JP2006003494A - Intaglio printing plate for printing photosensitive alignment layer, and photosensitive composition for manufacturing intaglio printing plate for printing alignment layer and laminate of intaglio printing original plate for printing alignment layer to be used for the intaglio printing plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive composition for manufacturing a printing plate, the composition having durability against various kinds of printing solutions and excellent printability, and to provide a layered body of a photosensitive printing original plate for printing and a printing plate using the composition. <P>SOLUTION: In the photosensitive composition for manufacturing a printing plate containing at least a binder resin, a photopolymerizable monomer and a photopolymerization initiator, the obtained photosensitive composition has excellent durability against a variety of printing solutions, in particular, a printing solution such as an alignment layer solution by using an elastomer resin and terpene resin together as the binder resin. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an intaglio printing plate for photosensitive alignment film printing, a photosensitive composition for producing an intaglio printing plate for alignment film printing used therein, and an intaglio printing original laminate for photosensitive alignment film printing. An intaglio printing plate for photosensitive alignment film printing having resistance to an alignment film printing liquid for forming a liquid crystal alignment film and having excellent printability, and a photosensitive composition for producing an intaglio printing plate for alignment film printing used therefor The present invention relates to an intaglio printing original laminate for printing a photosensitive alignment film.

  The intaglio printing plate for alignment film printing is an intaglio printing plate used for printing an alignment film on a display panel in a liquid crystal display or the like. (Patent Document 1)

  In recent years, photosensitive resins have been used for alignment film printing plates. This photosensitive resin generally comprises an elastomeric binder, at least one photopolymerizable monomer and a photoinitiator. A printing original plate using the photosensitive resin is a plate-like member in which at least the photosensitive resin layer is provided on a support.

  In the production of a printing plate using the printing original plate, first, a film (mask) having a negative pattern of an image such as characters and images to be printed is placed on the photosensitive resin layer of the printing original plate, and this mask is used. Then, the photosensitive resin layer is irradiated with actinic radiation. The portion irradiated with actinic radiation is cured by a photopolymerization reaction. Thereafter, when the uncured portion is washed away with a developer, a pattern corresponding to the image remains. As a result, a printing plate is completed. In alignment film printing, ink is applied to the concave portion of the concave pattern, pressed against the display substrate, or transferred to apply a predetermined pattern of ink onto the print medium, thereby efficiently forming a uniform alignment film on the substrate. Form.

JP-A-10-161124

However, conventional printing plates do not have sufficient resistance depending on the type of printing liquid such as the alignment film liquid used, and the patterned cured resin layer of the printing plate absorbs the components contained in the printing liquid as printing continues. The problem of swelling is pointed out.
In the production of a liquid crystal display element, when an alignment film is formed on a substrate, a roll coater method, a spinner method, a printing method, or the like is used. However, when an intaglio printing plate is used, the N− contained in the alignment film liquid is used. There is a problem that the patterned cured resin layer swells due to components such as methyl-2-pyrrolidone, butyl cellosolve, and γ-butyrolactone.

  The present invention has been made in view of the above, and is an intaglio printing plate for printing a photosensitive alignment film having excellent resistance to various printing liquids, particularly an alignment film liquid, and alignment film printing used therefor. It is an object of the present invention to provide a photosensitive composition for producing an intaglio printing plate and an intaglio printing original laminate for printing a photosensitive alignment film.

  As a result of intensive studies to solve the above problems, the present inventors have added a terpene resin to a conventional photosensitive composition for producing a printing plate containing an elastomer resin, a photopolymerizable monomer and a photopolymerization initiator. Thus, it has been found that a printing plate having excellent ink resistance can be obtained, and the present invention has been completed based on this finding.

  That is, the photosensitive composition for producing a printing plate of the present invention is characterized by containing an elastomer resin, a terpene resin, a photopolymerizable monomer, and a photopolymerization initiator.

  According to a preferred embodiment of the photosensitive composition for producing a printing plate of the present invention, it is preferable to use a hydrogenated terpene resin as the terpene resin. Moreover, it is preferable to use a styrene-isoprene-styrene block copolymer as the elastomer resin. Furthermore, it is preferable to contain 30 to 90 parts by weight of the elastomer resin and 70 to 10 parts by weight of the terpene resin with respect to 100 parts by weight of the total of the elastomer resin and the terpene resin.

