JPH05313376A - Adhesion preventing layer for photosensitive resin printing plate - Google Patents

Abstract

PURPOSE:To obtain an adhesion preventing layer having satisfactory peeling property to a flexible photosensitive resin printing plate, generating no fine wrinkles and independent of temp. and humidity. CONSTITUTION:This adhesion preventing layer for a photosensitive resin printing plate is obtd. with a compsn. contg. a polymer developable with water or an aq. soln. and an anionic, nonionic or amphoteric surfactant. The angle of contact of the adhesion preventing layer with a methylene iodide soln. is 35-60 deg.C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an anti-adhesion layer suitable for a flexible photosensitive resin printing plate, especially a flexographic printing plate developable with an aqueous processing solution.

[0002]

2. Description of the Related Art Usually, in the process of forming a photosensitive resin into a printing plate,
A method in which an original film is brought into close vacuum contact with a photosensitive layer of a photosensitive resin original plate and exposed with an actinic ray is mainly used. However, the surface of the photosensitive layer of the photosensitive resin original plate is usually tacky, and if this tackiness is strong, uniform adhesion cannot be achieved when the original drawing film is adhered, resulting in poor image reproducibility. Become. In addition, when the original film is peeled from the original plate after exposure, there is a problem in that peeling is caused by adhesion between the two and damage occurs to both. On the other hand, in recent years, the demand for rubber-like flexible photosensitive resin relief printing plates has increased in the business home printing field, so that the photosensitive resin original printing plates tend to become softer, and when the hardness of the original printing plates becomes low There is a problem that

In order to solve such a problem, the most commonly used method is a technique of applying a thin film of a polymer having low tackiness on the surface of a photosensitive resin. For example, JP-A-51-49803 (polyvinyl alcohol having a saponification degree of 90% or more), JP-A-52-110010 (polymerization degree of 800 or more,
Polyvinyl alcohol having a saponification degree of 70% to 90%)
54-68224 (water-soluble polymer), JP-A-56-110941
Japanese Patent Publication (Soluble Polyamide) and the like are known. However, these methods have the following problems.

When a polyvinyl alcohol thin film is provided between the cover film and the photosensitive layer as an anti-adhesion layer,
When the cover film is peeled off in the plate making process, the peeling trigger may be poor and the peeling may not be successful. The peeling trigger is an operation of first peeling the cover film from the anti-adhesion layer, and more specifically, an operation of flipping the edge with the thumb several times. Further, if the peeling trigger is good, there is a problem that the original plate bends inward or outward, small wrinkles are generated on the surface of the original plate, and these small wrinkles remain on the relief surface, resulting in ink density unevenness of the printed matter.

Among the water-soluble polymers, amorphous polymers other than polyvinyl alcohol having a saponification degree of 90% or more (for example, alkyl cellulose, vinyl polymer maleic acid copolymer, etc.) are not sticky due to the moisture absorption of the thin film. It rises significantly, and the adhesion of the target original film is hindered. Further, there is a problem such as blocking in the manufacturing process of the thin film.

Thin films other than the water-soluble polymer have no humidity dependency, but in recent years, a type using an aqueous processing liquid has become the mainstream for developing a photosensitive resin printing plate. Therefore, if the polymer is not a water-soluble or water-dispersible polymer, it is not preferable because the step of removing the thin film before development requires an additional step of removing the thin film with an organic solvent that dissolves the thin film.

By the way, when the photosensitive resin composition is used for flexographic printing plates, the non-adhesive coating layer is highly required because the photosensitive resin is more flexible and has strong adhesiveness. Occurrence problems are likely to occur. Therefore, a technique in which a release layer is further provided for a flexographic printing plate is disclosed in JP-A-57
-208556 and the technique of blending polyvinyl alcohol with a plasticizer to prevent wrinkles are disclosed in JP-A-2-113254.

However, the former application of the release agent not only increases the number of manufacturing steps, but further coating a non-adhesive coating layer on the release agent tends to cause coating defects, so that a high level coating technique is required. It On the other hand, the latter coating layer of polyvinyl alcohol containing a plasticizer is easily affected by humidity, and there is a drawback that the original purpose of non-tackiness is lost due to sticking of the coating layer due to moisture absorption under high humidity.

