JP2009139598A - Photosensitive resin printing plate original plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin printing plate original plate, applicable to a computer-platemaking process, which will not produce breaks or flaws in thermosensitive mask layer, when a cover film is peeled therefrom and which can create a high-quality resin letterpress plate. <P>SOLUTION: In the photosensitive resin printing plate precursor, a photosensitive resin layer (A) containing a water-soluble or water-dispersible resin and an ultraviolet-curable monomer, an adhesive strength adjusting layer (B), and the thermosensitive mask layer (C) containing an infrared absorbing substance are installed, in this order on a substrate, wherein the adhesive strength adjusting layer (B) contains at least an amine compound. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a photosensitive resin printing plate precursor, and more particularly to a photosensitive resin printing plate precursor used when a resin relief printing plate is produced by computer plate making technology.

  In recent years, computer plate making technology (computer-to-plate (CTP) technology) known as digital image forming technology has become common in various printing fields. As CTP technology in the field of relief printing plates such as photosensitive resin relief printing and flexographic printing, information processed on a computer is printed without using a conventional photomask (also called a photomask or negative film). Output directly on the plate precursor, form an image mask on the photosensitive resin layer 'in situ' from digital data, and then expose the entire surface from the image mask side with actinic rays, in many cases ultraviolet rays. A method for selectively curing only the non-covered portion of the mask to cure the photosensitive resin layer to obtain a printing plate has been actively proposed. The advantages of this method are: (1) no negative film manufacturing process is required, (2) the treatment of negative film development waste is unnecessary and environmentally friendly, and (3) the adhesion of the negative film. In addition to eliminating foreign matters, (4) a relief having a sharp structure can be obtained.

  Currently, there are two techniques as a specific method for forming a printing plate by forming an image mask on the photosensitive resin layer “in situ” from the digital data described above. One is a method of forming an image mask film on a photosensitive resin layer using an ink jet printer or an electrophotographic printer, and the other is a method of forming a thermal mask layer opaque to ultraviolet light on the photosensitive resin layer. This is a method of forming an image mask by providing an infrared laser to the thermal mask layer in advance and ablating the thermal mask layer.

By the way, in the photosensitive resin printing plate precursor having the thermal mask layer, the thermal mask layer includes a composition containing carbon black in a polymer binder (see, for example, Patent Document 1), and an IR such as an aluminum vapor deposition film. An absorptive metal film (for example, Patent Document 2) is used. Usually, a cover film is provided on the heat-sensitive mask layer to protect the surface of the printing plate precursor during storage and handling, and this cover film is pre-irradiation or after irradiation (usually the main film). It is removed after exposure and before development. However, in the photosensitive resin printing plate precursor having a thermal mask layer, when the cover film is peeled off, the thermal mask layer is peeled off together with the cover film, and the thermal mask layer is torn or scratched, and a desired printed image cannot be obtained. There was a thing. In particular, when a photosensitive resin layer containing a resin that is soluble or dispersible in water and a monomer that can be cured by ultraviolet light and a heat-sensitive mask layer that is water-insoluble, both layers are incompatible with each other, so the adhesion is low. When the cover film is peeled off, the heat-sensitive mask layer is easily torn or scratched. For this reason, it has been proposed to provide an adhesive force adjusting layer that is in close contact with both layers between the photosensitive resin layer and the thermal mask layer (for example, Patent Document 3). Further, as an effect of providing the adhesive force adjusting layer, it is also possible that defects such as floating and cracking of the mask layer hardly occur when the photosensitive resin printing plate precursor is bent. However, in the case of the material used for the adhesive force adjusting layer reported so far, a process such as a high temperature treatment or a corona discharge treatment is required at the time of layer formation (for example, Patent Document 4).
Japanese Patent No. 3429634 (pages 3-7) JP 2003-270778 A (page 1-9) JP 2004-163925 A (page 2-12) Japanese Patent Laying-Open No. 2005-326442 (page 2-14)

  In view of the above problems, an object of the present invention is to provide a photosensitive resin printing plate precursor capable of making a computer plate capable of producing a high-quality resin relief printing plate that does not tear or damage the heat-sensitive mask layer when the cover film is peeled off. There is to do.

  In order to solve the above problems, according to the present invention, a photosensitive resin printing plate precursor mainly having the following configuration is provided.

That is,
“A photosensitive resin layer (A) containing a resin that can be dissolved or dispersed in water and a monomer curable by ultraviolet light, an adhesive force adjusting layer (B), and a thermal mask layer containing an infrared absorbing substance on the substrate. (C) is a photosensitive resin printing plate precursor laminated in this order, wherein the adhesive force adjusting layer (B) contains at least an amine compound.

  ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin printing plate precursor which can form a convex-shaped relief image without requiring an original image film can be provided easily. Since the photosensitive resin printing plate precursor of the present invention does not break or damage the heat-sensitive mask layer when the cover film is peeled off, it is excellent in handleability and can provide a high-quality resin relief printing plate.

  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), an adhesive force adjusting layer (B), and a thermal mask layer (C) containing an infrared absorbing substance in this order on a substrate.

  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, etc., 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 Relate, Alkyl halide (meth) acrylate such as chloropropyl (meth) acrylate, Alkoxyalkyl (meth) acrylate such as methoxyethyl (meth) acrylate, Ethoxyethyl (meth) acrylate, 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) acrylami (Meth) acrylamides such as 2,2-dimethylaminoethyl (meth) acrylate, 2,2-diethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, N, N-dimethylamino Compounds having only one ethylenically unsaturated bond such as propyl (meth) acrylamide, polyethylene glycol di (meth) acrylate such as diethylene glycol di (meth) acrylate, polypropylene such as dipropylene glycol di (meth) acrylate Glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, glycerol tri (meth) acrylate Polyhydric (meth) acrylates, glycidyl (meth) acrylates, etc. obtained by addition reaction of ethylenic unsaturated bonds such as unsaturated carboxylic acids and unsaturated alcohols and compounds with active hydrogen to ethylene glycol diglycidyl ether Multivalent (meth) acrylamides such as polyvalent (meth) acrylates and methylenebis (meth) acrylamides obtained by addition reaction of saturated epoxy compounds and compounds with active hydrogen such as carboxylic acids and amines, and polyvalents such as divinylbenzene Examples thereof include compounds having two or more ethylenically unsaturated bonds, such as vinyl 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. Examples include benzoin alkyl ethers, benzophenones, anthraquinones, benzyls, acetophenones, diacetyls, and the like.

  The photosensitive resin composition has other components such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, glycerin, trimethylolpropane, and trimethylolethane 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, Add a photopolymerization initiator and other additives as necessary and stir well to obtain a photosensitive resin composition solution. After removing the solvent from this solution, preferably melt on the substrate coated with adhesive It can be obtained by extrusion. Alternatively, a solution in which a part of the solvent remains can be obtained by melt-extrusion onto a substrate coated with an adhesive, and the part of the solvent remaining in the solvent can be naturally dried over time.

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

  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 heat sensitive mask layer (C) is a heat sensitive layer containing an infrared absorbing material. Layer (C) is an ultraviolet ray having a function of blocking ultraviolet light and a thermally decomposable compound having a function of evaporating and ablating by heat, in addition to an infrared absorbing material having a function of absorbing an infrared laser and converting it into heat. An absorbent material may be included.

Here, having the function of blocking ultraviolet light means that the optical density of the thermal mask layer (C) is 2.5 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 pigment 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, iron Powder, Diamine-based metal complex, Dithiol-based metal complex, Phenolthiol-based metal complex, Mercaptophenol-based metal complex, Aryl aluminum metal salts, Crystallized water-containing inorganic compound, Copper sulfate, Chromium sulfide, Silicate compound, Titanium oxide, Oxidation Examples thereof include metal oxides such as vanadium, manganese oxide, iron oxide, cobalt oxide, and tungsten oxide, hydroxides and sulfates of these metals, and metal powders of bismuth, tin, tellurium, iron, and aluminum.

  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.

  Examples of the thermally decomposable compound preferably used for the layer (C) include, for example, a polymer compound and a nitro compound that are easily thermally decomposed, an organic peroxide, an azo compound, a diazo compound, a hydrazine derivative, and an infrared absorbing substance. Although the enumerated metals or metal oxides are mentioned, a polymer compound is preferable from the viewpoint of the coating property of the solution. For example, an acrylic resin is relatively easy to thermally decompose, and a general acrylic resin has a thermal decomposition temperature of 190 ° C. to 250 ° C. 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, the mass transfer to the lower photosensitive resin layer (A) can be suppressed. Therefore, a water / alcohol insoluble acrylic resin is more preferable. Used.

