JPH07333861A - Treatment method and treatment apparatus of wash out liquid for photosensitive resin plate - Google Patents

Abstract

PURPOSE:To maintain a wash-out liquid clean at all times and to make stable wash-out operations of many sheets of the photosensitive resin plates over a long period of time possible without discarding the wash-out liquid. CONSTITUTION:This treatment method of the wash-out liquid of the photosensitive resin plates comprises treating the wash-out liquid. contg. the resins generated in a method of developing the photosensitive resin plates by rubbing out the unexposed parts while immersing the resin plates into the wash-out liquid after exposure. The wash-out liquid 11 contg. the resins are filtered by a filter 13 and the filtrate thereof is reused as the wash-out liquid in this method. On the other hand, the filter 13 clogged by the resins is successively irradiated with light to cure the resins sticking to the filter 13 and thereafter, the resins are stripped from the filter and the filter is reused. This treatment apparatus of the wash-out liquid for the photosensitive resin plates is constituted to filter the wash-out liquid 11 for the photosensitive resin plates with the filter 13 to remove the resins therefrom and to reuse the filtrate as the wash-out liquid. The apparatus described above is provided with a photoirradiation section 7 for curing the resins and a stripping section 8 for the cured resins.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a processing method and a processing apparatus for a wash-out solution generated when developing a photosensitive resin plate, and in particular, it is generated by a method of scraping an unexposed area while developing it while immersing it in the wash-out solution. And a device for removing the dispersed resin from the resin-containing washout solution and reusing the washout solution. More specifically, by filtering a wash-out liquid containing unexposed resin in a dispersed state generated in the wash-out process of the photosensitive resin with a filter, the resin is efficiently removed from the wash-out liquid, and the filter clogged with the resin is removed. Sequentially irradiate light to cure the resin adhering to the filter, peel off the resin and reuse it as a filter, and reuse the filtered wash-out solution for wash-out to always clean the wash-out solution. The present invention relates to a method for treating a wash-out liquid of a photosensitive resin plate and an apparatus therefor, which enables stable washing out of a large number of photosensitive resin plates for a long period of time without discarding the wash-out liquid.

[0002]

2. Description of the Related Art A printing plate using a photosensitive resin is excellent in operability, productivity, economy and printing characteristics as compared with a conventional printing plate, and has recently been rapidly spread in various printing fields. As a method of developing such a photosensitive resin plate, a method of forming a relief by blowing off the unexposed portion by using compressed air or a method of spraying a washout liquid onto a print at a constant pressure or a washout liquid is used. A method has been invented and put to practical use in which a plate is dipped and an unexposed portion is washed out with a brush or the like and rubbed into a liquid.

[0003]

In the developing method as described above, the wash-out liquid for the photosensitive resin plate exists in a state in which the resin of the unexposed portion washed out after the wash-out is dispersed,
When a large number of photosensitive resin plates are washed out, the concentration of the resin in the washout liquid increases, and as a result, the washout speed decreases, and the dispersed resin agglomerates to form scum that adheres to the plate or brush. Therefore, it was necessary to frequently discard the used wash-out solution and prepare a new wash-out solution.

Therefore, this method is not only disadvantageous in terms of cost, but also causes a large amount of waste in terms of the environment, because the treatment cost of a large amount of waste liquid of the washing liquid and the cost of a new washing liquid are large. There was a big problem. In order to solve these problems, several methods have been proposed in which the dispersed resin is removed from the resin-containing washing liquid and the washing liquid is reused. For example, install a cartridge filter in the circulation system of the washout liquid to remove scum, and further remove a part of the washout liquid during the washout or the whole amount after the washout is completed and leave it to stand to disperse and disperse the dispersed resin. , A method of reusing the supernatant as a washout solution (JP-A-4-185363), or a method of adding a coagulant to the washout solution after completion of the washout to remove the resin by aggregating and then reusing the washout solution. is there.

However, the cartridge filter only removes the scum generated by agglomeration, and it takes a long time to remove the dispersed particles by coagulation and sedimentation by standing still, and a large amount of the photosensitive resin plate is continuously applied. It was not suitable for washing out. Further, when a coagulant is added to the wash-out liquid, the regenerated wash-out liquid also contains the coagulant, which causes problems such as a decrease in the wash-out speed and a tendency to generate scum, which is not suitable for practical use. . There is also a method of filtering the washout liquid with a filter whose pore size is smaller than the particle size of the dispersed resin, but the filter is clogged with the resin immediately, and even if the filter is washed because the resin is sticky The resin did not come off and was not put to practical use.

