JP2008208282A - Photocurable inkjet ink - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sensitive photocurable inkjet ink polymerizing a radically polymerizable compound in a short time due to effective generation of active radicals by irradiating with an energy ray, in particular photo irradiation using a new oxime ester compound as a photopolymerization initiator. <P>SOLUTION: The invention relates to the photocurable inkjet ink comprising at least a monomer, pigment, and the photo polymerization initiator represented by general formula (1) (wherein A and B are each independently H or a monovalent organic residue; X is a mono valent organic residue in the formula; and A and B may be an integrally bonded ring structure). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a photocurable inkjet ink containing a photopolymerization initiator that is cured by light irradiation, and more specifically, by using a diketo oxime ester compound as a photopolymerization initiator, by irradiation with energy rays, particularly light. The present invention relates to a highly sensitive photocurable ink jet ink that can efficiently generate active radicals and polymerize radically polymerizable compounds in a short time.

  Conventionally, ink-jet printing has been widely known, and its greatest feature is that it is good even for recording materials that are not flat because the nozzle for ejecting ink and the non-recording material are in a non-contact state. It is to be able to print. Therefore, this printing method is expected to be applied to various fields.

  In recent years, the UV-IJ technology in which the UV curing technology is fused with the ink jet method has been rapidly developed. Typically, this is a system in which an ink containing a photopolymerization initiator and a polymerizable compound is used to cure the ejected ink after landing on the recording material by light irradiation. This method is useful because it is fast-curing compared to the evaporation drying method and the oxidation drying method. Furthermore, in such a photocurable ink-jet ink, a system that uses an initiator that generates active radicals by ultraviolet light and an acrylate compound can be applied to non-absorbing recording materials such as plastics and metals, It is solventless (VOC-free), and its importance is increasing more and more because it can reduce the environmental load that has been demanded in recent years.

  The curability of the photocurable ink-jet ink greatly depends on the sensitivity of the initiator. If only high speed and high hardness are required, improvement can be expected by increasing the initiator content in the formulation, for example. However, since many of the initiators have poor solubility, they are deposited when used in a large amount and cause clogging of the nozzle. Furthermore, since the initiator or the component derived from the initiator causes odor after curing, it is not desirable to use it excessively. In addition, for example, means for improving the curability by using a strong light irradiation device or a plurality of light irradiation devices or extending the irradiation time can be considered, but these impose a very heavy load on the production process. Accordingly, there is a need for an initiator that can achieve sufficient curing characteristics with a lower content.

  Benzyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, and acylphosphine oxide compounds are disclosed as photoradical polymerization initiators used in photocurable inkjet inks (Patent Documents 1 to 9). In recent years, α-ketoxime ester compounds have also been disclosed as initiators (see Patent Documents 10 to 14). All of these can function as polymerization initiators, but it cannot be said that the above-mentioned requirements are sufficiently satisfied, and the high sensitivity of polymerization initiators to improve productivity and various newly proposed processes. There is a universal need for it.

JP-A-8-2180817 JP 2002-356737 A JP 2003-012971 A JP 2004-027211 A JP 2002-241654 A JP 2002-187343 A JP 2004-124077 A JP 2005-187343 A JP 2004-175906 A JP 2006-232968 A JP 2006-241406 A JP 2006-249154 A JP 2006-249155 A

  The object of the present invention is to use a diketo-type oxime ester compound as a photoinitiator, thereby efficiently generating active radicals upon irradiation with energy rays, particularly light, and capable of polymerizing radically polymerizable compounds in a short time. It is in providing a photocurable ink-jet ink.

  As a result of intensive studies to solve the above problems, the present inventors have arrived at the present invention. That is, the present invention relates to a photocurable inkjet ink comprising at least a monomer, a pigment, and a photopolymerization initiator represented by the following general formula (1).

General formula (1)

(In the formula, A and B each independently represent a hydrogen atom or a monovalent organic residue, X represents a monovalent organic residue, and A and B are cyclically bonded together. It may be a structure.)

  In the present invention, the photopolymerization initiators A and B each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. The present invention relates to a curable inkjet ink.

  The present invention also relates to a photocurable inkjet ink in which A and B of the photopolymerization initiator are each independently a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group.

  The present invention also relates to a photocurable inkjet ink in which A and B of the photopolymerization initiator are each independently a substituted or unsubstituted condensed polycyclic hydrocarbon group or a substituted or unsubstituted heterocyclic group. .

  The present invention also relates to a photocurable inkjet kinking in which A of the photopolymerization initiator is a substituted or unsubstituted carbazolyl group or a substituted or unsubstituted naphthyl group.

  Further, the present invention provides a photocurable inkjet ink wherein A of the photopolymerization initiator is a group represented by the following general formula (2) which is substituted or unsubstituted, or a general formula (3) which is substituted or unsubstituted. About.

General formula (2)

(In general formula (2), Y represents a monovalent organic residue.)

General formula (3)

  Further, in the present invention, A in the photopolymerization initiator is a group represented by the following general formula (2) which is substituted or unsubstituted, and B is represented by the following general formula (3) which is substituted or unsubstituted. The present invention relates to a photocurable inkjet ink which is a group to be used.

General formula (2)

(In general formula (2), Y represents a monovalent organic residue.)

General formula (3)

  Moreover, this invention relates to the manufacturing method of printed matter which prints the said photocurable inkjet ink and makes it harden | cure by light irradiation.

  Moreover, this invention relates to the printed matter obtained with said manufacturing method.

  The photocurable ink-jet ink of the present invention can obtain sufficient curing with less light irradiation as compared with a photocurable ink-jet ink containing a conventional oxime ester as a photopolymerization initiator. As a result, the production process can be improved.

  The photocurable inkjet ink of the present invention comprises a monomer, a pigment, and the above photopolymerization initiator. Various additives (for example, other photopolymerization initiators, photosensitizers, polymerization inhibitors, etc.) can also be used in combination.

  First, the photopolymerization initiator will be described. The photopolymerization initiator of the present invention is characterized by having a structure represented by the general formula (1). In general formula (1), A and B each independently represent a hydrogen atom or a monovalent organic residue. A and B may be combined to form a ring.

  Monovalent organic residues include substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, substituted or unsubstituted alkenyl groups, substituted or unsubstituted alkynyl groups, substituted or unsubstituted alkoxy groups, substituted Or an unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted acyloxy group, a substituted or unsubstituted alkylsulfanyl group, a substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted alkyl Sulfinyl group, substituted or unsubstituted arylsulfinyl group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted acyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted Substituted carbamoyl , A substituted or unsubstituted sulfamoyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted heterocyclic group, substituted or is phosphinoyl group unsubstituted and the like, but is not limited thereto.

  As the substituted or unsubstituted alkyl group, an alkyl group having 1 to 30 carbon atoms is preferable. For example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, Decyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, tetrafluoroethyl group, phenylmethyl Group, diphenylmethyl group, trityl group, 2-phenylethyl group, methoxymethyl group, cyanomethyl group and the like, but are not limited thereto.

  The substituted or unsubstituted aryl group is preferably an aryl group having 6 to 40 carbon atoms, and includes a phenyl group, 2-methylphenyl group, 2-ethylphenyl group, 2-propylphenyl group, 2-isopropylphenyl group, 2- Butylphenyl group, 2-isobutylphenyl group, 2-sec-butylphenyl group, 2-t-butylphenyl group, 2-chlorophenyl group, 2-fluorophenyl group, 2-methoxyphenyl group, 3-chlorophenyl group, 3- Fluorophenyl group, 3-trifluoromethylphenyl group, 3-nitrophenyl group, 3-cyanophenyl group, 3-methoxycarbonylphenyl group, 4-methylphenyl group, 4-ethylphenyl group, 4-propylphenyl group, 4 -Isopropylphenyl group, 4-t-butylphenyl group, 4-methoxyphenyl group, 4-sia Phenyl group, 4-chlorophenyl group, 4-fluorophenyl group, 4-trifluoromethylphenyl group, 4-dimethylaminophenyl group, 4-methylsulfanylphenyl group, 4-phenylsulfanylphenyl group, 2,4-dimethylphenyl group 2,4-dimethoxyphenyl group, 2,4-dichlorophenyl group, 2,4-difluorophenyl group, 3,4-ethylenedioxyphenyl group, 2,4,6-trimethylphenyl group, 2,4,6- Trifluorophenyl group, 2,3,4,5,6-pentafluorophenyl group, 1-naphthoyl group, 2-naphthoyl group, biphenyl group, indenyl group, naphthoquinonyl group, indanonyl group, azulenyl group, terphenyl group, quarter Phenyl group, binaphthalenyl group, pentarenyl group, heptalenyl group, bif Nylenyl group, indacenyl group, acenaphthylenyl group, fluorenyl group, phenalenyl group, phenanthryl group, anthracenyl group, anthraquinonyl group, fluoranthenyl group, acephenatrirenyl group, aceanthrylenyl group, triphenylenyl group, pyrenyl group, chrysenyl group, tetracenyl group Group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, hexaphenyl group, hexacenyl group, rubicenyl group, coronenyl group, trinaphthylenyl group, heptaphenyl group, heptacenyl group, pyrantrenyl group , An ovalenyl group, a dibenzosuberonyl group, and the like, but are not limited thereto.

