WO2007063652A1

WO2007063652A1 - Photoacid generator composition, cationically photopolymerizable composition, inkjet ink and inkjet recording method using same

Info

Publication number: WO2007063652A1
Application number: PCT/JP2006/320895
Authority: WO
Inventors: Satoshi Masumi
Original assignee: Konica Minolta Medical & Graphic, Inc.
Priority date: 2005-11-29
Filing date: 2006-10-20
Publication date: 2007-06-07
Also published as: JPWO2007063652A1

Abstract

Disclosed is a photoacid generator composition containing a sulfonium salt compound which does not discharge benzene while being excellent in long-term storage stability. Also disclosed are a cationically photopolymerizable composition containing such a photoacid generator composition, an inkjet ink and an inkjet recording method. The photoacid generator composition is characterized by containing a sulfonium salt having a structure represented by the general formula (1) below and a sulfonium salt other than the sulfonium salt having a structure represented by the general formula (1) below.

Description

Photoacid generator composition, cationic photopolymerizable composition, inkjet ink, and inkjet recording method using the same

Technical field

The present invention relates to a photoacid generator composition having excellent stability and excellent photosensitivity in the near ultraviolet region.

The present invention relates to a cationic photopolymerizable yarn composition, an inkjet ink, and an inkjet recording method using the same.

Background art

[0002] In recent years, light-powered thione curable compositions have attracted attention because they have no polymerization inhibition by oxygen and new odor and low viscosity monomers have been developed. It is also attracting attention as an effective chemically amplified resist in the field of photoresists. For example, it has been shown that there is no generation of benzene, and excellent injection properties and cured product adhesion (for example,

See Patent Document 1. ) It was found that the stability of the ink-jet ink composition could not be satisfied when used for applications other than the ink jet recording system while applying force. In addition, a novel photoacid generator for photoregister is disclosed (for example, see Patent Document 2). ₀ Also, an initiator having photosensitivity in the near ultraviolet region is disclosed (for example, Patent Document 3). ₀ ) However, these proposed photoacid generators have insufficient solubility in monomers when constituting a curable composition, and particularly when used for inkjet inks, they are stored for a long period of time. As a result, it was found that the injection properties were not sufficiently satisfactory. Patent Document 1: Japanese Patent Laid-Open No. 2005-97557

Patent Document 2: Japanese Patent Laid-Open No. 9-15848

Patent Document 3: International Publication No. 04Z29037 Pamphlet

Disclosure of the invention

Problems to be solved by the invention

[0003] The present invention has been made in view of the above-mentioned problems, and its object is to provide a photoacid generator composition containing a sulfonium salt compound excellent in long-term storage stability without releasing benzene, and Cationic photopolymerizable composition, inkjet ink and inkjet recording using the same It is to provide a method.

Means for solving the problem

[0004] The above object of the present invention is achieved by the following configurations.

[0005] 1. Contains a sulfonium salt having a structure represented by the following general formula (1) and a sulfo-um salt excluding the sulfo-um salt having a structure represented by the general formula (1) A photoacid generator composition characterized by comprising:

[0006] [Chemical 1]

[Wherein Ri to R ¹⁷ are each a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, an alkyl group, an alkoxy group, an acyl group, a phenoxy group, an ester group, an aryl group, a thioether group, or a thiocarbole group. , Sulfiel groups, sulfo groups, amino groups, amide groups, imide groups, nitrile groups, phosphi groups, phospho groups, phosphoryl groups, and fluoroalkyl groups having 1 to 8 carbon atoms. The groups selected may be the same or different, and the portion other than the functional group of these groups is a C1-C12 saturated aliphatic hydrocarbon group or unsaturated aliphatic carbon group. It may be a hydrogen group, an alicyclic hydrocarbon group, a carbocyclic aromatic hydrocarbon or a bicyclic aromatic hydrocarbon group. R ⁵ and R ⁶ may be condensed with each other to form a covalent bond. X is an atomic group that can be a monovalent key. ]

2. The sulfonium salt excluding the sulfonium salt having the structure represented by the general formula (1) is a sulfo-um salt having a structure represented by the following general formula (A): 2. The photoacid generator composition as described in 1 above, wherein

[0008]

[Wherein Ra Ra represents an alkyl group or an aromatic group, and Z ¹ represents an oxygen atom or a sulfur group.

1 2

Represents a yellow atom, and Ra Ra represents an alkyl group, an aromatic group, an alkoxy group, an aryloxy group, respectively.

3 4

Represents an integer of 0 4; nl and pi each represent an integer of 15; Y represents Z—SO (Z is CF (n is an integer of 1 10); )

3 n 2n + l

Represents an alkyl group or an alkyl-substituted or unsubstituted aromatic group), PF BF AsF

6 4

SbF B (C F) CIO Br CI or I is represented. ]

6 6 6 5 4 4

3. The photoacid generator composition as described in 1 or 2 above, which comprises at least one compound selected from a polycyclic aromatic compound, a strong rubazole derivative and a thixanthone derivative.

[0010] 4. At least one compound force selected from the polycyclic aromatic compounds, force rubazole derivatives and thixanthone derivatives anthracene, fluorene, pyrene, thalene, phenanthrene, anthraquinone, perylene, carbazole, phenothiazine, thixanthone, thianthrene, 4. The photoacid generator composition according to 3 above, which is at least one compound selected from benzanthracene, naphthacene, triphenylene and the following general formula (3).

[0011] [Chemical 3]

[In the formula, R ²¹ R ²⁸ has the same meaning as Ri R ¹⁷ in the general formula (1). ]

5. Sulfonium salt power having the structure represented by the general formula (A) The following general formula (B), (C) and (D) power 4. The photoacid generator composition according to item 1 of 4. [0013] [I 匕 4]

[In the formula, R represents an alkyl group having 1 to 10 carbon atoms, and R R represents an alkyl group having 1 to 10 carbon atoms.

31 32 33

Represents an alkyl group or an alkoxy group having 1 to 10 carbon atoms, Y is Z—SO (Z is C F (n

3 3 n 2n + l represents an integer of 1 to: L0), an alkyl group, or an alkyl-substituted or unsubstituted aromatic group), PF,: BF AsF SbF,: B (CF) CIO Br CI or I Represents. ]

6 4 6 6 6 5 4 4

[0015] [Chemical 5] (C)

[In the formula, R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R represents a substituent.]

41 42

m4 represents an integer of 0 4, R R represents an alkyl group having 1 to 10 carbon atoms, and Y represents

43 44 4 Z-SO (Z is C F (n is an integer of 1 10), alkyl group, or alkyl substitution or

3 n 2n + l

Represents an unsubstituted aromatic group), PF BF AsF SbF B (C F) CIO Br

6 4 6 6 6 5 4 4 Represents α or I. ]

[0017] [Chemical 6] (D

[In the formula, R represents a hydrogen atom or an alkyl group having 1 to L0 carbon atoms, and R represents a substituent.

51 52

m5 represents an integer of 0 4, RR represents an alkyl group having 1 to 10 carbon atoms, and Y represents , Z-SO (Z is CF (n is an integer of 1 to 10), alkyl group, or alkyl substitution

3 n 2n + l

Represents an unsubstituted aromatic group), PF, BF, AsF, SbF, B (C F), CIO, Br, Jiho

6 4 6 6 6 5 4 4 or I ]

6. A cationic photopolymerizable composition comprising the photoacid generator composition according to any one of 1 to 5 above and a cationically polymerizable compound.

[0019] 7. The force thione photopolymerizable composition as described in 6 above, wherein the cationically polymerizable compound is at least one selected from the group consisting of an epoxy compound, an oxetane compound and a vinyl ether compound. .

[0020] 8. The cationic photopolymerizable composition as described in 6 or 7 above, which contains a pigment.

[0021] 9. An ink-jet ink comprising the photoacid generator composition according to any one of 1 to 5 above.

[0022] 10. An ink-jet ink comprising the cationic photopolymerizable composition according to any one of 6 to 8 above.

