WO2014003134A1 - 平版印刷版前駆体用現像液組成物及び平版印刷版の作製方法 - Google Patents
平版印刷版前駆体用現像液組成物及び平版印刷版の作製方法 Download PDFInfo
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- WO2014003134A1 WO2014003134A1 PCT/JP2013/067696 JP2013067696W WO2014003134A1 WO 2014003134 A1 WO2014003134 A1 WO 2014003134A1 JP 2013067696 W JP2013067696 W JP 2013067696W WO 2014003134 A1 WO2014003134 A1 WO 2014003134A1
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- developer
- printing plate
- lithographic printing
- alkali
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Classifications
-
- 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
- G03F7/32—Liquid compositions therefor, e.g. developers
- G03F7/325—Non-aqueous compositions
- G03F7/327—Non-aqueous alkaline compositions, e.g. anhydrous quaternary ammonium salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C1/00—Forme preparation
- B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
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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
-
- 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
- G03F7/004—Photosensitive materials
-
- 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
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
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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
- G03F7/32—Liquid compositions therefor, e.g. developers
-
- 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
- G03F7/32—Liquid compositions therefor, e.g. developers
- G03F7/322—Aqueous alkaline compositions
Definitions
- the present invention generally relates to a novel developer composition for developing a lithographic printing plate precursor.
- the present invention also relates to a method for preparing a lithographic printing plate using a novel developer composition.
- a lithographic printing plate precursor having a photosensitive image forming layer
- PS plate lithographic printing plate precursor
- the negative plate uses a negative film at the time of exposure, and is developed with a negative plate developer after exposure.
- the unexposed portion of the photosensitive layer is removed to form a non-image portion, which is cured by exposure and the insolubilized portion (exposed portion) remains as an image portion.
- the positive type plate uses a positive film at the time of exposure, and is developed with a developer for positive type plate after the exposure.
- the photosensitive layer of the portion solubilized by exposure (exposed portion) is removed to form a non-image portion, and the unexposed portion not solubilized remains as an image to form an image portion.
- a positive plate developer is generally used in sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, potassium silicate, sodium metasilicate, trisodium phosphate, etc. It contains an inorganic strong alkali component such as a representative alkali metal hydroxide, carbonate, silicate, and phosphate, and is a high pH aqueous solution.
- the developer for the negative type plate usually depends on the composition of the image forming layer of the negative type plate, but usually contains water and contains a small amount of an organic solvent. In addition to these, organic amines, surfactants Etc. are configured.
- the negative type developer is usually an aqueous solution having a relatively low pH (7 to 11.5) that does not contain an inorganic strong alkali component.
- the use of a high pH developer using a strong alkali agent has recently been pointed out from the viewpoint of environmental impact, and various problems have been pointed out, and the need for a low pH developer that does not use a strong alkali agent has increased. Yes.
- the composition of the image forming layer of the lithographic printing plate precursor has also been improved so as to be dissolved in a low pH alkaline developer.
- the lithographic printing plate precursors described in JP 2007-17913 A, JP 2009-524110 A, JP 2009-98368 A, JP 2010-511202 A, etc. all have a pH of 12 or less.
- a lithographic printing plate precursor improved so that it can be processed with a low pH developer.
- the image forming layer of these lithographic printing plate precursors does not contain a resin having a phenolic OH group in the structure such as a phenol resin or a novolac resin, or a small amount thereof.
- a resin having a phenolic OH group in the structure such as a phenol resin or a novolac resin, or a small amount thereof.
- the composition of the image forming layer of the lithographic printing plate precursor has been improved.
- the lithographic printing plate precursor having the improved composition of the image forming layer described in the above publication is usually more easily penetrated by the developer so that it can be processed with a developer having a low pH, and the developer is more difficult than before. It has the property of being easily dissolved.
- these lithographic printing plate precursors having an improved composition of the image forming layer have a narrow development latitude, and when the development activity is high, the developer tends to penetrate into the image area and cause film reduction. Meat may get worse. Further, if the surface of the lithographic printing plate is scratched before the development process, the developer easily penetrates from there and has a disadvantage that the image portion is easily lost.
- the object of the present invention is to solve the above-mentioned drawbacks from the viewpoint of a developer by providing a novel low-pH developer that does not contain a strong inorganic alkali component.
- the inventors of the present invention have studied a low-pH alkaline developer that has been conventionally used, and as a result, a lithographic plate that can solve the above-mentioned object by combining an alkali agent with a specific compound, a specific metal salt, and a specific polymer. It has been found that a novel low pH alkaline developer composition for printing plate development can be provided.
- the present invention includes (A) an alkali agent, (B) a compound represented by the following general formula (I), (C) a metal salt of a Group 2 element in the periodic table of elements, and (D) a carboxylic acid.
- an alkaline developer composition for preparing a lithographic printing plate comprising a polymer having a salt thereof is provided.
- the present invention also provides: A lower layer containing a water-insoluble and alkali-soluble or dispersible resin on a substrate having a hydrophilic surface; and an upper layer containing a water-insoluble and alkali-soluble or dispersible resin formed on the lower layer, the lower layer and the upper layer A step of imagewise exposing a positive planographic printing plate precursor, at least one of which contains a photothermal conversion substance, using an infrared laser; A method for producing a lithographic printing plate comprising a step of developing the exposed lithographic printing plate precursor with the above-described alkaline developer composition of the present invention to remove an exposed portion, thereby forming an image portion and a non-image portion. Also provide.
- the developer composition of the present invention is used, stable development processing for a long period of time becomes possible. Further, there is no accumulation of sludge in the developing tank of the automatic developing machine, and it is easy to clean the developing tank when changing the developer, and it is possible to construct a developing system with excellent maintainability.
- the alkali agent (A) used in the developer composition of the present invention can be either an inorganic alkali agent or an organic alkali agent.
- An inorganic alkali agent can be used together with the organic alkali agent. When only one of them is used as the alkali agent in the developer composition of the present invention, the use of a strong alkali inorganic alkali agent is not preferred, and the use of an organic alkali agent is preferred. Any inorganic alkali agent having a low alkalinity can be used alone as an alkali agent in the developer composition of the present invention.
- organic alkaline agent examples include monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, mono Ethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, ethyleneimine, ethylenediamine, pyridine, N-2-hydroxyethylenediamine, benzylamine, 2- (2-aminoethylamino) ethanol, 2 (2-aminoethoxy) ethanol, sodium citrate, potassium citrate, sodium acetate, potassium acetate, sodium malate Sodium tartrate and the like.
