JP2006292779A - Photosensitive lithographic printing plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive lithographic printing plate which excels in storage stability and ensures little variation of dot area ratio due to long-term storage even in laser exposure under use of an FM screen. <P>SOLUTION: The photosensitive lithographic printing plate has, on a hydrophilic support, a photopolymerizable photosensitive layer containing (1) a sensitizing dye having an absorption maximum in a wavelength region of 360-450 nm, (2) a hexaarylbisimidazole compound, (3) an addition polymerizable compound having an ethylenically unsaturated double bond, (4) a binder polymer and (5) a urethane group-containing compound represented by formula (1), wherein R<SB>1</SB>denotes a 1-20C alkyl group or an aromatic group; R denotes H, a 1-24C linear or branched alkyl group, an alkyl group having a 5-20C alicyclic structure, a group having a 6-20C aromatic ring, a hydroxyl group, an amino group, a substituted amino group, a carboxyl group, an alkoxy group or the like; n represents an integer of 0-5; and when a plurality of symbols R exist, they may be the same or different. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a photosensitive lithographic printing plate, and more particularly to a photosensitive lithographic printing plate suitable for drawing with a laser beam and suitable for high-definition AM screen printing or FM screen printing having a screen line number of 200 lines or more.

Conventionally, a lithographic printing plate has a structure in which a photosensitive resin layer is provided on a support having a hydrophilic surface. As a plate-making method, usually, surface exposure (mask exposure) is performed through a lithographic film. The desired printing plate was obtained by removing the non-image area with a developer. However, computer-to-plate that directly exposes the plate surface without using a lith film by scanning the plate surface according to digitized image information with highly directional light such as laser light by recent digitization technology. (CTP) technology has been developed and photosensitive lithographic printing plates adapted to this have been developed.
Examples of the photosensitive lithographic printing plate suitable for exposure with the laser beam include a photosensitive lithographic printing plate using a polymerizable photosensitive layer. This is because the polymerizable photosensitive layer can be easily increased in sensitivity as compared with other conventional photosensitive layers by selecting a photopolymerization initiator or a polymerization initiator system (hereinafter also simply referred to as an initiator or an initiator system).

However, since the photosensitive lithographic printing plate as described above is drawn with a laser beam, the edge of the image depends on the shape of the energy distribution of the laser beam, and an insufficiently polymerized region is formed due to an insufficient exposure amount. . For this reason, the sharpness of the image edge is impaired, leading to a decrease in resolution. In addition, such poorly polymerized image edges have poor removal due to the alkali concentration of the developer and the state of the developing brush in the development processing step, and the in-plane variation in the halftone dot area of the plate making plate is increased. It was.
Furthermore, since such a printing plate uses a support having irregularities formed on the surface by electrolytic treatment or brush treatment to ensure hydrophilicity, the printing plate is further scattered by reflected light during laser exposure. Image quality and sharpness are impaired, and the reproducibility of the shadow portion is greatly reduced.

  On the other hand, in recent years, the demand for high-definition AM screen printing and FM screen printing has increased in the CTP technology, and the resolution of the lithographic printing original plate has become an important performance.

  The FM (Frequency Moduration) screen is a system in which minute dots of about 20 microns are randomly arranged regardless of the screen angle and the number of lines, and the density gradation is expressed by the dot density per unit area. Features of this FM screen printed matter include no interference moiré or rosette pattern, no tone jump in the halftone area near 50%, and halftone dots are small. The colors appear bright.

  An AM (Amplitude Moduration) screen is a system in which halftone dots are regularly arranged at an angle with respect to the FM screen and the density gradation is expressed by the size of the halftone dots per unit area. The number of AM screen lines in Japan is 175 lines per inch. On the other hand, what uses a screen line number of 200 lines or more is generally called high definition.

  Features of high-definition printed materials include a reduction in moire and rosetta patterns, an improvement in image texture, a sense of existence, and an improvement in reproducibility of details.

  Patent Document 1 (Japanese Patent Laid-Open No. 2003-295426) discloses a lithographic printing plate comprising a combination of a hexaarylbisimidazole compound as a photosensitive layer, a compound containing a mercapto group, and a sensitizing dye having a fluorescent whitening effect. However, the non-image area is easily covered by the heat treatment performed during the development process, and the storage stability is not sufficient. In particular, the sensitivity fluctuation due to the storage conditions is large, and even if drawing and developing under the same conditions, the FM screen There is a problem that the halftone dot area ratio is not constant, or non-image areas are covered, which causes unevenness due to development, and in particular, there is a problem that the unevenness of the flat screen of the FM screen is severe. It was difficult to use an FM screen.

JP 2003-295426 A

  Provided is a photosensitive lithographic printing plate which has excellent storage stability and has little fluctuation in the dot area ratio due to storage over time even in laser exposure using an FM screen.

As a result of intensive studies, the present inventors have succeeded in achieving the object with the following configuration.
That is, a photosensitive lithographic printing plate having a photopolymerizable photosensitive layer containing the following (i) to (v) on a hydrophilic support.
(I) Sensitizing dye having absorption maximum in a wavelength range of 360 nm to 450 nm (ii) Photopolymerization initiator (iii) Addition polymerizable compound having ethylenically unsaturated double bond (iv) Binder polymer (v) General formula A urethane group-containing compound represented by (1).

In the formula, R ₁ represents an alkyl group or an aromatic group having 1 to 20 carbon atoms, R represents a hydrogen atom, a linear alkyl group or branched alkyl group having 1 to 24 carbon atoms, alicyclic of 5 to 20 carbon atoms An alkyl group having a structure, a group having an aromatic ring having 6 to 20 carbon atoms, a hydroxyl group, an amino group, a substituted amino group, a carboxyl group, an alkoxyl group, or —C (═O) O—Ra or —OC (═O ) -Ra represents a group.
Ra represents an alkyl group having 1 to 12 carbon atoms, an aromatic group, an alkyl-substituted aromatic group, or an alicyclic alkyl group.
n represents an integer of 0 to 5, and when a plurality of Rs are present, they may be the same or different.

  According to the present invention, a good negative photosensitive lithographic printing plate suitable for laser exposure is provided, particularly suitable for drawing with laser light, and high-definition AM screen printing or FM screen printing with a screen line number of 200 lines or more, particularly There is provided a photosensitive lithographic printing plate having good storage stability and good uniformity of halftone flat halftone unevenness using an FM screen.

[Photosensitive planographic printing plate]
The constitution of the photosensitive lithographic printing plate (lithographic printing plate precursor) having spectral sensitivity in the wavelength range of 360 nm to 450 nm used in the present invention will be described in order.

(Photopolymerizable photosensitive layer)
The photosensitive lithographic printing plate of the present invention contains the following components (i) to (v), and has a photopolymerizable photosensitive layer having spectral sensitivity in a wavelength range of at least 360 nm to 450 nm (hereinafter also simply referred to as a photosensitive layer). Have
(I) Sensitizing dye having absorption maximum in a wavelength range of 360 nm to 450 nm (ii) Photopolymerization initiator (iii) Addition polymerizable compound having ethylenically unsaturated double bond (iv) Binder polymer (v) General formula A urethane group-containing compound represented by (1).

In the formula, R ₁ represents an alkyl group or an aromatic group having 1 to 20 carbon atoms, R represents a hydrogen atom, a linear alkyl group or branched alkyl group having 1 to 24 carbon atoms, alicyclic of 5 to 20 carbon atoms An alkyl group having a structure, a group having an aromatic ring having 6 to 20 carbon atoms, a hydroxyl group, an amino group, a substituted amino group, a carboxyl group, an alkoxyl group, or —C (═O) O—Ra or —OC (═O ) -Ra represents a group.
Ra represents an alkyl group having 1 to 12 carbon atoms, an aromatic group, an alkyl-substituted aromatic group, or an alicyclic alkyl group.
n represents an integer of 0 to 5, and when a plurality of Rs are present, they may be the same or different.

Hereinafter, the components (i) to (v) will be described in detail.
[Sensitizing dye]
The sensitizing dye used in the photopolymerization type photosensitive lithographic printing plate used in the present invention is a sensitizing dye having an absorption maximum in a wavelength range of 360 nm to 450 nm. Examples of such a sensitizing dye include merocyanine dyes represented by the following general formula (2), benzopyrans and coumarins represented by the following general formula (3), and fragrances represented by the following general formula (4). Group ketones, anthracenes represented by the following general formula (5), and the like.

(In the formula, A represents —S— or —N (R ₆ ) —, R ₆ represents a monovalent non-metallic atomic group, Y represents a group with an adjacent A and an adjacent carbon atom. Represents a non-metallic atomic group forming a basic nucleus of the dye, X ₁ and X ₂ each independently represent a monovalent non-metallic atomic group, and X ₁ and X ₂ are bonded to each other to form an acidic nucleus of the dye. It may be formed.)

(In the formula, = Z represents a carbonyl group, a thiocarbonyl group, an imino group or an alkylidene group represented by the partial structural formula (a), and X ₁ and X ₂ have the same meaning as in the general formula (2); R _{7 to} R ₁₂ each independently represents a monovalent nonmetallic atomic group.)

