JPH0569423B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a developer composition and a developing method for photosensitive materials, and more specifically, to a developer composition suitable for removing non-image areas of a photosensitive material having a water-insoluble image forming layer. The present invention relates to a composition and a developing method. [Prior Art] So-called wash-off type photosensitive materials, which obtain relief images by removing non-image areas through development, are used in many applications, such as resin letterpress plates and photosensitive lithographic printing plates. (PS version), printed wiring resists, non-silver salt reversible films, photosensitive peel mask films, color proof films, etc. Alkaline aqueous developers are generally used for these developments, but since photosensitive materials often contain lipophilic substances that are insoluble or poorly soluble in water or alkaline aqueous solutions, development is slow and non-image areas are It may take too much time to remove or may leave undeveloped images. 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-Sho
No. 53-44202 discloses an aqueous developer using benzyl alcohol;
No. 86328 discloses an aqueous developer containing phenyl glycols. Although these techniques improve developability by adding a small amount of organic solvent, they are still insufficient.
Moreover, each has its own unique odor, which causes discomfort to workers and is unfavorable in terms of health and safety. [Object of the Invention] A first object of the present invention is to provide a developer composition and a developing method that can suitably develop a photosensitive material having an image forming layer containing a lipophilic substance. A second object of the present invention is to provide a developer composition and a developing method that are suitable for the above-mentioned photosensitive materials and are low in odor, have excellent workability, and have improved safety and health problems. [Structure of the Invention] The object of the present invention is to provide a developer composition for a photosensitive material, which is characterized by comprising an aqueous solution containing a compound represented by the following general formula [1], and to provide a water-insoluble image on a support. In a method of obtaining an image by treating a photosensitive material having a forming layer with a developer after image exposure and removing non-image areas, the developer contains a compound represented by the following general formula [1]. This is achieved by a characteristic developing method for photosensitive materials. General formula [1]

[Formula] In the formula, R ₁ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a hydroxyalkyl group, or a halogen atom, and R ₂ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a halogen atom. Alkyl group, carbon number 1~
4 represents a hydroxyalkyl group or a hydroxyalkoxyalkyl group having 2 to 4 carbon atoms, R ₃ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group having 1 to 4 carbon atoms, and n represents 1
Represents an integer from ~3. The present invention will be explained in detail below. In the above general formula [1], the alkyl group represented by R ₁ is preferably a methyl group, a preferable example of the alkoxy group represented by R ₁ is a methoxy group, and the hydroxyalkyl group represented by R ₁ is preferably a carbon Numbers 1 to 4, such as hydroxymethyl group, hydroxypropyl group, etc.
Examples of the halogen atom represented by R ₁ include a fluorine atom, a chlorine atom, a bromine atom, and the like. Preferred examples of the alkyl group represented by R ₂ and R ₃ include a methyl group and an ethyl group, and examples of the hydroxyalkyl group include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, and the hydroxyalkoxyalkyl group of R ₂ Examples of the group include hydroxyethoxyethyl group. As specific examples of the compound represented by the general formula [1] used in the developer composition of the present invention, particularly preferred compounds are shown below, but the present invention is not limited thereto. Compound example

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[Formula] The compound represented by the general formula [1] can be synthesized by a known method, and the synthesis method is Beilstein
Handbuch der Organischen Chemie Volume 12 299
You can refer to the page. The concentration of the compound represented by formula [1] in the developer composition is suitably in the range of 0.01 to 10% by weight, more preferably in the range of 0.5 to 5% by weight. The developer composition of the present invention has water as its main solvent, and has an excellent effect of wetting and solubilizing lipophilic substances or lipophilic polymers using only water as a solvent. It consists of an aqueous solution containing the compound represented by formula [1], and various additives can be used in combination, and additives that are preferably used in combination include alkaline agents, anionic surfactants, and water-soluble reducing agents. etc. Examples of alkaline agents include sodium silicate,
Potassium silicate, sodium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, tribasic potassium phosphate, dibasic potassium phosphate,
Inorganic alkaline agents such as tertiary ammonium phosphate, dibasic ammonium phosphate, sodium metasilicate, sodium bicarbonate, sodium carbonate, potassium carbonate, ammonium carbonate etc., mono-, di- or triethanolamine and tetraalkylammonium hydroxide. Organic alkaline agents such as organic alkaline agents and organic ammonium silicates are useful. The content of alkaline agent in the developer composition is
A range of 0.05 to 20% by weight is preferred, more preferably a range of 0.1 to 10% by weight. Examples of anionic surfactants include higher alcohol ( _C8 - _C22 ) sulfate 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-81" (trade name, manufactured by Ciel Chemical Co., Ltd.), disodium alkyl sulfate, etc.), fat group alcohol phosphate ester salts (for example, sodium salt of cetyl alcohol phosphate ester, etc.), alkylaryl sulfonate salts (for example, dodecylbenzenesulfonic acid sodium salt, isopropylnaphthalene sulfonic acid sodium salt, dinaphthalene disulfonic acid sodium salt) , the sodium salt of metanitrobenzenesulfonic acid), the sulfonates of alkylamides (e.g.

