JP2008076948A - Photosensitive lithographic printing plate material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive lithographic printing plate material suitable for exposure with laser light of which the emission wavelength is 350-450 nm, having high sensitivity and excellent storage stability, less liable to produce sludge in development and ensuring little ink stain on a non-image area. <P>SOLUTION: The photosensitive lithographic printing plate material has on a support a photosensitive layer containing a polymerization initiator, a polymerizable ethylenic double bond-containing compound, a sensitizing dye and a polymer binder, wherein a compound represented by general formula (1-1) is contained as the sensitizing dye. In the formula, R<SB>1</SB>represents H, alkyl, cycloalkyl or aryl; and R<SB>11</SB>-R<SB>16</SB>each represent H or a substituent, provided that at least one of R<SB>11</SB>-R<SB>16</SB>is a group represented by general formula (1-2), wherein R<SB>17</SB>represents a substituent; and n1 represents an integer of 1-5. <P>COPYRIGHT: (C)2008,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 particularly to a photosensitive lithographic plate suitable for exposure with a laser beam having a wavelength of 350 to 450 nm. It relates to printing plate materials.

  In recent years, photosensitive lithographic printing plate materials capable of image exposure with a laser having a wavelength of 390 to 430 nm, which have improved safe light properties from the viewpoint of handleability of the printing plate, are known. And, a high-power and small-sized blue-violet laser with a wavelength of 390 to 430 nm can be easily obtained, and by developing a photosensitive lithographic printing plate suitable for this laser wavelength, a bright room has been developed. (For example, see Patent Documents 1, 2, and 3). Further, a printing plate material having improved safelight property under a yellow light, for example, containing biimidazole in a photosensitive layer is known (for example, see Patent Document 4), and further has high sensitivity and low sublimation. As a photopolymerizable 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 5).

On the other hand, it is known to use distyrylbenzene, phenylquinolone 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 Documents). 6-8). However, these photosensitive lithographic printing plate materials have problems such as insufficient sensitivity, large fluctuations in sensitivity over time, and sludge generated during development to cause ink stains in non-image areas.
JP 2000-35673 A JP 2000-98605 A JP 2001-264978 A JP 2001-194882 A JP 2004-137152 A JP 2003-295426 A JP 2002-287342 A International Publication No. 04/74929 Pamphlet

  The present invention has been made in view of the above problems, and its purpose is to synthesize a sensitizing dye in which a substituent is introduced into the phenyl group of phenylquinolone, and an emission wavelength by using the sensitizing dye is 350 to 450 nm. It is an object of the present invention to provide a photosensitive lithographic printing plate material that is suitable for exposure with a laser beam, has high sensitivity, is excellent in storability, is less prone to 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 formula (1-1):

[Wherein, R ₁ represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and R _{11 to} R ₁₆ represent a hydrogen atom or a substituent. However, at least one of R _{11 to} R ₁₆ is a group represented by the general formula (1-2). In the formula, R ₁₇ represents a substituent, and n1 represents an integer of 1 to 5. ]
2. 2. The photosensitive lithographic printing plate material as described in 1 above, wherein R _{17 in the} general formula (1-2) is an electron donating group.

  3. 3. The photosensitive lithographic printing plate material as described in 1 or 2 above, wherein the sensitizing dye is represented by the following general formula (2).

Wherein, R ₂₁ to R ₂₅ represents a hydrogen atom or a substituent, R ₂₆ represents a substituent, n2 is an integer of 1 to 5. R ₁ has the same meaning as R ₁ in the general formula (1-1). ]
4). 4. The photosensitive lithographic printing plate material as described in any one of 1 to 3 above, wherein the sensitizing dye is represented by the following general formula (3).

[Wherein R _{31 to} R ₃₄ represent a hydrogen atom or a substituent, R ₃₇ represents a substituent, n3 represents an integer of 1 to 5, and R ₃₅ and R ₃₆ represent a hydrogen atom, an alkyl group, a cycloalkyl. Represents a group or an aryl group. R ₁ has the same meaning as R ₁ in the general formula (1-1). ]
5. The photosensitive lithographic printing plate material as described in any one of 1 to 4 above, which contains a hexaarylbiimidazole compound as the polymerization initiator.

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

  7. 7. The photosensitive lithographic printing plate material as described in any one of 1 to 6, wherein the polymerizable ethylenic double bond-containing compound is a compound represented by the following general formula (4).

[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 having ]

  The above configuration of the present invention is suitable for exposure with a laser beam having an emission wavelength of 350 to 450 nm, is highly sensitive, has excellent storability, is less susceptible to sludge during development, and has less ink stains in non-image areas. A lithographic printing plate material 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. In the above, by using the compound represented by the general formula (1-1), (2) or (3) as the sensitizing dye, it is suitable for exposure with a laser beam having an emission wavelength of 350 to 450 nm and has high sensitivity. It was also found that a photosensitive lithographic printing plate material having excellent storage stability, less sludge during development, and less ink stains in non-image areas can be obtained.

