JP2007322618A - Developer for photosensitive lithographic printing plate material and plate making method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a developer stably having good developing property to a non-image area and less liable to damage an image area in development of a photopolymerizable photosensitive lithographic printing plate material, and capable of giving a lithographic printing plate having high image strength, excellent in printing durability and free of soiling of a plate surface by sludge accumulated in a developing tank, and a plate making method using the same. <P>SOLUTION: The developer for photosensitive lithographic printing plate materials is used when a photosensitive lithographic printing plate material having on a support a photosensitive layer containing at least (A) a polymerization initiator, (B) a spectral sensitizer, (C) a polymerizable compound containing an ethylenically unsaturated bond and (D) a polymer binder is developed after image exposure, and the developer is an alkaline aqueous solution containing at least a nonionic surfactant represented by formula (1) and an inorganic alkali agent. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a developer for a photosensitive lithographic printing plate material and a plate making method using the same. Specifically, a novel developer of a photopolymerization type photosensitive lithographic printing plate material applicable to a so-called computer-to-plate (hereinafter referred to as “CTP”) system and lithographic printing using the same It relates to a plate making method.

  As for the photosensitive lithographic printing plate material, conventionally, there has been known a photosensitive lithographic printing plate material in which a photopolymerizable photosensitive layer and a protective layer are laminated on a support subjected to a hydrophilic surface treatment. In particular, in recent years, in order to quickly obtain a high-resolution lithographic printing plate material, and for the purpose of filmlessness, digital exposure based on image information using a laser is performed and developed to develop a lithographic printing plate. The manufacturing method has been generalized.

  For example, a light source is modulated by an output signal from an electronic plate making system or an image processing system or an image signal transmitted through a communication line, etc., and a printing plate is formed by directly scanning and exposing a photosensitive material. Systems that do this are known.

  A CTP plate material for recording digital data with a laser is required to have high sensitivity in order to shorten the recording time. In addition, printing materials having printing durability are required in many printing fields including newspaper printing and commercial printing such as advertisements.

  The photopolymerizable photosensitive layer generally contains an acrylic monomer, an alkali-soluble resin, a photopolymerizable initiator, and, if necessary (especially when performing laser writing), a sensitizing dye to match the wavelength. It is known to do.

  It is also known to provide a protective layer for the purpose of preventing polymerization inhibition by oxygen.

  As a light source for exposing and making a photopolymerization type photosensitive lithographic printing plate material, a visible light source having a wavelength such as an Ar laser (488 nm) or an FD-YAG laser (532 nm) is used. Furthermore, in recent years, for example, semiconductor lasers that can continuously oscillate in the 350 to 450 nm region using InGaN-based or ZnSe-based materials have been put into practical use. The scanning exposure system using these short-wave light sources has an advantage that an economical system can be constructed while having a sufficient output because a semiconductor laser can be manufactured at a low cost because of its structure. Furthermore, compared with a system using a conventional FD-YAG or Ar laser, there is a possibility that it can be used for a photosensitive lithographic printing plate material having a short photosensitive area capable of working under a brighter safelight.

  The photopolymerization type photosensitive lithographic printing plate material is usually subjected to image exposure, heat treatment as necessary, followed by washing with water for removing the protective layer, development treatment for dissolving and removing unexposed portions, washing with water, non-washing. A finisher gum treatment for hydrophilizing the image area is performed to obtain a lithographic printing plate. At this time, it is known that after image exposure, a heat treatment is performed to accelerate the polymerization reaction, thereby obtaining high sensitivity and high printing durability.

  An orthoquinonediazide compound is used in combination with a novolak resin in the photosensitive layer of a positive photosensitive lithographic printing plate that has been used in the past, and an alkaline silicate aqueous solution that can dissolve the novolak resin is used as a developer. . However, the pH at which the novolak resin can be dissolved is about 13, and such a high pH developer has a strong irritation when adhering to the skin and mucous membranes, and not only required careful handling. At the point (small point) where the image area is small, there is a problem that the aluminum below the small point is melted by side etching, and the small point is likely to fly at the time of printing, resulting in deterioration of printing durability and print quality.

  On the other hand, the developer of the photosensitive lithographic printing plate material is usually used at a pH of 12.5 or more as a water-based alkaline developer in order to completely remove the non-image area photosensitive layer, that is, to perform development. Was common. However, in recent years, processing with an alkaline developer having a lower pH has been desired from the viewpoint of workability, safety, environmental suitability, and the like.

  As a developer having a low pH (pH 12 or less) and not containing an alkali silicate, Patent Document 1 discloses a developer composed of an aqueous potassium hydroxide solution containing an anionic surfactant, and Patent Document 2 discloses a pH of 8.5 to 11. A developer comprising an aqueous alkali metal carbonate solution of .5 is disclosed. However, such a relatively low pH developer basically has poor dissolving power of the photopolymerization type photosensitive layer, so that, for example, with a lapsed plate material, development does not proceed sufficiently, resulting in a residual film, There were problems such as development residue.

  In the photosensitive lithographic printing plate material, titanocene compounds, iron arene complex compounds, copper phthalocyanine compounds, etc., which are conventionally used as polymerization initiators, are compounds that are hardly soluble in water, Even if it was eluted from the photosensitive layer once into the developer and dispersed, it precipitated, aggregated and precipitated over time, accumulated as sludge sludge in the developing tank, and reattached to the plate surface, causing stains.

