JP2009047796A - Photosensitive planographic printing plate material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive planographic printing plate material, suitable for exposure with a laser beam having an emission wavelength of 350-450 nm using sensitizing dye, having high sensitivity and excellent preservability, hardly causing sludge in development, and reducing ink stains on a non-image area. <P>SOLUTION: In the photosensitive planographic printing plate material, a photosensitive layer containing a polymerization initiator, a polymerizable ethylenic double bond containing compound, a sensitizing dye and polymeric binder is provided on a support. A compound expressed by the general formula (1) is contained as the sensitizing dye. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

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

  In recent years, photosensitive lithographic printing plate materials capable of image exposure with a laser having a wavelength of 390 to 430 nm and having improved safe light properties are known from the viewpoint of handleability of the printing plate. A high-power and small-sized blue-violet laser with a wavelength of 390 to 430 nm can be easily obtained, and a bright room has been achieved by developing a photosensitive lithographic printing plate suitable for this laser wavelength. (For example, refer to Patent Document 1).

  Also known is a printing plate material that improves the safelight property under yellow light, for example, containing a biimidazole compound in the photosensitive layer (see, for example, Patent Document 2), and has high sensitivity and low sublimation photopolymerization. As a polymerizable composition, for example, a photopolymerizable composition containing a hexaarylbiimidazole compound containing an aryl group having a substituent such as an alkyl group is known (see, for example, Patent Document 3).

On the other hand, distyrylbenzene, coumarin, benzoxazole, oxazole, imidazole, and the like are known as sensitizing dyes used in a polymerization type photosensitive layer corresponding to exposure with laser light having an emission wavelength of 350 to 450 nm (for example, (See Patent Documents 4 and 5). However, these photosensitive lithographic printing plate materials have problems that sensitivity is insufficient and sensitivity fluctuations with time are large. Furthermore, although there has been a report using thiazole as a sensitizing dye for higher sensitivity (see, for example, Patent Document 6), the thiazole dye exemplified has poor solubility in organic solvents and sludge is generated during development. As a result, there are problems such as ink smearing in non-image areas.
JP 2000-35673 A JP 2001-194882 A JP 2004-137152 A JP 2003-295426 A WO04 / 74930 pamphlet JP 2002-116540 A

  The present invention has been made in view of the above problems, and its purpose is suitable for exposure with laser light having an emission wavelength of 350 to 450 nm, high sensitivity, high storage stability, and excellent solubility in organic solvents. Another object of the present invention is to provide a photosensitive lithographic printing plate material which is less likely to generate sludge during development and has less ink stains in non-image areas.

The above object of the present invention can be achieved by the following configuration.
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 following general sensitizing dye A photosensitive lithographic printing plate material comprising a compound represented by the formula (1):

[Wherein, X ₁ and X ₂ each represent NR ₂ (R ₂ represents a hydrogen atom or a substituent), a sulfur atom or an oxygen atom. R ₁ represents an n-propyl group, an i-propyl group, an aliphatic group having 4 or more carbon atoms, an aromatic group, or a heterocyclic group. Q ₁ and Q ₂ each represent NR ₃ (R ₃ represents a hydrogen atom or a substituent), a sulfur atom or an oxygen atom. W ₁ represents a nonmetallic atom group necessary for forming a ring together with X ₂ . ]
2.
_2. The photosensitive lithographic printing plate material as described in 1 above, wherein, in the general formula (1), X ₂ is NR ₂ (R ₂ represents a hydrogen atom or a substituent).
3.
3. The photosensitive lithographic printing plate material as described in 1 or 2 above, wherein in the general formula (1), Q ₁ is an oxygen atom and Q ₂ is a sulfur atom.
4).
4. The photosensitive lithographic printing plate material as described in any one of 1 to 3 above, wherein the polymerization initiator is a hexaarylbiimidazole compound.
5.
The photosensitive lithographic printing plate as described in any one of 1 to 4 above, wherein the polymerizable ethylenic double bond-containing compound is a reaction product of the following compounds (C1) to (C3): 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 in the molecule Having a secondary amine structure and one hydroxyl group.
6).
6. The photosensitive lithographic printing plate material as described in any one of 1 to 5 above, wherein the polymerizable ethylenic double bond-containing compound is a compound represented by the following general formula (2): .

[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 structure. Represents a divalent substituent. ]
7.
The photosensitive lithographic printing plate material as described in any one of 1 to 6 above, wherein the photosensitive layer contains a thiol compound.

  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, has high sensitivity and high storage stability, is excellent in solubility, hardly generates sludge during development, and has a non-image portion. A photosensitive lithographic printing plate material with less ink stains can be provided.

  Next, the best mode 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 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. Furthermore, by using the compound represented by the above general formula (1) as a sensitizing dye, it is suitable for exposure with a laser beam having an emission wavelength of 350 to 450 nm, has high sensitivity and excellent storage stability, and has sludge during development. It has been found that a photosensitive lithographic printing plate material that is less likely to occur and has less ink stains in non-image areas can be obtained.

  Hereinafter, materials, layer structures and the like relating to the photosensitive lithographic printing plate material of the present invention (hereinafter referred to as lithographic printing plate material) will be described in detail.

<Sensitizing dye represented by formula (1)>
In general, a compound having a branched substituent in the molecule or a bulky substituent introduced has an effect of improving the solubility in an organic solvent. In the present invention, by improving the solubility in a coating solvent, it is possible to prevent precipitation and aggregation of the pigment after coating, and a lithographic printing plate material having excellent storage stability can be provided.

In the present invention, an n-propyl group, an i-propyl group, an aliphatic group having 4 or more carbon atoms, an aromatic group, or a heterocyclic group is introduced into R ₁ by the general formula (1) for the organic solvent. The solubility of the sensitizing dye to be improved. In the present specification, the “aliphatic group” means a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, and aralkyl group, respectively.

Specific examples of the aliphatic group having 4 or more carbon atoms represented by R ₁ include butyl, t-butyl, pentyl, hexyl, decyl, dodecyl, pentadecyl, cyclobutyl, cyclobutenyl, cyclopentyl, cyclopentenyl, cyclopentadienyl, Cyclohexyl, cyclohexenyl, cyclohexadienyl, cycloheptyl, cycloheptynyl, cycloheptadienyl, cyclooctanyl, cyclooctenyl, cyclooctadienyl, cyclooctatrienyl, cyclononanyl, cyclononenyl, cyclononadienyl, cyclononatrienyl, cyclodecanyl , Cyclodecenyl, cyclodecadienyl, cyclodecatrienyl, 1-butenyl, 2-butenyl, 1-hexenyl, benzyl, 1-phenylethyl and the like. These groups may further have a substituent or a halogen atom. Examples of the substituent include an alkyl group, a cyano group, an alkoxy group, a hydroxyl group, an amino group, a carboxyl group, a carbooxy group, an aryl group, and a heterocyclic group. Aryloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group and the like. Also, having a bulky group such as a branched alkyl group or a cyclic compound (cyclic alkyl group, etc.) rather than a linear alkyl group prevents aggregation after coating and improves solubility in organic solvents. Preferred above.