[0009]

As described above, even in the conventional technique, there is no suitable anti-adhesion layer for a photosensitive resin plate which can be developed with an aqueous processing solution and is flexible. Is. Particularly, in the photosensitive laminate, the peeling trigger of the cover film and the quality of the peeling property have a great influence on the generation of fine wrinkles on the surface of the photosensitive layer as it is. For example, in the case of a cover film having poor peeling trigger and peeling property, it is attempted to peel the cover film from the photosensitive laminate with an unreasonable force, and as a result, the photosensitive resin plate is deformed into a convex shape and small wrinkles occur. In addition, if the peeling is restarted after the peeling is interrupted once, linear streaky wrinkles will occur at the interrupted position.
In general, it is required to peel the cover film in one machine without interruption, but there is an opportunity to interrupt the peeling due to a mistake in peeling operation, and it is not possible to completely prevent the generation of wrinkles. difficult. On the other hand, if the releasability is too good, the above problems can be mitigated, but the biggest problem is
Abnormal peeling may occur at the time of manufacturing the photosensitive laminate, when carrying it in packaging, or cutting it into a desired size, and small wrinkles occur at the peeled portion. Furthermore, it is difficult to carry (handling) during plate making work. In other words, it is not simply necessary to improve the peelability. Therefore, in the present invention, it is possible to develop with an aqueous processing solution, the handling of the cover film including the production of the photosensitive laminate and the plate making process is easy, the adhesion to the original film is good, and the generation of small wrinkles on the original plate is prevented. At the same time, it is an object to obtain an anti-adhesion layer that is not affected by humidity.

[0010]

Means for Solving the Problems As a result of intensive studies made by the present inventors to solve the above-mentioned drawbacks of the anti-adhesion layer,
Finally, the present invention has been completed. That is, the present invention is an anti-adhesive layer for a photosensitive resin printing plate that can be developed with an aqueous processing liquid, wherein the layer comprises one or more surface active agents selected from water-soluble polymers and anionic, nonionic and amphoteric systems. Agent, and the contact angle of methylene iodide in the layer is 3
It is an anti-adhesion layer for a photosensitive resin printing plate, characterized in that it is at an angle of 5 to 60 degrees.

The water-soluble polymer used in the present invention is at least 60% or more hydrolyzed polyvinyl alcohol and carboxyl-modified polyvinyl alcohol, silane-modified polyvinyl alcohol and other modified polyvinyl alcohol, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl isobutyl. Polyvinyl ethers such as ether, polyvinylpyrrolidone, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, cellulose derivatives such as carboxymethylcellulose, sodium polyalginate, sodium polyacrylate, aqueous silicone acrylic graft polymer, polyethylene oxide, water-soluble And water-dispersible polyester, water-soluble urethane, ethyl A water-soluble high-molecular polymer such as lulose and an aqueous-soluble high-molecular polymer, an aqueous swelling polymer such as an ethylenenopolyvinyl alcohol copolymer, and the like can be arbitrarily used, but the high-molecular polymer for the anti-adhesion layer is preferably used. , Oxygen barrier, film forming, temperature and humidity resistance,
Degree of polymerization 500-3000, degree of saponification 80 due to coatability
~ 99% polyvinyl alcohol and modified polyvinyl alcohol are preferred.

In the present invention, the surfactant contained in the water-soluble or high-polymer developable polymer is, for example, one selected from anionic, nonionic and amphoteric systems having an alkyl group having 5 to 21 carbon atoms. The above surfactants,
Specific examples of anionic surfactants include fatty acid salts, alkylbenzene sulfonates, alkylnaphthalene sulfonates, α-alkyl sulfonates, olefin sulfonates, dialkyl sulfosuccinates, α-sulfonated fatty acid salts, N -Methyl-N-oleyl taurine, alkyl sulfates, sulfated oils and fats such as funnel oil, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates , Polyoxyethylene alkylphenyl ether phosphate, etc., one or more can be arbitrarily selected in consideration of the coating property and peeling property of the anti-adhesion layer, and the content thereof is not restricted, but is particularly contained. The amount is 0.01-based on water or an aqueous polymer. 20% by weight, preferably 0.01-
The content is preferably 10% by weight, more preferably 0.01 to 3% by weight. The wetting contact angle of the anti-adhesion layer obtained by blending the anionic surfactant with the methylene iodide solution is preferably 35 to 60 degrees, and particularly preferably 37 to 52 degrees.

Specific examples of the nonionic surfactant include:
Polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene polystyryl phenyl ether, polyoxyethylene-polyoxypropylene glycol, polyoxyethylene-
Polyoxypropylene alkyl ether, polyhydric alcohol fatty acid partial ester, polyoxyethylene polyhydric alcohol fatty acid partial ester, polyoxyethylene fatty acid ester, polyglycerin fatty acid ester, polyoxyethylenated castor oil, etc. In consideration of the release property and peeling property, etc., one or more can be arbitrarily selected, with respect to water or an aqueous polymer,
It is preferable to contain 0.01 to 10% by weight, preferably 0.01 to 3% by weight, and more preferably 0.01 to 0.5% by weight. The wet contact angle of the anti-adhesion layer thus obtained with the methylene iodide solution was from 35 degrees to 60 degrees.
The angle is preferably 45 to 55 degrees.

