JPH0160132B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing a photosensitive resin composition.

It is well known that photosensitive resins are useful in the fields of printing, photoengraving, printed wiring boards, semiconductors, electronic parts such as integrated circuits, and precision metal processing, and photosensitive resin compositions made of various polymer compounds are widely used. It has been invented.

The present invention has polyhalogenated methyl groups that generate free radicals upon the action of light. This invention relates to a method for producing a free radical photosensitive resin composition comprising a photoactive agent and an arylamine polymer compound having an N,N-disubstituted aniline derivative as a pendant group as two essential components. The type of dye that can be used in this method is a type that generates a dye (diphenylmethane and/or triphenylmethane type dye) by a free radical mechanism accompanied by a crosslinking reaction when irradiated with light.
Although it falls under the category of so-called free radical photosensitive resin compositions, it is particularly characterized by the fact that new innovations have been taken in the synthesis method of arylamine-based polymer compounds.

That is, conventionally known freelamine-based polymer compounds for free radical-based photosensitive resins are disclosed in Japanese Patent Publication No. 4605-1983, Japanese Patent Application Publication No. 73206-1973, and Japanese Patent Application Publication No. 48-73206.
As described in Japanese Patent No. 73207, it was synthesized by first synthesizing a vinyl monomer having an arylamino group, and then homopolymerizing or copolymerizing this monomer with other vinyl monomers. By the way, this vinyl monomer having an arylamino group is a special monomer, so it requires great care when synthesizing it, and it is also sensitive to natural oxidation and has problems in storage, making it an extremely difficult monomer to handle industrially. It is. During polymerization, since it has bulky pendant groups, the polymerization rate is slow and it is difficult to achieve a high degree of polymerization.Furthermore, it is actually necessary to copolymerize with other vinyl monomers for the purpose of adjusting physical properties such as making it water-soluble. This makes it even more difficult to achieve a high degree of polymerization.

However, in the present invention, ar-chloromethylstyrene (monomer) is first polymerized, and then an N-monosubstituted aniline derivative is reacted therewith.
Arylamino polymer compounds are synthesized by using the technique of "polymer right science reaction" in which a reagent that can react with an N-substituent is further reacted as needed to adjust physical properties such as solubility. be done. By this method, the above-mentioned difficulties in the conventional method were solved at once.

In other words, the degree of polymerization of the arylamine-based polymer compound synthesized by this method is almost equal to the degree of polymerization of the initial ar-chloromethylstyrene polymer, and the degree of polymerization changes, especially decreases, in the substitution reaction during the process. Since this does not actually occur, the degree of polymerization can be controlled extremely easily, and target products with a high degree of polymerization can be synthesized. Moreover, the initial ar-chloromethylstyrene (monomer) is extremely stable and easy to handle. and,
The substitution reaction to poly-ar-chloromethylstyrene does not involve any special synthetic operations and is extremely simple and practical.

The present invention includes the following technical advances. This is a method for synthesizing an arylamino polymer into which a carboxyl group has been introduced (a free radical photosensitive resin composition containing this polymer as one component synthesized by this method is described later) (to give a photosensitive layer developable with a water-based developer), a polymer solution of ar-chloromethylstyrene solution-polymerized in dioxane is added with dioxane if necessary to give a photosensitive layer developable with a water-based developer. Concentration and nil, N-(β
-Hydroxyethyl)aniline is preferably added in an amount equivalent to or more than the chloromethyl group of the polymer, and an aqueous solution containing an alkali metal hydroxide is added in an amount equivalent or more, and the reaction is caused by heating and stirring, and then the reaction solution is After neutralizing by adding a mineral acid such as hydrochloric acid or sulfuric acid, water is removed by azeotropic distillation using the azeotropic phenomenon of dioxane/water, or an inorganic desiccant (anhydrous sodium sulfate, anhydrous calcium sulfate, etc.) is added. By adding dehydration or using both in combination, a dioxane solution of ar-{N-(β-hydroxyethyl)-N-phenylaminomethyl}styrene polymer that does not actually contain water can be obtained ( Dioxane-insoluble components such as alkali metal chloride salts and drying agents generated during the reaction can be easily removed by filtration), then an organic dicarboxylic acid anhydride and, if necessary, dioxane are added thereto, preferably by heating. (At this time, N-β
- An organic dicarboxylic acid is bonded to the hydroxyethyl group in the form of a monoester) to obtain an arylamine polymer into which a carboxyl group has been introduced. can be altered by the action of an alkali metal salt, for example with a controlled amount of alkali hydroxide). After adding the organic dicarboxylic anhydride, wait for a sufficient time (usually 10 minutes).
After reacting (within 1 hour), for example, by pouring the reaction solution into several times the amount of water or more, the desired polymer will be separated as a solid, or it may be purified by other methods.