The aromatic group represented by R ₁ may be a single ring or a condensed ring, and examples thereof include a ring such as phenyl, naphthyl, anthracenyl, phenanthrenyl, naphthacenyl, triphenylenyl and the like. These rings may have various substituents at any position, and as a preferable substituent, a linear or branched alkyl group (preferably a methyl group having 1 to 20 carbon atoms, ethyl, propyl, i-- Propyl, dodecyl, etc.), alkoxy groups (preferably methoxy, ethoxy, propoxy, i-propoxy, dodecyloxy, etc. having 1 to 20 carbon atoms), amino groups, aliphatic acylamino groups (preferably having 1 to 21 carbon atoms) Acetylamino, heptylamino and the like having an alkyl group), aromatic acylamino groups and the like.

Specific examples of the heterocyclic group represented by R ₁ include pyrrole, indole, furan, thiophene, imidazole, pyrazole, indolizine, quinoline, carbazole, phenothiazine, indoline, thiazole, pyridine, pyridazine, thiadiazine, pyran, thiopyran, Examples include oxadiazole, benzoquinoline, thiadiazole, pyrrolothiazole, pyrrolopyridazine, tetrazole, oxazole, coumarin, and chroman. These heterocyclic rings may be monocyclic or may form condensed rings with other rings. Furthermore, you may have various substituents, Preferably, an alkyl group, an aryl group, an alkoxy group etc. are mentioned as a substituent.

R ₁ preferably has a bulky group such as a branched alkyl chain or a cyclic compound rather than a linear alkyl chain in order to improve the solubility in a solvent. Accordingly, R ₁ is preferably an i-propyl group, an aliphatic group having 4 to 20 carbon atoms, or an aromatic group, more preferably an i-propyl group, an alkyl group having 4 to 20 carbon atoms, or a carbon number having 6 to 10 carbon atoms. A cycloalkyl group and a phenyl group.

X ₁ and X ₂ each represent NR ₂ (R ₂ represents a hydrogen atom or a substituent), a sulfur atom or an oxygen atom. Specific examples of the substituent represented by R ₂ include an alkyl group (methyl , Ethyl, propyl, i-propyl, t-butyl, pentyl, hexyl, etc.), cycloalkyl group (cyclohexyl, cyclopentyl etc.), alkenyl group, cycloalkenyl group, alkynyl group (propargyl etc.), aromatic group (phenyl, naphthyl) , Anthracenyl, etc.), heterocyclic groups (pyridyl, thiazolyl, oxazolyl, imidazolyl, furyl, pyrrolyl, pyrazinyl, pyrimidinyl, pyridazinyl, selenazolyl, triphoranyl, piperidinyl, pyrazolyl, tetrazolyl, etc.), alkoxycarbonyl groups (methyloxycarbonyl, ethyloxycarbonyl) , Butyloxycal Nyl etc.), aryloxycarbonyl group (phenyloxycarbonyl etc.), acyl group (acetyl, propionyl, butanoyl, hexanoyl, cyclohexanoyl, benzoyl, pyridinoyl etc.), carbamoyl group (aminocarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, Propylaminocarbonyl, pentylaminocarbonyl, cyclohexylaminocarbonyl, phenylaminocarbonyl, 2-pyridylaminocarbonyl, etc.), sulfonyl groups (methylsulfonyl, ethylsulfonyl, butylsulfonyl, cyclohexylsulfonyl, phenylsulfonyl, 2-pyridylsulfonyl, etc.), etc. be able to. These groups may be further substituted with these groups.

R ₂ is preferably a hydrogen atom or an alkyl group, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably an alkyl group having 1 to 4 carbon atoms.

X ₁ is preferably a sulfur atom or an oxygen atom, more preferably a sulfur atom. X ₂ is preferably NR ₂ or a sulfur atom, more preferably NR ₂ .

Q ₁ and Q ₂ each represent NR ₃ (R ₃ represents a hydrogen atom or a substituent), a sulfur atom or an oxygen atom. Specific examples of the substituent represented by R ₃ are the same as those given as examples of the substituent represented by R ₂ .

Q ₁ and Q ₂ are preferably a sulfur atom or an oxygen atom, more preferably Q ₁ is a sulfur atom or an oxygen atom, and Q ₂ is a sulfur atom.

W ₁ represents a nonmetallic atom group necessary for forming a ring together with X ₂ . Specific examples of the ring formed from X ₂ and W ₁ are shown below, but are not limited thereto.

In the formula, each of R _a , R _b and R _c represents a hydrogen atom or a substituent. Specific examples of the substituent represented by R _a , R _b and R _c include the examples given as the substituent represented by R ₂ in the general formula (1), preferably an alkyl group or an aryl group. An alkoxy group, an alkoxycarbonyl group, an amino group, an acyl group, and the like. n represents an integer of 0 to 4.

  Although the specific example of the sensitizing dye of this invention is given to the following, this invention is not limited to these.

  The compound represented by the general formula (1) can be synthesized by a known method. For example, F.R. M.M. KAI, a method described in Hammer et al., “The Cyanine Soybean and Relaid Compounds” (FM Hamer et al., “The Cyanine Dyes and Related Compounds”), pages 511-611 (1964). It can be synthesized by referring to the method described in ACTA CHEMICA SCANDINAVICA Vol. 22, 1107 to 1128 (1968), such as ARNE JENSEN and LARS HENRIKSEN, or Japanese Patent No. 2552550.

  The content of the sensitizing dye of the present invention is preferably from 0.01 to 10% by mass, more preferably from 0.1 to 8% by mass, based on the total solid content of the photosensitive layer.

  In addition to the above sensitizing dyes, for example, JP-A Nos. 2000-98605, 2000-147763, 2000-206690, 2000-258910, 2000-309724, 2001-042524, 2002-202598. No. 2000-221790 may be used in combination.

<Polymerization initiator>
The polymerization initiator is capable of initiating polymerization of a polymerizable ethylenic double bond-containing compound by image exposure. As the polymerization initiator, a titanocene compound, a monoalkyltriarylborate compound, an iron arene complex compound, Polyhalogen compounds, biimidazole compounds and the like are preferably used. Among these, the effect of the present invention is particularly preferable when a biimidazole compound is used.

(Biimidazole compound)
A biimidazole compound is a derivative of biimidazole, and examples thereof include compounds described in JP-A No. 2003-295426. In the present invention, hexaarylbiimidazoles (abbreviated as HABI: a dimer of triaryl-imidazole) can be preferably used as the biimidazole compound.

  The production process of HABIs is described in German Patent 1,470,154 and their use in photopolymerizable compositions is described in European Patents 24,629, 107,792, US Pat. 410,621, European Patent 215,453 and German Patent 3,211,312.

  Preferred derivatives are, for example, 2,4,5,2 ', 4', 5'-hexaphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,5,4 ', 5'-tetraphenylbiimidazole. Imidazole, 2,2'-bis (2-bromophenyl) -4,5,4 ', 5'-tetraphenylbiimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,5,4' , 5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,5,4 ', 5'-tetrakis (3-methoxyphenyl) biimidazole, 2,2'-bis (2- Chlorophenyl) -4,5,4 ', 5'-tetrakis (3,4,5-trimethoxyphenyl) -biimidazole, 2,5,2', 5'-tetrakis (2-chlorophenyl) -4,4 ' -Bis (3,4-dimethyl) Xylphenyl) biimidazole, 2,2'-bis (2,6-dichlorophenyl) -4,5,4 ', 5'-tetraphenylbiimidazole, 2,2'-bis (2-nitrophenyl) -4,5 , 4 ', 5'-tetraphenylbiimidazole, 2,2'-di-o-tolyl-4,5,4', 5'-tetraphenylbiimidazole, 2,2'-bis (2-ethoxyphenyl) -4,5,4 ', 5'-tetraphenylbiimidazole and 2,2'-bis (2,6-difluorophenyl) -4,5,4', 5'-tetraphenylbiimidazole.

