JPH07301920A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To improve the developing rate in a developing process for a photosensitive resin plate and to improve reproducibility of images by preparing the compsn. having specified or lower solubility of a hydrophilic component with water and having specified or higher solubility with water containing a surfactant. CONSTITUTION:This photosensitive resin compsn. contains a hydrophobic component and a hydrophilic component. The solubility of the hydrophilic component with water is <2% and the solubility with water containing a surfactant is >2%. The hydrophobic component consists of a compsn. of polymers insoluble with water, and for example, polymers to give hardness and stability to the plate such as 1,4-polybutadiene is used. As for the hydrophilic component, a compsn. of hydrophilic polymer such as poly(meth)acrylic acid and its esters are used. Thereby, the obtd. compsn. can be developed with a water-base developer but has high durability against a water-base ink.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition, and more particularly to a photosensitive resin composition which has rubber elasticity, can be developed by water, and is excellent in ink resistance and useful for flexographic printing. More specifically, the present invention relates to a photosensitive resin composition which can be developed with an aqueous developer containing a surfactant and which has high durability when printed with an aqueous ink.

[0002]

2. Description of the Related Art Conventional photosensitive resin plates for flexographic printing are known to be developed with an organic solvent, but these printing plates have problems in safety to humans and the environment such as toxicity and flammability. It was Therefore, as an alternative to this, a water-developable photosensitive resin composition has been proposed. For example, a conjugated diene hydrocarbon and α, β-ethylenically unsaturated carboxylic acid or a salt thereof as an essential component, a copolymer containing a monoolefin unsaturated compound therein and a photopolymerizable unsaturated monomer, A method using a photosensitive resin composition containing a photosensitizer (JP-A-52-134655, JP-A-5-134655).
3-10648, JP-A-61-2339), a conjugated diene hydrocarbon polymer or a copolymer of a conjugated diene hydrocarbon and a monoolefin unsaturated compound, and a hydrophilic polymer compound, Photosensitive elastomer composition containing a gaseous ethylenically unsaturated compound and a photopolymerization initiator as essential components (see JP-A-60-212451), and a hydrophobic oligomer containing an α, β-ethylenically unsaturated group. , A photosensitive resin composition containing an elastomer, a water-swelling substance and a photopolymerization initiator as essential components (see JP-A-60-173055).

Further, a photosensitive resin composition containing hard organic fine particles (see JP-A-63-8648) for the purpose of improving the mechanical strength and impact resilience of the printing plate.
A photosensitive resin composition containing cross-linkable resin fine particles for the purpose of imparting water developability, imparting water-based ink resistance, and improving printability (JP-A-2-175702, JP-A-3-175702).
-228060, JP-A-4-293907, JP-A-4-293909, JP-A-4-294
353, JP-A-4-340968, JP-A-5-32743, JP-A-5-150451, and JP-A-5-204139), and two-phase for the purpose of improving ink acceptability of the printing plate. A photosensitive resin composition having a structure, containing a diazo compound and a dichromate in a continuous phase, and a dispersed phase containing particles having a particle size of 10 μm or less (JP-A-59-3
6731 gazette).

The photosensitive resin composition described in the above publications can be developed with an alkaline aqueous solution containing sodium carbonate or borax or neutral water by introducing a carboxyl group or a salt thereof into the plate composition. It has become possible.
However, these compositions increase the hydrophilic component's affinity for water and the hydrophilicity of the printing plate after curing is too high, and when printing with an aqueous ink that is often used in flexographic printing, When the printing plate is swollen or softened by water and a large amount of printing is performed, the reproducibility and color tone of the fine parts of the printed matter may change during printing, and in some cases the fine parts of the printing plate may be missing As a result, there is a problem in that it cannot be used, which has hindered the spread of the photosensitive resin plate for water development.

[0005]

SUMMARY OF THE INVENTION Therefore, the present invention solves the above-mentioned drawbacks, that is, a photosensitive resin composition which can be developed with an aqueous developer but has high durability to an aqueous ink. The challenge is to obtain.

[0006]

[Means for Solving the Problems] In order to solve the above-mentioned problems, the present inventors have focused their attention on the relationship between a hydrophilic component, which is the most important component for realizing water development, and a developing solution, and have earnestly studied. As a result of repeated studies, the present invention has finally been completed. That is, the present invention is a photosensitive resin composition containing a hydrophobic component and a hydrophilic component, the hydrophilic component,
The photosensitive resin composition has a solubility in water of 2% or less and a solubility of water containing a surfactant of 2% or more.

In the present invention, the hydrophobic component is a component that does not dissolve or swell in water, and mainly represents a composition of water-insoluble polymers. Such water-insoluble polymers include For example, 1,4-polybutadiene,
1,2-polybutadiene, acrylonitrile rubber, butadiene acrylonitrile rubber, chloroprene rubber, polyurethane rubber, butadiene styrene copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, polyamide resin, unsaturated polyester resin, butadiene- ( (Meth) acrylic acid copolymer, butadiene- (meth) acrylic acid-acrylic ester copolymer, silicone rubber,
Polymers such as polyoxypropylene glycol and polyoxytetramethylene glycol that give rubber elasticity to the plate, polymethyl (meth) acrylate, polyethyl (meth) acrylate, polyisopropyl (meth) acrylate, poly n-butyl (meth) acrylate, etc. Acrylic resin, polystyrene, polypropylene, polyethylene, chlorinated polyethylene, polyacrylonitrile, polyvinyl chloride, polyvinyl acetate and their copolymers, polyurethane resin, polyester resin, polyamide resin,
Examples of the hydrophobic component include polymers such as epoxy resin that impart hardness and stability to the plate, and these may be used alone or in combination as needed as a hydrophobic component, but are not limited thereto. Further, the polymer may be modified as necessary in order to make it reactive. Further, these resins can be modified so that they can react with a monomer or a cross-linking agent or with each other.
The blending amount of the hydrophobic component in the composition of the present invention is 20 to 90.
%, Preferably 30-80% by weight.

