JP2007218951A - Disposal method for developing solution for planographic printing plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a disposal method for a developing solution for a planographic printing plate by which a precipitate is well separated and the precipitate is less tacky and easily disposed. <P>SOLUTION: The disposal method for a developing solution for a planographic printing plate is characterized in that: after a photosensitive planographic printing plate material having a photosensitive layer comprising a photosensitive resin composition formed on an aluminum support is exposed and developed in an automatic developing machine having a developing unit and a rinsing unit to obtain a photosensitive planographic printing plate, a flocculant is added to the waste liquid of the developing solution for a planographic printing plate to produce a solid precipitate in a flammable container; the liquid component excluding the precipitate is eliminated by 70 to 100%; and the residue is brought into contact with a water-absorbing polymer and then disposed as a waste material. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for discarding a lithographic printing plate developer.

  In the field of printing today, offset printing methods using photosensitive lithographic printing plate materials are widely used. In general, in this offset printing method, a photosensitive lithographic printing plate material is image-exposed and then developed to print an image area that accepts printing ink and a non-image area that accepts water and does not accept printing ink. It is formed on a plate and used for printing.

  As the support for the above photosensitive lithographic printing plate material, it is required to have excellent hydrophilicity, water retention, and adhesion to the photosensitive layer from the viewpoint of printability. Is provided with a hydrophilic layer on an aluminum plate base material that has been subjected to a roughening treatment called graining.

  As the developer used in the development process, a developer containing a solvent as a main component, an acid aqueous solution, an alkaline aqueous solution, or the like is used, but an alkaline aqueous solution is widely used from the viewpoint of environmental load. As an alkaline aqueous developer, a silicate-containing developer is widely used because it is advantageous in terms of pH buffering property, development stability, etc., but when a large number of printing plate materials are processed, There were problems such as the generation of sludge that would cause dirt.

  When discarding the alkaline developer, neutralization treatment with an acid is necessary. However, since a large amount of alkali is generally dissolved in the alkaline developer, a large amount of acid is required during neutralization. When potassium silicate or sodium silicate is used, a large amount of silicate precipitates due to neutralization, which causes a problem in filtration. Furthermore, it is necessary to remove organic substances derived from the photosensitive layer dissolved and dispersed in the developing solution. However, removal of such organic substances may be difficult only by neutralization treatment, which has been a problem.

  In order to cope with this situation, a technique for absorbing and solidifying a developer of a photosensitive lithographic printing plate material in a water-absorbent resin is known (see, for example, Patent Document 1), and solid waste obtained thereby has a stickiness. It is said that it will be easy to handle.

In the developer to be discarded, the alkali-soluble resin eluted from the photosensitive layer of the plate material, the dye and the aluminum eluted from the aluminum support are dissolved, and solid sludge and sludge are generated with the passage of time. For this reason, a technique is known in which a dissolved component contained in a waste developer is precipitated in advance by adding a flocculant (see, for example, Patent Document 2). However, sludge sludge adheres to the agglomerated container and is difficult to remove, and has a problem of poor handling.
JP 2002-233860 A JP 2003-35959 A

  An object of the present invention is to provide a method for discarding a lithographic printing plate developer, in which precipitates are well separated and sedimentation is less sticky and can be easily discarded.

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

  1. The photosensitive lithographic printing plate material in which a photosensitive layer made of a photosensitive resin composition is formed on an aluminum support is subjected to development processing by an automatic developing machine equipped with a developing unit and a water washing unit after exposure, and the photosensitive lithographic plate After preparing the printing plate, a flocculant is added to the waste liquid of the lithographic printing plate developer to form a solid precipitate in a flammable container, and the liquid component excluding the precipitate is removed by 70 to 100%, and the residue A method of disposing a developer for a lithographic printing plate, comprising contacting a water-absorbing polymer with the liquid and then discarding it as a waste.

  2. 2. The method according to 1 above, wherein 70 to 100% removal of the liquid component excluding the precipitate is allowed to stand for 1 minute or more after adding the flocculant to produce a solid precipitate, and the supernatant liquid is discarded. Disposal of lithographic printing plate developer.

  3. 70 to 100% removal of liquid components excluding the precipitate is provided with a filter having a coarseness of 0.1 to 2 m and adding a flocculant, and then separating and discarding the liquid. The method for disposing of a developer for a lithographic printing plate as described in 1 above.

  According to the present invention, it is possible to provide a method for discarding a lithographic printing plate developer, in which precipitates are well separated and precipitation is less sticky and can be easily discarded.

  Hereinafter, the present invention will be described in detail.

  In the present invention, a photosensitive lithographic printing plate material in which a photosensitive layer composed of a photosensitive resin composition is formed on an aluminum support is subjected to development processing by an automatic developing machine having a developing unit and a washing unit after exposure. After forming a photosensitive lithographic printing plate, a flocculant is added to the waste liquid of the lithographic printing plate developer to produce a solid precipitate in a flammable container, and 70 to 100% removal of liquid components excluding the precipitate is removed. And after making the residue contact the water-absorbing polymer, it is discarded as waste.

(Water-absorbing polymer)
The water-absorbing polymers used in the present invention are roughly classified into natural polymer systems and synthetic polymer systems from the raw material polymers. Natural polymer systems include starch-acrylonitrile graft polymer hydrolyzate, starch-acrylic acid graft polymer, starch-styrene sulfonic acid graft polymer, starch-vinyl sulfonic acid graft polymer, starch-acrylamide graft polymer, etc. Such as: starch-based; cellulose-acrylonitrile graft polymer; cellulose-styrene sulfonic acid graft polymer; cellulose-based crosslinked carboxymethyl cellulose; polysaccharides such as hyaluronic acid and agarose; and proteins such as collagen.

  Synthetic polymer systems include polyvinyl alcohol cross-linked polymers, polyvinyl alcohol water-absorbing gel freezing / thawing elastomers, etc .; sodium polyacrylate cross-linked, sodium acrylate-vinyl alcohol copolymer, methyl acrylate-vinyl acetate Acrylates such as saponified copolymers, saponified polyacrylonitrile polymers, hydroxyethyl methacrylate polymers; polyvinyl alcohols such as maleic anhydride (co) polymers and vinylpyrrolidone (co) polymers, addition polymers other than acrylics Polyether-based polymers such as polyethylene glycol diacrylate cross-linked polymers; condensation polymers such as ester-based polymers and amide-based polymers.

