JPH01170941A - Developing agent composition for photosensitive planographic plate improved in deterioration of visible image - Google Patents

Abstract

PURPOSE:To prevent the deterioration of a visible image by incorporating N- phenyl diethanol amine or N-phenyl ethanol amine, an anionic surfactant and 0.001-1wt.% of a dyestuff in the developing agent composition. CONSTITUTION:Each of N-phenyl diethanol amine or N-phenyl ethanol amine or both of them are incorporated in the developing agent composition, and the compounding amount of the amine is preferably 0.01-10wt.%, more preferably 0.5-5wt.% based on the developing composition. An alkali agent is preferably incorporated in the developing agent composition. The alkali agent is exemplified by an org. alkali agent such as triethanol amine or tetraalkyl ammonium hydroxide or an ammonium org. silicate, etc. The compounding amount of the alkali agent is preferably 0.05-20wt.%, more preferably 0.1-10wt.%. Thus, the deterioration of the visible image can be prevented.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a developer composition for photosensitive lithographic printing plates,
More specifically, the present invention relates to a developer composition particularly suitable for negative-working photosensitive lithographic printing plates.

[Conventional technology]

So-called "on-off" type photosensitive materials, which obtain relief images by removing non-image areas during development, are used for many purposes, such as resin letterpress plates and photosensitive lithographic printing plates (PS plates). , resist for printed wiring, non-silver salt reversing film, photosensitive beer mask film, color blue film, etc.

Alkaline aqueous developers are generally used for these developments, but since photosensitive materials often contain lipophilic substances that are insoluble or sparingly soluble in water or alkaline aqueous solutions, the development progresses slowly It may take too much time to remove the image area or may leave undeveloped areas. Furthermore, it often happens that the removed components are not sufficiently dissolved and float, and the components adhere to non-image areas, causing stains.

Several techniques have been proposed to solve this problem. JP-A-51-77401 and JP-A-53-4
No. 4202 discloses an aqueous developer using benzyl alcohol, and JP-A-54-86328 discloses an aqueous developer containing phenyl glycols.

Although these technologies improve developability by adding a small amount of organic solvent, they are still insufficient, and each has its own unique odor, which causes discomfort to workers and poses health and safety concerns. It is also undesirable.

The present inventors have developed a technique to improve these problems and have already filed an application (Japanese Patent Application No. 176455/1983).

The present invention relates to an improvement of this invention.

That is, among the compounds represented by the general formula of Japanese Patent Application No. 176455/1982, N-phenyldiethanolamisha N-
Phenylethanolamine has a particularly low odor and has excellent developability, but during development, the dye contained in the negative photosensitive lithographic printing plate is removed, resulting in a decrease in image density, poor visibility, and poor character quality. The inventors of the present invention have discovered that there is a problem in that it is difficult to confirm the images and patterns.

[Purpose of the invention]

An object of the present invention is to be able to suitably develop a photosensitive lithographic printing plate having an image forming layer containing an oleophilic substance;
To provide a developer composition which has little odor, has excellent workability, improves safety and health problems, and does not deteriorate visible image quality when a negative is applied to a photosensitive planographic printing plate.

[Structure of the invention]

The above object of the present invention is to provide N-phenyldiethanolamine or N-phenylethanolamine one surfactant,
This is achieved by a developer composition for a photosensitive lithographic printing plate characterized by containing 0.001-1% by weight of a dye.

The present invention will be explained in detail below.

N-phenyldiethanolamine or N-phenylethanolamine contained in the developer composition of the present invention is
One of these may be used alone or two of these may be used in combination, and the content thereof is preferably in the range of 0.01 to 10% by weight, and more preferably in the range of 0.5 to 5% by weight.

Examples of the anionic surfactant to be contained in the developer composition of the present invention include higher alcohols (C.

~C2□) Sulfuric ester salts [e.g., sodium salt of lauryl alcohol sulfate, sodium salt of octyl alcohol sulfate, ammonium salt of lauryl alcohol sulfate, "T-ball B-81J"
(Product name: Shell Chemistry Department), (sodium alkyl sulfate), aliphatic alcohol phosphate ester salts (e.g., sodium salt of cetyl alcohol phosphate, etc.), alkylaryl sulfonates (e.g., dodecylbenzene sulfone), sodium salt of isopropylnaphthalenesulfonic acid, sodium salt of sinapthalenedisulfonic acid, sodium salt of metanitrobenzenesulfonic acid, etc.), sulfonic acid salts of alkylamides (e.g., C., H3) CONCH, CH2So, Na
etc.), dibasic CH.

