WO2014021322A1 - 感光性樹脂組成物および感光性樹脂印刷版原版 - Google Patents
感光性樹脂組成物および感光性樹脂印刷版原版 Download PDFInfo
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- WO2014021322A1 WO2014021322A1 PCT/JP2013/070615 JP2013070615W WO2014021322A1 WO 2014021322 A1 WO2014021322 A1 WO 2014021322A1 JP 2013070615 W JP2013070615 W JP 2013070615W WO 2014021322 A1 WO2014021322 A1 WO 2014021322A1
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- WIPO (PCT)
- Prior art keywords
- photosensitive resin
- resin composition
- printing plate
- layer
- partially saponified
- Prior art date
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Classifications
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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
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
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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
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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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
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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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
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
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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
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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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
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
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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
- G03F7/322—Aqueous alkaline compositions
Definitions
- the present invention relates to a photosensitive resin composition and a photosensitive resin printing plate precursor using the same, and in particular, a printing plate photosensitive material that provides a photosensitive resin relief plate material with improved printing durability and improved printing quality.
- the present invention relates to a resin composition.
- a printing plate material having a layer made of a photosensitive resin composition generally contains a soluble polymer, a photopolymerizable unsaturated group-containing monomer, and a photopolymerization initiator as essential components in the photosensitive resin layer. Additives such as stabilizers and plasticizers are blended.
- Such a printing plate material is obtained by irradiating the photosensitive resin layer with ultraviolet light through a negative or positive original film or an image mask layer opaque to the ultraviolet light provided on the photosensitive resin layer.
- a relief image is formed by forming a part that dissolves in a solvent and a part that does not dissolve in the photosensitive resin layer, and is used as a printing plate material.
- Most of the photosensitive resin relief plates currently used can form relief by developing a relief image formed by exposure with water. Soluble polymers in the photosensitive resin layer are soluble in water. Or water-swellable ones are used.
- Partially saponified polyvinyl acetate and its derivatives have been used because they are water-soluble and excellent in water developability, but because of their high crystallinity, they are brittle against repeated impact forces during printing, There have been problems such as cracks in the relief during printing.
- Patent Documents 1 and 2 As a method for solving the above problem, for example, as disclosed in Patent Documents 1 and 2, it has been proposed to solve the above problem by blending a polyvinyl acetate derivative and a polyamide having basic nitrogen.
- the present invention has been made in view of the above circumstances, and provides a photosensitive resin composition and a photosensitive resin printing plate precursor having excellent relief image reproducibility, toughness and improved printing durability. It is aimed.
- the present invention provides (A) a modified partially saponified polyvinyl acetate having a reactive group in the side chain, (B) a polyamide having basic nitrogen, and (C) a molecular weight of 300 or less.
- a photosensitive resin composition comprising a compound having a 5- to 7-membered ring and having a polymerizable ethylenic double bond, and (D) a photopolymerization initiator.
- relief printing is unlikely to cause relief cracks even when subjected to repeated impacts in printing in a state where tensile tension is applied when the relief is applied to a plate cylinder of a printing press. You can get a version.
- the reactive group in the modified partially saponified polyvinyl acetate having a reactive group in the side chain, which is the component (A) constituting the photosensitive resin composition, is a functional group that can be crosslinked by a radical reaction. is there.
- a functional group a non-aromatic unsaturated carbon-carbon bond, particularly an ethylenic double bond is often used, and examples thereof include a vinyl group and a (meth) acryloyl group.
- Examples of methods for introducing such reactive groups into the side chains of partially saponified polyvinyl acetate include the methods described in Patent Documents 3 and 4 and the method described in Patent Document 5.
- a partially saponified polyvinyl acetate and an acid anhydride are reacted, and a carboxyl group is introduced into a polymer side chain starting from a hydroxyl group of the partially saponified polyvinyl acetate.
- a reactive group is introduced by reacting a carboxyl group of the polymer with an unsaturated epoxy compound.
- the partially saponified polyvinyl acetate obtained by the former method is preferably used because the introduction of a reactive group is easy and the effects of the present invention are remarkably exhibited.
- Such reactive groups are preferably present in the compound (A) in an amount of 0.08 to 0.72 mol / kg, more preferably 0.12 to 0.36 mol / kg.
- the amount is more than 0.72 mol / kg, water solubility is deteriorated, and a level at which water developability is satisfactory cannot often be obtained.
- the amount is less than 0.08 mol / kg, effects such as relief chipping during development, which are improved by the reaction of the reactive group, often do not appear.
- the modified partially saponified polyvinyl acetate (A) having a reactive group thus obtained has at least the following structural units (I), (II) and (III).
- the unit of the structure (I) is preferably 60 to 99 mol%, more preferably 70 to 95 mol%.
- the structural unit of (I) is less than 60 mol%, water solubility is often lowered and sufficient water developability cannot be obtained, and when it is more than 99 mol%, solubility in room temperature water is sufficiently lowered. In many cases, the water developability cannot be obtained.
- the average degree of polymerization of the modified partially saponified polyvinyl acetate as the component (A) is preferably in the range of 300 to 2000, more preferably 500 to 1000. If the average degree of polymerization is less than 300, the water resistance is lowered and sufficient water resistance cannot be obtained. When the average degree of polymerization exceeds 2000, the water solubility is remarkably lowered, and sufficient water developability cannot be obtained.
- the method described in Patent Document 5 is a method in which a reactive group is introduced into the side chain of partially saponified polyvinyl acetate by the reaction of partially saponified polyvinyl acetate and an acrylic compound having an N-methylol group.
- the amount of the acrylic compound having an N-methylol group is preferably 2 to 40 parts by weight, more preferably 5 to 30 parts by weight, based on 100 parts by weight of polyvinyl acetate.
- the blending amount of the acrylic compound having an N-methylol group is more than 40 parts by weight, the water solubility is deteriorated and a level at which water developability is satisfactory cannot often be obtained.
- the amount is less than 2 parts by weight, effects such as relief chipping at the time of development, which are improved by reacting reactive groups, often do not appear.
- acrylic compound having an N-methylol group examples include N-methylol acrylamide, N-methylol methacrylamide, N-methyl-N-methylol acrylamide, N-methyl-N-methylol methacrylamide, N-ethyl-N.
- -Methylol acrylamide, N-ethyl-N-methylol methacrylamide and the like can be mentioned, and N-methylol acrylamide and N-methylol methacrylamide are particularly preferable. These may be used alone or in combination of two or more.
- the polyamide having basic nitrogen which is the component (B) of the present invention can improve the problem of relief chipping at the time of development and relief chipping at the time of printing, which are often caused by the blending of the component (A). Since the basic nitrogen of the component (B) is hydrogen bonded to the hydroxyl group of the component (A), there is an effect of suppressing the crystallization of the component (A). On the other hand, since the component (B) is easy to absorb moisture and has high adhesiveness, when it is not contained together with the component (A), it is not suitable as a raw material in the photosensitive resin composition.