  Among these, starch-based or acrylic water-absorbing polymers have a water absorption rate substantially twice or more, that is, 100 parts by mass or more of the developer is absorbed with respect to 50 parts by mass of the water-absorbing polymer. In addition, it is more preferable that the volume swell ratio of the developer after addition of the water-absorbing polymer is 2 times or less. Particularly preferred are starch-acrylic acid graft polymerized body partial sodium salt and crosslinked acrylic acid polymer sodium salt.

  In the present invention, by using these water-absorbing polymers, the photosensitive resin developer for printing plates can be processed with a small amount of water-absorbing polymer in a short time without using any other processing agent. It is not necessary to separate the photosensitive resin and the surfactant in the process, the volume swelling after processing is small, and after disposal, even if pressure is applied to the waste, it is difficult for the developer to separate water and after processing. Occurrence of stickiness of solid waste can be prevented.

  The amount of water-absorbing polymer added to the developer is 0.1 to 50% by mass. When the addition amount is within this range, the solidification of the developer proceeds sufficiently and the generation amount of solidified waste can be suppressed. Examples of the form of the water-absorbing polymer suitable for the present invention include powder, film, and fiber, but powder is preferred from the viewpoint of water absorption speed. More preferably, 50% by mass or more of the water-absorbing polymer is particles having a particle size of 100 μm or more and 1 mm or less.

(Flocculant)
When the photosensitive lithographic printing plate material according to the present invention is brought into contact with an alkaline aqueous solution and the non-image area photosensitive layer is removed with water not containing an organic solvent having a pH of 4 to 9 in the water-washed portion, Various components constituting the photosensitive lithographic printing plate material are present in a dissolved or dispersed state. When the liquid in such a state is recovered and processed, an aggregating agent is added to agglomerate and precipitate the organic matter, which can be separated into a clear supernatant and a precipitate. Since the washing water does not contain an organic solvent, the supernatant liquid from which the aggregated precipitate has been separated is substantially free of harmful substances and can be treated as general waste water. In the present invention, it is preferable to leave it for 1 minute or more after the addition of the flocculant, and the upper limit is 5 minutes.

  Examples of the flocculant used in the present invention include inorganic salts and organic polymer compounds, and the inorganic salts are preferably metal salt compounds such as aluminum salts and iron salts. For example, aluminum sulfate, sodium aluminate, base Basic aluminum chloride (abbreviated as PAC), ferrous sulfate, ferric chloride, ferric sulfate, chlorinated copper, etc. Among them, aluminum sulfate and PAC are particularly preferably used. When such an inorganic flocculant is used, the amount added to the washing water waste liquid is preferably in the range of 0.01% by mass to 10% by mass.

  As the organic polymer compound used as the flocculant, an anionic, nonionic or cationic polymer compound can be used, and particularly high molecular weight polyacrylamide, high molecular weight polyethylene glycol, or quaternary ammonium base is introduced. A cationic polymer such as a cationic polyacrylamide is preferably used. In general, a molecular weight of 100,000 or more is preferably used as the molecular weight. When such an organic polymer compound-based flocculant is used, the amount added to the washing water waste liquid is preferably in the range of 0.0001% by mass to 0.1% by mass.

  The inorganic flocculants and organic polymer compound flocculants as the flocculants described above are effective even when used alone, but by using both in combination, the organic matter is coagulated and precipitated from the washing water waste liquid. It can be preferably used because it has a high agglomeration rate, reduces the bulk of the floc produced, and has a high filtration rate when filtering the floc.

  The supernatant from which the organic substances have been separated and removed as described above is preferably adjusted to a pH of around 7 again if necessary, and any acid or alkali is preferably used as a neutralizing agent.

  In order to allow the supernatant water treated as described above to be discharged into sewage or the like as general wastewater, BOD (biochemical oxygen demand) and COD (chemical oxygen demand) may be within acceptable ranges. It must be free of heavy metals and other hazardous substances. The supernatant liquid from the washing water waste liquid treated by the above method is substantially free of organic matter and free of heavy metals and other harmful substances, so both BOD and COD are within the allowable range. This is one of the effects of the present invention.

(filter)
The filter used in the present invention has a mesh size of 0.1 to 2 m. If it is too fine, it will be clogged and it will take a long time to separate the water and the precipitate. On the other hand, if the eyes are too coarse, the precipitates pass through the eyes and cannot be separated. The material is not particularly specified, but is preferably made of polyethylene which is resistant to alkalis and hardly generates harmful substances by incineration.

(Aluminum support)
The support that can be used for the photosensitive lithographic printing plate material according to the present invention is preferably an aluminum plate. In this case, a pure aluminum plate, an aluminum alloy plate, or the like may be used.

  Various aluminum alloys can be used as the support, for example, an alloy of a metal such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel, titanium, sodium, iron, and aluminum is used. Aluminum plates manufactured by various rolling methods can be used. In addition, recycled aluminum plates obtained by rolling recycled aluminum ingots such as scrap materials and recycled materials that are becoming popular in recent years can also be used.

(Degreasing treatment of support)
The aluminum support that can be used for the photosensitive lithographic printing plate material according to the present invention is preferably subjected to a degreasing treatment in order to remove the rolling oil on the surface prior to roughening (graining treatment). As the degreasing treatment, a degreasing treatment using a solvent such as trichlene or thinner, an emulsion degreasing treatment using an emulsion such as kesilon or triethanol, or the like is used. An alkaline aqueous solution such as caustic soda can also be used for the degreasing treatment. When an alkaline aqueous solution such as caustic soda is used for the degreasing treatment, dirt and oxide film that cannot be removed only by the degreasing treatment can be removed. When an alkaline aqueous solution such as caustic soda is used for the degreasing treatment, smut is generated on the surface of the support. In this case, it is immersed in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid, or a mixed acid thereof and desmutted. It is preferable to apply.

