JPH0239157A - Developer for photosensitive planographic printing plate - Google Patents

Abstract

PURPOSE:To obtain a developer having superior developing stability, high developing ability and low foaming property over a long period and especially suitable for use in an automatic developing machine by adding a specified alkali metal silicate and a specified water soluble ethylene oxide adduct. CONSTITUTION:This developer contains an alkali metal silicate having 0.6-2.0 ratio of SiO2 to M2O (M is the alkali metal) and a water soluble ethylene oxide adduct obtd. by adding >=4mol ethylene oxide to an acid, aliphat. or arom. alcohol or a hydroxy compd. or compd. is made from an acid and the ethylene oxide by addition-condensation or further bonding sulfonic acid or sulfonate. The developer has high developing stability, easily undergoes control of developing conditions and also has high developing ability, so a large amt. of a photosensitive material can be developed with a small amt. of the developer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a developer for a photosensitive lithographic printing plate 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. It is extremely important as a photosensitive layer or a photoresist composition for etching. In particular, a composition in which an alkali-soluble resin is mixed with an 〇-quinonediazide compound is advantageously used from the point of view of economy and practicality, and among these, a composition in which it is mixed with a novolac type phenol formaldehyde condensation resin or a cresol formaldehyde condensation resin is generally used. It is being As developing solutions for automatic processing machines 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, trisodium phosphate aqueous solutions, etc. have a strong etching effect on metals such as aluminum, and if the development time becomes long, it is difficult to use them as a developing solution for lithographic printing plates. . Furthermore, the development results are extremely variable and in severe cases, images may be missing due to a slight excess of the development time. 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, a sodium silicate aqueous solution or a potassium silicate aqueous solution has been used relatively advantageously. It has a weak etching effect on metals, and at the same time the content ratio of silicon oxide (SiCh) and sodium oxide (Na2O) or potassium oxide (K2O), which are the components of sodium silicate or potassium silicate (generally 3102/Na2O or SiO2/ to 2O). This is because it is possible to adjust the developability to some extent by adjusting the molar ratio (expressed in molar ratio) and concentration. In other words, as the amount of 5102 increases, the developing power is suppressed and the development stability increases,
When Na2O or Na2O 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 the amount of Na2O or only Na2O is increased, the image is likely to be lost in a short period of time.

The higher the Na, O, or 2O content, the better the treatment capacity at a given capacity. Therefore, S+02/Na2O ratio or 5i0
By increasing the total density while adjusting the 2/2O 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,
It was insufficient to meet all of the requirements, and if developing power was taken as a standard, it lacked stability, and if stability was taken as a standard, it tended to be lacking in developing power and processing ability. Furthermore, since automatic developing machines operated by boat carry out development by supplying developing solution using a spray method, the alkaline content is likely to be neutralized by carbon dioxide gas contained in the air, resulting in a deterioration in processing capacity. Therefore, 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. To summarize the problems with developing solutions such as caustic soda, sodium triphosphate, sodium silicate, and potassium silicate mentioned above, increasing the alkaline strength will improve developing power and processing ability, but they will lack development stability. In order to obtain this, the alkali concentration must be low, resulting in a lack of throughput. 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 developer as a method of obtaining development stability in a state of high alkaline strength, and a method of adding a water-soluble thionic polymer. The method is JP-A-55-
95946, and JP-A-56-142528 describes a method of adding a water-soluble amphoteric polymer electrolyte.

However, all of these developers have the disadvantage that they foam during development when developed using an automatic processor.

Furthermore, in Japanese Patent Application Laid-open No. 55-25100, periodic table I [A
, IIIA and II[B are 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.

[Problem to be solved by the invention]

Therefore, an object of the present invention is to provide a developer which has excellent development stability and processing ability over a long period of time, and has low foaming I, and is particularly suitable for use in automatic processors.

Another object of the present invention is to provide a developing method that uses the above-mentioned developer and can provide a lithographic printing plate with excellent ink receptivity.

