JP3024655B2 - Anti-adhesive layer composition for photosensitive resin printing plate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an anti-adhesive layer composition for a flexible photosensitive resin printing plate, particularly a water-developable flexographic printing plate.

[0002]

2. Description of the Related Art Usually, in a process of making a photosensitive resin into a printing plate,
A method in which an original film is vacuum-contacted on the photosensitive layer of the photosensitive resin master plate and exposed to actinic rays is mainly used.

[0003] In recent years, in the field of business home printing, the demand for rubber-like flexible photosensitive resin letterpress has been increasing, and as a result, the photosensitive resin original plate tends to be softer. However, in general, the surface of the photosensitive layer of the original is often tacky, and the lower the hardness of the original, the more the adhesiveness increases. If the tackiness is strong, uniform adhesion cannot be achieved when the original film is brought into close contact, and therefore, the reproducibility of the image deteriorates.
Further, when the original film is peeled off from the original plate after the exposure, there is a problem that the adhesion of the original film causes a peeling failure and both of them are damaged.

[0004] 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 adhesiveness to 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 (polyvinyl alcohol having a polymerization degree of 800 or more and saponification degree of 70% to 90%),
JP-A-54-68224 (water-soluble polymer) is known. However, these methods have the following problems.

In recent years, a type using water has become the mainstream for developing a photosensitive resin printing plate. Therefore, an anti-adhesion layer using a water-soluble or water-dispersible polymer is necessary, but in the production of a thin film of the anti-adhesion layer using an aqueous solution of the water-soluble or water-dispersible polymer, There is a problem in that fatal coating defects such as flipping of the aqueous solution due to poor wetting, generation of citron skin or a spiral pattern, and generation of pinholes due to generation of air bubbles occur.

When a cover film having this coat defect is used, it is difficult to separate the cover film from the photosensitive resin laminate (original plate) in the plate making process. Even if it can be peeled off, the coating defect remains as a defect on the photosensitive resin surface as it is, causing problems such as poor adhesion to the original film, poor image reproducibility, and defective printed matter due to uneven ink density. .

Various surfactants, silicone-based antifoaming agents, non-silicone-based antifoaming agents, etc. have been added to prevent such coating defects and improve coating properties. At present, it is not enough to resolve defects.

By the way, when the photosensitive resin composition is a flexographic printing plate, since the photosensitive resin is more flexible and has a strong tackiness, a high demand for a non-adhesive coating layer is required. A technique in which a release layer is further provided is disclosed in
No. 7,208,556.

However, the application of a release agent not only increases the number of manufacturing steps, but also the application of a non-adhesive coating layer on the release agent tends to cause coat defects as described above,
Advanced coating technology is required.

[0010]

As described above, even in the prior art, there is no water-developable and flexible anti-adhesion material for a photosensitive resin plate at present.

[0011] In particular, the coating defects include, for example, the case where the aqueous solution cannot be repelled at the time of coating and the coating cannot be processed. The disadvantage of this is that the problem occurs. In the former case, it cannot be used as an anti-adhesion layer and should be stopped. However, in the latter case, there is a case where the problem is not necessarily a coat defect. However, when the cover film having the anti-adhesion layer is used, as described above, there is a problem in that releasability from the original plate is poor, image reproducibility is poor, and a clear printed image cannot be obtained.

In the present invention, therefore, it is an object of the present invention to provide an anti-adhesion thin film material which does not cause coat defects and which does not adversely affect the releasability and the photosensitive resin layer surface in an aqueous solution using a water-soluble or water-dispersible polymer. The purpose is.

[0013]

Means for Solving the Problems The present inventors have conducted intensive studies on the composition of the anti-adhesion layer in order to solve the above-mentioned drawbacks, and have finally completed the present invention. That is, the present invention provides a water-soluble polymer and / or a water-dispersible polymer,
An anti-adhesion layer composition for a photosensitive resin printing plate, comprising an alkyl ester sulfone compound represented by the following general formula (1) and an alkyl phosphate ester derivative represented by the following general formula (2): is there.