[0023] 11. An ink jet recording method comprising performing ink jet recording on the fibrous recording material using the ink jet ink described in 9 or 10 above.

The invention's effect

[0024] According to the present invention, a photoacid generator composition containing a sulfoyuium salt compound excellent in long-term storage stability without releasing benzene, and a cationic photopolymerizable composition and ink jet ink using the same And an ink jet recording method.

Brief Description of Drawings

FIG. 1 is a front view showing a configuration of a main part of a recording apparatus of the present invention.

Explanation of symbols

[0026] 1 Recording device

2 Head carriage

3 Recording head

31 Ink outlet

4 Irradiation means 5 Platen section

6 Guide member

7 Bellows structure

P Recording material

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the best mode for carrying out the present invention will be described in detail.

[0028] As a result of intensive studies in view of the above problems, the present inventor has found that a sulfonium salt having a structure represented by the general formula (1) and a sulfone salt having a structure represented by the general formula (1). By using a photoacid generator composition characterized by containing a sulfo-um salt excluding a humic salt, a sulfoyuum salt compound having excellent long-term storage stability without releasing harmful benzene to the human body. It has been found that a photoacid generator composition can be realized, and the present invention has been achieved.

[0029] Details of the present invention will be described below.

(Compound represented by the general formula (1))

The photoacid generator composition of the present invention contains a sulfo-salt having a structure represented by the general formula (1) as a photoacid generator.

[0031] By using the sulfonium salt having the structure represented by the general formula (1) according to the present invention, the curing inhibition by oxygen does not occur, the curing accuracy is high, and the irradiation energy is high. With sensitivity, it has a sufficient depth of cure and can further suppress the generation of benzene.

In the general formula (1), Ri to R ¹⁷ are each a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, an alkyl group, an alkoxy group, an acyl group, a phenoxy group, an ester group, an aryl group, or a thioether group. , Thiocarbol group, sulfiel group, sulfol group, amino group, amide group, imide group, nitrile group, phosphide group, phosphoro group, phosphoryl group, and a fluoroalkyl group having 1 to 8 carbon atoms Group power Group selected, which may be the same or different, except for the functional group of these groups, a saturated aliphatic hydrocarbon group or unsaturated aliphatic group having 1 to 12 carbon atoms It may be a hydrocarbon group, an alicyclic hydrocarbon group, a carbocyclic aromatic hydrocarbon group, or a heterocyclic aromatic hydrocarbon group. R ⁵ and R ⁶ may be condensed with each other to form a covalent bond. X is an atomic group that can be a monovalent key. In the general formula (1), R 1 -R is particularly preferably a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, an alkyl group, an alkoxy group, an acyl group, or a fluoroalkyl group having 1 to 8 carbon atoms. , May be the same or different. Also preferred is when R ⁵ and R ⁶ condense with each other to form a covalent bond!

[0034] As the halogen atom, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are listed. From the viewpoint of active energy ray sensitivity, a fluorine atom is preferable. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tertiary butyl group, a neopentyl group, a hexyl group, an isohexyl group, a peptide group, An octyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, an isotridecyl group, a myristyl group, a palmityl group, a stearyl group, and the like, preferably 1 In particular, a methyl group or an ethyl group is preferable. Examples of the alkoxy group include methoxy group, ethoxy group, propyloxy group, butyloxy group, pentyloxy group, hexyloxy group, peptyloxy group, octyloxy group, noroxy group, decyloxy group, undecyloxy group, dodecyloxy group, tridecyloxy group, A myristyloxy group, a normyloxy group, a stearyloxy group, etc. can be mentioned, Preferably it is a C1-C4 alkoxy group, and especially a methoxy group and an ethoxy group are preferable. Examples of the fluoroalkyl group include a fluormethyl group, a difluoromethyl group, a trifluoromethyl group, a difluoroethyl group, a perfluoroethyl group, and the like, and a trifluoromethyl group is particularly preferable!

Examples of the acyl group include a group represented by R—CO— or Ar—CO—. Examples of R include a linear or branched alkyl group or an alicyclic hydrocarbon group.

[0036] Specific examples of R include, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tertiary butyl group, a pentyl group, an isopentyl group, a tertiary monopentyl group, a neopentyl group, Hexyl, isohexyl, peptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, isotridecyl, myristyl, palmityl, stearyl Group, cyclopentyl group, cyclohexyl group and the like. [0037] Examples of Ar include groups represented by the following general formulas (a) to (f).

[0038] [Chemical 7]

In the above general formulas (a) to (f), R ^{18 to} R ^M each represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group or an alkoxy group, and they may be the same or different. May be.

[0040] Specific examples of R ¹⁸ to R ⁶³ in the general formula (a) ~ (f), as the halogen atom, e.g., fluorine atom, chlorine atom, bromine atom, and an iodine atom. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tertiary butyl group, a pentyl group, an isopentyl group, a tertiary pentyl group, a neopentyl group, and a hexyl group. , Isohexyl group, peptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, isotridecyl group, myristyl group, palmityl group, stearyl group, etc. Examples of the alkoxy group include methoxy group, ethoxy group, propyloxy group, ptyloxy group, pentyloxy group, hexyloxy group, peptyloxy group, octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group. Group, tridecyloxy group, myristyloxy group Roh Rumichiruokishi group, Ru can be exemplified Suteariruokishi group, and the like.

In the general formula (1) according to the present invention, the groups represented by Ri to R ¹⁷ may be the same or different, but preferably all of 1 ^ to 1 ^ ° are hydrogen atoms. force is, or Ri～R ⁵ sac Chi, either force 1 or 2, preferably is other than one hydrogen atom, and all others are hydrogen More preferably, one of the atoms R ^{1 to} R ^1Q is one or two, preferably one is other than a hydrogen atom, and the others are all hydrogen atoms! ^ ¹ ~! ^ Are all hydrogen atoms, or any one of ~ is a group selected from a methyl group, a fluorine atom, a nitro group, and an acyl group, and the others are all hydrogen atoms. It is preferable that any one of R ^{6 to} R ^1Q is a group selected from a methyl group, a fluorine atom, a nitro group, and an acyl group, and the others are all hydrogen atoms. It is also preferred that R ⁵ and R ⁶ are condensed with each other to form a covalent bond.

[0042] R ^{U to} R ¹⁷ are the same as R -R (except for the case where R ⁵ and R ⁶ are condensed to form a covalent bond), and one of them is Ar—CO. —A group and the others are preferably hydrogen atoms.

[0043] Specific examples of the cationic moiety of the sulfonium salt having the structure represented by the general formula (1) according to the present invention are shown below, but the present invention is not limited to these exemplified compounds.

[0044] [Chemical 8]

[0045] [Chemical 9]

[0046] In addition, preferred specific examples of the sulfone salt cation (X-) having the structure represented by the general formula (1) according to the present invention include, for example, SbF- and PF-. Can be mentioned.

6 6

[0047] (Compound represented by formula (A))

In the photoacid generator composition of the present invention, the sulfonium salt having the structure represented by the general formula (1) and the sulfonium salt having the structure represented by the general formula (1) are excluded. It contains a sulfo-um salt.

[0048] In the present invention, sulfo excluding the sulfo-um salt having the structure represented by the general formula (1).

The -um salt is not particularly limited, but is preferably a sulfonium salt having the structure represented by the general formula (A).

[0049] Te you, the general formula (A), Ra, Ra each represents an alkyl group or an aromatic group, Z ¹

1 2

Represents an oxygen atom or a sulfur atom, and Ra and Ra are an alkyl group, aromatic group,

3 4

Represents an oxy group, an aryloxy group, an alkylthio group, or an allylthio group, ml represents an integer of 0 to 4, nl and pi each represent an integer of 1 to 5, Y represents Z—SO (Z represents C F (n

3 n 2n + l represents an integer of 1 to: L0), an alkyl group, or an alkyl-substituted or unsubstituted aromatic group), PF, BF, AsF, SbF, B (CF), CIO, Br , CI or I.

