JP2000056473A - Developing solution for printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable development without coagulating a polymer even in the case of high solution temperature by incorporating a surfactant having at least one of alkyl and aryl groups having a specified carbon number or more. SOLUTION: The photosensitive resin composition which constitutes the photosensitive layer and used for the printing plate contains a water-soluble or water-swellable polyamide having polyether segments in a molecular chain, and the developing solution for the printing plate contains the surfactant having at least one of a >=12C alkyl or aryl group, and a surfactant having only a <12C alkyl group cannot attain a sufficient coagulation preventive effect, thus permitting coagulation of a polymer to be prevented and coagulation products to be perfectly eliminated.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a developer for a printing plate at the time of plate making of a photosensitive resin printing plate material.

[0002]

2. Description of the Related Art A photosensitive resin composition is generally used as a printing plate, and has become mainstream in relief printing, planographic printing and intaglio printing.

[0003] In such a printing plate, a negative or positive original film is brought into close contact with the photosensitive layer, and an actinic ray is irradiated through the original film to form a portion that is soluble in a solvent and a portion that is not dissolved in the photosensitive layer. Thus, a relief image is formed and used as a printing plate.

A photosensitive resin composition for a printing plate using such a method is generally composed of a polymer, an ethylenically unsaturated compound, and a photopolymerization initiator. Most of printing plates currently mainly used can be developed with water, and therefore, a water-soluble or water-swellable polymer is used as a polymer. As these polymers, those using partially saponified polyvinyl acetate and derivatives thereof, and those obtained by introducing a hydrophilic component into polyamide have been proposed.

A photosensitive resin printing plate material containing a partially saponified polyvinyl acetate derivative (Japanese Patent Publication No. 63-48327) as a polymer component, and a photosensitive resin containing a piperazine-based polyamide (Japanese Patent Publication No. 54-22229). When developing a printing plate material or a photosensitive resin printing plate material containing a polyamide having a polyether segment in a molecular chain (Japanese Patent Publication No. 59-50051), the polymer in the unexposed portion is dissolved in a developer or Distributed. However,
When the temperature of the developer is increased, particularly in a photosensitive resin printing plate material containing a polyamide having a polyether segment in a molecular chain as a polymer component, the polymer component is extremely strongly agglomerated, and the developer is agglomerated and transparent. Separate from the supernatant. This massive agglomerate has a problem that it has tackiness and adheres to the bottom surface of the developing device or the entire surface of the developing brush, so that development cannot be performed. As a method of suppressing the occurrence of scum polymer in the developer is caused by aggregation (aggregates), water -SO ₃ M (M is a monovalent metal atom, a divalent metal atom, 3
Represents either a valence metal atom or an ammonium compound)
A method using a developing solution to which a group-containing hydrocarbon compound having 11 or less carbon atoms is added (Japanese Patent Application Laid-Open No. Hei 7-234523) has been proposed.

[0006]

However, in the above-mentioned method, the amount of agglomerates is reduced, but it is not completely eliminated. In addition, a photosensitive material containing a polyamide containing a polyether segment in a molecular chain as a polymer component is used. During development of the resin printing plate material, no effect was observed in preventing a lump of polymer aggregates characteristically observed when the developer temperature was high.

[0007] Accordingly, the present invention provides a printing method in which a photosensitive resin composition can be developed in a developing solution of a photosensitive resin printing plate material containing a water-soluble or water-swellable polyamide at a liquid temperature of 50 ° C or less without polymer aggregation. An object of the present invention is to provide a plate developer.

[0008]

Means for Solving the Problems In order to solve the above problems, the present invention mainly has the following constitutions:
"A photosensitive resin printing plate material, wherein the photosensitive resin composition constituting the photosensitive layer contains a water-soluble or water-swellable polyamide, and the water-soluble or water-swellable polyamide is a polyamide having a polyether segment in a molecular chain. Wherein the developer contains a surfactant having at least one of an alkyl group and an allyl group having 12 or more carbon atoms. "

[0009]

Embodiments of the present invention will be described below.

The surfactant used in the present invention has 12 carbon atoms.
It has at least one of the above alkyl groups or allyl groups. A surfactant having only an alkyl group having less than 12 carbon atoms cannot provide a sufficient aggregation-preventing effect.