[Means to solve the problem]

The above purpose is to use an alkali metal silicate salt having a SiO□/M2O (M represents an alkali metal) ratio of 0.6 to 2.0;
A patent characterized by containing a water-soluble ethylene oxide adduct compound obtained by adding 4 moles or more of ethylene oxide to an acid or alcohol - achieved by a developer for a photosensitive lithographic printing plate having a photosensitive layer containing a quinonediazide compound .

The alkali silicate used in the present invention includes sodium silicate, potassium silicate, and lithium silicate, which can be used alone or in combination. Alkali silicate SiO□/M
2O molar ratio (M stands for alkali metal) is 0.6
-2.0 is preferable, and 0.8-1.5 is especially preferable.

As the above molar ratio exceeds 2.0, developability tends to decrease. In addition, as the molar ratio becomes smaller than 0.6, 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 5% by weight. When the content is higher than 10% by weight, precipitates and crystals tend to form, and the waste liquid tends to gel during neutralization, making waste liquid treatment troublesome. In addition, when it is lower than 1% by weight, the developing power
Processing capacity decreases.

The water-soluble ethylene oxide adduct compound used in the developer of the present invention is a compound obtained by addition condensation of ethylene oxide to an aliphatic or aromatic alcohol or hydroxy compound or acid, and a compound to which a sulfonic acid or a sulfonic acid group is further bonded. When an aliphatic alcohol is used, the number of carbon atoms in the alcohol is preferably 3 or more, more preferably 5 or more. Examples of alcohols include n-propyl alcohol, isopropyl alcoholonopene n-butanonovaisobutanol,
Secondary butanol, tertiary butanol, n-amyl alcohol, isoamyl alcohol, 3-pentanol, n-hexanol, methyl amyl alcohol, 2-ethylbuquinol, n-heptatool, n-octatool, 2-ethylhexanol, Nonanol, n-decanol, undecanol, n-dodecanonobe 3,5.5-trimethylhexanol, n-dodecanonobe trimethylnonyl alcoholonobetetradecanol, heptadecanol, cyclohexanol, benzyl alcohol, 2,6.
8-) Tsumethyl-4-nonanol, 2-methyl-7-ethyl-4-undecanol, 5-ethyl-2-nonanol, 3-ethyl-6-undecanol, 3.9-diethyl-6-undecanol, 3.9 -diethyl-6-undecanol, 3.9-diethyl-6-tridecanol,
tridecanol, oleylalconovelauryl alcohol, octyl alcohol, acetyl alcohol B-nobe
Examples include trimethylene glycol, butanediol, 1,5-bentanediol, hexylene glycol, octylene glycol, and octylene glycol.

Examples of aromatic hydroxy compounds include P-isobutylphenol, P-isohexylphenol, P-inoctylphenol, P-indodecylphenol,
Octylphenol, hexadecylphenol, alkyl (C6-CI4) beta naphthol, dialkyl (c
e~C,,) phenol, β-naphthonobe P-phenylphenol, etc., and further examples of acids include:
Examples include valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, and stearic acid.

If necessary, these compounds further block copolymerized with propylene oxide can also be used. Further, a method for bonding a sulfonic acid group to these compounds is described, for example, in JP-A-59-195641. These compounds, along with novolac resins used in the photosensitive layer of photosensitive lithographic printing plates, gently adhere to the image area during the development process, slowing down the intrusion of the developer into the image area and stabilizing the development latitude. This is considered to be effective. When the amount of ethylene oxide added is less than 4 moles, the effect of stabilizing the development latitude is small.

The preferred amount of ethylene oxide to be added is 6 to 50 moles; if it exceeds 50 moles, the development speed will be slow or the ink adhesion to the plate surface will be poor during printing. Further, if 15 moles or more of ethylene oxide is added, foaming tends to occur in an automatic processor, but in such a case, the problem can be solved by block co-condensing propylene oxide.

The appropriate amount of these water-soluble ethylene oxide addition compounds to be added is 0.003 to 10% by weight based on the developer.
A more preferable addition amount range is 0.05 to 5% by weight.

If the photosensitive layer has a narrow development latitude,
By using a compound with a large number of moles of ethylene oxide added, or conversely, if the development latitude of the photosensitive layer is relatively wide but still insufficient, by using a compound with a small number of moles of ethylene oxide added, the desired result can be obtained. A developer having a development latitude is obtained.

The developing solution of the present invention can maintain development stability even in a developing method in which the temperature of the developing solution is raised to 28 to 40° C. in an automatic developing machine to improve developability.

The developer used in the present invention may further contain the following known compounds.

For example, NaCR1K described in JP-A-58-75152
1. Neutral salts such as KBr, chelating agents such as EDTA and NTA described in JP-A-58-190952, JP-A-59-1
Complexes such as CCo (NH3)6) C13 described in JP-A No. 5525100, ionizable compounds of elements of group ■a, group ■a, or mb of the periodic table described in JP-A-5525100; Sodium alkylnaphthalene sulfonate, N-tetradecyl-N, described in No.-51324.

Anionic or amphoteric surfactants such as N-dihydroxyethylbetaine, tetramethyldecynediol described in U.S. Pat. No. 4,374,92O, or JP-A-60-21
Nonionic surfactant described in No. 3943, JP-A-55-
Cationic polymers such as the quaternized methyl chloride of p-dimethylaminomethylpolystyrene described in No. 95946, amphoteric polymers such as the copolymer of vinylbenzyltrimethylammonium chloride and sodium acrylate described in JP-A-56-142528, Electrolyte 1, JP-A-57-
Reducing inorganic salts such as sodium sulfite described in No. 192952,
Alkali-soluble mercapto compounds or thioether compounds such as thiosalicylic acid, cysteine, and thiodiglycolic acid, inorganic lithium compounds such as lithium chloride described in JP-A No. 58-59444, lithium benzoate described in JP-A No. 50-34442, etc. Organolithium compounds, JP-A-59-
Organometallic surfactants containing 81, T1, etc. described in No. 75255, organoboron compounds described in JP-A-59-84241, quaternary ammonium salts such as tetraalkylammonium oxides described in European Patent No. 101010, Japanese Patent Application No. 1983 Examples include disinfectants such as sodium dehydroacetate described in No.-298534.

Furthermore, an organic solvent having a solubility in water of 10% by weight or less can be used in combination, if necessary.

Carboxylic acid esters such as propyl acetate, butyl acetate, amyl acetate, benzyl acetate, ethylene glycol monobutyl acetate, butyl lactate, butyl levulinate; ketones such as ethyl butyl ketone, methyl isobutyl ketone, cyclohexanone; ethylene Alcohols such as glycol monobutyl ether, ethylene glycol benzyl ether, ethylene glycol monophenyl ether, benzyl alcohol, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol; alkyl-substituted aromatic hydrocarbons such as xylene: methylene These include halogenated hydrocarbons such as dichloride, ethylene dichloride, and monochlorobenzene.

More than one kind of these organic solvents may be used. Among these organic solvents, benzyl alcohol is particularly preferred.

The content in the developer is 5% by weight or less, preferably 1 to 4% by weight.

In the development processing method using the developer of the present invention, it is advantageous to perform the development using an automatic developing machine, and it is preferable to perform the development while compensating for deterioration of the developer by replenishing the developer with a replenisher, using a so-called replenishment method. A known technique is used as the replenishment method. For example, 'vf open Pa 55 11503
9, a method of replenishing continuously or intermittently depending on the throughput of the 23rd plate and time; a sensor for measuring the degree of elution of the photosensitive layer is provided in the middle of the development zone, as described in JP-A-58-95349; Method of replenishing according to the detected degree of elution, Japanese Patent Application No. 178457/1983, Japanese Patent Application No. 1983=456
The method of measuring the impedance of the developer described in No. 0, processing the detected impedance value by computer, and replenishing the developer is preferably used.

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 John Koser [Light-Sensitive Systems J (John 1llile)].
y & 5ons, Inc.) or ``Photosensitive Resin Data Collection'' (Sogo Kagaku Kenkyu Shin-Edition).

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 used to develop a positive-working photosensitive printing plate (hereinafter referred to as a positive-working PS plate) having an 0-quinonediazide photosensitive layer.

It is particularly excellent as a developer. Such a positive PS plate is basically made of aluminum plate as a support.
- It has a photosensitive layer made of a quinonediazide compound. 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 preferably subjected to a surface treatment such as graining treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate, or the like, or anodization treatment. In addition, after graining, an aluminum plate is immersed in an aqueous solution of silicic acid as described in U.S. Pat. An aluminum plate which is anodized and then immersed in an aqueous solution of an alkali metal silicate is also preferably used. The above-mentioned anodizing treatment may be carried out by electrolysis using an aqueous or non-aqueous solution of an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid, or boric acid, or an organic acid such as oxalic acid or sulfamic acid, or a salt thereof alone or in combination of two or more. 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.

Further, a support coated with electrolytic grains as disclosed in U.S. Pat. Oxidized products are also useful. Further, chemical etching after graining as described in U.S. Pat. No. 3,834,998,
An aluminum plate which is subsequently anodized is also preferred. 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 improving the quality of life.

Furthermore, U.S. Patent No. 3511661, Japanese Patent Publication No. 57-163
No. 49, Japanese Patent Publication No. 46-35685, Japanese Patent Publication No. 1987-14
Also preferred is the method of applying an undercoat as described in No. 9491, JP-A No. 60-232998, and the like.

The photosensitive layer provided on the hydrophilic surface of the support consists of an 0-quinonediazide compound. Particularly preferred O-quinonediazide compounds are O-naphthoquinonediazide compounds, such as U.S. Pat.
No. 46,111, No. 3,046,112, No. 3.
No. 046.115, No. 3,046,118, No. 3
, No. 3,046,119, No. 3,046,12O, No. 3,046,121, No. 3,046,122, No. 3,046,123, No. 3,061,430 ,
No. 3,102,809, No. 3,106,465, No. 3,635,709, No. 3,647.443
It is written in numerous publications, including the specifications of each issue.
These can be suitably used. Among these, in particular, O-naphthoquinonediazide sulfonic acid ester or O-naphthoquinonediazidecarboxylic acid ester of aromatic hydroxy compounds, and O-naphthoquinonediazide carboxylic acid ester of aromatic amine compounds.
- Naphthoquinonediazide sulfonic acid amide or O-naphthoquinonediazidecarboxylic acid amide is preferred, especially esterifying O-naphthoquinonediazide sulfonic acid to the condensate of pyrogallol and acetone as described in U.S. Pat. No. 3,635,709. A polyester having a hydroxyl group at the end described in U.S. Patent No. 4.028.111 is subjected to an ester reaction with 0-naphthoquinonediazide sulfonic acid or 0-naphthoquinonediazidecarboxylic acid, British Patent No. 1.
0-naphthoquinonediazide sulfonic acid or 0-naphthoquinonediazidecarboxylic acid is added to a homopolymer of p-hydroxystyrene or a copolymer of these with other copolymerizable monomers as described in No. 494,043. Ester-reacted product, U.S. Patent No. 3,759
, 711, in which a copolymer of 0-aminostyrene and other copolymerizable monomers is subjected to an amide reaction with ○-quinonediazide sulfonic acid or 0-quinonediazidecarboxylic acid is extremely Excellent.

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, specifically phenol formaldehyde resins, O
-cresol formaldehyde resin, m-cresol formaldehyde resin, etc. Furthermore, JP-A-501
As described in Publication No. 25806, a phenol resin such as the above is used together with 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. Then, it is even more preferable. 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.

Furthermore, the composition of the present invention may contain an alkali-soluble resin other than the above-mentioned alkali-soluble novolak resin, if necessary. For example, styrene-acrylic acid copolymer, methyl methacrylate to methacrylic acid copolymer, alkali-soluble polyurethane resin,
Alkali-soluble vinyl resin described in Publication No. 28401,
- Alkali-soluble I raw polybutyral (sealing resin etc. can also be contained).

Additives such as dyes, plasticizers, and components imparting printout performance as described in JP-A No. 58-2O3433 can be added to the photosensitive layer made of the 0-quinonediazide compound, if necessary. .

The coating weight of the photosensitive layer made of an O-quinonediazide compound provided on the support is about 0.5 to about 7 g/m', more preferably 1.5 to 3 g/m'.

When the positive PS plate thus obtained is exposed through a transparent original to a light source rich in actinic rays such as a carbon arc lamp, mercury lamp, metal halide lamp, xenon lamp, or tungsten lamp, that portion 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.

〔Effect of the invention〕

The developer of the present invention has high development stability, it is extremely easy to manage the development conditions, and its high processing capacity allows it to develop a large number of photosensitive materials with a small amount.Moreover, there is little discharge of used waste solution, and waste solution treatment is possible. is also easy.

Furthermore, high-temperature development can also be carried out stably.

〔Example〕

The present invention will be described in detail below with reference to Examples.

Examples 1 to 6 Polyhydroxyphenyl naphthoquinone-1,2-diazide obtained by condensation of acetone and pyrogallol as described in Example 1 of Japanese Patent Publication No. 43-28403
0.8 parts by weight of 5-sulfonic acid ester, 2.2 parts by weight of 7-volac type metapara mixed cresol formaldehyde resin, 0.02 parts by weight of novolac type octylphenol formaldehyde resin, 0.08 parts by weight of phthalic anhydride, 2
-Trichloromethyl-5-(p-methoxystyryl)-
0.04 parts by weight of 1,3,4-oxadiazole and 0.04 parts by weight of crystal violet paratoluenesulfonate.
A photosensitive solution was prepared by dissolving 3 parts by weight of 03 parts by weight in 2 parts by weight of methyl cellosolve acetate and 8 parts by weight of methyl ethyl ketone. 0.3mm thick grained with nylon brush
After etching the aluminum plate with alkali, it was further electrolytically etched in a nitric acid aqueous solution, and then anodized in a sulfuric acid aqueous solution to obtain an anodized film amount of 2.7 g/m').
Thereafter, it was treated with an aqueous zinc acetate solution at 70° C., thoroughly washed, and then dried. The photosensitive solution was coated thereon using a spin coater and dried to obtain a photosensitive plate having a photosensitive layer of about 2.0 g/m'. A step wedge with a density difference of 0.15 and a halftone dot wedge are passed through this photosensitive plate to make the PS manufactured by Fuji Photo Film 0.1.
Exposure was performed using a light (2 kW metal halide lamp). On the other hand, as a developer, the molar ratio of SiO□/Na2O is approximately 0.
．． A developing solution was prepared by adding the compounds shown in Table 1 to a 2% by weight aqueous sodium silicate solution 1β of No. 9.

The exposed and baked photosensitive plates were immersed in respective developers whose temperatures were kept at 25° C. and 35° C., and one plate was taken out after 1 minute and the others after 3 minutes and washed with water. Table 2 shows the results of the number of bleed-out step wedges and the reproducibility of halftone dots in highlighted areas of the halftone dot wedge.

It can be seen from Table 2 that the developing solutions of Examples 1 to 6 have extremely high stability over temperature, time, etc., compared to the sodium silicate aqueous solution of Comparative Example 1 alone. Furthermore, the development processing ability of the developer of Example 1.2 was investigated, and in all cases, the development processing capacity was 3 m/11.
Even after developing the photosensitive plate ', the developing ability was maintained sufficiently. Further, even when potassium silicate was used in place of sodium silicate in Examples 1 to 6, performance equivalent to that of sodium silicate was maintained.

Claims (1)

[Claims] Contains an alkali metal silicate salt with a SiO_2/M_2O (M represents an alkali metal) ratio of 0.6 to 2.0 and a water-soluble ethylene oxide addition compound obtained by adding 4 moles or more of ethylene oxide to an acid or alcohol. A developer for a photosensitive lithographic printing plate having a photosensitive layer containing an o-quinonediazide compound.