The substituted or unsubstituted alkenyl group is preferably an alkenyl group having 2 to 30 carbon atoms, such as a vinyl group, 1-methylvinyl group, 2-methylvinyl group, 2,2-dimethylvinyl group, 1-phenylvinyl. Group, 2-phenylvinyl group (styryl group), 2-thienylvinyl group, 2-furanylvinyl group, 2,2-diphenylvinyl group, 2,2-difluorovinyl group, 1,2,2-trifluorovinyl group, 2-benzoylvinyl group, 2-methoxycarbonylvinyl group, 2-ethoxycarbonylvinyl group, 1-propenyl group, allyl group, 2-butenyl group, 3-butenyl group, isopropenyl group, isobutenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, cyclopentyl group Thenyl group, cyclohexenyl group, a cycloalkyl pentenoyl groups, cyclohexenol alkanoyl group, allenyl group, 1,3-butadienyl group, 4-methyl _- 1,3 _- butadienyl group, 4-phenyl-1,3-butadienyl group, 4 -Phenyl-1,3-butadienyl group, cyclopentadienyl group, cyclohexadienyl group and the like are exemplified, but not limited thereto.

  The substituted or unsubstituted alkynyl group is preferably an alkynyl group having 2 to 30 carbon atoms. For example, ethynyl group, methylethynyl group, ethylethynyl group, isopropylethynyl group, t-butylethynyl group, phenylethynyl group, 4- Phenylsulfanylphenylethynyl group, 4-benzoylphenylethynyl group, cyclopropylethynyl group, cycloptylethynyl group, cyclopentylethynyl group, cyclohexylethynyl group methoxyethynyl group, vinylethynyl group, trimethylsilylethynyl group, triethylsilyletynyl group, t-butyl Dimethylsilylethynyl group, triisopropylsilylethynyl group, methoxyethynyl group, ethoxyethynyl group, benzoylethynyl group, naphthoylethynyl group, propargyl group, 3-butynyl (homopro Rugiru) group, pentynyl group, hexynyl group, Puropajiiniru group, and a phenylpropanoid Jiini Le group, but is not limited thereto.

  As the substituted or unsubstituted alkoxy group, an alkoxy group having 1 to 30 carbon atoms is preferable. For example, methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group, isobutoxy group, sec-butoxy group, t- Butoxy, pentyloxy, isopentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, methoxycarbonylmethyloxy, ethoxycarbonylmethyloxy, vinyloxy, benzyloxy, tri Fluoromethyloxy group, tetrahydropyranyloxy group, N, N-dibutylaminocarbonylmethyloxy group, N-methylaminocarbonylmethyloxy group, N-ethylaminocarbonylmethyloxy group, N-methyl-N-benzylaminocarbonyl Yloxy group, a benzyloxy group, cyanomethyl group, 1-phenylvinyl group, 2-but-phenylvinyl group, and the like, but is not limited thereto.

  The substituted or unsubstituted aryloxy group is preferably an aryloxy group having 1 to 30 carbon atoms, such as a phenyloxy group, a 2-methylphenyloxy group, a 2-ethylphenyloxy group, a 2-propylphenyloxy group, 2-isopropylphenyloxy group, 2-butylphenyloxy group, 2-isobutylphenyloxy group, 2-sec-butylphenyloxy group, 2-t-butylphenyloxy group, 2-chlorophenyloxy group, 2-fluorophenyloxy Group, 2-methoxyphenyloxy group, 3-chlorophenyloxy group, 3-fluorophenyloxy group, 3-trifluoromethylphenyloxy group, 3-nitrophenyloxy group, 3-cyanophenyloxy group, 3-methoxycarbonylphenyl Oxy group, 4-methylphenyloxy group 4-ethylphenyloxy group, 4-propylphenyloxy group, 4-isopropylphenyloxy group, 4-t-butylphenyloxy group, 4-methoxyphenyloxy group, 4-cyanophenyloxy group, 4-chlorophenyloxy group, 4-fluorophenyloxy group, 4-trifluoromethylphenyloxy group, 4-dimethylaminophenyloxy group, 4-methylsulfanylphenyloxy group, 4-phenylsulfanylphenyloxy group, 2,4-dimethylphenyloxy group, 2 , 4-Dimethoxyphenyloxy group, 2,4-dichlorophenyloxy group, 2,4-difluorophenyloxy group, 3,4-ethylenedioxyphenyloxy group, 2,4,6-trimethylphenyloxy group, 2,4 , 6-trifluorophenyloxy group, 2 3,4,5,6 pentafluorophenyl group, 1-naphthoyloxy group, 2-naphthoyloxy group, although a biphenyl group, and the like, but is not limited thereto.

  Examples of the heterocyclic oxy group include a monocyclic or condensed polycyclic heterocyclic oxy group containing a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Specific examples include a 2-furanyloxy group and a 2-thienyloxy group. 2-indolyloxy group, 3-indolyloxy group, 2-benzofuryloxy group, 2-benzothienyloxy group, 2-carbazolyloxy group, 3-carbazolyloxy group, 4-carbazolyl group Examples thereof include, but are not limited to, an oxy group and a 9-acridinyloxy group.

  As the substituted or unsubstituted acyloxy group, an acyloxy group having 2 to 30 carbon atoms is preferable. For example, an acetyloxy group, a propanoyloxy group, a butanoyloxy group, a pentanoyloxy group, a hexanoyloxy group, a cyclohexylcarbonyloxy group. Group, trifluoromethylcarbonyloxy group, vinyloxy group, 2-phenylvinyloxy group, isopropenoyloxy group, benzoyloxy group, toluoyloxy group, 3-phenylcarbonylbenzoyloxy group, 3-phenylsulfanylbenzoyloxy group, 4-phenylcarbonylbenzoyloxy group, 4-phenylsulfanylbenzoyloxy group, thenoyloxy group, furoyloxy group, 1-naphthylcarbonyloxy group, 2-naphthylcarbonyloxy group, 2-anthracoxy Ylcarbonyl group, 2-thio-key but Sante alkanoyloxy group, and the like, but is not limited thereto.

  The substituted or unsubstituted alkylsulfanyl group is preferably an alkylsulfanyl group having 1 to 20 carbon atoms. For example, a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, an isopropylsulfanyl group, a butylsulfanyl group, an isobutylsulfanyl group, sec -Butylsulfanyl group, t-butylsulfanyl group, 1-ethylpentylsulfanyl group, hexylsulfanyl group, cyclohexylsulfanyl group, octylsulfanyl group, 2-ethylhexylsulfanyl group, benzylsulfanyl group, cyanomethylsulfanyl group, methoxymethylsulfanyl group, Examples include trifluoromethylsulfanyl group, tetrafluoroethylsulfanyl group, vinylsulfanyl group, 2-phenylvinylsulfanyl group and the like. However, it is not limited to these.

  The substituted or unsubstituted arylsulfanyl group is preferably an arylsulfanyl group having 6 to 30 carbon atoms, such as a phenylsulfanyl group, a 2-methylphenylsulfanyl group, a 2-ethylphenylsulfanyl group, a 2-butylphenylsulfanyl group, 2-chlorophenylsulfanyl group, 2-methoxyphenylsulfanyl group, 3-chlorophenylsulfanyl group, 3-trifluoromethylphenylsulfanyl group, 3-cyanophenylsulfanyl group, 3-nitrophenylsulfanyl group, 3-benzoylphenylsulfanyl group, 4 -Methylphenylsulfanyl group, 4-fluorophenylsulfanyl group, 4-cyanophenylsulfanyl group, 4-methoxyphenylsulfanyl group, 4-dimethylaminophenylsulfan Group, 4-benzoylphenylsulfanyl group, 2,4-dimethylphenylsulfanyl group, 2,4,6-trimethylphenylsulfanyl group, 1-naphthoylsulfanyl group, 2-naphthoylsulfanyl group, etc. It is not limited to.

  The substituted or unsubstituted alkylsulfinyl group is preferably an alkylsulfinyl group having 1 to 30 carbon atoms, such as methylsulfinyl group, ethylsulfinyl group, propylsulfinyl group, butylsulfinyl group, pentylsulfinyl group, hexylsulfinyl group, heptyl. Sulfinyl group, octylsulfinyl group, nonylsulfinyl group, decylsulfinyl group, isopropylsulfinyl group, isobutylsulfinyl group, sec-butylsulfinyl group, t-butylsulfinyl group, 1-ethylpentylsulfinyl group, cyclopropylsulfinyl group, cyclobutylsulfinyl group Group, cyclopentylsulfinyl group, cyclohexylsulfinyl group, trifluoromethylsulfinyl group, tetrafluoroethylsulfinyl group, Examples include phenylmethylsulfinyl group, diphenylmethylsulfinyl group, triphenylmethylsulfinyl group, 2-phenylethylsulfinyl group, methoxymethylsulfinyl group, cyanomethylsulfinyl group, 2-phenylvinylsulfinyl group, vinylmethylsulfinyl group, etc. It is not limited to these.

