JPH0354339B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to an improved developer for photosensitive lithographic printing plates containing an 0-quinonediazide compound as a photosensitive component. [Prior Art] It is known that the diazo group of an 0-quinonediazide compound is decomposed by irradiation with actinic rays, resulting in a compound having a carboxyl group. Therefore, when a photosensitive layer containing an 0-quinonediazide compound is treated with an alkaline developer after image exposure, the exposed area is removed and the unexposed area becomes an image, so that it becomes a so-called positive layer.
In recent years, it has been extremely used as a positive-working photosensitive component, particularly in photosensitive layers of photosensitive lithographic printing plates or photoresist compositions for etching. In particular, a composition in which an alkali-soluble resin is mixed with an 0-quinonediazide compound is advantageously used from the economic and practical standpoint, and among these, a mixture with a novolac type phenol formaldehyde condensation resin or a cresol formaldehyde condensation resin is generally used. As the developer for these 0-quinonediazide photosensitive layers, aqueous solutions of sodium phosphate, caustic soda, sodium silicate, potassium silicate, ammonium silicate, etc., alone or in combination, are used. However, caustic soda, an aqueous solution of sodium triphosphate, etc. have a strong etching effect on metals such as aluminum, and are therefore inconvenient as developing solutions for photosensitive lithographic printing plates using metal supports due to the long development time. Furthermore, the development results were extremely variable, and in severe cases, even a slight excess of the development time could result in image loss. In addition, the developing ability is severely reduced by repeated use, and the processable amount (processing capacity) of a photosensitive lithographic printing plate at a given capacity is extremely small. Therefore, in recent years, an aqueous solution of sodium silicate or an aqueous solution of potassium silicate has been used relatively advantageously. It has a poor etching effect on metals, and at the same time the content ratio of silicon oxide (SiO ₂ ) and sodium oxide (Na ₂ O) or potassium oxide (K ₂ O), which are the components of sodium silicate or potassium silicate (generally SiO ₂ /Na ₂ O or
This is because the developability can be adjusted to some extent by adjusting the molar ratio of SiO ₂ /K ₂ O) and concentration. That is, as the amount of SiO ₂ increases, the developing power is suppressed and the development stability increases, and as the amount of Na ₂ O or K ₂ O increases, the developing power increases and the development stability decreases.
The development stability referred to here refers to the stability of the image with respect to the development time, and if only Na ₂ O or K ₂ O is increased, the image is likely to be lost in a short period of time. The higher the Na ₂ O or K ₂ O content, the better the processing capacity at a given capacity. Therefore, the SiO ₂ /Na ₂ O ratio or
By increasing the total density while adjusting the SiO ₂ /K ₂ O ratio in terms of developing power and development stability, it is possible to obtain a certain degree of developing power and stability as well as throughput. However, they were insufficient to meet all of the requirements; they tended to lack stability when developing power was taken as a standard, and they tended to lack developing power and processing ability when stability was taken as a standard. Furthermore, since the concentration is relatively high, precipitates are likely to form, and there are drawbacks such as a large amount of neutralizing acid being used when treating waste liquid after use. The above-mentioned caustic soda, tribasic sodium phosphate, sodium silicate,
To summarize the problems with developing solutions such as potassium silicate, if the alkaline strength is increased, the developing power and processing ability will be excellent, but development stability will be lacking, and in order to obtain development stability, the alkali concentration must be lowered. , and therefore lacks processing power. Therefore, if development stability can be obtained in a state of high alkaline strength, a developer excellent in both developing power and processing ability can be obtained. JP-A-50-51324 discloses a method of adding an anionic surfactant or an amphoteric surfactant to the developing solution as a method of obtaining development stability under conditions of high alkaline strength, and a method of adding a water-soluble cationic polymer. However, in JP-A-55-95946, a method of adding a water-soluble amphoteric polymer electrolyte is disclosed in JP-A-56-95946.
It is described in Publication No. 142528. However, all of these developers have the disadvantage that they foam during development when developed using an automatic processor. Also, in Japanese Patent Application Laid-Open No. 55-25100, periodic table A,
The addition of ionic compounds of redundant elements A and B is described. In this case, although there was an effect of suppressing etching of the anodized aluminum support due to strong alkali, the development stability was not sufficient. [Object of the invention] Therefore, the object of the present invention is to improve developing power, development stability,
The purpose of the present invention is to provide a developer that is excellent in both processing ability and foaming properties. [Structure of the Invention] As a result of intensive research into these points, the present inventors found that by incorporating a water-soluble polyoxyethylene/polyoxypropylene block polymerization type compound described below into an aqueous alkali silicate solution, 0- It has been found that improved developers of quinonediazide photosensitive layers can be obtained. Examples of the alkali silicate used in the present invention include sodium silicate, potassium silicate, lithium silicate, ammonium silicate, and the like, which can be used alone or in combination. The SiO ₂ /M ₂ O molar ratio of the alkali silicate (M represents an alkali metal) is 0.5 to 3.0.
