WO2013065853A1 - 製版処理廃液のリサイクル方法 - Google Patents

製版処理廃液のリサイクル方法 Download PDF

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Publication number
WO2013065853A1
WO2013065853A1 PCT/JP2012/078539 JP2012078539W WO2013065853A1 WO 2013065853 A1 WO2013065853 A1 WO 2013065853A1 JP 2012078539 W JP2012078539 W JP 2012078539W WO 2013065853 A1 WO2013065853 A1 WO 2013065853A1
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WIPO (PCT)
Prior art keywords
waste liquid
group
developer
water
lithographic printing
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PCT/JP2012/078539
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English (en)
French (fr)
Japanese (ja)
Inventor
史和 小林
年宏 渡辺
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富士フイルム株式会社
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Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Priority to CN201280053379.1A priority Critical patent/CN103907062B/zh
Priority to BR112014010571-5A priority patent/BR112014010571A2/pt
Priority to IN3280CHN2014 priority patent/IN2014CN03280A/en
Priority to EP12846108.4A priority patent/EP2762977B1/en
Publication of WO2013065853A1 publication Critical patent/WO2013065853A1/ja
Priority to US14/266,834 priority patent/US20140234778A1/en

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/3092—Recovery of material; Waste processing
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C02F1/048—Purification of waste water by evaporation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/40—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture or use of photosensitive materials
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/06—Pressure conditions
    • C02F2301/063—Underpressure, vacuum

Definitions

  • the present invention relates to a method for recycling a platemaking treatment waste liquid of a photosensitive lithographic printing plate precursor, and in particular, a developer containing a specific surfactant is used, the generated platemaking waste liquid is concentrated, and the obtained recycled water is reused.
  • the present invention relates to a method for recycling platemaking process waste liquid.
  • Japanese Patent Application Laid-Open No. 5-341535 discloses a method in which hot air is blown into a waste liquid storage tank to concentrate, and Japanese Patent Application Laid-Open No. 2-157084 neutralizes a processing waste liquid and adds a flocculant.
  • a technique for aggregating the aggregating components has been proposed.
  • a developer containing a non-reducing sugar and a base has been proposed from the viewpoint of formulation of a developer of a lithographic printing plate to the problem of a development processing waste solution of a lithographic printing plate (see, for example, JP-A-2011-90282). ).
  • the problem of the present invention is that foaming at the time of concentration of the platemaking process waste liquid is suppressed, and the platemaking process waste liquid is not mixed in the reclaimed water, the viscosity is not significantly increased during the concentration, or the solid content is not precipitated.
  • a plate making process for developing the exposed lithographic printing plate precursor is performed using a naphthalene skeleton.
  • the plate making process waste liquid discharged when the plate making process is performed so that the plate making process waste liquid volume after concentration / plate making waste liquid volume before concentration is in the range of 1/2 to 1/10.
  • a method for recycling a plate making process waste liquid of a photosensitive lithographic printing plate precursor comprising using the obtained reclaimed water as at least one of a diluting water and a rinsing water for preparing a developing replenisher in the automatic processor.
  • ⁇ 2> The method for recycling a platemaking treatment waste liquid according to ⁇ 1>, wherein the development replenisher further contains 0.05 to 5% by mass of an organic acid or a salt thereof.
  • ⁇ 3> The method for recycling a platemaking waste liquid according to ⁇ 1> or ⁇ 2>, wherein the content of the silicate component in the development replenisher is 1% by mass or less.
  • ⁇ 4> The method according to any one of ⁇ 1> to ⁇ 3>, wherein the anionic surfactant having a naphthalene skeleton is at least one anionic surfactant selected from sulfonates and sulfates. Recycling process for platemaking waste.
  • the photosensitive lithographic printing plate precursor has a protective layer on a radically polymerizable image recording layer, and in the automatic processor, prior to the development, the protective layer is further washed with water.
  • ⁇ 1> to ⁇ 4> The method for recycling a platemaking waste liquid according to any one of ⁇ 1> to ⁇ 4>.
  • the waste liquid concentrating apparatus includes a heating unit, and the plate-making process waste liquid is evaporated and concentrated by heating the plate-making process waste liquid by the heating unit. Any one of ⁇ 1> to ⁇ 5> Recycling method for plate making waste liquid as described in 1.
  • the waste liquid concentrating device further includes a decompression unit that decompresses the waste liquid concentrating device, and heating of the plate making waste liquid is performed in a reduced pressure state. Method.
  • the heating means in the waste liquid concentrating device includes a heat pump including a heat radiating portion and a heat absorbing portion, heats the plate making waste liquid by the heat radiating portion of the heat pump to generate water vapor, and a heat absorbing portion of the heat pump.
  • the method further includes pressurizing the concentrate after separating the water vapor of the platemaking process waste liquid concentrated by evaporation in the waste liquid concentrator with a pump and collecting the concentrate in a recovery tank.
  • the recycling method of the platemaking process waste liquid of any one of 8>.
  • the content of an organic solvent having a boiling point of 100 ° C. to 300 ° C. containing 1% by mass to 10% by mass of an anionic or nonionic surfactant having a naphthalene skeleton as a development replenisher By using a development replenisher with a concentration of 2% by mass or less, foaming that occurs when the platemaking waste liquid is concentrated can be suppressed, and the concentrator is soiled due to entrainment caused by foaming, etc. It is possible to prevent the platemaking process waste liquid from being mixed.
  • the reclaimed water obtained is suitably used as dilution water or rinsing water for preparing the development replenisher.
  • the rinse water refers to water used for washing the lithographic printing plate after the development treatment and removing each processing solution remaining on the lithographic printing plate surface. Further, by using the developer replenisher and setting the concentration rate in the evaporation concentration in a range of 1/2 to 1/10 on a volume basis, the concentrated waste liquid causes a significant increase in viscosity or a solid content is precipitated. There is nothing to do. Therefore, there is no problem that the platemaking waste liquid cannot be concentrated due to these causes, and it is possible to suppress the occurrence of dirt in the concentrator and the recovery equipment, so that the concentrator and the like can be easily cleaned. As a result, maintainability is significantly improved.
  • An anionic or nonionic surfactant having a naphthalene skeleton is presumed to promote emulsification of a solid contained in the platemaking waste liquid, and has an anionic or nonionic naphthalene skeleton. It is considered that an emulsion with a surfactant has a small increase in viscosity due to concentration, suppresses precipitation of solids, and hardly adheres to equipment such as a concentrating device, thereby facilitating washing.
  • foaming at the time of concentration of the platemaking process waste liquid is suppressed, so that the platemaking process waste liquid is not mixed in the reclaimed water, the viscosity is remarkably increased during the concentration, or solid matter is not precipitated.
  • it is easy to wash the concentrator even when the plate making process is continued for a long time and the reclaimed water obtained can be reused, and the waste liquid to be discarded as the plate making process waste liquid is extremely small. Recycling methods can be provided.
  • the recycling method of the plate making process waste liquid of the photosensitive lithographic printing plate precursor according to the present invention is an exposure in an automatic processor for developing a photosensitive lithographic printing plate precursor having a radical polymerizable image recording layer on a support after exposure.
  • the subsequent plate making treatment for developing the lithographic printing plate precursor comprises 1% by mass to 10% by mass of at least one selected from an anionic surfactant having a naphthalene skeleton and a nonionic surfactant having a naphthalene skeleton, Is contained in an organic solvent whose temperature is in the range of 100 ° C.
  • the plate-making process waste liquid discharged at the time of vaporization is steamed using a waste liquid concentrator so that the plate-making process waste liquid volume after concentration / plate-making process waste liquid volume before concentration is in the range of 1/2 to 1/10.
  • Separating the water vapor and the waste liquid concentrate by concentrating the water, condensing the separated water vapor into reclaimed water, and using the obtained reclaimed water as a diluting water for developing replenisher in the automatic processor; Use of at least one of rinsing water, and a method for recycling a platemaking process waste liquid of a photosensitive lithographic printing plate precursor.
  • photosensitive lithographic printing plate precursor means a lithographic printing plate precursor having a photosensitive image recording layer before exposure. Since a lithographic printing plate precursor having an image recording layer after exposure does not already have photosensitivity, it is simply referred to as a “lithographic printing plate precursor”. Exposure, development, and other processes for obtaining a “lithographic printing plate” applied to printing from a “photosensitive lithographic printing plate precursor” are collectively referred to as “plate making process”. The “development process” described in the present specification is one step included in the “plate making process”.
  • the developing liquid discharged from the automatic developing machine 10 and the developing replenishing liquid waste liquid are intermediated during the plate making process of the photosensitive lithographic printing plate precursor.
  • the waste liquid stored in the tank 20 and sent from the intermediate tank 20 is heated or heated under reduced pressure using a waste liquid concentrating device 30 equipped with evaporation and concentration means, and evaporated water (water vapor).
  • the water separated into the remaining concentrate (slurry) and separated as water vapor is cooled and condensed to generate reclaimed water, and the regenerated water generated is introduced into the reclaimed water tank 50.
  • this system contains 1% by mass to 10% by mass of at least one selected from an anionic surfactant having a naphthalene skeleton and a nonionic surfactant having a naphthalene skeleton. , Not containing an organic solvent having a boiling point in the range of 100 ° C.
  • the evaporation concentration of the plate-making process waste liquid generated when the plate-making process of the photosensitive lithographic printing plate precursor is performed and the generation of reclaimed water are efficiently performed, and the dirt in the waste liquid concentrating device is obtained. Is suppressed.
  • the waste liquid sent from the intermediate tank 20 is heated without reducing pressure, or heated under reduced pressure, and remains with the evaporated water.
  • Evaporation pot (not shown) that separates into concentrate (slurry) and water separated as water vapor (which may contain an organic solvent) in the evaporation pot are introduced, cooled and condensed to regenerate water And a shuttle (not shown). It is preferable that a heat pump unit that moves heat between the inside of the evaporation pot and the inside of the cooling pot is provided.
  • a heat pump is used as a heating means for the evaporating pot and a cooling means for the cooling pot, and the plate making waste liquid is heated by the heat radiating portion of the heat pump, while the heat absorbing portion of the heat pump functions as a cooling means for the cooling pot, It is preferable to cool the water vapor at the endothermic part.
  • Concentration of the waste liquid is performed by a method of reducing the boiling point of the waste liquid and concentrating the waste liquid at a lower temperature than under atmospheric pressure by reducing the boiling point of the evaporation pot with a decompression means and heating and concentrating. preferable.