  The substituted or unsubstituted arylsulfinyl group is preferably an arylsulfinyl group having 6 to 30 carbon atoms, such as a phenylsulfinyl group, 2-methylphenylsulfinyl group, 2-ethylphenylsulfinyl group, 2-butylphenylsulfinyl group, 2-chlorophenylsulfinyl group, 2-methoxyphenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group, 3-nitrophenylsulfinyl group, 3-benzoylphenylsulfinyl group, 4 -Methylphenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-cyanophenylsulfinyl group, 4-methoxyphenylsulfinyl group, 4-dimethylaminophenylsulfinyl group Group, 4-benzoylphenylsulfinyl group, 4-phenylsulfanylphenylsulfinyl group, 2,4-dimethylphenylsulfinyl group, 2,4,6-trimethylphenylsulfinyl group, 1-naphthoylsulfinyl group, 2-naphthoylsulfinyl group Group, biphenylsulfinyl group, and the like, but are not limited thereto.

  The alkylsulfonyl group which may have a substituent is preferably an alkylsulfonyl group having 1 to 20 carbon atoms. For example, a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group. Group, cyclohexylsulfonyl group, octylsulfonyl group, 2-ethylhexylsulfonyl group, decanoylsulfonyl group, dodecanoylsulfonyl group, octadecanoylsulfonyl group, cyanomethylsulfonyl group, methoxymethylsulfonyl group, etc. Is not to be done.

  The arylsulfonyl group which may have a substituent is preferably an arylsulfonyl group having 6 to 30 carbon atoms, such as a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 2-naphthylsulfonyl group, a 2-chlorophenylsulfonyl group, 2-methylphenylsulfonyl group, 2-methoxyphenylsulfonyl group, 2-butoxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-nitrophenylsulfonyl group, 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-methoxyphenylsulfonyl group, 4-methylsulfanylphenylsulfonyl group, 4-phenylsulfanylphenylsulfonyl group, 4-dimethylaminopheny Sulfonyl groups and the like, but not limited thereto.

  The substituted or unsubstituted acyl group is preferably an acyl group having 2 to 20 carbon atoms, for example, an acetyl group, a propanoyl group, a butanoyl group, a trifluoromethylcarbonyl group, a pentanoyl group, a benzoyl group, a 1-naphthoyl group, 2 -Naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2-methoxybenzoyl group, 2 -Butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group, 4-methoxybenzoyl group, furoyl Group, thenoyl group 2 Antorakinoiru group, 2-thio-key Sante alkanoyl group, such as N- ethyl-carbazolyl group, and the like, but not limited thereto.

  The substituted or unsubstituted alkoxycarbonyl group or aryloxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 30 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, or a hexyloxycarbonyl group. Octyloxycarbonyl group, decyloxycarbonyl group, octadecyloxycarbonyl group, phenoxycarbonyl group, trifluoromethyloxycarbonyl group, benzyloxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-methylsulfanyl Phenyloxycarbonyl group, 4-phenylsulfanylphenyloxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyl group Nyloxycarbonyl group, 2-chlorophenyloxycarbonyl group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxycarbonyl group, 3-chlorophenyloxycarbonyl group, 3-trifluoromethylphenyloxy Examples include carbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 4-fluorophenyloxycarbonyl group, 4-cyanophenyloxycarbonyl group, 4-methoxyphenyloxycarbonyl group, etc. It is not limited.

  The carbamoyl group which may have a substituent is preferably a carbamoyl group having 1 to 30 carbon atoms, for example, an N-methylcarbamoyl group, an N-ethylcarbamoyl group, an N-propylcarbamoyl group, or an N-butylcarbamoyl group. N-hexylcarbamoyl group, N-cyclohexylcarbamoyl group, N-octylcarbamoyl group, N-decylcarbamoyl group, N-octadecylcarbamoyl group, N-phenylcarbamoyl group, N-2-methylphenylcarbamoyl group, N-2- Chlorophenylcarbamoyl group, N-2-isopropoxyphenylcarbamoyl group, N-2- (2-ethylhexyl) phenylcarbamoyl group, N-3-chlorophenylcarbamoyl group, N-3-nitrophenylcarbamoyl group, N-3-cyanophenyl A carbamoyl group, -4-methoxyphenylcarbamoyl group, N-4-cyanophenylcarbamoyl group, N-4-methylsulfanylphenylcarbamoyl group, N-4-phenylsulfanylphenylcarbamoyl group, N-methyl-N-phenylcarbamoyl group, N, N -Dimethylcarbamoyl group, N, N-dibutylcarbamoyl group, N, N-diphenylcarbamoyl group and the like are exemplified, but not limited thereto.

The sulfamoyl group which may have a substituent is preferably a sulfamoyl group having 0 to 30 carbon atoms, for example, a sulfamoyl group, an N-alkylsulfamoyl group, an N-arylsulfamoyl group, N, N- Examples thereof include a dialkylsulfamoyl group, an N, N-diarylsulfamoyl group, and an N-alkyl-N-arylsulfamoyl group. More specifically, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-butylsulfamoyl group, N-hexylsulfamoyl group, N-cyclohexylsulfur group. Famoyl group, N-octylsulfamoyl group, N-2-ethylhexylsulfamoyl group, N-decylsulfamoyl group, N-octadecylsulfamoyl group, N-phenylsulfamoyl group, N-2- Methylphenylsulfamoyl group, N-2-chlorophenylsulfamoyl group, N-2-methoxyphenylsulfamoyl group, N-2-isopropoxyphenylsulfamoyl group, N-3-chlorophenylsulfamoyl group, N-3-nitrophenylsulfamoyl group, N-3-cyanophenylsulfamoyl group, N-4-methoxyphenyl Nylsulfamoyl group, N-4-cyanophenylsulfamoyl group, N-4-dimethylaminophenylsulfamoyl group, N-4-methylsulfanylphenylsulfamoyl group, N-4-phenylsulfanylphenylsulfamoyl Group, N-methyl-N-phenylsulfamoyl group, N, N-dimethylsulfamoyl group, N, N-dibutylsulfamoyl group, N, N-diphenylsulfamoyl group and the like. It is not limited to.

The substituted or unsubstituted amino group is preferably an amino group having 0 to 50 carbon atoms in total, for example, —NH ₂ , N-alkylamino group, N-arylamino group, N-acylamino group, N-sulfonylamino group. N, N-dialkylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, N, N-disulfonylamino group and the like. More specifically, N-methylamino group, N-ethylamino group, N-propylamino group, N-isopropylamino group, N-butylamino group, Nt-butylamino group, N-hexylamino group, N-cyclohexylamino group, N-octylamino group, N-2-ethylhexylamino group, N-decylamino group, N-octadecylamino group, N-benzylamino group, N-phenylamino group, N-2-methylphenylamino Group, N-2-chlorophenylamino group, N-2-methoxyphenylamino group, N-2-isopropoxyphenylamino group, N-2- (2-ethylhexyl) phenylamino group, N-3-chlorophenylamino group, N-3-nitrophenylamino group, N-3-cyanophenylamino group, N-3-trifluoromethylphenylamino group, -4-methoxyphenylamino group, N-4-cyanophenylamino group, N-4-trifluoromethylphenylamino group, N-4-methylsulfanylphenylamino group, N-4-phenylsulfanylphenylamino group, N- 4-dimethylaminophenylamino group, N-methyl-N-phenylamino group, N, N-dimethylamino group, N, N-diethylamino group, N, N-dibutylamino group, N, N-diphenylamino group, N N-diacetylamino group, N, N-dibenzoylamino group, N, N- (dibutylcarbonyl) amino group, N, N- (dimethylsulfonyl) amino group, N, N- (diethylsulfonyl) amino group, N , N- (dibutylsulfonyl) amino group, N, N- (diphenylsulfonyl) amino group and the like. No.

  As the substituted or unsubstituted heterocyclic group, an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom is preferable. For example, pyrrolidinyl group, piperidinyl group, piperazinyl group, morpholinyl group, furyl group, thienyl group, 2H-pyrrolyl group, N-methylpyrrolyl group, pyrrolyl group, pyridyl group, pyrimidinyl group, pyridazinyl group, pyrazinyl group, 1,2,4 -Triazinyl group, 1,2,3-triazinyl group, 1,3,5-triazinyl group, 1,4-dioxinyl group, 1,4-dithiinyl group, 1,4-oxathiinyl group, dihydropyrazinyl group, 7 -Oxabicyclo [2,2,1] hepter 2,5-dienyl group, pyranyl group, thiopyranyl group, 2H-pyranonyl group, 2H-thiopyranonyl group, 4H-pyranonyl group, 4H-thiopyranonyl group, pyridinonyl group, oxazolyl group , Isoxazolyl group, thiazolyl group, isothiazolyl group, pyrazolyl group, 2H-pi Zolyl group, 3H-pyrazolyl group, imidazolyl group, 2H-imidazolyl group, 3H-imidazolyl group, N-methylimidazolyl group, oxadiazolyl group, 1,3,4-thiadiazolyl group, 1,3,5-thiadiazolyl group, flazanyl group Tetrazolyl group, N-methyltetrazolyl group, benzofuranyl group, benzothienyl group, 2H-indolyl group, 3H-indolyl group, indolyl group, N-methylindolyl group, isobenzofuranyl group, isobenzothienyl group, 2H-isoindolyl group, isoindolyl group, N-methylisoindolyl group, quinolinyl (quinolyl) group, isoquinolinyl group, quinazolinyl group, cinnolinyl group, quinoxalinyl group, phthalazinyl group, quinolidinyl group, naphthyridinyl group, pteridinyl group, pyrazinopyrazinyl Le Zodioxidyl group, benzodithiinyl group, benzooxathiinyl group, isochromenyl group, isothiochromenyl group, isochromalinyl group, isothiochromalinyl group, isocarbostyryl group, chromenyl group, thiochromenyl group, coumarinyl group, thiochromalinyl group, carbostyryl group, 4H-chromenyl group, 4H-thiochromenyl group, chromonyl group, thiochromonyl group, quinolonyl group, echinopsinyl group, benzoxazolyl group, benzoisoxazolyl group, benzothiazolyl group, benzisothiazolyl group, indazolyl group, 3H-indazolyl group Group, N-methylindazolyl group, benzimidazolyl group, 2H-benzoimidazolyl group, N-methylbenzimidazolyl group, benzotriazolyl group, N-methyltriazolyl group, purinyl group, benzoti Asiazolyl group, isoindolonyl group, indronyl group, phthalimide group, dibenzofuranyl group, dibenzothienyl group, carbazolyl group, N-methylcarbazolyl group, N-ethylcarbazolyl group, β-carbolinyl group, xanthenyl group, thioxanthenyl group, Dihydroacridinyl group, xanthonyl group, thioxanthonyl, acridonyl group, oxatrenyl group, thiantenyl group, dihydrophenazinyl group, phenoxathinyl group, phenoxazinyl group, phenothiazinyl group, acridinyl group, iminostilbenyl group, N- Methyliminostilbenyl group, phenazyl group, antiridinyl group, phenanthridinyl group, benzoquinolinyl group, phenanthrolinyl group, perimidinyl group, thebenidinyl group, benzophenanthridinyl group, indoloquino Group, India lower chestnut isoxazolidinyl group, and a isoindolinone Rope Limited isoxazolidinyl group, but is not limited thereto.