6 4 6 6 6 5 4 4

[0050] The alkyl group may be linear, branched or cyclic. For example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a hexyl group. Group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, cyclopentyl group, cyclohexyl group and the like. [0051] The aromatic group may have a condensed ring which may be an aromatic hydrocarbon ring group or an aromatic heterocyclic group. For example, an aromatic hydrocarbon group (for example, a phenyl group, a naphthyl group) Etc.), an aromatic heterocyclic group (for example, furyl group, chenyl group, pyridyl group, pyridazyl group, pyrimidyl group, birazyl group, triazyl group, imidazolyl group, pyrazolyl group, thiazolyl group, benzoimidazolyl group, benzoxa Zolyl group, quinazolyl group, phthalazyl group, etc.).

[0052] The above-mentioned alkyl group or aromatic group may further have a substituent, and these substituents may be bonded to each other to form a ring, and have a condensed ring. You can ask. Examples of the substituent include an alkyl group (for example, a bialkyl group) in addition to the alkyl group described above.

-Alkyl groups, aryl groups, etc.), alkyl groups (eg, ethur groups, propargyl groups, etc.), aromatic hydrocarbon groups (eg, phenyl groups, naphthyl groups, etc.), heteroaromatic groups (eg, free radicals). Group, chenyl group, pyridyl group, pyridazyl group, pyrimidyl group, birazyl group, triazyl group

, Imidazolyl group, pyrazolyl group, thiazolyl group, benzoimidazolyl group, benzoxazolyl group, quinazolyl group, phthalazyl group, etc.), heterocyclic group (for example, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxy group (for example, , Methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group, etc.), cycloalkoxy group (for example, cyclopentyloxy group, cyclohexyloxy group, etc.), aryloxy group (for example, Phenoxy group, naphthyloxy group, etc.), alkylthio group (for example, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio group (for example, cyclo Nylthio group, cyclohexylthio group, etc.), arylthio group (for example, phenylthio group, naphthylthio group, etc.), alkoxy carbo yl group (for example, methyloxy carbo yl group, eth oxy carbo yl group, Butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (for example, phenylcarbol group, naphthyloxycarbonyl group, etc.), sulfamoyl group (For example, aminosulfol group, methylaminosulfol group, dimethylaminosulfol group, butylaminosulfol group, hexylaminosulfol group, cyclohexylaminosulfol group, octyl) Aminosulfo group, dodecylaminosulfo Group, phenylaminosulfol group, naphthylaminosulfol group, 2-pyridylaminosulfol group, etc.), acyl group (eg, acetyl group, ethylcarbonyl group, propyl group carbonyl group, pentylcarbonyl group) Group, cyclohexyl carbonyl group, octyl carbonyl group, 2-ethyl hexyl carbonyl group, dodecyl carbo ol group, phenyl carbo yl group, naphthyl carbo yl group, pyridyl carbonyl group, etc.), isyloxy group (for example, , Acetyloxy group, ethyl carbo-loxy group, butyl carbo-loxy group, octyl carbo-loxy group, dodecyl carbo-loxy group, phenyl carbo-loxy group, etc.), amide group (for example, methyl carbo-lamino group, ethyl carbo-lamino group, dimethyl group) Tyl carbolumino group, propyl carbolumino group, pentyl carbole Amino group, cyclohexyl carbolumino group, 2-ethyl hexyl carbolumino group, octyl carbolumino group, dodecyl carbolumino group, phenyl carbolumino group, naphthyl carbonylamino group, etc.) Groups (e.g., aminocarbonyl group, methylaminocarbol group, dimethylaminocarbol group, propylaminocarbol group, pentylaminocarboro group, cyclohexylaminocarboro group, octylamino) Carbon group, 2-ethylhexylaminocarbol group, dodecylaminocarbol group, phenolaminocarbol group, naphthylaminocarbole group, 2-pyridylaminocarbol group, etc. ), Ureido groups (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group). Group, dodecylureido group, phenylureido group, naphthylureido group, 2-pyridylaminoureido group, etc.), sulfier group (for example, methylsulfuryl group, ethylsulfuryl group, butylsulfuryl group, cyclohexylsulfuryl group) 2-ethylhexylsulfyl group, dodecylsulfyl group, phenylsulfyl group, naphthylsulfyl group, 2-pyridylsulfyl group, etc.), alkylsulfol group (for example, methylsulfo- group) Group, ethylsulfol group, butylsulfol group, cyclohexylsulfol group, 2-ethylhexylsulfol group, dodecylsulfol group, etc.), arylsulfol group (phenylsulfol group, naphthyl) Sulfo group, 2-pyridyl sulfo group, etc.), amino group (eg, amino group, ethylamino group, dimethylamino group) Groups, butyramino groups, cyclopentylamino groups, 2-ethylhexylamino groups, dodecylamino groups, arlino groups, naphthylamino groups, 2-pyridylamino groups, etc.), halogen sources (For example, fluorine atom, chlorine atom, bromine atom, etc.), fluorinated hydrocarbon group (for example, fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, pentafluorophenyl group, etc.) , A cyano group, a nitro group, a hydroxy group, a mercapto group, a silyl group (for example, a trimethylsilyl group, a triisopropyl silyl group, a tributylsilyl group, a fluorethylsilyl group, etc.). These substituents may be further substituted with the above substituents, and a plurality of these substituents may be bonded to each other to form a ring.

[0053] The alkyl group or aromatic group represented by Ra or Ra may further have a substituent.

1 2

May be an unsubstituted alkyl group or an aromatic group, or an aromatic group substituted by an alkyl group or an alkoxy group substituted with a halogen atom, more preferably Examples of an alkyl group substituted with an alkyl group substituted with an alkyl group substituted with an alkyl group or an aromatic group, or an aromatic group substituted with an alkoxy group, such as a fluoromethyl group or a trifluoromethyl group. Examples thereof include a fluoromethyl group, a pentafluoroethyl group, and a pentafluorophenyl group.

[0054] Z ¹ represents an oxygen atom or a sulfur atom, and Z ¹ binds to a benzene ring to which a sulfonium ion is bonded at the para position, preferably bonded to the ortho or para position. preferable.

[0055] Ra and Ra are an alkyl group, an aromatic group, an alkoxy group, an aryloxy group, an alkyl group, respectively.

3 4

Represents a ruthio group and an arylthio group.

[0056] The alkyl group and the aromatic group are groups having the same meanings as Ra and Ra described above.

1 2

[0057] The alkoxy group and the aryloxy group have the same meanings as Ra and Ra described above for the oxygen atom.

1 is a group in which two groups are bonded at one position, and examples thereof include an alkoxy group (for example, methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group, fluoromethyl group, trifluoromethyl group) Methyl group, pentafluoroethyl group, pentafluorophenyl group, etc.), cycloalkoxy group (eg, cyclopentyloxy group, cyclohexyloxy group, etc.), aryloxy group (eg, phenoxy group, naphthyloxy group, etc.) Etc.

[0058] As the alkylthio group and the arylthio group, the sulfur atom has the same meaning as Ra and Ra described above.

1 2 is a group in which one group is bonded, and examples thereof include an alkylthio group (for example, a methylthio group, Ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc., cycloalkylthio group (eg, cyclopentylthio group, cyclohexylthio group, etc.), arylthio group (eg, phenylthio group, naphthylthio group, etc.) Etc.) and the like. The above-mentioned aromatic group, aryloxy group, and arylothio group may have a condensed ring.

[0059] The above-mentioned alkyl group, aromatic group, alkoxy group, aryloxy group, alkylthio group, and arylothio group may further have a substituent. A plurality of these substituents are bonded to each other to form a ring. It may have a condensed ring. Examples of the substituent include the same groups as the examples of the substituent for Ra described above.

