JP2007226104A - Photosensitive planographic printing plate and method for processing photosensitive planographic printing plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive planographic printing plate and a method for processing the photosensitive planographic printing plate that can prevent stains like minute dots which generates in a non-image part upon restarting to print after a printing machine is stopped for a while for registering, a break, etc. during printing, that can reduce sludge accumulating in a developing tank when the process is carried out for a long period of time and that can reduce burden of cleaning work. <P>SOLUTION: The photosensitive planographic printing plate has a photopolymerizable layer essentially comprising a photopolymerizable composition and a protective layer containing a water-soluble polymer and a compound expressed by general formula (A) on the photopolymerizable layer. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a photosensitive lithographic printing plate and a method for processing the photosensitive lithographic printing plate.

  Conventionally, the lithographic printing method is a printing method that utilizes the fact that water and oil do not essentially mix, and the printing plate surface accepts water and repels oil-based ink, and repels water and oil-based ink. Is formed, and water and oil-based ink are supplied from a printing machine, and printing is performed by transferring only the oil-based ink received in the image portion to paper. The printing machine generally uses an offset printing method in which the oil-based ink received in the image portion of the printing plate surface is once transferred to a rubber blanket and then transferred to paper.

  Conventionally, as a support used for a photosensitive lithographic printing plate, from the viewpoint of printability, those having excellent hydrophilicity, water retention, and adhesion to a photosensitive layer are required. An aluminum plate having a roughened surface called a grained surface is used.

  As the roughening treatment, mechanical surface roughening methods such as ball polishing, brush polishing, blast polishing, buff polishing, honing polishing, etc., and electrolysis of the support surface by alternating current or direct current in an acidic electrolyte such as hydrochloric acid and nitric acid. An electrochemical surface roughening method for processing is known. The aluminum plate grained by such a method is relatively soft and easy to wear as it is, and then anodized to form an oxide film. The surface of the aluminum plate treated in this way is hard and has excellent wear resistance.

  When the exposed lithographic printing plate is developed with an alkaline aqueous solution, the exposed or unexposed portion of the photosensitive layer is removed to expose the support surface. Since the surface of the aluminum support is hydrophilic, the portion where the surface of the support is exposed by development (non-image portion) receives water and repels the oil-based ink. On the other hand, the portion where the photosensitive layer has not been removed by development (image portion) is oleophilic and therefore repels water and accepts the oil-based ink.

  In general, the higher the sensitivity of a photosensitive lithographic printing plate, the shorter the time required for exposure, and the faster the operation can be performed. When printing such a photosensitive lithographic printing plate, after the printing machine is stopped for a while due to consideration or breaks during printing work, fine dot-like stains that occur in the non-image area when printing resumes. In order to prevent this stain, a method for maintaining the hydrophilicity of the plate surface of the non-image portion has been desired.

  Conventionally, an aqueous solution of an alkali metal silicate has been widely used for development processing of a photosensitive lithographic printing plate, and the hydrophilicity of the support surface is increased by the reaction of aluminum on the support surface with silicic acid in the developer. However, with this method alone, the hydrophilicity was not sufficiently maintained, and stop dirt could not be completely suppressed.

Further, in the photopolymerizable photosensitive lithographic printing plate of the type that forms a latent image by a free radical reaction by a combination of a photo free radical generator and an ethylenically unsaturated compound, an alkali aqueous solution is used to perform light exposure after image exposure. When a photosensitive lithographic printing plate having a polymerizable layer is developed, a highly sensitive lithographic printing plate can be obtained. In addition, the photosensitive lithographic printing plate of the type that forms a latent image by the above free radical reaction generally has an excellent sensitivity, but has a drawback that the free radical reaction is inhibited by oxygen, so that the protective layer It is known that it is effective to provide some oxygen barrier layer on the photosensitive layer, and it is known that such an oxygen barrier layer is mainly composed of polyvinyl alcohol as a main component. In addition, this oxygen barrier layer tends to generate sludge and sludge in the developer by being brought into the developer, and is provided with a step (pre-water washing or pre-development water washing) of removing the oxygen barrier layer by washing with water before development. It is effective. However, when a photosensitive lithographic printing plate provided with an oxygen barrier layer mainly composed of polyvinyl alcohol on the photosensitive layer is repeatedly processed using an automatic processor, sludge and sludge are generated in the pre-wash solution. Therefore, work burdens such as cleaning and clogging of the pump have been a problem. As a countermeasure against this, a technique using various additives in pre-development washing water has been disclosed (see Patent Document 1), but no solution including prevention of stop contamination has been made.
Japanese Patent Laid-Open No. 10-010754

  The present invention has been made in view of the above-described problems, and the object of the present invention is to provide a fine dot-like shape that occurs in a non-image area when printing is resumed after the printing press is stopped for a while due to consideration or break during printing. It is an object of the present invention to provide a photosensitive lithographic printing plate capable of preventing contamination and a method for processing the photosensitive lithographic printing plate. Another object of the present invention is to provide a photosensitive lithographic printing plate and a method for processing the photosensitive lithographic printing plate that can reduce sludge sludge accumulated in a developing tank when processed for a long period of time and reduce the burden of cleaning work.

  The above object of the present invention can be achieved by the following constitution.

  1. Photosensitivity comprising a photopolymerization layer mainly containing a photopolymerization composition, and a protective layer containing a water-soluble polymer and a compound represented by the following general formula (A) on the photopolymerization layer. Sex lithographic printing plate.

(In the formula, A ₁ represents an alkyl group having 1 to 5 carbon atoms, a hydroxylalkyl group, an aryl group, a hydroxylaryl group, an oxyalkyl group, an oxyaryl group, —CH ₂ —COOH, —CH ₂ —COONa, —CH. ₂ represents —COOK, —COOH, —COONa, —COOK, —C ₂ H ₅ —COOH, —C ₂ H ₅ —COONa or —C ₂ H ₅ —COOK, wherein M ₁ , M ₂ and M ₃ each represents Independently represents an alkali metal.)
2. Photosensitive lithographic printing comprising a photopolymerizable layer mainly comprising a photopolymerizable composition, and a protective layer containing a water-soluble polymer and the compound represented by formula (A) described in 1 above the photopolymerized layer A method for processing a photosensitive lithographic printing plate, characterized in that after the image is exposed to an image, the protective layer is washed and removed in a water washing step, followed by development.

  3. 3. The method for processing a photosensitive lithographic printing plate according to 2, wherein the developer used for the development is an alkaline aqueous solution substantially free of silicate.

  According to the present invention, a photosensitive lithographic printing plate capable of preventing fine spot-like stains generated in a non-image area when printing is resumed after stopping the printing machine for a while due to examination or break at the time of printing, and A method for processing the photosensitive lithographic printing plate can be provided. Further, it is possible to provide a photosensitive lithographic printing plate and a processing method for the photosensitive lithographic printing plate that can reduce sludge sludge accumulated in a developing tank when processed for a long period of time and reduce the burden of cleaning work.

  Hereinafter, although the best mode for carrying out the present invention will be described, the present invention is not limited to these.

  The photosensitive lithographic printing plate of the present invention comprises a photopolymerization layer mainly containing a photopolymerization composition, a water-soluble polymer and a compound represented by the general formula (A) of the present invention on the photopolymerization layer. It has the protective layer to contain.

  The processing method of the photosensitive lithographic printing plate of the present invention includes a photopolymerization layer mainly containing a photopolymerization composition, a water-soluble polymer on the photopolymerization layer, and a general formula (A) of the present invention. The photosensitive lithographic printing plate having a protective layer containing the compound represented is characterized in that after the image exposure, the protective layer is washed and removed in a water washing step, followed by development.

  The compound represented by the general formula (A) of the present invention will be described.

In the general formula (A), A ₁ represents an alkyl group having 1 to 5 carbon atoms, a hydroxylalkyl group, an aryl group, a hydroxylaryl group, an oxyalkyl group, an oxyaryl group, —CH ₂ —COOH, —CH ₂ —. COONa, represents _{-CH 2 -COOK, -COOH, -COONa,} -COOK, -C 2 H 5 -COOH, -C 2 H 5 -COONa or a -C ₂ H ₅ -COOK. M ₂ and M ₃ each independently represents an alkali metal (sodium, potassium, lithium, etc.).

  Among the compounds represented by the general formula (A) of the present invention, the following compounds such as A-1 and A-2 can be more preferably used, but the present invention is not limited thereto.

(Photopolymerization initiator composition)
Preferred photopolymerization initiators related to the photopolymerization composition of the present invention include bromine compounds, titanocene compounds, monoalkyltriaryl borate compounds, and iron arene complex compounds having a structure represented by the following general formula (1).

Formula (1) R ¹ —CBr ₂ — (C═O) —R ²
In the formula, R ¹ represents a hydrogen atom, a bromine atom, an alkyl group, an aryl group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, or a cyano group. R ² represents a monovalent substituent. R ¹ and R ² may be bonded to form a ring.

Formula (2) Br 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.

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

  Examples of the monoalkyltriaryl borate compound include compounds described in JP-A-62-154024 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 -Butyl ammonium n-hexyl root- (3-chloro-4-methylphenyl) -borate, tetra-n-butylammonium n-hexyl root- (3-fluorophenyl) -borate and the like.