  The phosphinoyl group which may have a substituent is preferably a phosphinoyl group having 2 to 50 carbon atoms, for example, dimethylphosphinoyl group, diethylphosphinoyl group, dipropylphosphinoyl group, diphenylphosphinoyl group. Group, dimethoxyphosphinoyl group, diethoxyphosphinoyl group, dibenzoylphosphinoyl group, bis (2,4,6-trimethylphenyl) phosphinoyl group and the like.

  Alkyl group, aryl group, alkenyl group, alkynyl group, alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, aryl described above Substituents that the sulfonyl group, acyl group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, amino group, heterocyclic group, phosphinoyl group and the like may have include hydroxyl group, mercapto group, cyano group, nitro group, halogen Atom, alkyl group, aryl group, heterocyclic group, acyl group, alkoxyl group, aryloxy group, heterocyclic oxy group, acyloxy group, alkylthio group, arylthio group, heterocyclic thio group, amino group, alkylamino group, dialkylamino Base Arylamino group, diarylamino group, an alkylaryl group, benzylamino group, dibenzylamino group and the like.

  Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Examples of the alkyl group include linear, branched, monocyclic or condensed polycyclic alkyl groups having 1 to 18 carbon atoms, and specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, octadecyl group, isopropyl group, isobutyl group, isopentyl group, sec-butyl group, tert-butyl group, sec-pentyl group, tert-pentyl group Tert-octyl group, neopentyl group, cyclopropyl group, cyclobutyl, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, 4-decylcyclohexyl group and the like.

  Examples of the aryl group include monocyclic or condensed polycyclic aryl groups having 6 to 18 carbon atoms. Specific examples include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, and a 9-phenanthryl group. 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 1-acenaphthyl group, 9-fluorenyl group and the like.

  Examples of the heterocyclic group include a monocyclic or condensed polycyclic heterocyclic group containing a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Specific examples include a 2-furanyl group, a 2-thienyl group, 2- Indolyl group, 3-indolyl group, 2-benzofuryl group, 2-benzothienyl group, 2-carbazolyl group, 3-carbazolyl group, 4-carbazolyl group, 9-acridinyl group and the like can be mentioned.

  The acyl group includes a hydrogen atom, a carbonyl group to which a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded, or a monocyclic or condensed polyvalent group having 6 to 18 carbon atoms. Examples include a carbonyl group to which a cyclic aryl group is bonded, a carbonyl group to which a monocyclic or condensed polycyclic heterocyclic group having 4 to 18 carbon atoms is bonded, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. It may have an unsaturated bond, and specific examples thereof include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, myristoyl group, palmitoyl group , Stearoyl group, cyclopentylcarbonyl group, cyclohexylcarbonyl group, acryloyl group, methacryloyl group, croto Yl group, isocrotonoyl group, oleoyl group, benzoyl group, 2-methylbenzoyl group, 4-methoxybenzoyl group, 1-naphthoyl group, 2-naphthoyl group, cinnamoyl group, 3-furoyl group, 2-thenoyl group, nicotinoyl group , Isonicotinoyl group, 9-anthroyl group, 5-naphthacenoyl group and the like.

  Examples of the alkoxyl group include linear, branched, monocyclic or condensed polycyclic alkoxyl groups having 1 to 18 carbon atoms, and specific examples include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy. Group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, isopropoxy group, isobutoxy group, isopentyloxy group, sec-butoxy group, t-butoxy group, sec-pentyloxy group, t-pentyloxy group, t-octyloxy group, neopentyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, adamantyloxy group, norbornyloxy group , Boronyloxy group, 4-de Le cyclohexyloxy group, 2-tetrahydrofuranyl group, 2-tetrahydrofuranyl group, and the like.

  Examples of the aryloxy group include monocyclic or condensed polycyclic aryloxy groups having 6 to 18 carbon atoms. Specific examples include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, and 9-anthryloxy. Group, 9-phenanthryloxy group, 1-pyrenyloxy group, 5-naphthacenyloxy group, 1-indenyloxy group, 2-azurenyloxy group, 1-acenaphthyloxy group, 9-fluorenyloxy group, etc. Is mentioned.

  Examples of the heterocyclic oxy group include a monocyclic or condensed polycyclic heterocyclic oxy group containing a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Specific examples include a 2-furanyloxy group and a 2-thienyloxy group. 2-indolyloxy group, 3-indolyloxy group, 2-benzofuryloxy group, 2-benzothienyloxy group, 2-carbazolyloxy group, 3-carbazolyloxy group, 4-carbazolyl group An oxy group, 9-acridinyloxy group, etc. are mentioned.

  The acyloxy group includes a carbonyloxy group to which a hydrogen atom or a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded, or a monocyclic or condensed group having 6 to 18 carbon atoms. A carbonyloxy group to which a monocyclic or condensed polycyclic heterocyclic group having 4 to 18 carbon atoms is bonded, including a carbonyloxy group to which a polycyclic aryl group is bonded, a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom; Specific examples include acetoxy group, propionyloxy group, butyryloxy group, isobutyryloxy group, valeryloxy group, isovaleryloxy group, pivaloyloxy group, lauroyloxy group, myristoyloxy group, palmitoyloxy group, stearoyloxy group, cyclopentyl Carbonyloxy group, cyclohexylcarbonyloxy group, Royloxy group, methacryloyloxy group, crotonoyloxy group, isocrotonoyloxy group, oleoyloxy group, benzoyloxy group, 1-naphthoyloxy group, 2-naphthoyloxy group, cinnamoyloxy group, 3-furoyloxy group 2-thenoyloxy group, nicotinoyloxy group, isonicotinoyloxy group, 9-anthroyloxy group, 5-naphthathenoyloxy group and the like.

  Examples of the alkylthio group include a linear, branched, monocyclic or condensed polycyclic alkylthio group having 1 to 18 carbon atoms, and specific examples include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, and a pentylthio group. Hexylthio group, octylthio group, decylthio group, dodecylthio group, octadecylthio group and the like.

  Examples of the arylthio group include monocyclic or condensed polycyclic arylthio groups having 6 to 18 carbon atoms, and specific examples thereof include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, a 9-anthrylthio group, and a 9-phenanthri group. And a ruthio group.

  Examples of the heterocyclic thio group include a monocyclic or condensed polycyclic heterocyclic thio group containing a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Specific examples include a 2-furylthio group, a 2-thienylthio group, Examples include 2-pyrrolylthio group, 6-indolylthio group, 2-benzofurylthio group, 2-benzothienylthio group, 2-carbazolylthio group, 3-carbazolylthio group, 4-carbazolylthio group and the like.

  Examples of the alkylamino group include methylamino group, ethylamino group, propylamino group, butylamino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, nonylamino group, decylamino group, dodecylamino group, octadecylamino group Group, isopropylamino group, isobutylamino group, isopentylamino group, sec-butylamino group, tert-butylamino group, sec-pentylamino group, tert-pentylamino group, tert-octylamino group, neopentylamino group, Cyclopropylamino group, cyclobutylamino group, cyclopentylamino group, cyclohexylamino group, cycloheptylamino group, cyclooctylamino group, cyclododecylamino group, 1-adamantamino group, 2-adamantamino group, etc. It is below.

  Dialkylamino group includes dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, dipentylamino group, dihexylamino group, diheptylamino group, dioctylamino group, dinonylamino group, didecylamino group, didodecylamino group, Dioctadecylamino group, diisopropylamino group, diisobutylamino group, diisopentylamino group, methylethylamino group, methylpropylamino group, methylbutylamino group, methylisobutylamino group, cyclopropylamino group, pyrrolidino group, piperidino group, And piperazino group.

  As an arylamino group, an anilino group, 1-naphthylamino group, 2-naphthylamino group, o-toluidino group, m-toluidino group, p-toluidino group, 2-biphenylamino group, 3-biphenylamino group, 4- Biphenylamino group, 1-fluoreneamino group, 2-fluoreneamino group, 2-thiazoleamino group, p-terphenylamino group and the like can be mentioned.