[Formula], etc.), and sulfonic acid salts of dibasic fatty acid esters (for example, 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 0.1 to 20
% by weight, more preferably in the range of 1.0 to 10% by weight. Water-soluble reducing agents include organic and inorganic reducing agents. Examples of organic reducing agents include phenol 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,
Sulfites such as ammonium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, sodium phosphite, potassium phosphite, sodium hydrogen phosphite, potassium hydrogen phosphite, potassium dihydrogen phosphite, sodium dihydrogen phosphite , phosphates such as dipotassium hydrogen phosphite, hydrazine, sodium thiosulfate, sodium dithionite, etc., but the reducing agent that is particularly effective in the present invention is sulfite. The water-soluble nature of the above-mentioned water-soluble reducing agents includes alkali-solubility, and these water-soluble reducing agents have a concentration of 0.1 to 10
It is contained in an amount of 0.5 to 5% by weight, preferably 0.5 to 5% by weight. The present invention eliminates the need to contain a solvent that has an odor or a problem in terms of health and safety by containing the compound represented by the above general formula [1] in a developer composition, or Therefore, it is desirable that the developer composition of the present invention does not contain solvents other than water in an amount exceeding the limit that causes odor or health and safety problems. The proportion of water in the water is preferably 80% or more. Photosensitive materials suitable for processing with the developer composition of the present invention are those having an image forming layer containing components that are insoluble or poorly soluble in water or aqueous alkaline solutions, and particularly suitable are those having a lipophilic group. A photosensitive material 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 non-image areas are removed by development, so-called wash-off type photosensitive materials. In the wash-off type photosensitive material, the area irradiated with actinic rays hardens and becomes insoluble in the developing solution, and remains as an image area. On the other hand, there are positive-working photosensitive materials that have increased solubility and are removed during development, leaving the actinic ray irradiated areas as images. The present invention works well on both negative-type and positive-type photosensitive materials, but is particularly effective on negative-type photosensitive materials. Specific examples of such wash-off type photosensitive materials include photosensitive planographic printing plates, resin letterpress plates,
There are color proof films, resists for printed wiring, non-silver salt reversible films, photosensitive peel mask films, etc. Among these, photosensitive lithographic printing plates use highly lipophilic components to make the image areas easier to accept oil-based ink, and in non-image areas, it is necessary to completely remove the lipophilic components during development. Applying inventions can have great effects. The image forming layer of the photosensitive material according to the present invention contains a photosensitive substance as an essential component, and the physical and chemical substances of the photosensitive substance change upon exposure or subsequent development processing. Some products have different solubility in developing solutions, some have different adhesive forces between molecules before and after exposure, and some have different affinity for water and oil due to exposure or subsequent development processing. Those that can form an image area, and those that can be used in Japanese Patent Application Laid-Open No. 55-
The multilayer structure described in No. 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-O compounds that decompose with acids.
Examples include compounds having a -C- group. Typical positive-type compounds that become alkali-soluble upon exposure include o-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 o-quinonediazide compounds include:
For example, JP-A No. 47-5303, JP-A No. 48-63802, JP-A No. 48
−63803, No. 49-38701, No. 56-1044, No. 56
−1045, Special Publication No. 41-11222, Special Publication No. 43-28403,
No. 45-9610, No. 49-17481, U.S. Patent No. 2797213
No. 3046120, No. 3188210, No. 3454400,
3544323, 3573917, 3674495, 3573917, 3674495,
3785825, British Patent No. 1227602, British Patent No. 1251345,
1267005, 1329888, 1330932, and German Patent No. 854890. Examples of acid-decomposable compounds include JP-A-60-37549, JP-A-60-10247, and JP-A-60-
Examples include those described in No. 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 o-quinonediazidecarphonic acid esters or o-quinonediazidecarboxylic acid esters of aromatic hydroxy compounds, and o-quinonediazide sulfonic acid or o-quinonediazidecarboxylic acid amide of aromatic amino compounds; These include those in which an o-quinonediazide compound is used alone, and those in which it is mixed with an alkali-soluble resin and this mixture is provided as a photosensitive layer. Alkali-soluble resins include novolac 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, JP-A-1987-
As described in No. 125806, in addition to the above phenol resin, a condensate of phenol or cresol substituted with an alkyl group having 3 to 8 carbon atoms such as t-butylphenol formaldehyde resin and formaldehyde is used. A combination of these can also be applied. The photosensitive layer containing an o-quinonediazide compound as a photosensitive component may further contain dyes,
Additives such as plasticizers, components that provide printout performance, etc. can be added. The amount per unit area of the photosensitive layer containing the o-quinonediazide compound as a photosensitive component is preferably about 0.5 to 7.
The invention can be applied in the range of g/m ² . Typical photosensitive components of the negative photosensitive layer are diazo compounds, such as diazonium salts and/or
or diazo resin, which is a condensate of p-diazophenylamine and formaldehyde,
Phenol salt or fluorocaprate of p-diazophenylamine described in No. 7364, 3-methoxydiphenylamine-4-diazonium chloride and 4-nitrodiphenyl chloride described in Japanese Patent Publication No. 49-48001. Diazo resin consisting of an organic solvent soluble salt of a copolycondensate of enylamine and formaldehyde, 2-methoxy-4- of a condensate of p-diazophenylamine and formaldehyde
Examples thereof include hydroxy-5-benzoylbenzenesulfonate, tetrafluoroborate of a condensate of p-diazophenylamine and formaldehyde, and hexafluorophosphate. The present invention can be preferably applied at least to negative photosensitive materials 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 Cieraac and polyvinyl alcohol derivatives, as well as
Examples include a copolymer having an alcoholic hydroxyl group in the side chain described in Japanese Patent Application Laid-open No. 118802, and a copolymer having a phenolic hydroxyl group in the side chain described in JP-A-55-155355. These resins include copolymers containing at least 50% by weight of structural units represented by the general formula:

〔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 0.24 mm was degreased by immersing it in a 20% sodium phosphate aqueous solution, and then 0.2N
After electrolytic polishing in a hydrochloric acid bath at a current density of 3 A/m ² , anodization was performed in a sulfuric acid bath. At this time, the amount of anodic oxidation was 4 g/m 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, apply the following photosensitive liquid-1 on this aluminum plate with a Whaler, and heat it at 85°C.
The plate was dried for 3 minutes to obtain a photosensitive planographic printing plate (1). Photosensitive liquid 1 N-(4-hydroxyphenyl) methacrylamide: acrylonitrile: ethyl acrylate: methacrylic acid = 27:33:41:6 (weight ratio)
Copolymer (acid value = 80) (High molecular polymer exemplified in JP-A-55-155355) ...5.0g ・Hexafluorophosphate of paraformaldehyde condensate of p-diazodiphenylamine
...0.5g ・Julymar AC10L (trade name, manufactured by Nippon Pure Chemical Industries, Ltd.)
Acrylic oxidation polymer)...0.05g ・Tartaric acid...0.05g ・Victoria Pure Blue BOH (trade name, Hodogaya Chemical Co., Ltd., dye)...0.1g ・Novolac resin (PP-3121) (Gunei Chemical Co., Ltd.) (KK)
(manufactured by Asahi Denka Co., Ltd.) ...0.15g ・Pluronik L-64 (trade name, manufactured by Asahi Denka Co., Ltd.)
Surfactant) ...0.005g ・Methyl cellosolve ...100ml The thickness of the photosensitive layer of the obtained photosensitive lithographic printing plate (1) is
It was 18mg/ ^dm2 . Next, this photosensitive lithographic 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 80 cm, and using the following developer composition (1), Sakura PAS 860 PS was used.
A lithographic printing plate was obtained by developing at 27° C. for 40 seconds using an automatic plate developing machine (manufactured by Konishi Roku Photo Co., Ltd.). Developer composition (1) - Sodium silicate (Japanese Industrial Standard Sodium Silicate No. 3, solid content 40%) ...1.7g - Pionin A-44B (trade name, Takemoto Yushi Co., Ltd.,
Sodium dibutylnaphthalene sulfonate solid content 80%) ...2.0g ・ Exemplary compound (1) of general formula [1] ...3.0g ・ Sodium sulfite ...1.0g ・ Water ...92.3g Developer composition (1 ) had almost no odor and was favorable in terms of the working environment. Furthermore, the resulting plate had no residual film and had excellent developability. Next, when this lithographic printing plate was attached to a Heidelberg GTO type printing machine and printing was carried out, a clean and sharp printed matter was obtained. Example 2 The following photosensitive liquid 2 was coated on the aluminum plate used in Example 1 and dried in the same manner as in Example 1 to obtain a photosensitive lithographic printing plate (2). Photosensitive liquid 2 ・ Copolymer of 2-hydroxyethyl methacrylate: acrylonitrile: methyl methacrylate: methacrylic acid = 39:10:36:15 (weight ratio) (acid value = 97) ......5.5 g ・ p-diazodiphenyl 2-Methoxy-4-hydroxy-5-benzoylbenzenesulfonic acid hydrochloride, a paraformaldehyde condensation product of amine
...0.6g ・Tartaric acid ...0.05g ・Oil Blue (product name, Orient Chemical Co., Ltd.)
2-methoxyethanol (33g), methanol (33g), ethylene dichloride (33g) The thickness of the photosensitive layer of the obtained photosensitive lithographic printing plate (2) is
It was 19mg/ ^dm2 . Next, this photosensitive planographic printing plate (2) was 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 planographic printing plate. Ta. Developer composition (2) - Diethanolamine...1.5g - Pellex NBL (trade name, manufactured by Kao Atlas,
Sodium alkylnaphthalenesulfonate solid content 35%) ...3.0g ・ Exemplary compound (3) of general formula [1] ...1.0g ・ 3-Methyl-3-methoxybutanol
...3.5g ・Sodium sulfite ...0.5g ・Water ...90.5g The developer composition (2) above shows good developability with the addition of a relatively small amount of organic solvent, and is low in toxicity and danger. The developer was hot. Furthermore, a developer composition obtained by removing the exemplified compound (3) of general formula [1] from the above developer (comparison (1)) had extremely poor developability and had virtually no developing ability. . Example 3 The negative photosensitive lithographic printing plate used in Example 2 was
A step wedge with a density difference of 0.15 was used as an original for exposure, and was subjected to batch development at 30° C. for 20 seconds using the developer shown in Table 1 to obtain the results shown in Table 2. The development evaluation was performed using development ink SPO-1 (manufactured by Konishiroku Photo Industry Co., Ltd.). The meanings of the symbols in the odor column of Table 2 are as follows. ◎…There is no odor or almost no odor, and it is not bothersome during work. ○...The odor is slight, but it's bothersome to workers. △...The odor is strong and makes you uncomfortable during work.