  • Depressurization means include general water-sealed, oil-rotating, and diaphragm-type mechanical vacuum pumps, diffusion pumps using oil and mercury, multistage turbo compressors, reciprocating compressors, screw compressors, and other compressors Among these, an aspirator is preferably used in terms of maintainability and cost. Examples of the depressurization condition include depressurization until 13332.2 Pa (100 mmHg) or less, preferably 3999.66 Pa (30 mmHg) or less.
  • a heat pump as a heating means in the evaporation pot and a cooling means in the cooling pot. While the heat-dissipating part of the heat pump heats the plate-making process waste liquid, the heat-absorbing part of the heat pump can cool the water vapor. Compared with the case where heating means such as an electric heater is used, there are advantages such as no locally high heat, higher safety, and a reduced carbon dioxide emission.
  • the plate making process waste liquid is heated by a heating means in an evaporating pot and evaporated and concentrated so that it becomes 1/2 to 1/10 on a volume basis. .
  • the concentration ratio is less than 1/2, the amount of waste liquid to be treated is not effectively reduced, and if the concentration exceeds 1/10, the liquid is concentrated in the evaporation pot of the waste liquid concentrator 30. There is a concern that precipitation of solid matter due to the waste liquid is likely to occur and the maintainability is lowered.
  • heat pump type XR-2000 and XR-5000 (trade name) manufactured by Takagi Chiller Co., Ltd. and a friendly series (trade name) manufactured by Cosmotech Co., Ltd. are commercially available.
  • a reclaimed water tank 50 that temporarily stores the separated reclaimed water and a distilled reclaimed water reuse device 60 that controls the supply of the reclaimed water to the automatic processor 10 are provided.
  • the distilled reclaimed water reuse device 60 preferably has a replenishment water tank 80 for supplying reclaimed water to the automatic processor 10, a pipe connecting the replenishment water tank 80 and the developing bath of the automatic developer 10, A pressure gauge for measuring pressure and a pump are provided.
  • it may have a means for adjusting the composition of the reclaimed water by providing an analyzer and analyzing the components of the reclaimed water, performing neutralization, supplying fresh water, etc. according to the components.
  • the recovered reclaimed water is supplied from the replenishing water tank 80 to the automatic developing device 10 by controlling the driving of the pump according to the pressure value measured by the pressure gauge provided in the distilled reclaimed water recycling device 60.
  • the A developing replenisher is supplied from the developer replenisher tank 70 to the automatic developing machine 10.
  • the reclaimed water obtained by this system may contain an organic solvent as long as it is 0.5% or less based on the volume.
  • the obtained reclaimed water is reclaimed water having a low biochemical oxygen demand (BOD value) and chemical oxygen demand (COD value).
  • BOD value biochemical oxygen demand
  • COD value chemical oxygen demand
  • the BOD value is approximately 250 mg / L or less
  • the COD value is 200 mg / L or less.
  • excess reclaimed water may be discharged as it is into general waste water.
  • a treatment with activated sludge or the like is performed before discharge.
  • the composition and pH of the developer replenisher defined in the present invention refers to the composition and pH of the developer replenisher when used for development in an automatic processor.
  • a developer replenisher satisfying the composition and pH of the developer replenisher defined in the present invention may be supplied as it is.
  • a development replenisher obtained by diluting a stock solution for developing replenisher so as to satisfy the composition and pH specified in the invention may be supplied.
  • the stock solution for developing replenisher preparation is diluted, it is supplied from the replenishing water tank 80 according to the supply amount of the stock solution for developing replenisher solution from the developer replenisher tank 70 as in the system shown in FIG.
  • the replenishing solution obtained by mixing the stock solution and reclaimed water and diluting the stock solution to a magnification satisfying the predetermined composition and pH conditions may be supplied into the developing bath. That is, in the present invention, the mode of dilution of the stock solution for developing replenisher solution is not particularly limited.
  • plate making waste liquid generated from a plurality of automatic processors is collected and processed in one waste liquid concentrating device 30, and the obtained reclaimed water is supplied as dilution water or rinse water to a plurality of automatic processors. May be.
  • a developer suitably used for developing the photosensitive lithographic printing plate precursor after exposure will be described.
  • the term “developer” is used to include a development initiating solution (a developing solution in a narrow sense) and a developing replenisher.
  • the developer and development replenisher to which the present invention is applied are negative developers for developing a photosensitive lithographic printing plate precursor having a radically polymerizable image recording layer. Details of the developer will be described later.
  • the negative developer in this specification refers to a developer used for development after exposure of a photosensitive lithographic printing plate precursor having a negative image recording layer.
  • the development replenisher used in the present invention contains 1% by mass to 10% by mass of at least one selected from an anionic surfactant having a naphthalene skeleton and a nonionic surfactant having a naphthalene skeleton, and has a boiling point of 100 ° C. It is characterized in that it contains no organic solvent in the range of ⁇ 300 ° C. or contains it in an amount of 2% by mass or less and has a pH of 10-13.
  • the development replenisher is replaced with the development replenisher added in the developing bath after a certain amount of the plate has been processed.
  • at least the composition and pH of the “developing replenisher” used satisfy the conditions defined in the present invention. It is preferable that any of the replenishers satisfy the composition and pH defined in the present invention.
  • the degree of concentration is based on volume, and the total amount of platemaking waste before concentration is used as the denominator, the total amount of platemaking waste after concentration is used as the numerator, and the platemaking waste after concentration is standardized as 1. .
  • the reclaimed water stored in the reclaimed water tank 50 is sent to the replenishing water tank 80 via the distilled reclaimed water reuse device 60.
  • the developer replenisher stock solution is appropriately fed from the developer replenisher tank 70 to the automatic developing machine 10.
  • the waste liquid processing apparatus described in the above include, for example, a planographic printing plate making waste liquid reducing device described in Japanese Patent No. 4774124, and Japanese Patent Application Laid-Open No. 2011-90282.
  • Examples of the developer used for the photosensitive lithographic printing plate precursor having the radically polymerizable image recording layer of the present invention include a negative developer. Further, the developer according to the present invention contains an organic solvent having a content of a surfactant having an anionic or nonionic naphthalene skeleton of 1 to 10% by mass and a boiling point of 100 ° C. to 300 ° C. The amount is 2% by mass or less and the pH is 10 to 13.
  • the negative developer used for the development of the lithographic printing plate precursor according to the present invention contains at least the surfactant and an alkali metal hydroxide, and the content of the organic solvent is 2% by mass or less.
  • An alkaline developer containing no silicate component and having a pH of 10 to 12.5 is preferred.
  • the surfactant contained in the negative developer in the present invention is an anionic surfactant having a naphthalene skeleton or a nonionic surfactant having a naphthalene skeleton.
  • the optimum anionic surfactant used in the negative developer is preferably a sulfonate having a naphthalene skeleton or a sulfate having a naphthalene skeleton, more preferably a naphthalene sulfonate which may have a substituent, And at least one selected from compounds represented by the following general formula (A).
  • the substituent is preferably an alkyl group having 1 to 20 carbon atoms, and these alkyl groups are preferably substituted with 1 to 4 naphthalene rings. More preferably, it is substituted with 1 to 2 naphthalene rings. Those in which 1 to 3 sulfonate groups are substituted on the naphthalene ring are preferred, and those in which 1 to 2 are substituted are more preferred.
  • the salt sodium salt, potassium salt, ammonium salt and the like are preferable.
  • the anionic surfactant having a naphthalene skeleton is preferably an anionic surfactant represented by the following general formula (A).
  • R 5 represents a linear or branched alkylene group having 1 to 5 carbon atoms
  • R 6 represents a linear or branched alkyl group having 1 to 20 carbon atoms
  • q represents 0, 1 or 2
  • Q represents a single bond or an alkylene group having 1 to 10 carbon atoms
  • p represents an integer of 1 to 100.
  • R represents 6 and R 5 may be the same group or may be selected from two or more groups
  • M + represents Na + , K + , Li + , or NH 4 + .
  • R 5 include —CH 2 —, —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, or —CH 2 CH. (CH 3 ) — is preferred, and —CH 2 CH 2 — is more preferred.
  • Preferred examples of R 6 is, CH 3, C 2 H 5 , C 3 H 7, or the like C 4 H 9. Further, q is preferably 0 or 1. Q is preferably a single bond. Further, p is preferably an integer of 1 to 20.
  • the nonionic surfactant having a naphthalene skeleton is preferably a surfactant represented by the following general formula (B).
  • R 4 represents a hydrogen atom or an alkyl group having 1 to 100 carbon atoms.
  • N and m each independently represents an integer of 0 to 100, and n and m are simultaneously 0. Nothing.
  • Preferred examples of the compound represented by the general formula (B) include polyoxyethylene naphthyl ether, polyoxyethylene methyl naphthyl ether, polyoxyethylene octyl naphthyl ether, polyoxyethylene nonyl naphthyl ether, and the like.
  • the number of repeating units of the polyoxyethylene chain is preferably 3 to 50, more preferably 5 to 30.
  • the polyoxyethylene part and the polyoxypropylene part may be random or block copolymers, and when the number of repeating units of the polyoxyethylene chain is 3 to 50, the number of repeating units of the polyoxypropylene chain is 1 to 10 It is preferable. In the case of only polyoxypropylene chains, m is preferably 1 to 10.
  • the nonionic surfactant represented with the said general formula (B) is used individually or in combination of 2 or more types. Specific examples of the compound represented by formula (B) are shown below.
  • surfactants can be used alone or in combination of two or more. Further, the content of these surfactants in the developer is in the range of 1 to 10% by mass, preferably in the range of 2 to 10% by mass in terms of active ingredients. If the content is 1% by mass or more, the developability and the solubility of the image recording layer components in the non-exposed area are good. The same applies to the surfactant content in the development replenisher.
  • the content of the organic solvent having a boiling point in the range of 100 ° C. to 300 ° C. in the developer (including the development replenisher) used for developing the photosensitive lithographic printing plate precursor is in the range of 2% by mass or less. Yes, the organic solvent may not be contained. If the boiling point of the organic solvent contained in the developer is lower than 100 ° C, it tends to volatilize, and if it exceeds 300 ° C, it becomes difficult to concentrate.