(Roughening 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 roughening by the brush polishing method is, for example, by rotating a rotating brush using a bristle having a diameter of 0.2 to 0.8 mm, and for example, volcanic ash particles having a particle size of 10 to 100 μm on water. While supplying the uniformly dispersed slurry, the brush can be pressed. The roughening by honing polishing is performed by, for example, uniformly dispersing volcanic ash particles having a particle size of 10 to 100 μm in water, injecting pressure from a nozzle, and causing the surface to collide obliquely with the support surface. Can do. Further, for example, a sheet in which abrasive particles having a particle size of 10 to 100 μm are coated on the support surface so as to exist at a density of 2.5 × 10 ³ to 10 × 10 ³ particles / cm ² at intervals of 100 to 200 μm. And roughening can be performed by transferring a rough surface pattern of the sheet by applying pressure.

After the surface is roughened by the above-described mechanical surface roughening method, it is preferable to immerse in an aqueous solution of acid or alkali in order to remove the abrasive that has digged into the surface of the support, formed aluminum scraps, and the like. 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 aqueous alkali solution such as sodium hydroxide. The dissolution amount of aluminum in the support surface, 0.5 to 5 g / m ² is preferred. After the immersion treatment with an alkaline aqueous solution, it is preferable to carry out a neutralization treatment by immersion in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid or a mixed acid thereof.

  The electrochemical surface roughening method is not particularly limited, but a method of electrochemical surface roughening in an acidic electrolyte is preferable. As the acidic electrolytic solution, an acidic electrolytic solution usually used in an electrochemical surface roughening method can be used, but a hydrochloric acid-based or nitric acid-based electrolytic solution is preferably used. As the electrochemical surface roughening method, for example, methods described in Japanese Patent Publication No. 48-28123, British Patent No. 896,563 and Japanese Patent Laid-Open No. 53-67507 can be used.

This roughening method can be generally performed by applying a voltage in the range of 1 to 50 volts, but is preferably selected from the range of 10 to 30 volts. Current density may be in the range of 10 to 200 A / dm ^2, preferably selected from the range of 50 to 150 A / dm ^2. The quantity of electricity may be in the range of 5000 C / dm ^2, preferably selected from the range of 100~2000C / dm ^2. The temperature at which the roughening method is performed can be in the range of 10 to 50 ° C, but is preferably selected from the range of 15 to 45 ° C.

When electrochemical surface roughening is performed using a nitric acid-based electrolyte as the electrolyte, it can be generally performed by applying a voltage in the range of 1 to 50 volts, but is selected from the range of 10 to 30 volts. Is preferred. Current density may be in the range of 10 to 200 A / dm ^2, preferably selected from the range of 20 to 100 A / dm ^2. The quantity of electricity may be in the range of 5000 C / dm ^2, preferably selected from the range of 100~2000C / dm ^2. The temperature at which the electrochemical surface roughening method is performed can be in the range of 10 to 50 ° C, but is preferably selected from the range of 15 to 45 ° C. The concentration of nitric acid in the electrolytic solution is preferably 0.1 to 5% by mass. If necessary, nitrate, chloride, amines, aldehydes, phosphoric acid, chromic acid, boric acid, acetic acid, oxalic acid, and the like can be added to the electrolytic solution.

When a hydrochloric acid-based electrolyte is used as the electrolyte, it can be generally applied by applying a voltage in the range of 1 to 50 volts, but is preferably selected from the range of 2 to 30 volts. Current density may be in the range of 10 to 200 A / dm ^2, preferably selected from the range of 50 to 150 A / dm ^2. The quantity of electricity may be in the range of 5000 C / dm ^2, preferably 100~2000C / dm ^2, and more and more preferably selected from the range of 200~1000C / dm ^2. The temperature at which the electrochemical surface roughening method is performed can be in the range of 10 to 50 ° C, but is preferably selected from the range of 15 to 45 ° C. The concentration of hydrochloric acid in the electrolytic solution is preferably 0.1 to 5% by mass. If necessary, nitrate, chloride, amines, aldehydes, phosphoric acid, chromic acid, boric acid, acetic acid, oxalic acid, and the like can be added to the electrolytic solution.

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

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

(Anodizing treatment)
Following the roughening treatment, an anodizing 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.

For the anodizing treatment, a method of electrolyzing an aqueous solution containing sulfuric acid and / or phosphoric acid at a concentration of 10 to 50% as an electrolytic solution at a current density of 1 to 10 A / dm ² is preferably used. A method of electrolyzing at a high current density in sulfuric acid described in the specification of No. 1,412,768, a method of electrolysis using phosphoric acid described in the specification of No. 3,511,661, chromic acid , A method using a solution containing one or more succinic acid, malonic acid and the like. The formed anodic oxidation coating amount is suitably 1 to 50 mg / dm ² , preferably 10 to 40 mg / dm ² . The anodic oxidation coating amount is obtained by, for example, immersing an aluminum plate in a chromic phosphate solution (85% phosphoric acid solution: 35 ml, prepared by dissolving 20 g of chromium (IV) oxide in 1 L of water) to dissolve the oxide coating. It can be obtained from the measurement of mass change before and after dissolution of the coating on the plate.

(Sealing treatment)
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.

(Polyvinylphosphonic acid treatment)
Furthermore, in this invention, after performing these processes, the process which coat | covers a support body surface with polyvinylphosphonic acid can be performed. The coating treatment is not limited to a coating method, a spray method, a dip method, or the like, but a dip method is suitable for making the equipment inexpensive. In the case of a dip type, it is preferable to treat polyvinylphosphonic acid with a 0.05 to 3% aqueous solution. The treatment temperature is preferably 20 to 90 ° C., and the treatment time is preferably 10 to 180 seconds. After the treatment, it is preferable to perform a squeegee treatment or a water washing treatment in order to remove the excessively laminated polyvinylphosphonic acid. Furthermore, it is preferable to perform a drying process. The drying temperature is preferably 20 to 95 ° C. Preferably the coating weight of polyvinylphosphonic acid of the aluminum support surface is 3 to 15 mg / m ^2, further preferably 3.5~10mg / m ^2. Various combinations of polyvinyl phosphonic acid aqueous solution concentration, treatment temperature, and treatment time can be used to obtain a desired coating amount.

(Photopolymerization initiator)
In the present invention, preferred photopolymerization initiators include bromine compounds, titanocene compounds, monoalkyltriaryl borate compounds, and iron arene complex compounds having a structure represented by the following general formulas (1) and (2).

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

Formula (2) 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 combine to form a ring.

