JPH0331249B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to aqueous processing liquids used in the development or reduction processing of image reproduction materials containing colorants. In recent years, various non-silver salt-based image duplicating materials have been developed with the aim of precisely duplicating images on lithographic film for plate making, photographic paper, photo tools for printing printed circuit boards, etc. A photopolymerizable element comprising a support carrying a photopolymerizable layer having an optical density of at least 3.0 and containing an actinic radiation absorbing substance is also disclosed in JP-A-52
From Japanese Patent No. 89916, an image forming material is known in which a coating layer of a polymer material containing carbon black is provided on a support, and a photoresist layer is provided thereon. However, when using image duplicating materials such as those described above, there are various problems.Among them, when using a photosensitive resin layer in which the soluble portion is removed with an aqueous developer after image exposure, the colorant is washed off. The photosensitive resin composition or colorant-containing resin floats in the aqueous developer as visible-sized debris, and this is washed off in the white areas of the image duplicating material, that is, in the presence of the support or undercoating layer. When this happens, it adheres to the exposed parts of the undercoating layer and remains as visible spots in the white areas of the image after duplication is complete. If such spots are colorless and transparent (in the present invention, colorless and transparent refers to those whose average absorbance within the active light range of the photosensitive layer of the image duplication material is 0.3 or less), there is no substantial damage; When the support is colored and opaque, the purpose is particularly high-precision image duplication, and when the support is a transparent plastic film, etc., the purpose is to repeat further duplication using the same image duplication material based on the obtained duplicated image. Since images with such spots cause pinholes when inverted, the presence of such spots is a fatal drawback. Therefore, the inventors of the present invention have conducted extensive research with the aim of preventing the above-mentioned disadvantage from re-deposition of washed-off colorant-containing photosensitive resins or colorant-containing resins, and as a result, they have finally completed the present invention. It was done. That is, the present invention relates to a development treatment of an image duplicating material having a photosensitive resin layer containing a coloring agent on a support, or a resin layer containing a coloring agent between the support and the photosensitive resin layer. An aqueous treatment liquid used for power reduction treatment,
This is an aqueous processing liquid for image duplicating materials, characterized in that it contains more than 0.1% by weight and not more than 1.0% by weight of a metal chelating agent and a nonionic surfactant. Suitable supports for use in the image reproduction material of the present invention include glass plates, plastic films, metal plates, papers and the like. Examples of the plastic film include films of polyester, polypropylene, polyethylene, polyvinyl chloride, polyvinylidene chloride, polycarbonate, cellulose acetate, and the like. In particular, a biaxially stretched polyester film is preferred because it has excellent dimensional stability and transparency. Although there is no strict limit to the thickness of the support, a thickness of 75 to 175μ is suitable. In the present invention, the effect is also observed when the support is in direct contact with the photosensitive resin layer (or the intermediate layer when there is an intermediate layer), and in particular, the support improves the adhesive strength to the photosensitive resin layer. This is true in cases where the adhesive compound is impregnated with an adhesive compound that can be used as an adhesive, but in general, it is preferable to It has a subbing layer. A thin layer of polymeric material can be used as the subbing layer. Preferred polymer thin layers include, for example, polyacrylate, polyvinylidene chloride/acrylonitrile/itaconic acid copolymer, vinyl chloride/vinyl acetate/maleic anhydride copolymer, terephthalic acid/isophthalic acid/glycol copolymer, and Examples include thin films of polymeric substances such as isocyanate compounds. The layer thickness is usually 0.2-2μ. In the present invention, the photosensitive resin refers to a resin that undergoes rapid physicochemical changes upon irradiation with actinic rays, resulting in a change in solubility in an aqueous developer, and that forms a resist pattern through a wash-off process. Therefore, it can be applied to many types of resins, such as negative types using diazonium salt as a photoinitiator and positive types using naphthoquinonediazide as a photoinitiator, but photopolymerizable photosensitive resins are most preferable from the viewpoint of photosensitivity. It is something. The photopolymerizable photosensitive resin has the following main components: a photoinitiator, a monomer or oligomer having an ethylenically unsaturated bond, and a polymeric binder. a Photoinitiator A photoinitiator has the ability to initiate a polymerization reaction or a crosslinking reaction with actinic rays, and is used alone or in combination with other compounds. Examples of typical compounds include benzyl, benzophenone, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, benzophenone derivatives such as 4-methoxy-4'-dimethylaminobenzophenone, anthraquinone, and 2-chloroanthraquinone. , aromatic ketones such as 2-ethyl anthraquinone, 1-chloro anthraquinone, and phenanthraquinone, benzoin, benzoin alkyl ethers, benzoin derivatives such as α-methylbenzoin, benzyl dimethyl ketal, polynuclear quinones, 2, Examples include a combination system of a 4,5-triarylimidazole dimer and a free radical generator. Furthermore, the sensitivity can be further improved by adding a sensitizer or a sensitizing dye.