  In addition, the intaglio printing original laminate for printing a photosensitive alignment film according to the present invention is a photosensitive formed on a support from at least an elastomer resin, a terpene resin, a photopolymerizable monomer, and a photopolymerization initiator. It has a resin layer. According to a preferred embodiment of the photosensitive laminated printing original plate for intaglio printing of the present invention, it is preferable to form a protective layer covering the surface opposite to the support.

  Further, the intaglio printing plate for printing a photosensitive alignment film according to the present invention is a printing plate formed by forming a cured resin layer having a concave pattern for printing on a support, and the patterned cured resin layer has a configuration. It is characterized by containing at least an elastomer resin and a terpene resin simultaneously as components.

  The photosensitive resin layer formed using the photosensitive composition for producing a printing plate of the present invention becomes a cured resin layer having a concave pattern for printing by exposure and development, and this patterned cured resin layer is The inks have excellent resistance to various inks, particularly printing liquids such as alignment film liquids. For this reason, even if printing is continued for a long time, the patterned cured resin layer is not swollen by the printing liquid, and a high-quality printed matter can be obtained.

  Conventionally, the resistance to the alignment film liquid is insufficient, and there is a problem that the patterned cured resin layer swells, and the resistance of the patterned cured resin layer to the alignment film liquid has been demanded. The present invention is based on a novel discovery that printing liquid resistance is improved by adding a terpene resin to a photosensitive composition for producing an intaglio printing plate.

Moreover, in the photosensitive composition for printing plate manufacture of this invention, there exists an effect that it has the outstanding printing liquid resistance by using hydrogenated terpene resin as terpene resin. Further, by using a styrene-isoprene-styrene block copolymer as the elastomer resin, it is possible to ensure the transparency required for forming an exposure pattern and to impart further excellent printing liquid resistance. Moreover, sufficient tolerance with respect to a printing liquid is contained by including 30 to 90 parts by weight of the elastomer resin and 70 to 10 parts by weight of the terpene resin with respect to 100 parts by weight of the total of the elastomer resin and the terpene resin. As well as sufficient flexibility required for an intaglio printing plate.

  In addition, the intaglio printing original laminate for printing a photosensitive alignment film of the present invention has a configuration in which a photosensitive resin layer made of the photosensitive composition of the present invention is formed on a support. Thus, it is possible to manufacture in advance and store a predetermined period of time even though there is an expiration date. Therefore, when a printing plate is manufactured, it can be used immediately, and the efficiency of manufacturing the printing plate can be increased. In addition, in the intaglio printing original laminate for printing a photosensitive alignment film of the present invention, storage, transportation and handling can be facilitated by forming a protective layer covering the surface opposite to the support.

  Further, the printing plate of the present invention is a printing plate obtained by forming a cured resin layer having a concave pattern for printing on a support, and the elastomer resin and the terpene resin are simultaneously contained in the patterned resin layer. Excellent resistance to various printing liquids. For this reason, even if printing is continued for a long time, the patterned cured resin layer is not swollen by the ink component, and a high-quality printed matter can be obtained. The printing plate of the present invention can be suitably used as an intaglio printing plate, particularly as an intaglio printing plate for alignment films.

  The photosensitive composition for producing a printing plate according to the present invention is a photosensitive composition for producing a printing plate containing at least a binder resin, a photopolymerizable monomer, and a photopolymerization initiator, and an elastomer as a binder resin. It contains resin and terpene resin at the same time.

  By using a combination of an elastomer resin and a terpene resin as the binder resin, the resistance of the obtained printing plate to the printing liquid can be remarkably improved, and excellent printability can be imparted.

  Hereinafter, the photosensitive composition for producing a printing plate of the present invention, and the photosensitive laminated printing original plate and printing plate using the same will be described in detail in the following order.