- organic alkali agents Two or more of these organic alkali agents may be used in combination.
- monoethanolamine, monoisopropanolamine, 2- (2-aminoethylamino) ethanol, and 2 (2-aminoethoxy) ethanol are preferable.
- the amount of the organic alkali agent in the developer composition is preferably 0.05 to 90% by mass with respect to the total mass of the developer composition.
- the amount of the alkali agent is less than 0.05% by mass, the non-image area cannot be sufficiently developed, which is not preferable.
- the film thickness of the image area is increased, which is not preferable.
- a more preferable amount of the organic alkali agent is 0.1 to 50% by mass, and a particularly preferable amount is 1 to 20% by mass with respect to the total mass of the developer composition.
- inorganic alkali agents with low alkalinity such as dibasic sodium phosphate (Na 2 HPO 4 ), tribasic sodium phosphate (Na 3 PO 4 ), etc. Can be used alone as an alkaline agent in the developer composition of the present invention.
- an inorganic alkaline agent may be used together with an organic alkaline agent, and when the inorganic alkaline agent is used together with an organic alkaline agent, the amount is at most 10% by mass with respect to the total mass of the developer composition. If it exceeds 10% by mass, the film thickness of the image area is increased, which is not preferable.
- Inorganic alkaline agents that can be used with the organic alkaline agent include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium metasilicate, potassium metasilicate, dibasic sodium phosphate, tribasic sodium phosphate Etc.
- Another component used in the developer composition of the present invention is (B) a compound represented by the following general formula (I).
- the compound of the component (B) accelerates development of the exposed area, and (C) is used in combination with a metal salt of the Group 2 element in the periodic table of the element, thereby allowing the developer to penetrate into the unexposed area.
- the component (C) it was found that the effect of suppressing the penetration of the developer into the unexposed area was not exhibited, and only the effect of promoting the development of the exposed area was provided.
- R 1 to R 4 each independently represent H, R 8 OH, or — (AO) a (BO) b R 9 .
- AO and BO are selected from an ethyleneoxy group and a propyleneoxy group.
- a and b represent integers from 0 to 300, but (a + b) ⁇ 0.
- R 8 represents a divalent linking group
- R 9 represents H, CH 3 , COR 10 , CONHR 11
- R 10 and R 11 represent an alkyl group, an aryl group, an alkenyl group, or an alkynyl group.
- Examples of the alkyl group represented by R 10 and R 11 include CH 3 —, CH 3 CH 2 —, CH 3 (CH 2 ) 2 —, CH 3 (CH 2 ) 3 —, and CH 3 (CH 2 ) 4. -, (CH 3 ) 2 CH (CH 2 ) 2- , CH 3 CH 2 CH (CH 3 ) -CH 2- , CH 3 (CH 2 ) 2 CH (CH 3 )-, CH 3 (CH 2 ) 7 -, CH 3 (CH 2) 8 -, CH 3 (CH 2) 10 -, CH 3 (CH 2) 12 -, CH 3 (CH 2) 14 -, CH 3 (CH 2) 16 -, CH 3 ( A linear or branched alkyl group having 1 to 25 carbon atoms such as CH 2 ) 18 —, CH 3 (CH 2 ) 20 —, CH 3 (CH 2 ) 22 —, and CH 3 (CH 2 ) 24 — is preferred. .
- Examples of the aryl group represented by R 10 and R 11 include phenyl
- a monocyclic or bicyclic aryl group such as those having a substituent with a linear or branched alkyl group is included.
- R 5 and R 6 each independently represent a divalent linking group and may be the same or different.
- R 5 and R 6 include alkylene groups such as ethylene group and propylene group.
- R 7 can be selected from the groups defined in the above R 1 to R 4 .
- R 7 is The following general formula (II)
- R 3 ′ is the same as R 3 defined in formula (I)
- R 4 ′ is the same as R 4 defined in formula (I)
- R 5 ′ is the same as R 5 defined in formula (I)
- R 6 ′ is the same as R 6 defined in formula (I)
- R 7 ′ is the same as R 7 defined in formula (I).
- N in the formulas (I) and (II) represents an integer of 0 to 20, and when n is 2 or more, R 7 and R 7 ′ can be independently selected.
- the compound represented by the general formula (I) is, for example, a compound represented by the following formula (I-1).
- R 1 to R 8 may be the same or different and each represents H or CH 3
- R 9 to R 12 may be the same or different
- H, CH 3 , COR 13 , CONHR 14 are
- R 13 and R 14 represent an alkyl group, an aryl group, an alkenyl group or an alkynyl group
- a is an integer of 2 to 12
- b, c, d, e, f, g, h and i are They may be the same or different and represent an integer of 0 to 300
- Particularly preferred among the compounds represented by the general formula (I-1) are those in which R 1 to R 8 are H or CH 3 and the terminal is a hydroxyl group, that is, R 9 , R 10 , R 11 , R 12 are , All are H and have an average molecular weight of 280 to 1100.
- the group represented by R 13 and R 14 can be selected from the groups described as R 10 and R 11 in the formula (I).
- the compound represented by the general formula (I) can be specifically a compound represented by the following formula (I-2).
- R 1 to R 10 may be the same or different and each represents H or CH 3
- R 11 to R 15 may be the same or different
- H, CH 3 , COR 16 , CONHR 17 are
- R 16 and R 17 represent an alkyl group, an aryl group, an alkenyl group or an alkynyl group
- a and b are integers of 2 to 12
- c, d, e, f, g, h, i, j, k, and l may be the same or different and each represents an integer of 0 to 300
- Particularly preferred among the compounds represented by the general formula (I-2) are those in which R 1 to R 10 are H or CH 3 and the terminal is a hydroxyl group, that is, R 11 , R 12 , R 13 , R 14 , R 15 is a compound having all H and an average molecular weight of 320 to 1300.
- the groups represented by R 16 and R 17 can be selected from the groups described as R 10 and R 11 in the formula (I).
- ADEKA polyether EDP-300 manufactured by ADEKA Corporation, modified ethylenediaminepropylene oxide: molecular weight 300
- EDP-450 manufactured by ADEKA Corporation, ethylenediamine
- Propylene oxide modified product molecular weight 450
- ADEKA polyether BM-34 manufactured by ADEKA Corporation, ethylenediamine ethylene oxide modified product: molecular weight 280.