  Although it does not specifically limit as an ultraviolet-absorbing substance used preferably for a layer (C), Preferably, it is a compound which has absorption in the area | region of 300 nm-400 nm. For example, benzotriazole-based compounds, triazine-based compounds, benzophenone-based compounds, carbon black, and metals or metal oxides listed in infrared absorbing materials can be used. 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 heat-sensitive mask layer (C) used in the present invention may be hydrophilic or hydrophobic, but is preferably hydrophobic. In the present invention, the hydrophilic property means that the layer itself can be developed with water, and the hydrophobic property means a so-called water-insoluble property that the layer cannot be developed with water. Say. When the heat-sensitive mask layer (C) has a hydrophilic composition, mass transfer occurs in the photosensitive resin layer (A) that can be dissolved or dispersed in water, thereby reducing the functions unique to each layer. For example, (1) when the monomer of the photosensitive resin layer (A) moves to the thermal mask layer (C), the laser ablation of the thermal mask layer (C) is impaired, and (2) the photosensitive resin. When an ultraviolet absorbing substance is mixed in the layer (A), curing by ultraviolet light is inhibited, but the above-described phenomenon hardly occurs when the thermal mask layer (C) is hydrophobic. The method for imparting water insolubility is not particularly limited, and can be achieved by, for example, a method in which the entire composition of the heat-sensitive mask layer (C) is composed of a hydrophobic 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, the hydrophobicity referred to in the present invention means that a load of 500 g (of which the weight of the friction element is 200 g) is applied to a white cotton cloth wetted with water by a friction tester II for dyeing fastness test described in JIS standard L0823. In this test method, an additional weight of 300 g) is applied and the surface of the thermal mask layer (C) is rubbed. It means that no penetrating scratches are observed after 5 reciprocating rubs, and further penetrates after 10 reciprocating rubs. More preferably, no sexual scratches are attached.

  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.

  Urea resins include butylated urea resin, butylated melamine resin, butylated benzoguanamine resin, butylated urea melamine co-condensation resin, amino alkyd resin, iso-butylated melamine resin, methylated meminin resin, 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. .

  In addition, examples of amide compounds include polyamide curing agents and dicyandiamide used as epoxy resin curing agents. Examples of hydroxyl group-containing compounds include phenol resins and polyhydric alcohols. Examples of thiol compounds include polyvalent thiols. and so on.

  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 amount of these thermosetting resins used is preferably 10% by weight to 75% by weight or less, more preferably 30% by weight to 60% by weight, based on the total composition of the heat sensitive 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.

  When a pigment such as carbon black is used as the infrared absorbing material, a plasticizer, a surfactant or a dispersion aid may be added to facilitate the dispersion.

  Further, the heat-sensitive mask layer (C) may be a metal thin film obtained by vapor deposition or sputtering of an infrared absorbing metal or metal oxide.

  The photosensitive resin printing plate precursor of the present invention is provided with an adhesion adjusting layer (B) between the photosensitive resin layer (A) and the heat sensitive mask layer (C), and the adhesion adjusting layer (B) contains at least an amine compound. It is characterized by doing. By providing the above-mentioned adhesion adjustment layer, in particular, a photosensitive resin layer (A) containing a resin that can be dissolved or dispersed in water and a monomer that can be cured by ultraviolet light, an adhesion adjustment layer (B), and a thermal mask layer (C) Optimize the adhesion between each layer and prevent tearing and scratching of the thermal mask layer (C) generated when the cover film (E) is peeled off in the photosensitive resin printing plate precursor having the cover film (E). Can do. In addition, the optimization of the adhesive force between each layer described here is photosensitive resin layer (A) / adhesive strength adjusting layer (B) / thermal mask layer (C) / peeling auxiliary layer (D) / cover film (E ) In the photosensitive resin printing plate precursor sequentially laminated, the adhesive force between the cover film (E) and the peeling auxiliary layer (D) when peeling the cover film (E) from the peeling auxiliary layer (D), or The photosensitive resin layer (A) / adhesion is based on the adhesive force between the release auxiliary layer (D) and the thermal mask layer (C) when peeling the cover film (E) and the release auxiliary layer (D) from the thermal mask layer (C). This is to increase the adhesive force at the interface between the force adjusting layer (B) and the adhesive force adjusting layer (B) / thermosensitive mask layer (C).

  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.).

  Further, by providing an adhesive force adjusting layer (B), (1) further preventing the monomer from diffusing from the photosensitive resin layer (A) to the thermal mask layer (C), and (2) the photosensitive resin layer (A). ) Is protected from the action of laser light during laser ablation.

