KR20060045600A - Photosensitive intaglio printing plate for printing alignment film, photosensitive composition for producing intaglio printing plate for printing alignment film, and photosensitive laminate as printing original plate for intaglio printing for printing alignment film - Google Patents

Abstract

(Problem) The photosensitive composition for printing plate manufacture which has tolerance to various printing liquids and has the outstanding printability, and the photosensitive printing original laminated body for printing and printing plate using the same are provided.

(Solution means) At least, in a photosensitive composition for manufacturing a printing plate containing a binder resin, a photopolymerizable monomer, and a photopolymerization initiator, by using an elastomer resin and a terpene resin together as a binder resin, various printing liquids, especially printing liquids such as alignment film liquids, etc. With respect to the above, a photosensitive composition having excellent resistance is obtained.

Photosensitive composition for printing plate production, terpene resin

Description

Concave plate printing plate for photosensitive alignment film printing and photosensitive composition for manufacturing concave plate printing plate for alignment film printing used for this, concave plate printing original laminate for photosensitive alignment film printing {PHOTOSENSITIVE INTAGLIO PRINTING PLATE FOR PRINTING ALIGNMENT FILM LAMINATE AS PRINTING ORIGINAL PLATE FOR INTAGLIO PRINTING FOR PRINTING ALIGNMENT FILM}

The present invention relates to a concave plate printing plate for photosensitive alignment film printing, and a photosensitive composition for producing a concave plate printing plate for alignment film printing used for this, and a concave plate printing original laminate for photosensitive alignment film printing, which specifically has resistance to alignment film printing liquid for forming a liquid crystal alignment film, The recessed plate printing plate for photosensitive alignment film printing which has the outstanding printability, and the photosensitive composition for manufacturing the recessed plate printing plate for alignment film printing used for this, and the recessed plate printing original laminated body for photosensitive alignment film printing are used.

An intaglio printing plate for alignment film printing is a intaglio printing plate used for printing an alignment film on a display panel in a liquid crystal display or the like (Patent Document 1: Japanese Patent Application Laid-Open No. 10-161124).

Photosensitive resin is used for the orientation film printing plate in recent years. This photosensitive resin generally consisted of an elastomeric binder, at least one photopolymerizable monomer, and a photoinitiator. The printing original plate using this photosensitive resin is a plate-shaped member in which the said photosensitive resin layer was formed at least on the support body.

In the manufacture of a printing plate using this printing original plate, a film (mask) having a negative pattern of an image such as a character or an image to be printed is first placed on the photosensitive resin layer of the printing original plate, and the actinic ray is exposed through the mask. Irradiate to the resin layer. The part irradiated with actinic radiation hardens due to a photopolymerization reaction. Thereafter, when the uncured portion is washed away with a developer, a pattern corresponding to the image remains. As a result, the printing plate is completed. In alignment film printing, a uniform alignment film is efficiently formed on a substrate by adhering ink to the concave portion of the concave pattern, pressing or transferring the ink onto a display substrate, and applying the ink in a predetermined pattern onto the print medium.

However, conventional printing plates do not have sufficient resistance depending on the type of printing liquid such as the alignment film liquid to be used, and the patterned cured resin layer of the printing plate absorbs and swells the components contained in the printing liquid during printing. The problem is pointing out.

In the manufacture of a liquid crystal display element, when forming an alignment film on a board | substrate, the roll coater method, the spinner method, the printing method, etc. are used, When using a recessed-plate printing plate, N-methyl-2 contained in an alignment film liquid There was a problem that the patterned cured resin layer was flattened by components such as -pyrrolidone, butyl cellosolve, and -butyrolactone.

SUMMARY OF THE INVENTION The present invention has been made in view of the above-described circumstances, and the concave plate printing plate for photosensitive alignment film printing having excellent resistance to various printing liquids, especially the alignment film liquid, and the concave plate printing plate for alignment film printing used therein, the concave plate printing original plate for photosensitive alignment film printing The purpose is to provide a sieve.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to solve the said subject, the present inventors added a terpene resin to the conventional photosensitive composition for printing plate manufacture containing an elastomer resin, a photopolymerizable monomer, and a photoinitiator, and can obtain a printing plate with excellent ink resistance. It discovered that the present invention was completed based on this knowledge.