Embedded image

Embedded image (In the general formulas (1) and (2), R1 to R4 are
It is an alkyl group having a prime number of 6 to 12. )

In the present invention, the water-soluble polymer has a hydrophilic group such as a hydroxyl group, a carboxyl group and an amino group,
It is a polymer that hydrates via this hydrophilic group and monodisperses in water, and specifically, polyvinyl alcohol (PVA), hydroxyethyl cellulose (HEC),
Examples include methylcellulose (MC), carboxymethylcellulose (CMC), sodium polyacrylate, sodium polyalginate, polyethylene oxide, hydroxypropylcellulose (HPC), and hydroxypropylmethylcellulose (HPMC). Further, the water-dispersible polymer is a polymer that can be dispersed in water in a state of a particle diameter of about 0.01 to 10 μ, and specific examples include an acrylic copolymer emulsion, an epoxy ester emulsion, and a synthetic rubber latex. .

In the present invention, the alkyl ester sulfone compound and the alkyl phosphate ester derivative are preferably compounds represented by the following formulas (1) and (2) , respectively.

Embedded image

Embedded image In the general formulas (1) and (2), R ^{1 to} R ⁴ are preferably an alkyl group having 6 to 12 carbon atoms, particularly preferably an octyl group having 8 carbon atoms in consideration of seasonal variation and the like. The compounding amount of the compound is about 0.001 to water-soluble polymer and / or water-dispersible polymer.
The content is 1 to 70% by weight, and particularly preferably 0.01 to 30% by weight. When a plasticizer is further added to the composition of the present invention, the compounding amount of the alkyl phosphate ester derivative is about 0.5.
It may be 001 to 7% by weight.

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, The cover film is coated with an anti-adhesion layer in advance, and the support is coated with an adhesive layer in advance. A method of laminating layer materials by a method such as pressure bonding is generally performed.

As the cover film, a polyethylene terephthalate film is optimal from the viewpoint of dimensional stability, heat resistance, and mechanical performance. Can be used. The surface of the cover film may be smooth, but more preferably a so-called mat shape having a surface roughness of 5 μ or less. When applying the composition of the present invention on the cover film,
1-5% of a water-soluble and / or water-dispersible polymer,
It is preferable to apply as a 1.5 to 2% aqueous solution. The composition of the present invention may contain a preservative, a chelating agent, and the like for water-soluble storage stability. The thickness of the anti-adhesion layer after drying is 0.1 to 10 μm, preferably 2 to 10 μm.
5 μm.

Next, the photosensitive resin composition in the photosensitive resin laminate in which the composition of the present invention is used contains, as its components, 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,
The present invention may be applied to any known photosensitive layer, but is particularly preferably water- or aqueous developer, a polymer which dissolves or swells, and an ethylenically unsaturated monomer. And (and) or those obtained by a method comprising a hydrophobic polymer and a photoinitiator. For example, Japanese Patent Application Laid-Open Nos. 60-211141, 60-1730
It is known from, for example, Japanese Patent Publication No. 55-55.

Examples of the above photosensitive resin composition include (A) a hydrophobic polymer having a glass transition temperature of 5 ° C. or less;
(B) a photosensitive polymer containing (H) 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. In a photosensitive resin composition or a photosensitive resin printing original plate and a printing plate, particles in which a phase mainly composed of a hydrophobic polymer and a phase mainly composed of a hydrophilic polymer are surrounded in the photosensitive resin layer. Are present as a dispersed phase, and a photosensitive resin composition, and the like, and these compositions are particularly preferable in the invention.

The component (A) having a glass transition temperature of 5
Examples of the hydrophobic polymer having a temperature of not more than ℃ include those used as general-purpose elastomers.For example, a polymer obtained by polymerizing a conjugated diene-based hydrocarbon or a polymer obtained by polymerizing a conjugated diene-based hydrocarbon with a monoolefin-based unsaturated compound is used. And a polymer containing no conjugated diene-based hydrocarbon. As the conjugated diene hydrocarbon, 1,3-butadiene, isoprene, chloroprene and the like are used. The conjugated diene-based hydrocarbon may be used alone or in combination of two or more.