Specific examples of the amphoteric surfactant include N,
N-dimethyl-N-alkyl-N-carboxymethylammonium betaine, N, N-dialkylaminoalkylenecarboxylic acid salt, N, N, N-trialkyl-N-sulfoalkyleneammonium betaine, N, N-dialkyl-N, N-bis polyoxyethylene ammonium sulfate ester betaine, 2-alkyl-1-carboxymethyl-1-hydroxyethylene imidazolinium betaine and the like can be mentioned. Considering the coating property and peeling property of the anti-adhesive layer, one or Any more can be selected,
It is preferably contained in an amount of less than 1% by weight, and more preferably 0.01 to 0.5% by weight, based on water or the aqueous polymer. The wetting contact angle of the anti-adhesion layer thus obtained with the methylene iodide solution is preferably 35 to 60 degrees, and particularly preferably 45 to 59 degrees.

In the present invention, the methylene iodide solution used for measuring the wet contact angle of the anti-adhesion layer is a solid surface chemistry relating to the wettability of the liquid to the solid surface, and further the adhesiveness of the resin to the solid surface. It is a known liquid that is often used for surface chemistry. In this way, the regulation of the wet contact angle of the anti-adhesion layer is not only for the purpose of facilitating the peeling trigger and peeling property of the cover film, but also during the production of the photosensitive laminate or the work in the plate making process. It is also an important factor to prevent such peeling. For example, in the case of the technique in which the release layer described above is further provided, the wetting contact angle with the methylene iodide solution is 60 degrees or more, and when the cover film of the upper layer of the photosensitive laminate is attempted to be peeled from the release layer, Although it can be easily peeled off, it often causes abnormal peeling during the production of the photosensitive laminate and the work of the plate making process, and it is often difficult to handle the photosensitive laminate, which makes it difficult to commercialize. In some cases.

The present invention relates to an anti-adhesion layer in a photosensitive resin laminate for a photosensitive resin printing plate. As the laminate, an adhesive layer, a photosensitive resin layer, an anti-adhesion layer and a cover are provided on at least a support. It is composed of a film, and as its manufacturing method, an anti-adhesion layer is applied to the cover film in advance,
On the other hand, a method in which an adhesive layer is applied to a support in advance and then the materials for both layers are laminated around the photosensitive resin composition by pressure bonding or the like is commonly used.

Polyethylene terephthalate film is most suitable as the cover film from the viewpoint of dimensional stability, heat resistance and mechanical performance, but polyethylene, polypropylene, polystyrene and other peelable materials may be used as a single or laminated coat. What has been done can be used. The surface of the cover film may be smooth, but it is more preferable if it has a so-called matte surface roughness of 5 μm or less. When applying the composition of the present invention on the cover film,
It is preferred to apply the composition as an aqueous solution of 1-5%, preferably 1.5-3%. Further, the composition of the present invention,
In addition to the water-soluble polymer and the surfactant, various antifoaming agents, leveling agents, penetrants, etc. may be added in order to improve the coatability with the cover film. Therefore, a preservative may be added. The thickness of the anti-adhesion layer after drying is 0.1 to 10 μm, preferably 2 to 5
μm.

Next, the photosensitive resin composition in the photosensitive resin layered product in which the anti-adhesion layer of the present invention is used has as its components a filling polymer, a photocuring agent, a photosensitizer, a polymerization inhibitor and other additives. However, depending on the type of the filled polymer as the main component, it is called, for example, polyamide-based, polyurethane-based, polyvinyl alcohol-based, polyester-based, polyvinyl acetic acid-based, etc., and the present invention can be applied to any known photosensitive layer. Although it may be applied, it is particularly preferably obtained by a method comprising a polymer that dissolves or swells in water or an aqueous developer, an ethylenically unsaturated compound, and / or a hydrophobic polymer, and a photoinitiator. Can be applied to things. For example, JP-A-60-211451 and JP-A-60-1730
It is known by No. 55 and others.

As the above-mentioned photosensitive resin composition, for example, (A) a hydrophobic polymer having a glass transition temperature of 5 ° C. or lower,
Photosensitization containing (B) a hydrophilic polymer, (C) an ethylenically unsaturated compound, (D) a solvent in which the solubility of the component (B) is higher than that of the component (A), and (E) a photopolymerization initiator Particles in a photosensitive resin composition, or a photosensitive resin printing original plate and a printing plate, in which a phase containing a hydrophobic polymer as a main component surrounds a phase containing a hydrophilic polymer as a main component in the photosensitive resin layer Are present as a dispersed phase, and a photosensitive resin composition and the like are listed, and in the present invention, these compositions are particularly preferable.

The glass transition temperature of the component (A) is 5
Examples of the hydrophobic polymer having a temperature of not higher than 0 ° C. include those used as general-purpose elastomers. Examples include polymers obtained by polymerizing conjugated diene hydrocarbons, copolymers obtained by polymerizing conjugated diene hydrocarbons and monoolefin unsaturated compounds, polymers containing no conjugated diene hydrocarbons, and the like. Be done. As the conjugated diene hydrocarbon, 1,3-butadiene, isoprene, chloroprene and the like are used. The conjugated diene hydrocarbons may be used alone or in combination of two or more.

