JPS60263147A - Developing solution composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a photosensitive resin containing a photosensitive unsaturated double bond adjacent to an aromatic nucleus and a phenolic hydroxyl group in the entire photosensitive layer in the molecule. The present invention relates to a developer composition for photosensitive image forming materials.

[Conventional technology]

Because of its unique photodimerization reaction, various photosensitive resins in which a cinnamic acid skeleton is introduced into the side chain or main chain of the molecule have been studied. Examples include polyvinyl alcohol, polyepichlorohydrin, polystyrene, acrylic resins, epoxy resins, and polyesters and polyamides having a cinnamic acid skeleton in the main chain, some of which have been put into practical use. For example, polyvinyl cinnamate produced by the reaction of polyvinyl alcohol and cinnamic acid chloride, and polyester produced by the condensation of diethyl phenylene diacrylate and 1,4-di-β-hydroxyethoxycyclohexane. These are used as image forming materials for printing plates, LSI devices, etc.

Among the photodimerizable photosensitive resins mentioned above, photosensitive polyester resins having a Katsura F3L acid skeleton in the molecular main chain produced by condensation of phenylene diacrylic acid or its alkyl ester with glycol are comparatively It is said to have high photosensitivity.

However, since these W&photosensitive resin lines are soluble only in organic bath agents, organic solvents are used as developing solutions when developing photosensitive layers made from these resins. When using an organic solvent as a developer, there are many problems in terms of development workability, safety and hygiene of the working environment, economic efficiency, and prevention of pollution such as air pollution.Therefore, photosensitive resins that can be developed with an aqueous developer development is desired.

The present applicant first developed the product using an aqueous alkaline developer.
In addition, is a photosensitive image that has sufficient photosensitivity and excellent printing durability and oil sensitivity when used as a printing plate a forming material? This was proposed in patent application No. 59-59591.

[Problem that the invention seeks to solve]

The object of the present invention is to form a photosensitive image that can be developed with an aqueous alkaline developer containing a photosensitive layer containing a photosensitive resin that has a photosensitive unsaturated double bond adjacent to an aromatic nucleus and a phenolic hydroxyl group in the molecule. It is an object of the present invention to provide a developer composition having the best developability as a developer composition for a material.

[Means to solve the problem]

The present invention uses at least 1111 organic solvents and alkaline agents selected from the group consisting of benzyl alcohol, α-methylbenzyl alcohol, ethylene glycol monobenzyl ether, and ethylene glycol monophenyl ether as a developer composition for the above image forming material. The present invention provides an aqueous developer composition containing:

In general, it is extremely difficult to develop a photosensitive resin containing all photosensitive unsaturated double bonds and phenolic hydroxyl groups adjacent to the aromatic nucleus in 8AK of the present invention with an alkaline water column solution alone, so it is recommended not to use an organic solvent. I don't have an older brother. However, as mentioned above, the use of organic solvents is not desirable in view of the impact it has on the working environment, such as air pollution. In order to achieve these social demands, it is necessary to find an organic acid agent that has extremely high solubility in the photosensitive tree Hf1K and has low volatility. The number of organic solvents that can be used is limited. Benzyl alcohol, α-methylbenzyl alcohol, ethylene glycol monobenzyl ether, and ethylene glycol monophenyl ether, which are essentially contained in the developer composition of the present invention, are all organic solvents having the above-mentioned two properties. be. Therefore, these essential ingredients contain organic solvents! # is 11% light in the developer composition, and the upper limit is not strictly limited, but from the viewpoint of developing workability, safety and hygiene of the working environment, prevention of pollution such as air pollution, etc. % or less is preferable.

The developer composition of the present invention is an alkaline water bath solution, and has an alkaline agent of 1μ, sodium silicate, potassium silicate, sodium metasilicate, sodium carbonate, potassium carbonate, sodium bicarbonate, trisodium phosphate, and triphosphoric acid. Potassium, tertiary ammonium phosphate, sodium diphosphate, dibasic potassium phosphate% ammonium diphosphate, sodium borate, ammonium borate, sodium hydroxide,
Inorganic alkalis such as potassium hydroxide, lithium hydroxide, ammonia, etc.; and organic amines such as monoethanolamine, jetanolamine, triethanolamine, 2-diethylaminoethanol, ethylenediamine, etc.; Can be used by mixing more than one species.

