atoms. Even more preferred are -12 substituted or unsubstituted sulfamoylamino groups. Examples of the substituent include the same substituent that may be introduced when having an alkyl group is further substituted group represented by Z ¹ to Z ⁴ above.
Examples of the sulfamoylamino group include sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino and the like.

The alkylsulfonylamino group and 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. More preferably, they are a C1-C18 substituted or unsubstituted alkylsulfonylamino group, and a C6-C24 substituted or unsubstituted arylsulfonylamino group. More preferred are a substituted or unsubstituted alkylsulfonylamino group having 1 to 12 carbon atoms, and a substituted or unsubstituted arylsulfonylamino group having 6 to 18 carbon atoms. Examples of the substituent include the same substituent that may be introduced when having an alkyl group is further substituted group represented by Z ¹ to Z ⁴ above.
Examples of the alkylsulfonylamino group and arylsulfonylamino group include, for example, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino and the like. Can do.

The alkylthio group is preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, more preferably a substituted or unsubstituted alkylthio group having 1 to 24 carbon atoms, and still more preferably a substituted group having 1 to 16 carbon atoms. Or it is an unsubstituted alkylthio group. Examples of the substituent include the same substituent that may be introduced when having an alkyl group is further substituted group represented by Z ¹ to Z ⁴ above.
Examples of the alkylthio group include methylthio, ethylthio, n-hexadecylthio and the like.

The arylthio group is preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, more preferably a substituted or unsubstituted arylthio group having 6 to 18 carbon atoms, and still more preferably a substituted or unsubstituted arylthio group having 6 to 12 carbon atoms. An unsubstituted arylthio group. Examples of the substituent include the same substituent that may be introduced when having an alkyl group is further substituted group represented by Z ¹ to Z ⁴ above.
Examples of the arylthio group include phenylthio, p-chlorophenylthio, m-methoxyphenylthio and the like.

The heterocyclic thio group is preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, more preferably a substituted or unsubstituted heterocyclic thio group having 3 to 18 carbon atoms, more preferably carbon. It is a substituted or unsubstituted heterocyclic thio group of formula 3-12. Examples of the substituent include the same substituent that may be introduced when having an alkyl group is further substituted group represented by Z ¹ to Z ⁴ above.
Examples of the heterocyclic thio group include 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio and the like.

The sulfamoyl group is preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, more preferably a substituted or unsubstituted sulfamoyl group having 1 to 18 carbon atoms, and further preferably a substituted group having 2 to 12 carbon atoms. Or it is an unsubstituted sulfamoyl group. Examples of the substituent include the same substituent that may be introduced when having an alkyl group is further substituted group represented by Z ¹ to Z ⁴ above.
Examples of the sulfamoyl group include, for example, N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl. N- (N′-phenylcarbamoyl) sulfamoyl 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. More preferred are a substituted or unsubstituted alkylsulfinyl group having 1 to 18 carbon atoms and a substituted or unsubstituted arylsulfinyl group having 6 to 18 carbon atoms. More preferred are a substituted or unsubstituted alkylsulfinyl group having 1 to 12 carbon atoms and a substituted or unsubstituted arylsulfinyl group having 6 to 12 carbon atoms. Examples of the substituent include the same substituent that may be introduced when having an alkyl group is further substituted group represented by Z ¹ to Z ⁴ above.
Examples of the alkylsulfinyl group and arylsulfinyl group include methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl and the like.

The alkylsulfonyl group and 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. More preferably, it is a substituted or unsubstituted alkylsulfonyl group having 1 to 18 carbon atoms, or a substituted or unsubstituted arylsulfonyl group having 6 to 18 carbon atoms. More preferably, it is a substituted or unsubstituted alkylsulfonyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted arylsulfonyl group having 6 to 12 carbon atoms. Examples of the substituent include the same substituent that may be introduced when having an alkyl group is further substituted group represented by Z ¹ to Z ⁴ above.
Examples of the alkylsulfonyl group and arylsulfonyl group include methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-toluenesulfonyl and the like.