  Examples of the diarylamino group include a diphenylamino group, a ditolylamino group, an N-phenyl-1-naphthylamino group, and an N-phenyl-2-naphthylamino group.

  Examples of the alkylarylamino group include N-methylanilino group, N-methyl-2-pyridino group, N-ethylanilino group, N-propylanilino group, N-butylanilino group, N-isopropyl, N-pentylanilino group, N -Ethylanilino group, N-methyl-1-naphthylamino group and the like.

  Furthermore, the above-mentioned alkyl group, aryl group, alkenyl group, alkynyl group, alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl Group, arylsulfonyl group, acyl group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, amino group, heterocyclic group, and phosphinoyl group, which may have an alkyl group, aryl group, heterocyclic group, acyl Group, alkoxyl group, aryloxy group, heterocyclic oxy group, acyloxy group, alkylthio group, arylthio group, heterocyclic thio group, alkylamino group, dialkylamino group, arylamino group, diarylamino group, alkylarylamino group In addition, the hydrogen atom in the substituent may be further substituted with another substituent. Examples of such a substituent include a halogen group such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, methoxy Group, ethoxy group, alkoxy group such as tert-butoxy group, aryloxy group such as phenoxy group, p-tolyloxy group, alkoxycarbonyl group such as methoxycarbonyl group, butoxycarbonyl group, phenoxycarbonyl group, acetoxy group, propionyloxy group , Acyloxy group such as benzoyloxy group, acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group, methacrylyl group and other acyl groups, methylsulfanyl group, tert-butylsulfanyl group and other alkylsulfanyl groups, phenylsulfanyl group, p-Torrils Arylsulfanyl groups such as fanyl groups, alkylamino groups such as methylamino groups and cyclohexylamino groups, aryls such as dialkylamino groups such as dimethylamino groups, diethylamino groups, morpholino groups and piperidino groups, phenylamino groups and p-tolylamino groups Other than alkyl groups such as amino group, methyl group, ethyl group, tert-butyl group, dodecyl group, aryl groups such as phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, etc. , Hydroxy group, carboxy group, formyl group, mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, phosphono group Group, trimethylammonium Group, dimethylsulfonyl group, triphenylphenacyl phosphoniumyl group and the like.

  Furthermore, the substituents in A and B may form a cyclic structure together with other substituents or hydrogen atoms on the ring.

  Furthermore, in the general formula (1), A and B may be combined to form a ring. Specific examples are shown below, but are not limited thereto.

  In A and B in the general formula (1), preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aryl group, substituted or unsubstituted Specific examples thereof include a substituted heterocyclic group, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a trifluoromethyl group, a methylphenyl group, a vinyl group, and a 2-phenylvinyl group. , Phenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group, phenyl group, 1-naphthyl group, 2-naphthyl group, benzoquinoyl group, naphthoquinoyl group, indenyl group, indanonyl group, 1,3-indadionyl group, azulenyl Group, anthracenyl group, carbazoyl group, furyl group, thienyl group, pyridinyl group, benzofuryl , Benzothienyl group, benzoxazolyl group, benzothiazolyl group, triazolyl group, quinazolyl group, xanthenyl group, Chiokisantoniru group does not but phenazinyl group and the like is not limited thereto.

  In A and B in the general formula (1), more preferably, a substituted or unsubstituted condensed polycyclic hydrocarbon group, a substituted or unsubstituted heterocyclic group and the like can be mentioned, and specific examples thereof include a 1-naphthyl group. , 2-naphthyl group, indanonyl group, naphthoquinoyl group, anthraquinolyl group, furyl group, thienyl group, benzofuryl group, benzothienyl group, triazolyl group, carbazolyl group, thioxanthonyl group and the like, but are not limited thereto.

  In A and B in general formula (1), A in general formula (1) is more preferably a substituted or unsubstituted carbazolyl group or a substituted or unsubstituted naphthyl group. In this case, a part of substituents on the carbazolyl group and naphthyl group may be bonded to a carbon atom of the carbazolyl group or naphthyl group or a part of other substituents to form a ring together. The carbazolyl group and naphthyl group may be bonded at any substitution position as long as they can form a covalent bond with the adjacent carbon atom of the general formula (1).

  The carbazolyl group and naphthyl group may be substituted with other substituents, and examples of such substituents include the same substituents as those mentioned for the substituents that A and B may have.

  In A and B in the general formula (1), even more preferably, A in the general formula (1) is a group represented by the substituted or unsubstituted general formula (2) or the substituted or unsubstituted general formula (3). It is. As long as it is a substitution position capable of forming a covalent bond with the adjacent carbon atom of the general formula (1), it may be bonded at any substitution position.

  In the general formula (2), Y represents a monovalent organic residue, and a substituted or unsubstituted alkyl group is preferable from the viewpoint of availability of raw materials and ease of synthesis.

  In the substituents A and B in the general formula (1), even more preferably, A in the general formula (1) is a group represented by the substituted or unsubstituted general formula (2), and B is a substituted or unsubstituted group. It is a group represented by the general formula (3) of substitution.

  The groups represented by the general formulas (2) and (3) may be substituted with other substituents. Examples of such other substituents include the substituents that A and B may have. And the same substituents as those described above. The other substituent in the general formula (2) is preferably an acyl group, more preferably a substituted or unsubstituted benzoyl group or a substituted or unsubstituted alkylcarbonyl group.

  X in the general formula (1) represents a monovalent organic residue. Here, the monovalent organic residue in X has the same meaning as the monovalent organic residue in A and B described above.

  X in the general formula (1) preferably has an alkyl group which may have a substituent, an aryl group which may have a substituent, an acyl group which may have a substituent, and a substituent. A phosphinyl group which may have a substituent, a heterocyclic group which may have a substituent, and the like, more preferably an alkyl group which may have a substituent and an aryl group which may have a substituent. Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a trifluoromethyl group, a phenyl group, and a benzyl group, but the present invention is not limited to these.

  Specific preferred examples of the photopolymerization initiator of the present invention described above are shown in Table 1, but the structure of the photopolymerization initiator of the present invention is not limited thereto.

Table 1

  The photopolymerization initiator of the present invention is used in the ink-jet ink in an amount of 0.1 to 20% by weight, preferably 1 to 12% by weight.

  The monomer in the photocurable inkjet ink of the present invention is a monomer having an ethylenically unsaturated bond capable of radical polymerization, and the monomer having an ethylenically unsaturated bond capable of radical polymerization is capable of radical polymerization in the molecule. Any monomer having at least one ethylenically unsaturated bond may be used. These may be used alone or may be a system in which two or more kinds are mixed at an arbitrary ratio in order to improve the intended characteristics.

  Specific examples of monomers used in the present invention include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and ethoxylation. 1,6-hexanediol diacrylate, neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene Glycol diacrylate, 1,4-butanediol di (meth) acrylate, 1,9-nonanediol diacrylate, tetraethylene glycol diacrylate, 2-n-butyl-2- Tyr-1,3-propanediol diacrylate, dimethylol-tricyclodecane diacrylate, hydroxypivalic acid neopentyl glycol diacrylate, 1,3-butylene glycol di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, Propoxylated bisphenol A di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, dimethylol dicyclopentane diacrylate, trimethylolpropane triacrylate, hydroxypivalic acid trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, Propoxylated trimethylolpropane triacrylate, ethoxylated phosphate triacrylate, ethoxylated tripropylene glycol Diacrylate, neopentyl glycol modified trimethylolpropane diacrylate, stearic acid modified pentaerythritol diacrylate, pentaerythritol triacrylate, tetramethylolpropane triacrylate, tetramethylol methane triacrylate, pentaerythritol tetraacrylate, caprolactone modified trimethylolpropane triacrylate , Ethoxylated isocyanuric acid triacrylate, tri (2-hydroxyethyl isocyanurate) triacrylate, propoxylate glyceryl triacrylate, tetramethylol methane tetraacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, ethoxylated pentaerythritol tetraacrylate Relate, dipentaerythritol hexaacrylate, caprolactone-modified dipentaerythritol hexaacrylate, dipentaerythritol hydroxypentaacrylate, neopentyl glycol oligoacrylate, 1,4-butanediol oligoacrylate, 1,6-hexanediol oligoacrylate, trimethylolpropane Oligoacrylate, pentaerythritol oligoacrylate, 2-phenoxyethyl acrylate, acryloylmorpholine, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, isobutyl acrylate, t-butyl acrylate, isooctyl acrylate, isobornyl Acrylate, cyclohexyl acrylate, 2 Methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, benzyl acrylate, ethoxyethoxyethyl acrylate, butoxyethyl acrylate, ethoxydiethylene glycol acrylate, methoxydipropylene glycol acrylate, methyl Phenoxyethyl acrylate, dipropylene glycol acrylate, β-carboxyl ethyl acrylate, phenoxy diethylene glycol acrylate, vinyl caprolactam, vinyl pyrrolidone, N-vinyl formamide, ethyl diglycol acrylate, trimethylolpropane formal monoacrylate, 4-t-butylcyclohexyl Acrylate, tri (meth) allyl isocyanurate, imide acrylate, isoamyl acrylate, ethoxylated succinic acid acrylate, caprolactone modified tetrahydrofurfuryl acrylate, tribromophenyl acrylate, ethoxylated tribromophenyl acrylate, trifluoroethyl acrylate, ω-carboxypoly Examples include caprolactone monoacrylate. Furthermore, edited by Shinzo Yamashita et al., "Crosslinking agent handbook" (1981, Taiseisha), Kiyoto Kato, "UV / EB curing handbook (raw material)", (1985, Polymer publication society), Radtech. Study Group, “Application and Market of UV / EB Curing Technology”, Item 79, (1989, CMC), Akamatsu Kiyoshi, “Practical Technology of New Photosensitive Resin”, (1987, CMC), Commercially available products described in Teiyama Soichiro's "Polyester Resin Handbook" (1988, Nikkan Kogyo Shimbun) or radically polymerizable or crosslinkable monomers known in the industry can be mentioned, but the present invention is limited to these. is not.

