JP2009013314A - Photocurable type ink - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide photocurable type ink containing a resin, a monomer, a pigment, a photopolymerization initiator curable by light irradiation, a photosensitizer and an amine-based compound, exhibiting excellent curing property of the ink by the light irradiation and excellent preservation stability with time and suppressing the odor after the ink is cured. <P>SOLUTION: The photocurable type ink is composed of the resin, the monomer, the pigment, the α-amino ketone-based photopolymerization initiator, the photosensitizer and the amine-based compound. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a photocurable ink containing a photopolymerization initiator, a photosensitizer and an amine compound that are cured by light irradiation. More specifically, the photocurable ink has good curability and storage stability over time. The present invention relates to a photocurable ink that can be reliably cured in a short time and can suppress odor after ink curing.

  Photocurable coating compositions, especially UV curable coating compositions are printing inks, overcoat varnishes, paints, photosensitive resins for printing plates, adhesives, adhesives, resists for color filters, resists for printed circuit boards, and semiconductors. Active research is being conducted in the fields of photoresist, hologram material, molding resin, casting resin, resin for optical modeling, sealant, various devices and the like. These include photopolymerization initiators, resins (including both radically polymerizable resins and non-radically polymerizable resins), radically polymerizable monomers, pigments (not included in overcoat varnish), additives Etc. Commonly used photopolymerization initiators include benzophenone series such as methyl o-benzoylbenzoate, Darocur 1173, Darocur 2959, Irgacure 184, Irgacure 907 (Irgacure and Darocur are trademarks of Ciba Specialty Chemicals), etc. Hydrogen donation systems such as amino ketone, benzoin such as Irgacure 651, thioxanthone, EAB (made by Hodogaya Chemical Co., Ltd.), Seikol PAA (made by Seiko Chemical Co., Ltd.), Kayacure EPA (made by Nippon Kayaku Co., Ltd.) are used , Photopolymer Society, “Sensitive Material List Book”, pages 55-72, 1996 (Bunshin Publishing).

  Among these commercially available photopolymerization initiators, aminoketone photopolymerization initiators are known to be suitable as photopolymerization initiators for photocurable coloring compositions such as photocurable inks. , Α-aminoketone derivatives (Patent Document 1), and in particular, aminoketone derivatives in which the above derivative is introduced with a substituent at the 4-position of the phenyl group via an ether bond (—O—) or a thioether bond (—S—) (Patent Documents 2 and 3) and α-aminoketone derivatives having an amino group at the 4-position of the phenyl group (Patent Document 4) are known. The α-aminoketone derivative has an N-substituted carbazole group as an α-aminoketone derivative (Patent Document 5) and the α-aminoketone derivative has at least one allyl group or arylalkyl group at the α-position. A polymerizable composition containing an α-aminoketone derivative has been proposed (Patent Document 6). Furthermore, a polymerizable composition containing an α-aminoketone derivative (Patent Document 7) in which the phenyl group of the α-aminoketone derivative is a heteroatom-containing aromatic ring condensed group into which an arylcarbonyl group is introduced has also been proposed. The polymerizable composition containing the α-aminoacetophenone derivative is known to be a highly sensitive polymerizable composition that can be cured with a small amount of light irradiation. However, in order to achieve further high curability, It is known that additives such as a sensitizer and a polymerization accelerator may be used in combination (Patent Documents 1 to 7). In particular, Patent Documents 2 to 4 and 6 describe that aromatic ketone compounds such as benzophenone and thioxanthone, and amine compounds such as Michler's ketone and diethanolamine can be suitably used as photosensitizers or polymerization accelerators. ing. However, even in the polymerizable composition, the curability is still insufficient, and further improvement in curability is desired.

  In addition, although the photocurable ink containing the photopolymerization initiator, the photosensitizer, and the polymerization accelerator described in Patent Documents 1 to 6 exhibits high curability, the storage stability of the ink with time is low, so that the ink after the ink preparation is completed. There have been problems such as precipitation of a photopolymerization initiator and the like, and generation of odor after ink curing.

JP-A-54-99185 JP 58-157805 A JP 59-167546 A JP-A-60-84248 JP 61-21104 A Japanese Unexamined Patent Publication No. 63-264560 JP 2006-206799 A

  As the productivity of printed matter increases, the photocurable ink must be cured by light irradiation for a very short time, so in the case of a general photocurable ink, in addition to the photopolymerization initiator, Polymerization accelerators are used. However, various problems occur when these are used. For example, photopolymerization initiators, photosensitizers, polymerization accelerators, and the like are poorly soluble in resins and monomers in the ink, causing problems that the compound precipitates during storage of the ink over time. Furthermore, the curability of the ink may be lowered, and the film hardness of the printed matter may be deteriorated. Moreover, since these inks generate odors after curing, not only the printed materials and coated materials, but also the environment of printing and coating sites are impaired, which is not preferable. In the above-mentioned photocurable ink, it is difficult to satisfy all the requirements regarding ink curability, storage stability with time, and odor after ink curing. Accordingly, an object of the present invention is to provide a photocurable ink that has good curability and long-term storage stability in a photocurable ink and can suppress odor after ink curing.

  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 is represented by a resin, a monomer, a pigment, an α-aminoketone photopolymerization initiator represented by the following general formula (1), a general formula (3), or a general formula (4). The present invention relates to a photocurable ink comprising a photosensitizer and an amine compound.

General formula (1)

(Wherein R ¹ and R ² each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted alkenyl group) R ¹ and R ² may be integrated to form a ring.
R ³ and R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, or COR ⁵ Represents. R ³ and R ⁴ may be combined to form a ring.
R ⁵ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted alkenyl group.
X represents a divalent aromatic ring condensed group having 4 to 16 carbon atoms which may contain a hetero atom.
Ar ¹ represents the following general formula (2) or a substituted or unsubstituted heterocyclic group. )

General formula (2)

(Wherein R ^{6 to} R ¹⁰ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, Substituted or unsubstituted acyl group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted acyloxy group, substituted or unsubstituted alkoxycarbonyl Oxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted heterocyclic thio group, substituted or unsubstituted alkylamino group, substituted or unsubstituted dialkylamino group, substituted or unsubstituted Substituted arylamino group, substituted or unsubstituted diarylamino group, substituted Properly represents the unsubstituted alkyl arylamino group, or a halogen atom. In addition, adjacent substituents of R ⁶ to R ¹⁰ may form a ring together.)

General formula (3)

(Wherein R ^{11 to} R ²⁰ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, Substituted or unsubstituted acyl group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted acyloxy group, substituted or unsubstituted alkoxycarbonyl Group, substituted or unsubstituted alkoxycarbonyloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted heterocyclic thio group, substituted or unsubstituted alkylamino group, substituted or unsubstituted A substituted dialkylamino group, a substituted or unsubstituted arylamino group, Represents a substituted or unsubstituted diarylamino group, a substituted or unsubstituted alkylarylamino group, or a halogen atom, and R ^{11 to} R ¹⁵ and R ^{16 to} R ²⁰ are each formed by combining adjacent substituents together; R ¹⁵ and R ¹⁶ may be combined to form —O—, —S—,>S═O,> SO ₂ , —N (R ²¹ ) —, —CO—, _{-CH 2 -, - CH 2 CH} 2 -, - CH = CH-, alkylidene group having 2 to 6 carbon atoms or may form a direct bond.
R ²¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkoxyl group, substituted or It represents an unsubstituted aryloxy group or a substituted or unsubstituted heterocyclic oxy group. )

General formula (4)

(Wherein R ^{22 to} R ³⁹ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, Substituted or unsubstituted acyl group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted acyloxy group, substituted or unsubstituted alkoxycarbonyl Group, substituted or unsubstituted alkoxycarbonyloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted heterocyclic thio group, substituted or unsubstituted alkylamino group, substituted or unsubstituted A substituted dialkylamino group, a substituted or unsubstituted arylamino group, Represents a substituted or unsubstituted diarylamino group, a substituted or unsubstituted alkylarylamino group, or a halogen atom, and R ^{22 to} R ²⁶ , R ^{27 to} R ³⁰ , R ^{31 to} R ³⁴ , and R ^{35 to} R ^{In 39} , the adjacent substituents may be united independently to form a ring, and R ²⁶ and R ²⁷ , or R ³⁴ and R ³⁵ are each united independently of —O—, — S -,> S = O, > SO 2, -N (R 21) -, - CO -, - CH 2 -, - CH 2 CH 2 -, - CH = CH-, alkylidene of 2 to 6 carbon atoms Groups or direct bonds may be formed.
R ²¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkoxyl group, substituted or It represents an unsubstituted aryloxy group or a substituted or unsubstituted heterocyclic oxy group.
R ⁴⁰ represents —O—, —S—, —N (R ²¹ ) —, —CO—, —OCO—, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted divalent group. Valent heterocyclic group, substituted or unsubstituted alkenylene group, alkynylene group, —O—J—, —O—J—O—, —O—J—CO—, —CO—J—, —CO—J—. CO-, -COO-J-, -COO-J-O-, -COO-J-OOC-, -OCO-J-, -OCO-J-O-, -OCO-J-OCO-, -COO- J-OCO-, -Q-COO-J-OOC-Q-, -O-Q-COO-J-OOC-QO-, or a direct bond is represented.
J represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, or a substituted or unsubstituted divalent heterocyclic group.
Q represents a substituted or unsubstituted alkylene group. )

  Furthermore, this invention relates to the said photocurable ink whose photosensitizer is the following general formula (5) or general formula (6).

General formula (5)

(Wherein R ^{41 to} R ⁴⁸ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, Substituted or unsubstituted acyl group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted acyloxy group, substituted or unsubstituted alkoxycarbonyl Group, substituted or unsubstituted alkoxycarbonyloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted heterocyclic thio group, substituted or unsubstituted alkylamino group, substituted or unsubstituted A substituted dialkylamino group, a substituted or unsubstituted arylamino group, Represents a substituted or unsubstituted diarylamino group, a substituted or unsubstituted alkylarylamino group, or a halogen atom, and R ^{41 to} R ⁴⁴ , and R ^{45 to} R ⁴⁸ each represent an integral group of adjacent substituents. To form a ring.
A ¹ is —O—, —S—,>S═O,> SO ₂ , —N (R ²¹ ) —, —CO—, —CH ₂ —, —CH ₂ CH ₂ —, —CH═CH—. Represents an alkylidene group having 2 to 6 carbon atoms, or a direct bond.
R ²¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkoxyl group, substituted or It represents an unsubstituted aryloxy group or a substituted or unsubstituted heterocyclic oxy group. )

General formula (6)

(Wherein R ^{49 to} R ⁶² are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, Substituted or unsubstituted acyl group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted acyloxy group, substituted or unsubstituted alkoxycarbonyl Group, substituted or unsubstituted alkoxycarbonyloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted heterocyclic thio group, substituted or unsubstituted alkylamino group, substituted or unsubstituted A substituted dialkylamino group, a substituted or unsubstituted arylamino group, A substituted or unsubstituted diarylamino group, a substituted or unsubstituted alkylarylamino group, or a halogen atom, and R ^{49 to} R ⁵² , R ^{53 to} R ⁵⁵ , R ^{56 to} R ⁵⁸ , and R ^{59 to} R ^{In 62} , adjacent substituents may be combined to form a ring.
A ² and A ³ are each independently —O—, —S—,>S═O,> SO ₂ , —N (R ²¹ ) —, —CO—, —CH ₂ —, —CH ₂ CH ₂ —. , -CH = CH-, an alkylidene group having 2 to 6 carbon atoms or a direct bond.
R ²¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkoxyl group, substituted or It represents an unsubstituted aryloxy group or a substituted or unsubstituted heterocyclic oxy group.
R ⁶³ represents —O—, —S—, —N (R ²¹ ) —, —CO—, —OCO—, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted divalent group. Valent heterocyclic group, substituted or unsubstituted alkenylene group, alkynylene group, —O—J—, —O—J—O—, —O—J—CO—, —CO—J—, —CO—J—. CO-, -COO-J-, -COO-J-O-, -COO-J-OOC-, -OCO-J-, -OCO-J-O-, -OCO-J-OCO-, -COO- J-OCO-, -Q-COO-J-OOC-Q-, -O-Q-COO-J-OOC-QO-, or a direct bond is represented.
J represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, or a substituted or unsubstituted divalent heterocyclic group.
Q represents a substituted or unsubstituted alkylene group. )

The present invention further, A ^1, A ^2, and A ³ are about the light-curable ink is -S-.

  Furthermore, this invention relates to the said photocurable ink whose amine compound is a tertiary amine.

  Furthermore, this invention relates to the said photocurable ink whose amine compound is following General formula (7) or General formula (8).

General formula (7)

(Wherein R ⁶⁴ and R ⁶⁵ each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. Also, R ⁶⁴ and R ⁶⁵ represent The adjacent substituents may be combined to form a ring.
R ⁶⁶ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted acyl group, substituted or unsubstituted Unsubstituted alkoxyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted acyloxy group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted alkoxycarbonyloxy Group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted heterocyclic thio group, substituted or unsubstituted dialkylamino group, substituted or unsubstituted diarylamino group, substituted or unsubstituted An alkylarylamino group or a halogen atom Represent.
Ar ³ represents a substituted or unsubstituted arylene group or a substituted or unsubstituted divalent heterocyclic group. )

General formula (8)

(Wherein R ^{67 to} R ⁷⁰ each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and R ⁶⁷ , R ⁶⁸ and R ⁶⁹ and R ⁷⁰ may be combined with each other to form a ring.
R ⁷¹ represents —O—, —S—, —N (R ²¹ ) —, —CO—, —OCO—, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted divalent group. Valent heterocyclic group, substituted or unsubstituted alkenylene group, alkynylene group, —O—J—, —O—J—O—, —O—J—CO—, —CO—J—, —CO—J—. CO-, -COO-J-, -COO-J-O-, -COO-J-OOC-, -OCO-J-, -OCO-J-O-, -OCO-J-OCO-, -COO- J-OCO-, -Q-COO-J-OOC-Q-, -O-Q-COO-J-OOC-QO-, or a direct bond is represented.
R ²¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkoxyl group, substituted or It represents an unsubstituted aryloxy group or a substituted or unsubstituted heterocyclic oxy group.
J represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, or a substituted or unsubstituted divalent heterocyclic group.
Q represents a substituted or unsubstituted alkylene group.
Ar ⁴ and Ar ^{5 each} represents a substituted or unsubstituted arylene group or a substituted or unsubstituted divalent heterocyclic group. )

  Furthermore, this invention relates to the printed matter obtained by printing the said photocurable ink and making it harden | cure by light irradiation.