- the polyamide having basic nitrogen is a polymer containing basic nitrogen in a part of the main chain or side chain.
- Basic nitrogen is a nitrogen atom constituting an amino group that is not an amide group.
- An example of such a polyamide is a polyamide having a tertiary amino group in the main chain.
- a polyamide having basic nitrogen can be obtained by subjecting a monomer having basic nitrogen alone or another monomer to polycondensation, polyaddition reaction, or the like.
- the basic nitrogen is preferably piperazine or an N, N-dialkylamino group, and more preferably piperazine.
- monomers having basic nitrogen for providing the polyamide required in the present invention include N, N′-bis (aminomethyl) -piperazine, N, N′-bis ( ⁇ -amino). Ethyl) -piperazine, N, N′-bis ( ⁇ -aminobenzyl) -piperazine, N- ( ⁇ -aminoethyl) piperazine, N- ( ⁇ -aminopropyl) piperazine, N- ( ⁇ -aminohexyl) piperazine, N- ( ⁇ -aminoethyl) -2,5-dimethylpiperazine, N, N-bis ( ⁇ -aminoethyl) -benzylamine, N, N-bis ( ⁇ -aminopropyl) -amine, N, N′- Diamines such as dimethyl-N, N′-bis ( ⁇ -aminopropyl) -ethylenediamine, N, N′-dimethyl-N, N′-bis ( ⁇ -amino
- the polyamide of the present invention can be obtained by polymerization in combination with diamine, dicarboxylic acid, ⁇ -amino acid, lactam and the like.
- These monomer components containing basic nitrogen are all polyamide constituents, that is, 10 to 100 mol% with respect to the sum of aminocarboxylic acid units (including lactam as a raw material), dicarboxylic acid units and diamine structural units. Further, it is preferably 10 to 80 mol%. If it is less than 10 mol%, the water solubility is low and the compatibility with the component (A) may be lowered.
- the photosensitive resin composition in the present invention contains (C) a compound having a molecular weight of 300 or less, a 5- to 7-membered ring, and a polymerizable ethylenic double bond.
- C a compound having a molecular weight of 300 or less, a 5- to 7-membered ring, and a polymerizable ethylenic double bond.
- a 5- to 7-membered ring is a bulky substituent
- a compound having a 5- to 7-membered ring has a high molecular motion barrier. Therefore, when compounded in the photosensitive resin composition, the molecular motion of the compound around the compound having an ethylenic double bond polymerizable with a 5- to 7-membered ring is also limited. Suppress. As a result, it is considered that resistance is improved against repeated impact force during printing of the resin printing plate.
- the compound having an ethylenic double bond that can be polymerized with a 5- to 7-membered ring in the molecule has at least one functional group selected from a hydroxyl group, a carboxyl group, and an amino group in the heterocyclic ring or the molecule.
- the heterocyclic ring and these functional groups interact with the hydroxyl group of the component (A) by hydrogen bonding, and the effect of suppressing crystallization of the component (A) is improved, and the combination of the components (C) and (A) There is an effect of improving the compatibility.
- a compound having an ethylenic double bond that can be polymerized with a 5- to 7-membered ring in the molecule needs to have a molecular weight of 300 or less.
- the molecular weight is larger than 300, the compatibility with the component (A) is lowered, and the resin composition may be turbid and non-uniform.
- component (C) examples include the following, but are not limited thereto.
- the content of the component (C) is preferably 5 to 200 parts by weight with respect to 100 parts by weight of the component (A). If the amount is less than 5 parts by weight, the image reproducibility is insufficient, and if it exceeds 200 parts by weight, it tends to be difficult to mold the photosensitive resin composition.
- the (C) component has an effect of suppressing the crystallization of the (A) component and improving the compatibility between the (C) component and the (A) component by using the (B) component together.
- (A) The problem of the relief chipping at the time of development and the relief chipping at the time of printing which were often caused by the blending of the component can be improved.
- adhesiveness is high, it is not suitable as a raw material in the photosensitive resin composition.
- the photosensitive resin layer of the present invention may contain a compound having a polymerizable ethylenic double bond other than the component (C) in order to adjust image reproducibility.
- the photosensitive resin composition of the present invention contains a photopolymerization initiator as component (D).
- a photopolymerization initiator can be used as long as it can polymerize a polymerizable carbon-carbon unsaturated group by light.
- generate a radical by self-decomposition or hydrogen abstraction by light absorption is used preferably.
- Examples include benzoin alkyl ethers, benzophenones, anthraquinones, benzyls, acetophenones, diacetyls, and the like.
- the blending amount of the photopolymerization initiator is preferably in the range of 0.1 to 20 parts by weight with respect to 100 parts by weight of component (A).
- ethylene glycol, diethylene glycol, triethylene glycol, glycerin and derivatives thereof, trimethylolpropane and derivatives thereof, trimethylolethane and derivatives thereof It is also possible to add polyhydric alcohols such as pentaerythritol and its derivatives. It is preferable that these polyhydric alcohols are 30 weight% or less with respect to the whole photosensitive resin composition.
- a conventionally known polymerization inhibitor can be added.
- Preferable polymerization inhibitors include phenols, hydroquinones, catechols, hydroxyamine derivatives and the like. These compounding amounts are generally used in the range of 0.001 to 5% by weight based on the total photosensitive resin composition.
- the dye is preferably a water-soluble triphenylmethane dye.
- the dye is water-soluble, aggregation and precipitation in the photosensitive resin composition are less likely to occur, and color unevenness is less likely to occur.
- triphenylmethane-based dyes are not easily faded by heat in the molding process of the photosensitive resin composition, and also have excellent light resistance, so that the color tone of the photosensitive composition and the printing plate material obtained from the photosensitive resin composition is excellent. Is stable.
- triphenylmethane dyes are not limited to these, but C.I. I. Acid Blue 9, C.I. I. Acid Blue 83, C.I. I. Acid Blue90, C.I. I. Acid Blue93, C.I. I. Acid Blue 100, C.I. I. Acid Blue 103, C.I. I. Acid Blue 104, C.I. I. Acid Green3, C.I. I. Acid Green5, C.I. I. Acid Green 9, C.I. I. The dye chosen from Food Green3 can be mentioned. The added amount of such a dye is preferably 0.001% to 0.2% by weight in the photosensitive resin composition, and by making such a range, the distinguishability of the relief of the printing plate material is improved. I can be satisfied.
- the photosensitive resin printing plate precursor of the present invention has at least a support (E) and a photosensitive resin layer (F) formed from the above-described photosensitive resin composition of the present invention.
- a plastic sheet such as polyester, a synthetic rubber sheet such as styrene-butadiene rubber, a metal plate such as steel, stainless steel, and aluminum can be used.