That is, the photosensitive composition for printing plate production 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 printing plate production of the present invention, it is preferable to use a hydrogenated terpene resin as the terpene resin. In addition, it is preferable to use a styrene-isoprene-styrene block copolymer as the elastomer resin. Moreover, it is preferable to contain 30-90 weight part of said elastomer resins and 70-10 weight part of said terpene resins with respect to a total of 100 weight part of an elastomer resin and the said terpene resin.

Moreover, the recessed plate printing disc laminated body for photosensitive aligning film printing which concerns on this invention has a photosensitive resin layer formed from an elastomer resin, a terpene resin, a photopolymerizable monomer, and a photoinitiator on a support body at least. According to a preferred embodiment of the photosensitive laminated printing original plate for concave printing of the present invention, it is preferable to form a protective layer covering the surface opposite to the support.

Moreover, the recessed plate printing plate for photosensitive alignment film printing which concerns on this invention is a printing plate which forms the cured resin layer which has a recessed pattern for printing on a support body, and a patterned cured resin layer is at least an elastomer resin and a terpene resin as a structural component. It is characterized by containing at the same time.

Best Mode for Carrying Out the Invention

The photosensitive composition for printing plate manufacture which concerns on this invention is a photosensitive composition for printing plate manufacture containing at least binder resin, a photopolymerizable monomer, and a photoinitiator, It is characterized by simultaneously containing an elastomer resin and a terpene resin as a binder resin.

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

EMBODIMENT OF THE INVENTION Hereinafter, the photosensitive composition for printing plate manufacture of this invention, the photosensitive laminated printing original plate for printing, and printing plate using this are demonstrated in detail in the following procedure.

[A] Photosensitive composition for manufacturing recessed plate printing plate for alignment film printing

(a) terpene resin

(b) elastomer resin

(c) photopolymerizable monomer

(d) photopolymerization initiator

[B] Concave plate printing disc laminate for photosensitive alignment film printing

[C] Concave plate printing plate for photosensitive alignment film printing

[A] Photosensitive composition for manufacturing recessed plate printing plate for alignment film printing

(a) terpene resin

In this invention, a "terpene resin" is a polymer obtained by copolymerizing terpenes homopolymerized or the monomer copolymerizable with terpenes.

Examples of the terpenes serving as raw materials for terpene resins include hydrocarbons having a molecular formula of C10H16, and oxygen compounds (alcohol, aldehydes, ketones, and the like) derived therefrom.

Specific examples of such terpenes include α-pinene, β-pinene, myrsen, oshimene, limonene, terpinolene, terpinene, fellandene, sylvestrene, savinen, karen, canpen, tricyclene, Hydrocarbons such as penchen, citronellol, geraniol, nerol, linalol, menthol, terpineol, carpeol, twill alcohol, pinocanphenol, phenanthyl alcohol, bornol, alcohols such as borneol, cineral, sheet Aldehydes such as ral, cyclocitral, safranal, pelandal, and perylaldehyde, ketones such as taketone, ionone, menton, carbomentone, carbotanacetone, piperitenone, tuzon, charon and camphor Acids, such as oxides, such as a cineol, a pinol, and a scaritol, and citronelic acid, can be illustrated. Of these, α-pinene, β-pinene and limonene are particularly preferably used.

These terpenes can be used 1 type or in combination of 2 or more types.

As monomers copolymerizable with terpenes, styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, chlorstyrene, dichlorstyrene, α-ethylstyrene, methyl-α-methylstyrene, Dimethyl styrene, 2, 4- diisopropyl styrene, 4-tert- butyl styrene, tert- butoxy styrene, vinyltoluene, etc. can be illustrated.

The polymerization ratio between terpenes and monomers copolymerizable with terpenes is in the range of monomers 0 to 5 copolymerizable with terpenes relative to terpenes 1 to 10 in the monomer ratio, preferably terpenes 1 to 7 and monomers 0 -4, More preferably, they are terpenes 2-5 and monomers 0-3.