(Titanocene compound)
Examples of the titanocene compound include compounds described in JP-A-63-41483 and JP-A-2-291. As more preferred specific examples, bis (cyclopentadienyl) -Ti-di-chloride, bis (cyclopentadienyl) -Ti-bis-phenyl, bis (cyclopentadienyl) -Ti-bis-2,3, 4,5,6-pentafluorophenyl, bis (cyclopentadienyl) -Ti-bis-2,3,5,6-tetrafluorophenyl, bis (cyclopentadienyl) -Ti-bis-2,4 6-trifluorophenyl, bis (cyclopentadienyl) -Ti-bis-2,6-difluorophenyl, bis (cyclopentadienyl) -Ti-bis-2,4-difluorophenyl, bis (methylcyclopentadi) Enyl) -Ti-bis-2,3,4,5,6-pentafluorophenyl, bis (methylcyclopentadienyl) -Ti-bis-2,3,5 -Tetrafluorophenyl, bis (methylcyclopentadienyl) -Ti-bis-2,6-difluorophenyl (IRUGACURE 727L: manufactured by Ciba Specialty Chemicals), bis (cyclopentadienyl) -bis (2,6- Difluoro-3- (pyridin-1-yl) phenyl) titanium (IRUGACURE784: Ciba Specialty Chemicals), bis (cyclopentadienyl) -bis (2,4,6-trifluoro-3- (pyri-) 1-yl) phenyl) titanium bis (cyclopentadienyl) -bis (2,4,6-trifluoro-3- (2-5-dimethylpy-1-yl) phenyl) titanium and the like.

(Monoalkyltriaryl borate compound)
Examples of the monoalkyltriaryl borate compound include compounds described in JP-A Nos. 62-150242 and 62-143044. Further preferred examples include tetrabutylammonium-butyl-trinaphthalen-1-yl-borate, tetrabutylammonium-butyl-triphenyl-borate, tetrabutylammonium-butyl-tri (4-t-butylphenyl) -borate Tetrabutylammonium-hexyl-tri (3-chloro-4-methylphenyl) -borate, tetrabutylammonium-hexyl-tri (3-fluorophenyl) -borate and the like.

(Iron arene complex compound)
Examples of the iron arene complex compound include compounds described in JP-A-59-219307. More preferable specific examples include η-benzene- (η-cyclopentadienyl) iron hexafluorophosphate, η-cumene- (η-cyclopentadienyl) iron hexafluorophosphate, η-fluorene- (η-cyclopenta Dienyl) iron hexafluorophosphate, η-naphthalene- (η-cyclopentadienyl) iron hexafluorophosphate, η-xylene- (η-cyclopentadienyl) iron hexafluorophosphate, η-benzene- (η-cyclo Pentadienyl) iron tetrafluoroborate and the like.

(Polyhalogen compound)
As the polyhalogen compound, a compound having a trihalogenmethyl group, a dihalogenmethyl group or a dihalomethylene group is preferably used. In particular, a halogen compound represented by the following general formula (5) or (6) and a compound in which the above group is substituted with an oxadiazole ring are preferably used. Among these, a halogen compound represented by the following general formula (3) or (4) is particularly preferable.

Formula (3) R ₁₁ —C (Y) ₂ —CO—R ₁₂
In the formula, R ₁₁ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, an iminosulfonyl group, or a cyano group, and R ₁₂ represents a monovalent substituent. R ₁₁ and R ₁₂ may be bonded to each other to form a ring. Y represents a halogen atom.

Formula (4) C (Y) ₃ —CO—X—R ₁₃
In the formula, R ₁₃ represents a monovalent substituent. X represents —O— or —NR ₁₄ —. R ₁₄ represents a hydrogen atom or an alkyl group. R ₁₃ and R ₁₄ may be bonded to each other to form a ring. Y represents a halogen atom. Among these, those having a polyhalogen acetylamide group are particularly preferably used.

  Furthermore, the compounds described in JP-A Nos. 5-34904 and 8-240909 in which a polyhalogen methyl group is substituted with an oxadiazole ring are also preferably used.

<Combinable polymerization initiator>
In addition, any polymerization initiator can be used in combination. For example, J. et al. Carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo, diazo compounds, halogen compounds, and photoreductive dyes as described in Chapter 5 of “Light Sensitive Systems” by J. Kosar Etc. Further specific compounds are disclosed in British Patent 1,459,563.

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

  Benzoin derivatives such as benzoin methyl ether, benzoin-i-propyl ether, α, α-dimethoxy-α-phenylacetophenone; benzophenone, 2,4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4,4′-bis (dimethyl) Benzophenone derivatives such as amino) benzophenone; thioxanthone derivatives such as 2-chlorothioxanthone and 2-i-propylthioxanthone; anthraquinone derivatives such as 2-chloroanthraquinone and 2-methylanthraquinone; N-methylacridone, N-butylacridone and the like In addition to α, α-diethoxyacetophenone, benzyl, fluorenone, xanthone and uranyl compounds, JP-B-59-1281, 61-9621 and JP-A-60-60104 Triazine derivatives; organic peroxides described in JP-A-59-1504 and JP-A-61-243807; JP-B-43-23684, JP-A-44-6413, JP-A-44-6413, JP-A-47-1604, and US patents Diazonium compounds described in US Pat. No. 3,567,453; organic azide compounds described in US Pat. Nos. 2,848,328 and 2,852,379 and 2,940,853; O-quinonediazides described in JP-A Nos. 13109, 38-18015 and 45-9610; JP-B-55-39162, JP-A-59-14023 and “Macromolecules”, Vol. 10, 1307 Various onium compounds described on page 1977; azo compounds described in JP-A-59-142205 Compound: JP-A-1-54440, European Patents 109,851, 126,712 and “J. Imag. Sci.”, Vol. 30, 174 (1986) (Oxo) sulfonium organoboron complexes described in JP-A Nos. 5-213861 and 5-255347; "Coordination Chemistry Review", 84, 85-277 (1988) and special Transition metal complexes containing a transition metal such as ruthenium described in Kaihei 2-182701; 2,4,5-triarylimidazole dimer described in JP-A-3-209477; carbon tetrabromide, JP-A 59- Organohalogen compounds described in 107344, etc. .

  The content of the polymerization initiator (total amount of the polymerization initiator) is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass with respect to the polymerizable ethylenically unsaturated bond-containing compound.

<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 image-exposed photosensitive layer. As the polymerizable ethylenic double bond-containing compound, reaction products of the following compounds (C1) to (C3) are particularly preferably used in the present invention.