[0011] As such a surfactant, specifically,
Aliphatic carboxylate such as sodium laurate and sodium oleate; higher alcohol sulfate such as sodium lauryl sulfate, sodium cetyl sulfate and sodium oleyl sulfate; polyoxyethylene such as sodium polyoxyethylene lauryl ether sulfate Alkyl ether sulfates, sodium polyoxyethylene octyl phenyl ether sulfate, sodium polyoxyethylene nonyl phenyl ether sulfate, etc.Polyoxyethylene alkyl allyl ether sulfates, alkyl diphenyl ether disulfonate, alkyls such as sodium dodecyl sulfonate Sulfonate, alkyl disulfonate, sodium dodecylbenzene sulfonate,
Alkyl allyl sulfonates such as sodium dibutylnaphthalenesulfonate and sodium triisopropylnaphthalenesulfonate; higher alcohol phosphates such as monosodium lauryl phosphate disodium, sodium lauryl phosphate diester; polyoxyethylene lauryl ether monophosphate Examples thereof include polyoxyethylene alkyl ether phosphate salts such as disodium ester and sodium polyoxyethylene lauryl ether phosphate, and these can be used in combination. In addition, although the sodium salt was mentioned as a specific example, it is not specifically limited.

It is preferable that the surfactant used in the present invention further contains polyoxyethylene. In this case, the number of moles of ethylene oxide added is preferably 20 or less, more preferably 5 or less. Within this range, polymer aggregation can be effectively prevented. In addition, a surfactant having an alkyl group is preferable because the effect of preventing aggregation is particularly high when the alkyl group is a dodecyl group.

The amount of the surfactant to be added to the developer in the present invention is preferably 0.0
It is 1 to 15 parts by weight, more preferably 0.01 to 10 parts by weight. When the amount is 0.01 part by weight or more, the effect of the addition of the surfactant can be exhibited, and when the amount is 15 parts by weight or less, the effect does not saturate with an increase in the added amount.

For the purpose of suppressing foaming during development, in addition to a surfactant, a lower alcohol-based antifoaming agent such as methanol, ethanol and isopropanol, amyl alcohol, diisobutylcarbinol, olein Acid, tall oil, sorbitan lauric acid monoester, sorbitan oleic acid monoester, sorbitan oleic acid triester, pluronic nonionic surfactant, organic polar compound-based defoamer such as polyalkylene glycol, polyalkylene glycol derivative, silicone It is preferable to add a small amount of a silicone resin-based defoaming agent such as a resin, a surfactant compound of a silicone resin, and an inorganic powder compound of a silicone resin. 0.01 as the addition amount
-10% by weight is preferred.

The photosensitive resin composition developed by these developing solutions generally contains a polymer component, an ethylenically unsaturated compound, and a photopolymerization initiator. In the present invention, the polymer component preferably contains a water-soluble or water-swellable polyamide. The water-soluble or water-swellable polyamide in the present invention is a polyamide that is dissolved or dispersed in water when immersed in water at 25 ° C. for 24 hours. Among such polyamides, it is preferable to use a polyamide containing a polyether segment in the molecular chain, since the effect of the present invention is remarkably exhibited. Specifically, (A) polyoxyethylene diamine or polyoxyethylene dicarboxylic acid and (B) oxalic acid,
Aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandionic acid, dodecandionic acid, diglycolic acid, or ethylenediamine, trimethylenediamine, tetramethylenediamine, Copolyamide containing units derived from aliphatic diamines such as hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine as main constituent units Is mentioned.

The number average molecular weight of the polyether segment of polyoxyethylene diamine or polyoxyethylene dicarboxylic acid is preferably from 150 to 1500. Further, (A) and (B) contained in the copolymerized polyamide
Is preferably in the range of 30 to 70% by weight.

The amide group-forming copolymerizable component which can be copolymerized with the structural unit composed of the above (A) and (B) is not particularly limited, and known components such as ε-caprolactam, ω-laurolactam, 6-aminocaproic acid And lactams such as 11-aminoundecanoic acid and 12-aminododecanoic acid, and components selected from amino acids and salts derived from combinations of the above-mentioned aliphatic, alicyclic, aromatic diamines and dicarboxylic acids.

Further, it is also possible to use a mixture of the above-mentioned polymer and another type of polymer. Polymers to be mixed include polybutadiene, acrylonitrile rubber,
Butadiene-acrylonitrile copolymer, butadiene-
Styrene copolymer, isoprene-styrene copolymer, cellulose derivative, polyester resin, silicone rubber,
Acrylic resins, polyurethane resins, epoxy resins, polystyrene, polypropylene, polyethylene, chlorinated polyethylene, polyvinyl chloride, partially saponified polyvinyl acetate, and copolymers of these are commonly used in photosensitive resin compositions. No.