Terpene resins obtained by homopolymerizing terpenes or copolymerizing monomers copolymerizable with terpenes may have unsaturated bonds between carbon and carbon or unsaturated bonds between oxygen and carbon in their molecular structure. In this invention, it is preferable to use the hydrogenated terpene resin which partially or fully hydrogenated these unsaturated bonds, and it is especially preferable to use fully hydrogenated terpene resin. By using a hydrogenated terpene resin, further excellent print liquid resistance can be improved.

As a commercial item of such a hydrogenated terpene resin, the Crylon P series, the Crylon M series, the Crylon K series (all are the Yasuhara Chemical company make) can be illustrated.

The average molecular weight of the terpene resin is 300 to 1500, preferably 400 to 1000, more preferably 500 to 800. When the average molecular weight of a terpene resin is less than 300, since synthesis | combination of resin is difficult and more than 1500, since flexibility is inadequate and a printed original laminated body may be damaged, it is unpreferable.

As for the compounding quantity of terpene resin, it is preferable to make terpene resin into 1-90 weight part with respect to a total of 100 weight part of elastomer resin and terpene resin mentioned later. If the terpene resin is less than 1 part by weight, the resistance to the printing liquid is not sufficient, and if the terpene resin is 90 parts by weight or more, the flexibility is insufficient and the printed disc laminated body may be damaged, which is not preferable. It is preferable that the terpene resin is 10 to 70 parts by weight based on 100 parts by weight of the total of the elastomer resin and the terpene resin in order to provide sufficient resistance to the printing liquid and to secure sufficient flexibility required as the concave plate printing plate.

(b) elastomer resin

In the present invention, the elastomer resin is a resin other than the terpene resin, and has a elastomer property as a homopolymer, a copolymer or a mixture thereof, and is a polymer that can be soluble, swelled or dispersed in a developing solution of an aqueous or organic solvent to be washed and removed. Can be. As these binders, for example, polybutadiene, polyisoprene, polydiolefin, copolymer and block copolymer of vinyl aromatic compound / diolefin, 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, graft copolymer of polyvinyl alcohol / polyethylene glycol, cellulose such as amphoteric interpolymer, alkyl cellulose, hydroxyalkyl cellulose, nitrocellulose, ethylene / vinylacetate copolymer , Cellulose Acetate Butyrate, Polybutyral, Cyclic Rubber, Styrene / Arc Acid copolymers, polyvinylpyrrolidone, copolymers of polyvinylpyrrolidone and vinyl acetate, chloroprene polymers, styrene-chloroprene copolymers, acrylonitrile-butadiene copolymers, acrylonitrile-isoprene copolymers, acrylonitrile -Chloroprene copolymer, methyl methacrylate-butadiene copolymer, methyl methacrylate-isoprene copolymer, methyl methacrylate-chloroprene copolymer, methyl acrylate-butadiene copolymer, methyl acrylate-isoprene copolymer, methyl chloroprene acrylate 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 polyol Liethylene, vinyl chloride copolymer, vinylidene chloride copolymer, chlorinated polypropylene, chlorinated ethylene-propylene rubber, ethyl acrylate-acrylonitrile copolymer, butyl acrylate-acrylonitrile copolymer, methyl methacrylate-acrylonitrile A copolymer and a butyl acrylate styrene- acrylonitrile copolymer are mentioned. The polymers may be used alone or in combination. Others include US Patent Nos. 3,458,311, 4,442,302, 4,361,640, 3,794,494, 4,177,074, 4,431,723, 4,517,279, etc., which are binders soluble or dispersible in an aqueous developer. And resins disclosed in the specifications of US Pat. Nos. 4,323,636, 4,430,417, and 4,045,231, which are soluble, swellable, or dispersible in an organic solvent developer.

In this invention, it is preferable to use a styrene / isoprene copolymer and a styrene / butadiene copolymer, and it is especially preferable to use a styrene-isoprene-styrene block copolymer. By using the styrene-isoprene-styrene block copolymer, the transparency necessary for forming the exposure pattern can be ensured, and the resistance to the printing liquid can be further improved.

