JP2006150722A - Method for making lithographic printing plate, photosensitive lithographic printing plate material and lithographic printing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for making a lithographic printing plate which can produce an excellent lithographic printing plate with the superb ability to develop an image aboard a printing machine and recover from smudginess and high resistance to plate wear, and a photosensitive lithographic printing plate material to be used for this method and a printing method using the method for making the lithographic printing plate/the printing plate material. <P>SOLUTION: The photosensitive lithographic printing plate material has a photosensitive layer comprising (A) a photopolymerization initiator, (B) a bonding agent, (C) a polymerizable ethylenic unsaturated bond-containing compound and (D) a coloring matter with an absorption maximum in 350 to 450 nm wavelength range, formed on a support. The method for making the lithographic printing plate is to expose the lithographic printing plate material and, after this image exposure, perform an image development process aboard the lithographic printing machine to make the lithographic printing plate. The photosensitive layer contains a polyhalogen compound as (A) the photopolymerization initiator and a water-soluble polymer compound as (B) the bonding agent. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a lithographic printing plate making method using a processless type printing plate material used in a computer-to-plate system (hereinafter referred to as CTP), a photosensitive printing plate material used therefor, and a printing method using the lithographic printing plate. About.

  In recent years, CTP recording digital image data directly on a photosensitive printing plate with a laser light source has been developed and is being put to practical use in the technology for producing printing plates for offset printing.

  Among these, in the field of printing that requires relatively high printing durability, it is necessary to use a printing plate material having a negative photosensitive layer having an image recording layer containing a polymerizable compound on an aluminum support. Are known.

  On the other hand, as a photosensitive lithographic printing plate for CTP which records digital data with a laser, for example, photopolymerization containing titanocene which is a polymerization initiator described in JP-A-9-80750 and JP-A-10-101719 and a specific dye. Those having a photosensitive layer are known. However, since these photosensitive lithographic printing plates use a relatively long-wavelength visible light source as a light source, it is necessary to perform plate-making work for preparing the printing plate under a safe light of a dark red light. There was a demand for being able to handle under a brighter yellow light (lighting room).

  In addition, high-power and small-sized lasers such as blue-violet lasers having emission wavelengths at short wavelengths can be obtained relatively easily, and by developing photosensitive lithographic printing plates suitable for these laser wavelengths, The use of photopolymerization type photosensitive lithographic printing plate material corresponding to laser exposure in the 350 nm to 450 nm region has been proposed (for example, see Patent Documents 1 to 3).

  However, these printing plate materials require a wet development process such as an alkaline aqueous solution after exposure.

  On the other hand, as a printing plate material used in the CTP system, there is a printing plate material that does not require a development treatment with a processing solution containing a special agent (for example, alkali, acid, solvent, etc.) and can be applied to a conventional printing press. For example, there is known a printing plate material called a processless type printing plate material that is developed at an initial stage of printing on a printing press and does not require a development step after image exposure.

  Examples of the above processless type printing plate materials include JP-A-8-507727, JP-A-6-186750, JP-A-6-199064, JP-A-7-314934, JP-A-10-58636, and JP-A-10-244773. A printing plate material configured to form a printing plate by laminating either a hydrophilic layer or a lipophilic layer as a surface layer on a film substrate as disclosed, and ablating the surface layer by laser exposure Alternatively, as disclosed in Japanese Patent No. 2938397 and Japanese Patent No. 2938398, a printing plate material provided with an image forming layer containing a thermoplastic fine particle, a water-soluble binder, and a photothermal conversion material on a hydrophilic layer, photocuring A printing plate material having an image forming layer containing a polymer having a possible group and an acidic group (see Patent Document 4) is known.

  However, these printing plate materials can be developed on a printing press and can be used as printing plate materials for processless CTP, and can form relatively high-definition images, but still have insufficient printing durability. In some cases, there is a problem that the recovery of stains during printing may be slow.

Furthermore, in recent years, in the printing industry, from the viewpoint of environmental protection, inks that do not use petroleum-based volatile organic compounds (VOC) have been developed and are becoming popular in printing inks. In particular, such printing inks are used. The printing has the above-mentioned problems.
JP 2003-21901 A JP 2000-147663 A JP 2002-202598 A Japanese National Patent Publication No. 11-504435

  An object of the present invention is to provide a lithographic printing plate making method capable of developing on a printing press and obtaining a lithographic printing plate excellent in printing durability and stain recovery, a photosensitive lithographic printing plate material used therefor, and It is to provide a printing method used.

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

(Claim 1)
Contains (A) a photopolymerization initiator, (B) a binder, (C) a polymerizable ethylenically unsaturated bond-containing compound, and (D) a dye having an absorption maximum in the wavelength range of 350 nm to 450 nm on the support. A method for making a lithographic printing plate, comprising: exposing a photosensitive lithographic printing plate material having a photosensitive layer to be image-exposed, developing the image on the lithographic printing machine after the image exposure; The method of making a lithographic printing plate comprises: (A) a polyhalogen compound as a photopolymerization initiator, and (B) a water-soluble polymer compound as a binder.

(Claim 2)
The lithographic printing plate making method according to claim 1, wherein the water-soluble polymer compound is a water-soluble polymer compound having a nonionic hydrophilic group.

(Claim 3)
The lithographic printing plate making method according to claim 1, wherein the image exposure is performed using a laser beam having a wavelength of 350 nm to 450 nm.

(Claim 4)
The lithographic printing plate making method according to any one of claims 1 to 3, wherein the water-soluble polymer compound has a weight average molecular weight of 1,000 to 50,000.

(Claim 5)
The lithographic printing plate making method according to any one of claims 1 to 4, wherein the support is an aluminum support subjected to a roughening treatment and an anodizing treatment.

(Claim 6)
A photosensitive lithographic printing plate material, which is used in the plate making method of a lithographic printing plate according to any one of claims 1 to 5.

(Claim 7)
A lithographic printing method comprising printing using a lithographic printing plate produced by the lithographic printing plate making method according to any one of claims 1 to 5.

  According to the configuration of the present invention, a lithographic printing plate making method capable of developing on a printing press and obtaining a lithographic printing plate excellent in printing durability and stain recovery, a photosensitive lithographic printing plate material used therefor, and The printing method used can be provided.

  The present invention is described in detail below.

  The present invention provides (A) a photopolymerization initiator, (B) a binder, (C) a polymerizable ethylenically unsaturated bond-containing compound and (D) a wavelength range of 350 nm to 450 nm on a support. A photosensitive lithographic printing plate material having a photosensitive layer containing a dye having an image exposure, and after the image exposure, development processing on a lithographic printing machine to produce a lithographic printing plate The photosensitive layer contains (A) a polyhalogen compound as a photopolymerization initiator and (B) a water-soluble polymer compound as a binder.