  The photocurable ink of the present invention has higher storage stability over time than conventional photocurable inks containing additives such as general-purpose photopolymerization initiators, photosensitizers and polymerization accelerators. Additives such as initiators, photosensitizers and polymerization accelerators are not deposited, and further, ink curability and film hardness of printed materials are not deteriorated. In addition, since the photocurable ink of the present invention can suppress the generation of odor after curing, it leads not only to printed materials and coated materials but also to improvements in the environment of printing and coating sites as compared with conventional photocurable inks. . The photocurable ink of the present invention has good curability and storage stability over time, which cannot be satisfied by conventional inks, and can suppress odor after ink curing.

  The photocurable ink of the present invention includes a resin, a monomer, a pigment, an α-aminoketone photopolymerization initiator represented by the following general formula (1), a general formula (3), or a general formula (4). And a amine compound. Various additives (for example, other polymerization initiators, photosensitizers, polymerization inhibitors, etc.) can also be used in combination.

  First, the photopolymerization initiator will be described. The photopolymerization initiator used in the present invention is represented by the general formula (1).

General formula (1)

(Wherein R ¹ and R ² each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted alkenyl group) R ¹ and R ² may be integrated to form a ring.
R ³ and R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, or COR ⁵ Represents. R ³ and R ⁴ may be combined to form a ring.
R ⁵ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted alkenyl group.
X represents a divalent aromatic ring condensed group having 4 to 16 carbon atoms which may contain a hetero atom.
Ar ¹ represents the following general formula (2) or a substituted or unsubstituted heterocyclic group. )

General formula (2)

(Wherein R ^{6 to} R ¹⁰ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, Substituted or unsubstituted acyl group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted acyloxy group, substituted or unsubstituted alkoxycarbonyl Oxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted heterocyclic thio group, substituted or unsubstituted alkylamino group, substituted or unsubstituted dialkylamino group, substituted or unsubstituted Substituted arylamino group, substituted or unsubstituted diarylamino group, substituted Properly represents the unsubstituted alkyl arylamino group, or a halogen atom. In addition, adjacent substituents of R ⁶ to R ¹⁰ may form a ring together.)

  Next, the structure of the photopolymerization initiator of the present invention will be described in detail.

  As shown in the general formula (1), the photopolymerization initiator of the present invention can introduce various substituents as long as the properties are not impaired. By introducing a substituent, the photopolymerization initiator of the present invention can be used by appropriately adjusting the absorption characteristics of energy rays such as the maximum absorption wavelength and transmittance, and the solubility in the resin or solvent used together.

The substituents R ¹ and R ² in the general formula (1) are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted group. An alkenyl group.

Here, the substituted or unsubstituted alkyl group in R ¹ and R ² is a linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms, or 2 to 18 carbon atoms. Examples include linear, branched, monocyclic or condensed polycyclic alkyl groups optionally interrupted by one or more —O—. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group. 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 group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, 4-decylcyclohexyl group and the like, but are not limited thereto. Specific examples of the linear or branched alkyl group having 2 to 18 carbon atoms and optionally interrupted by one or more of —O— include —CH ₂ —O—CH ₃ , —CH _2. —CH ₂ —O—CH ₂ —CH ₃ , —CH ₂ —CH ₂ —CH ₂ —O—CH ₂ —CH ₃ , — (CH ₂ —CH ₂ —O) _n —CH ₃ (where n is 1) 8 of an integer), - (CH ₂ is _{-CH 2 -CH 2 -O) m -CH} 3 ( wherein m is an integer from 1 to _{5), - CH 2 -CH (CH} 3) -O Examples include —CH ₂ —CH ₃ —, —CH ₂ —CH— (OCH ₃ ) _2, but are not limited thereto.

  Specific examples of the monocyclic or condensed polycyclic alkyl group having 2 to 18 carbon atoms and optionally interrupted by one or more of —O— include, but are not limited to: Is not to be done.

Examples of the substituted or unsubstituted aryl group in R ¹ and R ² include a monocyclic or condensed polycyclic aryl group having 6 to 24 carbon atoms, and specific examples thereof include a phenyl group, a 1-naphthyl group, and 2-naphthyl. Group, 1-anthryl group, 9-anthryl group, 2-phenanthryl group, 3-phenanthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 1-acenaphthyl group Group, 2-fluorenyl group, 9-fluorenyl group, 3-perylenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-xylyl group, 2,5-xylyl group, mesityl group, p -Cumenyl group, p-dodecylphenyl group, p-cyclohexylphenyl group, 4-biphenyl group, o-fluorophenyl group, m-chlorophenyl group, p-bromo A phenyl group, a p-hydroxyphenyl group, an m-carboxyphenyl group, an o-mercaptophenyl group, a p-cyanophenyl group, an m-nitrophenyl group, an m-azidophenyl group, and the like can be mentioned. It is not something.

Examples of the substituted or unsubstituted heterocyclic group in R ¹ and R ² include an aromatic or aliphatic heterocyclic group having 4 to 24 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. 2-thienyl group, 2-benzothienyl group, naphtho [2,3-b] thienyl group, 3-thianthrenyl group, 2-thianthrenyl group, 2-furyl group, 2-benzofuryl group, pyranyl group, isobenzofuranyl Group, chromenyl group, xanthenyl group, phenoxathiinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group 2-indolyl group, 3-indolyl group, 1H-indazolyl group, purinyl group, 4H-quinolidinyl group, Isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, β-carbolinyl group, phenanthridinyl group, 2-acridinyl group, perimidinyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, 3-phenixazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, Imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, thioxan Lil group, 4-quinolinyl group, 4-isoquinolyl group, 3-phenothiazinyl group, 2-phenoxathiinyl group, 3-coumarinyl of the group and the like, but is not limited thereto.

Examples of the substituted or unsubstituted alkenyl group for R ¹ and R ² include straight-chain, branched-chain, monocyclic or condensed polycyclic alkenyl groups having 1 to 18 carbon atoms. -It may have a carbon double bond, and specific examples include vinyl 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, 4-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, cyclopentenyl group, cyclohexenyl group, 1 , 3-butadienyl group, cyclohexadienyl group, cyclopentadienyl group and the like, but are not limited thereto.

R ¹ and R ² may be bonded to the carbon atom of the general formula (1) at substitution positions other than those described above, and these are also in the category of the substituent represented by R ¹ and R ² of the present invention. included.

R ¹ and R ² may be combined to form a ring.

When R ¹ and R ² are combined to form a ring, the formed site is a substituted or unsubstituted alkylene group having 2 to 8 carbon atoms or oxaalkylene group having 3 to 9 carbon atoms. Or an azaalkylene group having 3 to 9 carbon atoms.

  Here, examples of the ring formed in the case of an alkylene group having 2 to 8 carbon atoms include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, and a cyclooctane ring. However, it is not limited to these.

  Examples of the ring formed when the oxaalkylene group having 3 to 9 carbon atoms or the azaalkylene group having 3 to 9 carbon atoms include a tetrahydrofuran ring, a pyrrolidine ring, and a piperidine ring. It is not limited to.

Among the above substituents, R ¹ is preferably an alkyl group or an alkenyl group in terms of the difficulty of synthesis and sensitivity as a radical generator, and specifically includes a methyl group, an ethyl group, a benzyl group, A p-methylbenzyl group or a 2-propenyl group is particularly preferable.

The substituents R ³ and R ⁴ in the general formula (1) are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted Or an unsubstituted alkenyl group, or COR ⁵ .

The substituted or unsubstituted alkyl group in R ³ and R ⁴ has the same meaning as the alkyl group described for R ¹ in the general formula (1).

The substituted or unsubstituted aryl group in R ³ and R ⁴ has the same meaning as the aryl group described for R ¹ in the general formula (1).

The substituted or unsubstituted heterocyclic group for R ³ and R ⁴ has the same meaning as the heterocyclic group described for R ¹ in formula (1).

The substituted or unsubstituted alkenyl group for R ³ and R ⁴ has the same meaning as the alkenyl group described for R ¹ in formula (1).

R ⁵ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted alkenyl group.

The substituted or unsubstituted alkyl group in R ⁵ has the same meaning as the alkyl group described for R ¹ in the general formula (1).

The substituted or unsubstituted aryl group for R ⁵ has the same meaning as the aryl group described for R ¹ in formula (1).

The substituted or unsubstituted heterocyclic group for R ⁵ has the same meaning as the heterocyclic group described for R ¹ in formula (1).

The substituted or unsubstituted alkenyl group for R ⁵ has the same meaning as the alkenyl group described for R ¹ in formula (1).

R ³ and R ⁴ may be combined to form a ring.

When R ³ and R ⁴ are combined to form a ring, the formed site includes an alkylene group having 2 to 6 carbon atoms, an oxaalkylene group having 2 to 6 carbon atoms, and 2 to 6 carbon atoms. Or azaalkylene group having 2 to 6 carbon atoms.

  Here, examples of the ring formed in the case of an alkylene group having 2 to 6 carbon atoms include formation of a propyleneimine ring, a pyrrolidine ring, a piperidine ring, a pipecoline ring, and the like, It is not limited to these.

  Examples of the ring formed when the oxaalkylene group having 2 to 6 carbon atoms, the thiaalkylene group having 2 to 6 carbon atoms, or the azaalkylene group having 2 to 6 carbon atoms include morpholine ring and thiomorpholine ring Examples include, but are not limited to, forming a thiazolidine ring, piperazine ring, or homopiperazine ring.

Among the above-mentioned substituents, R ³ and R ⁴ are substituted or unsubstituted alkyl groups, substituted or unsubstituted alkenyl groups, R in view of synthesis difficulty and sensitivity as radical generators. ^{When 3} and R ⁴ are combined to form a ring, a substituted or unsubstituted alkylene group, a substituted or unsubstituted oxaalkylene group, a substituted or unsubstituted thiaalkylene group, a substituted or unsubstituted aza An alkylene group is preferable, and —NR ³ (R ⁴ ) is, for example, dimethylamino group, diethylamino group, bis-2-methoxyethylamino group, morpholino group, thiomorpholino group, prolidino group, piperidino group, piperazino group, or 1- A methylpiperazino group is particularly preferred.

Ar ¹ in the general formula (1) is the above general formula (2) or a substituted or unsubstituted heterocyclic group.

The substituents R ^{6 to} R ¹⁰ in the general formula (2) are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or Unsubstituted alkenyl group, substituted or unsubstituted acyl group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted acyloxy group, substituted Or unsubstituted alkoxycarbonyloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted heterocyclic thio group, substituted or unsubstituted alkylamino group, substituted or unsubstituted dialkyl Amino group, substituted or unsubstituted arylamino group, substituted or unsubstituted diary Amino group, a substituted or unsubstituted alkyl arylamino group, or a halogen atom.

The substituted or unsubstituted alkyl group in R ^{6 to} R ¹⁰ has the same meaning as the alkyl group described in the general formula (1).

The substituted or unsubstituted aryl group in R ^{6 to} R ¹⁰ has the same meaning as the aryl group described in the general formula (1).

The substituted or unsubstituted heterocyclic group in R ^{6 to} R ¹⁰ has the same meaning as the heterocyclic group described in the general formula (1).

The substituted or unsubstituted alkenyl group in R ^{6 to} R ¹⁰ has the same meaning as the alkenyl group described in the general formula (1).

Examples of the substituted or unsubstituted acyl group in R ^{6 to} R ¹⁰ include 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, carbon A monocyclic or condensed polycyclic heterocyclic group having 4 to 18 carbon atoms, including a carbonyl group, a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom to which a monocyclic or condensed polycyclic aryl group of 6 to 18 is bonded. Examples include a bonded carbonyl group, and specific examples 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, cyclopentyl Carbonyl group, cyclohexylcarbonyl group, acryloyl group, methacryloyl group, crotonoyl group, isocrotono Group, oleoyl group, cinnamoyl group benzoyl group, 1-naphthoyl group, 2-naphthoyl group, 9-anthrylcarbonyl group, 3-furoyl group, 2-thenoyl group, nicotinoyl group, isonicotinoyl group and the like. However, it is not limited to these. Further, the aryl group and the carbonyl group, the heterocyclic group and the carbonyl group may be bonded at positions other than those described above, and these are also included in the category of the substituent represented by R ^{6 to} R ¹⁰ of the present invention. .

The substituted or unsubstituted alkoxyl group in R ^{6 to} R ¹⁰ is a linear, branched, monocyclic or condensed polycyclic alkoxyl group having 1 to 18 carbon atoms, or optionally having 2 to 18 carbon atoms. Examples include a linear, branched, monocyclic or condensed polycyclic alkoxyl group interrupted by one or more —O—. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkoxyl group having 1 to 18 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyl Oxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, isopropoxy group, isobutoxy group, isopentyloxy group, sec-butoxy group, tert-butoxy group, sec-pentyloxy group, tert -Pentyloxy group, tert-octyloxy group, neopentyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, adamantyloxy group, norbornyloxy group, boronyloxy group, 4-decyl Cyclohexyl It can be given group and the like, but not limited thereto. Specific examples of the linear or branched alkoxyl group having 2 to 18 carbon atoms and optionally interrupted by one or more —O— include —O—CH ₂ —O—CH ₃ , — O—CH ₂ —CH ₂ —O—CH ₂ —CH ₃ , —O—CH ₂ —CH ₂ —CH ₂ —O—CH ₂ —CH ₃ , —O— (CH ₂ —CH ₂ —O) _n — CH ₃ (where n is an integer from 1 to 8), —O— (CH ₂ —CH ₂ —CH ₂ —O) _m —CH ₃ (where m is an integer from 1 to 5), — _{OCH 2 -CH (CH 3) -O} -CH 2 -CH 3 -, - OCH 2 -CH- (OCH 3) can be cited _2, etc., but is not limited thereto.

  Specific examples of the monocyclic or condensed polycyclic alkoxyl group having 2 to 18 carbon atoms and optionally interrupted by one or more of —O— include, but are not limited to: Is not to be done.

Examples of the substituted or unsubstituted aryloxy group in R ^{6 to} R ¹⁰ include a monocyclic or condensed polycyclic aryloxy group having 4 to 18 carbon atoms. Specific examples include a phenoxy group, a 1-naphthyloxy group, 2- Naphtyloxy group, 9-anthryloxy group, 9-phenanthryloxy group, 1-pyrenyloxy group, 5-naphthacenyloxy group, 1-indenyloxy group, 2-azurenyloxy group, 1-acenaphthyloxy group , 9-fluorenyloxy group and the like, but are not limited thereto. In addition, the aryl group and the oxygen atom may be bonded at positions other than those described above, and these are also included in the category of the substituent represented by R ^{6 to} R ¹⁰ of the present invention.