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

(c) photopolymerizable monomer

As one or more types of monomers contained in the photosensitive resin layer used for this invention, it is necessary to use the monomer compatible with the said binder so that the transparent photosensitive resin layer can be formed. As said monomer, in addition to the monomer which comprises the said binder, For example, polybutadiene diacrylate, polybutadiene dimethacrylate, polyisoprene diacrylate, polyisoprene dimethacrylate, (alpha) -methylstyrene, m-methylstyrene, aromatic vinyl monomers such as p-methoxystyrene; Α, β-ethylenically unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile; Acrylates and corresponding methacrylates of alkyl alcohols having 1 to 23 carbon atoms such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate and t-butyl acrylate; Acrylates and corresponding methacrylates of hydroxyalkyl alcohols such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; Acrylates and methacrylates of alkoxyalkylene glycols such as methoxy ethylene glycol and methoxy propylene glycol; Monoesters of unsaturated polyhydric carboxylic acids such as monoethyl maleate, monomethyl fumarate and monoethyl itaconic acid; Diesters such as dimethyl maleate, diethyl maleate, dibutyl maleate, dioctyl maleate, diethyl fumarate, dibutyl fumarate, dioctyl fumarate, dimethyl itaconic acid, diethyl itaconate, dibutyl itaconate and dioctyl itaconic acid Ryu; Acrylamides such as acrylamide, methacrylamide, N, N'-methylenebisacrylamide and N, N'-hexamethylenebisacrylamide and corresponding methacrylamides; Diacrylates of glycols of ethylene glycol diacrylate and polyalkylene glycol (2 to 23 alkylene glycol units) and corresponding methacrylates; Diacrylates, triacrylates, tetraacrylates, oligoacrylates and the like of trivalent or higher polyhydric alcohols such as glycerin, pentaerythritol, trimethylolalkane, and tetramethylolalkane (as alkanes methane, ethane, propane) Methacrylates to be used; Acrylates and corresponding methacrylates having acidic functional groups such as 2-acryloyloxyethyl succinic acid, 2-acryloylethylhexahydrophthalic acid and 2-acryloyloxyethyl acid phosphate; Etc. can be mentioned. These photopolymerizable ethylenically unsaturated monomers may be used individually by 1 type, and may be used in combination of 2 or more type. Moreover, the monomer described in each specification of US Patent 4,323,636, US 4,753,865, US 4,726,877, US 4,894,315 is mentioned. The photopolymerizable monomers may be used alone or in combination. Especially preferred are polybutadiene diacrylate and 1,6-hexanediol diacrylate.

When the said monomer is 100 weight part of sum total of an elastomer resin and a terpene resin, 5-30 weight part, Preferably the range of 10-20 weight part is good. When content of a monomer is less than the said range, the abrasion resistance and chemical-resistance of the film after exposure hardening fall, and when it exceeds the said range, the elastomer property of the photosensitive resin layer will fall, and it is unpreferable as a flexographic printing plate.

(d) photopolymerization initiator

As a photoinitiator, what is generally known can be used. Examples of such initiators include aromatic ketones such as benzophenone; Benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, α-methylol benzoin methyl ether, α-methoxybenzoin methyl ether, and 2,2-diethoxyphenylacetophenone; Substituted and unsubstituted multinuclear quinones; 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane -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- Diethyl thioxanthone, 2-chloro thioxanthone, 2,4-dimethyl thioxanthone, 3,3-dimethyl-4-methoxybenzophenone, benzophenone, 1-chloro-4-propoxy thioxanthone, 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, 4-dimethylaminobenzoic acid methyl, 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoate butyl, 4-dimethylaminobenzoic acid-2-ethylhexyl, 4- Dimethylaminobenzoic acid-2- Sodium wheat, 2,2-diethoxyacetophenone, benzyldimethyl ketal, benzyl-β-methoxyethyl acetal, methyl o-benzoylbenzoate, bis (4-dimethylaminophenyl) ketone, 4,4'-bisdiethylamino Benzophenone, 4,4'-dichlorobenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, p-dimethyl Aminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, thioxanthone, 2- Methyl thioxanthone, 2-isopropyl thioxanthone, dibenzosuberon, α, α-dichloro-4-phenoxycetophenone, pentyl-4-dimethylaminobenzoate, 9-phenylacridine, 1,7 -Bis- (9-acridinyl) heptane, 1,5-bis- (9-acridinyl) pentane, 1,3-bis- (9-acridinyl) propane and the like. Other initiators disclosed in the specifications of US Pat. Nos. 4,460,675 and 4,894,315. The initiators may be used alone or in combination.

