WO2008018272A1

WO2008018272A1 - Photosensitive lithographic plate material

Info

Publication number: WO2008018272A1
Application number: PCT/JP2007/064160
Authority: WO
Inventors: Emiko Kataoka
Original assignee: Konica Minolta Medical & Graphic, Inc.
Priority date: 2006-08-09
Filing date: 2007-07-18
Publication date: 2008-02-14

Abstract

A photosensitive lithographic plate material which comprises a substrate and, formed thereon, a photosensitive layer comprising a polymerization initiator, a polymerizable compound having an ethylenic double bond, a sensitizing dye, and a polymeric binder, characterized in that the sensitizing dye comprises a compound represented by the following general formula (1-1) or (1-2). It is suitable for exposure to a laser light having a wavelength of 350-450 nm and has high sensitivity and storability. It is less apt to form a sludge upon development and is reduced in scumming in non-image areas.

Description

Photosensitive lithographic printing plate material

Technical field

[0001] The present invention relates to a photosensitive lithographic printing plate material used in a computer tow plate system (hereinafter referred to as CTP) using a photopolymerizable composition, and more particularly to exposure with a single laser beam having a wavelength of 350 to 450 nm. The present invention relates to a suitable photosensitive lithographic printing plate material.

Background art

[0002] In recent years, CTPs for recording digital image data directly on a photosensitive lithographic printing plate with a laser light source have been developed and put into practical use, as a printing plate manufacturing technique for offset printing. . Among these, in the field of printing that requires a relatively high printing durability, for example, polymerization is performed as in printing plate materials described in JP-A-1-105238 and JP-A-2-127404. It is known to use negative photosensitive lithographic printing plate materials having a polymerizable photosensitive layer containing possible compounds.

[0003] Further, a photosensitive lithographic printing plate material capable of image exposure with a laser having a wavelength of 390 to 430 nm and having improved safe light properties is known. A high-power and small-sized blue-violet laser with a wavelength of 390 to 430 nm is now readily available. By developing a photosensitive lithographic printing plate suitable for this laser wavelength, the bright room has been developed. (For example, see Patent Documents 1, 2, and 3). Also known is a printing plate material with improved light-safety under yellow light, such as disclosed in JP-A-2001-194782, which contains biimidazole in the photosensitive layer. As a sublimable photopolymerizable composition, for example, photopolymerization containing a hexaarylbiimidazole compound containing an aryl group having a substituent such as an alkyl group as described in JP-A-2004-137152. Sexual compositions are known.

On the other hand, it is known to use distyrylbenzene or the like as a sensitizing dye used in a polymerization type photosensitive layer corresponding to exposure with a laser beam having an emission wavelength of 350 to 450 nm (for example, patent (Ref. 4, 5, and 6). However, these photosensitive lithographic printing plate materials have insufficient sensitivity, large variations in sensitivity over time, and sludge is generated during development. As a result, there is a problem that ink stains occur in the non-image area.

Patent Document 1: Japanese Unexamined Patent Publication No. 2000-35673

Patent Document 2: JP 2000-98605 A

Patent Document 3: Japanese Patent Laid-Open No. 2001-264978

Patent Document 4: Japanese Patent Laid-Open No. 2003-295426

Patent Document 5: Japanese Patent Application Laid-Open No. 2002-287342

Patent Document 6: International Publication No. 04Z74929 Pamphlet

Disclosure of the invention

Problems to be solved by the invention

[0005] The present invention has been made in view of the above problems, and its purpose is suitable for exposure with a laser beam having an emission wavelength of 350 to 450 nm, high sensitivity, excellent storage stability, and development. It is an object of the present invention to provide a photosensitive lithographic printing plate material that is less likely to generate sludge and has less ink stains on non-image areas.

Means for solving the problem

[0006] The object of the present invention is achieved by the following constitution.

1. In a photosensitive lithographic printing plate material having a photosensitive layer containing a polymerization initiator, a polymerizable ethylenic double bond-containing compound, a sensitizing dye and a polymer binder on a support, the photosensitive layer comprises A photosensitive lithographic printing plate material comprising a compound represented by the following general formula (11) or (12) as the sensitizing dye.

[0007] [Chemical 1]

—General formula (1— 1) General formula (1 1 2)

[In the formula, R represents a substituent, n represents an integer of 0 to 5, 1 represents an integer of 0 to 7, Het represents

11

Substituted or unsubstituted indazole, benzimidazole, imidazole, thiazole, benzoxazole, oxazole, pyrrole, thiophene, furan, pyrazole, iso Represents a cyclic group represented by thiazole, indole, benzothiophene, benzofuran, or pyridine. ]

2. In the general formula (11) or (12), Het is a cyclic group represented by substituted or unsubstituted benzimidazole, benzoxazole, thiophene, furan, benzothiophene, or benzofuran. 2. The photosensitive lithographic printing plate material as described in 1.

3. The compound represented by the general formula (11) or (12) is a compound represented by the following general formula (2-1) or (2-2): The photosensitive lithographic printing plate material described.

[0009] [Chemical 2]

—General Formula (2 General Formula (2— 2)

[Wherein R 1 and R 2 represent substituents, n represents an integer of 0 to 5, 1 represents an integer of 0 to 7, m

21 22

Represents an integer of 0-3. ]

4. The photosensitive lithographic printing plate material according to any one of 1 to 3, wherein the photosensitive layer contains a hexaarylbiimidazole compound as the polymerization initiator.

5. The photosensitivity according to any one of 1 to 4, wherein the polymerizable ethylenic double bond-containing compound is a reaction product of the following compounds (C1) to (C3): Planographic printing plate material.

(C1) Compound containing at least one ethylenic double bond and one hydroxyl group in the molecule

(C2) Diisocyanate compound

(C3) Diol compound having a tertiary amine structure in the molecule, or compound having one secondary amine structure and one hydroxyl group in the molecule

6. The photosensitive lithographic printing plate material according to any one of 1 to 5, wherein the polymerizable ethylenic double bond-containing compound is a compound represented by the following general formula (3): Fee. [0011] [Chemical formula 3] General formula (3)

[Wherein, R ¹ represents a hydrogen atom or a methyl group, X ¹ represents a divalent aliphatic group, X ² represents a divalent hydrocarbon group having an aromatic ring, and X ³ represents Represents a divalent substituent having a tertiary amine structure. ]

7. The content of the sensitizing dye in the photosensitive layer is 0.5 to 8.0% by mass with respect to the total solid content of the photosensitive layer. The photosensitive lithographic printing plate material described.

8. The content of the polymerizable, ethylenic double bond-containing compound in the photosensitive layer is 20 to 80% by mass with respect to the total solid content of the photosensitive layer, and the content of the polymer binder in the photosensitive layer is The content is 15 to 70% by mass with respect to the total solid content of the photosensitive layer, and the content of the polymerization initiator in the photosensitive layer is 0.05 to 20% by mass with respect to the total solid content of the photosensitive layer. The photosensitive lithographic printing plate material as described in 7 above.

The invention's effect

[0013] With the above configuration of the present invention, it is suitable for exposure with a laser beam having an emission wavelength of 350 to 450 nm, is highly sensitive, has excellent storage stability, and generates sludge during development. A photosensitive lithographic printing plate material with less ink stains can be provided.

BEST MODE FOR CARRYING OUT THE INVENTION

Next, preferred modes for carrying out the present invention will be described, but the present invention is not limited thereto.

As a result of intensive studies, the present inventor has developed a photosensitive lithographic plate having a photosensitive layer containing a polymerization initiator, a polymerizable ethylenic double bond-containing compound, a sensitizing dye and a polymer binder on a support. In a printing plate material, the photosensitive layer uses a compound represented by the above general formula (11) or (1-2) as the sensitizing dye, so that a laser having an emission wavelength of 350 to 450 nm is used. It was found that a photosensitive lithographic printing plate material suitable for one-light exposure, high sensitivity, excellent storability, less sludge during development, and less ink stains in non-image areas can be obtained.

Hereinafter, the present invention will be described in detail.

[0017] [Sensitizing dye]

(Compound represented by the general formula (1 1) or (1 2))

The present invention is characterized in that it contains a compound represented by the above general formula (1-1) or (1-2) as a sensitizing dye for the photosensitive layer.

[0018] In the general formulas (1-1) and (1-2), R represents a substituent.

11

Kill group (methyl, ethyl, isopropyl, hydroxyethyl, stearyl, dodecyl, eicosyl, docosyl, oleyl, etc.), cycloalkyl group (cyclopropyl, cyclohexyl, etc.), aryl group (phenyl, p-tetradeca-) Roxyphenyl, o-octade force-luminophenol, naphthyl, hydroxyphenyl, etc.), hydroxy, carboxy, nitro, trifluoromethyl, amide (acetoamide, benzamide, etc.), rubamoyl (methyl) Strong rubamoyl, butylcarbamoyl, phenylcarbamoyl, etc.), alkyl carboxylic groups (such as ethyl carboxy carbonyl, isopropyl oxy carboxylic groups), aryloxy carboxylic groups (such as phenoxy carboxylic balls) ), Carbo-loxy group (methyl carbonyloxy, propyl carbo-roo Sheet, Hue - Rukarupo - Ruokishi etc.), Shiano group

, Halogen (chlorine atom, bromine atom, iodine atom, fluorine atom), alkoxy group (methoxy, ethoxy, butoxy, etc.), aryloxy group (phenoxy, etc.), sulfonyl group (methanesulfone)

, P-toluenesulfol, etc.), sulfonamide groups (methanesulfonamide, dodecylsulfonamide, p-toluenesulfonamide, etc.), sulfamoyl groups (methylsulfamoyl)

And sulfamimoyl), amino groups, alkylamino groups (such as ethylamino-containing hydroxyamino) and the like.