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[Table] As is clear from Table 2, the developer of the present invention is
The photosensitive lithographic printing plate was developed well, had a weak odor, and had good workability. Example 4 An aluminum plate with a thickness of 0.24 mm was immersed in a 20% sodium phosphate aqueous solution to degrease it, and then electrolytically polished in a 0.2N hydrochloric acid bath at a current density of 3 A/m ² .
Anodized in a sulfuric acid bath. At this time, the amount of anodic oxidation was 4 g/m ² . Further, the aluminum plate was sealed with an aqueous sodium metasilicate solution to prepare an aluminum plate for use in a lithographic printing plate. Next, the following photosensitive liquid 3 was coated on this aluminum plate to obtain a negative photosensitive lithographic printing plate, and photosensitive liquid 4 was coated to obtain a positive photosensitive lithographic printing plate. Coating is done using a rotary coater at 100°C.
and dried for 4 minutes. Coating film thickness and weight for both versions
It was 2.5g/ ^m2 . Photosensitive liquid 3 N-(4-hydroxyphenyl) methacrylamide: acrylonitrile: ethyl acrylate: methacrylic acid = 27:33:41:6 (weight ratio)
Copolymer of (acid value = 80)...5.0g ・Hexafluorophosphate of paraformaldehyde condensate of p-diazodiphenylamine
...0.5g ・Julymar AC10L (trade name, manufactured by Nippon Pure Chemical Industries, Ltd.)
Acrylic oxidation polymer)...0.05g ・Tartaric acid...0.05g ・Victoria Pure Blue BOH (trade name, Hodogaya Chemical Co., Ltd., dye)...0.1g ・Novolac resin (PP-3121) (Gunei Chemical Co., Ltd.) (KK)
(manufactured by Asahi Denka Co., Ltd.) ...0.15g ・Pluronik L-64 (trade name, manufactured by Asahi Denka Co., Ltd.)
Surfactant) ...0.005g ・Methyl cellosolve ...100ml Photosensitive liquid 4 ・Naphthoquinone-(1,2)-diazide-(2)-5
- Condensate of sulfonic acid chloride and resorcinol-benzaldehyde resin......3.5g ・m-cresol-formaldehyde novolac resin "MP-707" (manufactured by Gunei Chemical Co., Ltd.)......9g ・Naphthoquinone-(1,2 )-Diazide-(2)-4
-Sulfonic acid chloride...0.15g ・Victoria Pure Blue BOH (trade name, manufactured by Hodogaya Chemical Industry Co., Ltd., dye)...0.2g ・Methyl cellosolp...100g Negative and positive type thus obtained The photosensitive lithographic printing plate was exposed using a 2 Kw metal halide lamp through a step wedge with a density difference of 0.15. Thereafter, development was carried out at 25° C. using the developing composition (6) in an automatic developing machine. The pH of the developer was adjusted to 12.65 with 10% NaOH or 1N-HC immediately before use after adding the additives. Developer composition (6) - Sodium silicate (Japanese Industrial Standard Sodium Silicate No. 3) ...250g - Sodium hydroxide ...30g - Exemplary compound of general formula [1] (1) ...100g - Peretskus NB- L (trade name, manufactured by Kao Corporation, anionic surfactant) ...1.700g ・Sodium sulfite ...200g ・Emulgen A-500 (trade name, manufactured by Kao Corporation, nonionic surfactant) ...10g ・Water...10 When the negative-type and positive-type photosensitive lithographic printing plates were developed indiscriminately using the above developer,
Both versions were developed well. When the planographic printing plate obtained by the development treatment was attached to a Heidelberg GTO type printing machine and printed, sharp printed matter without stains was obtained for both the negative planographic printing plate and the positive planographic printing plate. Moreover, it had almost no odor, was excellent in workability, and had no hygienic problems. Example 5 An undercoat layer coating solution having the following composition was coated on a polyethylene terephthalate film to prepare a support having a releasable surface. Torezin F-30 (alcohol-soluble nylon,
(manufactured by Toray Industries) 10 g Methanol 90 g Next, colored recording layer dispersions of four colors having the following compositions were prepared and coated to give a dry film thickness of 3 μm.・Photosensitive resin with the following structure (average molecular weight 800) 10g