In this synthesis method, the reason why poly-ar-chloromethylstyrene is synthesized by first polymerizing ar-chloromethylstyrene is that the degree of polymerization can be freely adjusted, and in particular, the degree of polymerization can be made high. It is a point.

The reason why dioxane is consistently used as a solvent in polymerization and subsequent substitution reactions is that dioxane does not react with chloromethyl groups. Poly-ar-chloromethylstyrene, poly-ar
―{N-β-Hydroxyethyl)-N-phenylaminomethyl}styrene and dioxane are good solvents for both styrene and arylamine polymers with carboxyl groups made by reacting organic dicarboxylic anhydrides with styrene. be freely miscible with water, be able to be azeotropically distilled with water {thereby, the amount of water mixed in the reaction solution (this water is added as a solvent for the alkali metal hydroxide, and It is convenient to apply the principle of azeotropy to remove water from the system together with dioxane when removing the water (mainly consisting of the part produced during the reaction and the part produced when excess alkali is neutralized). (The fact that dioxane is azeotropic with water is described, for example, in Merck Index, 8th edition, p. 384, published in 1968, published by Merck & Co., USA).

As described above, dioxane as a solvent has various favorable properties. In other words, the present invention employs a synthetic method in which polymerization and the subsequent two-step substitution reaction can be carried out consistently and continuously, and this point is a feature of the earlier application (Japanese Patent Application No.
2102) is more advanced.

Next, the synthesis method carried out in the present invention will be explained in detail using specific examples.

Poly-ar-{N-β-hydroxyethyl)-N
-Phenylaminomethyl}styrene synthesis example: ar
-Chloromethylstyrene (CMS manufactured and sold by Kiyomi Kagaku Co., Ltd.) 400g, dioxane 400g
g and α,α′-azopis-iso-butyronitrile 1.0 g were mixed and polymerized at 70°C for 20 hours while passing nitrogen gas (40 g of the viscous solution thus obtained was sampled and When added to twice the amount of methanol to obtain a white precipitate and dried, 19 g of polymer was obtained, indicating that the polymerization rate in this solution polymerization was 95%.) 322 g of this polymer solution (polymer Contains 153g) dioxane
Add 600g, N-(β-hydroxyethyl)
Add 206g of aniline and add potassium hydroxide on top.
An aqueous alkaline solution prepared by dissolving 90 g in 200 ml of water was added dropwise, and the reaction was carried out by heating and refluxing on an oil bath at about 130° C. for 8 hours with stirring. Half of this reaction solution was dropped into 10 times the amount of water, and the resulting precipitate was washed with water and methanol, and then vacuum dried at 50°C to obtain 108 g of an almost white solid. The infrared absorption spectrum of this product (observed as a solid film after it was made into a dioxane solution) was exactly the same as that published in the inventor's previous application (Japanese Patent Application No. 49-2102), so the poly-ar-
It was found to be {N-(β-hydroxyethyl)-N-phenylaminomethyl}styrene.