  In the present invention, a lithographic printing plate having excellent printing durability and stain recovery can be obtained, particularly by including a combination of a water-soluble polymer compound and a polyhalogen compound in the photosensitive layer. Can be provided.

((A) Photopolymerization initiator)
The photopolymerization initiator according to the present invention is capable of initiating polymerization of an ethylenically unsaturated bond-containing compound that can be polymerized by image exposure, and the photosensitive layer according to the present invention comprises a polyhalogen compound as a photopolymerization initiator. Including.

(Polyhalogen compound)
The polyhalogen compound according to the present invention is a compound having a trihalogenmethyl group, a dihalogenmethyl group or a dihalogenmethylene group, and in particular, the halogen compound represented by the following general formula (1) and the above group are present in the oxadiazole ring. Substituted compounds are preferably used. Among these, a halogen compound represented by the following general formula (2) is particularly preferably used.

Formula (1) 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 (2) 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 polyhalogenacetylamide group are particularly preferably used.

  Specific examples of the structure represented by the general formula (1) include the following compounds BR1 to BR76. In addition, a compound in which a polyhalogenmethyl group is substituted with an oxadiazole ring is also preferably used, and examples thereof are listed in H-1 to H-14. Furthermore, oxadiazole compounds described in JP-A-5-34904, Do-45875, and 8-240909 are also preferably used.

  In addition, the compound which substituted the halogen atom from bromine to chlorine can also be used suitably for these compounds in this invention. Specific examples of polyhalogen compounds preferably used in the present invention are listed below.

  In the photosensitive layer according to the present invention, the following polymerization initiator may be used in combination with the polyhalogen compound as a photopolymerization initiator.

  Preferred examples of the photopolymerization initiator that can be used in combination include titanocene compounds, monoalkyltriaryl borate compounds, and iron arene complex compounds.

  Examples of titanocene compounds 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-bis- , 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 (IRUGACURE 784: 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) titanium and the like It is below.

  Examples of the monoalkyl triaryl borate compound include compounds described in JP-A-62-150242 and JP-A-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 and the like.

  Examples of the iron arene complex compound include compounds described in JP-A-59-219307. More preferred 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- Examples include xylene- (η-cyclopentadienyl) iron hexafluorophosphate, η-benzene- (η-cyclopentadienyl) iron tetrafluoroborate.

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

  That is, the following can be used as a photopolymerization initiator that can be used in combination.

  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 “Journal of Imaging Science (J. Imag. Sci.)”, Vol. 30, 174 (1986) (Oxo) sulfonium organoboron complexes described in Japanese Patent Application Nos. 4-56831 and 4-89535; "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 Organic halogen compounds described in JP-A-59-107344, etc.

  The content of the photopolymerization initiator according to the present invention is preferably 0.1% by mass to 20% by mass and particularly preferably 0.5% by mass to 15% by mass with respect to the polymerizable ethylenically unsaturated bond-containing compound.

(Binder)
The binder according to the present invention can carry the constituent components contained in the photosensitive layer, and the photosensitive layer contains a water-soluble polymer compound as the binder.

(Water-soluble polymer compound)
The water-soluble polymer compound according to the present invention means a compound having a solubility in water (g number dissolved in water 100 at 25 ° C.) of 0.1 or more and a molecular weight (weight average) of 500 or more.

  Examples of the water-soluble polymer compound according to the present invention include polyvinyl alcohol having various saponification degrees, polymers of hydroxystyrene and copolymers thereof, polyamide resins, copolymers of polyvinyl pyrrolidone and vinyl pyrrolidone, polyethylene oxide, polyethylene Examples include imine, polyacrylic acid amide, corn starch, mannan, pectin, agar, dextran, pullulan, glue, hydroxymethylcellulose, alginic acid, carboxymethylcellulose, sodium polyacrylate, and the like.

  As the water-soluble polymer compound according to the present invention, a polymer compound having a nonionic hydrophilic group is particularly preferably used.

  The molecular weight is preferably in the range of 1,000 to 100,000, particularly preferably in the range of 1,000 to 50,000 in terms of printing durability and image reproducibility.

  The photosensitive layer according to the present invention may contain a compound other than the water-soluble polymer compound as a binder, but the proportion of the water-soluble polymer compound in the binder is 80 to 100 with respect to the total binder. % By mass is preferable, and 90 to 100% is particularly preferable.

  The content of the binder according to the present invention is preferably 10% by mass to 95% by mass and particularly preferably 30% by mass to 90% by mass with respect to the photosensitive layer.

  Examples of the binder that can be used in combination include polyvinyl butyral resin, polyester resin, epoxy resin, phenol resin, polycarbonate resin, polyvinyl butyral resin, polyvinyl formal resin, shellac, and other natural resins.

(High molecular compound having nonionic hydrophilic group)
The nonionic hydrophilic group of the polymer compound having a nonionic hydrophilic group is a group or bond that exhibits hydrophilicity without being ionized in water. For example, an alcoholic hydroxyl group, an aromatic hydroxyl group, an acid Examples include an amide group, a sulfonamide group, a thiol group, a pyrrolidone group, a polyoxyethylene group, a polyoxypropylene group, and a sugar residue.

  As the polymer compound having a nonionic hydrophilic group, a compound containing 30% by mass or more of the nonionic hydrophilic group is particularly preferable from the viewpoint of developability.

  The compound containing a nonionic hydrophilic group is preferably an oligomer or polymer having a weight average molecular weight of 1,000 to 50,000 from the viewpoint of developability and image reproducibility. Examples thereof include polymers obtained by polymerizing one or more unsaturated monomers having a functional group in the side chain, polyvinyl alcohol polymers, cellulose polymers that are polysaccharides, and glucose polymers.

  For example, as an unsaturated monomer having an amide group in the side chain, an amidation monomer of unsubstituted or substituted (meth) acrylamide, itaconic acid, fumaric acid, maleic acid or the like, N-vinylacetamide, N- Examples include vinylformamide and N-vinylpyrrolidone.

  More specific examples of unsubstituted or substituted (meth) acrylamide include (meth) acrylamide, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-ethyl (meth) acrylamide, N, N- Diethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, butoxymethyl (meth) ) Acrylamide, propyl (meth) acrylamide, (meth) acryloylmorpholine, and the like.