On the other hand, a developer having good developability for non-image areas is damaged by penetration of the surfactant and developer into the image area (exposed area) or the interface between the photosensitive layer and the plate surface. A small portion (small dot) has a particularly large influence and a strong image could not be formed.
JP 2000-81711 A JP-A-11-65126

  The present invention has been made in view of the above-mentioned problems, and the object thereof is to stably develop a non-image area in a development process of a photopolymerization type photosensitive flat plate material, and to provide an image area. A developer capable of obtaining a lithographic printing plate with little damage and having a strong image strength, excellent printing durability, and free from stains on the plate surface due to sludge accumulated in a developing tank, and a plate making method using the same Is to provide.

  The above-mentioned problem according to the present invention is solved by the following means.

  1. A photosensitive layer containing at least (A) a polymerization initiator, (B) a spectral sensitizer, (C) a polymerizable ethylenically unsaturated bond-containing compound, and (D) a polymer binder on a support. An alkaline aqueous solution containing at least a nonionic surfactant represented by the following general formula (1) and an inorganic alkaline agent, which is a developer used for performing development processing after image exposure of a photosensitive lithographic printing plate material having A developer of a photosensitive lithographic printing plate material, characterized in that

[Wherein, x and y are integers of 0 to 12, m is an integer of 0 to 7, and n is an integer of 1 to 10. ]
2. 2. The developer for photosensitive lithographic printing plate material as described in 1 above, wherein the pH of the alkaline aqueous solution at 25 ° C. is 8.5 to 13.5.

  3. 3. The developer for a photosensitive lithographic printing plate material as described in 1 or 2 above, wherein the alkaline aqueous solution contains an anionic surfactant having an ethylene oxide group.

  4). The alkaline aqueous solution contains the nonionic surfactant represented by the general formula (1) in a range of 0.5 to 10% by mass, according to any one of the above items 1 to 3. Developer of photosensitive lithographic printing plate material.

  5. 5. The developer for photosensitive lithographic printing plate material according to any one of 1 to 4, wherein the photosensitive layer contains at least one of a titanocene compound and an iron arene complex as a photopolymerization initiator. .

  6). A plate making method for a photosensitive lithographic printing plate material, wherein the developing treatment is performed using the developer described in 1 to 5 above.

  With the above configuration of the present invention, in the development processing of the photopolymerization type photosensitive flat plate material, the non-image area has stable and good developability, the image area has little damage and strong image strength. It is possible to provide a developer capable of obtaining a lithographic printing plate having excellent printing durability and having no plate surface contamination due to sludge accumulated in a developing tank, and a plate making method using the developer.

That is, the developer of the present invention containing the nonionic surfactant represented by the general formula (1) is eluted into the developer with respect to the water-insoluble photosensitive layer composition such as a polymerization initiator and a visible paint. The non-image area (unexposed area) can be developed satisfactorily. The developer of the present invention does not penetrate the photosensitive layer of the non-image area and the interface with the support. Although sufficient, the penetration of the exposed portion into the interface between the photosensitive layer and the support is suppressed, so that a strong image can be formed and good printing durability with a small dot can be obtained.

  The developer of the present invention comprises at least (A) a polymerization initiator, (B) a spectral sensitizer, (C) a polymerizable ethylenically unsaturated bond-containing compound, and (D) a polymer bond on a support. A developer used for performing a development treatment after image exposure of a photosensitive lithographic printing plate material having a photosensitive layer containing an agent, comprising at least a nonionic surfactant represented by the general formula (1) and an inorganic surfactant It is an alkaline aqueous solution containing an alkaline agent.

  Hereinafter, the present invention and its components will be described in detail.

(Developer)
When the photosensitive lithographic printing plate material according to the present invention is image-exposed, the exposed portion of the photosensitive layer of the lithographic printing plate material is cured. By developing this with an alkaline developer, the unexposed areas are removed and image formation becomes possible. As a developer used in such development processing, an alkaline aqueous solution containing the following various additives in addition to the following surfactant can be used.

[Nonionic surfactants represented by the general formula (1)]
The developer of the present invention is characterized by containing a nonionic surfactant represented by the above general formula (1).

  The surfactant can be obtained by various known synthesis methods. For example, it can be obtained by adding ethylene oxide or the like to a secondary alcohol obtained by oxidation of n-paraffin having an average carbon number of 8 to 20.

  In General formula (1), x and y represent the integer of 0-12, m represents 0-7, n represents the integer of 1-10. Here, the sum x + y of the number of repetitions of the methylene group indicated by the symbol x and the number of repetitions of the methylene group indicated by the symbol y is 5 to 17, and when it is less than 5, the hydrophobicity increases, and the storage stability of the developer is increased. Deteriorate. On the other hand, if it exceeds 17, the hydrophobic effect of the terminal alkyl group is lowered, and the effect as a surfactant is lowered. As x + y, 6 to 12 is particularly preferable.

  In the said General formula (1), the polymerization degree of the propylene oxide shown by the code | symbol m is an integer of 0-7. If it is less than 1, the compound does not contain ethylene oxide. Moreover, when it exceeds 7, hydrophobicity will become high and solubility will fall. As m, 0-4 is especially preferable.

