JPH0980744A - Original plate of photosensitive planographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the ink deposition property of image parts and to obtain an excellent ink repulsive property by laminating a photosensitive layer and hydrophilic swelling layer in this order on a substrate, thereby forming an original plate. SOLUTION: The original plate is formed by laminating the photosensitive layer and hydrophilic swelling layer in this order on the substrate. The original plate may be provided with a protective layer on this hydrophilic swelling layer. The photosensitive layer is a photosetting photosensitive layer including a photosetting compd. The photosetting compd. means a compd. contg. a functional group which is changed in polymn., crosslinking, etc., by irradiation with active rays. The hydrophilic swelling layer has a phase sepn. structure composed of two phases; a phase consisting essentially of a hydrophilic polymer and a phase consisting essentially of a hydrophobic polymer. The hydrophilic polymer is a polymer which is substantially insoluble in water and exhibits a water swelling property. Namely, the hydrophilic polymer means a polymer which adsorbs or absorbs water under ordinary use conditions and means a polymer which dissolves in water or swells in water. The hydrophobic polymer mainly composed of an aq. emulsion is preferably used.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive lithographic printing plate precursor, which has a high ink repellency without desensitizing treatment, and a novel photosensitive material which can use pure water as a dampening solution. It relates to a lithographic printing plate.

[0002]

2. Description of the Related Art In planographic printing, the image area and the non-image area are basically on the same plane, and the image area is ink-receptive and the non-image area is ink repellent. After applying ink to only the image area using the difference in adhesion,
It means a method of printing by transferring ink to a printing medium such as paper. A PS plate is usually used for such lithographic printing.

[0003] The PS plate mentioned here means the following.

[0004] That is, Teruhiko Yonezawa Station "PS Version Overview"
As described in pp. 18-81 of the Printing Society of Japan (1993), a lipophilic photosensitive resin layer is applied on an aluminum substrate that has been subjected to hydrophilic treatment, and the image portion is formed by photolithography. The photosensitive layer remains, while the non-image area exposes the surface of the aluminum substrate described above, forms a dampening solution layer on the surface, repels ink, and forms a PS plate with water for forming an image and a dampening solution layer. Instead, a waterless PS plate using a silicone rubber layer as an ink repellent layer, a so-called waterless planographic plate.

The term "waterless lithographic printing plate" as used herein means that the non-image area is made of a substance such as silicone rubber or a fluorine-containing compound which has ink repellency against oil-based ink used in normal lithographic printing. Means a printing plate on which an image can be formed and printed with an ink-imprintable image portion without printing.

The former PS plate with water is a printing plate which is excellent in practical use, and aluminum is usually used for the support, and the surface of the aluminum has water retentivity and a lipophilic photosensitive resin layer is formed on the surface during printing. It was necessary to have excellent adhesiveness to the photosensitive layer so as not to peel off. Therefore, the aluminum surface is usually grained, and if necessary, a treatment such as anodizing is performed on the grained surface to improve water retention and reinforce adhesion to the photosensitive resin layer. I have been. Further, in order to obtain the storage stability of the photosensitive resin layer, the aluminum surface is generally subjected to chemical treatment with zirconium fluoride, sodium silicate or the like.

As described above, the PS plate with water has a complicated manufacturing process and its simplification has been desired. However, the PS plate has been widely used because of its excellent printing characteristics (printing durability, image reproducibility, etc.). I have.

In order to solve the above-mentioned problem, there is a proposal of a new planographic material having printing characteristics equal to or better than that of an aluminum substrate and having a low material cost and different from an aluminum substrate by a simple manufacturing process. For example, Japanese Patent Publication No. Sho 56-2938 proposes a method of forming a photosensitive layer on a support using an ink repellent layer made of a hydrophilic polymer material instead of an aluminum substrate. ing. However, in this method, since a urea resin is simply applied as a hydrophilic layer on a water-resistant layer of an aldehyde condensate of polyvinyl chloride, polyurethane, or polyvinyl alcohol, the layer has insufficient ink repellency. In addition, the adhesiveness to the photosensitive resin layer was poor, and the printing durability was insufficient. In JP-A-57-179852, a hydrophilic radical polymerizable compound is coated on a support, the surface of the support is hydrophilized by irradiation with actinic rays, and a photosensitive resin layer is coated. A method has been proposed. However, the hydrophilic surface layer formed by this method is also rigid, the ink repulsion property is insufficient, and the printing durability is also poor.

In the development of the PS plate with water, since the photosensitive layer is dissolved to expose the aluminum substrate surface, it is essential that the photosensitive layer components be dissolved in the developing solution. In this case, the composition fluctuates greatly in a short period of time, causing fatigue, and a large amount of developing waste liquid is generated.

Therefore, the developer has to be frequently maintained and replaced. In addition, a great deal of labor and cost are required for treating the generated developing waste liquid.

Further, as a simple form of the PS plate with water,
An image receiving layer such as toner is formed on a support such as paper
A direct-drawing lithographic printing plate precursor that forms an image using a PC, desensitizes non-image areas with an etchant or the like, and converts the image receiving layer into an ink repellent layer for use is widely used. . Specifically, an image receiving layer comprising a water-soluble binder polymer, an inorganic pigment, a water-proofing agent and the like is generally provided on a water-resistant support, and is disclosed in US Pat. No. 2,532,865, Japanese Patent Publication No. 40-23581, and JP-A-48-9802, JP-A-57-205196, JP-A-60-2
309, JP-A-57-1791, JP-A-5-1791
JP-A-7-15998, JP-A-57-96900, JP-A-57-205196, JP-A-63-1
66590, JP-A-63-166593,
JP-A-63-317388, JP-A-1-1144
No. 88, JP-A-4-366868, and the like. These direct-drawing lithographic printing plate precursors include PVA, starch, hydroxyethylcellulose, casein, gelatin, polyvinylpyrrolidone, vinyl acetate-crotonic acid copolymer, styrene-maleic acid copolymer as an image receiving layer to be converted into an ink repellent layer. Water-dispersible polymers such as water-soluble binder polymers and acrylic resin emulsions that exhibit hydrophilicity before the desensitization treatment such as coalescence, inorganic pigments such as silica and calcium carbonate, and melamine-formaldehyde resin condensates There are proposals made of such a waterproofing agent. Also, JP-A-63-2
Japanese Patent No. 56493 proposes a direct drawing type lithographic printing plate precursor using as a main component a hydrophobic polymer which is hydrolyzed by a desensitizing treatment to generate a hydrophilic group.

In order to convert the image receiving layer into an ink repellent layer, the direct drawing type lithographic printing plate requires desensitization treatment, and without such treatment, shows little ink repellency. It was.

That is, in order to obtain a practical level of ink repellency, it is necessary to desensitize the ink and to use a large amount of a hydrophilic binder polymer. However, the water resistance tends to be poor, and the printing durability deteriorates. . Further, when the hydrophilicity is increased, there is a problem that the adhesiveness to an image such as a toner tends to decrease. On the other hand, if the water resistance is increased by increasing the amount of a water-proofing agent or by adding a hydrophobic polymer in order to improve printing durability, the hydrophilicity is reduced, and the ink repellency is greatly reduced. There was a problem.

A so-called exposure-only, one-step version of the technology developed by Union Carbide, which does not require any development, lacquer embossing, or desensitization treatment utilizing a hydrophilic / hydrophobic conversion reaction is disclosed in No. 131, Japanese Patent Publication No. Sho 4
No. 2-5365, Japanese Patent Publication No. 42-14328,
JP-B-42-20127, US Pat. No. 3,321,377
JP, USP3231381, USP3231
No. 382, for example. The plate is obtained by coating an association of polyethylene oxide and a phenol resin together with a photosensitizer, but the non-image area is rigid and inferior in flexibility, and ink repulsion is insufficient, and the non-image area and the image area are Ink repulsion / ink inking difference between
It was poor in practicality.

Further, in the PS plate with water, it is necessary to constantly control the amount of dampening water during printing, and considerable skill and experience have been required to control an appropriate amount of dampening water. IPA added as an essential component to the fountain solution
In recent years, the use of (isopropanol) has been strictly regulated from the standpoint of the occupational health environment and wastewater treatment, and countermeasures are urgently needed.

On the other hand, in the latter case of a waterless PS plate having a silicone rubber layer as an ink repellent layer instead of dampening water, JP-B-54-26923, JP-B-57-3060 and JP-B-56-12862. Publication, Japanese Patent Publication No. 56-23
No. 150, JP-B-56-30856, JP-B-60-60051, JP-B-61-54220, JP-B-61-54222, and JP-B-61-54.
No. 223, Japanese Patent Publication No. 61-616, Japanese Patent Publication No. 63
No. 23544, No. 2-25498, No. 3-56622, No. 4-28098, No. 5-1934, and No. 3-63050.
As described in Japanese Patent Publication No. 2-63051 and Japanese Patent Laid-Open No. 2-63051, it is possible to print without using dampening water, so the former printing with PS plate does not require any dampening water control work. Since the work is extremely simple, it is a plate material with high practicality that is rapidly spreading in recent years, but due to the use of a silicone rubber layer with weak mechanical strength as the ink repellent layer, lack of durability is pointed out. There is a strong demand for ink repellent materials with excellent durability. Further, at the time of development, it is necessary to mechanically peel and remove the silicone rubber layer by brush rubbing, so that a large amount of development waste liquid containing the peeled and removed silicone rubber residue is generated. Therefore, the service life of the brush is short and it is necessary to frequently replace the brush, and maintenance measures such as collecting and discarding the silicone rubber residue have been required.

[0017]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention The inventors of the present invention have expanded the control range of the fountain solution in the conventional lithographic printing of PS plates with water, and made IPA-less from the fountain solution, which has hitherto been impossible. In addition, a waterless planographic printing plate in which a silicone rubber layer is used as an ink repellent layer is provided without a complicated plate making process such as image formation by a PPC method and desensitizing treatment like a direct drawing planographic printing original plate. As a result of diligent studies on the development of an ideal lithographic material that can solve the shortcoming of lack of durability, which does not require the development and maintenance that was necessary for conventional PS plates, and has a simple manufacturing process, hydrophilic swelling It has been found that this can be realized by making the layer an ink repellent layer.

[0018]

That is, the present invention has the following configuration.

(1) A photosensitive lithographic printing plate precursor comprising at least a photosensitive layer and a hydrophilic swelling layer laminated in this order on a substrate.

(2) The hydrophilic swelling layer has a phase-separated structure composed of at least two phases of at least a hydrophilic polymer-based phase and a hydrophobic polymer-based phase. (1) The photosensitive lithographic printing plate precursor as described above.

(3) The photosensitive lithographic printing plate precursor as described in (1) above, wherein the photosensitive layer is photocurable.

(4) The photosensitive lithographic printing plate precursor as described in (1) above, which has a protective layer on the hydrophilic swelling layer.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION The hydrophilic swelling layer used in the photosensitive lithographic printing plate precursor according to the invention will be described.

The hydrophilic swelling layer used in the photosensitive lithographic printing plate precursor according to the present invention is a phase separation composed of at least two phases including a phase containing a hydrophilic polymer as a main component and a phase containing a hydrophobic polymer as a main component. It is preferable to have a structure.

The hydrophilic polymer is a known water-soluble polymer (meaning one completely soluble in water) or a pseudo-water-soluble polymer (amphiphilic polymer) which is substantially insoluble in water and shows water swelling property. The macro means that it is soluble in water, but the micro means that it contains an insoluble portion, and the water-swellable polymer (means that it swells in water but does not dissolve).
That is, it means a polymer that adsorbs or absorbs water under normal use conditions, and a polymer that dissolves in water or swells in water.

The hydrophilic polymer used in the present invention will be described.

