JP4736734B2 - Method for producing photosensitive resin printing plate precursor and method for producing resin relief printing plate using the same - Google Patents

Description

  The present invention relates to a photosensitive resin printing plate precursor and a method for producing a resin relief printing plate using the same. More specifically, a photosensitive resin printing plate precursor suitable for digital information transfer, which is developed with a liquid mainly composed of water and / or alcohol after being exposed in an image form, and a method for producing a resin relief printing plate using the same It is about.

  The use of a photosensitive resin composition as a printing plate material is generally performed, and has become mainstream in each field of resin relief printing, planographic printing, intaglio printing, and flexographic printing.

  In such a printing plate material, an original film is adhered to the photosensitive resin layer, and exposed to actinic rays through the original film, thereby forming a part that dissolves in the solvent and a part that does not dissolve in the photosensitive resin layer. A relief image is formed and used as a printing plate material.

  Such a printing plate material requires negative and positive original film, and therefore requires manufacturing time and cost. Furthermore, the development of the original image film requires chemical processing and also requires processing of the development waste liquid, which is disadvantageous in terms of environmental hygiene.

  Along with the advancement of computers, a so-called CTP (computer to plate) method has been proposed in which information processed on a computer is directly output onto a printing plate material to obtain a relief printing plate without requiring an original film production process. ing. In this CTP method, an image mask is formed on the photosensitive resin “in situ” from digital data, and then the entire surface is exposed from the image mask side with actinic rays, in many cases ultraviolet rays, so that the image mask is not covered. Only the part selectively cures the photosensitive resin layer. The advantages of this method are that the above-described original film production process is not required, the processing of the development waste liquid of the original film is unnecessary and preferable for environmental hygiene, and foreign matters are not mixed when the original film is brought into close contact. That is, a relief having a sharp structure can be obtained.

  Specifically, a method of forming an image mask film on a photosensitive recording component using an ink jet printer or an electrophotographic printer has been proposed (for example, see Patent Document 1). However, this method has a problem that a fine image cannot be formed.

  A method of forming an image mask film by irradiating a photosensitive flexographic recording material formed from a photosensitive elastomeric layer, an infrared-sensitive layer opaque to ultraviolet light, and a cover sheet with an infrared laser is proposed. (For example, refer to Patent Document 2). The upper part of the infrared-sensitive layer of the infrared irradiation part is fixed to the cover sheet, and the infrared-sensitive layer of the infrared laser irradiation part is selectively removed when the cover sheet is peeled off. However, in this method, there is a problem that damage such as scratches may occur in the cover sheet that also functions as a protective layer, resulting in incomplete information transfer. Further, the means of peeling and developing the infrared-sensitive layer easily peels off the infrared laser unirradiated portion, and is inappropriate for forming a fine image mask.

  Among letterpress plates, the CTP method is generally proposed in the field of flexographic plates that use an elastomeric binder such as butadiene rubber or styrene rubber as a resin and can be printed using water-based ink. On the other hand, a CTP method has been proposed in the field of resin letterpress capable of printing using oil-based ink using a soluble resin instead of an elastomer binder as a resin, but a photosensitivity comprising an infrared-sensitive layer and a soluble resin. There are problems that the polarity of the resin layer is likely to be similar, and the infrared-sensitive layer and the photosensitive resin layer are likely to be mixed with time, and there are few proposals for a CTP resin letterpress.

  When printing using a flexographic plate, the relief between which the image is transferred is flexible, so the printing pressure between the plate cylinder and the impression cylinder is set weak. The flexographic plate is suitable for printing on corrugated cardboard with a step or a film for soft packaging that cannot withstand a very strong printing pressure. On the other hand, in the resin relief printing, the printing pressure between the plate cylinder and the impression cylinder can be set strong. This is because the relief is hard, so that the relief does not lose its shape against a strong printing pressure and does not cause a decrease in print quality such as thickening of characters. By using a resin relief plate and increasing the printing pressure, the ink can be thickened to give strength to the printed matter, and printing can also be performed on metals that are relatively difficult to transfer ink to. .

  Photosensitive resin letterpress recording material formed from a photosensitive resin layer, an oxygen-permeable dividing layer, an infrared-sensitive layer that is opaque to ultraviolet light, and a protective layer is proposed as a photosensitive resin letterpress that uses the CTP method. (For example, see Patent Document 3). After the protective layer is peeled off, an image mask is formed from the infrared sensitive layer by irradiating an infrared laser, and after the entire surface is exposed to ultraviolet light, the uncured portion of the image mask and the photosensitive layer is removed with the same developer. The oxygen-permeable intermediate layer has a role of preventing mass transfer between the photosensitive resin layer and the infrared-sensitive layer and preventing the laser engraving removal of the photosensitive resin layer. The infrared-sensitive layer is a mixture of a water-soluble or water-dispersible binder and a substance that has a function of blocking ultraviolet light such as carbon black and absorbs infrared light. However, since the infrared-sensitive layer is directly laminated on the protective layer, when the protective layer is peeled off, a part of the infrared-sensitive layer adheres to the protective layer and peels off together, resulting in a problem that the infrared-sensitive layer is damaged. In addition, since the infrared-sensitive layer is fragile to trauma, it is necessary to pay attention to handling after the protective layer is peeled off.

  In addition, a method of forming an image mask by irradiating an infrared laser onto a photosensitive resin relief original plate formed of a photosensitive resin layer, a film layer and an infrared sensitive layer on a substrate has been proposed (for example, Patent Document 4). reference). In this proposal, after exposing the entire surface of the formed image mask with ultraviolet light, the image mask is peeled and removed together with the film layer, and developed with water to obtain a resin relief printing plate. The film of the film layer between the photosensitive resin layer and the infrared-sensitive layer is advantageous in that the material of the infrared-sensitive layer constituting the image mask is not mixed in the developer and the processing of the development waste liquid is easy. If the thickness is large, bending or scattering of the ultraviolet light is likely to occur correspondingly, and if an ultraviolet light source with low directivity is selected, there may be disadvantages such as an image becoming thick.

In addition, a photosensitive resin printing plate precursor in which a photosensitive resin layer and a water-insoluble heat-sensitive mask layer are laminated in this order on a substrate has been proposed (see, for example, Patent Document 5). An image mask is formed by imagewise irradiating the heat-sensitive mask layer with an infrared laser, exposed from the formed image mask side using ultraviolet light, and developed with a liquid containing water as a main component. Get. Furthermore, in order to prevent the heat-sensitive mask layer from being damaged, it is also proposed to laminate a protective layer and a peeling assist layer on the heat-sensitive mask layer. When the peeling auxiliary layer is laminated, the heat-sensitive mask layer is not peeled off when the protective layer is peeled off, and plays a role of protecting the heat-sensitive mask layer after the protective layer is peeled off. However, the peeling assist layer prevents the heat-sensitive mask layer from being ablated by the laser, and the heat-sensitive mask layer component remains in the laser-irradiated part, or the optical density difference between the laser-irradiated part and the non-irradiated part does not appear clearly. Problem arises. For this reason, adjustments such as increasing the laser output or extending the laser irradiation time are necessary, which may cause a decrease in workability.
German Patent No. 4117127 (first page) Japanese Patent No. 2773847 (pages 3-9) Japanese Patent No. 3429634 (pages 3-7) International Patent 01/18605 pamphlet (pages 2-3 and 17) JP 2004-163925 A

An object of the present invention, in view of the above problems, without damaging the heat-sensitive mask layer in handling and manufacturing method of forming easy photosensitive resin printing plate precursor of the image mask by laser irradiation, and using the same It is providing the manufacturing method of a resin relief printing plate.

In order to solve the above problems, a method for producing a photosensitive resin printing plate precursor mainly having the following configuration is provided.
That is, “(1) A step of obtaining a photosensitive resin sheet by laminating a photosensitive resin layer (A) on a substrate,
(2) A step of obtaining a thermal mask element by laminating a peeling auxiliary layer (D) having a thickness of 0.3 μm or less and a thermal mask layer (C) on the protective layer (E),
(3) A method for producing a photosensitive resin printing plate precursor comprising a step of laminating a photosensitive resin sheet and a thermal mask element so that the thermal mask layer (C) is in contact with the surface of the photosensitive resin layer (A). A method for producing a photosensitive resin printing plate precursor, comprising controlling the film thickness of the peeling auxiliary layer (D) by using the absorbance of the peeling auxiliary layer (D) with respect to visible light and / or ultraviolet light. Is.

Furthermore, the manufacturing method of the resin relief printing plate mainly having the following structures is provided. That is, "(1) Using the photosensitive resin printing plate precursor according to any one of claims 1 to 4,
(2) peeling off the protective layer (E),
(3) An image mask (C ′) is formed by imagewise irradiation of the thermal mask layer (C) with an infrared laser,
(4) Exposure is performed using ultraviolet light from the formed image mask (C ′) side, and a negative latent image is formed on the photosensitive resin layer (A) with respect to the image mask (C ′).
(5) Resin letterpress printing characterized in that the image mask (C ′) and the photosensitive resin layer (A) in the ultraviolet light unexposed area are removed by developing with a liquid mainly composed of water and / or alcohol. Plate manufacturing method. Is.

  According to the present invention, a photosensitive resin printing plate precursor capable of forming a convex relief image without requiring an original image film can be easily provided. By making the film thickness of the auxiliary peeling layer (D) constituting the photosensitive resin printing plate precursor in the present invention 0.3 μm or less, it is easy to form an image mask by infrared laser irradiation. The photosensitive resin printing plate precursor of the present invention can be applied not only to a resin relief plate that is a printing plate having a convex relief, but also to a flexographic plate, an intaglio plate, a lithographic plate, and a stencil if a photosensitive resin is used. However, the application range is not limited to these.

  Embodiments of the present invention will be described below.

  The photosensitive resin printing plate precursor in the present invention has a photosensitive resin layer (A), a thermal mask layer (C), a peeling auxiliary layer (D), and a protective layer (E) in this order on a support.