The content of the alkaline agent in the developer composition is not particularly limited as long as the alkaline agent is contained so that the final developer composition has alkaline properties, but preferably, the content of the alkaline agent in the developer composition is It is suitable to use it in the range of 0.05 to 10% by weight, more preferably 0.1 to 5Nit%. 0.
If the amount is less than 051r, it becomes difficult to remove the uncured photosensitive layer, and if it is more than 10% by weight, the corrosive effect on the metal support such as aluminum tends to be strong and the strength of the support tends to decrease. The mechanical and chemical strength of exposed areas also tends to decrease.

The developer used in the present invention has an interface for promoting development, such as improving the miscibility of the organic solvent, which is an essential component, with the J7" potassium aqueous solution and improving the permeability of the developer to the unexposed photosensitive layer. It can contain active split tubes.

As the surfactant, anionic surfactants, nonionic surfactants, and amphoteric surfactants can be used. Examples of the anionic surfactants include sodium salt of lauryl alcohol sulfate and sodium octyl alcohol sulfate. Higher alcohol sulfate ester salts such as salts; aliphatic alcohol phosphate ester salts such as sodium salt of cetyl alcohol phosphate; sodium salt of dodecylbenzenesulfonic acid, inpropyl naphtha 1/
Alkylaryl sulfonates such as the sodium salt of sulfone moromi; sulfonates of dibasic fatty acid esters such as the sodium salt of di(2-ethylhexyl)sulfosuccinic acid; sulfonates of alkylamides; formalin condensation of naphthalene sulfonates There are things etc. Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and polyoxyethylene polyoxypropylene ethers.

Examples of amphoteric surfactants include imidacillin derivatives and betaine compounds. These surfactants can be used alone or in combination for 2 seconds or more, and the amount used is not particularly limited, but the preferred range is as follows:
10]1% by weight or less of the developer composition.

In addition, organic solvents other than the essential components are also required for the purposes of preventing swelling in the exposed areas, adjusting the solubility of the resin in the unexposed areas, and improving the miscibility of the essential organic solvents with the alkaline hydroxide solution. It can be included depending on the situation.

Other organic acid media that can be used in the present invention include, for example, diacetone alcohol, tetrahydrofurfuryl alcohol, n-7'' lobil alcohol, and cyclohexanol.

Alcohol solvents such as ethylene glycol, polyethylene glycol, glycerin, methyl lactate, ethyl lactate;
Glycol monoalkyl ether mortar such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether; Glycol monoalkyl ether acetate medium 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; tetrahydrofuran , dioxane,
Ether solvents such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether; ketone solvents such as methyl ethyl ketone, methyl imbutyl ketone, cyclohexanone, and 4-methyl-4-methoxy-2-pentanone; ethyl acetate, butyl acetate, amyl acetate, and sulfur acetate , ester solvents such as methyl levulinate, and ethyl levulinate; and nitrogen-containing solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. These may be used alone or in combination of two or more.

Although the amount of these organic solvents used is not particularly limited, the preferred range is 15% by weight or less of the developer composition.

Furthermore, additives such as antifoaming agents, wetting agents, lipophilicity improvers, etc. can be included as necessary.

The developer composition of the present invention prepared as described above can be used to produce photosensitive images whose photosensitive layer contains a photosensitive resin containing a photosensitive unsaturated double bond adjacent to an aromatic nucleus and a phenolic hydroxyl group in the molecule. It is used when developing the forming material.

The photosensitive resin can be prepared, for example, by the following method, a dicarboxylic acid having a photosensitive unsaturated double bond adjacent to a fil aromatic nucleus (hereinafter referred to as photosensitive unsaturated dicarboxylic acid), and a dicarboxylic acid having a phenolic hydroxyl group. Method for obtaining by reacting a polyhydric carboxylic acid component containing an acid or a derivative thereof with a polyhydric alcohol component: (2) Photosensitive unsaturated dicarboxylic acid and dicarboxylic acid having a phenolic hydroxyl group or a derivative thereof Kurayoshi polyhydric Producing a polyester having alcoholic hydroxyl groups by reacting a carboxylic acid component and a polyhydric alcohol component in a ratio where the alcoholic hydroxyl groups are in excess of the carboxyl groups,
Photosensitive unsaturated dicarbonate can then be produced by reacting this polyester with a chain extender having at least two in the functional group molecule which has higher reactivity towards alcoholic hydroxyl groups than phenolic hydroxyl groups. As the acid, for example, the following general formula +11 to (7
), and derivatives of these dicarboxylic acids include dialkyl esters such as dimethyl ester and diethyl ester, di(ethylene glycol) ester, and di(ethylene glycol) ester of these dicarboxylic acids.
Examples include di(alkylene glycol) esters such as propylene glycol esters and dicarboxylic acid halides such as dicarboxylic acid chlorides.