1

May be further substituted with a substituent, and a plurality of these substituents may be bonded to each other to form a ring. Ra, an alkyl group represented by Ra, an aromatic group,

3 4

The alkoxy group, aryloxy group, alkylthio group, and arylothio group may or may not further have a substituent, but preferably an unsubstituted alkyl group, aromatic group, alkoxy group, aryloxy group, alkylthio group. A group, an arylthio group, or an alkyl group substituted with a rogen atom, or an aromatic group substituted with an alkoxy group, more preferably an unsubstituted alkyl group, aromatic group, alkoxy group, aryloxy group An alkylthio group, an arylthio group, an alkyl group substituted with a fluorine atom, or an aromatic group substituted with an alkoxy group. Examples of the alkyl group substituted with a fluorine atom include a fluoromethyl group and a trifluoromethyl group. , Pentafluoroethyl group, pentafluorophenyl group, etc. That.

[0060] ml represents an integer of 0 to 4, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and nl and pi each represent an integer of 1 to 5, preferably 1 Is an integer of -3, more preferably an integer of 1-2.

[0061] A plurality of Ra, Ra and Ra may be the same or different from each other.

2 3 4 1 2

Ras may combine to form a ring Ra and Ra or multiple Ras

2 2 3 3 Combined to form a ring Ra and Ra or multiple Ras combine to form a ring

2 4 4

Alternatively, Ra and Ra may combine to form a ring. At least one of Ra is sulfoni

2 4 3

It is preferable to bond to the ortho or para position with respect to the benzene ring to which the muon ion is bonded. It is more preferable to bond at the para position. At least one of Ra is sulfoyuumio

Four

It is preferable to bond at the ortho or para position to the benzene ring to which the bond is bonded. It is more preferable to bond at the normal position.

[0062] Y is Z-SO (Z is C F (n is an integer of 1 to 10), an alkyl group, or alkyl-substituted.

3 n 2n + l

Or represents an unsubstituted aromatic group), PF, BF, AsF, SbF, B (C F), CIO, Br ゝ

6 4 6 6 6 5 4 4

C is a force representing I. Preferably, PF, CFSO, BF, AsF, and B (C F).

6 3 3 4 6 6 5 4

[0063] The sulfoyuium salt compound represented by the general formula (A) according to the present invention is more preferably a compound represented by the general formulas (B) to (D) according to the present invention, A compound represented by formula (B) is preferred.

[0064] (Compound represented by formula (B))

In the general formula (B), R 1 represents an alkyl group having 1 to 10 carbon atoms. Alkyl group is

31

Examples that may be linear, branched, or cyclic include methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, hexyl, and heptyl groups. Octyl group, tert-amyl group, cyclopentyl group, cyclohexyl group and the like, and these may further have a substituent. Examples of the substituent are groups having the same meaning as the Ra substituent in the general formula (A) described above. R is preferably an alkyl having 1 to 6 carbon atoms.

1 31

More preferably an alkyl group having 1 to 4 carbon atoms.

[0065] R 1 and R 2 each represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

32 33

To express. The alkyl group is the same as R described above, and the alkoxy group is above the oxygen atom.

31

The group having the same meaning as R described above is a group bonded at one position, and examples include a methoxy group, an ethoxy group,

31

Examples thereof include a propyloxy group, an isopropyloxy group, a tert-butyloxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a cyclopentyloxy group, and a cyclohexyloxy group. R 1 and R 2 are each preferably charcoal

32 33

A C1-C6 alkyl group or C1-C6 alkoxy group, more preferably a C1-C4 alkyl group or C1-C4 alkoxy group, and most preferably a methyl group or methoxy group. It is a group. Y is synonymous with Y in the general formula (A) described above.

Three

[0066] (Compound represented by formula (C))

In the general formula (C), R 1 represents an alkyl group having 1 to 10 carbon atoms. As an alkyl group Examples of straight-chain, branched, or cyclic examples include methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, hexyl, and Examples include a butyl group, an octyl group, a tert-amyl group, a cyclopentyl group, a cyclohexyl group, and the like, which may further have a substituent. An example of the substituent is a group having the same meaning as the Ra substituent in the general formula (A) described above. R preferably has 1 to 6 carbon atoms.

1 41

An alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, and most preferably a methyl group.

[0067] R represents a substituent, and examples of the substituent include the Ra substituent in the general formula (A) described above.

42 1 Synonymous group.

[0068] m4 represents an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 force 1. [0069] R 1 and R 2 each represents an alkyl group having 1 to 10 carbon atoms. As the alkyl group,

43 44

R is synonymous with R. R 1 and R 2 are each preferably an alkyl group having 1 to 6 carbon atoms,

31 43 44

More preferred is an alkyl group having 1 to 4 carbon atoms, and most preferred is a methyl group. Y is above

4 Synonymous with Y in formula (A).

[0070] (Compound represented by formula (D))

In the general formula (D), R 1 represents a hydrogen atom or an alkyl group having 1 to: LO. Finished

51

The alkyl group is the same as the substituent for R described above. R is preferably a hydrogen atom

31 51

Or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0071] R represents a substituent. As the substituent, the substituent of Ra in the general formula (A) described above and

52 1 Synonymous group.

[0072] m5 represents an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1.

R 1 and R 2 each represent an alkyl group having 1 to 10 carbon atoms. As the alkyl group,

53 54

31 53 54

5 It is synonymous with Y in the general formula (A) described above. [0074] Specific examples of the triarylsulfonium salt compound represented by the general formulas (A) to (D) according to the present invention are shown below, but the present invention is not limited thereto. is not.

[0075] [Chemical 10]

One

. y

[0076] [Chemical 11]

[0078] [Chemical 13]

[0079] These compounds are described in Bull. Chem. Soc. Jpn., 42, 312 (1969)., J. Polym. Sci., Poly. M. Chem. Ed., 17, 2877 (1979). The compounds can be synthesized according to the methods described in JP-A-11-80118, JP-A-2002-241474, JP-A-2005-139425, and US Pat. No. 4,440,459.

[0080] (Polycyclic aromatic compounds, strong rubazole derivatives and thixanthone derivatives)

The photoacid generator composition of the present invention preferably contains at least one compound selected from a polycyclic aromatic compound, a strong rubazole derivative and a thixanthone derivative together with the photoacid generator described above. Furthermore, anthracene, fluorene, pyrene, thalene, phenanthrene, anthraquinone, perylene, carbazole, phenothiazine, thixanthone, thianthrene, benzanthracene, naphthacene, triphenylene, and at least one compound selected from the following general formula (3) are contained. It is preferable to do.

[0081] The polycyclic aromatic compound that can be used in the present invention is preferably a naphthalene derivative, anthracene derivative, a taricene derivative, or a phenanthrene derivative. Substituent al As the alkoxy group, those having 1 to 18 carbon atoms are preferred, and those having 1 to 8 carbon atoms are particularly preferred. As the aralkyloxy group, those having 7 to 10 carbon atoms are preferable, and in particular, a benzyloxy group and phenethyloxy group having 7 to 8 carbon atoms are preferable.