  In the said General formula (1), the polymerization degree of ethylene oxide shown by the code | symbol n is an integer of 1-10. If it is less than 1, it becomes a compound containing no ethylene oxide, and a desired effect cannot be expected. Moreover, when it exceeds 10, hydrophilicity will become high and a defoaming effect will fall. As n, 4 to 10 is particularly preferable.

  When n is 1 or more, the degree of polymerization of ethylene oxide represented by symbol n is preferably larger than the degree of polymerization of propylene oxide represented by symbol m (n> m).

  The nonionic surfactant represented by the general formula (1) is preferably contained in the alkaline aqueous solution in the range of 0.5 to 10% by mass.

  In the present invention, an anionic surfactant is preferably used in combination, and an anionic surfactant having an ethylene oxide group is preferred.

  Specifically, the following anionic surfactants are preferable.

  In the present invention, a nonionic polymer surfactant can be used in combination. For example, a polyethylene glycol-polypropylene glycol-polyethylene glycol block copolymer is preferable.

  The anionic surfactant and the nonionic polymer surfactant are preferably contained in the alkaline aqueous solution in the range of 0.5 to 10% by mass.

(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. The pH is preferably an alkaline aqueous solution having a pH higher than 8.5 and lower than 13.0 at 25 ° C. 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 is replenished to correct the activity of the solution that decreases due to the processing of the PS plate. Contains retained liquid (so-called running liquid). 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]
The developer of the present invention is characterized by containing a surfactant having a specific structure as described above. However, the developer and replenisher used in the present invention have an increase in developability and dispersion of development residue. In addition to the above-described surfactants, various surfactants and organic solvents can be added as necessary for the purpose of improving the 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.

[Others]
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 11-0665129, JP 11-0665126, JP 2000-206706, JP 2000-081711, JP 2002-091014, JP 2002-091015, JP 2002-091016, JP 2002-091017, JP 2002-174907, JP2002-182401, JP2002-196506, JP2002-196507, JP2002-202616, JP2002-229187, JP2002-202615, JP2002-251019, JP2002 365813, JP2003-029427, JP2003-021908, JP2003-015318, JP2003-035960, JP2003-043693, JP2003-043701, JP2003043702. JP 2003-043703 Patent Laid developing solution and the material that is described in, plate surface protective agent of the treating agent and the material, an automatic developing machine, can be suitably used for the processing method or the like.

[Concentrate]
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, JP-A-7-2 Granules and tablets can be obtained by a conventionally well-known method described in US Pat. 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 developing machine used in the present invention is preferably provided with a mechanism for automatically replenishing a replenisher with a necessary 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, preferably a mechanism for detecting plate passing is provided, and preferably the processing area of the plate based on detection of plate passing A mechanism for controlling the replenishment amount and / or replenishment timing of the replenisher and / or water to be replenished, preferably based on detection of the plate and / or estimation of the processing area. Preferably, a mechanism for controlling the temperature of the developer is provided, preferably a mechanism for detecting the pH and / or conductivity of the developer is provided, preferably the pH of the developer and Or mechanism for controlling the replenishment amount and / or replenishment timing of replenishment solution and / or water attempts to replenish based on conductivity is imparted. 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 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.

(printing)
The lithographic printing plate material according to the present invention is subjected to printing after image exposure, and a general lithographic offset printing machine can be used as a printing machine. Printing paper, printing ink, etc. used for printing are not particularly limited.

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

  These inks are preferably inks containing soybean oil.

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

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

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

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

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

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

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

(Photosensitive planographic printing plate material)
Below, the component of the photosensitive lithographic printing plate material which concerns on this invention is demonstrated.

(Photopolymerization initiator)
Preferable photopolymerization initiators include bromine compounds having a structure represented by the following general formula (PH1), titanocene compounds, monoalkyltriaryl borate compounds, and iron arene complex compounds.

Formula (PH1): 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 (PH2): CBr ₃ — (C═O) —X—R ³
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 titanocene compounds include compounds described in JP-A-63-41483 and JP-A-2-291. More preferred specific examples include bis (cyclopentadienyl) -Ti-di-chloride, bis (Cyclopentadienyl) -Ti-bis-phenyl, bis (cyclopentadienyl) -Ti-bis-2,3,4,5,6-pentafluorophenyl, bis (cyclopentadienyl) -Ti-bis -2,3,5,6-tetrafluorophenyl, bis (cyclopentadienyl) -Ti-bis-2,4,6-trifluorophenyl, bis (cyclopentadienyl) -Ti-bis-2,6 -Difluorophenyl, bis (cyclopentadienyl) -Ti-bis-2,4-difluorophenyl, bis (methylcyclopentadienyl) -Ti-bis- , 3,4,5,6-pentafluorophenyl, bis (methylcyclopentadienyl) -Ti-bis-2,3,5,6-tetrafluorophenyl, bis (methylcyclopentadienyl) -Ti-bis -2,6-difluorophenyl (IRUGACURE 727L: manufactured by Ciba Specialty Chemicals), bis (cyclopentadienyl) -bis (2,6-difluoro-3- (py-1-yl) phenyl) titanium (IRUGACURE 784: Ciba Specialty Chemicals), bis (cyclopentadienyl) -bis (2,4,6-trifluoro-3- (pyridin-1-yl) phenyl) titanium bis (cyclopentadienyl) -bis (2, 4,6-trifluoro-3- (2-5-dimethylpy-1-yl) phenyl) titanium and the like It is below.