Next, in the present invention, the hydrophilic component is a component that is soluble or dispersed or swelled in water, and mainly represents a composition of hydrophilic polymers. Examples of hydrophilic polymers include polymers of poly (meth) acrylic acid or salts thereof, (meth) acrylic acid or salts thereof-alkyl (meth) acrylate copolymers, (meth) acrylic acid or salts thereof-styrene copolymers. Polymer, (meth) acrylic acid or salts thereof-vinyl acetate copolymer, (meth) acrylic acid or salts thereof-acrylonitrile copolymer, polyvinyl alcohol, carboxymethyl cellulose, polyacrylamide, hydroxyethyl cellulose, polyethylene oxide, polyethyleneimine, -COOM group-containing polyurethane, -COOM group-containing polyureaurethane, -COOM group-containing polyester, -COOM group-containing epoxy compound, -COOM group-containing polyamic acid, and salts and derivatives thereof (herein, may be mentioned. Geta M is a hydrogen atom, a monovalent metal atom, a divalent metal atom, 3
Indicates either a valent metal atom or an ammonium compound). Similarly, for the hydrophilic component, these hydrophilic polymers can be used alone or in combination of two or more, if necessary, and can be modified so that they can react with a monomer or a cross-linking agent or with each other. Is.
The content of the hydrophilic component in the composition of the present invention is 3 to 50% by weight, preferably 5 to 30% by weight, and particularly 5 to 20% by weight.
Is desirable.

In the photosensitive resin composition of the present invention, in addition to the above-mentioned hydrophobic component and hydrophilic component, a cross-linking agent, a photoreaction initiator, etc. are blended, and further radical-polymerizable monomers, oxidation stabilizers, polymerization inhibitors, etc. May be added if necessary. Examples of the cross-linking agent include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol. Di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1,4-butanediol di (meth) acrylate,
Neopentyl glycol di (meth) acrylate, 1,
6-hexanediol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, glycerol di (meth) acrylate, glycerol aryloxydi (meth)
Acrylate, 1,1,1-trishydroxymethylethane di (meth) acrylate, 1,1,1-trishydroxymethylethane tri (meth) acrylate, 1,
1,1-trishydroxymethylpropane di (meth) acrylate, 1,1,1-trishydroxymethylpropane tri (meth) acrylate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diallyl terephthalate, diallyl 1 such as phthalate, divinylbenzene, polyurethane (meth) acrylate, polyester (meth) acrylate etc.
Compounds having two or more radically polymerizable ethylene groups in the molecule are mentioned, but in addition, ethylene group in one molecule,
A compound having a plurality of reactive functional groups such as an epoxy group, an isocyanate group, an amino group, a hydroxyl group and a carboxyl group can also be mentioned.

Examples of the radical-polymerizable monomer include styrene, vinyltoluene, chlorostyrene, t-
Butyl styrene, α-methyl styrene, acrylonitrile, acrylic acid, methacrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth ) Acrylate, iso-
Butyl (meth) acrylate, sec-butyl (meth)
Acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate,
Lauryl (meth) acrylate, n-tridecyl (meth) acrylate, stearyl (meth) acrylate,
Ethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol Monomethyl ether mono (meth) acrylate,
Polypropylene glycol monomethyl ether mono (meth) acrylate, polyethylene glycol monoethyl ether mono (meth) acrylate, polypropylene glycol monoethyl ether mono (meth) acrylate, n-butoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2 -Phenoxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, tribromophenyl (meth) acrylate, 2, Three
-Dichloropropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, N,
N-diethylaminoethyl (meth) acrylate, N,
N-dimethylaminoethyl (meth) acrylate, N-
t-butylaminoethyl (meth) acrylate, acrylamide, N, N-dimethylacrylamide, N, N-
Diethyl acrylamide etc. are mentioned.

The structure of a photosensitive resin composition containing such a hydrophobic component and a hydrophilic component is a structure in which the hydrophobic component is a particulate dispersed phase and the hydrophilic component surrounds it to form a continuous phase. , A structure in which the hydrophobic component is the core and the hydrophilic component is the shell, and the core-shell particle is a structure in which another hydrophobic component is the continuous phase, the hydrophilic component is the particulate dispersed phase, and the hydrophobic component is the continuous phase. And a structure in which both the hydrophobic component and the hydrophilic component are intertwined with each other in a continuous phase to form a mosaic pattern, a structure in which the hydrophobic component and the hydrophilic component are uniformly compatible, and the like. Further, in these structures, it is preferable that the hydrophilic component and the hydrophobic component which has become the continuous phase are not chemically crosslinked in the uncured state. On the other hand, the particulate hydrophobic component may or may not be crosslinked in the uncured state. Further, the hydrophobic component and the hydrophilic component may or may not be chemically bonded to each other.