[0006]

The present inventors have diligently studied a method for treating a washout liquid containing a resin in an unexposed portion of a photosensitive resin plate in a dispersed state for the purpose of improving the present state of the art. As a result, the wash-out liquid containing the resin was filtered with a filter, and the filter clogged with the resin was irradiated with light to cure the resin adhering to the filter, and then the resin was peeled off and reused as a filter. By reusing it as a wash-out liquid, we have always found that the wash-out liquid can be kept clean, and it is possible to stably wash out a large number of photosensitive resin plates for a long time without discarding the wash-out liquid. The invention was completed.

That is, the present invention relates to a method for treating a wash-out solution containing a resin generated by a method of exposing a photosensitive resin plate to light and immersing it in a wash-out solution and then scraping off an unexposed portion to develop the resin. The wash-out liquid containing is filtered with a filter, and the filtrate is reused as a wash-out liquid,
On the other hand, a filter clogged with a resin is treated by irradiating light sequentially to cure the resin adhering to the filter, then peeling off the resin and reusing it. is there.

Further, according to the present invention, in a treatment device for a wash-out liquid of a photosensitive resin plate, the resin is removed by filtering the wash-out liquid of the photosensitive resin plate with a filter, and the filtrate is reused as a wash-out liquid. The apparatus for treating a wash-out liquid of a photosensitive resin plate is provided with a light irradiation section for curing and a stripping section for the cured resin.

As the photosensitive resin plate used in the present invention, a solvent-developable photosensitive resin plate which uses a solvent such as a CFC solvent, a chlorine solvent, a petroleum solvent or an alcohol solvent as a washout solution can be used. From the viewpoint of environment and local environment, water, surfactant aqueous solution, alkaline aqueous solution,
A water-developable photosensitive resin plate using an aqueous acid solution as a washout solution is preferable.

As such a water-developable photosensitive resin composition, a polyamide-based photosensitive resin composition containing polyamide as an essential component, a polyvinyl alcohol-based photosensitive resin composition containing polyvinyl alcohol as an essential component, and a low-molecular unsaturated group A polyester-based photosensitive resin composition containing a contained polyester as an essential component, an acrylic photosensitive resin composition containing an acrylic low-molecular monomer as an essential component, and a polyurethane-based photosensitive resin composition containing polyurethane as an essential component. To be These photosensitive resin compositions impart photosensitivity by adding a photopolymerizable unsaturated monomer, a photosensitizer, and the like.

Recently, also in a photosensitive flexographic plate,
From the viewpoint of toxicity and safety, those which can be developed in an aqueous washout solution have been proposed, and these are also preferably used as the photosensitive resin plate of the present invention. 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 monoolefinic unsaturated compound therein and a photopolymerizable unsaturated monomer, Photosensitive resin composition containing a photosensitizer, conjugated diene hydrocarbon polymer or copolymer of conjugated diene hydrocarbon and monoolefin unsaturated compound, hydrophilic polymer compound, non-gaseous ethylenic compound A photosensitive elastomer composition containing an unsaturated compound and a photopolymerization initiator as essential components, a hydrophobic oligomer containing an α, β-ethylenically unsaturated group, an elastomer water-swelling substance, and a photoassembly initiator as essential components There is a photosensitive resin composition to be contained.

Further, a photosensitive resin composition containing hard organic fine particles for the purpose of improving the mechanical strength and impact resilience of the printing plate, water-developing property, water-based ink resistance, and printing. A photosensitive resin composition containing fine particles of a crosslinkable resin for the purpose of improving the property, and a two-phase structure for the purpose of improving the ink receptivity of a printing plate, containing a diazo compound and a dichromate in a continuous phase, There are photosensitive resin compositions containing particles having a dispersed phase of 10 μm or less, and any of them can be preferably used as the photosensitive resin composition of the present invention.

As described above, various types of photosensitive resin plates can be used in the present invention. As a method for imparting a hydrophilic component to a hydrophobic component, a hydrophobic polymer is modified with a carboxylic acid or a salt thereof. The main component is a resin, the main component is a mixture of a hydrophobic component having a hydrophobic polymer as a main component and the hydrophilic component having a hydrophilic polymer as a main component, and the hydrophobic polymer and the hydrophilic polymer are Chemically bonded ones as a main component, hydrophobic polymer raw material hydrophobic monomers and hydrophilic polymer raw hydrophilic block monomers as a main polymer, etc. As a particularly preferable example, a photosensitive flexographic plate of a dispersion type in an aqueous developer by combining a hydrophobic component with a hydrophilic component in some form is mentioned as a preferable example. It is.