(In the formula, Ar ₃ represents an aromatic group or a heteroaromatic group which may have a substituent, and R ₁₃ represents a monovalent nonmetallic atomic group. More preferred R ₁₃ represents an aromatic group or It is a heteroaromatic group, and Ar ₃ and R ₁₃ may be bonded to each other to form a ring.)

(In the formula, X ₃ , X ₄ and R _{14 to} R ₂₁ each independently represent a monovalent non-metallic atomic group, and more preferable X ₃ and X ₄ are electron donating groups having a negative Hammett's substituent constant. .)

In the general formulas (2) to (5), preferred examples of the monovalent nonmetallic atomic group represented by X ₁ to X ₄ and R ₆ to R ₂₁ include a hydrogen atom, an alkyl group (for example, a methyl group, Ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group, eicosyl group, isopropyl group, isobutyl group , S-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group, 2-norbornyl group, chloromethyl group , Bromomethyl group, 2-chloroethyl group, trifluoromethyl group, methoxymethyl group, methoxyethoxy Ethyl group, allyloxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl Group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxycarbonylethyl group, allyloxycarbonylbutyl group, chloro Phenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl Ru-N- (sulfophenyl) carbamoylmethyl group, sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoyl group Propyl group, N-methyl-N- (phosphonophenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphine group Onatobutyl group, tolylphosphonohexyl group, tolylphosphonatohexyl group, phosphonooxypropyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, syn Namyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, etc.), aryl group (for example , Phenyl group, biphenyl group, naphthyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, Acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group, Noxycarbonylphenyl group, N-phenylcarbamoylphenyl group, phenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl group, phosphonatophenyl group, etc.), heteroaryl group (for example, thiophene, thiathrene) , Furan, pyran, isobenzofuran, chromene, xanthene, phenoxazine, pyrrole, pyrazole, isothiazole, isoxazole, pyrazine, pyrimidine, pyridazine, indolizine, isoindolizine, indoyl, indazole, purine, quinolidine, isoquinoline, phthalazine , Naphthyridine, quinazoline, cynoline, pteridine, carbazole, carboline, phenanthrine, acridine, perimidine, phenanthroline, phthalazine, phenazazine, fu Noxazine, furazane, phenoxazine, etc.), alkenyl groups (eg, vinyl, 1-propenyl, 1-butenyl, cinnamyl, 2-chloro-1-ethenyl, etc.), alkynyl (eg, ethynyl, 1 -Propynyl group, 1-butynyl group, trimethylsilylethynyl group, etc.), halogen atom (-F, -Br, -Cl, -I), hydroxyl group, alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyl Dithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group , Carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoy Ruoxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group, acylamino group, N- Alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group, N′-arylureido group, N ′, N′-diarylureido group, N '-Alkyl-N'-arylureido group, N-alkylureido group, N-arylureido group, N'-alkyl-N-alkylureido group, N'-alkyl-N-arylureido group, N', N ' -Dialkyl-N-alkylureido groups, N ', N'-dialkyl-N-arylureido groups N′-aryl-N-alkylureido group, N′-aryl-N-arylureido group, N ′, N′-diaryl-N-alkylureido group, N ′, N′-diaryl-N-arylureido group, N'-alkyl-N'-aryl-N-alkylureido group, N'-alkyl-N'-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxy Carbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl Group, aryloxycarbonyl group, carbamoyl group, N-alkyl group Vamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group , Sulfo group (—SO ₃ H) and its conjugate base group (hereinafter referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfina Moyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfur group Famoyl group, N-aryl Sulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group (—PO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as phosphonate group), dialkylphosphine Phono group (—PO ₃ (alkyl) ₂ ), diaryl phosphono group (—PO ₃ (aryl) ₂ ), alkylaryl phosphono group (—PO ₃ (alkyl) (aryl)), monoalkyl phosphono group (— PO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkyl phosphonate group), monoaryl phosphono group (—PO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as aryl phosphonate group) ), Phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as phosphonatooxy group), dialkylphosphonooxy group (—OPO). ₃ (alkyl) ₂ ), diaryl phosphonooxy group (—OPO ₃ (aryl) ₂ ), alkylaryl phosphonooxy group (—OPO ₃ (alkyl) (aryl)), monoalkyl phosphonooxy group (—OPO ₃₎ H (alkyl)) and its conjugate base group (hereinafter referred to as alkylphosphonateoxy group), monoarylphosphonooxy group (—OPO ₃ H (aryl)) and its conjugate base group (hereinafter arylphosphonatooxy group) ), A cyano group, a nitro group, and the like. Among the above substituents, a hydrogen atom, an alkyl group, an aryl group, a halogen atom, an alkoxy group, and an acyl group are particularly preferable.

  In the general formula (2), as the basic nucleus of the dye formed in cooperation with A adjacent to Y and the adjacent carbon atom, a 5, 6 or 7-membered nitrogen-containing heterocyclic ring or sulfur-containing heterocyclic ring is Preferably, a 5- or 6-membered heterocyclic ring is preferable.

  Examples of nitrogen-containing heterocycles include L. G. Any of those known to constitute basic nuclei in merocyanine dyes described in Brooker et al., J. Am. Chem. Soc., 73, 5326-5358 (1951) and references are preferably used. be able to. Specific examples include thiazoles (for example, thiazole, 4-methylthiazole, 4-phenylthiazole, 5-methylthiazole, 5-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole, 4,5- Di (p-methoxyphenylthiazole), 4- (2-thienyl) thiazole, etc.), benzothiazoles (for example, benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 7- Chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 4-phenylbenzothiazole, 5-phenylbenzothiazole, 4-methoxybenzothiazole, 5-methoxybenzo Cheer , 6-methoxybenzothiazole, 5-iodobenzothiazole, 6-iodobenzothiazole, 4-ethoxybenzothiazole, 5-ethoxybenzothiazole, tetrahydrobenzothiazole, 5,6-dimethoxybenzothiazole, 5,6-di Oxymethylenebenzothiazole, 5-hydroxybenzothiazole, 6-hydroxybenzothiazole, 6-dimethylaminobenzothiazole, 5-ethoxycarbonylbenzothiazole, etc.), naphthothiazoles (for example, naphtho [1,2] thiazole, naphtho [2 , 1] thiazole, 5-methoxynaphtho [2,1] thiazole, 5-ethoxynaphtho [2,1] thiazole, 8-methoxynaphtho [1,2] thiazole, 7-methoxynaphtho [1,2] thiazole, etc.) , Chianafuteno 7 ′, 6 ′, 4,5-thiazole (for example, 4′-methoxythianaphtheno-7 ′, 6 ′, 4,5-thiazole, etc.), oxazole (for example, 4-methyloxazole, 5-methyloxazole) 4-phenyloxazole, 4,5-diphenyloxazole, 4-ethyloxazole, 4,5-dimethyloxazole, 5-phenyloxazole, etc.), benzoxazoles (benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole) 5-phenylbenzoxazole, 6-methylbenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 6-methoxybenzoxazole, 5-methoxybenzoxazole, 4-ethoxybenzoxazole, 5-chloroben Zoxazole, 6-methoxybenzoxazole, 5-hydroxybenzoxazole, 6-hydroxybenzoxazole, etc.), naphthoxazoles (eg, naphtho [1,2] oxazole, naphtho [2,1] oxazole, etc.), selenazoles ( For example, 4-methylselenazole, 4-phenylselenazole, etc.), benzoselenazoles (for example, benzoselenazole, 5-chlorobenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, tetrahydrobenzo Selenazole etc.), naphthoselenazoles (eg naphtho [1,2] selenazole, naphtho [2,1] selenazole etc.), thiazolines (eg thiazoline, 4-methylthiazoline etc.), 2-quinolines (eg Quinoline, 3- Tilquinoline, 5-methylquinoline, 7-methylquinoline, 8-methylquinoline, 6-chloroquinoline, 8-chloroquinoline, 6-methoxyquinoline, 6-ethoxyquinoline, 6-hydroxyquinoline, 8-hydroxyquinoline, etc.), 4 -Quinolines (eg, quinoline, 6-methoxyquinoline, 7-methylquinoline, 8-methylquinoline, etc.), 1-isoquinolines (eg, isoquinoline, 3,4-dihydroisoquinoline, etc.), 3-isoquinolines (eg, , Isoquinoline, etc.), benzimidazoles (eg, 1,3-diethylbenzimidazole, 1-ethyl-3-phenylbenzimidazole, etc.), 3,3-dialkylindolenins (eg, 3,3-dimethylindolenin, 3,3,5-trimethylindolenine, 3,3 7, - trimethyl indolenine, etc.), 2-pyridines (e.g., pyridine, 5-methyl-pyridine, etc.), 4-pyridine (for example, a pyridine, etc.) or the like.

Examples of the sulfur-containing heterocycle include a dithiol partial structure in dyes described in JP-A-3-296759.
Specific examples include benzodithiols (for example, benzodithiol, 5-t-butylbenzodithiol, 5-methylbenzodithiol, etc.), naphthodithiols (for example, naphtho [1,2] dithiol, naphtho [2,1] Dithiols, etc.), dithiols (for example, 4,5-dimethyldithiols, 4-phenyldithiols, 4-methoxycarbonyldithiols, 4,5-dimethoxycarbonylbenzodithiols, 4,5-ditrifluoromethyldithiols, 4 , 5-dicyanodithiol, 4-methoxycarbonylmethyldithiol, 4-carboxymethyldithiol and the like.