The method for producing the photosensitive resin composition of the present invention includes a kneader and a particulate dispersed phase component obtained by emulsion polymerization or suspension polymerization or by pulverizing the polymer, alone or together with a continuous phase component. Mixing with an extruder and molding, hydrophobic components and hydrophilic components are kneaded in a kneader or extruder as a lump and phase separated.
Various methods such as a method of molding after dispersion, a method of kneading a hydrophobic component and a hydrophilic component in a kneading state with a kneader or an extruder, and making them compatible evenly and then molding can be adopted. . The polymers of the hydrophilic component and the hydrophobic component may be those polymerized in advance, or the monomers may be blended and polymerized during the production process of the photosensitive resin composition. Especially when arranging the hydrophilic component around the particles of the hydrophobic component, emulsion polymerization or the like is often used.

As described above, the desired photosensitive resin plate can be obtained by appropriately selecting the raw materials, the structure, the manufacturing method and the like according to the required physical properties. For example, the physical properties required for printing plates include JIS A hardness of 30-
It is desirable in view of printing characteristics that the impact resilience is 80% or more and 20% or more. In order for a printing plate made of such a photosensitive resin plate to have sufficient durability against an aqueous ink, the hydrophilic component in the photosensitive resin composition must have a solubility in water of 2% or less. It is necessary to be present, and particularly preferably 1% or less. Further, the solubility in water containing a surfactant is preferably 2% or more, and particularly preferably 3% or more.

A printing original plate is prepared by a usual method using the photosensitive resin composition of the present invention and then cured by ultraviolet rays. The ultraviolet rays used for curing are 150 to 5
A wavelength of 00 nm, particularly a wavelength of 300 to 400 nm is effective, and a low pressure mercury lamp, a high pressure mercury lamp, a carbon arc lamp, an ultraviolet fluorescent lamp, a chemical lamp, a xenon lamp, and a zirconium lamp are preferable as a light source used.

Next, in the present invention, the photosensitive resin plate is subjected to image exposure by exposing it to a negative film having a transparent image under the above light source, exposing it to ultraviolet rays, and then removing the non-exposed non-image area with a developing solution. Thus, a relief image is obtained, while the uncured photosensitive resin that has been dissolved and removed remains as an emulsion or suspension in the developing tank. In the present invention, the developer is preferably an aqueous developer to which a surfactant is added, and the hydrophilic component used is one which is dissolved or dispersed in the developer to which the surfactant is added. There is a need. That is, the usable developing solution is determined from the viewpoint of work safety, environmental safety, availability, etc., and the hydrophilic component in the photosensitive resin composition is selected in accordance with this.

The hydrophilic component dissolves or disperses in the developing solution means that when 2 parts of the hydrophilic component is added to 98 parts of the developing solution in the developing solution at 5 to 50 ° C. and the mixture is stirred. It refers to the state of being dissolved or dispersed without maintaining the original shape and with a particle size of 1 mm or less. On the contrary, if the hydrophilic component only swells in the developer, it cannot be said that the developer has a dissolving ability or a dispersing ability with respect to the hydrophilic component. The photosensitive resin composition of the present invention does not dissolve or disperse in water alone but retains the original form, but contains a hydrophilic component having a characteristic of being dissolved or dispersed in water containing a surfactant. Therefore, it is considered that high durability to the water-based ink was realized.

As the surface active agent in the present invention, anionic surface active agents, cationic surface active agents, nonionic surface active agents, amphoteric surface active agents and the like can be widely used. Specific examples include anionic surfactants, sodium laurate, sodium stearate, aliphatic carboxylic acid salts such as sodium oleate, sodium abietic acid, resin soaps such as sodium rosinate, sodium lauryl sulfate, Primary and secondary alkyl sulfates such as lauryl sulfate triethanolamine, primary and secondary polyoxyethylene alkyl ether sulfates such as polyoxyethylene lauryl ether sulfate soda and polyoxyethylene lauryl ether sulfate triethanolamine , Sodium laurylbenzene sulfonate, sodium stearylbenzene sulfonate, etc. alkylbenzene sulfonates, sodium propylnaphthalene sulfonate, sodium butylnaphthalene sulfonate, etc. Polyoxyethylene alkylphenyl ether sulfonates such as sodium ethylene lauryl phenyl ether sulfonate, sulfated oils such as sulfated castor oil and sulfated beef oil, sulfated fatty acid esters such as sulfated butyl oleate, dioctyl sulfo Alkylsulfosuccinates typified by sodium succinate, α-olefinsulfonates, hydroxyalkanesulfonates, N-methyl-N-alkyltaurine salts, N-alkylsulfosuccinic acid monoamide salts, fatty acid monoglyceride sulfate esters , Alkyl diphenyl ether disulfonates, lauryl alcohol phosphate monoester disoda salt, lauryl alcohol phosphate diester soda salt, and other alkyl phosphate salts,
Polyoxyethylene lauryl ether phosphate monoester disodium salt and polyoxyethylene lauryl ether phosphate diester soda salt, polyoxyethylene alkyl phosphate salts, naphthalene sulfonate formalin condensates, styrene-maleic anhydride copolymer partial saponification And salts of partially saponified olefin-maleic anhydride copolymers. Although sodium salt is mainly mentioned as a specific example, potassium salt, ammonium salt, magnesium salt, calcium salt and the like are also possible and are not particularly limited thereto.