Specifically, 1-naphthol, 2 naphthol, 1-methoxynaphthalene, 1-stearyloxynaphthalene, 2-methoxynaphthalene, 2 dodecyloxynaphthalene, 4-methoxy 1 naphthol, glycidyl 1 naphthyl ether, 2- (2 —Naphthoxy) ethyl vinyl ether, 1,4-dihydroxynaphthalene, 1,5 dihydroxynaphthalene, 1,6 dihydroxynaphthalene, 2,7 dihydroxynaphthalene, 2,7 dimethoxynaphthalene, 1,1′-thiobis (2 naphthol) 1, 1'B 2 naphthol, 1,5 naphthyl diglycidyl ether, 2,7 di (2 buroxetyl) naphthyl ether, 4-methoxy-1-naphthol, ESN-175 (Epoxy cage made by Nippon Steel Chemical Co., Ltd.) Naphthalenes such as condensates of naphthol derivatives and formalin Derivatives 9, 10, 10 Dimethoxyanthracene, 2 Ethyl-9,10 Dimethoxyanthracene, 2-tbutyl-9,10 Dimethoxyanthracene, 2,3 Dimethynole 9,10 Dimethoxyanthracene, 9-methoxy 10-Methylanthracene, 9,10 Toxianthracene, 2 ethyl 9,10 Jetoxyanthracene, 2 tButyl 9,10 Jetoxyanthracene, 2,3 Dimethyl 9,10 Jetoxyanthracene, 9 Ethoxy 10-methylanthracene, 9, 10 Dipropoxyanthracene, 2 Ethyl 9 , 10 Dipropoxyanthracene, 2 t Butinole 9, 10 Dipropoxyanthracene, 2, 3 Dimethylolene 9, 10 Dipropoxyanthracene, 9 Isopropoxy 10-Methylanthracene, 9, 10 Dibenzyloxyanthracene, 2 Ethyl 9, 10 Dibenzyl Oxyanthracene, 2—t Butyl-9,10 Dibenzyloxyanthracene, 2,3 Dimethyl-9,10 Dibenzyloxyanthracene, 9-Benzyloxy 10-methylanthracene, 9,10 dia a Methylbenzyloxyanthracene, 2 ethyloxy 9,10 Methyl benzyl dioxyanthracene, 2-t-butyl-9,10 ee at methyl benzyloxy anthracene, 2, 3 dimethyl 9, 10 ee at methyl benzyloxy anthracene, 9 (a-methyl benzyloxy) 10-methyl anthracene 9, 10 di (2 hydroxyethoxy) anthracene, 2 ethyl 9,10 di (2 carboxyethoxy) anthracene, etc. Anthracene derivatives such as 1,4 dimethoxychrysene, 1,4 methoxychrysene, 1,4 dipropoxytalicene, 1,4-dibenzyloxytalicene, 1,4-di at methylbenziloxychrysene, etc., 9 hydroxy Examples thereof include phenanthrene derivatives such as phenanthrene, 9,10 dimethoxyphenanthrene, and 9,10 diethoxyphenanthrene. Among these derivatives, a methoxy group and an ethoxy group are particularly preferable as the alkoxy group preferred by the 9,10 dialkoxyanthracene derivative which may have an alkyl group having 1 to 4 carbon atoms as a substituent.

[0083] Examples of strong rubazole derivatives include N-methylcarbazole, N-ethylcarbazole (hereinafter referred to as "NEC"), N-propylcarbazole, N-butylcarbazole, N-vinylcarbazole, 1, 3, 6, 8 , 9 Pentamethylcarbazole, 1, 4, 5, 8, 9 Pentamethylcarbazole (hereinafter referred to as “NMPC”), 3-formyl N-ethylcarbazole, N-phenylcarbazole, N-ethyl-3, 6— Bis (benzoyl) rubazole (hereinafter referred to as “NEBC”), 9, 9 ′ Jetyl 3, 3 ′ —dicarbazole (hereinafter referred to as “NEDC”), and the like.

[0084] Examples of thixanthone derivatives include thixanthone, 2,4 dimethylthioxanthone, 2,4 jetylthioxanthone, isopropylthioxanthone 2 chlorothixanthone, and the like.

[0085] In the general formula (3), R ^{21 to} R ²⁸ have the same meanings as Ri to R ¹⁷ in the general formula (1).

[0086] << Cationic Photopolymerizable Composition >>

The cationic photopolymerizable composition of the present invention is characterized by containing a cationic polymerizable compound together with the photoacid generator composition of the present invention.

[0087] (Cationically polymerizable compound)

As the cationically polymerizable compound according to the present invention, various known cationically polymerizable monomers can be used. Particularly, JP-A-6-9714, JP-A-2001-31892, JP-A-2001- Epoxy compounds, vinyl ether compounds, and oxetanes shown in column f of 40068, JP 2001-55507, JP 2001-310938, JP 2001-310937, JP 2001-220526. A compound is preferred. [0088] Examples of the epoxy compound include the following aromatic epoxides, alicyclic epoxides, and aliphatic epoxides.

[0089] A preferable aromatic epoxide is a di- or diol produced by the reaction of a polyhydric phenol having at least one aromatic nucleus or an alkylene oxide-attached cage thereof and epichlorohydrin. Polyglycidyl ethers, such as di- or polyglycidyl ethers of bisphenol A or alkylene oxide adducts thereof, di- or polyglycidyl ethers of hydrogenated bisphenol A or alkylene oxide-attached bodies, and novolac type epoxy resins Etc. Here, examples of the alkylene oxide include ethylene oxide and propylene oxide.

[0090] As the alicyclic epoxide, a compound having at least one cycloalkane ring such as cyclohexene or cyclopentene ring is epoxidized with an appropriate oxidizing agent such as hydrogen peroxide or peracid. The resulting cyclohexene oxide or cyclopentene oxide-containing compound is preferred.

[0091] Preferred aliphatic epoxides include aliphatic polyhydric alcohols or di- or polyglycidyl ethers of their alkylene oxide adducts, typical examples of which include diglycidyl ether of ethylene glycol, propylene Polyglycidyl of polyhydric alcohol such as diglycidyl ether of glycol or diglycidyl ether of alkylene glycol such as diglycidyl ether of 1,6-hexanediol, di- or triglycidyl ether of diglycidyl ether of glycerin or alkylene oxide thereof Of polyalkylene glycols such as diglycidyl ethers of ethers, polyethylene glycols or alkylene oxides thereof, and diglycidyl ethers of polyethylene glycols or alkylene oxides thereof. Glycidyl ether, and the like. Here, examples of the alkylene oxide include ethylene oxide and propylene oxide.

[0092] Among these epoxides, in view of fast curability, aromatic epoxides and alicyclic epoxides are preferred, and alicyclic epoxides are particularly preferred. In the present invention, one of the epoxides may be used alone, or two or more may be used in appropriate combination.

[0093] In the present invention, the alicyclic epoxy compound is described in JP-A-2005-139425. The compounds represented by the general formulas (A), (I) to (VI) are preferred.

[0094] Examples of the butyl ether compound that can be preferably added to the present invention include known vinyl ether compounds. For example, ethylene glycol dibutyl ether, polyethylene glycol divininole ether, triethylene glycol divininole ether, propylene glycol divininole ether, dipropylene glycol divininole ether, butane diol divinyl ether, hexanediol divinyl ether, cyclohexane divinyl ether Di- or tributyl ether compounds such as methanol divinyl ether and trimethylolpropane trivinyl ether, ethyl vinyl ether, _n -butyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, hydroxybutynole vinylenole Ethenore, 2-ethynolehexinolevinoleetenore, cyclohexanedimethanol monovinyl ether, n-propylbiene Examples thereof include monobutyl ether compounds such as nyl ether, isopropyl vinyl ether, isopropylene ether o propylene carbonate, dodecyl vinyl ether, diethylene glycol monobutyl ether, and octadecyl vinyl ether.

[0095] Among these vinyl ether compounds, in consideration of curability, adhesion, and surface hardness, di- or trivinyl ether compounds are preferred, and in particular dibuty ether compounds are preferred. In the present invention, one of the above vinyl ether compounds may be used alone, or two or more may be used in appropriate combination.

[0096] The oxetane compound that can be used in the present invention is a compound having an oxetane ring, and is described in Japanese Patent Application Laid-Open No. 2001-220526, 2001-310937. Any known oxetane compound can be used. In particular, a compound represented by the general formula (Ε) described in JP-A-2005-139425 is preferred, specifically, described in paragraph No. 0218 of the same specification, る -1 to Ε-13. Etc.

[0097] In the photocurable composition of the present invention, a monofunctional oxetane compound containing one oxetane ring and a polyfunctional oxetane compound containing two or more oxetane rings may be used in combination. Is more preferable for improving the film strength after curing. However, when a compound having 5 or more oxetane rings is used, the viscosity of the photocurable composition is increased, which makes it difficult to handle and increases the glass transition temperature of the photocurable composition. The cured product is not sufficiently sticky. The compound having an oxetane ring used in the present invention is preferably a compound having 1 to 4 oxetane rings.