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

  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: described in JP-A-1-54440, European Patents 109,851, 126,712 and “Journal of Imaging Science (J. Imag. Sci.)”, Vol. 30, 174 (1986) Metallocene allene complexes; (oxo) sulfonium organoboron complexes described in JP-A Nos. 5-213861 and 05-255347; "Coordination Chemistry Review", 84, 85-277 (1988) And transition metal complexes containing a transition metal such as ruthenium described in JP-A-2-182701; 2,4,5-triarylimidazole dimer described in JP-A-3-209477; carbon tetrabromide, JP Organic halogen compounds described in 59-107344 ;, Etc..

  When laser light is used as the light source, a sensitizing dye is preferably added to the photosensitive layer. It is preferable to use a dye having an absorption maximum wavelength in the vicinity of the wavelength of the light source.

  Examples of compounds for wavelength sensitization from visible light to near infrared include cyanine, phthalocyanine, merocyanine, porphyrin, spiro compound, ferrocene, fluorene, fulgide, imidazole, perylene, phenazine, phenothiazine, polyene, azo compound, diphenylmethane, triphenyl Ketone alcohol borate complexes such as methane, polymethine acridine, coumarin, coumarin derivatives, ketocoumarin, quinacridone, indigo, styryl, pyrylium compounds, pyromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, etc. Further, European Patent No. 568,993, US Patent Nos. 4,508,811, 5,227,227, JP 2001-125255 A, JP 11 Compounds described in such Patent 271,969 may also be used.

  Specific examples of the combination of the photopolymerization initiator and the sensitizing dye include combinations described in JP-A Nos. 2001-125255 and 11-271969.

  Although the compounding quantity of these polymerization initiators is not specifically limited, Preferably, it is 0.1-20 mass parts with respect to 100 polymerization parts of compound which can be addition-polymerized or bridge | crosslinked. The mixing ratio of the photopolymerization initiator and the sensitizing dye is preferably in the range of 1: 100 to 100: 1 in terms of molar ratio.

(Addition-polymerizable ethylenic double bond-containing monomer)
The compound containing an ethylenic double bond capable of addition polymerization according to the photopolymerizable composition of the present invention is capable of addition polymerization in the molecule generally used for general radical polymerizable monomers and UV curable resins. Polyfunctional monomers having multiple ethylenic double bonds and polyfunctional oligomers can be used. The compound is not limited, but preferred examples include 2-ethylhexyl acrylate, 2-hydroxypropyl acrylate, glycerol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, nonylphenoxyethyl acrylate, tetrahydrofurfuryloxyethyl acrylate, tetrahydro Furfuryloxyhexanolide acrylate, acrylate of ε-caprolactone adduct of 1,3-dioxane alcohol, monofunctional acrylic acid esters such as 1,3-dioxolane acrylate, or these acrylates as methacrylate, itaconate, crotonate, maleate Methacrylic acid, itaconic acid, crotonic acid, maleic acid esters such as ethylene glycol diacrylate , Triethylene glycol diacrylate, pentaerythritol diacrylate, hydroquinone diacrylate, resorcin diacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, dipentylate of hydroxypentylate neopentyl glycol, Diacrylate of neopentyl glycol adipate, Diacrylate of ε-caprolactone adduct of neopentyl glycol hydroxypivalate, 2- (2-hydroxy-1,1-dimethylethyl) -5-hydroxymethyl-5-ethyl-1, Ε-caprolactone adduct of 3-dioxane diacrylate, tricyclodecane dimethylol acrylate, tricyclodecane dimethylol acrylate Difunctional acrylic acid esters such as diglycidyl ether diacrylate of 1,6-hexanediol, or methacrylic acid, itaconic acid, crotonic acid, maleic acid ester in which these acrylates are replaced with methacrylate, itaconate, crotonate, maleate, For example, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, trimethylolethane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, dipentaerythritol Ε-caprolactone adduct of hexaacrylate, pyrogallol triacrylate Polyfunctional acrylic acid esters such as propionic acid / dipentaerythritol triacrylate, propionic acid / dipentaerythritol tetraacrylate, hydroxypivalylaldehyde-modified dimethylolpropane triacrylate, or these acrylates with methacrylate, itaconate, crotonate, Examples thereof include methacrylic acid, itaconic acid, crotonic acid, and maleic acid ester instead of maleate.

  Prepolymers can also be used as described above. Examples of the prepolymer include compounds as described below, and a prepolymer obtained by introducing acrylic acid or methacrylic acid into an oligomer having an appropriate molecular weight and imparting photopolymerizability can be 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 Chlorates such as bisphenol A, epichlorohydrin, (meth) acrylic acid, and epoxy acrylates in which (meth) acrylic acid is introduced into an epoxy resin such as phenol novolac, epichlorohydrin, (meth) acrylic acid, such as ethylene glycol, adipine Acid / tolylene diisocyanate / 2-hydroxyethyl acrylate, polyethylene glycol / tolylene diisocyanate / 2-hydroxyethyl acrylate, hydroxyethylphthalyl methacrylate / xylene diisocyanate, 1,2-polybutadiene glycol / tolylene diisocyanate / 2-hydroxyethyl acrylate , Trimethylolpropane, propylene glycol, tolylene diisocyanate, 2-hydroxyethyl acrylate In addition, urethane acrylates in which (meth) acrylic acid is introduced into urethane resin, for example, silicone resin acrylates such as polysiloxane acrylate, polysiloxane diisocyanate, 2-hydroxyethyl acrylate, etc., and (meth) acryloyl in oil-modified alkyd resins Examples thereof include prepolymers such as alkyd-modified acrylates having introduced groups and spirane resin acrylates.

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

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

  In addition, JP-A-58-212994, 61-6649, 62-46688, 62-48589, 62-173295, 62-187092, 63- 67189, JP-A-1-244891, and the like. Further, “11290 Chemical Products”, Chemical Industry Daily, p. 286-p. 294, “UV / EB Curing Handbook (raw material)”, Kobunshi Publishing Co., p. The compounds described in 11 to 65 can also be suitably used in the present invention. Of these, compounds having two or more acrylic groups or methacryl groups in the molecule are preferred in the present invention, and those having a molecular weight of 10,000 or less, more preferably 5,000 or less are preferred.

  In the present invention, it is preferable to use an addition-polymerizable ethylenic double bond-containing monomer containing a tertiary amino group in the molecule. Although there is no particular limitation on the structure, a tertiary amine compound having a hydroxyl group modified with glycidyl methacrylate, methacrylic acid chloride, acrylic acid chloride or the like is preferably used. Specifically, collectable compounds described in JP-A-1-165613, JP-A-1-203413, and JP-A-1-197213 are preferably used.

  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 containing 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, Although 2-propanediol etc. are mentioned, it is not limited to this.

  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. Examples of the compound containing an ethylenic double bond capable of addition polymerization with a hydroxyl group in the molecule include compounds such as MH-1 to MH-13, but are not limited thereto. Preferable examples include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxypropylene-1,3-dimethacrylate, 2-hydroxypropylene-1-methacrylate-3-acrylate, and the like.

  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 (isocyanatomethyl) ) Reaction of 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) An acrylate or an alkyl acrylate described in JP-A-1-105238 and JP-A-2-127404 can be used.

(Polymer binder)
The photosensitive lithographic printing plate of the present invention contains a polymer binder in a photopolymerizable layer (also referred to as a photopolymerizable photosensitive layer or a photosensitive layer).

  In the present invention, as the polymer binder, acrylic polymer, polyvinyl butyral resin, polyurethane resin, polyamide resin, polyester resin, epoxy resin, phenol resin, polycarbonate resin, polyvinyl butyral resin, polyvinyl formal resin, shellac, other Natural resins can be used. Two or more of these may be used in combination.

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

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

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

  Furthermore, in the polymer binder of the present invention, monomers described in the following (1) to (14) can be used as other copolymerization monomers.

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

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

  Furthermore, an unsaturated bond-containing vinyl copolymer obtained by addition-reacting a compound having a (meth) acryloyl group and an epoxy group in the molecule to a carboxyl group present in the molecule of the vinyl copolymer. Is also preferred as a polymer binder. Specific examples of the compound containing both an unsaturated bond and an epoxy group in the molecule include glycidyl acrylate, glycidyl methacrylate, and an epoxy group-containing unsaturated compound described in JP-A No. 11-271969.

  These copolymers preferably have a weight average molecular weight of 1 to 200,000 as measured by gel permeation chromatography (GPC), but are not limited to this range.

  The content of the high molecular polymer in the photosensitive layer composition is preferably in the range of 10 to 90% by mass, more preferably in the range of 15 to 70% by mass, and the sensitivity to use in the range of 20 to 50% by mass. Particularly preferred from the viewpoint.

  Furthermore, the acid value of the resin is preferably used in the range of 10 to 150, more preferably in the range of 30 to 120, and the use in the range of 50 to 90 from the viewpoint of balancing the polarity of the entire photosensitive layer. Particularly preferred, this can prevent pigment aggregation in the photosensitive layer coating solution.

(Overcoat layer)
In the photosensitive lithographic printing plate of the present invention, a photopolymerizable layer (photosensitive layer) can be protected by providing an overcoat layer preferable as the protective layer of the present invention.

  For the overcoat layer, a water-soluble polymer capable of forming a film having low oxygen permeability is used. Specifically, it contains polyvinyl alcohol and polyvinyl pyrrolidone. Polyvinyl alcohol has an effect of suppressing permeation of oxygen, and polyvinyl pyrrolidone has an effect of ensuring adhesion with an adjacent photosensitive layer.