The cationic surfactants include primary, secondary and tertiary amine salts such as monostearyl ammonium chloride, distearyl ammonium chloride, tristearyl ammonium chloride, stearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, stearyl. Quaternary ammonium salts such as dimethylbenzylammonium chloride, alkylpyridinium salts such as N-cetylpyridinium chloride and N-stearylpyridinium chloride, N, N dialkylmorpholinium salts, fatty acid amide salts of polyethylene polyamine, aminoethylethanolamine and stearin Acetates of urea compounds of amides with acids, 2-alkyl-1-alkyl-1-hydroxyethyl imidazoles Li chloride, and the like. Although chloride was mainly mentioned as a specific example, bromide, alkyl sulfate, acetate and the like are also possible, and are not particularly limited thereto.

The nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether and polyoxyethylene lauryl ether, polyoxyethylene alkyl ethers such as polyoxyethylene nonylphenyl ether and polyoxyethylene octylphenyl ether. Phenyl ethers, polyoxyethylene polyoxypropylene glycols, polyethylene glycol monostearate, polyethylene glycol monooleate, mono and diesters of fatty acid with polyethylene glycol such as polyethylene glycol dilaurate, sorbitan monolaurate, sorbitan monooleate, etc. Esters of fatty acids and sorbitan, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbi Esters of sorbitan polyoxyethylene adducts such as polyoxyethylene sorbitan trilaurate with fatty acids, sorbit monopartimate, sorbit dilaurate esters of fatty acids with sorbit, polyoxyethylene sorbit Esters of polyoxyethylene adducts of sorbit such as monostearate and polyoxyethylene sorbitiodiol with fatty acids, esters of fatty acids such as pentaerythritol monostearate and pentaerythritol, fatty acids such as glycerin monolaurate Esters with glycerin, fatty acid esters of sugar and sucrose, aliphatic alkanolamides such as lauric acid diethanolamide and lauric acid monoethanolamide, lauryldimethylamine Amine oxides such as id, aliphatic alkanol amines such as stearyl diethanolamine, polyoxyethylene alkylamine, triethanolamine fatty acid esters and the like.

Examples of the amphoteric surfactant include amino acid type double-sided surfactants such as sodium laurylaminopropionate,
Carboxybetaine type double-sided surfactants such as lauryl dimethyl betaine and lauryl dihydroxyethyl betaine, sulfobetaine type amphoteric surfactants such as stearyl dimethylsulfoethylene ammonium ethylene ammonium betaine, imidazolinium betaine type amphoteric surfactants, lecithin Etc.

The amount of the surfactant added is preferably 0.01 to 10% in terms of weight percentage in the developer. Further, a plurality of these surfactants may be mixed so that optimum developability can be obtained. The developer to which the surfactant is added is preferably a water-based developer from the viewpoint of worker safety and consideration for the environment, and if necessary, ethanol, isopropanol, cellosolve, glycerin, polyethylene glycol, dimethylformamide, dimethylacetamide, acetone, etc. Other organic solvents that dissolve in water may be mixed. Furthermore, this developer contains neutral and alkaline and acidic sodium carbonate, sodium tripolyphosphate, potassium pyrophosphate, sodium silicate, sodium sulfate, sodium borate, sodium acetate, magnesium acetate, sodium citrate, sodium succinate, etc. Inorganic and organic salts, polymeric additives such as carboxymethylcellulose and methylcellulose, acids such as sulfuric acid, hydrochloric acid and phosphoric acid for pH adjustment, sodium hydroxide, potassium hydroxide, calcium hydroxide alkali, other viscosity modifiers, dispersions Various additives such as a stabilizer, a coagulant, and zeolite can be added as necessary. The pH of the developer is preferably in the range of 3-12. When the pH is less than 3, the ability to dissolve or disperse the hydrophilic component is low, and the developability is remarkably reduced. pH is 1
When it exceeds 2, when the developer adheres to the skin, it is highly corrosive to the skin and is dangerous. Furthermore, from the viewpoint of safety, pH
Is preferably in the range of 5-10. From the above, among the developing solutions, especially sulfonates in water,
Neutral developer mainly containing surfactants such as alkylsulfates and phosphonates, weak alkaline developer mainly containing surfactants such as aliphatic carboxylates and aliphatic alkanolamides into water, water Preferable examples include weakly alkaline developing solutions to which these active agents, nonionic surfactants, cationic surfactants and salts showing weak basicity are mainly added.

These surfactants and various additives are appropriately selected and used as a developing solution. When the hydrophilic component of the photosensitive resin composition is not dissolved or dispersed in the prepared developing solution, Not only the developing speed becomes remarkably slow, but also the image reproducibility is deteriorated, which makes it extremely difficult to use as a photosensitive resin composition for water-based development. On the other hand, when the hydrophilic component is dissolved or dispersed in the developing solution, satisfactory development such as developing speed and image reproducibility can be performed. When expressed as the solubility of the hydrophilic component in water containing a surfactant as a developing solution, it is necessary that the solubility is 2% or more, and further preferably 4% or more. In addition, the term “dissolved in water or water to which a surfactant is added” as used herein does not need to be completely dissolved in a molecular state and is transparent, and may be an emulsified state. Even if the hydrophilic component does not dissolve or disperse in water alone, it is possible to give a dissolving ability or a dispersing ability to the hydrophilic component by adding a surfactant or the like to the water. Solubilization phenomenon and emulsification / dispersion phenomenon due to agents, change in hydrophilicity of hydrophilic components due to pH change, decrease in surface tension due to addition of surfactant (50 dyne / cm or less), improvement in permeability, etc. have occurred. It seems that this is the cause, but details are unknown. Further, the present invention is not limited by the cause of this phenomenon. The development is carried out by immersing the photosensitive resin composition in a developing solution and rubbing the photosensitive resin composition with a brush to remove the uncured portion, if necessary. The temperature during development is preferably 10 to 50 ° C.

