JPH0120732B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a light-emitting device containing a mixture of a high esterification degree polymer and a low esterification degree polymer synthesized from an alkali-soluble hydroxyl group-containing polymer compound and a photosensitive acid chloride. This invention relates to a curable photosensitive resin composition.

Conventionally, polyvinyl alcohol or a similar polymer compound with many hydroxyl groups, cinnamic acid, cinnamylidene acetic acid, those having substituents such as cyano group, methyl group, phenyl group at the alpha position, and furyl acrylic acid, etc. Numerous studies, including U.S. Pat. No. 2,670,285, have proposed synthesizing ester compounds with photosensitive acids and utilizing the fact that these photosensitive groups are activated and dimerized by light to be used as photocurable photosensitive resins. This has been disclosed in literature and is a widely known fact. In the production of various printing original plates or printed wiring boards, etc., a photosensitizer solution containing a photosensitive resin, sensitizer, coating film modifier, etc. dissolved is applied onto a predetermined support in advance, and the solvent is removed by evaporation. After forming the photosensitive layer, active light such as ultraviolet rays is selectively irradiated through the original image to harden the photosensitive layer, and only the unexposed layer is dissolved and removed using an organic solvent, taking advantage of the insolubility of the cured portion. The process of forming (developing) an image is performed. Furthermore, if necessary, it is common practice to etch the support other than the portion covered with the photocurable photosensitive layer, that is, the so-called resist layer. Photosensitive resins that can be developed with alkali, in which an aqueous alkaline solution is used instead of an organic solvent to dissolve and remove unexposed areas in the development process, have recently been strongly desired in the industry from the viewpoint of workability, safety, etc. Various proposals have been made to impart alkali-soluble properties to photodimerizable photosensitive resins, but none have yet been found that are satisfactory in terms of practical performance.

One proposal for making a photodimerizable photosensitive resin alkali-soluble is a partial cinnamic acid ester of a novolac type phenol resin disclosed in Japanese Patent Publication No. 8499/1983. Since the novolac type phenolic resin itself is alkali-soluble, the aim is to introduce cinnamic acid groups to an extent that does not impair its solubility, thereby making it have both the properties of photosensitivity and alkali-solubility. However, if enough cinnamic acid groups are introduced to have practical photosensitivity, the esterified product will become insoluble in alkali, and a compound with a low degree of esterification that maintains alkali solubility will not have sufficient photosensitivity for practical purposes. It has no performance.

The present inventors have made extensive studies to improve the drawbacks of this prior art, and have arrived at the present invention. That is, ester compounds of an alkali-soluble polymer having a hydroxyl group and an acid having a photosensitive group are classified into two types: one has a high degree of esterification and is insoluble in aqueous alkaline solutions and soluble in organic solvents, and the other has a degree of esterification and is insoluble in aqueous alkaline solutions and organic solvents. Surprisingly, when a film made of a photosensitive resin containing this mixture as a main component is treated with an alkaline aqueous solution, the alkaline aqueous solution soluble part dissolves and the alkali aqueous solution insoluble part dissolves. It was discovered that the membrane disintegrates because the parts become fine powder and disperse. Therefore, it becomes possible to remove the uncured portion after the photocuring reaction with an alkaline aqueous solution, that is, so-called alkaline development. Thus, the presence of a highly esterified polymer increases the concentration of photosensitive groups and improves photosensitive performance, while at the same time maintaining substantial alkaline development performance despite containing an alkali-insoluble portion. can.

The photosensitive resin composition of the present invention requires the presence of a photosensitive acid ester polymer with a high degree of esterification and a photosensitive acid ester polymer with a low degree of esterification. It is advantageous for photosensitivity to have a high degree of oxidation. The latter preferably has 50 mol% or more and 90 mol% or less of hydroxyl groups remaining, and accounts for 60 wt% or more of the total ester compound. However, it is preferably 98 wt% or less, more preferably 90 wt% or less. If 90 mol% or more of hydroxyl groups remain and the solubility performance is substantially the same as that of an unsubstituted polymer, it can be mixed with a highly esterified polymer to form a film with good alkaline development performance. I won't give it. Probably, due to poor compatibility with the highly esterified polymer, it is not possible to obtain a film in which the highly esterified polymer and the low esterified polymer are microdispersed, resulting in fine dispersion collapse of the alkali-insoluble portion. This is thought to be because it does not occur.