The acyl group includes 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, and a substituted or unsubstituted carbon group having 4 to 30 carbon atoms. A heterocyclic carbonyl group bonded to the carbonyl group by an atom is preferred. More preferably, it is a substituted or unsubstituted alkylcarbonyl group having 2 to 24 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 24 carbon atoms, a substituted or unsubstituted carbon atom having 4 to 24 carbon atoms, and a carbonyl group. It is a bonded heterocyclic carbonyl group. More preferably, it is a substituted or unsubstituted alkylcarbonyl group having 2 to 16 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 16 carbon atoms, a carbonyl group at a substituted or unsubstituted carbon atom having 4 to 16 carbon atoms, and It is a bonded heterocyclic carbonyl group. Examples of the substituent include the same substituent that may be introduced when having an alkyl group is further substituted group represented by Z ¹ to Z ⁴ above.
Examples of the acyl group include acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl and the like.

The aryloxycarbonyl group is preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, more preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 18 carbon atoms, and 7 to 12 carbon atoms. A substituted or unsubstituted aryloxycarbonyl group is more preferable. Examples of the substituent include the same substituent that may be introduced when having an alkyl group is further substituted group represented by Z ¹ to Z ⁴ above.
Examples of the aryloxycarbonyl group include phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl, and the like.

The alkoxycarbonyl group is preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, more preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 24 carbon atoms, and a substituted or unsubstituted alkoxy group having 2 to 12 carbon atoms. More preferred is a carbonyl group. Examples of the substituent include the same substituent that may be introduced when having an alkyl group is further substituted group represented by Z ¹ to Z ⁴ above.
Examples of the alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl and the like.

The carbamoyl group is preferably a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms, more preferably a substituted or unsubstituted carbamoyl group having 1 to 18 carbon atoms, and a substituted or unsubstituted carbamoyl group having 2 to 12 carbon atoms. More preferred are groups. Examples of the substituent include the same substituent that may be introduced when having an alkyl group is further substituted group represented by Z ¹ to Z ⁴ above.
Examples of the carbamoyl group include carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl and the like.

The phosphino group is preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, more preferably a substituted or unsubstituted phosphino group having 2 to 16 carbon atoms, and a substituted or unsubstituted phosphino group having 2 to 10 carbon atoms. More preferred are groups. Examples of the substituent include the same substituent that may be introduced when having an alkyl group is further substituted group represented by Z ¹ to Z ⁴ above.
Examples of the phosphino group include dimethylphosphino, diphenylphosphino, methylphenoxyphosphino and the like.

The phosphinyl group is preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, more preferably a substituted or unsubstituted phosphinyl group having 2 to 18 carbon atoms, and a substituted or unsubstituted phosphinyl group having 2 to 12 carbon atoms. More preferred are groups. Examples of the substituent include the same substituent that may be introduced when having an alkyl group is further substituted group represented by Z ¹ to Z ⁴ above.
Examples of the phosphinyl group include phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl and the like.

The phosphinyloxy group is preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, more preferably a substituted or unsubstituted phosphinyloxy group having 2 to 18 carbon atoms, and 2 carbon atoms. More preferred are -12 substituted or unsubstituted phosphinyloxy groups. Examples of the substituent include the same substituent that may be introduced when having an alkyl group is further substituted group represented by Z ¹ to Z ⁴ above.
Examples of the phosphinyloxy group include diphenoxyphosphinyloxy and dioctyloxyphosphinyloxy.

The phosphinylamino group is preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, more preferably a substituted or unsubstituted phosphinylamino group having 2 to 18 carbon atoms, and 2 carbon atoms. More preferred are -12 substituted or unsubstituted phosphinylamino groups. Examples of the substituent include the same substituent that may be introduced when having an alkyl group is further substituted group represented by Z ¹ to Z ⁴ above.
Examples of the phosphinylamino group include dimethoxyphosphinylamino and dimethylaminophosphinylamino.