[A] Photosensitive composition for producing intaglio printing plate for alignment film printing (a) Terpene resin (b) Elastomer resin (c) Photopolymerizable monomer (d) Photopolymerization initiator [B] Intaglio for printing photosensitive alignment film Printing original plate laminate [C] Intaglio printing plate for photosensitive alignment film printing

[A] Photosensitive composition for producing intaglio printing plate for alignment film printing (a) Terpene resin In the present invention, "terpene resin" refers to a monomer capable of homopolymerizing terpenes or copolymerizing with terpenes. It is a polymer obtained by copolymerization.

  Examples of terpenes that are raw materials for terpene resins include hydrocarbons having a molecular formula of C10H16 and oxygen-containing compounds (alcohols, aldehydes, ketones, etc.) derived therefrom.

Specific examples of such terpenes include hydrocarbons such as α-pinene, β-pinene, myrcene, osimene, limonene, terpinolene, terpinene, ferrandrene, sylbestrene, sabinene, kalene, camphene, tricyclene, fenchen, etc. , Citronellol, geraniol, nerol, linalool, menthol, terpineol, carpeol, twill alcohol, pinocampheol, phenanthryl alcohol, borneol and other alcohols, citonellal, citral, cyclocitral, safranal, ferrandral, perylaldehyde, etc. Aldehydes, daketones, yonons, menthones, carbomentones, carbotanacetons, piperitones, ketones such as thoyon, caron, camphor, cineole, pinol, ascarito Examples thereof include oxides such as citric acid and acids such as citronellic acid. Of these, α-pinene, β-pinene and limonene are particularly preferably used.
These terpenes can be used alone or in combination of two or more.

  Examples of monomers copolymerizable with terpenes include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, chlorostyrene, dichlorostyrene, α-ethylstyrene, methyl-α. -Methyl styrene, dimethyl styrene, 2,4-diisopropyl styrene, 4-tert-butyl styrene, tert-butoxy styrene, vinyl toluene and the like can be exemplified.

  The polymerization ratio of the terpenes and the monomers copolymerizable with the terpenes is in the range of the monomers 0 to 5 copolymerizable with the terpenes with respect to the terpenes 1 to 10 in the monomer ratio, preferably the terpenes 1-7, monomers 0-4, more preferably terpenes 2-5, monomers 0-3.

  A terpene resin obtained by homopolymerizing terpenes or copolymerizing monomers that can be copolymerized with terpenes has a carbon-carbon unsaturated bond or an oxygen-carbon bond in its molecular structure. May have saturated bonds. In the present invention, it is preferable to use a hydrogenated terpene resin in which these unsaturated bonds are partially or completely hydrogenated, and it is particularly preferable to use a fully hydrogenated terpene resin. By using the hydrogenated terpene resin, it is possible to further improve the printing liquid resistance.

  Examples of such commercially available hydrogenated terpene resins include Clearcron P series, Clearcron M series, and Clearcron K series (all manufactured by Yasuhara Chemical Co., Ltd.).

  The average molecular weight of the terpene resin is 300-1500, preferably 400-1000, more preferably 500-800. When the average molecular weight of the terpene resin is less than 300, it is difficult to synthesize the resin. When the average molecular weight is more than 1500, the flexibility becomes insufficient and the printing original plate laminate may be damaged.

  The blending amount of the terpene resin is preferably 1 to 90 parts by weight of the terpene resin with respect to 100 parts by weight of the total of the elastomer resin and the terpene resin described later. When the terpene resin is less than 1 part by weight, the resistance to the printing liquid is not sufficient, and when the terpene resin is 90 parts by weight or more, the flexibility is insufficient and the printing original plate laminate may be damaged. . In order to provide sufficient resistance to the printing liquid and to ensure sufficient flexibility required as an intaglio printing plate, the terpene resin is 10 to 10 parts by weight based on the total of 100 parts by weight of the elastomer resin and the terpene resin. It is preferable that it is 70 weight part.