There are sulfonic acid salts of fatty acid esters (eg, sodium sulfosuccinate dioctyl ester, sodium sulfosuccinate dihexyl ester, etc.). Among these, alkylnaphthalene sulfonates are particularly preferably used.

The amount of these anionic surfactants added is in the range of 0.1 to 20% by weight, more preferably 1.0 to 10% by weight.

Any known type of dye can be used as the dye to be included in the developer composition of the present invention. Types of dyes that can be used include azo dyes, anthraquinone dyes, indigo dyes, sulfur dyes, carbonium dyes, quinone imine dyes, phthalocyanine dyes, reactive dyes, fluorescent dyes, and cyanine dyes, among which carbonium dyes and quinone imine dyes are Preferably, basic dyes are particularly effective. Further structural classification includes diphenylmethane dyes, triphenylmethane dyes, xanthine dyes, phthalein dyes, acridine dyes, azine dyes,
Particularly preferred are oxazine dyes and thiazine dyes.

Specific examples of preferred dyes used in the present invention include Victoria Pure Blue BOH, Victoria Blue BO, Victoria Pure Blue B1 Oil Blue #603, Crystal Violet, Methyl Violet, Patent Pure Blue, Ethyl Violet, Brilliant Milling Green B1 Methyl Green, Brilliant Green, malachite green, auramine, tsuksin, rhodamine B, etc.

The dye used in the present invention is preferably one that is soluble in the developer contained therein, but in some cases, the dye may not be in a dissolved state but in a dispersed state in the form of fine particles. therefore,
Even pigments can be suitably used if they can be made into a good dispersion state.

The concentration of the dye in the developer composition of the present invention needs to be at least 0.001% by weight in order to prevent deterioration of visible image quality.On the other hand, if the concentration is too high, the dye may not dissolve. It is necessary that the amount does not exceed 1% by weight, as this may cause problems.

The developer composition of the present invention preferably contains a water-soluble reducing agent in addition to the above components. By containing a water-soluble reducing agent, the developability of the developer composition of the present invention can be further improved.

Water-soluble reducing agents include organic and inorganic reducing agents.

Examples of organic reducing agents include phenolic compounds such as hydroquinone, methol, and methoxyquinone, and amine compounds such as phenylenediamine and phenylhydrazine. Examples of inorganic reducing agents include sodium sulfite, potassium sulfite, ammonium sulfite, and hydrogen sulfite. Sulfites such as sodium and potassium hydrogen sulfite, sodium phosphite, potassium phosphite, sodium hydrogen phosphite,
Examples include phosphates such as potassium hydrogen phosphite, potassium dihydrogen phosphite, sodium dihydrogen phosphite, potassium hydrogen sulfite, hydrazine, sodium thiosulfate, sodium dithionite, etc. In the present invention, A particularly effective reducing agent is sulfite. The water-soluble reducing agent mentioned above includes alkali-soluble, and these water-soluble reducing agents are contained in an amount of 0.1 to 10% by weight, more preferably 0.5 to 5% by weight. be done.

The developer composition of the present invention preferably contains an alkaline agent. By containing an alkaline agent, the developability of the developer composition of the present invention can be further improved.

Examples of alkaline agents include sodium silicate, potassium silicate, sodium hydroxide, lithium hydroxide, sodium triphosphate, sodium diphosphate, potassium triphosphate, potassium diphosphate, ammonium triphosphate, and diphosphate. Inorganic alkaline agents such as ammonium acid, sodium metasilicate, sodium bicarbonate, sodium carbonate, potassium carbonate, ammonium carbonate etc., organic alkaline agents such as heptan, di- or triethanolamine and tetraalkylammonium hydroxide and organic silicic acids. Ammonium and the like are useful.

The content of alkaline agent in the developer composition is 0.05
A range of 20% by weight is preferred, more preferably 0.5% by weight.
It is in the range of 1-10% by weight.

The developer composition of the present invention has water as a main solvent,
It has an excellent effect of wetting and solubilizing lipophilic substances or lipophilic polymers using only water as a solvent, and basically consists of an aqueous solution containing the above compounds, but various additives can also be used in combination. Can be done.

The present invention eliminates the need to include solvents that have odor or safety and health problems, or reduces the concentration of such solvents by incorporating the amine into the developer composition. Therefore, in the developer composition of the present invention, it is desirable that the solvent other than the quince is not contained in an amount exceeding the limit that causes odor or health and safety problems, and the proportion of water in the solvent is 80% or more. It is preferable that there be.