[0019] Preferable! / As the substituent, an alkyl group (methyl, ethyl, isopropyl, hydroxyethyl, stearyl, dodecyl, eicosyl, docosyl, oleyl, etc.), cycloalkyl group (cyclopropyl, cyclohexyl, etc.) , Aryl groups (such as phenol, p-tetrade-l-oxyphenyl, o-octade-de-laminophenol, naphthyl, hydroxyphenyl, etc.), alkoxy Si group (methoxy, ethoxy, butoxy, etc.), aryloxy group (phenoxy, etc.), amino group, alkylamino group (ethylamino-containing dimethylamido-hydroxyamino), etc., more preferably alkoxy group (methoxy, ethoxy, butoxy, etc.) Etc.), aryloxy groups (phenoxy, etc.), amino groups, alkylamino groups (ethylamino-containing hydroxyamino-containing hydroxyamino, etc.).

[0020] Het is a substituted or unsubstituted indazole, benzimidazole, imidazole, thiazole, benzoxazole, oxazole, pyrrole, thiophene, furan, pyrazole, isothiazole, indole, benzothiophene, benzofuran, pyridine. Represents a cyclic group. Het is preferably a cyclic group represented by benzimidazole, benzoxazole, thiophene, furan, benzothiophene, or benzofuran.

[0021] Substituents include alkyl groups (methyl, ethyl, isopropyl, hydroxyethyl, stearyl, dodecyl, eicosyl, docosyl, oleyl, etc.), cycloalkyl groups (cyclopropyl, cyclohexyl, etc.), aryl groups ( Phenol, p-tetradecaoxyphenyl, o-octade force-luminophenol, naphthyl, hydroxyphenol, etc.), hydroxy group, force alkoxy group, nitro group, trifluoromethyl group, amide group (acetoamide, Benzamide, etc.), strong rubamoyl groups (methylcarbamoyl, butylcarbamoyl, phenylcarbamoyl, etc.), alkyloxycarbonyl groups (ethyloxycarbol, isopropyloxy group, etc.), aryloxy Carbo group (such as phenyl carbol), carbo-loxy group (methyl carboro) Si, propyl carbonyloxy, phenol carbonyloxy, etc.), cyano group, halogen (chlorine atom, bromine atom, iodine atom, fluorine atom), alkoxy group (methoxy, ethoxy, butoxy etc.), aryloxy group (phenoxy etc.), Sulfol groups (methanesulfur, p-toluenesulfol, etc.), sulfonamides (methanesulfonamide, dodecylsulfonamide, p-toluenesulfonamide, etc.), sulfamoyl groups (methylsulfamoyl, phenylsulfamoyl, etc.) ), An amino group, an alkylamino group (such as ethylamino-containing dimethylamino-containing hydroxyamino), and the like.

[0022] Preferable! /, As a substituent, an alkyl group (methyl, ethyl, isopropyl, hydroxyethyl, stearyl, dodecyl, eicosyl, docosyl, oleyl, etc.), cycloalkyl group (cyclopropyl, cyclohexyl, etc.) , Aryl group (fehl, p-tetrade force-ruxifer) -O, o octade force-luminophenol, naphthyl, hydroxyphenol, etc.), alkoxy group (methoxy, ethoxy, butoxy, etc.), aryloxy group (phenoxy, etc.), amino group, alkylamino group (dimethylamino containing dimethylamino) Hydroxyamino and the like, and more preferable examples include alkoxy groups (methoxy, ethoxy, butoxy, etc.), aryloxy groups (phenoxy, etc.), amino groups, alkylamino groups (such as ethylamino-containing hydroxyamino). It is.

[0023] (Compound represented by formula (2-1) or (2-2))

Among the compounds represented by the general formula (11) or (12), the compounds represented by the general formula (2-1) or (2-2) are preferable.

[0024] In the general formulas (2-1) and (2-2), R represents R in the general formula (1 1) or (1 2).

It is synonymous with 21 1. R represents a substituent, and R represents an alkyl group (methyl, ethyl, isop

1 22 22

Mouth pills, hydroxyethyl, stearyl, dodecyl, eicosyl, docosyl, oleyl, etc., cycloalkyl groups (cyclopropyl, cyclohexyl, etc.), aryl groups (phenol, p-tetradeoxy-hydroxyphenyl, O octade) Force-laminophenol, naphthyl, hydroxyphenyl, etc.), hydroxy group, carboxy group, nitro group, trifluoromethyl group, amide group (acetamido, benzamide, etc.), force rumomoyl group (methylcarbamoyl, butylcarbamoyl) , Vinyl carbamoyl, etc.), alkyl carboxy groups (such as eth oxy carbo yl, isopropyl oxy carbo ls), aryloxy carboxylic groups (such as phenoxy carbo ls), Carboxyoxy group (methylcarboxoxy, propylcarboxoxy, phenylcarboxoxy, etc.) Cyan group, halogen (chlorine atom, bromine atom, fluorine atom, fluorine atom), alkoxy group (methoxy, ethoxy, butoxy, etc.), aryloxy group (phenoxy, etc.), sulfo group (methane sulfo, p— Toluenesulfol, etc.), sulfonamide groups (methanesulfonamide, dodecylsulfonamide, p-toluenesulfonamide, etc.), sulfamoyl groups (methylsulfamoyl, phenylsulfamoyl, etc.), amino groups, alkylamino groups (ethylamino) Dimethylamino-containing hydroxyamino, etc.).

[0025] Preferred examples of the substituent represented by R include an alkyl group (methyl, ethyl, isop

twenty two

Mouth pills, hydroxyethyl, stearyl, dodecyl, eicosyl, docosyl, oleyl, etc.), Cycloalkyl groups (cyclopropyl, cyclohexyl, etc.), aryl groups (phenyl, p-tetrade-loxyphenyl, O octade-de-laminophenol, naphthyl, hydroxyphenyl, etc.), alkoxy groups ( Methoxy, ethoxy, butoxy, etc.), aryloxy groups (phenoxy, etc.), amino groups, alkylamino groups (ethylamino-containing dimethylamido hydroxyamino, etc.), more preferably alkoxy groups (methoxy, ethoxy, butoxy, etc.), aryloxy Ci groups (such as phenoxy), amino groups, and alkylamino groups (such as ethylamino-containing hydroxyamino).

[0026] Specific examples of the compound represented by the general formula (11) or (12) are given below.

[0027] [Chemical 4]

[0028] [Chemical 5]

[0029] [6]

[0030] [7] SO

[0032] [Chemical 9]

[0033] [Chemical 10]

59 60

[0034] These compounds according to the present invention can be synthesized by a known method such as a Wittig reaction. Although a synthesis example is shown below, it is not limited to this.

Under a nitrogen atmosphere, 17.5 ml of n-butyllithium hexane solution (1.52 mol / l) was added dropwise to a solution of 13.9 g of 3a suspended in 150 ml of THF at -78 ° C. After stirring for 30 minutes, the temperature was returned to room temperature, and 3b 5g dissolved in THFlOml was slowly added dropwise. After completion of the dropwise addition, the mixture was reacted at room temperature for 2 hours. After the completion of the reaction, water was added and the mixture was extracted with ethyl acetate. The solvent was removed under reduced pressure, and 20 ml of ethanol was added to the residue and dissolved by heating, followed by recrystallization. The precipitate was filtered to obtain compound 36.4 g (yield 68%). The structure was confirmed by NMR and MS spectra.

[0036] [Chemical 11]

Three

[0037] The content of the compound represented by the general formula (11) or (12) is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass with respect to the photosensitive layer. .

[0038] As the sensitizing dye, in addition to the above compounds, for example, JP 2000-98605, 2000-147763, 2000-206690, 2000-258910, 2000-309724, 2001 — Sensitizing dyes described in 042524, 2002-202598 and 2000-221790 may be used in combination.

[Polymerization initiator]

The polymerization initiator according to the present invention is capable of initiating polymerization of a polymerizable ethylenic double bond-containing compound by image exposure. Examples of the polymerization initiator include titanocene compounds, mono-polymers, and the like. Forces in which alkyltriarylborate compounds, iron arene complex compounds, polyhalogen compounds, and biimidazole compounds are preferably used Among these, the effects of the present invention are particularly significant when biimidazolol compounds are used. Favored ,.

[0040] (Biimidazole compound)

Biimidazole compound is a derivative of biimidazole, and examples thereof include compounds described in JP-A-2003-295426.