(3) (In the above general formulas (11 to (7), R1 and Rr are each a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and 1 to 4 carbon atoms)
represents an alkoxyl group, a halogen atom or a nitro group, R2 represents an alkylene group having 2 to 4 carbon atoms, and l represents 1
n represents an integer from 1 to 4, and m represents an integer from 1 to 5. ) A preferred example of the above dicarboxylic acid or its derivative is p-phenylene diacrylic acid 2.
m-fenireage 7ri! J luic acid.

2.5-dimethoxy-p-phenylene diacrylic acid, 2
- ditrophic p-phinidia diacrylic acid, p-carboxycinnamic W1% cinnamylidene malonic acid, bis(p-II
[Acid] dicarboxylic acids or derivatives thereof such as diethylene glycol ether, bis(p-carboxybenzal)cyclohexanone, bis(p-carboxybenzal)cyclopentanone, p, p'-condicarbonate, etc. can.

Examples of the dicarboxylic acid having a phenolic hydroxyl group include units represented by the following general formulas (8) to a2.

<gs)j ......(8) (Rs)g (OR)h (O)i)h' (In the above general formula (8)-aa, R1 is a hydrogen atom, carbon number 1 to 4 represents an alkyl group, an alkoxyl group having 1 to 4 carbon atoms, a halogen atom or a -tro group, %R4 and R1 represent a hydrogen atom, a halogen atom, a nitro group, or a cyano group, and l represents all integers from 1 to 5. , j represents an integer of (5-i), represents 0 or 1, f represents O or 1, h and h' represent an integer of 1 to 4, and g represents (4-
h) represents an integer of g'ti(4-h'); Malonic acid, 3-hydroxybenzylidenemalonic acid, 3.4-
Dibenzylidene malone moromi in dihydro, 4-hydroxy-
5-Methoxybenzylidenemalonic acid, 5-hydroxy-
4-Methoxybenzylidenemalonic acid, 4-hydroxy-
6-nitropenzylidenemalonum, 4-hydroxycinnamylidenemalonic acid, 6-hydroxycinnamylidenemalonic acid, 4-hydroxy-3-methoxycinnamylidenemalonic acid, 4-hydroxy-6-nidrocinnamyl Dicarboxylic acids such as thenmalonic acid; 6-hydroxyphthalic acid, 4-hydroxyphthalic acid, 4-hydroxyisophthalic acid, 5-hydroxyisophthalic acid, hydroxyterephthalic acid, 3+6-hydroxyphthalic acid, 2,5-dihydroxy Isophthalic acid, 4゜5-dihydroxyisophthalic acid #2.5-dihydroxyterephthalic acid, 2.5-dihydroxyterephthalic acid, 2,4゜6-dolihydroxyisophthalic acid, 4,5.6-)dihydroxyisophthalic acid #
4-hydroxy-5-ditroisophthalic acid, 4-hydroxy-5-chloroisophthalic acid, 6-bitroxy-6
-Dicarboxylic acids such as methΦshiphthal@, 2,4-dihydroxy-6-methylisophthalic acid, etc.; acid, 6.6'
-dihydroxy-5,5'-dimethoxy5,3'-biphenyldicarboxylic acid, 4,5-dihydroxy-2,4
Dicarboxylic acids such as '-oxydibenzoic acid; 2-hydroxy-p-benzenodiacetic acid, 2,5-dihydroxy-p-benzenodiacetic acid, α,α'-dicyano 2,5-
Dihydroxy-p-benzenenedioacetic acid, α, α′-dinitro 2,5-dihydroxy-p-benzenenedioacetic acid, α,
α′-Dichloro2,5-dihydroxy-p-benzenivine vinegar rI! , 5-hydroxy-m-phenylene di(oxyacetic acid), etc.; dialkyl esters of the dicarboxylic acids such as dimethyl ester, diethyl ester; di(ethylene glycol) esters, di(propylene) of the dicarboxylic acids; Examples include di(alkylene glycol) esters such as Nistyl glycol.