(C1) A 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 in the molecule A compound having a secondary amine structure and one hydroxyl group each for (C1) is, for example, 2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate, 2-hydroxypropyl methacrylate; (C2) is 1,3- Bis (1-isocyanato-1-methylethyl) benzene, 1,3-diisocyanatobenzene, 1,3-diisocyanato-4-methylbenzene, 1,3-di (isocyanatomethyl) benzene; (C3) N-butyldiethanolamine, N-methyldiethanolamine, N-ethyldie Noruamin, and the like.

<Compound represented by formula (2)>
As the reaction product, a compound represented by the general formula (2) is particularly preferably used. In the formula, 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 divalent group having a tertiary amine structure. Represents a substituent of

X ¹ is, for example, —CH ₂ CH ₂ —, —CH ₂ CH (CH ₃ ) —, —CH (CH ₃ ) CH ₂ —, —CH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ CH _2— can be mentioned, —CH ₂ CH ₂ —, —CH ₂ CH (CH ₃ ) —, and —CH (CH ₃ ) CH ₂ — are preferred.

Examples of X ² include the following structures X2-1 to X2-10, and X2-3, X2-4, X2-7, X2-9, and X2-10 are preferable.

Examples of X ³ include the structures of X3-1 to X3-10, and X3-1, X3-2, X3-5, and X3-9 are preferable.

  Examples of the compound represented by the general formula (2) include the following compounds.

<Compound containing ethylenic double bond>
Examples of polymerizable ethylenic double bond-containing compounds include general radical polymerizable monomers, polyfunctional monomers having a plurality of addition-polymerizable ethylenic double bonds commonly used in UV curable resins, Polyfunctional oligomers can be used in combination.

  These compounds are not limited, but preferred examples include 2-ethylhexyl acrylate, 2-hydroxypropyl acrylate, glycerol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, nonylphenoxyethyl acrylate, tetrahydrofurfuryloxyethyl acrylate, tetrahydro Furfuryloxyhexanolide acrylate, acrylate of ε-caprolactone adduct of 1,3-dioxane alcohol, monofunctional acrylic acid ester such as 1,3-dioxolane acrylate, or these acrylates as methacrylate, itaconate, crotonate, maleate Methacrylic acid, itaconic acid, crotonic acid, maleic acid ester instead of Relate, Triethylene glycol diacrylate, Pentaerythritol diacrylate, Hydroquinone diacrylate, Resorcin diacrylate, Hexanediol diacrylate, Neopentyl glycol diacrylate, Tripropylene glycol diacrylate, Diacrylate of hydroxypivalate neopentyl glycol, Neo Diacrylate of pentyl glycol adipate, diacrylate of ε-caprolactone adduct of neopentyl glycol hydroxypivalate, 2- (2-hydroxy-1,1-dimethylethyl) -5-hydroxymethyl-5-ethyl-1,3 -Dioxane diacrylate, tricyclodecane dimethylol acrylate, tricyclodecane dimethylol acrylate with ε-caprolactone , Difunctional acrylates such as diglycidyl ether of 1,6-hexanediol, or methacrylic acid, itaconic acid, crotonic acid, maleic acid in which these acrylates are replaced with methacrylate, itaconate, crotonate, maleate Esters; for example, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, trimethylolethane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, di Ε-caprolactone adduct of pentaerythritol hexaacrylate, pyrogallol tria Polyfunctional acrylic acid esters such as relates, propionic acid-dipentaerythritol triacrylate, propionic acid-dipentaerythritol tetraacrylate, hydroxypivalylaldehyde-modified dimethylolpropane triacrylate, or these acrylates with methacrylate, itaconate, crotonate, Examples thereof include methacrylic acid, itaconic acid, crotonic acid, and maleic acid ester instead of maleate.

  Prepolymers can also be used 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 and imparting photopolymerizability can be suitably used. These prepolymers may be used singly or in combination of two or more, and may be used by mixing with the above-mentioned monomers and / or oligomers.

  Examples of prepolymers include adipic acid, trimellitic acid, maleic acid, phthalic acid, terephthalic acid, hymic acid, malonic acid, succinic acid, glutaric acid, itaconic acid, pyromellitic acid, fumaric acid, glutaric acid, pimelic acid, Polybasic acids such as sebacic acid, dodecanoic acid, tetrahydrophthalic acid, and ethylene glycol, propylene glycol, diethylene glycol, propylene oxide, 1,4-butanediol, triethylene glycol, tetraethylene glycol, polyethylene glycol, glycerin, trimethylol Polyester polymers obtained by introducing (meth) acrylic acid into polyesters obtained by combining polyhydric alcohols such as propane, pentaerythritol, sorbitol, 1,6-hexanediol and 1,2,6-hexanetriol. Relates; for example, bisphenol A-epichlorohydrin- (meth) acrylic acid, phenol novolac-epichlorohydrin-epoxy acrylates in which (meth) acrylic acid is introduced into an epoxy resin such as (meth) acrylic acid; for example, ethylene glycol-adipic acid- Tolylene diisocyanate-2-hydroxyethyl acrylate, polyethylene glycol-tolylene diisocyanate-2-hydroxyethyl acrylate, hydroxyethyl phthalyl methacrylate-xylene diisocyanate, 1,2-polybutadiene glycol-tolylene diisocyanate-2-hydroxyethyl acrylate, tri Like methylolpropane-propylene glycol-tolylene diisocyanate-2-hydroxyethyl acrylate Urethane acrylates with (meth) acrylic acid introduced into urethane resins; silicone resin acrylates such as polysiloxane acrylate and polysiloxane-diisocyanate-2-hydroxyethyl acrylate; and other (meth) acryloyl groups introduced into oil-modified alkyd resins And prepolymers such as alkyd-modified acrylates and spirane resin acrylates.

  The photosensitive layer according to the present invention includes a phosphazene monomer, triethylene glycol, isocyanuric acid EO (ethylene oxide) modified diacrylate, isocyanuric acid EO modified triacrylate, dimethylol tricyclodecane diacrylate, trimethylolpropane benzoic acid benzoic acid. Addition-polymerizable oligomers and prepolymers having monomers such as esters, alkylene glycol type acrylic acid-modified, urethane-modified acrylates, and structural units formed from the monomers can be contained.

  Furthermore, examples of the ethylenic monomer that can be used in combination with the present invention include a phosphoric ester compound containing at least one (meth) acryloyl group. The compound is not particularly limited as long as it is a compound in which at least part of the hydroxyl group of phosphoric acid is esterified and has a (meth) acryloyl group.

  In addition, JP-A-58-212994, JP-A-61-6649, JP-A-62-46688, JP-A-62-48589, JP-A-62-173295, JP-A-62-187092, JP-A-63-67189, JP-A-1- The compounds described in No. 244891 and the like can be mentioned, and further, “11290 Chemical Products”, Chemical Industry Daily, pages 286 to 294, “UV-EB Curing Handbook (raw material)” Polymer Publication Association The compounds described on pages 11 to 65 can also be suitably used. Of these, compounds having two or more (meth) acryl groups in the molecule are preferred, and those having a molecular weight of 10,000 or less, more preferably 5,000 or less are preferred.

  In addition, acrylates or alkyl acrylates described in JP-A-1-105238 and JP-A-2-127404 can be used.

  The content of the polymerizable ethylenic double bond-containing compound in the photosensitive layer is preferably 20 to 80% by mass and more preferably 30 to 70% by mass with respect to the photosensitive layer.

