JPH022571A - Developing solution for photosensitive material - Google Patents

Abstract

PURPOSE:To improve preservable stability and development stability without lowering a developing speed by consisting the developing soln. of an aq. soln. of the silicate of an alkaline metal, specifying the ratios of the SiO2 and alkaline metal to be incorporated in this developing soln. to specific ratios and adding carbonate further to the soln. CONSTITUTION:This developing soln. is the aq. soln. of the silicate of the alkaline metal and the [SiO2]/[M] ([SiO2] denotes the content of the SiO2 in unit volume expressed in gram molecular unit; [M] denotes the content of the alkaline metal in unit volume expressed in gram atom) is <=0.75. Further, the carbonate is added to this soln. The silicate of the alkaline metal to be incorporated into the developing soln. is exemplified by, for example, potassium silicate, sodium silicate, lithium silicate, potassium metasilicate, sodium metasilicate, lithium metasilicate, etc. The representative examples of the carbonate include the carbonate, acidic carbonate, ammonium salt, etc., of the alkaline metal and the amt. of the carbonate to be added is preferably at 0.1-5wt.% range. The preservable stability and development stability are improved in this way without lowering the developing speed.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is used for dissolution type development of photosensitive lithographic printing plates, etc., which have a photosensitive layer whose dissolution to an alkaline aqueous solution changes imagewise by imagewise exposure. , relates to a developer consisting of an alkaline aqueous solution using an alkali metal silicate as an alkaline agent.

[Background of the invention]

Conventionally, positive type 2 has a photosensitive layer containing an 0-quinonediazide compound as a photosensitive substance on an aluminum support.
As a developer for the 8th plate, a developer consisting of an aqueous solution of an alkali metal silicate has a poor etching effect on the aluminum support compared to those using other alkaline agents, and 5iOz, M, O (M represents an alkali metal atom (the same applies in the following description), which is known to be preferable because the developability can be adjusted by adjusting the concentration and ratio.

In this type of developer, increasing the concentration of MtO increases the developing power and processing capacity, but the development stability (stability of the image with respect to development time) decreases, and increasing the concentration of SiO□ decreases the stability of development. However, it is also known that there is a problem in that development is suppressed and it is difficult to increase both developing power and development stability.

JP-A-54-62004 discloses that by limiting the molar ratio of SiO, /Na02 of the developer and its replenisher and the SiO□ concentration of the developer to a certain range, the frequency of replacing and replenishing the developer is reduced. It has been disclosed that it is possible.

In addition, in Special Publication No. 57-7427, SiO□/M20
For the molar ratio of and the concentration of SiO2, the former is 1.0
~1.5, and the latter is preferably 1 to 4 times i%.

JP-A-58-75152 discloses that by incorporating a neutral salt such as NaC(2) or KCQ into an aqueous alkaline developer using sodium metasilicate as a basic substance, development stability and development speed can be improved. , processing capacity, etc. are disclosed to be increased. However, even if such a neutral salt is included, the storage stability of the developer is not improved.

The present inventors have achieved excellent development speed, development stability, and storage stability by keeping the SiJ/M ratio below a certain value and adding carbonate to a developer consisting of an aqueous alkali metal silicate solution. The inventors have discovered that it is possible to obtain a developer having the following properties, and have arrived at the present invention.

[Purpose of the invention]

Therefore, an object of the present invention is to provide a developer containing an alkali metal silicate as an alkaline agent, which has improved storage stability and development stability without reducing the development speed. It is.

[Structure of the invention]

The above object of the present invention is to provide an aqueous solution of an alkali metal silicate, wherein [5iO21/[Ml
([S1o□1 indicates the content of Sin in a unit volume when expressed in gram molecules, [Ml indicates the content in a unit volume when an alkali metal is expressed in gram atoms.) 0.75 or less, and is achieved by a developer to which carbonate is further added.

The present invention will be explained in detail below.