(B) Elastomer resin In the present invention, the elastomer resin is a resin other than a terpene resin, and is a single polymer, copolymer or mixture thereof, has an elastomeric property, and is an aqueous or organic solvent developer. Polymers that are soluble, swelled or dispersed and can be washed away. Examples of these binders include polybutadiene, polyisoprene, polydiolefin, vinyl aromatic compound / diolefin copolymer and block copolymer, styrene / butadiene copolymer, styrene / isoprene copolymer, diolefin / Acrylonitrile copolymer, ethylene / propylene copolymer, ethylene / propylene / diolefin copolymer, ethylene / acrylic acid copolymer, diolefin / acrylic acid copolymer, diolefin / acrylate / acrylic acid copolymer, Ethylene / (meth) acrylic acid / (meth) acrylate copolymer, polyamide, polyvinyl alcohol, polyvinyl alcohol / polyethylene glycol graft copolymer, amphoteric interpolymer, alkyl cellulose, hydroxyalkyl cellulose Celluloses such as nitrocellulose, ethylene / vinyl acetate copolymer, cellulose acetate butyrate, polybutyral, cyclic rubber, styrene / acrylic acid copolymer, polyvinyl pyrrolidone, polyvinyl pyrrolidone and vinyl acetate copolymer, chloroprene heavy Polymer, styrene-chloroprene copolymer, acrylonitrile-butadiene copolymer, acrylonitrile-isoprene copolymer, acrylonitrile-chloroprene copolymer, methyl methacrylate-butadiene copolymer, methyl methacrylate-isoprene copolymer, methacrylic acid Methyl-chloroprene copolymer, methyl acrylate-butadiene copolymer, methyl acrylate-isoprene copolymer, methyl acrylate-chloroprene copolymer, acrylonitrile-butadiene -Styrene copolymer, acrylonitrile-isoprene-styrene copolymer, acrylonitrile-chloroprene-styrene copolymer, epichlorohydrin polymer, epichlorohydrin-ethylene oxide copolymer, epichlorohydrin-propylene oxide copolymer, epichlorohydrin rubber, chlorinated polyethylene , Vinyl chloride copolymer, vinylidene chloride copolymer, chlorinated polypropylene, chlorinated ethylene-propylene rubber, ethyl acrylate-acrylonitrile copolymer, butyl acrylate-acrylonitrile copolymer, methyl methacrylate-acrylonitrile copolymer And butyl acrylate-styrene-acrylonitrile copolymer. The polymers may be used alone or in combination. In addition, U.S. Pat. Nos. 3,458,311, 4,442,302, 4,361,640, and 3,794, which are binders that are soluble or dispersible in an aqueous developer. No. 494, No. 4,177,074, No. 4,431,723, No. 4,517,279, etc. Soluble and swelling in resins and organic solvent developers Alternatively, the resins disclosed in specifications such as U.S. Pat. Nos. 4,323,636, 4,430,417, and 4,045,231, which are dispersible, can also be mentioned.

  In the present invention, it is preferable to use a styrene / isoprene copolymer or a styrene / butadiene copolymer, and it is particularly preferable to use a styrene-isoprene-styrene block copolymer. By using the styrene-isoprene-styrene block copolymer, it is possible to ensure the transparency required for forming the exposure pattern and to further improve the resistance to the printing liquid.

  The blending amount of the elastomer resin is 10 to 99 parts by weight, preferably 30 to 90 parts by weight, based on 100 parts by weight of the total of the elastomer resin and the terpene resin.