  As mentioned above, for the sake of convenience, the description used in the description of the heterocyclic ring has conventionally used the name of the heterocyclic mother skeleton, but when forming the basic skeleton partial structure of the sensitizing dye, for example, in the case of the benzothiazole skeleton It is introduced in the form of an alkylidene type substituent with one degree of unsaturation, such as a 3-substituted-2 (3H) -benzothiazolylidene group.

  Of the sensitizing dyes having an absorption maximum in the wavelength range of 360 nm to 450 nm, a dye more preferable from the viewpoint of high sensitivity is a dye represented by the following general formula (6).

(In General Formula (6), A represents an aromatic ring or a heterocyclic ring which may have a substituent, and X represents ═O, ═S, or ═N—R _5. R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and A and R ₃ and R ₄ and R ₅ each form an aliphatic or aromatic ring with each other. May be combined.)

The general formula (6) will be described in more detail. R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or a monovalent nonmetallic atomic group, preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, substituted or non-substituted It represents a substituted aryl group, a substituted or unsubstituted aromatic heterocyclic residue, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, a hydroxyl group, and a halogen atom.

Preferable examples of R ₃ , R ₄ and R ₅ will be specifically described. Examples of preferable alkyl groups include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, Butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, s-butyl, Examples thereof include t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group and 2-norbornyl group. Of these, linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 5 to 10 carbon atoms are more preferable.

  As the substituent of the substituted alkyl group, a monovalent nonmetallic atomic group excluding a hydrogen atom is used. Preferred examples include halogen atoms (—F, —Br, —Cl, —I), hydroxyl groups, and alkoxy groups. , Aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino Group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy , Arylsulfoxy group, an acylthio group, an acylamino group, N- alkylacylamino group, N- arylacylamino group, a ureido group, N'- alkylureido group, N ', N'- dialkyl ureido group,

  N'-arylureido group, N ', N'-diarylureido group, N'-alkyl-N'-arylureido group, N-alkylureido group, N-arylureido group, N'-alkyl-N-alkylureido Group, N′-alkyl-N-arylureido group, N ′, N′-dialkyl-N-alkylureido group, N ′, N′-dialkyl-N-arylureido group, N′-aryl-N-alkylureido group Group, N′-aryl-N-arylureido group, N ′, N′-diaryl-N-alkylureido group, N ′, N′-diaryl-N-arylureido group, N′-alkyl-N′-aryl -N-alkylureido group, N'-alkyl-N'-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonyl Mino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl Group, acyl group, carboxyl group,

Alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, An alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfo group (—SO ₃ H) and its conjugate base group (hereinafter referred to as a sulfonate group), an alkoxysulfonyl group, an aryloxysulfonyl group, a sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphono Group (—PO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as phosphonate group),

Dialkyl phosphono group (—PO ₃ (alkyl) ₂ ), diaryl phosphono group (—PO ₃ (aryl) ₂ ), alkylaryl phosphono group (—PO ₃ (alkyl) (aryl)), monoalkyl phosphono group (—PO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkylphosphonate group), monoarylphosphono group (—PO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as arylphosphonate) Group), phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as phosphonatooxy group), dialkyl phosphonooxy group (—OPO ₃ (alkyl) ₂ ), diaryl phosphono An oxy group (—OPO ₃ (aryl) ₂ ), an alkylarylphosphonooxy group (—OPO ₃ (alkyl) (aryl)), a monoalkylphosphonooxy group (—OPO ₃ H (a lkyl)) and its conjugate base group (hereinafter referred to as alkylphosphonatooxy group), monoarylphosphonooxy group (—OPO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as arylphosphonatooxy group). ), Cyano group, nitro group, aryl group, heteroaryl group, alkenyl group, alkynyl group.

  Specific examples of the alkyl group in these substituents include the above-described alkyl groups, and specific examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, a mesityl group, and a cumenyl group. , Chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylamino Phenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, phenyl group Cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl phenyl group, phosphonophenyl phenyl group and the like.

As a preferred heteroaryl group as R ₃ , R ₄ and R ₅ , a monocyclic or polycyclic aromatic ring containing at least one of nitrogen, oxygen and sulfur atoms is used. Examples of particularly preferred heteroaryl groups Is, for example, thiophene, thiathrene, furan, pyran, isobenzofuran, chromene, xanthene, phenoxazine, pyrrole, pyrazole, isothiazole, isoxazole, pyrazine, pyrimidine, pyridazine, indolizine, isoindolizine, indolizine, indazole, indazole, Purine, quinolidine, isoquinoline, phthalazine, naphthyridine, quinazoline, sinoline, pteridine, carbazole, carboline, phenanthrine, acridine, perimidine, phenanthrolin, phthalazine, phenalazine, phenoxazine, furazane And phenoxazine and the like, and these may be further benzo-fused or may have a substituent.

Examples of preferred alkenyl groups for R ₃ , R ₄ and R ₅ include vinyl group, 1-propenyl group, 1-butenyl group, cinnamyl group, 2-chloro-1-ethenyl group and the like, and alkynyl Examples of the group include ethynyl group, 1-propynyl group, 1-butynyl group, trimethylsilylethynyl group and the like. Examples of G ₁ in the acyl group (G ₁ CO—) include a hydrogen atom, and the above alkyl group and aryl group. Among these substituents, even more preferred are halogen atoms (—F, —Br, —Cl, —I), alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, N-alkylamino groups, N, N— Dialkylamino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group Group, N-arylsulfa Yl group, N-alkyl-N-arylsulfamoyl group, phosphono group, phosphonate group, dialkyl phosphono group, diaryl phosphono group, monoalkyl phosphono group, alkyl phosphonate group, monoaryl phosphono group, aryl phosphine group Examples include an onato group, a phosphonooxy group, a phosphonateoxy group, an aryl group, and an alkenyl group.

On the other hand, examples of the alkylene group in the substituted alkyl group include divalent organic residues obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. Can include linear alkylene groups having 1 to 12 carbon atoms, branched chains having 3 to 12 carbon atoms, and cyclic alkylene groups having 5 to 10 carbon atoms.

Specific examples of preferable substituted alkyl groups as R ₃ , R ₄ and R ₅ obtained by combining the substituent with an alkylene group include chloromethyl group, bromomethyl group, 2-chloroethyl group, trifluoromethyl group, methoxy Methyl group, methoxyethoxyethyl group, allyloxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N -Cyclohexylcarbamoyloxyethyl group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxycarboni Ruethyl group, allyloxycarbonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl- N- (sulfophenyl) carbamoylmethyl group,

  Sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-N- (phosphono Phenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphosphonohexyl group, tolylphosphine group Onatohexyl group, phosphonooxypropyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, cinnamyl group, allyl group, 1-propenylmethyl group, 2- Thenyl group, 2-methylallyl group, 2-methyl propenyl methyl group, 2-propynyl group, 2-butynyl, 3-butynyl, and the like.

Specific examples of preferred aryl groups as R ₃ , R ₄ and R ₅ include those in which 1 to 3 benzene rings form a condensed ring, and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Specific examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. Among these, a phenyl group and a naphthyl group are more preferable. .

Specific examples of preferred substituted aryl groups as R ₃ , R ₄ and R ₅ include those having a monovalent nonmetallic atomic group excluding a hydrogen atom as a substituent on the ring-forming carbon atom of the aryl group. It is done. Examples of preferred substituents include the alkyl groups, substituted alkyl groups, and those previously shown as substituents in the substituted alkyl group. Preferred examples of such a substituted aryl group include biphenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, fluorophenyl group, chloromethylphenyl group, trifluoromethylphenyl group. Hydroxyphenyl group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, Benzoyloxyphenyl group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group,

  Acetylaminophenyl group, N-methylbenzoylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-di Propylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group, N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoyl Phenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phos Onatophenyl group, diethylphosphonophenyl group, diphenylphosphonophenyl group, methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonatophenyl group, allyl group, 1-propenylmethyl group, 2 -Butenyl group, 2-methylallylphenyl group, 2-methylpropenylphenyl group, 2-propynylphenyl group, 2-butynylphenyl group, 3-butynylphenyl group and the like can be mentioned.

Next, A in the general formula (6) will be described. A represents an aromatic ring or a heterocyclic ring which may have a substituent. Specific examples of the aromatic ring or heterocyclic ring which may have a substituent include R ₃ and R in the general formula (6). It includes the same as those described for ₄ and R _5.

  The sensitizing dye represented by the general formula (6) of the present invention includes an acidic nucleus as shown above, an acidic nucleus having an active methylene group, a substituted or unsubstituted aromatic ring or heterocyclic ring, These can be synthesized by referring to Japanese Patent Publication No. 59-28329.

  Preferred specific examples (D1) to (D38) of the compound represented by the general formula (6) are shown below. In addition, an isomer with a double bond connecting an acidic nucleus and a basic nucleus is not limited to either isomer.

  In addition, 1.0-10.0 mass% of these sensitizing dyes of all the components of a photosensitive layer is preferable, and 1.0-5.0 mass% is more preferable.