Typical alkali metal silicates to be contained in the developer of the present invention include potassium silicate, sodium silicate, lithium silicate, potassium metasilicate, sodium metasilicate, lithium metasilicate, and the like.

[5iOz]/[Ml in the developer of the present invention is 0
．． It is 75 or less, preferably 0.1 to 0.5.

The developing solution of the present invention is made by incorporating a carbonate into an aqueous developing solution using an alkali metal silicate as an alkaline agent, thereby reducing the buffering that becomes noticeable when [5iO21/[Ml] is lowered to 0.75 or less. Since a decrease in performance can be prevented, the development speed can be increased without reducing storage stability and development stability. [SiO2]/[Ml is
From the viewpoint of buffering capacity, it is usually better to set it to 0.1 or more.

Carbonates added to the developer of the present invention include alkali metal carbonates (e.g., sodium carbonate, potassium carbonate, etc.) and acidic carbonates (e.g., sodium hydrogen carbonate),
Representative examples include ammonium salts (eg, ammonium carbonate).

The amount added is preferably in the range of 0.1 to 5% by weight.

An alkaline aqueous solution containing an alkali metal silicate is
During storage in contact with air, carbon dioxide gas in the air is absorbed and carbonate is produced, but the developer of the present invention has a buffering effect by adding carbonate in advance during preparation. The storage stability and development stability are significantly improved.

The developing solution of the present invention may contain alkaline agents other than those mentioned above within a range that does not impede the effects of the present invention, and depending on the purpose of use, components other than those mentioned above may optionally be included as additives.

The following additives can be added to the developer of the present invention. For example, Na described in JP-A No. 58-75152
Neutral salts such as CQ, KCQ, KBr, etc., JP-A-58-1
Chelating agents such as EDTA and NTA described in JP-A-59-121336;
]CQ3. C0C (complexes such as 22.6H20, sodium alkylnaphthalenesulfonate, N-tetradecyl-N, described in JP-A-50-51324).

Anionic or amphoteric surfactants such as N-dihydroxyethyl betaine, nonionic surfactants such as tetramethyldecynediol described in U.S. Pat. No. 4,374,920, and p-dimethyl as described in JP-A-55-95946. Cationic polymers such as the quaternized methyl chloride of aminomethyl polystyrene; ampholytic polymer electrolytes such as the copolymer of vinylbenzenetrimethylammonium chloride and sodium acrylate described in JP-A-56-142528; JP-A-57-192952; Reducing inorganic salts such as sodium sulfite described in JP-A No. 58-59444, inorganic lithium compounds such as lithium chloride described in JP-A No. 58-59444, JP-B No. 50-34
Organolithium compounds such as lithium benzoate described in No. 442, organometallic surfactants containing Si, Ti, etc. described in JP-A-59-75255, organoboron compounds described in JP-A-59-84241, European Patent No. Examples include quaternary ammonium salts such as tetraalkylammonium oxide described in No. 101010, organic solvents such as benzyl alcohol, and ethylene glycol monophenyl ether. Furthermore, the developer used in the present invention can contain an antifoaming agent. Preferred antifoaming agents include U.S. Pat.
No. ゜250.727, No. 3,545,970, British Patent No. 1,382゜901, No. 1.387,713
Examples include compounds described in No. 1, etc.

The photosensitive material to which the developer of the present invention is applied can be developed with a developer containing water as a main component and an alkaline agent, and a photosensitive layer whose solubility changes upon irradiation with light is coated on a support. For example, photosensitive lithographic printing plates, color proof photosensitive materials, etc. are those in which a soluble layer is provided on a support to form an image-like resist layer by an electrophotographic method or the like.