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

  Examples of the monoalkyl triaryl borate compound include compounds described in JP-A Nos. 62-150242 and 62-143044, and more preferable specific examples include tetra-n-butylammonium n-butylate. Rootulinaphthalen-1-yl-borate, tetra-n-butylammonium n-butyl-triphenyl-borate, tetra-n-butylammonium n-butyl-tri- (4-tert-butylphenyl) -borate, tetra-n- Examples include butyl ammonium n-hexyl root- (3-chloro-4-methylphenyl) -borate and tetra-n-butyl ammonium n-hexyl root- (3-fluorophenyl) -borate.

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

  In addition, any photopolymerization initiator can be used in combination. For example, J. et al. Carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo, diazo compounds, halogen compounds, and photoreductive dyes as described in Chapter 5 of “Light Sensitive Systems” by J. Kosar Etc. Further 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, JP-A-61-9621 and JP-A-60-60104 Triazine derivatives described in Japanese Patent Publication No. JP-A-59-1504 and JP-A-61-243807; JP-B Nos. 43-23684, 44-6413, 44-6413 47-1604 and U.S. Pat. No. 3,567,453; U.S. Pat. Nos. 2,848,328, 2,852,379 and 2,940. , 853; O-quinonediazides described in JP-B 36-22062b, JP-A-37-13109, JP-A-38-18015 and JP-A-45-9610; JP-B 55- 39162, JP-A-59-14023 and “Macromolecules”, Vol. 10 Various onium compounds described on page 1307 (1977); azo compounds described in JP-A-59-142205; JP-A-1-54440, European Patents 109,851 and 126,712 And metal allene complexes described in “Journal of Imaging Science (J. Imag. Sci.)”, Vol. 30, page 174 (1986); disclosed in JP-A Nos. 5-213861 and 05-255347 ( Oxo) sulfonium organoboron complexes; transition metal complexes containing transition metals such as ruthenium described in "Coordination Chemistry Review" 84, 85-277 (1988) and JP-A-2-182701 Japanese Patent Laid-Open No. 3-209 2,4,5-triarylimidazole dimer of JP 77; carbon tetrabromide, organic halogen compounds in JP 59-107344 JP like.

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

  Examples of the compound for wavelength sensitizing from visible light to near infrared include cyanine, phthalocyanine, merocyanine, porphyrin, spiro compound, ferrocene, fluorene, fulgide, imidazole, perylene, phenazine, phenothiazine, polyene, azo compound, diphenylmethane, Phenylmethane, polymethine acridine, coumarin, coumarin derivatives, ketocoumarin, quinacridone, indigo, styryl, pyrylium compounds, pyromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, etc., keto alcohol borate complexes Further, European Patent No. 568,993, U.S. Pat. Nos. 4,508,811, 5,227,227, JP-A-2001-1 5255 JP, compounds described in JP-A 11-271969 Patent Publication also used.

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

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

(Compound containing an ethylenic double bond capable of addition polymerization)
The compound containing an ethylenic double bond capable of addition polymerization according to the present invention includes general radical polymerizable monomers and ethylenic double bonds capable of addition polymerization in a molecule generally used for UV curable resins. Polyfunctional monomers having a plurality of 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 ester such as 1,3-dioxolane acrylate, or these acrylates as methacrylate, itaconate, crotonate, maleate Methacrylic acid, itaconic acid, crotonic acid, maleic acid ester such as ethylene glycol diamine Rate, triethylene glycol diacrylate, pentaerythritol diacrylate, hydroquinone diacrylate, resorcin diacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate of hydroxypivalate, neo Diacrylate of pentyl glycol adipate, diacrylate of ε-caprolactone adduct of neopentyl glycol hydroxypivalate, 2- (2-hydroxy-1,1-dimethylethyl) -5-hydroxymethyl-5-ethyl-1,3 -Ε-caprolactone addition of dioxane diacrylate, tricyclodecane dimethylol acrylate, tricyclodecane dimethylol acrylate , Bifunctional acrylic acid esters such as diglycidyl ether diglycidyl ether 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, dipenta Ε-Caprolactone adduct of erythritol hexaacrylate, pyrogallol triac Polyfunctional acrylic acid ester such as acrylate, 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 suitably 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 the prepolymer 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, and 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, tri Polyester obtained by introducing (meth) acrylic acid into a polyester obtained by combining polyhydric alcohols such as methylolpropane, pentaerythritol, sorbitol, 1,6-hexanediol, 1,2,6-hexanetriol Acrylates 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 As described above, urethane acrylates obtained by introducing (meth) acrylic acid into urethane resins, for example, silicone resin acrylates such as polysiloxane acrylate, polysiloxane diisocyanate, 2-hydroxyethyl acrylate, and other oil-modified alkyd resins (meth) Examples thereof include prepolymers such as alkyd-modified acrylates and spirane resin acrylates into which acryloyl groups are introduced.

  The photosensitive composition according to the present invention includes phosphazene monomer, triethylene glycol, isocyanuric acid EO (ethylene oxide) modified diacrylate, isocyanuric acid EO modified triacrylate, dimethylol tricyclodecane diacrylate, trimethylolpropane acrylic acid. Addition-polymerizable oligomers and prepolymers having monomers such as benzoic 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 a phosphoric ester compound containing at least one (meth) acryloyl group. The compound is not particularly limited as long as at least a 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. Among these, compounds having two or more acrylic groups or methacryl groups in the molecule are preferred in the present invention, and those having a molecular weight of 10,000 or less, more preferably 5000 or less are preferred.

  In addition, 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 Nos. 1-165613, 1-203413, and 1-1197213 are preferably used.

  Furthermore, in the present invention, 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 used. Is preferred.

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

  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.

  The compound containing an ethylenic double bond capable of addition polymerization with a hydroxyl group in the molecule is preferably 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxypropylene-1,3. -Dimethacrylate, 2-hydroxypropylene-1-methacrylate-3-acrylate, etc. are mentioned.

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

  Specific examples of reaction products of polyhydric alcohols containing a tertiary amino group in the molecule, diisocyanate compounds, and compounds containing an ethylenic double bond capable of addition polymerization with a hydroxyl group in the molecule are as follows. 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) The product M-5: N-methyldiethanolamine (1 mole), tolylene-2,4-diisocyanate (2 moles), 2-hydroxypropylene-1,3-dimethacrylate reaction product of (2 moles).

  In addition, acrylates or alkyl acrylates described in JP-A-1-105238 and 2-127404 can be used.