  Further, in the case of an amidation monomer of a dibasic acid such as itaconic acid, a monoamide in which one carboxyl group is amidated, a diamide in which both carboxyl groups are amidated, and further one carboxyl group is amidated, An amide ester in which the other carboxyl group is esterified may be used.

  Examples of unsaturated monomers having a hydroxyl group include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and monomers obtained by adding ethylene oxide or propylene oxide to these (meth) acrylates. And methylol (meth) acrylamide, and methoxymethyl (meth) acrylamide and butoxymethyl (meth) acrylamide which are condensates of methylol (meth) acrylamide and methyl alcohol or butyl alcohol.

  The description such as “(meth) acryl”, “(meth) acrylate”, “(meth) acryloyl” means acryl or methacryl, acrylate or methacrylate, acryloyl or methacryloyl, respectively.

  The polyvinyl alcohol polymer will be described in more detail. A polymer obtained by completely or partially hydrolyzing a homopolymer or copolymer of a fatty acid vinyl monomer such as vinyl acetate or vinyl propionate, and a partial formalization or acetalization of this polymer. Examples include butyralized polymers.

  A compound containing 30% by mass or more of a nonionic hydrophilic group may have a crosslinkable functional group that reacts with a crosslinking agent. Specific examples of the crosslinkable functional group vary depending on the type of the crosslinking agent to be used, but nonionic ones are preferable, and examples thereof include a hydroxyl group, an isocyanate group, a glycidyl group, and an oxazoline group. In order to introduce these crosslinkable functional groups, unsaturated monomers having these functional groups, such as unsaturated monomers having a hydroxyl group described above, glycidyl (meth) acrylate, etc. as other unsaturated monomers having a glycidyl group ( What is necessary is just to copolymerize with a meth) acrylate monomer.

  In order to further improve the effect of the present invention, the compound containing 30% by mass or more of the nonionic hydrophilic group is other than the unsaturated monomer having the nonionic hydrophilic group and the unsaturated monomer having a crosslinkable functional group. In addition, other copolymerizable unsaturated monomers can be copolymerized.

  Examples of other copolymerizable unsaturated monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, and methoxy (C1 to C50). ) Ethylene glycol (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, isopolonyl (meth) acrylate, adamantyl (meth) acrylate, cyclohexyl ( (Meth) acrylate, styrene, α-methylstyrene, acrylonitrile, methacrylonitrile, vinyl acetate, and α-olefin (C4 to C30).

  Reaction described in “Crosslinking agent handbook” (Tosuke Kaneko, Junzo Yamashita, Taiseisha, 1981) as a crosslinking agent used to crosslink a compound containing 30% by mass or more of a nonionic hydrophilic group A combination of a crosslinking agent and a functional group can be selected.

  For example, known polyhydric alcohol compounds that react with a hydroxyl group, a glycidyl group, or an amide group as the crosslinkable functional group in a compound containing 30% by mass or more of a nonionic hydrophilic group as a crosslinking agent, Carboxylic acid compounds and their anhydrides, polyvalent glycidyl compounds (epoxy resins), polyvalent amine compounds, polyamide resins, polyvalent isocyanate compounds (including block isocyanates), oxazoline resins, amino resins And glyoxal.

  Among the crosslinking agents described above, various curing agents for epoxy resins such as various polyvalent glycidyl compounds (epoxy resins), oxazoline resins, amino resins, polyvalent amine compounds, and polyamide resins are known in terms of developability and printability. And glyoxal are preferred.

  Examples of amino resins include known melamine resins, urea resins, benzoguanamine resins, glycoluril resins, and modified resins of these resins, such as carboxy-modified melamine resins. In order to accelerate the crosslinking reaction, tertiary amines are used in combination with the above-described glycidyl compounds, and acidic compounds such as paratoluenesulfonic acid, dodecylbenzenesulfonic acid, and ammonium chloride are used in combination with amino resins. May be. When the photosensitive resin composition is heated with hot air, heated with a roller, heated with a laser, or the like, these crosslinking agents react to crosslink with a compound containing 30% by mass or more of a nonionic hydrophilic group.

Examples of the compound containing 30% by mass or more of a nonionic hydrophilic group include the following.
1. Vinylpyrrolidone-vinyl acetate copolymer (60/40) weight average molecular weight 34000
Product name: Lubiscol 64, manufactured by BASF Japan, VP / VA = 60 mol% / 40 mol% copolymer Vinylpyrrolidone-1 butene copolymer (90/10) Weight average molecular weight 17000
Product Name: GANEX P-904 LC ISP chemicals
3. Vinylpyrrolidone-glycidyl methacrylate copolymer (70/30) weight average molecular weight 10,000
4). Polyacrylamide average molecular weight 1700
Product Name: Mitsui Chemicals Aqua Polymer Co., Ltd. Acoflock N104
((C) Polymerizable ethylenically unsaturated bond-containing compound)
The polymerizable ethylenically unsaturated bond-containing compound according to the present invention is a compound having a polymerizable ethylenically unsaturated bond in the molecule, and is generally used for general radical polymerizable monomers and ultraviolet curable resins. Polyfunctional monomers having a plurality of addition-polymerizable ethylenic double bonds in the molecule used, and polyfunctional oligomers can be used.

  These polymerizable ethylenically unsaturated bond-containing compounds are not particularly limited. For example, 2-ethylhexyl acrylate, 2-hydroxypropyl acrylate, glycerol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, nonylphenoxyethyl acrylate, tetrahydro Monofunctional acrylic acid esters such as furfuryloxyethyl acrylate, tetrahydrofurfuryloxyhexanolide acrylate, ε-caprolactone adduct of 1,3-dioxane alcohol, 1,3-dioxolane acrylate, or these acrylates. Methacrylic acid, itaconic acid, crotonic acid, maleic acid ester instead of methacrylate, itaconate, crotonate, maleate Diglycol diene, triethylene glycol diacrylate, pentaerythritol diacrylate, hydroquinone diacrylate, resorcin diacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol hydroxypivalate Acrylate, dipentyl neopentyl glycol adipate, diacrylate of ε-caprolactone adduct of neopentyl glycol hydroxypivalate, 2- (2-hydroxy-1,1-dimethylethyl) -5-hydroxymethyl-5-ethyl- 1,3-dioxane diacrylate, tricyclodecane dimethylol acrylate, tricyclodecane dimethylol acrylate -Bifunctional acrylates such as caprolactone adduct, diglycidyl ether diacrylate of 1,6-hexanediol, or methacrylic acid, itaconic acid, crotonic acid in which these acrylates are replaced with methacrylate, itaconate, crotonate, maleate Maleic esters such as trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, trimethylolethane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexa Acrylate, ε-caprolactone adduct of dipentaerythritol hexaacrylate, Multifunctional acrylic acid ester acid such as rogalol triacrylate, propionic acid / dipentaerythritol triacrylate, propionic acid / dipentaerythritol tetraacrylate, hydroxypivalylaldehyde-modified dimethylolpropane triacrylate, or acrylate of these acrylates, itaconate , Methacrylic acid, itaconic acid, crotonic acid, maleic acid ester, etc., instead of crotonate and maleate.