(Photopolymerization initiator)
Subsequently, the photoinitiator contained in the photosensitive layer used by this invention is demonstrated. As the photopolymerization initiator contained in the photosensitive layer used in the present invention, various photopolymerization initiators known in patents, literatures, etc., or a combination system of two or more photopolymerization initiators (photopolymerization initiation) System) can be appropriately selected and used. In the present invention, a photopolymerization initiator used alone and a system in which two or more photopolymerization initiators are used in combination are collectively referred to as a photopolymerization initiator.
For example, when light near 400 nm is used as a light source, benzyl, benzoyl ether, Michler's ketone, anthraquinone, thioxanthone, acridine, phenazine, benzophenone, hexaarylbiimidazole, etc. are widely used.

Also, various photopolymerization initiators have been proposed when using visible light of 400 nm or more as a light source. For example, some photoreductive properties described in US Pat. No. 2,850,445 are described. Dyes, such as rose bengal, eosin, erythrosine, etc., or a combination of a dye and a photopolymerization initiator, such as a complex initiation system of a dye and an amine (Japanese Patent Publication No. 44-20189), hexaarylbiimidazole and a radical A combination system of a generator and a dye (Japanese Patent Publication No. 45-37377), a system of hexaarylbiimidazole and p-dialkylaminobenzylidene ketone (Japanese Patent Publication Nos. 47-2528 and 54-155292), Cyclic cis-α-dicarbonyl compound and dye system (Japanese Patent Laid-Open No. 48-84183), cyclic triazine and merocyanine dye System (Japanese Patent Laid-Open No. 54-151024), a system of 3-ketocoumarin and an activator (Japanese Patent Laid-Open Nos. 52-112681, 58-15503), a system of biimidazole, styrene derivative, thiol ( JP-A-59-140203), organic peroxide and dye system (JP-A-59-1504, JP-A-59-140203, JP-A-59-189340, JP-A-62-174203) JP-B-62-1641, U.S. Pat. No. 4,766,055), dyes and active halogen compounds (JP-A 63-178105, JP-A 63-258903, JP-A 2 -63054, etc.), dye and borate compound systems (JP-A-62-143044, JP-A-62-1050242, JP-A-64-13140, JP-A-64-13141, JP-A-64-13142, JP-A-64-13143, JP-A-64-13144, JP-A-64-17048, JP-A-1-229003, JP-A-1-298348, JP-A-1- No. 138204, etc.), a dye having a rhodanine ring and a radical generator (JP-A-2-17943, JP-A-2-244050).
Furthermore, a titanocene compound is mentioned as a preferable photoinitiator. As the titanocene compound, for example, known compounds described in JP-A Nos. 59-152396 and 61-151197 can be appropriately selected and used.

Specifically, di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,3,4,5, 6-pentafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2, 4,6-trifluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4-difluoro Phen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2, 3, 5, 6 Tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4-difluorophen-1-yl, bis (cyclopentadienyl) -bis (2,6-difluoro-3- ( Pyrid-1-yl) phenyl) titanium and the like.
In addition, it is preferable that these photoinitiators are used in 0.5-10.0 mass% of the total component of a photosensitive layer.

As another preferred example of the photopolymerization initiator contained in the photosensitive layer used in the present invention, hexaarylbisimidazole (HABI, triaryl-imidazole dimer) is preferred. The production process of HABIs is described in DE 1470 154 and their use in photopolymerizable compositions is described in EP 24 629, EP 107 792, US 4 410 621, EP 215 453 and DE 3 211 312. is described. Preferred derivatives are, for example, 2,4,5,2 ', 4', 5'-hexaphenylbisimidazole, 2,2'-bis (2-chlorophenyl) -4,5,4 ', 5'-tetraphenylbis Imidazole, 2,2'-bis (2-bromophenyl) -4,5,4 ', 5'-tetraphenylbisimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,5,4' , 5'-tetraphenylbisimidazole, 2,2'-bis (2-chlorophenyl) -4,5,4 ', 5'-tetrakis (3-methoxyphenyl) bisimidazole, 2,2'-bis (2- Chlorophenyl) -4,5,4 ', 5'-tetrakis (3,4,5-trimethoxyphenyl) -bisimidazole, 2,5,2', 5'-tetrakis (2-chlorophenyl) -4,4 ' -Bis (3,4-dimethoxyphenyl) bisimidazole 2,2'-bis (2,6-dichlorophenyl) -4,5,4 ', 5'-tetraphenylbisimidazole, 2,2'-bis (2-nitrophenyl) -4,5,4', 5 '-Tetraphenylbisimidazole, 2,2'-di-o-tolyl-4,5,4', 5'-tetraphenylbisimidazole, 2,2'-bis (2-ethoxyphenyl) -4,5, 4 ', 5'-tetraphenylbisimidazole and 2,2'-bis (2,6-difluorophenyl) -4,5,4', 5'-tetraphenylbisimidazole.
The amount of the HABI photoinitiator is generally 0.01 to 30% by mass with respect to the total mass of nonvolatile components of the photopolymerizable composition (photopolymerizable composition) for forming the photosensitive layer, Preferably it is the range of 0.5-20 mass%.

[Addition polymerizable compound having an ethylenically unsaturated double bond]
The addition-polymerizable compound having an ethylenically unsaturated double bond contained in the photosensitive layer used in the present invention can be selected from compounds having at least one ethylenically unsaturated double bond group, preferably two or more. Can be selected.
For example, it has a chemical form such as a monomer, a prepolymer, that is, a dimer, a trimer and an oligomer, or a mixture thereof and a copolymer thereof.
Examples of monomers and copolymers thereof include esters of unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) with aliphatic polyhydric alcohol compounds, unsaturated Examples include amides of carboxylic acids and aliphatic polyvalent amine compounds.

  Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, Examples include polyester acrylate oligomers.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p (3-methacryloxy-2-hydroxypropoxy) phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

  Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate.

Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate.
Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.

Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.
Furthermore, the mixture of the above-mentioned ester monomer can also be mention | raise | lifted.

  Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like.

  Further, urethane acrylates such as those described in JP-A-51-37193, JP-A-48-64183, JP-B-49-43191, JP-B-52-30490 are described. Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid can be used. Furthermore, Journal of Japan Adhesion Association Vol. 20, no. 7, pages 300 to 308 (1984), those introduced as photocurable monomers and oligomers can also be used.

  Specifically, NK oligo U-4HA, U-4H, U-6HA, U-108A, U-1084A, U-200AX, U-122A, U-340A, U-324A, UA-100 (above, new Nakamura Chemical Co., Ltd.), UA-306H, AI-600, UA-101T, UA-101I, UA-306T, UA-306I (above, manufactured by Kyoeisha Yushi), Art Resin UN-9200A, UN-3320HA, UN-3320HB , UN-3320HC, SH-380G, SH-500, SH-9832 (manufactured by Negami Kogyo Co., Ltd.) and the like.

  In addition, the addition amount of the addition polymerizable compound having an ethylenically unsaturated double bond is preferably in the range of 5 to 90% by mass, more preferably in the range of 10 to 80% by mass, based on all components of the photosensitive layer.

[Binder polymer]
In the present invention, a binder polymer is contained in the photosensitive layer.
As the binder polymer, an organic high molecular polymer that is soluble or swellable in alkaline water is used because it needs to be dissolved in an alkaline developer as well as a film forming agent for the photosensitive layer. That is, since it is a polymer that is soluble or swellable in alkaline water, it can be removed by applying pressure, such as a brush, as necessary by alkaline development.

  The binder polymer suitable in the present invention preferably has at least all three types of structural units represented by the following formulas (B1) to (B3).

In formulas (B1) to (B3), R _a1 , R _a2 and R _a3 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
In the formula (B1), X represents a functional group selected from —COOH, —CO—W ₁ —L ₁ —COOH, and —SO ₃ H, and W ₁ represents an oxygen atom, a sulfur atom or a —NH— group. L ₁ represents a divalent organic group.
In Formula (B2), Y represents a —CO—O—CH ₂ —CH═CH ₂ group or a —CO—W ₂ —L ₂ —O—CO—CR ₀ ═CH ₂ group. W ₂ represents an oxygen atom, sulfur atom or —NH— group, L ₂ represents a divalent organic group, and R ₀ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
In Formula (B3), W ₃ represents an oxygen atom, a sulfur atom or a —NH— group, and R _4a represents an alkyl group having 1 to 18 carbon atoms, an alkyl group having an alicyclic structure having 5 to 20 carbon atoms, or A group having an aromatic ring having 6 to 20 carbon atoms is shown.

Specific examples of the structural units represented by formulas (B1) to (B3) are described below, but are not limited thereto.
Specific examples of the repeating unit represented by the formula (B1) include compounds having the following structures.

  Specific examples of the repeating unit represented by the formula (B2) include the structures shown below.

Specific examples of the repeating unit represented by the formula (B3) include methyl (meth) acrylate, ethyl (meth) acrylate, isobutyl (meth) acrylate, normal butyl (meth) acrylate, isopropyl (meth) acrylate, cyclohexyl (meth) ) Acrylates, n-hexyl (meth) acrylates, adamantyl (meth) acrylates, benzyl (meth) acrylates, phenethyl (meth) acrylates, and other alkyl or aryl (meth) acrylates, and (meth) acrylates represented by the following formula: Can be mentioned.
In the following, preferred substituents for R include methyl group, ethyl group, isopropyl group, n-butyl group, t-butyl group, cyclohexyl group, phenethyl group, benzyl group, and n-hexyl group.