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

  In the photosensitive lithographic printing plate material of the present invention, the peeling force between the photosensitive layer and the overcoat layer is preferably 35 g / 10 mm or more, more preferably 50 g / 10 mm or more, and further preferably 75 g / 10 mm or more. Preferred overcoat layer compositions include those described in JP-A-10-10742.

  The peeling force in the present invention is that when an adhesive tape having a predetermined width is applied on the overcoat layer and the adhesive tape is peeled off with the overcoat layer at an angle of 90 degrees with respect to the plane of the planographic printing plate material. The force was measured.

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

  The thickness of the overcoat layer is preferably from 0.1 to 5.0 μm, particularly preferably from 0.5 to 3.0 μm.

  As combinations with the configuration of the present invention, JP-A-11-065129, JP-A-11-0665126, JP-A-2000-206706, JP-A-2000-081711, JP-A-2002-091014, JP-A-2002-091015 JP, 2002-091016, JP 2002-091017, JP 2002-174907, JP 2002-182401, JP 2002-196506, JP 2002-196507, JP 2002-202616, JP 2002-229187, JP 2002-202615, JP 2002-251019, JP 2002-365413, JP 2003-029427, JP 2003-021908, JP 2003-015318, No. 2003-035960, JP-A-2 No. 03-043693, JP 2003-043701 A, JP 2003-0437702 A, JP 2003-043703 A, etc., plate materials, plate surface protecting agents, developer materials, automatic developing machines, etc. Can also be suitably used.

<Developer>
(Alkaline agent)
The main component of the developer and replenisher used in the processing method of the present invention may contain at least one compound selected from silicic acid, phosphoric acid, carbonic acid, boric acid, phenols, saccharides, oximes and fluorinated alcohols. preferable. An alkaline aqueous solution having a pH higher than 8.5 and lower than 13.0 is preferable. More preferably, the pH is 8.5-12. Among these, as weakly acidic substances such as phenols, saccharides, oximes and fluorinated alcohols, those having a dissociation index (pKa) of 10.0 to 13.2 are preferable. Such an acid is selected from those described in IONISATION CONSTANTS OF ORGANIC ACIDS INAQUEOUS SOLUTION published by PergamonPress, and specifically, salicylic acid (13.0) and 3-hydroxy-2-naphthoic acid. (Same as 12.84), catechol (12.6), gallic acid (12.4), sulfosalicylic acid (11.7), 3,4-dihydroxysulfonic acid (12.2), 3,4 -Dihydroxybenzoic acid (11.94), 1,2,4-trihydroxybenzene (11.82), hydroquinone (11.56), pyrogallol (11.34), o-cresol (10. 33), resorsonol (same as 11.27), p-cresol (same as 10.27), - phenols having a phenolic hydroxyl group, such as cresol (same 10.09) and the like.

  As the saccharide, a non-reducing sugar that is stable even in an alkali is preferably used. Such non-reducing sugars are saccharides that do not have a free aldehyde group or ketone group and do not exhibit reducing properties, and are trehalose-type oligosaccharides in which reducing groups are bonded to each other, and glycosides in which a reducing group of saccharides and non-saccharides are bonded. These are classified into sugar alcohols reduced by hydrogenation of the body and saccharides, both of which are preferably used in the present invention. Trehalose type oligosaccharides include saccharose and trehalose. Examples of glycosides include alkyl glycosides, phenol glycosides, mustard oil glycosides, and the like. Examples of the sugar alcohol include D, L-arabit, rebit, xylit, D, L-sorbit, D, L-mannit, D, L-exit, D, L-talit, durisit and allozulcit. Furthermore, maltitol obtained by hydrogenation of a disaccharide and a reduced form (reduced water candy) obtained by hydrogenation of an oligosaccharide are preferably used. Furthermore, 2-butanone oxime (12.45), acetoxime (12.42), 1.2-cycloheptanedione oxime (12.3), 2-hydroxybenzaldehyde oxime (12.10), dimethyl Oximes such as glyoxime (11.9), ethanediamide dioxime (11.37) and acetophenone oxime (11.35) such as 2,2,3,3-tetrafluoropropanol-1 (12) .74), trifluoroethanol (12.37), trichloroethanol (12.24), and the like. In addition, aldehydes such as pyridine-2-aldehyde (12.68) and pyridine-4-aldehyde (12.05), adenosine (12.56), inosine (12.5), guanine ( 12.3), nucleic acid-related substances such as cytosine (12.2), hypoxanthine (12.1), xanthine (11.9), diethylaminomethylsulfonic acid (12.32), 1-amino-3,3,3-trifluorobenzoic acid (12.29), isopropylidenedisulfonic acid (12.10), 1,1-ethylidene diphosphonic acid (11.54), 1,1 -1-hydroxyethylidene disulfonate (11.52), benzimidazole (12.86), thiobenzamide (12.8), picolinethioamide (12.55), barbi It includes weak acid, such as Le acid (same 12.5). These acidic substances may be used alone or in combination of two or more. Among these acidic substances, preferred are silicic acid, phosphoric acid, carbonic acid, sulfosalicylic acid, salicylic acid and sugar alcohols and saccharose of non-reducing sugars, especially silicic acid, D-sorbitol, saccharose, and reduced water candy in an appropriate pH range. It is preferable that it has a buffering action and is inexpensive.

The proportion of these acidic substances in the developer is preferably from 0.1 to 30% by mass, and more preferably from 1 to 20% by mass. Below this range, a sufficient buffering effect cannot be obtained, and when the concentration is above this range, it is difficult to achieve high concentration, and the problem of increased costs arises. As the base to be combined with these acids, sodium hydroxide, ammonium, potassium and lithium are preferably used. These alkali agents are used alone or in combination of two or more. When the pH of the developer is 8.5 or less, the image portion of the printing plate obtained from the photosensitive lithographic printing plate that can be developed with such a developer is physically fragile, and the wear during printing is sufficient. Printing durability cannot be obtained. Further, the image portion is chemically weak, and an image of a portion wiped with an ink washing solvent or a plate cleaner is damaged during printing, and as a result, sufficient chemical resistance cannot be obtained. A developer having a high pH such that the pH exceeds 13.0 is strongly irritating when adhering to the skin or mucous membrane, and is not preferable because it requires sufficient care in handling.

Other examples include potassium silicate, sodium silicate, lithium silicate, ammonium silicate, potassium metasilicate, sodium metasilicate, lithium metasilicate, ammonium metasilicate, tripotassium phosphate, trisodium phosphate, trilithium phosphate, triammonium phosphate, phosphoric acid. Dipotassium, disodium phosphate, dilithium phosphate, diammonium phosphate, potassium carbonate, sodium carbonate, lithium carbonate, ammonium carbonate, potassium bicarbonate, sodium bicarbonate, lithium bicarbonate, ammonium bicarbonate, potassium borate, sodium borate, boric acid Lithium, ammonium borate and the like can be mentioned and may be added in the form of a preformed salt. Again, sodium hydroxide, ammonium, potassium and lithium can be added to the pH adjustment. Moreover, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, Organic alkali agents such as ethyleneimine, ethylenediamine, and pyridine are also used in combination. The developer used in the present invention preferably has a low silicate concentration, preferably 0.0 to 0.5% by mass, more preferably 0.0 to 0.1% by mass in terms of SiO ₂ concentration. Further, a developing machine containing no silicate is most preferable.

  The developing solution referred to in the present invention is not only an unused solution used at the start of development, but also a replenishing solution for correcting the activity of the solution that is lowered by the processing of the PS plate (photosensitive lithographic printing plate). Is included, and a liquid whose activity is maintained (so-called running liquid) is included. The replenisher therefore needs to have a higher activity (alkali concentration) than the developer, so the pH of the replenisher may exceed 13.0.