Examples of hydrophilic polymers that effectively exhibit the effects of the present invention include carboxylate-based copolymers. The carboxylate-based copolymer preferably used in the present invention, from the viewpoint of water absorption and durability, a carboxyl group such as a carboxyl group, a carboxylate, a carboxylic acid amide, a carboxylic acid imide, or a carboxylic acid anhydride, or a carboxyl group. A saponification reaction product of a carboxylic acid-based copolymer containing, as a monomer component, an α, β-unsaturated compound having one or two groups capable of being induced in a group is mentioned.

Specific examples of the α, β-unsaturated compound include:
Acrylic acid, methacrylic acid, acrylamide, methacrylamide, maleic anhydride, maleic acid, maleic amide, maleic imide, itaconic acid, crotonic acid, fumaric acid, mesaconic acid, and the like, which are necessary for the present invention. It is possible to combine with another monomer component copolymerizable within a range showing hydrophilicity.

Examples of other monomer components which can be copolymerized include ethylene, propylene, isobutylene, 1-butylene, diisobutylene, methyl vinyl ether, styrene, vinyl acetate, acrylic acid ester, methacrylic acid ester and acrylonitrile. Examples thereof include olefins, vinyl compounds and vinylidene compounds.

When combined with another monomer, the α, β-unsaturated compound containing a carboxyl group or a group convertible to this is usually 10 mol% or more in all monomer components,
More preferably, it is at least 40 mol%.

The polymer containing, as a monomer, an α, β-unsaturated compound containing a carboxyl group or a group capable of being converted into a carboxyl group is usually prepared by radical polymerization. The degree of polymerization is not particularly limited.

Among the polymers thus prepared, a polymer or copolymer of acrylic acid or methacrylic acid, a copolymer of α-olefin or vinyl compound and maleic anhydride is preferable.

These polymers or copolymers are prepared by using compounds such as hydroxides, oxides or carbonates of alkali metals or alkaline earth metals such as sodium, potassium, magnesium and barium, ammonia, amines and the like. Hydrophilicity is preferably imparted by carrying out a saponification reaction. In these reactions, the polymer or the copolymer is dissolved or dispersed in various organic solvents or water, and the above-mentioned alkali metal compound, alkaline earth metal compound, ammonia, amine, etc. are added thereto with stirring. It is carried out by

Among such carboxylic acid salt type copolymers, the vinyl ester / (meth) acrylic acid ester copolymer has a hydrophilic swelling layer exhibiting an appropriate water swelling property, and has printing durability and ink repulsion. It is preferable in satisfying both of the sex.

A vinyl ester / (meth) acrylic acid ester copolymer preferably used in the present invention ((meth) □□□□ is referred to as □□□□ or meta □ in the following description.
□□□ is abbreviated. ) Can be produced using a known method. For example, Polymer Chemistry, Volume 7, 142
Page (1950). That is, it is appropriately selected depending on the polymerization method, for example, polymerization initiation of peroxides such as di-t-butyl peroxide and benzoyl peroxide, persulfates such as ammonium persulfate, and azo compounds such as azobisisobutyronitrile. It is synthesized by radical polymerization using an agent. As the polymerization method, solution polymerization,
Emulsion polymerization, suspension polymerization, etc. are required. When the amount of the (meth) acrylic acid ester component in the copolymer is small, the water absorption is small. When the amount is too large, the water absorption state is high and the film strength tends to be extremely lowered.

Therefore, the proportion of the (meth) acrylic acid ester component in the copolymer as the starting material is generally preferably in the range of 20 to 80 mol%, which makes both water absorption and mechanical strength when water is contained. 30 for
It is preferably 70 mol%.

Examples of the vinyl ester used in the present invention include vinyl acetate, vinyl propionate and vinyl stearate. As the (meth) acrylic acid ester, an alkyl ester of (meth) acrylic acid,
Specific examples include methyl ester, ethyl ester, n-propyl ester, isopropyl ester, n-butyl ester and t-butyl ester.

The above-described copolymer preferably undergoes a saponification reaction in the presence of an alkali catalyst. As the solvent used for the saponification reaction, alcohol and an aqueous alcohol solution are preferable. As the catalyst used for the saponification reaction, a known alkali catalyst is used, and an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is particularly preferable. The saponification reaction is completed at 20 to 80 ° C for 1 to 10 hours. The salt of the saponification reaction product of the present invention can be arbitrarily changed by a known method. Commonly used salt-forming substances include sodium hydroxide, potassium hydroxide, ammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, and monoethanolamine. , Diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, N, N-dimethylethanolamine, N, N-
Examples include dimethylisopropanolamine, cyclohexylamine, benzylamine, aniline, pyridine and the like.

It is also possible to add polyvalent metal salts of alkaline earth metal salts such as magnesium and calcium in the form of a mixed salt with the above-mentioned salts.

As a hydrophilic polymer that effectively exhibits the effects of the present invention, an N-vinylcarboxylic acid amide copolymer can be mentioned.

The N-vinylcarboxylic acid amide copolymer is a copolymer (hereinafter, referred to as N-vinylcarboxylic acid amide (hereinafter abbreviated as NVA) represented by the following general formula (1) as an essential repeating unit. , And NVA-based copolymer).

[0042]

Embedded image (Where R1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R2 is a hydrogen atom, a methyl group, a phenyl group, R3
Represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms. ) Specific examples of NVA include N-vinylformamide, N
-Vinylpropionic acid amide, N-vinylbenzoic acid amide, N-methyl-N-vinylbenzoic acid amide, N-phenyl-N-vinylacetamide, N-phenyl-N-vinylbenzoic acid amide, etc. The invention is not limited to these examples.

The NVA copolymer preferably used in the present invention is a carboxyl group or carboxyl group such as a carboxyl group, a carboxylate, a carboxylic acid amide, a carboxylic acid imide or a carboxylic acid anhydride, from the viewpoint of water absorption and durability. It is preferable to contain, as a copolymerized unit, an α, β-unsaturated compound having one or two groups capable of being induced to a group in the molecule.

Specific examples of the α, β-unsaturated compound include:
Acrylic acid, methacrylic acid, acrylamide, methacrylamide, maleic anhydride, maleic acid, maleic amide, maleic imide, itaconic acid, crotonic acid, fumaric acid, mesaconic acid, and the like, which are necessary for the present invention. It is possible to combine with another monomer component copolymerizable within a range showing hydrophilicity.

Examples of other copolymerizable monomer components include ethylene, propylene, isobutylene, 1-butylene, diisobutylene, methyl vinyl ether, styrene, vinyl acetate, acrylic acid ester, methacrylic acid ester, and acrylonitrile. Examples thereof include olefins, vinyl compounds and vinylidene compounds.

When combined with other monomers, the NVA unit is usually 10 mol% or more and 40 mol% or more in all the monomer components.
More preferably, it is the above.

Polymers containing NVA are usually prepared by radical polymerization. The degree of polymerization is not particularly limited.

The following polymers can be mentioned as specific examples of the NVA type copolymer.

Poly (N-vinylacetamide), N-vinylacetamide / (meth) acrylic acid copolymer and its partially or completely neutralized product ("partial or fully neutralized product")
The carboxylic acid, sulfonic acid, phosphoric acid in the copolymer is part or all of the hydrogen ions in the polymerizable functional group such as sodium, potassium and other alkali metal salts, calcium, barium and other metal earth chlorination N-vinylacetamide / crotonic acid copolymer and its partially or completely neutralized product, N-vinylacetamide / maleic acid copolymer and its partially or completely neutralized product, N-vinyl Acetamide / fumaric acid copolymer and its partially or completely neutralized product, N-vinylacetamide / citraconic acid copolymer and its partially or completely neutralized product, N-vinylacetamide / cinnamic acid copolymer and its partial or Completely neutralized product, N-vinylacetamide / vinylsulfonic acid copolymer and partially or completely neutralized product thereof, N-vinyl Acetamide / maleic anhydride copolymer and its partially or completely neutralized product, N-vinylacetamide / itaconic acid copolymer and its partially or completely neutralized product, N-vinylacetamide / aconitic acid copolymer and its partially or Completely neutralized product, N-vinylacetamide / 3-butenoic acid copolymer and its partially or completely neutralized product, N-vinylacetamide / 4-pentenoic acid copolymer and its partially or completely neutralized product, N-vinyl Acetamide / allylsulfonic acid copolymer and its partially or completely neutralized product, N-vinylacetamide /
Methallyl sulfonic acid copolymer and its partially or completely neutralized product, N-vinyl acetamide / allyl phosphoric acid copolymer and its partially or completely neutralized product, N-vinyl acetamide / carboxyethyl acrylate copolymer and its partial or Completely neutralized product, N-vinylacetamide / 2-acryloylethylphosphoric acid copolymer and its part or complete neutralized product, N-vinylacetamide / 3-acryloylpropylphosphoric acid copolymer and its part or complete medium Solvate, N-vinylacetamide / 8-methacryloyloctylphosphoric acid copolymer and partially or completely neutralized product thereof, N-vinylacetamide / 2-acrylamide-
n-Propanesulfonic acid copolymer and its partially or completely neutralized product, N-vinylacetamide / 2-acrylamido-n-octane sulfonic acid copolymer and its partially or completely neutralized product, N-vinylacetamide / 2-
Examples thereof include acrylamido-2-methylpropanesulfonic acid copolymer and a partially or completely neutralized product thereof.

Among the polymers prepared as described above, among the copolymers of NVA and carboxylic acid salts such as acrylic acid, methacrylic acid, maleic anhydride, the hydrophilic swelling layer exhibits an appropriate water swelling property. In addition, it is preferable from the viewpoint of satisfying both printing durability and ink repellency.

A known hydrophilic polymer can be added to the hydrophilic swelling layer of the present invention within a range that does not impair the effects of the invention. The following examples can be given as known hydrophilic polymers.

(A) Natural polymers Starch-acrylonitrile-based graft polymer hydrolyzate, starch-acrylic acid-based graft polymer, starch-styrene sulfonic acid-based graft polymer, starch-
Vinyl sulfonic acid type graft polymer, starch-acrylamide type graft polymer, carboxylated methyl cellulose, methyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, cellulose xanthate, cellulose-acrylonitrile type graft polymer, cellulose-styrene sulfonic acid type graft Polymer, carboxymethyl cellulose cross-linked product,
Hyaluronic acid, agarose, collagen, milk casein, acid casein, rennet casein, ammonia casein, potash casein, borax casein, glue, gelatin, gluten, soy protein, alginate, ammonium alginate, potassium alginate, sodium alginate arabia gum , Tragacanth gum, karaya gum, guar gum, locust bean gum, Irish moss,
Soy lecithin, pectic acid, starch, carboxylated starch, agar, dextrin, mannan, etc. (B) Synthetic polymers.

Polyvinyl alcohol, polyethylene oxide, poly (ethylene oxide-co-propylene oxide), aqueous urethane resin, water-soluble polyester, hydroxyethyl (meth) acrylate polymer,
Poly (vinyl methyl ether-co-maleic anhydride), maleic anhydride-based copolymer, vinylpyrrolidone-based copolymer, polyethylene glycol di (meth) acrylate-based cross-linked polymer, polypropylene glycol di (meth) acrylate-based cross-linked polymer Coalescence etc.

The above-mentioned hydrophilic polymers may be one or two monomers or copolymer components having different substituents for the purpose of imparting flexibility or controlling hydrophilicity, as long as the effects of the invention are not impaired. It is possible to appropriately mix and use one or more species.

Next, the hydrophobic polymer used in the hydrophilic swelling layer of the present invention will be described.

As the hydrophobic polymer used in the present invention, those mainly composed of an aqueous emulsion are preferably used.

The aqueous emulsion referred to in the present invention means a hydrophobic polymer suspension aqueous solution in which particles comprising fine polymer particles and, if necessary, a protective layer surrounding the particles are dispersed in water.