(Polymer binder)
The photosensitive lithographic printing plate material according to the present invention contains a polymer binder in the photopolymerizable photosensitive layer.

  Examples of the polymer binder include acrylic polymer, polyvinyl butyral resin, polyurethane resin, polyamide resin, polyester resin, epoxy resin, phenol resin, polycarbonate resin, polyvinyl butyral resin, polyvinyl formal resin, shellac, and other natural resins. Can be used. Two or more of these may be used in combination.

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

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

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

  Furthermore, the polymer binder according to the present invention may use the monomers described in the following 1) to 14) as other copolymerization monomers.

1) Monomer having an aromatic hydroxyl group, such as o- (or p-, m-) hydroxystyrene, o- (or p-, m-) hydroxyphenyl acrylate, etc. 2) Monomer having an aliphatic hydroxyl group, such as 2 -Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N-methylol acrylamide, N-methylol methacrylamide, 4-hydroxybutyl methacrylate, 5-hydroxypentyl acrylate, 5-hydroxypentyl methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl Methacrylate, N- (2-hydroxyethyl) acrylamide, N- (2-hydroxyethyl) methacrylamide, hydroxyethyl vinyl ether, etc. 3) Monomer having an aminosulfonyl group, eg For example, m- (or p-) aminosulfonylphenyl methacrylate, m- (or p-) aminosulfonylphenyl acrylate, N- (p-aminosulfonylphenyl) methacrylamide, N- (p-aminosulfonylphenyl) acrylamide, etc. 4 ) Monomers having sulfonamide groups such as N- (p-toluenesulfonyl) acrylamide, N- (p-toluenesulfonyl) methacrylamide 5) Acrylamide or methacrylamides such as acrylamide, methacrylamide, N-ethylacrylamide N-hexylacrylamide, N-cyclohexylacrylamide, N-phenylacrylamide, N- (4-nitrophenyl) acrylamide, N-ethyl-N-phenylacrylamide, N- (4-hydro Shifeniru) acrylamide, N-(4-hydroxyphenyl) methacrylamide.

6) Monomers containing fluorinated alkyl groups such as trifluoroethyl acrylate, trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, hexafluoropropyl methacrylate, octafluoropentyl acrylate, octafluoropentyl methacrylate, heptadecafluorodecyl methacrylate, N -Butyl-N- (2-acryloxyethyl) heptadecafluorooctylsulfonamide, etc. 7) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether, etc. 8) Vinyl Esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, vinyl benzoate 9) Styrenes such as styrene, methyl styrene, chloromethyl styrene 10) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, phenyl vinyl ketone 11) Olefins such as ethylene, Propylene, i-butylene, butadiene, isoprene, etc. 12) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, etc. 13) Monomers having a cyano group, such as acrylonitrile, methacrylonitrile, 2-pentenenitrile, 2- Methyl-3-butenenitrile, 2-cyanoethyl acrylate, o- (or m-, p-) cyanostyrene, etc. 14) Monomers having amino groups such as N, N-diethylaminoethyl methacrylate, N, N-dimethylaminoethyl Acrylate, N, N-dimethylaminoethyl methacrylate, polybutadiene urethane acrylate, N, N-dimethylaminopropylacrylamide, 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.

  Further, 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 particularly preferably in the range of 50 to 90 from the viewpoint of balancing the polarity of the entire photosensitive layer. Preferably, this can prevent aggregation of the pigment in the photosensitive layer coating solution.

The coating amount on the support of the photopolymerizable photosensitive layer containing these components is preferably 0.1 to 5 g / m ² , more preferably 0.5 to ³ g / m ² in terms of the mass after drying.

(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 necessary Water-soluble polymers such as polyvinylamine, polyethylene oxide, polystyrene sulfonic acid, polyacrylic acid, and water-soluble polyamide can also be used in combination.

(Overcoat layer)
In the photosensitive lithographic printing plate material according to 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, still more preferably 75 g / 10 mm or more. Preferred overcoat layer compositions include those described in JP-A-10-10742. The peeling force was measured by applying a pressure-sensitive adhesive tape having a sufficiently large adhesive force on the overcoat layer, and peeling it with the overcoat layer at an angle of 90 degrees with respect to the plane of the lithographic printing plate material. .

  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.

(Developer and replenisher)
The main component of the developer and replenisher used in the processing method according to the present invention is at least one compound selected from silicic acid, phosphoric acid, carbonic acid, boric acid, phenols, saccharides, oximes and fluorinated alcohols, or an alkali thereof. It is preferable to contain a metal salt. These compounds are preferably coexisted with alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide and the like, and an alkaline aqueous solution having a pH higher than 8.5 and lower than 13.0 is preferable. . More preferably, the pH is 8.5-12. Among these, as weakly acidic substances such as phenols, saccharides, oximes and fluorinated alcohols, those having a dissociation index (pKa) of 10.0 to 13.2 are preferable.

  Such an acid is selected from those described in IONISATION CONSTANTS OF ORGANIC ACIDS INAQUEOUS SOLUTION published by Pergamon Press, 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 (11.27), p-cresol (10.27). , Phenols having a phenolic hydroxyl group such as m- 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 reducibility, and are trehalose-type oligosaccharides in which reducing groups are bonded to each other, glycosides in which the reducing group of saccharides and non-saccharides are bonded. And sugar alcohols reduced by hydrogenation of saccharides, both of which are preferably used in the present invention. Examples of trehalose type oligosaccharides include saccharose and trehalose, and examples of glycosides include alkyl glycosides, phenol glycosides, and mustard oil glycosides.

  Examples of the sugar alcohol include D, L-arabit, rebit, xylit, D, L-sorbit, D, L-mannit, D, L-exit, D, L-talit, zulsiit 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), Barbitu Weak acid such as an acid (at 12.5) and the like.

  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 0.1 to 30% by mass, more preferably 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 a high concentration, and there is a problem of increased costs. 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 the image of the 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 may 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.

Most preferred are potassium silicate and sodium silicate. The concentration of the silicate is preferably 1.0 to 4.0% by mass in terms of SiO ₂ concentration. Moreover, it is preferable if the molar ratio of SiO ₂ to alkali metal M (SiO ₂ / M) is in the range of 0.25-4.