<Polymer binder>
The polymer binder according to the present invention is capable of supporting the components contained in the photosensitive layer on a support. Examples of the polymer binder include acrylic polymers, polyvinyl butyral resins, polyurethane resins, polyamide resins, Polyester resin, epoxy resin, phenol resin, polycarbonate resin, polyvinyl butyral resin, polyvinyl formal resin, shellac, and other natural resins can be used. Two or more of these may be used in combination. A vinyl 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.

  Specific examples of the carboxyl group-containing monomer include α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride and the like. In addition, carboxylic acids such as phthalic acid and 2-hydroxymethacrylate half ester are also preferable.

  Specific examples of alkyl methacrylates and alkyl esters include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, nonyl methacrylate. , Decyl methacrylate, undecyl methacrylate, dodecyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, nonyl acrylate, acrylic In addition to unsubstituted alkyl esters such as decyl acid, undecyl acrylate and dodecyl acrylate, cyclic alkyl esters such as cyclohexyl methacrylate and cyclohexyl acrylate Substituted alkyl esters such as benzyl methacrylate, 2-chloroethyl methacrylate, N, N-dimethylaminoethyl methacrylate, glycidyl methacrylate, benzyl acrylate, 2-chloroethyl acrylate, N, N-dimethylaminoethyl acrylate, and glycidyl acrylate Also mentioned.

  Further, in the polymer binder, monomers described in the following (1) to (14) can be used as a copolymerization monomer.

(1) Monomers having an aromatic hydroxyl group, such as o- (or p-, m-) hydroxystyrene, o- (or p-, m-) hydroxyphenyl acrylate,
(2) Monomers having an aliphatic hydroxyl group, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N-methylol acrylamide, N-methylol methacrylamide, 4-hydroxybutyl methacrylate, 5-hydroxypentyl acrylate, 5-hydroxy Pentyl methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, N- (2-hydroxyethyl) acrylamide, N- (2-hydroxyethyl) methacrylamide, hydroxyethyl vinyl ether, etc.
(3) A monomer having an aminosulfonyl group, such as m- (or p-) aminosulfonylphenyl methacrylate, m- (or p-) aminosulfonylphenyl acrylate, N- (p-aminosulfonylphenyl) methacrylamide, N- ( p-aminosulfonylphenyl) acrylamide, etc.
(4) Monomers having a sulfonamide group, such as N- (p-toluenesulfonyl) acrylamide, N- (p-toluenesulfonyl) methacrylamide,
(5) Acrylamide or methacrylamides such as acrylamide, methacrylamide, N-ethylacrylamide, N-hexylacrylamide, N-cyclohexylacrylamide, N-phenylacrylamide, N- (4-nitrophenyl) acrylamide, N-ethyl-N -Phenylacrylamide, N- (4-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) methacrylamide, etc.
(6) Monomers containing fluorinated alkyl groups such as trifluoroethyl acrylate, trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, hexafluoropropyl methacrylate, octafluoropentyl acrylate, octafluoropentyl methacrylate, heptadecafluorodecyl methacrylate, N -Butyl-N- (2-acryloxyethyl) heptadecafluorooctylsulfonamide, etc.
(7) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether, etc.
(8) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, vinyl benzoate, etc.
(9) Styrenes such as styrene, methyl styrene, chloromethyl styrene, etc.
(10) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, phenyl vinyl ketone,
(11) Olefins such as ethylene, propylene, i-butylene, butadiene, isoprene,
(12) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, etc.
(13) Monomers having a cyano group, such as acrylonitrile, methacrylonitrile, 2-pentenenitrile, 2-methyl-3-butenenitrile, 2-cyanoethyl acrylate, o- (or m-, p-) cyanostyrene,
(14) A monomer having an amino group, such as N, N-diethylaminoethyl methacrylate, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, polybutadiene urethane acrylate, N, N-dimethylaminopropyl acrylamide, N , N-dimethylacrylamide, acryloylmorpholine, Ni-propylacrylamide, N, N-diethylacrylamide and the like.

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

  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-reacting a compound having a (meth) acryloyl group and an epoxy group in the molecule to a carboxyl group present in the molecule of the vinyl copolymer. Is also preferred as a polymer binder.

  Specific examples of the compound containing both an unsaturated bond and an epoxy group in the molecule include glycidyl acrylate, glycidyl methacrylate, and an epoxy group-containing unsaturated compound described in JP-A No. 11-271969. In addition, an unsaturated bond-containing vinyl copolymer obtained by addition reaction of a compound having a (meth) acryloyl group and an isocyanato group in the molecule to a hydroxyl group present in the molecule of the vinyl polymer is also provided. Preferred as a polymer binder.

  Examples of the compound having both an unsaturated bond and an isocyanato group in the molecule include vinyl isocyanate, (meth) acrylic isocyanate, 2- (meth) acryloyloxyethyl isocyanate, m- or pi-propenyl-α, α'-dimethyl. Benzyl isocyanate is preferable, and (meth) acryl isocyanate, 2- (meth) acryloyloxyethyl isocyanate, and the like can be given.

  The vinyl polymer having a carboxyl group and a polymerizable double bond in the side chain is preferably 50 to 100% by mass, more preferably 100% by mass, based on the total polymer binder.

  The content of the polymer binder in the photosensitive layer is preferably 10 to 90% by mass, more preferably 15 to 70% by mass, and particularly preferably 20 to 50% by mass from the viewpoint of sensitivity.

<Thiol compound>
The thiol compound used in the present invention is not particularly limited, but is complex such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 1-phenyl-5-mercapto-1,2,4-triazole. A compound containing a mercapto group linked to a ring is preferred.

<Various additives>
In addition to the components described above, a polymerization inhibitor is added to the photosensitive layer to prevent unnecessary polymerization of the polymerizable ethylenic double bond monomer during the production or storage of the lithographic printing plate material. It is desirable to do.

(Polymerization inhibitor)
Suitable polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol) 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxylamine cerium salt, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5) -Methylbenzyl) -4-methylphenyl acrylate and the like.

  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. Further, if necessary, a higher fatty acid derivative such as behenic acid or 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 in the drying process after coating. . The amount of the higher fatty acid derivative added is preferably about 0.5 to 10% by mass of the total composition.

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

  Examples of the pigment include black pigment, yellow pigment, red pigment, brown pigment, purple pigment, blue pigment, green pigment, fluorescent pigment, and metal powder pigment. Specifically, inorganic pigments (titanium dioxide, carbon black, graphite, zinc oxide, Prussian blue, cadmium sulfide, iron oxide, and lead, zinc, barium and calcium chromates) and organic pigments (azo-based, thioindigo) , Anthraquinone, anthanthrone, and triphendioxazine pigments, vat dye pigments, phthalocyanine pigments and derivatives thereof, quinacridone pigments, and the like.

  Among these, it is preferable to select and use a pigment having substantially no absorption in the absorption wavelength region of the spectral sensitizing dye corresponding to the exposure laser to be used. In this case, an integrating sphere at the laser wavelength to be used is used. It is preferable that the reflection absorption of the used pigment is 0.05 or less. Moreover, as an addition amount of a pigment, 0.1-10 mass% is preferable with respect to solid content of the said composition, More preferably, it is 0.2-5 mass%.