(Surfactant)
To the developer and replenisher used in the present invention, various surfactants and organic solvents can be added as necessary for the purpose of promoting developability, dispersing development residue, and improving ink affinity of the printing plate image area. Preferred surfactants include anionic, cationic, nonionic and amphoteric surfactants. Preferable examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene aryl ether, ester polyoxyethylene alkyl phenyl ethers, polyoxyethylene naphthyl ether, polyoxyethylene benzyl ether, polyoxyethylene polystyryl phenyl ether , Polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene polyoxypropylene aryl ethers, glycerin fatty acid partial esters, sorbitan fatty acid partial esters, pentaerythritol fatty acid partial esters, propylene glycol mono fatty acid esters, sucrose fatty acid Partial esters, polyoxyethylene sorbitan fatty acid partial esters, polyoxyethylene sorbitol fatty acid partial esters Tells, polyethylene glycol fatty acid esters, polyglycerin fatty acid partial esters, polyoxyethylenated castor oil, polyoxyethylene glycerin fatty acid partial esters, polyoxyethylene-polyoxypropylene block copolymers, polyoxyethylene of ethylenediamine Nonionic interfaces such as polyoxypropylene block copolymer adducts, fatty acid diethanolamides, N, N-bis-2-hydroxyalkylamines, polyoxyethylene alkylamines, triethanolamine fatty acid esters, trialkylamine oxides Activators, fatty acid salts, abietic acid salts, hydroxyalkane sulfonic acid salts, alkane sulfonic acid salts, dialkyl sulfosuccinic acid ester salts, linear alkyl benzene sulfonic acid salts, Branched alkylbenzene sulfonates, alkylnaphthalene sulfonates, polyoxyethylene aryl ether carboxylic acids, polyoxyethylene naphthyl ether sulfates, alkyl diphenyl ether sulfonates, alkylphenoxy polyoxyethylene propyl sulfonates, polyoxyethylene alkyl Sulfophenyl ether salts, polyoxyethylene aryl ether ether sulfate, N-methyl-N-oleyl taurine sodium salt, N-alkylsulfosuccinic acid monoamide disodium salt, petroleum sulfonates, sulfated beef oil, fatty acid alkyl ester Sulfuric acid ester salts, alkyl sulfuric acid ester salts, polyoxyethylene alkyl ether sulfuric acid ester salts, fatty acid monoglyceride sulfuric acid ester salts, poly Oxyethylene alkylphenyl ether sulfates, polyoxyethylene styrylphenyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkylphenyl ether phosphates, styrene / anhydrous maleic Anionic surfactants such as partially saponified products of acid copolymers, partially saponified products of olefin / maleic anhydride copolymers, naphthalene sulfonate formalin condensates, alkylamine salts, tetrabutylammonium bromide, etc. Cationic surfactants such as quaternary ammonium salts, polyoxyethylene alkylamine salts, polyethylene polyamine derivatives, carboxybetaines, aminocarboxylic acids, sulfobetaines, aminosulfurs Esters, amphoteric surfactants such as imidazolines. Among the surfactants listed above, those having polyoxyethylene can be read as polyoxyalkylenes such as polyoxymethylene, polyoxypropylene and polyoxybutylene, and these surfactants are also included. A more preferred surfactant is a fluorosurfactant containing a perfluoroalkyl group in the molecule. Such fluorosurfactants include perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, anionic types such as perfluoroalkyl phosphates, amphoteric types such as perfluoroalkyl betaines, and perfluoroalkyltrimethylammonium salts. Cationic and perfluoroalkylamine oxides, perfluoroalkyl ethylene oxide adducts, perfluoroalkyl group and hydrophilic group-containing oligomers, perfluoroalkyl group and lipophilic group-containing oligomers, perfluoroalkyl groups, hydrophilic groups and lipophilic groups Nonionic types such as group-containing oligomers, perfluoroalkyl groups, and lipophilic group-containing urethanes can be mentioned. Said surfactant can be used individually or in combination of 2 or more types, and is added in 0.001-10 mass% in a developing solution, More preferably, it is added in 0.01-5 mass%.

(Development stabilizer)
For the developer and replenisher used in the present invention, various development stabilizers are preferably used. Preferred examples thereof include polyethylene glycol adducts of sugar alcohols described in JP-A-6-282079, tetraalkylammonium salts such as tetrabutylammonium hydroxide, phosphonium salts such as tetrabutylphosphonium bromide, and iodonium such as diphenyliodonium chloride. A salt is a preferred example. Further, anionic surfactants or amphoteric surfactants described in JP-A-50-51324, water-soluble cationic polymers described in JP-A-55-95946, and JP-A-56-142528 are described. There are water-soluble amphoteric polyelectrolytes that have been described. Furthermore, an organic boron compound to which an alkylene glycol is added as described in JP-A-59-84241, a polyoxyethylene / polyoxypropylene block polymerization type water-soluble surfactant as described in JP-A-60-111246, An alkylenediamine compound substituted with polyoxyethylene / polyoxypropylene disclosed in JP-A-60-129750, a polyethylene glycol having a weight average molecular weight of 300 or more described in JP-A-61-215554, and a cation described in JP-A-63-175858 And a water-soluble ethylene oxide addition compound obtained by adding 4 mol or more of ethylene oxide to an acid or alcohol disclosed in JP-A-2-39157, a water-soluble polyalkylene compound, and the like.

(Organic solvent)
If necessary, an organic solvent is added to the developer and the development replenisher. As such an organic solvent, those having a solubility in water of about 10% by mass or less are suitable, and are preferably selected from those having 5% by mass or less. For example, 1-phenylethanol, 2-phenylethanol, 3-phenyl-1-propanol, 4-phenyl-1-butanol, 4-phenyl-2-butanol, 2-phenyl-1-butanol, 2-phenoxyethanol, 2- Benzyloxyethanol, o-methoxybenzyl alcohol, m-methoxybenzyl alcohol, p-methoxybenzyl alcohol, benzyl alcohol, cyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol and 4-methylcyclohexanol, N-phenylethanol Examples thereof include amines and N-phenyldiethanolamine. The content of the organic solvent is 0.1 to 5% by mass with respect to the total mass of the liquid used, but it is preferably substantially not contained, and particularly preferably not contained at all. Here, “substantially not contained” means 1% by mass or less.

(Reducing agent)
A reducing agent is added to the developer and replenisher used in the present invention as necessary. This prevents stains on the printing plate, and is particularly effective when developing a negative photosensitive lithographic printing plate containing a photosensitive diazonium salt compound. Preferable organic reducing agents include phenol compounds such as thiosalicylic acid, hydroquinone, metol, methoxyquinone, resorcin, and 2-methylresorcin, and amine compounds such as phenylenediamine and phenylhydrazine. More preferable inorganic reducing agents include sodium, potassium and ammonium salts of inorganic acids such as sulfurous acid, bisulfite, phosphorous acid, hydrogen phosphite, dihydrogen phosphite, thiosulfuric acid and dithionite. A salt etc. can be mentioned. Among these reducing agents, sulfites are particularly excellent in the antifouling effect. These reducing agents are preferably contained in the range of 0.05 to 5% by mass with respect to the developer at the time of use.

(Organic carboxylic acid)
If necessary, an organic carboxylic acid can be further added to the developer and replenisher used in the present invention. Preferred organic carboxylic acids are aliphatic carboxylic acids and aromatic carboxylic acids having 6 to 20 carbon atoms. Specific examples of the aliphatic carboxylic acid include caproic acid, enanthylic acid, caprylic acid, lauric acid, myristic acid, palmitic acid and stearic acid, and particularly preferred are alkanoic acids having 8 to 12 carbon atoms. . Further, it may be an unsaturated fatty acid having a double bond in the carbon chain or a branched carbon chain. The aromatic carboxylic acid is a compound in which a carboxyl group is substituted on a benzene ring, naphthalene ring, anthracene ring or the like, and specifically includes o-chlorobenzoic acid, p-chlorobenzoic acid, o-hydroxybenzoic acid, p- Hydroxybenzoic acid, o-aminobenzoic acid, p-aminobenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 3, There are 5-dihydroxybenzoic acid, gallic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 2-hydroxy-1-naphthoic acid, 1-naphthoic acid, 2-naphthoic acid and the like. Naphthoic acid is particularly effective. The aliphatic and aromatic carboxylic acids are preferably used as sodium salts, potassium salts or ammonium salts in order to enhance water solubility. The content of the organic carboxylic acid in the developer used in the present invention is not particularly limited, but if it is less than 0.1% by mass, the effect is not sufficient, and if it is 10% by mass or more, the effect cannot be further improved. In addition, dissolution may be hindered when other additives are used in combination. Therefore, the preferable addition amount is 0.1 to 10% by mass, more preferably 0.5 to 4% by mass with respect to the developing solution in use.

(Other)
In addition to the above, the following additives can be added to the developer and replenisher used in the present invention in order to improve the development performance. For example, neutral salts such as NaCl, KCl and KBr described in JP-A-58-75152, complexes such as [Co (NH ₃ )] ₆ Cl ₃ described in JP-A-59-121336, JP-A-56 Ampholytic polymer electrolytes such as a copolymer of vinylbenzyltrimethylammonium chloride and sodium acrylate described in JP-A-142258, organometallic surfactants containing Si, Ti, etc. described in JP-A-59-75255, JP And organic boron compounds described in JP-A-59-84241. The developer and replenisher used in the present invention may further contain a preservative, a colorant, a thickener, an antifoaming agent, a hard water softener, and the like, if necessary. Examples of the antifoaming agent include mineral oil, vegetable oil, alcohol, surfactant, silicone and the like described in JP-A-2-244143. Examples of the water softener include polyphosphoric acid and its sodium salt, potassium salt and ammonium salt, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminedisuccinic acid, methyliminodiacetic acid, β-alaninediacetic acid, triethylenetetraminehexaacetic acid, hydroxyethylethylenediaminetrimethyl. Aminopolycarboxylic acids such as acetic acid, nitrilotriacetic acid, 1,2-diaminocyclohexanetetraacetic acid and 1,3-diamino-2-propanoltetraacetic acid and their sodium, potassium and ammonium salts, aminotri (methylenephosphonic acid), Ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), triethylenetetraminehexa (methylenephosphonic acid) Hydroxyethyl ethylene diamine tri (methylene phosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid and their sodium salts, potassium salts and ammonium salts. The optimum value of such a hard water softening agent varies depending on its chelating power, the hardness of the hard water used and the amount of hard water. % By mass, more preferably in the range of 0.01 to 0.5% by mass. If the addition amount is less than this range, the intended purpose is not sufficiently achieved. If the addition amount is more than this range, adverse effects on the image area such as color loss will occur. The remaining component of the developer and replenisher is water. The conductivity of the obtained developer is more preferably in the range of 3 to 100 mS.