As the mono-olefin unsaturated compound,
Styrene, α-methylstyrene, 0-methylstyrene,
m-methylstyrene, P-methylstyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide vinyl acetate,
Acrylic acid ester, methacrylic acid ester and the like are used.

A polymer obtained by polymerizing a conjugated diene hydrocarbon or a copolymer obtained by polymerizing a conjugated diene hydrocarbon and a monoolefin unsaturated compound is a butadiene polymer or isoprene polymer. , Chloroprene polymer, styrene-butadiene copolymer, styrene-
Isoprene copolymer, styrene-chloroprene copolymer, acrylonitrile-butadiene copolymer, acrylonitrile-isoprene copolymer, acrylonitrile-chloroprene copolymer, methyl methacrylate-butadiene copolymer, methyl methacrylate-isoprene copolymer ,
Methyl methacrylate-chloroprene copolymer, methyl acrylate-butadiene copolymer, methyl acrylate-isoprene copolymer, methyl acrylate-chloroprene copolymer, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-isoprene-styrene Examples thereof include copolymers and acrylonitrile-chloroprene-styrene copolymers.

Examples of the polymer containing no conjugated diene hydrocarbon include an elastomer containing a specific amount of chlorine and a non-conjugated diene hydrocarbon. Those exhibiting rubber elasticity are polymers having a chlorine content of 50 to 10% by weight and a glass transition temperature (hereinafter referred to as Tg) of 5 ° C or less, such as polymerization of a monomer containing a chlorine atom, or chlorine. It results from the copolymerization of the atom-containing monomer with other monomers which are copolymerizable. It can also be obtained by reacting chlorine or an active substance containing chlorine with a polymer containing no chlorine atom. Specifically, the following can be mentioned. Epichlorohydrin polymer, epichlorohydrin-ethylene oxide copolymer, epichlorohydrin-propylene oxide copolymer and or epichlorohydrin rubber which is a copolymer of these and allyl glycidyl ether (Epichromer manufactured by Osaka Soda Industrial Co., Ltd., Goodvich HYDRIN, Nippon Zeon strain) GECHRON, Zeospan, Hercules Strains HERCLO
R], chlorinated polyethylene [Showa Denko KK, Erasulen, Osaka Soda Industrial Co., Ltd. Diisolac, Hoechst HO
RTALITZ, DOWCPE manufactured by Dow Chemical Co., Ltd., vinyl chloride copolymer, vinylidene chloride, chlorinated polypropylene, chlorinated ethylene-propylene rubber, and the like, and these polymers may be used alone or in combination of two or more kinds. The chlorine content of the polymer is 10-50% by weight, preferably 15-
It is 40% by weight, and if it deviates from this range, the flexibility is impaired, the thermal stability is deteriorated, the photosensitive resin composition becomes too hard, and coloring is likely to occur, which is not preferable. Since the conjugated diene hydrocarbon polymer containing a chlorine atom or its copolymer contains a carbon unsaturated bond in the main chain, it has a drawback that chemical stability such as weather resistance is inferior to that of a saturated bond alone. Further, since the physical properties of the photosensitive resin composition after light irradiation largely depend on the properties of the component (A) in the present invention, it is preferable that the component (A) is essentially a rubber elastic body. Therefore, its Tg needs to be 5 ° C or lower, and particularly preferably -10 ° C or lower.

The photosensitive resin composition used in the present invention is not limited to the polymer as the component (A), but also has an elastomer having good compatibility with and ozone resistance such as acrylic rubber and polyurethane elastomer. May be blended. The content of the component (A) in the entire composition is determined in consideration of physical properties and shape retention as a printing plate.
20% by weight or more, particularly 30% by weight or more is preferable, and from the viewpoint of photopolymerizability, 80% by weight or less, particularly 70% by weight or less is preferable.

The hydrophilic polymer as the component (B) is water,
Or, as a main component of water, it means a polymer that is soluble or swells (disperses) in a developing solution containing an alkaline aqueous solution, an acidic aqueous solution, an organic solvent, or a surfactant, a —CO ₂ M group,
-SO ₃ M group, (M is a hydrogen atom, group I, II, III element of the periodic table, amine, ammonium) having a hydrophilic group such as -NH ₂ , -OH, and is chain-like and has no cross-linking It is a polymer.
Examples of such a hydrophilic polymer, polyvinyl alcohol (PVA) in addition to general-purpose resins such as carboxymethyl cellulose (meth) diene rubber copolymerized with acrylic acid and a diene compound, liquid polybutadiene modified with maleic anhydride, Further, a particularly effective skeleton is a polymer having 50 to 50,000 equivalent / 10 ⁶ g of --COOM (M is hydrogen atom, group I, II and III elements of the periodic table, amine and ammonium). Examples of the Group I, II and III elements include alkali metals such as sodium, potassium and lithium, alkaline earth metals such as calcium and magnesium, boron and aluminum. In the present invention, if the --COOM group is less than 50 equivalent / 10 ⁶ g, the affinity for water is poor and it is difficult to develop with neutral water.
When it exceeds 00 equivalent / 10 ⁶ g, the water-based ink resistance is poor, which is not preferable.