In addition, 2,4,5-triarylimidazole 2
As a mer, 2-(0-methoxyphenyl)-
4,5-diphenylimidazole dimer, 2-
Triphenylimidazole dimers such as (0-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(p-methylmercaptophenyl)-4,5-diphenylimidazole dimer, 2-
(1-naphthyl)-4,5-diphenylimidazole dimer, 2-(9-anthryl)-4,5-diphenylimidazole dimer, 2-(2-methoxy-1-naphthyl)-4, 5-diphenylimidazole dimer, 2-(2-chloro-1-naphthyl)-
Polycyclic aryl-4,5-diphenylimidazole 2 such as 4,5-diphenylimidazole dimer
Quantities can be mentioned. The free radical generator used in combination with the 2,4,5-triarylimidazole dimer includes:
p-aminophenyl ketone compounds such as p,p'-bis(dimethylamino)benzophenone; leucotriphenylmethane dyes such as leucomalachite green and leuco crystal violet; 2.
Cyclic diketone compounds such as 4-diethyl-1,3-cyclobutanedione, thioketone compounds such as 4,4'-bis(dimethylamino)thiobenzophenone, mercaptan compounds such as 2-mercaptobenzothiazole, N-phenylglycine , dimedone, 7-diethylamino-4-methylcoumarin, and the like. As the sensitizer or the sensitizing dye, xanthene-based, acridine-based, thiazine-based, cyanine-based dyes and the like are effective. b Monomer or oligomer having an ethylenically unsaturated bond The monomer or oligomer used may have one or more polymerizable double bonds. Examples of such compounds include alkyl acrylates or alkyl methacrylates such as hexyl acrylate, hexyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, lauryl acrylate, lauryl methacrylate, benzyl acrylate, benzyl methacrylate, hydroxyalkyl acrylate, hydroxy Alkyl methacrylates, N,N-dialkylaminoalkyl acrylates or methacrylates, alkyl ether acrylates or methacrylates such as methoxyethyl acrylate, ethoxyethyl methacrylate, halogenated alkyl acrylates or methacrylates, alkylacrylic or methacrylamides, hydroxyalkyl acrylates or methacrylates,
Acrylates or methacrylates of polyalkyl ethers such as diethylene glycol diacrylate or methacrylate, triethylene glycol diacrylate or methacrylate, ethylene glycol diacrylate or dimethacrylate, polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol Acrylate or methacrylates, acrylic acid, methacrylic acid, reaction product of glycidyl acrylate or methacrylate with active hydrogen-containing substance, reaction product of glycidyl compound and acrylic acid or methacrylic acid, condensation of N-methylol compound and urea compound and reaction products of polyisocyanate compounds and hydroxyalkyl acrylates or methacrylates. The monomer or oligomer to be used is not limited to one type, but may vary depending on the type of binder, the ratio of monomers or oligomers, the type and amount of photoinitiator, and the type and amount of active light absorbing compounds when they coexist. Therefore, it is necessary to select the monomer or oligomer to be used, including compatibility, film formation, stability,
Determined based on photosensitivity, etc. If the monomer used has a low boiling point, it will volatilize and decrease during or after film formation, so a higher boiling point is desirable. c. Binder The binder must be an organic polymer that is soluble in an aqueous solvent, solid at temperatures below 50°C, and compatible with the polymerizable monomer or oligomer. The binder may or may not be thermoplastic, but it must have film-forming ability, and in particular it must have film-forming ability even when monomers or oligomers, photoinitiators, and actinic light absorbers are added. be. Such examples include polyvinyl alcohol,