  The developer referred to in the present invention is not only an unused solution used at the start of development, but also a replenisher that is replenished to correct the activity of the solution that is reduced by 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.

  Various surfactants and organic solvents can be added to the developer and replenisher according to the present invention as needed for the purpose of promoting developability, dispersing development residue, and improving ink affinity of the printing plate image area. Preferred surfactants include anionic, cationic, nonionic and amphoteric surfactants.

  Preferable examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene aryl ether, ester polyoxyethylene alkyl phenyl ethers, polyoxyethylene naphthyl ether, polyoxyethylene benzyl ether, polyoxyethylene polystyryl phenyl ether , Polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene polyoxypropylene aryl ethers, glycerin fatty acid partial esters, sorbitan fatty acid partial esters, pentaerythritol fatty acid partial esters, propylene glycol mono fatty acid esters, sucrose fatty acid Partial esters, polyoxyethylene sorbitan fatty acid partial esters, polyoxyethylene sorbitol fatty acid partial esters Tells, polyethylene glycol fatty acid esters, polyglycerin fatty acid partial esters, polyoxyethylenated castor oil, polyoxyethylene glycerin fatty acid partial esters, polyoxyethylene-polyoxypropylene block copolymers, polyoxyethylene of ethylenediamine Nonionic interfaces such as polyoxypropylene block copolymer adducts, fatty acid diethanolamides, N, N-bis-2-hydroxyalkylamines, polyoxyethylene alkylamines, triethanolamine fatty acid esters, trialkylamine oxides Activators, fatty acid salts, abietic acid salts, hydroxyalkane sulfonic acid salts, alkane sulfonic acid salts, dialkyl sulfosuccinic acid ester salts, linear alkyl benzene sulfonic acid salts Branched alkylbenzene sulfonates, alkylnaphthalene sulfonates, polyoxyethylene aryl ether carboxylic acid, polyoxyethylene naphthyl ether sulfate ester, alkyl diphenyl ether sulfonates, alkylphenoxy polyoxyethylene propyl sulfonates, polyoxyethylene alkyl Sulfophenyl ether salts, polyoxyethylene aryl ether sulfate, N-methyl-N-oleyl taurine sodium salt, N-alkylsulfosuccinic acid monoamide disodium salt, petroleum sulfonates, sulfated beef oil, sulfuric acid of fatty acid alkyl ester Ester salts, alkyl sulfate salts, polyoxyethylene alkyl ether sulfate salts, fatty acid monoglyceride sulfate salts, Polyoxyethylene alkylphenyl ether sulfates, polyoxyethylene styryl phenyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkylphenyl ether phosphates, styrene / maleic anhydride Partially saponified products of polymers, partially saponified products of olefin / maleic anhydride copolymer, anionic surfactants such as naphthalenesulfonate formalin condensates, quaternary compounds such as alkylamine salts and tetrabutylammonium bromide Cationic surfactants such as ammonium salts, polyoxyethylene alkylamine salts, polyethylene polyamine derivatives, carboxybetaines, aminocarboxylic acids, sulfobetaines, aminosulfuric acid Ester ethers, amphoteric surfactants such as imidazolines.

  Among the surfactants mentioned above, those having polyoxyethylene can be read as polyoxyalkylenes such as polyoxymethylene, polyoxypropylene, polyoxybutylene, and these surfactants are also included. . A more preferred surfactant is a fluorosurfactant containing a perfluoroalkyl group in the molecule. Examples of such fluorosurfactants include anionic types such as perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, 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 containing oligomers, perfluoroalkyl groups, and lipophilic group-containing urethanes.

  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%.

  Various development stabilizers are preferably used in the developer and replenisher according to the present invention. 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. Further, an organoboron 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.

  If necessary, an organic solvent is added to the developer and the 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 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 not substantially contained, and particularly preferably not contained at all. Here, “substantially not contained” means 1% by mass or less.

  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. 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.

  If necessary, an organic carboxylic acid can be further added to the developer and replenisher according to 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, 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, etc. Hydroxynaphthoic 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 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. Dissolving may be hindered when using other additives. Therefore, the preferable addition amount is 0.1 to 10% by mass, and more preferably 0.5 to 4% by mass with respect to the developing solution at the time of use.

In addition to the above, the following additives can be added to the developer and replenisher according to 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, Amphoteric polymer electrolytes such as vinylbenzyltrimethylammonium chloride and sodium acrylate copolymer described in JP-A-56-142258, organometallic surfactants containing Si, Ti, etc. described in JP-A-59-75255, And organic boron compounds described in JP-A-59-84241.

  The developer and replenisher according to the present invention may further contain a preservative, a colorant, a thickener, an antifoaming agent, a hard water softening agent, 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 water softeners include polyphosphoric acid and its sodium, potassium and ammonium salts, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminedisuccinic acid, methyliminodiacetic acid, β-alaninediacetic acid, triethylenetetraminehexaacetic acid, hydroxyethylethylenediamine. Aminopolycarboxylic acids such as triacetic 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), hydro Shi 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 and the hardness and amount of hard water used. It is 5 mass%, More preferably, it is the range of 0.01-0.5 mass%. If the addition amount is less than this range, the intended purpose is not sufficiently achieved, and 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. It is more preferable that the obtained developer has a conductivity of 3 to 100 mS and a surface tension of 2.0 × 10 ^{−2 to} 8.0 × 10 ⁻² Nm ⁻¹ .

  JP-A-11-0665129, JP-A-11-0665126, JP-A-2000-206706, JP-A-2000-081711, JP-A-2002-091014, 2002-091015, 2002-0991016 Gazette, 2002-091017 gazette, 2002-174907 gazette, 2002-182401 gazette, 2002-196506 gazette, 2002-196507 gazette, 2002-202616 gazette, 2002-229187 gazette. Gazette, 2002-202615, 2002-251019, 2002-365813, 2003-029427, 2003-021908, 2003-015318, 2003-035960 JP, 2003-043693, 2003-043701, 2003-043702, 2003-043703, etc., plate materials, plate surface protecting agents, developer materials, automatic development It can use suitably also about a machine etc.

(Developer concentrate)
The developer and the replenisher according to the present invention are advantageous in terms of transportation in the form of a concentrated solution having a lower water content 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, toluenesulfonic acid, xylenesulfonic acid and alkali metal salts thereof described in JP-A-6-32081 are preferably used.