After adding 500 g of dioxane to the remaining half of the reaction solution, approximately 10 ml of concentrated hydrochloric acid was added to neutralize the remaining alkali, and the mixture was concentrated by azeotropic distillation on an oil bath to a boiling point of 88.0°~
Approximately 500 g of a fraction at 91.0°C was obtained. Dioxane 500 again
About 500 grams of distilled water with a boiling point of 93.0° to 101.2°C is distilled.
I got g. Add a small amount of anhydrous sodium sulfate to the concentrated solution, tightly stopper it, shake it for a while, remove the solid by filtration, and add dioxane to the solution to obtain a polymer concentration of 10%.
(W/W) to obtain a dioxane solution of poly-ar-{N-(β-hydroxyethyl)-N-phenylaminomethyl}styrene which does not actually contain water or inorganic substances. Intrinsic viscosity number [η] 30℃ Dioxane is poly-ar-chloromethylstyrene, poly-ar-{N-(β-hydroxyethyl)-N-
phenylaminomethyl}styrene respectively
It was 0.470, 0.505g ^-1・dl.

Synthesis example of arylamine polymer with carboxyl group introduced: Poly-ar-{N-(β
-Hydroxyethyl)-N-phenylaminomethyl}styrene in 10% (W/W) dioxane solution (concentration adjusted by neutralization, dehydration/drying, filtration, and addition of dioxane after substitution reaction) to 80 g of dioxane Add 30g of succinic anhydride to approx.
The reaction was carried out by heating and refluxing on an oil bath at 0.degree. C. for 8 hours with stirring. The reaction solution was dropped into 10 times the volume of water, and the resulting precipitate was crushed in water, washed, and dried (vacuum drying at 50°C).
30g of almost white solid was obtained. The infrared absorption spectrum of this product (observed as a solid film after being made into a dioxane solution) was obtained from the inventor's earlier application (patent application
49-2102), so it was exactly the same as the one posted in
The chemical structural formula below, i.e. (However, n is a positive integer of 2 or more.) It was found that it can be expressed as follows. Ultimate viscosity [η] 30℃ Dioxane is 0.505 and 0.540g ^-1・dl for raw polymer and produced polymer, respectively.
It was hot.

Poly-ar-{N-(β-hydroxyethyl)-
The reaction of N-phenylaminomethyl}styrene with other organic dicarboxylic acid anhydrides can also be achieved under similar synthetic conditions. Any of the resulting polymers can be used in the present invention.

Specific examples of organic dicarboxylic acid anhydrides suitable for reaction here include the following.

Among the specific examples of acid anhydrides mentioned above, trimellitic anhydride ((v)) can be considered a derivative of phthalic anhydride (f), and therefore is included in the scope of organic dicarboxylic anhydrides in this specification. do.

In order to produce a free radical photosensitive resin composition using the arylamine polymer compound synthesized by the above method as a component, it is necessary to contain polyhalogenated methyl which generates free radicals by the action of light. A photoactivator is essential, and possibly other additives (eg, stabilizers, sensitizers, dyes, etc. to improve shelf life). A solution in which these constituent elements (plurality) are dissolved can already be commercialized as a photosensitive liquid (it is also possible to make two or more solutions of each constituent separately and mix them immediately before use), and each constituent A product (so-called printed photosensitive material, PS plate,
etc.) can also be commercialized, so both can be advantageously manufactured by applying the manufacturing method of the present invention.

Examples of photoactive agent compounds having polyhalogenated methyl groups, which are essential components mentioned above, include carbon tetrabromide, bromotrichloromethane, carbon tetraiodide, hexachloroethane, iodoform,
Polyhalogenated alkanes represented by 1,1,2,2-tetrapromoethane, promoform, pentapromoethane, hexapromoethane, 2,2,
Polyhalogenated alcohols represented by 2-tribromoethanol, 1,1,1-tripromo-2-methyl-2-propanol, etc., represented by benzotrichloride, benzotripromide, para-nitrobenzotripromide, etc. Polyhalogenated alkylbenzene, para-nitro-α, α, α
-Tripromoacetophenone, α,α,α-tripromoacetophenone, α,α,α-m-tetrapromoacetophenone, α,α,α-tripromo-2,5-dimethylacetophenone, α、α、α
-Tribromo-2,5-dichloroacetophenone, etc., polyhalogenated alkyl phenyl ketones, trichloromethylsulfonylbenzene, tripromomethylsulfonylbenzene, tripromomethylsulfonyl-para-nitrobenzene, α-tripromomethyl sulfonylpyridine,
Polyhalogenated alkylsulfonyl compounds such as α-tribromomethylsulfonylbenzothiazole, 1-ethyl-2-tripromomethylsulfonylbenzimidazole, hexapromodimethylsulfone, and other pyridine or quinoline N-oxides, Known materials such as hexapromodimethylsulfine can be used, and they are appropriately selected and used depending on the purpose. To 100 parts by weight of the arylamine-based polymer compound of the present invention, 10 to 1000 parts by weight of one or more of these polyhalogenated methyl compounds is added to form a solution with an appropriate solid content concentration and a photosensitive solution is prepared. Just use it.

In addition to the above-mentioned two essential components, the photosensitive resin composition of the present invention contains various sensitizers (styryl color,
Acridine dyes, merocyanine dyes, etc.), other additives (stabilizers, etc.), other polymers (whether photoactive or inert), dyes, etc. can be further added to increase the practical value. be able to.

A feature of the photosensitive resin composition containing an arylamine polymer into which a carboxyl group has been introduced, which is used in the production method of the present invention, is that a developer mainly containing water is used when developing the image-exposed photosensitive layer. If it can be used and at least several tens of percent of the total carboxyl groups of the arylamine-based polymer used in the present invention are alkali metal salts, use "plain water" as a developer. When it is not a salt, it can be used as a dilute aqueous solution of alkali metal hydroxide (LiOH, NaOH, KOH, etc.) or alkali metal carbonate (Na ₂ CO ₃ , K ₂ CO ₃ , etc.) or ammonia. It can be developed with dilute aqueous solutions of organic amines and organic amines. In some cases, water-miscible organic solvents such as alcohols, ketones, ethylene glycol monoalkyl ethers, dioxane, etc. may be added to the developer solution. It refers to a developer containing more than % by weight of water.
It is desirable to heat the developer to several tens of degrees (°C), thereby shortening the time required for development.

Further, if there is no problem, development can be carried out with a liquid mainly containing alcohols, ketones, ethylene glycol monoalkyl ethers, dioxane, or other organic solvents.

The photosensitive resin layer produced by applying the method of the present invention forms a colored image (blue, blue-green, green, indigo, purple, etc.) by image exposure.
Permanent visible images can be obtained by suitable fixing methods such as heating, contact with solvents, etc., and are therefore useful as print-out sensitizers (radical photography), and the unexposed areas can be removed with solvents. Therefore, a photocurable colored relief image can be obtained, and therefore, it is useful as a printing plate material that can be used for lithographs (offset plates), resin letterpress plates, corroded metal letterpress plates, gravure plates, etc. Furthermore, when applied to a porous support such as cloth, it can be used for screen (stencil) printing. Furthermore, it can be used in various nameplates, metal precision processing, printed wiring boards, IC production, etc.

As used herein, "development" refers to an operation of dissolving and removing unexposed portions from a photosensitive layer that has been image-exposed (that is, a colored image has already been formed in the form of a light image).

In this specification, ar in ar-chloromethylstyrene, etc. is an abbreviation for aromatic.
For example, the aromatic ring of styrene is substituted with a chloromethyl group (specifically, O-chloromethyl, m
-Chloromethyl or p-chloromethylstyrene or a mixture of two or more isomers of these) is referred to as ar-chloromethylstyrene.

Next, the present invention will be explained in more detail using representative examples.

Example 1 Poly-ar-{N-
(β-Hydroxyethyl)-N-phenylaminomethyl} 1 g of an alkali-soluble arylamine polymer compound, which is a reaction product of styrene and maleic anhydride, and 2 g of carbon tetrabromide are dissolved in 20 ml of ethylene glycol monomethyl ether. , applied to resin-coated photographic paper and dried.