Specific examples of the hydrophilic polymer include -COOM group-containing polyurethane, -COOM group-containing polyureaurethane,
-COOM group-containing polyester, -COOM group-containing epoxy compound, -COOM group-containing polyamic acid, -COOM group-containing acrylonitrile-butadiene copolymer, -COOM group-containing styrene-butadiene copolymer, -COOM group-containing polybutadiene, polyacrylamide, polyacrylic Sodium acid, polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC), hydroxyethyl cellulose (HEC),
Methyl cellulose (MC), polyethylene oxide, polyethylene imine, and derivatives of the compounds can be used, but are not limited thereto.

The compounds used to neutralize at least a part of the carboxyl groups contained in the hydrophilic polymer are lithium hydroxide, potassium hydroxide,
Sodium hydroxide and other alkali metal hydroxides, lithium carbonate, potassium carbonate, sodium carbonate and other alkali metal carbonates, potassium t-butoxide, sodium methoxide and other alkali metal alkoxides, calcium hydroxide, magnesium hydroxide, water Polyhydric metal hydroxides such as aluminum oxide, polyvalent metal alkoxides including aluminum isopropoxide, tertiary amines such as triethylamine and tri-n-propylamine, diethylamine, di-n-propylamine, etc. Primary amines Ethylamine, primary amines such as n-propylamine, cyclic amines such as morpholine, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth)
Examples thereof include amino group-containing (meth) acrylates such as acrylates, ammonium carbonate, ammonium salts, and the like. These may be used alone or in combination of plural kinds. The hydrophilic polymer may have a polyoxyalkylene chain as a hydrophilic part in addition to the -COOM group, and may contain an ethylenically unsaturated group so that it can act as a crosslinking agent.

As the component (B), in addition to the hydrophilic polymer, for example, a polymer having a hydrophilic group such as a hydroxyl group, an amino group, a sulfonic acid group and / or a polyoxyalkylene chain may be used in combination. The content of the component (B) in the total composition is 5 to 50% by weight, especially 7 to 40% by weight, in consideration of the aqueous developability and the water resistant ink resistance.
30% by weight is particularly preferred. Further, it is essential that the content of the component (B) in the entire composition is lower than that of the component (A),
If the amount is larger than the amount of the component (A), the water resistant ink resistance deteriorates.

Component (C), the ethylenically unsaturated compound, contains at least one terminal ethylenic group, and this compound can form a high molecular polymer by free radical initiated chain growth addition polymerization. It is a thing. Suitable ethylenically unsaturated compounds are unsaturated esters of polyols, especially such esters with α-methylenecarboxylic acid, such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, glycerol diacrylate, 1 , 3-Propanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,2,4-butanetriol tri (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, 1 , 6-Mexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate diallyl phthalate, fumaric acid diethyl ester, maleic acid dibutyl ester, and the like, and also N-methylmaleimide, N-ethylmaleimide, N- N such as lauryl maleimide Oligos such as maleimide compound, oligonitrile / budadiene di (meth) acrylate, oligonitrile / urethane (meth) acrylate, oligourethane di (meth) acrylate, oligobutanediene di (meth) acrylate, oligobutadiene / urethane di (meth) acrylate (Meth) acrylate may be used, and these may be used alone or in combination.

The content of the component (C) in the composition is preferably 1 to 50% by weight, and if it is less than 1% by weight, the photopolymerizability is impaired, and no image remains after development. On the other hand, if the amount is more than 50% by weight, the shape retaining property is impaired. Further, the plate after irradiation with light becomes hard and brittle, which makes it unsuitable as a plate material for flexographic printing, which is not preferable. More preferably 5
40% by weight.

As the solvent in which the solubility of the component (B) which is the component (D) is higher than the solubility of the component (A), a highly polar solvent can be mentioned. That is, it is a solvent which swells, disperses and dissolves the hydrophilic polymer (B) component, but has a small degree of swelling with respect to the hydrophobic polymer. Specific examples of such a solvent include water, an alcohol having 1 to 5 carbon atoms, and the like, and the water includes sodium alkylbenzenesulfonate, sodium alkylnaphthalenesulfonate, sodium alkylsulfonate, and alkyl ether. It may contain a surfactant such as sodium sulfonate, a fatty acid, lithium hydroxide, potassium hydroxide, sodium hydroxide, sodium borate, sodium carbonate, sodium acetate, magnesium acetate, or a salt thereof. As alcohol, methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol,
Examples thereof include isobutyl alcohol, t-butyl alcohol, pentyl alcohol and neopentyl alcohol. Further, if they satisfy the requirement of (D), ester-based, ketone-based, amide-based solvents and the like can be mentioned.
Specifically, ethyl acetate, butyl acetate, isobutyl acetate,
Methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, methyl butyl ketone, formamide,
Examples thereof include dimethylformamide and dimethylacetamide. These solvents can be used alone or in combination as a mixed solvent.