  The amine compound suitable for the adhesive force adjusting layer (B) preferably has an amine value (mmol / g) of 5 or more, more preferably 7 or more. Further, the upper limit of the amine value (mmol / g) is preferably 50 or less, and more preferably 30 or less. The number average molecular weight is preferably 300 to 200,000, and more preferably 500 to 200,000. Furthermore, the amine compound is preferably water-soluble. As an effect when the amine compound is added, the amine compound forms a hydrogen bond with the composition of the heat-sensitive mask layer or the photosensitive layer, thereby improving the adhesion. The amine compound may contain a primary, secondary, or tertiary amine in the molecule. When the amine value (mmol / g) of the amine compound is 5 or more and the molecular weight is 300 or more, for example, it reacts with (1) a polyfunctional isocyanate compound or polyfunctional epoxy compound contained in the heat-sensitive mask layer (C). (2) When the heat-sensitive mask layer (C) is a metal, the adhesion between the layers can be further improved by bonding the amine compound to the metal surface, which is preferable. Furthermore, when the molecular weight is 200,000 or less, viscosity adjustment when coating is easy. Moreover, if the amine value of the amine compound is 5 or more, an adhesive force adjusting layer having excellent adhesion can be formed, but if the amine value is larger than 25, repelling is likely to occur during film formation during drying. The amine value is preferably in the range of 5-25. Now, since the amine compound is water-soluble, compatibility with the photosensitive resin layer (A) containing a resin that can be dissolved or dispersed in water is improved, and adhesion with the photosensitive resin is improved. Further, when the amine compound contains a primary, secondary or tertiary amine in the molecule, there is an effect that the reaction with the polyfunctional isocyanate compound or the polyfunctional epoxy compound is completed in a short time.

  Examples of the amine compound included in the present invention include, but are not limited to, polyethyleneimine, acrylic polymer having an amino group, polyallylamine, allylamine / dimethylallylamine copolymer, amino resin, and alkylamine compound.

  These amine compounds may be used by adding to a polymer that is soluble or dispersible in water or water and alcohol. Examples of polymers include partially hydrolyzed polyester, partially hydrolyzed polyvinyl acetate, polyvinyl alcohol derivatives, partially hydrolyzed polyvinyl acetate / alkylene oxide graft copolymers, maleic anhydride Copolymers, such as copolymers of maleic anhydride and isobutene, or maleic anhydride and vinyl methyl ether, water-soluble polyesters, water-soluble polyethers, vinyl pyrrolidone, vinyl caprolactam, vinyl imidazole, vinyl acetate and acrylamide Homopolymers or copolymers, water-soluble polyurethanes, polyamides, water-soluble phenol resins, and mixtures of these polymers.

  The method of forming the adhesive force adjusting layer (B) is not particularly limited, but for the convenience of thin film formation, the adhesive force adjusting layer (B) component is dissolved on a solvent and coated on the thermal mask layer (C). The method of removing the solvent from is preferably carried out.

  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).

  In addition, the film thickness of the adhesive force adjusting layer (B) of the present invention is preferably 15 μm or less, and more preferably 0.1 μm to 5 μm. 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 1.3 micrometers or more, formation of B layer will become easy. As a method of measuring the film thickness, a method of measuring by a film weight per unit area or a film thickness measurement by a micrometer is possible.

  A cover film (E) may be provided on the thermal mask layer (C). The cover film (E) can be used for the purpose of protecting the heat-sensitive mask layer (C) from injury. For the cover film (E), a polymer film that can be peeled off from the heat-sensitive mask layer (C) is preferably used. Examples of such a cover film (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 cover film (E).

  The film thickness of the cover film (E) is preferably 25 μm to 200 μm, more preferably 50 μm to 150 μm. If it is 50 μm or more, it is easy to handle and has a function of protecting the thermal mask layer (C) from external damage. If it is 200 μm or less, it has the advantage of being inexpensive and economically advantageous and easy to peel off. . As a method for measuring the film thickness, it is possible to measure the film thickness using a micrometer.

  A peeling auxiliary layer (D) may be provided on the thermal mask layer (C). The peeling auxiliary layer (D) is provided between the thermal mask layer (C) and the cover film (E). The peeling auxiliary layer (D) has a function of easily peeling only the peeling auxiliary layer (D) or only the cover film (E) or both the cover film (E) and the peeling auxiliary layer (D) from the photosensitive resin printing plate precursor. It is preferable to have. If the cover film (E) and the thermal mask layer (C) are directly laminated and the adhesive strength between the two layers is strong, the cover film (E) cannot be peeled off or may be peeled off together with the thermal mask layer (C). There is sex.

  Therefore, the peeling auxiliary layer (D) has a strong adhesive force with the thermal mask layer (C) and is weak enough to peel the adhesive force with the cover film (E), or with the thermal mask layer (C). It is preferable that the adhesive force is weak enough to be peeled off and is made of a substance having a strong adhesive force with the cover film (E). In addition, after peeling a cover film (E), since a peeling auxiliary | assistant layer (D) may remain in the thermal mask layer (C) side and may become an outermost layer, it is not sticky from the surface of handling, or this layer It is preferable that it is substantially transparent because it is exposed to ultraviolet light through.

