JPS6088945A - Aqueous processing solution for image copying material - Google Patents

Abstract

PURPOSE:To prevent reattachment of a colorant washed off from the photosensitive resin or the resin which contained the colorant before, by incorporating a metal chelating agent and a nonionic surfactant. CONSTITUTION:A metal chelating agent and a nonionic surfactant are incorporated in an aq. processing soln. to be used for development processing or reduction processing of an image copying material contg. a colorant. As the metal chelating agent, a compd. capable of coordinating a metal ion to form a chelate compd., such as polysulfonic acids, aminocarboxylic acids, etc. can be enumerated, and it is especially preferable to use aminocarboxylic acids in an amt. of 0.1wt%. As the nonionic surfactant, polyethylene glycol nonylphenyl ether, polyethylene glycol octylphenyl ether, etc. are used, preferably, in an amt. of 0.01- 0.1wt%.

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.1 For example, Japanese Patent Publication No. 57-22372 C. 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,
Furthermore, according to JP-A-52-89916, a coating layer of a polymeric substance containing carbon black is provided on a support,
Image forming materials on which a photoresist layer is provided are known.

However, there are various problems when using image duplicating materials such as ε, and among them, those using a photosensitive resin layer whose soluble portion is removed with an aqueous developer after image exposure, are washed off. The colorant-containing photosensitive resin composition or the colorant-containing resin floats in the aqueous developer as visible-sized debris, and this remains in the white area of the washed-off image reproduction material, i.e., the support is also under construction. When a subbing layer is present, it attaches to the exposed part of the subbing layer,
After the duplication is completed, the white areas in the image remain as visible spots on the image. 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. However, 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., further duplication is repeated using the same image duplication material based on the duplicated image obtained. Since it is often used for various purposes, images with spots like this will cause pinholes when inverted, so
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 drawback 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 has arrived. That is, the present invention relates to an image duplicating material having a photosensitive resin layer containing a coloring agent on a support, or a method for developing an image duplicating material having a resin layer containing a coloring agent between the support and a photosensitive VJ resin layer. The present invention is an aqueous processing liquid for image duplicating materials, which is used for processing or force reduction processing, and is characterized by containing 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 and papers. Examples of plastic films 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 175 μm is appropriate.

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 sublayer. 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/hinyl 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 0.2-2
μ.

In the present invention, the photosensitive resin is one 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. refers to 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 from the viewpoint of photosensitivity, photopolymerizable photosensitive resins are the most preferable. It is. The photopolymerizable photosensitive resin mainly contains a photoinitiator, a polymer or oligomer having an ethylenically unsaturated bond, and a polymeric binder as shown below.

a) Photoinitiator A photoinitiator has the ability to dissolve and initiate polymerization reactions and crosslinking reactions with actinic light, and is used alone or in combination with other compounds. Examples of representative compounds include:
Benzyl, benzophenone.

Benzophenone derivatives such as Smithler's ketone, 4,4'-bij(diethylamino)benzophenone, and 4-methoxy-4'-dimethylaminobenzophenone.

Aromatic ketones such as anthraquinone, 2-chloroanthraquinone, 2-ethylanthraquinone, l-chloroanthraquinone, and phenanthraquinone.

Examples include benzoin, benzoin alkyl ethers, benzoin derivatives such as α-methylbenzoin, benzyl dimethyl ketal, polynuclear quinones, and a combination system of 2,4,5-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 2, 2-(0-chlorophenyl-4,5-diphenylimidazole 2, ti.2
Triphenylimidazole 2 such as -(p-methylmeIcaptophenyl)-4,5-diphenylimidazole dimer
Quantity. 2-(1-naphthyl)-4.5-diphenylimidazole dimer, 2-(9-anthryl)-4.
5-diphenylimidazole 2f1 body.

2-(2-methoxy-1-naphthyl)-4,5-diphenylimidazole 2ii,2-(2-chloro-1-
Examples include polycyclic aryl-4.5-diphenylimidazole dimers such as f-7fk)-4.5-diphenylimidazole dimers.