[0098] In the present invention, the cationically polymerizable compound is preferably 25 to 90% by mass of a compound having an oxetane ring, 10 to 70% by mass of a compound having an oxsilane group, and a vinyl ether compound. In this structure, both curability and ejection stability are improved.

[0099] [Various additives]

In the cationic photopolymerizable composition of the present invention, various additives other than those described above can be used. For example, leveling additives, matting agents, polyester resin, polyurethane resin, bull resin, acrylic resin, rubber resin, waxes to adjust film properties should be added. Can do. In addition, for the purpose of improving storage stability, any known basic compound can be used. Representative examples include basic alkali metal compounds, basic alkaline earth metal compounds, and amines. Organic organic compounds.

[0100] [Pigment]

The cationic photopolymerizable composition of the present invention preferably contains a pigment.

[0101] Examples of the pigment used in the present invention include carbon-based pigments such as carbon black, carbon refined, and carbon nanotubes, iron black, cobalt blue, zinc oxide, titanium oxide, chromium oxide, and iron oxide. Metal oxide pigments, sulfide pigments such as zinc sulfide, phthalocyanine pigments, pigments composed of salts such as metal sulfates, carbonates, kaates, and phosphates, and aluminum powders, bronze powders, and Inorganic pigments such as metal powders such as zinc powder, nitro pigments, alin black, naphthol green B-toroso pigments, Bordeaux 10B, lake red 4R and azo pigments such as chromoftal red (azo lake) , Insoluble azo pigments, condensed azo pigments, chelate azo pigments, etc.), peacotton lakes and rhodamines Lake pigments such as a rk, Futaroshia - phthalocyanine pigments such as Nbunore mono-, polycyclic pigments (perylene pigments, perinone pigments, anthraquinone Pigments, quinacridone pigments, Jiokisan pigments, Chioinjigo pigments, isoindolinone pigments, keno Furanone pigments), selenium pigments such as thioindigo red and indatron blue, quinacridone pigments, quinacridine pigments, and organic pigments such as isoindolinone pigments.

[0102] Specific examples of pigments include

C. I Pigmen Yellow—1, 3, 12, 13, 14, 17, 42, 81, 83, 87, 95, 109, 1 14, 120, 128, 129, 138, 150, 151, 154, 180, 185 ,

C. I Pigmen Orange— 16, 36, 38,

C. I Pigmen Red—5, 22, 38, 48: 1, 48: 2, 48: 4, 49: 1, 53: 1, 57: 1, 63: 1, 101, 122, 123, 144, 146, 168, 184, 185, 202,

C. I Pigmen Violet—19, 23,

C. I Pigmen Blue—15: 1, 15: 3, 15: 4, 18, 27, 29, 60,

C. I Pigmen Green—7, 36,

C. I Pigmen White—6, 18, 21,

C. I Pigmen Black—7, etc.

[0103] For the dispersion of the pigment, for example, a ball mill, a sand mill, an attritor, a roll mill, an agitator, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, a pearl mill, a wet jet mill, a paint shaker, or the like can be used. Further, a dispersing agent can be added when dispersing the pigment. As the dispersant, it is preferable to use a polymer dispersant, for example, Avecia Solsperse series and Ajinomoto Fine Techno PB series. In addition, a synergist according to various pigments can be used as a dispersion aid. These dispersants and dispersion aids are preferably added in an amount of 1 to 50 parts by mass with respect to 100 parts by mass of the pigment. The dispersion medium is a solvent or a polymerizable compound. The photocurable ink of the present invention is preferably solvent-free because it is reacted and cured after printing. If the solvent remains in the cured image, the solvent resistance deteriorates and the VOC problem of the remaining solvent occurs. Therefore, it is preferable in view of dispersibility that the dispersion medium is not a solvent but a polymerizable compound, and among them, a monomer having the lowest viscosity is selected.

[0104] Inkjet ink The ink-jet ink of the present invention contains at least the photoacid generator composition of the present invention or the cationic photopolymerizable composition of the present invention.

[0105] In the inkjet ink of the present invention, in addition to the constituent elements described in the photoacid generator composition of the present invention or the cationic photopolymerizable composition of the present invention, for example, a leveling additive, a matting agent, etc. Polyester-based resin, polyurethane-based resin, vinyl-based resin, acrylic-based resin, rubber-based resin, and waxes for adjusting film physical properties can be added. For the purpose of improving storage stability, any known basic compound can be used, but representative examples include basic alkali metal compounds, basic alkaline earth metal compounds, and amines. And basic organic compounds. It is also possible to combine radically polymerizable monomers and initiators into radical cation hybrid curable inks.

[0106] Further, in the inkjet ink of the present invention, when used for inkjet image formation, the viscosity at 25 ° C is preferably 7 to 50 mPa's.

[0107] Recording material

As the recording material that can be used in the present invention, various non-absorbable plastics and films used for so-called soft packaging, as well as ordinary uncoated paper and coated paper, can be used. For example, polyethylene terephthalate (PET) film, stretched polystyrene (OPS) film, stretched polypropylene (OPP) film, stretched nylon (ONy) film, polychlorinated butyl (PVC) film, polyethylene (PE) film, tria A cetyl cellulose (TAC) film etc. can be mentioned. Other plastics that can be used include polycarbonate, acrylic resin, ABS, polyacetal, polybutyl alcohol (PVA), and rubbers. It can also be applied to metals and glass. Among these recording materials, the configuration of the present invention is effective particularly when an image is formed on a PET film, an OPS film, an OPP film, an ONy film, and a PVC film that can be shrunk by heat. In these base materials, if the film is easily curled or deformed due to curing shrinkage of the ink or heat generated during the curing reaction, it is difficult for the ink film to be followed by the force to follow the shrinkage of the base material.

[0108] The surface energy of these various plastic films varies greatly, Therefore, the dot strength after ink landing has changed, and the conventional power has also been a problem. With the configuration of the present invention, good high-definition images are formed on a wide range of recording materials with a surface energy of 35 to 60 mNZm, including OPP films with low surface energy, OPS films, relatively large surface energy, and even PET. it can.

[0109] Furthermore, a fabric having natural fiber or synthetic fiber strength can also be used. Specific examples include cotton, silk, Trevira CS (polyester: made from hextone), Tyvek (polyethylene: made from Dubon), turbolin (salt vine), nylon, and the like.

[0110] <Ink jet recording method>

In the present invention, it is preferable that the total ink film thickness after recording ink on the recording material and curing by irradiation with actinic rays is 2 to 20 m. The recording material is often a thin plastic material! In the flexible packaging printing field, there is a problem that the texture of the entire printed matter changes due to the above-mentioned problem of curling of the recording material. Ink ejection with a thick film thickness is not preferable.

[0111] Here, "total ink film thickness" means the maximum value of the film thickness of the ink drawn on the recording material, and even with a single color, the other two colors (secondary color) or three colors are superimposed. Even when 4-color superposition (white ink base) is recorded, the meaning of the total ink film thickness is the same.

[0112] In the printing method of the present invention, it is preferable that the actinic ray is irradiated for 0.001 to 2.0 seconds after ink printing as the actinic ray irradiation condition, more preferably 0.001. Seconds to 1.0 seconds. In order to form a high-definition image, it is particularly important that the irradiation timing is as early as possible.

[0113] The method of irradiating actinic rays in two stages, first irradiating actinic rays between 0.001 and 2.0 seconds after ink printing, and further irradiating actinic rays after the completion of all printing Is also one of the preferred embodiments. By dividing the actinic ray irradiation into two stages, it is possible to suppress the shrinkage of the recording material that occurs during ink curing.