In order to maintain the developability of the photopolymerizable photosensitive layer, the binder polymer used preferably has an appropriate molecular weight and acid value, and has a mass average molecular weight of 5000 to 300,000 and an acid value of 0.5 to 200. High molecular polymers are particularly preferred. Here, the acid value refers to the number of mg of potassium hydroxide necessary to neutralize free fatty acids contained in 1 g of a sample. The acid value is more preferably 5.0 to 180, and particularly preferably 10 to 150.
The ratio of the total amount of the structural unit represented by the formula (B1) and the structural unit represented by the formula (B3) to the structural unit having an ethylenically unsaturated double bond represented by the formula (B2) is as follows: The mass ratio is preferably in the range of 0.1 to 3.0, more preferably 0.1 to 2.0, and most preferably 0.1 to 1.0.
As long as the combination satisfies the above molecular weight, acid value, and double bond amount, the mixing ratio of the structural units represented by the formulas (B1), (B2), and (B3) may be any combination. good. If it is a range which satisfies these, you may further add structural units other than the structural unit represented by Formula (B1)-(B3).

  These binder polymers can be contained in an arbitrary amount in the photosensitive layer, but are generally 90% by mass or less, preferably 10 to 90% by mass, in terms of the formed image strength and the like. Preferably it is 30-80 mass%.

In the present invention, a polymer that is soluble or swellable in alkaline water other than the above-mentioned polymer can be used, or the above-mentioned polymer and another polymer can be mixed and used.
Examples of other organic polymer polymers that are polymers soluble or swellable in alkaline water include various polymers. When water development is desired, for example, water-soluble organic polymer polymers are used. Examples of such an organic polymer include addition polymers having a carboxylic acid group in the side chain, such as JP 59-44615, JP-B 54-34327, JP-B 58-12577, JP-B 54-. No. 25957, JP 54-92723, JP 59-53836, JP 59-71048, ie, methacrylic acid copolymer, acrylic acid copolymer, itacon Cyclic acid anhydrides for acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, acidic cellulose derivatives having a carboxylic acid group in the side chain, and addition polymers having a hydroxyl group Products, polyvinyl pyrrolidone, polyethylene oxide, and alcohol-soluble polyamide or 2,2-bis- (4-hydride) that can increase the strength of the cured film Kishifeniru) - and a polyether of propane and epichlorohydrin.
Furthermore, JP-B-7-120040, JP-B-7-120041, JP-B-7-120042, JP-B-8-12424, JP-A-63-287944, JP-A-63-287947, JP-A-1 Polyurethane resins described in JP-A Nos. -271741 and JP-A No. 11-352691 can also be used in the application of the present invention.

  In order to maintain the developability of the photosensitive layer, the binder polymer used preferably has an appropriate molecular weight and acid value, and a high molecular weight polymer having a mass average molecular weight of 5000 to 300,000 and an acid value of 20 to 200 is preferable. Particularly preferred.

[Urethane group-containing compound]
The photosensitive layer of the photosensitive lithographic printing plate of the present invention contains a urethane group-containing compound represented by the formula (1).

In the formula, R ₁ represents an alkyl group or an aromatic group having 1 to 20 carbon atoms, R represents a hydrogen atom, a linear alkyl group or branched alkyl group having 1 to 24 carbon atoms, alicyclic of 5 to 20 carbon atoms An alkyl group having a structure, a group having an aromatic ring having 6 to 20 carbon atoms, a hydroxyl group, an amino group, a substituted amino group, a carboxyl group, an alkoxyl group, or —C (═O) O—Ra or —OC (═O ) -Ra represents a group.
Ra represents an alkyl group having 1 to 12 carbon atoms, an aromatic group, an alkyl-substituted aromatic group, or an alicyclic alkyl group.
n represents an integer of 0 to 5, and when a plurality of Rs are present, they may be the same or different.

  The compound represented by the formula (1) can be obtained by reacting a compound having a phenolic hydroxyl group and a compound containing an isocyanate group in an equimolar amount under desired conditions. Any compound may be used as long as it is a combination of a phenolic compound and an isocyanate compound, and the present invention is not limited to the following.

Preferable examples of the compound containing a phenolic hydroxyl group constituting this compound include the following compounds.
Phenol, mono-t-butyl-p-cresol, cresol, catechol, pyrogallol, gallic acid, mono-t-butyl-m-cresol, butylhydroxyanisole, 2,6-di-t-butyl-p-cresol, 2, , 6-di-t-butylphenol, 2,4,6-tri-t-butylphenol, 4-hydroxymethyl-2,6-di-t-butylphenol, 4-t-butylcatechol, 2,5-di- t-butylhydroquinone, propyl pyrogallate, 4,4′-methylenebis (2,6-di-t-butylphenol), 4,4′-isopropylenebis (2,6-di-t-butylphenol), 2,2 '-Methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol) ), 2,2′-thiobis (4-ethyl-6-tert-butylphenol), 2-hydroxy-5-chlorobenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy- 4-benzyloxybenzophenone, phenyl salicylate, resorcinomonobenzoate, and the like.

Furthermore, as the isocyanate compound for reacting with this phenolic compound to form a urethane group-containing compound, the following general-purpose isocyanate compounds can be used.
Phenyl isocyanate, benzene sulfonyl isocyanate, p-chloro isocyanate, t-butyl isocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, 2,5-dichlorophenyl isocyanate, hexamethylene diisocyanate, n-butyl isocyanate, o-chlorophenyl isocyanate, m-chlorophenyl isocyanate Cyclohexyl isocyanate, isopropyl isocyanate, ethyl isocyanate, 1-naphthyl isocyanate, 4-nitrophenyl isocyanate, propyl isocyanate, phenylethyl isocyanate, methylbenzyl isocyanate, naphthylethyl isocyanate, o-fluorophenyl isocyanate, m-fluorophenyl ester Cyanate, p-fluorophenyl isocyanate, o-trifluoromethylphenyl isocyanate, m-trifluoromethylphenyl isocyanate, p-trifluoromethylphenyl isocyanate, benzyl isocyanate, m-toluene isocyanate, n-hexyl isocyanate, m-methoxyphenyl isocyanate , 1,3-phenylene diisocyanate, toluene-2,4-diisocyanate, o-toluene isocyanate, m-toluene isocyanate, toluene-2,6-diisocyanate, m-xylene diisocyanate, etc. New compounds may be used.

  For the compound represented by the formula (1), an isocyanate compound and a phenol derivative are appropriately selected from known solvents such as tetrahydrofuran, dimethylacetamide, and toluene, and a solvent in which both compounds are dissolved is appropriately mixed. Depending on the case, it can be obtained by heating or adding a known catalyst such as triethylamine or an organic tin compound and purifying it by a method such as concentration and recrystallization. A commercially available product may be used.

  The compound represented by formula (1) is generally from 0.001 to 10 in terms of the total mass of non-volatile components of the photopolymerizable composition (photopolymerizable composition) for forming the photosensitive layer. % By mass, preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass.

[Mercapto compound]
In the present invention, when hexaarylbisimidazoles are used as the initiator, the best results can be obtained by using a specific mercapto compound in combination.
The mercapto compound that can be used in the present invention is a compound selected from 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, or a compound represented by the following formula (7) as a good compound.

In formula (7), R ₂ represents a hydrogen atom, a C1-C18 linear alkyl group or branched alkyl group, a C5-C20 alkyl group having an alicyclic structure, or a C6-C20 aromatic ring group. , X represents an oxygen atom, a sulfur atom, or —N (R ₃ ) —, and R ₃ is a C1-C18 linear alkyl group or branched alkyl group, a C5-C20 alkyl group having an alicyclic structure, or A group having a C6-C20 aromatic ring is shown.

  Preferable examples of the compound represented by the formula (7) include the following compounds.

  The addition amount of the mercapto compound such as the compound represented by the formula (7) is generally 0.1 to 20% by mass, preferably 1 to 15% by mass, further based on all components constituting the photosensitive layer. Preferably it is 2-10 mass%.

  Further, in the photosensitive layer used in the present invention, in addition to the above basic components, an ethylenically unsaturated double during the production or storage of a composition (photopolymerizable composition) for forming the photosensitive layer. In order to prevent unnecessary thermal polymerization of the addition polymerizable compound having a bond, it is desirable to add a small amount of a thermal polymerization inhibitor. Suitable thermal 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, N-nitrosophenylhydroxylamine aluminum salt and the like. The addition amount of the thermal polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass of the total components of the composition. Also, if necessary, in order to prevent polymerization inhibition by oxygen, higher fatty acid derivatives such as behenic acid and behenamide are added and unevenly distributed on the surface of the photopolymerizable photosensitive layer in the process of drying after coating. You may let them. The addition amount of the higher fatty acid derivative is preferably about 0.5% by mass to about 10% by mass of the total components of the photopolymerizable composition.