The content of the present invention will be described in more detail below with reference to a flexographic plate of a water-developable photosensitive resin which is particularly preferably used as the photosensitive resin plate of the present invention.

First, the photosensitive resin plate will be described. Examples of the hydrophobic polymer used in the photosensitive flexographic plate particularly preferable in the present invention mentioned above include, for example, 1,4-polybutadiene, 1,2-polybutadiene, acrylonitrile rubber, butadiene acrylonitrile rubber, chloroprene rubber, and 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-
Polymers such as (meth) acrylic acid-acrylic ester copolymer, silicone rubber, polyoxypropylene glycol, polyoxytetramethylene glycol, etc. that impart rubber elasticity to the plate, polymethyl (meth) acrylate, polyethyl (meth) acrylate, poly Acrylic resins such as isopropyl (meth) acrylate and poly n-butyl (meth) acrylate, polystyrene, polypropylene, polyethylene, chlorinated polyethylene, polyacrylonitrile, polyvinyl chloride, polyvinyl acetate and copolymers thereof, polyurethane resin, polyester There may be mentioned polymers such as resins, polyamide resins and epoxy resins which impart hardness and stability to the plate, and these may be used alone or in combination of two or more as necessary. Further, these resins can be modified so that they can react with a monomer or a cross-linking agent or with each other.

As the hydrophilic polymer, for example, a polymer of poly (meth) acrylic acid or a salt thereof, (meth)
Acrylic acid or salts thereof-alkyl (meth) acrylate copolymer, (meth) acrylic acid or salts thereof-styrene copolymer, (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, polyethylene imine, -COOM group-containing polyurethane, -COOM group-containing polyurea urethane , -COO
Examples thereof include M group-containing polyester, -COOM group-containing epoxy compound, -COOM group-containing polyamic acid and salts and derivatives thereof (where M is a hydrogen atom, a monovalent metal atom or a divalent metal atom). Indicates either a trivalent metal atom or an ammonium compound). Similarly, hydrophilic components can be used alone or in combination, and may be modified as necessary.

As the raw material of the photosensitive resin composition, other than the above, a radical polymerizable monomer, a crosslinking agent, a photoreaction initiator,
If necessary, an oxidation stabilizer, a polymerization inhibitor and the like can be added to the above-mentioned polymers.

Examples of the radical polymerizable monomer include styrene, vinyltoluene, chlorostyrene, t-butylstyrene, α-methylstyrene, 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, 2,3-dichloropropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, N, N-diethylamino Ethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, Nt-butylaminoethyl (meth) acrylate, acrylamide, N, N
-Dimethyl acrylamide, N, N-diethyl acrylamide, and the like.

Examples of the crosslinking 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 allyloxy ( (Meth) acrylate, 1,1,1-trishydroxymethylethanedi (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 isocyanate Nulate, triallyl trimellitate, diallyl terephthalate, diallyl phthalate, divinylbenzene, polyurethane (meth)
Examples include compounds having two or more radically polymerizable ethylene groups in one molecule such as acrylate and polyester (meth) acrylate. In addition, ethylene group, epoxy group, isocyanate group, amino group in one molecule, A compound having a plurality of reactive functional groups such as a hydroxyl group and a carboxyl group is also included.

A preferred structure of such a photosensitive resin composition is a structure in which a hydrophobic component (polymer) is a particulate dispersed phase and a hydrophilic component (polymer) surrounds it to form a continuous phase, and a hydrophobic structure. A structure in which a core-shell particle in which a hydrophilic component (polymer) is a core and a hydrophilic component (polymer) is a shell, and another hydrophobic component (polymer) is a continuous phase,
A structure in which the hydrophilic component (polymer) is a particulate dispersed phase and the hydrophobic component (polymer) is a continuous phase, and both the hydrophobic component (polymer) and the hydrophilic component (polymer) are entwined with each other in the continuous phase Examples thereof include a mosaic structure and a structure in which a hydrophobic component (polymer) and a hydrophilic component (polymer) are uniformly compatible with each other. In these cases, it is necessary that the continuous phase is not crosslinked in the uncured state, but the particulate hydrophobic component may or may not be crosslinked in the uncured state.

The method for producing the photosensitive resin composition is as follows: the components of the dispersed phase obtained by emulsion polymerization or suspension polymerization or by crushing the polymer are mixed alone or together with the components of the continuous phase in a kneader or an extruder. ,
Molding method, hydrophobic component and hydrophilic component are kneaded in a kneader or an extruder in a kneading state and phase-separated and dispersed, and then a molding method, hydrophobic component and hydrophilic component are kneaded in a kneader or Various methods such as a method of kneading with an extruder and making them compatible with each other and then molding are used.