[0114] Conventionally, in the UV ink printing method, a light source with high illuminance in which the total power consumption of the light source exceeds lkW'hr is usually used in order to suppress dot spread and bleeding after ink landing. However, when these light sources are used, particularly in printing on a shrink label or the like, the shrinkage of the recording material is so large that it cannot be used. [0115] In the present invention, it is preferable to use an actinic ray having the highest illuminance in the wavelength region of 254 nm. Even if a light source with a total power consumption of lkW'hr or more is used, a high-definition image can be formed, and The shrinkage of the recording material is within a practically acceptable level.

[0116] In the present invention, it is preferable that the total power consumption of the light source for irradiating active light is less than lkW'hr. Examples of light sources with a total power consumption of less than lkW'hr include, but are not limited to, fluorescent tubes, cold cathode tubes, LEDs and the like.

Hereinafter, a recording apparatus applicable to the ink jet recording method of the present invention will be described with reference to the drawings as appropriate.

FIG. 1 is a front view showing the configuration of the main part of the recording apparatus. The recording apparatus 1 includes a head carriage 2, a recording head 3, an irradiation unit 4, a platen unit 5, and the like. In this recording apparatus 1, a platen section 5 is installed under the recording material P. The platen section 5 has a function of absorbing ultraviolet rays and absorbs excess ultraviolet rays that have passed through the recording material P. As a result, high-definition images can be reproduced very stably.

[0119] The recording material P is guided by the guide member 6 and moves from the front side to the back side in Fig. 1 by the operation of the conveying means (not shown). Head scanning means (not shown) scans the recording head 3 held by the head carriage 2 by reciprocating the head carriage 2 in the Y direction in FIG.

[0120] The head carriage 2 is installed on the upper side of the recording material P, and a plurality of recording heads 3 to be described later are arranged in accordance with the number of colors used for image printing on the recording material P, and the discharge ports are arranged on the lower side. Store. The head carriage 2 is installed on the main body of the recording apparatus 1 in such a manner that it can reciprocate in the Y direction in FIG. 1, and reciprocates in the Y direction in FIG. 1 by driving the head scanning means.

[0121] In FIG. 1, the head carriage 2 is white (W), yellow (Y), magenta (M), shean (C), black (K), light yellow (Ly), light magenta (Lm), Drawing as if the light cyan (Lc), light black (Lk), and white (W) recording heads 3 were to be stored! The number of colors is determined as appropriate.

The recording head 3 has an actinic ray curable ink supplied by an ink supply means (not shown). The discharge roller is also discharged toward the recording material P by the operation of a plurality of discharge means (not shown) provided therein (for example, UV curable ink). The UV ink discharged from the recording head 3 is composed of a coloring material, a polymerizable monomer, an initiator, etc., and the monomer crosslinks when the initiator acts as a catalyst when irradiated with ultraviolet rays. It has the property of being cured by a polymerization reaction.

[0123] The recording head 3 has a certain area (landing) in the recording material P during the scan that moves from one end of the recording material P to the other end of the recording material P in the Y direction in FIG. UV ink is ejected as ink droplets onto the possible region), and ink droplets are landed on the landable region.

[0124] After the above scanning is performed as many times as necessary and UV ink is discharged toward one landable area, the recording material P is appropriately moved in the forward direction in FIG. 1 by the transport means, and head scanning is performed again. While performing scanning by means, the recording head 3 discharges UV ink to the next landable area adjacent in the rear direction in FIG.

[0125] The above operation is repeated, and UV ink is ejected from the recording head 3 in conjunction with the head scanning means and the conveyance means, whereby an image having the collective force of UV ink droplets is formed on the recording material P.

The irradiation means 4 includes an ultraviolet lamp that emits ultraviolet light in a specific wavelength region with stable exposure energy and a filter that transmits ultraviolet light of a specific wavelength. Here, mercury lamps, metal nanoride lamps, excimer lasers, ultraviolet lasers, cold cathode tubes, hot cathode tubes, black lights, LEDs (light emitting diodes), etc. are applicable as ultraviolet lamps.ヽ Ride lamp, cold cathode tube, hot cathode tube, mercury lamp or black light are preferred. In particular, a low-pressure mercury lamp, a hot cathode tube, a cold cathode tube, and a germicidal lamp that emit ultraviolet light having a wavelength of 254 nm are preferable because they can prevent bleeding and efficiently control the dot diameter. By using black light as the radiation source of the irradiation means 4, the irradiation means 4 for hardening the UV ink can be produced at low cost.

[0127] The irradiation means 4 is provided by the recording device (UV inkjet printer) 1 in the landable area where the recording head 3 ejects UV ink by one scan by driving the head scanning means. It has almost the same shape as the largest one that can be determined, or a shape larger than the landable area.

The irradiating means 4 is installed on both sides of the head carriage 2 so as to be substantially parallel to the recording material P.

As described above, as a means for adjusting the illuminance of the ink discharge portion, the entire recording head 3 is not only shielded, but in addition, the recording head is determined by the distance hi between the irradiation means 4 and the recording material P. It is effective to increase the distance h2 between the ink ejection part 31 and the recording material P in Fig. 3 (hl <h2), or to increase the distance d between the recording head 3 and the irradiation means 4 (d is increased). is there. Further, it is more preferable that the space between the recording head 3 and the irradiation means 4 is a bellows structure 7.

Here, the wavelength of the ultraviolet rays irradiated by the irradiation means 4 can be appropriately changed by replacing the ultraviolet lamp or filter provided in the irradiation means 4.

Example

[0131] Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In the examples, “part” or “%” is used as a force to indicate “part by mass” unless otherwise specified. “/” Represents “% by mass”.

[0132] Example 1

A pigment dispersion a was prepared by dispersing the pigment according to the following method.

[0133] Each of the following compounds was placed in a stainless beaker and dissolved by stirring with heating for 1 hour while heating on a 65 ° C hot plate.

[0134] PB822 (Ajinomoto Fine Technone Earth Dispersant) 8 parts

OXT221 (Oxetane compound manufactured by Toa Gosei Co., Ltd.) 72 parts After cooling to room temperature, add 20 parts of Pigment Blue 15: 4 (manufactured by Dainichi Seika Co., Ltd.) and add it to a glass bottle with 200 g of Zircoyu beads of 0.3 mm Sealed and sealed, and dispersed with a paint shaker for 4 hours, after which the zircoyour beads were removed to obtain a pigment dispersion a.

[0135] <Preparation of ink>

Inks 1 to 7 were prepared by sequentially adding and mixing the additives listed in Table 1. The numerical values listed in Table 1 are addition amounts (parts).

[0136] [Table 1]

[0137] The details of the additives abbreviated in Table 1 are as follows.

[Photopolymerizable compound]

OXT-101: Toagosei Co., Ltd.

OXT -212: Toagosei Co., Ltd.

OXT-221: Made by Toagosei

(Photopolymerization initiator: photoacid generator)

UVI6992: Propion carbonate 50% solution manufactured by Dow Chemical Company SP152: Sulfonium salt (Asahi Denka Kogyo Co., Ltd.)

[Sensitizer]

DBA: 9, 10—Dibutoxyanthracene

[Basic compounds]

* A: Triisopanol propane

[Surfactant]

KF— 351: Silicone oil manufactured by Shin-Etsu Chemical [0139] [Chemical 14]

[0140] <Inkjet image forming method>

The above-prepared cured composition ink is loaded into an ink jet recording apparatus having the constitutional power shown in FIG. 1 equipped with a piezo-type ink jet nozzle, and the recording material is 600 mm wide and 20 m long Trevira CS (polyester film, hexone The following image recording was continuously carried out on the earthenware. The ink supply system was an ink tank, supply pipe, front chamber ink tank just before the head, pipe with filter, and piezo head force. Heating was performed from the front chamber tank to the head and heated to 50 ° C. The head portion was heated in accordance with the viscosity of each curable composition ink, and was driven so that it could be ejected at a resolution of 720 × 720 dpi, so that the curable composition ink described above was continuously ejected. The recording material was adjusted to 40 ° C with a surface heater and a cooling device. After landing, 120WZcm metal nanoride lamps on both sides of the carriage (MAL 400NL manufactured by Nihon Batteries) were irradiated with UV light of '400mWZcm ² and cured instantaneously (less than 0.5 seconds after landing). Ink discharge was printed with a minimum droplet volume of 4 pl and a maximum liquid volume of 80 pl. Inkjet images were formed at a temperature of 23 ° C and a humidity of 30%.