  Hereinafter, the present invention will be described in detail.

[Sensitizing dye]
[Compound represented by formula (1-1)]
The present invention is characterized in that it contains the compound represented by the general formula (1-1) as a sensitizing dye for the photosensitive layer.

In the general formula (1-1), R _{11 to} R ₁₆ represent a hydrogen atom or a substituent, and at least one of R _{11 to} R ₁₆ is a group represented by the general formula (1-2). R ₁₇ represents a substituent. Examples of the substituent include alkyl groups (methyl, ethyl, isopropyl, hydroxyethyl, stearyl, dodecyl, eicosyl, docosyl, oleyl, etc.), cycloalkyl groups (cyclopropyl, cyclohexyl, etc.), aryl groups (phenyl, p-tetradecanyl). Oxyphenyl, o-octadecanylaminophenyl, naphthyl, hydroxyphenyl, etc.), hydroxy group, carboxy group, nitro group, trifluoromethyl group, amide group (acetamide, benzamide, etc.), carbamoyl group (methylcarbamoyl, butylcarbamoyl, Phenylcarbamoyl etc.), alkyloxycarbonyl groups (ethyloxycarbonyl, isopropyloxycarbonyl etc.), aryloxycarbonyl groups (phenyloxycarbonyl etc.), carbonyloxy groups (methyl) Rubonyloxy, propylcarbonyloxy, phenylcarbonyloxy, etc.), cyano group, halogen (chlorine atom, bromine atom, iodine atom, fluorine atom), alkoxy group (methoxy, ethoxy, butoxy, etc.), aryloxy group (phenoxy, etc.), Sulfonyl group (methanesulfonyl, p-toluenesulfonyl, etc.), alkylthio group (methylthio, ethylthio, butylthio, etc.), arylthio (phenylthio, etc.), sulfonamide group (methanesulfonamide, dodecylsulfonamide, p-toluenesulfonamide, etc.), A sulfamoyl group (methylsulfamoyl, phenylsulfamoyl etc.), an amino group, an alkylamino group (ethylamino, dimethylamino, hydroxyamino etc.) etc. are represented.

  Preferably, an alkyl group (methyl, ethyl, isopropyl, hydroxyethyl, stearyl, dodecyl, eicosyl, docosyl, oleyl, etc.), a cycloalkyl group (cyclopropyl, cyclohexyl etc.), an aryl group (phenyl, p-tetradecanyloxyphenyl, o-octadecanylaminophenyl, naphthyl, hydroxyphenyl, etc.), alkoxy groups (methoxy, ethoxy, butoxy, etc.), aryloxy groups (phenoxy, etc.), amino groups, alkylamino groups (ethylamino, dimethylamino, hydroxyamino, etc.) And more preferably an alkoxy group (methoxy, ethoxy, butoxy, etc.), an aryloxy group (phenoxy, etc.), an amino group, an alkylamino group (ethylamino, dimethylamino, hydroxyamino, etc.), an alkylthio group Methylthio, ethylthio, butylthio, etc.), an arylthio (such as phenylthio).

R ₁ is a hydrogen atom, an alkyl group (methyl, ethyl, isopropyl, hydroxyethyl, stearyl, dodecyl, eicosyl, docosyl, oleyl, etc.), a cycloalkyl group (cyclopropyl, cyclohexyl, etc.), an aryl group (phenyl, p-tetradeca). Nyloxyphenyl, o-octadecanylaminophenyl, naphthyl, hydroxyphenyl, etc.).

  The electron donating group represents a substituent having a Hammett's substituent constant σp value of less than 0, σp represents an electronic parameter, Med. Chem. 16, 1207 (1973) and J.A. Med. Chem. 20, 304 (1977).

