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
  • G03F7/004—Photosensitive materials
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
  • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
• • 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
  • G03F7/20—Exposure; Apparatus therefor
  • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
  • G03F7/2014—Contact or film exposure of light sensitive plates such as lithographic plates or circuit boards, e.g. in a vacuum frame
  • G03F7/2016—Contact mask being integral part of the photosensitive element and subject to destructive removal during post-exposure processing
  • G03F7/202—Masking pattern being obtained by thermal means, e.g. laser ablation

Definitions

• the present invention relates to a photosensitive resin printing plate precursor.
• CTP computer to plate
• digital image forming technology has become commonplace in the fields of letterpress printing and flexographic printing.
• an image mask is formed by digital data on the mask layer element of a photosensitive resin printing plate precursor having a mask layer element.
• a relief pattern is formed by partially photocuring a layer.
• a photosensitive resin printing plate precursor suitable for such CTP technology a photosensitive resin layer (A) containing at least a resin soluble or dispersible in water and a monomer curable by ultraviolet rays is formed on a support, and an infrared A photosensitive resin printing plate precursor, characterized in that a water-insoluble heat-sensitive mask layer (C) containing an absorbing substance is laminated in this order, and the water permeation time of the heat-sensitive mask layer (C) is 50 to 400 seconds.
• Patent Document 1 or a water-soluble or water-dispersible thermosensitive material containing at least (A) a support, (B) a photosensitive resin layer, (C) an oxygen-blocking split layer, and (D) carbon black.
• a water-developable photosensitive letterpress printing original plate in which mask layers are sequentially laminated wherein (B) the photosensitive resin layer contains a synthetic polymer compound, a photopolymerizable unsaturated compound, and a photopolymerization initiator, The synthetic polymer compound contains polyamide or polyether urea urethane containing tertiary nitrogen atoms, and (C) the oxygen-blocking split layer has a degree of saponification of 60 to 85 mol% and a degree of polymerization of 200 to 800.
• a photosensitive letterpress printing original plate containing polyvinyl alcohol has been proposed (see, for example, Patent Document 2).
• a photosensitive resin printing plate precursor having an infrared-sensitive layer such as a heat-sensitive mask layer in the above technology is damaged when the infrared-sensitive layer is scratched during handling.
• the infrared layer is required to have excellent scratch resistance.
• An object of the present invention is to provide a photosensitive resin printing plate precursor having an infrared sensitive layer with excellent scratch resistance.
• the present invention is a photosensitive resin printing plate precursor having, on a support, a photosensitive resin layer, an intermediate layer and an infrared-sensitive layer in this order, wherein the intermediate layer has a saponification degree of 60 to 100 mol % and an average polymerization degree of 1. It is a photosensitive resin printing plate precursor containing 200 to 3,000 polyvinyl alcohol.
• the photosensitive resin printing plate precursor of the present invention has excellent scratch resistance of the infrared-sensitive layer.
• the photosensitive resin printing plate precursor of the present invention (hereinafter sometimes abbreviated as "printing plate precursor”) has a photosensitive resin layer, an intermediate layer and an infrared-sensitive layer in this order on a support.
• the support has a function of holding the photosensitive resin layer in the printing plate precursor.
• the photosensitive resin layer has a function of forming an uneven pattern (relief) corresponding to the image mask by irradiation with actinic rays through the image mask.
• the infrared-sensitive layer has the action of forming an image mask by partial decomposition (ablation) by infrared rays.
• the intermediate layer brings the photosensitive resin layer and the infrared-sensitive layer into close contact with each other, suppresses migration of low-molecular-weight components from the photosensitive resin layer to the infrared-sensitive layer, and improves the scratch resistance of the infrared-sensitive layer.
• the "scratch resistance of the infrared-sensitive layer” means the scratch resistance of the infrared-sensitive layer in the printing plate precursor.