As the ethylenically unsaturated compound, generally known compounds are used. Specific examples include the following, but are not limited thereto.

2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2
-Hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, β-
(Meth) acrylates having a hydroxyl group such as hydroxy-β '-(meth) acryloyloxyethyl phthalate;
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth)
Acrylate, isoamyl (meth) acrylate, 2-
Alkyl (meth) acrylates such as ethylhexyl (meth) acrylate, lauryl (meth) acrylate and stearyl (meth) acrylate; cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate; chloroethyl (meth) acrylate; chloropropyl (meth) Halogenated alkyl (meth) acrylates such as acrylates, alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, phenoxyethyl acrylate, nonylphenoxyethyl (meth) Phenoxyalkyl (meth) acrylates such as acrylates, ethoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth ) Acrylate, methoxy dipropylene gray call (meth) alkoxy alkylene glycol acrylates such as (meth) acrylates, (meth)
Acrylamide, diacetone (meth) acrylamide,
(Meth) acrylamides such as N, N'-methylenebis (meth) acrylamide, 2,2-dimethylaminoethyl (meth) acrylate, 2,2-diethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl ( Compounds having only one ethylenically unsaturated bond such as meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate Poly (ethylene glycol) di (meth) acrylate such as diethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate such as dipropylene glycol di (meth) acrylate, trimellilol propane tri (meth) acrylate Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, glycerol tri (meth) acrylate, ethylene glycol diglycidyl ether, ethylenically unsaturated bonds such as unsaturated carboxylic acids and unsaturated alcohols and active hydrogen Obtained by subjecting an unsaturated epoxy compound such as polyvalent (meth) acrylate or glycidyl (meth) acrylate obtained by an addition reaction to a compound having an active hydrogen and a compound having active hydrogen such as carboxylic acid or amine to an addition reaction Polyvalent (meth) acrylamides such as (meth) acrylate, methylenebis (meth) acrylamide,
Compounds having two or more ethylenically unsaturated bonds, such as polyvalent vinyl compounds such as divinylbenzene, and the like.

In general, a photopolymerization initiator is added to the photosensitive resin composition. Any photopolymerization initiator can be used as long as it can polymerize a polymerizable carbon-carbon unsaturated group by light. Among them, those having a function of generating radicals by self-decomposition or hydrogen abstraction by light absorption are preferably used. For example, there are benzoin alkyl ethers, benzophenones, anthraquinones, benzyls, acetophenones, diacetyls and the like.

Ethylene glycol, diethylene glycol, triethylene glycol, glycerin, and so forth are used as compatibilizers for enhancing compatibility and flexibility in the photosensitive resin composition.
It is also possible to add polyhydric alcohols such as trimethylolpropane and trimethylolethane.

In order to increase the thermal stability of the photosensitive resin composition, a known polymerization inhibitor can be added. Preferred polymerization inhibitors include phenols, hydroquinones, catechols and the like.

As other components, dyes, pigments, surfactants, ultraviolet absorbers, fragrances and the like can be added.

In the usual production of a photosensitive resin printing plate material comprising these components, a polymer component is heated and dissolved in a water / alcohol mixed solvent, and then an ethylenically unsaturated compound, a photopolymerization initiator and a photosensitizer, A thermal polymerization inhibitor and the like are added, and the mixture is sufficiently mixed by stirring. Thus, a photosensitive resin solution is obtained. After distilling off the solvent from this solution, melt-extrude onto a substrate coated with an adhesive, and bring a cover film coated with an anti-adhesion layer into close contact with the photosensitive layer to obtain a photosensitive resin plate material for a printing plate. be able to. Further, a photosensitive resin sheet is prepared by dry film formation, and the photosensitive resin sheet is sandwiched between the substrate and the cover film to obtain a photosensitive resin plate material for a printing plate. As the substrate, a metal such as steel, stainless steel or aluminum, a plastic sheet such as polyester, or a synthetic rubber sheet such as styrene-butadiene rubber is used.