  The photosensitive resin layer (A) in the present invention contains a resin that can be dissolved or dispersed in water or alcohol and a monomer that can be cured by ultraviolet light. The layer (A) is photocured by irradiation with ultraviolet light, preferably 300 to 400 nm. As a raw material of the photosensitive resin layer (A), a photosensitive resin composition is used, and it is preferably formed into a sheet having a thickness of 0.1 to 10 mm.

  The above-described photosensitive resin composition contains a resin that can be dissolved or dispersed in water or alcohol and a monomer that can be cured by ultraviolet light. Furthermore, a photopolymerization initiator is preferably contained.

  The resin that can be dissolved or dispersed in water or alcohol in the present invention has a function as a carrier resin for maintaining the form of the photosensitive resin composition in a solid state, and the water in the photosensitive resin layer (A) or Used to impart developability with alcohol. Examples of such resins include polyvinyl alcohol, polyvinyl acetate, partially saponified polyvinyl acetate (partially saponified polyvinyl alcohol), cellulose resin, acrylic resin, polyamide resin, polyamide resin into which a hydrophilic group such as polyethylene oxide is introduced, ethylene / Vinyl acetate copolymer and the like, and modified products of these resins. Of these, polyvinyl alcohol, partially saponified polyvinyl alcohol, polyamide resin having a hydrophilic group introduced therein, and modified products of these resins are preferably used.

  Monomers curable by ultraviolet light are generally substances that can be cross-linked by radical polymerization. Although it will not specifically limit if it is a substance which can be bridge | crosslinked by radical polymerization, For example, the following can be mentioned. 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, β-hydroxy-β ′-(meth) (Meth) acrylate having a hydroxyl group such as acryloyloxyethyl phthalate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isoamyl (meth) acrylate, 2-ethylhexyl (meth) Alkyl (meth) acrylates such as acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate, chloroethyl (meth) acrylate Rate, halogenated alkyl (meth) acrylates such as chloropropyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, alkoxyalkyl (meth) acrylate such as butoxyethyl (meth) acrylate, phenoxyethyl acrylate , Alkoxyalkylene glycol (meth) acrylates such as phenoxyalkyl (meth) acrylates such as nonylphenoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate , (Meth) acrylamide, diacetone (meth) acrylamide, N, N'-methylenebis (meth) acrylamide (Meth) acrylamides, 2,2-dimethylaminoethyl (meth) acrylate, 2,2-diethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl ( Compounds having only one ethylenically unsaturated bond such as (meth) acrylamide, polyethylene glycol di (meth) acrylate such as diethylene glycol di (meth) acrylate, polypropylene glycol di such as dipropylene glycol di (meth) acrylate (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, glycerol tri (meth) acrylate, ethyl Unsaturation such as polyvalent (meth) acrylate and glycidyl (meth) acrylate obtained by addition reaction of ethylenic unsaturated bonds such as unsaturated carboxylic acids and unsaturated alcohols and active hydrogen to diglycol diglycidyl ether Multivalent (meth) acrylamides such as polyvalent (meth) acrylates and methylenebis (meth) acrylamides obtained by addition reaction of epoxy compounds and compounds having active hydrogen such as carboxylic acids and amines, and polyvalent vinyls such as divinylbenzene And compounds having two or more ethylenically unsaturated bonds, such as compounds.

  The photopolymerization initiator preferably used in the present invention is not particularly limited as long as it can polymerize a polymerizable carbon-carbon unsaturated group by light. Among these, those having a function of generating radicals by self-cleavage or hydrogen abstraction are preferably used. For example, benzoin alkyl ethers, benzophenones, anthraquinones, benzyls, acetophenones, diacetyls and the like.

  In the photosensitive resin composition, other components such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, glycerin, trimethylolpropane, and trimethylolethane are used for the purpose of increasing compatibility and flexibility. Alcohols can be contained, and conventionally known polymerization inhibitors can also be contained in order to increase the thermal stability. Preferable polymerization inhibitors include phenols, hydroquinones, catechols and the like. Moreover, dye, a pigment, surfactant, a ultraviolet absorber, a fragrance | flavor, antioxidant, etc. can also be contained.

  The method for obtaining the photosensitive resin layer (A) from the photosensitive resin composition is not particularly limited. For example, after dissolving a resin that can be dissolved or dispersed in water or alcohol in a solvent, a monomer that can be cured by ultraviolet light, After adding a photopolymerization initiator and other additives as necessary and stirring sufficiently to obtain a photosensitive resin composition solution, after removing the solvent from this solution, preferably on the support coated with an adhesive It can be obtained by melt extrusion. Alternatively, a solution in which a part of the solvent remains can be obtained by melt-extrusion on a support on which an adhesive has been applied, and the part of the solvent remaining in the solvent can be naturally dried over time.

  The material used for the support in the present invention is not particularly limited, but a dimensionally stable material is preferably used. For example, a metal sheet such as steel, stainless steel, and aluminum, a plastic sheet such as polyester, and a synthetic rubber such as styrene-butadiene rubber. Sheet.

  The heat-sensitive mask layer (C) in the present invention (1) efficiently absorbs an infrared laser, and a part or all of the layer is instantaneously evaporated or ablated by the heat, and the irradiated portion of the laser and the unirradiated portion are not. A difference occurs in the optical density of the irradiated portion, that is, the optical density of the irradiated portion is lowered, and (2) the function of blocking ultraviolet light practically.

  The thermal mask layer (C) contains an infrared absorbing material having a function of absorbing an infrared laser and converting it into heat. Furthermore, it is preferable to contain a thermally decomposable compound having a function of evaporating and ablating by heat and an ultraviolet absorbing material having a function of blocking ultraviolet light.

Here, having the function of blocking ultraviolet light means that the optical density of the thermal mask layer (C) is 2.0 or more, and more preferably 3.0 or more. The optical density is generally represented by D and is defined by the following equation.
D = log ₁₀ (100 / T) = log ₁₀ (I ₀ / I)
(Here, T is transmittance (unit:%), I ₀ is incident light intensity at the time of measuring transmittance, and I is transmitted light intensity).

  For optical density measurement, there are known methods of calculating from the measured value of transmitted light intensity with a constant incident light intensity and calculating from the measured value of incident light intensity required to reach a certain transmitted light intensity. However, 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 Kollmorgen Instruments Corp.) using an orthochromatic filter.

  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. For example, black pigments such as carbon black, aniline black, cyanine black, phthalocyanine, naphthalocyanine green pigment, rhodamine dye, naphthoquinone dye, polymethine dye, diimonium salt, azoimonium dye, chalcogen dye, carbon graphite, diamine Metal complexes, dithiol metal complexes, phenolthiol metal complexes, mercaptophenol metal complexes, arylaluminum metal salts, crystal water-containing inorganic compounds, copper sulfate, chromium sulfide, silicate compounds, titanium oxide, vanadium oxide, oxidation Examples thereof include metal oxides such as manganese, iron oxide, cobalt oxide, and tungsten oxide, hydroxides and sulfates of these metals, and metal powders of bismuth, tin, tellurium, iron, and aluminum.

  Among these, carbon black is particularly preferable from the viewpoints of the photothermal conversion rate, economy, handleability, and the ultraviolet absorbing function described later. Carbon black is classified into furnace black, channel black, thermal black, acetylene black, lamp black, etc. according to its manufacturing method, but various types of furnace black are commercially available in terms of particle size and other aspects. In view of its low cost, it is preferably used.

  The content of the infrared absorbing material is preferably 2 to 75% by weight, more preferably 5 to 70% by weight, based on the total composition of the thermal mask layer (C). If it is 2% by weight or more, photothermal conversion is efficiently performed, and if it is 75% by weight or less, other components are insufficient, and the problem that the thermal mask layer (C) is easily damaged does not occur.

  Examples of the thermally decomposable compound preferably used for the layer (C) include nitro compounds such as ammonium nitrate, potassium nitrate, sodium nitrate and nitrocellulose, organic peroxides, polyvinylpyrrolidone, azo compounds, diazo compounds or hydrazine derivatives, and The metals or metal oxides listed in the section of the infrared absorbing substance can be mentioned. From the viewpoint of the coating property of the solution, a polymer compound such as polyvinyl pyrrolidone or nitrocellulose is preferable.

  When nitrocellulose is used, the viscosity of nitrocellulose is preferably 1/16 second to 1 second, and more preferably 1/8 second to 1/2 second, according to the measurement method specified in ASTM D301-72. Here, the viscosity corresponds to the degree of polymerization of nitrocellulose, and a low viscosity means that the degree of polymerization is low. If the viscosity is 1/16 second or more, the degree of polymerization of nitrocellulose is sufficiently high so that the surface of the heat-sensitive mask layer (C) is not easily scratched. Does not occur.

  Nitrocellulose tends to generate harmful NOx gas when thermally decomposed. When the thermal mask layer (C) contains nitrocellulose, the plate setter that performs mask drawing with an infrared laser needs to be directly connected to a gas collection facility that sucks generated NOx and a facility that decomposes NOx into harmless compounds. There is a problem that the platesetter is large and expensive.

  This problem can be solved by using a thermally decomposable compound that does not contain a NOx generation source such as a nitro group.

  Acrylic resin is comparatively easily pyrolyzed and does not contain any nitrogen atoms and has no fear of generating NOx. Therefore, it is particularly preferably used as a thermally decomposable compound that changes to nitrocellulose. The thermal decomposition temperature of a general acrylic resin is 190 ° C to 250 ° C. When the main purpose is to suppress the generation of NOx, it is preferable that substantially no nitrocellulose is contained. The phrase “substantially containing no nitrocellulose” means that it is 2% by weight or less based on the total composition of the heat-sensitive mask layer (C). This is because if the content of nitrocellulose is 2% by weight or less, the amount of NOx generated can be suppressed to a level that is not problematic in terms of environmental hygiene.