Examples include polyacrylamide, polyvinylpyrrolidone, polyethyleneimine, sulfone groups, units obtained by quaternizing tertiary nitrogen-containing polymers with acids, and polymers containing carboxyl groups. Examples of binders soluble in acidic or alkaline aqueous solutions include carboxyl group-containing cellulose derivatives such as carboxymethyl cellulose, cellulose methyl ether terephthalate, and cellulose methyl ether succinate, methacrylic acid, acrylic acid, maleic acid, itaconic acid, and crotonic acid. Examples include copolymers of vinyl monomers, tertiary nitrogen group-containing polyesters, polyamides, polyethers, styrene, and maleic anhydride copolymers. Note that the main chain or side chain of the binder may contain a polymerizable unsaturated double bond group. The thickness of such a photosensitive resin layer is preferably 1 μm or more and 15 μm or less from the viewpoint of high resolution. In the present invention, the same material as the binder which is the main component of the photosensitive resin can be used as the colorant-containing resin layer provided between the support and the photosensitive resin layer. In the present invention, the photosensitive resin layer or the colorant contained in the resin layer has an ultraviolet and visible absorption spectrum that overlaps with that of the photoinitiator used. Examples of such colorants include ultraviolet absorbers, ultraviolet absorbing dyes, and other dyes and pigments. Examples of these include powders of compounds such as carbon black, titanium oxide, iron oxide, various metals and metal oxides, and sulfides, pigment black (C.1.50440), chrome yellow light (C.1.77603), 2,2 '-dihydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone hydroxyphenylbenzotriazole, 2-(2'-hydroxy-5'-methoxyphenyl)benzotriazole, resorcinol monobenzoate, ethyl-2 -Cyano-3,3-diphenyl acrylate, toluidine yellow GW
(C.1.71680), molybdenum orange (C.1.77605),
These include Sudan Yellow (C.1.30) and Oil Orange (C.1.12055). Such colorants are not only useful for the purpose of making the image more visible, but because they absorb actinic radiation, it is possible to use the same image reproduction material further on the basis of the image obtained when the support is transparent. If a large amount of colorant is included in the photosensitive resin layer, a resist image is obtained in which only the upper layer is cured and the lower layer is not cured. It is also effective for the purpose of maintaining force-reducing properties, which is an advantageous characteristic for applications such as Such a coloring agent can be directly blended into the photosensitive resin layer as described above, or alternatively, as an intermediate layer, a coloring agent may be blended into a resin layer made of a binder and then a photosensitive layer containing no colorant may be added. It is also possible to use a method of providing a synthetic resin layer. In any case, in order to achieve the purpose of blending the colorant, there is a preferred range of blending amount. The absorbance of the combined layer) is within the active light range.