The silyl group is preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms, more preferably a substituted or unsubstituted silyl group having 3 to 18 carbon atoms, and a substituted or unsubstituted silyl group having 2 to 10 carbon atoms. More preferred are groups. Examples of the substituent include the same substituent that may be introduced when having an alkyl group is further substituted group represented by Z ¹ to Z ⁴ above.
Examples of the silyl group include trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl and the like.

  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.

In the general formula (I), Z ¹ and Z ² , Z ³ and Z ⁴ can be bonded to each other to form a ring. In this case, the ring that can be formed is a 5-membered ring or a 6-membered ring. Is preferred.

As a preferred combination of substituents in the general formula (I), R ¹ is a substituted or unsubstituted alkyl group, R ² is a substituted or unsubstituted aryl group, and R ³ and R ⁴ are substituted or unsubstituted. Z ¹ is a substituted or unsubstituted alkyl group, and Z ² , Z ³ and Z ⁴ are hydrogen atoms.

  Further, from the viewpoint of solubility, the LogP value of the compound represented by the general formula (I) is preferably 6 or more, and more preferably 8 or more.

Of the dyes represented by the general formula (I), a dye represented by the following general formula (II) is preferable.
Hereinafter, the general formula (II) will be described in detail.

In the general formula (II), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom or a monovalent substituent. R ¹⁶ and R ¹⁷ each independently represents an alkyl group, an aryl group, or a heteroaryl group, and may be bonded to each other to form a ring.
In addition, the alkyl group, aryl group, and heteroaryl group represented by R ¹⁶ and R ¹⁷ may further have a substituent when it can be introduced.

In the general formula (II), as the monovalent substituents represented by R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ , the monovalent groups exemplified in Z ^{1 to} Z ⁴ of the general formula (I) And the same substituents as
^As the substituents represented by ^{R 16} and ^{R 17,} the same as those of a substituent mentioned in ^{R 3} and ^{R 4} in the general formula (I).

  Specific examples of the dye represented by the general formula (I) (exemplary dye DYE-1 to 30) are shown below, but the dye used in the present invention is not limited to the following examples.

  Among the above exemplified dyes, DYE-1, DYE-3, DYE-6, DYE-8, DYE-10, DYE-13, DYE-17, and DYE-24 are more preferable, DYE-1, DYE-6, DYE-10 is more preferred.

  The dye represented by the general formula (I) in the present invention has a light fastness with respect to its skeleton, in particular, adjustment of an oxidation potential by introducing / modifying a substituent to the paraphenylenediamine site, and addition of steric hindrance. Various performances can be adjusted by changing structural factors such as improvement and selection of functional groups that avoid polymerization-inhibiting functional groups such as nitro groups. In addition, it is possible to relatively easily realize the change of the structure factor in the skeleton in terms of synthetic chemistry. For example, the dye represented by the general formula (I) may be used in accordance with the structure of the monomer species used together. Fine tuning to an appropriate structure becomes possible.

  The content of the dye represented by the general formula (I) is preferably 0.05 to 20% by mass, more preferably 0.1 to 15% by mass, and more preferably 0.2 to 6% with respect to the total amount of the photocurable composition. More preferred is mass%.

  In addition, in the range which does not prevent the effect of this invention, dyes other than the dye represented by the said general formula (I) can be used together for the purpose of hue adjustment. In this case, the other dye is preferably equal to or less than the dye represented by the general formula (I), and the total content of the dye (the dye represented by the general formula (I) + the other 0.1-40 mass% is preferable with respect to the photocurable composition whole quantity, 0.2-25 mass% is more preferable, and 0.3-12 mass% is further more preferable.