It is preferable to contain the said initiator in the range of 0.001 to 10 weight% with respect to the total weight of the photosensitive composition for printing plate manufacture of this invention.

In addition, the photosensitive resin composition of this invention can add dye, a pigment, a polymerization inhibitor, antioxidant, a photodegradation inhibitor, etc. as needed, and can also improve the performance.

[B] Concave plate printing disc laminated body for photosensitive alignment film printing

The recessed plate printing disc laminated body for photosensitive aligning film printing of this invention is a laminated body which has a support body and the photosensitive resin layer which contains at least the elastomer resin, terpene resin, a photopolymerizable monomer, and a photoinitiator formed on this support body.

There is no restriction | limiting in particular about the formation method of the photosensitive resin layer, It can select arbitrarily from the method conventionally used for laminating | stacking a photosensitive layer on a support body at the time of manufacture of a photosensitive printing original laminated body. 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, which is formed into a desired thickness by using a calender or by using an extruder or by using an extruder. The resin composition is melted, mixed, degassed and filtered, and then extruded between the support and the temporary cover sheet to a desired thickness using a calender. Alternatively, a photosensitive resin layer is formed by forming a coating film of the photosensitive resin composition on the support layer by placing a support body and a cover sheet in a metal mold and injecting the photosensitive resin composition therebetween.

The thickness of this photosensitive resin layer is 0.1-10.0 mm normally, Preferably it is the range of 0.5-7.0 mm.

As a support layer which comprises the photosensitive laminated printing original disk for printing of this invention, the well-known metal, plastic film, paper used for the normal flexographic printing plate which satisfy | fills physical performance, such as the mechanical strength required for the printing conditions to be used, and these composited Any support in the form can be used. These include polymeric films formed by addition polymerized polymers and linear condensation polymers, transparent foams and fabrics, nonwovens such as glass fiber fabrics, and metals such as steel, aluminum, and the like. The support is preferably transparent to the exposure light so as to facilitate back exposure. As a more preferable support body, polyethylene, a polypropylene, or a polyester film is mentioned, A polyester film and a polyethylene terephthalate film are especially preferable. As said film, the film of 50-400 micrometers in thickness, Preferably the film of 75-300 micrometers in thickness is used. This support layer may be further covered with a thin adhesive layer between the photosensitive resin layers as necessary. Examples of the pressure-sensitive adhesive layer include polyester resins, urethane resins, and ethyl cellulose, and those comprising a mixture of polycarbonate, phenoxy resin, and polyvalent isocyanate can be preferably used.

In this invention, it is preferable to form a protective layer on the surface on the opposite side to a support layer as needed. 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 with silicon is preferable. This protective layer is temporarily attached in order to facilitate storage, conveyance and handling. During the production of a printing plate, the protective layer is peeled off to expose the photosensitive resin layer to the surface, and pattern light is irradiated. As needed, this protective layer may be coat | covered with the thin anti-sticking layer between the photosensitive resin layers. As this adhesion prevention layer, polypropylene, polyester, polystyrene, a cellulose derivative, polyamide resin is mentioned, for example.

In this invention, it is preferable to form a mask material layer on the photosensitive resin layer as needed. On the photosensitive resin layer, a mask material layer that is opaque to the 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, and the exposure light is irradiated from above the mask image layer. Since the pattern for printing can be formed in a resin layer, the efficiency of manufacture of a printing plate can be further improved.

As a method of forming a mask image layer by patterning a portion of the mask material layer to transmit the exposure light, an infrared ablation layer made of an infrared sensitive material is formed as a mask material layer, and the infrared ablation layer is selectively abbreviated with an infrared laser. The main method is to form a negative pattern by encasing. 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, and Japanese Patent Application Laid-Open No. 9-166875, Japanese Unexamined Patent Publication No. 2001-324815, and Japanese Patent No. 2773981 can be referred to.

