JPH05297594A - Composition for sticking preventing layer for photosensitive resin printing plate - Google Patents

Abstract

PURPOSE:To obtain a sticking preventing layer having satisfactory releasability to a flexible photosensitive resin printing plate and not affected by any environment. CONSTITUTION:This compsn. for a sticking preventing layer for a photosensitive resin printing plate developable with an aq. processing soln. contains silane modified polyvinyl alcohol represented by the formula (where R is H, hydroxyl, 1-6C alkyl or OM, M is H, an alkali metal or ammonium, (l) is an integer of 1,000-2,000, (m) is an integer of 10-500 and (n) is an integer of 1-10).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an anti-sticking layer composition for a flexible photosensitive resin printing plate, especially a flexographic printing plate which can be developed 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.

Among water-soluble polymers, polyvinyl alcohol having a saponification degree of 90% or more generally has a relative humidity of 80% R
Below H, the adhesiveness rarely increases remarkably due to the moisture absorption of the thin film, but above 80% RH, the thin film absorbs moisture rapidly, 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.

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 prior art, there is still no suitable anti-adhesive agent for a photosensitive resin plate which can be developed with an aqueous processing solution and has flexibility. Is. In particular, the problem of wrinkling is large, for example, if the peeling of the cover film is once interrupted and then the peeling is restarted, linear streak wrinkles 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. Further, when the photosensitive resin laminated body from which the cover film has been peeled off is deformed into a concave or convex shape, when it is returned to a normal flat surface, wrinkles are generated in the anti-adhesion layer. Therefore, the photosensitive resin laminate after peeling the cover film is dealt with by avoiding moving it as much as possible, but sometimes it is necessary to move it, and avoid bending deformation of the photosensitive resin laminate. It is not easy to move. Therefore, in the present invention, a water-soluble or water-dispersible polymer, which has good adhesion to the original film, and does not cause wrinkles even if the original plate is bent, and at the same time is not affected by humidity, provides an anti-adhesive thin film. The purpose is to give material.

[0010]

Means for Solving the Problems The inventors of the present invention have made extensive studies on the anti-adhesion layer composition to solve the above-mentioned drawbacks, and as a result, finally completed the present invention. That is, the present invention is an anti-adhesion layer composition for a photosensitive resin printing plate which can be developed with an aqueous processing solution, wherein the composition contains a silane-modified polyvinyl alcohol represented by the following general formula (2). It is a characteristic anti-adhesion layer composition for a photosensitive resin printing plate.

[0011]

[Chemical 2] (In Chemical formula 2, R represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms or OM, M represents a hydrogen atom,
Indicates alkali metal and ammonium. l is 1000 to 2
000, m are 10-500, n shows the integer of 1-10. )

The silane-modified polyvinyl alcohol used in the present invention is obtained by copolymerizing a vinyl ester and a silane-containing polymerizable monomer in the presence of an alcohol such as methanol or ethanol using a radical polymerization initiator.
The obtained copolymer is saponified, for example, JP-A-58-59203, JP-A-58-79003, and JP-A-58-79003.
It is a modified polyvinyl alcohol obtained by the production method disclosed in Japanese Patent Laid-Open No. 58-1164604, and its structure and characteristics are completely different from those of ordinary polyvinyl alcohol. Specifically, trade names R-1130 and R-21
05 (manufactured by Kuraray Co., Ltd.) and the like can be used. In the above Chemical formula 2, l is 100
0 to 2000, preferably 1500 to 1800, m is 1
0-500, preferably 30-300, n is 1-10,
It is preferably 1 to 5 and represents the repeating number of each unit. When it is expressed in mol%, 1 is 85 to 99 mol%, particularly 87 to 98 mol%, m is 1 to 12 mol%, and particularly 1 to 5 mol%, n is 0.1 to 10 mol%, particularly 0.2 to 5 mol%
Is preferred.

The composition of the present invention is used as an anti-adhesion layer in a photosensitive resin laminate for a photosensitive resin printing plate. As the laminate, at least an adhesive layer, a photosensitive resin layer and an anti-adhesion layer are provided on a support. It is composed of a layer and a cover film, and as a manufacturing method thereof, a cover film is coated with an anti-adhesion layer in advance, and a support is coated with an adhesive layer in advance. A method of laminating layer materials by a method such as pressure bonding is commonly used.

Polyethylene terephthalate film is most suitable as the cover film from the viewpoint of dimensional stability, heat resistance and mechanical performance. However, polyethylene or polypropylene, polystyrene or 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 preferable to apply the silane-modified polyvinyl alcohol as an aqueous solution of 1 to 5%, preferably 1.5 to 3%.
In addition to the plasticizer and the surfactant, various antifoaming agents, leveling agents, penetrants and the like may be added to the composition of the present invention in order to improve the coatability to the cover film. A water-soluble preservative may be added for stability. 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 composition of the present invention is used has components such as a filled polymer, a photocuring agent, a photosensitizer, a polymerization inhibitor and other additives. However, depending on the type of the filling polymer that is the main component, for example, polyamide-based, polyurethane-based, polyvinyl alcohol-based, polyester-based,
Although the present invention may be applied to any known photosensitive layer, it is particularly preferably referred to as polyvinyl acetic acid type, but particularly preferably, a polymer and an ethylenically unsaturated compound which dissolve or swell in water or an aqueous developing solution ( And) or a polymer obtained by a method comprising a hydrophobic polymer and a photoinitiator. For example, JP-A-60-21451 and JP-A-60-173055.
It is known by the issue.