• the printing plate precursor of the invention may further have an easy-adhesion layer between the support and the photosensitive resin layer, if necessary, to increase the adhesion between the support and the photosensitive resin layer. can be done. Further, a protective layer may be provided on the infrared-sensitive layer, which suppresses the damage of the infrared-sensitive layer due to external force, and further improves the scratch resistance of the infrared-sensitive layer in the printing plate precursor.
• the printing plate precursor of the present invention is characterized by containing polyvinyl alcohol having a degree of saponification of 60 to 100 mol % and an average degree of polymerization of 1,200 to 3,000 in the intermediate layer.
• the degree of saponification and the average degree of polymerization of polyvinyl alcohol in the present invention are values measured according to JIS K 6726-1994 (polyvinyl alcohol test method).
• the saponification degree and average polymerization degree of the polyvinyl alcohol mean the saponification degree and average polymerization degree of the two or more polyvinyl alcohols as a whole, respectively.
• the degree of saponification of polyvinyl alcohol in the intermediate layer By setting the degree of saponification of polyvinyl alcohol in the intermediate layer to 60 mol% or more, the solubility in a developing solution containing water as a main component can be improved.
• the infrared-sensitive layer to be described later can be removed with a developer containing water as a main component, the photosensitive resin layer, the intermediate layer and the infrared-sensitive layer can be combined and developed with a developer containing water as a main component. can be done.
• the degree of saponification is preferably 65 mol % or more.
• the degree of saponification of polyvinyl alcohol in the intermediate layer is preferably 97 mol % or less, and can improve the adhesion to the photosensitive resin layer.
• the intermediate layer tends to become brittle because it tends to swell due to migration of low-molecular-weight components from the photosensitive resin layer.
• the average degree of polymerization is preferably 1,400 or more.
• the intermediate layer can be easily formed.
• the thickness of the intermediate layer is preferably 0.1-3 ⁇ m. By setting the thickness of the intermediate layer to 0.1 ⁇ m, the scratch resistance of the infrared-sensitive layer can be further improved. More preferably, the thickness of the intermediate layer is 0.3 ⁇ m or more. On the other hand, by setting the thickness of the intermediate layer to 3 ⁇ m or less, it is possible to form a deep relief of the recessed portion image, thereby improving the reproducibility of the blanked character image. More preferably, the thickness of the intermediate layer is 2 ⁇ m or less.
• the thickness of the intermediate layer in the present invention can be measured by magnifying and observing the cross section of the printing plate using a transmission electron microscope or scanning electron microscope. Moreover, when the coating amount per unit area is known, it can be calculated from the coating amount and the specific gravity.
• the infrared-sensitive layer efficiently absorbs the infrared laser, and the heat evaporates or ablates part or all of the layer, causing a difference in optical density between the laser-irradiated and non-irradiated areas.
• (2) practically blocking ultraviolet light It should be noted that the practical blocking of ultraviolet light referred to here means that the optical density of the infrared-sensitive layer is 2.0 or more, and more preferably 2.5 or more.
• T is the transmittance (in units of %)
• I0 the incident light intensity when measuring the transmittance
• I is the transmitted light intensity.
• the optical density in the present invention refers to a value calculated from the measured value of the transmitted light intensity with the incident light intensity kept constant.
• the optical density can be measured with a Macbeth transmission densitometer "TR-927" (manufactured by Kollmorgen Instruments Corp.) using an orthochromatic filter.
• the infrared-sensitive layer preferably contains an infrared-absorbing substance. Furthermore, it is preferable to contain polyvinyl alcohol.
• the infrared absorbing substance substances having absorption characteristics in the wavelength range of 750 nm to 20,000 nm are preferable.
• Inorganic pigments such as copper, and dyes such as phthalocyanines, substituted phthalocyanine derivatives, cyanine dyes, merocyanine dyes, polymethine dyes, and metal thiolate dyes are included. You may contain 2 or more types of these. Among these, carbon black is preferable from the viewpoint of ablation efficiency and ultraviolet absorption performance.
• Carbon black preferably has an anionic group.
• an anionic group By having an anionic group, the dispersibility of carbon black can be enhanced without using a dispersant.
• a sulfo group and a carboxyl group are preferred.