  From the viewpoints of pigment absorption in the above-mentioned photosensitive wavelength region and visible image properties after development, violet pigments and blue pigments are preferably used. Such as, for example, cobalt blue, cerulean blue, alkali blue lake, phonatone blue 6G, Victoria blue lake, metal-free phthalocyanine blue, phthalocyanine blue first sky blue, indanthrene blue, indico, dioxane violet, iso Violanthrone Violet, Indanthrone Blue, Indanthrone BC and the like can be mentioned. Among these, phthalocyanine blue and dioxane violet are more preferable.

(Surfactant)
In the photosensitive layer, a surfactant can be contained as a coating property improving agent as long as the performance of the present invention is not impaired. Of these, fluorine-based surfactants are preferred.

  Moreover, in order to improve the physical properties of the cured film, additives such as inorganic fillers and 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 of the photosensitive layer.

<solvent>
Solvents used for preparing the photosensitive layer coating solution include, for example, alcohols and polyhydric alcohol derivatives such as sec-butanol, i-butanol, hexanol, benzyl alcohol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1 , 5-pentanediol; propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether as ethers; diacetone alcohol, cyclohexanone, methylcyclohexanone as ketones and aldehydes; ethyl lactate, butyl lactate as esters Preferred examples include diethyl oxalate and methyl benzoate.

Although the photosensitive layer coating solution has been described above, the photosensitive layer according to the present invention is configured by coating on a support using the photosensitive layer. Preferably 0.1 to 10 g / m ² as the amount urging on the support of the photosensitive layer, in particular 0.5 to 5 g / m ² is preferred.

<Protective layer>
A protective layer can be provided on the photosensitive layer as necessary. This protective layer (oxygen barrier layer) is preferably highly soluble in a developer solution (generally an alkaline aqueous solution) described later, and specific examples include polyvinyl alcohol (PVA) and polyvinyl pyrrolidone (PVP). . PVA has an effect of suppressing the permeation of oxygen, and PVP has an effect of ensuring adhesion with an adjacent photosensitive layer.

  In addition to the above two polymers, polysaccharides, polyethylene glycol, gelatin, glue, casein, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl starch, gum arabic, sucrose octaacetate, ammonium alginate, sodium alginate as required Water-soluble polymers such as polyvinylamine, polyethylene oxide, polystyrene sulfonic acid, polyacrylic acid, and water-soluble polyamide can also be used in combination.

  When a protective layer is provided on the lithographic printing plate material, the peeling force between the photosensitive layer and the protective layer is preferably 35 mN / mm or more, more preferably 50 mN / mm or more, and even more preferably 75 mN / mm or more. A preferred protective layer composition includes those described in JP-A-10-10742. In the present invention, the peeling force is obtained by applying an adhesive tape having a predetermined width on the protective layer and having a sufficiently large adhesive force, and peeling it together 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 determined by measuring the force.

  The protective layer can further contain a surfactant, a matting agent and the like as required. The protective layer composition is dissolved in a suitable solvent, applied onto the photosensitive layer and dried to form a protective layer. The main component of the coating solvent is particularly preferably water or alcohols such as methanol, ethanol and i-propanol.

  When providing a protective layer, the thickness is preferably from 0.1 to 5.0 μm, particularly preferably from 0.5 to 3.0 μm.

<Support>
The support is a plate or film that can carry the photosensitive layer, and preferably has a hydrophilic surface on the side where the photosensitive layer is provided.

  Examples of the support according to the present invention include metal plates such as aluminum, stainless steel, chromium and nickel, and those obtained by laminating or vapor-depositing the above-mentioned metal thin film on a plastic film such as polyester, polyethylene and polypropylene.

  Further, a polyester film, a vinyl chloride film, a nylon film or the like having a surface subjected to hydrophilic treatment can be used, but an aluminum support is preferably used.

  In the case of an aluminum support, pure aluminum or an aluminum alloy is used. Various aluminum alloys can be used. For example, an alloy of metal such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel, titanium, sodium, iron, and aluminum is used. In addition, an aluminum support having a roughened surface is used for water retention.

  In the case of using an aluminum support, 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 trichlene 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 sodium hydroxide can be used for the degreasing treatment. When an alkaline aqueous solution such as sodium hydroxide is used for the degreasing treatment, dirt and oxide film that cannot be removed only by the degreasing treatment can be removed. When an alkaline aqueous solution such as sodium hydroxide 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.

  The mechanical roughening method used is not particularly limited, but a brush polishing method and a honing polishing method are preferable.

  The electrochemical surface roughening method is not particularly limited, but a method of electrochemical surface roughening in an acidic electrolyte is preferable.

  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. Examples of the base include sodium hydroxide and potassium hydroxide. Among these, it is preferable to use an alkaline aqueous solution.

The dissolution amount of aluminum in the support surface, 0.5 to 5 g / m ² is preferred. In addition, it is preferable to carry out a neutralization treatment by immersing in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid or a mixed acid thereof after immersing with an alkaline aqueous solution.

  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. And may be roughened.

  Following the roughening treatment, an anodic oxidation treatment can be performed. There is no restriction | limiting in particular in the method of the anodizing process which can be used in this invention, A well-known method can be used. By performing the anodizing treatment, an oxide film is formed on the support.

  The anodized support may be sealed as necessary. The sealing treatment can be performed using a known method such as hot water treatment, boiling water treatment, water vapor treatment, sodium silicate treatment, dichromate aqueous solution treatment, nitrite treatment, ammonium acetate treatment and the like.

  Further, after performing these treatments, a water-soluble resin such as polyvinyl phosphonic acid, a polymer or copolymer having a sulfonic acid group in the side chain, polyacrylic acid, a water-soluble metal salt (for example, zinc borate) or Those having a primer such as a yellow dye or an amine salt are also suitable. Further, a sol-gel treated substrate having a functional group capable of causing an addition reaction by a radical as disclosed in JP-A-5-304358 is also preferably used.

<Preparation of lithographic printing plate material>
The above-mentioned photosensitive layer coating solution can be applied and dried on a support by a conventionally known method to prepare a lithographic printing plate material. Examples of the application method of the coating liquid include an air doctor coater method, a blade coater method, a wire bar method, a knife coater method, a dip coater method, a reverse roll coater method, a gravure coater method, a cast coating method, a curtain coater method, and an extrusion coater method. Can be mentioned.

  The drying temperature of the photosensitive layer is preferably in the range of 60 to 160 ° C, more preferably 80 to 140 ° C, and particularly preferably 90 to 120 ° C.

<Preparation of planographic printing plate>
The lithographic printing plate material is produced as a lithographic printing plate by the following process, and the lithographic printing plate is placed on an offset printing machine.

(Image exposure)
As a light source for recording an image on the planographic printing plate material of the present invention, it is preferable to use a laser beam having an emission wavelength of 370 to 440 nm.

As an exposure light source, for example, a He—Cd laser (441 nm), a combination of Cr: LiSAF and SHG crystal (430 nm) as a solid state laser, KNbO ₃ , a ring resonator (430 nm), and AlGaInN (350 to 450 nm) as a semiconductor laser system And AlGaInN semiconductor laser (commercially available InGaN-based semiconductor laser 400 to 410 nm).