2,4.5-)! The free radical generators used in combination with j arylimidazole dimer include p, p
p- such as '-bis(dimethylamino)benzophenone
Aminophenyl ketone compounds, leucotriphenylmethane compounds such as leucomalachite green and leuco crystal violet, and cyclic diketone compounds such as 2,4-diethyl-1,3-cyclobutanedione. 4.4'-
Examples include thioketone compounds such as bis(dimethylamino)thiobenzophenone, mercaptan compounds such as 2-mercaptobenzothiazole*, N-phenylglycine, dimedone, 7-danitylamine-4-methylcoumarin, and the like.

As a sensitizer or a sensitizing agent, use xanthine.

Acridine, thiazine, and cyanine dyes are effective.

b) Chemicals or oligomers having ethylenically unsaturated bonds The chemical compounds or oligomers used may have one or more polymerizable double bonds. Examples of such compounds include hexyl acrylate v-)b hexyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, lauryl acrylate, lauryl methacrylate, benzyl acrylate,
Alkyl acrylate or alkyl methacrylates such as benzyl methacrylate, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, N,N-dialkylaminoalkyl acrylate or methacrylates, alkyl ether acrylate such as methoxyethyl acrylate, ethoxyethyl methacrylate, or methacrylates, halogenated alkyl acrylates or methacrylates, alkyl acrylics or methacrylamides, hydroxyalkyl acrylates or methacrylates, diethylene glycol diacrylates or methacrylates,
Acrylates or methacrylates of polyalkyl ethers such as triethylene glycol diacrylate or methacrylate, ethylene glycol diacrylate or dimethacrylate, acrylates or methacrylates of glycerin, trimethylolpropane, bentaerythritol natonopolyhydric alcohols.

Acrylic acid. Reactant of methacrylic acid, glycidyl acrylate or methacrylate with active hydrogen-containing substance,
Examples include reaction products of glycysyl compounds, acrylic acid compounds, and hydroxyalkyl acrylates or methacrylates. The compound or oligomer to be used is not limited to one type, but the type of binder, the ratio of the compound or oligomer, the type and amount of the photoinitiator, and the type and amount of active light absorbing compound when present. Depending on the amount etc.
It is necessary to select the polymer or oligomer to be used, which is determined based on compatibility, film-forming properties, stability, 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 DEG C., and compatible with the polymerizable polymer or oligomer.

The binder may or may not be thermoplastic, but it must have film-forming ability, especially thermoplastic or oligomer,
Even if a photoinitiator and an actinic ray absorber are added, it is necessary to have film-forming properties.

An example of this is 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 and soots soluble in acidic or alkaline aqueous solutions include carboxyl group-containing cellulose derivatives such as carboxymethyl cellulose f, cellulose methyl ether phthalate, and cellulose methyl ether succinate;
Copolymer of methacrylic acid, Ac IJ/L/acid 1 maleic acid, itaconic acid, natotohynyl crotonate monomer,
Examples include tertiary nitrogen group-containing polyester, polyamide, polyether, styrene, and maleic anhydride copolymer.

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.

Note that in the present invention, as the resin layer containing a colorant provided between the support and the photosensitive resin layer, the same substance as the binder that is the main component of the photosensitive resin can be used. In the present invention, the colorant contained in the photosensitive Wd finger layer or 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), and chromium yellow light (C, 1,77603). , 2,2'-dihydroxy-
4-methoxybenzophenone, 2.4-dihydroxybenzophenone hydroxyphenylbenzotriazole.

2- (2'-hydroxy-5'-methoxyphenyl)
Benzotriazole, resolunol monobenzoate, ethyl-2-cyano-3,3-diphenylacrylate, 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 useful not only for the purpose of making an image more visible, but because they absorb actinic radiation, it is possible to use the same image reproduction material again based on the image obtained when the support is transparent. In addition, 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 uncured, and the resist image is used as a plate-making film. 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 I- as described above, or alternatively, the colorant can be blended into a resin layer made of a binder as an intermediate layer and no colorant is included thereon. A method of providing a photosensitive resin layer can also be used.

In any case, in order to achieve the purpose of blending the colorant, there is a preferable blending amount range. The absorbance of the combined layer) within the active light range is 1.
It is preferable to mix it so that it is in the range of 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 can be clearly exhibited.

In the present invention, for the purpose of protecting the surface or, in particular, preventing 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, polyvinyl alcohol is soluble in water-based solvents.