The component (D) is contained in the entire composition in a limited amount in view of performance of the photosensitive resin printing plate, and the range is 0.001 to 5% by weight based on the total composition. Preferably, it is from 0.001% to less than 2.0% by weight. (D)
When the content of the components exceeds 5% by weight based on the total composition,
The original plate before photopolymerization becomes soft and cold flow, plastic deformation, etc. will occur, and as a relief after photopolymerization and plate making, deformation of convex parts (so-called low spot) occurs,
A clear image cannot be obtained.

As the component (E) photopolymerization initiator, for example, benzophenones, benzoins, acetophenones,
Examples thereof include benzyls, benzoin alkyl ethers, benzyl alkyl ketals, anthraquinones and thioxanthones. Specifically, benzophenone, chlorobenzophenone, benzoin, acetophenone, benzylbenzoin, methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, benzyl diethyl ketal, benzyl diisopropyl ketal, anthraquinone, 2-chloroanthraquinone. , Thioxanthone, 2-chlorothioxanthone and the like. These are preferably contained in the composition in an amount of 0.01 to 5% by weight. If it is less than 0.01%, the photopolymerization initiating ability is impaired, and if it is more than 5%, the curing depth cannot be obtained by ordinary light, and the image tends to be chipped due to development, which is not preferable. More preferably, it is 0.1 to 3% by weight.

In order to prevent only thermal polymerization without suppressing photocrosslinking reaction 4, 0.001 to 5% by weight of (F) a thermal polymerization inhibitor is contained in addition to the above requirements (A) to (E). Good. Examples of useful thermal polymerization inhibitors include hydroquinone, hydroquinone monoethyl ether, catechol, pt-butylcatechol, 2,6-di-t-butyl-
p-cresol and the like can be mentioned.

As the other plasticizer in the photosensitive resin composition,
Liquid polybutadiene rubber, liquid polyacrylonitrile butadiene rubber, liquid polystyrene butadiene rubber, liquid isoprene rubber, liquid rubber and polyvinyl chloride,
It may contain a relatively low molecular weight elastomer such as chlorinated polyethylene and chlorinated polypropylene, fine powder such as silica and diatomaceous earth.

As a method for preparing a printing original plate and a printing plate using the above-mentioned photosensitive resin plate composition, the above-mentioned respective composition components are selected in an arbitrary order in a suitable solvent such as tetrahydrofuran, dioxane, methyl ethyl ketone, toluene cyclohexanone, chloroform. And a hydrophilic polymer such as water and alcohol are dissolved and mixed in a solvent for swelling, dispersing and dissolving, that is, the component (D) under normal conditions, and the solvent is removed, and then a suitable support such as polyester, polyethylene, It can be made by heating and pressing to a film such as polypropylene. A cover film, which is coated with a hydroxyalkyl cellulose coating film containing a plasticizer, which is the composition of the present invention, so as to be a photosensitive resin surface, is pressure-bonded to the surface different from the support to prepare a photosensitive resin laminate. Although the peelability of the cover film is preferably as easy as possible, the equilibrium peel strength is 3 to 6 in consideration of production, packaging and transportation of the photosensitive laminate, and work in the plate making process.
It is desirable to be g / cm, preferably 4 to 5 g / cm.

The ultraviolet rays used for curing the photosensitive resin printing original plate obtained by the above method are 150 to 500 mμ.
Is particularly effective in the wavelength range of 300 to 400 mμ. Light sources used include low pressure mercury lamps, high pressure mercury lamps,
Carbon arc lamp, ultraviolet fluorescent lamp, chemical lamp,
A xenon lamp and a zirconium lamp are preferable.
The photosensitive resin printing original plate is exposed to ultraviolet rays by irradiating a negative film having a transparent image with the above light source to expose the image, and then the non-exposed non-image area is removed with a developing solution at about 25 ° C to 45 ° C. By doing so, the printing plate of the present invention having a clear relief image can be obtained.

The developer includes general domestic water.
Water with a pH of 5.0 to 9.0 is optimal, and with this water as the main component,
You may contain alkaline compounds, such as sodium hydroxide and sodium carbonate, surfactant, a water-soluble organic solvent, etc.
As the above-mentioned surfactant, sodium alkylnaphthalene sulfonate, sodium alkylbenzene sulfonate, etc. are most suitable, and other anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants are used. it can.