Further, a colorant may be added for the purpose of coloring the photosensitive layer. Examples of the colorant include phthalocyanine pigments (CI Pigment Blue 15: 3, 15: 4, 15: 6, etc.), azo pigments, pigments such as carbon black and titanium oxide, ethyl violet, crystal violet, There are azo dyes, anthraquinone dyes, and cyanine dyes. The addition amount of the dye and the pigment is preferably about 0.5% by mass to about 5% by mass of the total components of the photopolymerizable composition.
In addition, in order to improve the physical properties of the cured film, an additive such as an inorganic filler or a plasticizer such as dioctyl phthalate, dimethyl phthalate, or tricresyl phosphate may be added. These additives are preferably 10% by mass or less of the total components of the photopolymerizable composition.
Further, a surfactant can be added to the composition for forming the photosensitive layer in order to improve the coating surface quality. Suitable surfactants include, for example, fluorine-based nonionic surfactants.

In the present invention, the photopolymerizable composition is applied onto a support that has been subjected to various surface treatments as described in detail later. The photopolymerizable composition is applied onto the support. When used, it is dissolved in various organic solvents and used. Solvents that can be used here include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether. , Acetylacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether , Diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, methyl lactate, lactic acid There are ethyl and the like. These solvents can be used alone or in combination. In addition, 1-50 mass% is suitable for solid content concentration in a coating solution.
The coverage of the photosensitive layer is in the range of about 0.1 g / m ² ~ about 10 g / m ² in weight after coating and drying are suitable, more preferably from 0.3 to 5 g / m ^2, more preferably it is a 0.5~3g / m ^2.

[Protective layer]
In general, an oxygen-blocking protective layer (overcoat layer) is provided on the photosensitive layer in order to prevent the action of inhibiting the polymerization of oxygen.
The coating weight of the protective layer in the present invention is preferably in the range of 0.7~3.0g / m ^2. If it is less than 0.7 g / m ² , the sensitivity may decrease, and if it exceeds 3.0 g / m ² , the burden on the treatment process may increase.
The protective layer is mainly formed from an oxygen-blocking water-soluble resin. Oxygen-blocking water-soluble vinyl polymers include polyvinyl alcohol and its partial esters, ethers, and acetals, or copolymers thereof containing a substantial amount of unsubstituted vinyl alcohol units to provide them with the necessary water solubility. A polymer is mentioned. Examples of the polyvinyl alcohol include those having a hydrolysis degree of 71 to 100% and a polymerization degree in the range of 300 to 2400. Specifically, Kuraray PVA-105, PVA-110, PVA-117, PVA-117H, PVA-120, PVA-124, PVA-124H, PVA-CS, PVA-CST, PVA-HC, PVA -203, PVA-204, PVA-205, PVA-210, PVA-217, PVA-220, PVA-224, PVA-217EE, PVA-217E, PVA-220E, PVA-224E, PVA-405, PVA-420 , PVA-613, L-8, and the like. Examples of the copolymer include 88-100% hydrolyzed polyvinyl acetate chloroacetate or propionate, polyvinyl formal and polyvinyl acetal, and copolymers thereof. Other useful polymers include polyvinyl pyrrolidone, gelatin and gum arabic, and these may be used alone or in combination.

As a solvent used for applying the protective layer, pure water is preferable, but alcohols such as methanol and ethanol, and ketones such as acetone and methyl ethyl ketone may be mixed with pure water. The concentration of the solid content in the coating solution is suitably 1 to 20% by mass. In the protective layer, known additives such as a surfactant for improving the coating property and a water-soluble plasticizer for improving the physical properties of the film may be added. Examples of the water-soluble plasticizer include propionamide, cyclohexanediol, glycerin, sorbitol and the like. Further, a water-soluble (meth) acrylic polymer or the like may be added.
The coating amount of the protective layer is preferably about 0.1 g / m ² to about 15 g / m ² , more preferably 1.0 g / m ² to about 5.0 g / m ² in terms of the mass after drying.

[Hydrophilic support]
As the support that can be used in the present invention, any material can be used as long as the surface is hydrophilic, but a dimensionally stable plate-like material is preferable, for example, paper, plastic (for example, polyethylene, polypropylene, polystyrene, etc. ) And laminated metal, and also metals such as aluminum (including aluminum alloys), zinc, copper etc. or alloys thereof (eg silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel and Alloy) plates, and plastics such as cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose butyrate acetate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc. the film The above-described metal or alloys having laminated or vapor-deposited paper or plastic films. Of these supports, the aluminum plate is particularly preferred because it is dimensionally remarkably stable and inexpensive. Further, a composite sheet in which an aluminum sheet is bonded on a polyethylene terephthalate film as described in Japanese Patent Publication No. 48-18327 is also preferable. Usually, the thickness is about 0.05 mm to 1 mm.

  Further, in the case of a support having a surface of metal, particularly aluminum, surface treatment such as graining treatment described later, immersion treatment in an aqueous solution of sodium silicate, potassium fluoride zirconate, phosphate or the like, or bipolar oxidation treatment, etc. It is preferable that

[Graining process]
Examples of the graining method include mechanical graining, chemical etching, and electrolytic grain as disclosed in JP-A-56-28893. Furthermore, electrochemical graining method that electrochemically grains in hydrochloric acid or nitric acid electrolyte solution, and wire brush grain method that scratches aluminum surface with metal wire, and ball grain method that graines aluminum surface with polishing ball and abrasive. Further, a mechanical graining method such as a brush grain method in which the surface is grained with a nylon brush and an abrasive can be used, and the above graining methods can be used alone or in combination.
Among them, the method of making the surface roughness usefully used in the present invention is an electrochemical method in which the surface roughness is chemically ground in hydrochloric acid or nitric acid electrolyte, and a suitable current density is 100 C / dm ^{2 to} 400 C. / Dm ² range. More specifically, in the electrolytic solution containing from 0.1 to 50% hydrochloric acid or nitric acid, the temperature 20 to 100 ° C., for 1 second to 30 minutes, electrolysis at a current density of 100C / dm ² ~400C / dm ² It is preferable to carry out.

The grained aluminum support is chemically etched with acid or alkali. When an acid is used as an etching agent, it takes time to destroy the fine structure, which is disadvantageous when the present invention is applied industrially, but it can be improved by using an alkali as the etching agent.
Examples of the alkali agent suitably used in the present invention include caustic soda, sodium carbonate, sodium aluminate, sodium metasilicate, sodium phosphate, potassium hydroxide, lithium hydroxide and the like. The conditions are 50%, 20 to 100 ° C., and the amount of aluminum dissolved is 5 to 20 g / m ³ .
After etching, pickling is performed to remove dirt (smut) remaining on the surface. Examples of the acid used include nitric acid, sulfuric acid, phosphoric acid, chromic acid, hydrofluoric acid, and borohydrofluoric acid. In particular, as a method for removing smut after the electrochemical surface roughening treatment, contact with 15 to 65 mass% sulfuric acid at a temperature of 50 to 90 ° C. as described in JP-A-53-12739 is preferable. And an alkali etching method described in Japanese Patent Publication No. 48-28123.
In addition, the surface roughness (Ra) of the aluminum support preferable in the present invention is 0.3 to 0.7 μm.

[Anodic oxidation treatment]
The aluminum support treated as described above is further anodized.
The anodizing treatment can be performed by a method conventionally performed in this technical field.
Specifically, sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid, benzene sulfonic acid, etc., or a combination of two or more of these, and when direct current or alternating current is applied to aluminum in an aqueous solution or non-aqueous solution, aluminum is supported. An anodized film can be formed on the body surface.
The conditions of the anodizing treatment cannot be determined unconditionally because they vary depending on the electrolytic solution used. In general, the concentration of the electrolytic solution is 1 to 80%, the liquid temperature is 5 to 70 ° C., the current density is 0.00. A range of 5 to 60 amperes / dm ² , a voltage of 1 to 100 V, and an electrolysis time of 10 to 100 seconds is appropriate.
Among these anodizing treatments, in particular, the method of anodizing at high current density in sulfuric acid described in British Patent 1,412,768, and US Pat. No. 3,511,661. A method of anodizing phosphoric acid described in the book as an electrolytic bath is preferred.
In the present invention, the anodized film is preferably from ^{1~10g / m 2, 1g / m} 2 less than the plate to easily enter the wound to be, requires significant power production exceeds 10 g / m ² It is economically disadvantageous. Preferably, it is 1.5-7 g / m < ² >, More preferably, it is 2-5 g / m < ² >.

  Furthermore, in the present invention, the support may be subjected to a sealing treatment after graining treatment and anodizing. Such sealing treatment is performed by immersing the substrate in a hot aqueous solution containing hot water and an inorganic salt or an organic salt, a steam bath, or the like. The support used in the present invention may be subjected to a surface treatment such as a treatment other than a silicate treatment with an alkali metal silicate, for example, an immersion treatment in an aqueous solution of potassium fluorinated zirconate or phosphate.

  In the present invention, a photopolymerizable photosensitive layer made of, for example, a photopolymerizable composition is applied onto a support (in the case of aluminum, aluminum that has been appropriately surface-treated as described above is preferable), and then By coating the protective layer, a photopolymerization type photosensitive lithographic printing plate is formed, but an organic or inorganic undercoat layer may be provided as necessary before coating the photopolymerizable photosensitive layer. Alternatively, a sol-gel treatment in which a functional group capable of causing an addition reaction with a radical is covalently bonded as disclosed in JP-A-7-159983.