That is, it means a self-emulsified or forced emulsified aqueous solution basically composed of emulsion particles composed of polymer particles as a dispersoid and a protective layer formed as necessary, and a dilute aqueous solution as a dispersion medium. Specific examples of the aqueous emulsion used in the present invention include vinyl polymer latex, conjugated diene polymer latex and aqueous or water dispersed polyurethane resin.

Examples of the vinyl polymer type latex include acrylic type, vinyl acetate type, vinylidene chloride type and the like. Examples of the conjugated diene polymer-based latex include styrene / butadiene-based (hereinafter abbreviated as SB-based), acrylonitrile / butadiene-based (hereinafter abbreviated as NB-based), methyl methacrylate / butadiene-based (hereinafter abbreviated as MB-based),
Chloroprenes and the like can be mentioned.

Examples of the acrylic latex include copolymers containing acrylate and methacrylate as essential components. Specific examples include those obtained by copolymerizing at least one or more of methyl methacrylate, ethyl acrylate, butyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, and styrene.

Examples of the vinyl acetate-based latex include vinyl acetate alone or copolymers with acrylic esters, higher vinyl acetate esters, ethylene and the like.

Examples of the vinylidene chloride-based latex include copolymers of vinylidene chloride with methyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, acrylonitrile, vinyl chloride, and the like.

The SB type latex contains styrene and butadiene as essential components, methyl methacrylate,
Examples include higher acrylic acid esters, acrylonitrile, acrylamide, hydroxyethyl acrylate, and copolymers with unsaturated carboxylic acids (such as itaconic acid, maleic acid, acrylic acid, and methacrylic acid).

As the water-based or water-dispersed polyurethane resin, a hydrophobic polyurethane resin composed of polyester polyol, polyether polyol, poly (ester / ether) polyol and polyisocyanate is compulsorily emulsified by using a surfactant. Emulsion type, a hydrophilic group or a hydrophilic segment is added to the resin itself, and self-emulsifying type obtained by self-dispersing and emulsifying. In both cases, a non-reactive one and a blocking group such as an isocyanate group are reactive groups. The reactive ones that are blocked are mentioned.

Among these aqueous emulsions, SB is particularly preferable as the hydrophobic polymer used in the present invention.
Latex containing conjugated diene-based compounds such as styrene, NB-based, MB-based, and chloroprene-based compounds.

As the conjugated diene rubber mentioned here,
1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene (chloroprene)
Means a compound having an unsubstituted or substituted 1,3-butadiene skeleton having a carbon-carbon double bond at the 1,3-position, such as a homo- or block copolymer rubber (polymer) having these as essential components. .

Block copolymer rubbers include 1,3-dienes such as 1,3-butadiene and 2-methyl-1,3-butadiene (isoprene), and styrene and α-methyl which give glassy polymers at room temperature. Examples thereof include block copolymers with monovinyl-substituted aromatic compounds such as styrene and vinyltoluene.

As such a copolymer rubber, various known types can be exemplified, but an ABA type block copolymer rubber (where A is a monovinyl-substituted aromatic compound, preferably a glass transition) is used. An amorphous polymer segment having a point of 70 ° C. or higher and a degree of polymerization of 10 to 2500, B means 1,3-diene, and preferably a number average molecular weight of 500 to 25,000. (Meaning) and the like. The same applies to the hydrogenated product of the block copolymer rubber.

Specific examples of the homo- and copolymer rubbers used in the present invention include polybutadiene, polyisoprene (including natural rubber), polychloroprene, styrene-butadiene copolymer, carboxy-modified styrene-butadiene copolymer, and acrylic. Acid ester-butadiene copolymer (for example, butadiene-2-ethylhexyl acrylate copolymer, butadiene-n-octadecyl acrylate copolymer), methacrylic acid ester-butadiene copolymer, isobutylene-isoprene copolymer, acrylonitrile-butadiene copolymer Polymer, carboxy-modified acrylonitrile-butadiene copolymer, acrylonitrile-isoprene copolymer, vinylpyridine-butadiene copolymer, vinylpyridine-styrene-butadiene copolymer,
Examples thereof include a styrene-chloroprene copolymer and a styrene-isoprene copolymer.

The conjugated diene polymer latex preferably used in the present invention is prepared by a known method, for example, 0.1 to 20% by weight of an emulsion polymerization dispersant based on a vinyl monomer composition containing a conjugated diene compound as an essential component. Additives (molecular weight modifiers, antioxidants) used for ordinary emulsion polymerization by degassing and nitrogen-substituting in an aqueous medium containing (surfactant etc.) and 2 to 50% by weight of water and emulsifying. Etc.) and then an initiator for emulsion polymerization (for example, hydrogen peroxide, potassium persulfate, etc.) is added, and emulsion polymerization is carried out according to a conventional method.

The vinyl monomer used in the raw material vinyl monomer composition other than the conjugated diene compound is not particularly limited, but mainly the following 1 group: hydrophobic monomer, 2
It can be classified into three groups: group: hydrophilic monomer and group 3: crosslinkable monomer.

Group 1: As a hydrophobic monomer, a hydrophobic vinyl monomer having one vinyl group (hydrophobicity as used herein means that the solubility in water at 20 ° C. is 8% by weight or less), and acrylic Examples thereof include acid esters, methacrylic acid esters, vinyl esters, styrenes and olefins.

Specific examples of acrylic acid esters include:
Methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, 2-phenoxyethyl acrylate, 2
-Chloroethyl acrylate, benzyl acrylate,
Examples include cyclohexyl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, 2-methoxyethyl acrylate, and 2-ethoxyethyl acrylate.

Specific examples of the methacrylic acid esters include methyl methacrylate, ethyl methacrylate, n
-Propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, acetoacetoxyethyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, furfuryl methacrylate, tetrahydrofur Furyl methacrylate, phenyl methacrylate, trimethylolpropane monomethacrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate and the like can be mentioned.

Specific examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl acetoacetate, vinyl benzoate, vinyl salicylate and chlorobenzoic acid. Examples thereof include vinylate.

Specific examples of styrenes include styrene,
Examples thereof include α-methylstyrene, chloromethylstyrene, trifluoromethylstyrene, acetoxymethylstyrene, methoxystyrene, chlorostyrene, dichlorostyrene, trichlorostyrene and bromostyrene.

Specific examples of olefins include propylene, vinyl chloride, vinyl bromide, vinylidene chloride, vinylidene bromide and vinylidene fluoride.

Other examples include acrylonitrile and maleic anhydride.

Group 2: As the hydrophilic monomer, a hydrophilic vinyl monomer having one vinyl group (the term "hydrophilic" as used herein means a monomer having a large solubility in water and incapable of aqueous emulsion polymerization by itself). Monomers having functional groups such as amino groups, carboxyl groups, sulfonic acid groups, amide groups, and hydroxyl groups.

Specific examples of the monomer having an amino group include dimethylaminomethyl acrylate, dimethylaminomethyl methacrylate, diethylaminomethyl acrylate, diethylaminomethyl methacrylate and ter.
Examples thereof include t-butylaminoethyl acrylate and tert-butylaminoethyl methacrylate.

Specific examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itacone, maleic acid, crotonic acid, fumaric acid, methylenemalonic acid, monoalkyl itaconate (for example, monomethyl itaconate,
Monoethyl itaconate, monobutyl itaconate, etc.),
Examples thereof include monoalkyl maleate (eg, monomethyl maleate, monoethyl maleate, monobutyl maleate), citraconic acid, sodium acrylate, ammonium acrylate, ammonium methacrylate and the like.

Specific examples of the monomer having a sulfo group include styrene sulfonic acid, vinylbenzyl sulfonic acid, vinyl sulfonic acid, vinyl sulfonic acid, acryloyloxyalkyl sulfonic acid (eg acryloyloxymethyl sulfonic acid, acryloyloxypropyl sulfonic acid, Acryloyloxybutyl sulfonic acid, etc.), methacryloyloxyalkyl sulfonic acid (eg, methacryloyloxymethyl sulfonic acid, methacryloyloxymethyl sulfonic acid, methacryloyloxypropyl sulfonic acid, methacryloyloxybutyl sulfonic acid, etc.), acrylamidoalkyl sulfonic acid (eg, 2-acrylamido) 2-Methylethanesulfonic acid, 2-acrylamido-2-methylpropane sulfone Phosphate, 2-acrylamido-2
Methyl butane sulfonic acid, etc.), methacrylamide amido alkyl sulfonic acid (eg 2-methacrylamide-2)
-Methylethanesulfonic acid, 2-methacrylamide-
2-methylpropanesulfonic acid, 2-methacrylamido-2-methylbutanesulfonic acid, etc.).

Specific examples of the monomer having an amide group include acrylamide, methyl acrylamide and propyl acrylamide.

Specific examples of the monomer having a hydroxyl group include:
Examples include allyl alcohol, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, and aryl ethers of polyhydric alcohols.

Other examples include N-acryloylpiperidine, vinyl pyridine, vinyl pyropide and the like.

Group 3: As crosslinkable monomers, monomers having a reactive crosslinkable group (glycidyl group, hydroxymethylamide group, alkoxymethylamide group, acyloxymethylamide group, isocyanate group, etc.) and two or more vinyls. Mention may be made of polyfunctional monomers having groups.

Specific examples of the monomer having a glycidyl group include glycidyl acrylate, glycidyl methacrylate, glycidyl p-vinylbenzoate, glycidyl crotonate, diglycidyl itaconate, diglycidyl maleate, diglycidyl methylene malonate, glycidyl vinyl ether, Examples thereof include allyl glycidyl ether and glycidyl-α-chloroacrylate.

Specific examples of the monomer having a hydroxymethylamide group include hydroxymethyl acrylamide,
And hydroxymethyl methacrylamide.

Specific examples of the monomer having an alkoxymethylamide group include methoxymethylacrylamide, methoxymethylmethacrylamide, ethoxymethylacrylamide, ethoxymethylmethacrylamide, butoxymethylacrylamide, butoxymethylmethacrylamide, and hexyloxymethylmethacrylamide. Can be mentioned.

Specific examples of the monomer having an acyloxymethylamide group include acetoxymethylacrylamide,
Examples include acetoxymethyl methacrylamide and propionyloxymethyl acrylamide.

Specific examples of the monomer having an isocyanate group include vinyl isocyanate and allyl isocyanate.

Specific examples of the polyfunctional monomer include divinylbenzene, polyethylene glycol diacrylate (ethylene number n = 1 to 23), polyethylene glycol dimethacrylate (ethylene number n = 1 to 23), trimethylolpropane triacrylate, triethylene. Methylolpropane trimethacrylate, pentaerythritol triacrylate and the like can be mentioned.

As a suitable combination of monomers for preparing the latex preferably used in the present invention, in addition to the conjugated diene compound which is an essential component, (1) at least one or more 1-group monomer copolymer ( 2) Copolymer with at least one or more one-group monomer and at least one or more two-group monomer (3) At least one or more one-group monomer and at least one or more two-group monomer and at least one or more Three
Copolymers with Group Monomers (4) Combinations of at least one or more copolymers of 1-group monomers and 3-group monomers are mentioned, but the present invention is not limited to these combinations.