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 monoolefin 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 elastomers containing a specific amount of chlorine and non-conjugated diene hydrocarbons. 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 includes not only the polymer as the component (A) but also 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), a polymer having a hydrophilic group such as a hydroxyl group, an amino group and a sulfonic acid group and / or a polyoxyalkylene chain may be used in combination with the hydrophilic polymer. 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.

The component (C), an ethylenically unsaturated compound, contains at least one terminal ethylenic group, and this compound can form a 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.

Examples of the solvent in which the solubility of the component (B), which is the component (D), is higher than the solubility of the component (A) include solvents having high polarity. 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% by weight to 5% by weight based on the entire 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 the photocrosslinking reaction, 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 of preparing a printing original plate and a printing plate using the above-mentioned photosensitive resin plate composition, the respective composition components are selected in an arbitrary order, for example, tetrahydrofuran, dioxane, methyl ethyl ketone, toluene cyclohexanone, chloroform. Etc. and water, a hydrophilic polymer such as alcohol is swelled, dispersed and dissolved in a solvent, ie, component (D) under normal conditions, dissolved and mixed, 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. In the present invention, the laminate can be used in various fields such as ordinary relief printing, planographic printing, intaglio printing, screen printing printing in addition to flexographic printing printing.

The ultraviolet ray used for curing the photosensitive resin printing original plate obtained by the above method is 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 surfactant, sodium alkylnaphthalene sulfonate, sodium alkylbenzene sulfonate, etc. are most suitable, and in addition, anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants are Can be used.

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, while bringing a brush into contact therewith. Upon contact with the developing solution, the anti-adhesion layer comprising the composition of the present invention swells, becomes brittle, and is easily removed by brushing, and then the non-exposed 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.

[0038]

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, 25 parts of silane-modified polyvinyl alcohol [R-1130 silane-containing polymer (Kuraray Co., Ltd., about 1 mol%)] having a saponification degree of about 98 mol% was added, and the amount was 70 to 70%. 8
The mixture was stirred in a hot water bath at 0 ° C. for about 1 hour to obtain a transparent aqueous solution. Next, this aqueous solution was coated on a 125 μm chemically matted polyethylene terephthalate film (TC-5000 manufactured by Toyo Cloth Co., Ltd.) at a rate of 6 m / min with a roll coater and dried at 100 ° C. The anti-adhesion layer thus obtained had a thickness of 2.0 μm.

Example 2 To 974 parts of pure water, 25 parts of a silane-modified polyvinyl alcohol having a saponification degree of about 98 mol% [R-2150 silane-containing polymer (about 1.5 mol%) manufactured by Kuraray Co., Ltd.] was added, After dissolution in the same manner as in Example 1, a transparent aqueous solution was obtained, which was coated and dried in the same manner as in Example 1 to give 2.0 μm.
An anti-adhesion layer having a thickness of m was obtained.

Example 3 A transparent aqueous solution obtained in the same manner as in Example 1 was further mixed with a surfactant funnel oil (Kyoeisha Oil and Fat Chemical Co., Ltd., solid content 47).
%) 0.14 part was added and stirred for 30 minutes. Then, this aqueous solution was used for coating and drying in the same manner as in Example 1 to obtain an anti-adhesion layer having a thickness of 1.8 μm.

Reference Example 1 A photosensitive resin composition was prepared by the following method.
Hexamethylene diisocyanate 21.8 parts, dimethylol propionic acid 15.4 parts, polytetramethylene glycol (PG-100 Nippon Polyurethane Industry Co., Ltd.)
7.6 parts and a solution of 1.0 part of di-n-butyltin dilaurate dissolved in 300 parts of tetrahydrofuran are placed in a 1 liter flask equipped with a stirrer, and the flask is heated to 65 ° C. for 3 hours while continuing stirring. The reaction continued. In a separate container, a terminal amino group-containing acrylonitrile-butadiene oligomer (Hycar ATBNX 1300 x 1
A solution prepared by dissolving 55.3 parts of 6 Ube Industries, Ltd. in 100 parts of methyl ethyl ketone was added to the above 1 liter flask with stirring at room temperature. The obtained polymer solution was dried under reduced pressure to remove tetrahydrofuran and methyl ethyl ketone to obtain a polymer having a number average molecular weight of 21,000. Next, a solution prepared by dissolving 4.8 parts of lithium hydroxide in 100 parts of methyl alcohol was added to a solution prepared by dissolving 100 parts of the polymer in 100 parts of methyl ethyl ketone at room temperature with stirring, and further stirred for 30 minutes to obtain hydrophilicity. Polymer [I] was obtained.