[0041] In the present invention, hexaarylbiimidazole (H ABI, a dimer of triarylmonoimidazole) i compound can be preferably used.

[0042] The production process of HABIs is described in German Patent 1,470,154, and their use in photopolymerizable compositions is described in European Patent Nos. 24,629, 107, 792, U.S. Pat. No. 4,410,621, European Patent No. 215,453 and German Patent No. 3, 211,312.

[0043] Preferred derivatives are, for example, 2, 4, 5, 2 ', 4', 5 '—hexaphenol imidazole, 2, 2' —bis (2-crophage) 1, 4, 5, 4 ', 5' — Tetraphenyl-biimidazole, 2, 2 '— Bis (2 bromophenol) — 4, 5, 4', 5 '— Tetraphenyl-biimidazole, 2, 2' — Bis (2, 4 dichlorophenol Diru) 1, 4, 5, 4 ', 5' — Tetraphenyl rubi imidazole, 2, 2 '— Bis (2 black fue-nore) 1, 4, 5, 4', 5 '— Tetrakis (3-methoxyphene- B) Biimidazole, 2, 2 '— Bis (2 black-mouthed phenol) 1, 4, 5, 4', 5 '— Tetrakis (3,4, 5 Trimethoxyphenol) monobiimidazole, 2, 5 , 2 ', 5' — Tetrakis (2 black mouth) 1, 4, 4 '— Bis (3,4 dimethoxyphenol) biimidazole, 2, 2' — Bis (2, 6 dichlorophenyl) 1, 4, 5, 4 ', 5' —tetraphenyl midazole, 2, 2 '—Bis (2-Trophele) — 4, 5, 4', 5 '—Tetraphenol Midylazole, 2, 2 ′ —Di-o-Tolyl— 4, 5, 4', 5 '—Tetrahue -Rubiimidazole, 2, 2 '— Bis (2 ethoxyphenol) 1, 4, 5, 4', 5 '— Tetraphenyl imidazole and 2, 2' — Bis (2, 6 difluorophenol) , 5, 4 ', 5'-tetraphenylbiimidazole.

[0044] (Titanosen compound)

Examples of the titanocene compound include compounds described in JP-A-63-41483 and JP-A-2-291. More preferable specific examples include bis (cyclopentadienyl) Ti-dioxide. Chloride, bis (cyclopentagel) Ti-bis monophenyl, bis (cyclopentagel) Ti-bis 1, 3, 4, 5, 6 pentafluorophenol, bis (cyclo Pentagel) Ti-Bis-1,2,5,5,6-Tetrafluorofel, Bis (Successed Pentagel) Ti-Bis-1,2,4,6 Trifnoreolophenol, Bis (Cyclopentadi B) Ti-bis-1,6 difluorophenol, bis (cyclopentagel) Ti—bis-1,2,4 difluorophenol, bis (methylcyclopentagel) Ti-bis -2, 3, 4, 5, 6 Pentafluorophenyl, bis (methylcyclopentagel) Ti bis 2, 3, 5, 6-tetrafluorophenol, bis (methylcyclopentadiene- ) Ti bis-2,6 difluorofel (IRUGACURE727L: Ciba Specialty Chemicals), bis (cyclopentagel) bis (2,6 difluoro 3 (pyri-1-yl) file ) Titanium (IRUGACURE784: Chinoku's Specialty Chemicals), Bis (cyclopentagel) Bis (2, 4, 6 Trifluoro 3 (Pyri 1 -yl) Fehl) Titanium bis (cyclopenta) Gel) bis (2, 4, 6 trifluoro) 3— (2-5 dimethylpyri-1-yl) phenol) titanium and the like.

[0045] (Monoalkyltriaryl borate compound)

Examples of monoalkyl triaryl borate compounds include compounds described in JP-A-62-150242 and 62-143044. More preferred specific examples include tetra-n-butylammonium n-butylate. Linaphthalene 1-rubolate, tetra-n-butylammonium-n-butyl-triphenyl-rubolate, tetra-n-butylammonium-mu-n-butyltitol (4 tert-butylphenol) -borate, tetra-n-butylammonium-n —Hexyl root (3-chlorophenyl) -borate, tetra-n-butylammonium n-hexyl root (3-fluorophenyl) borate, and the like.

[0046] (Iron arene complex compound)

Examples of iron arene complex compounds include the compounds described in JP-A-59-219307. More preferred specific examples include 7} -benzene mono (7} -cyclopentadienyl) iron. Xafluorophosphate, cumene mono (η-cyclopentagel) iron hexafluorophosphate, η-fluorene mono (-cyclopentagel) iron hexafluorophosphate, -naphthalene mono (- Cyclopentagel) Iron hexafluorophosphate, xylene mono (-cyclopentagel) iron hexafluorophosphate, 7} Benzene mono (7? -Cyclopentagel) iron tetrafluoroborate, etc. Is mentioned.

[0047] (Polyhalogen compound)

Polyhalogen compounds include trihalogen methyl groups, dihalogen methyl groups or dihalo A compound having a gemmethylene group is preferably used, and in particular, a halogen compound represented by the following general formula (4) and an oxadiazole compound having the above group in the oxadiazole ring are preferably used.

[0048] General formula (4) R— C (Y) — (C = 0) — R

1 2 2

In the formula, R represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an acyl group, an alkyl group,

1

Represents a rusulfonyl group, an arylsulfol group, an iminosulfol group or a cyano group. R represents a monovalent substituent. Even if R and R combine to form a ring, it does not work. Y is halo

2 1 2

Represents a gen atom.

[0049] The monovalent substituent represented by R is a substituted, unsubstituted alkyl group, substituted or unsubstituted aryl.

2

And a substituted, unsubstituted heterocyclic group, substituted, unsubstituted alkoxy group, substituted, unsubstituted aryloxy group, substituted, unsubstituted amino group or hydroxyl group.

[0050] Of these, polyhalogen compounds represented by the following general formula (5) are particularly preferably used.

Formula (5) C (Y)-(C = 0) -X-R

3 3

Where R is

3 represents a monovalent substituent. X represents —O or —NR and R represents hydrogen

4 4 represents an atom or an alkyl group. When X is -NR-, R and R are bonded together to form a ring

4 3 4

You may make it. Y represents a halogen atom.

The monovalent substituent represented by R is a substituted, unsubstituted alkyl group, substituted, or unsubstituted aryl.

Three

Or a substituted or unsubstituted heterocyclic group.

Among these, as the polyhalogen compound, those having a polyhalogen acetylamide group are particularly preferable.

[0052] Oxadiazole compounds having a polyhalogenmethyl group in the oxadiazole ring are also preferably used. Further, oxazazolyl compounds described in JP-A-5-34904 and 8-240909 are also preferably used.

[0053] (Polymerization initiator that can be used in combination)

In addition, any polymerization initiator can be used in combination. For example, «J. Kosar Ci. Kosar ',“ Carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds as described in Chapter 5 of “Light Sensitive Systems”. Thing, halogene Compounds, photoreducible dyes and the like. In addition, specific compounds are disclosed in British Patent 1,459,563.

[0054] Examples of the polymerization initiator that can be used in combination include the following compounds.

[0055] Benzoin methyl ether, benzoin monopropyl ether, α, α-dimethoxy

-a-benzoin derivatives such as phen-l-acetophenone; benzophenone, 2,4 dichlorobenzophenone, o benzophenone derivatives such as methyl benzoylbenzoate, 4, 4 'bis (dimethylamino) benzophenone; 2-chlorothioxanthone, 2-ipropyl Thixanthone derivatives such as Sandton; anthraquinone derivatives such as 2-chloro-anthraquinone and 2-methylanthraquinone; atalidon derivatives such as N-methylataridon and N-butylataridon; _α , _a In addition to xanthone and ura ninolei compounds, triazine derivatives described in Japanese Patent Publication Nos. 59-1281, 61-9621 and JP-A-60-60104; JP-A-59-1504, 61 — Organic peracid compounds described in 243807; JP-B 43-23684, 44-6413, 44- Diazo-um compounds described in US Pat. Nos. 6413, 47-1604 and US Pat. No. 3,567,453; US Pat. Nos. 2,848,328, 2,852,379 and 2,940,853 Organic azide compounds described in Japanese Patent Publication Nos. 36-22062b, 37-13109, 38-18015 and 45-9610; o-quinonediazides; Japanese Patent Publication Nos. 55-39162, JP 59-14023 and various macromolecules described in “Macromolecules” 10 卷, page 1307 (1977); Azoi compounds described in JP-A-59-142205; 1-54440, European Patents 109, 851, 126, 712, and “Journal Iobu Imaging Science (J. Imag. Sci.)” 30 p. 174 (1986). (Oxo) sulfo-um organic boron complexes described in Japanese Patent Application Nos. 56831 and 4-89535; “Coordination—Chemistry ^ —— Coordination Chemistry Review (84), pp. 85-277 (1988) and transition metal complexes containing transition metals such as luteum described in JP-A-2-182701; JP-A-3-209477 Of 2, 4, 5

A triarylimidazole dimer; carbon tetrabromide, an organic halogen compound described in JP-A-59-107344, and the like.