Examples of the substituted or unsubstituted heterocyclic oxy group in R ^{6 to} R ¹⁰ include a monocyclic or condensed polycyclic heterocyclic oxy group having 4 to 18 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Specific examples include 2-furanyloxy group, 2-thienyloxy group, 2-indolyloxy group, 3-indolyloxy group, 2-benzofuryloxy group, 2-benzothienyloxy group, 2-carba A zolyloxy group, a 3-carbazolyloxy group, a 4-carbazolyloxy group, a 9-acridinyloxy group, and the like can be mentioned, but are not limited thereto. Further, the heterocyclic group and the oxygen atom may be bonded at positions other than those described above, and these are also included in the category of the substituent represented by R ^{6 to} R ¹⁰ of the present invention.

As the substituted or unsubstituted acyloxy group in R ^{6 to} R ^10, 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, Alternatively, a carbonyloxy group to which a monocyclic or condensed aryl group having 6 to 18 carbon atoms is bonded, or a monocyclic or condensed polycyclic group having 4 to 18 carbon atoms including a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom Examples include a carbonyloxy group to which a heterocyclic group is bonded. Specific examples include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a valeryloxy group, an isovaleryloxy group, a pivaloyloxy group, a lauroyloxy group, Myristoyloxy group, palmitoyloxy group, stearoyloxy group, cyclopentylcarbonyloxy Cyclohexylcarbonyloxy group, acryloyloxy group, methacryloyloxy group, crotonoyloxy group, isocrotonoyloxy group, oleoyloxy group, benzoyloxy group, 1-naphthoyloxy group, 2-naphthoyloxy group, cinnamoyl Examples thereof include, but are not limited to, an oxy group, a 3-furoyloxy group, a 2-thenoyloxy group, a nicotinoyloxy group, an isonicotinoyloxy group, a 9-anthroyloxy group, and a 5-naphthacenoyloxy group. It is not something. In addition, the aryl group and the carbonyloxy group, the heterocyclic group and the carbonyloxy group may be bonded at positions other than those described above, and these are also in the category of the substituent represented by R ^{6 to} R ¹⁰ of the present invention. included.

Examples of the substituted or unsubstituted alkoxycarbonyloxy group in R ^{6 to} R ¹⁰ include a carbonic acid ester group having 1 to 12 carbon atoms, and specific examples include a tert-butoxycarbonyloxy group and a tert-pentyloxycarbonyloxy group. 1,1-diethylpropyloxycarbonyloxy group, 1-ethyl-2-cyclopentenyloxycarbonyloxy group, 2-tetrahydropyranyloxycarbonyloxy group, 1-ethylcyclopentyloxycarbonyloxy group and the like. However, it is not limited to these.

Examples of the substituted or unsubstituted alkylthio group in R ^{6 to} R ¹⁰ include a linear, branched, monocyclic or condensed polycyclic alkylthio group having 1 to 18 carbon atoms, and specific examples include a methylthio group. , Ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, octylthio group, decylthio group, dodecylthio group, octadecylthio group and the like, but are not limited thereto.

Examples of the substituted or unsubstituted arylthio group in R ^{6 to} R ¹⁰ include a monocyclic or condensed polycyclic arylthio group having 4 to 18 carbon atoms, and specific examples thereof include a phenylthio group, a 1-naphthylthio group, and a 2-naphthylthio group. Groups, 9-anthrylthio groups, 9-phenanthrylthio groups, and the like, but are not limited thereto. Moreover, the aryl group and the sulfur atom may be bonded at positions other than those described above, and these are also included in the category of the substituent represented by R ^{6 to} R ¹⁰ of the present invention.

Examples of the substituted or unsubstituted heterocyclic thio group in R ^{6 to} R ¹⁰ include a monocyclic or condensed polycyclic heterocyclic thio group having 4 to 18 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Specific examples include 2-furylthio group, 2-thienylthio group, 2-pyrrolylthio group, 6-indolylthio group, 2-benzofurylthio group, 2-benzothienylthio group, 2-carbazolylthio group, 3-carbazolylthio group. Group, 4-carbazolylthio group and the like can be mentioned, but not limited thereto. Moreover, the heterocyclic group and the sulfur atom may be bonded at positions other than those described above, and these are also included in the category of the substituent represented by R ^{6 to} R ¹⁰ of the present invention.

Examples of the substituted or unsubstituted alkylamino group in R ^{6 to} R ¹⁰ include a methylamino group, an ethylamino group, a propylamino group, a butylamino group, a pentylamino group, a hexylamino group, a heptylamino group, an octylamino group, and a nonylamino group. Group, decylamino group, dodecylamino group, octadecylamino 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-adapto Ntamino group, can be exemplified such as 2-Adamantamino group, but is not limited thereto.

Examples of the substituted or unsubstituted dialkylamino group in R ^{6 to} R ¹⁰ include 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, Examples thereof include, but are not limited to, a cyclopropylamino group, a pyrrolidino group, a piperidino group, and a piperazino group.

Examples of the substituted or unsubstituted arylamino group in R ^{6 to} R ¹⁰ include an N-arylamino group, anilino group, 1-naphthylamino group, 2-naphthylamino group, o-toluidino group, m-toluidino group, p- Toluino group, 2-biphenylamino group, 3-biphenylamino group, 4-biphenylamino group, 1-fluoreneamino group, 2-fluoreneamino group, 2-thiazoleamino group, p-terphenylamino group, indolino group, etc. It can be mentioned, but is not limited to these.

Examples of the substituted or unsubstituted diarylamino group in R ^{6 to} R ¹⁰ include a diarylamino group, a diphenylamino group, a ditolylamino group, an N-phenyl-1-naphthylamino group, and an N-phenyl-2-naphthylamino group. However, it is not limited to these.

Examples of the substituted or unsubstituted alkylarylamino group in R ^{6 to} R ¹⁰ 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 can be mentioned, but are not limited thereto.

Examples of the halogen atom in R ^{6 to} R ¹⁰ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Among the above substituents, examples of the substituent R ⁶ to R ^10, and faces the difficulty of synthesis, in view of the sensitivity of the radical generator, the substituents R ⁶ to R ¹⁰ all simultaneously hydrogen atom, a substituent R ⁶ is a methyl group and the substituents R ^{7 to} R ¹⁰ are simultaneously hydrogen atoms, the substituent R ¹⁰ is a methyl group and the substituents R ^{6 to} R ⁹ are simultaneously hydrogen atoms, the substituent R ⁸ is a methyl group and the substituent R ⁶ , It is particularly preferred that R ⁷ , R ⁹ and R ¹⁰ are simultaneously hydrogen atoms.

Moreover, the adjacent substituents of R ^{6 to} R ¹⁰ may be integrated to form a ring.

When adjacent substituents of R ^{6 to} R ¹⁰ are combined to form a ring, examples of the site to be formed include those shown in Table 1 below, but are not limited thereto. It is not a thing.

Table 1

Examples of the substituted or unsubstituted heterocyclic group for Ar ¹ include, but are not limited to, the same substituents as those exemplified as the heterocyclic group described above.

Ar ¹ is preferably a substituent represented by the general formula (2) from the viewpoint of synthesis and sensitivity.

  X in the general formula (1) is a divalent condensed polycyclic aromatic group which may contain a hetero atom.

  In the present invention, the condensed polycyclic aromatic group is an aromatic ring in which two or more rings are condensed and at least one ring may contain a hetero atom.

  Examples of the aromatic ring in X include aromatic rings having 4 to 30 carbon atoms, and specifically include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring, a naphthacene ring, a pyrenyl group, a phenyl group. Naphthalene ring, indenyl ring, azulene ring, furan ring, pyrrole ring, thiophene ring, indole ring, benzofuran ring, benzothiophene ring, indene ring, quinoline ring, isoquinoline ring, carbazole ring, dibenzofuran ring, dibenzothiophene ring, phenoxathiin Ring, phenothiazine ring, thianthrene ring, xanthene ring, thioxanthene ring, phenoxazine ring, phenazine ring, acridine ring, xanthone ring, benzoxazole ring, benzothiazole ring, benzimidazole ring, indazole ring, 1,2-benzisoxazo Le ring, phenanthridine ring, phenanthroline ring, a pyrazine ring, a pyridazine ring, an acridone ring, there may be mentioned N- phenyl pyrrole ring, etc., but is not limited thereto.

  The aromatic ring in X is not particularly limited, and the type of heteroatom, the number of heteroatoms, and the substitution position of the heteroatom are not particularly limited.

  Although the kind of hetero atom in the aromatic ring in X is not particularly limited, a nitrogen atom, an oxygen atom and a sulfur atom are preferable.

  The number of heteroatoms in the aromatic ring in X is not particularly limited, but is preferably 0 to 4.

  Although the substitution position of the hetero atom in the aromatic ring in X is not particularly limited, it is bonded so as not to block the conjugation between the aromatic ring contained in X and at least one of the two carbonyl groups of the general formula (1). It is preferable.

  The number of carbon atoms in the aromatic ring in X is not particularly limited, but is preferably 4 to 16 carbon atoms.

  Preferred examples of the aromatic ring in X include furan ring, pyrrole ring, thiophene ring, indole ring, benzofuran ring, benzothiophene ring, carbazole ring, dibenzofuran ring, dibenzothiophene ring, phenoxathiin ring, phenothiazine ring, thianthrene ring. , Xanthene ring, thioxanthene ring, phenoxazine ring, phenazine ring, acridine ring, xanthone ring, benzoxazole ring, benzothiazole ring, benzimidazole ring, indazole ring, 1,2-benzisoxazole ring, phenanthridine ring , An acridone ring, and particularly preferably a carbazole ring.

The substituents that R ^{1 to} R ¹⁰ in the general formula (1) and the general formula (2) may have include a hydroxyl group, a mercapto group, a cyano group, a nitro group, a halogen atom, an alkyl group, and an aryl group. 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 group, arylamino group, A diarylamino group, an alkylarylamino group, a benzylamino group, a dibenzylamino group and the like can be mentioned.

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

The alkyl group is a linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms, or 2 to 18 carbon atoms and optionally interrupted by one or more —O—. Examples include linear, branched, monocyclic or condensed polycyclic alkyl groups. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group. 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 group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, 4-decylcyclohexyl group and the like, but are not limited thereto. Specific examples of the linear or branched alkyl group having 2 to 18 carbon atoms and optionally interrupted by one or more of —O— include —CH ₂ —O—CH ₃ , —CH _2. —CH ₂ —O—CH ₂ —CH ₃ , —CH ₂ —CH ₂ —CH ₂ —O—CH ₂ —CH ₃ , — (CH ₂ —CH ₂ —O) _n —CH ₃ (where n is 1) 8 of an integer), - (CH ₂ is _{-CH 2 -CH 2 -O) m -CH} 3 ( wherein m is an integer from 1 to _{5), - CH 2 -CH (CH} 3) -O _{-CH 2 -CH 3 -, - CH} 2 -CH- (OCH 3) 2 , and the like.

  Specific examples of the monocyclic or condensed polycyclic alkyl group having 2 to 18 carbon atoms and optionally interrupted by one or more of —O— include, but are not limited to: Is not to be done.

  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, a 9-phenanthryl group, Examples include 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 having 4 to 18 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Specific examples include a 2-furanyl group, 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, crotonoy 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, An isonicotinoyl group, a 9-anthroyl group, a 5-naphthacenoyl group, etc. are mentioned.

Examples of the alkoxyl group include linear, branched, monocyclic or condensed polycyclic alkoxyl groups having 1 to 18 carbon atoms. Or a linear, branched, monocyclic or condensed polycyclic alkoxyl group having 2 to 18 carbon atoms and optionally interrupted by one or more —O—. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkoxyl group having 1 to 18 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyl Oxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, isopropoxy group, isobutoxy group, isopentyloxy group, sec-butoxy group, tert-butoxy group, sec-pentyloxy group, tert -Pentyloxy group, tert-octyloxy group, neopentyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, adamantyloxy group, norbornyloxy group, boronyloxy group, 4-decyl Cyclohexyl It can be given group and the like, but not limited thereto. Specific examples of the linear or branched alkoxyl group having 2 to 18 carbon atoms and optionally interrupted by one or more —O— include —O—CH ₂ —O—CH ₃ , — O—CH ₂ —CH ₂ —O—CH ₂ —CH ₃ , —O—CH ₂ —CH ₂ —CH ₂ —O—CH ₂ —CH ₃ , —O— (CH ₂ —CH ₂ —O) _n — CH ₃ (where n is an integer from 1 to 8), —O— (CH ₂ —CH ₂ —CH ₂ —O) _m —CH ₃ (where m is an integer from 1 to 5), — _{OCH 2 -CH (CH 3) -O} -CH 2 -CH 3 -, - OCH 2 -CH- (OCH 3) 2 , and the like.

  Specific examples of the monocyclic or condensed polycyclic alkoxyl group having 2 to 18 carbon atoms and optionally interrupted by one or more of -O- include the following, but are not limited thereto. Is not to be done.

  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, a 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. It is done.

  Examples of the heterocyclic oxy group include a monocyclic or condensed polycyclic heterocyclic oxy group having 4 to 18 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom, and specific examples include a 2-furanyloxy group. 2-thienyloxy group, 2-indolyloxy group, 3-indolyloxy group, 2-benzofuryloxy group, 2-benzothienyloxy group, 2-carbazolyloxy group, 3-carbazolyloxy group , 4-carbazolyloxy group, 9-acridinyloxy group and the like.

  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, acrylo Ruoxy 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 linear, branched, monocyclic or condensed polycyclic alkylthio groups 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 having 4 to 18 carbon atoms including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom, and specific examples include a 2-furylthio group. 2-thienylthio group, 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.

  Specific examples of particularly preferred photopolymerization initiators described above are shown below, but the structure of the photopolymerization initiator of the present invention is not limited thereto.

  Next, the photosensitizer will be described. The photosensitizer used in the present invention is represented by general formulas (3) to (6).

R ^{11 to} R ²⁰ in the general formula (3) are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl. Group, substituted or unsubstituted acyl group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted acyloxy group, substituted or unsubstituted Alkoxycarbonyl group, substituted or unsubstituted alkoxycarbonyloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted heterocyclic thio group, substituted or unsubstituted alkylamino group, substituted Or an unsubstituted dialkylamino group, a substituted or unsubstituted aryl Represents a ruamino group, a substituted or unsubstituted diarylamino group, a substituted or unsubstituted alkylarylamino group, or a halogen atom.