The monoolefinically unsaturated compounds include:
Styrene, α-methylstyrene, 0-methylstyrene,
m-methylstyrene, P-methylstyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamido vinyl acetate,
Acrylic esters and methacrylic esters are used.

Examples of the polymer obtained by polymerizing a conjugated diene-based hydrocarbon or the copolymer obtained by polymerizing a conjugated diene-based hydrocarbon and a monoolefinic unsaturated compound include a butadiene polymer and an 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 And acrylonitrile-chloroprene-styrene copolymer.

Examples of the polymer containing no conjugated diene-based hydrocarbon include elastomers containing a specific amount of chlorine and non-conjugated diene-based 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. For example, polymerization of a monomer containing a chlorine atom or chlorine Obtained from copolymerization of an atom-containing monomer with another monomer that can be copolymerized. 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, or epichlorohydrin rubber which is a copolymer of these and allyl glycidyl ether [Osaka Soda Kogyo Co., Ltd. Epichromer, Goodvich Co., Ltd.HYDRIN, Nippon Zeon Co., Ltd. GECHRON, Zeospan, Hercules strain HERCLO
R], chlorinated polyethylene (Showa Denko KK, Eraslen, Osaka Soda Kogyo Co., Ltd.
ORTALITZ, DOWCPE manufactured by Dow Chemical Co., Ltd.), vinyl chloride copolymer, vinylidene chloride, chlorinated polypropylene, chlorinated ethylene-propylene rubber, and the like. These polymers may be used alone or in combination of two or more.
The chlorine content of the polymer is between 10 and 50% by weight, preferably
If it is out of this range, the flexibility is impaired, the thermal stability is deteriorated, and the photosensitive resin composition is too hard or easily colored, which is not preferable. Since the conjugated diene-based hydrocarbon polymer containing a chlorine atom or its copolymer contains a carbon unsaturated bond in the main chain, there is a drawback that the chemical stability such as weather resistance is inferior to the case of only a saturated bond. In addition, since the physical properties of the photosensitive resin composition after light irradiation greatly 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 must be 5 ° C. or lower, and particularly preferably −10 ° C. or lower.

The above-mentioned photosensitive resin composition is obtained by blending not only the polymer as the component (A) but also an elastomer having good compatibility and ozone resistance such as acrylic rubber and polyurethane elastomer. You may. The content of the component (A) in the entire composition is 20% by weight in consideration of the physical properties and shape retention of the printing plate.
As described above, the content is preferably at least 30% by weight, and from the viewpoint of photopolymerizability, is at most 80% by weight, particularly preferably at most 70% by weight.

Next, (B) in the photosensitive resin composition
The hydrophilic polymer as a component is soluble or swells (disperses) in water or a developer containing water as a main component and containing an alkaline aqueous solution, an acidic aqueous solution, an organic solvent, or a surfactant.
And a hydrophilic group such as —CO ₂ M group, —SO ₃ M group, (M represents a hydrogen atom, group I, II, or III element, amine or ammonium) —NH ₂ or —OH. It is a polymer that has a group and is linear and has no cross-linking. Examples of such a hydrophilic polymer include, in addition to general-purpose resins such as polyvinyl alcohol (PVA) carboxymethyl cellulose, (meth)
Diene rubber in which acrylic acid and a diene compound are copolymerized, liquid polybutadiene modified with maleic anhydride, particularly preferably -COOM (M is a hydrogen atom, Periodic Tables I and I)
50 to 5)
It is a polymer having an equivalent weight of 10,000 equivalents / 10 ⁶ g. Examples of the Group I, II, and III elements of the periodic table include alkali metals such as sodium, potassium, and lithium, alkaline earth metals such as calcium and magnesium, boron, and aluminum. No. The -COOM group is 50 equivalents / 10 ⁶ g
Undesirable difficult to developed with affinity inferior neutral water, whereas when it exceeds 50,000 equivalents / 10 ⁶ g, since water-based ink is poor in water is less than.