It is preferable to mix it so that it is in the range of 1.5 to 4. Among the colorants mentioned above, it is most preferable to use carbon black, since a good image duplicating material can be obtained and the effects of the present invention will be more pronounced. In the present invention, in order to protect the surface or, in particular, to prevent inhibition of the photopolymerization reaction by oxygen when the photosensitive resin layer is a photopolymerization type, the photosensitive resin layer is a removable protective film with good light transmittance, Alternatively, it may be coated with a protective layer soluble in an aqueous solvent. Therefore, resins such as polyvinyl alcohol, polyacrylic acid, and methyl cellulose that are soluble in aqueous solvents can be used. In particular, polyvinyl alcohol is preferable because it has excellent oxygen barrier properties and can reduce the radical polymerization damage prevention effect caused by oxygen. The aqueous treatment liquid mentioned in the present invention is one whose main component is water, such as simple water, caustic soda, caustic potash, sodium borate, sodium bicarbonate,
Metal chelating agents in aqueous solutions containing alkaline salts such as sodium and potassium pyrophosphate tetrasubstituted phosphonium, aqueous solutions containing acids such as hydrochloric acid, sulfuric acid, or acetic acid, and aqueous solutions in which organic solvents such as ethylene glycol monoethyl ether are added to the above aqueous solutions. It refers to an aqueous solution containing a nonionic surfactant. The temperature of the processing solution may be room temperature, but
It is easier to achieve the purpose of the present invention by slightly heating the temperature.
The temperature is preferably 25 to 40°C, more preferably 25 to 40°C. When copying an image by wash-off using the processing solution of the present invention, it can be carried out by spraying in the processing solution or by rubbing with a brush, sponge roller, etc.; Another effective method is to only infiltrate the developer into the portion of the reproduction material to be removed, and then remove this portion by spraying or brushing in water. In such a case, the water to be removed is also considered to be the treatment liquid of the present invention and preferably contains a metal ion chelating agent and a nonionic surfactant. The metal ion chelating agent used in the present invention is a compound that forms a chelate compound by coordinate bonding with a metal ion, and includes, for example, polysulfonic acids, aminopolycarboxylic acids, and especially aminopolycarboxylic acids. is preferred. These aminocarboxylic acids have the general formula N( _-CH2 ) _-o
A compound having a group represented by COOR (in the formula, n is 1 or 2, R is a hydrogen atom or an alkali metal) in the molecule, and (-CH ₂ )- _o in the group
With COOR as X, it can be classified as follows. (1) RNX type ₂ compound (2) NX type ₃ compound (3) R-NX-CH ₂ -CH ₂ -NX-R type compound (4) R-NX-CH ₂ -CH ₂ -NH ₂ type compound ( 5) X ₂ N-R'-NX ₂ type and compounds containing 4 or more (R′ represents an organic group such as a chain or cyclic alkylene or phenylene, or a substituted product thereof.) Representative examples of the aminopolycarboxylic acids include iminodiacetic acid, iminodipropionic acid, N -(3,3-dimethylbutyl)iminodiacetic acid, mercaptoethyliminodiacetic acid, methoxyethyliminodiacetic acid, N-(carbamoyl)iminodiacetic acid, aminoethyliminodiacetic acid, 2-ethoxycarbonylaminoethyliminodiacetic acid, sulfoethyl Iminodiacetic acid, nitrilotriacetic acid, carboxyethyliminodiacetic acid, N,N'-ethylenediaminediacetic acid, N-(2-hydroxycyclohexyl)ethylenediaminetriacetic acid, N'-hydroxyethyl-ethylenediamine-N,N,N'-
Triacetic acid, ethylenediaminetetraacetic acid, ethylenediamine-N,N'-diacetic acid-N,N'-dipropionic acid, 1,2-propylenediaminetetraacetic acid, 1,2-cyclopentanediaminetetraacetic acid, trans-cyclohexane-1 , 2-diaminetetraacetic acid, 2,2'-diaminoethyl ether-N,N,N',N'-tetraacetic acid, diethylenetriaminepentaacetic acid, glycoldiaminetetraacetic acid, thioglycoldiaminetetraacetic acid, 2,
2'-diaminoethylthioether-N,N,N',
N'-tetraacetic acid, N,N'-dimethyltrimethylenetetramine-N,N,N',N'-tetraacetic acid,
Examples include trimethylenetetraminehexaacetic acid and their sodium salts. Among these, ethylenediaminetetraacetic acid or its alkali metal salt is particularly preferred. The aqueous treatment liquid used in the method of the present invention is
At least one of the metal ion chelating agents
It is an aqueous solution containing more than 0.1% by weight and less than 1.0% by weight. If this content is less than 0.1% by weight, no effect will be observed, and if it exceeds 1.0% by weight, no improvement in the effect can be expected. The aqueous treatment liquid of the present invention must also contain a nonionic surfactant, such as polyethylene glycol nonyl phenyl ether, polyethylene glycol octyl phenyl ether, polyethylene glycol alkyl allyl ether, Examples include polyethylene glycol oleyl ether, polyethylene glycol oleate, polyethylene glycol alkyl ether, polypropylene glycol polyethylene glycol ether, and polyethylene glycol alkylamine ether. Its preferred content is 0.01% by weight
The content ranges from 0.1% to less than 0.1% by weight, preferably from 0.01% to 0.05% by weight. If the amount is less than 0.01% by weight, the effect will be small, while if it is more than 0.1% by weight, not only will no improvement in the effect be obtained, but undesirable effects such as foaming of the processing liquid itself will become more noticeable. Comparing the method of image duplication using the processing solution of the present invention with the conventional technology, JP-A-57-52053 discloses that when manufacturing a photosensitive resin plate, a metal ion chelating agent of 0.001% is used as an aqueous developer. % to 0.1% by weight, and in some cases surfactants.