The photosensitive resin composition of the present invention, when using a resin having rubber elasticity as a hydrophobic component and / or a hydrophilic component, is useful as a flexographic printing plate, and also has ink resistance and ink transfer resistance. Excellent printability. The photosensitive resin composition used in the present invention can be applied not only to the flexographic printing plate but also to photoresists and sand plasts, and is also used as an elastomer curable by ultraviolet rays, for example, an adhesive or a film. ,paint,
It can also be used for other purposes.

[0024]

The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The characteristic values in the examples were measured by the following methods. 1) Solubility of hydrophilic component in water and water to which a surfactant is added: Ion exchange in which 20 parts of the hydrophilic component is added with a surfactant and other additives so that it has the same composition as ion-exchanged water or a developer. After 80 parts of water was added and the mixture was stirred at 25 ° C. for 1 day, the insoluble matter was filtered off with a 150-mesh stainless steel wire net. The solubility in water was taken as the solid content concentration of the filtrate, and the solubility in water with the added surfactant was obtained by subtracting the solid content concentration of the water with added surfactant from the solid content concentration of the filtrate. 2) Durability against water-based ink: The convex portion of the obtained relief was cut into 2 cm × 5 cm, and the weight (a) was measured with the polyester film at the bottom attached, and this was 25
After immersion in water at ℃ for 1 day, wipe off the attached water, measure the weight (b) immediately, and obtain the water absorption rate by the following mathematical formula (1),
This was used as an index of durability against water-based ink. Water absorption rate (%) = (ba) / a × 100 (1)

Example 1 119.0 parts of hexamethylene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd.), 62.0 parts of dimethylolpropionic acid (Fujii Yoshitsusho) Polytetramethylene glycol (G-850 Hodogaya Chemical Co., Ltd.) 29.0 parts and 5.0 parts of di-n-butyltin dilaurylate dissolved in 300 parts of tetrahydrofuran are placed in a 1 liter flask equipped with a stirrer and heated to 65 ° C. for 2 hours while continuing stirring. The reaction continued. In a separate container, acrylonitrile butadiene oligomer containing terminal amino groups (Hyc
ar ATBNX 1300 X16 Ube Industries, Ltd.
A solution prepared by dissolving 184.0 parts of (produced by K.K.) in 270 parts of tetrahydrofuran was added to the above 1 liter flask with stirring at room temperature. The resulting polymer solution was dried under reduced pressure to remove tetrahydrofuran, and the number average was 67
00 polymer was obtained. Next, a solution prepared by dissolving 4.8 parts of lithium hydroxide in 100 parts of methyl alcohol was added to a solution prepared by dissolving 100 parts of the polymer in 100 parts of methyl ethyl ketone at room temperature with stirring, and further stirred for 30 minutes to obtain hydrophilicity. Polymer [1] was obtained.

10 parts of the above hydrophilic polymer [1], chlorinated polyethylene (ESLAN 352F as a hydrophobic polymer)
A Showa Denko KK 45 parts, styrene-butadiene rubber (SBR 1507 Nippon Synthetic Rubber Co., Ltd.) 15
Part, butadiene oligoacrylate (PB-A Kyoeisha Co., Ltd.) 28.5 parts, benzyl dimethyl ketal (Irgacure 651 Ciba Geigy Co., Ltd.) 1 part, and hydroquinone monomethyl ether 0.5 part 40 parts toluene, water 10 Part, dissolved and dispersed, kneaded at 105 ° C. using a heating kneader, degassed, and the resulting photosensitive resin composition is heated at 105 ° C. at 100 kg / cm.
2 μm on the same polyester film with a thickness of 125 μm polyethylene terephthalate film at a pressure of 2
The film (printing original plate) having a thickness of 2.8 mm was prepared by heating and pressing for 1 minute so that the polyvinyl alcohol coat layer was in contact with the photosensitive resin between the films coated with polyvinyl alcohol on one side.

Next, the uppermost polyester film is peeled off to leave a polyvinyl alcohol film on the photosensitive resin layer,
An image-bearing negative film is adhered onto the film and a mercury lamp (manufactured by Dainippon Screen Co., Ltd.) is used to provide an illuminance of 25 W / m ² , 5
Exposure was performed for a minute. After removing the negative film, development was carried out with a brush at 40 ° C. for 15 minutes with a developing solution containing 2% by weight of sodium butylnaphthalenesulfonate (manufactured by Perex NB-L Kao Co., Ltd.), and a relief depth of 1. A 2 mm image pattern was obtained. This image pattern faithfully reproduced the image on the negative film used. In addition, the obtained relief has good ink transferability,
It showed a clear image. The water absorption of the obtained relief was 0.6%, which shows that the relief has high durability to water-based ink. Further, 2 parts of the dried hydrophilic polymer [1] was soaked in 98 parts of the developer used for the development of this example, and the mixture was stirred at 25 ° C.
After gently stirring for a period of time, the hydrophilic polymer [1] was dissolved in the developer. The solubility of the hydrophilic polymer [1] in water was 0.6%, and the solubility in water containing a surfactant (developing solution used for development in this example) was 18%.