  The acrylic resin refers to a polymer or copolymer of one or more monomers selected from the group consisting of acrylic acid, methacrylic acid, acrylic acid ester, and methacrylic acid ester. Among the acrylic resins, by selecting a grade that does not dissolve in water or alcohol, mass transfer to the lower photosensitive resin layer (A) can be suppressed. Therefore, a water / alcohol insoluble acrylic resin is more preferable. Used.

  The content of the thermally decomposable compound is preferably 80% by weight or less, and more preferably 15 to 60% by weight with respect to the total composition of the thermal mask layer (C). If content is 80 weight% or less, the problem that decomposition | disassembly of a thermally decomposable compound cannot succeed with the fall of the amount of photothermal conversion substances mentioned later does not generate | occur | produce.

  Although the ultraviolet-absorbing substance preferably used for the layer (C) is not particularly limited, it is preferably a compound having absorption in a region of 300 nm to 400 nm. Examples thereof include benzotriazole compounds, triazine compounds, benzophenone compounds, carbon black, and metals or metal oxides enumerated in infrared absorbing materials. Among these, carbon black is particularly preferably used because it has absorption characteristics not only in the ultraviolet light region but also in the infrared light region and functions as a photothermal conversion substance.

  The content of the ultraviolet absorbing material is preferably 0.1% by weight to 75% by weight and more preferably 1% by weight to 50% by weight with respect to the total composition of the heat sensitive mask layer (C). If the content is 0.1% by weight or more, the required optical density can be obtained, and if it is 75% by weight or less, the other components are insufficient and the thermal mask layer (C) is not easily damaged. .

  The heat-sensitive mask layer (C) is laminated directly on the photosensitive resin layer (A) or via the adhesion adjusting layer (B). The photosensitive resin layer (A) has a so-called hydrophilic composition containing a resin that can be dissolved or dispersed in water or alcohol. Since the adhesion adjusting layer (B) described later also contains partially saponified polyvinyl acetate having a saponification degree of 60 mol% or more, that is, a hydrophilic composition, each of the heat-sensitive mask layers (C) has a hydrophilic composition. There is a case where mass transfer occurs between the layers and the functions unique to each layer are lowered. For example, if the monomer or the like of the photosensitive resin layer (A) moves to the thermal mask layer (C), the laser ablation property of the thermal mask layer (C) is impaired, and in the photosensitive resin layer (A). When an ultraviolet absorbing material is mixed, curing by ultraviolet light is inhibited.

  Therefore, the heat-sensitive mask layer (C) used in the present invention is preferably water-insoluble. That is, it is preferable that the layer alone has a property that water development is impossible. When a metal or metal oxide is used, it is insoluble in water, but when an organic substance such as carbon black is used, it is necessary to take measures. The method for imparting water insolubility is not particularly limited. For example, it can be achieved by a method in which the entire composition of the heat-sensitive mask layer (C) is composed of a water-insoluble component, or a method in which a layer is crosslinked using a curable resin as a binder. The latter method is preferable because an effect of making the inter-layer mass transfer less likely to occur by polymerizing the composition component and an effect of imparting scratch resistance to the surface of the thermal mask layer (C) are obtained. Specifically, with a dyeing fastness test friction tester type II described in JIS standard L0849, a load of 500 g (of which the weight of the friction element is 200 g and the additional weight is 300 g) is applied to a white cotton cloth wetted with water. In the test method for rubbing the surface of the heat-sensitive mask layer (C), it is preferable that no penetrating scratches are obtained even after 5 reciprocating rubbings, and it is more preferable that no penetrating scratches are obtained after 10 reciprocating rubbing. .

  When a curable resin is used as a binder, the method for curing the resin is not particularly limited. However, since the thermal mask layer (C) has a function of absorbing ultraviolet light, photocuring is difficult or inefficient. Is preferred. Examples of the thermosetting resin used as the binder include at least one compound selected from the group consisting of polyfunctional isocyanates and polyfunctional epoxy compounds, urea resins, amine compounds, amide compounds, hydroxyl group-containing compounds, and carboxylic acids. The combination with the at least 1 sort (s) of compound chosen from the group which consists of a compound and a thiol type compound is mentioned.

  When a polyfunctional isocyanate compound is used, the reaction is not completed in a short time, so it is necessary to cure at a high temperature. However, when nitrocellulose is used as the thermally decomposable compound, the decomposition temperature is 180 ° C. There is a restriction that curing cannot be performed at the above temperature. Therefore, as a crosslinking method, a combination of a polyfunctional epoxy compound and at least one compound selected from the group consisting of a urea resin, an amine compound, an amide compound, a hydroxyl group-containing compound, a carboxylic acid compound, and a thiol compound is used. Are preferably used.

  Here, examples of the polyfunctional epoxy compound include bisphenol A type epoxy resin, bisphenol F type epoxy resin, and glycidyl ether type epoxy resin.

  Examples of urea resins include butylated urea resins, butylated melamine resins, butylated benzoguanamine resins, butylated urea melamine cocondensation resins, aminoalkyd resins, iso-butylated melamine resins, methylated meminine resins, hexamethoxymethylol. Examples include melamine, methylated benzoguanamine resin, butylated benzoguanamine resin and the like.

  Examples of the amine compound include diethylenetriamine, triethylenetriamine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, metaxylenediamine, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, and isophoronediamine. .

  Examples of amide compounds include polyamide curing agents and dicyandiamide used as epoxy resin curing agents. Examples of hydroxyl-containing compounds include phenol resins and polyhydric alcohols. Examples of thiol compounds include polyvalent thiols. Etc.

  As the carboxylic acid, phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dodecinyl succinic acid, pyromellitic acid, chlorenic acid, maleic acid, fumaric acid and anhydrides thereof are preferably used.

  Apart from the method of using a curable resin with a plurality of components, a single component or a curable resin may be used. Resins that are curable even when used alone include melamine resins, urethane resins, crosslinkable polyester resins, crosslinkable polyamide resins, and the like in addition to epoxy resins. These resins can also be used in combination.

  The content of these thermosetting resins is preferably 10% by weight to 75% by weight or less, and more preferably 30% by weight to 60% by weight with respect to the total composition of the thermosensitive mask layer (C). If it is 10% by weight or more, a crosslinked structure sufficient to impart water insolubility is obtained, and if it is 75% by weight or less, laser ablation of the thermal mask layer (C) is efficiently performed.

  Further, when a pigment such as carbon black is used as the infrared absorbing material, a plasticizer, a surfactant or a dispersion aid may be contained in order to facilitate the dispersion.

  The method for forming the thermal mask layer (C) is not particularly limited. However, when a metal oxide is used, the thermal mask layer composition is obtained, for example, by vapor deposition or sputtering, and when an organic substance such as carbon black is used. Can be obtained as such or by dissolving in an appropriate solvent, coating, and heat curing.

  The thickness of the heat-sensitive mask layer (C) obtained by coating is preferably 0.5 μm to 10 μm, and more preferably 1 μm to 3 μm. When the thickness is 0.5 μm or more, surface scratches are hardly generated and light leakage hardly occurs, a constant high optical density can be obtained, and a high coating technique is not required. Moreover, if it is 10 micrometers or less, since a high energy is not required for ablating the thermal mask layer (C), it is advantageous in terms of cost.

  The thermal mask layer (C) obtained by vapor deposition or sputtering of metal or metal oxide is preferably a thin film if a high optical density can be obtained. The thickness of the thin film greatly affects the sensitivity. That is, if the film thickness is too thick, extra energy is required to evaporate and melt the thin film, so that the ablation sensitivity of the thermal mask layer (C) is lowered. Therefore, the thickness of the thin film is preferably 100 nm or less, more preferably 2 to 100 nm, and particularly preferably 4 to 20 nm. Even if the film thickness is thinner than 2 nm, the sensitivity may decrease.

When using the vapor deposition method, vacuum vapor deposition is preferably used. Specifically, a method of forming a thin film on the surface of the substrate by heating and evaporating metal and carbon in a vacuum container of 10 ⁻⁴ to 10 ⁻⁷ mmHg, etc. Is used.

When the sputtering method is used, for example, a direct current or an alternating voltage is applied to a pair of electrodes in a vacuum container of 10 ⁻¹ to 10 ⁻³ mmHg to cause glow discharge, and in the case of a cathode or an alternating current, a ground electrode A thin film can be formed on a substrate using the sputtering phenomenon.

  As a thin film layer that provides the high optical density required in the present invention, a carbon thin film layer can be mentioned first. The carbon thin film here is not a so-called diamond thin film or graphite thin film but an amorphous carbon thin film. The amorphous carbon thin film can be selectively obtained by performing ordinary vacuum deposition such as ion beam deposition or ionization deposition or sputtering such as ion beam sputtering.

  As a carbon thin film formation method, it is preferable to carry out by any one of vacuum vapor deposition and sputtering.

As a vacuum deposition condition for forming a carbon thin film, for example, a method of forming a thin film on the surface of a substrate by heating and evaporating carbon in a 10 ⁻⁴ to 10 ⁻⁷ mmHg vacuum vessel is preferably used. Since carbon has a high melting point of 3923K, it is preferable to increase the heating temperature and deposition time of carbon for vapor deposition.

As sputtering conditions for forming a carbon thin film, a direct current or an alternating voltage is applied to a pair of electrodes in a vacuum vessel of 10 ⁻¹ to 10 ⁻³ mmHg to cause glow discharge, and the sputtering phenomenon of the cathode is used. A method of forming a thin film on a substrate is preferably used. In this method, a thin film can be formed relatively easily even with carbon having a high melting point.