  A monomer is used in 30.0-90.0 weight% in inkjet ink.

  In addition to the above monomers, what is called an oligomer or prepolymer can be used for the photocurable inkjet ink of the present invention. Specifically, “Ebecryl 230, 244, 245, 270, 280 / 15IB, 284, 285, 4830, 4835, 4858, 4883, 8402, 8803, 8800, 254, 264, 265, 294 / 35HD, manufactured by Daicel UCB, 1259, 1264, 4866, 9260, 8210, 1290.1290K, 5129, 2000, 2001, 2002, 2100, KRM7222, KRM7735, 4842, 210, 215, 4827, 4849, 6700, 6700-20T, 204, 205, 6602, 220, 4450, 770, IRR567, 81, 84, 83, 80, 657, 800, 805, 808, 810, 812, 1657, 1810, IRR302, 450, 670, 830, 835, 870, 1 30, 1870, 2870, IRR267, 813, IRR483, 811, 436, 438, 446, 505, 524, 525, 554W, 584, 586, 745, 767, 1701, 1755, 740 / 40TP, 600, 601, 604, 605, 607, 608, 609, 600 / 25TO, 616, 645, 648, 860, 1606, 1608, 1629, 1940, 2958, 2959, 3200, 3201, 3404, 3411, 3412, 3415, 3500, 3502, 3600, 3603, 3604, 3605, 3608, 3700, 3700-20H, 3700-20T, 3700-25R, 3701, 3701-20T, 3703, 3702, RDX63182, 6040, IRR419 ", manufactured by Sartomer CN104, CN120, CN124, CN136, CN151, CN2270, CN2271E, CN435, CN454, CN970, CN971, CN972, CN9782, CN981, CN9873, CN991, "Laromar EA81L, F87" manufactured by BASF LR8800, PE46T, LR8907, PO43F, PO77F, PE55F, LR8967, LR8981, LR8982, LR8992, LR9004, LR8956, LR8985, LR8987, UP35D, UA19T, LR9005, PO83F, PO33F, L8489, L9489 LR8996, LR9013 LR9019, PO9026V, PE9027V "manufactured by Cognis" Photomer 3005, 3015, 3016, 3072, 3982, 3215, 5010, 5429, 5430, 5432, 5662, 5806, 5930, 6008, 6010, 6019, 6184, 6210, 6217, 6230, 6891, 6892, 6893-20R, 6363, 6572, 3660 "," Art Resin UN-9000HP, 9000PEP, 9200A, 7600, 5200, 1003, 1255, 3320HA, 3320HB, 3320HC, 3320HS, 901T, manufactured by Negami Kogyo Co., Ltd. 1200TPK, 6060PTM, 6060P "," Nippon Gosei Chemical Co., Ltd. "" purple light UV-6630B, 7000B, 7510B, 7461TE, 3000B, 320 " 0B, 3210EA, 3310B, 3500BA, 3520TL, 3700B, 6100B, 6640B, 1400B, 1700B, 6300B, 7550B, 7605B, 7610B, 7620EA, 7630B, 7640B, 2000B, 2010B, 2250EA, 2750B, “Kayarad” R-280, R-146, R131, R-205, EX2320, R190, R130, R-300, C-0011, TCR-1234, ZFR-1122, UX-2201, UX-2301, UX3204, UX-3301, UX-4101, UX-6101, UX-7101, MAX-5101, MAX-5100, MAX-3510, UX-4101 "and the like.

  Examples of the pigment of the photocurable inkjet ink used in the present invention include pigments conventionally used in inkjet inks, such as achromatic pigments such as carbon black, titanium oxide, and calcium carbonate, or chromatic organic pigments. It is done. These may be used alone or may be a system in which two or more kinds are mixed at an arbitrary ratio in order to improve the properties for the purpose of adjusting hue and density.

  Specific organic pigments include insoluble azo pigments such as Toluidine Red, Toluidine Maroon, Hansa Yellow, Benzidine Yellow, and Pyrazolone Red, soluble azo pigments such as Ritolol Red, Helio Bordeaux, Pigment Scarlet, and Permanent Red 2B, Alizarin, Indantron Derivatives from vat dyes such as thioindigo maroon, phthalocyanine organic pigments such as phthalocyanine blue and phthalocyanine green, quinacridone organic pigments such as quinacridone red and quinacridone magenta, perylene organic pigments such as perylene red and perylene scarlet, Isoindolinone organic pigments such as indolinone yellow and isoindolinone orange, and pyranthrone organic pigments such as pyranthrone red and pyranthrone orange Thioindigo organic pigments, condensed azo organic pigments, benzimidazolone organic pigments, quinophthalone organic pigments such as quinophthalone yellow, isoindoline organic pigments such as isoindoline yellow, and other pigments such as flavanthrone yellow and acylamide yellow And publicly known various pigments such as nickel azo yellow, copper azomethine yellow, perinone orange, anthrone orange, dianthraquinonyl red, and dioxazine violet.

  When organic pigments are exemplified by color index (C.I.) numbers, CI pigment yellows 12, 13, 14, 17, 20, 24, 74, 83, 8893, 109, 110, 117, 120, 125 128, 129, 137, 138, 139, 147, 148, 150, 151, 153, 154, 155, 166, 168, 180, 185, CI Pigment Orange 16, 36, 43, 51, 55, 59, 61, CI Pigment Red 9, 48, 49, 52, 53, 57, 97, 122, 123, 149, 168, 177, 180, 192, 202, 206, 215, 216, 217, 220, 223, 224, 226, 227, 228, 238, 240, CI Pigment Violet 19, 23, 29, 30, 37, 40, 50, C.I. Mento Blue 15, 15: 1, 15: 3, 15: 4, 15: 6, 22, 60, 64, CI Pigment Green 7, 36, CI Pigment Brown 23, 25, 26, etc. It is done.

  Specific examples of carbon black include “Special Black 350, 250, 100, 550, 5, 4, 4A, 6” “Printex U, V, 140 U, 140 V, 95, 90, 85, 80, 75, 55, manufactured by Degussa. 45, 40, P, 60, L6, L, 300, 30, 3, 35, 25, A, G ", Cabot's" REGAL 400R, 660R, 330R, 250R "," MOGUL E, L ", Mitsubishi Chemical “MA7, 8, 11, 77, 100, 100R, 100S, 220, 230” “# 2700, # 2650, # 2600, # 200, # 2350, # 2300, # 2200, # 1000, # 990, # 980, # 970, # 960, # 950, # 900, # 850, # 750, # 650, # 52, # 50, # 47, # 45, # 4 5L, # 44, # 40, # 33, # 332, # 30, # 25, # 20, # 10, # 5, CF9, # 95, # 260 ”and the like.

  Specific examples of titanium oxide include “Taipeku CR-50, 50-2, 57, 80, 90, 93, 95, 953, 97, 60, 60-2, 63, 67, 58, 58- manufactured by Ishihara Sangyo Co., Ltd. 2, 85 "" Tipekes R-820, 830, 930, 550, 630, 680, 670, 580, 780, 780-2, 850, 855 "," Tipekes A-100, 220 "," Tipekes W-10 "," Tipekes " PF-740, 744 "" TTO-55 (A), 55 (B), 55 (C), 55 (D), 55 (S), 55 (N), 51 (A), 51 (C) " "TTO-S-1, 2", "TTO-M-1, 2", "Titanics JR-301, 403, 405, 600A, 605, 600E, 603, 805, 806, 701, 800, 808" manufactured by Teika "Titanic EN-1, C, 3, 4, 5 ", DuPont" Taipyua R-900,902,960,706,931 ', and the like.

  Among the above pigments, quinacridone organic pigments, phthalocyanine organic pigments, benzimidazolone organic pigments, isoindolinone organic pigments, condensed azo organic pigments, quinophthalone organic pigments, isoindoline organic pigments, etc. are light-resistant. Is preferable because it is excellent. The organic pigment is preferably a fine pigment having an average particle diameter of 10 to 150 nm as measured by laser scattering. When the average particle diameter of the pigment is less than 10 nm, the light resistance is lowered due to the small particle diameter, and when it exceeds 150 nm, it is difficult to maintain stable dispersion, and the pigment is likely to precipitate.

  The organic pigment can be refined by the following method. That is, a mixture comprising at least three components of an organic pigment, a water-soluble inorganic salt that is at least 3 times the weight of the organic pigment, and a water-soluble solvent is made into a clay-like mixture, and is kneaded strongly with a kneader or the like and then refined. And stirred with a high speed mixer or the like to form a slurry. Next, filtration and washing of the slurry are repeated to remove the water-soluble inorganic salt and the water-soluble solvent. In the miniaturization step, a resin, a pigment dispersant and the like may be added.