Example 2 21.8 parts of hexamethylene diisocyanate, 15.4 parts of dimethylolpropionic acid, 7.6 parts of polytetramethylene glycol and 1.0 part of di-n-butyltin dilaurate were dissolved in 300 parts of tetrahydrofuran. The solution was put into a 1 liter flask equipped with a stirrer, and heated to 65 ° C. while continuing stirring, and the reaction was continued for 3 hours. In a separate container, a solution prepared by dissolving 55.3 parts of acrylonitrile / butadiene oligomer containing terminal amino groups in 100 parts of methyl ethyl ketone was added to the above 1 liter flask with stirring at room temperature. The obtained polymer solution was dried under reduced pressure to remove tetrahydrofuran and methyl ethyl ketone to obtain a polymer having a number average of 21,000. Next, a solution prepared by dissolving 4.8 parts of lithium hydroxide in 100 parts of methyl alcohol was added to a solution prepared by dissolving 100 parts of the polymer in 100 parts of methyl ethyl ketone at room temperature with stirring, and further stirred for 30 minutes to obtain hydrophilicity. Polymer [2] was obtained.

10 parts of the hydrophilic polymer [2], 45 parts of chlorinated polyethylene (H-135 manufactured by Osaka Soda Co., Ltd.) as a hydrophobic polymer, 15 parts of styrene-butadiene rubber.
Parts, 28.5 parts of butadiene oligoacrylate, 1 part of benzyl dimethyl ketal, and 0.5 parts of hydroquinone monomethyl ether are dissolved and dispersed in 40 parts of toluene and 10 parts of water, and the mixture is kneaded at 105 ° C. using a heating kneader, and demolded. After foaming, the resulting photosensitive resin composition was heated at 105 ° C. under a pressure of 100 kg / cm ² to give a thickness of 12
Between a 5 μm polyethylene terephthalate film and a 2 μm polyvinyl alcohol film coated on the same polyester film on one side, a polyvinyl alcohol coating layer was heated and pressed for 1 minute so that the polyvinyl alcohol coating layer was in contact with the photosensitive resin, and a sheet having a thickness of 2.8 mm ( The original printing plate) was created.
When this sheet was exposed and developed in the same manner as in Example 1, an image pattern with a relief depth of 1.2 mm was obtained. This image pattern faithfully reproduced the image on the negative film used. Further, the obtained relief had a good ink transfer property and showed a clear image. The water absorption of the obtained relief was 0.6%, which shows that the relief has high durability to water-based ink. 2 parts of the dried hydrophilic polymer [2] was dipped in 98 parts of the developer used for the development of this example, and gently stirred at 25 ° C. for 1 hour. The hydrophilic polymer [2] was dissolved in the developer. . The solubility of the hydrophilic polymer [2] in water was 0.9%, and the solubility in water containing a surfactant (developing solution used for development in this example) was 20% or more.

Example 3 In the hydrophilic polymer [1] of Example 1, 4.56 parts of sodium hydroxide was used instead of 4.8 parts of lithium hydroxide, and polyoxyethylene lauryl ether sodium sulfate (Pionine A-) was used as a developing solution. 28-B Takemoto Yushi Co., Ltd.
A relief pattern was obtained in the same manner as in Example 1 except that the relief film was used, and a relief having an excellent ink-receptive transfer property was faithfully reproduced.
The water absorption of the obtained relief is 0.7%, which shows that the relief has high durability to water-based ink. 2 parts of the dried hydrophilic polymer used in this example was immersed in 98 parts of the developing solution used in the development of this example, and gently stirred at 25 ° C. for 1 hour to find that the hydrophilic polymer used in this example Dissolved in the developer. The solubility of this hydrophilic polymer in water was 0.6%, and the solubility in water containing a surfactant (developing solution used for development in this example) was 17%.

Example 4 Instead of chlorinated polyethylene in Example 1, epichlorohydrin rubber (Epichromer H Osaka Soda Co., Ltd.) was used.
Was used, and a relief pattern was obtained in the same manner as in Example 1 except that dioctyl sulfosuccinate soda (Pionine A-51-B manufactured by Takemoto Yushi Co., Ltd.) was used as a developer. An image was faithfully reproduced and a relief having excellent ink-transferability was obtained. The water absorption of the obtained relief is 0.7%, which shows that the relief has high durability to water-based ink. 2 parts of the dried hydrophilic polymer [1] was immersed in 98 parts of the developer used for the development of this example, and gently stirred at 25 ° C. for 1 hour, the hydrophilic polymer [1] was dissolved in the developer. Dispersion resulted in a milky white solution. The solubility of the hydrophilic polymer [1] in water containing the surfactant (developing solution used for development in this example) was 14%.

Example 5 A styrene-butadiene-styrene block copolymer (Kraton 1101 Shell Petrochemical Co., Ltd.) was used in place of the chlorinated polyethylene in Example 1, and polyoxyethylene nonylphenyl ether (Pionine) was used as a developer. D-414 A relief pattern was obtained in the same manner as in Example 1 except that 2 parts of Takemoto Yushi Co., Ltd. and 1.3 parts of borax were used, and an image of a negative film was faithfully reproduced to receive an ink. A relief having excellent transferability was obtained. The water absorption of the obtained relief is 0.5%, which shows that the relief has high durability to water-based ink. 2 parts of the dried hydrophilic polymer [1] was immersed in 98 parts of the developing solution used for the development of this example, and gently stirred at 25 ° C. for 1 hour, the hydrophilic polymer [1] was dissolved in the developing solution. . In addition,
The solubility of the hydrophilic polymer [1] in water containing the surfactant (the developer used for the development in this example) was 20% or more.