[Compound represented by formula (2)]
In the general formula (2), R _{21 to} R ₂₅ represent a hydrogen atom or a substituent, and R ₂₆ represents a substituent. Examples of the substituent include alkyl groups (methyl, ethyl, isopropyl, hydroxyethyl, stearyl, dodecyl, eicosyl, docosyl, oleyl, etc.), cycloalkyl groups (cyclopropyl, cyclohexyl, etc.), aryl groups (phenyl, p-tetradecanyl). Oxyphenyl, o-octadecanylaminophenyl, naphthyl, hydroxyphenyl, etc.), hydroxy group, carboxy group, nitro group, trifluoromethyl group, amide group (acetamide, benzamide, etc.), carbamoyl group (methylcarbamoyl, butylcarbamoyl, Phenylcarbamoyl etc.), alkyloxycarbonyl groups (ethyloxycarbonyl, isopropyloxycarbonyl etc.), aryloxycarbonyl groups (phenyloxycarbonyl etc.), carbonyloxy groups (methyl) Rubonyloxy, propylcarbonyloxy, phenylcarbonyloxy, etc.), cyano group, halogen (chlorine atom, bromine atom, iodine atom, fluorine atom), alkoxy group (methoxy, ethoxy, butoxy, etc.), aryloxy group (phenoxy, etc.), Sulfonyl group (methanesulfonyl, p-toluenesulfonyl, etc.), alkylthio group (methylthio, ethylthio, butylthio, etc.), arylthio (phenylthio, etc.), sulfonamide group (methanesulfonamide, dodecylsulfonamide, p-toluenesulfonamide, etc.), A sulfamoyl group (methylsulfamoyl, phenylsulfamoyl etc.), an amino group, an alkylamino group (ethylamino, dimethylamino, hydroxyamino etc.) etc. are represented.

  Preferably, alkyl groups (methyl, ethyl, isopropyl, hydroxyethyl, stearyl, dodecyl, eicosyl, docosyl, oleyl, etc.), cycloalkyl groups (cyclopropyl, cyclohexyl, etc.), aryl groups (phenyl, p-tetradecanyloxyphenyl) , O-octadecanylaminophenyl, naphthyl, hydroxyphenyl, etc.), alkoxy groups (methoxy, ethoxy, butoxy, etc.), aryloxy groups (phenoxy, etc.), amino groups, alkylamino groups (ethylamino, dimethylamino, hydroxyamino) More preferably, alkoxy groups (methoxy, ethoxy, butoxy, etc.), aryloxy groups (phenoxy, etc.), amino groups, alkylamino groups (ethylamino, dimethylamino, hydroxyamino, etc.), alkylthio (Methylthio, ethylthio, butylthio, etc.), an arylthio (such as phenylthio).

R ₁ has the same meaning as R ₁ in the general formula (1-1).

[Compound represented by formula (3)]
In the general formula (3), R _{31 to} R ₃₄ represent a hydrogen atom or a substituent, and R ₃₇ represents a substituent. Examples of the substituent include alkyl groups (methyl, ethyl, isopropyl, hydroxyethyl, stearyl, dodecyl, eicosyl, docosyl, oleyl, etc.), cycloalkyl groups (cyclopropyl, cyclohexyl, etc.), aryl groups (phenyl, p-tetradecanyl). Oxyphenyl, o-octadecanylaminophenyl, naphthyl, hydroxyphenyl, etc.), hydroxy group, carboxy group, nitro group, trifluoromethyl group, amide group (acetamide, benzamide, etc.), carbamoyl group (methylcarbamoyl, butylcarbamoyl, Phenylcarbamoyl etc.), alkyloxycarbonyl groups (ethyloxycarbonyl, isopropyloxycarbonyl etc.), aryloxycarbonyl groups (phenyloxycarbonyl etc.), carbonyloxy groups (methyl) Rubonyloxy, propylcarbonyloxy, phenylcarbonyloxy, etc.), cyano group, halogen (chlorine atom, bromine atom, iodine atom, fluorine atom), alkoxy group (methoxy, ethoxy, butoxy, etc.), aryloxy group (phenoxy, etc.), Sulfonyl group (methanesulfonyl, p-toluenesulfonyl, etc.), alkylthio group (methylthio, ethylthio, butylthio, etc.), arylthio (phenylthio, etc.), sulfonamide group (methanesulfonamide, dodecylsulfonamide, p-toluenesulfonamide, etc.), A sulfamoyl group (methylsulfamoyl, phenylsulfamoyl etc.), an amino group, an alkylamino group (ethylamino, dimethylamino, hydroxyamino etc.) etc. are represented.

  Preferably, alkyl groups (methyl, ethyl, isopropyl, hydroxyethyl, stearyl, dodecyl, eicosyl, docosyl, oleyl, etc.), cycloalkyl groups (cyclopropyl, cyclohexyl, etc.), aryl groups (phenyl, p-tetradecanyloxyphenyl) , O-octadecanylaminophenyl, naphthyl, hydroxyphenyl, etc.), alkoxy groups (methoxy, ethoxy, butoxy, etc.), aryloxy groups (phenoxy, etc.), amino groups, alkylamino groups (ethylamino, dimethylamino, hydroxyamino) More preferably, alkoxy groups (methoxy, ethoxy, butoxy, etc.), aryloxy groups (phenoxy, etc.), amino groups, alkylamino groups (ethylamino, dimethylamino, hydroxyamino, etc.), alkylthio (Methylthio, ethylthio, butylthio, etc.), an arylthio (such as phenylthio).

R _1, has the same meaning as R ₁ in the general formula (1-1).