is preferable, and 1.0 to 2.0 is particularly preferable. As the above molar ratio exceeds 3.0, developability tends to decrease. In addition, as the molar ratio becomes smaller than 0.5, the alkaline strength increases, causing the problem of etching metals such as aluminum plates, which are commonly used as supports for photosensitive planographic printing plates. The concentration of alkali silicate in the developer is preferably 1 to 10% by weight, particularly preferably 1.5 to 7% by weight. When the content is higher than 10% by weight, precipitates and crystals tend to form, and waste liquid tends to gel when neutralized, making waste liquid treatment troublesome. Further, when the content is less than 1% by weight, developing power and processing ability become low. The water-soluble polyoxyethylene/polyoxypropylene block polymerization type surfactant, which is the most characteristic component used in the present invention, is represented by the following structural formula. HO-( _C2H4O- ) _a- ( _C3H6O- ) _b ( _C2H4O ) _cH In the formula, a, b _{, and} c represent integers _from 1 to 10,000. The range of polymers suitable for the present invention is 40 to 80% by weight of ethylene oxide, preferably 40 to 60% by weight of the total molecule.
As molecular weight of polyoxypropylene in weight%
A range of 1000 to 4000, preferably 2000 to 3500 is particularly good. The appropriate amount of these water-soluble polyoxyethylene/polyoxypropylene block polymerization type surfactants to be added is 0.001 to 10% by weight of the developer, and the more preferable range is 0.05 to 7% by weight. . The 0-quinonediazide photosensitive layer to which the developer of the present invention is applied is a photosensitive copying layer containing an 0-quinonediazide compound as a photosensitive component, which increases its alkali solubility upon irradiation with actinic light. Such light-sensitive materials are described in "Light-Sensitive Systems" by J. Coser (John Wiley & Co., Ltd.).
Sons, Inc.) or “Photosensitive Resin Data Collection”
(edited by the Institute of Chemical Research) and other publications.
In particular, mixtures of 0-quinonediazide sulfonic acid esters of aromatic polyhydroxy compounds and alkali-soluble resins such as phenol resins, cresol resins, styrene/maleic anhydride copolymers, etc. are commonly used, and are photosensitive for lithographic printing. It is used for plates (presensitized plates), photoetching resists, etc. Among these, the developer of the present invention is particularly excellent as a developer for a positive-type photosensitive printing plate (hereinafter referred to as a positive-type PS plate) having an 0-quinonediazide photosensitive layer. Such a positive type PS plate basically has a photosensitive layer made of an 0-quinonediazide compound on an aluminum plate as a support. Suitable aluminum plates include pure aluminum plates and aluminum alloy plates, as well as plastic films laminated or vapor-deposited with aluminum. The surface of the aluminum plate is grained,
It is preferable that the surface be subjected to a surface treatment such as immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate, etc., or anodization treatment. In addition, after graining, the U.S. patent
As described in the specification of No. 2714066, an aluminum plate is immersed in an aqueous sodium silicate solution, and as described in Japanese Patent Publication No. 47-5125, an aluminum plate is anodized and then treated with an alkali metal silicate. Those treated by immersion in an aqueous solution of are also suitably used. The above-mentioned anodizing treatment is carried out by electrolysis using an aqueous solution or a non-aqueous solution of an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid, boric acid, etc., or an organic acid such as oxalic acid, sulfamic acid, or a salt thereof alone or in combination of two or more kinds. This is carried out by passing an electric current through a liquid using an aluminum plate as an anode. Also effective is silicate electrodeposition as described in US Pat. No. 3,658,662. Furthermore, US Patent No. 4087341, Japanese Patent Publication No. 46
Also useful are supports coated with electrolytic grains as disclosed in Japanese Patent Laid-Open No. 52-30503 and No. 52-30503, which are anodized as described above.
Also preferred are aluminum plates that are grained, chemically etched, and then anodized, as described in U.S. Pat. No. 3,834,998. These hydrophilic treatments are performed not only to make the surface of the support hydrophilic, but also to prevent harmful reactions with the photosensitive composition provided thereon, and to improve the adhesion with the photosensitive layer. It is applied for various purposes, such as to improve the quality of life. The photosensitive layer provided on the hydrophilic surface of the support consists of an 0-quinonediazide compound. Particularly preferred 0-quinonediazide compounds are 0-naphthoquinonediazide compounds, such as those described in U.S. Pat.
No. 3046110, No. 3046111, No. 3046112, No. 3046115, No. 3046118, No. 3046119,
Same No. 3046120, Same No. 3046121, Same No. 3046122,
Same No. 3046123, Same No. 3061430, Same No. 3102809,
It is described in numerous publications including the specifications of the same No. 3106465, the same No. 3635709, and the same No. 3647443, and these can be suitably used. Among these, especially the aromatic hydroxy compound 0-
naphthoquinone diazide sulfonic acid ester or 0-naphthoquinone diazide carboxylic acid ester,
and 0-naphthoquinonediazide sulfonic acid amide or 0-naphthoquinonediazidecarboxylic acid amide of aromatic amino compounds, particularly 0-naphthoquinonediazide sulfonate in the condensate of pyrogallol and acetone described in U.S. Pat. No. 3,635,709. A product obtained by ester reaction with an acid, a product obtained by ester reacting a polyester having a hydroxyl group at the terminal with 0-naphthoquinonediazide sulfonic acid or 0-naphthoquinonediazidecarboxylic acid as described in U.S. Pat. No. 4,028,111, UK. 0-naphthoquinonediazide sulfonic acid or 0-naphthoquinonediazidecarboxylic acid is added to a p-hydroxystyrene homopolymer or a copolymer of this and other copolymerizable monomers as described in Patent No. 1494043. ester reaction, a copolymer of p-aminostyrene and other copolymerizable monomers as described in U.S. Pat. No. 3,759,711, and 0-naphthoquinonediazide sulfonic acid or 0-naphthoquinonediazidecarboxylic acid. Products made by subjecting acids to amide reactions are very good. Although these 0-quinonediazide compounds can be used alone, it is preferable to mix them with an alkali-soluble resin and provide this mixture as a photosensitive layer. Suitable alkali-soluble resins include novolak type phenolic resins, and specifically include phenol formaldehyde resins, 0-cresol formaldehyde resins, m-cresol formaldehyde resins, and the like. Furthermore, JP-A-1987-