Specific examples of the hydrophilic polymer include a polyurethane containing -COOM group, a polyurea urethane containing -COOM group,
-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, polyacryl Sodium acid, polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC), hydroxyethyl cellulose (HE
C), methylcellulose (MC), polyethylene oxide, polyethyleneimine, and derivatives of the compound can be used, but are not limited thereto.

The compound used to neutralize at least a part of the carboxyl groups contained in the hydrophilic polymer includes lithium hydroxide, potassium hydroxide,
Alkali metal hydroxides such as sodium hydroxide, alkali metal carbonates such as lithium carbonate, potassium carbonate and sodium carbonate, alkali metal alkoxides such as potassium t-butoxide and sodium methoxide, calcium hydroxide, magnesium hydroxide, water Hydroxides of polyvalent metals such as aluminum oxide; alkoxides of polyvalent metals such as aluminum isopropoxide; tertiary amines such as triethylamine and tri-n-propylamine; secondary amines such as diethylamine and di-n-propylamine. Primary amines such as primary amine ethylamine and n-propylamine, cyclic amines such as morpholine, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth)
Amino group-containing (meth) acrylates such as acrylates; ammonium carbonates and the like; ammonium salts; and the like. These may be used alone or in combination of two or more. Further, the hydrophilic polymer may have a polyoxyalkylene chain as a hydrophilic part other than the -COOM group, and may contain an ethylenically unsaturated group so as to act as a crosslinking agent.

As the component (B), a polymer having a hydrophilic group such as a hydroxyl group, an amino group or a sulfonic acid group and / or a polyoxyalkylene chain may be used in addition to the hydrophilic polymer. The content of the component (B) in the entire composition is preferably 5 to 50% by weight, particularly 7 to 40% by weight, and more preferably 7 to 40% by weight in consideration of aqueous developing property and water-resistant ink property.
30% by weight is particularly preferred. It is essential that the content of the component (B) in the entire composition is less than that of the component (A).
If the amount is more than the component (A), the water-resistant ink properties deteriorate.

In the photosensitive resin composition, the ethylenically unsaturated compound as the component (C) contains at least one terminal ethylenic group, and this compound is obtained by free radical-initiated chain growth addition polymerization. It can form a high-molecular polymer. Suitable ethylenically unsaturated compounds are unsaturated esters of polyols, especially such esters with α-methylene carboxylic acid, such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, glycerol diacrylate, 1 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 N-methylmaleimide, N
N such as -ethylmaleimide and N-laurylmaleimide
Oligos such as substituted maleimide compounds, oligonitrile / butadiene di (meth) acrylate, oligonitrile / urethane (meth) acrylate, oligourethane di (meth) acrylate, oligobutadiene di (meth) acrylate, oligobutadiene / urethane di (meth) acrylate (Meth) acrylates, which may be used alone or in combination.

The content of the component (C) in the composition is preferably from 1 to 50% by weight, and if it is less than 1% by weight, the photopolymerizability is impaired, so that no image remains after development. Conversely, if it is more than 50% by weight, shape retention will be impaired. Further, the plate after light irradiation is hard and brittle, which is not suitable for a flexographic printing plate material, which is not preferable. More preferably 5-
40% by weight.