  • the organic solvent contained in the developer may be any organic solvent as long as the boiling point is in the range of 100 ° C. to 300 ° C., preferably 2-phenylethanol (boiling point: 219 ° C.), 3-phenyl-1-propanol (boiling point: 238 ° C), 2-phenoxyethanol (boiling point: 244 to 255 ° C), benzyl alcohol (boiling point: 205 ° C), cyclohexanol (boiling point: 161 ° C), monoethanolamine (boiling point: 170 ° C), diethanolamine (boiling point: 268 ° C), cyclohexanone (boiling point: 155 ° C), ethyl lactate (boiling point: 155 ° C), propylene glycol (boiling point: 187 ° C), ethylene glycol (boiling point: 198 ° C), ⁇ -butyrolactone (
  • the developer according to the present invention has a pH of 10 to 13, but the pH of the developer may be adjusted using a pH adjuster.
  • pH adjusting agents include citric acid, malic acid, tartaric acid, benzoic acid, phthalic acid, p-ethylbenzoic acid, pn-propylbenzoic acid, p-isopropylbenzoic acid, pn-butylbenzoic acid, p- organic carboxylic acids such as t-butylbenzoic acid, pt-butylbenzoic acid, p-2-hydroxyethylbenzoic acid, decanoic acid, salicylic acid, 3-hydroxy-2-naphthoic acid or their metal salts, ammonium salts, etc.
  • citric acid has a function as a buffer, and is added as trisodium citrate or tripotassium citrate, for example.
  • it is contained in the developer in a range of 0.05 to 5% by mass, more preferably 0.3 to 3% by mass.
  • the developer may contain a chelating agent for the divalent metal.
  • divalent metals include magnesium and calcium.
  • the chelating agent for the divalent metal include Na 2 P 2 O 7 , Na 5 P 3 O 3 , Na 3 P 3 O 9 , Na 2 O 4 P (NaO 3 P) PO 3 Na 2 , and Calgon.
  • Polyphosphates such as (sodium polymetaphosphate) such as ethylenediaminetetraacetic acid, its potassium salt, its sodium salt; diethylenetriaminepentaacetic acid, its potassium salt, sodium salt; triethylenetetraminehexaacetic acid, its potassium salt, its sodium salt; hydroxy Ethylethylenediaminetriacetic acid, its potassium salt, its sodium salt; nitrilotriacetic acid, its potassium salt, its sodium salt; 1,2-diaminocyclohexanetetraacetic acid, its potassium salt, its sodium salt; 1,3-diamino-2-propanol Tetraacetic acid, its potash 2-phosphonobutanetricarboxylic acid-1,2,4, potassium salt, sodium salt thereof; 2-phosphonobutanone tricarboxylic acid-2,3, in addition to aminopolycarboxylic acids such as um salt, sodium salt thereof, etc.
  • sodium polymetaphosphate such as ethylenediaminetetraacetic acid,
  • an antifoaming agent may be further added to the developer.
  • an antifoaming agent it is preferably added at 0.00001% by mass or more, more preferably about 0.0001 to 0.5% by mass with respect to the developer.
  • the antifoaming agent that can be used in the developer of the present invention include a fluorine-based antifoaming agent, a silicone-based antifoaming agent, acetylene alcohol, and acetylene glycol.
  • fluorine-type antifoamer As a fluorine-type antifoamer, the compound etc. which are represented by a following formula are mentioned. Of these, fluorine-based antifoaming agents of HLB 1 to 9, particularly fluorine-based antifoaming agents of HLB 1 to 4 are preferably used.
  • the fluorine-based antifoaming agent is added to the developer as it is or in the form of an emulsion mixed with water or other solvent.
  • R represents a hydrogen atom or an alkyl group
  • Rf represents a fluorocarbon group (about C5 to C10) in which part or all of the hydrogen atoms of the alkyl group are replaced by fluorine atoms
  • X represents CO or Represents SO 2
  • n represents an integer of 1 to 10.
  • a dialkyl polydioxane preferably a dimethyl polydioxane shown below, as it is or as an O / W type emulsion,
  • dimethylpolydioxane is modified by partially introducing a carboxylic acid group or a sulfonic acid group, or an emulsion obtained by mixing these silicone compounds with water with a generally known anionic surfactant. Good.
  • Acetylene alcohol is an unsaturated alcohol having an acetylene bond (triple bond) in the molecule.
  • Acetylene glycol is also called alkynediol, and is an unsaturated glycol having an acetylene bond (triple bond) in the molecule. More specifically, there are those represented by the following general formulas (1) and (2).
  • R 1 represents a linear or branched alkyl group having 1 to 5 carbon atoms.
  • R 2 and R 3 each independently represents a linear or branched alkyl group having 1 to 5 carbon atoms, and a and b each independently represent an integer of 0 or more.
  • a + b is a number from 0 to 30.
  • examples of the linear or branched alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an isopropyl group, an isobutyl group, and an isopentyl group.
  • acetylene alcohols and acetylene glycols are commercially available, and are commercially available, for example, from Air Products and Chemicals Inc.
  • the brand name Safinol series and the brand name Olfin series manufactured by Nissin Chemical Co., Ltd. are known.
  • Specific examples of commercially available products include safinol 61 as (3), orphine B as (4), orphine P as (5), orphine Y as (7), safinol 82 as (8), 9) includes Safinol 104 and Orphine AK-02, (10) includes the Safinol 400 series, and (11) includes Safinol DF-110 (all trade names).
  • an alkali metal salt of an organic acid or an alkali metal salt of an inorganic acid may be added to the negative developer as a development regulator.
  • sodium carbonate, potassium, ammonium, sodium citrate, potassium, ammonium and the like may be used alone or in combination of two or more.
  • the negative developer includes an inorganic agent such as tribasic sodium phosphate, potassium, ammonium, sodium borate, potassium, ammonium, sodium hydroxide, potassium, ammonium, and lithium as alkali agents.
  • Organic alkali agents such as panolamine, ethyleneimine, ethylenediamine, pyridine, and tetramethylammonium hydroxide are used alone or in combination of two or more. It may be mixed by.
  • the following components can be used in combination with the negative developer as required.
  • chelating agents, reducing agents, dyes, pigments, water softeners, preservatives and the like can be mentioned.
  • the pH of the developer is essential to be 10 to 13, and preferably 11 to 12.5.
  • the conductivity x is preferably 2 ⁇ x ⁇ 30 mS / cm, and more preferably 5 to 25 mS / cm.
  • the conductivity can be adjusted by adding an alkali metal salt of an organic acid or an alkali metal salt of an inorganic acid as a conductivity adjusting agent.
  • the developing solution (developing stock solution) of the present invention is a concentrated solution in which the water content is less than that in use, and is diluted with water at the time of use. In this case, the degree of concentration is appropriate such that each component does not cause separation or precipitation.
  • the developer of the present invention may contain a silicate component, but the content of the silicate component in the developer is preferably 1% by mass or less, more preferably 0.5% by mass or less. Is desirable. If the content of the silicate component exceeds 1% by mass, the silicate component is likely to stick in the concentrator of the platemaking process waste liquid. After concentrating, the silicate component is fixed inside the waste liquid concentrator, reducing the concentration efficiency or discharging. It is not preferable because it may cause defects.
  • the silicate component is a compound containing an anion having a structure centered on one or several silicon atoms and surrounded by an electronegative ligand, and silicic acid having oxygen as a ligand. It is a compound having a chemical species such as salt or hexafluorosilicate [SiF 6 ] 2- .
  • developer is used to include “development replenisher”.
  • development initiator means a developer in a developing bath before being subjected to plate making processing unless otherwise specified
  • development replenisher means a lithographic printing plate. It means a developing replenisher that replenishes the developer in the developing bath that has deteriorated due to the development of the original plate or the absorption of carbon dioxide.
  • the developer replenisher needs to satisfy the composition and pH defined in the present invention when used in the development process, and in order to recover the activity of the deteriorated developer as long as these conditions are satisfied, It may be more active than the development initiator.
  • Developers include various types of surfactants other than the above-described surfactants as necessary for the purpose of promoting and suppressing developability, improving development residue dispersibility and printing plate image portion ink affinity.
  • a surfactant or an organic solvent may be added.
  • reducing agents such as sodium salts and potassium salts of inorganic acids such as hydroquinone, resorcin, sulfurous acid, and bisulfite can be added to the developer as necessary, and organic carboxylic acids and hard water softeners can be added.
  • the development start solution initially charged in the developing bath of the automatic developing machine 10 is deteriorated by the eluate generated by the processing of the lithographic printing plate precursor. Further, since the developer is alkaline, the pH is lowered and deteriorated due to absorption of carbon dioxide in the air. Therefore, in order to perform development processing continuously for a long period of time in the automatic developing machine 10, normally, in order to maintain the development quality of the lithographic printing plate precursor, a development replenisher that compensates for deterioration is intermittently or continuously applied. Need to replenish.
  • a stock solution for preparing a development replenisher having a higher activity than the originally used developer and water are separately developed at a certain ratio.
  • a developing replenisher prepared at a constant concentration from the beginning is introduced into a developing bath as it is. In any case, the development replenisher must satisfy the composition and pH specified in the present invention when used in the development process.
  • the recycling method of the present invention The development activity is equal to or higher than that of the developer used, but the standard concentration [stock solution + water for preparing the replenisher used in the method (1) or (2) + water or the method (3) Standard concentration of undiluted development replenisher used]
  • the stock solution for the development replenisher having a lower concentration + reclaimed water is introduced into the developing bath in an amount larger than the standard replenishment amount in order to achieve the same activity. This makes it difficult for the eluate generated by the development process to precipitate.
  • the salt concentration caused by the developer in the developer bath can be kept low, and the eluate generated by the development process can be reduced. Since the concentration becomes low, high-quality development processing can be continued while suppressing the generation of precipitates, but the amount of development processing waste liquid also increases.
  • recycled water separated from the development processing waste liquid is used. Compared to the conventional method, the amount of the development processing waste liquid discharged outside the system is drastically reduced with respect to the amount of the development replenisher supplied in order to supply the toner to the automatic processor 10 for reuse. Can do.
  • the lithographic printing plate precursor can be processed without exchanging.
  • the alkali strength (addition amount of alkali agent per unit volume) of the development replenisher is also preferably 2 to 20 times the alkali strength of the development starter.
  • Photosensitive planographic printing plate precursor ⁇ Photosensitive planographic printing plate precursor>
  • the photosensitive lithographic printing plate precursor that can be preferably applied in the method for recycling a platemaking waste liquid of the present invention will be described in detail.
  • a photosensitive composition used for forming a photosensitive image recording layer of a preferred lithographic printing plate precursor to be treated in the method for recycling a plate making waste liquid of the present invention an infrared absorber, a polymerization initiator, an ethylenically unsaturated bond
  • a photopolymerization type photosensitive composition is explained.