As described in Publication No. 125806, in addition to the above-mentioned phenol resin, a phenol substituted with an alkyl group having 3 to 8 carbon atoms such as t-butylphenol formaldehyde resin or a condensate of cresol and formaldehyde is used. It is even more preferable to use them together. The alkali-soluble resin is contained in the photosensitive layer in an amount of about 50 to about 85% by weight, more preferably 60 to 80% by weight. Additives such as dyes, plasticizers, and components imparting printout performance can be added to the photosensitive layer made of the 0-quinonediazide compound, if necessary. Dyes are used to make the image area contrast with the non-image area (support surface) after exposure and development of the PS plate. For example, C.
I.26105 (oil red RR), CI21260 (oil scarlet #308), CI42595 (oil blue),
Alcohol soluble dyes such as CI52015 (methylene blue) and CI42555 (crystal violet) are preferred. Such dyes need only be added in an amount sufficient to provide a clear contrast between the color of the hydrophilic surface of the support exposed by exposure and development of the photosensitive printing plate and the remaining portion of the photosensitive layer; It is appropriate that the content be within a range of about 7% by weight or less based on the total amount of the photosensitive composition. Plasticizers are effective for making the photosensitive layer provided on the support have desired flexibility, and include, for example, dimethyl phthalate, diethyl phthalate,
Dibutyl phthalate, diisobutyl phthalate,
Phthalate esters such as dioctyl phthalate, octyl capryl phthalate, dicyclohexyl phthalate, ditridecyl phthalate, butylbenzyl phthalate, diisodecyl phthalate, diaryl phthalate, dimethyl glycol phthalate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, butyl Glycol esters such as phthalyl butyl glycolate and triethylene glycol dicaprylate, phosphate esters such as tricresyl phosphate and triphenyl phosphate, diisobutyl adipate, dioctyl adipate,
Aliphatic dibasic acid esters such as dimethyl sebacate, dibutyl sebacate, dioctyl azelate, and dibutyl maleate, polyglycidyl methacrylate, triethyl citrate, glycerin triacetyl ester, butyl laurate, and the like are effective. The plasticizer is contained in an amount of about 5% by weight or less based on the total amount of the photosensitive composition. The printout material is used so that a visible image can be immediately observed by imagewise exposing the photosensitive layer of the PS plate. For example, British patent no.
PH indicator as described in specification No. 1041463,
Examples include a combination of 0-naphthoquinonediazide-4-sulfonyl chloride and a dye as described in US Pat. No. 3,969,118, and a photochromic compound as described in Japanese Patent Publication No. 44-6413. Furthermore, as described in JP-A-52-80022, the sensitivity can be increased by adding a cyclic acid anhydride to the photosensitive layer. A photosensitive composition comprising such O-naphthoquinone diazide is coated onto a support from a solution in a suitable solvent. Suitable solvents include glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and 2-methoxyethyl acetate, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, and chlorinated hydrocarbons such as ethylene dichloride. . The coating amount of the photosensitive layer made of an 0-quinonediazide compound provided on the support is about 0.5 to about 7 g/m ²
and more preferably 1.5 to 3 g/m ² . When the positive PS plate thus obtained is exposed through a transparent original to a light beam rich in actinic light such as a carbon arc lamp, mercury lamp, metal halide lamp, xenon lamp, or tungsten lamp,
That part becomes alkali-soluble. Therefore, when treated with the developer of the present invention, the exposed portions of the photosensitive layer are eluted and the hydrophilic surface of the support is exposed. [Effects of the Invention] By using the developer of the present invention in these light-sensitive materials, firstly, development stability is increased and development conditions can be extremely easily controlled. Second, the processing capacity is increased and a large amount of light-sensitive material can be developed with a small amount. Thirdly, there are advantages such as less discharge of used liquid and easy waste liquid treatment. [Example] The present invention will be explained in detail with reference to Examples below. Examples 1 to 5 Polyhydroxyphenyl naphthoquinone obtained from the condensate of acetone and pyrogallol described in Example 1 of Japanese Patent Publication No. 43-28403
1,2-Diazido-5-sulfonic acid ester 0.8
2.2 parts by weight of novolak-type meta-para mixed cresol formaldehyde resin, 0.02 parts by weight of novolak-type octylphenol formaldehyde resin, 0.08 parts by weight of phthalic anhydride, 2-trichloromethyl-5-(p-methoxystyryl)-1,3, 4
- A photosensitive solution was prepared by dissolving 0.04 parts by weight of oxadiazole and 0.03 parts by weight of crystal violet paratoluenesulfonate in 20 parts by weight of methyl cellosolve acetate and 8 parts by weight of methyl ethyl ketone. After etching the grained aluminum plate with alkali using a 0.3mm thick nylon brush, it was further electrolytically etched in a nitric acid aqueous solution.
Subsequently, it was anodized in an aqueous sulfuric acid solution (anodized film amount: 2.7 g/m ² ), then treated with an aqueous zinc acetate solution at 70°C, thoroughly washed and dried, and then the above photosensitive solution was applied using a spin coating machine. Approximately 2.0g/approximately 2.0g after applying and drying
A photosensitive plate with a photosensitive layer of m ² was obtained. This photosensitive plate was exposed using a PS light (2kw metal halide lamp) manufactured by Fuji Photo Film Co., Ltd. through a step wedge and a dot wedge with a density difference of 0.15. On the other hand, a developer was prepared by adding the compounds shown in Table 1 to a 2% by weight aqueous solution of sodium silicate 1 having a SiO ₂ /Na ₂ O molar ratio of about 1.1.

