JPS6217746A - Developing solution for photosensitive lithographic plate - Google Patents

Abstract

PURPOSE:To improve development stability by developing a photosensitive layer containing an o-quinonediazide compound with an aqueous solution containing alkali silicate and at least one of mono-, di-, and tri-alkanol quaternary ammonium compound. CONSTITUTION:An oxide film is formed by roughening an aluminum plate electrochemically in a solution of nitric acid, and after washing, anodizing it in a solution of sulfuric acid. After washing and drying, the obtained support is coated with a photosensitive solution prepared by dissolving 3pts. of the esterified product of a resorcinol-benzaldehyde resin and naphthoquinone-1,2- diazido-5-sulfonyl chloride, 9pts. of a cresol-formalin novolak resin, and 0.12pt. of Victoria Pure Blue BOH in 100pts. of 2-methoxyethanol by using a rotary coater and dryed to obtain the photosensitive lithographic plate having the photosensitive layer. This printing plate is exposed and developed.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to an improved developer for photosensitive planographic printing plates (hereinafter abbreviated as PS plates) containing an 0-quinonediazide compound as a photosensitive component. be.

[Conventional technology]

It is known that the diazo group of an 0-quinonediazide compound is decomposed by irradiation with actinic light, resulting in a compound having a carboxyl group. Therefore, when a photosensitive layer containing an O-quinonediazide compound is treated with an alkaline atomizer after one image exposure, the light-absorbing area is removed and the unexposed area becomes an image. It is extremely important as a photosensitive layer for printing plates or as a photoresist composition for etching. In particular, a composition in which an alkali-soluble resin is mixed with an 0-quinonediazide compound is advantageously used from the viewpoint of economy and practicality.

As a developer for these O-quinonediazide photosensitive layers, an aqueous solution of sodium triphosphate, sodium hydroxide, sodium silicate, potassium silicate, ammonium silicate, etc. alone or in combination is used. However, aqueous solutions of sodium hydroxide and tribasic sodium phosphate have a strong etching effect on metals such as aluminum, and are therefore inconvenient as developing solutions for 28 plates using such metal supports.

In addition, the development results are extremely variable, and furthermore, the developing ability is significantly reduced by repeated use, and the amount that the PS plate can process (processing capacity) with respect to a fixed volume of developer is very small.

Therefore, in recent years, a sodium silicate aqueous solution or a potassium silicate aqueous solution has been used because it is relatively advantageous in solving such problems. It has a weak enching effect on metals, and at the same time, silicon oxide (SiO□) and sodium oxide (Na2), which are components of sodium silicate or potassium silicate, are
This is because the development performance can be adjusted to some extent by adjusting the content ratio (generally expressed as a molar ratio of 20 to SiO2/Na2O or SiO□/) and the concentration. However, when trying to increase the developing power, development stability (the allowable development time range in which image quality is maintained at the optimum development time), a developer with poor development stability becomes more likely to cause image loss as the development time becomes longer. )
However, when trying to improve the development stability, there was a tendency for the development power and processing ability to be insufficient.

In other words, the point of this developer is that if the alkaline strength is increased, it will have excellent developing power and processing ability, but it will lack development stability, and in order to obtain sufficiently good development stability, the alkali concentration must be lowered. Therefore, the processing capacity was lacking. 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 No. 50-51324 describes a method of adding an anionic surfactant or an amphoteric surfactant to a developer as a method of obtaining development stability in a state of high alkaline strength, and also a method of adding a water-soluble thionic polymer. The method is JP-A-55-1995.
946, a method of adding a water-soluble amphoteric polymer electrolyte is described in JP-A-56-142528. However, all of these developing solutions have the disadvantage that they foam during development when developed using an automatic processor.

[Purpose of the invention]

Therefore, the object of the present invention is to have excellent developing power, developing stability, processing ability, foaming property, etc. An object of the present invention is to provide a developer suitable for a photosensitive lithographic printing plate containing an 0-quinonediazide compound as a photosensitive component.

[Structure of the invention]

The object of the present invention is to provide a photosensitive layer containing an 0-quinonediazide compound, characterized in that an aqueous solution containing an alkali silicate contains at least one of mono-, di-, and trialkanol quaternary ammonium compounds. This is achieved by a developer of a photosensitive lithographic printing plate having the following properties.

The alkali silicate used in the present invention is preferably one that exhibits alkalinity when dissolved in water, such as alkali metal silicates such as sodium silicate, potassium silicate, lithium silicate, ammonium silicate, etc. These may be used alone or Two or more types can be used in combination.

In a preferred embodiment of the present invention, the alkali silicate is an alkali metal silicate or ammonium silicate, and the S
i027M, 0 molar ratio (M represents an alkali metal atom or an ammonium group) is 0.5 to 3.0, particularly preferably 1.0 to 2.0, and the alkali silicate concentration is 1.
-15% by weight, particularly preferably from 1.5 to 0% by weight.

Mono-, di- and trialkanol quaternary used in the present invention
Ammonium compounds include the following compounds.