- the thickness of the support is not particularly limited, but is preferably in the range of 100 to 350 ⁇ m from the viewpoint of handleability and flexibility. If it is 100 micrometers or more, the handleability as a support body will improve, and if it is 350 micrometers or less, the flexibility as a printing original plate will improve.
- the support (E) is preferably subjected to an easy adhesion treatment for the purpose of improving the adhesion with the photosensitive resin layer (F).
- Examples of the easy adhesion treatment method include mechanical treatment such as sandblasting, physical treatment such as corona discharge, and chemical treatment such as coating.
- mechanical treatment such as sandblasting
- physical treatment such as corona discharge
- chemical treatment such as coating.
- the photosensitive resin layer (F) is formed from the above-described photosensitive resin composition.
- the thickness of the photosensitive resin layer (F) is preferably 0.3 mm or more, and more preferably 0.5 mm or more from the viewpoint of having a sufficient relief depth and improving printability. On the other hand, 5 mm or less is preferable and 3 mm or less is more preferable from the viewpoint of sufficiently increasing the actinic ray used for exposure to the bottom and further improving image reproducibility.
- the photosensitive resin printing plate precursor of the present invention preferably has a cover film (H) on the photosensitive resin layer (F) from the viewpoint of surface protection and prevention of adhesion of foreign substances and the like.
- the photosensitive resin layer (F) may be in direct contact with the cover film (H), or may have one or more layers between the photosensitive resin layer (F) and the cover film (H). Good.
- Examples of the layer between the photosensitive resin layer (F) and the cover film (H) include an anti-adhesion layer provided for the purpose of preventing adhesion on the surface of the photosensitive resin layer.
- the material of the cover film (H) is not particularly limited, but a plastic film such as polyester or polyethylene is preferably used.
- the thickness of the cover film (H) is not particularly limited, but a range of 10 to 150 ⁇ m is preferable from the viewpoints of handleability and cost.
- the cover film surface may be roughened for the purpose of improving the adhesion of the original film.
- the photosensitive resin printing plate precursor of the present invention may further have a thermal mask layer (I) on the photosensitive resin layer (F).
- the heat-sensitive mask layer (I) preferably has a function of effectively blocking ultraviolet light, absorbs infrared laser light during drawing, and partially or entirely sublimates or ablates instantaneously by the heat. As a result, a difference occurs in the optical density between the laser irradiated portion and the unirradiated portion, and the same function as that of the conventional original image film can be achieved.
- the optical density of the thermal mask layer (I) is 2.5 or more, and more preferably 3.0 or more.
- T the transmittance (%)
- I 0 the incident light intensity when measuring the transmittance
- I is the transmitted light intensity.
- the optical density in the present invention is a value calculated from the former transmitted light intensity.
- the optical density can be measured by using a Macbeth transmission densitometer “TR-927” (manufactured by Kollorgen Instruments Corp.) using an orthochromatic filter.
- the thermal mask layer (I) As a preferable specific example of the thermal mask layer (I), a resin in which an infrared absorbing material is dispersed can be exemplified.
- the infrared absorbing substance is not particularly limited as long as it is a substance that can absorb infrared light and convert it into heat.
- black pigments such as carbon black, aniline black, cyanine black, phthalocyanine, naphthalfurocyanine green pigment, rhodamine dye, naphthoquinone dye, polymethine dye, diimonium salt, azoimonium dye, chalcogen dye, carbon graphite, Iron powder, diamine-based metal complex, dithiol-based metal complex, phenolthiol-based metal complex, mercapton phenol-based metal complex, arylaluminum metal salts, crystal water-containing inorganic compounds, copper sulfate, chromium sulfide, silicate compounds, titanium oxide, Examples include metal oxides such as vanadium oxide, manganese oxide, iron oxide, cobalt oxide, and tungsten oxide, hydroxides and sulfates of these metals, and metal powders of bismuth, tin, tellurium, iron, and aluminum.
- thermosetting resin can be preferably used from a viewpoint of stability of a thermosensitive mask layer (I) and scratch resistance.
- the photosensitive resin printing plate precursor of the present invention may have an adhesion adjusting layer (J) between the photosensitive resin layer (F) and the thermal mask layer (I).
- the adhesion adjusting layer (J) preferably contains a water-soluble and / or water-dispersible resin such as partially saponified polyvinyl acetate or polyamide having a saponification degree of 30 mol% or more.
- the adhesive strength adjusting layer (J) contains additives such as resins and monomers for optimizing the adhesive strength, and surfactants and plasticizers for ensuring coating properties and stability. May be.
- the film thickness of the adhesion adjusting layer (J) is preferably 15 ⁇ m or less, more preferably 0.1 ⁇ m or more and 5 ⁇ m or less. If it is 15 ⁇ m or less, refraction and scattering of light by the layer when exposed to ultraviolet light is suppressed, and a sharper relief image can be obtained. Moreover, if it is 0.1 micrometer or more, formation of an adhesive force adjustment layer (J) will become easy.
- the photosensitive resin printing plate precursor of the present invention may have a peeling auxiliary layer (K) on the thermal mask layer (I).
- the peeling auxiliary layer (K) is preferably provided between the thermal mask layer (I) and the cover film (H). There is no peeling auxiliary layer (K) between the cover film (H) and the heat-sensitive mask layer (I), and the cover film (H) and the heat-sensitive mask layer (I) are laminated adjacent to each other, and adhesion between both layers If the force is strong, the cover film (H) cannot be peeled off or the heat-sensitive mask layer (I) remains partially adhered to the cover film (H) when peeled off, and the heat-sensitive mask layer (I) is not detached. It can happen.
- the peeling auxiliary layer (K) has a strong adhesive force with the thermal mask layer (I) and is weak enough to peel the adhesive force with the cover film (H), or the thermal mask layer (I). It is preferable that the adhesive force is weak enough to be peeled off and is made of a substance having a strong adhesive force with the cover film (H). In the former case, the peeling auxiliary layer (K) remains on the thermal mask layer (I), and only the cover film (H) peels off. In the latter case, the cover film (H) and the peeling auxiliary layer (K) are peeled together from the thermal mask layer (I).
- assistant layer (K) remains on the thermal mask layer (I) side and becomes an outermost layer, it is not sticky from a handling surface, or through this layer Since it is exposed to ultraviolet light, it is preferably substantially transparent.
- Examples of the material used for the peeling auxiliary layer (K) include polyvinyl alcohol, polyvinyl acetate, partially saponified polyvinyl alcohol, hydroxyalkyl cellulose, alkyl cellulose, polyamide resin and the like, which are dissolved or dispersed in water. It is preferable that the main component is a resin having a low adhesiveness.
- partially saponified polyvinyl alcohol having a saponification degree of 60 to 99 mol%, hydroxyalkyl cellulose having 1 to 5 carbon atoms and alkyl cellulose are particularly preferably used from the viewpoint of tackiness.