In the photosensitive resin composition, as the solvent (D) in which the solubility of the component (B) is higher than the solubility of the component (A), a highly polar solvent may be mentioned. That is, the solvent 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 and carbon
Examples of the water include surfactants such as sodium alkyl benzene sulfonate, sodium alkyl naphthalene sulfonate, sodium alkyl sulfonate, and sodium alkyl ether sulfonate, fatty acids, lithium hydroxide, and water. It may contain potassium oxide, sodium hydroxide, sodium borate, sodium carbonate, sodium acetate, magnesium acetate or salts thereof. Examples of the alcohol include methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, t-butyl alcohol, pentyl alcohol, and neopentyl alcohol. Further, as long as it satisfies the requirement of (D), ester-based, ketone-based, amide-based solvents and the like can be mentioned. Specific examples include ethyl acetate, butyl acetate, isobutyl acetate, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, methyl butyl ketone, formamide, dimethylformamide, dimethylacetamide and the like. These solvents can be used alone or in combination as a mixed solvent.

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

The photopolymerization initiator (E) in the photosensitive resin composition includes, for example, benzophenones, benzoins, acetophenones, benzyls, benzoin alkyl ethers, benzylalkyl ketals, anthraquinones, thioxanthone And the like. Specifically, benzophenone, chlorobenzophenone, benzoin, acetophenone, benzyl benzoin, 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 initiation ability is impaired, and if it is more than 5%,
It is not preferable because the curing depth cannot be obtained by the light itself and the image is easily chipped by the development. More preferably, it is 0.1 to 3% by weight.

In order to simply prevent thermal polymerization without inhibiting the photocrosslinking reaction, in addition to the above requirements (A) to (E), (F) a thermal polymerization inhibitor is contained in an amount of 0.001 to 5% by weight. Is also good. Useful thermal polymerization inhibitors include, for example, hydroquinone, hydroquinone monoethyl ether, catechol, pt-butylcatechol, 2,6-di-t-butyl-
p-cresol and the like.

In the photosensitive resin composition, as another plasticizer,
Liquid rubber or polyvinyl chloride, such as liquid polybutadiene rubber, liquid polyacrylonitrile butadiene rubber, liquid polystyrene butadiene rubber, liquid isoprene rubber,
It can contain relatively low molecular weight elastomers such as chlorinated polyethylene and chlorinated polypropylene, and fine powders 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 components are mixed in an arbitrary order with a suitable solvent such as tetrahydrofuran, dioxane, methyl ethyl ketone, toluenecyclohexanone, chloroform. And a solvent capable of swelling, dispersing, and dissolving hydrophilic polymers such as water and alcohol, that is, the components (D) are dissolved and mixed under ordinary conditions, the solvent is removed, and then a suitable support such as polyester, polyethylene, It can be prepared by heating and pressing on a film such as polypropylene. A cover film in which a coating film of the anti-adhesion layer composition of the present invention is coated on the surface different from that of the support so as to be a photosensitive resin surface is pressure-bonded to form a photosensitive resin laminate.

The ultraviolet light used for curing the photosensitive resin printing plate obtained by the above method is 150 to 500 m.
A wavelength of μ, especially a wavelength range of 300 to 400 μm is effective, and a low-pressure mercury lamp, a high-pressure mercury lamp, a carbon arc lamp, an ultraviolet fluorescent lamp, a chemical lamp, a xenon lamp, a zirconium lamp, etc. are preferable as a light source. . The photosensitive resin printing original plate is exposed to ultraviolet light by irradiating a negative film having a transparent image with the light source using the above light source, and after exposing the image, non-image portions not exposed are removed using 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 above-mentioned developing solution includes domestic water in general.
Optimum is water with a pH of 5.0 to 9.0.
It may contain an alkaline compound such as sodium hydroxide and sodium carbonate, a surfactant, and a water-soluble organic solvent.
As the above-mentioned surfactant, sodium alkylnaphthalenesulfonate, sodium alkylbenzenesulfonate and the like are most suitable, and in addition, anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants are preferable. Can be used.

The developing device used in the present invention is immersed or sprayed while the brush is in contact with the photosensitive resin printing plate exposed to the developing solution. Upon contact with the developer, the anti-adhesion layer composed of the composition of the present invention swells and zeits, is easily removed by brushing, and then the non-exposed portion of the photosensitive resin layer is removed.

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

[0041]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the examples, “parts” means “parts by weight”.