When the negative image was exposed to a chemical lamp (20W) for 2 minutes, a blue-green positive image was obtained.
Then, it was immersed in a 2% aqueous sodium carbonate solution (50°C) to dissolve and remove the unexposed areas (non-image areas). A fixed positive photograph was obtained by washing with water and drying. This was useful as a printout sensitive material (radical photography) that did not require a binder resin.

Example 2 [Poly-ar-{N
-(β-hydroxyethyl)-N-phenylaminomethyl}reaction product of styrene and succinic anhydride]
25 g and 20 g of α,α,α-tripromo-2,5-dimethylacetophenone were dissolved in 500 ml of dioxane to obtain a slightly yellow colored flame sensitive liquid. This liquid was applied onto a zinc plate for letterpress printing (thickness: 1.0 mm) using a rotary coating machine and dried. The thickness of the photosensitive layer after drying was about 5 microns.

A transparent negative original (lith film) was closely attached to this photosensitive plate and exposed for 5 minutes using a fluorescent ultraviolet lamp vacuum printer, and a green positive image was obtained. This is 1.5%
The non-image areas were removed by developing with an aqueous sodium carbonate solution (around 60°C). Then, after hardening and burning, the plate was etched by powderless etching to obtain an eroded zinc letterpress. Then, when applied to a letterpress printing machine, many clear prints were obtained.

Example 3 The photosensitive solution prepared in Example 2 was applied to a zinc plate for offset printing in the same manner and dried.

After similar exposure and development, the film was hardened by immersing it in a citric acid-acetic acid aqueous solution. Then washed with water at 100℃
It was dried. After imparting water retention properties to the plate with dampening water, the plate was run on an offset printing machine and many good prints were obtained.

Example 4 [Poly-ar-{N-
(β-hydroxyethyl)-N-phenylaminomethyl} reaction product of styrene and phthalic anhydride]
50 g and 35 g of α,α,α-tribromo-2,5-dimethylacetophenone were dissolved in methanol/ethylene glycol monomethyl ether equivalent mixture 1 containing 6 g of sodium methylate. This solution was applied to a printed wiring board (copper-clad laminate) and dried. A transparent negative original was attached to the coated surface and exposed for 5 minutes using a fluorescent ultraviolet lamp vacuum printing machine. A clear green positive image was obtained. . This was developed with tap water at room temperature for about 1 minute and then dried in a hot air dryer. Next, it was etched by placing it in a POME 40° ferric chloride aqueous solution, and after washing with water, it was immersed in a 2% sodium hydroxide aqueous solution to remove the photocured resist, and after washing and drying, a high-quality printed wiring board was obtained. .

Example 5 The same amount of tripromomethylsulfonylbenzene was used as a photoactive agent instead of the photoactive agent α,α,α-tribromo-2,5-dimethylacetophenone in Example 2, and all other conditions were the same. When a photosensitive plate was manufactured and a plate was made, a satisfactorily corroded zinc letterpress plate was obtained. Moreover, letterpress printing was also successful.

Claims (1)

[Claims] 1 ar-Chloromethylstyrene is solution-polymerized in dioxane, and N-(β-
Contains a polymer of ar-{N-(β-hydroxyethyl)-N-phenylaminomethyl}styrene obtained by reacting hydroxyethyl)aniline with an aqueous solution of alkali metal hydroxide and dioxane as necessary. If necessary, the reaction solution is neutralized with a mineral acid, and then dehydrated and dried by azeotropic distillation and/or addition of an inorganic desiccant, using practically anhydrous dioxane as a solvent. A polymer solution is prepared, and an organic dicarboxylic anhydride and, if necessary, dioxane are added thereto and reacted to obtain an arylamine polymer into which a carboxyl group has been introduced and/or at least one of the carboxyl groups. 1. A method for producing a free radical photosensitive resin composition, which comprises containing as one component a polymer in which part of the composition has been changed to an alkali metal salt.