- the peeling auxiliary layer (K) may further contain an infrared absorbing material in order to facilitate ablation with infrared rays.
- an infrared absorbing material those exemplified in the heat-sensitive mask layer (I) can be used.
- you may contain surfactant for coating property, wettability, and peelability improvement.
- a phosphate ester-based surfactant is contained in the peeling auxiliary layer (K)
- the peelability from the cover film (H) is improved.
- the film thickness of the peeling assist layer (K) is preferably 6 ⁇ m or less, more preferably 0.1 ⁇ m or more and 1 ⁇ m or less.
- the thickness is 6 ⁇ m or less, laser ablation of the lower thermal mask layer (I) is possible, and when it is 1 ⁇ m or less, laser ablation is easy.
- it is 0.1 micrometer or more, formation of a peeling auxiliary
- the obtained photosensitive resin composition solution is cast on a support (E) having an easy-adhesion layer (G) if necessary, and dried to form a photosensitive resin layer (F) made of the photosensitive resin composition.
- the photosensitive resin printing plate precursor can be obtained by sticking the cover film (H) coated with an anti-adhesion layer on the photosensitive resin layer (F) if necessary.
- a photosensitive resin printing plate precursor can also be obtained by preparing a photosensitive resin sheet by dry film formation and laminating the photosensitive sheet between the support (E) and the cover film (H).
- the method for forming the thermal mask layer (I) is not particularly limited.
- a resin in which carbon black is dispersed is dissolved and diluted with an appropriate solvent.
- the heat-sensitive mask layer (I) can be formed by coating on the photosensitive resin layer (F) and drying the solvent.
- the above-described carbon black solution is once applied to the cover film (H) and laminated so that the photosensitive resin layer (F) is sandwiched between the cover film (H) and the support (E). I) can be formed.
- the method for forming the adhesive strength adjusting layer (J) is not particularly limited.
- a method of applying a solution dissolved in a solvent on the thermal mask layer (I) and removing the solvent is particularly preferably performed.
- the method for removing the solvent include hot air drying, far-infrared drying, and natural drying.
- dissolves an adhesive force adjustment layer (J) component is not specifically limited, Water, alcohol, or the mixture of water and alcohol is used preferably. When water or alcohol is used, it is preferable that the heat-sensitive mask layer (I) is water-insoluble because the heat-sensitive mask layer (I) will not be eroded even when applied on the heat-sensitive mask layer (I).
- the method of forming the release auxiliary layer (K) is not particularly limited, but for ease of thin film formation, the release auxiliary layer (K) component is dissolved in a solvent.
- a method in which the solution is applied onto the cover film (H) and the solvent is removed is particularly preferably performed. Examples of the method for removing the solvent include hot air drying, far-infrared drying, and natural drying.
- the solvent for dissolving the peeling auxiliary layer (K) component is not particularly limited, but water, alcohol, or a mixture of water and alcohol is preferably used.
- the resin printing plate of the present invention can be obtained by exposing and developing the above-described photosensitive resin printing plate precursor of the present invention.
- the photosensitive resin printing plate precursor does not have the thermal mask layer (I) (hereinafter referred to as an analog plate), and when it has the cover film (H), on the photosensitive resin layer (F) from which the photosensitive resin printing plate precursor is peeled off
- the photosensitive resin layer (F) is photocured by adhering a negative or positive original film and irradiating it with ultraviolet rays.
- the photosensitive resin printing plate precursor is a so-called CTP (computer-to-plate) plate having a thermal mask layer (I)
- the cover film (H) is peeled off, and then the original film is formed using a laser drawing machine. After drawing the corresponding image, the photosensitive resin layer (F) is photocured by irradiating with ultraviolet rays.
- Ultraviolet irradiation is usually performed using a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a xenon lamp, a carbon arc lamp, a chemical lamp, or the like that can irradiate a wavelength of 300 to 400 nm.
- a high-pressure mercury lamp an ultrahigh-pressure mercury lamp, a metal halide lamp, a xenon lamp, a carbon arc lamp, a chemical lamp, or the like that can irradiate a wavelength of 300 to 400 nm.
- back exposure back exposure from the support (E) side before peeling of the cover film (H).
- the photosensitive resin printing plate precursor is immersed in a developer, and a relief image is formed on the substrate by a brush type developing device that removes uncured portions by rubbing with a brush.
- a brush type developing device that removes uncured portions by rubbing with a brush.
- the developer is preferably water or water to which a surfactant is added.
- the liquid temperature during development is preferably 15 to 40 ° C. After forming the relief image, it can be dried at 50 to 70 ° C. for about 10 minutes, and further subjected to actinic light treatment in the air or in a vacuum as necessary to obtain a resin printing plate.
- the photosensitive resin layer of the obtained resin printing plate was exposed to the substrate portion from which the non-exposed portion was removed.
- the color difference ( ⁇ E * ab) according to the formula (1) obtained from the L * a * b * color system color coordinates of the portion of the photosensitive resin layer remaining as a relief layer after development is preferably in the range of 5 to 70. More preferably, it is in the range of 12-50.
- ⁇ E * ab [( ⁇ L * ) 2 + ( ⁇ a * ) 2 + ( ⁇ b * ) 2 ] 1/2 (1)
- the color difference ( ⁇ E * ab) is larger than 5
- the portion of the substrate with the adhesive layer and the portion of the substrate with the adhesive layer having the relief layer formed from the photosensitive resin layer can be easily distinguished.
- the color difference ( ⁇ E * ab) is smaller than 70, the relief character portion can be easily identified.
- the photosensitive resin composition of the present invention is most suitably used for letterpress printing, but can also be used for planographic printing, intaglio printing, stencil printing, and photoresist.
- Synthesis example 1 Partially saponified polyvinyl acetate “KL-05” (degree of polymerization: about 500, degree of saponification: 80 mol%) manufactured by Nippon Synthetic Chemical Industry Co., Ltd. is swollen in acetone, and 1.0 mol% of succinic anhydride is added. Then, the mixture was stirred at 60 ° C. for 6 hours to add a carboxyl group to the molecular chain. The polymer was washed with acetone to remove unreacted succinic anhydride and dried. The acid value was measured and found to be 10.0 mgKOH / g.
- Synthesis Example 3 100 parts by weight of partially saponified polyvinyl acetate “KL-05” (polymerization degree: about 500, saponification degree: 80 mol%) manufactured by Nippon Synthetic Chemical Industry Co., Ltd. is dissolved in 100 parts by weight of water, and N-methylolacrylamide It is obtained by adding 15 parts by weight, adding 1 part by weight of phosphoric acid as an acid catalyst, stirring and adjusting at 100 ° C. for 4 hours, removing water, and reacting with an acrylic compound having an N-methylol group. Further, modified partially saponified polyvinyl acetate A3 as component (A) was obtained.