In the production of photosensitive resins, other polycarboxylic acids or derivatives thereof can be used in combination with the above-mentioned photosensitive unsaturated dicarboxylic acids or derivatives thereof, and examples of such compounds include amber ff, adipic acid, azelaic acid, cepatine, etc. Acid, phthalic acid, isophthalic acid? ! ! 1% terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, tetrabromophthalic acid, tetrachlorophthalic acid, 1,4-cyclohexane dicarboxylic acid, maleic acid, fumaric acid, itaconic acid, 5-sodium sulfoiphthalic acid, Hymic acid, carboxynorbornane acetic acid, trimellitic acid, pyromellitic acid, etc.

On the other hand, as the polyhydric alcohol component, six glazes can be used without any particular restrictions, such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, 1. 5-butylene glycol, 1,6-hexanediol, 2-butene-1,4-diol, 2.2
．． 4-trimethyl-1,5-bentanediol, 1,4
-bis-β-hydroxyethoxycyclohexane, cyclohexane dimetatool, tricyclodecane dimetatool, hydrogenated bisphenol A, hydrogenated bisphenol F1 ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, bisphenol F Ethylene oxide adduct, globylene oxide adduct of bisphenol F, ethylene oxide adduct of hydrogenated bisphenol A, propylene oxide adduct of hydrogenated bisphenol, ethylene oxide adduct of tricyclodecane dimethatol, tricyclodecane di Propylene oxide adduct of metatool, 5-norbornene-2,6-dimetatool, 5-norbornene-2
, 2-dimethatol, trimethylolpropane, pentaerythritol and the like.

Examples of the chain extender having at least two functional groups in the whole molecule that have high reactivity toward dialcoholic hydroxyl groups than phenolic hydroxyl groups include diaryl oxalate compounds, diaryl phthalate compounds, diaryl carbonate compounds, and tetracarbonate compounds. Acid dianhydrides are produced.

As a diaryl oxalate compound, the following k formula 0
Examples of the compound represented by 3 and the diaryl phthalate compound include a compound represented by the following general formula I, and examples of the diaryl carbonate compound include a compound represented by the following general formula (I9).

00 0 0 RTO-C-0-R, -.-+149 1 (In the above general formula ahas, R6 and R7 each independently represent an aromatic hydrocarbon group which may have a substituent.

)J I can.

Detracarvone dianhydride has the following general formula ai!
Compounds represented by can be mentioned.

0 0 (In the above general formula ae, R and Vi represent a tetravalent organic group having at least two carbon atoms.) As a preferable example of the tetracarboxylic dianhydride used in the present invention, pyromellit Acid dianhydride, 3,3', 4.4
'-hensiphenotetracarboxylic dianhydride, 3.3
', 4. , i'-diphenyltetracarboxylic dianhydride, 2.3,6.7-naphthalenetetracarboxylic dianhydride, 1. d, 5.8-naphthalenetetracarboxylic dianhydride% 4.41-sulfonylsiphthalic dianhydride,
2,2-bis(6,4-dicarboxyphenyl)propanihydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 4,4'-C5,5'-(alkylphosphoryldiphenylene)-bis (iminocarbonyl)]
Aromatic tetracarboxylic dianhydrides such as cyphthalic dianhydride, adducts of hydroquinone diacetate and trimellitic anhydride, and adducts of diacetyldiamine and trimellitic anhydride; 5-(2,5-dioxylene, sotetrahydrofuryl)-5-methyl-5-cyclohexene-1,2-dicarboxylic anhydride (manufactured by Dainippon Ink Chemical Co., Ltd., Epiclon B-4400), butane-1,2,3,4-tetracarboxylic acid dianhydride Examples include anhydrides and aliphatic tetracarboxylic dianhydrides such as cyclopentane tetracarboxylic dianhydride.

The photosensitive image-forming material is generally prepared by dissolving the above-mentioned photosensitive resin in a suitable solvent, or further containing sensitizers, pigments, dyes, fillers, stabilizers, crosslinkers, etc. as necessary. It can be produced by coating and drying a material to which an agent has been added onto a support by a well-known method.

Specific examples of the support include aluminum plates, zinc plates, steel plates, stainless steel plates, sheets and plates of other synthetic resins such as gold Pi4J polyethylene terephthalate, polycarbonate, and cellulose derivatives; Examples include a string coated with a coating or a synthetic resin solution, and a composite material: a silicon wafer, in which a gold f% layer is provided on a synthetic resin by vacuum deposition, lamination, or other techniques.