  Materials used for the peeling assisting layer (D) include 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 and are adhesive. It is preferable to use a resin having a small amount 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 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. Further, a surfactant may be added to improve coatability and wettability.

  The film thickness of the peeling assist layer (D) is preferably 6 μm or less, and more preferably 0.1 μm or more and 3 μm or less. If it is 3 μm or less, the laser ablation of the lower thermal mask layer (C) will not be impaired. Moreover, if it is 0.1 micrometer or more, formation of a peeling auxiliary | assistant layer (D) will be easy. As a method for measuring the film thickness, a method of measuring by the film weight per unit area is easy.

  When peeling the cover film (E) from the photosensitive resin printing plate precursor at a speed of 200 mm / min, the peel force per 1 cm is preferably 0.5 to 20 g / cm, and 1 to 15 g / cm. Further preferred. If it is 0.5 g / cm or more, it is preferable because the protective layer (E) can be worked without peeling off during the work, and if it is 20 g / cm or less, the cover film (E) can be peeled without difficulty. Therefore, it is preferable.

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

  The first example has a structure in which a photosensitive resin layer (A), an adhesive force adjustment layer (B), a thermal mask layer (C), a peeling assist layer (D), and a protective layer (E) are sequentially laminated on a substrate. It is an original version. A sheet having the thermal mask layer (C) in which the layer (D), the layer (C) and the layer (B) are laminated, and the layer (A) on the substrate were sequentially coated on the protective layer (E). It can be obtained by laminating a photosensitive resin sheet. The laminating method is not particularly limited. For example, the surface of the layer (A) or the layer (B) is swollen with water and / or alcohol, and a heat-sensitive mask sheet is bonded, the same as or similar to the layer (A). There are a method of pouring a high-viscosity liquid between the photosensitive resin sheet and the heat-sensitive mask sheet and bonding them together, and a method of pressing with a press machine at room temperature or while heating.

  The second example is an original plate having a structure in which a photosensitive resin layer (A), an adhesion adjusting layer (B), and a thermal mask layer (C) are sequentially laminated on a substrate. First, the photosensitive resin sheet in which the photosensitive resin layer (A) is laminated on the substrate is coated with a solution in which the component of the layer (B) is dissolved, dried, and then the component of the thermal mask layer (C). Can be obtained by coating, heating and curing a solution in which is dissolved or dispersed.

  As another method, a sheet having a thermal mask layer (C) in which layers (C) and (B) are sequentially laminated on a release paper by the same coating method is prepared, and then the layer (A) is laminated on the substrate. The laminated photosensitive resin sheet and heat-sensitive mask sheet can be obtained by laminating the release paper after laminating the layer (A) so as to be in contact with the layer (B). The peeled release paper has the advantage that it can be reused for the same purpose.

  A third example is an original plate having a structure in which a photosensitive resin layer (A), an adhesive force adjustment layer (B), a thermal mask layer (C), and a peeling assist layer (D) are sequentially laminated on a substrate. This original plate can be obtained by peeling off the protective layer (E) from the original plate obtained in the first example. In this example, there is an advantage that the protective layer (E) can be reused.

  The fourth example is an original plate having a structure in which a photosensitive resin layer (A), an adhesion adjusting layer (B), a thermal mask layer (C), and a protective layer (E) are sequentially laminated on a substrate. Obtained by laminating a heat-sensitive mask sheet in which layers (C) and (B) are sequentially laminated on the protective layer (E) and a photosensitive resin sheet in which layers (A) are laminated on the substrate. Can do.

  The photosensitive resin printing plate precursor obtained as described above can produce a resin relief printing plate through the following steps.

  The method for producing a resin relief printing plate according to the present invention includes (1) using the above-described photosensitive resin printing plate precursor, and (2) image mask (C) by imagewise irradiating the thermal mask layer (C) with an infrared laser. ') Forming step, (3) forming the latent image on the photosensitive resin layer (A) by exposing the formed image mask (C') side using ultraviolet light, and (4) mainly using water. It consists of a step of developing with a liquid as a component to remove the image mask (C ′) and the photosensitive resin layer (A) in the ultraviolet light unexposed area.

  When the layer (D) and / or the layer (E) is present, at least the layer (E) is peeled off, and then the thermal mask layer (C) is imagewise irradiated with an infrared laser to form an image mask. Preferably, (C ′) is formed. More preferably, the layer (D) and the layer (E) are present, and only the layer (E) is peeled off, and then the thermal mask layer (C) is imagewise irradiated with an infrared laser to form an image mask ( C ′).