- propylene oxide modified products of diethylenetriamine, N, N, N ′, N ′′, N ′′ -pentakis (2-hydroxypropyl) diethylenetriamine ethylene oxide modified product of diethylenetriamine
- propylene oxide modified product of dipropylenetriamine ethylene oxide-modified products of dipropylene triamine.
- Examples of the compound in which n in the general formula (I) is 4 or more include propylene oxide-modified polyethyleneimine, triethylenetetramine-modified propylene oxide, and tetraethylenepentamine-modified propylene oxide.
- polyethyleneimine propylene oxide modified polyethyleneimine, manufactured by Nippon Shokubai Co., Ltd.
- polyethyleneimine is represented by the following formula.
- the compound represented by the general formula (I) can include a compound having a branched structure as shown below.
- n in the general formula (I) is 21 or more can also be used.
- the n in the general formula (I) is up to 20. are preferred for use in the developing compositions of the present invention.
- the amount of the compound represented by formula (I) as the component (B) is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, based on the total amount of the developer composition. is there.
- the amount of the component (B) used is less than 0.001% by mass, the above effect cannot be obtained, and when it exceeds 10% by mass, the compatibility with other components is affected.
- Another component used in the developer composition of the present invention is a metal salt of a group 2 element in the periodic table of (C) element.
- the metal salt of component (C) can suppress penetration of the developer into the image area.
- Group 2 elements are beryllium, magnesium, calcium, strontium, and barium. In the developing composition of the present invention, these elements are used in the form of metal salts. Specifically, for example, halide, carbonate, sulfate, nitrate, phosphate, formate, acetate, propionate, maleate, lactate, levulinate, malonate, adipate Or it is a fumarate.
- halides, carbonates, sulfates, nitrates, phosphates, and acetates are preferable, and particularly preferable metal salts are calcium chloride and magnesium chloride.
- the amount of group 2 element metal salt used is preferably 0.01 to 5% by mass, more preferably 0.05 to 1% by mass, based on the total amount of the developer composition. If the amount of the metal salt of the Group 2 element is more than 5% by mass, the developability of the exposed area is remarkably lowered, which is not preferable.
- Another component used in the developer composition of the present invention is (D) a polymer having a carboxylic acid or a salt thereof.
- the metal ion of the component (C) is usually easily precipitated as a carbonate in combination with carbon dioxide in the air in an alkaline aqueous solution.
- (D) component can accelerate
- the polymer having a carboxylic acid or a salt thereof that can be used in the developer composition of the present invention is specifically a compound having a structural unit represented by the following formula (III).
- B represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a —R a —COOX group, wherein R a represents an alkylene group which may have a substituent, A represents a hydrogen atom, A carbamoyl group, an alkoxycarbonyl group, a carboxyl group or a salt thereof is represented, and X represents a hydrogen atom, an alkali metal atom, a protonated organic amine group or a quaternary ammonium group.
- Examples of the polymer having a carboxylic acid or a salt thereof that can be used in the present invention include polyacrylic acid (salt), polymethacrylic acid (salt), acrylic acid / maleic acid copolymer (salt), and polyitaconic acid (salt). And homopolymers of monomers containing acid groups, such as polymaleic acid (salts) and styrene / acrylic acid copolymers (salts), and copolymers with other monomers.
- a in Formula (III) is a carbamoyl group or an alkoxycarbonyl group
- a polymer obtained by modifying a (co) polymer having maleic anhydride with ammonia, an amine or an alcohol can be given.
- particularly preferred polymers are sodium acrylic acid / maleic acid copolymer and sodium polyacrylate.
- the amount of the polymer having a carboxylic acid or a salt thereof used is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, based on the total amount of the developer composition. (D) If the amount of the polymer having a carboxylic acid or a salt thereof is less than 0.01% by mass, the above effect cannot be obtained, and if it exceeds 20% by mass, the developer tends to penetrate into the image area. Yes, it may cause film loss, which is not preferable.
- the polymer having the metal salt of the Group 2 element in the periodic table of the element and the (D) carboxylic acid or the salt thereof has a molar ratio of the metal ion of the (C) component and the carboxylic acid of (D) of 1 : 2 to 1:40 is preferable, and 1: 3 to 1:20 is more preferable. If the ratio is less than 1: 2, the developability of the non-image area is lowered, and the development remains in the non-image area.
- the metal salt (C) is an insoluble substance such as carbonate in the developer. As it becomes easy to precipitate as, it is not preferable.
- the ratio exceeds 1:40 the effect of suppressing the penetration of the developer into the image part of the component (C) is diminished, and the developer may penetrate into the image part to cause film reduction. Absent.
- a surfactant an organic solvent and the like can be added in addition to the essential components (A) to (D).
- Preferred surfactants are alkali metal salts of alkylnaphthalene sulfonates, alkali metal alkylbenzene sulfonates, alkali metal salts of alkyldiphenyl ether disulfonates, alkali metal salts of dialkylsulfosuccinic acids, typically 6 to 9 carbon atoms.
- Alkali metal salts of sulfuric monoesters of aliphatic alcohols typically alkali metal salts of sulfonic acids having 6 to 9 carbon atoms.
- a preferred alkali metal is sodium.
- the surfactant or mixture of surfactants is typically about 0.5% to about 15% by weight based on the weight of the developer composition, preferably about 3% based on the weight of the developer composition. % To about 8% by weight.
- many surfactants are supplied as aqueous surfactant solutions. These percentages are based on the amount of surfactant in the developer (i.e., the weight of the active ingredient, i.e. the weight of the ingredient excluding water and other inert materials in the aqueous surfactant solution).
- Examples of the organic solvent that can be added to the developer composition of the present invention include ethyl acetate, butyl acetate, amyl acetate, benzyl acetate, ethylene glycol monobutyl acetate, butyl lactate, butyl levulinate, methyl ethyl ketone, and ethyl butyl ketone.
- the organic solvent is added to the developer composition, the amount of the organic solvent added is preferably 20% by mass or less, and particularly preferably 10% by mass or less.
- the developer composition can also include a buffer system that maintains the pH relatively constant.
- buffer systems are known to those skilled in the art. Typical buffer systems are, for example; water soluble amines such as monoethanolamine, diethanolamine, triethanolamine, or tri-i-propylamine and sulfonic acids such as benzenesulfonic acid or 4-toluenesulfonic acid.