A method using 0.1% to 3% by weight is described. However, as stated in the specification, the above method "concerns a method for producing a photosensitive resin plate free of adhesiveness and residual grain agglomerates" and "is a method for producing a photosensitive resin plate free of adhesiveness and residual grain agglomerates," and "is a method for producing a photosensitive resin plate free of adhesiveness and residual grains." The purpose is to obtain a resin plate with a good finish. In contrast, the present invention relates to a processing liquid used in an image duplication method in which the washed-off photosensitive resin composition does not adhere to the image duplication material again, and achieves a completely different effect. . Incidentally, such redeposition cannot be prevented at all even if an aqueous treatment liquid having a composition within the range described in the above-mentioned publication is used. Such re-deposition prevention can only be achieved with an aqueous developer that simultaneously contains a metal ion chelating agent and a nonionic surfactant in the concentration range described in the present invention. As described above, when the processing liquid of the present invention having such a configuration is used, it is possible to prevent the washed-off colorant-containing photosensitive resin or colorant-containing resin from re-adhering to the white areas of the image, thereby significantly improving the accuracy of the image. In addition, when the support is a transparent film, defects such as pinholes do not appear even if the image is closely inverted based on the image, so that it is possible to repeatedly use the copy. It should be noted that the image duplication method using the processing solution of the present invention is particularly advantageous when developing, fixing,
When making copies using a so-called "automatic processor," which connects necessary processes such as washing with water and drying as a series, automatic processors require continuous use of developer for a relatively long period of time due to workability. However, since they are not replaced, the washed-off debris accumulates along with the duplication, increasing the probability of the above-mentioned adhesion.In addition, automatic processors often use opposed rollers for conveyance, and the attached debris is supported by the opposed rollers. It is pressed onto the body and further adhered by heating during the final drying process, making it extremely difficult to remove even if adhering spots are found after replication is complete. Therefore, when the processing liquid of the present invention is used, the above-mentioned drawbacks are solved at once, and it can therefore be said to be very effective particularly in image duplication methods using automatic processors. EXAMPLES Hereinafter, the present invention will be specifically explained using Examples, but the present invention is not limited thereto.