The support used in the photosensitive lithographic printing plate is as follows:
Paper, plastics (e.g. polyethylene, polypropylene, polystyrene), laminated paper, aluminum (including aluminum alloys), metal plates such as zinc, copper, etc., cellulose diacetate, cellulose triacetate, cellulose propionate, polyethylene terephthalate, Examples include plastic films such as polyethylene, polypropylene, polycarbonate, polyvinyl acetal, etc., paper or plastic films laminated or vapor-deposited with metals such as those mentioned above, aluminum or chrome-plated copper plates, etc. Among these, especially aluminum The present invention is preferably applied to photosensitive materials having aluminum-coated composite supports.

The surface of the aluminum material is preferably roughened for the purpose of increasing water retention and adhesion to the photosensitive layer.

The photosensitive layer whose solubility changes upon irradiation with light 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. Examples of usable materials include those that cause a difference in solubility in a developing solution depending on the composition, those that exhibit a difference in intermolecular adhesive strength before and after exposure, and those that exhibit a difference in affinity for water and oil due to exposure or subsequent development treatment.

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, silyl ether polymers that decompose with acids, and C-0-
Examples include a combination of a compound having a C-group and a photoacid generator. As a photosensitive diazo compound, it is a positive-type compound that becomes alkali-soluble when exposed to light. - Quinonediazide compounds, aromatic diazonium salts, etc. are examples of negative-type compounds whose solubility decreases upon exposure to light.

〔Example〕

Hereinafter, the present invention will be explained in detail with reference to Examples.

Example 1 A JIS 1050 aluminum plate with a thickness of 24 mm (L) was immersed in a 2% sodium hydroxide aqueous solution, degreased, electrochemically roughened in a dilute nitric acid solution, thoroughly washed, and then diluted. 2.5 by anodizing in nitric acid solution
g/m" oxide film was formed on the surface of the aluminum plate. The aluminum plate thus treated was washed with water,
After drying, photosensitive liquid A with the following composition was applied to dry type i2.5g/m"
A positive photosensitive lithographic printing plate A was obtained by coating and drying.

Photosensitive liquid A Naphthoquinone-1,2diazide(2)-5-sulfonic acid ester of pyrogallol acetone resin (Japanese Patent Publication No. 43-2
Synthesized by the method described in Example 1 of No. 8403. )...1 part by weight m + p-talesol-formaldehyde resin...
2 parts by weight Lert-butylphenol-formaldehyde resin
...0.3 parts by weight Victoria Pure Blue BOH (trade name, manufactured by Hodogaya Chemical Co., Ltd., dye) ...0.3 parts by weight Crystal Violet (B, A, S, F, manufactured by Hodogaya Chemical Co., Ltd., dye)・・・
・0.01 part by weight Ethylene diglycol 7-ethyl ether...20 parts by weight Positive-working photosensitive material was prepared in the same manner as the above-mentioned positive-working photosensitive lithographic printing plate A except that the above photosensitive liquid A was changed to the following photosensitive liquid B. A lithographic printing plate B was obtained.

Photosensitive solution B 2.3.4-1-lyhydroxybenzophenone and 1.2
-Ester compound with naphthoquinone diazide-5-sulfonic acid chloride...20 parts by weight Copolymerized polymer compound of p-hydroxymethacrylanilide, acrylonitrile, ethyl acrylate, and methyl methacrylate...80 parts by weight2- IJ chloromethyl-
5-Cβ-(2'-benzofuryl)vinyl)-1,3,
4-Oxadiazole...2 parts by weight Victoria Blue BOH...1 part by weight p-tert-octylphenol formaldehyde novolak resin (Mw=130
Esterified product of 0) and 1.2-su7toquinone diazido 5-sulfonic acid chloride ・
...1 part by weight glutaric anhydride ...3
Part by weight Methyl cellosolve...2001
iW.

Ethyl cellosolve...500 weight J1
The above two types of positive-working photosensitive planographic printing plates were placed in close contact with a transparent positive film and exposed for 60 seconds from a distance of 70 cm using a 2kW metal halide lamp. It was developed using a developing machine for 30°C12O seconds.

The developer used was as follows.

Developer A concentrated developer having the following composition was prepared, and then this concentrated developer was diluted 6 times with water to prepare a developer.