The substituted or unsubstituted alkyl group in R ^{11 to} R ²⁰ has the same meaning as the alkyl group described in the general formula (1).

The substituted or unsubstituted aryl group in R ^{11 to} R ²⁰ has the same meaning as the aryl group described in the general formula (1).

The substituted or unsubstituted heterocyclic group in R ^{11 to} R ²⁰ has the same meaning as the heterocyclic group described in the general formula (1).

The substituted or unsubstituted alkenyl group in R ^{11 to} R ²⁰ has the same meaning as the alkenyl group described in the general formula (1).

The substituted or unsubstituted acyl group in R ^{11 to} R ²⁰ has the same meaning as the acyl group described in the general formula (2).

The substituted or unsubstituted alkoxyl group in R ^{11 to} R ²⁰ has the same meaning as the alkoxyl group described in the general formula (2).

The substituted or unsubstituted aryloxy group in R ^{11 to} R ²⁰ has the same meaning as the aryloxy group described in the general formula (2).

The substituted or unsubstituted heterocyclic oxy group in R ^{11 to} R ²⁰ has the same meaning as the heterocyclic oxy group described in the general formula (2).

The substituted or unsubstituted acyloxy group in R ^{11 to} R ²⁰ has the same meaning as the acyloxy group described in the general formula (2).

Examples of the substituted or unsubstituted alkoxycarbonyl group in R ^{11 to} R ²⁰ include an alkoxycarbonyl group having 2 to 20 carbon atoms, and specific examples include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, and a butoxycarbonyl group. Hexyloxycarbonyl group, octyloxycarbonyl group, decyloxycarbonyl group, octadecyloxycarbonyl group, phenoxycarbonyl group, trifluoromethyloxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-methylsulfanyl Phenyloxycarbonyl group, 4-phenylsulfanylphenyloxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, Lolophenyloxycarbonyl group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 4-fluoropheno Examples include a ruoxycarbonyl group, a 4-cyanophenyloxycarbonyl group, and a 4-methoxyphenyloxycarbonyl group.

The substituted or unsubstituted alkoxycarbonyloxy group in R ^{11 to} R ²⁰ has the same meaning as the alkoxycarbonyloxy group described in the general formula (2).

The substituted or unsubstituted alkylthio group in R ^{11 to} R ²⁰ has the same meaning as the alkylthio group described in the general formula (2).

The substituted or unsubstituted arylthio group in R ^{11 to} R ²⁰ has the same meaning as the arylthio group described in the general formula (2).

The substituted or unsubstituted heterocyclic thio group in R ^{11 to} R ²⁰ has the same meaning as the heterocyclic thio group described in the general formula (2).

The substituted or unsubstituted alkylamino group in R ^{11 to} R ²⁰ has the same meaning as the alkylamino group described in the general formula (2).

The substituted or unsubstituted dialkylamino group in R ^{11 to} R ²⁰ has the same meaning as the dialkylamino group described in the general formula (2).

The substituted or unsubstituted arylamino group in R ^{11 to} R ²⁰ has the same meaning as the arylamino group described in the general formula (2).

The substituted or unsubstituted diarylamino group in R ^{11 to} R ²⁰ has the same meaning as the diarylamino group described in the general formula (2).

The substituted or unsubstituted alkylarylamino group in R ^{11 to} R ²⁰ has the same meaning as the alkylarylamino group described in the general formula (2).

The halogen atom in R ^{11 to} R ²⁰ has the same meaning as the halogen atom described in the general formula (2).

In addition, R ^{11 to} R ¹⁵ and R ^{16 to} R ²⁰ may each independently form adjacent rings to form a ring.

Specific examples of the case where R ^{11 to} R ¹⁵ and R ^{16 to} R ²⁰ are each independently adjacent to each other integrally form a ring include those shown in Table 2 below. It is not limited to.

Table 2

R ¹⁵ and R ¹⁶ are integrally formed with —O—, —S—,>S═O,> SO ₂ , —N (R ²¹ ) —, —CO—, —CH ₂ —, —CH _2. CH ₂ —, —CH═CH—, an alkylidene group having 2 to 6 carbon atoms, or a direct bond may be formed.

R ²¹ in the general formula (3) is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, substituted or unsubstituted Represents an alkoxyl group, a substituted or unsubstituted aryloxy group, or a substituted or unsubstituted heterocyclic oxy group.

The substituted or unsubstituted alkyl group for R ²¹ has the same meaning as the alkyl group described in formula (1).

The substituted or unsubstituted aryl group in R ²¹ has the same meaning as the aryl group described in the general formula (1).

The substituted or unsubstituted heterocyclic group for R ²¹ has the same meaning as the heterocyclic group described in formula (1).

The substituted or unsubstituted alkenyl group for R ²¹ has the same meaning as the alkenyl group described in formula (1).

The substituted or unsubstituted alkoxyl group in R ²¹ has the same meaning as the alkoxyl group described in the general formula (2).

The substituted or unsubstituted aryloxy group for R ²¹ has the same meaning as the aryloxy group described in formula (2).

The substituted or unsubstituted heterocyclic oxy group for R ²¹ has the same meaning as the heterocyclic oxy group described in formula (2).

R ^{22 to} R ³⁹ in the general formula (4) are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl. Group, substituted or unsubstituted acyl group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted acyloxy group, substituted or unsubstituted Alkoxycarbonyl group, substituted or unsubstituted alkoxycarbonyloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted heterocyclic thio group, substituted or unsubstituted alkylamino group, substituted Or an unsubstituted dialkylamino group, a substituted or unsubstituted aryl Represents a ruamino group, a substituted or unsubstituted diarylamino group, a substituted or unsubstituted alkylarylamino group, or a halogen atom.

The substituted or unsubstituted alkyl group in R ^{22 to} R ³⁹ has the same meaning as the alkyl group described in the general formula (1).

The substituted or unsubstituted aryl group in R ^{22 to} R ³⁹ has the same meaning as the aryl group described in the general formula (1).

The substituted or unsubstituted heterocyclic group in R ^{22 to} R ³⁹ has the same meaning as the heterocyclic group described in the general formula (1).

The substituted or unsubstituted alkenyl group in R ^{22 to} R ³⁹ has the same meaning as the alkenyl group described in the general formula (1).

The substituted or unsubstituted acyl group in R ^{22 to} R ³⁹ has the same meaning as the acyl group described in the general formula (2).

The substituted or unsubstituted alkoxyl group in R ^{22 to} R ³⁹ has the same meaning as the alkoxyl group described in the general formula (2).

The substituted or unsubstituted aryloxy group in R ^{22 to} R ³⁹ has the same meaning as the aryloxy group described in the general formula (2).

The substituted or unsubstituted heterocyclic oxy group in R ^{22 to} R ³⁹ has the same meaning as the heterocyclic oxy group described in the general formula (2).

The substituted or unsubstituted acyloxy group in R ^{22 to} R ³⁹ has the same meaning as the acyloxy group described in the general formula (2).

The substituted or unsubstituted alkoxycarbonyl group in R ^{22 to} R ³⁹ has the same meaning as the alkoxycarbonyl group described in the general formula (3).

The substituted or unsubstituted alkoxycarbonyloxy group in R ^{22 to} R ³⁹ has the same meaning as the alkoxycarbonyloxy group described in the general formula (2).

The substituted or unsubstituted alkylthio group in R ^{22 to} R ³⁹ has the same meaning as the alkylthio group described in the general formula (2).

The substituted or unsubstituted arylthio group in R ^{22 to} R ³⁹ has the same meaning as the arylthio group described in the general formula (2).

The substituted or unsubstituted heterocyclic thio group in R ^{22 to} R ³⁹ has the same meaning as the heterocyclic thio group described in the general formula (2).

The substituted or unsubstituted alkylamino group in R ^{22 to} R ³⁹ has the same meaning as the alkylamino group described in the general formula (2).

The substituted or unsubstituted dialkylamino group in R ^{22 to} R ³⁹ has the same meaning as the dialkylamino group described in the general formula (2).

The substituted or unsubstituted arylamino group in R ^{22 to} R ³⁹ has the same meaning as the arylamino group described in the general formula (2).

The substituted or unsubstituted diarylamino group in R ^{22 to} R ³⁹ has the same meaning as the diarylamino group described in the general formula (2).

The substituted or unsubstituted alkylarylamino group in R ^{22 to} R ³⁹ has the same meaning as the alkylarylamino group described in the general formula (2).

The halogen atom in R ^{22 to} R ³⁹ has the same meaning as the halogen atom described in the general formula (2).

In addition, R ^{22 to} R ²⁶ , R ^{27 to} R ³⁰ , R ^{31 to} R ³⁴ , and R ^{35 to} R ³⁹ may each independently form substituents to form a ring.

As specific examples in the case where R ^{22 to} R ²⁶ , R ^{27 to} R ³⁰ , R ^{31 to} R ³⁴ , and R ^{35 to} R ³⁹ are each independently adjacent to each other to form a ring, Although what is represented by Table 3, 4 is mentioned, it is not limited to these.

Table 3

Table 4

R ²⁶ and R ²⁷ , or R ³⁴ and R ³⁵ are combined with each other as —O—, —S—,>S═O,> SO ₂ , —N (R ²¹ ) —, —CO—, — CH ₂ —, —CH ₂ CH ₂ —, —CH═CH—, an alkylidene group having 2 to 6 carbon atoms, or a direct bond may be formed.

R ²¹ in the general formula (4) has the same meaning as R ²¹ described in Formula (3).

R ⁴⁰ in the general formula (4), -O -, - S -, - N (R 21) -, - CO -, - OCO-, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, Substituted or unsubstituted divalent heterocyclic group, substituted or unsubstituted alkenylene group, alkynylene group, —O—J—, —O—J—O—, —O—J—CO—, —CO—J— , -CO-J-CO-, -COO-J-, -COO-JO-, -COO-J-OOC-, -OCO-J-, -OCO-J-O-, -OCO-J- It represents OCO-, -COO-J-OCO-, -Q-COO-J-OOC-Q-, -O-Q-COO-J-OOC-QO-, or a direct bond.

The substituted or unsubstituted alkylene group for R ⁴⁰ is a divalent linear or branched monocyclic ring formed by removing one hydrogen atom from the same substituent as the alkyl group described in formula (1). A condensed polycyclic group can be exemplified, but is not limited thereto.

Examples of the substituted or unsubstituted arylene group for R ⁴⁰ include a divalent linear, branched, or single divalent group formed by removing one hydrogen atom from the same substituent as the aryl group described in the general formula (1). Although a cyclic | annular and condensed polycyclic group can be mentioned, it is not limited to these.

As the substituted or unsubstituted divalent heterocyclic group for R ^{40, a} divalent straight chain formed by removing one hydrogen atom from the same substituent as the heterocyclic group described in formula (1), Examples thereof include, but are not limited to, branched, monocyclic, and condensed polycyclic groups.

Examples of the substituted or unsubstituted alkenylene group for R ⁴⁰ include a divalent linear, branched, or single divalent group formed by removing one hydrogen atom from the same substituent as the alkenyl group described in the general formula (1). Although a cyclic | annular and condensed polycyclic group can be mentioned, it is not limited to these.

  J in the general formula (4) represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, or a substituted or unsubstituted divalent heterocyclic group.

  The substituted or unsubstituted alkylene group in J is a divalent linear or branched monocyclic ring formed by removing one hydrogen atom from the same substituent as the alkyl group described in the general formula (1). Although a condensed polycyclic group can be mentioned, it is not limited to these.

  The substituted or unsubstituted arylene group in J is a divalent linear, branched, or monocyclic ring formed by removing one hydrogen atom from the same substituent as the aryl group described in the general formula (1). A condensed polycyclic group can be exemplified, but is not limited thereto.

  The substituted or unsubstituted divalent heterocyclic group in J is a divalent linear or branched group formed by removing one hydrogen atom from the same substituent as the heterocyclic group described in the general formula (1). Examples thereof include, but are not limited to, chain, monocyclic, and condensed polycyclic groups.

  Q in the general formula (4) represents a substituted or unsubstituted alkylene group.

  The substituted or unsubstituted alkylene group for Q has the same meaning as the alkylene group described in formula (4).

R ⁴¹ to R ⁴⁸ each independently in the general formula (5), a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl Group, substituted or unsubstituted acyl group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted acyloxy group, substituted or unsubstituted Alkoxycarbonyl group, substituted or unsubstituted alkoxycarbonyloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted heterocyclic thio group, substituted or unsubstituted alkylamino group, substituted Or an unsubstituted dialkylamino group, a substituted or unsubstituted aryl Represents a ruamino group, a substituted or unsubstituted diarylamino group, a substituted or unsubstituted alkylarylamino group, or a halogen atom.

The substituted or unsubstituted alkyl group in R ^{41 to} R ⁴⁸ has the same meaning as the alkyl group described in the general formula (1).

The substituted or unsubstituted aryl group in R ^{41 to} R ⁴⁸ has the same meaning as the aryl group described in the general formula (1).

The substituted or unsubstituted heterocyclic group in R ^{41 to} R ⁴⁸ has the same meaning as the heterocyclic group described in the general formula (1).

The substituted or unsubstituted alkenyl group in R ^{41 to} R ⁴⁸ has the same meaning as the alkenyl group described in the general formula (1).

The substituted or unsubstituted acyl group in R ^{41 to} R ⁴⁸ has the same meaning as the acyl group described in the general formula (2).

The alkoxyl group having a substituted or unsubstituted in R ⁴¹ to R ^48, the same meaning as alkoxy groups described for the general formula (2).

The substituted or unsubstituted aryloxy group in R ^{41 to} R ⁴⁸ has the same meaning as the aryloxy group described in the general formula (2).

The substituted or unsubstituted heterocyclic oxy group in R ^{41 to} R ⁴⁸ has the same meaning as the heterocyclic oxy group described in the general formula (2).

The substituted or unsubstituted acyloxy group in R ^{41 to} R ⁴⁸ has the same meaning as the acyloxy group described in the general formula (2).

The substituted or unsubstituted alkoxycarbonyl group in R ^{41 to} R ⁴⁸ has the same meaning as the alkoxycarbonyl group described in the general formula (3).

The alkoxycarbonyl group substituted or unsubstituted in R ⁴¹ to R ^48, the same meanings as alkoxycarbonyloxy group described by formula (2).

The substituted or unsubstituted alkylthio group in R ^{41 to} R ⁴⁸ has the same meaning as the alkylthio group described in the general formula (2).