- EDTA ethylenediaminetetraacetic acid
- phosphate salts such as a mixture of monoalkali phosphate salts and trialkyl phosphate salts; including a mixture of alkali borate and boric acid .
- water-soluble sulfites such as lithium sulfite, sodium sulfite, potassium sulfite, and magnesium sulfite; hydroxy-fragrances such as alkali-soluble pyrazolone compounds, alkali-soluble thiol compounds, and methyl resorcin Group water compounds: Hard water softeners such as polyphosphates and aminopolycarboxylic acids and various antifoaming agents may be added.
- the developer composition of the present invention has a pH of about 12 at the highest, preferably about 11 at the highest.
- the processable lithographic printing plate precursor has a lower layer on the substrate and an upper layer on the lower layer.
- the lower layer and the upper layer constitute an image forming layer of a lithographic printing plate precursor.
- An intermediate layer may be formed between the substrate and the lower layer as necessary, but it is preferable that there is no intermediate layer between the lower layer and the upper layer.
- a back coat layer may be formed on the back surface of the substrate as necessary.
- the lower layer constituting the lithographic printing plate precursor contains a resin that is soluble or dispersible in an alkaline aqueous solution.
- the resin preferably has at least a functional group such as a carboxyl group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, an active imino group, and a sulfonamide group.
- the resin used in the lower layer and soluble or dispersible in an alkaline aqueous solution is an ethylenic group having a functional group such as a carboxyl group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, an active imino group, a sulfonamide group, and a combination thereof. It can be suitably produced by polymerizing a monomer mixture containing one or more unsaturated monomers.
- the ethylenically unsaturated monomer has the following formula:
- R 1 represents a hydrogen atom, a C 1-22 linear, branched or cyclic alkyl group, a C 1-22 linear, branched or cyclic substituted alkyl group, C 6- 24 aryl groups or substituted aryl groups, wherein the substituents are selected from C 1-4 alkyl groups, aryl groups, halogen atoms, keto groups, ester groups, alkoxy groups, or cyano groups;
- X is O, S and an NR 2
- R 2 represents hydrogen, straight-chain C 1-22, branched or cyclic alkyl group, a linear, branched or cyclic substituted alkyl group C 1-22, C 6- 24 aryl groups or substituted aryl groups, wherein the substituent is selected from a C 1-4 alkyl group, an aryl group, a halogen atom, a keto group, an ester group, an alkoxy group, or a cyano group; Y is a single bond, Or C 1-22
- Examples of the ethylenically unsaturated monomer include, in addition to acrylic acid and methacrylic acid, a compound represented by the following formula and a mixture thereof.
- the mass average molecular weight of the water-insoluble and alkali-soluble or dispersible resin is preferably in the range of 20,000 to 100,000.
- the mass average molecular weight of the water-insoluble and alkali-soluble or dispersible resin is less than 20,000, the solvent resistance and wear resistance tend to be inferior.
- the mass average molecular weight of the water-insoluble and alkali-soluble or dispersible resin exceeds 100,000, the alkali developability tends to be inferior.
- the content of the resin soluble or dispersible in the alkaline aqueous solution in the lower layer is preferably in the range of 20 to 95% by mass with respect to the solid content of the layer. If the content of the resin soluble or dispersible in the alkaline aqueous solution is less than 20% by mass, it is inconvenient in terms of chemical resistance, and if it exceeds 95% by mass, it is not preferable in terms of exposure speed. Moreover, you may use together a resin soluble or dispersible in 2 or more types of alkaline aqueous solution as needed.
- the upper layer constituting the lithographic printing plate precursor contains an alkali-soluble or dispersible resin.
- the alkali-soluble or dispersible resin that can be used for the upper layer is preferably a resin having a carboxylic acid or an acid anhydride group, and is one of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, or an unsaturated carboxylic acid and an unsaturated carboxylic acid. Examples thereof include a copolymer obtained by polymerizing a monomer mixture containing both acid anhydrides and a polyurethane having a substituent containing an acidic hydrogen atom.
- Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, and itaconic acid, and examples of the unsaturated carboxylic acid anhydride include maleic anhydride and itaconic anhydride.
- Examples of the copolymerizable ethylenically unsaturated monomer unit include the above-mentioned other ethylenically unsaturated comonomers.
- a photothermal conversion substance is contained in at least one of the lower layer and the upper layer.
- a photothermal conversion material is contained in the lower layer of the lithographic printing precursor and no photothermal conversion material is contained in the upper layer
- the lower photothermal conversion material turns the laser light into heat.
- the molecular structure of a part of the alkali-soluble or dispersible resin in the uppermost layer collapses, or pores are formed in the upper layer, allowing the developer to penetrate into the lower layer It is thought to be.
- a photothermal conversion substance means any material that can convert electromagnetic waves into thermal energy, and has a maximum absorption wavelength in the near infrared to infrared range, specifically, a maximum absorption wavelength range of 760 nm to 1200 nm. It is a material in. Examples of such materials include various pigments or dyes.
- pigments examples include commercially available pigments and the Color Index Handbook “Latest Pigment Handbook” (published by the Japan Pigment Technology Association, published in 1977), “Latest Pigment Applied Technology” (CMC Publishing, 1986), “Printing Ink Technology” (CMC) Publications, published in 1984) can be used.
- the pigment include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, and other polymer-bonded pigments.
- insoluble azo pigments azo lake pigments, condensed azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments
- quinophthalone pigments dyed lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, carbon black, and the like can be used.
- azo dyes metal chain salt azo dyes, pyrazolone azo dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, indigo dyes, quinoline dyes, nitro dyes, xanthene dyes And dyes such as thiazine dyes, azine dyes, and oxazine dyes.
- Examples of the dye that efficiently absorbs near infrared rays or infrared rays include, for example, azo dyes, metal complex azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, Dyes such as squarylium dyes, pyrylium salts, metal thiolate complexes (for example, nickel thiolate complexes) can be used.
- cyanine dyes are preferred, and examples include cyanine dyes represented by general formula (I) in JP-A No. 2001-305722 and compounds shown in [0096] to [0103] in JP-A No. 2002-079772. Can do.
- the lithographic printing plate precursor may contain a matting agent in the uppermost layer for the purpose of improving the peelability of the interleaf and improving the plate transportability of the automatic plate feeder.
- the lithographic printing plate precursor may contain a matting layer on the uppermost layer. It may be provided.