(Polymerizable ethylenically unsaturated bond-containing compound containing a group that can be oxidized by light)
The polymerizable ethylenically unsaturated bond-containing compound used in the photosensitive layer according to the present invention is preferably an addition-polymerizable ethylenically unsaturated bond-containing compound containing at least one group capable of being oxidized by light.

  Particularly preferred are addition polymerizable compounds containing at least one photooxidizable group and at least one urethane group in the molecule. Suitable photooxidizable groups are in particular thio groups, thioether groups, ureido groups, amino groups and enol groups which may be members of the heterocyclic ring. Examples of these groups are triethanolamino group, triphenylamino group, thioureido group, imidazolyl group, oxazolyl group, thiazolyl group, acetylacetonyl residue, N-phenylglycine residue and ascorbic acid residue. Preference is given to addition-polymerizable compounds containing a tertiary amino group and a thioether group.

  Examples of the compound containing a photooxidizable group are described in European Patent Publication Nos. 287,818, 353,389 and 364,735. Preferred among the compounds described therein are those containing a ureido group and / or a urethane group in addition to the tertiary amino group.

  Examples of the compound having at least one photooxidizable group and at least one urethane group are described in JP-A Nos. 63-260909, 2666949, 6-35189, and 2001-125255. Can be mentioned.

  Furthermore, the present invention uses a reaction product of a polyhydric alcohol containing a tertiary amino group in the molecule, a diisocyanate compound, and a compound containing an ethylenic double bond capable of addition polymerization with a hydroxyl group in the molecule. Is preferred.

  Examples of the polyhydric alcohol having a tertiary amino group in the molecule include triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-tert. -Butyldiethanolamine, N, N-di (hydroxyethyl) aniline, N, N, N ', N'-tetra-2-hydroxypropylethylenediamine, p-tolyldiethanolamine, N, N, N', N'- Tetra-2-hydroxyethylethylenediamine, N, N-bis (2-hydroxypropyl) aniline, allyldiethanolamine, 3- (dimethylamino) -1,2-propanediol, 3-diethylamino-1,2-propanediol N, N-di (n-propyl) amino-2,3-propanediol, N, N-di (iso-propyl) amino-2,3-propanediol, 3- (N-methyl-N-benzylamino) ) -1,2-propanediol and the like, but not limited thereto.

  Examples of the diisocyanate compound include butane-1,4-diisocyanate, hexane-1,6-diisocyanate, 2-methylpentane-1,5-diisocyanate, octane-1,8-diisocyanate, 1,3-diisocyanate methyl-cyclohexanone. 2,2,4-trimethylhexane-1,6-diisocyanate, isophorone diisocyanate, 1,2-phenylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene-2,4-diisocyanate, tolylene- Examples include 2,5-diisocyanate, tolylene-2,6-diisocyanate, 1,3-di (isocyanatomethyl) benzene, 1,3-bis (1-isocyanato-1-methylethyl) benzene, and the like. Limited to Not. Although it does not specifically limit as a compound containing the ethylenic double bond which can be addition-polymerized with a hydroxyl group in a molecule | numerator, Preferably, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, 2- Examples include hydroxypropylene-1,3-dimethacrylate and 2-hydroxypropylene-1-methacrylate-3-acrylate.

  These reactions can be carried out in the same manner as a method for synthesizing urethane acrylate by a reaction of a normal diol compound, diisocyanate compound, and hydroxyl group-containing acrylate compound.

  Specific examples of reaction products of polyhydric alcohols containing tertiary amino groups in the molecule, diisocyanate compounds, and compounds containing ethylenic double bonds capable of addition polymerization with hydroxyl groups in the molecule are shown below. Shown in

M-1: reaction product of triethanolamine (1 mol), hexane-1,6-diisocyanate (3 mol), 2-hydroxyethyl methacrylate (3 mol) M-2: triethanolamine (1 mol), isophorone Reaction product of diisocyanate (3 mol) and 2-hydroxyethyl acrylate (3 mol) M-3: Nn-butyldiethanolamine (1 mol), 1,3-bis (1-isocyanato-1-methylethyl) Reaction product of benzene (2 mol) and 2-hydroxypropylene-1-methacrylate-3-acrylate (2 mol) M-4: Nn-butyldiethanolamine (1 mol), 1,3-di (isocyanate) Reaction of methyl) benzene (2 mol), 2-hydroxypropylene-1-methacrylate-3-acrylate (2 mol) Product M-5: Reaction product of N-methyldiethanolamine (1 mol), tolylene-2,4-diisocyanate (2 mol), 2-hydroxypropylene-1,3-dimethacrylate (2 mol) (other polymerization) Possible compounds containing ethylenically unsaturated bonds)
As the polymerizable ethylenically unsaturated bond-containing compound, a prepolymer can also be used in the same manner as described above.

  Examples of the prepolymer include compounds as described below, and a prepolymer obtained by introducing acrylic acid or methacrylic acid into an oligomer having an appropriate molecular weight and imparting photopolymerizability can be preferably used.

  These prepolymers may be used alone or in combination of two or more, and may be used by mixing with the above-mentioned monomers and / or oligomers.

  Examples of prepolymers include adipic acid, trimellitic acid, maleic acid, phthalic acid, terephthalic acid, hymic acid, malonic acid, succinic acid, glutaric acid, itaconic acid, pyromellitic acid, fumaric acid, glutaric acid, pimelic acid, Polybasic acids such as sebacic acid, dodecanoic acid, tetrahydrophthalic acid, and ethylene glycol, propylene glycol, diethylene glycol, propylene oxide, 1,4-butanediol, triethylene glycol, tetraethylene glycol, polyethylene glycol, glycerin, trimethylol Polyester 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; for example, epoxy acrylates in which (meth) acrylic acid is introduced into an epoxy resin such as bisphenol A, epichlorohydrin, (meth) acrylic acid, phenol novolac, epichlorohydrin, (meth) acrylic acid; 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 , 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, polysiloxane diisocyanate, 2-hydroxyethyl acrylate, etc .; and (meth) acryloyl in oil-modified alkyd resins Examples include prepolymers such as alkyd-modified acrylates and spirane resin acrylates having a group introduced therein.