R ₃₅ and R _{36 each} represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and examples thereof include the same groups as R ₁ in the general formula (1-1).

  These compounds according to the present invention can be synthesized by known methods. Although a synthesis example is shown below, it is not limited to this.

  [Synthesis of Compound 1]

  The compound (1-a) 4.2g was melt | dissolved in 50 ml of acetonitrile, and 2.8g of triethylamine was added to ice-cooling. While cooling with ice, 5.1 g of the compound (1-b) dissolved in acetonitrile was added dropwise. After returning to room temperature after completion of the dropwise addition, the mixture was heated to 50 ° C. and stirred for 3 hours. After completion of the reaction, water was added and extracted with ethyl acetate. The solvent of the organic layer was removed under reduced pressure, separation and purification were performed by silica gel column chromatography, and recrystallization was performed with ethyl acetate to obtain 5.3 g (yield 67%) of (1-c).

  Next, 0.92 g of (1-c) was dissolved in 10 ml of methanol, 0.62 g of a 28% sodium methoxide methanol solution was added, and the mixture was stirred with heating under reflux for 5 hours. After completion of the reaction, the mixture was allowed to cool to room temperature, and the precipitate was filtered and dried. Recrystallization from acetonitrile gave 0.72 g (yield 83%) of compound (1). The structure was identified by NMR and MS spectra.

  The content of the compound represented by the general formula (1-1), (2) or (3) is preferably 0.1 to 10% by mass and more preferably 0.5 to 8% by mass with respect to the photosensitive layer. .

  Specific examples of the compound represented by the general formula (1-1), (2) or (3) of the present invention are shown below, but the present invention is not limited to these.

  As the sensitizing dye, in addition to the above-mentioned compounds, for example, JP-A Nos. 2000-98605, 2000-147773, 2000-206690, 2000-258910, 2000-309724, 2001-042524 Sensitizing dyes described in JP-A Nos. 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, monoalkyltriaryl borate compounds, An iron arene complex compound, a polyhalogen compound, and a biimidazole compound are preferably used. Among them, 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, a hexaarylbiimidazole (HABI, triaryl-imidazole dimer) compound 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 Patent Nos. 24,629, 107,792, US No. 4,410,621, European Patent No. 215,453 and German Patent No. 3,211,312.

  Preferred derivatives are, for example, 2,4,5,2 ', 4', 5'-hexaphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,5,4 ', 5'-tetraphenyl Biimidazole, 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-di Toxiphenyl) 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. More preferred specific examples include 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 (methylcyclopentadienyl) -Ti- -2,3,4,5,6-pentafluorophenyl, bis (methylcyclopentadienyl) -Ti-bis-2,3,5,6-tetrafluorophenyl, bis (methylcyclopentadienyl)- Ti-bis-2,6-difluorophenyl (IRUGACURE 727L: manufactured by Ciba Specialty Chemicals), bis (cyclopentadienyl) -bis (2,6-difluoro-3- (py-1-yl) phenyl) titanium ( IRUGACURE784: Ciba Specialty Chemicals), bis (cyclopentadienyl) -bis (2,4,6-trifluoro-3- (pyridin-1-yl) phenyl) titanium bis (cyclopentadienyl) -bis (2,4,6-trifluoro-3- (2-5-dimethylpy-1-yl) phenyl) titaniu Etc. The.

[Monoalkyltriaryl borate compound]
Examples of the monoalkyl triaryl borate compound include compounds described in JP-A Nos. 62-150242 and 62-143044, and more preferable specific examples include tetra-n-butylammonium-n-butyl. -Trinaphthalen-1-yl-borate, tetra-n-butylammonium-n-butyl-triphenyl-borate, tetra-n-butylammonium-n-butyl-tri- (4-tert-butylphenyl) -borate, Tetra-n-butylammonium-n-hexyl-tri- (3-chloro-4-methylphenyl) -borate, tetra-n-butylammonium-n-hexyl-tri- (3-fluorophenyl) -borate, etc. It is done.

[Iron arene complex compound]
Examples of the iron arene complex compound include compounds described in JP-A-59-219307, and more preferable specific examples include η-benzene- (η-cyclopentadienyl) iron hexafluorophosphate, η -Cumene- (η-cyclopentadienyl) iron hexafluorophosphate, η-fluorene- (η-cyclopentadienyl) iron hexafluorophosphate, η-naphthalene- (η-cyclopentadienyl) iron hexafluorophosphate, η-xylene- (η-cyclopentadienyl) iron hexafluorophosphate, η-benzene- (η-cyclopentadienyl) iron tetrafluoroborate, and the like.

[Polyhalogen compounds]
As the polyhalogen compound, a compound having a trihalogenmethyl group, a dihalogenmethyl group or a dihalomethylene group is preferably used, and in particular, a halogen compound represented by the following general formula (5) or (6) and the above group is an oxadiazole A compound substituted on a ring is preferably used.