  JP-A-11-065129, JP-A-11-0665126, JP-A-2000-206706, JP-A-2000-081711, JP-A-2002-091014, JP-A-2002-091015, JP-A-2002-091016, Special JP 2002-091017, JP 2002-174907, JP 2002-182401, JP 2002-196506, JP 2002-196507, JP 2002-202616, JP 2002-229187, JP 2002-202615, JP 2002-251019, JP 2002-365813, JP 2003-029427, JP 2003-021908, JP 2003-015318, JP 2003-035960, JP 2003. No. 043693, JP-A-200 No. 0437701, JP-A-2003-0437702, JP-A-2003-043703, etc., and the processing agents such as developing materials and materials thereof, plate surface protecting agents, and the materials, automatic developing machines, processing methods, etc. It can be used suitably.

(Concentrated liquid)
It is advantageous in terms of transportation that the developer and replenisher used in the present invention are concentrated solutions in which the water content is less than in use, and diluted with water during use. The degree of concentration in this case is appropriate so that each component does not separate or precipitate, but it is preferable to add a solubilizing agent if necessary. As such a solubilizer, a so-called hydrotrope such as toluenesulfonic acid, xylenesulfonic acid and alkali metal salts thereof described in JP-A-6-32081 is preferably used.

  The content of water in the concentrate can be further reduced to form a solid or paste. In this case, the developer may be once evaporated and then evaporated to dryness, but it is preferable that the concentrated state is obtained by mixing the materials without adding water when adding a plurality of materials or by adding a small amount of water. Is preferred. Further, this developer concentrate is disclosed in JP-A-51-61837, JP-A-2-109042, JP-A-2-109043, JP-A-3-39735, JP-A-5-142786, JP-A-6-266062. Can be made into granules or tablets by a conventionally well-known method described in Japanese Patent No. 7-13341. The material contained in the solid or paste developer concentrate can use the components used in the developer of ordinary photosensitive lithographic printing plates, but it does not return to its original state even if diluted with water. Is preferably not included. For example, since silicate is converted into stone when it becomes low in moisture, it becomes difficult to dissolve in water, and therefore it is preferable to contain carbonate, phosphate, organic acid salt, etc. described later instead of silicate.

  These developer concentrates or solid or paste concentrates may be divided into a plurality of parts having different material types, material mixing ratios, and the like. These concentrated developer concentrates are preferably used for development after dilution to a predetermined concentration with water before development. In addition, when this developer concentrate or concentrate is used as a developer replenisher, it is most preferable to dilute with water to a predetermined concentration and then add it to the developer in use. It is also possible to put it in a developing solution as it is without diluting to a predetermined concentration. When adding the developer concentrate to a developing solution in use at a concentration higher than a predetermined concentration or without diluting to a predetermined concentration, water is added directly to the developing solution in use at the same timing or at another timing. May be added.

(Automatic processor)
The automatic processor used in the present invention is preferably provided with a mechanism for automatically replenishing a replenisher with a required amount in a developing bath, and preferably provided with a mechanism for discharging a developer exceeding a certain amount. Preferably, a mechanism for automatically replenishing a required amount of water to the developing bath is provided, and preferably a mechanism for detecting plate passing is provided, preferably processing of the plate based on detection of plate passing A mechanism for estimating the area is provided, and preferably a mechanism for controlling the replenishment amount and / or replenishment timing of the replenisher and / or water to be replenished based on detection of the plate and / or estimation of the processing area Is preferably provided, and a mechanism for controlling the temperature of the developer is preferably provided, preferably a mechanism for detecting the pH and / or conductivity of the developer is provided, and preferably the pH of the developer is adjusted. Mechanism for controlling the replenishment amount and / or replenishment timing of replenishment solution and / or water tries to refill beauty / or conductivity to the original has been granted. Moreover, when there exists a washing process after a image development process, the washing water after use can be used as a dilution water of the concentrate of a development concentrate and a development replenisher.

  The automatic processor used in the present invention may have a pretreatment unit that immerses the plate in the pretreatment liquid before the development step. The pretreatment unit is preferably provided with a mechanism for spraying the pretreatment liquid onto the plate surface, and preferably provided with a mechanism for controlling the temperature of the pretreatment liquid to an arbitrary temperature of 25 ° C to 55 ° C. Preferably, a mechanism for rubbing the plate surface with a roller-like brush is provided. Moreover, water etc. are used as this pretreatment liquid.

  The automatic processor used in the present invention preferably has a function of replenishing water in order to compensate for the evaporation of water in the developer. If the automatic processor has a water supply mechanism for diluting the concentrated developer, it may be used. A method of replenishing water determined per hour is the simplest and preferable method for replenishing water. However, the water replenishment amount may be corrected based on measured values from sensors such as pH of the developer and electric power. Further, the replenishment amount of water may be corrected using the temperature and / or humidity of the outside air, the temperature of the developer, the temperature and / or humidity of the air in the automatic developing machine, and the like.

(Post-processing)
The plate developed with the developer having such a composition is subjected to post-processing with washing water, a rinsing solution containing a surfactant, a finisher mainly composed of gum arabic or starch derivatives, or a protective gum solution. For the post-treatment of the PS plate of the present invention, these treatments can be used in various combinations. For example, a post-development → water wash → surfactant-containing rinse solution treatment or development → water wash → finisher solution treatment is a rinse solution. And less finisher fluid fatigue. Furthermore, a countercurrent multistage process using a rinse liquid or a finisher liquid is also a preferred embodiment. These post-processing are generally performed using an automatic developing machine including a developing unit and a post-processing unit. As the post-treatment liquid, a method of spraying from a spray nozzle or a method of immersing and conveying in a treatment tank filled with the treatment liquid is used. There is also known a method in which a small amount of washing water after development is supplied to the plate surface and washed, and the waste solution is reused as dilution water for the developer stock solution. In such automatic processing, processing can be performed while each replenisher is replenished with each replenisher according to the processing amount, operating time, and the like. In addition, a so-called disposable processing method in which treatment is performed with a substantially unused post-treatment liquid can also be applied. The lithographic printing plate obtained by such processing is loaded on an offset printing machine and used for printing a large number of sheets.

(Gum solution)
It is preferable to add an acid or a buffering agent to the gum solution in order to remove alkali components from the developer, and in addition, a hydrophilic polymer compound, a chelating agent, a lubricant, a preservative, a solubilizing agent, and the like can be added. When the gum solution contains a hydrophilic polymer compound, it also has a function as a protective agent for preventing scratches and stains on the developed plate.

  By adding a surfactant to the gum solution used in the present invention, the surface state of the coating layer is improved. Surfactants that can be used include anionic surfactants and / or nonionic surfactants. For example, anionic surfactants include fatty acid salts, abietic acid salts, hydroxyalkane sulfonates, alkane sulfonates, dialkyl sulfosuccinates, linear alkyl benzene sulfonates, branched alkyl benzene sulfonates, alkyl naphthalene sulfones. Acid salts, alkylphenoxy polyoxyethylene propyl sulfonates, polyoxyethylene alkyl sulfophenyl ether salts, polyoxyethylene aryl ether sulfonates, polyoxyethylene naphthyl ether sulfonates, N-methyl-N-oleyl taurine sodium salts N-alkylsulfosuccinic acid monoamido disodium salts, petroleum sulfonates, nitrated castor oil, sulfated beef tallow oil, sulfate esters of fatty acid alkyl esters, Rualkyl nitrates, polyoxyethylene alkyl ether sulfates, fatty acid monoglyceride sulfates, polyoxyethylene alkylphenyl ether sulfates, polyoxyethylene styryl phenyl ether sulfates, alkyl phosphate esters, polyoxyethylene alkyl ethers Phosphate ester salts, polyoxyethylene alkylphenyl ether phosphate ester salts, partially saponified products of styrene-maleic anhydride copolymer, partially saponified products of olefin-maleic anhydride copolymer, naphthalenesulfonate formalin condensates Etc. Among these, dialkyl sulfosuccinates, alkyl sulfate esters, and alkyl naphthalene sulfonates are particularly preferably used.

  Nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene aryl ethers, polyoxyethylene naphthyl ether, polyoxyethylene polystyryl phenyl ether, polyoxyethylene polyoxy Propylene alkyl ether, glycerin fatty acid partial ester, sorbitan fatty acid partial ester, pentaerythritol fatty acid partial ester, propylene glycol mono fatty acid ester, sucrose fatty acid partial ester, polyoxyethylene sorbitan fatty acid partial ester, polyoxyethylene sorbitol fatty acid moiety Esters, polyethylene glycol fatty acid esters, polyglycerol fatty acid partial esters, polyoxyethylenated ester List oils, polyoxyethylene glycerin fatty acid partial esters, fatty acid diethanolamides, N, N-bis-2-hydroxyalkylamines, polyoxyethylene alkylamines, triethanolamine fatty acid esters, trialkylamine oxides, etc. It is done. Of these, polyoxyethylene alkylphenyl ethers, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene-polyoxypropylene block polymers and the like are preferably used. Fluorine-based and silicon-based anions and nonionic surfactants can also be used. Two or more of these surfactants can be used in combination. For example, two or more different from each other can be used in combination. For example, a combination of two or more different anionic surfactants or a combination of an anionic surfactant and a nonionic surfactant is preferable. Although the usage-amount of the said surfactant does not need to specifically limit, Preferably it is 0.01-20 mass% of a post-processing liquid.