  • the photopolymerizable photosensitive composition mentioned as the photosensitive composition for forming an image recording layer of a lithographic printing plate precursor to be treated in the method for recycling a platemaking waste liquid of the present invention is sensitive to light in the visible light to ultraviolet wavelength region. It comprises a photopolymerization initiation system, a polymerizable compound having at least one ethylenically unsaturated group, and a binder polymer.
  • the photosensitive composition is coated on a support such as an aluminum plate to provide a photosensitive layer (image recording layer), and can be used as a photosensitive lithographic printing plate precursor.
  • Such a photosensitive lithographic printing plate precursor is obtained by sequentially laminating a photosensitive layer and optionally a protective layer on a support provided with an undercoat layer if desired.
  • “sequential lamination” means that an undercoat layer, a photosensitive layer, and a protective layer are provided in this order on a support.
  • the undercoat layer and the protective layer are layers provided as necessary. Other layers (for example, an intermediate layer, a backcoat layer, etc.) may be provided depending on the purpose.
  • the photopolymerization initiating system sensitive to light in the visible light to ultraviolet wavelength range means a system containing a compound capable of initiating photopolymerization by absorbing light in the visible light to ultraviolet wavelength range. More specifically, a combination of a sensitizing dye having a maximum absorption wavelength in the visible light to ultraviolet wavelength region, preferably 330 to 700 nm, and a photopolymerization initiator may be mentioned. Two or more photopolymerization initiators may be used as the photopolymerization initiator (combination system).
  • photopolymerization initiation system various types of sensitizing dyes (dyes) known in patents, literatures, etc., and photoinitiators or combinations of two or more photoinitiators are used depending on the wavelength of the light source used. It can be appropriately selected and used.
  • JP-A 63-258903, JP-A 2-63054, etc.
  • dyes and borate compounds JP A) JP-A-62-143044, JP-A-62-1050242, JP-A-64-13140, JP-A-64-13141, JP-A-64-13142, JP-A-64-13 No.
  • a dye having a rhodanine ring and a radical generator Systems JP-A-2-179433, JP-A-2-244050
  • titanocene and 3-ketocoumarin dyes JP-A 63-221110
  • titanocene and xanthene dyes addition polymerization containing amino groups or urethane groups
  • JP-A-4-221958, JP-A-4-219756 titanocene and a specific merocyanine dye system
  • JP-A-6-295061 having a titanocene and a benzopyran ring And dye systems
  • a laser having a wavelength of 400 to 410 nm (violet laser) has been developed, and a photopolymerization initiation system exhibiting high sensitivity at a wavelength of 450 nm or less is developed, and these photoinitiation systems are also used.
  • photoinitiation systems include cationic dyes / borate systems (Japanese Patent Laid-Open No. 11-84647), merocyanine dyes / titanocene systems (Japanese Patent Laid-Open No. 2000-147663), carbazole type dyes / titanocene systems (Japanese Patent Laid-Open No. 2001-42524), and the like. be able to.
  • thiol compounds such as 2-mercaptobenzthiazole, 2-mercaptobenzimidazole and 2-mercaptobenzoxazole, and amines such as N-phenylglycine and N, N-dialkylamino aromatic alkyl esters
  • a hydrogen-donating compound such as a compound.
  • the amount of these photopolymerization initiation systems used may be in the range of 0.05 to 100 parts by weight, preferably 0.1 to 70 parts by weight, based on 100 parts by weight of the ethylenically unsaturated compound described later. More preferably, it is in the range of 0.2 to 50 parts by mass.
  • a polymerizable compound having at least one ethylenically unsaturated group (hereinafter also referred to as an ethylenically unsaturated bond-containing compound) is an action of a photopolymerization initiator when the photosensitive composition is irradiated with actinic rays. It is a compound having an ethylenically unsaturated bond that undergoes addition polymerization, crosslinking, and curing.
  • the compound containing an ethylenically unsaturated bond capable of addition polymerization can be arbitrarily selected from compounds having at least one, preferably two or more terminal ethylenically unsaturated bonds. For example, it has a chemical form such as a monomer, a prepolymer, that is, a dimer, a trimer and an oligomer, or a mixture thereof and a copolymer thereof.
  • Examples of monomers and copolymers thereof include esters of unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid) and aliphatic polyhydric alcohol compounds, unsaturated Examples include amides of carboxylic acids and aliphatic polyvalent amine compounds.
  • Specific examples of the ester monomer of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol.
  • Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis p-(3- methacryloxy-2-hydroxypropoxy) phen
  • Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,5-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate Sorbitol tetritaconate, etc.
  • crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate.
  • isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.
  • maleic acid esters examples include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate. Furthermore, the mixture of the above-mentioned ester monomer can also be mentioned.
  • Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide and the like.
  • a polyisocyanate compound having two or more isocyanate groups in one molecule described in JP-B-48-41708 contains a hydroxyl group represented by the following general formula (A).
  • examples thereof include a vinyl urethane compound containing two or more polymerizable vinyl groups in one molecule to which a vinyl monomer is added.
  • CH 2 C (R) COOCH 2 CH (R ') OH (A) (However, R and R ′ represent H or CH 3. )
  • urethane acrylates as described in JP-A-51-37193 and JP-B-2-32293, JP-A-48-64183, JP-B-49-43191, JP-B-52-30490 Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid, as described in each publication.
  • the binder polymer (polymer binder) in the image recording layer comprising the photopolymerizable photosensitive composition is not only used as a film forming agent for the image recording layer, but also needs to be dissolved in an alkali developer.
  • Organic high molecular polymers that are soluble or swellable in water are used. Examples of such organic high molecular polymers include addition polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54- No.
  • examples include polymers, crotonic acid copolymers, maleic acid copolymers, and partially esterified maleic acid copolymers.
  • an acidic cellulose derivative having a carboxylic acid group in the side chain there is an acidic cellulose derivative having a carboxylic acid group in the side chain.
  • a product obtained by adding a cyclic acid anhydride to an addition polymer having a hydroxyl group is useful.
  • Other addition polymerizable vinyl monomers] copolymers are preferred.
  • polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble organic polymer.
  • alcohol-soluble polyamide, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, etc. are also useful.
  • the polyurethane resins described in No. 271741 and JP-A-11-352691 are also useful for the use of the present invention.
  • These polymer polymers can improve the strength of the cured film by introducing a radical reactive group into the side chain.
  • Functional groups that can undergo an addition polymerization reaction include ethylenically unsaturated bond groups, amino groups, and epoxy groups, and functional groups that can become radicals upon light irradiation include mercapto groups, thiol groups, halogen atoms, triazine structures, and onium salt structures. Etc.
  • the functional group capable of undergoing addition polymerization reaction is particularly preferably an ethylenically unsaturated bond group such as an acryl group, a methacryl group, an allyl group, or a styryl group, but also an amino group, a hydroxy group, a phosphonic acid group, a phosphoric acid group, or a carbamoyl group.
  • a functional group selected from an isocyanate group, a ureido group, a ureylene group, a sulfonic acid group, and an ammonio group is also useful.
  • the binder polymer preferably has an appropriate molecular weight and acid value, and a high molecular weight polymer having a weight average molecular weight of 5000 to 300,000 and an acid value of 20 to 200 is effective. Used for.
  • These binder polymers can be mixed in an arbitrary amount in the total composition of the photopolymerization type photosensitive layer. Preferably it is 10 to 90%, more preferably 30 to 80%. In the case of 90% by mass or less, it is preferable because a preferable result is given in terms of the image strength to be formed.
  • the photopolymerizable ethylenically unsaturated bond-containing compound and the binder polymer are preferably in the range of 1/9 to 9/1 by mass ratio. A more preferred range is 2/8 to 8/2, and even more preferred is 3/7 to 7/3.
  • a small amount of thermal polymerization is prohibited in order to prevent unnecessary thermal polymerization of polymerizable ethylenically unsaturated compounds during production or storage of the photosensitive composition. It is desirable to add an agent.
  • a colorant may be added for the purpose of coloring the image recording layer. Examples of the colorant include phthalocyanine pigments (CI Pigment Blue 15: 3, 15: 4, 15: 6, etc.), azo pigments, pigments such as carbon black and titanium oxide, ethyl violet, crystal violet, There are azo dyes, anthraquinone dyes, and cyanine dyes.
  • Thermopolymerization type photosensitive composition for forming the photosensitive image recording layer of the planographic printing plate precursor used in the present invention will be described.
  • the thermal polymerization photosensitive composition usually contains an infrared absorber, a polymerization initiator, an ethylenically unsaturated bond-containing monomer, and a binder polymer.
  • the infrared absorber has a function of converting absorbed infrared rays into heat. With the heat generated at this time, a polymerization initiator (radical generator) described later is thermally decomposed to generate radicals.
  • the infrared absorber used in the present invention is preferably a dye or pigment having an absorption maximum at a wavelength of 760 nm to 1200 nm.
  • dyes such as azo dyes, metal complex azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, metal thiolate complexes, etc. Is mentioned.
  • preferable dyes include cyanine dyes described in, for example, JP-A-58-125246, JP-A-59-84356, JP-A-59-202829, JP-A-60-78787, and the like.
  • Examples include squarylium dyes described in Japanese Patent Publication No. 58-112792, and cyanine dyes described in British Patent 434,875. .
  • near infrared absorption sensitizers described in US Pat. No. 5,156,938 are also preferably used, and substituted aryl benzoates described in US Pat. No. 3,881,924 are also preferably used.
  • infrared absorber examples include specific indolenine cyanine dyes described in JP-A-2002-278057.
  • cyanine dyes cyanine dyes, squarylium dyes, pyrylium salts, nickel thiolate complexes, and indolenine cyanine dyes are particularly preferable. Further, cyanine dyes and indolenine cyanine dyes are preferred, and particularly preferred examples include cyanine dyes represented by the following general formula (a).
  • X 1 represents a hydrogen atom, a halogen atom, —NPh 2 , X 2 -L 1 or a group shown below.
  • X 2 represents an oxygen atom, a nitrogen atom, or a sulfur atom
  • L 1 represents a hydrocarbon group having 1 to 12 carbon atoms, an aromatic ring having a hetero atom, or 1 to 12 carbon atoms including a hetero atom.
  • a hetero atom here shows N, S, O, a halogen atom, and Se.
  • R 9 represents a hydrogen atom, an alkyl group, an aryl group, a substituted or unsubstituted amino group, substituted or unsubstituted amino group and a halogen atom.