By appropriately selecting these raw materials and methods as necessary, a photosensitive resin composition can be produced in accordance with the physical properties and performance required of the plate. For example, the physical properties required for printing plates are JIS A
It is desirable in terms of printing characteristics that the hardness is 30 to 80 degrees and the impact resilience is 10 to 60%.

The photosensitive resin composition is cured by ultraviolet rays, and 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, the developing method of the photosensitive flexographic plate which is particularly preferably used in the present invention will be described. The photosensitive resin plate obtained as described above is subjected to image exposure by irradiating UV with a negative film having a transparent image under the above light source, and then fixing the photosensitive resin plate to a flat plate or a cylinder. While immersing in the washout solution or spraying the washout solution in a shower shape, a relief image is obtained by rubbing with a brush or the like if necessary to remove the non-image areas that are not exposed, while the uncured photosensitive resin removed Becomes an emulsion or suspension and remains in the washing tank.
The relief thus obtained, in which the cured portion has a convex shape, is dried and, if necessary, further exposed to ultraviolet rays for post-exposure to be used as a printing plate for printing.

Examples of the washout liquid include water alone, a surfactant aqueous solution, an inorganic or organic alkali, acid or salt aqueous solution, and an aqueous solution of a water-soluble compound. As the surfactant used in the washout liquid, anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants and the like can be widely used.

Specific examples of the anionic surfactant include aliphatic carboxylic acid salts such as sodium laurate, sodium stearate and sodium oleate, resin soaps such as sodium abietic acid and sodium rosinate, and sodium lauryl sulfate. And secondary alkylsulfates such as triethanolamine and lauryl sulfate, primary and secondary polyoxyethylene alkyl ethersulfates such as sodium polyoxyethylene lauryl ether sulfate and triethanolamine polyoxyethylene lauryl ether sulfate ,
Alkylbenzenesulfonates such as sodium laurylbenzenesulfonate and sodium stearylbenzenesulfonate, alkylnaphthalenesulfonates such as sodium propylnaphthalenesulfonate and sodium butylnaphthalenesulfonate, polyoxyethylene such as polyoxyethylene laurylphenyl ethersulfonate Ethylene alkyl phenyl ether sulfonates, sulfated oils such as sulfated castor oil and sulfated beef oil, sulfated fatty acid esters such as sulfated butyl oleate, alkyl sulfo succinates represented by dioctyl sodium succinate , Α
-Olefin sulfonates, hydroxyalkane sulfonates, N-methyl-N-alkyl taurine salts,
N-alkylsulfosuccinic acid monoamide salts, fatty acid monoglyceride sulfate ester salts, alkyl diphenyl ether disulfonate salts, alkyl phosphate salts such as lauryl alcohol phosphoric acid monoester disodium salt and lauryl alcohol phosphoric acid diester soda salt, polyoxyethylene lauryl ether phosphoric acid monoester Polyoxyethylene alkyl phosphate salts such as ester disodium salt and polyoxyethylene lauryl ether phosphate diester soda salt, naphthalene sulfonate formalin condensates, styrene-maleic anhydride copolymer partially saponified salts, olefin-anhydrous Examples thereof include salts of partially saponified maleic acid copolymers. As specific examples, sodium salts were mainly mentioned, but potassium salts, ammonium salts,
Magnesium salts, calcium salts and the like are also possible, and are not particularly limited to these.

The cationic surfactants include primary, secondary and tertiary amine salts such as monostearyl ammonium chloride, distearyl ammonium chloride and tristearyl ammonium chloride, stearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride and stearyl dimethyl benzyl. Quaternary ammonium salts such as ammonium chloride, alkylpyridinium salts such as N-cetylpyridinium chloride and N-stearylpyridinium chloride, N, N-dialkylmorpholinium salts, fatty acid amide salts of polyethylene polyamide, aminoethylethanolamine and stearic acid Acetates of urea compounds of amides with 2-alkyl-1-alkyl-1-hydroxyethylimidazo Such as benzalkonium chloride. In addition, although chloride was mainly mentioned as a specific example,
Bromide, alkyl sulphate, acetate and the like are also possible and are not particularly limited to these.

The nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether and polyoxyethylene lauryl ether, and polyoxyethylene alkylphenyl such as polyoxyethylene nonylphenyl ether and polyoxyethylene octylphenyl ether. Ethers, polyoxyethylene polyoxypropylene glycols, mono and diester acids of fatty acids such as polyethylene glycol monostearate, polyethylene glycol monooleate and polyethylene glycol dilaurate with polyethylene glycol, sorbitan monolaurate and sorbitan monooleate Esters of fatty acids and sorbitan, polyoxyethylene sorbitan monolaurate and polyoxyethylene sol Esters of fatty acid and sorbitan polyoxyethylene adducts such as tan monostearate and polyoxyethylene sorbitan trilaurate, esters of fatty acid and sorbit such as sorbit monopartitate and sorbit dilaurate, polyoxyethylene sorbit Esters of sorbitol polyoxyethylene adducts such as monostearate and polyoxyethylene sorbitiodiol with fatty acids, 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 alkanolamines such as lauric acid diethanolamide and lauric acid monoethanolamide, lauryl dimethyl ester Amine oxides such as Le amine oxides, aliphatic alkanol amines such as stearyl diethanolamine, polyoxyethylene alkyl amines, and triethanolamine fatty acid esters.

Examples of the amphoteric surfactants 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, stearyl dimethylsulfoethylene ammonium ethylene ammonium. Examples thereof include sulfobetaine-type amphoteric surfactants such as betaine, imidazolium betaine-type amphoteric surfactants, lecithin and the like.

Examples of inorganic or organic alkalis, acids, salts, and other water-soluble compounds include alkalis and salts such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, sulfuric acid and nitric acid. Acids such as, phosphoric acid, formic acid, acetic acid, oxalic acid, succinic acid, citric acid, maleic acid, paratoluenesulfonic acid, sodium carbonate, sodium hydrogen carbonate, sodium tripolyphosphate, potassium pyrophosphate, sodium silicate, sodium sulfate, chloride Salts of sodium, sodium borate, sodium acetate, magnesium acetate, sodium citrate, sodium succinate, etc., sodium benzenesulfonate, sodium toluenesulfonate, sodium xylenesulfonate, sodium styrenesulfonate, sodium phenol 2,4-disulfonate , Methylsul Sulfonates and salts of alkyl sulfates such as sodium phosphate, high molecular compounds such as carboxymethyl cellulose and methyl cellulose, and the like. In addition, in an aqueous solution of a surfactant, these alkalis, acids or salts, water-soluble compounds, other viscosity modifiers,
Various additives such as a dispersion stabilizer, an aggregating agent, and a zeolite can be added as necessary.

Further, even if it is a water-based washing liquid, ethanol, isopropanol, cellosolve,
Other organic solvents that dissolve in water, such as glycerin, polyethylene glycol, dimethylformamide, dimethylacetamide, and acetone, can be mixed. The pH of the washout solution is not particularly limited, but it is preferably in the range of 3 to 12 from the viewpoint of work safety.
The temperature during development is preferably 10 to 50 ° C.

In the present invention, the wash-out solution containing the resin in the unexposed area in a dispersed state, which is generated when the photosensitive resin plate is washed out in this way, is filtered by a filter, and the filters clogged with the resin are After irradiating light to cure the resin attached to the filter, the resin is peeled off and reused as a filter.

The filter used for filtration is a wire mesh,
Any material such as net, woven cloth, sintered body of metal or inorganic material, slit-shaped processed material, non-woven fabric, porous film, etc. can be used.However, in order to improve the efficiency of filtration, the pore size of the filter should be in the washing liquid. It is desirable that it is smaller than the average particle size of the dispersed resin particles. Further, since it is necessary to remove the resin attached after filtration, it is preferable that the filter is of a type capable of surface filtration.

When a filter having a small pore size is used, the resin clogs the filter relatively early, and it is necessary to remove the resin adhering to the filter.
Usually, the resin used for the photosensitive resin plate is soft and sticky when it is uncured, so that it is difficult to scrape it off with an ordinary backwash method or a scraper. Therefore, in the method of the present invention, the uncured resin adhering to the filter is irradiated with light to be cured so as to remove the tackiness and to facilitate the removal of the resin from the filter. The light to be irradiated has a wavelength of 150 to 500 nm, particularly 300 to 400 n, like the one used for curing the photosensitive resin plate.
A light source having a wavelength of m is effective, and a light source used is preferably a low pressure mercury lamp, a high pressure mercury lamp, a carbon arc lamp, an ultraviolet fluorescent lamp, a chemical lamp, a xenon lamp, or a zirconium lamp.

The resin adhered to the filter thus hardened is peeled off by backwashing or scraping, and the filter is used again for filtration.

Examples of the shape of the filter include Nutsche filter, cartridge filter, bag filter, leaf filter, drum filter, horizontal belt filter, centrifugal filter, hollow fiber filter, etc., as in general filtration methods. However, the filter is structurally easy to irradiate the filter blocked by the resin with light sequentially,
It is important in actual use that the cured resin is devised so that it can be peeled off. For this reason, it is preferable to use a drum filter or a horizontal belt filter having a structure in which the resin is peeled off with a scraper or the like while filtering on the one hand and a light irradiation portion is attached to the horizontal belt filter or the like.