  Among these, a halogen compound represented by the following general formula (5) or (6) is particularly preferably used.

Formula (5) R ¹ —CY ₂ — (C═O) —R ²
In the formula, R ¹ 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. R ² represents a monovalent substituent. R ¹ and R ² may be bonded to form a ring. Y represents a halogen atom.

Formula (6) CY ₃ — (C═O) —X—R ³
In the formula, R ³ represents a monovalent substituent. X represents —O— or —NR ⁴ —. R ⁴ represents a hydrogen atom or an alkyl group. R ³ and R ⁴ may be bonded to form a ring. Y represents a halogen atom. Among these, those having a polyhalogen acetylamide group are particularly preferably used.

  A compound in which a polyhalogenmethyl group is substituted on the oxadiazole ring is also preferably used. Furthermore, oxadiazole compounds described in JP-A-5-34904 and 8-240909 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 and diazo compounds, halogen compounds, 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-5-213861 and JP-A-5-255347; "Coordination Chemistry Review" 84, 85-277 (1988) And transition metal complexes containing a transition metal such as ruthenium described in JP-A-2-182701; 2,4,5-triarylimidazole dimer described in JP-A-3-209477; carbon tetrabromide, JP Organohalogen compounds described in 59-107344 Etc..

  The content of the polymerization initiator according to the present invention (total amount of the polymerization initiator) is preferably 0.1 to 20% by mass, and 0.5 to 15% by mass with respect to the polymerizable ethylenically unsaturated bond-containing compound. Is more 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 image-exposed photosensitive layer.

  In the present invention, reaction products of the following compounds (C1) to (C3) are particularly preferably used as the polymerizable ethylenic double bond-containing compound.

(C1) a compound containing at least one ethylenic double bond and one hydroxyl group in the molecule (C2) a diisocyanate compound (C3) a diol compound having a tertiary amine structure in the molecule, or an intramolecular Compounds having a secondary amine structure and one hydroxyl group each as (C1) include, for example, 2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate, 2-hydroxypropyl methacrylate.

Examples of (C2) include 1,3-bis (1-isocyanato-1-methylethyl) benzene, 1,3-diisocyanatobenzene, 1,3-diisocyanate-4-methylbenzene, 1,3 -Di (isocyanatomethyl) benzene,
Examples of (C3) include Nn-butyldiethanolamine, N-methyldiethanolamine, 1,4-di (2-dihydroxyethyl), N-ethyldiethanolamine and the like.

[Compound represented by formula (4)]
As the reaction product, a compound represented by the general formula 4 is particularly preferably used.

In General Formula 4, 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.

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 -, but are mentioned _{-CH 2 CH 2 -, - CH} 2 CH (CH 3) -, - CH (CH 3) CH 2 - is 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 (4) include the following compounds.

[Compound containing ethylenic double bond]
Examples of the polymerizable ethylenic double bond-containing compound include general radical polymerizable monomers, and polyfunctional monomers having a plurality of addition-polymerizable ethylenic double bonds commonly used in UV curable resins. And 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, Tetrahydrofurfuryloxyhexanolide acrylate, acrylate of ε-caprolactone adduct of 1,3-dioxane alcohol, monofunctional acrylic esters such as 1,3-dioxolane acrylate, or these acrylates with methacrylate, itaconate, crotonate, Methacrylic acid instead of maleate, itaconic acid, crotonic acid, maleic acid ester such as ethylene glycol Acrylate, triethylene glycol diacrylate, pentaerythritol diacrylate, hydroquinone diacrylate, resorcin diacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, diacrylate of neopentyl glycol hydroxypivalate, 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 -Ε-caprolactate of dioxane diacrylate, tricyclodecane dimethylol acrylate, tricyclodecane dimethylol acrylate Adducts, bifunctional acrylic esters such as diacrylate of 1,6-hexanediol diglycidyl ether, or methacrylic acid, itaconic acid, crotonic acid, malein in which these acrylates are replaced by methacrylate, itaconate, crotonate, maleate Acid esters such as trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, trimethylolethane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, Ε-caprolactone adduct of dipentaerythritol hexaacrylate, pyrogallolto Acrylic acid, propionic acid-dipentaerythritol triacrylate, propionic acid-dipentaerythritol tetraacrylate, polyfunctional acrylic acid ester acid such as hydroxypivalylaldehyde-modified dimethylolpropane triacrylate, or these acrylates as 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 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 preferably used. These prepolymers may be used alone or in combination of two or more, and may be used in admixture with the monomers and / or oligomers described above.