- the easy-adhesion layer coating solution 1 was applied onto a 250 ⁇ m-thick “Lumirror” (registered trademark) T60 (polyester film, manufactured by Toray Industries, Inc.) with a bar coater so that the film thickness was 40 ⁇ m after drying. After removing the solvent by heating in an oven at °C for 3 minutes, the easy-adhesion layer coating solution 2 is applied thereon with a bar coater to a dry film thickness of 30 ⁇ m, and heated in an oven at 160 °C for 3 minutes And the board
- the easy-adhesion coating solution 3 obtained as described above was applied on a chrome-plated steel plate (thickness 250 ⁇ m) with a roll coater so that the film thickness after drying was 10 ⁇ m, and then placed in an oven at 250 ° C. After removing the solvent by putting in for 1 minute, after applying the coating liquid 4 for easy adhesion layer on the roll coater so that the film pressure after drying becomes 5 ⁇ m, it is put in an oven at 160 ° C. for 1 minute. It was set as the board
- “GOHSENOL” KL-05 polyvinyl alcohol having a saponification degree of 78 to 82 mol%, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.
- “GOHSENOL” AL-06 polyvinyl alcohol having a saponification degree of 91 to 94 mol%, manufactured by Nippon Synthetic Chemical Industry Co., Ltd. 11 parts by weight 55 parts by weight of water, 14 parts by weight of methanol, 10 parts by weight of n-propanol and n -Dissolved in 10 parts by weight of butanol to obtain a coating solution for the peeling assist layer (K).
- the coating film for the peeling auxiliary layer (K) is 0.25 ⁇ m in dry thickness with a bar coater on 100 ⁇ m thick “Lumirror” S10 (polyester film, manufactured by Toray Industries, Inc.) whose surface is not roughened. And dried at 100 ° C. for 25 seconds to obtain a laminate of the peeling assist layer (K) / cover film (H).
- a coating solution for the thermal mask layer (I) was applied to the peeling auxiliary layer (K) side of the laminate thus obtained with a bar coater so as to have a dry film thickness of 2 ⁇ m, and at 140 ° C. for 30 seconds.
- the whole surface exposure (exposure amount: 2400 mJ / cm 2 ) was performed again in the atmosphere with a chemical lamp to produce a resin sheet. Thereafter, using an SD-type lever type sample cutter (manufactured by Dumbbell Co., Ltd.), the sheet was cut into a shape having a parallel part width of 10 mm and a parallel part length of 20 mm, and a breaking point elongation measurement sheet was prepared.
- the halftone and independent points of the obtained printing plate were evaluated by the following method.
- Halftone dots A 150% 4% halftone dot formed in an area of 1 cm ⁇ 1 cm is observed using a magnifying glass with a magnification of 20 ⁇ , and whether or not the halftone dot is reproduced at the position where the negative is closely attached is indicated by the following score. Judgment was made based on criteria, and a score of 4 or more was considered acceptable. 5: No chipping 4: Chipping is seen in the halftone dots in the outermost peripheral area 3: Chipping is seen in the outermost peripheral area and the second row area from the outermost circumference 2: Internal area including the third row from the outermost circumference Chipping is observed 1: Chipping is observed in an area of 20% or more of the entire halftone dot area.
- composition solution 1 for photosensitive resin composition 1 ⁇ Preparation of composition solution 1 for photosensitive resin composition 1>
- components (A) and (B) shown in 1 of Table 2 were added, and “Solmix” (registered trademark) H-11 (alcohol mixture, A mixed solvent of 50 parts by weight of Nippon Alcohol Co., Ltd. and 50 parts by weight of water was mixed and then heated at 90 ° C. for 2 hours with stirring to dissolve the components (A) and (B). After cooling to 70 ° C., other components were added and stirred for 30 minutes to obtain a composition solution 1 for the photosensitive resin composition 1.
- Solmix registered trademark
- a composition solution 1 for the photosensitive resin composition 1 was cast on a polyester film, dried at 60 ° C. for 2 hours, and the film was peeled off to obtain a photosensitive resin sheet 1 having a thickness of 650 ⁇ m.
- the film thickness of the photosensitive resin sheet 1 was determined by placing a spacer having a predetermined thickness on the substrate and scraping out the protruding portion of the composition solution 1 with a horizontal metal scale.
- Examples 2, 4 to 9, Comparative Examples 1 to 5 A photosensitive resin sheet and a photosensitive resin printing plate precursor were prepared in the same manner as in Example 1 except that the composition of the photosensitive resin composition was changed as shown in Tables 2 and 3. The evaluation results are shown in Table 4 and Table 5.
- Example 3 (Example 3) ⁇ Manufacture of photosensitive resin sheet 3> A photosensitive resin sheet 3 was produced in the same manner as in Example 2.
- a photosensitive resin printing plate precursor 3 was produced in the same manner as in Example 2 except that the CTP plate cover film (H2) was used.
- Table 4 shows the results of evaluating the characteristics of the printing plate by the above method using the obtained photosensitive resin printing plate precursor of the CTP plate. The image reproducibility was evaluated according to the evaluation method for the CTP version.
- Example 11 Manufacture of photosensitive resin sheet 11> A photosensitive resin sheet 11 was produced in the same manner as in Example 2 except that the dye was added.
- a photosensitive resin printing plate precursor 11 was produced in the same manner as in Example 2 except that the dye was added.
- Table 4 shows the results of evaluating the characteristics of the printing plate by the above method using the obtained photosensitive resin printing plate precursor. The image reproducibility was evaluated according to the evaluation method for the analog version.
- Example 12 Manufacture of photosensitive resin sheet 12> A photosensitive resin sheet 12 was produced in the same manner as in Example 11.
- ⁇ Manufacture of photosensitive resin printing plate precursor 12> A photosensitive resin printing plate precursor 12 was produced in the same manner as in Example 11 except that the CTP plate cover film (H2) was used. Table 4 shows the results of evaluating the characteristics of the printing plate by the above method using the obtained photosensitive resin printing plate precursor of the CTP plate. The image reproducibility was evaluated according to the evaluation method for the CTP version. (Example 13) ⁇ Manufacture of photosensitive resin sheet 13> A photosensitive resin sheet 13 was produced in the same manner as in Example 11.