[C] Concave plate printing plate for photosensitive alignment film printing

The printing plate of this invention is a concave-plate printing plate which has a cured resin layer which has an uneven | corrugated pattern for printing on a support body, The said patterned cured resin layer contains at least an elastomer resin component and a terpene resin component simultaneously as a structural component, It is characterized by the above-mentioned. do. It is preferable to form this patterned cured resin layer by photocuring-reacting the photosensitive composition for manufacturing the intaglio printing plate of this invention. The presence form of the elastomer resin component and the terpene resin component in the patterned cured resin layer depends on the photocuring reaction conditions, and is present in the state crosslinked by the photopolymerizable monomer by the photocuring reaction or unreacted without crosslinking. You can think of the state. In the present invention, the elastomer resin component and the terpene resin component may be contained in any state in the patterned cured resin layer.

The printing plate of the present invention using the concave plate printing original laminate for printing the photosensitive alignment film is exposed to the photosensitive resin layer through a mask to cure the photosensitive resin layer of the pattern portion, and the exposure light is not irradiated and is in the uncured state. It is manufactured by making the said photosensitive resin layer into a patterned cured resin layer by removing the exposure light non-irradiation area | region of the photosensitive resin layer with a developing solution.

According to a preferred embodiment, after performing back exposure on the support layer side for the concave plate printing original laminate for photosensitive alignment film printing, the protective layer (slip sheet) of the concave plate printing original laminate for photosensitive alignment film printing is peeled off to form a photosensitive resin layer. Expose to surface. Subsequently, the main exposure is performed through the mask to cure the photosensitive resin layer of the pattern portion. By this main exposure, pattern light according to a mask pattern is irradiated to the photosensitive resin layer, and the area | region to which the exposure light was irradiated crosslinked reaction, and it hardens | cures.

When mask material layers, such as an infrared ablation layer, are formed on the photosensitive resin layer, a mask image is formed by removing an infrared ablation layer using an infrared laser beam, and this mask image layer is subjected to main exposure as a mask.

Subsequently, by removing the uncured part to which exposure light was not irradiated with the developing solution, the pattern for printing is made present and it is dried. After drying, you may perform post-exposure as needed.

As an exposure apparatus used for exposure, the actinic radiation irradiation apparatus etc. which are generally used for manufacture of a flexoplate can be used. As the radiation, ultraviolet rays and visible rays having a wavelength of 150 nm to 800 nm can be used, but 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 xeon lamp, an excimer laser, or the like can be used.

As the developer used in the development treatment, any one of an organic solution, water, an aqueous or semi-aqueous solution can be used as long as it has a property of dissolving the photosensitive resin layer, and the selection of the developer depends on the chemical properties of the resin to be removed. . Suitable organic solvent developers include aromatic or aliphatic hydrocarbons and aliphatic or aromatic halo hydrocarbon solvents or mixtures of these solvents with suitable alcohols. In addition, the semiaqueous developer contains water or an organic solvent and an alkaline material which can be mixed with water. Examples of the aqueous developer include water and esters such as heptyl acetate and 3-methoxybutyl acetate, petroleum distillates, hydrocarbons such as toluene and decalin, chlorine solvents such as tetrachlorethylene, monoethanolamine and di Amine, such as ethanolamine and a triethanolamine, aqueous solution, such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, is mentioned. Moreover, what mixed these alcohols, such as propanol, butanol, and pentanol, with these solvents can also be used, The washing | cleaning can employ | adopt arbitrary methods, such as dipping, spraying from a nozzle, brushing with a brush.

At the time of manufacture of the printing plate of this invention, the printing original plate laminated body is affixed to a drum in cylindrical shape, and exposure and development process further improve the productivity of a printing plate material.

Example

EMBODIMENT OF THE INVENTION Hereinafter, based on an Example, this invention is demonstrated in detail. In addition, this invention is not limited to the following Example.