  In the gum solution used in the present invention, polyhydric alcohols, alcohols and aliphatic hydrocarbons can be used as a wetting agent in addition to the above components as required.

  Among the polyhydric alcohols, preferred specific examples include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, tetraethylene glycol, polyethylene glycol, glycerin, sorbitol and the like. Examples of the alcohol include propyl alcohol, butyl alcohol, and pen. Examples include alkyl alcohols such as tanol, hexanol, heptanol, and octanol, and alcohols having an aromatic ring such as pendyl alcohol, phenoxyethanol, and phenylaminoethyl alcohol. The content of these wetting agents is suitably 0.1 to 50% by mass, more preferably 0.5 to 3.0% by mass in the composition.

  Moreover, various hydrophilic polymers can be contained for the purpose of improving the film-forming property.

  As such a hydrophilic polymer, any hydrophilic polymer that can be conventionally used in a gum solution can be preferably used. For example, gum arabic, fiber derivatives (eg, carboxymethylcellulose, carboxyethylcellulose, methylcellulose etc.) and modified products thereof, polyvinyl alcohol and derivatives thereof, polyvinylpyrrolidone, polyacrylamide and copolymers thereof, vinyl methyl ether / maleic anhydride copolymer Examples thereof include a polymer, a vinyl acetate / maleic anhydride copolymer, and a styrene / maleic anhydride copolymer.

  In general, the gum solution used in the present invention is more advantageously used in the acidic range of pH 3 to 6. In order to adjust the pH to 3 to 6, it is generally adjusted by adding a mineral acid, an organic acid, an inorganic salt, or the like in the post-treatment liquid. The addition amount is preferably 0.01 to 2% by mass. Examples of mineral acids include nitric acid, sulfuric acid, phosphoric acid, and metaphosphoric acid.

  Examples of the organic acid include citric acid, acetic acid, succinic acid, malonic acid, p-toluenesulfonic acid, tartaric acid, malic acid, lactic acid, levulinic acid, phytic acid, and organic phosphonic acid. Further, examples of the inorganic salt include magnesium nitrate, primary sodium phosphate, secondary sodium phosphate, nickel sulfate, sodium hexamethanoate, sodium tripolyphosphate, and the like. You may use together at least 1 sort (s) or 2 or more types, such as a mineral acid, an organic acid, or an inorganic salt.

  A preservative, an antifoaming agent, etc. can be added to the gum solution used in the present invention.

  For example, as a preservative, phenol or a derivative thereof, o-phenylphenol, p-chlorometacresol, hydroxybenzoic acid alkyl ester, formalin, imidazole derivative, sodium dehydroacetate, 4-isothiazolin-3-one derivative, benzoisothiazoline-3- ON, benztriazole derivatives, amiding anidine derivatives, quaternary ammonium salts, derivatives of pyridine, quinoline, guanidine, diazine, triazole derivatives, oxazole, oxazine derivatives and the like. A preferable addition amount is an amount that exerts a stable effect on bacteria, molds, yeasts, etc., and varies depending on the type of bacteria, molds, yeasts, but 0.01% with respect to the plate surface protective agent at the time of use. The range of ˜4% by mass is preferable, and it is preferable to use two or more kinds of preservatives in combination so as to be effective against various molds and sterilization. As the antifoaming agent, a silicon antifoaming agent is preferable. Among them, emulsification dispersion type and solubilization can be used. Preferably, the range of 0.01 to 1.0% by mass with respect to the gum solution at the time of use is optimal.

  Further, a chelate compound may be added. Preferred chelate compounds include, for example, ethylenediaminetetraacetic acid, potassium salt thereof, sodium salt thereof; diethylenetriaminepentaacetic acid, potassium salt thereof, sodium salt thereof; triethylenetetraminehexaacetic acid, sodium salt thereof; ethylenediamine disuccinic acid, potassium salt thereof. Triethylenetetramine hexaacetic acid, potassium salt thereof, sodium salt thereof, hydroxyethylethylenediaminetriacetic acid, potassium salt thereof, sodium salt thereof: nitrilotriacetic acid, sodium salt thereof; 1-hydroxyethane-1,1-diphosphone Acids, potassium salts, sodium salts; organic phosphonic acids or phosphonoalkanetricarboxylic acids such as aminotri (methylenephosphonic acid), potassium salts, sodium salts, etc. It can be mentioned. An organic amine salt is also effective in place of the sodium salt and potassium salt of the chelating agent. These chelating agents are selected so that they are stably present in the gum solution composition and do not impair the printability. The addition amount is suitably 0.001 to 1.0 mass% with respect to the gum solution at the time of use.

  In addition to the above components, a sensitizer can be added as necessary. For example, hydrocarbons such as turpentine oil, xylene, toluene, low heptane, solvent naphtha, kerosene, mineral spirit, petroleum fraction having a boiling point of about 120 ° C to about 250 ° C, such as dibutyl phthalate, dihebutyl phthalate, di-n-octyl Phthalic acid diester agents such as phthalate, di (2-ethylhexyl) phthalate, dinonyl phthalate, didecyl phthalate, dilauryl phthalate, butyl benzyl phthalate, such as dioctyl adipate, butyl glycol adipate, dioctyl azelate, dibutyl sebacate, di ( 2-ethylhexyl) aliphatic dibasic acid esters such as sebacate and dioctyl sebacate, epoxidized triglycerides such as epoxidized soybean oil, such as tricresyl phosphate, trioctylfolate Feto, phosphoric acid esters such as tris chloroethyl phosphate, for example, freezing point, such as benzoic acid esters of benzyl benzoate and at 15 ℃ below boiling point at one atmosphere include 300 ° C. or more plasticizers.

  In addition, caproic acid, enanthic acid, caprylic acid, helargonic acid, capric acid, undecyl acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachic acid, behenic acid, lignoserine Saturated fatty acids such as acid, serotic acid, heptacosanoic acid, montanic acid, melicinic acid, lactelic acid and isovaleric acid, acrylic acid, crotonic acid, isocrotonic acid, undecylenic acid, oleic acid, elaidic acid, celetic acid, nillic acid, buteticidin Examples also include unsaturated fatty acids such as acid, sorbic acid, linoleic acid, linolenic acid, arachidonic acid, propiolic acid, stearolic acid, sardine acid, talylic acid and licanoic acid. More preferably, it is a fatty acid that is liquid at 50 ° C., more preferably 5 to 25 carbon atoms, and most preferably 8 to 21 carbon atoms. These sensitizers can be used alone or in combination of two or more. A preferable range for the amount used is 0.01 to 10% by mass of the gum, and a more preferable range is 0.05 to 5% by mass.

  The sensitizers as described above may be prepared by emulsifying and dispersing the gum as an oil phase, or may be solubilized with the help of a solubilizer.

In the present invention, the solid content concentration of the gum solution is preferably 5 to 30 g / l. The film thickness of the gum can be controlled by the conditions of the squeeze means of the automatic machine. In the present invention, the gum application amount is preferably 1 to 10 g / m ² . If the amount of gum application exceeds 10, the plate surface needs to be very hot in order to dry in a short time, which is disadvantageous in terms of cost and safety, and the effects of the present invention cannot be sufficiently obtained. If it is less than 1 g / m ² , uniform coating becomes difficult and stable processability cannot be obtained.

  In the present invention, the time from the end of the application of the gum solution to the start of drying is preferably 3 seconds or less. More preferably, it is 2 seconds or less, and the shorter the time is, the better the ink deposition property is.

  In the present invention, the drying time is preferably 1 to 5 seconds. When the drying time is 5 seconds or more, the effect of the present invention cannot be obtained. When the drying time is 1 second or less, it is necessary to make the plate surface very hot in order to sufficiently dry the photosensitive lithographic printing plate, which is not preferable in terms of safety and cost.

  In the present invention, as a drying method, a known drying method such as a warm air heater or a far infrared heater can be used.

  In the drying step, the solvent in the gum solution needs to be dried. Therefore, it is necessary to ensure a sufficient drying temperature and heater capacity. The temperature required for drying varies depending on the components of the gum solution, but in the case of a gum solution in which the solvent is water, the drying temperature is preferably 55 ° C. or higher. The heater capacity is often more important than the drying temperature, and the capacity is preferably 2.6 kW or more in the case of the hot air drying method. The larger the capacity, the better, but 2.6-7 kW is preferable in terms of balance with cost.

(Washing water before development)
In the present invention, the washing liquid used in the water washing step (also called washing step) before development is usually water, but the following additives can be added as necessary.

  As the chelating agent, a compound that forms a chelate compound by coordination with a metal ion is used. Ethylenediaminetetraacetic acid, its potassium salt, its sodium salt, ethylenediaminedisuccinic acid, its potassium salt, its sodium salt, triethylenetetraminehexaacetic acid, its potassium salt, its sodium salt, diethylenetriaminepentaacetic acid, its potassium salt, its sodium salt Hydroxyethylethylenediaminetriacetic acid, potassium salt thereof, sodium salt thereof, nitriotriacetic acid, potassium salt thereof, sodium salt thereof, 1-hydroxyethane-1,1-diphosphonic acid, potassium salt thereof, sodium salt thereof, aminotri (methylenephosphone) Acid), potassium salt thereof, sodium salt thereof, phosphonoalkanetricarboxylic acid, ethylenediamine disuccinic acid, potassium salt thereof, sodium salt thereof and the like. Those chelating agents having an organic amine salt instead of the potassium salt and sodium salt are also effective. The addition amount of the chelating agent is suitably in the range of 0 to 3.0% by mass.