• a sulfo group has a large dissociation constant in water, and has a large effect of suppressing aggregation of carbon black in a dispersion of the infrared-sensitive layer composition described later.
• the carboxyl group suppresses aggregation of carbon black due to solvent shock, which tends to occur when an organic solvent such as a lower alcohol is added to the dispersion of the infrared-sensitive layer composition described later, and suppresses coating defects in the infrared-sensitive layer. can do.
• Carbon black having a carboxyl group as an anionic group preferably has a lactone group.
• a carboxyl group has a low dissociation constant in water and is easily affected by functional groups of other components and pH. Therefore, carbon black having carboxyl groups tends to aggregate easily.
• the lactone group acts as a steric hindrance to the electrostatic interaction with other components and has the effect of suppressing aggregation. Therefore, carbon black having a carboxyl group and a lactone group is superior in dispersibility in polyvinyl alcohol, and can suppress coating defects in the infrared-sensitive layer.
• the content of the infrared-absorbing substance in the infrared-sensitive layer is preferably 5% by mass or more based on the total solid content from the viewpoint of improving the ablation efficiency.
• the content of the infrared-absorbing substance in the infrared-sensitive layer is preferably 80% by mass or less from the viewpoint of further improving the scratch resistance of the infrared-sensitive layer.
• the infrared-sensitive layer in the present invention preferably contains an ultraviolet-absorbing substance that blocks ultraviolet rays.
• an ultraviolet-absorbing substance a substance having absorption characteristics in a wavelength range of 300 to 400 nm is preferable, and examples thereof include benzotriazole-based compounds, triazine-based compounds, and benzophenone-based compounds. You may contain 2 or more types of these.
• the infrared-sensitive layer preferably contains polyvinyl alcohol, which enhances the dispersibility of the infrared-absorbing substance and improves the film-forming properties of the infrared-sensitive layer. In addition, it is possible to improve the adhesion with the intermediate layer described above.
• Polyvinyl alcohol in the infrared-sensitive layer preferably has a saponification degree of 60 to 100 mol % and an average polymerization degree of 300 to 3,500.
• the saponification degree and polymerization degree of polyvinyl alcohol in the infrared-sensitive layer are values measured according to JIS K 6726-1994 (polyvinyl alcohol test method), as in the intermediate layer.
• the degree of saponification and average degree of polymerization of polyvinyl alcohol mean the degree of saponification and degree of polymerization of the two or more types of polyvinyl alcohol as a whole, respectively.
• the degree of saponification of polyvinyl alcohol in the infrared-sensitive layer is preferably 97 mol % or less, which can improve adhesion to the intermediate layer.
• the degree of saponification of polyvinyl alcohol in the infrared-sensitive layer is preferably higher than the degree of saponification of polyvinyl alcohol in the intermediate layer.
• a compound having an ethylenic double bond which is a low-molecular-weight component contained in the photosensitive resin layer to be described later, generally has high fat solubility.
• polyvinyl alcohol having a higher degree of saponification than that in the intermediate layer as the polyvinyl alcohol in the infrared-sensitive layer, migration of those compounds to the infrared-sensitive layer can be further suppressed, and the scratch resistance of the infrared-sensitive layer can be further improved.
• the difference between the degree of saponification of polyvinyl alcohol in the infrared-sensitive layer and the degree of saponification of polyvinyl alcohol in the intermediate layer is preferably 1 mol % or more, more preferably 3 mol % or more.
• the film strength of the infrared-sensitive layer can be improved, and the scratch resistance of the infrared-sensitive layer during the manufacturing process can be improved.
• the scratch resistance of the infrared-sensitive layer in the production process refers to the infrared-sensitive layer as an intermediate in the production of the printing plate precursor (for example, in the case of a printing plate precursor having a protective layer, a laminate of protective layer/infrared-sensitive layer Infrared-sensitive layer) scratch resistance.
• Such properties contribute to an improvement in yield in the manufacturing process of the printing plate precursor, unlike the scratch resistance of the infrared-sensitive layer in the printing plate precursor.