  Examples of the monoalkyl triaryl borate compound include compounds described in JP-A-62-150242 and JP-A-62-143044, and more preferable specific examples include tetra-n-butylammonium n-butyl-tri. Naphthalen-1-yl-borate, tetra-n-butylammonium n-butyl-triphenyl-borate, tetra-n-butylammonium n-butyl-tri- (4-tert-butylphenyl) -borate, tetra-n-butylammonium Examples include 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 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 -((Eta) -cyclopentadienyl) iron hexafluorophosphate, (eta) -benzene-((eta) -cyclopentadienyl) iron tetrafluoroborate, etc. are mentioned.

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

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

  Benzoin derivatives such as benzoin methyl ether, benzoin-i-propyl ether, α, α-dimethoxy-α-phenylacetophenone; benzophenone, 2,4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4,4′-bis (dimethyl) Benzophenone derivatives such as amino) benzophenone; thioxanthone derivatives such as 2-chlorothioxanthone and 2-i-propylthioxanthone; anthraquinone derivatives such as 2-chloroanthraquinone and 2-methylanthraquinone; N-methylacridone, N-butylacridone and the like In addition to α, α-diethoxyacetophenone, benzyl, fluorenone, xanthone and uranyl compounds, JP-B-59-1281, 61-9621 and JP-A-60-60104 Triazine derivatives; organic peroxides described in JP-A-59-1504 and JP-A-61-243807; JP-B-43-23684, JP-A-44-6413, JP-A-44-6413, JP-A-47-1604, and US patents Diazonium compounds described in US Pat. No. 3,567,453; organic azide compounds described in US Pat. Nos. 2,848,328 and 2,852,379 and 2,940,853; O-quinonediazides described in JP-A Nos. 13109, 38-18015 and 45-9610; JP-B-55-39162, JP-A-59-14023 and “Macromolecules”, Vol. 10, 1307 Various onium compounds described on page 1977; azo compounds described in JP-A-59-142205 Compound: JP-A-1-54440, European Patents 109,851, 126,712 and “Journal of Imaging Science (J. Imag. Sci.)”, Vol. 30, 174 (1986) 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 halogenation described in 59-107344 Compound, etc.

[Spectral sensitizer]
The lithographic printing plate material according to the present invention preferably contains a spectral sensitizer (including a sensitizing dye). The spectral sensitizer increases the sensitivity of the polymerization initiator to image exposure. In the present invention, various spectral sensitizers conventionally used in the technical field related to the photosensitive lithographic printing plate of the present invention are used. Can be used according to conditions such as the light emission wavelength region (wavelength region of ultraviolet light, visible light, infrared light, etc.). For example, it is preferable to use a spectral sensitizer that absorbs light in the same wavelength region as the emission wavelength region of a high-power semiconductor laser as a light source. In the present invention, a spectral sensitizer having an absorption maximum wavelength of 300 to 1200 nm can be used as the spectral sensitizer.

  Even if the spectral sensitizer according to the present invention is a compound having a function capable of transferring the energy obtained by light absorption to the polymerization initiator as light (electromagnetic wave), the energy is converted into heat and the polymerization initiator. It may be a compound having a function capable of migrating to. Moreover, you may have both functions.

  Examples of the compound that can function as a spectral sensitizer in any partial region in the wavelength region from visible light to near infrared include cyanine, phthalocyanine, merocyanine, porphyrin, spiro compound, ferrocene, fluorene, fulgide, imidazole, Perylene, phenazine, phenothiazine, polyene, azo compound, diphenylmethane, triphenylmethane, polymethine acridine, coumarin, coumarin derivative, ketocoumarin, quinacridone, indigo, styryl, pyrylium compound, pyromethene compound, pyrazolotriazole compound, benzothiazole compound, barbitur Examples thereof include ketoalcohol borate complexes such as acid derivatives and thiobarbituric acid derivatives, as well as European Patent No. 568,993, US Patent Nos. 4,508,811, and No. 5,227. No. 227, JP 2001-125255, compounds described in JP-A 11-271969 Patent etc. are also used.

  Specific examples of the combination of the photopolymerization initiator and the spectral sensitizer include those 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 blending ratio of the photopolymerization initiator and the spectral sensitizer is preferably in the range of 1: 100 to 100: 1 by molar ratio.

[Polymerizable ethylenically unsaturated bond-containing compound]
The polymerizable ethylenically unsaturated bond (double bond) -containing compound according to the present invention includes general radical-polymerizable monomers and ethylenic dimers that can be polymerized in a molecule generally used for ultraviolet curable resins. Polyfunctional monomers having a plurality of heavy 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 photosensitive composition of the present invention includes a phosphazene monomer, triethylene glycol, isocyanuric acid EO (ethylene oxide) modified diacrylate, isocyanuric acid EO modified triacrylate, dimethylol tricyclodecane diacrylate, trimethylolpropane benzoic acid 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 having a tertiary amino group in the molecule include triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-tert. -Butyldiethanolamine, N, N-di (hydroxyethyl) aniline, N, N, N ', N'-tetra-2-hydroxypropylethylenediamine, p-tolyldiethanolamine, N, N, N', N'- Tetra-2-hydroxyethylethylenediamine, N, N-bis (2-hydroxypropyl) aniline, allyldiethanolamine, 3- (dimethylamino) -1,2-propanediol, 3-diethylamino-1,2-propanediol N, N-di (n-propyl) amino-2,3-propanediol, N, N-di (iso-propyl) amino-2,3-propanediol, 3- (N-methyl-N-benzylamino) ) -1,2-propanediol and the like, but not limited thereto.