  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 obtained by introducing (meth) acrylic acid into a polyester obtained by combining polyhydric alcohols such as propane, pentaerythritol, sorbitol, 1,6-hexanediol, 1,2,6-hexanetriol Acrylates such as bisphenol A-epichlorohydrin- (meth) acrylic acid, phenol novolac-epichlorohydrin- (meth) acrylic acid, and epoxy acrylates in which (meth) acrylic acid is introduced into an epoxy resin, such as ethylene glycol-adipine Acid-tolylene diisocyanate-2-hydroxyethyl acrylate, polyethylene glycol-tolylene diisocyanate-2-hydroxyethyl acrylate, hydroxyethylphthalyl methacrylate-xylene diisocyanate, 1,2-polybutadiene glycol-tolylene diisocyanate-2-hydroxyethyl acrylate Of trimethylolpropane-propylene glycol-tolylene diisocyanate-2-hydroxyethyl acrylate In addition, urethane acrylates in which (meth) acrylic acid is introduced into urethane resins, for example, silicone resin acrylates such as polysiloxane acrylate and polysiloxane-diisocyanate-2-hydroxyethyl acrylate, and (meth) acryloyl in oil-modified alkyd resins. Examples thereof include prepolymers such as alkyd-modified acrylates having introduced groups 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 phosphate ester compounds 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 58-212994, 61-6649, 62-46688, 62-48589, 62-173295, 62-187092, 63-67189, JP-A-1 -244891 etc. can be mentioned, Furthermore, "Chemical product of 11290", Chemical Industry Daily, p. 286-p. 294, “UV-EB Curing Handbook (raw material)”, Kobunshi Publishing Co., p. The compounds described in 11 to 65 can also be suitably used in the present invention. Among these, compounds having two or more acrylic groups 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, 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 according to the present invention in the photosensitive layer is preferably 0.5 to 15.0% by mass, and 1.0 to 8.0% by mass with respect to the photosensitive layer. Is more preferable.

(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.

  Furthermore, the polymer binder can use the monomers described in the following (1) to (14) as copolymerization monomers.

(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-hydroxypentyl 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.

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

  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-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 adding a compound having a (meth) acryloyl group and an isocyanate group in the molecule to a hydroxyl group present in the molecule of the vinyl polymer is also high. Preferred as a molecular binder. Compounds having both an unsaturated bond and an isocyanate group in the molecule include vinyl isocyanate, (meth) acrylic isocyanate, 2- (meth) acryloyloxyethyl isocyanate, m- or p-isopropenyl-α, α'-dimethylbenzyl. Isocyanates are preferred, and (meth) acrylic isocyanate, 2- (meth) acryloyloxyethyl isocyanate and the like can be mentioned.

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

[Various additives]
In the photosensitive layer according to the present invention, in addition to the above-described components, in order to prevent unnecessary polymerization of the ethylenic double bond monomer that can be polymerized during the production or storage of the photosensitive lithographic printing plate material, It is desirable to add a polymerization inhibitor.

(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. If necessary, higher fatty acid derivatives such as behenic acid and behenic acid amide may be added to prevent polymerization inhibition due to oxygen, or it may be unevenly distributed on the surface of the photosensitive layer during the drying process after coating. Good. The amount of the higher fatty acid derivative added is preferably about 0.5 to 10% by mass of the total composition.

[Colorant]
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. Examples include those described in the revised new edition “Pigment Handbook”, edited by Japan Pigment Technology Association (Seikodo Shinkosha), Color Index Handbook, 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 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]
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-based surfactants are preferred.

  In order to improve the physical properties of the cured film, additives such as an inorganic filler, a plasticizer 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.

  Examples of the solvent used in preparing the photosensitive layer coating solution for the photosensitive layer according to the present invention include, for example, alcohol: polyhydric alcohol derivatives, sec-butanol, isobutanol, n-hexanol, benzyl alcohol, Diethylene glycol, triethylene glycol, tetraethylene glycol, 1,5-pentanediol, ethers: propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ketones, aldehydes: diacetone alcohol, cyclohexanone Preferred examples include methylcyclohexanone and esters: ethyl lactate, butyl lactate, diethyl oxalate, methyl benzoate and the like.

  Although the photosensitive layer coating solution has been described above, the photosensitive layer according to the present invention is formed by coating on a support using the photosensitive layer.

Photosensitive layer according to the present invention as the amount per on the support, preferably from 0.1 to 10 g / m ^2, in particular 0.5 to 5 g / m ² is preferred.

[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.

  This protective layer (oxygen barrier layer) is preferably highly soluble in a developer (described below, generally an aqueous alkali solution) described below, and specific examples include polyvinyl alcohol and polyvinyl pyrrolidone. Polyvinyl alcohol has an effect of suppressing permeation of oxygen, and polyvinyl pyrrolidone 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 photosensitive lithographic printing plate material of the present invention, 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. It is. Preferred protective layer compositions include 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 and applied to 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, 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 according to the present invention is a plate or film that can carry a 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 a metal plate such as aluminum, stainless steel, chromium and nickel, or a laminate obtained by laminating or vapor-depositing the above metal thin film on a plastic film such as a polyester film, a polyethylene film and a polypropylene film. .