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Abstract
Description
反応性基を有する部分ケン化ポリ酢酸ビニル(A)に水現像性が必要なことから、構造(I)の単位は60~99モル%が好ましく、さらに好ましくは70~95モル%である。(I)の構造単位が60モル%未満であると水溶解性が低下し十分な水現像性を得ることができないことが多く、99モル%より大きいと常温水に対する溶解性が低下して十分な水現像性を得ることができないことが多い。また、(A)成分である変性部分ケン化ポリ酢酸ビニルの平均重合度は300~2000の範囲が好ましく、500~1000がより好ましい。平均重合度が300未満であると耐水性が低下し、十分な耐水性を得ることができない。平均重合度が2000を越えると水溶解性が著しく低下し、十分な水現像性が得られない。
光学濃度の測定には、入射光強度を一定にして透過光強度の測定値から算出する方法と、ある透過光強度に達するまでに必要な入射光強度の測定値から算出する方法が知られているが、本発明における光学濃度は前者の透過光強度から算出した値をいう。
ΔE*ab=[(ΔL*)2+(Δa*)2+(Δb*)2]1/2 (1)
色差(ΔE*ab)が5より大きい場合は、接着層つき基板の部分と、感光性樹脂層から形成されたレリーフ層を有する接着層つき基板の部分が容易に識別できる。一方、色差(ΔE*ab)が70より小さい場合は、レリーフの抜き文字部の識別が容易となる。
合成例1:
日本合成化学工業(株)製の部分ケン化ポリ酢酸ビニル“KL-05”(重合度約500、ケン化度80モル%)をアセトン中で膨潤させ、無水コハク酸1.0モル%を添加し、60℃で6時間撹拌して分子鎖にカルボキシル基を付加させた。このポリマーをアセトンで洗浄して未反応の無水コハク酸を除去乾燥した。酸価を測定したところ、10.0mgKOH/gであった。このポリマー100重量部をエタノール/水=30/70(重量比)の混合溶媒200重量部に80℃で溶解した。ここにグリシジルメタクリレートを6重量部添加して部分ケン化ポリ酢酸ビニル中に反応性基を導入した。電位差滴定法による分析結果からポリマー中のカルボキシル基がグリシジルメタクリレートのエポキシ基と反応しポリマー側鎖中にメタクロイル基が導入されたことを確認し、(A)成分である変性部分ケン化ポリ酢酸ビニルA1を得た。
酢酸ビニルにメタクリル酸を共重合単位として1モル%含有させたポリマーを、ケン化し、平均重合度650、ケン化度75モル%にしたアニオン変性ポリ酢酸ビニルを得た。このポリマー100重量部をエタノール/水=30/70(重量比)の混合溶媒200重量部に80℃で溶解した。ここにグリシジルメタクリレートを6重量部添加して部分ケン化ポリ酢酸ビニル中に反応性基を導入した。電位差滴定法による分析結果からポリマー中のカルボキシル基がグリシジルメタクリレートのエポキシ基と反応しポリマー側鎖中にメタクロイル基が導入されたことを確認し、(A)成分である変性部分ケン化ポリ酢酸ビニルA2を得た。
日本合成化学工業(株)製の部分ケン化ポリ酢酸ビニル“KL-05”(重合度約500、ケン化度80モル%)100重量部を100重量部の水に溶解し、N-メチロールアクリルアミド15重量部を添加し、酸触媒としてリン酸1重量部を加え、100℃4時間攪拌して調整し、次いで水分を除去して、N-メチロール基を有するアクリル系化合物との反応により得られた(A)成分である変性部分ケン化ポリ酢酸ビニルA3を得た。
合成例4:
ε-カプロラクタム10重量部、N-(2-アミノエチル)ピペラジンとアジピン酸のナイロン塩90重量部および水100重量部をステンレス製オートクレーブに入れ、内部の空気を窒素ガスで置換した後に180℃で1時間加熱し、ついで水分を除去して水溶性ポリアミド樹脂である塩基性窒素を有するポリアミドを得た。
重合可能なエチレン性二重結合を有する化合物としては、表1記載のものを使用した。
“バイロン”(登録商標)31SS(不飽和ポリエステル樹脂のトルエン溶液、東洋紡績(株)製)260重量部および“PS-8A”(ベンゾインエチルエーテル、和光純薬工業(株)製)2重量部の混合物を70℃で2時間加熱後30℃に冷却し、エチレングリコールジグリシジルエーテルジメタクリレート7重量部を加えて2時間混合した。さらに、“コロネート”(登録商標)3015E(多価イソシアネート樹脂の酢酸エチル溶液、日本ポリウレタン工業(株)製)25重量部および“EC-1368”(工業用接着剤、住友スリーエム(株)製)14重量部を添加して混合し、易接着層用塗工液1を得た。
有機溶剤可溶なポリエステル樹脂である“ニチゴーポリエスター”LP-035(日本合成化学(株)製、分子量約20000)100重量部をトルエン/メチルエチルケトン=80/20(重量比)の混合溶剤2000重量部を80℃に加温して溶解した。冷却後、多価イソシアネートとしてへキサメチレンジイソシアネート170重量部、エポキシ化合物として“エピコート”828(油化シエルエポキシ(株)製、分子量約380)60重量部、エポキシ硬化剤として“エポン”DMP-30(半井化学(株)製)50重量部、硬化触媒としてエチルメチルイミダゾール1重量部、ハレーション防止剤としてアゾ系黄色顔科である“イエロー”PR359(住化カラー(株)製)50重量部添加して十分に撹拌混合し、易接着層用塗工液3を得た。
表面粗さRaが0.1~0.6μmとなるように粗面化された厚さ100μmの“ルミラー”S10(ポリエステルフィルム、東レ(株)製)に、“ゴーセノール”AL-06(ケン化度91~94モル%の部分ケン化ポリビニルアルコール、日本合成化学工業(株)製)を乾燥膜厚が1μmとなるように塗布し、100℃で25秒間乾燥し、粘着防止層を塗布したアナログ版用のカバーフィルムH1を得た。
“ゴーセノール”KL-05(ケン化度78~82モル%のポリビニルアルコール、日本合成化学工業(株)製)10重量部を水40重量部、メタノール20重量部、n-プロパノール20重量部およびn-ブタノール10重量部に溶解させ、接着力調整層(J)用塗工液を得た。
各実施例および比較例における評価は、次の方法で行った。
10cm×10cmの感光性樹脂組成物からなる厚さ600μmのシート(感光性樹脂シート)をケミカル灯FL20SBL-360 20ワット(三菱電機オスラム(株)製)を備えた製版装置DX-A3(タカノ(株)製)で、大気下で、全面露光した(露光量:2400mJ/cm2)。次いで、製版装置のブラシを備えた現像糟で25℃の水道水により1.5分間現像を行い、その後、60℃で10分間乾燥した。再度ケミカル灯で、大気下で、全面露光(露光量:2400mJ/cm2)し、樹脂シートを作製した。その後、SD型レバー式試料裁断器(ダンベル(社)製)を用いて、平行部巾10mm、平行部長さ20mmを有する形状に断裁し、破断点伸度測定用シートを作製した。
(i)アナログ版の場合
10cm×10cmの感光性樹脂印刷版原版からカバーフィルム(H1)のポリエステルフィルムのみを剥離し(剥離後の感光性樹脂印刷版原版の最表面は乾燥膜厚1μmの部分ケン化ポリビニルアルコール層)、感度測定用グレースケールネガフィルムおよび画像再現性評価用ネガフィルム(150線4%網点、φ200独立点を有する)を真空密着させ、ケミカル灯FL20SBL-360 20ワット(三菱電機オスラム(株)製)でグレースケール感度16±1段となる条件で露光した(主露光)。その後、現像液として水を用いて、現像液温25℃のブラシ式現像装置により現像し、60℃で10分間乾燥した後、さらにケミカル灯FL20SBL-360 20ワット(三菱電機オスラム(株)製)で主露光と同条件で後露光し、画像再現性評価用印刷版を得た。