  Further, the polymerizable ethylenically unsaturated bond-containing compound according to the present invention includes phosphazene monomer, triethylene glycol, isocyanuric acid EO (ethylene oxide) -modified diacrylate, isocyanuric acid EO-modified triacrylate, dimethylol tricyclodecanedi. Mention of monomers such as acrylate, trimethylolpropane acrylic acid benzoate, alkylene glycol type acrylic acid modified / urethane modified acrylate, and addition polymerizable oligomers and prepolymers having structural units formed from the monomer Can do.

  In addition, JP-A-58-212994, 61-6649, 62-46688, 62-48589, 62-173295, 62-187092, 63- No. 67189, JP-A-1-244891, and the like. Furthermore, “11290 Chemical Products”, Chemical Industry Daily, p. 286-p. 294, “UV / EB Curing Handbook (raw material)”, Kobunshi Shuppankai, p. The compounds described in 11 to 65 can also be used in the present invention.

  The content of the polymerizable ethylenically unsaturated bond-containing compound according to the present invention in the photosensitive layer is preferably in the range of 1.0 to 80.0% by mass, more preferably 3.0% with respect to the photosensitive layer. It is in the range of ˜70.0% by mass.

(Dye having an absorption maximum in the wavelength range of 350 nm to 450 nm)
The photosensitive layer of the present invention contains a sensitizing dye having an absorption maximum in the wavelength range of 350 to 450 nm.

  Examples of these dyes include cyanine, merocyanine, porphyrin, spiro compound, ferrocene, fluorene, fulgide, imidazole, perylene, phenazine, phenothiazine, acridine, azo compound, diphenylmethane, triphenylmethane, triphenylamine, coumarin derivative, quinacridone, Examples include indigo, styryl, pyrylium compounds, pyromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, ketoalcohol borate complexes, and the like.

  Of these sensitizing dyes, a coumarin dye represented by the following general formula (3) is preferably used.

In general formula (3), R < ¹ > -R < ⁶ > is a hydrogen atom, an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group) , Tridecyl group, tetradecyl group, pentadecyl group etc.), cycloalkyl group (eg cyclopentyl group, cyclohexyl group etc.), alkenyl group (eg vinyl group, allyl group etc.), alkynyl group (eg ethynyl group, propargyl group etc.) ), Aryl group (eg, phenyl group, naphthyl group, etc.), heterocyclic group (eg, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, propyloxy group, Pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group, etc.) Cycloalkoxy groups (eg, cyclopentyloxy group, cyclohexyloxy group, etc.), aryloxy groups (eg, phenoxy group, naphthyloxy group, etc.), alkylthio groups (eg, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group) Octylthio group, dodecylthio group, etc.), cycloalkylthio group (eg, cyclopentylthio group, cyclohexylthio group, etc.), arylthio group (eg, phenylthio group, naphthylthio group, etc.), alkoxycarbonyl group (eg, methyloxycarbonyl group, ethyl) Oxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (for example, phenyloxycarbonyl group, naphthyloxycarbonyl) Sulfonyl groups, such as aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenyl Aminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), acyl group (for example, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group) , Dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), amide group (for example, methylcarbonylamino group, Rucarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino Group), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, Dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc. Ureido groups (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group, naphthylureido group, 2-pyridylaminoureido group), alkylsulfonyl group ( For example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl group (phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), Amino group (for example, unsubstituted amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthyla) Mino group, 2-pyridylamino group and the like), halogen atom (for example, fluorine atom, chlorine atom, bromine atom and the like), cyano group, nitro group, hydroxy group and the like. These substituents may be further substituted with the above substituents. In addition, a plurality of these substituents may be bonded to each other to form a ring.

Among these, particularly preferred are coumarins having an amino group (unsubstituted amino group, alkylamino group, dialkylamino group, arylamino group, diarylamino group, alkylarylamino group) in R ⁵ . In this case, an alkyl group substituted with an amino group that forms a ring with the substituents R ⁴ and R ⁶ can also be preferably used.

Furthermore, either or both of R ¹ and R ² are alkyl groups (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group). Group, tetradecyl group, pentadecyl group etc.), cycloalkyl group (eg cyclopentyl group, cyclohexyl group etc.), alkenyl group (eg vinyl group, allyl group etc.), aryl group (eg phenyl group, naphthyl group etc.), Heterocyclic group (for example, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxycarbonyl group (for example, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group) Etc.), aryloxyca Bonyl group (for example, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), acyl group (for example, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group) , Dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylamino) Carbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthyla Minocarbonyl group, 2-pyridylaminocarbonyl group, etc.), 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-pyridylsulfinyl group, alkylsulfonyl groups (for example, methylsulfonyl group, ethylsulfonyl group) , Butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl group (phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), halogen atom (eg, fluorine atom, chlorine) Atom, bromine atom, etc.), cyano group, nitro group, halogenated alkyl group (trifluoromethyl group, tribromomethyl group, trichloromethyl group, etc.).

The most preferable dye represented by the general formula (1) is that R ⁵ is an amino group (unsubstituted amino group, alkylamino group, dialkylamino group, arylamino group, diarylamino group, alkylarylamino group). , R ¹ is an alkoxycarbonyl group or a pyridyl group and is an aluminum dye.

  Preferable specific examples of the compound represented by the general formula (3) include the following compounds.

  In addition to the above specific examples, coumarin derivatives of B-1 to B-22 in JP-A-8-129258, coumarin derivatives of D-1 to D-32 in JP-A-2003-21901, JP-A-2002-363206 No. 1 to 21 Coumarin Derivatives, JP-A No. 2002-363207 No. 1 to 40 Coumarin Derivatives, JP-A No. 2002-363208 No. 1 to 34 Coumarin Derivatives, JP-A No. 2002-363209 No. 1 56 coumarin derivatives and the like can also be preferably used.

(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 ethylenically unsaturated double bond compound that can be polymerized during the production or storage of the photosensitive lithographic printing plate material, A hindered phenol compound, a hindered amine compound, and other polymerization inhibitors may be added.

  Examples of hindered phenol compounds include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,2′-methylenebis (4-methyl-6-t-butylphenol), 4,4 '-Butylidenebis (3-methyl-6-tert-butylphenol), tetrakis- [methylene-3- (3', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate] methane, bis [3,3 '-Bis- (4'-hydroxy-3'-t-butylphenyl) butyric acid] glycol ester, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl)- 4-methylphenyl acrylate, 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphene Acrylate, etc., preferably 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate having a (meth) acrylate group, 2- [ And 1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate.