Resins such as polyacrylic acid and methyl cellulose can be used. In particular, polyvinyl alcohol is preferable because it has excellent oxygen barrier properties and can reduce the radical polymerization interfering 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,
The temperature of the aqueous solutions containing alkaline salts such as sodium borate, sodium carbonate, sodium and potassium pyrophosphates, tetrasubstituted phosphoniums, aqueous solutions containing acids such as hydrochloric acid, sulfuric acid or acetic acid, and the above-mentioned water treatment liquids may be at room temperature.

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 wipe or sponge roller. 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, it is preferable that the water to be removed is also regarded as the treatment liquid of the present invention and 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÷CH+-)nC
It is a compound that has a group represented by OOR (in the formula, n is 1 or 2, R is a hydrogen atom or an alkali metal) in the molecule, and in the above group (-CH2 + nC0OR is set as It can be classified.

(1) RNXZ type compound (2>NXs type compound (3) R-NX -CH2-CH2-NX-R type compound (4) R-NX -CH2-CH2-NH2 type compound (5) X2 N-R' -NX2 type and a compound containing 4 or more Examples of typical compounds 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,
Sulfoethyliminodiacetic acid, nitrilotriacetic acid, carpoxy-modified liminodiacetic acid, N,N'-ethylenediaminediacetic acid, N-C2-hydroxychlorohexyl)ethylenediaminetriacetic acid * N'-HiF a * x
Chill-ethylenediamine-NININ'-to! J Vinegar a
L x diaminetetraacetic acid, ethylenediamine-N, N'-diacetic acid-N, N'-dipropionic acid, 1
,2-propylenediaminetetraacetic acid s 1 *2-
Shi'y a HenpJ diaminetetraacetic acid, trans-
Cyclohexane-1,2-diaminetetraacetic acid, 2.2
'-Diaminoethyl ether-N, N, N', N'
-Tetraacetic acid, diethylenetriaminepentaacetic acid, glycoldiaminetetophacetic acid, thioglycoldiaminetetraacetic acid, 2,2'-diaminoethylthioether-N
,N,N',N'-tetraacetic acid-NUN'-dimethyltrimethylenetetramine-N,N,N',N
Examples include '-tetraacetic acid, trimethylenetetraminehexaacetic acid, and their sodium salts.

Among these, ethylenediaminetetraacetic acid or its alkali metal salt is particularly preferred.

The aqueous treatment liquid used in step 1 of the method of the present invention is as follows.

At least one of the metal ion chelating agents is 0.1
It is an aqueous solution containing more than 1.0% 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, and as the nonionic surfactant, 1
For example, polyethylene glycol nonylphenyl ether, polyethylene glycol) : l -/L/octylphenyl ether, polyethylene glycol alkyl allyl ether, polyethylene glycol oleyl ether, polyethylene glycol oleate, polyethylene glycol alkyl ether, polypropylene glycol polyethylene glycol All examples such as ether and polyethylene glycol alkylamine ether can be used, but the preferred content is 0.01 weight or more.
Less than 0.1% by weight, preferably 0.01% by weight or more - 0
．． 05 weight M% or less. If it 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 also unfavorable effects such as foaming of the treatment liquid itself will become more noticeable.

Comparing the method of duplicating one image using the processing solution of the present invention with the conventional technology, Japanese Patent Application Laid-Open No. 57-52053 discloses that when manufacturing a photosensitive resin plate, zero metal ion chelating agent is used as an aqueous developer. Contains in the range of .001% to 0.1% by weight, and in some cases 0.1% to 3% by weight of surfactants.
Methods using fi% are described. However, the above method, as described in the specification, "
``Related to a method for producing photosensitive resin plates free of adhesiveness and residual grain lumps'', the purpose of which is to obtain resin plates ``in a good finished state with white areas or ridges formed with sufficient depth''. This is what I did. 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 Ti resin or colorant-containing resin from re-adhering to the white areas of the image, thereby significantly improving the accuracy of the image. However, if the support is a transparent film, defects such as pinholes will not appear even if the image is closely inverted based on the image. Necessary processes such as drying are connected as a series. So-called"
When making copies using an automatic processor.

In automatic processors, the developer is used continuously for a relatively long period of time due to workability and is not replaced, so the washed-off residue accumulates with the copies, increasing the probability of the above-mentioned adhesion. Opposing rollers are often used for conveyance, and the adhering debris is pressed onto the support by the opposing rollers, and in the final drying process, it is further adhered by heating, making it extremely difficult to remove even if adhering spots are found after replication is complete. It becomes difficult. Therefore, when the treatment liquid of the present invention is used, the above-mentioned drawbacks are solved at once, so especially.