  Laser exposure is suitable for direct writing without using a mask material because light exposure can be performed in the form of a beam according to image data. 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.

  Examples of laser scanning methods include cylindrical outer surface scanning, cylindrical inner surface scanning, and planar scanning. In the cylindrical outer surface scanning, laser exposure is performed while rotating a drum around which the recording material is wound, and the rotation of the drum is the main scanning and the movement of the laser light 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 from the inside, and a main scanning is performed in the circumferential direction by rotating a part or all of the optical system. Sub scanning is performed in the axial direction by linearly moving all of them in parallel with the drum axis. In plane scanning, a laser beam main scan is performed by combining a polygon mirror, a galvanometer mirror, and an fθ lens, and a sub-scan is performed by moving a recording medium. Cylindrical outer surface scanning and cylindrical inner surface scanning are easier to increase the accuracy of the optical system and are suitable for high-density recording.

In the present invention, image exposure is preferably performed with a plate surface energy (energy on the plate material) of 10 mJ / cm ² or more, and the upper limit is 500 mJ / cm ² . More preferably, it is 10-300 mJ / cm < ² >. For this energy measurement, for example, a laser power meter PDGDO-3W manufactured by Ophir Optronics can be used.

(Developer)
The exposed portion of the photosensitive layer subjected to image exposure is cured. This is preferably developed with an alkaline developer to remove unexposed portions and form an image. 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; Examples thereof include an alkali developer using an inorganic alkali agent such as sodium borate, potassium, ammonium, and sodium hydroxide, potassium, ammonium, and lithium.

  Moreover, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, mono-i-propylamine, di-i-propylamine, tri-i-propylamine, butylamine, monoethanolamine, diethanolamine, triethanolamine, Organic alkali agents such as mono-i-propanolamine, di-i-propanolamine, ethyleneimine, ethylenediamine, and pyridine can also be used.

  These alkali agents are used alone or in combination of two or more. In addition, an organic solvent such as an anionic surfactant, an amphoteric surfactant or alcohol can be added to the developer as necessary.

  Alkaline developers can also be prepared from developer concentrates such as granules and tablets.

  The developer concentrate may be evaporated to dryness once it is made into a developer, but preferably the materials are mixed by adding a small amount of water without adding water when mixing a plurality of materials. A method of concentrating with 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-6-266062, 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 material types, material mixing ratios, and the like.

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

(Automatic processor)
It is advantageous to use an automatic processor for developing the photosensitive lithographic printing plate material. The automatic developing machine is preferably provided with a mechanism for automatically replenishing the required amount of the developing replenisher to the developing bath, and preferably provided with a mechanism for discharging the developer exceeding a certain amount, preferably the developing bath. Is provided with a mechanism for automatically replenishing the required amount of water, preferably a mechanism for detecting plate passing, preferably a mechanism for estimating the processing area of the plate based on detection of plate passing. Preferably, a mechanism for controlling the replenishment amount and / or replenishment timing of the replenisher and / or water to be replenished based on the detection of the printing plate and / or the estimation of the processing area is provided, preferably Provided with a mechanism for controlling the temperature of the developer, preferably a mechanism for detecting the pH and / or conductivity of the developer, preferably supplemented based on the pH and / or conductivity of the developer Try Replenisher and / or water replenishment rate and / or controlling the replenishing timing mechanism is applied. The developer concentrate preferably has a function of once diluting and stirring with water. When there is a rinsing step after the development step, the rinsing water after use can be used as dilution water for the concentrate of the development concentrate.

  The automatic processor may have a pretreatment unit that immerses the plate in the pretreatment liquid before the development step. The pretreatment unit is preferably provided with a mechanism for spraying the pretreatment liquid on 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. Is provided with a mechanism for rubbing the plate surface with a roller brush. Water or the like is used as the pretreatment liquid.

(Post-processing)
The lithographic printing plate material developed with an alkaline developer is subjected to post-processing with a washing water, a rinse solution containing a surfactant, a finisher mainly composed of gum arabic or starch derivatives, or a protective gum solution. . These treatments can be used in various combinations. For example, development → water washing → a rinsing liquid treatment containing a surfactant, or development → water washing → finishing liquid treatment is preferable because of less fatigue of the rinsing liquid or finisher liquid. Further, a counter flow multi-stage treatment using a rinsing liquid or a finisher liquid is also a preferred embodiment.

  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, after development, a small amount of washing water of a certain amount is supplied to the plate surface for washing, and the waste solution is reused as dilution water for the developing solution stock solution. In such automatic processing, each processing solution can be processed while being replenished with each replenishing solution according to the processing amount, operating time, and the like. In addition, a so-called disposable treatment method in which treatment is performed with a substantially unused post-treatment liquid is also applicable. The lithographic printing plate obtained by such processing is loaded on an offset printing machine and used for printing a large number of sheets.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, the aspect of this invention is not limited to this. In the examples, “%” and “part” represent “% by mass” and “part by mass”, respectively, unless otherwise specified.

(Production of support)
An aluminum plate (material 1050, tempered H16) having a thickness of 0.3 mm was immersed in a 5% aqueous sodium hydroxide solution maintained at 65 ° C., degreased for 1 minute, and then washed with water. This degreased aluminum plate was neutralized by dipping in a 10% aqueous hydrochloric acid solution maintained at 25 ° C. for 1 minute, and then washed with water.

Next, the 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 100 A / dm ² , and then kept at 60 ° C. In addition, desmutting treatment was performed for 10 seconds in a 5% aqueous sodium hydroxide solution.

The desmutted roughened aluminum plate was anodized in a 15% sulfuric acid solution at 25 ° C., a current density of 10 A / dm ² , and a voltage of 15 V for 1 minute, and further with 1% polyvinylphosphonic acid. Hydrophilic treatment was performed at 75 ° C. to prepare a support.

  The center line average roughness (Ra) of the support surface was 0.65 μm.

[Preparation of lithographic printing plate materials]
On the support, a photosensitive layer coating solution 1 having the following composition was applied with a wire bar so as to have a dry weight of 1.5 g / m ² , dried at 95 ° C. for 1.5 minutes, and subsequently oxygen-blocked with the following composition. The layer coating solution 1 was applied with a wire bar so as to be 1.5 g / m ² when dried, and dried at 75 ° C. for 1.5 minutes to prepare a lithographic printing plate material (Sample Nos. 101 to 126).
(Photosensitive layer coating solution 1)
Reaction product of N-butyldiethanolamine / 1,3-bis (1-isocyanato-1-methylethyl) benzene / 2-hydroxyethyl methacrylate (1/2/2 molar ratio)
42.0 parts Triethylene glycol dimethacrylate 6.0 parts Methacrylic acid / methyl methacrylate (25/75 mass ratio) copolymer (molecular weight 36,000) 35.0 parts Sensitizing dye (described in Table 1) 1.0 Part 2,2'-bis (2-chlorophenyl) -4,5,4 ', 5'-tetraphenylbiimidazole 3.0 part 2-mercaptobenzothiazole 0.3 part N-phenylglycine benzyl ester 4.0 part Phthalocyanine pigment (MHI # 454: produced by Mikuni Dye Co., Ltd.) 3.5 parts 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (Sumilyzer GS: 0.2 parts 2,4,6-tris (dimethylaminomethyl) phenol 1.0 part bis (2,2,6,6-tetramethyl) Lu-4-piperidyl) sebacate 0.1 part Fluorine-based surfactant (F-178K: manufactured by Dainippon Ink & Co.) 0.5 part Siloxane-based surfactant (BYK337: manufactured by BYK Chemie) 0.9 part Methyl ethyl ketone 80 parts 820 parts of propylene glycol methyl ether.
(Oxygen barrier layer coating solution 1)
PVA (Cell Ball 103: manufactured by Celaneas) 85.0 parts Vinylpyrrolidone / vinyl acetate copolymer (Rubitec VA64W: manufactured by BASF)
15.0 parts Surfinol 465 (manufactured by Air Products) 0.2 parts water 900 parts.