10 parts of the above hydrophilic polymer [I], 45 parts of chlorinated polyethylene (H-135 manufactured by Osaka Soda Co., Ltd.) as a hydrophobic polymer, styrene-butadiene rubber (manufactured by JSR1507 Nippon Synthetic Rubber Co., Ltd.) 15 Part, butadiene oligoacrylate (PB-A Kyoeisha Yushi Co., Ltd.) 28.5 parts, benzyl dimethyl ketal (Irgacure 651, Ciba Geigy Co., Ltd.) 1 part and hydroquinone monomethyl ether 0.5 part toluene 4
After dissolving and dispersing in 0 part and 10 parts of water and kneading at 105 ° C. using a heating kneader to dissolve and defoam, a photosensitive resin composition was obtained.

Using this photosensitive resin composition,
100 ℃, 150Kg / cm ²Pressure of 125
obtained in Examples 1 to 3 with a μ-thick polyester film
Chemical matte polyester film with anti-adhesion layer
Between the film (cover film), the anti-adhesion layer is a photosensitive resin.
It is heated and pressed for 10 seconds so that it comes into contact with fat, and the thickness is 2.0 mm.
The sheet (printing original plate) was created. Then each best
Of the polyester film which is the cover film of the layer
When the strength was measured, in Example 1, it was 6 g / cm.
In Example 2, 4 g / cm, in Example 3, 3 g / cm,
Peeling was easy. Also, the tackiness obtained in Examples 1 to 3
Observation of the surface of the protective layer shows a smooth and mirror-like surface.
However, it was not tacky by the tentacles. Next, 2.0 mm
Thick sheet heated at 35 ° C / 85% RH for 3 weeks
Leaving cover film peeling and cover film
When the adhesiveness of the surface of the photosensitive resin layer after peeling was evaluated,
There were no problems at all. Further cover film
Peeled sheet as it is at 35 ° C / 85% RH for 1 week
No stickiness was observed when left to stand.

Next, the cover film was peeled off in Reference Example 1,
Using a sheet left at 35 ° C / 85% RH for 1 week,
A negative film having an image was adhered thereon and exposed with a mercury lamp (manufactured by Dainippon Screen Co., Ltd.) at an illuminance of 25 W / m ² for 8 minutes. Removal of the negative film is easy, and after removing the negative film, development with a brush at 40 ° C for 15 minutes in neutral water containing 2% by weight of sodium alkylnaphthalene sulfonate gives a relief (printing plate). An image pattern having a depth of 0.8 mm was obtained. This image pattern faithfully reproduced the image of the negative film used. Further, the obtained relief had good ink transfer property and showed a clear image.

Comparative Example 1 The same as Example 1 except that polyvinyl alcohol having a saponification degree of about 98 mol% (AH26 manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) was used in place of the silane-modified polyvinyl alcohol. To obtain a sticking prevention layer having a thickness of 2.0 μm. Next, prepare a printing original plate in the same manner as in Reference Example 1,
When the peel strength with the cover film was measured, it was 13 g /
It was cm. Further peel off the cover film, 35 ℃
After leaving for 1 week at / 85% RH, the cover film could not be peeled off in only one day.

Comparative Example 2 In Comparative Example 1, the transparent aqueous solution obtained in the same manner as in Comparative Example 1 was added to polyethylene glycol 1.
A pressure-sensitive adhesive layer containing 8% polyethylene glycol having a thickness of 1.8 μm was obtained in the same manner as in Comparative Example 1 except that 9 parts were mixed and dissolved. Next, a printing original plate was prepared in the same manner as in Reference Example 1, and the peel strength from the cover film was measured.
It was 5 g / cm. Further peel off the cover film,
When left for 1 week at 35 ° C./85% RH, the cover film could not be peeled off after 2 days.

[0048]

The anti-adhesive layer composition of the present invention has non-adhesiveness which is an original function in any environment, and has an adhesive function under high humidity as seen in the conventional anti-adhesive layer. There is no decrease in As a result, the photosensitive resin printing plate can be used with peace of mind throughout the year, and trouble will not occur during work such as the plate making process even if it is stored for a long time. And contribute to the industrial world.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C09D 143/04 PGL 7921-4J G03F 7/00 502 7124-2H

Claims (1)

[Claims] 1. A pressure-sensitive adhesive layer composition for a photosensitive resin printing plate, which is developable with an aqueous treatment liquid, wherein the composition contains a silane-modified polyvinyl alcohol represented by the following general formula 1. A pressure-sensitive adhesive layer composition for a photosensitive resin printing plate, comprising: [Chemical 1] (In Chemical Formula 1, R represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms or OM, and M represents a hydrogen atom,
Indicates alkali metal and ammonium. l is 1000 to 2
000, m are 10-500, n shows the integer of 1-10. )