- substrates include metal plates such as aluminum, zinc, copper, stainless steel, and iron; plastic films such as polyethylene terephthalate, polycarbonate, polyvinyl acetal, and polyethylene; papers and plastic films coated with a synthetic resin or a synthetic resin solution And a composite material in which a metal layer is provided by a technique such as vacuum deposition or lamination; and other materials used as a substrate for a printing plate.
- metal plates such as aluminum, zinc, copper, stainless steel, and iron
- plastic films such as polyethylene terephthalate, polycarbonate, polyvinyl acetal, and polyethylene
- papers and plastic films coated with a synthetic resin or a synthetic resin solution And a composite material in which a metal layer is provided by a technique such as vacuum deposition or lamination; and other materials used as a substrate for a printing plate.
- the surface of the aluminum substrate is desirably surface-treated for the purpose of enhancing water retention and improving adhesion to the lower layer or an intermediate layer provided as necessary.
- Examples of such surface treatment include brush polishing, ball polishing, electrolytic etching, chemical etching, liquid honing, roughening treatment such as sand blasting, and combinations thereof.
- a roughening treatment including use of electrolytic etching is particularly preferable.
- Substrate preparation An aluminum plate having a thickness of 0.24 mm is degreased with an aqueous sodium hydroxide solution and electropolished in a 2% hydrochloric acid bath to obtain a grained plate with a center average roughness (Ra) of 0.5 ⁇ m. It was. Subsequently, it was anodized in a 20% sulfuric acid bath at a current density of 2 A / dm 2 to form an oxide film of 2.7 g / m 2 , washed with water and dried to obtain an aluminum substrate. The substrate thus obtained was immersed in a 0.5 g / L aqueous solution of polymer 1 heated to 60 ° C. for 10 seconds, washed with water and dried. In this way, a substrate for a lithographic printing plate precursor was obtained.
- lithographic printing plate precursor Preparation of lithographic printing plate precursor
- the lower layer coating solution (B-1) prepared in Table 1 was coated on the substrate obtained by the above substrate preparation method using a roll coater and dried at 100 ° C for 2 minutes. Thus, a first image forming layer was obtained. The amount of the dried coating film at this time was 1.5 g / m 2 .
- the upper layer coating solution (T-1) prepared in Table 2 was coated using a roll coater and dried at 100 ° C. for 2 minutes to form a two-layer lithographic printing precursor. Got. Only the upper image forming layer was peeled off with methyl isobutyl ketone, and the dry coating amount of the upper image forming layer was determined.
- the dry coating amount of the upper image forming layer was 0.5 g / m 2 .
- a protective material having a moisture content of 2.5%, a natural pulp paper material, a thickness of 70 ⁇ m, and a weight of 45 g / m 2 is supplied onto the surface of the photosensitive layer of the two-layer lithographic printing precursor obtained above. 30 sheets were deposited on a resin pallet. Thereafter, the side surface and the upper surface were wound with a special polyolefin film so as not to enter air, and conditioning treatment was performed at 60 ° C. for 24 hours. In this way, a two-layer lithographic printing plate precursor A was produced.
- Developer 1 includes (C) calcium chloride dihydrate as a metal salt of an element belonging to Group 2 of the periodic table of elements, and (D) a carboxylic acid or a salt thereof as a polymer having acrylic acid / maleic acid.
- a sodium salt (40% aqueous solution) of a polymer (molar ratio 40:60) and (B) ADEKA polyether EDP-300 were added as a compound represented by the general formula (I).
- Developer 2 is the same as Developer 1 except that Adeka Polyether EDP-300 in Developer 1 is replaced with N, N, N ′, N ′′, N ′′ -pentakis (2-hydroxypropyl) diethylenetriamine Made with composition.
- Developer 3 was prepared with the same composition as Developer 1, except that Adeka Polyether EDP-300 of Developer 1 was replaced with Epomin PP-061.
- Developer 4 was prepared with the same composition as Developer 1, except that Adeka Polyether EDP-300 in Developer 1 was replaced with Adeka Polyether EDP-450.
- Developer 5 was prepared with the same composition as Developer 1, except that Adeka Polyether EDP-300 in Developer 1 was replaced with Adeka Polyether BM-34.
- the developer component was adjusted so that the molar ratio of the metal ion of the component (C) and the carboxylic acid of (D) was 1: 2.3.
- the developer component was adjusted so that the molar ratio of the metal ion of the component (C) and the carboxylic acid of the component (D) was 1: 18.8.
- Developers 8 to 14 having the compositions shown in Table 5 were prepared as comparative developers.
- Table 6 shows a list of addition and non-addition of these three types of components in the developer for invention example and the developer for comparative example.
- developer 15 was prepared with the same composition as Developer 1 except that calcium chloride in Developer 1 was replaced with sodium chloride.
- the sodium salt (40% aqueous solution) of the acrylic acid / maleic acid copolymer (molar ratio 40:60) in developer 1 is replaced with dextrin ND-S, which is a water-soluble resin not containing carboxylic acid.
- Developer 17 was prepared with the same composition as Developer 1, except that Adequapolyether EDP-300 in Developer 1 was replaced with Adeca Polyether C-300, which is a modified glycerin propylene oxide.
- the two-layer type lithographic printing plate precursor A produced and imaged was exposed at 150 mJ / cm 2 using a plate setter PT-R4300 (Dainippon Screen Mfg. Co., Ltd.). Development processing was performed at 30 ° C. for 15 seconds using an automatic processor P-940X (manufactured by Kodak Co., Ltd.) and a developer obtained by diluting the developer obtained in Table 4 four times with water. Then, gumming was performed with finishing gum PF2 (made by Kodak Co., Ltd.). Further, the developing solution diluted to a 2.5-fold, while replenishing each 20ml per lithographic printing plate precursor A1m 2 processing, development processing was carried out of the lithographic printing plate precursor A of 2000 m 2 in a row.
- Results Table 9 shows the results obtained.
- the lithographic printing plate precursor A, the developability of the non-image part and the film thickness reduction of the image part of the lithographic printing plate precursor A were observed at 0 m 2 treatment, 500 m 2 treatment, 1000 m 2 treatment, and 2000 m 2 treatment.
- the developability of the non-image area was evaluated by observing the non-image area with a 25 ⁇ magnifying glass to determine whether or not the image forming layer had remained developed. Evaluation was made using the following criteria. ⁇ : Fully developed and no image recording layer remaining in non-image area. ⁇ : Some remaining image recording layer is observed on the non-image area.
- X Development failure is recognized on the non-image area, and the image recording layer remains.