The wash-out liquid from which the resin has been removed by the above method is reused as a wash-out liquid and is therefore returned to the wash-out tank. In addition, it is preferable that the thickness of the resin attached to the filter is thin in order for the attached resin to be sufficiently cured to the inside by light, and it is necessary to adjust the supply amount of the washout liquid and the filtration time so that the thickness is 2 mm or less. There is.

Further, the treatment of the wash-out liquid of the present invention is a batch treatment in which a plurality of photosensitive resin plates are washed out, the wash-out liquid is withdrawn from the wash-out tank, and after filtering the whole amount, the filtered wash-out liquid is supplied to the wash-out tank and reused. The method may also be a continuous treatment method in which a part of the washout liquid is withdrawn during the washout and immediately returned to the washout tank after the filtration treatment. In particular, when a large amount of photosensitive resin plate needs to be continuously washed out, the continuous processing method is preferable because it is not necessary to stop the workability and washing out.

Further, in order to explain the preferable method for treating the wash-out liquid of the photosensitive resin plate of the present invention shown above, a treatment device for the wash-out liquid of the photosensitive resin plate which can be used in the present invention is shown in FIG. 2 is specifically shown in the schematic view of FIG.

First, the processing apparatus of the present invention will be described with reference to FIG. The washout liquid 11 containing the uncured resin sent from the washout tank is supplied to the tank 2 through the washout liquid supply line 1. The washing liquid 11 is filtered by the drum filter 3, and the filtrate 12 stored inside the drum filter 3 is returned to the washing tank again by the pump 6 through the filtrate withdrawing lines 4 and 5 inserted inside from the rotary shaft of the drum. Be done. Further, the inside of the drum filter 3 is kept under reduced pressure by the pump 6 with respect to the outside. On the other hand, the drum filter 3 is slowly rotating clockwise, and the uncured resin 13 adhering to the surface of the drum filter 3 is pulled up from the washing liquid 11 in accordance with the rotation and is irradiated with ultraviolet rays by the lamp 7. Is cured. The cured resin is scraped off from the drum filter 3 by the scraper 8 and stored in the resin receiving box 10.
Further, as the drum rotates, the filter portion from which the resin has been scraped off is dipped in the tank 2 and filtration is performed again.

Next, a processing apparatus using a belt filter will be described with reference to FIG. The wash-out liquid 29 containing the uncured resin sent from the wash-out tank is supplied to the belt filter 19 of the filtering section through the wash-out liquid supply line 15. The filtrate 30 filtered by the belt filter 19 is stored in the filtrate receiver 25 and then returned to the washing tank by the pump 17 through the filtrate withdrawing lines 16 and 18. On the other hand, the belt filter 19 has two rollers 2
The uncured resin 31 is formed in a concave shape by 1 and slowly moves to the right according to the rotation of the driving roller 24. The uncured resin 31 adhered on the belt filter 19 is irradiated with ultraviolet rays from the lamp 26 and cured. To be done. The cured resin is scraped off from the belt filter 19 by the scraper 27 and stored in the resin receiving box 28. Further, as the belt filter 19 moves, the filter portion from which the resin has been scraped off is sent to the filtration portion and is again used for filtration.
In the treatment apparatus of FIG. 2, filtration is performed by gravity fall, but it is also possible to perform filtration under reduced pressure or pressure by attaching a header.

[0042]

EXAMPLES The present invention will be specifically described with reference to the following examples, but the present invention is not limited to these examples.

Production Example of Photosensitive Resin Plate (a) Hexamethylene diisocyanate 21.8 parts, dimethylol propionic acid 15.4 parts, polytetramethylene glycol 7.6 parts, and dilaurylate di-n-butyltin 1.0. A solution prepared by dissolving 300 parts of tetrahydrofuran in 300 parts of tetrahydrofuran was placed in 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 molecular weight of 21,000. Next, 100 parts of the polymer was mixed with 10 parts of methyl ethyl ketone.
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 in 0 part of the solution at room temperature with stirring, and further stirred for 30 minutes to obtain a hydrophilic polymer. 10 parts of the above hydrophilic polymer, 45 parts of chlorinated polyethylene as a hydrophobic polymer, 15 parts of styrene-butadiene rubber, 28.5 parts of acrylate oligomer modified with terminal acryl, 1 part of benzyl dimethyl ketal.
Parts, and 0.5 parts of hydroquinone monomethyl ether were dissolved in 40 parts of toluene and 10 parts of water, dispersed, kneaded and defoamed, and the resulting mixture was sandwiched between polyethylene terephthalate films and pressed at 80 ° C. for 15 seconds, Thickness 3mm
To obtain a photosensitive resin plate (a).