  Examples of the diisocyanate compound include butane-1,4-diisocyanate, hexane-1,6-diisocyanate, 2-methylpentane-1,5-diisocyanate, octane-1,8-diisocyanate, 1,3-diisocyanate methyl-cyclohexanone. 2,2,4-trimethylhexane-1,6-diisocyanate, isophorone diisocyanate, 1,2-phenylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene-2,4-diisocyanate, tolylene- Examples include 2,5-diisocyanate, tolylene-2,6-diisocyanate, 1,3-di (isocyanatomethyl) benzene, 1,3-bis (1-isocyanato-1-methylethyl) benzene, and the like. Limited to Not. 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-isocyanate-1-methylethyl ) Reaction product of benzene (2 mol), 2-hydroxypropylene-1-methacrylate-3-acrylate (2 mol) M-4: Nn-butyldiethanolamine (1 mol), 1,3-di (isocyanate) Natomethyl) benzene (2 mol), 2-hydroxypropylene-1-methacrylate-3-acrylate (2 mol) reaction 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 used in the present invention contains a polymer binder in the photopolymerizable photosensitive layer.

    Examples of the polymer binder of the present invention include acrylic polymers, polyvinyl butyral resins, polyurethane resins, polyamide resins, polyester resins, epoxy resins, phenol resins, polycarbonate resins, polyvinyl butyral resins, polyvinyl formal resins, shellacs, and other natural materials. Resin etc. 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 and the like.

  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 and the like.

  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 and the like.

  4) Monomers having a sulfonamide group, such as N- (p-toluenesulfonyl) acrylamide, N- (p-toluenesulfonyl) methacrylamide and the like.

  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 and the like.

  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 and the like.

  7) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether and the like.

  8) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, vinyl benzoate and the like.

  9) Styrenes such as styrene, methyl styrene, chloromethyl styrene and the like.

  10) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.

  11) Olefins such as ethylene, propylene, i-butylene, butadiene, isoprene and the like.

  12) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine and the like.

  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.

(Oxygen barrier layer)
For the oxygen barrier 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 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 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-A-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, JP2002-365813, JP2003-029427, JP2003-021908, JP2003-015318, JP2003-035960, JP2003-036993, JP2003-04373. 1, JP 2003-043702, JP 2003-043703, the plate material that is described in an equal, the plate surface protective agent, the developer material, an automatic developing machine or the like, can be suitably used for.

[Various additives]
In the photosensitive layer according to the present invention, in addition to the above-described components, in order to prevent unnecessary polymerization of the ethylenically unsaturated double bond compound that can be polymerized during the production or storage of the photosensitive lithographic printing plate material, A hindered phenol compound, a hindered amine compound, and other polymerization inhibitors may be added.

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

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

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

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

  In the photosensitive layer according to the present invention, a colorant can be used in addition to the above-mentioned components. As the colorant, conventionally known ones including commercially available ones can be suitably used. Examples include those described in the revised new edition “Pigment Handbook”, edited by Japan Pigment Technology Association (Seikodo Shinkosha), Color Index Handbook, and the like.

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

  Among these, it is preferable to select and use a pigment having substantially no absorption in the absorption wavelength region of the spectral sensitizing dye corresponding to the exposure laser to be used. In this case, an integrating sphere at the laser wavelength to be used is used. It is preferable that the reflection absorption of the used pigment is 0.05 or less.

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

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

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

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

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

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

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

  Examples of coating methods for the coating liquid include air doctor coater method, blade coater method, wire bar method, knife coater method, dip coater method, reverse roll coater method, gravure coater method, cast coating method, curtain coater method and extrusion coater method. Can be mentioned.

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

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

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

  In the case of an aluminum support, pure aluminum or an aluminum alloy is used.

  Various aluminum alloys can be used as the support, and for example, alloys of metals such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel, titanium, sodium, iron, and aluminum are used. . Further, the aluminum support having a roughened surface is used for water retention.

  Prior to roughening (graining treatment), it is preferable to perform a degreasing treatment in order to remove the rolling oil on the surface. As the degreasing treatment, a degreasing treatment using a solvent such as trichlene or thinner, an emulsion degreasing treatment using an emulsion such as kesilon or triethanol, or the like is used. In addition, an alkaline aqueous solution such as caustic soda can be used for the degreasing treatment. When an alkaline aqueous solution such as caustic soda is used for the degreasing treatment, dirt and oxide film that cannot be removed only by the degreasing treatment can be removed. When an alkaline aqueous solution such as caustic soda is used for the degreasing treatment, smut is generated on the surface of the support. In this case, the substrate is immersed in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid, or a mixed acid thereof and desmutted. It is preferable to perform the treatment. Examples of the roughening method include a mechanical method and a method of etching by electrolysis.