  Examples of the thin film layer for providing the thermal mask layer (C) include a metal thin film layer in addition to the carbon thin film layer. Specific examples of the metal include the following, but are not limited thereto. Tellurium, tin, antimony, gallium, magnesium, polonium, selenium, thallium, zinc, aluminum, silicon, germanium, tin, copper, iron, molybdenum, nichrome, indium, iridium, manganese, lead, phosphorus, bismuth, nickel, titanium, Cobalt, rhodium, osnium, mercury, barium, palladium, bismuth and compounds such as those described in Japanese Patent Publication No. 41-14510, such as silicon carbide, boron nitride, boron phosphide, aluminum phosphide, antimony and aluminum Alloys, alloys of gallium and phosphorus, alloys of gallium and antimony, and the like. Preferably, tellurium, tin, antimony, gallium, magnesium, polonium, selenium, thallium, zinc, bismuth, and aluminum are used.

  As the metal preferably used for the layer (C), when the metallic luster increases, the reflection of the laser on the surface becomes large. Therefore, a metal having a small metallic luster is preferable as the metal from the viewpoint of sensitivity.

  As the metal used for the layer (C), any metal can be preferably used as long as a part or all of the metal evaporates or melts instantaneously and the melting point is 2000K or less. If the melting point is larger than 2000K, it takes time to evaporate or melt even when irradiated with a laser, and as a result, the ablation sensitivity of the layer (C) decreases. The melting point is more preferably 1000 K or less. Specifically, tellurium, tin, antimony, gallium, magnesium, polonium, selenium, thallium, zinc, bismuth, and aluminum are preferably used, more preferably tellurium (melting point: 449.8 ° C.), tin (melting point: 232 ° C.), Examples include zinc (melting point: 419.5 ° C.) and aluminum (melting point: 660.4 ° C.). These metals are particularly preferable because they easily evaporate or melt by heat when the thin film is irradiated with laser.

  As the metal preferably used for the layer (C), it can be said that it is particularly preferable to use two or more kinds of the above-mentioned metals because the melting point is more easily lowered and the sensitivity is improved. Specifically, tellurium and tin, tellurium and antimony, tellurium and gallium, tellurium and bismuth, tellurium and zinc alloys are preferred, and tellurium and zinc, tellurium and tin alloys are more preferred. The three types of alloys are preferably tellurium and tin and zinc, tellurium and gallium and zinc, tin and antimony and zinc, tin and bismuth and zinc, and more preferably tellurium and tin and zinc, tin and bismuth and zinc. Is an alloy.

  The method for forming such a metal thin film is not particularly limited, but it is preferably performed by any one of vacuum deposition and sputtering.

  A thin film layer containing carbon and metal can also be used as the thin film layer for providing the thermal mask layer (C). By simultaneously depositing or sputtering carbon and metal, there is an advantage that the optical density of the thin film is improved and it becomes easier to absorb the infrared laser. In this case, many metals can be used. The metal or alloy used at this time is not particularly limited as long as it can be deposited or sputtered, but a metal having a melting point of 2000K or less is preferable, and 1000K or less is more preferable. When the melting point is higher than 2000K, it is difficult to form an image even if carbon is vapor-deposited or sputtered at the same time.

  When metal and carbon are vapor-deposited or sputtered simultaneously, the carbon content in the formed thin film is preferably 10% by weight or more, and more preferably 30% by weight or more. If carbon is 10 weight% or more, the absorption factor of an infrared laser will increase and the effect of a sensitivity improvement will be acquired.

  When a resin that can be dissolved or dispersed in water or alcohol is contained, that is, when the hydrophilic photosensitive resin layer (A) and the water-insoluble heat-sensitive mask layer (C) are laminated so as to be in contact with each other, Insufficient adhesion may cause problems such as easy peeling of the layer (C) and scratches and wrinkles. By providing the adhesion adjusting layer (B) of the present invention between the layers (A) / (C), these problems can be avoided.

  The adhesive force adjusting layer (B) of the present invention preferably contains partially saponified polyvinyl acetate having a saponification degree of 60 mol% or more. More preferably, the degree of saponification is 70 mol% or more and 99 mol% or less. When the saponification degree is 60 mol% or more, the adhesive force between the layers (A) / (C) is sufficient, and the water developability is also good. The degree of polymerization is not particularly limited as long as it is a partially saponified polyvinyl acetate having a saponification degree of 60 mol% or more, and those modified with an acid or the like can also be used.

  In addition to partially saponified polyvinyl acetate having a saponification degree of 60 mol% or more, the adhesive strength adjusting layer (B) adjusts resins and monomers for adjusting appropriate adhesive strength, coating properties and stability. It is also optional to include additives such as surfactants and plasticizers. After the lamination, the adhesive force adjusting layer (B) may be diffused and moved to the photosensitive resin layer (A) to be assimilated with the layer (A).

  The content of partially saponified polyvinyl acetate having a saponification degree of 60 mol% or more is preferably 50% by weight or more, more preferably 60% by weight, based on the total composition of the adhesive strength adjusting layer (B). If it is 50% by weight or more, a uniform film can be formed and sufficient adhesive strength with the heat-sensitive mask layer (C) can be obtained.

  The method for forming the adhesive force adjusting layer (B) is not particularly limited, but for the convenience of forming a thin film, the adhesive force adjusting layer component is dissolved in a solvent and coated on the thermal mask layer (C), and then the solvent is added. A method of removing is preferably performed. For example, hot air drying, far-infrared drying, or natural drying is performed as a method for removing the solvent. By removing the solvent at a temperature of 160 ° C. or higher after the solvent is removed, adhesion between the layers (B) / (C) is performed. The force is preferred because it further increases, and more preferably 180 ° C. or higher.

  In addition, when the surface of the heat-sensitive mask layer (C) is subjected to corona discharge treatment, and the adhesive strength adjusting layer (B) is laminated so as to be in contact with the layer (C), the adhesive strength between the layers (B) / (C) is increased. Can be increased. In this case, high temperature drying is not necessarily required.

  The solvent used for coating the adhesion adjusting layer (B) is not particularly limited, but water, alcohol, or a mixture of water and alcohol is mainly used. When water or alcohol is used, it is preferable that the heat-sensitive mask layer (C) is water-insoluble because the layer (C) is not eroded even if coated on the layer (C).

  The film thickness of the adhesive force adjusting layer (B) is preferably 15 μm or less, more preferably 0.1 μm or more and 5 μm or less. If it is 15 μm or less, bending and scattering of light by the layer when exposed to ultraviolet light can be suppressed, and a sharp relief image can be obtained. Moreover, if it is 0.1 micrometer or more, formation of an adhesive force adjustment layer (B) will become easy.

  After laminating the adhesive force adjusting layer (B) on the heat sensitive mask layer (C) in this way, the photosensitive resin layer (A) is further laminated so as to be in contact with the layer (B), whereby the layer (A) / (B ) / (C) in order, a laminated body laminated with sufficient adhesive force is obtained.

  Here, sufficient adhesive force means the force required to peel the thermal mask layer (C) from the adhesive force adjustment layer (B) alone or the thermal mask layer (C) and the adhesive force adjustment layer (B). It means that the force required to peel from the photosensitive resin layer (A) is 20 mN / cm or more. If this adhesive force is 20 mN / cm or more, the heat-sensitive mask layer (C) is adjusted to the photosensitive resin layer (A) or the adhesive force when peeling only the protective layer (E) from the resulting photosensitive resin printing plate precursor. When the photosensitive resin printing plate precursor after peeling off the protective layer (E) is incurred, the thermal mask layer (C) is wrinkled or the thermal mask layer (C) The image mask (C ′) formed by imagewise irradiation with infrared rays does not cause problems such as being easily displaced on the photosensitive resin printing plate precursor by an external stimulus.

  This adhesive force is obtained by attaching a 1 cm wide cello tape (registered trademark) (manufactured by Nichiban Co., Ltd.) to the surface of the thermal mask layer (C) of the laminate, and peeling the thermal mask layer (C) from the laminate. Tensilon Universal Tensile Tester “UTM-4-100” is applied to the force necessary to peel the thermal mask layer (C) and the adhesive force adjusting layer (B) from the photosensitive resin layer (A). It can be measured by using (Toyo Baldwin Co., Ltd.).

  When the thermal mask layer (C) is laminated so as to be in direct contact with the protective layer (E), it is difficult to peel off the protective layer (E) during use due to excessive adhesion between the layers (C) / (E). , Peeling between layers (A) / (C) or between layers (B) / (C) may occur. These problems can be avoided by providing the peeling auxiliary layer (D) of the present invention between the thermal mask layer (C) and the protective layer (E). Furthermore, the installation of the peeling auxiliary layer (D) is a problem that when the protective layer (E) is peeled and removed, the thermal mask layer (C) remains or adheres to the protective layer (E) side entirely or partially, It is possible to avoid the problem that the heat-sensitive mask layer (C) after the protective layer (E) is peeled and removed is damaged by an external stimulus.

  The peeling assisting layer (D) of the present invention has a strong adhesive force with the thermal mask layer (C) and is weak enough to peel off the adhesive strength with the protective layer (E), or the thermal mask layer (C). It is preferable that the material is composed of a substance that is weak enough to be peelable and has a strong adhesive force to the protective layer (E). After peeling off the protective layer (E), the peeling auxiliary layer (D) may remain on the thermal mask layer side and become the outermost layer. Since it is exposed, it is preferably substantially transparent.

  Materials used for the peeling auxiliary layer (D) are polyvinyl alcohol, polyvinyl acetate, partially saponified polyvinyl alcohol, hydroxyalkyl cellulose, alkyl cellulose, polyamide resin, and the like, which can be dissolved or dispersed in water or alcohol, and are adhesive. It is preferable to use a resin having low properties as a main component. Among these, partially saponified polyvinyl alcohol having a saponification degree of 60 to 99 mol%, hydroxyalkyl cellulose having 1 to 5 carbon atoms in the alkyl group, and alkyl cellulose are particularly preferably used from the viewpoint of tackiness.

  The content of these resins is preferably 70% by weight or more, and more preferably 80% by weight or more with respect to the total composition of the peeling auxiliary layer (D). When the content is 70% by weight or more, a uniform film can be formed, and the heat-sensitive mask layer (C) / protective layer (E) can be peeled off without difficulty.