Production Example of Photosensitive Resin Plate (b) Maleic polybutadiene obtained by reacting 100 parts of polybutadiene having a molecular weight of 40,000 with 6 parts of maleic anhydride is mixed with 5 parts of 2-hydroxyethyl methacrylate and polyoxyethylene nonylphenyl. Add 9 parts of ether and 0.5 part of dimethylbenzylamine, and 0.2 parts of hydroquinone as a polymerization inhibitor, and add 2 parts at 115 ° C in toluene.
Reacted for hours. After the reaction, it was neutralized with triethanolamine and the solvent was distilled off to obtain a resin. 100 of the resin obtained
Parts, 15 parts of methyl methacrylate and 1 part of ethylene glycol dimethacrylate were mixed, and then deionized water 40
After 0 parts and 30 parts of methanol were added and stirred to emulsify, 1 part of ammonium persulfate was further added to carry out emulsion polymerization at 80 ° C. After 4 hours, 5% calcium chloride aqueous solution was gradually added to precipitate the particles, which was filtered, washed with water and dried under reduced pressure to obtain water-insoluble particles having an average particle size of 0.2 μm. 60 parts of particles thus obtained, 6 parts of methacrylic acid, 10 parts of propylene glycol monomethyl monoacrylate, 5 parts of polyethylene glycol diacrylate, 4 parts of trimethylolpropane triacrylate, 2,2-dimethoxy-2-phenylacetophenone 2 Parts and 7 parts of polyethylene glycol nonyl phenyl ether were uniformly mixed with a biaxial mixing kneader, and the resulting mixture was sandwiched on a polyethylene terephthalate film and pressed at 80 ° C. for 15 seconds to form a photosensitive resin plate (thickness: 3 mm). b) was obtained.

Production Example of Photosensitive Resin Plate (c) 500 parts of 2-ethylhexyl acrylate, 6 parts of allyl methacrylate and 6.5 parts of 1,6-hexanediol diacrylate are ion-exchanged with 0.5% sodium dodecylbenzenesulfonate. Emulsion polymerization (temperature 80 to 90 ° C.) using ammonium persulfate in 1000 ml of an aqueous solution of water, and the resulting emulsion is further supplemented with an aqueous solution of ion-exchanged water of 0.5% sodium dodecylbenzenesulfonate.
0 ml and 3 parts of t-butyl perbivalate were added, and after substituting with nitrogen, a mixture of 150 parts of n-butyl acrylate and 33 parts of methacrylic acid was added dropwise thereto and reacted at 70 ° C. After 4 hours of the reaction, 5% calcium chloride aqueous solution was gradually added to precipitate the particles, which was filtered, washed with water and dried under reduced pressure to obtain an aggregate of rubber-like water-insoluble particles having an average particle diameter of 0.15 μm. It was To 100 parts of this agglomerate, 3 parts of 2,2-dimethoxy-2-phenylacetophenone and 30 parts of trimethylolpropane ethoxytriacrylate were added and uniformly mixed with a biaxial mixing kneader, and the resulting mixture was placed on a polyethylene terephthalate film. It was pressed with a sandwich at 80 ° C. for 15 seconds to obtain a photosensitive resin plate (c) having a thickness of 3 mm.

Production Example of Photosensitive Resin Plate (d) Styrene-isoprene-styrene block copolymer 50
Parts, methacrylic acid-acrylonitrile-butadiene copolymer 50 parts, distearyl fumarate 20 parts, phenyl maleimide 3 parts, benzyl dimethyl ketal 3 parts, and hydroquinone monomethyl ether 0.5 part are uniformly kneaded by a biaxial mixing kneader, The obtained mixture was sandwiched between polyethylene terephthalate films and pressed at 80 ° C. for 15 seconds to obtain a photosensitive resin plate (d) having a thickness of 3 mm.

Production Example of Photosensitive Resin Plate (e) Methacrylic acid-isoprene-methacrylic acid block copolymer (methacrylic acid / isoprene = 1/4 (molar ratio))
100 parts of it was dissolved in 600 parts of tetrahydrofuran, to which was added 13 parts of sodium hydroxide dissolved in 50 parts of methanol, and the mixture was stirred at room temperature for 30 minutes. 40 parts of the resin obtained by removing the solvent under reduced pressure, 10 parts of hexanediol diacrylate, 1 part of benzyl dimethyl ketal, and 0.5 parts of hydroquinone monomethyl ether were uniformly kneaded with a biaxial mixing kneader to obtain The mixture is sandwiched on polyethylene terephthalate film at 80 ° C.
And pressed for 15 seconds to obtain a photosensitive resin plate (e) having a thickness of 3 mm.