  Examples of the water-soluble inorganic salt include sodium chloride and potassium chloride. These inorganic salts are used in the range of 3 times by weight or more, preferably 20 times by weight or less of the organic pigment. When the amount of the inorganic salt is less than 3 times by weight, a treated pigment having a desired size cannot be obtained. On the other hand, if the amount is more than 20 times by weight, the washing process in the subsequent step is great, and the substantial amount of the organic pigment is reduced.

  The water-soluble solvent is an organic solvent and a water-soluble inorganic salt that is used as a crushing aid, and is used for efficient crushing efficiently, especially if it is a solvent that dissolves in water. Although not limited, a high boiling point solvent having a boiling point of 120 to 250 ° C. is preferable from the viewpoint of safety because the temperature rises during kneading and the solvent is easily evaporated. Examples of water-soluble solvents include 2- (methoxymethoxy) ethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether , Triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, low molecular weight Examples thereof include polypropylene glycol.

  In the present invention, the pigment is used in the range of 1 to 30% by weight in the ink jet ink in order to obtain a sufficient concentration and sufficient light resistance.

  In the present invention, it is preferable to add a pigment dispersant in order to improve the dispersibility of the pigment and the storage stability of the ink. Examples of the pigment dispersant include a hydroxyl group-containing carboxylic acid ester, a salt of a long chain polyaminoamide and a high molecular weight acid ester, a salt of a high molecular weight polycarboxylic acid, a salt of a long chain polyaminoamide and a polar acid ester, a high molecular weight unsaturated acid ester, Polymer copolymer, modified polyurethane, modified polyacrylate, polyether ester type anionic activator, naphthalene sulfonic acid formalin condensate salt, aromatic sulfonic acid formalin condensate salt, polyoxyethylene alkyl phosphate ester, polyoxyethylene Nonylphenyl ether, stearylamine acetate, etc. can be used.

  Specific examples of the dispersant include “Anti-Terra-U (polyaminoamide phosphate)”, “Anti-Terra-203 / 204 (high molecular weight polycarboxylate)”, “Disperbyk-101” (polyamino) manufactured by BYK Chemie. Amide phosphate and acid ester), 107 (hydroxyl group-containing carboxylic acid ester), 110, 111 (copolymer containing acid group), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (high Molecular copolymer) ”,“ 400 ”,“ Bykumen ”(high molecular weight unsaturated acid ester),“ BYK-P104, P105 (high molecular weight unsaturated acid polycarboxylic acid) ”,“ P104S, 240S (high molecular weight unsaturated) Acid polycarboxylic acid and silicon) "," Lactimon (long-chain amine and unsaturated acid polycarbonate) Rubonic acid and silicon).

  Also, “Efka CHEMICALS” “Efka 44, 46, 47, 48, 49, 54, 63, 64, 65, 66, 71, 701, 764, 766”, “Efka Polymer 100 (modified polyacrylate), 150 (aliphatic) System modified polymer), 400, 401, 402, 403, 450, 451, 452, 453 (modified polyacrylate), 745 (copper phthalocyanine system) "," Floren TG-710 (urethane oligomer) "," Flownon "manufactured by Kyoeisha Chemical Co., Ltd. “SH-290, SP-1000”, “Polyflow No. 50E, No. 300 (acrylic copolymer)”, “Disparon KS-860, 873SN, 874 (polymer dispersing agent), # 2150 (manufactured by Enomoto Kasei Co., Ltd.) Aliphatic polyvalent carboxylic acid), # 7004 (polyether ester type) ” That.

  Further, “Demol RN, N (Naphthalenesulfonic acid formalin condensate sodium salt), MS, C, SN-B (aromatic sulfonic acid formalin condensate sodium salt), EP”, “Homogenol L-18 (poly) Carboxylic acid type polymer), “Emulgen 920, 930, 931, 935, 950, 985 (polyoxyethylene nonylphenyl ether)”, “Acetamine 24 (coconut amine acetate), 86 (stearyl amine acetate)”, “Abisia” Solspers 5000 (phthalocyanine ammonium salt type), 13940 (polyesteramine type), 17000 (fatty acid amine type), 24000GR, 32000, 33000, 39000, 41000, 53000, “Nikkor T106 (polyoxy) manufactured by Nikko Chemical Co., Ltd. Ethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate), Hexagline 4-0 (hexaglyceryl tetraoleate), “Ajisper PB821, 822, 824” manufactured by Ajinomoto Fine Techno Co., etc.

  The addition amount of the dispersant is not particularly limited, but it is preferably used in the range of 0.1 to 10% by weight in the inkjet ink.

  In order to further improve the dispersibility of the pigment and the storage stability of the ink, it is preferable to add an acidic derivative of an organic pigment to the inkjet ink of the present invention when the pigment is dispersed.

  The photocurable ink-jet ink of the present invention can be used in combination with other polymerization initiators for the purpose of further improving sensitivity.

  Other polymerization initiators that can be used in combination with the photocurable inkjet ink of the present invention include Irgacure 651, Irgacure 184, Darocur 1173, Irgacure 500, Irgacure 1000, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure 1700, Irgacure 149, Irgacure 1800, Irgacure 1850, Irgacure 819, Irgacure 784, Irgacure 261, Irgacure OXE-01 (CGI124), CGI242 (Ciba Special) Tea Chemicals), Adekaoptomer N1414, Adekaoptomer N1717 (Asahi Denka), Esacure1001M (Lamberti), Lucillin T O (BASF Corp.), triazine derivatives described in JP-B-59-1281, JP-B-61-9621 and JP-A-60-60104, JP-A-59-1504 and JP-A-61-243807 Organic peroxides described in Japanese Patent Publication No. 43-23684, Japanese Patent Publication No. 44-6413, Japanese Patent Publication No. 47-1604 and US Pat. No. 3,567,453, Japanese Patent Publication No. 2,848,328. Organic azide compounds described in US Pat. No. 2,852,379 and US Pat. No. 2,940,853, Japanese Patent Publication No. 36-22062, Japanese Patent Publication No. 37-13109, Japanese Patent Publication No. 38-18015 and Japanese Patent Publication No. 45-9610. Ortho-quinonediazides described in Japanese Patent Publication No. 55-391 Various onium compounds such as iodonium compounds described in No. 2 and JP-A-59-140203 and “MACROMOLECULES”, Vol. 10, page 1307 (1977), JP-A-59 -142205, an azo compound described in JP-A-1-54440, European Patent No. 109851, European Patent No. 126712, "Journal of Imaging Science (J. IMAGE. SCI.)" 30, vol. 174 (1986), titanocenes described in JP-A No. 61-151197, “COORDINATION CHEMISTRY REVIEW”, Vol. 84, 85 ~ 277 (1988) and transition metal complexes containing a transition metal such as ruthenium described in JP-A-2-182701, aluminate complexes described in JP-A-3-209477, and boric acid described in JP-A-2-157760. Salt compound, 2,4,5-triarylimidazole dimer described in JP-A Nos. 55-127550 and 60-202437, 2,2′-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,1'-biimidazole, carbon tetrabromide and organic halogen compounds described in JP-A-59-107344, JP-A-5-213861, JP-A-5-255347 JP, JP 5-255421, JP 6-157623, JP 2000-344812, JP 2002-2655. No. 12, Japanese Patent Application No. 2004-053009, and Japanese Patent Application No. 2004-263413, sulfonium complexes or oxosulfonium complexes, Japanese Patent Application Laid-Open Nos. 2001-264530, 2001-261661, and 2000-80068. No. 1, JP-A-2001-233842, USP 3558309 (1971), USP4202697 (1980), JP-A 61-24558, JP-T 2004-534797, and JP-A 2004 Examples include oxime ester compounds described in JP-A-335939 and bifunctional photoinitiators described in JP-T-2002-530372, but the present invention is not limited thereto.

  In addition, by combining with a sensitizer that absorbs ultraviolet to near-infrared light to increase the activity for light from the ultraviolet to the near-infrared region, it is an extremely sensitive photopolymerizable composition. Is possible.

  Sensitizers that can be used in combination with the photocurable inkjet ink of the present invention include benzophenones, unsaturated ketones represented by chalcone derivatives and dibenzalacetone, and benzyl and camphorquinone. 1,2-diketone derivatives, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, etc. Polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenyl Ruphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives , Tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, and other specific examples include Okawara Shin et al., “Dye Handbook” (1986, Kodansha), edited by Nobu Okawara et al., "Chemicals of Functional Pigments" (1981, CMC), edited by Chusaburo Ikemori et al., "Special Functional Materials" (1986, CMC) Examples include, but are not limited to, dyes and sensitizers, and other dyes and sensitizers that absorb light in the ultraviolet to near infrared region. Two or more of them may be used in the ratio. Among the sensitizers, thioxanthone derivatives include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone. Examples of benzophenones include benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4,4′-dimethylbenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-bis. (Diethylamino) benzophenone and the like can be mentioned. Examples of coumarins include coumarin 1, coumarin 338 and coumarin 102. Examples of ketocoumarins include 3,3′-carbonylbis (7-diethylamino). Marine) and the like can be mentioned, but not limited thereto.