- the power was turned off, and after standing for 12 hours, the developer was removed from the developer tank, and the presence or absence of sludge on the bottom of the developer tank was observed.
- the developer component includes (C) an element belonging to group 2 of the periodic table of elements, (B) a compound represented by general formula (I), (D) a polymer having a carboxylic acid, and the like (C Inventive Examples 1 to 1 in which the lithographic printing plate precursor A was developed using Developers 1 to 7 having a molar ratio of the metal ion to the carboxylic acid of (D) of 1: 2 to 1:40. Regarding No. 7, even when the processing area was increased, the non-image area was sufficiently developed, and the film loss of the image area was maintained at a residual rate of 95% or more. In addition, after completion of the 2000 m 2 treatment, no sludge was deposited on the bottom of the developer tank, and the developer tank was easy to clean.
- Developer 8 adds (B) a compound represented by general formula (I), (D) a polymer having carboxylic acid, etc., and does not add an element belonging to Group 2 of the periodic table of (C) elements. It was. In the case of this developing solution, the 0 m 2 treatment, that is, immediately after putting the developing solution into the developing solution tank, the developing solution penetrated into the image portion, and the film thickness of the image portion became large (Comparative Example 1).
- Developer 9 includes (C) a metal salt of an element belonging to group 2 of the periodic table of elements, (B) a compound represented by general formula (I), and (D) a polymer having carboxylic acid or the like was not added.
- this developer development was impossible immediately after 0 m 2 treatment, that is, immediately after the developer was put in the developer tank (Comparative Example 2).
- the developer 10 comprises (C) a compound having a metal salt of an element belonging to Group 2 of the periodic table of elements, (D) a polymer having a carboxylic acid, etc., and (B) a compound represented by the general formula (I) Was not added.
- the non-image area was developed immediately after the 0 m 2 treatment, that is, immediately after the developer was charged, and the image area was in a good state with little film loss, but after 500 m 2 treatment, the film loss increased. After 1000 m 2 treatment, development residue was seen in the non-image area (Comparative Example 3).
- Developer 11 includes (C) a metal salt of an element belonging to Group 2 of the periodic table of elements, (B) a polymer represented by general formula (I), (D) a carboxylic acid, etc. was not added. In the case of this developer, development was impossible immediately after 0 m 2 treatment, that is, immediately after the developer was put in the developer tank (Comparative Example 4).
- Developer 12 is a polymer having (B) a compound represented by general formula (I), (C) a metal salt of an element belonging to Group 2 of the periodic table of elements, (D) a carboxylic acid, etc. Was not added.
- this developing solution the non-image area was developed, but the film thickness was reduced in the image area immediately after 0 m 2 processing, that is, immediately after the developing solution was charged, and the film thickness was further increased after 1000 m 2 processing. . (Comparative Example 5).
- Developer 13 includes (D) a polymer having carboxylic acid or the like, (C) a metal salt of an element belonging to Group 2 of the periodic table of elements, (B) a compound represented by general formula (I) Was not added.
- this developer the 0 m 2 treatment, that is, immediately after the developer was charged, the developer penetrated into the image area, and the film thickness of the image area was increased (Comparative Example 6).
- Developer 14 includes (D) a polymer having carboxylic acid, (B) a compound represented by general formula (I), and (C) a metal salt of an element belonging to Group 2 of the periodic table of elements. Not added.
- the non-image area was developed immediately after the 0 m 2 treatment, that is, immediately after the developer was charged, and the image area was in a good state with little film loss, but after 500 m 2 treatment, the film loss increased. After 1000 m 2 treatment, in addition to film reduction, a development residue was seen in the non-image area (Comparative Example 7).
- Developer 15 includes (D) a polymer having carboxylic acid or the like, (B) a compound represented by general formula (I), and (C) a metal salt of an element belonging to Group 2 of the periodic table of elements. Instead of, sodium chloride was added as a metal salt of an element belonging to Group 1. In the case of this developer, the 0 m 2 treatment, that is, immediately after the developer was charged, the developer penetrated into the image area, and the film thickness of the image area increased (Comparative Example 8).
- Developer 16 includes (B) a compound represented by general formula (I), (C) a metal salt of an element belonging to Group 2 of the periodic table of elements, and (D) a polymer having carboxylic acid or the like Instead of dextrin, which is a water-soluble resin.
- this developer development was impossible immediately after 0 m 2 treatment, that is, immediately after the developer was charged (Comparative Example 9).
- Developer 17 adds (C) a polymer having a metal salt of an element belonging to Group 2 of the periodic table of elements, (D) a carboxylic acid, etc., and (B) a compound represented by general formula (I) Instead of glycerin polyoxyethylene adduct was added.
- the non-image area was developed immediately after the 0 m 2 treatment, that is, immediately after the developer was charged, and the image area was in a good state with little film loss, but after 500 m 2 treatment, the film loss increased. After 1000 m 2 treatment, development residue was seen in the non-image area (Comparative Example 10).
- the developer 18 is an example in which the molar ratio of the metal ion of the component (C) of the developer 6 (Invention Example 6) to the carboxylic acid group of (D) is changed.
- B A compound represented by general formula (I), (C) a metal salt of an element belonging to Group 2 of the periodic table of elements, (D) a polymer having a carboxylic acid group, etc. were all added, C) The molar ratio of the metal ion to the carboxylic acid group of (D) was 1: 1.5. In the case of this developer, 0 m 2 treatment, that is, the image recording layer slightly remained on the non-image area immediately after the developer was charged, but the film reduction was satisfactory up to 2000 m 2 . (Invention Example 8).
- the developer 19 is an example in which the molar ratio of the metal ion of the component (C) of the developer 7 (Invention Example 7) to the carboxylic acid group of (D) is changed.
- B A compound represented by general formula (I), (C) a metal salt of an element belonging to Group 2 of the periodic table of elements, (D) a polymer having a carboxylic acid group, etc. were all added, C) The molar ratio of the metal ion to the carboxylic acid group of (D) was 1: 45.1.