The developing device used in the present invention is carried out by immersing or spraying the photosensitive resin printing original plate, which has been exposed to the above developing solution, in contact with a brush. Upon contact with the developing solution, the anti-adhesion layer comprising the composition of the present invention swells and becomes zey, and is easily removed by brushing, and then the unexposed portion is removed.

The developing solution adhering to the plate after development is washed off with water, and then the adhering water is wiped off and dried. Drying is performed by forced air or infrared rays, but the conditions are not particularly limited. The plate after drying is completely cured by a so-called post-exposure operation in which the plate is further exposed by the light source used for the exposure.

[0041]

EXAMPLES The present invention will be described in detail with reference to the following examples, but the present invention is not limited to these examples. In the examples, "parts" means "parts by weight".

Example 1 To 974 parts of pure water was added 25 parts of polyvinyl alcohol AH26 [saponification degree of Nippon Synthetic Chemical Industry Co., Ltd .: about 98 mol%], and the mixture was stirred in a hot water bath at 70 to 80 ° C. for about 2 hours. , A transparent aqueous solution was obtained. Anionic surfactant funnel oil [Kyoeisha Yushi-Seikagaku Co., Ltd., solid content 47%] 0.27
Two levels of 1 part addition and 0.8 part addition were prepared and further stirred for 30 minutes. Next, this aqueous solution was chemically matted at a rate of 6 m / min with polyethylene phthalate (Toyo Cross Co., Ltd.).
Co., Ltd., TC-5000) having a thickness of 95 μm was coated with a roll coater and dried at 100 ° C. The thus-obtained anti-adhesion layers each had a thickness of 2.0 μm. The contact angles of these anti-adhesion layers were measured with a methylene iodide solution using a Kyowa Chemical contact angle tester.
When 8 parts were added, it was 47.3 degrees.

Example 2 To 974 parts of pure water, 25 parts of polyvinyl alcohol AH26 was added and dissolved in the same manner as in Example 1 to obtain a transparent aqueous solution. Anionic surfactant Hitenol 183 [Daiichi Kogyo Seiyaku Co., Ltd., solid content 100%] 0.1
Two levels of 2 parts addition and 0.37 parts addition were prepared and further stirred for 30 minutes. Coating and drying were carried out in the same manner as in Example 1 to obtain an anti-adhesion layer having a thickness of 1.7 μm. Further, the contact angle was measured by the same method as in Example 1 and found to be 50.0 degrees when 0.12 part was added and 57.1 degrees when 0.37 part was added.

Example 3 25 parts of polyvinyl alcohol AH26 was added to 974 parts of pure water and dissolved in the same manner as in Example 1 to obtain a transparent aqueous solution. Anionic surfactant Sannole PP-2030 [Lion Co., Ltd., solid content 100%]
Create 2 levels of 12 parts addition and 0.37 parts addition, and further 3
Stir for 0 minutes. Coating and drying were carried out in the same manner as in Example 1 to obtain an anti-sticking layer having a thickness of 2.0 μm in each case.
When the contact angle was measured by the same method as in Example 1,
When 0.12 part was added, it was 37.5 degrees, and when 0.37 part was added, it was 40.2 degrees.

Example 4 To 974 parts of pure water, 25 parts of polyvinyl alcohol AH26 was added and dissolved in the same manner as in Example 1 to obtain a transparent aqueous solution. In this aqueous solution, the nonionic surfactant Neugen E
A-120 [Daiichi Kogyo Seiyaku Co., Ltd. solid content 100%]
2 levels of 12 parts addition and 0.37 parts addition were prepared, and further 3
Stir for 0 minutes. Coating and drying were carried out in the same manner as in Example 1 to obtain an anti-adhesion layer having a thickness of 1.7 μm.
When the contact angle was measured by the same method as in Example 1,
When 0.12 part was added, it was 48 degrees, and when 0.37 part was added, it was 54.1 degrees.

Example 5 To 974 parts of pure water, 25 parts of polyvinyl alcohol AH26 was added and dissolved in the same manner as in Example 1 to obtain a transparent aqueous solution. Amphoteric surfactant Lipomin CH in this aqueous solution
[Lion Co., Ltd., solid content 20%] 0.6 part was added, and the mixture was further stirred for 30 minutes. The coating and drying were carried out in the same manner as in Example 1 to obtain a 1.8 μm thick tackiness preventive layer. When the contact angle was measured by the same method as in Example 1, 57.
It was 3 degrees.

Example 6 Hydroxypropylmethylcellulose E was added to 974 parts of pure water.
-3 (Nippon Soda Co., Ltd., molecular weight: 30,000 to 50,000) was added thereto, and the mixture was stirred at room temperature for about 1 hour to obtain a transparent aqueous solution. 0.52 parts of anionic surfactant funnel oil was added to this aqueous solution, and the mixture was further stirred for 30 minutes. Coating and drying were carried out in the same manner as in Example 1 to obtain a sticking prevention layer having a thickness of 1.6 μm. When the contact angle was measured by the same method as in Example 1, it was 35.3 degrees.