  • R 1 and R 2 each independently represents a hydrocarbon group having 1 to 12 carbon atoms. From the storage stability of the recording layer coating solution, R 1 and R 2 are preferably hydrocarbon groups having 2 or more carbon atoms, and R 1 and R 2 are bonded to each other to form a 5-membered ring or It is particularly preferable that a 6-membered ring is formed.
  • Ar 1 and Ar 2 may be the same or different and each represents an aromatic hydrocarbon group which may have a substituent.
  • Preferred aromatic hydrocarbon groups include a benzene ring and a naphthalene ring.
  • a C12 or less hydrocarbon group, a halogen atom, and a C12 or less alkoxy group are mentioned.
  • Y 1 and Y 2 may be the same or different and each represents a sulfur atom or a dialkylmethylene group having 12 or less carbon atoms.
  • R 3 and R 4 may be the same or different and each represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent.
  • Preferred substituents include alkoxy groups having 12 or less carbon atoms, carboxyl groups, and sulfo groups.
  • R 5 , R 6 , R 7 and R 8 may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms. From the availability of raw materials, a hydrogen atom is preferred.
  • Z 1 ⁇ represents a counter anion. However, when the cyanine dye represented by the general formula (a) has an anionic substituent in its structure and neutralization of charge is not necessary, Z 1- is not necessary.
  • Preferred Z 1 ⁇ is a halogen ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, and a sulfonate ion, particularly preferably a perchlorate ion, from the storage stability of the recording layer coating solution.
  • thermopolymerizable photosensitive composition may be added to the same layer as other components when a thermopolymerizable photosensitive composition is applied to the image recording layer of a photosensitive lithographic printing plate precursor, or a separate layer is provided.
  • the absorbance at the maximum absorption wavelength in the wavelength range of 760 nm to 1200 nm of the image recording layer is 0.5 to Add to be in the range of 1.2. Preferably, it is in the range of 0.6 to 1.15.
  • the thermal polymerization type photosensitive composition is a sulfonium salt polymerization that is a thermal decomposition type radical generator that decomposes by heat to generate radicals as a polymerization initiator for initiating and advancing the curing reaction of the polymerizable compound described later. It is preferable to contain an initiator.
  • a sulfonium salt polymerization initiator in combination with the above-described infrared absorber, the infrared absorber generates heat when irradiated with an infrared laser, and radicals can be generated by the heat. In the present invention, these combinations are preferable because these combinations enable highly sensitive heat mode recording.
  • Examples of the sulfonium salt polymerization initiator suitably used in the present invention include onium salts represented by the following general formula (I).
  • R 11 , R 12 and R 13 may be the same or different and each represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent.
  • Preferred substituents include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, or an aryloxy group having 12 or less carbon atoms.
  • Z 11 ⁇ represents a counter ion selected from the group consisting of a halogen ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, a carboxylate ion, and a sulfonate ion, preferably a perchlorate ion, Hexafluorophosphate ions, carboxylate ions, and aryl sulfonate ions.
  • onium salt represented by the general formula (I) are [OS-1] to [OS-10] described in JP-A-2006-220931, but are not limited thereto.
  • radical generators include onium salts other than sulfonium salts, triazine compounds having a trihalomethyl group, peroxides, azo polymerization initiators, azide compounds, quinonediazides, oxime ester compounds, triaryl monoalkylborate compounds Etc. Of these, onium salts are preferred because of their high sensitivity.
  • Other onium salts in the present invention include onium salts represented by the following general formulas (II) and (III).
  • Ar 21 and Ar 22 each independently represent an aryl group having 20 or less carbon atoms, which may have a substituent.
  • Preferred substituents when this aryl group has a substituent include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, or a carbon atom having 12 or less carbon atoms.
  • An aryloxy group is mentioned.
  • Z 21- represents a counter ion having the same meaning as Z 11- in formula (I).
  • Ar 31 represents an aryl group having 20 or less carbon atoms, which may have a substituent.
  • Preferred examples of the substituent include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, an aryloxy group having 12 or less carbon atoms, and 12 or less carbon atoms. Examples thereof include an alkylamino group, a dialkylamino group having 12 or less carbon atoms, an arylamino group having 12 or less carbon atoms, or a diarylamino group having 12 or less carbon atoms.
  • Z 31- represents a counter ion having the same meaning as Z 11- in formula (I).
  • the general formula (II) and the onium salt represented by the general formula (III) that can be preferably used are [OI-1] to [OI-10] described in JP-A-2006-220931. [ON-1] to [ON-5], etc., but is not limited thereto.
  • onium salts that can be suitably used as a polymerization initiator (radical generator) include those described in JP-A-2001-133696.
  • the polymerization initiator (radical generator) preferably has a maximum absorption wavelength of 400 nm or less, and more preferably 360 nm or less. By making the absorption wavelength in the ultraviolet region in this way, the photosensitive lithographic printing plate precursor can be handled under white light.
  • the total content of the polymerization initiator in the heat-polymerizable photosensitive composition is 0.1 to 50% by mass, preferably 0.5 to 30% by mass, and particularly preferably 1 to 20% by mass in the total solid content. .
  • the content is 0.1% by mass or more, good sensitivity can be obtained, and when the content is 50% by mass or less, when applied to the image recording layer of the photosensitive lithographic printing plate precursor, in the non-image area at the time of printing. There is no problem of contamination.
  • the polymerization initiator particularly preferably contains a sulfonium salt polymerization initiator, and only one kind of sulfonium salt polymerization initiator may be used, or two or more kinds may be used in combination.
  • a sulfonium salt polymerization initiator may be used, or two or more kinds may be used in combination.
  • the content ratio (mass ratio) when the sulfonium salt polymerization initiator and another polymerization initiator are used in combination is preferably 100/1 to 100/50, more preferably 100/5 to 100/25.
  • the polymerizable compound used in the heat-polymerizable photosensitive composition is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and has at least one, preferably two or more ethylenically unsaturated bonds. Selected from compounds. Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention. These have chemical forms such as monomers, prepolymers, that is, dimers, trimers and oligomers, or mixtures thereof and copolymers thereof.
  • Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof.
  • unsaturated carboxylic acids for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.
  • esters and amides thereof examples include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof.
  • an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used.
  • a dehydration condensation reaction product with a functional carboxylic acid is also preferably used.
  • a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable.
  • a compound group in which the unsaturated carboxylic acid is replaced with unsaturated phosphonic acid, styrene, vinyl ether or the like can be used.
  • Specific examples of the polymerizable compound include those that can be used as the ethylenically unsaturated bond-containing compound described in the above-described photopolymerizable photosensitive composition.
  • esters examples include aliphatic alcohol esters described in JP-B-46-27926, JP-B-51-47334, JP-A-57-196231, and JP-A-59-5240. And those having an aromatic skeleton described in JP-A-59-5241, JP-A-2-226149, and those containing an amino group described in JP-A-1-165613. Used. Furthermore, the ester monomers described above can also be used as a mixture.
  • binder polymer used in the thermal polymerization photosensitive composition is contained from the viewpoint of improving the film property, and various types can be used as long as it has a function of improving the film property.
  • the suitable binder polymer used for the heat-polymerization type photosensitive composition in this invention is a binder polymer which has a repeating unit represented by the following general formula (i).
  • this polymer is appropriately referred to as “specific binder polymer” and will be described in detail.
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents a linking group
  • A represents an oxygen atom or NR 3 —
  • R 3 represents a hydrogen atom or a carbon number of 1 to 10.
  • n represents an integer of 1 to 5.
  • the linking group represented by R 2 in the general formula (i) is composed of an atom or a group of atoms selected from a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom and a halogen atom, and an atom excluding the substituent It may be a linking group having a number of 2 to 30. Specific examples thereof include alkylene, substituted alkylene, arylene, substituted arylene, and a structure in which a plurality of divalent groups selected from these are linked by an amide bond or an ester bond.
  • examples of the linking group represented by R 2 has a chain structure
  • examples of the linking group having the chain structure include ethylene and propylene.
  • a structure in which a plurality of the above alkylenes are linked via an ester bond is also an example of a preferred linking group.
  • the linking group represented by R 2 in the general formula (i) is preferably an (n + 1) -valent hydrocarbon group having an aliphatic cyclic structure having 3 to 30 carbon atoms. More specifically, a compound having an aliphatic cyclic structure such as cyclopropane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, dicyclohexyl, tercyclohexyl, norbornane and the like, which may be substituted one or more by any substituent. And (n + 1) valent hydrocarbon groups by removing (n + 1) hydrogen atoms on an arbitrary carbon atom constituting. R 2 preferably has 3 to 30 carbon atoms including a substituent.
  • R 2 is a condensed polycyclic aliphatic hydrocarbon, a bridged cyclic aliphatic hydrocarbon, a spiro aliphatic hydrocarbon, an aliphatic hydrocarbon ring assembly (a plurality of rings are connected by a bond or a linking group).
  • linking group represented by R 2 those having 5 to 10 atoms are further preferred.
  • the structure of the linking group represented by R 2 is preferably a chain structure having an ester bond in the structure, or a chain structure having a cyclic structure as described above in the structure.
  • Examples of the substituent that can be introduced into the linking group represented by R 2 include monovalent nonmetallic atomic groups other than hydrogen, such as halogen atoms (—F, —Br, —Cl, —I), hydroxyl groups Group, alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N- Diarylcarbamoyloxy group, N-alkyl-N-arylcarbamo
  • a substituent having a hydrogen atom capable of hydrogen bonding particularly a carboxylic acid
  • Substituents having an acidity with an acid dissociation constant (pKa) smaller than that of an acid are not preferred because they tend to lower the printing durability.
  • hydrophobic substituents such as halogen atoms, hydrocarbon groups (alkyl groups, aryl groups, alkenyl groups, alkynyl groups), alkoxy groups, aryloxy groups and the like are more preferable because they tend to improve printing durability.
  • the cyclic structure is a monocyclic aliphatic hydrocarbon having 6 or less members such as cyclopentane or cyclohexane, it preferably has such a hydrophobic substituent. If possible, these substituents may be bonded to each other or with a substituted hydrocarbon group to form a ring, and the substituent may be further substituted.
  • R 3 in the case where A in formula (i) is NR 3 — represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
  • Examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms represented by R 3 include an alkyl group, an aryl group, an alkenyl group, and an alkynyl group.