<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 polyhydridyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, and typical examples thereof include diglycidyl ether of ethylene glycol, diglycidyl ether of propylene glycol or 1,6. -Diglycidyl ether of alkylene glycol such as diglycidyl ether of hexanediol, polyglycidyl ether of polyhydric alcohol such as di- or triglycidyl ether of glycerin or its alkylene oxide adduct, diglycidyl of polyethylene glycol or its adduct of alkylene oxide Polyalkylene glycol diglycol represented by diglycidyl ether of ether, polypropylene glycol or its alkylene oxide adduct Jill ether, 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-propyl Pills 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, di- or trivinyl ether compounds are preferable from the viewpoints of curability, adhesion to a recording medium, surface hardness of the formed image, and the like, and divinyl ether compounds are 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, A lower alkyl carboxyl group, a carboxyl group, or a carbamoyl group is represented.
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 Formula (4), R ^a1 has the same ^meaning as in 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 formula (5), R ^a1 has the same meaning as in formula (1), and R ^a8 has the same meaning as in 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 tackiness 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 a cation polymerizable monofunctional monomer in a cation polymerizable compound, 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, Yamashita Junzo, “Crosslinker Handbook”, (1981 Taiseisha); Kato Kiyomi, “UV / EB Curing Handbook (Materials)” (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) A commercially available product as described above or a radically polymerizable or crosslinkable monomer known in the industry, Oligomers 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, octa 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 an acid upon irradiation with actinic rays or radiation include S.P. 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 light, or a compound in which a compound is introduced into the main chain or side chain of the polymer, for example, M.P. 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 above 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 in Rc ¹ include those having 1 to 30 carbon atoms, and 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 preferable one 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 from 1 to 30, preferably 1 to 20.
Two of R ^{201 to} R ²⁰³ may be bonded to form a ring structure, and the 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

  More preferable components (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, and 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. Preferable substituents are a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, and a linear, branched or cyclic alkoxy group having 1 to 12 carbon atoms, and most preferable. 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 represent 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), cyclic alkoxy group having 3 to 8 carbon atoms (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 are preferred, 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 Kayo Kiyomi (General Technology Center Co., Ltd .: 1989). Can be mentioned.
These photopolymerization initiators can be used alone or in combination of two or more, and may be used in combination with a sensitizer described later.

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

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 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 patents, 223739, 309401, 309402, 310551, 310552, 359416, and 3435443. JP, 54-85535, 62-262417, 63-113536, 63-163351, JP-A-2-262654, JP-A-2-71262, Examples thereof include those described in Kaihei 3-121449, 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-
When the photocurable composition of the present invention is used as an ink composition for inkjet recording, conductive salts such as potassium thiocyanate, lithium nitrate, ammonium thiocyanate and dimethylamine hydrochloride are added for the purpose of controlling ejection properties. can do.

-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 the adhesion to a recording medium.
Examples of the solvent include ketone solvents such as acetone, methyl ethyl ketone, and diethyl ketone, alcohol solvents such as methanol, ethanol, 2-propanol, 1-propanol, 1-butanol, and tert-butanol, and chlorine such as chloroform and methylene chloride. Solvents, aromatic solvents such as benzene and toluene, ester solvents such as ethyl acetate, butyl acetate and isopropyl acetate, ether solvents such as diethyl ether, tetrahydrofuran and dioxane, glycols such as ethylene glycol monomethyl ether and ethylene glycol dimethyl ether And 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 present invention in order to adjust film 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, as a copolymer composition of the polymer binder, a copolymer containing “carboxyl group-containing monomer”, “methacrylic acid alkyl ester”, or “acrylic acid alkyl ester” as a structural unit is also preferably used.

-Surfactant-
A surfactant may be added to 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 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 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, leveling additives, matting agents, waxes for adjusting film physical properties, polymerization to inhibit the adhesion to recording media such as polyolefin and PET, and the like, The tackifier which does not do 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.