  Examples of hindered amine compounds include bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1- [ 2- [3- (3,5-di-tert-butyl-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy]- 2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1, 3,8-triazaspiro [4.5] decane-2,4-dione and the like.

  Other polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol) Hindered amines such as 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxylamine primary cerium salt, 2,2,6,6-tetramethylpiperidine derivatives, and the like. .

  The addition amount of the polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass with respect to the mass of the photosensitive layer. Also, if necessary, higher fatty acid derivatives such as behenic acid and behenic acid amide are added to prevent polymerization inhibition by oxygen, or unevenly distributed on the surface of the photopolymerizable photosensitive layer during the drying process after coating. You may let them. The amount of the higher fatty acid derivative added is preferably about 0.5% by mass to about 10% by mass of the total composition.

  In the photosensitive layer according to the present invention, a colorant can be used in addition to the above-mentioned components. As the colorant, conventionally known ones including commercially available ones can be suitably used. 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.

  Further, the addition amount of the pigment is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass with respect to the solid content of the photosensitive layer.

  The photosensitive layer can contain a plasticizer in order to improve adhesion to the support.

  Plasticizers include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, didodecyl phthalate, diisodecyl phthalate, butyl benzyl phthalate, diisononyl phthalate, ethyl phthalyl ethyl Examples include glycol, dimethyl isophthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. The amount of the plasticizer added is preferably about 0 to 3% by mass, more preferably 0.1 to 2% by mass, based on the total solid content of the coating composition.

  In addition, a coating property improving agent such as a surfactant necessary for coating the photosensitive layer can be contained within a range not impairing the performance of the present invention. Of these, fluorine-based surfactants are preferred.

  In addition, an additive such as an inorganic filler, a plasticizer such as dioctyl phthalate, dimethyl phthalate, or tricresyl phosphate may be added to the photosensitive layer in order to improve the physical properties of the cured film. These addition amounts are preferably 10% by mass or less based on the total solid content of the photosensitive layer.

(Application)
The photosensitive layer according to the present invention is obtained by preparing a coating solution for the photosensitive layer, and applying and drying the coating solution on a support.

  Examples of the solvent used for coating include alcohols: sec-butanol, isobutanol, n-hexanol, benzyl alcohol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,5-pentanediol, etc .; ethers: Propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, etc .; ketones, aldehydes: diacetone alcohol, cyclohexanone, methylcyclohexanone, etc .; esters: ethyl lactate, butyl lactate, diethyl oxalate, methyl benzoate Etc. are preferred.

  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.

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

  Examples of the support of the present invention include metal plates such as aluminum, stainless steel, chromium and nickel, and plastic films such as polyester film, polyethylene film and polypropylene film laminated or vapor-deposited with the above metal thin 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 as the support, and for example, alloys of metals such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel, titanium, sodium, iron, and aluminum are used. . Further, the aluminum support having a roughened surface is used for water retention.

  Prior to roughening (graining treatment), it is preferable to perform a degreasing treatment in order to remove the rolling oil on the surface. 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. 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. In addition, it is preferable that after the immersion treatment with an alkaline aqueous solution, neutralization treatment is performed 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 for roughing, 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, water-soluble resins such as polyvinylphosphonic acid, polymers and copolymers having a sulfonic acid group in the side chain, polyacrylic acid, water-soluble metal salts (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 No. 5-304358 is covalently used.

(Protective layer)
A protective layer may be provided on the upper side of the photosensitive layer according to the present invention.

  The material constituting the protective layer is preferably polyvinyl alcohol, polysaccharide, polyvinyl pyrrolidone, polyethylene glycol, gelatin, glue, casein, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl starch, gum arabic, sucrose octaacetate, ammonium alginate , Sodium alginate, polyvinylamine, polyethylene oxide, polystyrene sulfonic acid, polyacrylic acid, water-soluble polyamide, polyvinylpyrrolidone copolymer, and the like. These compounds can be used alone or in combination of two or more as a protective layer coating composition. A particularly preferred compound is polyvinyl alcohol.

(Plate making method)
In the lithographic printing plate making method of the present invention, image exposure is performed with a laser beam having a wavelength of 350 nm to 450 nm.

  Available laser light sources having an emission wavelength of 350 to 450 nm include, for example, a combination of a waveguide wavelength conversion element and AlGaAs and InGaAs semiconductors (380 to 450 nm), and a combination of a waveguide wavelength conversion element and AlGaInP and AlGaAs semiconductors. In addition, AlGaInN (350 nm to 450 nm), N2 laser (337 nm, pulse 0.1 to 10 mJ), XeF (351 nm, pulse 10 to 250 mJ), etc. may be mentioned as pulse lasers. Preferably used.

  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.

(On-press development method)
In the plate-making method of the present invention, the image-exposed lithographic printing plate material is subjected to development processing with dampening water and / or printing ink on a printing machine without performing a wet processing step after image exposure, An image for printing is formed and printing is continued.

  Image exposure may be performed before the lithographic printing plate material is mounted on the printing press, or may be mounted on the printing press to perform image exposure, and then on-press development may be performed.

  The development processing on the lithographic printing machine according to the present invention is to remove non-image areas using dampening water and / or printing ink of the lithographic printing machine at the stage of printing preparation on the printing machine. The so-called development process is performed on the printing apparatus.

The removal of the non-image part (unexposed part) of the image forming layer on the printing press can be performed by contacting a watering roller or an ink roller while rotating the plate cylinder. Alternatively, it can be performed by various other sequences. In this case, the water amount may be adjusted by increasing or decreasing the amount of dampening water required for printing. The water amount adjustment may be divided into multiple stages or steplessly. You may change it to.
(1) As a sequence for starting printing, a watering roller is brought into contact with the plate cylinder to make one to several dozen rotations, then an ink roller is brought into contact with the plate cylinder to make one to several dozen rotations, and then Start printing.
(2) As a sequence for starting printing, an ink roller is contacted to rotate the plate cylinder 1 to several tens of turns, then a watering roller is contacted to rotate the plate cylinder 1 to tens of rotations, Start printing.
(3) As a sequence for starting printing, the watering roller and the ink roller are brought into contact with each other substantially simultaneously to rotate the plate cylinder 1 to several tens of times, and then printing is started.

  As the printing machine, generally known lithographic offset printing machines are used.