  As the surfactant, any of anionic, nonionic, cationic and amphoteric surfactants can be used, and anionic or nonionic surfactants are preferred. The preferred surfactant type varies depending on the composition of the overcoat layer and the photosensitive layer, and generally serves as a dissolution accelerator for the material of the overcoat layer and preferably has a low solubility for the components of the photosensitive layer.

  Examples of anionic surfactants include fatty acid salts, abichenates, hydroxyalkanesulfonates, alkanesulfonates, dialkylsulfosuccinates, alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkylphenoxypolyoxyethylenepropylsulfonates , Polyoxyethylene alkylsulfophenyl ether salts, sodium N-methyl-N-oleyl taurate, disodium N-alkylsulfosuccinic acid monoamide, petroleum sulfonates, sulfated castor oil, sulfated beef oil, fatty acid alkyl esters Sulfuric acid ester salts, alkyl sulfuric acid ester salts, polyoxyethylene alkyl ether sulfuric acid ester salts, fatty acid monoglyceride sulfuric acid ester salts, polyoxyethylene styrylpheny Ether sulfate ester salt, alkyl phosphate ester salt, polyoxyethylene alkyl ether phosphate ester salt, polyoxyethylene alkyl phenyl ether phosphate ester salt, partially saponified styrene-maleic anhydride copolymer, olefin-maleic anhydride copolymer And partially saponified products, naphthalenesulfonate formalin condensates and the like.

  Nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polystyryl phenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, glycerin fatty acid esters, sorbitan fatty acid partial esters , Pentaerythritol fatty acid partial esters, propylene glycol monofatty acid esters, sucrose fatty acid partial esters, polyoxyethylene sorbitan fatty acid partial esters, iethylene glycol fatty acid esters, polyglycerin fatty acid partial esters, polyoxyethylenated castor oil , Polyoxyethylene glycerin fatty acid partial esters, fatty acid diethanolamides, N, N-bis-hydroxyalkylamines Polyoxyethylene alkylamine, triethanolamine fatty acid esters, trialkylamine oxides and the like.

  A preferable addition amount of the surfactant is 0 to 10% by mass. Further, an antifoaming agent can be used in combination with the surfactant.

  Examples of preservatives include phenol or derivatives thereof, formalin, imidazole derivatives, sodium dehydroacetate, 4-isothiazolin-3-one derivatives, benzisothiazolin-3-one, benzotriazole derivatives, amiding anidine derivatives, quaternary ammonium salts, pyrozine, Examples include quinoline and guanidine derivatives, diazine, triazole derivatives, oxazole and oxazine derivatives. Preferred examples include 1,2-benzisothiazolin-3-one, o-phenylphenol, hydroxybenzoic acid ethyl ester, chlorocresol and the like.

  In the cleaning method of the present invention, the cleaning solution used for cleaning before development is preferably used with the temperature adjusted, and the temperature is preferably in the range of 10 to 60 ° C. As a cleaning method, known processing liquid supply techniques such as spraying, dipping, and coating can be used, and processing promoting means such as a brush, a drawing roll, and a submerged shower in the dip processing can be used as appropriate.

  In the present invention, the development treatment may be performed immediately after completion of the pre-development washing step, or the development treatment may be performed after drying before the pre-development washing step. After the development step, known post-treatments such as washing with water, rinsing and gumming can be performed. The pre-development rinse water used once or more can be reused as a part or all of the rinse water, rinse solution, gum solution and developer after development.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these. In addition, unless otherwise indicated, "part" in an Example shows a "mass part".

Example 1
(Binder synthesis)
A three-necked flask under a nitrogen stream is charged with 12 parts of methacrylic acid, 70 parts of methyl methacrylate, 8 parts of acrylonitrile, 10 parts of ethyl methacrylate, 500 parts of ethanol and 3 parts of α, α'-azobisisobutyronitrile. The reaction was carried out in an air stream at 80 ° C. for 6 hours. Thereafter, 3 parts of triethylammonium chloride and 2 parts of glycidyl methacrylate were added and reacted for 3 hours to obtain an acrylic copolymer 1. The weight average molecular weight measured using GPC was about 50,000, and the glass transition temperature (Tg) measured using DSC (differential thermal analysis) was about 85 ° C.

<Production of support>
An aluminum plate (material 1050, tempered H16) having a thickness of 0.24 mm was immersed in a 5% aqueous sodium hydroxide solution maintained at 65 ° C., degreased for 1 minute, and then washed with water. This degreased aluminum plate was neutralized by dipping in a 10% aqueous hydrochloric acid solution maintained at 25 ° C. for 1 minute, and then washed with water. Next, the aluminum plate was subjected to electrolytic surface roughening with an alternating current for 60 seconds under conditions of 25 ° C. and a current density of 100 A / dm ^{2 in} a 0.3% by mass nitric acid aqueous solution, and then kept at 60 ° C. Desmutting treatment was performed for 10 seconds in a 5% aqueous sodium hydroxide solution. The surface-roughened aluminum plate subjected to desmut treatment was anodized in a 15% sulfuric acid solution at 25 ° C., a current density of 10 A / dm ² and a voltage of 15 V for 1 minute, and further with 3% sodium oxalate. Sealing was performed at 90 ° C. to prepare a support.

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

(Installation of undercoat layer on support)
On the support, an undercoat layer coating solution having the following composition is applied with a wire bar so as to be 0.1 g / m ² when dried, dried at 90 ° C. for 1 minute, and further heated at 110 ° C. for 3 minutes. The under-drawn support was prepared.

Undercoat layer coating solution γ-methacryloxyxypropyltrimethoxysilane 1 part Methyl ethyl ketone 80 parts Cyclohexanone 19 parts << Preparation of lithographic printing plate material >>
On the support, a photopolymerizable photosensitive layer coating solution 1 having the following composition was applied with a wire bar so as to be 1.5 g / m ² when dried, and dried at 95 ° C. for 1.5 minutes. A coated sample was obtained.

(Photopolymerizable photosensitive layer coating solution 1)
Addition-polymerizable ethylenic double bond-containing monomer: M-3 25.0 parts Addition-polymerizable ethylenic double bond-containing monomer: NK ester 4G
(Polyethylene glycol dimethacrylate manufactured by Shin-Nakamura Chemical Co., Ltd.) 25.0 parts Polymerization initiator T-1 2.0 parts Polymerization initiator T-2 2.0 parts Polymerization initiator BR-22 1.0 part Polymerization initiator BR- 43 1.0 parts Spectral sensitizing dye D-1 1.5 parts Spectral sensitizing dye D-2 1.5 parts Acrylic copolymer 1 40.0 parts N-phenylglycine benzyl ester 4.0 parts Phthalocyanine pigment ( MHI454: manufactured by Mikuni Dye Co., Ltd. 6.0 parts 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (Sumilyzer GS: manufactured by Sumitomo 3M) 0.5 parts Fluorosurfactant (F-178K; manufactured by Dainippon Ink & Co., Inc.) 0.5 parts Methyl ethyl ketone 80 parts Cyclohexanone 820 parts M-3: Nn-butyldiethanolamine 1 mole), 1,3-bis (1-isocyanato-1-methylethyl) benzene (2 moles), 2-hydroxypropylene-1-methacrylate-3-acrylate (2 moles)

Apply a protective layer (overcoat layer, oxygen barrier layer) coating solution 1-6 having the following composition on the above photopolymerization photosensitive layer coating sample with an applicator so that it becomes 1.8 g / m ² when dried. And dried at 75 ° C. for 1.5 minutes to prepare photosensitive lithographic printing plate samples 1 to 6 each having a protective layer (oxygen blocking layer) 1 to 6 on the photosensitive layer.