The content (total amount) of the polymerization initiator is preferably 0.05% by mass to 20.0% by mass with respect to the photosensitive layer. Mashiku 1.0 mass% to 10.0 mass% is particularly preferable.

[Polymerizable ethylenic double bond-containing compound]

The polymerizable ethylenic double bond-containing compound according to the present invention is a compound having an ethylenic double bond that can be polymerized by a polymerization initiator in the photosensitive layer that has been image-exposed.

[0057] In the present invention, as the polymerizable ethylenic double bond-containing compound,

A reaction product of the compounds (C1) to (C3) is preferably used.

[0058] (C1) Compound containing at least one ethylenic double bond and one hydroxyl group in the molecule

(C2) Diisocyanate compound

(C3) A diol compound having a tertiary amine structure in the molecule, or a compound having a secondary amine structure and one hydroxyl group in the molecule

Examples of (C1) include 2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate, and 2-hydroxypropyl methacrylate.

[0059] The above (C2) includes 1,3-bis (1-isocyanato-1-methylethyl) benzene, 1,3-diisocyanatobenzene, 1,3-diisocyanatoto 4-methylbenzene, 1,3-di ( Isocyana-to-methylolene) benzene.

[0060] Examples of (C3) include N-n-butyljetanolamine, N-methyljetanolamine, N-ethyljetanolamine, 2- (2-hydroxyethyl) piperidine, N —Six-mouthed hexylethanolamine, 2- (isopropylamino) ethanol, n-butylaminoethanol, methylaminoethanol, t-butylaminoethanol, and the like.

[0061] (Compound represented by the general formula (3))

As the reaction product, a compound represented by the general formula (3) is particularly preferably used.

In general formula (3), R ¹ represents a hydrogen atom or a methyl group. X ¹ represents a divalent aliphatic group. X ² represents a divalent hydrocarbon group having an aromatic ring. X ³ represents a divalent substituent having a tertiary amine structure.

[0063] Examples of X ¹ include CH CH CH CH (CH) CH (CH) CH

2 2 2 3 3 2

— CH CH CH CH CH CH CH CH (CH 2) — and 1 CH (CH 2) 2 CH— are preferred.

3 3 2

[0064] Examples of X ² include forces X2-1 to X2-10 described below. X2-3, X2

4, X2—7, X2—9, X2—10 power likes! / ヽ.

[0065] [Chemical 12]

X2- 1 X2-2 X2

X2-4 X2-5 X2-6

X2-10

[0066] Examples of X ³ include forces X3-1—X3-10, X3-1—X3—2, X3—5,

3-9 is preferred.

[0067] [Chemical 13]

X3-10

Examples of the compound represented by the general formula (3) include the following compounds.

14]

Five]

R ¹ X ¹

]

7]

]

M3-1

M3-2

M3-3

M3-4

M3-5

M3-6

M3-7

M3-8

]

X

] [00075 3:23 M316HHCHCI—— 3T2 M315HCHCII I

3 M314CHI I 3 1 32 {HHCCHCHC II— I

3 1 2 <M123HCHCCH-II I 32) 3 M3HCHCH-I I 3> 2 1 M3HH CCHCII I 3} 23 M93CHCHCH—II II

1]

RXX ² X ³

[0077] (Compound containing ethylenic double bond)

Examples of the polymerizable ethylenic double bond-containing compound include general radical-polymerizable monomers, and many polymers having a plurality of addition-polymerizable ethylenic double bonds in a molecule generally used for UV curable resins. Functional monomers and polyfunctional oligomers can be used in combination.

[0078] Although these compounds are not limited, preferred examples thereof include 2-ethylhexyl acrylate, 2-hydroxypropyl acrylate, glycerol acrylate, tetrahydrofurfuryl acrylate, phenoxychetino rare acrylate. , Nonylphenoxychetyl acrylate, tetrahydrofurfuroxyxetyl acrylate, tetrahydrofurfuryloxyhexanolide acrylate, 1,3-dioxane alcohol ε Monofunctional acrylates such as talylate, 1,3-dioxolane acrylate, or methacrylic acid, itaconic acid, crotonic acid, maleic acid, where these acrylates are replaced with metatalate, itaconate, crotonate, maleate Esters such as ethylene glycol Over Ludiatalylate, Triethylenedarcol ditalylate, Pentaerythritol ditalarate, Hydone quinone ditalylate, Resorcin ditalylate, Hexanediol ditalarate, Neopentylglycol ditalylate, Tripropyleneglycol ditalarate , Diatalylate of neopentyl glycol hydroxypivalate, diatalylate of neopentyl glycol adipate, diatalylate of neopentyl glycol hydroxypivalate with ε-strength prolatatone, 2- (2-hydroxy-1,1-dimethylenoethyl) -15 hydroxymethyl 1 5 ethyl 1,3 Dioxanediatalylate, tricyclodecane dimethylol acrylate, tricyclodecane dimethylol acrylate, ε Difunctional acrylic acid esters such as porridge, diglycidyl ether of 1,6-hexanediol, or methacrylic acid, itaconic acid, crotonic acid, which replaces these acrylates with metatalate, itaconate, crotonate, maleate, Maleic acid esters, such as trimethylolpropane tritalate, ditrimethylolpropane tetraatalylate, trimethylolethanetritalate, pentaerythritol triatalate, pentaerythritol tetratalate, dipentaerythritol tetratalate, dipenta erythritol penta Atari rate, to dipentaerythritol hexa Atari rate, to dipentaerythritol of Kisa Atari rate _ε - force Purorataton with mosquito卩物, pyrogallol Polyfunctional acrylic acid esters such as rear acrylate, propionate-dipentaerythritol tritalylate, propionate-dipentaerythritol tetratalate, hydroxy pinolyl aldehyde modified dimethylol propane tritalylate, or these acrylates Methacrylic acid, itaconic acid, crotonic acid, maleic acid ester, etc., can be used instead of metatalate, itaconate, crotonate and maleate.

[0079] In addition, prepolymers can be used in the same manner as described above. Examples of the prepolymer include compounds as described below, and a prepolymer obtained by introducing acrylic acid or methacrylic acid into an oligomer having an appropriate molecular weight to impart photopolymerizability can also be used suitably. These prepolymers may be used alone or in combination of two or more, and may be used in combination with the above-mentioned monomers and cocoons or oligomers.

[0080] Examples of the prepolymer include adipic acid, trimellitic acid, maleic acid, phthalic acid, terephthalic acid, hymic acid, malonic acid, succinic acid, glutaric acid, itaconic acid, and pyromellitic acid. , Fumaric acid, glutaric acid, pimelic acid, sebacic acid, dodecanoic acid, tetrahydrophthalic acid and other polybasic acids, ethylene glycol, propylene alcohol, diethylene glycol, propylene oxide, 1,4 butanediol, triethylene glycol, tetraethylene (Meth) acrylic acid is added to polyester obtained by the combination of polyhydric alcohols such as glycol, polyethylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, 1,6 hexanediol, 1,2,6 hexanetriol, etc. Polyester atalylates introduced, for example, bisphenol A-epoxychlorohydrin mono (meth) acrylic acid, phenol novolak epic chlorohydrin mono (meth) acrylic acid, (meth) acrylic Acid-introduced epoxy acrylates such as ethylene glycol adipic acid monotolylene diisocyanate-1-hydroxyethyl acrylate, polyethylene glycol mono-tolylene diisocyanate 1-2-hydroxyethyl acrylate, hydroxy ether Tylphthalyl methacrylate di-xylene diisocyanate, 1, 2-polybutadiene glycol One-root reylene diisocyanate one 2-hydroxyethyl acrylate, trimethylol propylene one propylene glycol one tolylene diisocyanate one 2-hydroxy Urethane acrylate with (meth) acrylic acid introduced into urethane resin, such as ethyl acrylate, for example, polysiloxane acrylate, polysiloxane diisocyanate 2-hydroxyethyl acrylate, etc. Other examples include prepolymers such as alkyd-modified talylates, alkyd-modified acrylates in which a (meth) atallyloyl group is introduced into oil-modified alkyd oxalates, and spirane oxalate acrylates.

[0081] The photosensitive layer according to the present invention includes a phosphazene monomer, triethylene glycol, isocyanuric acid EO (ethylene oxide) -modified diatalylate, isocyanuric acid EO-modified tritalylate, dimethyloltricyclodecanediatalate, trimethylolpropane It can contain monomers such as acrylic acid benzoate, alkylene glycol-type acrylic acid-modified, urethane-modified acrylate, and addition polymerizable oligomers and prepolymers having structural units formed from the monomers.

[0082] Further, examples of the ethylenic monomer that can be used in the present invention include a phosphate ester compound containing at least one (meth) atheroyl group. The compound is a compound in which at least a part of the hydroxyl group of phosphoric acid is esterified, and further, a (meth) atalyloyl group is added. As long as it has, it is not particularly limited.