For example, trialkylmonoalkanolammonium compounds such as trimethylethanolammonium chloride; dialkylmonoarylmonoalkanolammonium compounds such as benzyldimethylethanolammonium hydroxide; dialkyldialkanolammonium compounds such as dimethyljetanolammonium chloride; hensylmethyl Monoalkylmonoaryl dialkanol ammonium compounds such as jetanolammonium chloride; methyltrieta/
Examples include monoalkyltrialkanolammonium compounds such as -ammonium hydroxide; monoaryltrialkanolammonium compounds such as benzyltriethanolammonium chloride.

Among these, mono- and dialcamel ammonium compounds are preferred, and mono-alkanol ammonium compounds are particularly preferred. Among the monoalkanol ammonium compounds, trimethylethanolanohyammonium and benzyldimethylammonium compounds are preferably used.

The content of mono-, di-, or trialkanol ammonium compound contained in the developer is 0.0001 to 1.0.
It is weight%, and the preferable content is 0.0005 to 0.
．． The content is 5% by weight, and the particularly preferable content is 0.00% by weight.
It is 1 to 0.1% by weight.

The following additives can be added to the developer of the present invention in order to further improve development performance.

For example, NaC1 described in JP-A-58-75152! ,
KCl.

"Neutral salts such as KBr, chelating agents such as EDTA and NTA described in JP-A-58-190952, JP-A-59-1909
[CO(NH3)a)c described in No. 121336
l! Complexes such as s, sodium alkylnaphthalenesulfonate described in JP-A-50-51324, N-tetradecyl-
Anionic or amphoteric surfactants such as N,N-dihydroxyethylbetaine, nonionic surfactants such as tetramethyldecynediol described in U.S. Pat. No. 4,374,920, p- as described in JP-A-55-95946 Cationic polymers such as methyl chloride quaternized product of dimethylaminomethyl polystyrene; ampholytic polymer electrolytes such as the copolymer of vinylbenzyltrimethylammonium chloride and sodium acrylate described in JP-A-56-142528;
Reducing inorganic salts such as sodium sulfite described in JP-A-57-192951, inorganic lithium compounds such as lithium chloride described in JP-A-58-59444, JP-A-59-75255
Organometallic surfactants containing Si, 'l''i, etc. described in the issue,
Examples thereof include organic boron compounds described in JP-A-59-84241 and quaternary ammonium salts such as tetraalkylammonium oxides described in European Patent No. 101°010.

On the other hand, the PS plate to which the developer of the present invention is applied has a photosensitive layer containing an O-quinonediazide compound on a support having a hydrophilic surface.

Preferred examples of the support 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 preferably treated in a grain chamber, immersed in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate, or the like, or anodized. Also, U.S. Patent No. 2,714,
As described in No. 066-, an aluminum plate is treated by immersion in a sodium silicate aqueous solution after graining, and an aluminum plate is anodized as described in Japanese Patent Publication No. 5125/1983. , those treated by immersion in an aqueous solution of an alkali metal silicate are also suitably used. The above anodizing treatment includes, for example, phosphoric acid, chromic acid, nitric acid,
It is carried out by passing an electric current through an aluminum plate as an anode in an electrolytic solution consisting of an aqueous or non-aqueous solution of an inorganic acid such as boric acid, an organic acid such as oxalic acid or sulfamic acid, or a salt thereof, or a combination of two or more thereof. .

Also effective is silicate electrodeposition as described in US Pat. No. 3,658,662.

Furthermore, U.S. Patent No. 4,087,341, Japanese Patent Publication No. 46-2
Also useful are supports woven with electrolytic grains, such as those disclosed in No. 7481 and JP-A-52-30503, which are anodized as described above. Furthermore, U.S. Patent 3,
Aluminum plates which are grained and then chemically etched and then anodized are also preferred, as described in US Pat. No. 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 contains an O-quinonediazide compound. Particularly preferred 0-quinonediazide compounds are 0-naphthoquinonediazide compounds, which are described, for example, in U.S. Pat. No. 3,046,110;
3,046,111, 3,046,121, 3,046,115, 3,046,118, 3,046,119, 3,046,120, 3 , 046,122, 3.046,123, 3,061,430, 3.102,809, 3,106.465, 3.635,707, 3,647 , No. 443, etc.

Among these compounds are O-naphthoquinonediazide sulfonic acid esters or O-naphthoquinonediazidecarboxylic acid esters of aromatic hydroxy compounds, and aromatic amine compounds. - naphthoquinone diazide sulfonamide or 0-naphthoquinone.

Nondiazidecarboxylic acid amide and the like are preferred, particularly esters of 1,2-diazobenzoquinonesulfonic acid chloride and polyhydroxyphenyl or 1,2-diazonaphthokyrinsulfonic acid chloride and resorcinol described in JP-A-56-1044. - Esters with benzaldehyde resins are preferred.