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

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

After the surface is roughened by the electrochemical surface roughening method, it is preferably immersed in an acid or alkali aqueous solution in order to remove aluminum scraps on the surface. Examples of the acid include sulfuric acid, persulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid, hydrochloric acid, and the like. Examples of the base include sodium hydroxide and potassium hydroxide. Among these, it is preferable to use an alkaline aqueous solution. The dissolution amount of aluminum in the support surface, 0.5 to 5 g / m ² is preferred. In addition, it is preferable that after the immersion treatment with an alkaline aqueous solution, neutralization treatment is performed by immersion in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid or a mixed acid thereof.

  The mechanical surface roughening method and the electrochemical surface roughening method may each be used alone for roughing, or the mechanical surface roughening method followed by the electrochemical surface roughening method. You may roughen.

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

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

  Furthermore, after performing these treatments, water-soluble resins such as polyvinylphosphonic acid, polymers and copolymers having sulfonic acid groups in the side chain, polyacrylic acid, water-soluble metal salts (for example, zinc borate) or Also suitable are those coated with a yellow dye, amine salt or the like. Further, a sol-gel treated substrate in which a functional group capable of causing an addition reaction by a radical as disclosed in JP-A No. 5-304358 is covalently used.

(Image exposure; plate making method)
As the light source for recording an image on the photosensitive lithographic printing plate material of the present invention, various light sources can be used in accordance with the photosensitive wavelength region of the material, but the use of a laser light source is preferred.

  The printing plate is obtained by irradiating the printing plate material with a laser beam according to image data from the surface having the photosensitive layer to form an image.

  Laser exposure is suitable for direct writing without using a mask material because light exposure can be performed in the form of a beam according to image data. When a laser is used as a light source, it is easy to reduce the exposure area to a very small size, and high-resolution image formation is possible.

As a laser light source for exposing the photosensitive lithographic printing plate of the present invention, a laser light source having an emission wavelength in the ultraviolet and visible short wavelength region can be used. Specifically, for example, a He—Cd laser (441 nm), a combination of Cr: LiSAF and SHG crystal (430 nm) as a solid laser, KNbO ₃ as a semiconductor laser system, a ring resonator (430 nm), AlGaInN (350 nm˜ 450 nm), AlGaInN semiconductor laser (commercially available InGaN-based semiconductor laser 400 to 410 nm), and the like.

  In addition, as a laser light source for exposing the photosensitive lithographic printing plate of the present invention, a laser light source having an emission wavelength in the infrared and / or near infrared region, that is, a wavelength range of 700 to 1500 nm can be used. Specifically, a YAG laser, a semiconductor laser, or the like can be preferably used.

  Laser scanning methods include cylindrical outer surface scanning, cylindrical inner surface scanning, and planar scanning. In the cylindrical outer surface scanning, laser exposure is performed while rotating a drum around which the recording material is wound, and the rotation of the drum is the main scanning and the movement of the laser light is the sub scanning.

  In cylindrical inner surface scanning, a recording material is fixed to the inner surface of the drum, a laser beam is irradiated from the inside, and a main scanning is performed in the circumferential direction by rotating a part or all of the optical system. Sub scanning is performed in the axial direction by linearly moving all of them in parallel with the drum axis.

  In plane scanning, a laser beam main scan is performed by combining a polygon mirror, a galvanometer mirror, and an fθ lens, and a sub-scan is performed by moving a recording medium. Cylindrical outer surface scanning and cylindrical inner surface scanning are easier to increase the accuracy of the optical system and are suitable for high-density recording.

  In the present invention, it is preferable to heat-treat the photosensitive lithographic printing plate material after exposing the image to the lithographic printing plate and before or during development. By performing the heat treatment in this manner, the adhesion between the photosensitive layer and the support is improved, and the effects of the invention according to the present invention can be improved.

  The preheating according to the present invention is performed by, for example, a preheating roller that heats a photosensitive lithographic printing plate carried during development processing to a predetermined temperature range before development in an automatic developing apparatus that develops photosensitive lithographic printing plate material. The method of heating can be mentioned. For example, the preheat roller is composed of a pair of rollers including at least one roller having heating means therein, and the roller having the heating means is a hollow made of a metal having high thermal conductivity (for example, aluminum, iron, etc.). It is possible to use a pipe in which a nichrome wire or the like is embedded as a heating element and the outer surface of the metal pipe is covered with a plastic sheet such as polyethylene, polystyrene, or Teflon (registered trademark). For details of such a preheat roller, reference can be made to JP-A No. 64-80962.

  The preheating in the present invention is preferably performed at 70 to 180 ° C. for about 3 to 120 seconds.

  Although a synthesis example, a support preparation example, and an example are specifically shown below, embodiments of the present invention are not limited thereto. In the examples, “parts” represents “parts by mass” unless otherwise specified.

(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 mass 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 undercoated support, a photopolymerizable photosensitive layer coating solution having the following composition was applied with a wire bar so as to be 1.4 g / m ² when dried, and dried at 95 ° C. for 1.5 minutes. Thereafter, an overcoat layer coating solution having the following composition is further applied onto the photosensitive layer with an applicator so as to have a dry weight of 2.0 g / m ² and dried at 75 ° C. for 1.5 minutes. A lithographic printing plate material having an overcoat layer on the layer was produced.