Substances forming the organic undercoat layer include water-soluble resins such as polyvinylphosphonic acid, polymers and copolymers having sulfonic acid groups in the side chain, polyacrylic acid, water-soluble metal salts (for example, zinc borate) or , Yellow dyes, amine salts and the like.
More specifically, examples of the organic compound used in the organic undercoat layer may include phosphonic acids having an amino group such as carboxymethylcellulose, dextrin, gum arabic, and 2-aminoethylphosphonic acid, and a substituent. Organic phosphonic acids such as phenylphosphonic acid, naphthylphosphonic acid, alkylphosphonic acid, glycerophosphonic acid, methylenediphosphonic acid and ethylenediphosphonic acid, optionally substituted phenylphosphonic acid, naphthylphosphonic acid, alkylphosphoric acid and Organic phosphoric acids such as glycerophosphoric acid, optionally substituted phenylphosphinic acid, naphthylphosphinic acid, organic phosphinic acids such as alkylphosphinic acid and glycerophosphinic acid, amino acids such as glycine and β-alanine, and triethanol Hydroxy such as amine hydrochloride -Alanine, and hydrochlorides of amines having a group may be used as a mixture of two or more.

This organic undercoat layer can be provided by the following method. That is, a method in which water or an organic solvent such as methanol, ethanol, methyl ethyl ketone or the like, or a mixed solvent thereof is dissolved on the support, and a method of providing the substrate by drying, water, methanol, ethanol, methyl ethyl ketone, etc. The organic compound is dissolved in a solution of the above organic compound or a mixed solvent thereof to immerse the support so that the organic compound is adsorbed, and then washed with water and dried to provide an organic undercoat layer. Is the method. In the former method, a solution having a concentration of 0.005 to 10% by mass of the organic compound can be applied by various methods. For example, any method such as bar coater coating, spin coating, spray coating, or curtain coating may be used. In the latter method, the concentration of the solution is 0.01 to 20% by mass, preferably 0.05 to 5% by mass, the immersion temperature is 20 to 90 ° C., preferably 25 to 50 ° C., and the immersion time. Is 0.1 second to 20 minutes, preferably 2 seconds to 1 minute.
The solution used for this can be used in a pH range of 1 to 12 by adjusting the pH with a basic substance such as ammonia, triethylamine or potassium hydroxide, or an acidic substance such as hydrochloric acid or phosphoric acid. A yellow dye can also be added to improve the tone reproducibility of the photopolymerization type photosensitive lithographic printing plate.
The coating amount after drying of the organic undercoat layer is preferably ² to 200 mg / m ^{2 and} more preferably 5 to 100 mg / m ² from the viewpoint of printing durability.

  Examples of the material used for the inorganic undercoat layer include inorganic salts such as cobalt acetate, nickel acetate, and potassium fluorotitanate. The method of providing this inorganic undercoat layer is the same as the organic undercoat layer described above. .

[Plate making process]
Next, the plate making method of the photosensitive lithographic printing plate of the present invention will be described in detail. In the exposure method of the photosensitive lithographic printing plate described above, an AlGaInN semiconductor laser (commercially available InGaN-based semiconductor laser 5 to 30 mW) is suitable as a light source in terms of wavelength characteristics and cost.

  The exposure mechanism may be any of an internal drum system, an external drum system, a flat bed system, and the like. Moreover, the photosensitive layer component of the photosensitive lithographic printing plate of the present invention can be made soluble in neutral water or weak alkaline water by using a highly water-soluble component. The planographic printing plate can be loaded on a printing press and then subjected to a method such as exposure-development on the press. After the image exposure, the entire surface may be heated between exposure and development as necessary. By such heating, an image forming reaction in the photosensitive layer is promoted, and advantages such as improvement in sensitivity and printing durability and stabilization of sensitivity may occur. Further, for the purpose of improving the image strength and printing durability, it is also effective to carry out whole surface post-heating or whole surface exposure on the developed image. Usually, heating before development is preferably performed under mild conditions of 150 ° C. or less. If the temperature is too high, problems such as covering the non-image area occur. Very strong conditions are used for heating after development. Usually, it is the range of 200-500 degreeC. If the temperature is low, sufficient image strengthening action cannot be obtained. If the temperature is too high, problems such as deterioration of the support and thermal decomposition of the image area occur.

(Developer)
The developer used in the plate making method of the lithographic printing plate is not particularly limited. For example, a developer containing an inorganic alkali salt and a nonionic surfactant and having a pH of 11.0 to 12.5. Preferably used.
The inorganic alkali salt can be used as appropriate. For example, sodium hydroxide, potassium, ammonium, lithium, sodium silicate, potassium, ammonium, lithium, tribasic sodium phosphate, potassium, ammonium Inorganic alkaline agents such as sodium carbonate, potassium, ammonium, sodium hydrogen carbonate, potassium, ammonium, sodium borate, potassium, and ammonium. These may be used alone or in combination of two or more.

In the case of using silicate, developability can be achieved by adjusting the mixing ratio and concentration of silicon oxide SiO ₂ which is a component of silicate and alkali oxide M ₂ O (M represents an alkali metal or ammonium group). Can be easily adjusted. Among the alkaline aqueous solutions, those having a mixing ratio (SiO ₂ / M ₂ O: molar ratio) of the silicon oxide SiO ₂ and the alkali oxide M ₂ O of 0.5 to 3.0 are preferable, and 1.0 to 2 0.0 is preferred. The total amount of SiO ₂ / M ₂ O is preferably 1 to 10% by mass, more preferably 3 to 8% by mass, and most preferably 4 to 7% by mass with respect to the mass of the alkaline aqueous solution. That is, it is preferably 1% by mass or more in terms of developability and processing capability, and is preferably 10% by mass or less in terms of suppressing precipitation and crystal formation, preventing gelation during neutralization during waste liquid, and treating waste liquid.

  In addition, an organic alkali agent may be supplementarily used for the purpose of finely adjusting the alkali concentration and assisting the solubility of the photosensitive layer. Examples of the organic alkali agent include monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, Examples thereof include diisopropanolamine, ethyleneimine, ethylenediamine, pyridine, tetramethylammonium hydroxide and the like. These alkali agents are used alone or in combination of two or more.

  The surfactant can be used as appropriate, for example, nonionic surfactants having a polyoxyalkylene ether group, polyoxyethylene alkyl esters such as polyoxyethylene stearate, sorbitan monolaurate, sorbitan monostearate, Nonionic surfactants such as sorbitan alkyl esters such as sorbitan distearate, sorbitan monooleate, sorbitan sesquioleate and sorbitan trioleate, monoglyceride alkyl esters such as glycerol monostearate and glycerol monooleate; dodecylbenzenesulfonic acid Alkylbenzene sulfonates such as sodium, sodium butyl naphthalene sulfonate, sodium pentyl naphthalene sulfonate, sodium hexyl naphthalene sulfonate Anion interfaces such as alkyl naphthalene sulfonates such as sodium and sodium octyl naphthalene sulfonate, alkyl sulfates such as sodium lauryl sulfate, alkyl sulfonates such as sodium dodecyl sulfonate, and sulfosuccinate esters such as sodium dilauryl sulfosuccinate Activators: Alkyl betaines such as lauryl betaine and stearyl betaine, amphoteric surfactants such as amino acids, and the like can be mentioned. Particularly preferred are nonionic surfactants having a polyoxyalkylene ether group.

  As the surfactant having a polyoxyalkylene ether group, those having the structure of the following general formula (I) are preferably used.

R ⁴⁰ —O— (R ⁴¹ —O) pH (I)

In the formula, R ⁴⁰ has an alkyl group having 3 to 15 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 15 carbon atoms which may have a substituent, or a substituent. A heteroaromatic cyclic group having 4 to 15 carbon atoms (wherein the substituent is an alkylene group having 1 to 20 carbon atoms, a halogen atom such as Br, Cl, or I, or an aromatic hydrocarbon having 6 to 15 carbon atoms) R ⁴¹ is a group, an aralkyl group having 7 to 17 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxy-carbonyl group having 2 to 20 carbon atoms, or an acyl group having 2 to 15 carbon atoms. , An optionally substituted alkylene group having 1 to 100 carbon atoms (in addition, examples of the substituent include an alkyl group having 1 to 20 carbon atoms and an aromatic hydrocarbon group having 6 to 15 carbon atoms). P represents an integer of 1 to 100.

  In the definition of the above formula (I), specific examples of the “aromatic hydrocarbon group” include phenyl group, tolyl group, naphthyl group, anthryl group, biphenyl group, phenanthryl group, etc. Specific examples of the “group” include furyl group, thionyl group, oxazolyl group, imidazolyl group, pyranyl group, pyridinyl group, acridinyl group, benzofuranyl group, benzothionyl group, benzopyranyl group, benzooxazolyl group, benzoimidazolyl group, and the like. It is done.