Although these photosensitive components, which are O-quinonediazide compounds, can form a photosensitive layer by themselves, it is preferable to mix a resin or the like into the carrier of the photosensitive layer for the purpose of improving the physical properties of the photosensitive layer.

Examples of the above resins include phenol formaldehyde resin, cresol formaldehyde resin, p-te
Alkali-soluble resins such as rt-7'' methylphenol resin and phenol-modified xylene resin are preferably used.The alkali-soluble resin preferably contains 40 to 8
It can be contained in an amount of 0% by weight.

The photosensitive layer may further contain additives such as dyes, plasticizers, components for imparting printout performance, and the like.

The photosensitive layer is applied onto the support using a suitable solvent solution. The coating amount of the photosensitive layer is preferably 0.1 to 79/
m', more preferably 0.5 to 39/m'.

When such a PS plate is exposed to active light from a carbon arc lamp, mercury lamp, metal halide lamp, xenon lamp, tungsten lamp, etc. through a transparent original, that part becomes alkali-soluble. Therefore, when treated with the developer of the present invention, the photosensitive areas are eluted, the hydrophilic surface of the support is exposed, and a lithographic printing plate is obtained.

The preferred temperature at which the development process is performed is 10°C to 35°C, and the more preferred range is 25°C to 30°C.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples. Note that "%" indicates weight % unless otherwise specified.

Example 1 An aluminum plate with a thickness of 0.3 m was electrochemically roughened in a nitric acid solution, thoroughly washed, and then anodized in a sulfuric acid solution to form an oxide film of 2.59 parts m'' on the aluminum plate. formed on the surface.

After washing with water and drying, 3 parts of the esterified product of resorcin benzaldehyde resin and 7-toquinone 1,2-diazide-5-sulbonyl chloride synthesized according to the example of JP-A-56-1044, 9 parts of cresol-formalin novolac resin, and A photosensitive solution prepared by dissolving 0.12 parts of Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Industry Co., Ltd.) in 100 parts of 2-methoxyethanol was applied onto the above support using a rotary coater and dried. ! i'/m
A photosensitive lithographic printing plate having a photosensitive layer of ' was obtained.

(7) P S The plate was exposed to light using a 2 kW metal halide lamp through a step wedge with a density difference of 0.15. On the other hand, a developer was prepared in which 5i02/Na2O molar ratio IIJ 1.7 and Si02 content was 5% silicic acid, IJum water W3 solution, and d) 0.03% by weight of remethylethanol ammonium chloride was added. .

Two of the exposed 28 plates were immersed in a developer maintained at 5°C, one plate was taken out after 1 minute, and the other plates were taken out after 5 minutes and washed with water. Table 1 shows the results of the number of stages of the step wedge eluted.

Comparative Example 1 As a developer, the molar ratio of s r O2/Na2 O was approximately 1.
Two sheets were developed in the same manner as in Example 1, except that in Example 7, an aqueous sodium silicate solution containing 5% of 5i02 was used.

Table 1 shows the results of the number of stages of the step wedge eluted.

Example 2 The same development process as in Example 1 was carried out, except that a developer containing 0.001% by weight of benzyldimethylethanolammonium chloride was used instead of the additive used in Example 1. Ta.

Table 1 shows the results of the number of stages of the step wedge eluted.

Example 3 The same procedure as in Example 1 was used, except that 0.005% by weight of benzylmethyljetanol ammonium chloride was added in place of the additive f) used in Example 1 as a developer. Development processing was performed.

Table 1 shows the results of the number of stages of the step wedge eluted.

Example 4 As a developer, the molar ratio of S10□/2O was 1.1 and 5i
Trimethylethanolammonium chloride 0.05% in potassium silicate aqueous solution with n2 content of 1.3% by weight
The same development process as in Example 1 was carried out except that the additive was used.

Table 1 shows the results of the number of stages of the step wedge eluted.

Comparative Example 2 As a developer, S 1o27 K, O% k ratio is 1.1
The development process was carried out in the same manner as in Example 4, except that an aqueous potassium silicate solution containing 1.3% by weight of 5in2 was used.

Table 1 shows the results of the number of stages of the step wedge eluted.

From Table 1, it can be seen that the developing solution of Example 4 to which quaternary ammonium of the present invention was added has extremely stable developability compared to an aqueous solution containing only alkali silicate.

Table 1 [Effects of the Invention] By using the developer of the present invention, development stability is increased and development conditions can be extremely easily managed. In addition, processing capacity is increased, and more 28 plates can be developed with a smaller amount of developer. (Also, since the ammonium compound used in the present invention has good solubility in the developer, it is advantageous when making a highly concentrated concentrated solution.) Therefore, the developer of the present invention reduces fatigue of the developer. It has significant advantages when used as a developer and replenisher when developing large quantities of 28 plates with compensation by addition of replenisher.

Claims (1)

[Claims] A photosensitive lithographic printing plate having a photosensitive layer containing an o-quinonediazide compound, characterized in that an aqueous solution containing an alkali silicate contains at least one of mono-, di- and trialkanol quaternary ammonium compounds. developer.