【formula】 ・ Phenol resin with the following structure (m:n=4:6, average molecular weight 2000) 5g

〔Effect of the invention〕

The developer composition according to the present invention can satisfactorily develop photosensitive materials containing lipophilic substances, has little odor and is excellent in workability, and also improves safety and health problems.

Claims (1)

[Scope of Claims] 1. A developer composition for photosensitive materials, comprising an aqueous solution containing a compound represented by the following general formula [1]. General formula [1] [Formula] [In the formula, R ₁ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a hydroxyalkyl group, or a halogen atom, and R ₂ represents a hydrogen atom , C1-C4 alkyl group, C1-C4 alkyl group
~4 hydroxyalkyl group or 2 to 4 carbon atoms
represents a hydroxyalkoxyalkyl group, R ₃
represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group having 1 to 4 carbon atoms, and n represents an integer of 1 to 3. ] 2 In a method of obtaining an image by treating a photosensitive material having a water-insoluble image forming layer on a support with a developer after image exposure and removing non-image areas, the developer has the following general formula [1 ] A method for developing a photosensitive material, characterized by containing a compound represented by the following. General formula [1] [Formula] [In the formula, R ₁ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a hydroxyalkyl group, or a halogen atom, and R ₂ represents a hydrogen atom , C1-C4 alkyl group, C1-C4 alkyl group
~4 hydroxyalkyl group or 2 to 4 carbon atoms
represents a hydroxyalkoxyalkyl group, R ₃
represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group having 1 to 4 carbon atoms, and n represents an integer of 1 to 3. ]