Specific examples of the conjugated diene polymer latex preferably used in the present invention include JSR0561.
(SB copolymer latex: manufactured by Nippon Synthetic Rubber Co., Ltd.), J
SR0589 (SB copolymer latex: manufactured by Nippon Synthetic Rubber Co., Ltd.), JSR0602 (SB copolymer latex:
JSR0700 (butadiene polymer latex: manufactured by Japan Synthetic Rubber Co., Ltd.), JSR21
08 (SB copolymer latex: Nippon Synthetic Rubber Co., Ltd.)
JSR0650 (vinyl pyridine-SB copolymer latex: manufactured by Nippon Synthetic Rubber Co., Ltd.), JSR0652
(Vinyl pyridine-SB copolymer latex: manufactured by Nippon Synthetic Rubber Co., Ltd.), JSR0545 (carboxy-modified SB copolymer latex: manufactured by Nippon Synthetic Rubber Co., Ltd.), JSR05
48 (carboxy-modified SB copolymer latex: manufactured by Nippon Synthetic Rubber Co., Ltd.), JSR0596 (carboxy-modified SB
Copolymer latex: manufactured by Nippon Synthetic Rubber Co., Ltd.), JSR0
597 (carboxy-modified SB copolymer latex: manufactured by Nippon Synthetic Rubber Co., Ltd.), JSR0598 (carboxy-modified S
B copolymer latex: manufactured by Nippon Synthetic Rubber Co., Ltd.), JSR
0619 (carboxy modified SB copolymer latex: manufactured by Japan Synthetic Rubber Co., Ltd.), JSR0624 (carboxy modified SB copolymer latex: manufactured by Japan Synthetic Rubber Co., Ltd.), JSR
SR0640 (carboxy modified SB copolymer latex:
Manufactured by Japan Synthetic Rubber Co., Ltd., JSR0693 (carboxy modified SB copolymer latex: manufactured by Japan Synthetic Rubber Co., Ltd.),
JSR0696 (carboxy modified SB copolymer latex: manufactured by Japan Synthetic Rubber Co., Ltd.), JSR0854 (carboxy modified SB copolymer latex: manufactured by Japan Synthetic Rubber Co., Ltd.)
Made), JSR0863 (carboxy modified SB copolymer latex: made by Nippon Synthetic Rubber Co., Ltd.), JSR0898
(Carboxy-modified SB copolymer latex: manufactured by Nippon Synthetic Rubber Co., Ltd.), LACSTAR 4940B (carboxy-modified NB copolymer latex: Dainippon Ink and Chemicals, Inc.)
Made), Rack Star 68-073S (carboxy modified N
B copolymer latex: Dainippon Ink and Chemicals, Inc.
Made), Rack Star DN-704 (carboxy modified NB
Copolymerized latex: Dainippon Ink and Chemicals, Inc.
Co., Ltd.), Luck Star DN-702 (carboxy-modified NB
Copolymer latex: manufactured by Dainippon Ink and Chemicals, Inc.)
Luck Star 68-074 (carboxy-modified NB copolymer latex: manufactured by Dainippon Ink and Chemicals, Inc.), Luck Star DN-703 (carboxy-modified NB copolymer latex: manufactured by Dainippon Ink and Chemicals, Inc.), Luck Star DM-801 (carboxy-modified MB copolymer latex:
Dainippon Ink and Chemicals, Ltd.), Luck Star DM-
401 (carboxy-modified MB copolymer latex: manufactured by Dainippon Ink and Chemicals, Inc.), Luck Star 4950C
(Carboxy-modified MB copolymer latex: manufactured by Dainippon Ink and Chemicals, Inc.) and Luckstar DM-806 (carboxy-modified MB copolymer latex: manufactured by Dainippon Ink and Chemicals, Inc.).

These conjugated diene polymer latexes can be used alone or in admixture of two or more.

The hydrophilic swelling layer of the present invention is preferably laminated on the substrate by mixing the above-mentioned hydrophilic polymer and hydrophobic polymer, cross-linking or pseudo-cross-linking them if necessary, and insolubilizing them in water. .

For cross-linking, it is preferable to carry out the cross-linking reaction using the reactive functional groups of the hydrophilic polymer and the hydrophobic polymer.

The cross-linking reaction may be a covalent bond or an ionic bond.

Examples of the compound used in the crosslinking reaction include known polyfunctional compounds having crosslinking properties, such as polyepoxy compounds, polyisocyanate compounds, poly (meth) acrylic compounds, polymercapto compounds, polyalkoxysilyl compounds, Polyvalent metal salt compounds, polyamine compounds, aldehyde compounds, polyvinyl compounds, hydrazine and the like can be mentioned. The crosslinking reaction is carried out by adding a known catalyst,
The reaction is promoted.

When an aqueous emulsion preferably used as the hydrophobic polymer of the present invention is prepared, a reactive functional group such as a carboxyl group, a hydroxyl group, a methylolamide group, an epoxy group, an arbonyl group or an amino group is used as a copolymerization component. And a method of forming a crosslinked structure by using the above polyfunctional compound as a crosslinking agent.

Specific examples of known polyfunctional compounds having crosslinkability include the following compounds.

(1) Sublimation sulfur, by-product sulfur produced by oxidizing hydrogen sulfide, colloidal sulfur produced by wet-oxidizing hydrogen sulfide, and the like. In addition, thiuram compounds such as dithiomorpholine, thioplast tetramethyl thiuram disulfide, tetramethyl thiuram monosulfide, dipentamethylene thiuram tetrasulfide, which decompose to generate sulfur when heated, piperidine pentamethylene thiocarbamate, pipecoline pipecolic Dithiocarbamate compounds such as ludithiocarbamate and sodium dimethyldithiocarbamate, xanthate compounds such as sodium isopropylxanthogenate and zinc butylxanthate, thiourea compounds such as thiourea and thiocarbanilide, zinc salts of thiazole such as diphenylguanidine, and mercaptobenzothiazole Sodium salt, dibenzothiazyl disulfide, cyclohexylamine salt of mercaptobenzothiazole Such as thiazole-based compound.

(2) Butyraldehyde-monobutylamine condensate, butyraldehyde-aniline condensate, heptaaldehyde-aniline reaction product, salt ethyl-formaldehyde-ammonia reaction product, and other aldehyde amine compounds, zinc oxide, tellurium, selenium, Zirconium carbonate ammonia, organic peroxides such as benzoyl peroxide and dicumyl peroxide.

Further, examples of the crosslinking accelerator include zinc carbonate, stearic acid, oleic acid, lauric acid, zinc stearate, dibutylammonium oleate, diethanolamine, triethanolamine, diethylene glycol and the like.

(3) Polyepoxy compounds, urea resins, polyamines, melamine resins, benzoguanamine resins, acid anhydrides, etc.

Specific examples of the polyepoxy compound include glycerin dipolylysidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, trimethylolpropane polyglycidyl ether, sorbitol polyglycidyl ether and the like. Is mentioned.

Specific examples of the polyamine include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine,
And polyamidoamine.

(4) Polyisocyanate compounds and the like.

Examples of polyisocyanate compounds include:
Tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane isocyanate, liquid diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate, xylylene diisocyanate, cyclohexyl diisocyanate, cyclohexane phenylene diisocyanate, naphthalene-1,5-diisocyanate, isopropylbenzene-2,4-diisocyanate, polypropylene Glycol / tolylene diisocyanate addition reactants.

These cross-linking agents can be used alone or in admixture of two or more. Water is mainly used as the dispersion medium, but a known organic solvent can be added as necessary. As a method of adding the organic solvent, a method of adding as a polymerization solvent and a method of adding as a mixed solvent to an emulsion solution after emulsion polymerization are possible.

As a method for mixing the hydrophilic polymer and the hydrophobic polymer of the hydrophilic swelling layer of the present invention, a kneading method using a roll mixer such as a three-roll mill or a mixer such as a kneader, a homogenizer, a ball mill, etc. The mixture is preferably mixed by a known method used for producing a paint or putty, such as a method of wet mixing and dispersion using the above disperser.

As a method for forming the hydrophilic swelling layer of the present invention, since an aqueous emulsion is preferably used as the hydrophobic polymer, each component (hydrophilic polymer, hydrophobic polymer, etc.) is mixed in an aqueous solution system, A method in which a crosslinking agent is added as necessary is preferable from the viewpoint of realizing a uniform phase-separated structure and improving ink repulsion.

Therefore, it is particularly preferable to use a water-soluble polyfunctional compound as the crosslinking agent used. That is, it is preferable to use a water-soluble polyepoxy compound, polyamine compound, melamine compound, or the like.

Next, the phase separation structure of the hydrophilic swelling phase according to the present invention will be described.

By adopting a phase-separated structure composed of a phase containing a hydrophilic polymer as a main component and a phase containing a hydrophobic polymer as a main component, both ink resilience and printing durability are realized in a wide composition range. It becomes possible.

The composition ratio of the hydrophilic polymer phase and the hydrophobic polymer phase constituting the phase-separated structure is free, and (1) either one is a continuous phase and the other is a dispersed phase, (2) hydrophilic A form in which the hydrophilic and hydrophobic polymer phases have a continuous phase and a dispersed phase, respectively (3) A form in which the hydrophilic and hydrophobic polymer phases are both continuous phases can be freely selected.

Examples of the phase separation structures (1) to (3) are shown in FIGS.

That is, when a material in which the hydrophilic polymer exhibits relatively strong hydrophilicity is selected (such as a water-soluble polymer and a pseudo-water-soluble polymer), the ratio of the hydrophilic polymer contained in the hydrophilic swelling layer depends on the ink repulsion property. In addition, a relatively small amount is sufficient from the viewpoint of printing durability, and the proportion of the hydrophobic polymer is relatively large, so that the form of (1) or (2) above in which the hydrophilic polymer is used as the dispersed phase is obtained. Is preferred. On the other hand, when a material whose hydrophilic polymer shows relatively weak hydrophilicity (such as a water-swellable polymer) is selected, the ratio of the hydrophilic polymer contained in the hydrophilic swelling layer is determined in terms of ink repellency and printing durability. From a relatively large amount, and the proportion of the hydrophobic polymer is relatively small.
It is preferable to take the form of (2) or (3).

That is, the preferred phase-separated structure of the hydrophilic swelling layer used in the present invention varies depending on the rubber elasticity and water swelling property of the layer, but it depends on the degree of hydrophilicity of the hydrophilic polymer.

In the case of the form (1), since the hydrophobic polymer phase is mainly a continuous phase, the composition of the hydrophobic polymer is 50% by weight or more, preferably 60 to 95% by weight, It is more preferably 70 to 90% by weight. When the composition ratio of the hydrophobic polymer is 50% by weight or less, the performance of the hydrophilic swelling layer as an ink repellent layer is improved in the initial stage of printing, but the printing durability tends to sharply decrease. On the other hand, when the composition ratio of the hydrophobic polymer exceeds 95% by weight, the hydrophilic polymer in the hydrophilic swelling layer cannot sufficiently absorb water, and the hydrophilicity is insufficient, and the ink repulsion tends to be extremely reduced.

In the cases of the forms (2) and (3), both the hydrophilic polymer and the hydrophobic polymer are 20% by weight or more, preferably 40% by weight or more.

The thickness of the hydrophilic swelling layer used in the present invention is
It is possible in principle to use 0.1 to 100 g / m2, but from the viewpoint of image reproducibility, it is 0.1 to 10 g / m2.
2 is highly preferred. The thickness is 0.1 g / m
If it is less than 2, the ink repellent property tends to be extremely reduced, and defects such as pinholes are likely to occur during coating. If it is 10 g / m @ 2 or more, the shape retention upon swelling with water tends to deteriorate, and the image reproducibility tends to extremely decrease.

Next, the photosensitive layer used in the present invention will be described.

Examples of the photosensitive layer include a photocurable photosensitive layer containing a photocurable compound.

As the photocurable compound used in the photosensitive layer, known compounds having a photocurable photosensitive group are widely used. That is, by irradiation with actinic rays, polymerization,
It means a compound containing a functional group that causes changes such as crosslinking.

Specifically, it means a photopolymerizable ethylenically unsaturated group, a photocrosslinkable group, a diazo group and the like.

First, the photocurable compound containing an ethylenically unsaturated group used in the invention will be described.

The composition ratio of the photosensitive layer containing an ethylenically unsaturated group used in the invention is preferably as follows.