Examples 1 to 8 and Comparative Examples 1 to 6 The photosensitive resin plates produced as in the production examples of the photosensitive resin plates (a) to (e) were cut into a size of A2, and thin lines of each line width were formed. Appropriate negative film (exposure part 50)
%), And a pattern was printed by irradiating with a mercury lamp having an illuminance of 25 W / m ² for 5 minutes. After removing the negative film, the film was developed in various washout liquids shown in Table 1 (70 liters) at 40 ° C. by a nylon brush rubbing so that the relief depth was about 1 mm. Wash out 3
The test was performed once every 0 minutes, and a total of 10 sheets were washed out. During the washing, the washing liquid is always taken out from the washing tank at a fixed amount, and the filtrate receiver is brought into close contact with the back surface of the belt filter by an apparatus as shown in Fig. 2 and intermittently filtered under reduced pressure (difference from atmospheric pressure 400 mmHg ). 50W / as light source
A m ² mercury lamp was used. For the belt filter, polyester cloth laminated with polytetrafluoroethylene porous film was used (filtration area 80 cm x
120 cm), the filtered washout liquid was immediately returned to the washout tank. The wash-out liquid was sampled from the wash-out layer every 30 minutes, and the solid content concentration in the wash-out liquid was measured.

The measurement results are summarized in Table 1 and FIGS. 3 and 4. The resin concentration here is the concentration of the resin flowing out from the photosensitive resin plate in the washout liquid, and is the value obtained by subtracting the solid content concentration of the initial unused washout liquid from the solid content concentration of the washout liquid. . Moreover, the moving speed in Table 1 is the speed including the time during which the moving of the filter is stopped during the vacuum filtration. As is clear from Table 1 and FIG. 3 and FIG. 4, in Examples 1 to 8, it is expected that the resin concentration of the washout liquid will be kept constant at a low concentration even after 10 sheets have been washed out and further washing is continued. In Examples 1 to 6, the resin concentration is expected to increase further.

[0050]

[Table 1]

[0051]

According to the processing method and the processing apparatus of the present invention, the wash-out solution of the photosensitive resin plate containing the resin in the exposed area is treated to remove the resin in the wash-out solution, and the filtrate is reused as the wash-out solution. By using it, the resin concentration in the washout liquid is always kept below a certain level, and stable washing out of a large number of photosensitive resin plates can be performed for a long period of time. In addition, there is no need to discard the wash-out liquid, which is advantageous in terms of cost,
It is pollution-free and can make a great contribution to the conservation of the local environment.

[Brief description of drawings]

FIG. 1 is a schematic view of an example of an apparatus for treating a wash-out liquid of a photosensitive resin plate of the present invention.

FIG. 2 is a schematic view of an example of a treatment device for a wash-out liquid of a photosensitive resin plate of the present invention.

FIG. 3 is a diagram showing a resin concentration per washed-out sheet number.

FIG. 4 is a diagram showing a resin concentration per washed sheet number.

[Explanation of symbols]

 1,15 Washout liquid supply line 2 Tank 3 Drum filter 4,5,16,18 Filtration extraction line 6,17 Pump 7,26 Lamp 8,27 Scraper 9 Shield 10,28 Resin receiving box 11,29 Washout liquid 12,30 Filtrate 13,31 Adhesive resin 14,32 Scraped resin 19 Belt filter 20,21 Roller 22 Scraper back roller 23 Tension roller 24 Drive roller 25 Filtrate receiver

Claims (2)

[Claims] 1. A method for treating a wash-out solution containing a resin, which is generated by a method in which after exposing a photosensitive resin plate, the unexposed portion is rubbed out while being immersed in the wash-out solution to develop, a resin-containing wash-out solution is treated. The washing liquid is filtered with a filter, and the filtrate is reused as the washing liquid.On the other hand, the filter clogged with the resin is irradiated with light in order to cure the resin adhering to the filter, and then the resin is peeled off and reused. A method for treating a wash-out liquid of a photosensitive resin plate, which is characterized by being used. 2. A photosensitive resin plate wash-out liquid is filtered through a filter to remove the resin, and the filtrate is reused as a wash-out liquid. An apparatus for treating a wash-out liquid of a photosensitive resin plate, which is provided with a light irradiation section and a cured resin peeling section.