(C) Photopolymerizable monomer As the one or more monomers contained in the photosensitive resin layer used in the present invention, it is necessary to use a monomer that is compatible with the binder so that a transparent and non-sensitive photosensitive resin layer can be formed. There is. As the monomer, in addition to the monomer constituting the binder, for example, polybutadiene diacrylate, polybutadiene dimethacrylate, polyisoprene acrylate, polyisoprene methacrylate, α-methyl styrene, m-methyl styrene, p-methoxy styrene, etc. Aromatic vinyl monomer; α, β-ethylenically unsaturated nitrile compound such as acrylonitrile and methacrylonitrile; carbon number such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate 1-23 alkyl alcohol acrylates and corresponding methacrylates; hydroxy alcohols such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate Alcohol acrylates and corresponding methacrylates; alkoxyalkylene glycol acrylates and methacrylates such as methoxyethylene glycol and methoxypropylene glycol; monounsaturated polycarboxylic acids such as monoethyl maleate, monomethyl fumarate and monoethyl itaconate Monoesters: Diesters such as dimethyl maleate, diethyl maleate, dibutyl maleate, dioctyl maleate, diethyl fumarate, dibutyl fumarate, dioctyl fumarate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, dioctyl itaconate Acrylics such as acrylamide, methacrylamide, N, N'-methylenebisacrylamide, N, N'-hexamethylenebisacrylamide Amides and corresponding methacrylamides; ethylene glycol diacrylates, diacrylates of glycols of polyalkylene glycols (2 to 23 alkylene glycol units) and corresponding methacrylates; glycerin, pentaerythritol, trimethylolalkanes, tetramethylolalkanes (Diacrylates, triacrylates, tetraacrylates, oligoacrylates and corresponding methacrylates of trihydric or higher polyhydric alcohols such as methane, ethane, and propane as alkanes; 2-acryloyloxyethyl succinic acid, 2-acryloyl Acrylates and corresponding methacrylates having acidic functional groups such as ethylhexahydrophthalic acid, 2-acryloyloxyethyl acid phosphate; Can be mentioned. These photopolymerizable ethylenically unsaturated monomers may be used singly or in combination of two or more. In addition, the monomers described in US Pat. Nos. 4,323,636, 4,753,865, 4,726,877, and 4,894,315 are listed. Can do. Photopolymerizable monomers may be used alone or in combination. Particularly preferred are polybutadiene diacrylate and 1,6-hexanediol diacrylate.

  The monomer has a range of 5 to 30 parts by weight, preferably 10 to 20 parts by weight, where the total of the elastomer resin and the terpene resin is 100 parts by weight. When the monomer content is less than the above range, the abrasion resistance and chemical resistance of the film after exposure curing are lowered, and when it exceeds the above range, the elastomeric property of the photosensitive resin layer is lowered, which is not preferable as a flexographic printing plate.

(D) Photopolymerization initiator As the photopolymerization initiator, those generally known can be used. Examples of such initiators include aromatic ketones such as benzophenone; benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, α-methylol benzoin methyl ether, α-methoxybenzoin methyl ether, 2,2-diethoxy Benzoin ethers such as phenylacetophenone; substituted and unsubstituted polynuclear quinones; 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1- [4- (Methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-hydroxy-2-methyl-1 -Phenylpropan-1-one, 2, 4, 6 -Trimethylbenzoyldiphenylphosphine oxide, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2 , 4-dimethylthioxanthone, 3,3-dimethyl-4-methoxybenzophenone, benzophenone, 1-chloro-4-propoxythioxanthone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4-benzoyl-4′-methyldimethylsulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, 4- Ethyl dimethylaminobenzoate, 4-dimethylaminobenzoate Butyl benzoate, 4-dimethylaminobenzoic acid-2-ethylhexyl, 4-dimethylaminobenzoic acid-2-isoamyl, 2,2-diethoxyacetophenone, benzyldimethyl ketal, benzyl-β-methoxyethyl acetal, o-benzoylbenzoic acid Acid methyl, bis (4-dimethylaminophenyl) ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n- Butyl ether, benzoin isobutyl ether, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, 2- (o-chlorophenyl) ) -4,5-diphenylimidazolyl dimer, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, α, α-dichloro-4-phenoxyacetophenone, pentyl-4-dimethylaminobenzoate, 9-phenyl Examples include acridine, 1,7-bis- (9-acridinyl) heptane, 1,5-bis- (9-acridinyl) pentane, and 1,3-bis- (9-acridinyl) propane. Other examples include initiators disclosed in US Pat. Nos. 4,460,675 and 4,894,315. The initiators may be used alone or in combination.

  The initiator is preferably contained in the range of 0.001 to 10% by weight with respect to the total weight of the photosensitive composition for producing a printing plate of the present invention.

  Furthermore, the photosensitive resin composition of the present invention may be added with dyes, pigments, polymerization inhibitors, antioxidants, photodegradation inhibitors, and the like, if necessary, to improve its performance.

[B] Intaglio printing original laminate for photosensitive alignment film printing The intaglio printing original laminate for photosensitive alignment film printing according to the present invention comprises a support, an elastomer resin formed on the support, a terpene resin, and a photopolymerization. And a photosensitive resin layer containing at least a photopolymerization initiator.