  The peeling auxiliary layer (D) may further contain an infrared absorbing substance and / or a thermally decomposable substance in order to facilitate removal by infrared rays. As the infrared absorbing material and the thermally decomposable material, those described above can be used. Moreover, you may contain surfactant for coating property and wettability improvement.

The film thickness of the peeling auxiliary layer (D) of the present invention needs to be 0.3 μm or less, and more preferably 0.01 μm or more and 0.25 μm or less. When the film thickness is 0.3 μm or less, the thermal mask layer (C) is prevented from being ablated by laser, and the thermal mask layer (C) component remains in the laser irradiated part, or is not irradiated with the laser irradiated part. Such a problem that the optical density difference of the portion does not appear clearly is avoided. Whether the heat-sensitive mask layer (C) component remains or not can be visually confirmed by checking the residue of the laser ablation portion, particularly the solid layer (C) component.

  The method for forming the peeling auxiliary layer (D) is not particularly limited, but for the convenience of forming a thin film, the solvent is removed after coating the protective auxiliary layer (E) with the peeling auxiliary layer component dissolved in the solvent. Is preferably performed. As the method for removing the solvent, for example, hot air drying, far-infrared drying, or natural drying is performed.

  In order to efficiently perform laser ablation of the thermal mask layer (C), the film thickness of the peeling assist layer (D) in the present invention needs to be 0.3 μm or less. It was difficult to accurately measure the thickness, and thus it was considered difficult to form a thin film layer stably. The inventors measure the thickness of the laminated layers by measuring the absorbance of the peeling assisting layer (D) with respect to visible light and / or ultraviolet light, and based on this, the coating amount of the forming material of the layer (D) is determined. It was found that such a thin film peeling auxiliary layer (D) can be stably formed by adjusting. That is, by measuring the relationship between the film thickness of the layer (D) and the absorbance with respect to visible light or ultraviolet light in an appropriate number and range, and preparing a calibration curve, film thickness measurement or film weight measurement using a micrometer can be performed. Even if it is a difficult thin film, the film thickness can be measured accurately and the film thickness of the peeling auxiliary layer (D) of the present invention can be controlled.

  In order to make the above-described film thickness control by absorbance more accurate, it is preferable that the peeling assisting layer (D) contains a substance having an ability to absorb light in the visible region or ultraviolet region.

  The substance having the ability to absorb light in the visible region or the ultraviolet region is not particularly limited. For example, known ultraviolet absorbers such as benzotriazoles, triazines, and benzophenones, and tris (4 -Dimethylaminophenyl) methane, 1,3-dimethyl-6-diethylaminofluorane, known dyes such as azo dyes, and the like.

  The protective layer (E) can be used for the purpose of protecting the heat-sensitive mask layer (C) from trauma. For the protective layer (E), a polymer film that can be easily peeled off from the heat-sensitive mask layer (C) is preferably used. Examples of such a protective layer (E) include films of polyester, polycarbonate, polyamide, fluoropolymer, polystyrene, polyethylene, polypropylene, and the like. Alternatively, release paper coated with silicone or the like can also be used as the layer (E).

  The thickness of the protective layer (E) is preferably 25 μm to 200 μm, more preferably 50 μm to 150 μm. If it is 25 μm or more, it is easy to handle, and the function of protecting the heat-sensitive mask layer (C) from external damage is expressed. If it is 200 μm or less, it is advantageous in that it is inexpensive and economical and easy to peel off. .

  When the protective layer (E) is peeled off from the photosensitive resin printing plate precursor at a speed of 200 mm / min, the peel force per 1 cm is preferably 4.5 to 200 mN / cm, and 9 to 150 mN / cm is preferable. Further preferred. If it is 4.5 mN / cm or more, it is preferable because the protective layer (E) can be worked without being peeled off during the work, and if it is 200 mN / cm or less, the protective layer (E) can be peeled reasonably. Therefore, it is preferable.

  Next, the preferable manufacturing method of the photosensitive resin printing plate precursor of this invention is described.

  The photosensitive resin printing plate precursor of the present invention comprises a photosensitive resin layer (A) on a substrate, an adhesion adjusting layer (B), a thermal mask layer (C), a peeling assist layer (D) and a protective layer as necessary. (E) is sequentially laminated. A thermal mask sheet in which the layer (D), the layer (C) and, if necessary, the layer (B) are laminated by a coating method on the protective layer (E), and the photosensitivity in which the layer (A) is laminated on the substrate. It can be obtained by laminating a resin sheet. The film thickness of the layer (D) is 0.3 μm or less, and the film thickness can be controlled by measuring the absorbance of the layer (D) with respect to visible light or ultraviolet light. The laminating method is not particularly limited. For example, a method in which the surface of the layer (A) is swollen with water and / or alcohol and a heat-sensitive mask sheet is bonded, a high-viscosity liquid having the same or similar composition as the layer (A) Are poured between a photosensitive resin sheet and a heat-sensitive mask sheet and bonded together, or a method of pressing with a press machine at room temperature or while heating. The protective layer (E) can be peeled off and reused.

  From the photosensitive resin printing plate precursor obtained as described above, a resin relief printing plate can be produced through the following steps.

  The method for producing a resin relief printing plate according to the present invention includes (1) using the photosensitive resin printing plate precursor described above, (2) peeling the protective layer (E) from the peeling auxiliary layer (D), and (3) red A step of forming an image mask (C ′) by irradiating the heat-sensitive mask layer (C) imagewise with an external laser, and (4) exposure using ultraviolet light from the formed image mask (C ′) side, A step of forming a latent image on the photosensitive resin layer (A), (5) a development treatment with a liquid containing water and / or alcohol as a main component, and an image mask (C ′) and a photosensitive resin layer in an ultraviolet light unexposed portion. A step of removing (A).

  (3) The step of forming an image mask (C ′) by imagewise irradiating the thermal mask layer (C) with an infrared laser is to turn on / off the infrared laser based on image data, This is a step of scanning irradiation with respect to C). When the thermal mask layer (C) is irradiated with an infrared laser, heat is generated by the action of the infrared absorbing material, and the thermal decomposable compound is decomposed by the action of the heat to remove the thermal mask layer (C). Laser ablation. The laser ablated portion has a greatly reduced optical density and is substantially transparent to ultraviolet light. An image mask (C ′) that can form a latent image on the photosensitive resin layer (A) is obtained by selectively laser ablating the thermal mask layer (C) based on the image data.

  For the infrared laser irradiation, one having an oscillation wavelength in the range of 750 nm to 3000 nm is used. Examples of such lasers include solid lasers such as ruby laser, alexandrite laser, perovskite laser, Nd-YAG laser and emerald glass laser, semiconductor lasers such as InGaAsP, InGaAs and GaAsAl, and dye lasers such as rhodamine dyes. Can be mentioned. A fiber laser that amplifies these light sources with a fiber can also be used. Among them, the semiconductor laser is preferable because it is downsized due to recent technological advances and is economically advantageous over other laser light sources. An Nd-YAG laser is also preferable because it has a high output, is widely used for dentistry and medical purposes, and is economically inexpensive.

  (4) The step of exposing from the image mask (C ′) side using ultraviolet light to form a latent image on the photosensitive resin layer (A) is a photosensitive resin printing plate precursor irradiated with laser by the above method. In addition, ultraviolet light, preferably ultraviolet light having a wavelength of 300 to 400 nm, is exposed on the entire surface through an image mask (C ′) on which an image is formed by a laser, and the lower part of the laser ablation part in the image mask (C ′) This is a step of selectively photocuring the photosensitive resin layer (A).

  Since ultraviolet light also enters from the side surface of the photosensitive resin printing plate precursor during exposure, it is preferable to cover the side surface with a cover that does not transmit ultraviolet light. As a light source capable of exposing 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 can be used. The portion of the photosensitive resin layer (A) exposed with ultraviolet light is changed into a substance that cannot be eluted and dispersed by the developer.

  (5) The step of developing with a liquid containing water and / or alcohol as a main component to remove the image mask (C ′) and the photosensitive resin layer (A) in the ultraviolet light unexposed area is, for example, a photosensitive resin. This is achieved by developing the layer (A) using a brush-type washing machine or a spray-type washing machine having a developer mainly composed of water and / or alcohol which can be dissolved and dispersed. Through this step, a portion exposed to ultraviolet light remains, and a resin relief printing plate having a relief image is obtained.

  When the peeling auxiliary layer (D) remains, it is preferably removed in the developing step (5).

  Here, the main component means 50% by weight or more. Tap water and distilled water are preferably used as the water, but are not limited thereto, and the alcohol is preferably an alcohol having 1 to 6 carbon atoms, but is not limited thereto. In addition, these liquids are mixed with the components of the photosensitive resin layer (A), the adhesion adjusting layer (B), the thermal mask layer (C) and the peeling assist layer (D), and additives such as surfactants. The thing containing can also be used. From the viewpoint of environmental hygiene, the alcohol is more preferably an alcohol having 2 to 3 carbon atoms.

  The image mask (C ′) is preferably water-insoluble for the purpose of improving scratch resistance. In this case, the image mask (C ′) is not dissolved in a developer composed of water or alcohol. However, since the image mask (C ′) is thin, it can be physically removed by rubbing with a brush. Among them, a strong brush, for example, a brush made of PBT (polybutylene terephthalate) or a brush made of nylon 6,10 is more preferable because physical removal is easy. At this time, the image mask (C ′) can be efficiently removed by using a relatively high temperature developer of 30 ° C. to 70 ° C.

  Thereafter, if necessary, a treatment for drying the developer adhering to the plate surface, post-exposure of the photosensitive resin printing plate material, an adhesive removal treatment, and the like can be performed.

  The resin relief printing plate produced by the production method of the present invention is preferably used as a resin relief printing plate that can be mounted on a printing machine.

  Hereinafter, the present invention will be described in detail with reference to examples.