Photocurable compound represented by the general formula (2) described later 1 to 50% by weight Monomer or oligomer other than the above 1 to 50% by weight Light selected from the group (I) to (III) described below Sensitizer 0.3-40 wt% Binder polymer 15-80 wt% Other additives 0-10 wt% The binder polymer of the present invention will be described.

The binder polymer having the function of retaining the shape in the present invention is not limited as long as it is soluble in an organic solvent and has a film-forming ability and the tensile properties described above. It is preferable to use a polymer or copolymer having a glass transition temperature (Tg) of 0 ° C. or lower, and it is preferable to use a polymer or copolymer having a Tg of −30 ° C. or lower.

Glass transition temperature Tg (glass transition t
Emperature) refers to the transition point (temperature) at which the physical properties of the amorphous polymer material change from the glass state to the rubber state (or vice versa). In a relatively narrow temperature range around the transition point, not only the elastic modulus but also various properties such as expansion coefficient, heat content, refractive index, diffusion coefficient, and dielectric constant change greatly. Therefore, the glass transition temperature is measured by measuring the volume (specific volume) -temperature curve, measuring the heat content by thermal analysis (DSC, DTA, etc.), measuring the properties of the substance as a whole, such as the refractive index and stiffness. (Dynamic viscoelasticity, etc.), dielectric loss tangent, and an amount that reflects molecular motion such as an NMR spectrum are measured. It is customary to use a dilatometer to measure the volume of the sample while raising the temperature and determine it as the point at which the slope of the volume (specific volume) -temperature curve changes abruptly.

Typical polymers which can be used as the binder polymer will be specifically described below, but the present invention is not limited to these examples.

(1) Vinyl Polymers Polymers and copolymers obtained from the following monomers and their dielectrics.

For example, ethylene, propylene, 1-butene, styrene, butadiene, isoprene, vinyl chloride,
Vinyl acetate, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, N-hexyl methacrylate, lauryl methacrylate, acrylic acid,
Methacrylic acid, maleic acid, itaconic acid, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, polyethylene glycol mono (meth) acrylate, polypropylene Glycol mono (meth) acrylate, phenoxyethyl (meth) acrylate, 2- (meth) acryloxyethyl hydrogen phthalate, 2- (meth) acryloxyethyl hydrogen succinate, acrylamide, N-methylol acrylamide, diacetone acrylamide, glycidyl methacrylate, Acrylonitrile, styrene, vinyltoluene, isobutene, 3-methyl-1-butene, butyl vinyl ether, N-vinylcarbazole, methyl vinyl ketone, nitroethyl Emissions, alpha-cyano acrylic acid methyl,
Vinylidene cyanide, polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth)
Acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyl) Oxypropyl)
After adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as ether, glycerin, trimethylolethane, or trimethylolpropane (meth)
An acrylated polymer and a polymer or copolymer obtained by polymerizing or copolymerizing these derivatives can be used as the binder polymer.

(2) Unvulcanized rubber Natural rubber (NR) or homopolymer or copolymer selected from butadiene, isoprene, styrene, acrylonitrile, acrylic acid ester, and methacrylic acid ester, such as polybutadiene (BR ), Styrene-butadiene copolymer (SBR), carboxy-modified styrene-
Butadiene copolymer, polyisoprene (NR), polyisobutylene, polychloroprene (CR), polyneoprene, acrylic acid ester-butadiene copolymer, methacrylic acid ester-butadiene copolymer, acrylic acid ester-acrylonitrile copolymer (ANM), isobutylene-isoprene copolymer (IIR), acrylonitrile-butadiene copolymer (NBR), carboxy-modified acrylonitrile-butadiene copolymer, acrylonitrile-chloroprene copolymer, acrylonitrile-isoprene copolymer, ethylene-propylene Copolymer (EP
M, EPDM), vinyl pyridine-styrene-butadiene copolymer, styrene-isoprene copolymer and the like.

Specific examples of these rubbers having a glass transition temperature of 0 ° C. or lower include poly (1,3-butadiene), poly (2-chloro-1,3-butadiene), poly (2-decyl-1, 3-butadiene), poly (2,3-dimethyl-
1,3-butadiene), poly (2-ethyl-1,3-butadiene), poly (2-heptyl-1,3-butadiene), poly (2-isopropyl-1,3-butadiene), poly (2- Methyl-1,3-butadiene), chlorosulfonated polyethylene and the like.

Further, modified products of these rubbers, for example, rubbers which have been modified normally by epoxidation, chlorination, carboxylation and the like, and blends with other polymers can also be used as the binder polymer.

(3) Polyoxides (Polyethers) Trioxane, ethylene oxide, propylene oxide, 2,3-epoxybutane, 3,4-epoxybutene, 2,3-epoxypentane, 1,2-epoxyhexane, Epoxy cyclohexane, epoxy cycloheptane, epoxy cyclooctane, styrene oxide, 2-
Phenyl-1,2-epoxypropane, tetramethylethylene oxide, epichlorohydrin, epibromohydrin, allyl glycidyl ether, phenyl glycidyl ether, n-butyl glycidyl ether, 1,4-dichloro-2,3-epoxybutane, 2,3 Polymers and copolymers can also be used as binder polymers by ring-opening polymerization of epoxypropionaldehyde, 2,3-epoxy-2-methylpropionaldehyde, 2,3-epoxydiethyl acetal and the like.

(4) Polyesters Polyesters obtained by polycondensation of polyhydric alcohols and polycarboxylic acids as shown below, polyesters obtained by polymerization of polyhydric alcohols and polycarboxylic acid anhydrides, ring opening of lactones Polyester obtained by polymerization and the like, polyester obtained from a mixture of these polyhydric alcohols, polyvalent carboxylic acids, polyvalent carboxylic anhydrides, and lactones can also be used as the binder polymer. Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol and diethylene glycol. Propylene glycol, neopentyl glycol, triethylene glycol, p-xylylene glycol, hydrogenated bisphenol A, bisphenol dihydroxypropyl ether, glycerin, trimethylolethane, trimethylolpropane, trishydroxymethylaminomethane, pentaerythritol, dipentaerythrite Trit, sorbitol, etc.

Examples of the polyvalent carboxylic acid and polyvalent carboxylic anhydride include fumaric anhydride, isophthalic acid, terephthalic acid, succinic anhydride, adipic acid, azelaic acid, sebacic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, Tetrabromophthalic anhydride, tetrachlorophthalic anhydride, hettic anhydride, hymic acid anhydride, maleic anhydride, fumaric acid, itaconic acid, trimellitic anhydride,
Methyl cyclohexene tricarboxylic acid anhydride, pyromellitic dianhydride, etc. are mentioned.

Examples of the lactone include β-propiolactone, γ-butyrolactone, δ-valerolactone and ε-caprolactone.

(5) Polyurethanes Polyurethanes obtained from the following polyisocyanates and polyhydric alcohols can also be used as the binder polymer. As the polyhydric alcohol, the polyhydric alcohols described in the above section of polyester and the following polyhydric alcohols, and both ends obtained by polycondensation of these polyhydric alcohol and the polyvalent carboxylic acid described in the section of polyester are hydroxyl groups Such condensed polyester polyols, polymerized polyester polyols obtained from the above lactones, polycarbonate diols, polyether polyols obtained by ring-opening polymerization of propylene oxide or tetrahydrofuran, or modification of epoxy resin, or acrylic (or methacrylic) monocarboxylic acid having a hydroxyl group. Acrylic polyols, polybutadiene polyols, and the like, which are copolymers of monomers and acrylic (or methacrylic) acid esters, can be used.

Examples of the isocyanates include paraphenylene diisocyanate, 2,4- or 2,6-toluylene diisocyanate (TDI), 4,4-diphenylmethane diisocyanate (MDI), tolidine diisocyanate (TODI) and xylylene diisocyanate (X.
DI), hydrogenated xylylene diisocyanate, cyclohexane diisocyanate, metaxylylene diisocyanate (MXDI), hexamethylene diisocyanate (HDI or HMDI), lysine diisocyanate (LDI) (also known as 2,6-diisocyanate methyl caproate), hydrogenated MDI (H12MDI) (Alias 4,
4′-methylenebis (cyclohexyl isocyanate)), hydrogenated TDI (HTDI) (also known as methylcyclohexane 2,4 (2,6) diisocyanate), hydrogenated XDI (X6XDI) (also known as 1,3- (isocyanatomethyl) cyclohexane), Isophorone diisocyanate (IPDI), diphenyl ether isocyanate,
Trimethylhexamethylene diisocyanate (TMD
I), tetramethylxylylene diisocyanate, polymethylene polyphenyl isocyanate, dimer acid diisocyanate (DDI), triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate, tetramethylxylylene diisocyanate, lysine ester triisocyanate, 1,6 , 11
-Undecane triisocyanate, 1,8-diisocyanate-4-isocyanatomethyl octane, 1,3
Examples thereof include 6-hexamethylene triisocyanate, bicycloheptane triisocyanate and the like, polyisocyanate polyvalent alkyl adducts, and polyisocyanate polymers.

Typical polyhydric alcohols other than those mentioned in the section of polyester are polypropylene glycol, poiethylene glycol, polytetramethylene glycol, ethylene oxide-propylene oxide copolymer, tetrahydrofuran-ethylene oxide copolymer. Coalesce, tetrahydrofuran-propylene oxide copolymer and the like, and as the polyester diol, polyethylene adipate, polypropylene adipate,
Polyhexamethylene neopentyl adipate, polyneopentyl adipate, polyhexamethylene neopentyl adipate,
Examples thereof include polyethylene hexamethylene adipate and the like, and poly-ε-caprolactone diol, polyhexamethylene carbonate diol, polytetramethylene adipate, sorbitol, methyl glucogit, sucrose and the like.

Also, various phosphorus-containing polyols, halogen-containing polyols, etc. can be used as the polyol.

Furthermore, branched polyurethane resins and polyurethane resins having various functional groups such as hydroxyl groups can also be used as the binder polymer.

In addition to these, poly (tetramethylene hexamethylene-urethane), poly (1,4- (2-butene))
Hexamethylene-urethane), poly (1,4- (2-butyne) hexamethylene-urethane) and the like.

(6) Polyamides Known polyamides can also be used as the binder polymer.

The basic composition is a copolymer of the following monomers. ε-caprolactam, ω-laurolactam, ω-aminoundecanoic acid, hexamethylenediamine, 4,4′-bis-aminocyclohexylmethane, 2,4,4-trimethylhexamethylenediamine,
Isophorone diamine, diglycols, isophthalic acid,
Adipic acid, sebacic acid, dodecanedioic acid and the like.

Explaining in more detail, polyamides are generally classified into water-soluble polyamides and alcohol-soluble polyamides. As the water-soluble polyamide, for example, a polyamide containing a sulfonic acid group or a sulfonate group obtained by copolymerizing sodium 3,5-dicarboxybenzenesulfonate as shown in JP-A-48-72250, A polyamide having an ether bond, which is obtained by copolymerizing any one of a dicarboxylic acid having an ether bond in the molecule, a diamine, and a cyclic amide as shown in JP-A-49-43465, 50-7605, polyamides containing basic nitrogen obtained by copolymerizing N, N'-di (γ-aminopropyl) piperazine and the like, and quaternization of these polyamides with acrylic acid and the like. Polyamide having a molecular weight of 150 to 1500 proposed in JP-A-55-74537 Copolyamide containing Le segments, and alpha-(N, N'-dialkylamino)-.epsilon.-caprolactam ring-opening polymerization or α of
Examples thereof include polyamides obtained by ring-opening copolymerization of-(N, N'-dialkylamino) -ε-caprolactam and ε-caprolactam.