  • alkyl group examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, isobutyl, sec-butyl, 1 carbon number such as tert-butyl, isopentyl, neopentyl, 1-methylbutyl, isohexyl, 2-ethylhexyl, 2-methylhexyl, cyclopentyl, cyclohexyl, 1-adamantyl, 2-norbornyl Examples include up to 10 linear, branched, or cyclic alkyl groups.
  • the aryl group include carbon having one heteroatom selected from the group consisting of an aryl group having 1 to 10 carbon atoms such as a phenyl group, a naphthyl group, an indenyl group, a nitrogen atom, an oxygen atom, and a sulfur atom.
  • examples thereof include heteroaryl groups of 1 to 10, such as furyl, thienyl, pyrrolyl, pyridyl, quinolyl and the like.
  • the alkenyl group include those having 1 to 10 carbon atoms such as vinyl group, 1-propenyl group, 1-butenyl group, 1-methyl-1-propenyl group, 1-cyclopentenyl group, 1-cyclohexenyl group and the like.
  • a linear, branched, or cyclic alkenyl group is mentioned.
  • alkynyl group examples include alkynyl groups having 1 to 10 carbon atoms such as ethynyl group, 1-propynyl group, 1-butynyl group and 1-octynyl group.
  • substituent that R 3 may have are the same as those exemplified as the substituent that R 2 can introduce.
  • R3 The number of carbon atoms of is 1 to 10 including the carbon number of the substituent.
  • a in the general formula (i) is preferably an oxygen atom or —NH— because synthesis is easy.
  • n represents an integer of 1 to 5, and is preferably 1 in terms of printing durability.
  • preferred specific examples of the repeating unit represented by the general formula (i) are specific examples described in JP-A-2006-220931 [0134] to [0143], but the present invention is not limited thereto. Is not to be done.
  • the repeating unit represented by the general formula (i) may be only one kind in the binder polymer, or may be contained in two or more kinds.
  • the specific binder polymer used in the heat-polymerizable photosensitive composition in the present invention may be a polymer consisting only of the repeating unit represented by the general formula (i), but is usually combined with other copolymerization components. Used as a copolymer.
  • the total content of the repeating unit represented by the general formula (i) in the copolymer is appropriately determined depending on the structure, the design of the composition, etc., but is preferably 1 to 99 mol% with respect to the total molar amount of the polymer component. More preferably, it is contained in the range of 5 to 40 mol%, still more preferably 5 to 20 mol%.
  • copolymerization component when used as a copolymer, conventionally known monomers can be used without limitation as long as they are radically polymerizable monomers. Specific examples include monomers described in "Polymer Data Handbook-Basics-(Science of Polymer Science, Bafukan, 1986)". One type of such copolymerization component may be used, or two or more types may be used in combination.
  • the molecular weight of the specific binder polymer in the present invention is appropriately determined from the viewpoints of image formability and printing durability of the resulting lithographic printing plate. Usually, when the molecular weight increases, the printing durability is excellent, but the image formability tends to deteriorate. On the other hand, if it is low, the image forming property is improved, but the printing durability is lowered.
  • the preferred molecular weight is in the range of 2,000 to 1,000,000, more preferably 5,000 to 500,000, and still more preferably 10,000 to 200,000.
  • the binder polymer used in the heat-polymerizable photosensitive composition in the present invention may be a specific binder polymer alone, or may be used as a mixture by combining one or more other binder polymers.
  • the binder polymer used in combination is used in the range of 1 to 60% by mass, preferably 1 to 40% by mass, and more preferably 1 to 20% by mass with respect to the total mass of the binder polymer component.
  • a conventionally known binder polymer can be used without limitation, and specifically, an acrylic main chain binder, a urethane binder, or the like often used in the industry is preferably used.
  • the total amount of the specific binder polymer and the binder polymer that may be used in combination in the heat-polymerizable photosensitive composition can be appropriately determined, but is usually 10 to 90 with respect to the total mass of nonvolatile components in the composition. It is in the range of mass%, preferably 20 to 80 mass%, more preferably 30 to 70 mass%.
  • the acid value (meq / g) of such a binder polymer is preferably in the range of 2.00 to 3.60.
  • the other binder polymer that can be used in combination with the specific binder polymer is preferably a binder polymer having a radical polymerizable group.
  • binder polymers that can be used in combination are preferably those having an alkali-soluble group.
  • the content of alkali-soluble groups in the binder polymer is preferably 0.1 to 3.0 mmol, more preferably 0.2 to 2.0 mmol, most preferably 0, per 1 g of binder polymer. .45 to 1.0 mmol. When this content is less than 0.1 mmol, it may be deposited during development to generate development residue. On the other hand, if the content is larger than 3.0 mmol, the hydrophilicity is too high and the printing durability may be lowered when applied to a photosensitive lithographic printing plate precursor.
  • thermo polymerization inhibitor In the present invention, it is desirable to add a small amount of a thermal polymerization inhibitor in order to prevent unnecessary thermal polymerization of a polymerizable compound having an ethylenically unsaturated double bond, that is, a polymerizable compound.
  • Suitable thermal polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol ), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt, and the like.
  • the addition amount of the thermal polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass with respect to the mass of the nonvolatile components in the entire composition.
  • higher fatty acid derivatives such as behenic acid and behenic acid amide may be added to prevent polymerization inhibition due to oxygen, and may be unevenly distributed on the surface of the photosensitive layer during the drying process after coating.
  • the addition amount of the higher fatty acid derivative is preferably about 0.5% by mass to about 10% by mass with respect to the non-volatile components in the entire composition.
  • thermopolymerization type photosensitive composition for the purpose of the coloring.
  • plate inspection properties such as visibility after plate making and suitability for an image density measuring machine as a printing plate can be improved.
  • the colorant many dyes cause a decrease in the sensitivity of the image recording layer (photosensitive layer) made of the thermal polymerization composition. Therefore, it is particularly preferable to use a pigment as the colorant.
  • pigments such as phthalocyanine pigments, azo pigments, carbon black and titanium oxide, and dyes such as ethyl violet, crystal violet, azo dyes, anthraquinone dyes, and cyanine dyes.
  • the addition amount of the dye and the pigment as the colorant is preferably about 0.5% by mass to about 5% by mass with respect to the non-volatile components in the entire composition.
  • the photosensitive composition further contains known additives such as inorganic fillers for improving the physical properties of the cured film, other plasticizers, and oil-sensitizing agents that can improve the ink inking property on the surface of the image recording layer. May be added.
  • plasticizers include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin, and addition polymerization with binder polymer. Generally, it can be added in a range of 10% by mass or less with respect to the total mass with the compound.
  • a UV initiator, a thermal crosslinking agent, etc. for enhancing the effect of heating and exposure after development for the purpose of improving the film strength (printing durability) of the image recording layer May be included.
  • thermal polymerization type or photopolymerization type photosensitive composition can be suitably used as an image recording layer (photosensitive layer) in the photosensitive lithographic printing plate precursor described below.
  • the photosensitive lithographic printing plate precursor is obtained by sequentially laminating a radically polymerizable image recording layer and optionally a protective layer on a support, and the image recording layer contains the above-described photosensitive composition. It is characterized by.
  • a photosensitive lithographic printing plate precursor is a coating obtained by dissolving an image recording layer coating solution containing the above-described photosensitive composition and, if necessary, a coating layer component of a desired layer such as a protective layer in a solvent.
  • the liquid can be produced by coating on a suitable support or an intermediate layer provided on the support.
  • the image recording layer (hereinafter appropriately referred to as a photosensitive layer) in the lithographic printing plate precursor according to the invention is a negative type containing the above-described photosensitive composition, in particular, a photopolymerizable photosensitive composition or a thermal polymerization photosensitive composition. It is a photosensitive layer.
  • a photopolymerization type or heat-polymerizable negative photosensitive layer has a mechanism in which a polymerization initiator is decomposed by light or heat to generate radicals, and a polymerizable compound causes a polymerization reaction by the generated radicals.
  • Photosensitive lithographic printing plate precursors having these photosensitive layers are particularly suitable for plate making by direct drawing with a laser beam having a wavelength of 300 to 1,200 nm, and are higher than conventional photosensitive lithographic printing plate precursors. It has the feature of exhibiting printing durability and image forming properties.
  • the coating amount of the photosensitive layer mainly affects the sensitivity of the photosensitive layer, the developability, and the strength and printing durability of the exposed film, and is preferably selected as appropriate according to the application. When the coating amount is too small, the printing durability is not sufficient. On the other hand, when the amount is too large, the sensitivity is lowered, it takes time for exposure, and a longer time is required for development processing, which is not preferable.
  • the coating amount is suitably in the range of about 0.1 g / m 2 to about 10 g / m 2 in terms of the mass after drying. More preferably, it is 0.5 to 5 g / m 2 .
  • the support of the photosensitive lithographic printing plate precursor according to the invention is preferably an aluminum support having a hydrophilic surface.
  • the aluminum plate is a metal plate mainly composed of dimensionally stable aluminum, and may be a pure aluminum plate, which is selected from alloy plates containing aluminum as a main component and containing a trace amount of foreign elements. May be.
  • the above-mentioned substrates made of aluminum or aluminum alloy are generically used as an aluminum substrate.
  • Examples of foreign elements contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, and titanium.
  • the content of foreign elements in the alloy is 10% by mass or less.
  • a pure aluminum plate is suitable.
  • the composition of the aluminum plate applied to the present invention is not specified, and a conventionally known material such as JIS A 1050, JIS A 1100, JIS A 3103, JIS A 3005 or the like is appropriately used. Can be used.
  • the thickness of the aluminum substrate used in the present invention is preferably about 0.1 mm to 0.6 mm. This thickness can be appropriately changed according to the size of the printing press, the size of the printing plate precursor, and the user's desire.
  • the aluminum substrate may be appropriately subjected to substrate surface treatment described below as necessary.
  • Examples of the surface roughening method include mechanical surface roughening, chemical etching, and electrolytic grain as disclosed in JP-A-56-28893. Furthermore, an electrochemical surface roughening method in which the surface is electrochemically roughened in hydrochloric acid or nitric acid electrolyte solution, and the aluminum surface is scratched with a metal wire, and the aluminum surface is ground with a polishing ball and an abrasive.
  • a mechanical graining method such as a ball graining method or a brush graining method in which the surface is roughened with a nylon brush and an abrasive can be used, and the above roughening methods can be used alone or in combination.