<Synthesis of water-soluble polyamide resin 1>
ε-Caprolactam 10 parts by weight, N- (2-aminoethyl) piperazine and 90 parts by weight of adipic acid nylon salt and 100 parts by weight of water were placed in a stainless steel autoclave, and the air inside was replaced with nitrogen gas at 180 ° C. The mixture was heated for 1 hour, and then water was removed to obtain a water-soluble polyamide resin 1.

<Synthesis of modified polyvinyl alcohol 1>
In a flask equipped with a cooling tube, partially saponified polyvinyl alcohol “GOHSENOL” KL-05 (degree of saponification 78.5% -82.0%, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 50 parts by weight, succinic anhydride 2% And 10 parts by weight of acetone were added and heated at 60 ° C. for 6 hours, and then the cooling tube was removed to volatilize acetone. Thereafter, the purification step of eluting unreacted succinic anhydride with 100 parts by weight of acetone was carried out twice, followed by drying under reduced pressure at 60 ° C. for 5 hours to obtain modified polyvinyl alcohol 1 in which succinic acid was ester-bonded to a hydroxyl group. Obtained.

<Preparation of coating liquid composition 1 for photosensitive resin layer (A1)>
In a three-necked flask equipped with a stirring spatula and a condenser tube, 7.5 parts by weight of water-soluble polyamide resin 1, 47.5 parts by weight of modified polyvinyl alcohol 1, 11 parts by weight of diethylene glycol, 38 parts by weight of water and ethanol 44 Part by weight was added, and the polymer was dissolved by stirring at 110 ° C. for 30 minutes and then at 70 ° C. for 90 minutes. Subsequently, 3 parts by weight of “Blemmer” G (glycidyl methacrylate, manufactured by Nippon Oil & Fats Co., Ltd.) was added and stirred at 70 ° C. for 30 minutes. Furthermore, 12 parts by weight of “Blenmer” GMR (methacrylic acid adduct of glycidyl methacrylate, manufactured by NOF Corporation), 5 parts by weight of “light ester” G201P (acrylic acid adduct of glycidyl methacrylate, manufactured by Kyoeisha Chemical Co., Ltd.), "Epoxy ester" 70PA (acrylic acid adduct of propylene glycol diglycidyl ether, manufactured by Kyoeisha Chemical Co., Ltd.), 6 parts by weight, "NK ester" A-200 (diacrylate of polyethylene glycol having an average molecular weight of 200, Shin-Nakamura Chemical Co., Ltd.) 5 parts by weight, “Irgacure” 651 (benzyldimethyl ketal, manufactured by Ciba-Geigy) 0.1 parts by weight, “Irgacure” 184 (α-hydroxyketone, manufactured by Ciba-Geigy) 1.5 parts by weight, “Suminol Fast Cyanine Green G conc.” Dex CI Acid Green 25, manufactured by Sumitomo Chemical Co., Ltd.) 0.01 parts by weight, “Direct Sky Blue 6B” (produced by Hamamoto Dye) 0.01 parts by weight, “Formaster” (antifoaming agent, San Nopco) (Manufactured by Co., Ltd.) 0.05 parts by weight, “Tinubin” 327 (UV absorber, manufactured by Ciba-Geigy Co., Ltd.) 0.015 parts by weight, “TTP-44” (bis- {2- (2-ethoxyethoxy) 0.2 parts by weight of carbonyl) ethylthio} octylthiophosphine (manufactured by Sakai Chemical Co., Ltd.) and 0.005 parts by weight of “Q-1300” (ammonium N-nitrosophenylhydroxylamine, manufactured by Wako Pure Chemical Industries, Ltd.) And it stirred for 30 minutes and obtained the coating liquid composition 1 of the photosensitive resin layer (A1) with fluidity | liquidity.

<Preparation of adhesive coated substrate 1>
A mixture of 260 parts by weight of “Byron 31SS” (toluene solution of unsaturated polyester resin, manufactured by Toyobo Co., Ltd.) and 2 parts by weight of “PS-8A” (benzoin ethyl ether, manufactured by Wako Pure Chemical Industries, Ltd.) The mixture was heated at 30 ° C. for 2 hours and then cooled to 30 ° C., and 7 parts by weight of ethylene glycol diglycidyl ether dimethacrylate was added and mixed for 2 hours. Further, 25 parts by weight of “Coronate” 3015E (ethyl acetate solution of polyvalent isocyanate resin, manufactured by Nippon Polyurethane Industry Co., Ltd.) and 14 parts by weight of “EC-1368” (industrial adhesive, manufactured by Sumitomo 3M Co., Ltd.) This was added to obtain an adhesive composition 1.

  50 parts by weight of “Gohsenol” KH-17 (polyvinyl alcohol having a saponification degree of 78.5% to 81.5%, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) is mixed with “Solmix” H-11 (alcohol mixture, Nippon Alcohol Co., Ltd.). )) 200 parts by weight and 200 parts by weight of water After dissolving at 70 ° C. for 2 hours, 1.5 parts by weight of “Blenmer” G (glycidyl methacrylate, manufactured by NOF Corporation) was added to After mixing for a while, 3 parts by weight of a copolymer (made by Kyoeisha Chemical Co., Ltd.) having a (dimethylaminoethyl methacrylate) / (2-hydroxyethyl methacrylate) weight ratio of 2/1, “Irgacure” 651 (benzyldimethyl ketal, Ciba -5 parts by weight of Geigy Co., Ltd., "epoxy ester" 70PA (acrylic acid addition of propylene glycol diglycidyl ether) , Kyoeisha Chemical Co., Ltd.) 21 parts by weight and ethylene glycol diglycidyl ether dimethacrylate 20 parts by weight, mixed for 90 minutes, cooled to 50 ° C., then “Florard” TM FC-430 (manufactured by Sumitomo 3M Limited) ) 0.1 part by weight was added and mixed for 30 minutes to obtain an adhesive composition 2.

  The adhesive layer composition 1 is applied on a 250 μm-thick “Lumirror” T60 (polyester film, manufactured by Toray Industries, Inc.) with a bar coater so that the film thickness becomes 40 μm after drying, and placed in an oven at 180 ° C. for 3 minutes. After removing the solvent, the adhesive layer composition 2 was coated thereon with a bar coater so as to have a dry film thickness of 30 μm and dried in an oven at 160 ° C. for 3 minutes to obtain an adhesive coated substrate 1.

<Manufacture of photosensitive resin sheet 1>
After the adhesive coated substrate 1 is exposed at 1000 mJ / cm ² with an ultrahigh pressure mercury lamp from the adhesive coating side, the coating liquid composition 1 for the photosensitive resin layer (A1) is coated with the adhesive coated surface of the adhesive coated substrate 1. And dried in an oven at 60 ° C. for 5 hours to obtain a photosensitive resin sheet 1 having a thickness of about 900 μm including the substrate. The thickness of the photosensitive resin sheet 1 was adjusted by setting a spacer having a predetermined thickness on the substrate and scraping out the coating liquid composition 1 in a portion protruding from the spacer with a horizontal metal scale.

<Preparation of coating liquid composition 2 for peeling auxiliary layer (D1)>
10 parts by weight of “GOHSENOL” AL-06 (polyvinyl alcohol having a saponification degree of 91% to 94%, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) and 1 part by weight of “Direct Sky Blue 6B” (produced by Hamamoto Dye Co., Ltd.) It was dissolved in 55 parts by weight, 14 parts by weight of methanol, 10 parts by weight of n-propanol and 10 parts by weight of n-butanol to obtain a coating liquid composition 2 for the peeling assist layer (D1).

  When the relationship between the dry film thickness and the absorbance at a wavelength of 660 nm when this coating liquid composition 2 was applied was examined, it was (dry film thickness [μm]) = 4.76 × (absorbance at a wavelength of 660 nm).

<Preparation of coating liquid composition 3 for thermal mask layer (C1)>
“MA100” (carbon black, manufactured by Mitsubishi Chemical Corporation) 23 parts by weight, “Dianal” BR-95 (alcohol-insoluble acrylic resin, manufactured by Mitsubishi Rayon Co., Ltd.) 15 parts by weight, plasticizer ATBC (acetyl citrate) Carbon black dispersion 1 was prepared by kneading and dispersing 6 parts by weight of tributyl (manufactured by J Plus Co., Ltd.) and 30 parts by weight of methyl isobutyl ketone using a three-roll mill. In dispersion 1, 20 parts by weight of “Araldite” 6071 (epoxy resin, manufactured by Asahi Ciba), 27 parts by weight of “Uban” 2061 (melamine resin, manufactured by Mitsui Chemicals), “light ester” P-1M ( Phosphoric acid monomer (manufactured by Kyoeisha Chemical Co., Ltd.) 0.7 parts by weight and methyl isobutyl ketone 140 parts by weight were added and stirred for 30 minutes. Thereafter, methyl isobutyl ketone was further added so that the solid content concentration was 33% by weight to obtain a coating liquid composition 3 for the thermal mask layer (C1).

<Preparation of Coating Solution Composition 4 for Adhesive Strength Adjustment Layer (B1)>
“Gosenol” KL-05 (polyvinyl alcohol having a saponification degree of 78% to 82%, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 10 parts by weight 40 parts by weight of water, 20 parts by weight of methanol, 20 parts by weight of n-propanol and n- It was made to melt | dissolve in 10 weight part of butanol, and the coating liquid composition 4 for adhesive force adjustment layers (B1) was obtained.

<Manufacture of thermal mask element 1>
On a 100 μm thick polyester film “Lumirror” S10 (manufactured by Toray Industries, Inc.), the coating liquid composition 2 was applied using a bar coater to a dry film thickness of 0.3 μm, at 100 ° C. for 25 seconds. It dried and the laminated body of peeling auxiliary layer (D1) / protective layer (E) was obtained. At this time, the absorbance at a wavelength of 660 nm of the peeling assist layer (D1) was 0.063. On the peeling auxiliary layer (D1) side of the laminate thus obtained, the coating liquid composition 3 was applied to a dry film thickness of 2 μm using a bar coater, dried at 140 ° C. for 30 seconds, A laminate of thermal mask layer (C1) / peeling auxiliary layer (D1) / protective layer (E) was obtained. On the thermal mask layer (C1) side of the laminate thus obtained, the coating liquid composition 4 was applied using a bar coater so that the dry film thickness was 1 μm, and dried at 180 ° C. for 30 seconds. A thermal mask element 1 which is a laminate of adhesion adjusting layer (B1) / thermal mask layer (C1) / peeling auxiliary layer (D1) / protective layer (E) was obtained. The optical density (orthochromatic filter, transmission mode) of the thermal mask element 1 was 3.6.