(Protective layer (overcoat layer) coating solution 1)
Polyvinyl alcohol (GL-03: manufactured by Nippon Synthetic Chemical Co., Ltd.) 89 parts Water-soluble polyamide (P-70: manufactured by Toray Industries, Inc.) 10 parts Surfactant (F142D: manufactured by Dainippon Ink Industries, Ltd.) 0.5 part Water 900 parts ( Protective layer (overcoat layer) coating solution 2)
Polyvinyl alcohol (GL-03: manufactured by Nippon Synthetic Chemical Co., Ltd.) 89 parts Water-soluble polyamide (P-70: manufactured by Toray Industries, Inc.) 10 parts Surfactant (F142D: manufactured by Dainippon Ink Industries, Ltd.) 0.5 part General of the present invention (Exemplary Compound A-1) of the compound represented by the formula (A) 1 part Water 900 parts (Protective layer (overcoat layer) coating solution 3)
Polyvinyl alcohol (GL-03: manufactured by Nippon Synthetic Chemical Co., Ltd.) 89 parts Water-soluble polyamide (P-70: manufactured by Toray Industries, Inc.) 10 parts Surfactant (F142D: manufactured by Dainippon Ink Industries, Ltd.) 0.5 part General of the present invention (Exemplary Compound A-1) of the compound represented by the formula (A) 5 parts Water 900 parts (Protective layer (overcoat layer) coating solution 4)
Polyvinyl alcohol (GL-03: manufactured by Nippon Synthetic Chemical Co., Ltd.) 89 parts Water-soluble polyamide (P-70: manufactured by Toray Industries, Inc.) 10 parts Surfactant (F142D: manufactured by Dainippon Ink Industries, Ltd.) 0.5 part General of the present invention (Exemplary Compound A-2) of the compound represented by the formula (A) 1 part Water 900 parts (Protective layer (overcoat layer) coating solution 5)
Polyvinyl alcohol (GL-03: manufactured by Nippon Synthetic Chemical Co., Ltd.) 88 parts Water-soluble polyamide (P-70: manufactured by Toray Industries, Inc.) 10 parts Surfactant (F142D: manufactured by Dainippon Ink Industries, Ltd.) 0.5 part General of the present invention (Exemplary Compound A-2) of the compound represented by the formula (A) 5 parts Water 900 parts (Protective layer (overcoat layer) coating solution 6)
Polyvinyl alcohol (GL-03: manufactured by Nippon Synthetic Chemical Co., Ltd.) 88 parts Water-soluble polyamide (P-70: manufactured by Toray Industries, Inc.) 10 parts Surfactant (F142D: manufactured by Dainippon Ink Industries, Ltd.) 0.5 part Ethylenediaminetetraacetic acid 2 Sodium (comparative) 1 part Water 900 parts << Developer formulation >>
(Formulation of Developer 1)
Potassium carbonate 2.5g / L
Potassium bicarbonate 5.0g / L
Polyoxyethylene (13) naphthyl ether 50.0 g / L
Ethylenediamine disuccinic acid trisodium salt 0.2g / L
Potassium hydroxide The following pH level The remaining component is water. PH: 11.4
(Developer replenisher formulation for developer 1)
Potassium carbonate 2.5g / L
Potassium bicarbonate 5.0g / L
Polyoxyethylene (13) naphthyl ether 50.0 g / L
Ethylenediamine disuccinic acid trisodium salt 0.2g / L
Potassium hydroxide The following pH level The remaining component is water. PH: 12.2
(Formulation of Developer 2)
Potassium silicate aqueous solution (SiO ₂ : 26% by mass, K ₂ O: 13.5% by mass)
40.0g / L
Ethylenediaminetetraacetic acid disodium salt 0.2g / L
Polyoxyethylene (13) naphthyl ether sulfonate sodium salt
40.0g / L
Potassium hydroxide The following pH level The remaining component is water. PH: 12.3
(Developer replenisher formulation for developer 2)
Potassium silicate aqueous solution (SiO ₂ : 26% by mass, K ₂ O: 13.5% by mass)
40.0g / L
Ethylenediaminetetraacetic acid disodium salt 0.2g / L
Polyoxyethylene (13) naphthyl ether sulfonate sodium salt
40.0g / L
Potassium hydroxide The following pH level The remaining component is water. PH: 12.7
《Gum solution (finisher solution)》
Plate surface protective agent (gum solution) (1L aqueous solution formulation)
White dextrin 5.0% by mass
Hydroxypropyl etherified starch 10.0% by mass
Gum arabic 1.0% by mass
1st Ammon Phosphate 0.1% by mass
Sodium dilauryl succinate 0.15% by mass
Polyoxyethylene naphthyl ether 0.5% by mass
Polyoxyethylene polyoxypropylene block copolymer (ethylene oxide ratio 50 mol%, molecular weight 5000) 0.3 mass%
Ethylene glycol 1.0% by mass
Ethylenediaminetetraacetic acid disodium 0.005 mass%
1,2 benzoisothiazolin-3-one 0.005 mass%
"Evaluation methods"
(Evaluation of protective layer adhesion)
The photosensitive lithographic printing plate sample was subjected to continuous load up to 100 g using a 0.1 mm (diameter) sapphire needle with a load tester (HEIDON), and the load at which the protective layer peeled was evaluated. The larger the number is, the better the adhesiveness is, and the number is 30 or more, which is a level with no practical problem.

(Evaluation of stop dirt)
Image formation 2400 dpi (dpi is 2.54 cm per 2.54 cm) using a plate setter (Tiger Cat: manufactured by ECRM) CTP exposure apparatus equipped with a light source equipped with a laser of 408 nm and 30 mW output for a photosensitive lithographic printing plate sample Image exposure (representing the number of dots) was performed (the exposure pattern used 100% image area and 175 LPI 50% square dots). Next, the preheating part, the pre-washing part, the developing part (developing liquid 22L in the bathtub), the alkaline aqueous solution processing part (alkaline aqueous solution 15L in the bathtub), the water washing part, the finisher liquid processing part, and the drying part in this order. A lithographic printing plate sample was prepared by performing 300 m ^{2 of} development so that the area ratio of the image area to the non-image area was 1: 9 with the CTP automatic developing machine provided. In the developing section, Developers 1 and 2 were used as shown in Table 1, and a development replenisher was replenished so as to be about 50 ml / m ² . Moreover, the following gum liquid (finisher liquid) was used as a plate surface protecting agent (gum liquid) in the finisher liquid processing section.

The prepared lithographic printing plate sample was applied to a printing machine (DAIYA 1F-1 manufactured by Mitsubishi Heavy Industries, Ltd.), coated paper, dampening water (etching solution SG-51 manufactured by Tokyo Ink Co., Ltd., concentration 1.5%), ink (Toyo Ink) Printing is performed using HI-PLUS M (manufactured by Manufacture Co., Ltd.). When 5000 sheets have been printed, the printing machine is stopped, and after leaving for 1 hour, printing is started, and the generated fine dot stains are within 100 cm ² . The number was evaluated. If it is 10 or less, it is good, and if it is 30 or more, it is a practically problematic level.

(Sludge sludge evaluation method)
In the automatic developing machine shown in FIG. 1 (same as FIG. 1 of JP-A-10-010754), 1 L of pre-developing water washing water (tap water) is stored in the pre-developing water washing tank 1 and the developing solution (as described in Table 1). 9 L) and 3 L of tap water in the washing tank 3 were set, an automatic developing machine was set, and the photosensitive lithographic printing plate sample subjected to image exposure was developed. In the development process, 50ml of developing pre-water washing water photosensitive lithographic printing plate each time through 1 m ^2, while the developing solution (as in Table 1) 50ml, the wash water was 50ml supplemented, 20 m ² at a time 30 day A development process of 600 m ² was performed in one day. The processing conditions were 15 seconds for the pre-development washing step, 30 seconds for the development step, and 20 seconds for the water washing step. After this treatment, the pre-development washing water in the pre-development washing tank was drained and the sludge adhesion in the pre-development washing tank was visually observed and evaluated according to the following criteria.

◎: No generation of sludge or sludge is observed. ○: Generation of sludge or sludge is slightly observed, but there is no problem in practical use. △: Generation of sludge or sludge is recognized slightly, but is practically acceptable. X: Sludge and sludge are conspicuously generated, the pump is clogged, and dirt is attached to the plate, which causes a problem in practical use.

  The results are shown in Table 1.

* EDTA: ethylenediaminetetraacetic acid disodium salt (comparison)
From Table 1, in the case of the photosensitive lithographic printing plate of the present invention and the processing method of the photosensitive lithographic printing plate, the adhesion between the photosensitive layer and the overcoat layer (protective layer) is improved, and the overcoat layer (protective layer) Since it is difficult to peel off, problems such as film peeling are reduced, and after printing is stopped for a while due to registration or breaks at the time of printing, it is suitable to prevent fine dot stains that occur in non-image areas when printing resumes You can see that it can be done. Further, it can be seen that sludge sludge accumulated in the developing tank when processing is performed for a long period of time can be reduced and the burden of cleaning work can be reduced.

It is a figure which shows an example of the automatic processor used in the Example.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Pre-development washing tank 2 Development tank 3 Washing tank A Pre-development washing part B Development part C Washing part T Conveyance path of photosensitive lithographic printing plate 11-15 Guide roll for conveying photosensitive lithographic printing plate 16 Drawing roll 17 Developing brush 18a, 18b Shower nozzle 19a, 19b Pump * 1 * 1 and * 1 are connected by piping * 2 * 2 and * 2 are respectively connected by piping

Claims (3)

Photosensitivity comprising a photopolymerization layer mainly containing a photopolymerization composition, and a protective layer containing a water-soluble polymer and a compound represented by the following general formula (A) on the photopolymerization layer. Sex lithographic printing plate.

(In the formula, A ₁ represents an alkyl group having 1 to 5 carbon atoms, a hydroxylalkyl group, an aryl group, a hydroxylaryl group, an oxyalkyl group, an oxyaryl group, —CH ₂ —COOH, —CH ₂ —COONa, —CH. ₂ represents —COOK, —COOH, —COONa, —COOK, —C ₂ H ₅ —COOH, —C ₂ H ₅ —COONa or —C ₂ H ₅ —COOK, wherein M ₁ , M ₂ and M ₃ each represents Independently represents an alkali metal.) Photosensitivity having a photopolymerization layer mainly containing a photopolymerization composition, and a protective layer containing a water-soluble polymer and the compound represented by formula (A) according to claim 1 on the photopolymerization layer. A method for processing a photosensitive lithographic printing plate, comprising developing the lithographic printing plate after image exposure and then washing and removing the protective layer in a water washing step. The method for processing a photosensitive lithographic printing plate according to claim 2, wherein the developer used for the development is an alkaline aqueous solution substantially free of silicate.

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