[0083] In addition, JP-A 58-212994, 61-6649, 62-46688, 62-48589, 62-173295, 62-187092, 63-67189, The compounds described in JP-A-1-244891 and the like can be mentioned, and further, the compound described in “11290 Chemical Products”, Gakkan Kogyo Nippo, p. 286 to p. 294, “UV-EB Curing Handbook” (Raw Materials) ”Compounds described in Polymer Publications, P. 11-65, etc. can also be suitably used in the present invention. Of these, compounds having two or more acryl or methacryl groups in the molecule are preferred in the present invention, and those having a molecular weight of 10,000 or less, more preferably 5,000 or less are preferred.

In addition to the above, the acrylate or alkyl acrylate described in JP-A Nos. 1105238 and 2-127404 can be used.

[0085] The content of the polymerizable ethylenic double bond-containing compound according to the present invention in the photosensitive layer is preferably 20% by mass to 80% by mass with respect to the photosensitive layer, particularly 30% by mass to 70%. Mass% is preferred.

[0086] [Polymer binder]

The polymer binder according to the present invention can carry the components contained in the photosensitive layer on a support, and examples of the polymer binder include acrylic polymers, polyvinylpropylene resins, polyurethane resins. Polyamide resin, polyester resin, epoxy resin, phenol resin, polycarbonate resin, polybutyral resin, polybulformal resin, shellac, and other natural resins can be used. Also, using two or more of these in combination does not work.

[0087] Bulle copolymer obtained by copolymerization of acrylic monomers is preferred. Furthermore, the copolymer composition of the polymer binder is preferably a copolymer of (a) a carboxyl group-containing monomer, (b) a methacrylic acid alkyl ester, or an acrylic acid alkyl ester.

[0088] Specific examples of the carboxyl group-containing monomer include α, j8-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, and itaconic anhydride. Other half esters of phthalic acid and 2-hydroxymetatalylate Also preferred are carboxylic acids, etc.

[0089] Specific examples of the alkyl methacrylate and the alkyl acrylate include methyl methacrylate, ethyl acetate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, heptyl methacrylate, To octyl methacrylate, nonyl methacrylate, decyl methacrylate, undecyl methacrylate, dodecyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, acrylic acid In addition to unsubstituted alkyl esters such as butyl, octyl acrylate, acrylate acrylate, decyl acrylate, undecyl acrylate, and dodecyl acrylate, cyclic alkyl ethers such as cyclohexyl methacrylate and cyclohexyl acrylate Stealth, benzyl methacrylate, 2-chloroethyl methacrylate, N, N dimethylaminoethyl methacrylate, glycidyl methacrylate, benzyl acrylate, 2-chloroethyl acrylate, N, N dimethylaminoethyl acrylate Substituted alkyl esters such as glycidyl acrylate are also included.

[0090] Furthermore, the polymer binder may be a monomer described in the following (1) to (14) as a copolymerization monomer.

[0091] (1) Monomers having an aromatic hydroxyl group, such as o- (or ρ-, m-) hydroxystyrene, o- (or p-, m-) hydroxyphenol acrylate, etc.

(2) Monomers having an aliphatic hydroxyl group, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N-methylol acrylamide, N-methylol methacrylate, 4-hydroxybutyl methacrylate, 5- Hydroxypentyl acrylate, 5-hydroxypentyl methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, N— (2-hydroxyethyl) acrylamide, N— (2-hydroxyethyl) Methacrylamide, hydroxyethyl beryl ether, etc.

(3) A monomer having an aminosulfol group, for example, m— (or p) aminosulfol phenol methacrylate, m— (or p—) aminosulfurphenolate, N— (p-aminosulfo- Sulfamide) methacrylamide, N— (p-aminosulfosulfuryl) acrylamide, etc.

(4) Monomers having a sulfonamide group, such as N— (p-toluenesulfol) atari Luamide, N— (p Toluenesulfol) methacrylamide, etc.

(5) Acrylamide or methacrylamides such as acrylamide, methacrylamide, N-ethyl acrylamide, N-hexyl acrylamide, N-cyclohexyl acrylamide, N-phenyl acrylamide, N- (4-Trophenyl) acrylamide N-ethyl-4-N-acrylamide, N- (4-hydroxyphenol) acrylamide, N- (4-hydroxyphenyl) methacrylamide, etc.

(6) Monomers containing fluorinated alkyl groups such as trifluoroethyl acrylate, trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, hexafluoropropyl methacrylate, octafluoro Lopentyl acrylate, octafluoropentyl methacrylate, heptadecafluorodecyl methacrylate, N-Butyl-N— (2-Atari mouth kischetil) heptadecafluorooctylsulfonamide, etc.

(7) butyl ethers, such as ethyl vinyl ether, 2-chloroethyl vinyl ethereol, propinorevinino reetenole, butinorevinino reetenore, otachinolevinino reetenole, vinyl ether, etc.

(8) Bull esters, such as, for example, bull acetate, bull black mouth acetate, bull butyrate, vinyl benzoate,

(9) Styrenes such as styrene, methyl styrene, chloromethyl styrene, etc.

(10) beer ketones such as methyl beer ketone, ethyl beer ketone, propyl beer ketone, ferrule beer ketone, etc.

(11) olefins such as ethylene, propylene, i-butylene, butadiene, isoprene, etc.

(12) N bull pyrrolidone, N bull carbazole, 4 bull pyridine, etc.

(13) Monomers having a cyano group, such as acrylonitrile, meta-tali-tolyl, 2-pentene-tolyl, 2-methyl-3-butene-tolyl, 2-cyanoethyl acrylate, o— (or m—, p—) Cyanstyrene, etc.

(14) A monomer having an amino group, for example, N, N jetylaminoethyl methacrylate, N, N-dimethylaminoethyl methacrylate, N, N-dimethylaminoethyl methacrylate, polybutadiene urethane acrylate, N, N Dimethylaminopropylacrylamide, N, N dimethyl acrylamide, attalyloyl morpholine, N-i-propyl acrylamide, N, N jetyl acrylamide, etc.

Furthermore, other monomers that can be copolymerized with these monomers may be copolymerized.

[0093] Furthermore, the polymer binder is preferably a vinyl polymer having a carboxyl group and a polymerizable double bond in the side chain. For example, an unsaturated bond-containing vinyl copolymer obtained by addition reaction of a compound having a (meth) attalyloyl group and an epoxy group in the molecule to a carboxyl group present in the molecule of the vinyl copolymer. Polymers are also preferred as the polymer binder.

[0094] Specific examples of the compound containing both an unsaturated bond and an epoxy group in the molecule include glycidinoaretalylate, glycidylmetatalylate, and epoxy group-containing unsaturated compounds described in JP-A-11 271969. Compounds and the like. There is also an unsaturated bond-containing vinyl copolymer obtained by addition reaction of a compound having a (meth) atalyloyl group and an isocyanate group in the molecule with a hydroxyl group present in the molecule of the vinyl polymer. Preferred as a polymer binder. Compounds having both an unsaturated bond and an isocyanate group in the molecule include burisocyanate, (meth) acrylic isocyanate, 2- (meth) atarylloyloxychetyl isocyanate, m or p isoprobe (Meth) acrylic isocyanate, 2- (meth) atarylloy luccietyl isocyanate, and the like that are preferred are α, a′-dimethylbenzyl isocyanate.

[0095] The vinyl polymer having a carboxyl group and a polymerizable double bond in the side chain is preferably from 50 to 100% by mass of LOO% by mass in the total polymer binder. I like it.

[0096] The content of the polymer binder in the photosensitive layer is preferably 10 to 90 mass%, more preferably 15 to 70 mass%, and particularly preferably 20 to 50 mass% in terms of sensitivity.

[Various additives]

In addition to the components described above, the photosensitive layer according to the present invention inhibits unnecessary polymerization of the polymerizable ethylenic double bond monomer during the production or storage of the photosensitive lithographic printing plate material. Therefore, it is desirable to add a polymerization inhibitor.

[0098] (Polymerization inhibitor) Suitable polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl p-cresol monole, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl 6-tert-butylphenol), 2 , 2 '-methylenebis (4-methyl 6-t butylphenol), torophenol hydroxylamine cerium salt, 2-t-butyl 6- (3-t-butyl 2-hydroxy-1-5-methylbenzyl) 4-methyl Examples include ruf-ruatrate.

[0099] The addition amount of the polymerization inhibitor is preferably about 0.01 to about 5% by mass with respect to the total solid content of the photosensitive layer. If necessary, higher fatty acid derivatives such as behenic acid and behenic acid amide may be added to prevent polymerization inhibition by oxygen, or it may be unevenly distributed on the surface of the photosensitive layer during the drying process after coating. May be. The amount of the higher fatty acid derivative added is preferably about 0.5 to 10% by mass of the total composition.

[0100] (Coloring agent)

Moreover, a coloring agent can also be used, and conventionally well-known things can be used conveniently as a coloring agent including a commercially available thing. Examples include those described in the revised new “Pigment Handbook”, edited by Japan Pigment Technology Association (Seibundo Shinkosha), and Color Index Handbook.

[0101] Examples of pigments include black pigments, yellow pigments, red pigments, brown pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, and metal powder pigments. Specific examples include inorganic pigments (titanium dioxide, carbon black, graphite, zinc oxide, Prussian blue, sulfidizing power domum, iron oxide, and lead, zinc, sodium and calcium chromates) and organic pigments ( And azo dyes, thioindigo, anthraquinone, anthanthrone, and triphendioxazine pigments, vat dye pigments, phthalocyanine pigments and derivatives thereof, and quinatalidone pigments).