In order to form a relief image for printing using the above photosensitive resin printing plate material, first, a negative or positive original image film is brought into close contact with the photosensitive layer from which the cover film has been peeled off, and usually 300 to 300 μm. Ultraviolet irradiation is performed by a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a xenon lamp, a carbon arc lamp, a chemical lamp, or the like that can emit a wavelength of 400 nm, and photocuring is performed by photopolymerization. Next, a relief image is formed on the substrate by a brush-type developing device in which the photosensitive resin printing plate material is immersed in a developer and the unpolymerized portion is rubbed off with a brush and removed. The liquid temperature during development is preferably from 10C to 50C. If you need this,
After drying, the printing plate can be obtained by performing an actinic ray treatment in the air or in a vacuum.

[0027]

The present invention will be described below in detail with reference to examples.

(Synthesis Example) Acrylonitrile was added to both ends of polyethylene glycol having a number average molecular weight of 600,
This was hydrogen reduced to obtain 60 parts by weight of equimolar salt of α, ω-diaminopolyoxyethylene and adipic acid, 20 parts by weight of ε-caprolactam, and 20 parts by weight of equimolar salt of hexamethylenediamine and adipic acid. Melt polymerization is carried out under normal conditions and the relative viscosity (1 g of polymer is chloral hydrate 100
(measured at 25 ° C.) to give a polyamide having a ratio of 2.50.

Example 1 Polyamide 50 obtained in the above synthesis example as a polymer component
Parts by weight, an addition reaction product 30 of 1 mol of glycidyl methacrylate as an ethylenically unsaturated compound and 1 mol of acrylic acid
Parts by weight, propylene glycol diglycidyl ether 1
15 parts by weight of an addition reaction product of 2 moles of acrylic acid and 2 moles of acrylic acid, 5 parts by weight of diethylene glycol as a compatibility aid, 1 part by weight of dimethylbenzyl ketal as a photopolymerization initiator, and 0.01 part by weight of hydroquinone monomethyl ether as a polymerization inhibitor Water / ethanol comprising the photosensitive resin composition of
After casting a 30/70 (weight ratio) mixed solution on a 0.25 mm thick polyester film coated with an adhesive,
Dried at 50 ° C. A mixture of water / ethanol = 50/50 (weight ratio) is thinly applied on the photosensitive layer thus obtained, and a cover film having an anti-adhesion layer is pressed on a matted 100 μm polyester film. Then, a cover film was attached to obtain a photosensitive resin printing plate material.

A gray scale negative film for sensitivity measurement and a negative film for evaluating image reproducibility (having 3% halftone dot of 133 lines and having an independent point of 200 μm) were brought into vacuum contact with this photosensitive resin printing plate material by an ultrahigh pressure mercury lamp. For 1.5 minutes. Next, a 30% by weight aqueous solution of lauryl alcohol sulfate sodium salt was added to 100 parts by weight of neutral water.
0 parts by weight, and further added a defoaming agent "Nopco" 8034 (manufactured by San Nopco Co., Ltd.) to this solution at a ratio of 0.1 part by weight to 100 parts by weight of the neutral water. It was placed in a brush developing device and heated to 50 ° C. for development to obtain a relief image. As a result of visually observing the developing solution in the developing device, it was confirmed that the developing solution was a cloudy liquid and there was no deposit on the developing device and the developing brush. As a result of evaluating the obtained relief image, the gray scale was 17 steps,
It was found that 3% halftone dots and 200 μm independent points in the image area were reproduced.

Example 2 A 30% by weight aqueous solution of oleyl alcohol sulfate was dissolved in 10 parts by weight of 100 parts by weight of neutral water, and an antifoaming agent "Nopco" 8034 (manufactured by San Nopco) was added to the solution. Then, development was carried out in the same manner as in Example 1 except that a developing solution added at a ratio of 0.1 part by weight to 100 parts by weight of the neutral water was heated to 50 ° C. As a result of visually observing the developing solution in the developing device, it was confirmed that the developing solution was a cloudy solution and there was no deposit on the developing device or the developing brush. As a result of evaluating the obtained relief image, the gray scale was 17
This is a step, and it was found that 3% halftone dots and 200 μm independent points of the image area were reproduced.

Example 3 3.0 parts by weight of a 40% by weight aqueous solution of polyoxyethylene nonyl phenyl ether sulfate (ethylene oxide addition mole number: 6) was dissolved in 100 parts by weight of neutral water, and an antifoaming agent was added. Nopco 8034 (San Nopco Co., Ltd.)
Was added to this solution at a ratio of 0.1 part by weight to 100 parts by weight of the neutral water, and a developing solution was heated in the same manner as in Example 1 except that the developing solution was heated to 50 ° C. . As a result of visually observing the developing solution in the developing device, it was confirmed that the developing solution was a cloudy solution and there was no deposit on the developing device or the developing brush. As a result of evaluating the obtained relief image, the gray scale was 17 steps, 3% of the image area, 20%.
It was found that the 0 μm independent point was reproduced.