Photosensitive lithographic printing plates suitable for processing with the developer composition of the present invention have an image forming layer containing components that are insoluble or poorly soluble in water or aqueous alkaline solutions, and lipophilic ones are particularly suitable. A photosensitive lithographic printing plate containing a water-insoluble substance or a high molecular weight polymer. Further, the developer composition of the present invention is particularly suitable for a type in which a non-image area is removed by development, a so-called wash-off type photosensitive lithographic printing plate. Wash-off type photosensitive lithographic printing plates have two types: a negative type where the area irradiated with actinic rays hardens and becomes insoluble in the developer and remains as an image area, and a negative type where the area irradiated with actinic rays hardens and becomes insoluble in the developer. There is a positive type in which the actinic ray irradiated area remains as an image after being removed during development. Although the present invention works well for both negative and positive type printing plates, it is particularly effective for negative type photosensitive lithographic printing plates.

The image forming layer of the photosensitive lithographic printing plate according to the present invention contains a photosensitive substance as an essential component, and the physical and chemical properties of the photosensitive substance change upon exposure or subsequent development treatment. For example, there is a difference in solubility in a developer due to exposure, a difference in intermolecular adhesion between before and after exposure, a difference in affinity for water and oil due to exposure or subsequent development, and A device that can form an image area using a photographic method, and
The multilayer structure described in No. 5-166645 is included.

Typical photosensitive substances include, for example, photosensitive diazo compounds, photosensitive azide compounds, compounds with ethylenically unsaturated double bonds, epoxy compounds that polymerize with acid catalysts, and C-0- that decomposes with acids. Examples include compounds having a C-group. Typical positive-type compounds that become alkali-soluble upon exposure include 0-quinonediazide compounds, acid-decomposable ether compounds, and ester compounds.

Aromatic diazonium salts are examples of negative-type compounds whose solubility decreases upon exposure to light.

Specific examples of 0-quinonediazide compounds include, for example, JP-A-47-5303, JP-A-48-63802, and JP-A-48.
-63803, 49-38701, 56-10
No. 44, No. 56-1045, Special Publication No. 41-11222
No. 43-28403, No. 45-9610, No. 4
9-17481, U.S. Patent No. 2,797.213, U.S. Patent No. 3,046,120, U.S. Patent No. 3.188.210, U.S. Pat.
, No. 454.400, No. 3,544,323, No. 3.
No. 573,917, No. 3,674.495, No. 3,7
No. 85.825, British Patent No. 1,227.602, No. 1
, 251.345, 1,267.005, 1,
329,888, 1,330,932, and German Patent No. 854°890. Examples of acid-decomposable compounds include JP-A-60-37549, JP-A-60-10247,
Examples include those described in Japanese Patent No. 60-3625, and the present invention can be preferably applied at least to photosensitive materials using these compounds alone or in combination as photosensitive components.

These photosensitive components include 0-quinonediazidecarboxylic acid esters of aromatic hydroxy compounds or 0-quinonediazidecarboxylic acid esters of aromatic hydroxy compounds and 0-quinonediazidecarboxylic acid esters of aromatic hydroxy compounds and
-Includes quinonediazide sulfonic acid or 0-quinonediazidecarboxylic acid amide, and also includes those in which these 0-quinonediazide compounds are used alone, and those in which they are mixed with an alkali-soluble resin and this mixture is provided as a photosensitive layer. .

Alkali-soluble resins include novolak-type phenolic resins, and specifically include phenol formaldehyde resins, cresol formaldehyde resins, phenol-cresol mixed formaldehyde resins, cresol xylenol mixed formaldehyde resins, and the like. Furthermore, as described in JP-A-50-125806, in addition to the above phenol resin, phenol or cresol substituted with an alkyl group having 3 to 8 carbon atoms such as t-butylphenol formaldehyde resin and formaldehyde are used. It is also possible to use a condensate of the same.

If necessary, additives such as dyes, plasticizers, and components imparting printout performance can be added to the photosensitive layer containing an 0-quinonediazide compound as a photosensitive component.

The present invention can be applied to a range in which the amount per unit area of the photosensitive layer containing the 0-quinonediazide compound as a photosensitive component is preferably in the range of about 0.5 to 797 m<2>.