Example 1 Hydroxyethyl cellulose SP40 was added to 4920 parts of pure water.
80 [degree of polymerization 843, manufactured by Daicel Chemical Industries, Ltd.] and stirred at room temperature for about 1 hour to obtain a transparent aqueous solution.
Next, in this aqueous solution, an alkyl ester sulfone compound in which R ¹ and R ² are octyl groups in Chemical formula 1 and Chemical formula 2
1 with R ^3, R ⁴ is an alkyl phosphoric acid ester derivative compounds is an octyl group in: 1 formulation (manufactured by IP de Fuo <br/> Ma LY72B one company Oil Industries Co.) added with stirring 20 parts And stirred for an additional 30 minutes. Next, this aqueous solution was coated on a 125 μm polyethylene terephthalate film (E-5000 manufactured by Toyobo Co., Ltd.) with a reverse roll at a speed of 6 m / min. The ratio of the base roll speed of the reverse roll to the metalling roll speed was 3: 1. E-
The wettability of the aqueous solution on the 5000 surface was good, and the coated surface dried at 100 ° C. did not have any of the problems of citron skin, spiral pattern and pinhole. The anti-adhesion layer thus obtained had a thickness of 1.6 μ.

Example 2 Hydroxyethyl cellulose SP40 was added to 4911 parts of pure water.
80 [degree of polymerization 843, manufactured by Daicel Chemical Industries, Ltd.] and stirred at room temperature for about 1 hour to obtain a transparent aqueous solution.
9 parts of polyethylene glycol having a molecular weight of 1,000 was added to this aqueous solution with stirring, and the mixture was further stirred for 30 minutes. Further I
2.8 parts of P Deformer LY72B are added with stirring,
Stir for 30 minutes. Next, using this aqueous solution, Example 1 was used.
Coating was performed under the same conditions as described above. Good coatability, 100 ° C
The dried coat surface was free from defects and no problem. The thickness of the anti-adhesion layer thus obtained was 1.7 μm.

Reference Example 1 A photosensitive resin composition was prepared by the following method.
Hexamethylene diisocyanate 21.8 parts, dimethylolpropionic acid 15.4 parts, polytetramethylene glycol (PG-100 Nippon Polyurethane Industry Co., Ltd.)
7.6 parts) and a solution prepared by dissolving 1.0 part of di-n-butyltin dilaurate in 300 parts of tetrahydrofuran were placed in a 1-liter flask equipped with a stirrer, and the flask was heated to 65 ° C. while stirring was continued. The reaction was continued for hours. In a separate container, acrylonitrile
Butadiene oligomer (Hycar ATBNX 13
A solution prepared by dissolving 55.3 parts of 00 × 16 (Ube Industries, Ltd.) in 100 parts of methyl ethyl ketone was added to the above one-liter flask with stirring at room temperature. The obtained polymer solution was dried under reduced pressure to remove tetrahydrofuran and methyl ethyl ketone, and the number average molecular weight was 21.
000 polymers were obtained. Next, a solution in which 4.8 parts of lithium hydroxide was dissolved in 100 parts of methyl alcohol was added to a solution of 100 parts of the polymer dissolved in 100 parts of methyl ethyl ketone while stirring at room temperature. The functional 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, and 15 parts of styrene-butadiene rubber (JSR1507 manufactured by Nippon Synthetic Rubber Co., Ltd.) Parts, 28.5 parts of butadiene oligoacrylate (PB-A Kyoeisha Yushi Co., Ltd.), 1 part of benzyldimethyl ketal (Irgacure 651, manufactured by Ciba Geigy) and 0.5 part of hydroquinone monomethyl ether in toluene 4
It was dissolved and dispersed in 0 parts and 10 parts of water, kneaded and melted at 105 ° C. using a heating kneader, and defoamed to obtain a photosensitive resin composition.