It can be said that this is a very effective method for image duplication using an automatic processor.

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 100 μm was coated with the following composition using a reverse coater and dried to prepare a polyester film having a subbing layer of 0.5 μm.

Pylon 20 S -50 parts (saturated polyester adhesive, manufactured by Toyobo Co., Ltd.) Coronate L
(Nippon Polyurethane Industry Co., Ltd. 4 parts U-Cat 5A-
AlO2 (manufactured by Sun Abbott) 0.1 part toluene
80 parts ' Methyl ethyl ketone 20 parts Next, a photosensitive composition was prepared by mixing the following composition, and it was coated on the polyester film with the above-mentioned undercoat layer using a reverse coater, thereby coating a photosensitive layer with a thickness of 3μ. did.

Methyl methacrylate (77 mol%), methacrylic acid (23 mol%) copolymer 41 parts Carbon black 1
2 parts trimethylolpropane triacrylate 34 parts 2-
(2-chloro-1-naphthyl)4.5-diphenylimidazole 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 1 part isopropyl alcohol 40 parts Further, a composition for a protective layer having the following composition was similarly coated on this film to prepare an image duplication material A having a protective layer having a thickness of 1 μm.

Polyvinyl alcohol 5 parts (degree of saponification 98.5% 1 degree of polymerization 500) Neugen EA-
140 (manufactured by Dai-Kogyo Seiyaku) 0.2 parts Methanol 5 parts Water 90 parts Image duplication material B On the polyester film having the subbing layer used in image duplication material A, a resin layer containing a mixture of the following composition was added. Coating was performed using a reverse coater to form a layer with a thickness of 2 μm.

Styrene, maleic anhydride copolymer: 50 parts Carbon black: 40 parts I got a B.

Vinyl acetate-acrylic acid copolymer 50 parts Baladiazodiphenylamine sulfate salt,! : Condensation product with roseformaldehyde 2 parts Water 55 parts The thus obtained image duplication materials A and B were divided into two A4 size sheets, and a flat-tone image with a dot area ratio of 50% of 150 J/1 nch remained in half. A test negative film, half of which was solid, was stacked on top of the other, and image exposure was performed using a bright room printer (manufactured by ORC).

Next, a roller conveyance type automatic developing machine having a 14-tank structure was prepared. Fill the second tank with the developer shown in Table 1,
The third tank was filled with a 5% aqueous solution of hydroquinone for image duplication material A, and plain water for image duplication material B, 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 was a hydroquinone aqueous solution, the temperature was 38°C. Third
If the cypress is water, its temperature is room temperature.

The image duplicating material after image exposure was passed through such an automatic processor to perform image duplication, and after drying, the sample was visually inspected for adhesion of vine black spots in the white areas (ie, the solid areas of the negative film). The results of the determination are shown in Table 1 Samples A1 to A5. The criteria for ○, Δ, and × in Table 1 are as follows.

○ White areas have no black dots △ White areas have 5 or less black spots x White areas have 5 or more black spots Comparative Example 1゜ Image duplication material A: 1 Metal ion chelate with a concentration p lower than that described in the present invention Example 1 and a developer containing a chelating agent and a nonionic 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. A similar evaluation was conducted. The results are also shown in Table 1 Samples 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 1 The true processing liquid is necessary for the first tank and the second tank.

In the case of this Example 1, only the main ingredient is the first. Although it is different in the second tank,
A common concentration was used for the metal ion chelating agent and surfactant.

Patent applicant: Toyobo Co., Ltd.

Claims (3)

[Claims] (1) An aqueous processing liquid used for development or reduction processing of a photosensitive resin layer duplication material containing a colorant on a support, which contains a metal chelating agent and a nonionic surfactant. Characteristic aqueous processing liquid for image duplication materials. (2) The content of metal chelates and other agents in the aqueous treatment liquid is 0.
The aqueous processing liquid for image duplicating materials according to claim (1), which contains more than 1% by weight and less than 1.0% by weight. (3) The aqueous processing liquid for image duplicating materials according to claim 1, wherein the nonionic surfactant content in the aqueous processing liquid is 0.01% by weight or more and less than 0.1% by weight.