(Dampening water)
As the fountain solution, a fountain solution generally used for printing on a lithographic printing plate can be used. Only water or an additive may be included.

  As the fountain solution, fountain solution containing no conventionally used isopropanol is preferably used. In this case, “not contained” means that the content is less than 0.5%.

  As the fountain solution, an aqueous solution containing a surfactant is preferably used.

  As the dampening water, tap water, well water, etc., which are generally obtained, can be used.

  The fountain solution contains, as a minor component, acids such as phosphoric acid or a salt thereof, citric acid or a salt thereof, nitric acid or a salt thereof, acetic acid or a salt thereof, and more specifically phosphoric acid, ammonium phosphate, phosphoric acid. Sodium, etc., citric acid, ammonium citrate, sodium citrate, acetic acid, ammonium acetate, sodium acetate and the like, and water-soluble polymer compounds such as carboxymethyl cellulose, carboxyethyl cellulose, etc.

  The content of these trace components is less than 0.1% by mass, preferably 0.05% by mass or less.

  Furthermore, glycol compounds such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol propyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether, dipropylene glycol dimethyl ether, dipropylene Glycol diethyl ether, dipropylene glycol dibutyl ether and the like can also be contained, and the content of these glycol compounds is also preferably small, less than 0.1% by mass, and preferably 0.05% by mass or less.

  Further, a surfactant may be included.

  The surfactant is a nonionic surfactant, an anionic surfactant, a cationic surfactant, or these surfactants are a nonionic surfactant, an anionic surfactant, a cationic surfactant, or a mixed interface thereof. An activator is preferably used.

  Specific examples of the anionic surfactant include, for example, fatty acid salts, abietic acid salts, hydroxyalkanesulfonic acid salts, alkanesulfonic acid salts, dialkylsulfosuccinic acid salts, linear alkylbenzene sulfonic acid salts, alkylnaphthalenesulfonic acid salts, Alkylphenoxy polyoxyethylene propyl sulfonates, polyoxyethylene alkyl sulfophenyl ether salts, N-methyl-N-oleyl taurine sodium salts, N-alkyl sulfosuccinic acid monoamide disodium salts, petroleum sulfone complex salts, sulfated castor oil, Sulfated tallow oil, sulfates of fatty acid alkyl esters, polyoxyethylene alkyl ether sulfates, fatty acid monoglyceride sulfates, polyoxyethylene alkylphenyl esters Sulfuric acid ester salts, polyoxyethylene styryl phenyl ether sulfuric acid ester salts, alkyl phosphoric acid ester salts, polyoxyethylene alkyl ether phosphoric acid ester salts, polyoxyethylene alkylphenyl ether phosphoric acid ester salts, partial saponification of styrene and maleic anhydride copolymer And naphthalene sulfonate formalin condensates.

  Specific examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polystyryl phenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, glycerin fatty acid partial esters , Sorbitan fatty acid partial esterified product, pentaerythritol fatty acid partial esterified product, propylene glycol monofatty acid ester, sucrose fatty acid partial esterified product, polyoxyethylene sorbitan fatty acid partial esterified product, polyoxyethylene sorbitol fatty acid partial ester Products, polyethylene glycol fatty acid esters, polyglycerol fatty acid partial esterified products, polyoxyethylenated castor oil, polyoxyethylene glycol Phosphorus fatty acid partial esterified products, fatty acid diethanolamides, N, N-bis-2-hydroxyalkylamines, polyoxyethylene alkylamines, triethanolamine fatty acid esters, trialkylamine oxides, polyoxyethylene-poly Examples thereof include oxypropylene block polymers. Other fluorine-based surfactants and silicon-based surfactants can also be used.

  Specific examples of the cationic surfactant include alkylamine salts, quaternary ammonium salts, polyoxyethylene alkylamine salts, polyethylene polyamine derivatives, and the like.

  These surfactants may be used alone or in combination of two or more. The amount of the surfactant in the fountain solution is preferably 0.01% by mass or less, and more preferably 0.05% by mass or less.

(printing)
The lithographic printing plate material of the present invention is subjected to printing after image exposure. As a printing machine, a general lithographic offset printing machine using fountain solution as described above can be used. Printing paper, printing ink, fountain solution, etc. used for printing are not particularly limited.

  In recent years, in the printing industry, from the viewpoint of environmental protection, inks that do not use petroleum-based volatile organic compounds (VOC) have been developed and are widely used as printing inks. It is particularly large when using the printing ink.

  These inks are preferably inks containing soybean oil.

  The ink containing soybean oil is usually a mixture of organic / inorganic pigments, binder resin, soybean oil, high boiling petroleum solvent, and other additives such as plasticizers, stabilizers, drying agents, thickeners, It may contain a dispersant, a filler, and the like.

  Inks that are preferably used for printing of the present invention include inks certified by the American Soybean Association (ASA) with a soy seal certification system.

  As soybean oil, known soybean oil can be used, and edible soybean oil (refined soybean oil) certified by Japanese Agricultural Standards is particularly preferably used.

  The preferred amount of soybean oil to be added varies depending on the type of ink, but is 20 to 50% by mass for sheet-fed ink and foam ink, 7 to 20% by mass for off-ring heat set ink, and 40 to 50 mass for black ink for newspaper ink. %, 30 to 40% by mass for color ink, and 20 to 30% by mass for business foam ink.

  As organic / inorganic pigments, disazo yellow, brilliant carmine 6B, phthalocyanine blue, lake red C, carbon black, titanium oxide, calcium carbonate and the like can be used.

  As binder resin, natural or processed resin such as rosin, copal, dammar, shellac, cured rosin, rosin ester, phenol resin, rosin modified phenol resin, 100% phenol resin, maleic acid resin, alkyd resin, petroleum resin, vinyl resin Acrylic resin, polyamide resin, epoxy resin, amino alkyd resin, polyurethane resin, amino blast resin and the like are preferable.

  Inks containing soybean oil are available from various ink manufacturers and can be easily obtained. For example, Naturalis 100 (Naturalith) sheet-fed ink, WebWorld Advan off-wheel ink, <above, Dainippon Ink Chemical Industry Co., Ltd.>, TK High Unity SOY Sheetfed Ink, TK High Echo SOY Sheetfed Ink, CK Win Echo SOY Sheetfed Ink, WD Super Leo Echo SOY Off Wheel Ink, WD Leo Echo SOY Off Wheel Ink, SCRSOY Business Form inki <above, Toyo Ink Co., Ltd.>, Soyselvo sheet-fed ink <Tokyo Ink Co., Ltd.> and the like.

  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, “parts” represents “parts by mass” unless otherwise specified.