Using this photosensitive resin composition in a heat press at 105 ° C. under a pressure of 100 kg / cm ² ,
Heating and pressing for 1 minute between the polyester film having a thickness of μ and the polyester film having the anti-adhesive layer obtained in Example 1 so that the anti-adhesive layer is in contact with the photosensitive resin, the thickness is 1.7 mm and 2.8 mm. Sheet (print original plate) was created. Next, the uppermost layer of the polyester film was peeled off, and the peeling strength was measured.
It was 12 g / cm for a 5 g / cm, 2.8 mm sheet. Observation of the surface of the anti-adhesion layer on the photosensitive resin showed a smooth and mirror-like surface, and no influence of coatability was observed.

REFERENCE EXAMPLE 2 The photosensitive resin composition obtained in Reference Example 1 was 1.7 mm thick between the polyester films having the anti-adhesion layer obtained in Example 2 in the same manner as in Reference Example 1. And 2.8 mm
Sheet (print original plate) was created. Next, when the peeling strength was measured by peeling the uppermost polyester film,
5g / cm for both 1.7mm sheet and 2.8mm sheet
And easy peeling. Observation of the surface of the anti-adhesion layer on the photosensitive resin showed a smooth and mirror-like surface, and no influence of coatability was observed. When the photosensitive resin layer from which the polyester film was peeled off was bent inward, the occurrence of wrinkles was observed. When the inner bending angle was 45 ° or less, no wrinkles were generated in both the 1.7 mm sheet and the 2.8 mm sheet.

Next, a negative film having an image on the plates obtained in Reference Examples 1 and 2 was closely adhered thereon and exposed to a mercury lamp (manufactured by Dainippon Screen) at an illuminance of 25 W / m ² for 5 minutes. went. After removing the negative film, development was performed with a brush at 40 ° C. for 15 minutes in neutral water containing 2% by weight of sodium alkylnaphthalenesulfonate. As a result, an image pattern having a relief (printing plate) having a depth of 1.2 mm was obtained. Was done. This image pattern faithfully reproduced the image of the negative film used. Next, printing was performed using this relief. The ink used was an aqueous ink (SAC Ink, manufactured by Morohoshi Ink Co., Ltd.), and the printing paper was high quality paper (Golden Form 55 Jujo Paper Co., Ltd.). First, a relief was set on the copper plate with an adhesive tape, and the gap with the anilox roll 300 LPI was 250 μm. Furthermore,
The gap between the pressure copper and the plate copper is 240 μ, and the printing speed is 50 μm.
Printing was performed at m / min. When the obtained printed matter was visually observed and observed using an image breaking apparatus (manufactured by Toyobo), the ink receiving transferability was good, a clear image was shown, and the influence of coatability was not recognized.

Comparative Example 1 To 4920 parts of pure water, 80 parts of a water-soluble polymer hydroxyethylcellulose SP400 (manufactured by Daicel Chemical Industries, Ltd., polymerization degree: 843) was added, and stirred at room temperature for about 1 hour to obtain a transparent aqueous solution. Next, this aqueous solution was added at a speed of 6 m / min.
25 μm polyethylene terephthalate film (E-5
000 Toyobo Co., Ltd.). The ratio of the reverse roll base roll speed to the metalling roll speed was 3: 1. On the E-5000 surface immediately after coating, a spiral pattern was generated, and when dried at 100 ° C., the spiral pattern portion was observed as a white spot defect, and the number of the defects was 25 / m ^{Was 2} . The thickness of the obtained anti-adhesion layer was 1.6 μ. Next, Reference Example 1
When sheets of 1.7 mm and 2.8 mm were prepared in the same manner as described above and the polyester film of the uppermost layer was to be peeled off, the photosensitive resin adhered to the defective portion and peeling was difficult. Observation of the surface of the anti-adhesion layer on the photosensitive resin revealed irregularities. Further, in the same manner as in Reference Example 2, exposure was performed using a negative film, and further developed, and a relief was prepared and printed. Only the white spot defect portion had poor ink acceptability and transferability. There was unevenness in ink density, and the printed matter had no commercial value.