In addition, in the examples, parts simply mean parts by weight. Example 1 Image Reproduction Material A A polyester film having a thickness of 100μ was coated with the following composition using a reverse coater and dried to produce a polyester film having a subbing layer of 0.5μ. Vylon 20S 50 parts (saturated polyester adhesive, manufactured by Toyobo Co., Ltd.) Coronate L (manufactured by Nippon Polyurethane Industries) 4 parts U-Cat SA-No.102 (manufactured by Sunabott Co., Ltd.) 0.1 part Toluene 80 parts Methyl ethyl ketone 20 parts Next, the following composition A photosensitive composition in which the components were mixed and dispersed was prepared and coated onto the polyester film provided with the above-mentioned undercoat layer using a reverse coater to form a photosensitive layer having a thickness of 3 μm. Methyl methacrylate (77 mol%), methacrylic acid (23 mol%) copolymer 41 parts Carbon black 12 parts Trimethylolpropane triacrylate 34 parts 2-(2-chloro-1-naphthyl) 4,5-diphthyl Enylimidazole dimer 8 parts Hydroquinone monomethyl ether 0.03 parts Dimedone 3 parts Michler's ketone 2.0 parts Methanol 140 parts Chloroform 120 parts Ethyl acetate 80 parts N-propyl acetate 40 parts Isopropyl alcohol 40 parts Furthermore, on this film, a protection consisting of the following composition is applied. Coating the layer composition in the same way, the thickness
Image reproduction material A was prepared with a 1μ protective layer. Polyvinyl alcohol 5 parts (saponification degree 98.5%, polymerization degree 500) Neugen EA-140 (manufactured by Daiichi Kogyo Seiyaku) 0.2 parts Methanol 5 parts Water 90 parts Image duplication material B Contains the undercoat layer used in image duplication material A A resin layer containing the following composition mixed and dispersed was coated on a polyester film using a reverse coater to form a layer with a thickness of 2 μm. Styrene, maleic anhydride copolymer 50 parts Carbon black 40 parts N-butyl alcohol 400 parts Further, on the resin layer, a photosensitive composition having the following composition was coated to a thickness of 1 μm using a reverse coater to form an image duplication material. I got a B. Vinyl acetate-acrylic acid copolymer 50 parts Condensation product of paradiazodiphenylamine sulfate and paraformaldehyde 2 parts Water 55 parts Image duplication materials A and B thus obtained
Divide an A4 size sheet into two, layer a test negative film with a 150/inch dot area ratio of 50% on one half, and a solid test negative film on the other half, and expose the image using a bright room printer (manufactured by ORC). I went. Next, a roller conveyance type automatic developing machine having a four-tank structure is prepared, and the first and second tanks are filled with the developer shown in Table 1, and the third tank is filled with the developer shown in Table 1. A 5% aqueous solution of hydroquinone was filled, and image duplication material B was filled with plain water, and the fourth tank was also filled with water. The temperature of the first and second tanks was 30°C, and when the third tank contained a hydroquinone aqueous solution, the temperature was 38°C. If the third tank is water, its temperature is room temperature. The image duplicating material after image exposure was passed through such an automatic processor for image duplication, and after drying, the sample was examined for adhesion of black spots that could be visually observed in white areas (ie, solid areas of the negative film). The results of the determination are shown in Table 1 Sample Nos. 1 to 5. The criteria for ○, △, and × in the table are as follows. 〇 No black spots attached to white areas △ 5 or less black spots attached to white areas × 5 or more black spots attached to white areas Comparative example 1 For image duplication material A, metal ion chelating agent and nonionic agent with lower concentration than stated in the present invention The same evaluation as in Example 1 was conducted for a developer using a surfactant, a developer containing a metal ion chelating agent within the concentration range of the present invention but not containing a nonionic surfactant, and vice versa. Ta. These results are also shown in Table 1 Sample Nos. 6 to 8. As is clear from the results in Table 1, it can be seen that the method of the present invention completely eliminates the problem of redeposition of the photosensitive resin composition to the white areas.

[Table] * Processing liquid is required for the first tank and the second tank. In the case of Example 1, only the main agent
Although the concentrations differed depending on the tank, the metal ion chelating agent and surfactant were kept at the same concentration.

Claims (1)

[Claims] 1 Development treatment or reduction treatment of an image duplication material having a photosensitive resin layer containing a colorant on a support or a resin layer containing a colorant between the support and the photosensitive resin layer 1. An aqueous processing solution for image duplicating materials, which is an aqueous processing solution used for image duplication materials, characterized in that it contains more than 0.1% by weight and not more than 1.0% by weight of a metal chelating agent and a nonionic surfactant.