• the average degree of polymerization is more preferably 1,000 or more. On the other hand, by setting the average degree of polymerization to 3,500 or less, the infrared-sensitive layer can be easily formed.
• the average degree of polymerization is more preferably 2,500 or less.
• the content of polyvinyl alcohol in the infrared-sensitive layer is preferably 10% by mass or more in the total solid content from the viewpoint of easier formation of the infrared-sensitive layer.
• the content of polyvinyl alcohol in the infrared-sensitive layer is preferably 80% by mass or less in the total solid content from the viewpoint of improving the abrasion efficiency.
• the infrared-sensitive layer may contain other polymers, fillers, surfactants, coating aids, etc. within limits that do not impair the effects of the present invention.
• Other polymers include, for example, polyacrylic acid, polyester, polyamide and derivatives thereof. You may contain 2 or more types of these.
• the photosensitive resin layer preferably contains at least a binder resin, an ethylenic double bond-containing compound, and a photopolymerization initiator.
• a binder resin an ethylenic double bond-containing compound
• a photopolymerization initiator an organic radical generated from the photopolymerization initiator in the photosensitive resin layer in the exposed areas.
• the generated free radicals can induce radical polymerization between compounds having an ethylenic double bond and form a relief for obtaining a desired printed image due to the crosslinked structure.
• radical polymerization also occurs between the binder resin and the compound having an ethylenic double bond. This makes it possible to further promote photocuring and improve the image reproducibility of the printing plate.
• binder resins include styrene-butadiene copolymer, polybutadiene latex, styrene-butadiene copolymer latex, acrylonitrile-butadiene copolymer latex, methyl methacrylate-butadiene copolymer latex, polyurethane, cellulose derivatives, polyester, poly Examples include acrylic acid derivatives, polyvinyl acetate, polyvinyl alcohol, polyvinylpyrrolidone, and polyamides. You may use 2 or more types of these. Polyvinyl alcohol is preferred from the viewpoint of film-forming properties, developability with water, and adhesion to the intermediate layer.
• the degree of saponification of polyvinyl alcohol contained in the photosensitive resin layer is preferably 60 to 95 mol%.
• the degree of saponification of polyvinyl alcohol in the photosensitive resin layer is preferably 60 to 95 mol%.
• the solubility in a developer containing water as a main component can be improved.
• the photosensitive resin layer, the intermediate layer and the infrared-sensitive layer can be combined and developed with a developer containing water as a main component. can be done.
• the degree of saponification of polyvinyl alcohol in the photosensitive resin layer is preferably 90 mol % or less.
• the degree of saponification of polyvinyl alcohol in the photosensitive layer is a value measured according to JIS K 6726-1994 (polyvinyl alcohol test method), as in the intermediate layer.
• the degree of saponification of polyvinyl alcohol means the degree of saponification of the two or more types of polyvinyl alcohol as a whole.
• the weight average molecular weight of polyvinyl alcohol is preferably 10,000 or more and 200,000 or less.
• the weight average molecular weight can be determined by GPC measurement. More specifically, using a Wyatt Technology gel permeation chromatograph-multi-angle light scattering photometer, column temperature: 40 ° C., flow rate: 0.7 mL / min, polyethylene oxide and polyethylene glycol as standard samples can be measured using
• the polyvinyl alcohol in the photosensitive resin layer preferably has an ethylenic double bond in its side chain.
• groups having an ethylenic double bond include vinyl groups, acryloyl groups, and methacryloyl groups. You may have 2 or more types of these.
• Methods for introducing an ethylenic double bond into polyvinyl alcohol include, for example, (1) reacting a hydroxyl group of polyvinyl alcohol with an acid anhydride, and starting from the hydroxyl group of polyvinyl alcohol, a reactive group such as a carboxyl group is added to the polymer side; (2) a copolymer of vinyl acetate and unsaturated carboxylic acid, unsaturated carboxylic acid salt and/or unsaturated carboxylic acid ester; A method of partially saponifying and reacting the carboxyl group of this polymer with an unsaturated epoxy compound can be used.