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Abstract
Description
親水性表面を有する基板上に、水不溶性かつアルカリ可溶性又は分散性樹脂を含む下層と、前記下層上に形成された水不溶性かつアルカリ可溶性又は分散性樹脂を含む上層とを含み、前記下層及び上層の少なくとも一方が、光熱変換物質を含むポジ型平版印刷版前駆体を、赤外線レーザーを用いて像様露光する工程、
前記露光済み平版印刷版前駆体を、上述の本発明のアルカリ現像液組成物で現像して露光部を除去し、画像部と非画像部を形成する工程
を含んで成る平版印刷版の作製方法も提供する。
下記一般式(II)
R4'は式(I)に規定したR4と同じであり、
R5'は式(I)に規定したR5と同じであり、
R6'は式(I)に規定したR6と同じであり、
R7'は式(I)に規定したR7と同じである。)
で表される置換基群から選択することができる。
平版印刷版前駆体を構成する下層は、アルカリ性水溶液に可溶性又は分散性の樹脂を含む。アルカリ性水溶液に可溶性又は分散可能であるためには、前記樹脂が少なくとも、カルボキシル基、スルホン酸基、リン酸基、ホスホン酸基、活性イミノ基、スルホンアミド基等の官能基を有することが好ましい。したがって、下層に用いる、アルカリ性水溶液に可溶性又は分散性の樹脂は、カルボキシル基、スルホン酸基、リン酸基、ホスホン酸基、活性イミノ基、スルホンアミド基及びその組合せ等の官能基を有するエチレン性不飽和モノマーを1つ以上含むモノマー混合物を重合することによって好適に生成することができる。
で表される化合物又はその混合物となることができる。
平版印刷版前駆体を構成する上層は、アルカリ可溶性又は分散性樹脂を含む。上層に用いることができるアルカリ可溶性又は分散性樹脂は、カルボン酸又は酸無水物基を有する樹脂が好ましく、不飽和カルボン酸及び不飽和カルボン酸無水物の一方、又は不飽和カルボン酸及び不飽和カルボン酸無水物の両方を含むモノマー混合物を重合して得られる共重合体、酸性水素原子を含む置換基を有するポリウレタン等が挙げられる。不飽和カルボン酸としては、アクリル酸、メタクリル酸、マレイン酸、イタコン酸等、不飽和カルボン酸無水物としては、無水マレイン酸、無水イタコン酸等を挙げることができる。共重合可能なエチレン性不飽和モノマー単位としては、前記のその他のエチレン性不飽和コモノマーを挙げることができる。
前記下層及び上層の少なくとも一方に、光熱変換物質を含む。平版印刷前駆体の下層に光熱変換物質を含有し、上層には光熱変換物質を含有しない場合は、平版印刷前駆体をレーザーで画像書き込みすると、下層の光熱変換物質が、レーザーの光を熱に変換し、その熱が上層に伝達されることにより最上部層のアルカリ可溶性又は分散性樹脂の一部の分子構造が崩壊し、又は上層に孔を生じせしめ、現像液の下層への浸透を可能にすると考えられる。
を有する染料が好ましい。
基板としては、例えば、アルミニウム、亜鉛、銅、ステンレス、鉄等の金属板;ポリエチレンテレフタレート、ポリカーボネート、ポリビニルアセタール、ポリエチレン等のプラスチックフィルム;合成樹脂を溶融塗布あるいは合成樹脂溶液を塗布した紙、プラスチックフィルムに金属層を真空蒸着、ラミネート等の技術により設けた複合材料;その他印刷版の基板として使用されている材料が挙げられる。これらのうち、特にアルミニウム及びアルミニウムが被覆された複合基板の使用が好ましい。
<ポリマー1>
ビニルホスホン酸/アクリルアミドコポリマー(モル比1:9)
攪拌器、コンデンサー、滴下装置を有する10リットルフラスコ中に、エタノール3500gを入れ70℃に加熱した。ビニルホスホン酸モノマー231.1g(2.14mol)とアクリルアミド1368.9g(19.26mol)、AIBN52gを、エタノール1000g中に溶解させ、この溶液を反応装置中に4時間かけて滴下した。モノマー溶液の滴下中、白色の沈殿が生成した。70℃に保温したまま、さらに2時間加熱攪拌を行った後、加熱を止め室温まで冷却した。沈殿した白色粉末を濾過により分離し、エタノール1000gで洗浄し乾燥した。
厚さ0.24mmのアルミニウム板を水酸化ナトリウム水溶液にて脱脂し、これを2%塩酸浴中で電解研磨処理して、中心平均粗さ(Ra)0.5μmの砂目板を得た。次いで、20%硫酸浴中、電流密度2A/dm2で陽極酸化処理して、2.7g/m2の酸化皮膜を形成し、水洗乾燥後アルミニウム基板を得た。このようにして得られた基板を、60℃に加熱したポリマー1の0.5g/L水溶液中に10秒間浸漬し、水洗乾燥した。このようにして平版印刷版前駆体用の基板を得た。
下層用塗布液の調製
以下の表1に示す、下層用塗布液を調製した。
表2に示す上層用塗布液を調製した。
上記基板作成の方法で得られた基板上に、ロールコーターを用いて、表1で調製した下層用塗布液(B-1)をコーティングし、100℃で2分間乾燥して第1の画像形成層を得た。この時の乾燥塗膜量は1.5g/m2であった。この第1の画像形成層の上に、表2で調製した上層用塗布液(T-1)を、ロールコーターを用いてコーティングし、100℃で2分間乾燥して二層型平版印刷前駆体を得た。メチルイソブチルケトンで、上層の画像形成層のみを剥離して、上層の画像形成層の乾燥塗膜量を求めた。この時の上層の画像形成層の乾燥塗膜量は0.5g/m2であった。
さらに、上記で得られた二層型平版印刷前駆体の感光層表面上に、水分含有量2.5%、材質天然パルプ紙、厚さ70μm、重さ45g/m2の保護材を供給し、樹脂製パレットの上に30枚堆積した。その後、側面および上面を特殊ポリオレフィンフィルムにて、空気が入らないように巻き、60℃、24時間のコンディショニング処理を行った。このようにして、二層型の平版印刷版前駆体Aを作製した。
以下に示す表3、4の組成に従って、種々の現像液を調製した。
現像液1は、(C)元素の周期律表の第2族に属する元素の金属塩として、塩化カルシウム2水和物、(D)カルボン酸又はその塩を有するポリマーとしてアクリル酸・マレイン酸共重合体(モル比40:60)のナトリウム塩(40%水溶液)、(B)一般式(I)で表される化合物としてアデカポリエーテルEDP-300をそれぞれ添加した。現像液2は、現像液1のアデカポリエーテルEDP-300をN,N,N’,N’’,N’’-ペンタキス(2-ヒドロキシプロピル)ジエチレントリアミンに換えた以外は、現像液1と同じ組成で作製した。現像液3は、現像液1のアデカポリエーテルEDP-300を、エポミンPP-061に換えた以外は、現像液1と同じ組成で作製した。現像液4は、現像液1のアデカポリエーテルEDP-300を、アデカポリエーテルEDP-450に換えた以外は、現像液1と同じ組成で作製した。現像液5は、現像液1のアデカポリエーテルEDP-300を、アデカポリエーテルBM-34に換えた以外は、現像液1と同じ組成で作製した。 現像液6は、(C)成分の金属イオンと(D)のカルボン酸のモル比が、1:2.3となるように、現像液成分を調整した。現像液7は、(C)成分の金属イオンと(D)のカルボン酸のモル比が、1:18.8となるように、現像液成分を調整した。