[0102] Among these, it is preferable to select and use a pigment that has substantially no absorption in the absorption wavelength region of the spectral sensitizing dye corresponding to the exposure laser to be used. It is preferable that the reflection / absorption of the pigment using an integrating sphere is 0.05 or less. The amount of the pigment added is preferably 0.1 to LO mass%, more preferably 0.2 to 5 mass%, based on the solid content of the composition.

[0103] From the viewpoints of absorption of pigments in the above-mentioned photosensitive wavelength region and visible image properties after development, purple pigments It is preferable to use a blue pigment. These include, for example, cobalt blue, cellulian blue, alkali blue lake, fonatone blue 6G, Victoria blue lake, metal-free phthalocyanine blue, phthalocyanine blue, first sky blue, indanthrene bunolais, indigo , Dioxane violet, isoviolanthrone violet, indanthrone blue, and indanthrone BC. Of these, phthalocyanine blue and dioxane violet are more preferable.

[0104] (Surfactant)

Further, the photosensitive layer can contain a surfactant as a coating property improving agent as long as the performance of the present invention is not impaired. Of these, fluorine surfactants are preferred.

[0105] In order to improve the physical properties of the cured film, additives such as plasticizers such as dioctyl phthalate, dimethyl phthalate, and tricresyl phosphate may be added. These addition amounts are preferably 10% by mass or less based on the total solid content.

[0106] The solvent used in preparing the photosensitive layer coating solution of the photosensitive layer according to the present invention includes, for example, alcohol: polyhydric alcohol derivatives such as sec-butanol, isobutanol, n-hexanol. , Benzyl alcohol, diethylene glycol, triethylene glycol, tetraethylenedaricol, 1,5-pentanediol, and ethers: propylene glycolenomonomonobutyl ether, dipropylene glycolenomonomethylenoether, tripropylene glycol monomethyl ether, Preferable examples include ketones, aldehydes: diacetone alcohol, cyclohexanone, methylcyclohexanone, and esters: ethyl lactate, butyl lactyl, jetyl oxalate, and methyl benzoate.

[0107] The force described above for the photosensitive layer coating solution The photosensitive layer according to the present invention is formed by coating on a support using the photosensitive layer.

[0108] The photosensitive layer according to the present invention is preferably applied in an amount of 0.1 to 10 gZm ² , particularly 0.5 to ⁵ g / m ² .

[Protective layer (oxygen barrier layer)]

A protective layer can be provided on the upper side of the photosensitive layer according to the present invention, if necessary.

[0110] This protective layer (oxygen barrier layer) is preferably highly soluble in a developer solution (generally an alkaline aqueous solution) described below. Specifically, polyvinyl alcohol and polyvinylpyrrolidone are preferred. Can be mentioned. Polyvinyl alcohol has an effect of suppressing the permeation of oxygen, and polybutyrolidone has an effect of ensuring adhesion with an adjacent photosensitive layer.

[0111] In addition to the above two polymers, polysaccharides, polyethylene glycol, gelatin, glue, casein, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl starch, gum arabic, sugar ota It can be achieved by using water-soluble polymers such as acetate, ammonium alginate, sodium alginate, polybulamine, polyethylene oxide, polystyrene sulfonic acid, polyacrylic acid and water-soluble polyamide in combination.

[0112] When a protective layer is provided on the photosensitive lithographic printing plate material of the present invention, the peeling force between the photosensitive layer and the protective layer is preferably 35 mNZmm or more, more preferably 50 mNZmm or more, and even more preferably 75 mNZmm. That's it. A preferred protective layer composition is described in Japanese Patent Application No. 8-161645.

[0113] The peeling force is applied when an adhesive tape with a predetermined width having a sufficiently large adhesive force is applied on the protective layer and peeled off with the protective layer at an angle of 90 degrees with respect to the plane of the photosensitive lithographic printing plate material. It can be obtained by measuring the force of.

[0114] The protective layer may further contain a surfactant, a matting agent, and the like as necessary.

The protective layer composition is dissolved in a suitable solvent, applied onto the photosensitive layer and dried to form a protective layer. It is particularly preferable that the main component of the coating solvent is water or alcohols such as methanol, ethanol, i-propanol.

[0115] When the protective layer is provided, the thickness is preferably 0.1 to 5. O / z m is particularly preferable.

3. Te at Ο μm.

[0116] [Support]

The support according to the present invention is a plate or film capable of carrying a photosensitive layer, and preferably has a hydrophilic surface on the side where the photosensitive layer is provided.

[0117] As the support according to the present invention, for example, a metal plate such as aluminum, stainless steel, chromium or nickel, or a plastic film such as polyester film, polyethylene film or polypropylene film laminated or vapor-deposited with the above-mentioned metal thin film or the like Can be mentioned. [0118] In addition, a force aluminum support that can be used such as a polyester film, a chlorinated chloride film, a nylon film or the like that has been subjected to a hydrophilic treatment is preferably used.

[0119] In the case of an aluminum support, pure aluminum or an aluminum alloy is used.

[0120] Various aluminum alloys can be used, for example, alloys of metals such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel, titanium, sodium, iron, and aluminum are used. It is done. As the aluminum support, a roughened surface is used for water retention.

[0121] When an aluminum support is used, it is preferable to perform a degreasing treatment in order to remove the rolling oil on the surface prior to roughening (graining treatment). As the degreasing treatment, a degreasing treatment using a solvent such as tritalene or thinner, an emulsion degreasing treatment using an emulsion such as kesilon or triethanol, or the like is used. In addition, an alkaline aqueous solution such as caustic soda can be used for the degreasing treatment. When an alkaline aqueous solution such as caustic soda is used for the degreasing treatment, it cannot be removed only by the above degreasing treatment, and dirt and oxide films can also be removed. When an alkaline aqueous solution such as caustic soda is used for the degreasing treatment, smut is generated on the surface of the support. In this case, the substrate is immersed in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid, or a mixed acid thereof. It is preferable to apply a desmut treatment. Examples of the roughening method include a mechanical method and a method of etching by electrolysis.

[0122] The mechanical surface roughening method used is not particularly limited, but a brush polishing method and a Houng polishing method are preferable.

[0123] Although the electrochemical surface roughening method is not particularly limited, a method of electrochemical surface roughening in an acidic electrolyte is preferred.

[0124] After the surface is roughened by the electrochemical surface roughening method, it is preferably immersed in an acid or alkali aqueous solution in order to remove aluminum scraps on the surface. Examples of the acid include sulfuric acid, persulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid, hydrochloric acid, and the like, and examples of the base include sodium hydroxide, potassium hydroxide, and the like. Among these, it is preferable to use an alkaline aqueous solution.

[0125] The amount of aluminum dissolved on the surface is preferably 0.5 to ⁵ gZm2. In addition, after immersion treatment with an alkaline aqueous solution, acids such as phosphoric acid, nitric acid, sulfuric acid, chromic acid, or their It is preferable to soak in a mixed acid and neutralize it.

[0126] The mechanical surface roughening method and the electrochemical surface roughening method may each be used alone to roughen the surface, or the mechanical surface roughening method followed by the electrochemical surface roughening method. To roughen the surface.

[0127] Following the roughening treatment, an anodizing treatment can be performed. As a method of anodizing treatment that can be used in the present invention, a known method without particular limitation can be used. By performing the anodizing treatment, an oxide film is formed on the support.

[0128] The anodized support may be subjected to a sealing treatment if necessary. These sealing treatments can be carried out using known methods such as hot water treatment, boiling water treatment, steam treatment, sodium silicate treatment, dichromate aqueous solution treatment, nitrite treatment, and acetic acid ammonium treatment.

[0129] Further, after these treatments, water-soluble rosin such as polyvinyl phosphonic acid, polymers and copolymers having sulfonic acid groups in the side chain, polyacrylic acid, water-soluble metal salts (for example boron Zinc acid) or a primer coated with a yellow dye, amine salt or the like is also suitable. Furthermore, a sol-gel-treated substrate in which a functional group capable of causing an addition reaction by a radical as disclosed in JP-A-5-304358 is covalently used.

[0130] Preparation of photosensitive lithographic printing plate material

The above photosensitive layer coating solution can be applied onto a support by a conventionally known method and dried to prepare a photosensitive lithographic printing plate material.

[0131] Examples of coating methods for the coating solution include air doctor coater method, blade coater method, wire bar method, knife coater method, dip coater method, reverse roll coater method, gravure coater method, cast coating method, curtain coater method and extrusion Examples include the coater method.

[0132] The drying temperature of the photosensitive layer is preferably from 60 to 160 ° C, more preferably from 80 to 140 ° C, and particularly preferably from 90 to 120 ° C! /.

[Preparation of planographic printing plate]

The photosensitive lithographic printing plate material of the present invention produces a lithographic printing plate by the following treatment, and the lithographic printing plate is placed on an offset printing machine and used for printing. [0134] (Image exposure)

As a light source for recording an image on the photosensitive lithographic printing plate material of the present invention, a laser beam having an emission wavelength of 350 to 450 nm, preferably 370 to 440 nm is preferably used.