  (2) 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 ′) capable of forming 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 ruby lasers, alexandrite lasers, perovskite lasers, solid state lasers such as Nd-YAG lasers and emerald glass lasers, 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.

  (3) 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 material that has been laser-irradiated 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).

  At the time of exposure, ultraviolet light also enters from the side surface of the photosensitive resin printing plate material. Therefore, 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.

  (4) The step of developing with a liquid containing water 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, the photosensitive resin layer (A). It is achieved by developing using a brush type washing machine or a spray type washing machine having a developer mainly composed of water that can dissolve and disperse water. 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 (4).

  The developer containing water as a main component may contain tap water, distilled water, or water as a main component and an alcohol having 1 to 6 carbon atoms. Here, the main component means 70% by weight or more. Moreover, what mixed the component of the photosensitive resin layer (A), the adhesive force adjustment layer (B), the heat sensitive mask layer (C), and the peeling auxiliary layer (D) in these liquids can also be used.

  The image mask (C ′) is insoluble in water for the purpose of improving scratch resistance and does not dissolve in a developer composed of water or alcohol. However, since the thin film is superior in terms of cost, it can be physically removed by rubbing with a strong brush such as PBT (polybutylene terephthalate). At this time, the image mask (C ′) can be efficiently removed by using a relatively high temperature developing water 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 specifically described with reference to examples. However, the present invention is not limited to this.

<Method of measuring amine value (mmol / g)>
A sample of 0.2 g of amine compound was dissolved in 10 ml of methanol. To the solution was added 30 ml of acetic acid. This solution was titrated with a 0.5 N paratoluenesulfonic acid / acetic acid solution with an automatic potentiometric titrator (AT-610, manufactured by Kyoto Electronics Industry Co., Ltd.). The amine value (mmol / g) was calculated by the following formula (1).
Amine value (mmol / g) = 0.5 × F × V / (S × NV / 100) (1)
F = 0.5N of paratoluenesulfonic acid / acetic acid solution V = 0.5N titration of paratoluenesulfonic acid (ml)
S = Sample collection amount (g)
NV = sample resin content (wt%)

<Measurement method of number average molecular weight>
The number average molecular weight was measured using a GPC system of a high performance liquid chromatograph (LaChrom Elite, manufactured by Hitachi High-Technologies Corporation). Shodex Asahipak GF-710HQ, GF-510HQ, GF-310HQ (manufactured by Showa Denko KK) was used for the column, and RI was used for the detector. Further, an aqueous solution of 0.2M monoethanolamine (adjusted to pH = 5.1 with acetic acid) was used as an eluent, and maltoheptaose (Mn = 1153) and pullulan (Mn = 5800, 12200, 23700) were used as standard substances. , 48000, 100,000). The measurement was performed at an eluent flow rate of 0.5 ml / min and a column temperature of 40 ° C.

<Tear of heat-sensitive mask layer / 10 cm ² measurement method>
To break the mask layer, use a digital camera (NIKOON COOLPIX S8) to take a picture of the thermal mask layer within 10 cm ² of the screen, and then use a personal computer to make the digital image grayscale using the Adobe software photoshop, then SCION CORPORATION. The torn part and the normal part were binarized with the software SCION Image 4.03.2 manufactured by the company, and the torn part area was determined. Thereafter, the area of the torn part was divided by 10 cm ² to obtain the ratio of the torn part. The binarization was performed by scrolling the threshold button while looking at the image so that the torn part and the normal part could be clearly identified in the Threshold menu and the Density Slice menu.

<Measurement of scratches of 50 μm or more / 10 cm ² >
Using an optical microscope (OPTIPHOTO 300 manufactured by NIKON), observation was performed with a 10 × objective lens. The examination of the number of scratches of 50 μm or more in an area of 10 cm ² was repeated twice, and the average value was set to 50 μm or more scratches / 10 cm ² .

<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 condenser 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 0 ° 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.). )) After being dissolved in a mixed solvent of 200 parts by weight and 200 parts by weight of water at 70 ° C. for 2 hours, 1.5 parts by weight of “Blenmer” G (glycidyl methacrylate, manufactured by NOF Corporation) was added, and 1 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・ Geigy Co., Ltd.) 5 parts by weight, "epoxy ester" 70PA (propylene glycol diglycidyl ether acrylic acid adduct) Kyoeisha Chemical Co., Ltd.) (21 parts by weight) and ethylene glycol diglycidyl ether dimethacrylate (20 parts by weight) were added and mixed for 90 minutes. After cooling to 50 ° C., “FLORARD” TM FC-430 (manufactured by Sumitomo 3M Ltd.) 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 controlled by installing 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)>
11 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.) 55 parts by weight of water, 14 parts by weight of methanol, 10 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 2 for peeling auxiliary | assistant layer (D1) was obtained.