• the ethylenic double bond equivalent of polyvinyl alcohol is preferably 1,000 g/eq or more and 19,000 g/eq or less.
• the ethylenic double bond equivalent is preferably 1,000 g/eq or more and 19,000 g/eq or less.
• the ethylenic double Binding equivalents can be calculated. Also, the number of moles of ethylenic double bonds in the partially saponified polyvinyl acetate is analyzed by 1 H-NMR, and the weight of the sample used for analysis is divided by the number of moles of detected ethylenic double bonds. By, the ethylenic double bond equivalent can be calculated.
• the content of polyvinyl alcohol in the photosensitive resin layer is preferably 30 to 85% by mass.
• the photosensitive resin layer contains a binder resin having a hydrophilic group, which is highly compatible with polyvinyl alcohol, and a binder resin having a water-swellable or water-soluble polymer main chain, together with the aforementioned polyvinyl alcohol.
• Hydrophilic groups include, for example, carboxyl groups, amino groups, hydroxyl groups, phosphoric acid groups, sulfonic acid groups and salts thereof.
• polymers having hydrophilic groups include carboxylated styrene butadiene latex, polymers of aliphatic conjugated dienes having carboxyl groups, emulsion polymers of ethylenically unsaturated compounds having phosphoric acid groups and/or carboxyl groups, sulfone and acid group-containing polyurethanes.
• polymers whose polymer main chain itself is water-swellable or water-soluble include vinyl alcohol-sodium acrylate copolymer, vinyl alcohol-sodium methacrylate copolymer, polyvinylpyrrolidone, polyether-containing polyamide, Tertiary nitrogen atom-containing polyamide, polyether, cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, starch, starch-sodium polyacrylate graft, starch-polyacrylonitrile graft saponified product, cellulose polyacrylic acid graft, partially crosslinked sodium polyacrylate, polyethylene glycol, polyethylene glycol derivatives, and the like. You may contain 2 or more types of these. Among these, tertiary nitrogen atom-containing polyamides are preferably used in terms of their high physical strength, the ability to further improve printing durability, and the balance between strength and solubility in solvents.
• a compound having an ethylenic double bond refers to a compound having an ethylenic double bond and having a molecular weight of less than 10,000.
• the molecular weight of the compound having an ethylenic double bond is preferably 2,000 or less.
• Examples of compounds having an ethylenic double bond include (meth)acrylates described in WO 2017/038970, glycerol di(meth)acrylate, and (meth)acrylic acid adducts of propylene glycol diglycidyl ether. , tetrahydrofurfuryl (meth)acrylate and the like. You may contain 2 or more types of these.
• (meth)acrylate is a generic term for acrylate and methacrylate
• (meth)acrylic acid is a generic term for acrylic acid and methacrylic acid.
• the content of the compound having an ethylenic double bond in the photosensitive resin layer is preferably 10-60% by weight.
• photopolymerization initiator those having the function of generating radicals by self-decomposition or hydrogen abstraction by light absorption are preferably used.
• examples include benzoin alkyl ethers, benzophenones, anthraquinones, benzyls, acetophenones, diacetyls and the like. You may contain 2 or more types of these.
• the content of the photopolymerization initiator in the photosensitive resin layer is preferably 0.1 to 10% by mass.
• the photosensitive resin layer may contain miscibility aids, ink-repellent agents, polymerization inhibitors, dyes, pigments, surfactants, antifoaming agents, UV absorbers, fragrances, etc., if necessary.
• compatibility aid in the photosensitive resin layer, the compatibility of the components constituting the photosensitive resin layer is enhanced, the bleeding out of low molecular weight components is suppressed, and the flexibility of the photosensitive resin layer is improved.
• compatible aids include polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, glycerin, trimethylolpropane, trimethylolethane, pentaerythritol and derivatives thereof. You may contain 2 or more types of these.
• the content of the compatibility aid in the photosensitive resin layer is preferably 30% by mass or less.