  Moreover, although what hydrophilized the surface, such as a polyester film, a vinyl chloride film, a nylon film, etc. can be used, an aluminum support body is used preferably.

  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 a metal such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel, titanium, sodium, iron, and aluminum is used. Further, the aluminum support having a roughened surface is used for imparting 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 caustic soda can be used for the degreasing treatment. When an alkaline aqueous solution such as caustic soda 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 caustic soda is used for the degreasing treatment, smut is generated on the surface of the support. In this case, it is immersed in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid, or a mixed acid thereof and desmutted. It is preferable to perform the 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. Further, after the immersion treatment with an alkaline aqueous solution, it is preferable to carry out a neutralization treatment by immersion in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid or a mixed acid thereof.

  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. You may roughen.

  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. These sealing treatments can be performed using known methods such as hot water treatment, boiling water treatment, water vapor treatment, sodium silicate treatment, dichromate aqueous solution treatment, nitrite treatment, and ammonium acetate treatment.

  Furthermore, after performing these treatments, a water-soluble resin such as polyvinylphosphonic 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 Also suitable are those coated with a yellow dye, amine salt or the like. Further, 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 is also preferably used.

[Preparation of photosensitive lithographic printing plate material]
The 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.

  Examples of coating methods for the coating liquid 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 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 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.

(Image exposure)
As a light source for recording an image on the photosensitive lithographic 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 a light source for exposing the photosensitive lithographic printing plate material of the present invention, for example, a He—Cd laser (441 nm), a combination of Cr: LiSAF and SHG crystals (430 nm) as a solid laser, and a semiconductor laser system as KNbO ₃ , Examples thereof include a ring resonator (430 nm), AlGaInN (350 nm to 450 nm), and an 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 OphirOptics 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 An alkali developer using an inorganic alkaline agent such as sodium borate, potassium, ammonium; sodium hydroxide, potassium, ammonium and lithium;

  Also, 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 it is preferable to mix the materials by adding a small amount of water without adding water when mixing multiple 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 is provided, 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 solution and / or water to be replenished based on detection of the printing plate and / or estimation of the processing area is provided. Is 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 based on the pH and / or conductivity of the developer. Supplement Mechanism for controlling the replenishment amount and / or replenishment timing of replenishment solution and / or water to try to have been granted. Moreover, it is preferable to have a function of once diluting and stirring the developer concentrate 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-like brush. Water or the like is used as the pretreatment liquid.

[Post-processing]
The photosensitive lithographic printing plate material that has been developed with an alkaline developer is subjected to post-treatment with a washing water, a rinse solution containing a surfactant, a finisher or a protective gum solution mainly composed of gum arabic or starch derivatives. Is done. These treatments can be used in various combinations. For example, the treatment with a rinsing solution containing development->washing-> surfactant or the development->washing-> finisher solution is preferable because of less fatigue of the rinse solution and the finisher solution. Further, a countercurrent multistage treatment using a rinse 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 a certain amount of a small amount of washing water is supplied to the plate surface after the development to wash it, and the waste solution is reused as dilution water for the developer stock solution. In such automatic processing, processing can be performed while each replenisher is replenished with each replenisher 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” unless otherwise specified.

Example [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 surface-roughened aluminum plate subjected to desmut treatment 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.

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

[Preparation of photosensitive lithographic printing plate material]
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 samples 101 to 121 of photosensitive lithographic printing plate materials.

[Photosensitive layer coating solution 1]
Reaction product (M2-15) of Nn-butyldiethanolamine (1 mol), 1,3-bis (1-isocyanato-1-methylethyl) benzene (2 mol), 2-hydroxyethyl methacrylate (2 mol) ) 42.0 parts Triethylene glycol dimethacrylate 6.0 parts Copolymer of methacrylic acid and methyl methacrylate in a mass ratio of 25:75 (molecular weight 36000) 35.0 parts Sensitizing dye (described in Table 1) 4.0 parts 2,2'-bis (2-chlorophenyl) -4,5,4 ', 5'-tetraphenylbiimidazole 3.0 parts 2-mercaptobenzothiazole 0.3 part N-phenylglycine benzyl ester 4.0 parts phthalocyanine Pigment (MHI # 454: manufactured by Mikuni Color Co., Ltd.) 3.5 parts 2-t-butyl-6- (3-t-butyl-2-hydroxy-5- Methylbenzyl) -4-methylphenyl acrylate (Sumilyzer GS: manufactured by Sumitomo 3M) 0.2 part 2,4,6-tris (dimethylaminomethyl) phenol 1.0 part bis (2,2,6,6-tetra Methyl-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 liquid 1]
Polyvinyl alcohol (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 2,2'-bis (2-chlorophenyl) -4,5 in preparation of samples 104 and 105 of the photosensitive lithographic printing plate material Samples 115 and 116 were prepared in the same manner except that, 4 ', 5'-tetraphenylbiimidazole was replaced with η-cumene- (η-cyclopentadienyl) iron hexafluorophosphate.