<Examples 1-3, Comparative Examples 1 and 2>

(Production of flexographic printing board)

As the thermoplastic elastomer, a styrene-isoprene-styrene block copolymer (trade name D-1107, manufactured by KRATON) and a hydrogenated terpene resin (trade name Crealon P-125, manufactured by Yashara Chemical Co., Ltd.) are mixed at a compounding ratio shown in Table 1 below. , 75% by weight of this mixture, 8.7% by weight of 1,6-hexanedioldiacrylate, 15% by weight of polybutadiene terminal acrylate (trade name BAC-45 manufactured by Osaka Organic Chemical Co., Ltd.), 1.3% by weight of benzyl methyl ketal ( Irgacure 651, manufactured by Chiba Specialty Chemicals Co., Ltd., was added to a twin screw kneader, a 2 mm thick sheet was produced using T dicing, laminated to a 125 μm thick polyester sheet (support layer), and the other side. The laminate was laminated on a polyester sheet (protective layer) on which an anti-stick layer composed of a polyamide resin layer was formed, and four layers of the support layer, the photosensitive resin layer, the anti-tack layer, and the protective layer were in order. Subsequently, a printing original laminated body integrated with lamination was produced.

Example Compounding ratio (% by weight) D-1107 Crealon P-125 Example 1 90 10 Example 2 50 50 Example 3 30 70 Comparative Example 1 100 0 Comparative Example 2 0 100

Next, these printed original 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, the printing original laminate of Comparative Example 2 was insufficient in flexibility, and the printing original laminate was damaged when adhered to the drum, so that the performance evaluation of the following flexographic printing plates was performed in Examples 1 to 3 and Comparative Examples. Only 1 was done.

(Evaluation of printed board)

(1) Alignment film liquid resistance evaluation

3 cm x 3 cm size plates were cut out from the printing plates of Examples 1 to 3 and Comparative Example 1, respectively, and each of the solvents for the alignment film solution was gamma -butyl lactone, N-methyl-2-pyrrolidone, and butyl cellosolve. It was immersed for 48 hours to evaluate the resistance to the alignment film solution. The decrease amount of plate surface hardness value (difference of hardness before and after various aligning film liquid solvent immersion by the hardness measuring machine based on JIS K 6301 A type standard), and the increase amount of the photosensitive layer film thickness are shown to Tables 2-4.

γ-butyrolactone Example Compounding ratio (% by weight) Plate surface hardness decrease (°) Photosensitive layer film thickness increase amount (㎛) D-1107 Crealon P-125 Example 1 90 10 0 0 Example 2 50 50 0 0 Example 3 30 70 0 0 Comparative Example 1 100 0 2 15 Comparative Example 2 0 100

N-methyl-2-pyrrolidone Example Compounding ratio (% by weight) Plate surface hardness decrease (°) Photosensitive layer film thickness increase amount (㎛) D-1107 Crealon P-125 Example 1 90 10 1.5 15 Example 2 50 50 0.5 5 Example 3 30 70 0 0 Comparative Example 1 100 0 8 150 Comparative Example 2 0 100

Butyl Cellosolve Example Compounding ratio (% by weight) Plate surface hardness decrease (°) Photosensitive layer film thickness increase amount (㎛) D-1107 Crealon P-125 Example 1 90 10 2 40 Example 2 50 50 One 10 Example 3 30 70 0.5 5 Comparative Example 1 100 0 15 300 Comparative Example 2 0 100

Through the above results, in Examples 1 to 3 using the terpene resin, the amount of decrease in the plate surface hardness value and the amount of increase in the photosensitive layer film thickness were not substantially observed or very small even if there was a change. It can be seen that it has excellent resistance.

On the other hand, in Comparative Example 1 in which no terpene resin was used, resistance to various alignment film liquid solvents was insufficient, and the decrease of the plate surface hardness value and the increase of 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 disc laminate was damaged when attached to the drum.

Industrial availability

As mentioned above, the photosensitive composition for printing plate manufacture which concerns on this invention uses an elastomer resin and a terpene resin together as a binder resin in the photosensitive composition for printing plate manufacture containing at least a binder resin, a photopolymerizable monomer, and a photoinitiator, It is characterized by the above-mentioned. do. By using together an elastomer resin and a terpene resin, the tolerance to the printing liquid of the printing plate obtained can be improved significantly.