• an ink-repellent agent in the photosensitive resin layer, it is possible to suppress the ink from entering the recesses of the relief during printing and improve the reproducibility.
• ink-repellent agents include silicone compounds and fluorine-containing compounds. You may contain 2 or more types of these.
• the content of the ink repellent agent in the photosensitive resin layer is preferably 5% by mass or less.
• the thermal stability can be improved.
• polymerization inhibitors include phenols, hydroquinones, catechols, and hydroxylamine derivatives. You may contain 2 or more types of these.
• the content of the polymerization inhibitor in the photosensitive resin layer is preferably 0.001 to 5 mass %.
• the support will be explained.
• the support include plastic sheets such as polyester, synthetic rubber sheets such as styrene-butadiene rubber, and metal plates such as steel, stainless steel, and aluminum.
• the thickness of the support is preferably in the range of 100 to 350 ⁇ m from the viewpoint of handleability and flexibility.
• the support is preferably treated for easy adhesion, and can improve adhesion to the relief and floor layers.
• the adhesive treatment method include mechanical treatment such as sandblasting, physical treatment such as corona discharge, and chemical treatment such as coating. Among these, from the viewpoint of adhesion, it is preferable to provide an easy-adhesion layer by coating.
• the printing plate precursor of the invention may optionally have a protective layer on the infrared sensitive layer.
• protective layers include plastic sheets made of polyester, polyethylene, polypropylene, and the like.
• the thickness of the protective layer is preferably 10 to 150 ⁇ m from the viewpoint of handleability and flexibility.
• the method for producing the printing plate precursor of the present invention will be described by taking as an example a case where the support has a photosensitive resin layer, an intermediate layer, an infrared-sensitive layer and a protective layer.
• polyvinyl alcohol a compound component having an ethylenic double bond
• other additives are heated and dissolved in a solvent to obtain a photosensitive resin composition solution.
• solvents include water/alcohol mixed solvents.
• a photosensitive resin composition solution is cast on a support having an easily adhesive layer, if necessary, and dried to form a photosensitive resin layer.
• a printing plate precursor can be obtained by adhering the protective layer formed with the intermediate layer and the infrared-sensitive layer onto the photosensitive resin layer.
• a protective layer comprising an intermediate layer and an infrared-sensitive layer is formed, for example, by coating the protective layer with an infrared-sensitive layer composition dispersion containing the components of the infrared-sensitive layer described above, drying, and forming the intermediate layer. Examples include a method of applying an intermediate layer composition solution containing the components and drying the solution.
• a method for manufacturing a printing plate using the printing plate precursor of the present invention will be described. It is preferable to have an exposure step of partially photocuring the photosensitive resin layer of the printing plate precursor and a development step of removing the uncured portion of the photosensitive resin layer with a liquid containing water.
• the printing plate precursor from which the protective layer has been removed, if any, is mounted on a digital imager having an infrared laser such as a fiber laser, and the infrared-sensitive layer is decomposed and evaporated (ablated) to form an image mask.
• a digital imager having an infrared laser such as a fiber laser
• the infrared-sensitive layer is decomposed and evaporated (ablated) to form an image mask.
• the exposure light source include high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, xenon lamps, carbon arc lamps, chemical lamps, UV-LED lamps, and the like.
• the developing process it is preferable to remove the photosensitive resin layer in the unexposed areas with a liquid containing water.
• the developing device include a spray type developing device and a brush type washing machine.
• a post-exposure step of irradiating with ultraviolet light may be provided after development.
• the post-exposure step makes it possible to make the relief stronger by reaction of compounds with unreacted ethylenic double bonds.
• the printing plate precursor of the present invention and the printing plate obtained by using it can be used for letterpress printing, dry offset printing, flexographic printing, etc. using a label printing rotary press or an intermittent rotary press. . Among these, it can be preferably used for relief printing applications and dry offset printing applications.