  In the preparation of the samples 104 and 105 of the photosensitive lithographic printing plate material, Nn-butyldiethanolamine (1 mol), 1,3-bis (1-isocyanato-1-methylethyl) benzene (2 mol), 2 Samples 117 and 118 of the photosensitive lithographic printing plate material were prepared in the same manner except that the reaction product of -hydroxyethyl methacrylate (2 mol) was replaced with (M2-15).

[Evaluation of photosensitive lithographic printing plate materials]
〔sensitivity〕
Using the plate setter (NewsCTP: manufactured by ECRM) equipped with a light source of 405 nm and 60 mW, the produced photosensitive lithographic printing plate material is exposed at 2400 dpi (dpi represents the number of dots per 2.54 cm). went.

  For the exposure pattern, original image data having a 100% image portion, Times New Rohman font, 3 to 10 point size, and uppercase and lowercase letters without alphabetic characters 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 processing unit for gum washing (GW-3: manufactured by Mitsubishi Chemical Co., Ltd., twice diluted) 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 Caustic potash pH = 12.3 [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.

[Sensitivity fluctuation during storage]
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 No. was used as a running solution developed for 1 month (30 days) under the processing conditions in which the above-mentioned automatic developing machine was used to replenish the development replenisher 50 ml per 1 m ² and the photosensitive lithographic printing material was processed 25 m ² per day. . 1 L was filtered with 2 (manufactured by Advantech Toyo Co., Ltd.), and the residue was sufficiently dried, and then the mass was measured.

[Ink stains on non-image areas]
The developer replenisher 1 month (30 days) the 1 m ² per 50ml supplemented photosensitive lithographic printing material under the processing conditions for 1 day 25 m ² treated were developed. Thereafter, the lithographic printing plate was coated with a printing press (DAIYA1F-1 manufactured by Mitsubishi Heavy Industries, Ltd.), printing ink (soybean oil ink “Naturalis 100” manufactured by Dainippon Ink and Chemicals) and dampening water (Tokyo Ink). Printing was performed using H liquid SG-51 concentration (1.5%). 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.

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

  The evaluation results are shown in Table 1.

  From Table 1, compared with Comparative Samples 101 to 103, Samples 104 to 118 of the present invention have higher sensitivity, less change in sensitivity during storage, less developer sludge, and better ink stains in non-image areas. I understand that there is. In particular, the samples 104 and 105 using the hexaarylbiimidazole compound are better than the samples 115 and 116.

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 formula (1-1):

[Wherein, R ₁ represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and R _{11 to} R ₁₆ represent a hydrogen atom or a substituent. However, at least one of R _{11 to} R ₁₆ is a group represented by the general formula (1-2). In the formula, R ₁₇ represents a substituent, and n1 represents an integer of 1 to 5. ] The photosensitive lithographic printing plate material according to claim 1, wherein R _{17 in the} general formula (1-2) is an electron donating group. The photosensitive lithographic printing plate material according to claim 1 or 2, wherein the sensitizing dye is represented by the following general formula (2).

Wherein, R ₂₁ to R ₂₅ represents a hydrogen atom or a substituent, R ₂₆ represents a substituent, n2 is an integer of 1 to 5. R ₁ has the same meaning as R ₁ in the general formula (1-1). ] The photosensitive lithographic printing plate material according to any one of claims 1 to 3, wherein the sensitizing dye is represented by the following general formula (3).

[Wherein R _{31 to} R ₃₄ represent a hydrogen atom or a substituent, R ₃₇ represents a substituent, n3 represents an integer of 1 to 5, and R ₃₅ and R ₃₆ represent a hydrogen atom, an alkyl group, a cycloalkyl. Represents a group or an aryl group. R ₁ has the same meaning as R ₁ in the general formula (1-1). ] The photosensitive lithographic printing plate material according to any one of claims 1 to 4, wherein the polymerization initiator contains a hexaarylbiimidazole compound. The photosensitive lithographic plate according to any one of claims 1 to 5, wherein the polymerizable ethylenic double bond-containing compound is a reaction product of the following compounds (C1) to (C3). Printing plate material.
(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. The photosensitive lithographic printing plate material according to any one of claims 1 to 6, wherein the polymerizable ethylenic double bond-containing compound is a compound represented by the following general formula (4): .

[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 having ]