  • a method usefully used for roughening is an electrochemical method in which roughening is chemically roughened in hydrochloric acid or nitric acid electrolyte, and a suitable amount of electricity at the time of anode is 50 C / dm 2 to 400 C / dm 2 . It is a range. More specifically, in the electrolytic solution containing from 0.1 to 50% by weight hydrochloric acid or nitric acid, the temperature 20 ⁇ 80 ° C., for 1 second to 30 minutes, at a current density of 100C / dm 2 ⁇ 400C / dm 2 It is preferable to perform alternating current and / or direct current electrolysis.
  • the thus roughened aluminum substrate may be chemically etched with acid or alkali.
  • Etching agents suitably used are caustic soda, sodium carbonate, sodium aluminate, sodium metasilicate, sodium phosphate, potassium hydroxide, lithium hydroxide and the like, and preferred ranges of concentration and temperature are 1 to 50% by mass, 20 to 100 ° C.
  • Pickling is performed to remove dirt (smut) remaining on the surface after etching.
  • As the acid used nitric acid, sulfuric acid, phosphoric acid, chromic acid, hydrofluoric acid, borohydrofluoric acid and the like are used.
  • contact with 15 to 65 mass% sulfuric acid at a temperature of 50 to 90 ° C. as described in JP-A-53-12739 is preferable.
  • the alkali etching method described in Japanese Patent Publication No. 48-28123 is not particularly limited as long as the center line average roughness Ra of the treated surface is 0.2 to 0.5 ⁇ m.
  • the aluminum substrate that has been treated as described above to form an oxide layer is then anodized.
  • sulfuric acid, phosphoric acid, oxalic acid, or an aqueous solution of boric acid / sodium borate is used as a main component of the electrolytic bath singly or in combination.
  • the electrolyte solution may of course contain at least components normally contained in at least an Al alloy plate, an electrode, tap water, groundwater, and the like. Further, the second and third components may be added.
  • the second and third components are, for example, metal ions such as Na, K, Mg, Li, Ca, Ti, Al, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn, and ammonium ions.
  • metal ions such as Na, K, Mg, Li, Ca, Ti, Al, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn
  • cations such as nitrate ions, carbonate ions, chloride ions, phosphate ions, fluorine ions, sulfite ions, titanate ions, silicate ions, borate ions, and the like. It may be about 10,000 ppm.
  • the treatment is preferably carried out by direct current or alternating current electrolysis at a treatment liquid temperature of 10 to 70 ° C.
  • the thickness of the formed anodized film is in the range of 0.5 to 1.5 ⁇ m. Preferably, it is in the range of 0.5 to 1.0 ⁇ m.
  • the support prepared by the above treatment is treated so that the pore diameter of the micropores existing in the anodized film is in the range of 5 to 10 nm and the pore density is in the range of 8 ⁇ 10 15 to 2 ⁇ 10 16 pieces / m 2. Conditions can be selected.
  • hydrophilization treatment of the support surface widely known methods can be applied.
  • a hydrophilization treatment with silicate or polyvinylphosphonic acid is performed.
  • the film is formed with a Si or P element amount of preferably 2 to 40 mg / m 2 , more preferably 4 to 30 mg / m 2 .
  • the coating amount can be measured by fluorescent X-ray analysis.
  • an alkali metal silicate or polyvinylphosphonic acid is preferably 1 to 30% by mass, more preferably 2 to 15% by mass, and an aqueous solution having a pH of 10 to 13 at 25 ° C. This is carried out by immersing the aluminum substrate on which the anodized film is formed, for example, at 15 to 80 ° C. for 0.5 to 120 seconds.
  • the photosensitive lithographic printing plate precursor may be provided with an intermediate layer for the purpose of improving the adhesion between the photosensitive layer and the support and the stain resistance.
  • an intermediate layer for the purpose of improving the adhesion between the photosensitive layer and the support and the stain resistance.
  • a protective layer is preferably provided on the photosensitive layer described above.
  • the protective layer prevents exposure of low molecular weight compounds such as oxygen and basic substances present in the atmosphere that hinder the image formation reaction caused by exposure in the photosensitive layer to allow exposure in the atmosphere.
  • Low molecular weight compounds such as oxygen and basic substances present in the atmosphere that hinder the image formation reaction caused by exposure in the photosensitive layer to allow exposure in the atmosphere.
  • To do Basically provided to protect the photosensitive layer, but when the photosensitive layer has a radically polymerizable image forming mechanism, it serves as an oxygen blocking layer and is exposed by a high-intensity infrared laser. Serves as an anti-ablation layer.
  • the transmission of light used for exposure is not substantially inhibited, it has excellent adhesion to the photosensitive layer, and can be easily removed in the development process after exposure. Is desirable.
  • Such a protective layer has been devised conventionally and is described in detail in US Pat. No. 3,458,311 and Japanese Patent Publication No. 55-49729.
  • a water-soluble polymer compound having relatively excellent crystallinity is preferably used.
  • polyvinyl alcohol, vinyl alcohol / vinyl phthalate copolymer, vinyl acetate / vinyl are used.
  • water-soluble polymers such as alcohol / vinyl phthalate copolymer, vinyl acetate / crotonic acid copolymer, polyvinyl pyrrolidone, acidic celluloses, gelatin, gum arabic, polyacrylic acid, and polyacrylamide. Or it can be used in combination.
  • the use of polyvinyl alcohol as the main component gives the best results in terms of basic properties such as oxygen barrier properties and development removability.
  • the polyvinyl alcohol used for the protective layer may be partially substituted with an ester, an ether, and an acetal as long as it contains an unsubstituted vinyl alcohol unit for having necessary oxygen barrier properties and water solubility. Similarly, some of them may have other copolymer components.
  • Specific examples of the polyvinyl alcohol include those having a hydrolysis degree of 71 to 100% and a polymerization repeating unit in the range of 300 to 2400. Specifically, Kuraray Co., Ltd.
  • the photosensitive lithographic printing plate precursor produced as described above is exposed imagewise, and thereafter subjected to development using the alkali developer / development replenisher described in detail above.
  • a pre-water washing step, a rinsing step (including a water washing step), a post-heating step described later, a gumming step, and the like are appropriately performed to make a plate and obtain a lithographic printing plate.
  • Development is performed by supplying the exposed lithographic printing plate precursor to the automatic processor 10 in FIG.
  • thermopolymerization photosensitive lithographic printing plate precursor In order to make a lithographic printing plate from a photosensitive lithographic printing plate precursor, in the present invention, at least an image exposure step and a development step are performed, and if necessary, an optional step such as a water washing step is further performed. Done.
  • an infrared laser is preferably used as the light source, and thermal recording with an ultraviolet lamp or a thermal head is also possible. .
  • Examples of the active light source used for image exposure of the photosensitive lithographic printing plate precursor include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, and a carbon arc lamp.
  • Examples of radiation include electron beams, X-rays, ion beams, and far infrared rays.
  • g-line, i-line, deep-UV light, and high-density energy beam (laser beam) are also used.
  • Examples of the laser beam include a helium / neon laser, an argon laser, a krypton laser, a helium / cadmium laser, and a KrF excimer laser.
  • a light source having an emission wavelength in the near infrared to infrared region is preferable, and a solid laser or a semiconductor laser is particularly preferable.
  • image exposure is preferably performed by a solid-state laser and a semiconductor laser that emit infrared rays having a wavelength of 750 to 1400 nm.
  • the laser output is preferably 100 mW or more, and a multi-beam laser device is preferably used in order to shorten the exposure time.
  • the exposure time per pixel is preferably within 20 ⁇ sec.
  • the energy applied to the photosensitive lithographic printing plate precursor is preferably 10 to 300 mJ / cm 2 . When the exposure energy is within the above preferred range, the image recording layer is sufficiently cured, and laser ablation in the image recording layer at the time of exposure hardly occurs, and image damage is suppressed.
  • Exposure can be performed by overlapping the light beams of the light source. Overlap means that the sub-scanning pitch width is smaller than the beam diameter.
  • the overlap can be expressed quantitatively by FWHM / sub-scanning pitch width (overlap coefficient), for example, when the beam diameter is expressed by the half width (FWHM) of the beam intensity.
  • the overlap coefficient is preferably 0.1 or more.
  • the scanning method of the light source of the exposure apparatus used in the exposure process is not particularly limited, and a cylindrical outer surface scanning method, a cylindrical inner surface scanning method, a planar scanning method, or the like can be used.
  • the channel of the light source may be a single channel or a multi-channel, but in the case of a cylindrical outer surface system, a multi-channel is preferably used.
  • development processing may be performed immediately after exposure, but heat treatment (so-called preheating) may be performed between the exposure step and the development step.
  • the conditions for this heat treatment are preferably 5 seconds to 5 minutes in the temperature range of 60 to 150 ° C.
  • the development is performed by supplying the exposed lithographic printing plate precursor to the automatic developing machine 10 in FIG. 1 and developing with the above-described negative developer.
  • pre-water washing which removes a protective layer prior to a image development process.
  • pre-washing for example, tap water is used, and recycled water generated by the method of the present invention may be used.
  • the recycling method of the present invention it is possible to eliminate pre-water washing. That is, when the protective layer and the image recording layer are removed simultaneously with the developer, the amount of the eluate in the developer increases, so that the viscosity of the developer increases and the precipitates increase. For this reason, pre-washing is generally performed, but in the method of the present invention, the amount of waste liquid after concentration is reduced by circulating recycled water obtained from the plate-making process waste liquid.
  • the heat-polymerized photosensitive lithographic printing plate precursor is exposed (or subjected to exposure and heating steps) and then developed with the above-described developer, and further has a chelating agent capable of forming a water-soluble chelate compound with aluminum ions. It is processed with water containing water.
  • the lithographic printing plate obtained by the plate making treatment as described above is a surfactant as described in JP-A Nos. 54-8002, 55-11545, 59-58431, and the like. Or the like, a desensitizing solution containing gum arabic, starch derivatives and the like may be post-treated. These processes can be used in various combinations for the post-processing of the lithographic printing plate.
  • the heating temperature is 200 to 500 ° C.
  • the heating temperature after development is in the above range, a sufficient image strengthening action can be obtained, and problems such as deterioration of the support and thermal decomposition of the image portion are unlikely to occur.
  • the planographic printing plate obtained by the above processing is loaded on an offset printing machine and used for printing a large number of sheets.
  • a conventionally known plate cleaner for PS plate is used.
  • CL-1, CL-2, CP, CN-4, CN, CG-1 , PC-1, SR, IC all trade names, manufactured by FUJIFILM Corporation
  • Developer HN-D (trade name) is a stock solution for preparing the development starter used in this embodiment, and when charged into an automatic processor, it is diluted with 4 times the amount (by mass) of water, The development initiator according to the present invention was used.