[SiO2]/[M] in the developer is 0.44, pH
It was 13.02.

Concentrated developer composition water
...610g benzoic acid
...122g50% KOH・=
250g 250g Nonionic world (Emulgen 147, manufactured by Kao Corporation)...5g Potassium silicate A...150
g Potassium carbonate...61
Development was carried out using both the developer immediately after preparation and the developer stored in an IH container with the lid (30 m+) removed for one month. As a result of development, no difference was observed between the two.

Furthermore, when the above developer (the above concentrated developer was diluted to 6@) was left exposed to air for 24 hours, there was no change in pH.

Comparative Example 1 An experiment similar to Example 1 was conducted except that a concentrated developer having the following composition was used.

Concentrated developer composition water
...610g benzoic acid
...122g50% KOII
-250g nonionic surfactant (Emulgen I47, manufactured by Kao Corporation)...5
g Potassium silicate...150
gThis concentrated developer was diluted 6 times with water [S1
0□1/[M] was 0.44.

0 development results showed that there was a difference in development speed between those used immediately after preparation and those used one month after preparation.

As a result of forced deterioration of the above developer under the same conditions as in Example 1, the pH fluctuation was -0.07.

Example 2 An experiment similar to Example 1 was conducted except that a concentrated developer having the following composition was used.

Concentrated developer composition water
...426g β-anilinoethanol ...25g propylene glycol ...25g 2-hydroxy-3-
Naphthoic acid...50gp-tert-
Butylbenzoic acid...99g50%K
OH...250g Nonionic surfactant (Emulgen 147, manufactured by Kao Corporation)...2.5g Potassium silicate A...178
g Potassium sulfite...60g
Potassium carbonate...60g
This concentrated developer was diluted 6 times with water, and the IQ developer [5i] was diluted with water.
Oz]/[Ml Ha 0.43, pH Ha 13. oO Te Atsuta.

The development results are for the one used immediately after preparation and the one used immediately after preparation.
No difference in development speed was observed between the two and those used after several months.

Further, the above developer was subjected to forced deterioration under the same conditions as in Example 1, but there was no change in pt+.

Comparative Example 2 An experiment similar to Example 1 was conducted except that a concentrated developer having the following composition was used.

Concentrated developer composition water
...426g β-anilinoethanol
...25g propylene glycol
...25g 3-hydroxy-2-su7toic acid ...50gp-tert-butylbenzoic acid ...99g50% K
O)l
...250g nonionic surfactant (Emulgen 147, manufactured by Kako Co., Ltd.) ...2.5g Potassium silicate A ...178
g Potassium sulfite...60
g This concentrated developer was diluted 6 times with water.
O□]/[Ml was 0.43, and pH was 12.99.

The development results are for the one used immediately after preparation and the one used immediately after preparation.
A difference in development speed was observed between the two and those used after several months.

As a result of forced deterioration of the above developer under the same conditions as in Example 1, the pll variation was -0.08.

Example 3 An experiment similar to Example 1 was conducted except that a concentrated developer having the following composition was used.

Concentrated developer composition water
...1220g benzoic acid
...122g50%KOH...4
50g Nonionic surfactant (Emulgen 147, manufactured by Kako Co., Ltd.)...5g Potassium silicate A...430g
Potassium carbonate...61g This concentrated developer is diluted 6 times [SiO2]/
[Ml ILL 0.21%pH 13.30'T
: Ara f:.

The development results are for the one used immediately after preparation and the one used immediately after preparation.
No difference in development speed was observed between the two and those used after several months.

Further, the above developer was subjected to forced deterioration under the same conditions as in Example 1, but there was no change in pH.

Comparative Example 3 An experiment similar to Example I was conducted except that a concentrated developer having the following composition was used.