  The method for forming the photosensitive resin layer is not particularly limited, and can be arbitrarily selected from methods commonly used for laminating the photosensitive layer on the support in the production of the photosensitive printing original plate laminate. . For example, a photosensitive resin composition prepared by mixing a terpene resin, an elastomer resin, a photopolymerizable monomer, a photopolymerization initiator, and other components is molded into a hot melt, and this is calendered to a desired thickness. Or the photosensitive resin composition is melted, mixed, deaerated and filtered using an extruder, and then extruded between a support and a temporary cover sheet, and calendered to a desired thickness. Alternatively, a coating film of the photosensitive resin composition is formed on the support layer by a method such as placing a support and a cover sheet in a mold and injecting the photosensitive resin composition between the two. A photosensitive resin layer is formed by solidifying the coating film.

  The thickness of the photosensitive resin layer is usually in the range of 0.1 to 10.0 mm, preferably 0.5 to 7.0 mm.

  As the support layer constituting the photosensitive laminated printing original plate for printing of the present invention, known metals and plastics used in ordinary flexographic printing plates satisfying physical performance such as mechanical strength required for printing conditions to be used. All supports in film, paper and their composite form can be used. These include polymeric films such as those formed by addition polymerization polymers and linear condensation polymers, transparent foams and fabrics, nonwoven fabrics such as glass fiber fabrics, and metals such as steel and aluminum. The support is preferably transparent to exposure light so that back exposure is easy. More preferred supports include polyethylene, polypropylene or polyester films, and polyester films and polyethylene terephthalate films are particularly preferable. As the film, a film having a thickness of 50 to 400 μm, preferably a film having a thickness of 75 to 300 μm is used. The support layer may be covered with a thin adhesive layer between the photosensitive resin layer as necessary. Examples of the adhesive layer include polyester-based resins, urethane-based resins, and ethyl cellulose, and those made of a mixture of polycarbonate, phenoxy resin, and polyvalent isocyanate can be suitably used.

In the present invention, it is preferable to provide a protective layer on the surface opposite to the support layer, if necessary. As the protective layer, a polyester film, a polyethylene terephthalate film, a polypropylene film, a polyethylene film, or the like having a thickness of about 15 to 125 μm coated or baked with silicone is suitable. This protective layer is temporarily affixed to facilitate storage, transportation, and handling. During the production of a printing plate, the protective layer is peeled off to expose the photosensitive resin layer on the surface. Light will be irradiated.
The protective layer may be covered with a thin anti-adhesion layer between the photosensitive resin layer as necessary. Examples of the anti-adhesion layer include polypropylene, polyester, polystyrene, cellulose derivatives, and polyamide resins.

  In the present invention, it is preferable to provide a mask material layer on the photosensitive resin layer as necessary. On the photosensitive resin layer, a mask material layer that is opaque to exposure light is formed, and a part of the mask material layer is patterned so that the exposure light is transmitted to form a mask image layer. Since the pattern for printing can be formed on the photosensitive resin layer by irradiating with exposure light, the efficiency of manufacturing the printing plate can be further increased.

  As a method of forming a mask image layer by patterning a part of the mask material layer so that exposure light is transmitted, an infrared ablation layer made of an infrared sensitive material is provided as the mask material layer, and this infrared ablation layer is formed by an infrared laser. A method of forming a negative pattern by selectively ablating (burning out) is the mainstream. As for the infrared ablation layer, for example, Japanese Patent No. 2916408, Japanese Patent Application Laid-Open No. 2003-35954, Japanese Patent Application Laid-Open No. 2003-35955, Japanese Patent Application Laid-Open No. 11-153865, Japanese Patent Application Laid-Open No. 9-166875, and Japanese Patent Application Laid-Open No. 2001-2001. Reference can be made to the descriptions in Japanese Patent No. 324815 and Japanese Patent No. 2773981.