<Preparation of coating liquid compositions 3 and 4 for heat-sensitive mask layers (C1, C2)>
“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 ( 0.7 parts by weight of phosphoric acid monomer (manufactured by Kyoeisha Chemical Co., Ltd.) and 140 parts by weight of methyl isobutyl ketone 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).

  Further, 11 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.) is 55 parts by weight of water, 14 parts by weight of methanol, 10 parts by weight of n-propanol, and After dissolving in 10 parts by weight of n-butanol, 8 parts by weight of “MA100” (carbon black, manufactured by Mitsubishi Chemical Corporation) was mixed and dispersed using a three-roll mill, and a thermal mask layer ( A coating liquid composition 4 for C2) was obtained.

<Preparation of Coating Solution Composition 5 for Adhesive Strength Adjustment Layer (B1)>
The coating liquid composition 5 for the adhesive strength adjusting layer (B1) was adjusted as shown in Table 1. “Gosenol” KH-17 (polyvinyl alcohol having a saponification degree of 78.5% to 81.5%, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 20 parts by weight of water 40 parts by weight, ethanol 20 parts by weight, n-propanol 10 parts by weight The polymer solution was obtained. By adding 10 parts by weight of “Epomin” SP-012 (polyethyleneimine, manufactured by Nippon Shokubai Co., Ltd., molecular weight 1200, amine number 19) to the solution and stirring until a uniform liquid is obtained, A coating liquid composition 5 for B1) was obtained.

<Preparation of Coating Solution Composition 6 for Adhesive Strength Adjustment Layer (B2)>
"Epomin" SP-012 (polyethyleneimine, Nippon Shokubai Co., Ltd., molecular weight 1200, amine number 19) instead of octadodecylamine (Wako Pure Chemical Industries, Ltd., molecular weight 269, amine number 3.7) It was adjusted in the same manner as the coating liquid composition 5 except that was used.

<Preparation of Coating Solution Composition 7 for Adhesive Strength Adjustment Layer (B3)>
“Epomin” SP-012 (polyethyleneimine, Nippon Shokubai Co., Ltd., molecular weight 1200, amine number 19) is used, and “Gosenol” KH-17 (saponification degree 78.5% to 81.5% polyvinyl alcohol) , Manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) was prepared in the same manner as in the coating liquid composition 5 except that 30 parts by weight was used.

<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 0.25 μm, and at 100 ° C. for 25 seconds. It dried and the laminated body of peeling auxiliary | assistant layer (D1) / cover film (E) was obtained. 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) / cover film (E) was obtained. On the thermal mask layer (C1) side of the laminate thus obtained, the coating liquid composition 5 was applied using a bar coater so that the dry film thickness was 0.5 μm, and dried at 140 ° C., A thermal mask element 1 shown in Table 2 as a laminate of adhesion adjusting layer (B1) / thermal mask layer (C1) / peeling auxiliary layer (D1) / cover film (E) was obtained.

<Manufacture of thermal mask element 2>
It was manufactured in the same manner as the thermal mask element 1 except that the coating liquid composition 6 was used instead of the coating liquid composition 5. A thermal mask element 2 shown in Table 2, which is a laminate of adhesion adjusting layer (B2) / thermal mask layer (C1) / peeling auxiliary layer (D1) / cover film (E), was obtained.

<Manufacture of thermal mask element 3>
A coating liquid composition 4 was produced in the same manner as the thermal mask element 1 except that the coating liquid composition 6 was used instead of the coating liquid composition 5 instead of the coating liquid composition 3. A thermal mask element 3 shown in Table 2 as a laminate of adhesion adjusting layer (B2) / thermal mask layer (C2) / peeling auxiliary layer (D1) / cover film (E) was obtained.

<Manufacture of thermal mask element 4>
It was manufactured in the same manner as the thermal mask element 3 except that the coating liquid composition 2 was not applied. A thermal mask element 4 shown in Table 3 as a laminate of adhesion adjusting layer (B2) / thermal mask layer (C2) / cover film (E) was obtained.

<Manufacture of thermal mask element 5>
It was manufactured in the same manner as the thermal mask element 1 except that the coating liquid composition 7 was used instead of the coating liquid composition 5. A thermal mask element 5 shown in Table 3 as a laminate of adhesion adjusting layer (B3) / thermal mask layer (C1) / peeling auxiliary layer (D1) / cover film (E) was obtained.