[0141] << Evaluation of formed image >>

[Evaluation of bleeding resistance]

After the print-cured sample was allowed to stand for 24 hours, the degree of bleeding was visually observed, and the bleeding resistance was evaluated according to the following criteria.

[0142] 5: No bleeding is observed

4: Almost no bleeding is observed に

3: Slight bleed is recognized Power that is acceptable for practical use 2: Smoke is observed and is a practically problematic quality

1: Severe blurring occurs, the quality is unbearable

[Evaluation of ejection stability]

After one hour of continuous injection with the above image forming method, 6 points at the target density MS Mincho Characters were printed, the texture of the characters was magnified with a loupe, character quality was evaluated according to the following criteria, and this was used as a measure of ejection stability.

[0143] 5: No roughness

4: Slight rustling is visible

3: Although you can see rustling, it can be recognized as letters and can be used at the last minute

2: There is a rustling, the letters are faint! /, Can be used! /, Level

1

,level

Table 2 shows the results obtained as described above.

[0144] [Table 2]

[0145] As is clear from the results shown in Table 2, the ink having the constitutional power defined in the present invention is excellent in the bleeding resistance of the formed image and the ejection stability after continuous ejection compared to the comparative example. It turns out that it is excellent.

[0146] Example 2

In the preparation of ink 17 described in Example 1, Pigment Black 7 (Mitsubishi Chemical Corporation # 52) Pigment Black 7 (Mitsubishi Chemical Co., Ltd.) was used instead of Pigment Blue 15: 4 (manufactured by Dainichi Seika). Chemical MA7) Pigment Blue 15: 4 (Sanyo Dye) Pigment Red 122 (Daiichi Seika CFR321), Pigment Violetl9 (Daiichi Seika CFR338-3) Pigment Yellow 138 (Daiichi Seika CFY340 ) Pigmen t Yellow 151 (Lanxess E4GN—GT) Pigment Yellow 180 (Daiichi Seika Chemical CFY313— 2), Pigment Yellow 180 (Clariant? ^^ 0 61: 111 Yell ow HG) Similarly, each ink was prepared. As a result of evaluation in the same manner as in Example 1 using each color ink having a different pigment type, the ink according to the constitution defined in the present invention is similar to the result in Example 1 with respect to the comparative example. It was confirmed that the formed image was excellent in bleeding resistance and excellent in discharge stability after continuous discharge. [0147] In addition, in the preparation of inks 1 to 7 described in Example 1, instead of the epoxy compound C202 1P, triethylene glycol dibule ether, Celoxide 2000 (manufactured by Daicel Chemical Industries), Celoxide 3000 (Daiceli) Each ink was prepared in the same manner except that EXP-1 was used, and the evaluation was performed in the same manner as in Example 1 using each ink. Similarly, it was confirmed that the ink having the constitutional power defined in the present invention was excellent in the bleeding resistance of the formed image and superior in the ejection stability after continuous ejection compared to the comparative example. .

[0148] [Chemical 15]

Claims

Claims: A sulfonium salt having a structure represented by the following general formula (1) and a sulfo-um salt excluding the sulfo-um salt having the structure represented by the general formula (1) A photoacid generator composition characterized by the above.

[Chemical 1]

[In the formula, Ri to R ¹⁷ are a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, an alkyl group, an alkoxy group, an acyl group, a phenoxy group, an ester group, an aryl group, a thioether group, a thiocarbon group, and a sulfier group, respectively. , Sulfo group, amino group, amide group, imide group, nitrile group, phosphide group, phospho group, phosphoryl group, and a group of 1 to 8 fluoroalkyl groups. The groups other than the functional groups of these groups may be a saturated aliphatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group having 1 to 12 carbon atoms, It may be an alicyclic hydrocarbon group, a carbocyclic aromatic hydrocarbon group or a bicyclic aromatic hydrocarbon group. R ⁵ and R ⁶ may be condensed with each other to form a covalent bond. X is an atomic group that can be a monovalent key. ]

The sulfonium salt excluding the sulfonium salt having a structure represented by the general formula (1) is a sulfonium salt having a structure represented by the following general formula (A): The photoacid generator composition according to claim 1.

[Chemical 2]

[In the formula, Ra and Ra each represents an alkyl group or an aromatic group, and Z ¹ represents an oxygen atom or a sulfur group. Represents yellow atom, Ra and Ra are alkyl group, aromatic group, alkoxy group, aryloxy

3 4

Represents an integer of 0 to 4, nl and pi each represents an integer of 1 to 5, Y represents Z—SO (Z represents CF (n represents 1 to 5), 10)

3 n 2n + l

Represents an alkyl group or an alkyl-substituted or unsubstituted aromatic group), PF, BF, AsF

6 4

, SbF, B (C F), CIO, Br, CI or I. ]

6 6 6 5 4 4

[3] Photoacid generation according to claim 1 or 2, characterized in that it contains at least one compound selected from polycyclic aromatic compounds, strong rubazole derivatives and thixanthone derivatives. Agent composition.

[4] The polycyclic aromatic compound, the force rubazole derivative and the thixanthone derivative force At least one compound force selected 4. The photoacid generator composition according to claim 3, which is at least one compound selected from anthracene, naphthacene, triphenylene and the following general formula (3).

[Chemical 3]

[Wherein, R ^{21 to} R ² ° has the same meaning as Ri to R ¹⁷ in the general formula (1). ]

The sulfone salt having a structure represented by the general formula (A) is at least one selected from the following general formulas (B), (C) and (D): The photoacid generator composition according to item 1 to item 4 in item 1 to item 4.

[Chemical 4]

[In the formula, R represents an alkyl group having 1 to 10 carbon atoms, and R 1 and R 2 each represent an alkyl group having 1 to 10 carbon atoms. Represents an alkyl group or an alkoxy group having 1 to 10 carbon atoms, Y is Z—SO (Z is CF (n

3 3 n 2n + l represents an integer of 1 to: L0), an alkyl group, or an alkyl-substituted or unsubstituted aromatic group), PF ,: BF, AsF, SbF ,: B (CF), CIO, Represents Br, CI or I. ]

6 4 6 6 6 5 4 4

[Chemical 5]

—General ^ c)

41 42

M4 represents an integer of 0 to 4, R 1 and R 2 each represents an alkyl group having 1 to 10 carbon atoms, and Y represents

43 44 4

, Z-SO (Z is C F (n is an integer from 1 to 10), alkyl group, or alkyl substitution

3 n 2n + l

Represents an unsubstituted aromatic group), PF, BF, AsF, SbF, B (C F), CIO, Br,

6 4 6 6 6 5 4 4 Represents α or I. ]

[Chemical 6]

"^ Expression

51 52

, M5 represents an integer of 0 to 4, R and R each represents an alkyl group having 1 to 10 carbon atoms, and Y represents

53 54 5

3 n 2n + l

6 4 6 6 6 5 4 4 Represents a or I. ]

[6] A cationic photopolymerizable composition comprising the photoacid generator composition according to any one of claims 1 to 5 and a cationically polymerizable compound.

[7] The cationically polymerizable compound comprises an epoxy compound, an oxetane compound, and a buler The cationic photopolymerizable composition according to claim 6, characterized in that it is at least one selected from telly compound strength.

[8] The cationic photopolymerizable composition according to claim 6 or 7, characterized by containing a pigment.

[9] An ink-jet ink comprising the photoacid generator composition according to any one of claims 1 to 5.

[10] An ink-jet ink comprising the cationic photopolymerizable composition according to any one of claims 6 to 8.

[11] An ink jet recording method comprising performing ink jet recording on a fibrous recording material using the ink jet ink according to claim 9 or 10.