The substituted or unsubstituted arylthio group in R ^{41 to} R ⁴⁸ has the same meaning as the arylthio group described in the general formula (2).

The substituted or unsubstituted heterocyclic thio group in R ^{41 to} R ⁴⁸ has the same meaning as the heterocyclic thio group described in the general formula (2).

The substituted or unsubstituted alkylamino group in R ^{41 to} R ⁴⁸ has the same meaning as the alkylamino group described in the general formula (2).

The substituted or unsubstituted dialkylamino group in R ^{41 to} R ⁴⁸ has the same meaning as the dialkylamino group described in the general formula (2).

The substituted or unsubstituted arylamino group in R ^{41 to} R ⁴⁸ has the same meaning as the arylamino group described in the general formula (2).

The substituted or unsubstituted diarylamino group in R ^{41 to} R ⁴⁸ has the same meaning as the diarylamino group described in the general formula (2).

The alkyl aryl amino group substituted or unsubstituted in R ⁴¹ to R ^48, the same meaning as alkyl aryl amino group explained in the general formula (2).

The halogen atom in R ^{41 to} R ⁴⁸ has the same meaning as the halogen atom described in the general formula (2).

In addition, R ^{41 to} R ⁴⁴ and R ^{45 to} R ⁴⁸ may each independently form adjacent rings to form a ring.

Specific examples of the case where R ^{41 to} R ⁴⁴ and R ^{45 to} R ⁴⁸ are each independently adjacent to each other integrally form a ring include those represented by Table 5 below. It is not limited to these.

Table 5

A ¹ in the general formula (5) represents —O—, —S—,>S═O,> SO ₂ , —N (R ²¹ ) —, —CO—, —CH ₂ —, —CH ₂ CH ₂ —. , -CH = CH-, an alkylidene group having 2 to 6 carbon atoms, or a direct bond.

R ²¹ in the general formula (5) has the same meaning as R ²¹ described in Formula (3).

R ^{49 to} R ⁶² in the general formula (6) are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl. Group, substituted or unsubstituted acyl group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted acyloxy group, substituted or unsubstituted Alkoxycarbonyl group, substituted or unsubstituted alkoxycarbonyloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted heterocyclic thio group, substituted or unsubstituted alkylamino group, substituted Or an unsubstituted dialkylamino group, a substituted or unsubstituted aryl Represents a ruamino group, a substituted or unsubstituted diarylamino group, a substituted or unsubstituted alkylarylamino group, or a halogen atom.

The substituted or unsubstituted alkyl group in R ^{49 to} R ⁶² has the same meaning as the alkyl group described in the general formula (1).

The substituted or unsubstituted aryl group in R ^{49 to} R ⁶² has the same meaning as the aryl group described in the general formula (1).

The substituted or unsubstituted heterocyclic group in R ^{49 to} R ⁶² has the same meaning as the heterocyclic group described in the general formula (1).

The substituted or unsubstituted alkenyl group in R ^{49 to} R ⁶² has the same meaning as the alkenyl group described in the general formula (1).

The substituted or unsubstituted acyl group in R ^{49 to} R ⁶² has the same meaning as the acyl group described in the general formula (2).

The alkoxyl group having a substituted or unsubstituted in R ⁴⁹ to R ^62, the same meaning as alkoxy groups described for the general formula (2).

The substituted or unsubstituted aryloxy group in R ^{49 to} R ⁶² has the same meaning as the aryloxy group described in the general formula (2).

The substituted or unsubstituted heterocyclic oxy group in R ^{49 to} R ⁶² has the same meaning as the heterocyclic oxy group described in the general formula (2).

The substituted or unsubstituted acyloxy group in R ^{49 to} R ⁶² has the same meaning as the acyloxy group described in the general formula (2).

The substituted or unsubstituted alkoxycarbonyl group in R ^{49 to} R ⁶² has the same meaning as the alkoxycarbonyl group described in the general formula (3).

The substituted or unsubstituted alkoxycarbonyloxy group in R ^{49 to} R ⁶² has the same meaning as the alkoxycarbonyloxy group described in the general formula (2).

The substituted or unsubstituted alkylthio group in R ^{49 to} R ⁶² has the same meaning as the alkylthio group described in the general formula (2).

The substituted or unsubstituted arylthio group in R ^{49 to} R ⁶² has the same meaning as the arylthio group described in the general formula (2).

The substituted or unsubstituted heterocyclic thio group in R ^{49 to} R ⁶² has the same meaning as the heterocyclic thio group described in the general formula (2).

The substituted or unsubstituted alkylamino group in R ^{49 to} R ⁶² has the same meaning as the alkylamino group described in the general formula (2).

The substituted or unsubstituted dialkylamino group in R ^{49 to} R ⁶² has the same meaning as the dialkylamino group described in the general formula (2).

The substituted or unsubstituted arylamino group in R ^{49 to} R ⁶² has the same meaning as the arylamino group described in the general formula (2).

The substituted or unsubstituted diarylamino group in R ^{49 to} R ⁶² has the same meaning as the diarylamino group described in the general formula (2).

The substituted or unsubstituted alkylarylamino group in R ^{49 to} R ⁶² has the same meaning as the alkylarylamino group described in the general formula (2).

The halogen atom in R ^{49 to} R ⁶² has the same meaning as the halogen atom described in the general formula (2).

In addition, R ^{49 to} R ⁵² , R ^{53 to} R ⁵⁵ , R ^{56 to} R ⁵⁸ , and R ^{59 to} R ⁶² may each independently form adjacent substituents to form a ring.

As specific examples in which R ^{49 to} R ⁵² , R ^{53 to} R ⁵⁵ , R ^{56 to} R ⁵⁸ , and R ^{59 to} R ⁶² are each independently adjacent to each other to form a ring, Table 6 Although what is represented by Table 7 is mentioned, it is not limited to these.

Table 6

Table 7

A ² and A ³ in the general formula (6) are —O—, —S—,>S═O,> SO ₂ , —N (R ²¹ ) —, —CO—, —CH ₂ —, —CH _2. It represents CH ₂ —, —CH═CH—, an alkylidene group having 2 to 6 carbon atoms, or a direct bond.

R ²¹ in the general formula (6) has the same meaning as R ²¹ described in Formula (3).

R ⁶³ in the general formula (6) is —O—, —S—, —N (R ²¹ ) —, —CO—, —OCO—, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, Substituted or unsubstituted divalent heterocyclic group, substituted or unsubstituted alkenylene group, alkynylene group, —O—J—, —O—J—O—, —O—J—CO—, —CO—J— , -CO-J-CO-, -COO-J-, -COO-JO-, -COO-J-OOC-, -OCO-J-, -OCO-J-O-, -OCO-J- It represents OCO-, -COO-J-OCO-, -Q-COO-J-OOC-Q-, -O-Q-COO-J-OOC-QO-, or a direct bond.

The substituted or unsubstituted alkylene group for R ⁶³ has the same meaning as the alkylene group described in formula (4).

The substituted or unsubstituted arylene group in R ⁶³ has the same meaning as the arylene group described in the general formula (4).

The substituted or unsubstituted divalent heterocyclic group for R ⁶³ has the same meaning as the divalent heterocyclic group described in formula (4).

The substituted or unsubstituted alkenylene group in R ⁶³ has the same definition as the alkenylene group described in the general formula (4).

  J in the general formula (6) represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, or a substituted or unsubstituted divalent heterocyclic group.

  The substituted or unsubstituted alkylene group in J has the same meaning as the alkylene group described in the general formula (4).

  The substituted or unsubstituted arylene group in J has the same meaning as the arylene group described in the general formula (4).

  The substituted or unsubstituted divalent heterocyclic group in J has the same meaning as the divalent heterocyclic group described in the general formula (4).

  Q in the general formula (6) represents a substituted or unsubstituted alkylene group.

  The substituted or unsubstituted alkylene group for Q has the same meaning as the alkylene group described in formula (4).

  Specific preferred examples of the photosensitizer described above are shown below, but the structure of the photosensitizer of the present invention is not limited thereto.

  Next, the amine compound will be described. The amine compound used in the present invention is a tertiary amine, and is preferably represented by the general formula (7) or the general formula (8).

  Specific examples of the tertiary amine include, for example, triethylamine, tributylamine, octyldimethylamine, N-butyl-diethanolamine, benzyldimethylamine, phenoldiethanolamine, 1-dimethylamino-2-phenyl-2-methylpropane, 1-dimethylamino. -3-methoxy-2,2-dimethylpropane, 1-dimethylamino-3-acetoxy-2,2-dimethylpropane, 1-diethylamino-3-isopropyloxy-2,2-dimethylpropane, 3-N, N- Pentamethylene-2,2-dimethylpropanol, 1-dimethylamino-3-acryloyloxy-2,2-dimethylpropane, 1-dimethylamino-3-methacryloyloxy-2,2-dimethylpropane, 1-dimethylamino-3 -Benzoyloxy 2,2-dimethylpropane, 1-dimethylamino-3-p-dimethylaminobenzoyl-2,2-dimethylpropane, N, N-dimethylaniline, 4-acetyl-N, N-dimethylaniline, 4-cyano-N , N-dimethylaniline, 4-bromo-N, N-dimethylaniline, 3-chloro-N, N-dimethylaniline, 4-ethoxy-N, N-diethylaniline, 4-amino-N, N-dimethylaniline, 4 -Fluoro-N, N-dimethylaniline, ethyl-4- (N, N-dimethylamino) benzoate, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, 2-ethylhexyl p-dimethylaminobenzoate , P-dimethylaminobenzoic acid-n-hexyl, benzyl p-dimethylaminobenzoate, p-dimethyl Aminoacetophenone, 4-dimethylamino benzophenone, 4,4'-bis-dimethylamino benzophenone, may be mentioned 4,4'-bis-diethylamino benzophenone, but is not limited thereto.

R ⁶⁴ and R ⁶⁵ in the general formula (7) each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.

The substituted or unsubstituted alkyl group in R ⁶⁴ and R ⁶⁵ has the same meaning as the alkyl group described in the general formula (1).

The substituted or unsubstituted aryl group in R ⁶⁴ and R ⁶⁵ has the same meaning as the aryl group described in the general formula (1).

The substituted or unsubstituted heterocyclic group in R ⁶⁴ and R ⁶⁵ has the same meaning as the heterocyclic group described in the general formula (1).

In addition, R ⁶⁴ and R ⁶⁵ may be combined with each other to form a ring.

Specific examples of the case where R ⁶⁴ and R ⁶⁵ are each independently adjacent substituents together to form a ring include those shown in Table 8, but are not limited thereto.
Table 8

In the general formula (7), each R ⁶⁶ is independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, substituted Or an unsubstituted acyl group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted acyloxy group, a substituted or unsubstituted alkoxycarbonyl group Substituted or unsubstituted alkoxycarbonyloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted heterocyclic thio group, substituted or unsubstituted dialkylamino group, substituted or unsubstituted Diarylamino group, substituted or unsubstituted alkyl It represents a Ruamino group or a halogen atom.

The substituted or unsubstituted alkyl group for R ⁶⁶ has the same meaning as the alkyl group described in formula (1).

Examples of the aryl group substituted or unsubstituted in the R ^66, the same meaning as the aryl group described for general formula (1).

The substituted or unsubstituted heterocyclic group for R ⁶⁶ has the same meaning as the heterocyclic group described in formula (1).

The substituted or unsubstituted alkenyl group for R ⁶⁶ has the same meaning as the alkenyl group described in formula (1).

The substituted or unsubstituted acyl group for R ⁶⁶ has the same meaning as the acyl group described in formula (2).

The substituted or unsubstituted alkoxyl group in R ⁶⁶ has the same meaning as the alkoxyl group described in the general formula (2).

The substituted or unsubstituted aryloxy group for R ⁶⁶ has the same meaning as the aryloxy group described in formula (2).

The substituted or unsubstituted heterocyclic oxy group for R ⁶⁶ has the same meaning as the heterocyclic oxy group described in formula (2).

The acyloxy group substituted or unsubstituted in the R ^66, the same meaning as acyloxy groups described by formula (2).
The substituted or unsubstituted alkoxycarbonyl group has the same meaning as the alkoxycarbonyl group described in the general formula (3).

The substituted or unsubstituted alkoxycarbonyloxy group in R ⁶⁶ has the same meaning as the alkoxycarbonyloxy group described in the general formula (2).

The substituted or unsubstituted alkylthio group for R ⁶⁶ has the same meaning as the alkylthio group described in formula (2).

The substituted or unsubstituted arylthio group for R ⁶⁶ has the same meaning as the arylthio group described in formula (2).

The substituted or unsubstituted heterocyclic thio group for R ⁶⁶ has the same meaning as the heterocyclic thio group described in formula (2).

The substituted or unsubstituted dialkylamino group for R ⁶⁶ has the same meaning as the dialkylamino group described in formula (2).

The substituted or unsubstituted diarylamino group in R ⁶⁶ has the same meaning as the diarylamino group described in the general formula (2).

The substituted or unsubstituted alkylarylamino group for R ⁶⁶ has the same meaning as the alkylarylamino group described in formula (2).

The halogen atom in R ⁶⁶ has the same meaning as the halogen atom described in the general formula (2).

Ar ³ in the general formula (7) represents a substituted or unsubstituted arylene group or a substituted or unsubstituted divalent heterocyclic group.

The arylene group substituted or unsubstituted in Ar ^3, the same meaning as the arylene group described by formula (4).

The substituted or unsubstituted divalent heterocyclic group in Ar ³ has the same meaning as the divalent heterocyclic group described in the general formula (4).

R ^{67 to} R ⁷⁰ in the general formula (8) each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.

Also, R ^67, R ⁶⁸ and R ^69, R ⁷⁰ is adjacent substituents each may form a ring together.

Specific examples of the case where R ⁶⁷ , R ⁶⁸ and R ⁶⁹ , R ⁷⁰ are each independently adjacent substituents together to form a ring include those shown in Table 9, but are not limited thereto. Is not to be done.

Table 9

The substituted or unsubstituted alkyl group in R ^{67 to} R ⁷⁰ has the same meaning as the alkyl group described in the general formula (1).

The substituted or unsubstituted aryl group in R ^{67 to} R ⁷⁰ has the same meaning as the aryl group described in the general formula (1).

The heterocyclic group substituted or unsubstituted in R ⁶⁷ to R ^70, the same meaning as the heterocyclic group described by formula (1).

Further, R ⁶⁷ , R ⁶⁸ and R ⁶⁹ , R ⁷⁰ may be combined with each other to form a ring.