Example 1
A calender roll heated to 80 ° C. with the heat-sensitive mask element 1 placed on the photosensitive resin layer (A1) of the photosensitive resin sheet 1 so that the adhesive force adjusting layer (B1) is in contact with the photosensitive resin layer (A1). Are laminated in the order of adhesive coated substrate 1 / photosensitive resin layer (A1) / adhesive strength adjusting layer (B1) / thermal mask layer (C1) / peeling auxiliary layer (D1) / cover film (E). A photosensitive resin printing plate precursor 1 was obtained. The clearance of the calender roll was adjusted so that the thickness of the laminate after peeling the cover film (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 cover film (E) from the photosensitive resin printing plate precursor 1, the thermal mask layer (C1) was examined on a light table, but the thermal mask layer was broken / 10cm ² or scratches of 50 μm or more / 10 cm ² was 0. It was a piece. After that, a test pattern with a resolution of 156 lines is mounted on 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 so that the substrate side is in contact with the drum. (The solid part, 1% to 99% halftone dot, 1 to 8 points of fine lines, 1 to 8 points of white lines) are laser-drawn under the conditions of a laser output of 9 W and a drum rotation speed of 500 rpm, and a thermal mask layer ( An image mask (C1 ′) was formed from C1).

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. The results are shown in Table 2.

(Example 2)
A photosensitive resin printing plate precursor 2 was prepared in the same manner as in Example 1 except that the thermal mask element 2 was used.

After peeling the cover film (E) from the photosensitive resin printing plate precursor 2 and examining the thermal mask layer (C1) on the light table, there was no thermal mask layer tear / 10 cm ² , but scratches of 50 μm or more / 10 cm ² was 0. Further, when the relief was formed, a defect was partially generated in the relief at the portion where the thermal mask layer (C1) was scratched, but the defect was at a usable level. The results are shown in Table 2.

(Example 3)
A photosensitive resin printing plate precursor 3 was prepared in the same manner as in Example 1 except that the thermal mask element 3 was used.

After peeling the cover film (E) from the photosensitive resin printing plate precursor 3, the thermal mask layer (C1) was examined on the light table, and there was no thermal mask layer tear / 10 cm ² . Moreover, the number of scratches / 10 cm ² of 50 μm or more was zero. Moreover, when the relief was formed, the negative relief was faithfully reproduced. The results are shown in Table 2.

Example 4
A photosensitive resin printing plate precursor 4 was produced in the same manner as in Example 1 except that the thermal mask element 4 was used.

After peeling the cover film (E) from the photosensitive resin printing plate precursor 4 and examining the thermal mask layer (C1) on the light table, there was no thermal mask layer tear / 10 cm ² . Moreover, the number of scratches / 10 cm ² of 50 μm or more was zero. Moreover, when the relief was formed, the negative relief was faithfully reproduced. The results are shown in Table 3.

(Comparative Example 1)
A photosensitive resin printing plate precursor 5 was prepared in the same manner as in Example 1 except that the thermal mask element 5 was used.

When the cover film (E) was peeled from the photosensitive resin printing plate precursor 5, the heat-sensitive mask layer (C1) was broken, and half was peeled off together with the cover film (E). Further, when the remaining heat-sensitive mask layer (C1) was examined on the light table, many scratches / 10 cm ^{2 of} 50 μm or more were generated. When the relief was formed, the part where the heat-sensitive mask layer (C1) was torn and peeled was a solid image on the entire surface, and the scratched part was also defective, and the desired relief could hardly be obtained. The results are shown in Table 3.

Claims (5)

  On the substrate, a photosensitive resin layer (A) containing a resin that can be dissolved or dispersed in water and a monomer that can be cured by ultraviolet light, an adhesive force adjusting layer (B), and a thermal mask layer containing an infrared absorbing substance ( C) is a photosensitive resin printing plate precursor laminated in this order, and the adhesive force adjusting layer (B) contains at least an amine compound.   2. The photosensitive resin printing plate precursor according to claim 1, wherein the amine compound has an amine value (mmol / g) of 5 or more and a number average molecular weight of 300 or more.   3. The photosensitive resin printing plate precursor according to claim 1, wherein the heat-sensitive mask layer (C) is hydrophobic.   The photosensitive resin printing plate precursor as claimed in claim 1, wherein a cover film (E) is laminated on the thermal mask (C).   The photosensitive resin printing plate precursor as claimed in claim 4, wherein a peeling auxiliary layer (D) is further laminated between the heat-sensitive mask layer (C) and the cover film (E).