[Table] Two exposed and baked photosensitive plates were immersed in each developer solution kept at 25°C, and one plate was taken out after 1 minute and the other plate was washed with water after 5 minutes. Table 2 shows the results of the number of eluted step wedges and the halftone reproducibility of the highlighted portion of the halftone dot wedge.

Table 2 shows that the developing solutions of Examples 1 to 5 have extremely stable developability compared to the sodium silicate aqueous solution of Comparative Example 1 alone. Furthermore, the developing processing ability of the developing solutions of Examples 1 and 2 was investigated, and both showed 1.
Sufficient developing power was maintained even after developing a 3 m ² photosensitive plate. Examples 6 to 10 Using the photosensitive plate of Example 1 as a developer
2.5% by weight of potassium silicate with _SiO2 / _K2O molar ratio 1.2
The compounds shown in Table 3 were added to the aqueous solution 1, and development was carried out in the same manner as in the examples. The results are shown in Table 4.

【table】

【table】

[Table] From Table 4, it can be seen that the developing solutions of Examples 6 to 10 have extremely stable development stability compared to the potassium silicate aqueous solution of Comparative Example 2 alone. Furthermore, the development processing ability of the developer of Example 8 was investigated, and all of them had 1
Sufficient developing power was maintained even after developing a 3 m ² photosensitive plate. In addition, the waste solution after processing each of the developing solutions of Examples 6 to 10 was diluted with water at a ratio of 1:1 and neutralized with hydrochloric acid, but no gel formation was observed in any case, and the neutralization treatment could be easily performed. did it. Example 11 In Example 1, a photosensitive plate using naphthoquinone-1,2-diazide-5-sulfonic acid ester of bisphenol A was used instead of the naphthoquinonediazide compound used there, and development was carried out in the same manner. Similar results as in Example 1 were obtained.

Claims (1)

[Claims] 1. It is characterized by containing 0.001 to 10% by weight of a polyoxyethylene polyoxypropylene block polymerization type water-soluble surfactant in an aqueous alkali silicate solution. - A developer for a photosensitive lithographic printing plate having a quinonediazide photosensitive layer.