(Preferred embodiment of the photocurable composition)
When the photocurable composition of the present invention is used as an ink for inkjet recording, the viscosity at the temperature at the time of discharge (for example, 40 ° C. to 80 ° C., preferably 25 ° C. to 30 ° C.) in consideration of discharge properties. However, it 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 monomers and odors can be reduced. Furthermore, it is preferable that ink bleeding at the time of ink droplet landing can be suppressed, and as a result, the image quality is improved.

  The surface tension of the photocurable composition of the present invention is preferably 20 mN / m to 30 mN / m, more preferably 23 mN / m to 28 mN / m. When recording on various recording media such as polyolefin, PET, coated paper, and non-coated paper, 20 mN / m or more is preferable from the viewpoint of bleeding and penetration, and the wettability is preferably 30 mN / m or less.

  The photocurable composition of the present invention is suitably used as an ink composition for ink jet recording. When used as an ink composition for ink jet recording, a photocurable composition is ejected onto a recording medium by an ink jet printer, and then the ejected photocurable composition is cured by irradiation with radiation to perform recording. .

  In the printed matter obtained with this ink, the image portion is cured by irradiation with radiation such as ultraviolet rays, and the strength of the image portion is excellent. Therefore, in addition to image formation with ink, for example, an ink receiving layer (image image of a lithographic printing plate) Part), and can be used for various purposes.

<Inkjet recording method and printed matter>
The ink jet recording method to which the photocurable composition of the present invention is suitably applied (the ink jet recording method of the present invention) will be described below.
The ink jet recording method of the present invention uses the above-described photocurable composition of the present invention as an ink composition for ink jet recording, and discharges the ink composition onto a recording medium (support, recording material, etc.) A step of irradiating the photocurable composition with active radiation to cure the photocurable composition. The cured photocurable composition forms an image on the recording medium.

The recording medium to be applied 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 material applicable to the present invention include a lithographic printing plate support.

Examples of the actinic 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 ink jet recording method of the present invention, the radiation irradiation 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.

  The printed matter obtained by the ink jet recording method of the present invention is an image formed with the photocurable composition of the present invention. Therefore, it becomes a printed matter having an image excellent in light fastness. In addition, since the photocurable composition of the present invention uses an oil-soluble dye instead of a pigment, it is not necessary to consider the deterioration of dispersibility associated with the use of the pigment, and more dye is added to the photocurable composition. It can also be contained. Therefore, a vivid color can be easily obtained even with an image having a small film thickness.

-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. That is, in the present invention, recording can be performed on a recording medium using a commercially available inkjet recording apparatus.
Examples of the ink jet recording apparatus that can be used in the present invention include an ink supply system, a temperature sensor, and an actinic radiation source.
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 the resolution of. In the present invention, dpi represents the number of dots per 2.54 cm.

  As described above, the radiation curable ink such as the ink composition for ink jet recording according to the present invention desirably has a constant temperature for the ejected ink. It is preferred that the temperature can be achieved. 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 in the vicinity of the ink supply tank and the nozzle of the inkjet head. Further, the head unit to be heated is preferably 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 thermal 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.
(Yellow color ink composition)
-Actilane 421 55.8 parts (Akcros acrylate monomer)
・ Photomer 2017 (manufactured by EChem, UV diluent) 20.0 parts ・ Dye (DYE-1) (previously exemplified pigment) 3.6 parts ・ Genorad 16 (manufactured by Rahn, stabilizer) 0.05 part ・ Rapi- Cure DVE-3 4.0 parts (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 color ink is printed on a sheet made of PET, and cured by passing through an iron-doped ultraviolet lamp (power 120 W / cm) at a speed of 40 m / min to cure the ink. A printed matter was obtained.

(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 defects or satellites are 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, the dye (DYE-1) was replaced with the dye or the comparative compound described below, and other compositions were changed as necessary. Ink compositions were prepared and evaluated in the same manner as in the production.