• Synthesis example 1 Partially saponified polyvinyl alcohol “Gosenol” (registered trademark) KL-05 (average degree of polymerization: 500, degree of saponification: 80 mol%, Mw: 38,000) manufactured by Mitsubishi Chemical Corporation is swollen in acetone to obtain “Gosenol” KL. 4.2 parts by mass of succinic anhydride was added to 100 parts by mass of -05, and the mixture was stirred at 60° C. for 6 hours to add carboxyl groups to the molecular chains. The polymer was washed with acetone to remove unreacted succinic anhydride and then dried.
• Gosenol registered trademark
• KL-05 average degree of polymerization: 500, degree of saponification: 80 mol%, Mw: 38,000
• the obtained polymer A had an ethylenic double bond equivalent of 5,611 g/eq and a weight average molecular weight of 40,000.
• the weight-average molecular weight was measured using a Wyatt Technology gel permeation chromatograph-multi-angle light scattering photometer under the conditions of column temperature: 40°C, flow rate: 0.7 mL/min, and polyethylene oxide and polyethylene as standard samples. Measured using glycol. Further, the ethylenic double bond equivalent was obtained by dissolving 30 mg of polymer A in 1 ml of heavy water/heavy methanol mixed solvent to which 3-(trimethylsilyl)sodium propionate- 2,2,3,3d4 was added as an internal standard . H-NMR measurement was performed to measure the number of moles of ethylenic double bonds. The ethylenic double bond equivalent was calculated by dividing the polymer A in the sample used for analysis by the number of moles of ethylenic double bonds detected.
• the easy-adhesion layer coating solution is dried using a bar coater so that the film thickness becomes 30 ⁇ m after drying. After coating, the solvent was removed by heating in an oven at 180° C. for 3 minutes to obtain a support having an easy-adhesion layer.
• ⁇ Preparation of photosensitive resin layer composition solution Add the polymer shown in Table 1 to a three-necked flask equipped with a stirring spatula and a cooling tube, and add "Solmix” (registered trademark) H-11 (alcohol mixture, manufactured by Nippon Alcohol Co., Ltd.) 50 parts by mass. and 50 parts by mass of water, and heated at 90° C. for 2 hours while stirring to dissolve the polymer. After cooling the resulting mixture to 70° C., other components shown in Table 1 were added and stirred for 30 minutes to obtain a solution of a photosensitive resin layer composition.
• Solmix registered trademark
• H-11 alcohol mixture, manufactured by Nippon Alcohol Co., Ltd.
• ⁇ Scratch resistance of infrared-sensitive layer in protective layer/infrared-sensitive layer laminate A sample having a size of 25 cm ⁇ 2 cm was cut out from the infrared-sensitive layer/protective layer laminate, which is an intermediate obtained in each of Examples and Comparative Examples.
• a carpet material cloth (#4008, manufactured by Shin Nissen Co., Ltd.) was attached to a friction element with a dead weight of 500 g of a fastness tester (RT-300 manufactured by Daiei Kagaku Seiki Seisakusho), and the sample was rubbed back and forth 20 times. After that, using a microscope (VHX2000 lens manufactured by KEYENCE, 100x transmitted light), the infrared-sensitive layer on the surface of the sample was magnified and observed.
• the area of each scratch in the observation field was calculated, the ratio of the total area of all scratches to the area of the observation field was calculated, and the scratch resistance of the infrared-sensitive layer in the protective layer/infrared-sensitive layer laminate was evaluated according to the following criteria.
• ⁇ Scratch resistance of the infrared-sensitive layer in the printing plate precursor> The protective layer was peeled off from the printing plate precursor obtained in each of Examples and Comparative Examples, and after storage for 1 hour in an environment of 25° C. and 80 RH %, a sample of 25 cm ⁇ 2 cm was cut out.
• a carpet material cloth (#4008, manufactured by Shin Nissen Co., Ltd.) was attached to a friction element with a dead weight of 500 g of a fastness tester (RT-300 manufactured by Daiei Kagaku Seiki Seisakusho), and the sample was rubbed back and forth twice.
• the protective layer was peeled off from the printing plate precursor obtained in each of Examples and Comparative Examples, and the plate was mounted on a rotating cylindrical drum of a digital imager CDI Spark 2530 (manufactured by Esko Graphics Co., Ltd.) with the support side facing inside. .