As the copolyamide containing a polyether segment having a molecular weight of 150 to 1500, polyoxyethylene having an amino group at the terminal and a polyether segment portion having a molecular weight of 150 to 1500 and an aliphatic dicarboxylic acid or diamine are mentioned. From 30 to 30 units
An example of the copolymerized polyamide is 70% by weight.

Examples of alcohol-soluble polyamides include linear polyamides synthesized by a known method from aliphatic dibasic acids and diamines, ω-amino acids, lactams or derivatives thereof, and not only homopolymers but also copolymers and block polymers. Etc. can also be used. Typical examples are nylon 3, 4, 5, 6, 8, 11, 1
2, 13, 66, 610, 6/10, 13/13, polyamide from metaxylylenediamine and adipic acid, trimethylhexamethylenediamine or polyamide from isophoronediamine and adipic acid, ε-caprolactam / adipic acid / hexamethylene Diamine / 4,4 '
-Diaminodicyclohexylmethane copolymerized polyamide,
ε-caprolactam / adipic acid / hexamethylenediamine / 2,4,4′-trimethylhexamethylenediamine copolymerized polyamide, ε-caprolactam / adipic acid / hexamethylenediamine / isophoronediamine copolymerized polyamide, or polyamide containing these components ,
Those N-methylol, N-alkoxymethyl derivative, etc. can also be used.

The above polyamides can be used alone or as a binder polymer by mixing them.

These polymers which can be used as the binder polymer can be used alone or as a mixture of several kinds of polymers.

Among these binder polymers, polyurethane, polyester, vinyl-based polymer, and polybutadiene-based unvulcanized rubber are preferable in order to effectively exhibit the effects of the present invention, and polyurethane is a photocurable compound. Is particularly preferable from the viewpoint of compatibility and the like.

The binder polymer used in the present invention is used in an amount of 15 to 80% by weight, preferably 15 to 65% by weight, based on the components of the photosensitive layer. Is important in setting a certain range.

Next, the photocurable compound will be described.

The photocurable compound having an ethylenically unsaturated group used in the present invention is preferably a monomer represented by the following general formula (2).

R1 R2 N- (X1) p- (X2) q -NR3 R4 (2) (wherein X1 is a substituted or unsubstituted cyclic or acyclic alkylene having 1 to 20 carbon atoms, substituted or It represents a divalent linking group selected from unsubstituted phenylene, substituted or unsubstituted aralkylene, and the substituent has 1 to 6 carbon atoms.
Represents an alkyl group, a halogen atom, a hydroxyl group, or an aryl group. X2 is -OE 1-, -S-E2-, -NH-E3-, -CO-OE
4-, -SO 2 -NH-E 5-, E1, E2, E3, E4
, E5 represent a divalent linking group selected from the above-mentioned alkylene, phenylene and aralkylene. p represents an integer of 1 or more, and p represents 0 or an integer of 1 or more. R
1, R2, R3 and R4 are each a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted aralkyl group, the following formula (3), (4 ), (5) means a functional group selected from
It may be the same or different. The substituent has 1 to 1 carbon atoms.
6 represents an alkyl group, a halogen atom, a hydroxyl group and an aryl group. However, at least 1 in one molecule of compound (2)
Containing one or more ethylenically unsaturated groups. R5, R6, R7
Represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted aralkyl group, a CH2 = CH- group, a CH2CCH3- group. Y represents -CO-O-, -CO-NH-, or a substituted or unsubstituted phenylene group. X3, X4 and X5 are the same as the above X1 or X2. m and n represent 0 or 1. )

Embedded image In particular, those obtained by subjecting the following diamine compound to an addition reaction with a glycidyl (meth) acrylate having a photopolymerizable group and a monoglycidyl ether compound having no photopolymerizable group are preferably used.

(1) Diamine compound (monooxyethylenediamine, dioxyethylenediamine, trioxyethylenediamine, tetraoxyethylenediamine, pentaoxyethylenediamine, hexaoxyethylenediamine, heptaoxyethylenediamine, octaoxyethylenediamine, nonaoxyethylenediamine, decaoxyethylenediamine, trioxyethylenediamine Triacontaoxyethylenediamine, monooxypropylenediamine, dioxypropylenediamine, trioxypropylenediamine,
Tetraoxypropylenediamine, pentaoxypropylenediamine, hexaoxypropylenediamine, heptaoxypropylenediamine, octaoxypropylenediamine, nonaoxypropylenediamine, decaoxypropylenediamine, tritriacontaoxypropylenediamine, N-hydroxyethylhexapropylenediamine, N-hydroxyisopropylhexapropylenediamine, N, N'-dihydroxyethylhexapropylenediamine, N, N'-dihydroxyisopropylhexapropylenediamine, trimethylenebis (4-aminobenzoate), (tetramethyleneglycolbis (4-aminobenzoate) ), Dibutylene glycol bis (4-aminobenzoate), o-xylylenediamine, m-xylylene Amine, p- xylylenediamine, N- hydroxyethyl -m- xylylenediamine,
N-hydroxyisopropyl-m-xylylenediamine, N, N'-dihydroxyethyl-m-xylylenediamine, N, N'-dihydroxyisopropyl-m-xylylenediamine, etc.) 1 mol (2) glycidyl (meth) acrylate
4-n mol (3) monoglycidyl ether compound (methyl glycidyl ether, ethyl glycidyl ether, n-propyl glycidyl ether, isopropyl glycidyl ether, n-butyl glycidyl ether, isobutyl glycidyl ether, n-hexyl glycidyl ether, 2 ethylhexyl glycidyl ether , N-decyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, glycidol, etc.)
The addition reaction product of nmol (n is an integer of 0 ≦ n4 ≦) is useful.

The photocurable compound used in the present invention includes
In addition to the monomers having these specific structures and functions, known monomers or oligomers may be added for the purpose of adjusting sensitivity.

Specific examples of such a monomer or oligomer are shown below.

Alcohols (ethanol, bropropanol, hexanol, octanol, cyclohexanol, glycerin, trimethylolpropane, pentaerythritol, isoamyl alcohol, ularyl alcohol, stearyl alcohol, butoxyethyl alcohol, ethoxyethylene glycol, methoxyethylene glycol, methoxy). (Meth) acrylic acid ester of propylene glycol, phenoxyethanol, phenoxydiethylene glycol, tetrahydrofurfuryl alcohol, etc., carboxylic acids (acetic acid, propionic acid, benzoic acid, acrylic acid, methacrylic acid, succinic acid, maleic acid, phthalic acid, tartaric acid, Cleic acid, etc.) and glycidyl (meth) acrylate or tetraglycidyl-m-xylylenediamine or tet Addition reaction product of an Gurijishiru -m- tetrahydroxy Li diamine, amide derivatives (acrylamide, methacrylamide, n- methylolacrylamide, methylenebisacrylamide, etc.),
Examples thereof include addition reaction products of epoxy compounds and (meth) acrylic acid.

More specifically, Japanese Patent Publication No. 48170
No. 8, JP-B-50-6034, JP-A-51-
Urethane acrylates described in JP-A-37193, JP-A-48-64183, JP-B-49-43
191 and Japanese Patent Publication No. 52-30490, polyester acrylates, polyfunctional epoxy (meth) acrylates obtained by reacting an epoxy resin with (meth) acrylic acid, and N described in US Pat. No. 4,540,649. -Methylol acrylamide derivatives and the like can be mentioned. Furthermore, Japan Adhesive Association magazine VOL.20, No.7, p300
Photocurable monomers and oligomers introduced in ~ 308 can be used.

Next, the sensitizer will be described. Examples of the photosensitizer used in the present invention include (I) to (II
It is preferable to use a mixture of photosensitizers each not selected from the group I).

(I) Bis (alkylamino) benzophenone (II) Thioxanthone derivative (III) Acridone derivative

Examples of the bis (dialkylamino) benzophenone of the group (I) include compounds represented by the following general formula (6).

[0168]

Embedded image (However, R1, R2, R3, and R4 represent an alkyl group having 1 to 20 carbon atoms.) Specific examples include 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone. , 4,4'-bis (dipropylamino) benzophenone, 4,4'-bis (piperidine) benzophenone and the like.

Examples of the thioxanthone derivative of group (II) include compounds represented by the following general formula (7).

[0170]

Embedded image (However, R5, R6, R7, and R8 are each a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, an alkenyl group, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or an aralkyl group. It represents a selected functional group and may be the same or different.) Specific examples include 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone and 2
-Uralyl thioxanthone, 3-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone,
2,4-diisopropylthioxanthone, 3,4-dicarboxyocrylthioxanthone, 2-methyl-3'-
Carboxylauryl thioxanthone etc. are mentioned.

As the acridone derivative of the group (III),
Examples thereof include compounds represented by the following general formula (8).

[0172]

Embedded image (However, R9, R10, R11, R12, and R13 are hydrogen atoms,
It represents a functional group selected from a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, an alkenyl group, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and an aralkyl group, which may be the same or different. ) As a specific example, 1-chloro-N-methylacridone,
1-bromo-N-methylacridone, 3-chloro-N-
Methylacridone, 2-chloro-N-butylacridone, 2-chloro-N-methylacridone, 3-chloro-
N-benzylacridone, 4-chloro-N-methylacridone, 2,3-dichloro-N-methylacridone,
2,6-dichloro-N-methylacridone, 2,6-dichloro-N-butylacridone, 2-chloro-N-allylacridone, 3-chloro-N-benzylacridone,
N-benzylacridone, N-butylacridone, N-
Examples include ethyl acridone.

The addition amount of these photosensitizers is 0.3 to 40% by weight, preferably the total addition amount of the photosensitizers relative to the dry weight of the photosensitive layer, in order to efficiently exert the effects of the present invention. Is 5 to 30% by weight, and the addition amount of the photosensitizer belonging to each group is (1) 0.1 to 5% by weight (2) 0.1 to 20% by weight (3) 0.1 to 15% % By weight Further, it is particularly preferable that the composition range is (1) 1 to 5% by weight (2) 3 to 15% by weight (3) 2 to 10% by weight.

In addition to the above components, it is optional to add additives such as an organic acid, a dye, a pigment, a photocoloring agent, a catalyst and a polymerization inhibitor, if necessary.

Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butylcresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol). , 2,2'-methylenebis (4-methyl-
6-t-butylphenol), 2-mercaptobenzimidazole, phenothiazine, tempol and the like are useful.

Next, the photosensitive layer containing a photocrosslinkable group used as the photocurable compound of the present invention will be described. Examples of the photocrosslinkable compound used in the present invention include polymer compounds having a photopolymerizable or photocrosslinkable functional group in the side chain.

The following composition ratios are preferred for the photosensitive layer containing a photocrosslinkable group used in the present invention.

The following photocrosslinkable compound 1 to 50% by weight Binder polymer 15 to 80% by weight Other additives 0 to 10% by weight The following are examples of the photocrosslinkable compound.

(1) Photodimerization type photosensitive resin, for example, a photosensitive layer containing polyvinyl cinnamate or the like, or polyesters, polycarbonates, polyamides, polys (Meth) acrylic acid esters, polyvinyl alcohol derivatives, epoxy resin derivatives and the like.

[0180]

[Chemical 6] (R and R'are alkyl groups having 1 to 10 carbon atoms, R "is hydrogen, halogen, alkyl groups having 1 to 10 carbon atoms or cyano groups.) For example, p-phenylenediacrylic acid and 1,4- Dihydroxyethyloxycyclohexyne 1: 1 polycondensation unsaturated polyesters and photosensitive polyesters derived from cinnamylidene malonic acid and difunctional glycols, and polymers of hydroxyl-containing polymers such as polyvinyl alcohol, starch and cellulose. Skin ester etc.