Example 6 In the hydrophilic polymer [2] of Example 2, 4.56 parts of sodium hydroxide was used instead of 4.8 parts of lithium hydroxide, and sodium isopropyl naphthalenesulfonate (Pionine A-44-) was used as a developing solution. PM Takemoto Yushi Co., Ltd.
A relief pattern was obtained in the same manner as in Example 2 except that the above was used. As a result, a negative film image was faithfully reproduced and a relief having an excellent ink receiving transfer property was obtained. The water absorption of the obtained relief was 0.6%, which shows that the relief has high durability to water-based ink. 2 parts of the dried hydrophilic polymer used in this example was immersed in 98 parts of the developing solution used in the development of this example, and gently stirred at 25 ° C. for 1 hour to find that the hydrophilic polymer used in this example Dissolved in the developer. The solubility of this hydrophilic polymer in water was 0.8%, and the solubility in water containing a surfactant (developing solution used for development in this example) was 20% or more.

Example 7 In the hydrophilic polymer [1] of Example 2, 17.9 parts of N, N-dimethylaminoethyl methacrylate was used instead of 4.8 parts of lithium hydroxide, and α-olefinsulfonic acid was used as a developing solution. Relief patterns were obtained in the same manner as in Example 2 except that soda (Pionine A-33-A, manufactured by Takemoto Yushi Co., Ltd.) was used. As a result, the image on the negative film was faithfully reproduced and ink transferability was excellent. A relief was obtained. The water absorption of the obtained relief is 0.5%, which shows that the relief has high durability to water-based ink. 2 parts of the dried hydrophilic polymer used in this example was immersed in 98 parts of the developing solution used in the development of this example, and gently stirred at 25 ° C. for 1 hour to find that the hydrophilic polymer used in this example Dissolved in the developer. The solubility of this hydrophilic polymer in water was 0.6%, and the solubility in water containing a surfactant (developing solution used for development in this example) was 2.
It was 0% or more.

Example 8 Epichlorohydrin rubber (Epichromer H, manufactured by Osaka Soda Co., Ltd.) was used in place of the chlorinated polyethylene of Example 2, and sodium dodecylbenzenesulfonate (Pionine A-41-B Takemoto) was used as a developing solution. Relief patterns were obtained in the same manner as in Example 2 except that Yushi and Fats Co., Ltd. were used. As a result, a negative film image was faithfully reproduced and a relief having excellent ink-accepting transferability was obtained. The water absorption of the obtained relief is 0.6%, which shows that the relief has high durability to the water-based ink. 2 parts of the dried hydrophilic polymer [2] was dipped in 98 parts of the developer used for the development of this example, and gently stirred at 25 ° C. for 1 hour. The hydrophilic polymer [2] was dissolved in the developer. . The solubility of the hydrophilic polymer (2) in water containing a surfactant (developing solution used for development in this example) was 10%.

Example 9 A styrene-isoprene-styrene block copolymer (Califlex 1107 Shell Petrochemical Co., Ltd.) was used in place of chlorinated polyethylene in Example 2, and cetyltrimethylammonium chloride (Pionine B) was used as a developing solution. -611 A relief pattern was obtained in the same manner as in Example 2 except that 2 parts of Takemoto Yushi Co., Ltd. and 1.5 parts of sodium carbonate were used, and a negative film image was faithfully reproduced and the ink receiving transfer was performed. A relief having excellent properties was obtained. The water absorption of the obtained relief is 0.6%
And shows that the durability against water-based ink is high.
2 parts of the dried hydrophilic polymer [2] was dipped in 98 parts of the developer used for the development of this example, and gently stirred at 25 ° C. for 1 hour. The hydrophilic polymer [2] was dissolved in the developer. . The solubility of the hydrophilic polymer [2] in water containing the surfactant (developing solution used for development in this example) was 16%.

Example 10 A styrene-butadiene-styrene block copolymer (Kraton 1101 Shell Petrochemical Co., Ltd.) was used in place of chlorinated polyethylene in Example 2, and a sulfated castor oil (Kyoeisha Co., Ltd.) was used as a developing solution. When a relief pattern was obtained in the same manner as in Example 2 except that it was used,
The image on the negative film was faithfully reproduced and a relief having excellent ink-accepting transferability was obtained. The water absorption of the obtained relief is 0.7%, which shows that the relief has high durability to water-based ink. 2 parts of the dried hydrophilic polymer used in this example was immersed in 98 parts of the developer used in the development of this example,
When the mixture was gently stirred at 25 ° C. for 1 hour, the hydrophilic polymer [1] was dissolved and suspended in the developer to give a milky white solution. The solubility of the hydrophilic polymer [1] in water containing the surfactant (developing solution used for development in this example) was 9
%Met.

Example 11 In Example 6, a styrene-butadiene-styrene block copolymer (Kraton 1101 Shell Petrochemical Co., Ltd.) was used in place of the chlorinated polyethylene, and lauric acid diethanolamide (Pionine D- was used as an image liquid. 95
A relief pattern was obtained in the same manner as in Example 6 except that 1-P Takemoto Yushi Co., Ltd. was used. As a result, a negative film image was faithfully reproduced and a relief having excellent ink-receiving transferability was obtained. It was The water absorption of the obtained relief was 0.6%, which shows that the relief has high durability to water-based ink. 2 parts of the dried hydrophilic polymer used in this example was immersed in 98 parts of the developer used for the development of this example, and 2
After gently stirring at 5 ° C. for 1 hour, the hydrophilic polymer used in this example was dissolved in the developing solution. The solubility of this hydrophilic polymer in water containing the surfactant (the developer used for the development in this example) was 13%.