  • the development replenisher HN-DR (trade name) is a stock solution for developing replenisher used in the present embodiment. Dilute to make a developer replenisher.
  • FIG. 1 Using the lithographic printing plate precursor, the development starter, and the development replenisher, FIG. 1 in combination with an automatic processor LP-1310NewsII (including developing means, rinsing means (including washing means) and gumming means) The plate making process of 3000 m 2 was performed in one month by the system described in the above.
  • the platemaking wastewater can be treated with XR-2000 (a heat pump type wastewater concentrator manufactured by Takagi Chiller Co., Ltd.), and the wastewater can be concentrated to 1/5 volume.
  • XR-2000 a heat pump type wastewater concentrator manufactured by Takagi Chiller Co., Ltd.
  • a part of the reclaimed water could be discharged into the general sewer.
  • a part of the recycled water was used as rinsing water for the lithographic printing plate after development.
  • the developer HN-D contains 25% by mass of the exemplary compound (1) as a surfactant, and does not contain an organic solvent having a boiling point of 100 ° C. to 300 ° C. and a silicate component (silicate compound). It contains 9.5% by mass of potassium hydroxide and has a pH of 12.3.
  • the development replenisher HN-DR contains 9% by mass of the exemplary compound (1) as a surfactant, and does not contain an organic solvent having a boiling point of 100 ° C. to 300 ° C. and a silicate compound.
  • the content of trisodium citrate is 2%, potassium hydroxide is 9.5% by mass, and the pH is 12.9.
  • Example 2 Developer for negative photosensitive lithographic printing plate precursor manufactured by Fuji Film Co., Ltd. when developing the CTP version of newspaper HN-NV, which is a negative photosensitive lithographic printing plate precursor manufactured by FUJIFILM Corporation, after exposure.
  • HN-D trade name
  • HN-DR development replenisher
  • developer HN-D (trade name) (stock solution for developing starter solution) was diluted with 4 times the amount (by mass) of water when charged into an automatic processor, and development started. Liquid.
  • the development replenisher HN-DR (trade name) (stock solution for developing replenisher) is diluted with twice the amount (mass basis) of water when replenishing the automatic developer to obtain a developer replenisher.
  • a plate making process of 3000 m 2 was performed in one month by the system shown in FIG. 1 in combination with the automatic processor LP-1310News II.
  • the development conditions are: development temperature: 30 ° C., development time: 12 seconds, the concentration conditions of the platemaking waste liquid are the concentration temperature: 30 ° C., the pressure: 30 mmHg, and the cooling conditions are the cooling temperature of 5 ° C. It was. In addition, the concentration of the plate-making process waste liquid was 1/5, and the obtained reclaimed water was used as dilution water for developing replenisher.
  • the stock solution was diluted with twice the amount of reclaimed water as the stock solution for preparing the development replenisher to prepare a development replenisher. There was no accumulation of deposits in the developing bath and washing bath of the automatic processor after continuous processing, and almost no stain was observed.
  • a waste liquid concentrator XR-2000 manufactured by Takagi Chiller was used.
  • XR-R60 manufactured by Takagi Chiller Co., Ltd. was used to feed the reclaimed water to the tank of the automatic developing machine and reuse it as dilution water for preparing the development replenisher as described above.
  • Example 3 the surfactant contained in developer HN-D (trade name) (stock solution for developing starter solution) and developer replenisher HN-DR (trade name) (stock solution for developing replenisher solution)
  • a developer and a developer replenisher were prepared in the same manner as in Example 2, except that a certain exemplified compound (1) was changed to surfactant B (sodium tert-butylnaphthalenesulfonate). That is, in Example 2, the stock solution for developing starter solution and the stock solution for developing replenisher solution containing surfactant B are used in place of developer HN-D and developer replenisher HN-DR, respectively.
  • surfactant B sodium tert-butylnaphthalenesulfonate
  • the plate making process was carried out in the same manner as in Example 2 except that the surfactant A in the developer component in the developer bath of the automatic processor was changed to the surfactant B (sodium tert-butylnaphthalenesulfonate).
  • the surfactant A in the developer component in the developer bath of the automatic processor was changed to the surfactant B (sodium tert-butylnaphthalenesulfonate).
  • Example 4 developer HN-D (trade name) (stock solution for developing starter solution) and development replenisher HN-DR (trade name) (stock solution for developing replenisher solution) were further added with a silicate component (silica A stock solution for preparing a development starter solution and a stock solution for preparing a development replenisher solution each containing 0.5% by mass of potassium acid) were prepared. In Example 2, this stock solution for developing starter solution and stock solution for developing replenisher solution were used instead of developer HN-D and developer replenisher HN-DR.
  • a silicate component sica
  • Example 5 the negative type photosensitive lithographic printing plate precursor was changed to TCC-353 (photosensitive lithographic printing plate precursor having a radical polymerizable image recording layer and a protective layer corresponding to thermal LD 800 nm to 850 nm) manufactured by Kodak Co., Ltd.
  • TCC-353 photosensitive lithographic printing plate precursor having a radical polymerizable image recording layer and a protective layer corresponding to thermal LD 800 nm to 850 nm
  • the plate making waste liquid can be concentrated to 1/4, and the deposit in the developing bath and washing bath of the automatic processor after continuous processing There was no accumulation and almost no dirt was observed.
  • Example 2 the dilution amounts of developer HN-D (trade name) (stock solution for developing starter solution) and developer replenisher HN-DR (product name) (stock solution for developing replenisher solution) were adjusted.
  • concentration of the surfactant A in the developing bath was 0.8% and the plate making treatment was carried out in the same manner as in Example 2 except for this, precipitation occurred in the concentrator of the plate making waste liquid, and concentration could not be performed.
  • Example 2 the types of surfactants in developer HN-D (trade name) (stock solution for developing starter solution) and developer replenisher HN-DR (trade name) (stock solution for developing replenisher solution) In addition, it was replaced with sodium dodecylbenzenesulfonate, which is an anionic surfactant having no naphthalene skeleton, and the surfactant content of the developer replenisher when adjusted for development was adjusted to 4%. Except for using one, plate-making treatment was carried out in the same manner as in Example 2. As a result, precipitation occurred in the concentration apparatus for the plate-making treatment waste liquid, and concentration was not possible.
  • Example 2 the type and amount of the surfactant in the development replenisher HN-DR (trade name) (stock solution for developing replenisher) are the same as the surfactant having a carboxyl group salt and an amino group in the same molecule.
  • Lipomin (trade name, manufactured by Takemoto Yushi Co., Ltd.) 2% and sodium dodecylbenzenesulfonate 2%, except that plate making treatment was performed in the same manner as in Example 2, and the plate making waste liquid was concentrated in the concentrator. The plate-making process waste liquid flows into the reclaimed water, and usable reclaimed water cannot be obtained.
  • Example 4 In Example 3, the type and amount of the surfactant in the development replenisher HN-DR (trade name) (stock solution for developing replenisher) were changed to surfactant B (sodium tert-butylnaphthalenesulfonate) 0.8. % And sodium dodecylbenzenesulfonate 0.2%, and the developer replenisher used for development processing is prepared to be a developer replenisher containing 2% silicate component (potassium silicate). did.
  • a plate making process was carried out in the same manner as in Example 3 except that the developer replenisher prepared in this way was used. As a result, sticking occurred in the concentrator of the plate making process waste liquid, and the concentration efficiency was lowered and discharged in one week. A defect occurred, and the platemaking process waste liquid could not be concentrated.
  • Example 5 the developer HN-D (trade name) (stock solution for developing starter solution) and the development replenisher HN-DR (product name) (stock solution for developing replenisher solution) were further mixed with benzyl alcohol.
  • the plate-making process was performed in the same manner as in Example 2 except that the benzyl alcohol concentration used for the development process was 2.5%.
  • the printing durability of the highlight portion of 10% or less of the lithographic printing plate after the treatment was reduced to 50% of Example 2, and a lithographic printing plate that could withstand practical use was not obtained.
  • Example 6 After exposure of Fujifilm's negative CTP photosensitive lithographic printing plate precursor LP-NNV (photosensitive lithographic printing plate precursor having a radical polymerizable image recording layer and a protective layer corresponding to Violet LD 405 nm), FUJIFILM Corporation A negative type photosensitive lithographic printing plate precursor developer LP-DS (trade name) and a developer replenisher LP-DRN (trade name) manufactured by Fuji Film Co., Ltd. A pre-heating means, a pre-water washing means for the protective layer, a developing means, a rinsing means (washing means) and a gumming means) were subjected to a plate making process of 1000 m 2 in one month by the system shown in Fig. 1.
  • the pre-water washing process which removes a protective layer before image development is performed.
  • the plate-making process waste liquid was treated with XR-2000, and the plate-making process waste liquid could be concentrated to 1 ⁇ 4 volume.
  • the organic solvent content in the range of 0 ° C. was 0 to 0.05%, and the silicate component content was 0%.
  • the developer LP-DS contains 5% by mass of surfactant C (Exemplary Compound Y-1) as a surfactant and an organic solvent and silicate compound having a boiling point in the range of 100 ° C. to 300 ° C. Absent.
  • the pH is adjusted to 12.0 with potassium hydroxide.
  • the development replenisher LP-DRN contains 5% by mass of surfactant C (Exemplary Compound Y-1) as a surfactant, and does not contain organic solvents and silicate compounds having a boiling point in the range of 100 ° C. to 300 ° C. .
  • the pH is adjusted to 12.8 with potassium hydroxide.
  • FIG. 1 shows a combination of the machine InterPlater 135 (providing developing means, rinsing means (washing means) and gumming means), developer LP-DS (trade name), and developer replenisher LP-DRN (trade name).
  • machine InterPlater 135 providing developing means, rinsing means (washing means) and gumming means
  • developer LP-DS trade name
  • developer replenisher LP-DRN trade name
  • the plate-making process waste liquid was treated with XR-2000, and the plate-making process waste liquid could be concentrated to 1 ⁇ 4 volume.
  • the composition of the developer in the developing bath of the automatic processor is an organic solvent having a surfactant C (naphthol ethylene oxide adduct) content in the range of 3 to 6% and a boiling point in the range of 100 ° C to 300 ° C.
  • the content of was 0 to 0.05%
  • the content of the silicate component was 0%
  • the pH ranged from 11.9 to 12.2.

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