10cm×10cmの感光性樹脂印刷版原版からCTP版用カバーフィルム(H2)のポリエステルフィルムのみを剥離し(剥離後の感光性樹脂印刷版原版の最表面は剥離補助層(K))、赤外線に発光領域を有するファイバーレーザーを備えた外面ドラム型プレートセッター“CDI SPARK”(エスコ・グラフィックス(株)製)に、支持体側がドラムに接するように装着し、レーザー出力9kW、ドラム回転数700rpmの条件で、テストパターン(150線4%網点、幅50μmの細線、φ120μmの独立点、300μm幅の抜き線を有する)を描画し、感熱マスク層(I)から画像マスク(I―1)を形成した。その後、大気下においてケミカル灯FL20SBL-360 20ワット(三菱電機オスラム(株)製)で感熱マスク層側から露光した(主露光)。なお、主露光の時間は、同じ感光性樹脂層を有するアナログ版の場合に要した主露光の時間の2倍とした。その後、現像液として水を用いて、現像液温25℃のブラシ式現像装置により現像し、60℃で10分間乾燥した後、さらに主露光と同様の条件で後露光し、画像再現性評価用印刷版を得た。
5:欠けなし
4:最外周部エリアの網点に欠けが見られる
3:最外周部および最外周から2列目のエリアに欠けが見られる
2:最外周から3列目を含む内部のエリアに欠けが見られる
1:全網点エリアの20%以上の面積に欠けが見られる。
1cm×3cmのベタ部を有する印刷版5個を用いて、M-3印刷適性試験機(宮腰機械製作所(株)製)により300μmの押し込み量で5万回、10万回、15万回、20万回回転させた後、印刷版のレリーフ表面を10倍の光学顕微鏡で観察し、100μm以上のレリーフのクラックが発生した印刷版の個数を計数した。
(2)で作製した樹脂印刷版の、現像により前記感光性樹脂層の非露光部分が除去された基板部分と、露光された感光性樹脂層が現像後にレリーフ層として残った部分のL*a*b*表色系色座標を色彩色差計CR-321(ミノルタ(株)製)を用いて測定した。なお、支持体にプラスチックシートを用いた印刷版材の測定は、白色紙(L*:92.37, a*:0.19, b*:-0.34)上にサンプル置き、L*a*b*表色系色座標を測定した。なお、得られた色座標から式(1)を用いて色差(ΔE*ab)を算出した。
<感光性樹脂組成物1用の組成物溶液1の調整>
攪拌用ヘラおよび冷却管を取り付けた3つ口フラスコ中に、表2の1に示す(A)成分及び(B)成分を添加し、“ソルミックス”(登録商標)H-11(アルコール混合物、日本アルコール(株)製)50重量部および水50重量部の混合溶媒を混合した後、攪拌しながら90℃2時間加熱し、(A)成分および(B)成分を溶解させた。70℃に冷却した後、その他の成分を添加し、30分攪拌し、感光性樹脂組成物1用の組成物溶液1を得た。
ポリエステルフィルムに感光性樹脂組成物1用の組成物溶液1を流延させ、60℃で2時間乾燥し、フィルムを剥がして、650μmの感光性樹脂シート1を得た。感光性樹脂シート1の膜厚は、基板上に所定の厚みのスペーサーを置き、はみ出している部分の組成物溶液1を、水平な金尺で掻き出すことによって行った。
得られた感光性樹脂組成物溶液を、前記易接着層(G1)を有する支持体(E1)に流延し、60℃で2.5時間乾燥した。このとき乾燥後の版厚(ポリエステルフィルム+感光性樹脂層)が0.95mmとなるよう調節した。このようにして得られた感光性樹脂層上に、水/エタノール=50/50(重量比)の混合溶剤を塗布し、表面に前記アナログ版用のカバーフィルム(H1)を圧着し、感光性樹脂印刷版原版を得た。得られた感光性樹脂印刷版原版を用いて、前記方法により印刷版の特性を評価した結果を表4に示す。なお、画像再現性の評価はアナログ版の場合の評価方法に従って行った。
感光性樹脂組成物の組成を表2および表3のとおり変更した以外は実施例1と同様にして、感光性樹脂シートおよび感光性樹脂印刷版原版を作製した。評価結果を表4および表5に示す。
<感光性樹脂シート3の製造>
実施例2と同様に感光性樹脂シート3を作製した。
CTP版用のカバーフィルム(H2)を用いる以外は実施例2と同様にして感光性樹脂印刷版原版3を作製した。得られたCTP版の感光性樹脂印刷版原版を用いて、前記方法により印刷版の特性を評価した結果を表4に示す。なお、画像再現性の評価はCTP版の場合の評価方法に従って行った。
前記易接着層(G1)を有する支持体(E1)上に水/エタノール=50/50(重量比)の混合溶剤を塗布し、感光性樹脂シート2を圧着し、60℃で2.5時間乾燥した。このとき乾燥後の版厚(ポリエステルフィルム+感光性樹脂層)が0.95mmとなるよう調節した。このようにして得られた感光性樹脂層上に、水/エタノール=50/50(重量比)の混合溶剤を塗布し、表面に前記アナログ版用のカバーフィルム(H1)を圧着し、感光性樹脂印刷版原版を得た。得られた感光性樹脂印刷版原版を用いて、前記方法により印刷版の特性を評価した結果を表4に示す。なお、画像再現性の評価はアナログ版の場合の評価方法に従って行った。
<感光性樹脂シート11の製造>
染料を添加する以外は実施例2と同様に感光性樹脂シート11を作製した。
染料を添加する以外は実施例2と同様にして感光性樹脂印刷版原版11を作製した。得られた感光性樹脂印刷版原版を用いて、前記方法により印刷版の特性を評価した結果を表4に示す。なお、画像再現性の評価はアナログ版の場合の評価方法に従って行った。
<感光性樹脂シート12の製造>
実施例11と同様に感光性樹脂シート12を作製した。
CTP版用のカバーフィルム(H2)を用いる以外は実施例11と同様にして感光性樹脂印刷版原版12を作製した。得られたCTP版の感光性樹脂印刷版原版を用いて、前記方法により印刷版の特性を評価した結果を表4に示す。なお、画像再現性の評価はCTP版の場合の評価方法に従って行った。
(実施例13)
<感光性樹脂シート13の製造>
実施例11と同様に感光性樹脂シート13を作製した。
得られた感光性樹脂組成物溶液を、前記易接着層(G2)を有する支持体(E2)に流延し、60℃で2.5時間乾燥した。このとき乾燥後の版厚(ポリエステルフィルム+感光性樹脂層)が0.95mmとなるよう調節した。このようにして得られた感光性樹脂層上に、水/エタノール=50/50(重量比)の混合溶剤を塗布し、表面に前記アナログ版用のカバーフィルム(H1)を圧着し、感光性樹脂印刷版原版を得た。得られた感光性樹脂印刷版原版を用いて、前記方法により印刷版の特性を評価した結果を表4に示す。なお、画像再現性の評価はアナログ版の場合の評価方法に従って行った。
Claims (10)
- (A)反応性基を側鎖に有する変性部分ケン化ポリ酢酸ビニル、
(B)塩基性窒素を有するポリアミド、
(C)分子量が300以下であり、5~7員環を有し、かつ重合可能なエチレン性二重結合を有する化合物、および