(Production of support)
Aluminum plate with a thickness of 0.3 mm (material 1052, Al: 99.3% or more, Na: 0.003%, Mg: 0.20%, Si: 0.08%, Ti: 0.06%, Mn: 0.004%, Fe: 0.32%, Ni: 0.004%, Cu: 0.002%, Zn: 0.015%, Ga: 0.007%, Cr: 0.001%) It was immersed in a 5% sodium hydroxide aqueous solution kept at 55 ° C., degreased for 15 seconds, and then washed with water.

  The degreased aluminum plate was neutralized by immersing it in a 10% nitric acid aqueous solution maintained at 25 ° C. for 10 seconds, and then washed with water.

  Next, the surface was electrolytically roughened using a 60 Hz sine wave AC power supply. Then, it was immersed in a 100 g / l phosphoric acid aqueous solution kept at 60 ° C. for 10 seconds, subjected to desmut treatment, and washed with water.

Next, using a direct current power source, an anodizing treatment was carried out in a sulfuric acid aqueous solution (200 g / l) at 35 ° C. with a current density of 10 A / dm ² and a film mass of 20 mg / dm ² .

  Next, a 0.44% aqueous solution of polyvinylphosphonic acid was subjected to dip treatment at 75 ° C. for 30 seconds, then washed with distilled water and dried.

  At this time, the centerline average roughness (Ra) of the surface was 0.45 μm.

(Preparation of photosensitive lithographic printing plate material)
On the above support, a photopolymerizable photosensitive layer coating solution having the following composition was coated with a wire bar so that the dried solution was 1.5 g / m ² and dried at 95 ° C. for 1.5 minutes. Got.

Further, on the photopolymerization photosensitive layer coating sample, an oxygen barrier layer coating solution having the following composition was coated with a wire bar so as to be 1.8 g / m ² at the time of drying, and dried at 75 ° C. for 1.5 minutes. Photosensitive lithographic printing plates 1 to 20 (shown in Table 1) having an oxygen blocking layer on the layer were prepared.

(Photopolymerizable photosensitive layer coating solution 1)
Binder (shown in Table-1) 40.0 parts Polymerizable monomer (shown in Table-1) 39.0 parts Dye (shown in Table-1) 10.0 parts Polyhalogen compound (shown in Table-1) ) 10.0 parts phthalocyanine pigment (MHI454: manufactured by Gokoku Color Co., Ltd.) 0.5 parts 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate ( Sumilizer GS: manufactured by Sumitomo 3M Co., Ltd.) 0.5 part Surfynol 465 (produced by Air Products) 0.5 part Methanol 75 parts Ethanol 75 parts Water 850 parts (Evaluation of printing durability)
Using a plate setter (NEWS custom-made product: manufactured by ECRM) with a light source of 405 nm under the condition that the exposure energy on the printing plate is 200 μJ / cm ² , 2400 dpi (dpi is the number of dots per 2.54 cm) And a lithographic printing plate was obtained.

  The produced lithographic printing plate was coated with a printing machine (DAIYA1F-1 manufactured by Mitsubishi Heavy Industries, Ltd.), printing ink (soybean oil ink, NCP Naturalis (Dainippon Chemical Co., Ltd.)) and dampening water ( Printing was performed using Tokyo ink Co., Ltd. H liquid SG-51 density 1.5%. After 1000 sheets were printed continuously, the plate surface was wiped with a cleaner, the highlight part was thinned, and the shadow part was entangled (image part) The number of printed sheets in which ink adheres to the peripheral non-image area) was used as an index of printing durability.

  The printing durability once refers to the operation of wiping with a cleaner after printing 1000 sheets continuously. The more it is, the better. The cleaner uses an ultra plate cleaner (manufactured by Dainichi Seika Co., Ltd.).

(Evaluation of dirt recovery)
Wiping with a cleaner after 1000 sheets of continuous printing was performed, and printing was resumed after 1 hour, and the number of sheets where there was no background smudge in the non-image area was determined. Less is better.

  The results are shown in Table 1. From Table 1, it can be seen that the plate making method of the present invention can be developed on a printing press, and a lithographic printing plate excellent in printing durability and stain recovery can be obtained.

x1: BR22 (above)
x4: BR43 (above)
p1: Polyvinyl alcohol (Gohsenol AL-06 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.))
p2: Carboxymethylcellulose (CMC Daicel (Daicel Chemical Industry Co., Ltd.))
p3: Vinylpyrrolidone homopolymer (LuvitecK30 (manufactured by BASF))
p4: Polyacrylic acid (Julimer AC-10H (manufactured by Nippon Pure Chemicals Co., Ltd.))
p5: Methyl methacrylate / methacrylic acid copolymer (4: 1 (mass ratio))
m1: Urethane acrylate (NK Oligo UA-7100 (manufactured by Shin-Nakamura Chemical Co., Ltd.))
m2: Ethoxylated glycerin triacrylate (NK ester A-GLY (manufactured by Shin-Nakamura Chemical Co., Ltd.))
m3: ethyl-α- (hydroxymethyl) acrylate m4: N methylol acrylamide m5: vinyl acetate monomer

Claims (7)

Contains (A) a photopolymerization initiator, (B) a binder, (C) a polymerizable ethylenically unsaturated bond-containing compound, and (D) a dye having an absorption maximum in the wavelength range of 350 nm to 450 nm on the support. A method for making a lithographic printing plate comprising: exposing a photosensitive lithographic printing plate material having a photosensitive layer to be image-exposed; and developing the lithographic printing plate by performing development processing on the lithographic printing machine after the image exposure; The method for making a lithographic printing plate comprises: (A) a polyhalogen compound as a photopolymerization initiator; and (B) a water-soluble polymer compound as a binder. The lithographic printing plate making method according to claim 1, wherein the water-soluble polymer compound is a water-soluble polymer compound having a nonionic hydrophilic group. The lithographic printing plate making method according to claim 1, wherein the image exposure is performed using a laser beam having a wavelength of 350 nm to 450 nm. The lithographic printing plate making method according to any one of claims 1 to 3, wherein the water-soluble polymer compound has a weight average molecular weight of 1,000 to 50,000. The lithographic printing plate making method according to any one of claims 1 to 4, wherein the support is an aluminum support subjected to a roughening treatment and an anodizing treatment. A photosensitive lithographic printing plate material, which is used in the lithographic printing plate making method according to any one of claims 1 to 5. A lithographic printing method comprising printing using a lithographic printing plate produced by the lithographic printing plate making method according to any one of claims 1 to 5.