R ⁷¹ in the general formula (8) is —O—, —S—, —N (R ²¹ ) —, —CO—, —OCO—, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, Substituted or unsubstituted divalent heterocyclic group, substituted or unsubstituted alkenylene group, alkynylene group, —O—J—, —O—J—O—, —O—J—CO—, —CO—J— , -CO-J-CO-, -COO-J-, -COO-JO-, -COO-J-OOC-, -OCO-J-, -OCO-J-O-, -OCO-J- It represents OCO-, -COO-J-OCO-, -Q-COO-J-OOC-Q-, -O-Q-COO-J-OOC-QO-, or a direct bond.

The alkylene group substituted or unsubstituted in the R ^71, the same meaning as the alkylene group described by formula (4).

The substituted or unsubstituted arylene group for R ⁷¹ has the same meaning as the arylene group described in the general formula (4).

The substituted or unsubstituted divalent heterocyclic group for R ⁷¹ has the same meaning as the divalent heterocyclic group described in formula (4).

The substituted or unsubstituted alkenylene group in R ⁷¹ has the same definition as the alkenylene group described in the general formula (4).

  J in the general formula (8) represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, or a substituted or unsubstituted divalent heterocyclic group.

  The substituted or unsubstituted alkylene group in J has the same meaning as the alkylene group described in the general formula (4).

  The substituted or unsubstituted arylene group in J has the same meaning as the arylene group described in the general formula (4).

  The substituted or unsubstituted divalent heterocyclic group in J has the same meaning as the divalent heterocyclic group described in the general formula (4).

  Q in the general formula (8) represents a substituted or unsubstituted alkylene group.

  The substituted or unsubstituted alkylene group for Q has the same meaning as the alkylene group described in formula (4).

R ²¹ in the general formula (8) has the same meaning as R ²¹ described in Formula (3).

Ar ⁴ and Ar ⁵ in the general formula (8) represent a substituted or unsubstituted arylene group or a substituted or unsubstituted divalent heterocyclic group.

The substituted or unsubstituted arylene group in Ar ⁴ and Ar ⁵ has the same meaning as the arylene group described in the general formula (4).

The Ar ^4, a substituted or unsubstituted in the Ar ⁵ divalent heterocyclic group, which is synonymous with a divalent heterocyclic group described by formula (4).

  Specific preferred examples of the amine compound described above are shown below, but the structure of the amine compound of the present invention is not limited thereto.

  As the resin of the photocurable ink used in the present invention, there are a resin having radical polymerizability and a resin not having it. Examples of the resin having radical polymerizability include polyols, polybasic acids and esterified products of (meth) acrylic acid, as well as epoxy (meth) acrylates and urethane (meth) acrylates.

  Resins having no radical polymerizability include thermosetting or thermoplastic resins, such as alkyd resins, polyester resins, polyvinyl chloride, poly (meth) acrylic acid esters, epoxy resins, polyurethane resins, cellulose derivatives (for example, Ethyl cellulose, cellulose acetate, nitrocellulose), vinyl chloride vinyl acetate copolymer, polyamide resin, polyvinyl acetal resin, diallyl phthalate resin, and synthetic rubber such as butadiene-acrylonitrile copolymer. These resins can be used alone or in combination of two or more thereof.

  The monomer in the photocurable 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.

Examples of monomers having such an ethylenically unsaturated bond capable of radical polymerization include
Examples include acrylic acid derivatives, methacrylic acid derivatives, itaconic acid derivatives, crotonic acid derivatives, isocrotonic acid derivatives, unsaturated carboxylic acid derivatives such as maleic acid derivatives, and radically polymerizable monomers such as styrene derivatives. Is not to be done.

  Specific examples of the radical polymerizable monomer include alkyl (having 1 to 18 carbon atoms) (meth) acrylate as monofunctional monomer, such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl ( There are (meth) acrylates, octyl (meth) acrylates, dodecyl (meth) acrylates, stearyl (meth) acrylates, and (meth) acrylates of alkylphenol ethylene oxide adducts such as benzyl (meth) acrylate, butylphenol, octylphenol or nonylphenol or dodecylphenol. ) Acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, tricyclodecane monomethylol (meth) acrylate and the like. Furthermore, as a bifunctional monomer, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di ( (Meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, pentyl glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hydroxypivalylhydroxy Pivalate di (meth) acrylate, hydroxypivalyl hydroxypivalate dicaprolactonate di (meth) acrylate, 1 6-hexanediol di (meth) acrylate, 1,2-hexanediol di (meth) acrylate, 1,5-hexanediol di (meth) acrylate, 2,5-hexanediol di (meth) acrylate, 1,7-heptane Diol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 1,2-octanediol di (meth) acrylate di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1, 2-decanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,2-decanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, 1,2- Dodecanediol di (meth) acrylate, 1,14-tetradecanediol di (Meth) acrylate, 1,2-tetradecanediol di (meth) acrylate, 1,16-hexadecanediol di (meth) acrylate, 1,2-hexadecanediol di (meth) acrylate, 2-methyl-2,4-pentanediol Di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, 2-methyl-2-propyl-1,3-propanediol di (meth) acrylate, 2,4-dimethyl-2, 4-pentanediol di (meth) acrylate, 2,2-diethyl-1,3-propanediol di (meth) acrylate, 2,2,4-trimethyl-1,3-pentanediol di (meth) acrylate, di Methyloloctane di (meth) acrylate, 2-ethyl-1,3-hexanediol di (meth) Acrylate, 2,5-dimethyl-2,5-hexanediol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol Di (meth) acrylate, 2,4-diethyl-1,5-pentanediol di (meth) acrylate, 1,2-hexanediol di (meth) acrylate, 1,5-hexanediol di (meth) acrylate, 2, 5-hexanediol di (meth) acrylate, 1,7-heptanediol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 1,2-octanediol di (meth) acrylate, 1,9- Nonanediol di (meth) acrylate, 1,2-decanediol di (meth) acrylate, 1,10 Decanediol di (meth) acrylate, 1,2-decanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, 1,2-dodecanediol di (meth) acrylate, 1,14-tetradecanediol Di (meth) acrylate, 1,2-tetradecanediol di (meth) acrylate, 1,16-hexadecanediol di (meth) acrylate, 1,2-hexadecanediol di (meth) acrylate, 2-methyl-2,4- Pentanedi (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, 2-methyl-2-propyl-1,3-propanediol di (meth) acrylate, 2,4-dimethyl-2, 4-pentanediol di (meth) acrylate, 2,2-diethyl- , 3-propanediol di (meth) acrylate, 2,2,4-trimethyl-1,3-pentanediol di (meth) acrylate, dimethyloloctane di (meth) acrylate, 2-ethyl-1,3-hexane Diol di (meth) acrylate, 2,5-dimethyl-2,5-hexanediol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, 2,4-diethyl -1,5-pentanediol di (meth) acrylate tricyclodecane dimethylol di (meth) acrylate, tricyclodecane dimethylol dicaprolactonate di (meth) acrylate, bisphenol A tetraethylene oxide adduct di (meth) acrylate Bisphenol F tetraethylene oxide adduct di (Meth) acrylate, bisphenol S tetraethylene oxide adduct di (meth) acrylate, water added bisphenol A tetraethylene oxide adduct di (meth) acrylate, water added bisphenol F tetraethylene oxide adduct di (meth) acrylate, water added Bisphenol A di (meth) acrylate, water-added bisphenol F di (meth) acrylate, bisphenol A tetraethylene oxide adduct dicaprolactonate di (meth) acrylate, bisphenol F tetraethylene oxide adduct dicaprolactonate di (meth) Examples include acrylates. Glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane tricaprolactonate tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolhexane tri (meth) acrylate as trifunctional monomers , Trimethylol octane tri (meth) acrylate, pentaerythritol tri (meth) acrylate and the like. Tetraerythritol tetra (meth) acrylate, pentaerythritol tetracaprolactonate tetra (meth) acrylate, diglycerin tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ditrimethylolpropane tetracapro Lactonate, tetra (meth) acrylate, ditrimethylolethanetetra (meth) acrylate, ditrimethylolbutanetetra (meth) acrylate, ditrimethylolhexanetetra (meth) acrylate, ditrimethyloloctanetetra (meth) acrylate, dipentaerythritol penta ( (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol hexa (meth) acrylate DOO, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol polyalkylene oxide hepta (meth) acrylate and the like.