Example 12 Instead of chlorinated polyethylene in Example 6, epichlorohydrin rubber (Epichromer H Osaka Soda Co., Ltd.) was used.
Was used, and a relief pattern was obtained in the same manner as in Example 6, except that potassium alkyl ether phosphate (Pionine A-73-DK, manufactured by Takemoto Yushi Co., Ltd.) was used as a developing solution. Was faithfully reproduced, and a relief having excellent ink receiving transferability was obtained. The water absorption of the obtained relief was 0.6%, which shows that the relief has high durability to water-based ink. 2 parts of the dried hydrophilic polymer used in this example was immersed in 98 parts of the developing solution used in the development of this example, and gently stirred at 25 ° C. for 1 hour to find that the hydrophilic polymer used in this example Dissolved in the developer. The solubility of this hydrophilic polymer in water containing the surfactant (the developer used for the development in this example) was 15%.

Example 13 Instead of the hydrophilic polymer [2] in Example 2, sodium chloride carboxyl group-containing styrene butadiene (SN
-307 A relief pattern was obtained in the same manner as in Example 2 except that Sumitomo Nogatac Co., Ltd. was used. As a result, a negative film image was faithfully reproduced and a relief having excellent ink-receiving transferability was obtained. It was The water absorption of the obtained relief is 0.7%, which shows that the relief has high durability to water-based ink. 2 parts of the dried hydrophilic polymer used in this example was immersed in 98 parts of the developing solution used in the development of this example, and gently stirred at 25 ° C. for 1 hour to find that the hydrophilic polymer used in this example Dissolved in the developer. In addition,
The solubility of this hydrophilic polymer in water was 0.9%, and the solubility in water containing a surfactant (developing solution used for development in this example) was 5%.

Comparative Example 1 A relief pattern was obtained in the same manner as in Example 1 except that 17.0 parts of aluminum acetate was used in place of 4.8 parts of lithium hydroxide in the hydrophilic polymer [1] of Example 1. As a result, the relief depth obtained was 0.1 mm.
It was not suitable for use as a printing plate. When 2 parts of the hydrophilic polymer used in this comparative example was dipped in 98 parts of the developing solution used in the developing solution of this comparative example and gently stirred at 25 ° C. for 1 hour, the hydrophilic polymer used in this comparative example swelled. However, it was found that this hydrophilic polymer did not dissolve or disperse in the developer of this comparative example. The solubility of this hydrophilic polymer in water is 0.2.
%, The solubility in water containing a surfactant (the developer used for the development in this example) was 1.8%.

COMPARATIVE EXAMPLE 2 In place of sodium carboxy group-containing styrene-butadiene in Example 13, 2 parts of water and 0.03 part of zinc acetate were previously added to 10 parts of sodium chloride-carboxyl group-containing styrene butadiene, and the mixture was heated at 110 ° C. for 1 hour. A relief pattern was obtained in the same manner as in Example 13 except that the mixture was used, and the relief depth obtained was 0.
It was 2 mm and was not suitable for use as a printing plate. When 2 parts of the hydrophilic polymer used in this comparative example was dipped in 98 parts of the developing solution used in the developing solution of this comparative example and gently stirred at 25 ° C. for 1 hour, the hydrophilic polymer used in this comparative example swelled. However, it was found that this hydrophilic polymer did not dissolve or disperse in the developer of this comparative example. The solubility of this hydrophilic polymer in water was 0.4%, and the solubility in water containing a surfactant (developing solution used for development in this example) was 1.8%.

Comparative Example 3 Instead of the hydrophilic polymer [1] in Example 1, sodium carboxymethyl cellulose (serogen F-SA was used.
Relief patterns were obtained in the same manner as in Example 1 except that Daiichi Kogyo Seiyaku Co., Ltd. was used. As a result, a negative film image was faithfully reproduced and a relief having excellent ink-receiving transferability was obtained. . The water absorption of the obtained relief is 1
It was 0.4%, and it was expected that the relief would swell and soften, resulting in poor durability against water-based ink. 2 parts of the dried hydrophilic polymer used in this example was immersed in 98 parts of the developing solution used in the development of this example, and gently stirred at 25 ° C. for 1 hour to find that the hydrophilic polymer used in this example Dissolved in the developer. The solubility of this hydrophilic polymer in water was 20% or more.

[0044]

EFFECTS OF THE INVENTION The photosensitive resin composition of the present invention having the above constitution is characterized in that it can be developed with water and has high durability against water-based ink. Further, the developing speed is fast and the image reproducibility is excellent. Further, the amount of scum generated by the resin flowing out into the developer coagulating is small, and the problem that the scum adheres to the developed printing plate and the image is disturbed during printing can be suppressed. Further, since the photosensitive resin plate of the present invention can be developed in an aqueous system, it is also a great advantage that the waste liquid of the developer can be easily treated by known waste liquid treatment techniques such as pH adjustment, addition of an adsorbent or a coagulant, and microbial treatment. It is one of the most important and contributes to the industrial world.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shinichi Tanaka 2-1-1 Katata, Otsu City, Shiga Toyobo Co., Ltd. (72) Inventor, Satoshi Taniyama 2-1-1 Katata, Otsu City, Shiga Prefecture No. Toyobo Co., Ltd.

Claims (1)

[Claims] 1. A photosensitive resin composition containing a hydrophobic component and a hydrophilic component, wherein the hydrophilic component has a solubility of 2% or less in water and a solubility of 2 in water containing a surfactant. % Or more, the photosensitive resin composition.