[C] Intaglio printing plate for photosensitive alignment film printing The printing plate of the present invention is an intaglio printing plate having a cured resin layer having a concavo-convex pattern for printing on a support, and the patterned cured resin layer However, it is characterized by containing at least an elastomer resin component and a terpene resin component as constituent components. This patterned cured resin layer is preferably formed by photocuring the photosensitive composition for producing an intaglio printing plate of the present invention. The presence form of the elastomer resin component and the terpene resin component in the patterned cured resin layer varies depending on the photocuring reaction conditions, and is present in a state where it is crosslinked by the photopolymerizable monomer by the photocuring reaction or unreacted without being crosslinked. The state to do is considered. In the present invention, the elastomer resin component and the terpene resin component may be contained in the patterned cured resin layer in any state.

  The printing plate of the present invention using the intaglio printing original laminate for printing a photosensitive alignment film, the photosensitive resin layer of the pattern portion is cured by exposing the photosensitive resin layer through a mask, and the exposure The photosensitive resin layer is produced as a patterned cured resin layer by removing the exposure light non-irradiated region of the photosensitive resin layer in an uncured state without being irradiated with light with a developer.

  According to a preferred embodiment, the intaglio printing precursor laminate for photosensitive alignment film printing is subjected to back exposure from the support layer side as necessary, and then the intaglio printing precursor laminate for photosensitive orientation film printing is protected. The layer (slip sheet) is peeled off to expose the photosensitive resin layer on the surface. Next, the photosensitive resin layer in the pattern portion is cured by performing main exposure through a mask. By this main exposure, the photosensitive resin layer is irradiated with pattern light in accordance with the mask pattern, and the region irradiated with the exposure light is cured by a crosslinking reaction.

  When a mask material layer such as an infrared ablation layer is provided on the photosensitive resin layer, a mask image is formed by removing the infrared ablation layer using infrared laser light, and this mask image layer is used as a mask. Perform main exposure.

  Next, the uncured portion that has not been irradiated with the exposure light is removed with a developer, thereby revealing the printing pattern and drying it. After drying, post-exposure may be performed as necessary.

  As an exposure apparatus used for exposure, an actinic radiation irradiation apparatus generally used for manufacturing a flexographic plate can be used. As the radiation, ultraviolet rays and visible rays having a wavelength of 150 nm to 800 nm can be used, and ultraviolet rays having a wavelength of 320 nm to 450 nm are preferable. As the light source, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, or the like can be used.

  The developer used in the development process may be any organic solution, water, aqueous or semi-aqueous solution as long as it has the property of dissolving the photosensitive resin layer. Depending on the chemical nature of the resin to be removed. Suitable organic solvent developers include aromatic or aliphatic hydrocarbons and aliphatic or aromatic halohydrocarbon solvents or mixtures of these solvents with suitable alcohols. The semi-aqueous developer contains water or an organic solvent miscible with water and an alkaline material. Examples of the aqueous developer include water, esters such as heptyl acetate and 3-methoxybutyl acetate, petroleum fractions, hydrocarbons such as toluene and decalin, chlorine solvents such as tetrachloroethylene, and monoethanolamine. And aqueous solutions of amines such as diethanolamine and triethanolamine, sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia and the like. Moreover, what mixed alcohols, such as a propanol, a butanol, and a pentanol, can also be used for these solvents, and arbitrary methods, such as immersion, spraying from a nozzle, and brushing with a brush, can be employ | adopted.

  In the production of the printing plate of the present invention, the printing plate material is further improved in productivity by attaching the printing plate laminate to a drum in a cylindrical shape, and exposing and developing.

  Hereinafter, the present invention will be described in more detail based on examples. In addition, this invention is not limited to the following Example.

<Examples 1-3, Comparative Examples 1 and 2>
(Preparation of flexographic printing plate)
As thermoplastic elastomer, styrene-isoprene-styrene block copolymer (trade name D-1107, manufactured by KRATON) and hydrogenated terpene resin (trade name: Clearon P-125, manufactured by Yasuhara Chemical Co.) are shown in Table 1 below. 75% by weight of this mixture was mixed with 8.7% by weight of 1,6-hexanediol diacrylate, 15% by weight of polybutylidene-terminated acrylate (trade name BAC-45 manufactured by Osaka Organic Chemical Co., Ltd.), 1.3% by weight. % Benzyl methyl ketal (trade name Irgacure 651, manufactured by Ciba Specialty Chemicals) was added to a twin-screw kneader, and a 2 mm thick sheet was prepared using T dicing, and a 125 μm thick polyester sheet (support layer) An anti-adhesion layer consisting of a polyamide resin layer on the other side Was laminated on a polyester sheet (protective layer) provided with a printing original plate laminate in which four layers of a support layer, a photosensitive resin layer, an anti-adhesion layer, and a protective layer were sequentially laminated and integrated.