  In the preparation of the samples 109 and 115, 2,2′-bis (2-chlorophenyl) -4,5,4 ′, 5′-tetraphenylbiimidazole was converted to η-cumene- (η-cyclopentadienyl) iron hexa Samples 121 and 122 were produced in the same manner except that the fluorophosphate was used.

  In the preparation of the samples 109 and 115, N-butyldiethanolamine / 1,3-bis (1-isocyanato-1-methylethyl) benzene / 2-hydroxyethyl methacrylate (1/2/2 molar ratio) reaction product was converted into M2. Samples 123 and 124 were produced in the same manner except that it was changed to −15.

  Samples 125 and 126 were prepared in the same manner as in the preparation of Samples 109 and 115 except that 2-mercaptobenzothiazole was excluded.

[Preparation of planographic printing plate]
Each prepared lithographic printing plate material was subjected to 2,400 dpi (dpi represents the number of dots per inch, that is, 2.54 cm) using a plate setter (NewsCTP: manufactured by ECRM) equipped with a light source of 405 nm and 60 mW. (Resolution).

  For the exposure pattern, original image data of 100% image portion, Times New Roman font, 3 to 10 point size, alphabet uppercase and lowercase letters were used.

Next, a preheating section set at 105 ° C., a pre-water washing section for removing the oxygen blocking layer, a developing solution having the following composition are filled, and the developing section whose temperature is adjusted to 30 ° C. and the developing solution adhering to the plate surface are removed. Developed with a CTP automatic developing machine (Raptor Polymer: made by Glunz & Jesen) equipped with a gum solution (GW-3: manufactured by Mitsubishi Chemical Co., Ltd. diluted twice) for protecting the water washing part and the image line part. A lithographic printing plate was obtained.
(Developer composition: aqueous solution containing the following additives)
A Potassium silicate 8.0 parts New Coal B-13SN (manufactured by Nippon Emulsifier Co., Ltd.) 3.0 parts Water 89.0 parts Potassium hydroxide pH = 12.3.

[Evaluation of planographic printing plate materials]
Each lithographic printing plate material was evaluated as follows.

"sensitivity"
In the 100% image area recorded on the plate surface of the lithographic printing plate, the minimum exposure energy amount at which no film reduction was observed was defined as the recording energy (μJ / cm ² ) and used as an index of sensitivity. The smaller the recording energy, the higher the sensitivity.

<Preservability>
After storing the lithographic printing plate material in a constant temperature bath at 55 ° C for 3 days, measure the sensitivity using the same method as above, calculate the percentage of the sensitivity before storage, calculate the change in sensitivity during storage, and store it. It was used as an index of sex. The closer to 100%, the smaller the fluctuation and the better the storage stability.

《Sludge amount》
ADVANTEC was developed as a running solution developed for one month (30 days) under the processing conditions in which 50 ml / m ^{2 of} replenishing replenisher was replenished and 25 m ^{2 of} lithographic printing plate material was treated per day using the automatic processor. No. 1 L was filtered through 2 (manufactured by Advantech Toyo Co., Ltd.), and the residue was sufficiently dried, and the mass was measured.

<Non-image area ink smear>
The developer replenisher was 50ml supplemented per 1 m ² under the processing conditions for 1 day 25 m ² treated planographic printing plate material, 1 month (30 days) was developed. After that, the lithographic printing plate was coated with a printing machine (Mitsubishi Heavy Industries, Ltd .: DAIYA1F-1), printing ink (soybean oil ink “Naturalis 100” manufactured by Dainippon Ink and Chemicals) and dampening water (Tokyo Ink Co., Ltd.). Printing was performed using H liquid SG-51 (density 1.5%). Ink stains in the non-image area of the 100th printed product from the printing were observed visually and with a magnifying glass, and evaluated according to the following five-step criteria.

◎: No smudges ○: Slight ink smudges are observed when observed with a magnifying glass △: Slight ink smudges can be confirmed with a magnifying glass, but can be used as a printed material ×: Small ink smudges observed with a magnifying glass Can be confirmed. Cannot be used as a printed material. XX: Ink stains can be visually confirmed on non-image areas. Cannot be used as printed material.

<Dye solubility>
The photosensitive layer coating solution was stirred and mixed, and then allowed to stand at room temperature for 1 hour. The presence or absence of a sensitizing dye that was precipitated without dissolving was visually observed, and the mass of the precipitate was measured.

A: All sensitizing dyes were completely dissolved B: Less than 10% by mass of sensitizing dye precipitated and remained C: 10% by mass or more of sensitizing dye precipitated and remained Table 1 summarizes the evaluation results. Show.

  As is apparent from Table 1, the samples 104 to 126 of the present invention have higher sensitivity than the comparative samples 101 to 103, have less fluctuation in sensitivity during storage, less developer sludge, and non-image area ink. It can be seen that the stain is good and the solubility of the sensitizing dye is also excellent. In particular, samples 109 and 115 using a hexaarylbiimidazole compound are better than samples 121 and 122.

Claims (7)

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 following general sensitizing dye A photosensitive lithographic printing plate material comprising a compound represented by the formula (1):

[Wherein, X ₁ and X ₂ each represent NR ₂ (R ₂ represents a hydrogen atom or a substituent), a sulfur atom or an oxygen atom. R ₁ represents an n-propyl group, an i-propyl group, an aliphatic group having 4 or more carbon atoms, an aromatic group, or a heterocyclic group. Q ₁ and Q ₂ each represent NR ₃ (R ₃ represents a hydrogen atom or a substituent), a sulfur atom or an oxygen atom. W ₁ represents a nonmetallic atom group necessary for forming a ring together with X ₂ . ] In Formula (1), the photosensitive planographic printing plate material of claim 1, wherein X ₂ is that a NR ₂ (R ₂ represents a hydrogen atom or a substituent). In Formula (1), a photosensitive lithographic printing plate material according to claim 1 or 2 Q ₁ is an oxygen atom, Q ₂ is characterized in that it is a sulfur atom. The photosensitive lithographic printing plate material according to any one of claims 1 to 3, wherein the polymerization initiator is a hexaarylbiimidazole compound. The photosensitive lithographic plate 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). 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 in the molecule Having a secondary amine structure and one hydroxyl group. The photosensitive lithographic printing plate material 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 (2). .

[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 structure. Represents a divalent substituent. ] The photosensitive lithographic printing plate material according to claim 1, wherein the photosensitive layer contains a thiol compound.