As a support for a printing plate, a mechanically, chemically, or electrochemically roughened metal plate made of aluminum, copper, zinc, etc. is used, and a plate with a thickness of 0.1 to 2.5 μm is usually used on this plate. A photosensitive layer with a high temperature is formed.

Development using the developer composition of the present invention can be carried out according to general operating procedures. For example, the photosensitive layer of the above-mentioned photosensitive image forming material is subjected to imagewise exposure using a negative image to harden and insolubilize the exposed portion of the photosensitive layer, and then a developer composition is supplied to the surface of the photosensitive layer that is not exposed to light. After removing the resin composition from the surface of the support, the support is subsequently washed with water. When applying a photosensitive image forming material to a printing plate, after removing the resin composition in the unexposed areas by the above-mentioned development operation,
This is followed by washing with water and/or treatment with an aqueous desensitizing agent.

Examples of water-based desensitizing agents include water-soluble natural polymers such as gum arabic, dextrin, and carboxymethyl cellulose; polyvinyl alcohol, and polyvinylpyrrolidone.

An aqueous solution of a water-soluble natural polymer such as polyacrylic η, etc., and if necessary, a surfactant or the like may be used.

The present invention will be specifically explained below using Example FC.
9. A dud BA does not go beyond its gist. The present invention is not limited to the following examples.

Examples and Comparative Examples p-Diethyl diacrylate 005 mol, 4-
005 mol of diethyl hydroxybenzylidenemalonoate,
Ethylene oxytite (6 mol) of bisphenol A (1 mol)
, 2-E-L) adduct α1 mol and hyethylene glycol [11 mol, photosensitive resin
2,000) was synthesized.

(Hereinafter, referred to as resin A.) This resin A2019 and 1.2 g of diphenyl terephthalate (chain extender) were reacted to create a photosensitive resin (! is average molecular weight 51.200)'! -Synthesized. (Hereinafter, resin B
That's what it means. ) A photosensitive resin composition was prepared by adding 2-benzoylmethylene-1-methyl-β-naphthothiazoline (5% by weight based on the resin) to a 4% by weight dichloroethanoic acid solution of Resin A or B.

At 1/11, a test pattern was applied to the photosensitive image forming material obtained as described above. Output 1 is placed 11L away from the negative film.
Exposure was carried out using a metal halide lamp (manufactured by Iwasaki Electric Co., Ltd., "Idol Fin 100(ll)t").

Next, the samples were immersed for 60 seconds in polishing solutions having various compositions shown in Table 1, and then developed by being lightly wiped with a cellulose sponge, and the developability was evaluated. Next, the current liquid on the plate surface was removed by washing with water, and a desensitizing liquid ("Dick Desensitizing Liquid DO-70J" manufactured by Dainippon Ink & Chemicals Co., Ltd.) was applied.
A printing plate was produced by processing. The printing plate produced in this way was attached to an offset printing machine and printed using standard ink for lithographic printing under conditions similar to actual lithographic printing, and when 50,000 sheets had been printed, halftone dots were The suitability for printing was evaluated based on whether a faithful NWMK printed matter could be obtained without occurrence of crushing, background smearing, etc.

The contents and results of each side above are summarized in Table 1.

In addition, Ao 1) and Kan 2) in the table are as shown below.

÷1)... Sodium tert-butylnaphthalene sulfonate thread anionic surfactant manufactured by Kao Atlas Shisha.

Appetizer 2)...Nonionic surfactant manufactured by Nikko Chemicals ■.

〔Effect of the invention〕

The developer composition of the present invention has extremely good developability for photosensitive image forming materials containing a photosensitive layer containing a photosensitive resin containing a photosensitive unsaturated double bond and a phenolic hydroxyl group. The developing VC of the am printing plate is extremely effective.

The use of the developer composition of the present invention is not necessarily limited to developing printing plates, but can also be used, for example, as a developer for photoresists for various microfabrication purposes.

Agent: Patent attorney Katsutoshi Takahashi

Claims (1)

[Claims] 1. A developer composition for a photosensitive image forming material containing in the photosensitive layer a photosensitive resin containing a photosensitive unsaturated double bond adjacent to an aromatic nucleus and a phenolic hydroxyl group in the molecule, the developer composition It is characterized by being an alkaline aqueous solution containing at least one organic acid agent selected from the group consisting of ethylene glycol monobenzyl alcohol, α-methylbenzyl alcohol, ethylene glycol monobenzyl ether, and ethylene glycol monophenyl ether. Developer composition.