Also of Formulas (I) - moiety of (R ⁴¹ -O) p, if the above-mentioned range, it may be two or three kinds of groups. Specific examples include random or block combinations of ethyleneoxy and propyleneoxy groups, ethyleneoxy and isopropyloxy groups, ethyleneoxy and butyleneoxy groups, ethyleneoxy groups and isobutylene groups, and the like. .
In the present invention, the surfactant having a polyoxyalkylene ether group is used alone or in combination, and is preferably added in an amount of 1 to 30% by mass, more preferably 2 to 20% by mass in the developer. 1 mass% or more is preferable from the point of developability, and 30 mass% or less is preferable at the point which prevents the printing durability fall of the printing plate by the damage of image development.

Examples of the nonionic surfactant having a polyoxyalkylene ether group represented by the above formula (I) include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, and polyoxyethylene stearyl ether. Polyoxyethylene aryl ethers such as polyoxyethylene phenyl ether and polyoxyethylene naphthyl ether, polyoxyethylene alkyl aryl ethers such as polyoxyethylene methyl phenyl ether, polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether Kind.
These surfactants can be used alone or in combination. Further, the content of these surfactants in the developer is preferably in the range of 0.1 to 20% by mass in terms of active ingredients.

  The pH of the developer used in the plate making method of the present invention is preferably 11.0 to 12.7, more preferably 11.5 to 12.5. By setting the pH to 11.0 to 12.7, image formation is improved, over-development is prevented, and damage to the exposed area during development can be reduced.

  The conductivity of the developer used in the present invention is preferably 3 to 30 mS / cm. By setting the electrical conductivity to 3 to 30 mS / cm, the elution rate of the photosensitive layer on the surface of the aluminum plate support can be appropriately adjusted, and the remaining film is prevented from being generated in the unexposed area and preventing the stain. be able to. Particularly preferred conductivity is in the range of 5-20 mS / cm.

The development of the photosensitive lithographic printing plate in the present invention is carried out according to a conventional method, for example, by immersing the exposed photosensitive lithographic printing plate in a developer at a temperature of about 0 to 60 ° C., preferably about 15 to 40 ° C. For example, rubbing with.
Further, when developing using an automatic developing machine, the developing solution becomes fatigued according to the amount of processing, so that the processing capability may be restored by using a replenishing solution or a fresh developing solution.
The photosensitive lithographic printing plate thus developed is washed with water, surface active as described in JP-A Nos. 54-8002, 55-1115045 and 59-58431. It is post-treated with a rinsing solution containing an agent and the like, a desensitizing solution containing gum arabic, starch derivatives and the like. In the present invention, these treatments can be used in various combinations for the post-treatment of the photosensitive lithographic printing plate.
The printing plate obtained by the above treatment can be improved in printing durability by post-exposure treatment or heating treatment such as burning according to the method described in JP-A-2000-89478.
The planographic 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 demonstrates this invention in detail, this invention is not limited to these.
[Examples 1 to 10]
[Support Example 1]
(Support 1: Anodized aluminum support)
An aluminum plate made of material 1S having a thickness of 0.30 mm was used with a No. 8 nylon brush and an aqueous suspension of 800 mesh Pamiston, and its surface was grained and washed thoroughly with water. After etching by immersing in a 10% aqueous sodium hydroxide solution at 70 ° C. for 60 seconds, washed with running water, neutralized with a 20% aqueous HNO ₃ solution, and washed with water. This was subjected to an electrolytic surface roughening treatment in a 1% nitric acid aqueous solution with a anodic electricity quantity of 300 coulomb / dm ² using a sinusoidal alternating current under the condition of VA = 12.7V. When the surface roughness was measured, it was 0.45 μm (Ra indication). Next, after dipping in a 30% H ₂ SO ₄ aqueous solution and desmutting at 55 ° C. for 2 minutes, a cathode was placed on the grained surface in 33 ° C., 20% H ₂ SO ₄ aqueous solution to obtain a current density. When anodized at 5 A / dm ² for 50 seconds, the thickness was 2.6 g / m ² . This was designated as Support 1.

(Support 2)
A solution of the following polymer (P1) was applied to the support (1) using a bar coater so that the dry coating amount was 2 mg / m ^2, and dried at 80 ° C. for 20 seconds.

[Undercoat liquid]
Polymer (P1) 0.3g
60.0g of pure water
Methanol 939.7g

    Structural formula of polymer (P1)

[Photopolymerizable compositions P-1 to P-10]
Each of the photopolymerizable compositions (P-1) to (P-10) having the following composition was coated on the support (2) using a bar coater and then dried at 100 ° C. for 1 minute. The mass of the photosensitive composition after drying was 1.1 g / m ² . The binder polymer is B-1 to B-3 shown in Table 1, and the urethane group-containing compound is S-1 to S-5 and phenyl isocyanate in a molar ratio of 1:
The compounds U-1 to U-5 reacted in 1 were used.

  Compounds U-1 to U-5 are the following compounds.

Photopolymerizable composition (P-1) to (P-10)
Ethylenically unsaturated bond-containing compound (A1) 0.46 parts by mass Binder polymer (described in Table 1) 0.51 parts by mass Sensitizing dye (D39 previously exemplified) 0.03 parts by mass Bisimidazole (manufactured by Kuroki Kasei) ) 0.12 parts by mass ε-phthalocyanine (F1) dispersion 0.47 parts by mass Mercapto compound (SH-1) 0.09 parts by mass Urethane group-containing compound (described in Table 1) 0.01 parts by mass Fluorine-based nonionic interface Activator MegaFuck F-780F
(Dainippon Ink Chemical Co., Ltd.) 0.009 parts by mass Clopen (manufactured by Wako Pure Chemical Industries, Ltd.) 0.003 parts by mass Methyl ethyl ketone 7.4 parts by mass Propylene glycol monomethyl ether 7.4 parts by mass

On this photosensitive layer,
Kuraray Co., Ltd. PVA205 (polyvinyl alcohol saponification degree 88 mol%, polymerization degree 500) 5.0 mass parts
EMALEX 710 (Nonionic surfactant manufactured by Nippon Emulsifier Co., Ltd.) 0.09 parts by mass A protective layer aqueous solution consisting of 94.91 parts by mass of pure water was applied with a bar coater so that the dry coating mass was 2.4 g / m ^2. And dried at 120 ° C. for 1 minute to obtain photosensitive lithographic printing plates 1 to 10.

(Storage stability evaluation)
After preparing a photosensitive lithographic printing plate as described above, a Violet semiconductor laser setter Vx9600 (InGaN-based semiconductor laser manufactured by FUJIFILM Electronic Imaging Ltd) was stored for 3 days at 25 ° C. and 50 RH% and stored for 3 days at 60 ° C. 405 nm ± 10 nm light emission / output 30 mW), and a 50% flat screen was drawn with a TAFFETA 20 FM screen manufactured by Fuji Photo Film at an exposure amount of 90 μJ / cm ² and a resolution of 2438 dpi. The plate after exposure is automatically sent to the connected automatic processor LP1250PLX, heated at 100 ° C. for 10 seconds, the PVA protective layer is washed away with water, and subsequently developed at 28 ° C. for 20 seconds. The developer was prepared by diluting a developer DV-2 manufactured by Fuji Photo Film Co., Ltd. five times with water. The developed plate was rinsed in a rinse bath, sent to a gumming bath, and a solution obtained by diluting a gum solution FP-2W manufactured by Fuji Photo Film Co., Ltd. with water twice. The plate after gumming was discharged after drying with hot air to obtain a planographic printing plate on which a 50% flat net of an FM screen was drawn. The area ratio of the obtained lithographic printing plate was measured using CC-dots, and the halftone dot area difference (δdot) reproduced between the printing plates stored at 25 ° C. for 3 days and 60 ° C. for 3 days was measured. . The results are shown in Table 1.

[Comparative Example 1]
Using the photosensitive lithographic printing plate produced in the same manner as in Example 1 except that the urethane group-containing compound was not added, δdot was measured in the same manner as in Example 1. The results are shown in Table 1.

  From the results in Table 1, it can be seen that the photosensitive lithographic printing plate of the present invention has excellent performance with no change over time even by laser exposure using an FM screen.

Claims (1)

A photosensitive lithographic printing plate having a photopolymerizable photosensitive layer containing the following (i) to (v) on a hydrophilic support.
(I) Sensitizing dye having absorption maximum in a wavelength range of 360 nm to 450 nm (ii) Photopolymerization initiator (iii) Addition polymerizable compound having ethylenically unsaturated double bond (iv) Binder polymer (v) General formula A urethane group-containing compound represented by (1).

In the formula, R ₁ represents an alkyl group or an aromatic group having 1 to 20 carbon atoms, R represents a hydrogen atom, a linear alkyl group or branched alkyl group having 1 to 24 carbon atoms, alicyclic of 5 to 20 carbon atoms An alkyl group having a structure, a group having an aromatic ring having 6 to 20 carbon atoms, a hydroxyl group, an amino group, a substituted amino group, a carboxyl group, an alkoxyl group, or —C (═O) O—Ra or —OC (═O ) -Ra represents a group.
Ra represents an alkyl group having 1 to 12 carbon atoms, an aromatic group, an alkyl-substituted aromatic group, or an alicyclic alkyl group.
n represents an integer of 0 to 5, and when a plurality of Rs are present, they may be the same or different.