Furthermore, there is an alkylene oxide adduct (meth) acrylate of an aliphatic alcohol compound as the acrylic monomer of the present invention. As alkylene oxide adduct (meth) acrylate monomer of aliphatic alcohol compound, mono or poly (1-20) alkylene (having 2 to 20 carbon atoms) oxide adduct of aliphatic alcohol compound (alkylene oxide such as ethylene oxide, Propylene oxide, butylene oxide, pentylene oxide, hexylene oxide and the like) mono or poly (1-10) (meth) acrylate. Alkylene oxide adduct (meth) acrylate having 2 to 20 carbon atoms as monofunctional monomer, for example, methanol mono- or poly (1 to 20) alkylene (2 to 20 carbon atoms) oxide adduct (for example, ethylene oxide as alkylene oxide) , Propylene oxide, butylene oxide) (meth) acrylate, ethanol mono or poly (1-20) alkylene (having 2 to 20 carbon atoms) oxide adduct (as alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide) ( (Meth) acrylate, butanol mono- or poly (1-20) alkylene (having 2 to 20 carbon atoms) oxide adduct (alkylene oxide such as ethylene oxide, propylene oxide, butylene o Side) (meth) acrylate, hexanol mono- or poly (1-20) alkylene (having 2 to 20 carbon atoms) oxide adduct (as alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide) (meth) acrylate, octanol Mono- or poly (1-20) alkylene (having 2 to 20 carbon atoms) oxide adducts (alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide) (meth) acrylate, dodecanol mono or poly (1-20) ) Alkylene (having 2 to 20 carbon atoms) oxide adduct (e.g., ethylene oxide, propylene oxide, butylene oxide) (meth) acrylate, stearyl mono or poly as alkylene oxide (1-20) alkylene (having 2 to 20 carbon atoms) oxide adduct (alkylene oxide such as ethylene oxide and propylene oxide. Furthermore, poly (1-20) alkylene (carbon) of butylphenol, octylphenol, nonylphenol or dodecylphenol The number of atoms is 2 to 20) Oxide adducts (alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide) (meth) acrylate, etc. Further, ethylene glycol mono or poly (1 to 20) as bifunctional monomers Alkylene (having 2 to 20 carbon atoms) oxide adduct (as alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate , Diethylene glycol mono- or poly (2-20) alkylene (having 2 to 20 carbon atoms) oxide adducts (eg, alkylene oxide, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, triethylene glycol poly (2 -20) alkylene (having 2 to 20 carbon atoms) oxide adduct (as alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, polyethylene glycol poly (2 to 20) alkylene (carbon atoms) 2 to 20) Oxide adducts (alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, propylene glycol poly (2-20) Xylene (having 2 to 20 carbon atoms) oxide adduct (as alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, dipropylene glycol poly (2 to 20) alkylene (having 2 carbon atoms) -20) Oxide adduct (As alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, tripropylene glycol poly (2-20) alkylene (having 2 to 20 carbon atoms) oxide adduct ( For example, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, polypropylene glycol poly (2-20) alkylene (2-20 carbon atoms) oxide as alkylene oxide Forms (for example, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, butylene glycol poly (2-20) alkylene (having 2 to 20 carbon atoms) oxide adduct (for example, ethylene as alkylene oxide) Oxide, propylene oxide, butylene oxide) di (meth) acrylate, pentyl glycol poly (2-20) alkylene (having 2 to 20 carbon atoms) oxide adduct (as alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide) Di (methaneopentyl glycol poly (2-20) (for example, ethylene oxide, propylene oxide, butylene oxide, etc.) adduct di (meth) acrylate, hydroxypivalyl Hydroxypivalate poly (2-20) alkylene (having 2 to 20 carbon atoms) oxide adduct (as alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate (commonly called manda), hydroxypivalyl Hydroxypivalate dicaprolactonate poly (2-20) alkylene (having 2-20 carbon atoms) oxide adduct (alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 1,6 Hexanediol poly (2 to 20) alkylene (having 2 to 20 carbon atoms) oxide adduct (as alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 1,6-hexanediol poly (2-20) alkylene oxide adducts (eg, ethylene oxide, propylene oxide, butylene oxide, etc.) di (meth) acrylate, 1,2-hexanediol di (meth) acrylate, 1,5-hexane Diol poly (2-20) alkylene (having 2 to 20 carbon atoms) oxide adduct (as alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 2,5-hexanediol poly (2 -20) alkylene (having 2 to 20 carbon atoms) oxide adduct (as alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 1,7-heptanediol poly (2-20) Xylene (having 2 to 20 carbon atoms) oxide adduct (as alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 1,8-octanediol poly (2 to 20) alkylene (carbon atom) 2 to 20) oxide adduct (as alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 1,2-octanediol poly (2 to 20) alkylene (having 2 to 2 carbon atoms) 20) Oxide adduct (for example, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate di (meth) acrylate, 1,9-nonanediol poly (2-20) alkylene (the number of carbon atoms is alkylene oxide) -20) Oxide adduct (for example, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 1,2-decanediol poly (2-20) alkylene (having 2-20 carbon atoms) oxide as alkylene oxide Adducts (e.g., ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 1,10-decanediol poly (2-20) alkylene (having 2 to 20 carbon atoms) oxide adduct (alkylene oxide as alkylene oxide) For example, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 1,2-decanediol poly (2-20) alkylene (having 2 to 20 carbon atoms) oxide adduct (alkylene oxide) For example, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 1,12-dodecanediol poly (2 to 20) alkylene (having 2 to 20 carbon atoms) oxide adduct (alkylene oxide such as ethylene Oxide, propylene oxide, butylene oxide) di (meth) acrylate, 1,2-dodecanediol mono- or poly (1-20) alkylene (having 2-20 carbon atoms) oxide adduct (alkylene oxide such as ethylene oxide, Propylene oxide, butylene oxide) di (meth) acrylate, 1,14-tetradecanediol poly (2-20) alkylene (having 2-20 carbon atoms) oxide adduct (alkylene oxide such as ethylene oxide , Propylene oxide, butylene oxide) di (meth) acrylate, 1,2-tetradecanediol poly (2-20) alkylene (having 2 to 20 carbon atoms) oxide adduct (alkylene oxide such as ethylene oxide, propylene oxide) , Butylene oxide) di (meth) acrylate, 1,16-hexadecanediol mono- or poly (2-20) alkylene (having 2 to 20 carbon atoms) oxide adduct (alkylene oxide such as ethylene oxide, propylene oxide, butylene) Oxide) di (meth) acrylate, 1,2-hexadecanediol poly (2-20) alkylene (having 2 to 20 carbon atoms) oxide adduct (alkylene oxide such as ethylene oxide, propylene oxide) Side, butylene oxide) di (meth) acrylate, 2-methyl-2,4-pentanediol poly (2-20) alkylene (having 2 to 20 carbon atoms) oxide adduct (alkylene oxide such as ethylene oxide, propylene Oxide, butylene oxide) di (meth) acrylate, 3-methyl-1,5-pentanediol poly (2-20) alkylene (having 2 to 20 carbon atoms) oxide adduct (alkylene oxide such as ethylene oxide, propylene Oxide, butylene oxide) di (meth) acrylate, 2-methyl-2-propyl-1,3-propanediol poly (2 to 20) alkylene (having 2 to 20 carbon atoms) oxide adduct (alkylene oxide, for example) Ethylene oxide, propylene Lenoxide, butylene oxide) di (meth) acrylate, 2,4-dimethyl-2,4-pentanediol poly (2-20) alkylene (having 2 to 20 carbon atoms) oxide adduct (alkylene oxide such as ethylene Oxide, propylene oxide, butylene oxide) di (meth) acrylate, 2,2-diethyl-1,3-propanediol mono- or poly (2-20) alkylene (having 2 to 20 carbon atoms) oxide adduct (alkylene) For example, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 2,2,4-trimethyl-1,3-pentanediol mono- or poly (2-20) alkylene (having 2 to 20 carbon atoms) ) Oxide adduct (alkylene oxide) For example, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, dimethyloloctane poly (2-20) alkylene (having 2 to 20 carbon atoms) oxide adduct (alkylene oxide such as ethylene oxide, propylene, etc.) Oxide, butylene oxide) di (meth) acrylate, 2-ethyl-1,3-hexanediol poly (2-20) alkylene (having 2-20 carbon atoms) oxide adduct (alkylene oxide such as ethylene oxide, propylene Oxide, butylene oxide) di (meth) acrylate, 2,5-dimethyl-2,5-hexanediol poly (2 to 20) alkylene (having 2 to 20 carbon atoms) oxide adduct (alkylene oxide, for example, Oxide, propylene oxide, butylene oxide) di (meth) acrylate, 2-methyl-1,8-octanediol poly (2-20) alkylene (having 2 to 20 carbon atoms) oxide adduct (alkylene oxide, for example) Ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol poly (2-20) alkylene (having 2-20 carbon atoms) oxide adduct (alkylene) For example, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 2,4-diethyl-1,5-pentanediol poly (2 to 20) alkylene (having 2 to 20 carbon atoms) oxide adduct (As alkylene oxide For example, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate is exemplified. Glycerin poly (2-20) alkylene (2-20 carbon atoms) oxide adduct (e.g., ethylene oxide, propylene oxide, butylene oxide) tri (meth) acrylate, trimethylolpropane poly ( 2-20) alkylene (2-20 carbon atoms) oxide adduct (as alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide) tri (meth) acrylate, trimethylolethane poly (2-20) alkylene (carbon 2-20) oxide adduct (e.g., ethylene oxide, propylene oxide, butylene oxide) tri (meth) acrylate, trimethylolhexane poly (2-20) Alkylene (having 2 to 20 carbon atoms) oxide adduct (e.g., ethylene oxide, propylene oxide, butylene oxide) tri (meth) acrylate, trimethyloloctane poly (2 to 20) alkylene (having 2 carbon atoms as alkylene oxide) -20) Oxide adduct (As alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide) tri (meth) acrylate, trimethyloloctane poly (3-20) alkylene (having 2 to 20 carbon atoms) oxide adduct ( Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide) tri (meth) acrylate, pentaerythritol poly (2-20) alkylene (having 2 to 20 carbon atoms) oxide. Adducts (e.g. ethylene oxide as alkylene oxide-de, propylene oxide, butylene oxide) tri (meth) acrylate and the like. Pentaerythritol poly (2-20) alkylene (2-20 carbon atoms) oxide adduct (e.g., ethylene oxide, propylene oxide, butylene oxide) tetra (meth) acrylate, ditrimethylol as tetrafunctional or higher monomer Propane poly (2-20) alkylene (having 2 to 20 carbon atoms) oxide adduct (as alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide) tetra (meth) acrylate, ditrimethylolpropane poly (2-20) Alkylene oxide (eg, ethylene oxide, propylene oxide, butylene oxide, etc.) tetra (meth) acrylate, ditrimethylolpropane tetracaprolactonate, tetra (meth ) Acrylate, ditrimethylol ethane poly (2-20) alkylene (2-20 carbon atoms) oxide adduct (as alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide) tetra (meth) acrylate, ditrimethylolethane poly (2-20) alkylene oxide (eg, ethylene oxide, propylene oxide, butylene oxide, etc.) tetra (meth) acrylate, ditrimethylolbutane poly (2-20) alkylene oxide (eg, ethylene oxide, propylene oxide, butylene oxide, etc.) tetra ( (Meth) acrylate, ditrimethylolhexane poly (2 to 20) alkylene (having 2 to 20 carbon atoms) oxide adduct (as alkylene oxide, for example) Tylene oxide, propylene oxide, butylene oxide) tetra (meth) acrylate, ditrimethylol hexane poly (2-20) alkylene oxide (such as ethylene oxide, propylene oxide, butylene oxide, etc.) tetra (meth) acrylate, ditrimethylol octane (2 20) Alkylene (having 2 to 20 carbon atoms) oxide adduct (as alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide) tetra (meth) acrylate, ditrimethyloloctane poly (4-200) alkylene oxide (for example, ethylene) Oxide, propylene oxide, butylene oxide, etc.) tetra (meth) acrylate, dipentaerythritol poly (5-20) alkylene (C2-C20) oxide adduct (e.g., ethylene oxide, propylene oxide, butylene oxide) penta (meth) acrylate, dipentaerythritol poly (2-20) alkylene (having 2 to 2 carbon atoms as alkylene oxide) 20) Oxide adducts (for example, ethylene oxide, propylene oxide, butylene oxide) hexa (meth) acrylate, propylene oxide, butylene oxide, etc. as alkylene oxide, hexa (meth) acrylate, dipentaerythritol hexacaprolactonate poly (2 -20) alkylene (having 2 to 20 carbon atoms) oxide adduct (as alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide) hexa (meth) a Relate, tripentaerythritol poly (2-20) alkylene (having 2 to 20 carbon atoms) oxide adduct (eg, alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide) hepta (meth) acrylate, tripentaerythritol poly ( 2-20) alkylene (having 2 to 20 carbon atoms) oxide adduct (e.g., ethylene oxide, propylene oxide, butylene oxide) octa (meth) acrylate, tripentaerythritol poly (2-20) alkylene (carbon as alkylene oxide) 2-20) oxide adduct (as alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide) hexa (meth) acrylate, tripentaerythritol Polyalkylene oxide hepta (meth) acrylate, tripentaerythritol poly (2-20) alkylene (having 2 to 20 carbon atoms) oxide adduct (eg alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide) octa (meta ) Acrylate and the like.

  More specifically, edited by Shinzo Yamashita et al., “Cross-linking 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”, 79, (1989, CMC), Akamatsu Kiyoshi, “New Technology for Photosensitive Resins”, (1987, C MC), Shinichiro Takiyama, “Polyester Resin Handbook”, (1988, Nikkan Kogyo Shimbun Co., Ltd.) or commercially known radically polymerizable or cross-linkable monomers, oligomers and polymers may be mentioned. Is not limited to these.

  Examples of the pigment of the photocurable ink used in the present invention include inorganic pigments and organic pigments including extender pigments. 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 inorganic pigments include titanium oxide, zinc white, zinc sulfide, lead white, calcium carbonate, precipitated barium sulfate, white carbon, alumina white, kaolin clay, talc, bentonite, black iron oxide, cadmium red, brown rice, molybdenum Red, molybdate orange, chrome vermilion, yellow lead, cadmium yellow, yellow iron oxide, titanium yellow, chromium oxide, viridian, titanium cobalt green, cobalt green, cobalt chrome green, Victoria green, ultramarine blue, bitumen, cobalt blue, cerulean Blue, cobalt silica blue, cobalt zinc silica blue, manganese violet, cobalt violet, or carbon black such as acetylene black, channel black, furnace black (neutral, acid Both basic available), but like the present invention is not limited thereto.

  Organic pigments include soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, perylene pigments, perinone pigments, dioxazine pigments, anthraquinone pigments, dianthraquinonyl pigments, anthrapyrimidine pigments , Anthanthrone pigment, indanthrone pigment, flavanthrone pigment, pyranthrone pigment, diketopyrrolopyrrole pigment and the like. More specific examples are represented by generic names of color indexes: Pigment Black 7, Pigment Blue 15, 15: 1, 15: 3, 15: 4, 15: 6, 60, Pigment Green 7, 36, Pigment Red 9 48, 49, 52, 53, 57, 97, 122, 144, 146, 149, 166, 168, 177, 178, 179, 185, 206, 207, 209, 220, 221, 238, 242, 254, 255 Pigment Violet 19, 23, 29, 30, 37, 40, 50, Pigment Yellow 12, 13, 14, 17, 20, 24, 74, 83, 86, 93, 94, 95, 109, 110, 117, 120 , 125, 128, 137, 138, 139, 147, 148, 150, 151, 154, 155 66,168,180,185, but Pigment Orange 13,36,37,38,43,51,55,59,61,64,71,74 etc. The present invention is not limited thereto.

  The photocurable 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 polymerizable composition of the present invention include Irgacure 651, Irgacure 184, Darocur 1173, Irgacure 500, Irgacure 1000, Irgacure 2959, Irgacure 907, Irgacure 907, Cure 369, IRGACURE 379, IRGACURE 1700, IRGACURE 149, IRGACURE 1800, IRGACURE 1850, IRGACURE 819, IRGACURE 784, IRGACURE 261, IRGACURE OXE-01 (CGI124), CGI242 (Ciba Specialty) Chemicals), Adekaoptomer N1414, Adekaoptomer N1717 (Asahi Denka), Esacure 1001M (Lamberti), Japanese Patent Publication No. 59-1281, Japanese Patent Publication No. 6 Triazine derivatives described in JP-A-69621 and JP-A-60-60104, organic peroxides described in JP-A-59-1504 and JP-A-61-2243807, JP-B-43-23684, As described in JP-B-44-6413, JP-B-47-1604 and diazonium compounds described in USP 3,567,453, USP 2,848,328, USP 2,852,379 and USP 2,940,853 Organic azide compounds, ortho-quinonediazides described in JP-B 36-22062, JP-B 37-13109, JP-B 38-18015 and JP-B 45-9610, JP-B 55-39162, JP 59-140203 A and “Macro” Various onium compounds including iodonium compounds described in “Moleculars”, Vol. 10, page 1307 (1977), azo compounds described in JP-A-59-142205, JP-A-1-54440, Metal allene complexes described in European Patent No. 109851 and European Patent No. 126712, “Journal of Imaging Science (J.IMAG.SCI.)”, Vol. 30, page 174 (1986) , Titanocenes described in JP-A-61-151197, “COORDINATION CHEMISTRY REVIEW”, Vol. 84, pages 85-277 (1988) and JP-A-2-182701. Transition metal complexes containing transition metals such as ruthenium, described in JP-A-3-209477 Aluminate complex, borate compound described in JP-A-2-157760, 2,4,5-triarylimidazole dimer described in JP-A-55-127550 and JP-A-60-202437, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,1′-biimidazole, carbon tetrabromide and organic halogens described in JP-A-59-107344 Compounds, JP-A-5-213861, JP-A-5-255347, JP-A-5-255421, JP-A-6-157623, JP-A-2000-344812, JP-A-2002-265512, The sulfonium complex or oxosulfonium complex described in Japanese Patent Application No. 2004-053009 and Japanese Patent Application No. 2004-263413 JP-A-2001-264530, JP-A-2001-261761, JP-A-2000-80068, JP-A-2001-233842, USP3558309 (1971), USP4202697 (1980) Oxime ester compounds described in JP-A Nos. 61-24558, 2004-534797 and 2004-359639, and bifunctional photoinitiators described in JP-A-2002-530372. However, the present invention is not limited to these.

  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 polymerizable composition of the present invention include benzophenones, unsaturated ketones represented by chalcone derivatives and dibenzalacetone, and 1 represented by benzyl and camphorquinone. , 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. Dye, acridine derivative, azine derivative, thiazine derivative, oxazine derivative, indoline derivative, azulene derivative, azurenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative , Triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetra Examples include filin derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, and other specific examples, edited by Nobu Okawara et al., “Dye Handbook” (1986, Kodansha) Dye and sensitization described in Okawara Nobu et al., “Functional dye chemistry” (1981, CMC), Ikemori Tadasaburo et al., “Special functional materials” (1986, CMC) However, it is not limited to these, and other dyes and sensitizers that absorb light from the ultraviolet to the near-infrared region are included, and these may be used in any ratio as necessary. The above may be used. 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 used in the present invention is preferably 0.01 to 20 parts by weight, more preferably 1 to 10 parts by weight with respect to 100 parts by weight of the monomer.

  The photosensitizer used in the present invention is preferably 0.01 to 10 parts by weight, more preferably 1 to 5 parts by weight, based on 100 parts by weight of the monomer.

  The amine compound used in the present invention is preferably 0.01 to 10 parts by weight, more preferably 1 to 5 parts by weight, based on 100 parts by weight of the monomer.

  The resin used in the present invention is preferably 0.1 to 600 parts by weight, more preferably 0.1 to 200 parts by weight with respect to 100 parts by weight of the monomer.

  The pigment used in the present invention is preferably 1 to 600 parts by weight, more preferably 10 to 300 parts by weight, based on 100 parts by weight of the monomer.

  The photocurable ink of the present invention can contain a polymerization inhibitor for the purpose of preventing polymerization during storage.

  Specific examples of the polymerization inhibitor that can be added to the photocurable ink of the present invention include (alkyl) phenol, hydroquinone, alkyl-substituted hydroquinone, catechol, t-butylcatechol, resorcin, p-methoxyphenol, pyrogallol, 1,1. -Picrylhydrazyl, phenothiazine, p-benzoquinone, nitrosobenzene, 2,5-di-tert-butyl-p-benzoquinone, dithiobenzoyl disulfide, picric acid, cuperone, aluminum N-nitrosophenylhydroxylamine, tri-p- Nitrophenylmethyl, N- (3-oxyanilino-1,3-dimethylbutylidene) aniline oxide, dibutylcresol, cyclohexanone oximecresol, guaiacol, o-isopropylphenol, butyraloxime, methyl Examples include ruethyl ketoxime and cyclohexanone oxime. The addition amount of the polymerization inhibitor is not particularly limited, but it is preferably used in the range of 0.001 to 10 parts by weight with respect to 100 parts by weight of the monomer.