This photosensitive resin composition was used in a heat press machine at 100 ° C. and a pressure of 150 kg / cm ² to obtain 125 μm.
A polyester film having a thickness and a chemical mat film having the anti-adhesion layer obtained in Examples 1 to 6 were heated and pressed for 10 seconds so that the anti-adhesion layer was in contact with the photosensitive resin, and a thickness of 2.0 mm. A sheet (printing original plate) was created. Next, using a tensile tester manufactured by Toyo Baldwin Co., Ltd. (hereinafter referred to as Tensilon), the peeling trigger strength and the equilibrium peel strength of the chemical matte film from the 2.0 mm thick sheets obtained in Examples 1 to 6 were measured. When measured, the peeling trigger strength was in the range of 2 to 5 g / cm and the equilibrium peel strength was in the range of 3 to 6 g / cm, indicating that the peeling was easy.
When the surface of the anti-adhesion layer on the photosensitive resin was observed, it showed a smooth and mirror-like surface, and there was no tackiness by the tentacle. Further, the 2.0 mm-thick sheets obtained in Examples 1 to 6 were treated for 1 week under heating and humidification at 35 ° C./85% RH, and the peeling property was evaluated. Was not recognized.

Next, a negative film having an image on the printing original plate obtained in Reference Example 1 was adhered thereon and exposed with a mercury lamp (Dainippon Screen Co., Ltd.) at an illuminance of 25 W / m ² for 8 minutes. After removing the negative film, it is treated with neutral water containing 2% by weight of sodium alkylnaphthalene sulfonate at 40 ° C. 1
After development with a brush for 5 minutes, a relief (printing plate) image pattern having a depth of 0.8 mm was obtained. This image pattern faithfully reproduced the image of the negative film used, and no wrinkles were observed in the relief. Further, the obtained relief had a good ink transfer property and showed a clear image. Table 1 shows the characteristics obtained in Examples 1 to 6.

[0050]

[Table 1]

Comparative Example 1 To 974 parts of pure water, 25 parts of polyvinyl alcohol AH26 [saponification degree of Nippon Synthetic Chemical Industry Co., Ltd., about 98 mol%] was added, and the mixture was stirred in a hot water bath at 70 to 80 ° C. for about 2 hours. , A transparent aqueous solution was obtained. 1.9 parts of polyethylene glycol having a molecular weight of 1000 was added to this aqueous solution, and the mixture was further stirred for 30 minutes. This aqueous solution was chemically matted at a rate of 6 m / min. To polyethylene matte phthalate (TC-made by Toyo Cross Co., Ltd.).
(5000) A roll coater was coated on a thickness of 95 μm, and the coating was dried at 100 ° C. to prepare an anti-adhesion layer containing 2.0% by weight of polyethylene glycol of 8% by weight. When the contact angle was measured using a methylene iodide solution using this anti-adhesive agent, it was 22.6 degrees.

Using the anti-adhesion layer prepared in Comparative Example 1,
A 2.0 mm sheet (printing original plate) was prepared in the same manner as in Reference Example 1, and the peel strength of the uppermost chemical matte film was measured by Tensilon. The peel trigger strength was 12 g / cm, the equilibrium peel strength. Was 15 g / cm. Furthermore, when the treatment was carried out under a humidified condition of 35 ° C./85% RH, peeling could not be done after 1 day. Next, using the sheet having a thickness of 2.0 mm obtained in Comparative Example 1,
When the chemical matte film was peeled off in order to create a relief having an image pattern in the same manner as in Reference Example 1,
The printing original plate was deformed into a convex shape. Although an image pattern having a depth of 0.8 mm was obtained on the obtained relief (printing plate), generation of small wrinkles was observed on the relief surface. When printing was performed using the obtained relief, ink transfer unevenness was observed in the printed matter.

[0053]

The anti-adhesion layer used in the photosensitive laminate of the present invention facilitates the work of peeling the cover film in the plate making process, and the greatest effect thereof is the photosensitivity caused by the easy peeling of the cover film. It is possible to prevent the convex deformation of the photosensitive resin plate and prevent the generation of small wrinkles that are likely to occur on the surface of the photosensitive resin plate. The anti-adhesion layer of the present invention,
There is also an effect that it is not affected by temperature and humidity, and since these can improve workability at the time of plate making and can obtain the reliability of the printed matter, it greatly contributes to the industrial world.

Claims (1)

[Claims] 1. An anti-adhesion layer for a photosensitive resin printing plate, which is developable with an aqueous processing solution, the layer comprising a water-soluble polymer and one or more interfaces selected from anionic, nonionic and amphoteric systems. An anti-adhesion layer for a photosensitive resin printing plate, comprising an activator and having a contact angle with methylene iodide of 35 to 60 degrees.