The polymer compound having an alkali-soluble hydroxyl group used in the present invention includes a novolak type phenolic resin obtained by a condensation reaction of phenols such as phenol and cresol with formaldehyde in the presence of an acidic catalyst, and poly-p- Vinylphenol etc. Photosensitive acid chlorides include cinnamic acid, cinnamylidene acetic acid, those having a substituent such as a cyano group, methyl group, or phenyl group at the alpha position thereof, and furyl acrylic acid chloride.

In producing the ester mixture of the present invention, when a polymer compound having an alkali-soluble hydroxyl group and a photosensitive acid chloride are reacted and esterified, a polymer with a low degree of esterification and a polymer with a high degree of esterification are used. Although it is possible to mix products manufactured separately, the inventors of the present invention applied the manufacturing method described in the invention (Patent Application No. 1981) for ``Method for manufacturing alkali-developable photosensitive resin'' filed on the same day. It has been found that the process advantageously yields ester mixtures according to the invention.

That is, a polymer compound (A) having an alkali-soluble hydroxyl group is dissolved in an alkaline aqueous solution,
A photosensitive esterified polymer compound is synthesized by mixing this solution with a solution in which photosensitive acid chloride (B) is dissolved in a water-insoluble organic solvent or a mixed solution of a water-soluble organic solvent and a water-insoluble organic solvent. In this method, the molar ratio of (B) to 1 mole of hydroxyl groups in (A) is 0.5 or less (0.1 or more, preferably 0.2 or more) to obtain an ester mixture that has the property of being substantially decomposed and dissolved in an aqueous alkaline solution. The photosensitive resin composition of the present invention can then be easily produced by simultaneously producing a highly esterified polymer and a low esterified polymer in a mixed state, as shown in the Examples below.

Therefore, the obtained photosensitive polymer can be recovered in a state dissolved in the solvent used as a reaction medium and used as it is to formulate a photosensitive resin composition solution, but if necessary, it can be concentrated or dried to solidify. After recovering the resin as a solid by appropriate means such as, depending on the purpose, a solvent such as acetone,
It can be made into a solution using methyl ethyl ketone, cellosolves, dioxane, butyl acetate, etc.

In order to apply the photosensitive resin composition of the present invention to a substrate depending on the purpose, it is dissolved in, for example, acetone, methyl ethyl ketone, cellosolves, dioxane, butyl acetate, etc. to improve coating properties, acid resistance, and corrosion resistance of the coated film. For the purpose of improving properties such as properties and strength, polymeric materials may be appropriately blended, and dyes, pigments, sensitizers, and other additives may be added. The polymeric materials are usually those soluble in aqueous alkaline solutions, such as cellulose derivatives such as ethyl cellulose, methyl cellulose, propyl cellulose, and half esters of cellulose acetate, polyacrylic acid, polymethacrylic acid, and acrylic acid or methacrylic acid having alcoholic hydroxyl groups. Acrylic resins such as copolymers of acid derivatives, maleic acid copolymers such as styrene-maleic anhydride copolymers, isobutylene-maleic anhydride copolymers, alkali-soluble novolac type phenolic resins, poly-p-vinyl Examples include phenol, but even alkali-insoluble polymers can be added in an amount that does not interfere with the development process. Examples of pigments include chrome yellow and carbon black.
Coloring is done to make the image easier to see and also to give the resulting image a light-shielding property so that it can be used as an original drawing. From this point of view, other pigments or dyes may be used in addition to the examples mentioned above. Examples of sensitizers include various nitro compounds, anthrones, alkylaminobenzophenones, and composite sensitizers of these compounds and bisazide compounds. Any cinnamylidene vinyl acetate that has a sensitizing effect can be used.

The photosensitive resin composition of the present invention can be prepared using a suitable support,
For example, it is uniformly applied to the surface of a metal plate such as aluminum, zinc, or copper, a plastic film such as polyester, polypropylene, or cellulose acetate, paper, or paper laminated with the above film or metal plate. Examples of this application method include a rotation method, a spray method, an impregnation method, and a coating method using a wheller or roll. After coating, the coating film is dried to remove the organic solvent. A desired negative image is superimposed on the film surface of the photosensitive material thus produced, and actinic light is irradiated. For the irradiation, for example, carbon arc lamps, mercury lamps, xenon lamps, chemical lamps, tungsten lamps, etc. can be used. As a result, the exposed portion of the photosensitive material undergoes a dimerization reaction of the photosensitive group.
Since it hardens by forming an infinite network, the unexposed areas are dissolved in an alkaline aqueous solution and developed.