  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, amines such as N-phenylglycine, triethanolamine, N, N-diethylaniline, USP No. 4414312 Thiols described in the specification, JP-A No. 64-13144, disulfides described in JP-A No. 2-291561, thiones described in USP No. 3558322 and JP-A No. 64-17048, Examples include O-acylthiohydroxamate and N-alkoxypyridinethiones described in JP-A-2-291560.

  For the photocurable ink of the present invention, materials used for conventional photocurable inks can be appropriately used. For example, viscosity adjusting agents, surfactants for adjusting the printing characteristics of ink, phosphoric acid additives for preventing sensitization of the plate, and auxiliary agents for adjusting the surface of the cured film such as wax. Anti-friction agents, anti-blocking agents, slip agents, anti-scratch agents include natural wax such as carnauba wax, wax, lanolin, montan wax, paraffin wax, microcrystalline wax, Fischer-Trops wax, polyethylene wax, polypropylene wax, Examples thereof include synthetic waxes such as polytetrafluoroethylene wax, polyamide wax, and silicone compound.

  In the polymerization reaction, the photocurable 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 ink of the present invention includes 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, 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, etc. Polymer or cured product can be obtained.

  The photocurable ink obtained in the present invention can be printed or cured using the same technique as in the prior art. The ink of the present invention has good curability and storage stability with time, and can suppress odor after ink curing.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to only the following Example at all.

  Tables 10 to 12 show the photopolymerization initiator, photosensitizer, and amine compound of the present invention used in the examples.

Table 10

Table 11

Table 12

  These compounds listed in Tables 10 to 12 are disclosed in European Patent Application No. 3002, JP-A-56-125383, JP-A-58-157805, JP-A-59-208541, JP-A-63. It can be obtained by using the synthesis methods described in JP-A Nos. 264560, 4-117404, and 2006-206799. Some compounds can also be obtained from Aldrich.

Manufacture of varnish (mixture of resin, monomer, etc.) 10 parts by weight of Dap Tote DT170 (diallyl phthalate resin manufactured by Toto Kasei Co., Ltd.), 89.9 parts by weight of ditrimethylolpropane tetraacrylate, and 0.10 parts by weight of hydroquinone are mixed and melted by heating. And produced.

Ink Production Examples 1-13
Varnish, pigment, photopolymerization initiator, photosensitizer and amine compound were mixed and kneaded with three rolls to obtain yellow, red, indigo and black ink. Table 13 shows the composition of the red ink.

Comparative Examples 1-22
An ink was prepared in the same manner as in the example. Among these, the composition of the red ink is shown in Tables 14 and 15.

The performance evaluation of the printing ink was performed as follows. The results are shown in Tables 16 and 17 for the ink performance evaluations (1) to (3) of Examples 1 to 13 and Comparative Examples 1 to 22.
・ (1) Curability: In the case of each printing ink, the ink is printed with an RI tester (a simple printing machine generally used in the printing ink industry can print the ink uniformly on paper) and irradiated with ultraviolet rays (metal halide) After the lamp 120W / cm1), the film was rubbed with a cotton cloth and judged at a conveyor speed at which the film was not damaged. The larger the number at the conveyor speed (m / min) of the ultraviolet irradiation device, the better the curability. In the table, “x” indicates that the composition was not cured.
(2) Storage stability: Depending on the type of initiator and sensitizer used in the photocurable ink, the particles agglomerate over time to produce coarse particles. In the particle size measurement of each printing ink by a grind gauge (a simple particle size measuring instrument generally used in the printing ink industry, which shows the coarse particle size present in the ink) The particle diameter change was measured and evaluated in five stages from 1 (bad) to 5 (good).
・ (3) Odoriness: Printed material cured under the same conditions as the curability is finely cut and packed in a glass bottle. The panelists of 5 persons have judged the odor relatively, and 1 (bad) to 5 (good) ). In the table, “x” indicates that the ink was not cured and thus evaluation was impossible.

Table 13

Table 14

Table 15

Table 16

Table 17

  According to Examples and Comparative Examples, the photopolymerization initiator used in the present invention can be slightly improved in curability by using a photosensitizer or an amine compound in combination, but it can be cured by using both in combination. It has become clear that not only drastically improved, but also storage stability over time and odor properties are improved.

  In the case of the photocurable ink of the present invention, it was found that the photocurable ink of the present invention has a high curability even when compared with a commonly used photocurable ink. In addition, the photocurable ink of the present invention not only has high storage stability of the ink, but also can suppress odor after ink curing, satisfying all these requirements that were difficult with conventional photocurable inks. It became clear.

Claims (6)

A resin, a monomer, a pigment, an α-aminoketone photopolymerization initiator represented by the following general formula (1), and a photosensitizer represented by the general formula (3) or (4) A photocurable ink comprising an amine compound.
General formula (1)

(Wherein R ¹ and R ² each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted alkenyl group) R ¹ and R ² may be integrated to form a ring.
R ³ and R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, or COR ⁵ Represents. R ³ and R ⁴ may be combined to form a ring.
R ⁵ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted alkenyl group.
X represents a divalent aromatic ring condensed group having 4 to 16 carbon atoms which may contain a hetero atom.
Ar ¹ represents the following general formula (2) or a substituted or unsubstituted heterocyclic group. )
General formula (2)

(Wherein R ^{6 to} R ¹⁰ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, Substituted or unsubstituted acyl group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted acyloxy group, substituted or unsubstituted alkoxycarbonyl Oxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted heterocyclic thio group, substituted or unsubstituted alkylamino group, substituted or unsubstituted dialkylamino group, substituted or unsubstituted Substituted arylamino group, substituted or unsubstituted diarylamino group, substituted Properly represents the unsubstituted alkyl arylamino group, or a halogen atom. In addition, adjacent substituents of R ⁶ to R ¹⁰ may form a ring together.)
General formula (3)

(Wherein R ^{11 to} R ²⁰ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, Substituted or unsubstituted acyl group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted acyloxy group, substituted or unsubstituted alkoxycarbonyl Group, substituted or unsubstituted alkoxycarbonyloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted heterocyclic thio group, substituted or unsubstituted alkylamino group, substituted or unsubstituted A substituted dialkylamino group, a substituted or unsubstituted arylamino group, Represents a substituted or unsubstituted diarylamino group, a substituted or unsubstituted alkylarylamino group, or a halogen atom, and R ^{11 to} R ¹⁵ and R ^{16 to} R ²⁰ are each formed by combining adjacent substituents together; R ¹⁵ and R ¹⁶ may be combined to form —O—, —S—,>S═O,> SO ₂ , —N (R ²¹ ) —, —CO—, _{-CH 2 -, - CH 2 CH} 2 -, - CH = CH-, alkylidene group having 2 to 6 carbon atoms or may form a direct bond.
R ²¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkoxyl group, substituted or It represents an unsubstituted aryloxy group or a substituted or unsubstituted heterocyclic oxy group. )
General formula (4)

(Wherein R ^{22 to} R ³⁹ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, Substituted or unsubstituted acyl group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted acyloxy group, substituted or unsubstituted alkoxycarbonyl Group, substituted or unsubstituted alkoxycarbonyloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted heterocyclic thio group, substituted or unsubstituted alkylamino group, substituted or unsubstituted A substituted dialkylamino group, a substituted or unsubstituted arylamino group, Represents a substituted or unsubstituted diarylamino group, a substituted or unsubstituted alkylarylamino group, or a halogen atom, and R ^{22 to} R ²⁶ , R ^{27 to} R ³⁰ , R ^{31 to} R ³⁴ , and R ^{35 to} R ^{In 39} , adjacent substituents may be combined to form a ring, and R ²⁶ and R ²⁷ , or R ³⁴ and R ³⁵ are each independently integrated to form —O—, —S—. ,>S═O,> SO ₂ , —N (R ²¹ ) —, —CO—, —CH ₂ —, —CH ₂ CH ₂ —, —CH═CH—, an alkylidene group having 2 to 6 carbon atoms, Alternatively, a direct bond may be formed.
R ²¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkoxyl group, substituted or It represents an unsubstituted aryloxy group or a substituted or unsubstituted heterocyclic oxy group.
R ⁴⁰ represents —O—, —S—, —N (R ²¹ ) —, —CO—, —OCO—, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted divalent group. Valent heterocyclic group, substituted or unsubstituted alkenylene group, alkynylene group, —O—J—, —O—J—O—, —O—J—CO—, —CO—J—, —CO—J—. CO-, -COO-J-, -COO-J-O-, -COO-J-OOC-, -OCO-J-, -OCO-J-O-, -OCO-J-OCO-, -COO- J-OCO-, -Q-COO-J-OOC-Q-, -O-Q-COO-J-OOC-QO-, or a direct bond is represented.
J represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, or a substituted or unsubstituted divalent heterocyclic group.
Q represents a substituted or unsubstituted alkylene group. ) The photocurable ink according to claim 1, wherein the photosensitizer is represented by the following general formula (5) or general formula (6).
General formula (5)

(Wherein R ^{41 to} R ⁴⁸ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, Substituted or unsubstituted acyl group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted acyloxy group, substituted or unsubstituted alkoxycarbonyl Group, substituted or unsubstituted alkoxycarbonyloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted heterocyclic thio group, substituted or unsubstituted alkylamino group, substituted or unsubstituted A substituted dialkylamino group, a substituted or unsubstituted arylamino group, Represents a substituted or unsubstituted diarylamino group, a substituted or unsubstituted alkylarylamino group, or a halogen atom, and R ^{41 to} R ⁴⁴ , and R ^{45 to} R ⁴⁸ each represent an integral group of adjacent substituents. To form a ring.
A ¹ is —O—, —S—,>S═O,> SO ₂ , —N (R ²¹ ) —, —CO—, —CH ₂ —, —CH ₂ CH ₂ —, —CH═CH—. Represents an alkylidene group having 2 to 6 carbon atoms, or a direct bond.
R ²¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkoxyl group, substituted or It represents an unsubstituted aryloxy group or a substituted or unsubstituted heterocyclic oxy group. )
General formula (6)

(Wherein R ^{49 to} R ⁶² are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, Substituted or unsubstituted acyl group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted acyloxy group, substituted or unsubstituted alkoxycarbonyl Group, substituted or unsubstituted alkoxycarbonyloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted heterocyclic thio group, substituted or unsubstituted alkylamino group, substituted or unsubstituted A substituted dialkylamino group, a substituted or unsubstituted arylamino group, A substituted or unsubstituted diarylamino group, a substituted or unsubstituted alkylarylamino group, or a halogen atom, and R ^{49 to} R ⁵² , R ^{53 to} R ⁵⁵ , R ^{56 to} R ⁵⁸ , and R ^{59 to} R ^{In 62} , adjacent substituents may be combined to form a ring.
A ² and A ³ are each independently —O—, —S—,>S═O,> SO ₂ , —N (R ²¹ ) —, —CO—, —CH ₂ —, —CH ₂ CH ₂ —. , -CH = CH-, an alkylidene group having 2 to 6 carbon atoms or a direct bond.
R ²¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkoxyl group, substituted or It represents an unsubstituted aryloxy group or a substituted or unsubstituted heterocyclic oxy group.
R ⁶³ represents —O—, —S—, —N (R ²¹ ) —, —CO—, —OCO—, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted divalent group. Valent heterocyclic group, substituted or unsubstituted alkenylene group, alkynylene group, —O—J—, —O—J—O—, —O—J—CO—, —CO—J—, —CO—J—. CO-, -COO-J-, -COO-J-O-, -COO-J-OOC-, -OCO-J-, -OCO-J-O-, -OCO-J-OCO-, -COO- J-OCO-, -Q-COO-J-OOC-Q-, -O-Q-COO-J-OOC-QO-, or a direct bond is represented.
J represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, or a substituted or unsubstituted divalent heterocyclic group.
Q represents a substituted or unsubstituted alkylene group. ) A ^1, A ^2, and claim 2, wherein the light-curable ink A ³ is -S-.   The photocurable ink according to any one of claims 1 to 3, wherein the amine compound is a tertiary amine. The photocurable ink according to any one of claims 1 to 4, wherein the amine compound is represented by the following general formula (7) or general formula (8).
General formula (7)

(Wherein R ⁶⁴ and R ⁶⁵ each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. Also, R ⁶⁴ and R ⁶⁵ represent The adjacent substituents may be combined to form a ring.
R ⁶⁶ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted acyl group, substituted or unsubstituted Unsubstituted alkoxyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted acyloxy group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted alkoxycarbonyloxy Group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted heterocyclic thio group, substituted or unsubstituted dialkylamino group, substituted or unsubstituted diarylamino group, substituted or unsubstituted An alkylarylamino group or a halogen atom Represent.
Ar ³ represents a substituted or unsubstituted arylene group or a substituted or unsubstituted divalent heterocyclic group. )
General formula (8)

(Wherein R ^{67 to} R ⁷⁰ each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and R ⁶⁷ , R ⁶⁸ and R ⁶⁹ and R ⁷⁰ may be combined with each other to form a ring.
R ⁷¹ represents —O—, —S—, —N (R ²¹ ) —, —CO—, —OCO—, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted divalent group. Valent heterocyclic group, substituted or unsubstituted alkenylene group, alkynylene group, —O—J—, —O—J—O—, —O—J—CO—, —CO—J—, —CO—J—. CO-, -COO-J-, -COO-J-O-, -COO-J-OOC-, -OCO-J-, -OCO-J-O-, -OCO-J-OCO-, -COO- J-OCO-, -Q-COO-J-OOC-Q-, -O-Q-COO-J-OOC-QO-, or a direct bond is represented.
R ²¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkoxyl group, substituted or It represents an unsubstituted aryloxy group or a substituted or unsubstituted heterocyclic oxy group.
J represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, or a substituted or unsubstituted divalent heterocyclic group.
Q represents a substituted or unsubstituted alkylene group.
Ar ⁴ and Ar ^{5 each} represents a substituted or unsubstituted arylene group or a substituted or unsubstituted divalent heterocyclic group. )   A printed matter obtained by printing the photocurable ink according to any one of claims 1 to 5 and curing it by light irradiation.