(C)の金属イオンと(D)のカルボン酸のモル比率を変えて、同様に発明例用現像液18~19として、表8に示す組成で現像液を作製した。現像液18は、現像液6の成分と同じであるが、(C)の金属イオンと(D)のカルボン酸のモル比率が、1:1.5となるように、現像液組成を作製した。現像液19は、現像液7の成分と同じであるが、(C)の金属イオンと(D)のカルボン酸のモル比率が、1:45.1となるように、現像液組成を作製した。
作製した二層型平版印刷版前駆体Aについて、プレートセッターPT-R4300(大日本スクリーン製造株式会社製)を用いて150mJ/cm2で露光した。現像処理は自動現像機P-940X(コダック株式会社製)、および表4で得られた現像液を水で4倍希釈した現像液を用いて、30℃15秒にて行った。その後、フィニッシングガムPF2(コダック株式会社製)でガム引きを行った。さらに、2.5倍に希釈した現像液を、平版印刷版前駆体A1m2処理当たり20mlずつ補充しながら、連続で2000m2の平版印刷版前駆体Aの現像処理を行った。
得られた結果を表9に示す。
平版印刷版前駆体A、0m2処理時、500m2処理時、1000m2処理時、2000m2処理時の、平版印刷版前駆体Aの非画像部の現像性及び画像部の膜減りを観察した。
非画像部の現像性は、25倍ルーペで非画像部を観察し、画像形成層の現像残りの有無を評価した。以下の基準を用いて評価した。
○:十分に現像され、非画像部に画像記録層の残存は認められない。
△:非画像部上に若干画像記録層の残存が認められる。
×:非画像部上に現像不良が認められ、画像記録層が残存している。
○:残存率95%以上
△:残存率90%以上95%未満
×:残存率90%未満
Claims (9)
- (A)アルカリ剤、
(B)下記一般式(I)で表される化合物、
(C)元素の周期律表の第2族元素の金属塩、及び
(D)カルボン酸又はその塩を有するポリマー
を含んで成る、平版印刷版作製用のアルカリ現像液組成物。
R5、R6は各々独立に2価の連結基を表し、同一であっても異なっていてもよい。
R7は、上記R1~R4において規定する基から選択することができ、又は
下記一般式(II)
R4'は式(I)に規定したR4と同じであり、
R5'は式(I)に規定したR5と同じであり、
R6'は式(I)に規定したR6と同じであり、
R7'は式(I)に規定したR7と同じである。)
で表される置換基群から選択することができる。
式(I)及び(II)中のnは0~20の整数を表し、nが2以上の場合、R7、R7'は、それぞれ独立して選択することができる。] - 前記(C)元素の周期律表の第2族元素が、マグネシウム、カルシウム、ストロンチウム、バリウムから成る群より選択される請求項1に記載のアルカリ現像液組成物。
- 前記(C)第2族元素の金属塩が、塩化物、炭酸塩、酢酸塩、硫酸塩、硝酸塩、リン酸塩から成る群より選択される請求項1又は2に記載のアルカリ現像液組成物。
- 前記(A)アルカリ剤が、有機アミン類である請求項1~4のいずれか1項に記載のアルカリ現像液組成物。
- さらに有機溶剤を含んで成る、請求項1~5のいずれか1項に記載のアルカリ現像液組成物。
- さらに界面活性剤を含んで成る、請求項1~6のいずれか1項に記載のアルカリ現像液組成物。
- 前記アルカリ現像液組成物のpHが12以下である請求項1~7のいずれか1項に記載のアルカリ現像液組成物。
- 親水性表面を有する基板上に、水不溶性かつアルカリ可溶性樹脂を含む下層と、前記下層上に形成された水不溶性かつアルカリ可溶性樹脂を含む上層とを含み、前記下層及び上層の少なくとも一方が、光熱変換物質を含むポジ型平版印刷版前駆体を、赤外線レーザーを用いて像様露光する工程、
前記露光済み平版印刷版前駆体を請求項1~8のいずれか1項に記載のアルカリ現像液組成物で現像して露光部を除去し、画像部と非画像部を形成する工程
を含んで成る平版印刷版の作製方法。
Priority Applications (4)
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US14/400,894 US9201307B2 (en) | 2012-06-29 | 2013-06-27 | Developing solution composition for lithographic printing plate precursor and method for producing lithographic printing plate |
EP13808667.3A EP2869123A4 (en) | 2012-06-29 | 2013-06-27 | DEVELOPMENT SOLUTION COMPOSITION FOR LITHOGRAPHIC PRINTING PLATE PRECURSOR AND METHOD FOR MANUFACTURING LITHOGRAPHIC PRINTING PLATE |
JP2014522687A JP6189838B2 (ja) | 2012-06-29 | 2013-06-27 | 平版印刷版前駆体用現像液組成物及び平版印刷版の作製方法 |
CN201380034525.0A CN104395835A (zh) | 2012-06-29 | 2013-06-27 | 平版印刷版前体用显影液组合物和平版印刷版的制作方法 |
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JP2012147310 | 2012-06-29 |
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EP (1) | EP2869123A4 (ja) |
JP (1) | JP6189838B2 (ja) |
CN (1) | CN104395835A (ja) |
WO (1) | WO2014003134A1 (ja) |
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Also Published As
Publication number | Publication date |
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US9201307B2 (en) | 2015-12-01 |
JP6189838B2 (ja) | 2017-08-30 |
CN104395835A (zh) | 2015-03-04 |
JPWO2014003134A1 (ja) | 2016-06-02 |
EP2869123A4 (en) | 2016-03-09 |
US20150125795A1 (en) | 2015-05-07 |
EP2869123A1 (en) | 2015-05-06 |
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