Comparative Example 1 Development was carried out in the same manner as in Example 1, except that only neutral water at 40 ° C. was used as a developer. The developing solution was separated into a lump aggregate and a supernatant, and the sticky lump aggregate adhered to the bottom surface of the developing device and the developing brush. As a result of evaluating the obtained relief image, defective development was recognized.

Comparative Example 2 40% by weight of 2-ethylhexyl ether sulfate
The aqueous solution was dissolved in 10 parts by weight with respect to 100 parts by weight of neutral water, and the antifoaming agent “Nopco” 8034 (San Nopco Co.
Was added to this solution at a ratio of 0.1 part by weight with respect to 100 parts by weight of the neutral water, and a developing solution was heated in the same manner as in Example 1 except that the developing solution was heated to 40 ° C. . The developing solution was separated into a lump aggregate and a supernatant, and the sticky lump aggregate adhered to the bottom surface of the developing device and the developing brush. As a result of evaluating the obtained relief image, defective development was recognized.

Comparative Example 3 A 35% by weight aqueous solution of polyoxyethylene dodecyl ether sulfate (the number of moles of ethylene oxide added: 30) was dissolved in 10 parts by weight with respect to 100 parts by weight of neutral water, and an antifoaming agent "Nopco" 8034 was further added. (San Nopco Co., Ltd.) was added to this solution at a rate of 0.1 part by weight with respect to 100 parts by weight of the neutral water, and a developing solution was heated to 40 ° C. in the same manner as in Example 1. Was developed. The developing solution was separated into a lump aggregate and a supernatant, and the adhesive aggregate adhered to the entire surface of the developing device bottom and the developing brush. As a result of evaluating the obtained relief image, defective development was recognized.

Comparative Example 4 In place of the polyamide obtained in the synthesis example, a copolymerized polyamide obtained by polycondensing 1 mol of ε-caprolactam and 9 mol of a nylon salt of N- (2-aminoethyl) piperazine and adipic acid was used. A photosensitive resin printing plate material was obtained in the same manner as in Example 1 except for using.

This photosensitive resin printing plate material was developed in the same manner as in Example 1. As a result of visually checking the developing solution in the developing device, aggregates were found in the developing solution, and sticky aggregates were attached to the developing brush.

[0038]

As described above, in the development of a photosensitive resin printing plate material containing a water-soluble or water-swellable polyamide, the photosensitive resin composition constituting the photosensitive layer is preferably an alkyl having 12 or more carbon atoms according to the present invention. By using a developer containing a surfactant having at least one of a group and an allyl group, polymer aggregation can be prevented and aggregates can be completely eliminated.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H025 AB02 AC01 AD01 BC31 CB24 CB53 CB55 FA17 2H096 AA02 BA05 BA20 EA02 GA08 GA10 GA11

Claims (5)

[Claims] 1. A photosensitive resin composition comprising a photosensitive layer comprising a water-soluble or water-swellable polyamide, wherein the water-soluble or water-swellable polyamide is a polyamide having a polyether segment in a molecular chain. A developing solution for a printing plate, wherein the developing solution contains a surfactant having at least one of an alkyl group and an allyl group having 12 or more carbon atoms. 2. A photosensitive resin composition constituting a photosensitive layer contains a water-soluble or water-swellable polyamide, and the water-soluble or water-swellable polyamide has (A) an amino group or a carboxyl group at a terminal. A photosensitive polyamide which is a copolymer polyamide containing 30 to 70% by weight of a structural unit composed of polyoxyethylene having a number average molecular weight of a polyether segment portion of 150 to 1500 and (B) an aliphatic dicarboxylic acid or a diamine. In the developer of resin printing plate material,
A developer for a printing plate, wherein the developer contains a surfactant having at least one of an alkyl group and an allyl group having 12 or more carbon atoms. 3. The printing plate according to claim 1, wherein the surfactant is an anionic surfactant containing polyoxyethylene and having an ethylene oxide addition mole number of 20 or less. Developer. 4. The printing plate developer according to claim 1, wherein the developer contains an antifoaming agent. 5. The printing plate developer according to claim 1, wherein the surfactant is added in an amount of 0.01 to 15 parts by weight based on 100 parts by weight of the neutral water. .