<Manufacture of thermal mask element 2>
On a 100 μm thick polyester film “Lumirror” S10 (manufactured by Toray Industries, Inc.), the coating liquid composition 2 was applied using a bar coater to a dry film thickness of 0.2 μm, and the coating film composition was 100 ° C. for 25 seconds. It dried and the laminated body of peeling auxiliary layer (D1) / protective layer (E) was obtained. At this time, the absorbance at a wavelength of 660 nm of the peeling assist layer (D1) was 0.043. On the peeling auxiliary layer (D1) side of the laminate thus obtained, the coating liquid composition 3 was applied to a dry film thickness of 2 μm using a bar coater, dried at 140 ° C. for 30 seconds, A laminate of thermal mask layer (C1) / peeling auxiliary layer (D1) / protective layer (E) was obtained. On the thermal mask layer (C1) side of the laminate thus obtained, the coating liquid composition 4 was applied using a bar coater so that the dry film thickness was 1 μm, and dried at 180 ° C. for 30 seconds. A thermal mask element 2 which is a laminate of adhesion adjusting layer (B1) / thermal mask layer (C1) / peeling auxiliary layer (D1) / protective layer (E) was obtained. The optical density (orthochromatic filter, transmission mode) of the thermal mask element 2 was 3.6.

<Manufacture of thermal mask element 3>
On a 100 μm thick polyester film “Lumirror” S10 (manufactured by Toray Industries, Inc.), the coating liquid composition 2 was applied using a bar coater to a dry film thickness of 0.5 μm, and 100 ° C. for 25 seconds. It dried and the laminated body of peeling auxiliary layer (D1) / protective layer (E) was obtained. At this time, the absorbance at a wavelength of 660 nm of the peeling assist layer (D1) was 0.105. On the peeling auxiliary layer (D1) side of the laminate thus obtained, the coating liquid composition 3 was applied to a dry film thickness of 2 μm using a bar coater, dried at 140 ° C. for 30 seconds, A laminate of thermal mask layer (C1) / peeling auxiliary layer (D1) / protective layer (E) was obtained. On the thermal mask layer (C1) side of the laminate thus obtained, the coating liquid composition 4 was applied using a bar coater so that the dry film thickness was 1 μm, and dried at 180 ° C. for 30 seconds. A thermal mask element 3 which is a laminate of adhesion adjusting layer (B1) / thermal mask layer (C1) / peeling auxiliary layer (D1) / protective layer (E) was obtained. The optical density (orthochromatic filter, transmission mode) of the thermal mask element 3 was 3.6.

<Manufacture of thermal mask element 4>
On a 100 μm thick polyester film “Lumirror” S10 (manufactured by Toray Industries, Inc.), the coating liquid composition 3 was applied to a dry film thickness of 2 μm using a bar coater and dried at 140 ° C. for 30 seconds. A laminate of heat-sensitive mask layer (C1) / protective layer (E) was obtained. On the thermal mask layer (C1) side of the laminate thus obtained, the coating liquid composition 4 was applied using a bar coater so that the dry film thickness was 1 μm, and dried at 180 ° C. for 30 seconds. A thermal mask element 4 which is a laminate of the adhesion adjusting layer (B1) / thermal mask layer (C1) / protective layer (E) was obtained. The optical density (orthochromatic filter, transmission mode) of the thermal mask element 4 was 3.6.

Example 1
The coating liquid composition 1 is spread on the photosensitive resin layer (A1) of the photosensitive resin sheet 1, and the adhesive layer (B1) is spread on the thermosensitive mask element 1 on top of which the coating liquid composition 1 is spread. The photosensitive resin layer (A1) is placed in contact with the laminate and laminated with a calender roll heated to 80 ° C., and adhesive coated substrate 1 / photosensitive resin layer (A1) / adhesive strength adjusting layer (B1) / The photosensitive resin printing plate precursor 1 laminated in the order of the heat-sensitive mask layer (C1) / peeling auxiliary layer (D1) / protective layer (E) was obtained. The clearance of the calender roll was adjusted so that the thickness of the laminate after peeling off the protective layer (E) from the original plate 1 was 950 μm. The developed coating liquid composition 1 is allowed to stand for 1 week after laminating, whereby the remaining solvent is naturally dried to form an additional photosensitive resin layer (A1).

  After peeling the protective film (E) from the photosensitive resin printing plate precursor 1, the outer drum type plate setter “CDI SPARK” (manufactured by Esco Graphics Co., Ltd.) equipped with a fiber laser having a light emitting region in the infrared, The substrate side is attached so as to be in contact with the drum, and a test pattern with a resolution of 156 lines (solid portion, 1% to 99% halftone dot, 1 to 8 point thin line image, etc.) is drawn, and from the thermal mask layer (C1) An image mask (C1 ′) was formed. Under the conditions of a laser output of 9 W and a drum rotational speed of 700 rpm, the solid heat-sensitive mask layer (C1) was substantially laser ablated, and there was no residual adhesion of the heat-sensitive mask layer (C1) component by visual observation.

  When the protective layer (E) is peeled from the photosensitive resin printing plate precursor 1, it is peeled between the peeling auxiliary layer (D1) and the protective layer (E), and the thermal mask layer (C1) and the adhesive strength adjusting layer are peeled off. There was no bad peeling between (B1) and the thermal mask layer was not damaged.

Subsequently, the entire surface was exposed from an image mask (C1 ′) side with an ultrahigh pressure mercury lamp (manufactured by Oak Co., Ltd.) having a light source in the ultraviolet region (exposure amount: 1000 mJ / cm ² ). Next, using a brush type developing machine FTW500II (manufactured by Toray Industries, Inc.) equipped with a brush made of PBT (polybutylene terephthalate), development was carried out with tap water at 35 ° C. for 1.5 minutes. D1), the image mask (C1 ′) and the portion of the photosensitive resin layer (A1) that is blocked by the image mask and not exposed to ultraviolet rays are selectively developed, and a negative relief is applied to the image mask (C1 ′). It was faithfully reproduced.

(Example 2)
The coating liquid composition 1 is developed on the photosensitive resin layer (A1) of the photosensitive resin sheet 1, and the adhesive layer (B1) is applied to the thermal mask element 2 on top of which the coating liquid composition 1 is developed. The photosensitive resin layer (A1) is placed in contact with the laminate and laminated with a calender roll heated to 80 ° C., and adhesive coated substrate 1 / photosensitive resin layer (A1) / adhesive strength adjusting layer (B1) / The photosensitive resin printing plate precursor 2 laminated in the order of the heat-sensitive mask layer (C1) / peeling auxiliary layer (D1) / protective layer (E) was obtained. The clearance of the calender roll was adjusted so that the thickness of the laminate after the protective layer (E) was peeled from the original plate 2 was 950 μm. The developed coating liquid composition 1 is allowed to stand for 1 week after laminating, whereby the remaining solvent is naturally dried to form an additional photosensitive resin layer (A1).

  After removing the protective film (E) from the photosensitive resin printing plate precursor 2, the outer drum type plate setter “CDI SPARK” (manufactured by ESCO Graphics Co., Ltd.) equipped with a fiber laser having a light emitting region in the infrared, The substrate side is attached so as to be in contact with the drum, and a test pattern with a resolution of 156 lines (solid portion, 1% to 99% halftone dot, 1 to 8 point thin line image, etc.) is drawn, and from the thermal mask layer (C1) An image mask (C1 ′) was formed. Under the conditions of a laser output of 9 W and a drum rotational speed of 700 rpm, the solid heat-sensitive mask layer (C1) was substantially laser ablated, and there was no residual adhesion of the heat-sensitive mask layer (C1) component by visual observation.

  When the protective layer (E) is peeled from the photosensitive resin printing plate precursor 2, it is peeled between the peeling auxiliary layer (D1) and the protective layer (E), and the thermal mask layer (C1) and the adhesion adjusting layer are peeled off. There was no bad peeling between (B1) and the thermal mask layer was not damaged.

Subsequently, the entire surface was exposed from an image mask (C1 ′) side with an ultrahigh pressure mercury lamp (manufactured by Oak Co., Ltd.) having a light source in the ultraviolet region (exposure amount: 1000 mJ / cm ² ). Next, using a brush type developing machine FTW500II (manufactured by Toray Industries, Inc.) equipped with a brush made of PBT (polybutylene terephthalate), development was carried out with tap water at 35 ° C. for 1.5 minutes. D1), the image mask (C1 ′) and the portion of the photosensitive resin layer (A1) that is blocked by the image mask and not exposed to ultraviolet rays are selectively developed, and a negative relief is applied to the image mask (C1 ′). It was faithfully reproduced.

(Comparative Example 1)
The coating liquid composition 1 is developed on the photosensitive resin layer (A1) of the photosensitive resin sheet 1, and the adhesive layer (B1) is applied to the thermosensitive mask element 3 on top of which the coating liquid composition 1 is developed. The photosensitive resin layer (A1) is placed in contact with the laminate and laminated with a calender roll heated to 80 ° C., and adhesive coated substrate 1 / photosensitive resin layer (A1) / adhesive strength adjusting layer (B1) / The photosensitive resin printing plate precursor 3 laminated in the order of the thermal mask layer (C1) / peeling auxiliary layer (D1) / protective layer (E) was obtained. The clearance of the calender roll was adjusted so that the thickness of the laminate after peeling off the protective layer (E) from the original plate 3 was 950 μm. The developed coating liquid composition 1 is allowed to stand for 1 week after laminating, whereby the remaining solvent is naturally dried to form an additional photosensitive resin layer (A1).