Typical photosensitive components of the negative photosensitive layer are diazo compounds, such as diazo resins which are condensates of diazonium salts and/or p-diazophenylamine and formaldehyde, as described in Japanese Patent Publication No. 7364/1983. Copolycondensates of 3-methoxydiphenylamine-4-diazonium chloride, 4-nitrodiphenylamine, and formaldehyde described in Japanese Patent Publication No. 49-48001, such as phenol salts or fluorocapric acid salts of p-diazophenylamine. Diazo resin consisting of an organic solvent-soluble salt of 2-methoxy-4-hydroxy-5 condensate of p-diazodiphenylamine and formaldehyde
Examples include -benzoylbenzenesulfonate, tetrafluoroborate of a condensate of p-diazophenylamine and formaldehyde, and hexafluorophosphate.

The present invention can be preferably applied at least to photosensitive lithographic printing plates having negatives containing these as photosensitive components. - In addition to the use of these diazo compounds alone, the present invention can also be applied to those used in combination with various resins in order to improve the physical properties of the photosensitive layer. Examples of such resins include shellac, polyvinyl alcohol derivatives, copolymers having alcoholic hydroxyl groups in the side chains described in JP-A-50-118802, and JP-A-50-118802.
A copolymer having a phenolic hydroxyl group in a side chain as described in No. 5-155355 can be mentioned.

These resins include copolymers containing at least 50% by weight of structural units represented by the following general formula, general formula R
1 (CHz-C) C00(CHz CHO)gH ■ (In the formula, R1 represents a hydrogen atom or a methyl group, R2 represents a hydrogen atom, methyl group, ethyl group, or chloromethyl group, and n represents 1-10 ) has 1 to 80 mol% of monomer units having aromatic hydroxyl groups and 5 to 90 mol% of acrylic ester and/or methacrylic ester monomer units, and has 10 to Includes polymer compounds with an acid value of 200.

Additives such as dyes, plasticizers, and components imparting printout performance can be added to the photosensitive layer of the negative photosensitive lithographic printing plate to which the developer composition and development method of the present invention are applied.

The amount per unit area of the photosensitive layer is at least 0.1 to 7
The invention is applicable to the range of g/m2.

Supports used in the photosensitive lithographic printing plate of the present invention include paper, plastics (e.g. polyethylene, polypropylene, polystyrene, etc.), laminated paper, aluminum (including aluminum alloys), zinc, copper, etc. board, cellulose diacetate, cellulose triacetate, cellulose propionate, polyethylene terephthalate,
Examples include plastic films such as polyethylene, polypropylene, polycarbonate, polyvinyl acetal, etc., paper laminated or vapor-deposited with the above-mentioned metals, and chrome-plated steel plates.

In addition to the development process, the development method using the developer composition of the present invention includes, if necessary, a development stop process (the stop process solution includes a disposable method or a cyclic use method), a non-sensitizing process, Each individual process of the desensitization process, a development stop process followed by a desensitization process, a process that combines the development process and the desensitization process, or a development stop process and a desensitization process For example, the treatment process described in Japanese Unexamined Patent Application Publication No. 54-8001 may be included.

The developer composition of the present invention is also suitable when negative-type and positive-type photosensitive lithographic printing plates are commonly developed with the same developer.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to specific examples, but the present invention is not limited thereto.

Example 1 A 3S aluminum plate with a thickness of 0 to 24 mm was immersed in a 20% aqueous sodium phosphate solution to degrease it, electrolytically polished in a 0.2N hydrochloric acid bath at a current density of 3A/m'', and then polished in a sulfuric acid bath. The anodic oxidation amount was 4 g/m
It was 2. Further, the pores were sealed with an aqueous sodium metasilicate solution to produce an aluminum plate for use in a lithographic printing plate.

Next, the following photosensitive liquid 1 was applied onto this aluminum plate using a Whaler and dried at 85° C. for 3 minutes to obtain a photosensitive lithographic printing plate (1).

Photosensitive liquid-1 -N-(4-hydroxyphenyl)methacrylamide:
Copolymer of acrylonitrile:ethyl acrylate:methacrylic acid-27:33:41:6 (weight ratio) (
Acid value -80) (High molecular weight polymer exemplified in JP-A No. 55-155355) ...5.0 g・p-
Hexafluorophosphate of paraformaldehyde condensate of diazodiphenylamine
・・・・・・0.59・Julimar-AC
IOL (product name, manufactured by Nippon Pure Chemical Industries, Ltd., acrylic acid polymer) ...0.059 ・Tartaric acid ...0.05g
・Victoria Pure Blue BOH (product name, made by Fukadogaya Chemical Co., Ltd., dye)...
・・0.19 ・Novolak resin (PP-3121) (manufactured by Gunei Chemical Co., Ltd.) ・・・・0.15g
・Pluronic L-64 (trade name, manufactured by Asahi Denka Co., Ltd., surfactant)...
0.0059 ・Methyl cellosolve ・・・・・・100+i
ff The thickness of the photosensitive layer of the obtained photosensitive lithographic printing plate (1) was 18+mg/dm''.