(Example 1-2)
<Ink 1-2>
DYE-6 was used instead of DYE-1 as the dye.

(Example 1-3)
<Ink 1-3>
DYE-10 was used instead of DYE-1 as a dye.

(Example 1-4)
<Ink 1-4>
DYE-13 was used in place of DYE-1 as the dye.

(Example 1-5)
<Ink 1-5>
As a dye, DYE-24 was used instead of DYE-1.

(Comparative Example 1-1)
<Ink 1-6>
In place of the dye (DYE-1), Chrophtal Yellow LA (manufactured by Ciba Specialty Chemicals, pigment) is used as a comparative compound, and 0.4 part of Solsperse 32000 (manufactured by Noveon) is added as a dispersant. Actilane 421 (Akcros, acrylate monomer) was changed to 55.4 parts.

(Comparative Example 1-2)
<Ink 1-7>
Comparative compound A represented by the following structural formula was used in place of the dye (DYE-1).

(Comparative Example 1-3)
<Ink 1-8>
Comparative compound B represented by the following structural formula was used in place of the dye (DYE-1).

(Comparative Example 1-4)
<Ink 1-9>
Comparative compound C represented by the following structural formula was used in place of the dye (DYE-1).

  The evaluation results of the obtained inks 1-1 to 1-9 are summarized in Table 1 below.

As is apparent from the results in Table 1, the inks (inks 1-1 to 1-5) of the present invention containing the dye represented by the general formula (I) are inks using conventional pigments (inks 1-6). It can be seen that the ejection stability, which is a problem, is greatly improved while the curability, light resistance, and storage stability are equivalent to those of
Further, even when the ink 1-1 to 1-5 is compared with the ink using the conventional dye (ink 1-7 to 1-9), the light resistance and the storage stability are greatly improved. Recognize.

(Examples 2-1 to 2-5 and Comparative Examples 2-1 to 2-4)
-Preparation of ink-
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).
The color materials (dyes or pigments) used in inks 2-1 to 2-9 were the same as those used in inks 1-1 to 1-9.
・ Light acrylate LA 15.4 parts (manufactured by Kyoeisha Chemical Co., Ltd., acrylate monomer)
-Actilane 421 36.4 parts (Akcros acrylate monomer)
・ Photomer 2017 (manufactured by EChem, UV diluent) 20.0 parts ・ Coloring material 3.6 parts ・ Genorad 16 (manufactured by Rahn, stabilizer) 0.05 part ・ Rapi-Cure DVE-3 8.0 parts ( 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 Actylene 421 (manufactured by Akcros, acrylate monomer) to 36.0 parts. .

  The results of evaluating the obtained inks 2-1 to 2-9 in the same manner as in Example 1-1 are summarized 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) using the dye of the present invention are ejected in comparison with the conventional pigments (inks 2-6). It can be seen that the stability has been greatly improved.
Further, as in Example 1-1, even when the inks 2-1 to 2-5 and the conventional dyes (inks 2-7 to 2-9) are compared, the light resistance and storage stability are greatly improved. You can see that

Claims (4)

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

(Wherein R ¹ , R ² , R ³ and R ⁴ each independently represents a substituted or unsubstituted alkyl group, aryl group or heteroaryl group. R ³ and R ⁴ are bonded to each other. Z ¹ , Z ² , Z ³ and Z ⁴ each independently represents a hydrogen atom or a monovalent substituent, and Z ¹ and Z ² , Z ³ and Z ⁴ are each They may combine with each other to form a ring.) The photocurable composition according to claim 1, wherein the dye represented by the general formula (I) is a dye represented by the following general formula (II).

(Wherein R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ each independently represents a hydrogen atom or a monovalent substituent. R ¹⁶ and R ¹⁷ each independently represent an alkyl group, aryl, Represents a group or a heteroaryl group, and may be bonded to each other to form a ring.)   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: