JPH01279245A - Developing solution composition - Google Patents

Abstract

PURPOSE:To attain the improvement to remove the non-exposed and non-cured photosensitive layer of a photosensitive material and to prevent the generation of printing stains in the non-image part by constituting the compsn. of an aq. soln. contg. a specific compd. CONSTITUTION:The photosetting photosensitive layer is provided and said layer is constituted of the aq. soln. contg. the compd. expressed by formula I. In formula I, R1 denotes a hydrogen atom, halogen atom, etc.; R2 denotes a hydrogen atom, alkyl group, etc.; R3 denotes a hydrogen atom or alkyl group of 1-2C; (m), (n) denote 1-3 integer. The content of the compd. expressed by formula I is confined to a 1-20wt.% range in the developing soln. compsn. The non-exposed part is thereby completely removed and the removing rate is improved; in addition, the generation of the printing stains in the non-image part is prevented.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a photosensitive image forming method having a photocurable photosensitive layer containing a photosensitive diazo resin, an original crosslinking resin, an addition monounsaturated compound, etc. The present invention relates to a developer composition for the material.

In particular, the present invention relates to a developer composition suitable for removing unexposed areas of a photosensitive lithographic printing plate having a photocurable photosensitive layer.

[Conventional technology]

A photosensitive lithographic printing plate having a photocurable photosensitive RIk (hereinafter referred to as
Negative type 28 edition and Necho. ) is a metal page with a hydrophilic surface,
A photocurable photosensitive layer is provided on the surface of a support such as a glass stick or a kite. 11 with activated Motobayashi through negative film! When the image is exposed to light, the exposed area hardens and becomes softer than the unexposed area, resulting in lower solubility. Therefore, the unexposed areas of the photosensitive layer can be removed with a suitable developer and the photosensitive layer
- is removed to expose the hydrophilic surface support. A lithographic printing plate can be obtained in which the exposed portion is used as a hydrophilic non-image area and the previously hardened portion of the N4 base layer is used as an oil-sensitive image area.

The photosensitive layer of such a negative type 28 plate includes a photosensitive layer containing a photosensitive diazo resin and a binder resin, a layer containing a base resin and a binder resin, a layer containing an addition polymerizable unsaturated compound and a Motowata Goshima initiator, etc. One compound is commonly used.

[Problem to be solved by the invention]

The developing solution is one that completely removes the non-exposed areas, and
It is desirable to use a material that does not reduce the water uptake of the exposed surface during development, but rather improves the hydrophilicity and does not impair the printing performance of the exposed area. Furthermore, it is required that development be completed in a short time. With the spread of automatic processors in recent years, this point has become increasingly important.

The printability of a photosensitive layer as a printing plate is largely influenced by the composition of the developer used during image formation.

For example, if a developer with low swelling of the photosensitive layer is used to remove the blemishes in the unexposed area, a strong image area can be obtained, but it will not remove the original photosensitive layer. It takes more time than necessary for fc cleaning, the removed material is deposited on the image area, and scum tends to form on the plate surface.

On the other hand, when using a developing solution with high swelling or solubility properties, the removal rate of unexposed areas is improved, but undesirable foreign substances obtained during development or post-development water washing, gum processing, etc. (For example, a small amount of developer component, gum liquid component)
may be included, and printability (particularly paulownia resistance and ink receptivity) may be extremely reduced.

Furthermore, the conditions under which the developer is used vary widely; for example, in cold regions, it is often used at temperatures below 10°C. Even under these difficult conditions, perfect developability is required. Therefore, there has been a desire for a developer composition that exhibits small changes in development speed and sensitivity even if the conditions for use of the developer vary.

Furthermore, there has been a desire to develop a developer that satisfies conditions such as the problem of pollution from developer waste, occupational health problems such as odor, and the risk of transportation, storage, etc.

Japanese Patent Publication No. 51-6565 proposes a water-bath type developer containing an organic solvent such as butyl cellosol which is readily miscible with water, an alkaline agent, and an anionic surfactant. Since organic bath additives that are easily contaminated with water are used, the developing capacity is not weak, and since the organic solvents with high electric current are required, there are problems from the viewpoint of pollution and occupational health.

q# Publication No. 77401/1987 proposes an aqueous solution type developer containing benzyl alcohol, an alkaline agent, and an anionic surfactant, but #28 of the negative type 28 plate, which has been produced for several months, is When used as a developer, there were 9 problems in that indo stains often occur in non-image areas.

Further, U.S. Pat. No. 3,954,472 proposes a developer consisting of a water bath solution of alcohol, ammonium sulfite, and polyvinylpyrrolidone, but printing plates made using this developer composition do not have ii! ! Although no staining occurred in the I image area, there was a problem in that the printing durability was insufficient. Furthermore, water-bathable low-boiling alcohols such as n-globil alcohol are used sparingly.
There were many problems in terms of occupational health, danger, and pollution due to odor, flammability, etc.

Therefore, the first object of the present invention is to
t. An object of the present invention is to provide an improved developer composition for removing unexposed and uncured photosensitive I#I of a photosensitive material having a curable photosensitive layer.

The second object of the present invention is to provide a lithographic print Adl that does not cause printing stains in non-image areas and has excellent ink receptivity and printing durability in image areas.
The object of the present invention is to provide a developer composition that can obtain J-plate metal and is free from problems such as occupational health and pollution.

[Means to solve the problem]

In order to solve the above-mentioned problems, the present invention provides a development fLiji composition of a photosensitive image forming frame material having a photocurable photosensitive layer, in which the developer composition has the general formula (I) 0, where R1 is
Represents a hydrogen atom, a halodane atom, an alkyl group or an alkoxyl group, R2 is hydrogen, R3 represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and m and n are
1-3! 1 represents the whole number. ] Provided is a developer composition that can be mixed in a water bath and contains a compound represented by the following formula.

In the compound formula (IJ) used in the present invention, specific examples of R4 include hydrogen atom, chlorine atom, bromine atom, iodine atom, methyl group, ethyl group, propyl group, Examples include a butyl group, a methoxy group, an ethoxy group, a propoxy island, and a butoxy group ring, and specific examples of B2 include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, and →CM2-CIiR.

10TH group etc. are removed, and specific examples of R6 include a hydrogen atom, a methyl group, and an ethyl group. mwork rA
represents the average added molar summation of oxides. Therefore, in the developer composition of the present invention, a mixture of polar oxides represented by formula (I) and compounds having different numbers of added moles can also be used.

Representative compounds of the compounds represented by the general formula (IJ) are shown below, but the present invention is not limited thereto.

The content of the compound represented by the general formula (I) in the developer composition is sufficient to be IX1%, and the upper limit is not strictly limited, but it is important for improving workability in development, safety and hygiene in the production range, and waste developer solution. From the viewpoint of pollution problems, etc., it is desirable that the weight be 20'x or less.

The developer composition of the present invention may contain an ef-alkali agent, if necessary.

As alkaline agents, sodium silicate, potassium silicate,
Sodium metasilicate, sodium carbonate, potassium carbonate,
l Sodium carbonate, tertiary sodium phosphate, tertiary potassium phosphate, tertiary ammonium phosphate, secondary salt/#1. Inorganic alkalis such as sodium, tribasic potassium phosphate, ammonium diphosphate, sodium borate, ammonium borate, sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia; and monoethanolamine% soethanolamine, triethanolamine , ingropanolamine, 2-noethylamine ethanol, ethylenediamine, and other prudent amines; these can be used alone or in combination of two or more. The content of the alkaline agent in the developer composition is not particularly limited as long as it is contained in an amount that makes the final developer composition alkaline, but preferably, the content of the alkaline agent in the developer composition is 0.05~1
It is preferable to use the electric current in the range of 0.1 to 51%. o, os weight - below,
It becomes difficult to remove the uncured photosensitive layer, and if the weight exceeds 10 weights, there is a strong corrosive effect on the metal support such as aluminum, which tends to reduce the strength of the support. Physical and chemical strength also tend to decrease.

Desk 1# of the present invention! The liquid composition has the general formula (I
) The surfactant gold can be included to promote development, such as improving the miscibility with the water bath solution and improving the transparency of the developing solution to the unexposed photosensitive layer.

As the surfactant, anionic surfactants, nonionic surfactants, and amphoteric surfactants can be used. Examples of anionic surfactants include sodium salt of lauryl alcohol sulfate, octyl alcohol, Higher alcohol sulfate ester salts such as sodium salts of sulfates; cetyl alcohol gl # fat 2 such as sodium salts of fine esters = r - # l! Tetra-acid ester salts; fulkylaryl sulfonates such as the sodium salt of dodecylbenzene sulfo/acid and the sodium salt of inglovir naphthalene sulfone; Examples include sulfonate; sulfonate of alkyl amide 9; formalin condensate of naphthalene sulfonate. Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, polyoxyethylene polyoxypropylene ethers, and the like.

Examples of ampholytic interfacially active compounds include imidacillin derivatives and betaine type compounds. These surfactants can be used alone or in a mixture of two or more, and the amount used is not particularly limited, but the preferred range is 101% or less of the developer composition.

In addition, the developer composition of the present invention includes improving or adjusting the solubility of the photosensitive layer in the unexposed area, preventing swelling of the non-element area, and improving the miscibility of the essential component of the formula (I) in the water bath liquid. For all purposes, various 1a solvents may also be included as required.

Examples of the organic solvent include benzyl alcohol,
Ethylene glycol monophenyl ether, ethylene glycol monopennor ether, diacet/alcohol, tetrahydrofurfuryl alcohol, n-7'lopyl alcohol, cyclohexanol, ethylene glycol/diethylene glycol, glycerin, methyl lactate,
Alcohol bath medium such as ethyl lactate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoptele ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, etc. glycol monoalkyl ether thread bath medium;
Glycol monoalkyl ether acetate series such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate), triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, etc. solvent;
Ether thread bath medium such as tetradofusin, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether; methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-methyl-4
- Ketone bath medium such as methoxy-2-pentanone; Ester-based bath medium such as ethyl sulfate, butyl acetate, amyl acetate, and benzyl acetate; Rodent-containing bath medium such as trimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. These bath media can be used alone or in combination of two or more. The amount of these organic heating media to be used is not particularly limited, but is preferably within 15 parts of the developer composition.

Furthermore, the desktop liquid composition of the present invention may contain additives such as an antifoaming agent, a wetting agent, and a lipophilicity improver, if necessary.

Typical photosensitive compositions contained in the original curable photosensitive layer to which the developer composition of the present invention can be applied include the following.

■ A photosensitive composition consisting of a photosensitive diazo resin and a binder Jugetsu: Examples of photosensitive diazo resins include diazo resins typified by salts of condensates of diazodiarylamines and active carbonyl compounds; Those insoluble in water and soluble in organic solvents are preferred. Particularly suitable diazo resins include 4-diazodiphenylamine, 4-diazo-3-methyldiphenylamine, 4-diazo-47-methyldiphenylamine, 4-diazo-3'-methyldiphenylamine, 4-diazo-4
'-methoxydiphenylamine, 4-nor/-3-methyl-47-nitoxydiphenylamine, 4-diazo-3
-Methoxydiphenylamine etc. and formaldehyde,
Organic rR salts or inorganic acid salts of animals with paraformaldehyde, acetaldehyde, benzaldehyde, 4,4'-bis(methoxymethyl)diphenyl ether, etc. Examples of the acidic acid include methanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, xylene sulfonic acid, mesiterene sulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, propylnaphthalenesulfonic acid, 1-naphthol-5 -sulfonic acid, 2-nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid,
Examples include 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2,4-dihydroxybenzophenone, and benzenephosphinic acid. Examples of inorganic acids include hexafluoroha and tetrafluoro(6) acid.

As other photosensitive diazo resins, JP-A-54-301
A diazo resin having a polyester group in the main chain as described in Publication No. 21; A diazo resin obtained by reacting a diazo compound having a hydroxyl group with a monomer having an anhydrous calgene residue as described in Publication E-Zhuo No. 61-273538; A diazo resin obtained by reacting a polyincyanate compound with a diazo compound having a hydroxyl group can also be used.

As the binder W fat, for example (methacrylic acid [
Hereinafter, acrylic acid and methacrylic acid will be collectively referred to as (meth)acrylic acid. ]-(Methane acrylic acid ester copolymer, hydroxyalkyl (meth)acrylate copolymer containing (meth)acrylonitrile having an acid value of 10 to 100, described in U.S. Pat. No. 4,123,276, Patent No. 111,957- A conjugate having an aromatic hydroxyl group as described in Japanese Patent Publication No. 43890, a conjugate having a 2-hydroxy-3-phenoxyglobyl (meth)acrylate unit as described in Japanese Patent Publication No. 57-51656, etc. ;Epoxy resin;Polyamide resin;Vinyl halide,
Especially polyvinyl chloride, polyvinylidene chloride; #IJ vinegar!
Vinyl; Polyester; Acetal resins such as formal resins and butyral resins; Soluble polyurethane resins sold by Gutdrich Co., Ltd. in the United States under the trade name Nissan;
Polystyrene; styrene-maleic anhydride copolymer or half ester thereof; cellulose derivatives; shellank; rosin or modified products thereof, etc. can be used.

■ Photosensitive composition containing a photocrosslinkable resin: As the optical crosslinking resin, it is preferable to use a photoresist type A resin that has an affinity for aqueous alkaline liquids.
A comonomer having a cinnamic acid group and a carboxyl group as described in Publication No. 1; a phenylene diacrylic acid residue and a carboxyl group as described in JP-A-60-165646! polyester resin having a phenylene diacrylic acid residue and a phenolic hydroxyl group as described in JP-A No. 60-203630; A polyester resin having a sulfonyl group; a monomer having an azide group and a carboxyl group in the side chain described in JP-A-59-208552 can be used.

■ Attachment 21 Photosensitive composition containing a DX-composable unsaturated compound and a nine-component initiator: Examples of the photosensitive composition include,
No. 60.863 Ming #1, U.S. Patent No. 3,060,02
There is a composition comprising an addition-polymerizable unsaturated compound having two or more terminal ethylene groups and a photo-initiator, as described in No. 3 Meihoma, Japanese Patent Application Laid-open No. 62-121448, and the like.

Furthermore, as the binder resin, the binder resin described in the above (■), q! A eutectic compound having an unsaturated group on the sidewall described in JP-A-61-285449 can be used.

The sensitizing composition is further added with dyes, pigments, stabilizers, light additives, crosslinking agents, etc. as necessary, dissolved in a suitable solvent, coated on a support and dried, and usually leaves at zero. .5~5. ! ii'/
It is considered to be a negative PS plate with a photosensitive number of m''.

Examples of the support include metal plates such as aluminum, zinc, copper, stainless steel, and iron; glass films such as polyethylene terephthalate, polycarbonate, polyvinyl acetal, and polyethylene; synthetic resin full-bath melt coating or synthetic resin bath solution coating. Examples include composite materials made by applying techniques such as vacuum deposition and lamination of metal to paper or glass film.

Development using the developer composition of the present invention can be carried out according to general operating procedures. For example, the above negative fiP8
If the photosensitive layer of the plate is imaged with a negative image to harden and insolubilize the exposed portions of the photosensitive layer, it is developed with the developer composition of the present invention to dissolve and remove the unexposed portions.
A corresponding image is formed on the support. Next, washing with water and/or treatment with an aqueous desensitizing agent is performed.

Examples of water-based desensitizing agents include gum arabic, r
Water bathing natural molecules such as kistrin, carboxymethylcellulose; polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic #MQl! Examples include water bath liquids such as water bathable synthetic polymers, and if necessary, acids, surfactants, etc. are added to these water-based desensitizers.

As explained above, the developer composition of the present invention! ! + is
Although the developer composition of the present invention is extremely effective for developing photosensitive lithographic printing having an original sandwiching photosensitive layer, the use of the developer composition of the present invention is not necessarily limited to the development of printing plates. It can also be used as a developer for photoresist materials, photomask materials, hologram materials, etc. for microfabrication.

Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded.

Examples 1 to 3, Comparative Examples 1 to 3 (I) Preparation of photosensitive planographic printing plate A 0.305 m thick aluminum plate was sanded using a nylon brush and a 400 mesh water suspension of pumice stone. Sharpen with 60℃ sodium aluminate water for 10 minutes.
Etched for 2 seconds and then anodized at 20% RT, sa at a current density of 2 A/4 m2 to 2.71 m2.
An oxide film with a thickness of 1.5 m" was formed. Thereafter, the pores were sealed in a No. 3 sodium silicate water bath solution at 60 DEG C. for 1 minute, washed with water, and dried to obtain a support.

The following photosensitive solution T was applied on a whirling cloth and dried at 100° C. for 2 minutes to obtain a photosensitive lithographic printing plate. At this time, dry!
m&]E lid is 2. O, li'/m" is 6-1).

The photosensitive liquid *rebinder resin had a composition shown by the following formula and an average molecular weight of Xff1 of 70,000.

*2) Diazo 114j is a hexafluorophosphate of 4-diazodiphenylamine and paraformaldehyde.

*3) “Victoria Pure Blue BOHJ is an oil-soluble dye manufactured by Hodogaya Chemical Industry Co., Ltd.

*Megafac Ii'-177J is a fluorine thread surfactant manufactured by Dainippon Ink and Chemicals Co., Ltd.

(2) Preparation of lithographic printing plate A fine dot negative image film and a 0.15 step wedge were attached to the photosensitive lithographic printing plate obtained in (I), and the output 1 was placed at a position ↓ sill R away from this. It was exposed for 85 seconds using a kW metal halide lanno (Idol Fin 10UOJ manufactured by Iwasaki Electric Co., Ltd.).Then, it was developed for 1 minute at 25°C with the mechanical solution shown in Table 1, and washed with water. Then, a 7°Be' water bath solution of Arabia I was coated and bag-dried to obtain a lithographic print.

(3) 1ff1 of photosensitive lithographic printing plate and lithographic printing M plate
11 Developability of lithographic Ingiri plate and abrasion resistance during development;
The ink receptivity, &11 resistance, and printing stain of the lithographic Ingiri plate were evaluated, and the results are all shown in Table 1.

Each test condition is shown below.

Abrasion resistance during development = After 1 minute flow at 25℃, the image area was rubbed 20 times with a nylon brush while immersed in the developer, and the bond value was 90 (○: no abrasion)・Δ: Slight wear observed, X: Wear) Ink receptivity, printing durability, printing stains: The lithographic printing plate was installed on a Roland Favorit printing machine, and the printing ink CAP
Printing was carried out using a 400-fold dilution of S-G Red (manufactured by Dainippon Ink & Chemicals Co., Ltd.) and dampening water DH-78 (manufactured by Dainippon Ink & Chemicals (a') Co., Ltd.). Ink receptivity is evaluated by the number of prints until a printed matter with appropriate ink strength is obtained at the time of printing, and the smaller the number of prints, the better the oil sensitivity.

(0210 sheets or less, Δ: 10 to 20 sheets, ×: 20 sheets or more) Printing durability is as follows: After printing 50,000 sheets, prints that are faithful to the original without thick dots or skipping occur. Evaluation was made based on whether or not the results could be obtained. Printing stains were evaluated by squeezing the dampening water to half of Doshichi's proper density during printing and checking the presence or absence of stains in non-image areas at that time.

Example 7 The following photosensitive solution was coated on the support obtained in Example 1, and dried at 100° C. for 2 minutes to give a dry coating film N weight 2.
A photosensitive layer with a thickness of 21/m" was formed. Further, a polyvinyl alcohol water bath GTM cloth was applied on top of the photosensitive layer, and a dry coating film N weight 2
．． A photosensitive planographic printing plate T- was obtained by providing a protective layer of 0.09/m''.

This photosensitive lithographic printing plate was imaged with silver light at an exposure time such that the photosensitivity was 5 steps, and then developed with the developer used in Example 1 to obtain a lithographic printing plate.

As a result of printing with a printing machine in the same manner as in Example 1, there was no printing stain, and the ink receptivity and printing durability were also good.

Practical Example 8 The following coating was applied to an aluminum plate which had been anodized in a grain chamber, and dried at 100°C for 2 minutes to form a photosensitive layer with a dry coating weight of 1.29/m”. A photosensitive lithographic printing plate was obtained.

This photosensitive lithographic printing plate was imagewise exposed at an exposure time such that the photosensitivity was 5 steps, and then developed with the developer used in Example 1 to obtain a lithographic printing plate t-.

As a result of printing with a printing machine in the same manner as in Example 1, there was no printing stain, and the ink receptivity and printing durability were also good.

〔Effect of the invention〕

The developer composition of the present invention has extremely good developability for photosensitive image forming materials having a photocurable photosensitive layer, and is useful for developing photosensitive lithographic printing plates. Further, the use of the developer composition of the present invention is not necessarily limited to the development of printing plates, but is also useful as a developer for photoresist materials, photomask materials, hologram materials, etc., for example.

Agent Patent Attorney Katsuri Takaa

Claims (1)

[Claims] 1. In a developer composition for a photosensitive image forming material having a photocurable photosensitive layer, the developer composition has a general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [Formula R_1 represents a hydrogen atom, a halogen atom, an alkyl group, or an alkoxyl group, R_2 represents a hydrogen atom, an alkyl group, or a ▲formula, chemical formula, table, etc., and R_3 represents a hydrogen atom or a carbon atom. It represents an alkyl group of number 1 to 2, and m and n represent integers of 1 to 3. ] A developer composition characterized by being an aqueous solution containing a compound represented by the following. 2. The developer composition according to claim 1, wherein the content of the compound represented by formula (I) in the developer composition is in the range of 1 to 20% by weight. 3. The developer composition according to claim 1, which contains an alkaline agent. 4. The content of alkaline agent is 0.05 to 1 in the developer composition.
4. A developer composition according to claim 3, wherein the content is in the range of 0% by weight. 5. The developer composition according to claim 1, which contains a surfactant. 6. The developer composition according to claim 5, wherein the content of the surfactant is 10% by weight or less of the developer composition. 7. The developer composition according to claim 1, containing an organic solvent selected from the group consisting of alcohol solvents, glycol monoalkyl ether solvents, glycol monoalkyl ether acetate solvents, ether solvents, and nitrogen-containing solvents. 8. The developer composition according to claim 7, wherein the content of the organic solvent is in the range of 15% by weight or less of the developer composition.