Next, this photosensitive planographic printing plate (1) was heated using a metal halide lamp “Idolfin 2000'' (manufactured by Iwasaki Electric Co., Ltd.).
Then, image exposure was carried out for 30 seconds from a distance of 80c11, and using the following developer composition (1), Sakura PAS 86
0 27° with a PS plate automatic developing machine (manufactured by Konishiroku Photo Co., Ltd.)
A C40 second development process was performed to obtain a lithographic printing plate.

Developer composition (1) ・N-7 enyldiethanolamine 5.0 fim・
Perex NB-L 5.0 parts by weight (
Product name, manufactured by Kao ATRAX, sodium alkylnaphthalene sulfonate (solid content 35%), jetanolamine
1.8 parts by weight Sodium sulfite
0.5 parts by weight Victoria Pure Blue BOH0,
02 parts by weight (trade name, manufactured by Fukadogaya Chemical Co., Ltd., dye), pure water 93.19 parts by weight The above developer (1) exhibited excellent developability with little odor and no residual film. In addition, when the red light reflection density of the photosensitive planographic printing plate (1) was measured using a Sakura densitometer PDA-65, it was 0.88 before development, but only 0.90 after development. The image density was increased, and images could be judged easily and accurately.

Comparative Example 1 When an experiment similar to Example 1 was conducted using a developer composition obtained by removing the dye Victoria Pure Blue BOH from the developer composition (1) in the experiment of Example 1, no residual film was observed. Although the development was successful, the image density was measured in the same manner as in Example 1 and was found to be 0.88 before development, but 0 after development.
, 71, and it was difficult to read the text and pictures in the image, making it difficult to judge whether it was a good version or not.

Example 2 The following photosensitive liquid-2 was applied to the aluminum plate used in Example 1.
was coated and dried in the same manner as in Example 1 to obtain a photosensitive lithographic printing plate (2).

Photosensitive liquid-2 ・2-Hydroxyethyl methacrylate: Acrylic nitrile: Methyl methacrylate dimethacrylic acid-39
:10:36:15 (weight ratio) copolymer (acid value -97
) ... 5.59 2- of parapolmaldehyde condensate of p-diazodiphenylamine
Methoxy-4-hydroxy-5-benzoylbenzenesulfone hydrochloric acid...0.6g ・Tartaric acid...0.059
・Oil Blue (trade name, manufactured by Orient Chemical Co., Ltd., dye) ...0.19.2-methoxyethanol ...339 Methanol ...339.Ethylene dichloride ...339 Obtained photosensitive lithographic plate The thickness of the photosensitive layer of printing plate (2) was 191119/dm2.

Next, this photosensitive lithographic printing plate (2) was imagewise exposed in the same manner as in Example 1, and developed in the same manner as in Example 1 using the following developer composition (2) to obtain a lithographic printing plate. Good deal.

Developing composition (2) ・N-phenyldiethanolamine 4.0 parts fc・
Perex NB-L 4.0 parts by weight
Jetanolamine 2.0 parts by weight, triethanolamine 2.0 parts by weight, sodium sulfite 0.3 parts by weight, Victoria Pure Blue 0.01 parts by weight (trade name, manufactured by Toko Tsuchigaya Chemical Co., Ltd., dye). Propylene glycol
0.5 parts by weight/pure water 87.1
The 9 parts by weight developer composition (2) has excellent developability, and the image density of the photosensitive planographic printing plate (2) is 1.17 before development,
After development, the value increased to 1.22, which was advantageous for determination from letters and pictures.

〔Effect of the invention〕

The developer composition according to the present invention can develop a photosensitive lithographic printing plate well, has little odor and is excellent in workability, and does not deteriorate visible image quality or improve visible image quality. be done.

Claims (4)

[Claims] (1) A developer composition for a photosensitive lithographic printing plate, characterized by containing N-phenyldiethanolamine or N-phenylethanolamine, an anionic surfactant, and 0.001 to 1% by weight of a dye. (2) The developer composition according to claim 1, wherein the dye is a basic dye. (3) The developer composition according to claim 2, wherein the basic dye is a triphenylmethane dye. (4) The developer composition according to claim 1, 2 or 3, wherein the developer composition further contains a water-soluble reducing agent.