(D)光重合開始剤、を含有することを特徴とする感光性樹脂組成物。 - 前記(C)分子量が300以下であり、5~7員環を有し、かつ重合可能なエチレン性二重結合を有する化合物の有する5~7員環が複素環であることを特徴とする請求項1記載の感光性樹脂組成物。
- 前記(C)分子量が300以下であり、5~7員環を有し、かつ重合可能なエチレン性二重結合を有する化合物が、水酸基、カルボキシル基、およびアミノ基から選ばれる官能基を有することを特徴とする請求項1記載の感光性樹脂組成物。
- 前記(A)反応性基を側鎖に有する変性部分ケン化ポリ酢酸ビニルが、部分ケン化ポリ酢酸ビニルと酸無水物とを反応させてカルボキシル基をポリマー側鎖に導入し、そのカルボキシル基に不飽和エポキシ化合物を反応させることにより反応性基を導入した変性部分ケン化ポリ酢酸ビニルである請求項1~3のいずれかに記載の感光性樹脂組成物。
- 前記(A)反応性基を側鎖に有する変性部分ケン化ポリ酢酸ビニルが、酢酸ビニルと不飽和カルボン酸またはその塩、あるいは不飽和カルボン酸エステルとの共重合物をケン化して得られるケン化度60~90モル%のアニオン変性ポリビニルアルコールに不飽和エポキシ化合物を付加させてなる変性部分ケン化ポリ酢酸ビニルである、請求項1~3のいずれかに記載の感光性樹脂組成物。
- 前記(A)反応性基を側鎖に有する変性部分ケン化ポリ酢酸ビニルが、部分ケン化ポリ酢酸ビニルと、N-メチロール基を有するアクリル系化合物との反応により得られた変性部分ケン化ポリ酢酸ビニルである請求項1~3のいずれかに記載の感光性樹脂組成物。
- 前記(B)塩基性窒素を有するポリアミドがピペラジン環をもつことを特徴とする請求項1~6のいずれかに記載の感光性樹脂組成物。
- さらに水溶性トリフェニルメタン系染料を含有することを特徴とする請求項1~7のいずれかに記載の感光性樹脂組成物。
- 支持体上に請求項1~7のいずれかに記載の感光性樹脂組成物を用いて形成した感光性樹脂層を有することを特徴とする感光性樹脂印刷版原版。
- 請求項1~8のいずれかに記載の感光性樹脂組成物より形成した感光性樹脂層を、紫外線を用いて部分的に露光し、水を主成分とする現像液を用いた現像により前記感光性樹脂層の非露光部分を除去してレリーフ層を形成することを特徴とする樹脂印刷版の製造方法。
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EP13825787.8A EP2881793B1 (en) | 2012-07-31 | 2013-07-30 | Photosensitive resin composition and photosensitive resin printing plate precursor |
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JP2013555107A JP5601425B2 (ja) | 2012-07-31 | 2013-07-30 | 感光性樹脂組成物および感光性樹脂印刷版原版 |
US14/418,710 US9678424B2 (en) | 2012-07-31 | 2013-07-30 | Photosensitive resin composition and photosensitive resin printing plate original |
KR1020157003896A KR102054033B1 (ko) | 2012-07-31 | 2013-07-30 | 감광성 수지 조성물 및 감광성 수지 인쇄판 원판 |
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WO2015122515A1 (ja) * | 2014-02-17 | 2015-08-20 | 東レ株式会社 | 樹脂積層体および凸版印刷版原版 |
WO2017038970A1 (ja) * | 2015-09-03 | 2017-03-09 | 東レ株式会社 | 感光性樹脂印刷版原版および印刷版の製造方法 |
JP6372599B1 (ja) * | 2017-08-07 | 2018-08-15 | 東洋紡株式会社 | 凸版印刷原版用感光性樹脂組成物及びそれを用いた凸版印刷原版 |
WO2019031406A1 (ja) | 2017-08-07 | 2019-02-14 | 東洋紡株式会社 | 凸版印刷原版用感光性樹脂組成物及びそれを用いた凸版印刷原版 |
WO2023277053A1 (ja) * | 2021-06-30 | 2023-01-05 | 富士フイルム株式会社 | フレキソ印刷版原版およびフレキソ印刷版の製造方法 |
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JP6798510B2 (ja) * | 2016-12-26 | 2020-12-09 | 東レ株式会社 | 感光性樹脂組成物、およびそれを含む感光性樹脂印刷版原版 |
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CN113453910B (zh) * | 2019-02-21 | 2022-09-30 | 东洋纺株式会社 | 能够水显影的感光性树脂印刷原版 |
CN111856876A (zh) * | 2019-04-25 | 2020-10-30 | 田菱智能科技(昆山)有限公司 | 一种感光性树脂组合物 |
NL2027002B1 (en) | 2020-11-27 | 2022-07-04 | Flint Group Germany Gmbh | Photosensitive composition |
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WO2019031406A1 (ja) | 2017-08-07 | 2019-02-14 | 東洋紡株式会社 | 凸版印刷原版用感光性樹脂組成物及びそれを用いた凸版印刷原版 |
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WO2023277053A1 (ja) * | 2021-06-30 | 2023-01-05 | 富士フイルム株式会社 | フレキソ印刷版原版およびフレキソ印刷版の製造方法 |
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CN104508555B (zh) | 2020-02-11 |
KR20150040928A (ko) | 2015-04-15 |
JP5601425B2 (ja) | 2014-10-08 |
CN104508555A (zh) | 2015-04-08 |
EP2881793A4 (en) | 2016-04-20 |
US9678424B2 (en) | 2017-06-13 |
US20150205201A1 (en) | 2015-07-23 |
JPWO2014021322A1 (ja) | 2016-07-21 |
EP2881793B1 (en) | 2017-03-15 |
EP2881793A1 (en) | 2015-06-10 |
KR102054033B1 (ko) | 2019-12-09 |
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