• An image mask containing fine lines with a line width of 300 ⁇ m was formed by ablation of the infrared-sensitive layer by irradiation with a fiber laser under the conditions of 4.0 J/cm 2 . - An LED exposure was performed.
• Example 1 A photosensitive resin layer composition solution was cast on the easy-adhesion layer of the support having the easy-adhesion layer obtained by the above-described method, and dried at 60° C. for 2 hours to form a photosensitive resin layer having a thickness of 650 ⁇ m. bottom.
• the thickness of the photosensitive resin layer was adjusted by placing a spacer with a predetermined thickness on a support having an easy-adhesion layer, and scraping out the protruding portion of the photosensitive resin layer composition solution with a horizontal metal ruler.
• a dispersion of the infrared-sensitive layer composition 1 obtained by the method described above was applied to a protective layer of 100 ⁇ m thick “Lumirror” (registered trademark) S10 (polyester film, manufactured by Toray Industries, Inc.) using a bar coater. and dried at 120° C. for 30 seconds to form an infrared-sensitive layer to obtain a protective layer/infrared-sensitive layer laminate.
• the thickness of the infrared-sensitive layer is determined by optical density using an orthochromatic filter with the value of the protective layer set to zero (transmission mode of a Macbeth transmission densitometer "TR-927" (manufactured by Kollmorgen Instruments Corp.)). was adjusted to 3.0.
• Polyvinyl alcohol 1 (JL-18E (manufactured by Nippon Acetate & Poval Co., Ltd., saponification degree 84 mol %, average degree of polymerization 1,800))) 5 mass dissolved at 70° C. is applied onto the infrared-sensitive layer of the protective layer/infrared-sensitive layer laminate using a bar coater. It was applied to a thickness of 0.1 ⁇ m and dried at 120° C. for 30 seconds to form an intermediate layer to obtain an intermediate layer/infrared sensitive layer/protective layer laminate.
• a mixed solvent of 50 parts by mass of water/50 parts by mass of ethanol is applied onto the photosensitive resin layer formed by the above-described method, and the intermediate layer/infrared-sensitive layer/protective layer laminate is formed so that the intermediate layer side is on the photosensitive resin layer.
• a printing plate precursor was obtained by laminating so as to Table 3 shows the results of evaluation by the method described above.
• Example 2 to 5 A printing plate precursor was obtained in the same manner as in Example 1, except that the thickness of the intermediate layer was changed as shown in Table 3. Table 3 shows the evaluation results.
• Example 6 A printing plate precursor was obtained in the same manner as in Example 3 except that the polyvinyl alcohol in the intermediate layer was changed as shown in Table 3. Table 3 shows the evaluation results.
• Example 7-9 A printing plate precursor was obtained in the same manner as in Example 2, except that the infrared-sensitive layer composition shown in Table 3 was used to form the infrared-sensitive layer. Table 3 shows the evaluation results.
• Example 10 A printing plate precursor was obtained in the same manner as in Example 9 except that the polyvinyl alcohol in the intermediate layer was changed as shown in Table 3. Table 3 shows the evaluation results.
• Example 11 A printing plate precursor was obtained in the same manner as in Example 10 except that the infrared-sensitive layer composition shown in Table 3 was used to form the infrared-sensitive layer. Table 3 shows the evaluation results.
• Example 12 A printing plate precursor was obtained in the same manner as in Example 11 except that the infrared-sensitive layer composition shown in Table 3 was used to form the infrared-sensitive layer. Table 3 shows the evaluation results.
• Example 2 A printing plate precursor was obtained in the same manner as in Example 9 except that the polyvinyl alcohol in the intermediate layer was changed as shown in Table 3. Table 3 shows the evaluation results.
• Example 3 A printing plate precursor was obtained in the same manner as in Example 2 except that the polyvinyl alcohol in the intermediate layer was changed as shown in Table 3. Table 3 shows the evaluation results.

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