(2) A photosensitive layer comprising a combination of a diazonium salt and a monomer, oligomer or polymer having an epoxy group. When exposed to light, a Lewis acid is generated by photolysis of the diazonium salt, and the epoxy group undergoes cationic polymerization to crosslink. As the diazonium salt, for example, 2,5-diethoxy-4- (p-toluylthio) benzenediazonium hexafluorophosphate or the like is used.

(3) A photosensitive layer comprising a combination of an allyl group-containing monomer, oligomer or polymer and a thiol group-containing monomer, oligomer or polymer. When exposed to light, thiol groups add to allyl groups and crosslink.

(4) Allyl (meth) acrylate / (meth) acrylic acid / if necessary, other addition-polymerizable vinyl monomer copolymers proposed in JP-A-59-53836, and alkali metal salts or amines thereof Salt, hydroxyethyl (meth) acrylate / (meth) acrylic acid / alkyl (meth) acrylate copolymer proposed in JP-B-59-45979, and alkali metal salt or amine salt thereof with (meth) acrylic acid chloride Reaction products, maleic anhydride copolymers proposed in JP-A-59-71048, pentaerythritol triacrylate added by half-esterification, alkali metal salts or amine salts thereof, and styrene / maleic anhydride. Monohydroxyalkyl (meth) in acid copolymer
Acrylate and / or polyethylene glycol mono (meth) acrylate and / or polypropylene glycol mono (meth) acrylate added by half-esterification, its alkali metal salt or amine salt, (meth) acrylic acid copolymer and crotonic acid copolymer One obtained by reacting glycidyl (meth) acrylate with a part of the carboxylic acid of the polymer, and its alkali metal salt or amine salt, hydroxyalkyl (meth) acrylate copolymer, polyvinyl formal and / or polyvinyl butyral and maleic anhydride or What reacted with itaconic anhydride, its alkali metal salt or amine salt, hydroxyalkyl (meth) acrylate / (meth) acrylic acid copolymer, and 2,4-tolylene diisocyanate / hydroxyalkyl (meth) Crylate = 1/1 molar ratio Further reaction of the addition reaction product, its alkali metal salt or amine salt, and allyl part of the (meth) acrylic acid copolymer proposed in JP-A-59-53836. Those reacted with glycidyl ether and its alkali metal salts or amine salts, (meth) allyl acrylate / sodium styrene sulfonate copolymer, vinyl (meth) acrylate / sodium styrene sulfonate copolymer, (meth) allyl acrylate / Acrylamide /
1,1-Dimethylethylene sodium sulfonate copolymer, vinyl (meth) acrylate / acrylamide /
Sodium 1,1-dimethylethylene sulfonate copolymer, 2-allyloxyethyl (meth) acrylate / methacrylic acid copolymer, 2-allyloxyethyl (meth) acrylate / 2-methacryloxyethyl hydrogen succinate copolymer, etc. Can be mentioned.

As the binder polymer and other additives, those having the same kind and composition as the compounds described in the photosensitive layer containing an ethylenically unsaturated group can be used.

Next, the photosensitive layer containing a diazo group used as the photocurable compound of the present invention will be described.

The following composition ratios are preferred for the photosensitive layer containing a diazo group used in the present invention.

Diazo compound represented by the following (9) 1 to 50% by weight Binder polymer 15 to 80% by weight Other additives 0 to 10% by weight

The diazo compounds preferably used in the present invention include water-insoluble organic solvent-soluble diazo resins represented by a condensation product of p-diazodiphenylamine and formaldehyde. Specifically, Japanese Patent Publication No. 47-1167 and Japanese Patent Publication No. 57-4389.
Examples thereof include those described in JP-A-0. Generally, a diazo resin represented by the following general formula (9) is preferably used.

[0189]

[Chemical 7] (In the formula, R1, R2, and R3 represent a hydrogen atom, an alkyl group, or an alkoxy group, and R4 represents a hydrogen atom, an alkyl group, or a phenyl group. X represents a chlorine ion,
Trichlorozinc acid, boron tetrafluoride, hexafluorophosphoric acid, triisopropylnaphthalene sulfonic acid, 4,4'-biphenyl sulfonic acid, 2,5-dimethylbenzene sulfonic acid, 2-nitrobenzene sulfonic acid, 2-methoxy-4- It means hydroxy-5-benzoyl-benzenesulfonic acid. Y means -NH-, -S-, -O-. ) Examples of the diazo monomer in the diazo resin used in the present invention include 4-diazo-diphenylamine, 1-
Diazo-4-N, N-dimethylaminobenzene, 1-diazo-4-N, N-diethylaminobenzene, 1-diazo-4-N-ethyl-N-hydroxyethylaminobenzene, 1-diazo-4-N- Methyl-N-hydroxyethylaminobenzene, 1-diazo-2,5-diethoxy-4-benzoylaminobenzene, 1-diazo-4-N
-Benzylaminobenzene, 1-diazo-4-N, N-
Dimethylaminobenzene, 1-diazo-4-morpholinobenzene, 1-diazo-2,5-dimethoxy-4-p
-Tolylmercaptobenzene, 1-diazo-2-ethoxy-4-N, N-dimethylaminobenzene, p-diazo-dimethylaniline, 1-diazo-2,5-dibutoxy-4-morpholinobenzene, 1-diazo- 2,5-diethoxy-4-morpholinobenzene, 1-diazo-
2,5-dimethoxy-4-morpholinobenzene, 1-
Diazo-2,5-diethoxy-4-p-tolylmercaptobenzene, 1-diazo-4-N-ethyl-N-hydroxyethylaminobenzene, 1-diazo-3-ethoxy-4-N-methyl-N-benzyl Aminobenzene, 1-
Diazo-3-chloro-4-diethylaminobenzene, 1
-Diazo-3-methyl-4-pyrrolidinobenzene, 1-
Diazo-2-chloro-4-N, N-dimethylamino-5
-Methoxybenzene, 1-diazo-3-methoxy-4-
Pyrrolidinobenzene, 3-methoxy-4-diazodiphenylamine, 3-ethoxy-4-diazodiphenylamine, 3- (n-propoxy) -4-diazodiphenylamine, 3- (isopropoxy) -4-diazodiphenylamine and the like can be mentioned. .

Examples of the aldehyde used as a condensing agent with these diazo monomers include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, benzaldehyde and the like. As the anion, a water-soluble diazo resin can be obtained by using chlorine ion or trichlorozinc acid, and boron tetrafluoride,
Hexafluorophosphoric acid, triisopropylnaphthalene sulfonic acid, 4,4'-biphenyl sulfonic acid, 2,5-dimethylbenzene sulfonic acid, 2-nitrobenzene sulfonic acid, 2-methoxy-4-hydroxy-5-benzoyl-benzene sulfonic acid An organic solvent-soluble diazo resin can be obtained by using, for example,

Further, these diazo resins are preferably used in a mixture with a polymer compound having a hydroxyl group as described below within a range that does not impair the effects of the present invention.
That is, as the polymer compound having a hydroxyl group, a monomer having an alcoholic hydroxyl group, for example, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2,3-hydroxypropyl (meth) acrylate, 2 -Hydroxyethyl (meth)
Acrylamide, triethylene glycol mono (meth)
Acrylate, tetraethylene glycol mono (meth)
Acrylate, 1,3-propanediol mono (meth)
Copolymerization between at least one or more kinds of monomers selected from acrylate, 1,4-butanediol mono (meth) acrylate, di (2-hydroxyethyl) maleate and the like and other monomers having no hydroxyl group. Coalescing,
A monomer having a phenolic hydroxyl group, for example, N-
(4-hydroxyphenyl) (meth) acrylamide,
N- (4-hydroxyphenyl) maleimide, o-, m
-, P-hydroxystyrene, o-, m-, copolymers with p-hydroxyphenyl (meth) acrylate, etc., and ring-opening reaction products of p-hydroxybenzoic acid and glycidyl (meth) acrylate, Salicylic acid and 2
-Copolymers with hydroxyl group-containing monomers and the like such as reaction products with hydroxyethyl (meth) acrylate. Further, polyvinyl alcohol, cellulose, polyethylene glycol, polypropylene glycol, glycerin, pentaerythritol, and the like, an epoxy addition reaction product thereof, and other hydroxyl-containing natural polymer compounds can also be used.

As the binder polymer and other additives, those having the same kind and composition as the compounds described in the photosensitive layer containing an ethylenically unsaturated group can be used.

The thickness of the photosensitive layer is 0.1 to 100 g / m 2,
It is preferably about 0.5 to 10 g / m 2. If it is too thin, pinholes are likely to occur in the photosensitive layer, and it is disadvantageous in improving printing durability, which is the object of the present invention. On the other hand, if it is too thick, the burden of the drying step is heavy and it is economically disadvantageous, and in view of printing durability, the range of 1 to 5 g / m @ 2 is particularly preferable.

The substrate used in the present invention may be any of those used in ordinary lithographic printing plate precursors and those proposed. That is, it is sufficient that it can be set in an ordinary planographic printing machine and can withstand the load applied during printing.

For example, a metal plate made of aluminum, copper, zinc, steel or the like, or a metal plate plated or vapor-deposited with chromium, zinc, copper, nickel, aluminum, iron or the like,
A plastic film or sheet such as polyethylene terephthalate, polystyrene, polypropylene, etc., a substrate having rubber elasticity such as chloroprene rubber, NBR, or a substrate having such rubber elasticity, or a metal foil such as paper, resin-coated paper, or aluminum. And the like. It is also possible to coat these supports with another substance for the purpose of preventing halation and for other purposes. Of these,
An aluminum plate is preferable, and the surface of the aluminum plate may be subjected to electrolytic etching, graining, polishing, degreasing, or the like.

In the lithographic printing plate precursor of the present invention, the adhesion between the substrate and the photosensitive layer and between the photosensitive layer and the hydrophilic swelling layer is very important for basic plate performance such as image reproducibility and printing durability. , Provide an adhesive layer between each layer if necessary,
It is possible to add an adhesion improving component to each layer. In order to adhere the photosensitive layer and the hydrophilic swelling layer, it is effective to provide a known primer or coupling agent between the layers or add a primer or coupling agent to the hydrophilic swelling layer or the photosensitive layer.

Before applying the photosensitive layer to the substrate, a primer layer may be provided on the substrate to obtain sufficient adhesion between the photosensitive layer and the substrate.

As the primer layer, for example, Japanese Patent Laid-Open No.
Various photosensitive polymers proposed in Japanese Unexamined Patent Publication No. 0-22903 are exposed and cured before laminating a photosensitive layer, and a methacrylic phosphorus-containing monomer proposed in JP-A-4-322181 is used as a photosensitive layer. Of the methacrylic epoxy compound proposed in Japanese Patent Laid-Open No. 7049/1990, which is exposed and cured before being laminated. Fifty
Heat-cured epoxy resin proposed in Japanese Patent Laid-Open No. 760, gelatin hardened in Japanese Patent Application Laid-Open No. 63-133151, Japanese Patent Laid-Open No. 1-28.
2270 and Japanese Patent Laid-Open No. 2-21072 can be used. Other than this, a casein-hardened casein is also effective.

For the purpose of further softening the primer layer, polyurethane, polyamide, styrene / butadiene rubber, carboxy-modified styrene / butadiene rubber, acrylonitrile / butadiene rubber, carboxy-modified acrylonitrile / having a glass transition temperature of room temperature or lower is added to the primer layer. It is also preferable to add polymers such as butadiene rubber, polyisoprene rubber, acrylate rubber, polyethylene, chlorinated polyethylene and chlorinated polypropylene.

[0200] The addition ratio is arbitrary, and the primer layer may be formed only with the additive as long as the film layer can be formed. In addition, for these primer layers, a dye, a pH indicator, an exposure printing-out agent, a photochromic compound, a photopolymerization initiator, an adhesion aid (for example, a polymerizable monomer, a diazo resin, a silane coupling agent) can be used in accordance with the above purpose. Agent, titanate coupling agent, aluminum coupling agent, zirconia coupling agent, boron coupling agent, etc.), titanium oxide, calcium carbonate, zinc oxide for the purpose of preventing halation from the substrate and improving plate inspection. Additives such as white pigments, yellow pigments, and silica particles can be included.