  The water content of 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 or by adding a small amount of water when mixing a plurality of materials. 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, and JP-A-6- Granules and tablets can be obtained by a conventionally well-known method described in Japanese Patent Nos. 266062 and 7-13341. The material contained in the solid or paste developer concentrate can use the components used in the developer of ordinary photosensitive lithographic printing plates, but it does not return to its original state even if diluted with water. Is preferably not included. For example, since silicate becomes calcified and hardly dissolves in water when the water content becomes low, it is preferable to contain carbonate, phosphate, organic acid salt or the like instead of silicate.

  The concentrated solution of these developing solutions, or the solid or pasty concentrate 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 a developer concentrate to a developer that is in use without being diluted to a concentration that is higher than a predetermined concentration or to a predetermined concentration, the developer concentrate is used separately at the same timing or at a different timing. Water may be added.

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

  The automatic processor according to 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 on the plate surface, and preferably provided with a mechanism for controlling the temperature of the pretreatment liquid to an arbitrary temperature of 25 to 55 ° C. Is provided with a mechanism for rubbing the plate surface with a roller-like brush. Moreover, water etc. are used as this pretreatment liquid.

  The automatic processor according to 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 the pH of the developer and electric power. Further, the replenishment amount of water may be corrected by 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 processor.

  Also, the developer surface should be as small as possible in order to prevent the pH of the developer from decreasing due to the absorption of carbon dioxide in the air by the alkaline developer and the concentration of the developer due to evaporation of water in the developer. preferable. A high effect can be obtained by shielding the developer surface with a floating lid or the like. It is also an effective method to limit the contact between the air inside the self-machine and the outside air. It is preferable that the entrance / exit of the plate material of the automatic machine is as small as possible and has an automatic opening / closing mechanism that opens only when the plate material passes. Further, a method of removing carbon dioxide in the air in the self-machine is also effective, and a method of removing carbon dioxide by bringing an alkaline aqueous solution or alkaline developer waste liquid into contact with the air in the self-machine can be used effectively.

  The plate developed with the developer having such a composition is subjected to post-treatment with washing water, a rinse solution containing a surfactant and the like, a finisher mainly composed of gum arabic or starch derivatives, or a protective gum solution. In the post-treatment according to the present invention, these treatments can be used in various combinations. For example, the post-development → water washing → surfactant-containing rinsing liquid treatment or development → water washing → finishing with a finisher liquid is a rinse liquid or finisher. Less liquid fatigue is preferable. 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 the inside of 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 is also applicable. The lithographic printing plate obtained by such processing is loaded on an offset printing machine and used for printing a large number of sheets.

(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, a function as a protective agent for preventing scratches and stains on the developed plate is also added.

  By adding a surfactant to the gum solution, 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 monoamide 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 polyoxypropylene. 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 partial ester , 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 in the same manner. 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, 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 for 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, it is more advantageous to use the gum solution in the acidic range of pH 3-6. In order to adjust the pH to 3 to 6, generally, a mineral acid, an organic acid, an inorganic salt, or the like is added to the post-treatment liquid for adjustment. 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. Furthermore, 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.

  An antiseptic, an antifoaming agent, and the like can be added to the gum solution.

  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 -Derivatives such as ones, benztriazole derivatives, amiding anidine derivatives, quaternary ammonium salts, pyridine, quinoline, guanidine, diazine, triazole derivatives, oxazole, oxazine derivatives and the like.

  A preferred addition amount is an amount that stably exerts an effect on bacteria, mold, yeast, etc., and it varies depending on the type of bacteria, mold, yeast, but 0.01 to The range of 4% by mass is preferable, and it is preferable to use two or more preservatives in combination so as to be effective against various molds and sterilization. Moreover, as an antifoamer, a silicon antifoamer 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 such as aminotri (methylenephosphonic acid), potassium salts, sodium salts, etc. or phosphonoalkanetricarboxylic acids Mention may be made of a kind. 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. As addition amount, 0.001-1.0 mass% is suitable 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 120 to 250 ° C., for example, dibutyl phthalate, dihebutyl phthalate, di-n-octyl phthalate , Di (2-ethylhexyl) phthalate, dinonyl phthalate, didecyl phthalate, dilauryl phthalate, butyl benzyl phthalate, and the like phthalic acid diester agents such as dioctyl adipate, butyl glycol adipate, dioctyl azelate, dibutyl sebacate, di ( 2-ethylhexyl) aliphatic dibasic acid esters such as sebacate and dioctyl sebacate, for example, epoxidized triglycerides such as epoxidized soybean oil, such as tricresyl phosphate, trioctyl Osufeto, phosphoric 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 and contained as an oil phase thereof, or may be solubilized with the aid of a solubilizer.

In the present invention, the solid 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 high 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.

  The time from the end of 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.

(Dry)
The drying time is preferably 1 to 5 seconds. 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. 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.

(Cleaning solution)
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.

  In the cleaning method according to the present invention, the cleaning liquid used for cleaning before development is preferably used by adjusting the temperature, and the temperature is preferably in the range of 10 to 60 ° C. As a cleaning method, a known processing liquid supply technique such as spraying, dipping, coating, or the like can be used, and processing promoting means such as a brush, a drawing roll, or a submerged shower in 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 carried out 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.

  Hereinafter, although a synthesis example, a support body preparation example, and an Example are shown concretely, the embodiment of this invention is not limited to these. In the examples, “parts” means “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, and a nitrogen stream. The reaction was performed in an oil bath at 80 ° C. for 6 hours. Thereafter, 3 parts of triethylammonium chloride and 2 parts of glycidyl methacrylate were added and reacted for 3 hours to obtain an acrylic copolymer 1. The weight average molecular weight measured using GPC was about 50,000, and the glass transition temperature (Tg) measured using DSC (differential thermal analysis) was about 85 ° C.