Comparative Examples 2, 3, 4 In Example 2, instead of the IP deformer LY72B, a water-soluble silicone defoamer TYN-211S (manufactured by YAS Co., Ltd.) and a non-silicone defoamer IP defoamer M-6500 (Ipposha oil Industries Co., Ltd.), was added the surfactant B F-75 (manufactured by NOF Corp.), was coated with a reverse roll to prepare an aqueous solution, silicone anti-foaming agent and The coating property of the aqueous solution to which the non-silicone-based antifoaming agent was added was repelled immediately after coating and was interrupted. Aqueous solution containing a surfactant, although pinholes occurred immediately after coating, were dried at it 100 ° C., pinhole-like defect was occurred many. Next, a sheet was prepared from the anti-adhesion layer in the same manner as in Reference Example 1 and the polyester film was peeled off.
A similar problem occurred. Also, as in Reference Example 2,
When a relief was prepared and printed by exposure and development, the defect in the pinhole portion was directly reflected on the printed material, and the printed material had no commercial value.

Example 3 Gohsenol GH-17 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)
250 parts of polyvinyl alcohol having a saponification degree of 86.5 to 89 mol%) was completely dissolved in 4705 parts of pure water by heating and stirring at 80 ° C. This aqueous solution was mixed and dissolved with 45 parts of polyethylene glycol having a molecular weight of 1,000. Further IP
0.25 parts of Deformer LY72B were added with stirring. Using this aqueous solution, coating was performed by the method described in Example 1 to form an anti-adhesion layer having a thickness of 2 μm. The coatability was good, and when the coat surface dried at 100 ° C was observed,
Although there was a defect of 1 to 3 pieces / m ^2, the level was not a problem. Next, a sheet was prepared by the method described in Reference Example 1 and Reference Example 2, a relief was prepared, and printing was performed. The finished print showed a clear image.

Example 4 An anti-adhesion layer was prepared in the same manner as in Example 2, except that a polyethylene phthalate film was used as the cover film and a chemical matte film (TC-5000 manufactured by Toyo Cloth Co., Ltd.) was used as the cover film. It was created. The coatability was good and there was no defect on the coated surface dried at 100 ° C. The resulting anti-adhesion layer had a thickness of 1.7μ. Using this coated film, sheets of 1.7 mm and 2.8 mm were prepared in the same manner as in Reference Example 1. Observation of the surface of the anti-adhesion layer on the photosensitive resin showed a smooth and chain-like surface, and no defects were observed. Next, Reference Example 2
A relief was prepared and printed by the method described in (1). The obtained printed matter showed a clear image.

[0053]

The anti-adhesion layer composition of the present invention prevents defects on the surface of the photosensitive resin by eliminating coating defects on the cover film, and faithfully reproduces the image in the intended image formation. And has the effect of expressing a clear image with good ink receiving transferability. Another effect obtained by the anti-adhesion layer composition of the present invention is to facilitate release of the cover film of the photosensitive resin laminate. These things make the plate making operation easy and improve the reliability of the printed matter, which greatly contributes to the industry.

Continuation of the front page (56) References JP-A-60-95430 (JP, A) JP-A-2-103051 (JP, A) JP-A-60-263141 (JP, A) JP-A-60-186835 (JP) , A) JP-A-49-70702 (JP, A) JP-A-49-103702 (JP, A) JP-A-47-469 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB G03F 7/115 G03F 7/00 502 G03F 7/11 501

Claims (1)

(57) [Claims] 1. A water-soluble polymer and / or a water-dispersible polymer, an alkyl ester sulfone compound represented by the following general formula (1) and an alkyl phosphate derivative represented by the following general formula (2): An anti-adhesion layer composition for a photosensitive resin printing plate, comprising: Embedded image Embedded image (In the general formulas (1) and (2), R ^{1 to} R ⁴ are charcoal.
It is an alkyl group having a prime number of 6 to 12. )