[0135] The light source for exposing the photosensitive lithographic printing plate material of the present invention includes, for example, a He-Cd laser (441 nm), a combination of Cr: LiSAF and SHG crystals (430 nm) as a solid laser, a semiconductor laser system KNbO, ring resonator (430nm), AlGaInN (350nm

3 to 4

50 nm), AlGalnN semiconductor lasers (sold by InGaN based semiconductor lasers 400 to 410 nm), and the like.

[0136] In the case of laser exposure, light can be narrowed down in the form of a beam and scanning exposure according to image data is possible, so that it is suitable for direct writing without using a mask material.

[0137] When a laser is used as a light source, it is easy to reduce the exposure area to a very small size, and high-resolution image formation is possible.

[0138] Laser scanning methods include cylindrical outer surface scanning, cylindrical inner surface scanning, and planar scanning. In the cylindrical outer surface scanning, one exposure of the laser is performed while rotating the drum around which the recording material is wound, the rotation of the drum is the main scanning, and the movement of the laser beam is the sub scanning. In cylindrical inner surface scanning, a recording material is fixed to the inner surface of the drum, a laser beam is irradiated with an inner force, and part or all of the optical system is rotated to perform main scanning in the circumferential direction. Alternatively, the sub-scan is performed in the axial direction by linearly moving all of them parallel to the drum axis. In plane scanning, laser scanning is performed by combining a polygon mirror, galvanometer mirror, and fΘ lens, and sub-scanning is performed by moving the recording medium. Cylindrical outer surface scanning and cylindrical inner surface scanning are suitable for high-density recording that facilitates increasing the accuracy of the optical system.

In the present invention, it is preferable that image exposure is performed with a plate surface energy (energy on the plate material) of lOmjZcm ² or more, and the upper limit is 500 mjZcm ² . More preferably, it is 10 to 300 mjZcm ² . For this energy measurement, for example, a laser power meter PDGDO-3W manufactured by OphirOptronics can be used.

[0140] (Developer)

The exposed portion of the photosensitive layer subjected to image exposure is cured. This is preferably developed with an alkaline developer to remove the unexposed areas and form an image. [0141] As such a developer, a conventionally known alkaline aqueous solution can be used. For example, sodium silicate, potassium, ammonium; dibasic sodium phosphate, potassium, ammonium; sodium bicarbonate, potassium, ammonium; sodium carbonate, potassium, Ammonium; Sodium bicarbonate, Potassium, Ammonium; Sodium borate, Potassium, Ammonium; Use of inorganic alkaline agents such as sodium hydroxide, potassium, ammonium, and lithium An alkaline developer is mentioned.

[0142] In addition, monomethylamine, dimethylamine, trimethylamine, monoethylamine, jetinoreamine, triethreamine, mono-i-propylamine, di-i-propylamine, tri-i-propylamine, butylamine, monoethanolamine, Organic alkali agents such as diethanolamine, triethanolamine, mono-i-propanolamine, di-i-propanolamine, ethyleneimine, ethylenediamine and pyridine can also be used.

[0143] These alkaline agents are used alone or in combination of two or more. In addition, the developer may contain an organic solvent such as a ionic surfactant, an amphoteric surfactant, and alcohol as necessary.

[0144] The alkaline developer may be prepared from a developer concentrate such as a granule or a tablet.

[0145] The developer concentrate may be once evaporated into a developer and then evaporated to dryness. However, it is preferable to add a small amount of water without adding water when mixing a plurality of materials. A method of concentrating the materials by mixing them is preferable. The developer concentrates are disclosed in JP-A-51-61837, JP-A-2-109042, JP-A-2-109043, JP-A-3-39735, JP-A-5-142786, JP-A-6-266606, and JP-A-7. — Granules and tablets can be obtained by a well-known method described in No. 13341 or the like. Further, the developer concentrate may be divided into a plurality of parts having different raw material types and raw material mixing ratios.

[0146] The alkaline developer and its replenisher may further contain a preservative, a colorant, a thickener, an antifoaming agent, a hard water softening agent, and the like, if necessary.

[0147] (Automatic processor)

It is advantageous to use an automatic processor for developing the photosensitive lithographic printing plate material. An automatic image processor is preferably provided with a mechanism for automatically replenishing a required amount of developer replenisher to the developing bath, and preferably a mechanism for discharging a developer exceeding a certain amount is provided. More preferably, a mechanism for automatically replenishing the required amount of water to the developing bath is provided, preferably a mechanism for detecting the plate passing is provided, and preferably the processing area of the plate based on the detection of the plate passing. A mechanism for controlling the replenisher solution and Z or water replenishment amount and Z or replenishment timing to be replenished based on detection of plate-passing and estimation of Z or processing area is preferably provided. A mechanism for controlling the temperature of the developer is preferably provided, and a mechanism for detecting the pH and Z of the developer or conductivity is preferably provided, preferably the pH and Z of the developer. Or, a replenisher to be replenished based on conductivity and a mechanism to control the replenishment amount and Z or replenishment timing of Z or water are provided. Further, it is preferable that the developer concentrate has a function of once diluting and stirring with water. When there is a washing step after the development step, the washing water after use can be used as dilution water for the concentrate of the development concentrate.

[0148] The automatic processor may have a pretreatment section that immerses the plate in the pretreatment liquid before the development step. The pretreatment section is preferably provided with a mechanism for spraying the pretreatment liquid onto the plate surface, and preferably provided with a mechanism for controlling the temperature of the pretreatment liquid to an arbitrary temperature of 25 to 55 ° C. Preferably, a mechanism for rubbing the plate surface with a roller-like brush is provided. Water or the like is used as the pretreatment liquid.

[0149] (Post-processing)

The photosensitive lithographic printing plate material that has been developed with an alkaline developer is post-treated with washing water, a rinse solution containing a surfactant, a finisher mainly composed of gum arabic or starch derivatives, or a protective gum solution. Applied. These treatments can be used in various combinations, for example, development → washing → treatment with a rinse solution containing a surfactant and development → water washing → processing power with a rinse solution. Better ,. Further, counter-flow multi-stage treatment using a rinse solution or a liquid is also preferred.

[0150] These post-processing are generally performed using an automatic developing machine including a developing unit and a post-processing unit. As the post-treatment liquid, a method of spraying from a spray nozzle or a method of immersing and conveying in a treatment tank filled with the treatment liquid is used. In addition, a method is also known in which a certain amount of a small amount of washing water is supplied to the printing plate after the development, and the waste solution is reused as dilution water for the developing solution stock solution. In such automatic processing, depending on the processing volume, operating time, etc. for each processing solution Processing can be performed while replenishing each replenisher. In addition, a so-called disposable treatment method in which treatment is performed with a substantially unused post-treatment liquid can also be applied. The planographic printing plate obtained by such a process is applied to an offset printing machine and used for printing a large number of sheets.

[0151] Hereinafter, the present invention will be described in detail with reference to examples, but the embodiments of the present invention are not limited thereto. In the examples, “%” and “part” represent “% by mass” and “part by mass” unless otherwise specified.

[0152] Examples

(Production of support)

A 0.3 mm thick aluminum plate (material 1050, tempered H16) was immersed in a 5% aqueous sodium hydroxide solution kept at 65 ° C, degreased for 1 minute, and then washed with water. This defatted aluminum film was neutralized by immersion in a 10% aqueous hydrochloric acid solution maintained at 25 ° C. for 1 minute, and then washed with water.

[0153] Next, this aluminum plate was subjected to electrolytic surface roughening with an alternating current for 60 seconds in a 0.3% nitric acid aqueous solution at 25 ° C and a current density of 100A Zdm ² , and then 60 ° The desmutting treatment was carried out in a 5% aqueous sodium hydroxide solution kept at C for 10 seconds.

[0154] The surface-roughened aluminum plate that had been desmutted was anodized for 1 minute in a 15% sulfuric acid solution at 25 ° C, a current density of 10AZdm ² , and a voltage of 15V. A support was prepared by hydrophilizing with phosphonic acid at 75 ° C.

At this time, the center line average roughness (Ra) of the surface was 0.65 m.

[Preparation of photosensitive lithographic printing plate material sample]

On the above support, photosensitive layer coating solution 1 with the following composition was applied with a wire bar to 1.5 gZm ² when dried, dried at 95 ° C for 1.5 minutes, and then oxygen-blocked with the following composition Layer coating solution 1 was applied with a wire bar to 1.5 gZm ² when dried, and dried at 75 ° C. for 1.5 minutes to prepare photosensitive lithographic printing plate material samples 101-121.