  After peeling the protective film (E) from the photosensitive resin printing plate precursor 3, the outer drum type plate setter “CDI SPARK” (manufactured by ESCO Graphics Co., Ltd.) equipped with a fiber laser having a light emitting region in the infrared, The substrate side is attached so as to be in contact with the drum, and a test pattern with a resolution of 156 lines (solid portion, 1% to 99% halftone dot, 1 to 8 point thin line image, etc.) is drawn, and from the thermal mask layer (C1) An image mask (C1 ′) was formed. Under the conditions of a laser output of 9 W and a drum rotation speed of 700 rpm, the solid heat-sensitive mask layer (C1) was mostly laser ablated, but the residue of the heat-sensitive mask layer (C1) component remained and adhered. This is because the laser ablation of the layer (C1) is hindered because the peeling assist layer (D1) laminated so as to be in contact with the thermal mask layer (C1) is thick.

  When the protective layer (E) is peeled from the photosensitive resin printing plate precursor 3, it is peeled between the peeling auxiliary layer (D1) and the protective layer (E), and the thermal mask layer (C1) and the adhesion adjusting layer. There was no bad peeling between (B1) and the thermal mask layer was not damaged.

Subsequently, the entire surface was exposed from an image mask (C1 ′) side with an ultrahigh pressure mercury lamp (manufactured by Oak Co., Ltd.) having a light source in the ultraviolet region (exposure amount: 1000 mJ / cm ² ). Next, using a brush type developing machine FTW500II (manufactured by Toray Industries, Inc.) equipped with a brush made of PBT (polybutylene terephthalate), development was carried out with tap water at 35 ° C. for 1.5 minutes. D1), the image mask (C1 ′) and the portion of the photosensitive resin layer (A1) that is blocked by the image mask and not exposed to ultraviolet rays are selectively developed, and a negative relief is applied to the image mask (C1 ′). Although mostly reproduced, unevenness derived from the heat-sensitive mask layer (C1) component residue was confirmed in the solid portion. Moreover, the relief of the fine line of 1 to 2 points was partially distorted. This is because the ultraviolet ray irradiation of the thin line was inhibited by the layer (C1) component residue.

(Comparative Example 2)
The coating liquid composition 1 is spread on the photosensitive resin layer (A1) of the photosensitive resin sheet 1, and the adhesive layer (B1) is spread on the thermosensitive mask element 4 on top of which the coating liquid composition 1 is spread. The photosensitive resin layer (A1) is placed in contact with the laminate and laminated with a calender roll heated to 80 ° C., and adhesive coated substrate 1 / photosensitive resin layer (A1) / adhesive strength adjusting layer (B1) / The photosensitive resin printing plate precursor 4 laminated in the order of the thermal mask layer (C1) / protective layer (E) was obtained. The clearance of the calender roll was adjusted so that the thickness of the laminate after the protective layer (E) was peeled from the original plate 4 was 950 μm. The developed coating liquid composition 1 is allowed to stand for 1 week after laminating, whereby the remaining solvent is naturally dried to form an additional photosensitive resin layer (A1).

  When the protective layer (E) was to be peeled off from the photosensitive resin printing plate precursor 4, the peeling force between the heat-sensitive mask layer (C1) and the protective layer (E) was so great that the protective layer (E) was not easily peeled off. As a result, the thermal mask layer was partially damaged.

<Preparation of coating liquid composition 5 for thermal mask layer (C2)>
"MA100" (carbon black, manufactured by Mitsubishi Chemical Corporation) 2.5 parts by weight, "Gosenol" KL-06 (polyvinyl alcohol having a saponification degree of 78% to 82%, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 7.5 A carbon black dispersion 2 was prepared by kneading and dispersing a mixture of parts by weight, 40 parts by weight of water and 10 parts by weight of n-propyl alcohol in advance using a three-roll mill. 40 parts by weight of water and 10 parts by weight of n-propyl alcohol were added to Dispersion 2 and stirred for 30 minutes to obtain a coating liquid composition 5 for the heat-sensitive mask layer (C2).

<Manufacture of thermal mask element 5>
On a 100 μm thick polyester film “Lumirror” S10 (manufactured by Toray Industries, Inc.), the coating liquid composition 2 was applied using a bar coater to a dry film thickness of 0.2 μm, and the coating film composition was 100 ° C. for 25 seconds. It dried and the laminated body of peeling auxiliary layer (D1) / protective layer (E) was obtained. At this time, the absorbance at a wavelength of 660 nm of the peeling assist layer (D1) was 0.042. On the peeling auxiliary layer (D1) side of the laminate thus obtained, the coating liquid composition 5 was applied to a dry film thickness of 2 μm using a bar coater, dried at 140 ° C. for 30 seconds, The thermal mask element 5 which is a laminated body of a thermal mask layer (C2) / peeling auxiliary layer (D1) / protective layer (E) was obtained. The optical density (orthochromatic filter, transmission mode) of the thermal mask element 5 was 3.6.

(Example 3)
The coating liquid composition 1 is spread on the photosensitive resin layer (A1) of the photosensitive resin sheet 1, and the thermal mask layer (C2) is spread on the thermal mask element 5 on top of which the coating liquid composition 1 is spread. Laminated with a calendar roll heated to 80 ° C. so as to be in contact with the photosensitive resin layer (A1), adhesive coated substrate 1 / photosensitive resin layer (A1) / thermal mask layer (C2) / peeling aid The photosensitive resin printing plate precursor 5 laminated in the order of layer (D1) / protective layer (E) was obtained. The clearance of the calender roll was adjusted so that the thickness of the laminate after peeling off the protective layer (E) from the original plate 5 was 950 μm. The developed coating liquid composition 1 is allowed to stand for 1 week after laminating, whereby the remaining solvent is naturally dried to form an additional photosensitive resin layer (A1).

  After peeling the protective layer (E) from the photosensitive resin printing plate precursor 5, an external drum type plate setter “CDI SPARK” (manufactured by Esco Graphics Co., Ltd.) equipped with a fiber laser having a light emitting region in the infrared, The substrate side is attached so as to be in contact with the drum, and a test pattern with a resolution of 156 lines (solid portion, 1% to 99% halftone dot, 1 to 8 point thin line image, etc.) is drawn, and from the thermal mask layer (C2) An image mask (C2 ′) was formed. Under the conditions of a laser output of 9 W and a drum rotational speed of 700 rpm, the solid heat-sensitive mask layer (C2) was substantially laser ablated, and the heat-sensitive mask layer (C2) component did not remain attached by visual observation.

  When the protective layer (E) is peeled from the photosensitive resin printing plate precursor 5, it is peeled between the peeling auxiliary layer (D1) and the protective layer (E), and the thermal mask layer (C2) and the photosensitive resin layer are peeled off. There was no bad peeling between (A1) and the thermal mask layer was not damaged.

Subsequently, the entire surface was exposed from the image mask (C2 ′) side with an ultrahigh pressure mercury lamp (manufactured by Oak Co., Ltd.) having a light source in the ultraviolet region (exposure amount: 1000 mJ / cm ² ). Next, using a brush type developing machine FTW500II (manufactured by Toray Industries, Inc.) equipped with a brush made of PBT (polybutylene terephthalate), development was carried out with tap water at 35 ° C. for 1.5 minutes. D1), the image mask (C2 ′) and the portion of the photosensitive resin layer (A1) that is blocked by the image mask and not exposed to ultraviolet rays are selectively developed, and a negative relief is applied to the image mask (C2 ′). It was faithfully reproduced.

Claims (4)

(1) A step of obtaining a photosensitive resin sheet by laminating a photosensitive resin layer (A) on a substrate,
(2) A step of obtaining a thermal mask element by laminating a peeling auxiliary layer (D) having a thickness of 0.3 μm or less and a thermal mask layer (C) on the protective layer (E),
(3) A method for producing a photosensitive resin printing plate precursor comprising a step of laminating a photosensitive resin sheet and a thermal mask element so that the thermal mask layer (C) is in contact with the surface of the photosensitive resin layer (A). A method for producing a photosensitive resin printing plate precursor, comprising controlling the film thickness of the peeling auxiliary layer (D) by using the absorbance of the peeling auxiliary layer (D) with respect to visible light and / or ultraviolet light. (1) A step of obtaining a photosensitive resin sheet by laminating a photosensitive resin layer (A) on a substrate,
(2) A step of obtaining a thermal mask element by laminating a peeling auxiliary layer (D) having a thickness of 0.3 μm or less, a thermal mask layer (C) and an adhesive force adjusting layer (B) on the protective layer (E),
(3) A method for producing a photosensitive resin printing plate precursor comprising a step of laminating a photosensitive resin sheet and a thermal mask element so that the adhesion adjusting layer (B) is in contact with the surface of the photosensitive resin layer (A). A method for producing a photosensitive resin printing plate precursor, comprising controlling the film thickness of the peeling assisting layer (D) using the absorbance of the peeling assisting layer (D) with respect to visible light and / or ultraviolet light. The production of the photosensitive resin printing plate precursor according to any one of claims 1 to 2, wherein the peeling auxiliary layer (D) contains a substance having an ability to absorb visible light and / or ultraviolet light. Method. (1) Using the photosensitive resin printing plate precursor obtained by the method according to any one of claims 1 to 3 ,
(2) peeling off the protective layer (E),
(3) An image mask (C ′) is formed by imagewise irradiation of the thermal mask layer (C) with an infrared laser,
(4) Exposure is performed using ultraviolet light from the formed image mask (C ′) side, and a negative latent image is formed on the photosensitive resin layer (A) with respect to the image mask (C ′).
(5) Resin letterpress printing characterized in that the image mask (C ′) and the photosensitive resin layer (A) in the ultraviolet light unexposed area are removed by developing with a liquid mainly composed of water and / or alcohol. Plate manufacturing method.