By using the photosensitive composition for printing plate manufacture of this invention which has the said characteristic structure, the photosensitive printing original laminated body for printing and printing plate which have the outstanding printability can be manufactured, and it can use suitably as a printing plate for orientation film liquids.

Although the photosensitive resin layer formed using the photosensitive composition for printing plate manufacture of this invention becomes a cured resin layer which has a concave pattern for printing by exposure and image development, this patterned cured resin layer prints various inks, especially an alignment film liquid, etc. It has excellent resistance to liquids. Therefore, 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 material can be obtained.

Conventionally, there exists a problem that the tolerance with respect to an alignment film liquid is insufficient, and a patterned cured resin layer swells, and the tolerance with respect to the alignment film liquid of a patterned cured resin layer was desired. The present invention is based on the novel finding that the printing liquid resistance is improved by adding a terpene resin to the photosensitive composition for manufacturing a concave plate printing plate.

Moreover, the photosensitive composition for printing plate manufacture of this invention WHEREIN: The use of the hydrogenated terpene resin as a terpene resin has the effect of having the outstanding printing liquid resistance. In addition, by using the styrene-isoprene-styrene block copolymer as the elastomer resin, the transparency necessary for forming the exposure pattern can be ensured, and further excellent printing liquid resistance can be given. Further, by containing 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, sufficient resistance to the printing liquid can be imparted. In addition, sufficient flexibility required as a concave plate printing plate can be ensured.

In addition, although the recessed plate printing original laminated body for photosensitive aligning film printing of this invention consists of the structure in which the photosensitive resin layer which consists of the photosensitive composition of this invention was formed on the support body, it has previously manufactured by taking such a structure, and there exists an expiration date, The predetermined period can be stored. Therefore, when manufacturing a printing plate, it can be used immediately and can raise the manufacturing efficiency of a printing plate. Moreover, in the concave-plate printing original laminated body for photosensitive alignment film printing of this invention, storage, conveyance, and handling can be made easy by forming the protective layer which coat | covers the surface on the opposite side to a support body.

Moreover, the printing plate of this invention is a printing plate which forms the cured resin layer which has a concave pattern for printing on a support body, and since it contains an elastomer resin and a terpene resin simultaneously in the said patterned resin layer, Has good resistance. Therefore, even if printing is continued for a long time, a patterned cured resin layer is not swollen by the ink component, and a high quality printed matter can be obtained. The printing plate of this invention can be used suitably as a recessed plate printing plate especially as a recessed plate printing plate for oriented films.

Claims (7)

A concave plate printing plate for photosensitive alignment film printing, 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. The recessed plate printing plate for printing a photosensitive alignment film according to claim 1, wherein the terpene resin is a hydrogenated terpene resin. The concave plate printing plate for photosensitive alignment film printing according to claim 1, wherein the elastomer resin is a styrene-isoprene-styrene block copolymer. The concave plate printing plate for photosensitive alignment film printing according to claim 1, wherein the elastomer resin is 30 to 90 parts by weight and the terpene resin is 70 to 10 parts by weight based on 100 parts by weight of the total of the elastomer resin and the terpene resin. At least as a photosensitive composition for manufacturing a concave plate printing plate for printing an alignment film containing a binder resin, a photopolymerizable monomer, and a photopolymerization initiator, As said binder resin, it contains an elastomer resin and a terpene resin simultaneously, and is used for the recessed plate printing plate for photosensitive alignment film printing as described in any one of Claims 1-4, The photosensitive composition for manufacturing the recessed plate printing plate for orientation film printing characterized by the above-mentioned. A photosensitive resin layer formed of at least an elastomer resin, a terpene resin, a photopolymerizable monomer, and a photopolymerization initiator on a support, and is used in the intaglio printing plate for printing the photosensitive alignment film according to any one of claims 1 to 4, The recessed plate printing original laminated body for photosensitive alignment film printing. The recessed plate printing original laminated body for photosensitive alignment film printing of Claim 6 which has a protective layer on the surface on the opposite side to the said support body.