(Photosensitive layer coating solution 1)
50% by mass of a reaction product of Nn-butyldiethanolamine (1 mol), 1,3-bis (1-isocyanato-1-methylethyl) benzene (2 mol), 2-hydroxyethyl methacrylate (2 mol) Dawanol PMA solution 84.0 parts Triethylene glycol dimethacrylate 6.0 parts Copolymer of methacrylic acid and methyl methacrylate having a mass ratio of 25:75 (molecular weight 36000) 35.0 parts Photopolymerization initiator shown in Table 2 3.0 Part Spectral sensitizer (sensitizing dye) described in Table 2 4.0 part 2-mercaptobenzothiazole 0.3 part N-phenylglycine benzyl ester 4.0 part phthalocyanine pigment (MHI # 454: manufactured by Gokoku Dye Co., Ltd.) 3.5 parts 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylpheny Rulacrylate (Sumilyzer GS: manufactured by Sumitomo 3M) 0.2 parts 2,4,6-tris (dimethylaminomethyl) phenol 1.0 part bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate 0.1 part Fluorosurfactant (F-178K; manufactured by Dainippon Ink and Co., Ltd.) 0.5 part Siloxane surfactant (BYK337; manufactured by Big Chemie) 0.9 part Methyl ethyl ketone 80 parts Propylene glycol methyl ether 820 parts ( Oxygen barrier coating solution 1)
Polyvinyl alcohol (Cell Ball 103: manufactured by Celaneas) 85.0 parts Vinylpyrrolidone / vinyl acetate copolymer (Rubitec VA64W: manufactured by BASF) 15.0 parts Surfinol 465 (manufactured by Air Products) 0.2 parts Water 900 parts (Developer example formulation)
<Developer 1>
Polyoxyethylene (13) naphthyl ether 20g / L
Polyoxyethylene (14) naphthyl ether sulfonate Na salt
20g / L
Compound represented by general formula (1) (described in Table 1) 1 g / L
Ethylenediamine succinic acid trisodium salt 0.2g / L
Potassium hydroxide added to pH 12.0 The remaining component is water <Developer 2>
Potassium carbonate 2.5g / L
Potassium bicarbonate 5g / L
Compound represented by general formula (1) (described in Table 1) 1 g / L
Ethylenediamine succinic acid trisodium salt 0.2g / L
Potassium hydroxide added to pH 11.4 The remaining component is water <Developer 3>
Polyoxyethylene (13) naphthyl ether 40 g / L
Compound represented by general formula (1) (described in Table 1) 1 g / L
Ethylenediamine succinic acid trisodium salt 0.2g / L
Ethylenediaminetetraacetic acid disodium salt 40g / L
Potassium hydroxide added to pH 12.3 The remaining component is water <Developer 4>
Polyoxyethylene (13) naphthyl ether 20g / L
Polyoxyethylene (14) naphthyl ether sulfonate ester Na salt 20 g / L
Ethylenediamine succinic acid trisodium salt 0.2g / L
Potassium hydroxide added to pH 12.0 The remaining component is water <Developer 5>
Potassium carbonate 2.5g / L
Potassium bicarbonate 5g / L
Ethylenediamine succinic acid trisodium salt 0.2g / L
Potassium hydroxide added to pH 11.4 The remaining component is water <Developer 6>
Polyoxyethylene (13) naphthyl ether 40 g / L
Ethylenediamine succinic acid trisodium salt 0.2g / L
Ethylenediaminetetraacetic acid disodium salt 40g / L
Potassium hydroxide added to pH 12.3 The remaining component is water <Developer replenisher 1>
Polyoxyethylene (13) naphthyl ether 20g / L
Polyoxyethylene (14) naphthyl ether sulfonate Na salt
20g / L
Compound represented by general formula (1) (described in Table 1) 1 g / L
Ethylenediamine succinic acid trisodium salt 0.2g / L
Potassium hydroxide added to pH 12.8 The remaining component is water <Developer replenisher 2>
Potassium carbonate 2.5g / L
Potassium bicarbonate 5g / L
Compound represented by general formula (1) (described in Table 1) 1 g / L
Ethylenediamine succinic acid trisodium salt 0.2g / L
Potassium hydroxide added to pH 12.2 The remaining component is water <Developer replenisher 3>
Polyoxyethylene (13) naphthyl ether 40 g / L
Compound represented by general formula (1) (described in Table 1) 1 g / L
Ethylenediamine succinic acid trisodium salt 0.2g / L
Ethylenediaminetetraacetic acid disodium salt 40g / L
Potassium hydroxide added to pH 12.7 The remaining component is water <Developer replenisher 4>
Polyoxyethylene (13) naphthyl ether 20g / L
Polyoxyethylene (14) naphthyl ether sulfonate ester Na salt 20 g / L
Ethylenediamine succinic acid trisodium salt 0.2g / L
Potassium hydroxide added to pH 12.8 The remaining component is water <Developer replenisher 5>
Potassium carbonate 2.5g / L
Potassium bicarbonate 5g / L
Ethylenediamine succinic acid trisodium salt 0.2g / L
Potassium hydroxide added to pH 12.2 The remaining component is water <Developer replenisher 6>
Polyoxyethylene (13) naphthyl ether 40 g / L
Ethylenediamine succinic acid trisodium salt 0.2g / L
Ethylenediaminetetraacetic acid disodium salt 40g / L
Potassium hydroxide Added to pH 12.7 The remaining component is water. The contents of the compound represented by the general formula (1) contained in the developer and developer replenisher are shown in Table 1. In the table, EO means ethylene oxide and PO means propylene oxide.