Further, it is optional to add a surfactant or the like for the purpose of improving the coatability.

The composition for forming the above-mentioned primer layer is prepared as a composition solution by dissolving it in a suitable organic solvent such as DMF, methyl ethyl ketone, methyl isobutyl ketone or dioxane. A primer layer is formed by uniformly applying the composition solution on a substrate and heating at a required temperature for a required time.

The thickness of the primer layer is 0.2 to 50 g / m2.
, Preferably 0.5 to 10 g / m 2, and 1 to 5 g / m 2.
A range of m2 is more preferred. If it is too thin, the effect of blocking morphological defects and chemical adverse effects on the substrate surface is poor, while if it is too thick, it is economically disadvantageous in the drying process, so the above range is preferred.

On the surface of the hydrophilic swelling layer of the lithographic printing plate precursor having the above-described structure, a suitable protective layer is coated on the hydrophilic swelling layer for the purpose of protecting the hydrophilic swelling layer. Alternatively, it is preferable to laminate a protective film.

In addition, the protective layer contains a photobleaching substance for the purpose of protecting the photosensitive layer from exposure to light (meaning that light other than the exposure light source is originally irradiated to the non-irradiated portion). You can also

Specific examples of the protective film include polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyethylene terephthalate and cellophane. In addition, these protective films are subjected to unevenness processing, matte treatment of the surface, or a plastic layer containing silica particles or the like on the surface of the protective film in order to improve the vacuum adhesion in the flame during image exposure. Coating and lamination are also preferably performed.

Next, the method for producing the lithographic printing plate precursor according to the invention will be described. An ordinary coater such as a reverse roll coater, an air knife coater, a Mayer bar coater, or a spin coater such as a whaler is used to coat the substrate with the primer layer composition, if necessary.
After curing at ˜300 ° C. for several minutes, the photosensitive layer composition coating liquid is applied, dried at a temperature of 50 to 150 ° C. for several minutes and optionally heat cured, and the hydrophilic swelling layer composition is applied thereon. It is formed by heat treatment at a temperature of 50 to 150 ° C. for several minutes and curing. After that, a protective film is laminated if necessary.

Next, the exposure and development process of the planographic printing plate precursor according to the invention will be described.

The lithographic printing plate precursor as referred to in the present invention is preferably used as a plate material for positive working. The plate material is image-exposed with a usual exposure light source through a positive film which is vacuum-contacted. As the light source used in this exposure process, for example, a high pressure mercury lamp, a carbon arc lamp,
Examples include xenon lamps, metal halide lamps, and fluorescent lamps. After carrying out such a normal exposure, the plate surface is rubbed with a developing pad or a brush containing a developer mainly composed of water, and only the hydrophilic swelling layer in the unexposed portion is removed to expose the photosensitive layer, The ink receiving portion (image area) is exposed to form a printing plate.

On the other hand, the hydrophilic swelling layer in the exposed area is firmly photo-adhered to the photosensitive layer due to the light effect of the photosensitive layer, and is not peeled off even in the above developing operation to form an ink repellent non-image area. .

Next, a printing method using a printing plate prepared by using the photosensitive lithographic printing plate precursor according to the invention will be described.

A known lithographic printing machine is used for printing the photosensitive lithographic printing plate precursor according to the invention. That is, sheet-fed and rotary printing machines of the offset and direct printing type are used.

After the photosensitive lithographic printing plate precursor of the invention is imagewise exposed, it becomes a printing plate through the plate making process described above.
Ink is attached to the plate cylinder of these planographic printing machines, and ink is supplied to the plate surface from an inking roller in contact therewith. In addition, prior to the contact of the inking roller on the plate surface,
The dampening water is supplied from the dampening water supply device, and the hydrophilic swelling layer in the portion corresponding to the non-image area absorbs the dampening water and swells to become ink repellent. On the other hand, the portion corresponding to the image area has a lower water swelling property than the non-image area and hardly absorbs dampening water, resulting in ink receptivity.
Subsequently, the printing ink supplied from the inking roller contacting the plate surface is received, and the received printing ink is transferred and supplied to the surface of the offset blanket cylinder or the surface of the printing medium to form a printing ink image.

The fountain solution used in printing with the printing plate obtained from the photosensitive lithographic printing plate precursor according to the invention is PS with water.
It is of course possible to use the etchant used in the plate, but it is also possible to use pure water containing no additives.

As means for supplying water to the on-press sales surface,
In addition to using the dampening water supply device, it is possible to install a water supply device separately.

For example, a non-contact irradiating or spraying device such as a shower, a spray, a mist or a steam is used, or a brush, a non-woven fabric, a raising cloth, a sponge or the like is brought into contact with the plate surface through the medium. And rubbing under wet conditions.

[0219]

The present invention will be described in more detail with reference to the following examples.

Example 1 An aluminum plate having a thickness of 0.3 mm (manufactured by Sumitomo Light Metal Co., Ltd.) degreased by a usual method was coated with the following primer composition and heat-treated at 200 ° C. for 2 minutes to give 5 g / m 2 Was applied. <Solid component: coating concentration 12%> (1) Polyurethane resin (“Samprene” LQ-SZ18; manufactured by Sanyo Chemical Industry Co., Ltd.) 75% by weight (2) Blocked isocyanate (“Takenate” B830; manufactured by Takeda Pharmaceutical Co., Ltd.) ) 15% by weight (3) Epoxy / urea resin 10% by weight <Solvent component> (4) Dimethylformamide

Subsequently, a photosensitive composition having the following composition was dried on this for 1 minute at 120 ° C. to form a photosensitive layer of 3 g / m 2 on it. <Solid component: coating concentration 15%> (1) Polyurethane obtained by reaction of polyester polyol of adipic acid with hexane-1,6-diol and 2,2-dimethylpropane-1,3-diol and isophorone diisocyanate 57% by weight (2) pentaoxypropylenediamine / glycidyl methacrylate / methylglycidyl ether = 1/3/1 mol ratio addition reaction product 15% by weight (3) m-xylylenediamine / glycidylmethacrylate / methylglycidyl ether = 1/2 / 2 mol ratio addition reaction product 15% by weight (4) CH2 = CHCOO- (CH2) 9 -OCOCH = CH2 8% by weight (5) Michler's ketone 2 parts by weight (6) 2,4-diethylrioxanthone 2 parts by weight (7) Victoria Pure BOH Naphthalene Sulfonate 0.5% by weight (8) Male 0.5 wt% phosphate <Solvent Component> (9) Propylene glycol monomethyl ether

Subsequently, the following composition was coated on this photosensitive layer and then heat-treated at 150 ° C. for 3 minutes to form a hydrophilic swelling layer having a thickness of 2 g / m 2.

<Solid component: 10%> <Hydrophilic swelling layer composition (parts by weight)> (1) Hydrophilic polymer 18 parts by weight (2) Tetraethylene glycol diglycidyl ether 5 parts by weight (3) Aqueous latex "JSR05696" 75 parts by weight [carboxy modified styrene-butadiene copolymer latex: manufactured by Dainippon Ink and Chemicals, Inc.] (4) 2-aminopropyltrimethoxysilane 2 parts by weight <solvent component> (5) Purified water 900 parts by weight

[Synthesis Example of Hydrophilic Polymer] Vinyl acetate 60
g and 40 g of acrylic acid to which 0.5 g of benzoyl peroxide was added as a polymerization initiator, and 3 g of partially saponified polyvinyl alcohol and NaCl as a dispersion stabilizer.
It was dispersed in 300 ml of water containing 10 g.

The dispersion was stirred at 65 ° C. for 6 hours to carry out suspension polymerization. The methyl acrylate component of the obtained copolymer was identified from the NMR spectrum to be 48 mol%. The intrinsic viscosity in a benzene solution at 30 ° C. was 2.10.

Next, 8.6 g of the copolymer was added to a saponification reaction liquid consisting of 200 g of methanol, 10 g of water and 40 ml of 5N NaOH, and the mixture was stirred and suspended at 25 ° C.
After performing the saponification reaction for 1 hour, the temperature was raised to 65 ° C., and the saponification reaction was further performed for 5 hours.

The obtained saponification reaction product was thoroughly washed with methanol and freeze-dried. The saponification degree is 98.3 mol%, and the result of measurement of infrared absorption spectrum is 1570 cm.
It was confirmed that -1 had a strong absorption attributed to the -COO- group.

A 12 micron thick single-sided matted biaxially oriented polypropylene film was applied to the laminate obtained as described above with a calender roller so that the non-matted surface was in contact with the hydrophilic swelling layer. Lamination was performed to obtain a positive type photosensitive lithographic printing plate precursor.

The image evaluation is a positive film having a halftone dot of 200 lines / inch 1 to 99%, a gray scale (G / S) having an optical density difference of 0.15, and model dust (fiber dust, film dust, etc.), Stretch the model film edge on the stretch polyester film, FT made by Nuark
261V UNDS ULTRA-PLUS FLIPTOP PLATEMAKER A vacuum exposure machine was used for 30 seconds of vacuum contact, followed by 30 count exposure and peeling of the laminate film.

Thereafter, an automatic processor (manufactured by Toray Industries, Inc .: TWL)
1160) was pretreated for 1 minute in tap water having a liquid temperature of 40 ° C., and the hydrophilic swelling layer in the unexposed area was peeled off with a developing brush in tap water having a liquid temperature of 25 ° C. to obtain a printing plate.

The obtained printing plate was mounted on a sheet-fed offset printing machine "Sprint 25: made by Komori Corporation", and then commercially available purified water was used as dampening water using a Dahlgren dampening water supply device. While supplying, fine paper (62.
5 kg / chrysanthemum) was used for printing. The ink repellency and ink adhesion were evaluated by visually observing the printed matter. At the time of printing about 1000 sheets, the printing plate was free from smearing and clear printing with sufficient contrast was obtained.

[0230]

Since the photosensitive lithographic printing plate precursor according to the invention uses a hydrophilic swelling layer as an ink repellent layer on the photosensitive layer,
A lithographic printing plate having excellent ink receptivity in the image area and excellent ink repulsion can be obtained.

The lithographic printing plate obtained from the original plate exhibits a high ink repellent property without performing a special surface treatment on the substrate necessary for developing the ink repellent property in the conventional PS plate. Further, the ink can be repelled efficiently with a small amount of dampening water supply, and the control range of dampening water is expanded. Further, printing can be performed without using a solvent such as isopropanol which is usually added to the dampening solution.

[Brief description of drawings]

FIG. 1 shows an example of a phase separation structure of a hydrophilic swelling layer of a photosensitive lithographic printing plate precursor according to the present invention.

FIG. 2 shows an example of a phase separation structure of a hydrophilic swelling layer of a photosensitive lithographic printing plate precursor according to the present invention.

FIG. 3 shows an example of a phase separation structure of a hydrophilic swelling layer of a photosensitive lithographic printing plate precursor according to the present invention.

Claims (4)

[Claims] 1. A photosensitive lithographic printing plate precursor comprising at least a photosensitive layer and a hydrophilic swelling layer laminated in this order on a substrate. 2. The hydrophilic swelling layer has a phase separation structure composed of at least two phases, at least a phase containing a hydrophilic polymer as a main component and a phase containing a hydrophobic polymer as a main component. 1. The photosensitive lithographic printing plate precursor as described in 1. 3. The photosensitive lithographic printing plate precursor as claimed in claim 1, wherein the photosensitive layer is photocurable. 4. The photosensitive lithographic printing plate precursor according to claim 1, further comprising a protective layer on the hydrophilic swelling layer.