(Production of support)
An aluminum plate (material 1050, tempered H16) having a thickness of 0.24 mm was immersed in a 5% aqueous sodium hydroxide solution kept at 65 ° C., degreased for 1 minute, and then washed with water. This degreased aluminum plate was neutralized by immersion in a 10% aqueous hydrochloric acid solution maintained at 25 ° C. for 1 minute, and then washed with water. Next, this aluminum plate was subjected to electrolytic surface roughening with an alternating current for 60 seconds in a 0.3 mass% nitric acid aqueous solution at 25 ° C and a current density of 100 A / dm ² , and then kept at 60 ° C. In addition, desmutting treatment was performed for 10 seconds in a 5% aqueous sodium hydroxide solution. The surface-roughened aluminum plate subjected to desmut treatment was anodized in a 15% sulfuric acid solution at 25 ° C., a current density of 10 A / dm ² , and a voltage of 15 V for 1 minute, and further 90% with 3% sodium oxalate. Sealing treatment was performed at 0 ° 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)
An undercoat layer coating solution having the following composition is applied to the above support with a wire bar so that it is 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]
A photopolymerizable photosensitive layer coating solution having the following composition was applied to the undercoated support 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 was 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 was produced.

<Photopolymerizable photosensitive layer coating solution>
Acrylic copolymer 1 (synthetic binder, molecular weight Mw = 50,000) 35.0 parts Spectral sensitizing dye 1 2.0 parts Spectral sensitizing dye 2 2.0 parts IRGACURE 784 (manufactured by Ciba Specialty Chemicals) 4.0 parts EO-modified tris (acryloxyethyl) isocyanuric acid (Allonics M-315: manufactured by Toagosei Co., Ltd.) 35.0 parts Polytetramethylene glycol diacrylate (PTMGA-250: manufactured by Kyoeisha Chemical Co., Ltd.) 10.0 parts Polyfunctional urethane acrylate ( U-15HA: manufactured by Shin-Nakamura Chemical Co., Ltd.) 5.0 parts phthalocyanine pigment (MHI454: manufactured by Gokoku Color Co., Ltd.) 6.0 parts 2-t-butyl-6- (3-t-butyl-2-hydroxy-5- Methylbenzyl) -4-methylphenyl acrylate (Sumilyzer GS: manufactured by Sumitomo 3M) 0.5 parts Fluorosurfactant (FC-431; manufactured by Sumitomo 3M) 0.5 parts methyl ethyl ketone (boiling point = 79.6 ° C) 80 parts cyclopentanone (boiling point = 129 ° C) 820 parts <Overcoat layer coating solution>
Polyvinyl alcohol (GL-03: manufactured by Nippon Synthetic Chemical Co., Ltd.) 89 parts Water-soluble polyamide (P-70: manufactured by Toray Industries, Inc.) 10 parts Surfactant (F142D: manufactured by Dainippon Ink Industries, Ltd.) 0.5 part Water 900 parts

  The developer formulation and developer replenisher formulation used in Examples 1 to 6 and Comparative Examples 1 and 2 are as follows.

<Developer formulation>
Potassium silicate aqueous solution (SiO ₂ 26%, K ₂ O 13.5%) 40.0 g / L
Ethylenediaminetetraacetic acid 0.5g / L
Polyoxyethylene (13) naphthyl ether 50.0 g / L
Potassium hydroxide The amount of the following pH The remaining component is water, pH: 12.3.

<Development replenisher formulation>
Potassium silicate aqueous solution (SiO ₂ 26%, K ₂ O 13.5%) 40.0 g / L
Ethylenediaminetetraacetic acid 0.5g / L
Polyoxyethylene (13) naphthyl ether 50.0 g / L
Potassium hydroxide The amount of the following pH The remaining component is water, pH: 12.7.

<Gum liquid (finisher liquid) 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-Benzisothiazolin-3-one 0.005% by mass
(Image formation)
Image exposure at 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 408 nm, 60 mW output laser ( The exposure pattern was 100% image area and 175 LPI 50% square dots).

Next, each processing section is provided in the order of a preheating section, a pre-water washing section, a developing section (developer 18L in the bathtub), an alkaline aqueous solution processing section (alkaline aqueous solution 15L in the bathtub), a washing section, a finisher liquid processing section, and a drying section. Further, development was carried out with a CTP automatic developing machine at 50 m ² 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 .

The developer after completion of development at 50 m ² / L is placed in a 1 L container, the flocculant shown in Table 1 is added and stirred, and then allowed to stand, and only the supernatant liquid is collected and discarded. A filter was installed and a flocculant was added to separate and discard the liquid.

  It was recorded what percentage of the total liquid was discarded. Thereafter, the water-absorbing polymer was brought into contact with the wet solid precipitate to absorb excess water in the precipitate, and then discarded. In the table, the liquid separation time refers to the time taken to separate the liquid component through the filter after the flocculant is added to generate the aggregate. When the filter is too fine, clogging occurs and it takes time to separate, while when the filter is too fine, the aggregate also passes through the filter, and the aggregate and the liquid component cannot be separated effectively.

○: The precipitate is separated, and the stickiness of the precipitate is small and easy to dispose. Δ: The aggregation is not sufficiently advanced, so that the separation is not sufficient, but a part of the precipitate is separated. There are few things and it cannot be separated, or the precipitate is separated, but the precipitate contains water and has high fluidity, and the burden of disposal work is large.

  From Table 1, it is clear that Examples 1 to 6 of the present invention are clearly superior in handling of waste liquid as compared with Comparative Examples 1 and 2. Example 7 of the present invention is incomplete in the formation and separation of precipitates due to aggregation, but is superior in handling of waste liquid compared to Comparative Examples 1 and 2.

Claims (3)

The photosensitive lithographic printing plate material in which a photosensitive layer made of a photosensitive resin composition is formed on an aluminum support is subjected to development processing by an automatic developing machine equipped with a developing unit and a water washing unit after exposure, and the photosensitive lithographic plate After preparing the printing plate, a flocculant is added to the waste liquid of the lithographic printing plate developer to form a solid precipitate in a flammable container, and the liquid component excluding the precipitate is removed by 70 to 100%, and the residue A method of disposing a developer for a lithographic printing plate, comprising contacting a water-absorbing polymer with the liquid and then discarding it as a waste. The method according to claim 1, wherein 70 to 100% removal of the liquid component excluding the precipitate is allowed to stand for 1 minute or more after adding the flocculant to form a solid precipitate, and the supernatant liquid is discarded. The disposal method of the developer for lithographic printing plates as described. 70 to 100% removal of liquid components excluding the precipitate is provided with a filter having a coarseness of 0.1 to 2 m and adding a flocculant, and then separating and discarding the liquid. The method for disposing of a lithographic printing plate developer according to claim 1.