Concentrated developer composition water
...1220g benzoic acid
...122g50%KOF+
-450g nonionic surfactant (Emulgen 147, manufactured by Kako Co., Ltd.)...5g Potassium silicate A...150
g This concentrated developer was diluted 6 times with water (s;
o21/[Ml was 0.21SpH was 13.28.

The development results are for the one used immediately after preparation and the one used immediately after preparation.
A difference in development speed was observed between the two and those used after several months.

As a result of forced deterioration of the above developer under the same conditions as in Example 1, the pH fluctuation was -0.06.

Example 4 An experiment similar to Example 1 was conducted except that a concentrated developer having the following composition was used.

Concentrated developer composition water
...610g benzoic acid
...122g50%KOH...250
g Nonionic surfactant (Emulgen 147, manufactured by Kako Co., Ltd.)...5g A Potassium silicate...300
g Potassium carbonate...61g
A developer obtained by diluting this concentrated developer 6 times [SiO].

/[Ml was 0.70, pH was 13.11.

The development results are those used immediately after preparation and those used immediately after preparation.
No difference in development speed was observed between the two and those used after several months.

Further, the above developer was subjected to forced deterioration under the same conditions as in Example 1, but there was no change in pH.

Comparative Example 4 An experiment similar to Example 1 was conducted except that a concentrated developer having the following composition was used.

Concentrated developer composition water
-610g benzoic acid
...122g 50% KO! (...25
0g Nonionic surfactant (Emulgen 147, manufactured by Kao Corporation)...5g Potassium silicate A...30g
A developer obtained by diluting this concentrated developer 6 times with water [S10
□]/[M] was 0.70, and pll was 13.10.

The development results are for the one used immediately after preparation and the one used immediately after preparation.
A difference in development speed was observed between the two and those used after several months.

As a result of forced deterioration of the above developer under the same conditions as in Example 1, the pH fluctuation was -0.05.

Comparative Example 5 An experiment similar to Example 1 was conducted except that a concentrated developer having the following composition was used.

Concentrated developer composition water
...610g benzoic acid
...122g50%KOH...
250g Nonionic surfactant (Emulgen 147, manufactured by Kao Corporation)...5g Potassium silicate A...150
g Potassium chloride...61
g This concentrated developer was diluted 6 times with water.
io□]/[M] was 0.44, and p+ was 13.00.

The development results are for the one used immediately after preparation and the one used immediately after preparation.
A difference in development speed was observed between the two and those used after several months.

As a result of forced deterioration of the above developer under the same conditions as in Example 1, the pH variation was -0.04.

From the above Examples and Comparative Examples, in an alkaline aqueous developer containing an alkali metal silicate, [SiO,]
It can be seen that even if the /[M] ratio is lowered, the buffering capacity does not deteriorate by adding carbonate. It is also found that the addition of carbonate has a superior effect of improving storage stability compared to the addition of neutral salt.

〔Effect of the invention〕

According to the present invention, it is possible to prevent a decrease in buffering capacity when [5tOzl/[M] of an aqueous developer containing an alkali metal silicate as an alkaline agent is lowered, so that (Si02]/[M] of the developer can be prevented. M], thereby increasing storage stability and development stability without reducing development speed.

[Brief explanation of drawings]

FIG. 1 is a schematic side sectional view of an automatic processor used in an embodiment of the present invention. ■...Transport roller pair 2...Photosensitive material 3...
・Press roller 4... Inclined roller 5... Developing tank 5a, 25a, 25b... Pump 6... Developer supply pipe 7... Developer supply member U... Developer tank 13...・Brush roller 21...Mixing tank 23...Dilution water storage tank 31...Gumming section

Claims (1)

[Claims] A developer consisting of an aqueous solution of an alkali metal silicate, the ratio of SiO_2 and alkali metal contained in the developer is [SiO_2]/[M] ([SiO_2] is SiO_
2 in unit volume when expressed in gram molecules, and [M] indicates the content in unit volume when alkali metal is expressed in gram atoms. ) is 0.75 or less, and further contains a carbonate.