  The photopolymerization initiator and sensitizer that may be used in combination in the present invention are used in the ink-jet ink in an amount of 0 to 20% by weight, preferably 0.1 to 10% by weight.

  Moreover, the photocurable inkjet ink of this invention can add a polymerization inhibitor in order to prevent the superposition | polymerization at the time of a preservation | save.

  Specific examples of the polymerization inhibitor that can be added to the photocurable inkjet ink of the present invention include hydroquinone, p-methoxyphenol, alkyl-substituted hydroquinone, catechol, tert-butylcatechol, and phenothiazine. Although the addition amount of a polymerization inhibitor is not specifically limited, Preferably it is used in 0.01-5 weight% in inkjet ink.

  Moreover, the polymerization composition of this invention can add the polymerization accelerator represented by amine, thiol, disulfide, etc. and a chain transfer catalyst for the purpose of further promoting superposition | polymerization.

  Specific examples of the polymerization accelerator and chain transfer catalyst that can be added to the polymerizable composition of the present invention include, for example, trimethylamine, methyldimethanolamine, N-phenylglycine, triethanolamine, N, N-diethylaniline and the like. Amines, thiols described in USP No. 4414312 and JP-A 64-13144, disulfides described in JP-A-2-291561, USP 3558322 and JP-A 64-17048 And the O-acylthiohydroxamates and N-alkoxypyridinethiones described in JP-A-2-291560. The addition amount of the polymerization accelerator and the chain transfer catalyst is not particularly limited, but is preferably used in the range of 0.001 to 5% by weight in the ink-jet ink.

  It is preferable to add a surface conditioner to the inkjet ink of the present invention in order to improve the wettability to the substrate. Specific examples of the surface conditioner include BYK-300, 302, 306, 307, 310, 315, 320, 322, 323, 325, 330, 331, 333, 337, 340, 344, 370, and 375 manufactured by BYK-Chemie. 377, 350, 352, 354, 355, 356, 358N, 361N, 357, 390, 392, UV3500, UV3510, UV3570, “Tegorad-2100, 2200, 2250, 2500, 2700” manufactured by Tego Chemie. These surface conditioners may be used alone or in combination of two or more as required.

  The addition amount of the surface conditioner is not particularly limited, but is preferably used in the range of 0.001 to 1% by weight in the inkjet ink.

  The active energy ray-curable inkjet ink of the present invention can use various additives such as a plasticizer, an ultraviolet light inhibitor, a light stabilizer, and an antioxidant.

  The ink-jet ink of the present invention is produced by well dispersing a pigment together with a monomer and a pigment dispersant using an ordinary dispersing machine such as a sand mill. It is preferable to prepare a concentrated solution having a high pigment concentration in advance and dilute with a monomer. Sufficient dispersion is possible even with dispersion by a normal disperser. Therefore, excessive dispersion energy is not required, and a large amount of dispersion time is not required. An ink having excellent properties is prepared. The ink is preferably filtered through a filter having a pore size of 3 μm or less, and more preferably 1 μm or less.

  The inkjet ink of the present invention is preferably adjusted to have a high viscosity at 25 ° C. of 5 to 50 mPa · s. An ink having a viscosity of 5 to 50 mPa · s at 25 ° C. exhibits stable ejection characteristics, particularly from a head having a normal frequency of 4 to 10 KHz to a head having a high frequency of 10 to 50 KHz.

  When the viscosity is less than 5 mPa · s, a decrease in the follow-up property of the discharge is recognized in the high-frequency head. When the viscosity exceeds 50 mPa · s, even if a mechanism for reducing the viscosity by heating is incorporated in the head, the discharge itself A drop occurs, the ejection stability becomes poor, and the ejection cannot be performed at all.

  The ink-jet ink of the present invention preferably has an electric conductivity of 10 μS / cm or less in the piezo head and does not cause electrical corrosion inside the head. Further, in the continuous type, it is necessary to adjust the electric conductivity by the electrolyte. In this case, it is necessary to adjust the electric conductivity to 0.5 mS / cm or more.

  In order to use the ink-jet ink of the present invention, first, the ink-jet ink is supplied to a printer head of a printer for an ink-jet recording system, discharged from the printer head onto a substrate, and then an active energy ray such as an ultraviolet ray or an electron beam is applied. Irradiate. This quickly cures the composition on the print medium.

  In the polymerization reaction, the photocurable ink-jet ink of the present invention can be polymerized by applying energy by ultraviolet rays, visible rays, near infrared rays, electron beams or the like to obtain a desired polymer. The definitions of ultraviolet rays, visible rays, near-infrared rays and the like in this specification are based on “Iwanami Rikagaku Dictionary 4th Edition” (1987, Iwanami) edited by Ryogo Kubo et al.

  Therefore, the photocurable inkjet ink of the present invention is a low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, xenon lamp, carbon arc lamp, metal halide lamp, fluorescent lamp, tungsten lamp, argon ion laser, helium cadmium laser, By applying energy from various light sources such as helium neon laser, krypton ion laser, various semiconductor lasers, YAG laser, light emitting diode, CRT light source, plasma light source, electron beam, gamma ray, ArF excimer laser, KrF excimer laser, F2 laser A polymer or a cured product can be obtained.

  Examples of the substrate that can be used in the present invention include non-coated paper, coated paper, and non-absorbent support.

  Specific non-absorbing supports include various non-absorbing plastics and films thereof. Examples of various plastic films include PET film, OPS film, OPP film, ONy film, PVC film, PE film, A TAC film can be mentioned. Examples of other plastics include, but are not limited to, polycarbonate, acrylic resin, ABS, polyacetal, PVA, and rubbers. Metals and glasses can also be used.

  The photocurable ink-jet ink obtained in the present invention can be printed and cured using the same technique as before.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to only the following Example at all. In the following examples, the numbers in the tables represent% by weight.

  Prior to the examples, the compounds of the present invention used in the examples are shown in Table 2.

Table 2

Table 2

Table 2

Table 2

Table 2

  The compounds 1-42 shown in Table 2 can be obtained by using the synthesis methods described in Japanese Patent Application Nos. 2006-5887, 2006-19293, 2006-19294, and 2006-194241. did it.

  First, yellow, magenta, cyan, and black pigment dispersions composed of a pigment, a pigment dispersant, and a monomer were prepared. Table 3 shows the composition of the cyan pigment dispersion. This dispersion was prepared by adding a pigment and a dispersant into an organic solvent, stirring until uniform with a high speed mixer or the like, and dispersing the obtained mill base with a horizontal sand mill for about 1 hour.

Table 3

Examples 1-42 and Comparative Examples 1-6
A pigment dispersion, a monomer, a resin, and a photopolymerization initiator were mixed to obtain yellow, magenta, cyan, and black inks. Among these, the composition of the cyan inkjet ink is shown in Table 4, and the photopolymerization initiator used is shown in Table 5.

Table 4

Table 5

  The curability of the printing ink was evaluated as follows. The results are shown in Table 6. An inkjet ink printed on PET with a UV-IJ printer was subjected to ultraviolet irradiation (metal halide lamp 120 W / cm1 lamp), then contacted with the ink surface, and judged at a non-sticky conveyor speed. The larger the number at the conveyor speed (m / min) of the ultraviolet irradiation device, the better the curability.

Table 6

  The photocurable inkjet ink (Example 1-42) using the photopolymerization initiator of the present invention is a photocurable inkjet ink (Comparative Example 1-4) using a commonly used photopolymerization initiator. It was found that it has a clearly better curability than Moreover, it turned out that it has clearly good curability even if it compares with the photocurable inkjet ink (Comparative Examples 5 and 6) which used oxime ester other than this invention as a photoinitiator. That is, it was found that by using a photopolymerization initiator for the diketo oxime ester of the present invention, a photocurable ink-jet ink with very high sensitivity can be realized.

Claims (9)

A photocurable inkjet ink comprising at least a monomer, a pigment, and a photopolymerization initiator represented by the following general formula (1).
General formula (1)

(In the formula, A and B each independently represent a hydrogen atom or a monovalent organic residue, X represents a monovalent organic residue, and A and B are cyclically bonded together. It may be a structure.) The photocurable inkjet ink according to claim 1, wherein A and B are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. The photocurable inkjet ink according to claim 1 or 2, wherein A and B are each independently a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group.   The photocurable inkjet ink according to any one of claims 1 to 3, wherein A and B are each independently a substituted or unsubstituted condensed polycyclic hydrocarbon group or a substituted or unsubstituted heterocyclic group. The photocurable inkjet kinky according to any one of claims 1 to 4, wherein A is a substituted or unsubstituted carbazolyl group or a substituted or unsubstituted naphthyl group. The photocurable inkjet ink according to any one of claims 1 to 5, wherein A is a group represented by the following general formula (2) which is substituted or unsubstituted, or a general formula (3) which is substituted or unsubstituted.


General formula (2)

(In general formula (2), Y represents a monovalent organic residue.)
General formula (3)

Either A is a group represented by the following general formula (2) which is substituted or unsubstituted, and B is a group represented by the following general formula (3) which is substituted or unsubstituted. The photocurable inkjet ink as described.
General formula (2)

(In general formula (2), Y represents a monovalent organic residue.)
General formula (3)

The manufacturing method of printed matter which prints the photocurable inkjet ink in any one of Claims 1-7, and makes it harden | cure by light irradiation. A printed matter obtained by the production method according to claim 8.