  Next, these printing original plate laminates were attached to a drum in a cylindrical shape, and processed into a printing plate by sequentially performing back exposure, main exposure, development, drying, and post-exposure. In addition, since the flexibility of the printing original plate laminate of Comparative Example 2 was insufficient and the printing original plate laminate was damaged when attached to the drum, the performance evaluation of the following flexographic printing plate was described in Examples. 1 to 3 and Comparative Example 1 only.

(Evaluation of printing plate)
(1) Evaluation of resistance to alignment film solution From each of the printing plates of Examples 1 to 3 and Comparative Example 1, 3 cm × 3 cm size plates were cut, and γ-butyllactone and N-methyl-2-pyrrolidone as solvents for the alignment film solution , And butyl cellosolve for 48 hours to evaluate the resistance to the alignment film solution. Tables 2 to 4 show the amount of decrease in the plate surface hardness value (difference in hardness before and after immersion in various alignment film liquid solvents by a hardness measuring machine conforming to JIS K 6301A type standard) and the amount of increase in the photosensitive layer thickness.

  From the above results, in Examples 1 to 3 using the terpene resin, the decrease amount of the plate surface hardness value and the increase amount of the photosensitive layer film thickness are not substantially observed or even if there is a change. It can be seen that it has excellent resistance to various alignment film liquid solvents.

  On the other hand, about the comparative example 1 which does not use a terpene resin, the tolerance with respect to various alignment film liquid solvents was inadequate, and the fall of a plate surface hardness value and the increase in the photosensitive layer film thickness were remarkable. In Comparative Example 2 in which the elastomer resin was not used, the flexibility was insufficient, and the printing original plate laminate was damaged when attached to the drum.

  As described above, the photosensitive composition for producing a printing plate according to the present invention includes at least a binder resin, a photosensitive composition for producing a printing plate containing a photopolymerizable monomer, and a photopolymerization initiator. As described above, an elastomer resin and a terpene resin are used in combination. By using the elastomer resin and the terpene resin in combination, the resistance of the obtained printing plate to the printing liquid can be remarkably improved.

By using the photosensitive composition for producing a printing plate of the present invention having the above characteristic configuration, a photosensitive printing original plate laminate for printing having excellent printability and a printing plate can be produced. It can be suitably used as a printing plate.

Claims (7)

An intaglio for printing a photosensitive alignment film, comprising a photosensitive resin layer formed of at least an elastomer resin, a terpene resin, a photopolymerizable monomer, and a photopolymerization initiator on a support. Printed version. The intaglio printing plate for printing a photosensitive alignment film according to claim 1, wherein the terpene resin is a hydrogenated terpene resin. The intaglio printing plate for photosensitive alignment film printing according to claim 1, wherein the elastomer resin is a styrene-isoprene-styrene block copolymer. The elastomer resin is 30 to 90 parts by weight and the terpene resin is 70 to 10 parts by weight with respect to 100 parts by weight of the total of the elastomer resin and the terpene resin. 2. An intaglio printing plate for printing a photosensitive alignment film according to item 1. A photosensitive composition for producing an intaglio printing plate for alignment film printing, comprising at least a binder resin, a photopolymerizable monomer, and a photopolymerization initiator,
5. An alignment film printing comprising an elastomer resin and a terpene resin as the binder resin, and used for the intaglio printing plate for photosensitive alignment film printing according to any one of claims 1 to 4. A photosensitive composition for producing an intaglio printing plate. An intaglio for printing a photosensitive alignment film, comprising a photosensitive resin layer formed of at least an elastomer resin, a terpene resin, a photopolymerizable monomer, and a photopolymerization initiator on a support. Printing master laminate. The intaglio printing original laminate for printing a photosensitive alignment film according to claim 6, further comprising a protective layer on a surface opposite to the support.