(Gum solution (finisher solution) formulation)
Plate surface protective agent (gum solution) Example Plate surface protective agent Example 1 (1 L 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 Benzisothiazoline-3-one 0.005% by mass
(Image formation)
An image with a resolution of 2400 dpi (dpi represents the number of dots 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. Exposure (exposure pattern used 100% image area and 175 LPI 50% square dots) was performed. Next, the preheating part, the pre-water 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 washing part, the finisher liquid processing part, and the drying part in this order. Development was performed 300 m ² with the CTP automatic developing machine provided so that the area ratio of the image area to the non-image area was 1: 9. A developing replenisher was replenished in the developing section so that the amount was about 50 ml / m ² .

<Evaluation>
(Non-image area and halftone dot ink stain prevention)
The developed printing plate was developed using the above automatic developing machine, and the prepared printing plate was coated with a printing machine (DAIYA1F-1 manufactured by Mitsubishi Heavy Industries, Ltd.), coated ink, printing ink (soybean oil ink manufactured by Dainippon Ink & Chemicals, Inc.) Naturalis 100 ") and dampening water (Tokyo ink Co., Ltd. H liquid SG-51 density | concentration 1.5%) performed printing. The degree of ink adhesion in the non-image area and 97% halftone dot was visually evaluated and used as an index of development processability (development of development stains).

Dirt evaluation rank explanation of non-image area ○: There is almost no ink smudge.
Δ: Ink stains can be confirmed with a magnifier.
X: Ink contamination is visually confirmed.

97% halftone dot quality rank explanation ○: No collapsed point is confirmed.
Δ: One or more points out of 100 are crushed.
X: 5 or more points out of 100 are crushed.

[Thin wire reproducibility]
◯: The 0.09 pt fine line is excellent.
(Triangle | delta): The omission of the 0.09pt thin line is a little crushed.
X: The drop of the 0.09 pt thin line is completely crushed.
[Stop dirt]
When 5000 sheets were printed, the printing machine was temporarily stopped, and the printing was started after being left for 1 hour, and the generated fine dot-like stain was evaluated by the number within 100 cm ² (good is 10 or less. 30 problems) more than.).

(Sludge and sludge prevention evaluation method)
The printing plate prepared so that the area ratio of the image area to the non-image area was 1: 9 was developed 3000 m ² . As the automatic processor, PHW32-V manufactured by Technigraph was used, and the developer was replenished to 60 ml / m ² . The amount of sludge sludge in the tank after completion of development was confirmed.
(Double-circle): Sludge sludge is not recognized by a roller.
○: Sludge sludge is slightly observed in the developing tank, but not on the roller.
(Triangle | delta): Sludge sludge is recognized slightly in a developing tank and a roller.
X: Dirt is recognized in the developing tank and the roller.

  The results of the evaluation are summarized in Table 2.

I-1: 2,2'-bis (2-chlorophenyl) -4,5,4 ', 5'-tetraphenylbisimidazole

I-3: (η6-cumene) (η5-cyclopentadienyl) iron (2) hexafluorophosphate

  As is apparent from Table 2, in the processing using the developer of the present invention, there are few ink stains and sludge / sludge in non-image areas and halftone dots, excellent development stain resistance, and fine line reproducibility. I understand that.

Claims (6)

A photosensitive layer containing at least (A) a polymerization initiator, (B) a spectral sensitizer, (C) a polymerizable ethylenically unsaturated bond-containing compound, and (D) a polymer binder on a support. An alkaline aqueous solution containing at least a nonionic surfactant represented by the following general formula (1) and an inorganic alkaline agent, which is a developer used for performing development processing after image exposure of a photosensitive lithographic printing plate material having A developer of a photosensitive lithographic printing plate material, characterized in that

[Wherein, x and y are integers of 0 to 12, m is an integer of 0 to 7, and n is an integer of 1 to 10. ] The developer for a photosensitive lithographic printing plate material according to claim 1, wherein the pH of the alkaline aqueous solution at 25 ° C is 8.5 to 13.5. The developer for a photosensitive lithographic printing plate material according to claim 1, wherein the alkaline aqueous solution contains an anionic surfactant having an ethylene oxide group. The said alkaline aqueous solution contains the nonionic surfactant represented by the said General formula (1) in 0.5-10 mass%, It is any one of Claims 1-3 characterized by the above-mentioned. Developer of photosensitive lithographic printing plate material. The photosensitive lithographic printing plate material development according to any one of claims 1 to 4, wherein the photosensitive layer contains at least one of a titanocene compound and an iron arene complex as a photopolymerization initiator. liquid. A plate making method of a photosensitive lithographic printing plate material, wherein the developing treatment is carried out using the developer according to claim 1.