[0157] (Photosensitive layer coating solution 1)

N-n-Butyljetanolamine (1 mole), 1,3-bis (1-isocyanate 1-to 1-me Chilletyl) benzene (2 mol), 2-hydroxyethyl methacrylate (2 mol) reaction product (M2-15) 42.0 parts

卜 Reethylene glycol dimethacrylate 卜 6.0 parts

Copolymer of methacrylic acid and methylmetatalylate with a mass ratio of 25:75 (molecular weight 36000)

35. 0

Sensitizing dyes (listed in Table 1) 4.0 parts

2, 2 '—Bis (2 black mouthpiece) 4, 5, 4', 5 '—Tetraferubiimidazole Nore 3.0

2 Mercaptobenzothiazole 0. 3 parts

N-Hue-Noreglycine Benzenoles Estenole 4.0 parts Phthalocyanine pigment (MHI # 454: Gokoku Color Co., Ltd.) 3.5 parts

2-t-Butyl 6- (3-T-Butyl 2-Hydroxy-1-5-Methylbenzyl) 4-Methylphenol acrylate (Sumilyzer GS: manufactured by Sumitomo 3M) 0.2

2, 4, 6 Tris (dimethylaminomethyl) phenol 1.0 parts

Bis (2, 2, 6, 6-tetramethyl-4 piperidyl) senocate 0.1 part

Fluorosurfactant (F—178K; manufactured by Dainippon Ink and Co., Ltd.) 0.5 part Siloxane surfactant (BYK337; manufactured by BYK-Chemichi Co., Ltd.) 0.9 part Methyl ethyl ketone 80 parts

820 parts of propylene glycol methyl ether

(Oxygen barrier coating solution 1)

Polybule alcohol (Celball 103: manufactured by Celaneas) 85.0 parts

Bulpyrrolidone Z Acetate Bull Copolymer (Rubitec VA64W: manufactured by BASF)

15. 0

Surfinol 465 (Air Products) 0.2 part

900 咅 water

However, for samples 118 and 119, 2, 2 'bis (2 black mouth phenyl) 4, 5, 4', 5 '-tetraphenylimidazole was used in the preparation of photosensitive lithographic printing plate samples 105 and 106. Cumene-I (η-cyclopentagel) iron hexafluorophosphate Samples 118 and 119 were prepared in the same manner, except that

[0158] However, for samples 120 and 121, in the preparation of samples 105 and 106 of the above-described photosensitive lithographic printing plate material, N-n-butyljetanolamine (1 mol), 1, 3-bis (1— Isocyanato 1-methinoreethinole) benzene (2 monole), 2-hydroxyethinoremethalate (2 mol) reaction product, 2- (2-hydroxyethyl) piperidine (1 mol), 1 Samples 120 and 121 of the photosensitive lithographic printing plate material were prepared in the same manner except that the reaction product was replaced with a reaction product of 1,2 disoanaanatohexane (2 mol) and 2-hydroxyethyl methacrylate (2 mol).

[0159] [Chemical 22] Comparison 1 Comparison 2

[Evaluation of photosensitive lithographic printing plate material]

(Sensitivity)

Using a plate setter (NewsCTP: manufactured by ECRM) equipped with a light source of 405 nm and 60 mW, the photosensitive lithographic printing plate material sample produced was exposed at 2400 dpi (dpi represents 2.5 dots per 54 cm) Went.

[0161] The exposure pattern used was 100% image area, Times New Rohman font, 3 point to 10 point size, original image data with uppercase and lowercase letters.

[0162] Next, the preheating section set at 105 ° C and the pre-water washing for removing the oxygen barrier layer Part, developer with the following composition, temperature adjusted to 30 ° C, washing part to remove developer adhering to the plate surface, gum solution for protecting the image area (GW-3: Mitsubishi A lithographic printing plate was obtained by developing with a CTP automatic processor (Raptor Polymer: Glunz & Jesen) equipped with a processing section.

[0163] (Developer composition (aqueous solution containing the following additives))

A Kei potassium (25.5 to 27.5 mass ^_0/0 of SiO, including KO of 12.5 to 14.5 mass ^_0/0)

twenty two

8. 0 咅

New Coal B—13SN (Nippon Emulsifier Co., Ltd.) 3. 0 parts

Wed 89.0

Caustic potash added to pH = 12.3

In the 100% image area recorded on the lithographic printing plate surface, the lowest exposure energy amount at which no film loss was observed was taken as the recording energy and used as an index of sensitivity. The recording energy is small! / Indicates that the sensitivity is higher.

[0164] (Sensitivity fluctuation during storage)

The lithographic printing plate material sample obtained above was stored in a thermostatic bath at 55 ° C for 3 days. The sensitivity of the stored lithographic printing plate material sample was measured by the same method as described above. The ratio of the sensitivity after storage to the sensitivity before storage was determined and used as an index of storage stability. The closer to 100%, the better the storage stability with less fluctuation.

[0165] (Sludge amount)

Using the above-mentioned automatic processor, a running replenisher was developed for 1 month (30 days) under the processing conditions of replenishing 50 ml of developer replenisher per lm ² and processing a photosensitive lithographic printing material sample at 25 m ² per day. 1 L was filtered with ADVANTEC No. 2 (manufactured by Advantech Toyo Co., Ltd.), the residue was sufficiently dried, and the mass was measured.

[0166] (Non-image area ink smear)

The development processing replenisher was processed for 1 month (30 days) under processing conditions of replenishing 50 ml per lm ² and processing a photosensitive lithographic printing material sample at 25 m ² per day. After that, a lithographic printing plate was printed on a printing machine (DAIYA1F-1 manufactured by Mitsubishi Heavy Industries, Ltd.), printing ink (soybean oil ink “Nachiyuraris 100” manufactured by Dainippon Ink Industries Co., Ltd.) and dampening water (Tokyo Ink). Co., Ltd. H liquid SG-51 density 1.5%) was used for printing. Ink stains in the non-image area of the 100th printed material from the start of printing were observed visually and with a magnifying glass, and evaluated according to the following criteria.

[0167] ◎: No dirt

◯: Slight ink stains observed when observed with a magnifying glass

△: Power to confirm slight ink stains when observed with a magnifying glass Can be used as printed material

X: When observed with a magnifying glass, small ink stains can be confirmed. Cannot be used as printed matter X X: Ink stains can be visually confirmed on non-image areas. Cannot be used as printed matter Table 1 shows the evaluation results.

[0168] [Table 1]

From Table 1, compared with Comparative Samples 101-104, Samples 105-121 of the present invention have higher sensitivity, and there is less variation in sensitivity during storage, and there is less developer sludge. It turns out that it is also favorable. In particular, Samples 105 and 106 using hexarylbiimidazole compounds are better than Samples 118 and 119.

Claims

A photosensitive lithographic printing plate material having a photosensitive layer containing a polymerization initiator, a polymerizable ethylenic double bond-containing compound, a sensitizing dye and a polymer binder on a support! The photosensitive lithographic printing plate material is characterized in that the photosensitive layer contains a compound represented by the following general formula (11) or (12) as the sensitizing dye.

[Chemical 1]

-General formula (1—1) General formula (1—2)

11

It represents a cyclic group represented by substituted or unsubstituted indazole, benzimidazole, imidazole, thiazole, benzoxazole, oxazole, pyrrole, thiophene, furan, pyrazole, isothiazole, indole, benzothiophene, benzofuran, and pyridine. ]

[2] In the general formula (1-1) or (1-2), Het is a cyclic group represented by substituted or unsubstituted benzimidazole, benzoxazolene, thiophene, furan, benzothiophene, or benzofuran. The photosensitive lithographic printing plate material according to claim 1, wherein the photosensitive lithographic printing plate material is.

[3] The compound power represented by the general formula (11) or (12) is a compound represented by the following general formula (2-1) or (2-2). The photosensitive lithographic printing plate material according to item 1.

[Chemical 2]

—General formula (2—1) General formula (2—2)

21 22

Represents an integer of 0-3. ]

[4] The photosensitive property according to any one of claims 1 to 3, wherein the photosensitive layer contains a hexaarylbiimidazole compound as the polymerization initiator. Lithographic printing plate material.

[5] The power according to any one of claims 1 to 4, wherein the polymerizable ethylenic double bond-containing compound is a reaction product of the following compounds (C1) to (C3): The photosensitive lithographic printing plate material described in 1.

(C2) Diisocyanate compound

[6] The power according to any one of claims 1 to 5, wherein the polymerizable ethylenic double bond-containing compound is a compound represented by the following general formula (3): The photosensitive lithographic printing plate material described.

[Chemical formula 3] General formula (3)

[Wherein, R ¹ represents a hydrogen atom or a methyl group, X ¹ represents a divalent aliphatic group, X ² represents a divalent hydrocarbon group having an aromatic ring, and X ³ represents a tertiary amine. Represents a divalent substituent having a structure; ]

7. The content of the sensitizing dye in the photosensitive layer is from 0.5 to 8.0% by mass based on the total solid content of the photosensitive layer. The photosensitive lithographic printing plate material described in 1 above.

[8] The content of the polymerizable ethylenic double bond-containing compound in the photosensitive layer is such that the photosensitive layer 20 to 80% by mass with respect to the total solid content of the polymer, and the content of the polymer binder in the photosensitive layer is 15 to 70% by mass with respect to the total solid content of the photosensitive layer. The photosensitive lithographic printing plate material according to claim 7, wherein the content thereof is 0.05 to 20% by mass relative to the total solid content of the photosensitive layer.