As the developer, an aqueous solution of sodium metasilicate, sodium hydroxide, potassium hydroxide, tribasic sodium phosphate, or a mixed aqueous solution of these can be used. In order to improve the permeability of the developer, an organic solvent soluble in the alkaline aqueous solution such as benzyl alcohol, methanol, ethanol, tetrahydrofuran, acetone, dioxane, anionic or nonionic surfactant, etc. is added as desired. It is also possible.

The photosensitive resin composition of the present invention has high chemical stability, is resistant to reactions other than photocuring, that is, dark reactions, and can be stored as a solution or coating for a long period of time without deterioration in quality. . Therefore, it has a wide range of uses as a photosensitive material, for example, as a printing plate material for Wipon plates, PS plates, letterpress plates, intaglio plates, etc., and also for metal etching masks, photomasks, and second originals for copying.

Next, the present invention will be specifically explained using examples.

Example 1 20 g of novolak type phenol formaldehyde resin is dissolved in an aqueous solution of 20 g of NaOH dissolved in 240 g of water, and 101 g of methyl ethyl ketone is further added.
The mixture is cooled to -10°C with vigorous stirring in a three-necked flask equipped with a sealed stir bar, condenser, and thermometer. This is called liquid A. On the other hand, 14 g of cinnamic acid chloride (approximately 0.45 mol per 1 mol of hydroxyl group of the resin) was dissolved in a mixed solution of 117 g of methyl ethyl ketone and 26 g of toluene, and -10
Cool to ℃ and use this as liquid B. When liquid B is added dropwise to liquid A while maintaining the temperature at -8°C to -12°C and the reaction is continued for 90 minutes, at the end of the reaction, the polymer with a low degree of esterification is in the aqueous phase and the polymer is highly esterified in the oil phase. degree polymer is generated. Add hydrochloric acid to adjust the pH of the aqueous phase of the reaction solution.
Make it less than 1. After the reaction solution is transferred to a separatory funnel and the aqueous phase is separated, the oil layer is vigorously mixed with 250 g of 2% aqueous sodium carbonate solution to extract the by-product cinnamic acid. 230 g of a phenol formaldehyde resin cinnamate ester solution having a solid content of 12.5% by weight was obtained.

To 10 parts by weight of the above solution, 0.1 part by weight of 5-nitroacenaphthene and 0.05 part by weight of 2,6-di(4'-azidobenthal)-4-methylcyclohexanone were added as sensitizers, and the oil-soluble phthalocyanine dye Spilon Blue Add 0.10 parts by weight of GNH, 50
The mixture was heated to 0.degree. C. to dissolve, thereby preparing a photosensitive resin composition. This photosensitizer solution was applied onto a polyester film using a bar coater, and after drying in air at 80°C for 5 minutes, a negative was layered and exposed to light at 8 mw/cm ² for 1 minute using a mercury lamp, followed by Na ₂ SiO ₃・9H ₂ O18 parts by weight,
It was immersed for about 30 seconds in a developer consisting of 10 parts by weight of benzyl alcohol, 3 parts by weight of surfactant Mignol 802 (30% aqueous solution) and 969 parts by weight of water, then washed with water and dried. An image with excellent resolution and good coating film properties was formed.

Example 2 A photosensitizer solution having the same formulation as the photosensitizer solution prepared in Example 1 was applied to a roughly polished zinc plate using a spin coater and dried. A negative film was brought into close contact with the photosensitive surface thus obtained, set in a fluorescent lamp vacuum printer, and exposed for 2 minutes. When this was immersed in the developer of Example 1 for 30 seconds and the non-exposed portions were removed, a positive resist image with excellent resolution was obtained. A zinc plate was corroded in 10% nitric acid for 5 minutes, and it had the performance as an acid-resistant resist.

Claims (1)

[Claims] 1. From the group consisting of an alkali-soluble polymer compound having a hydroxyl group, cinnamic acid, cinnamylidene acetic acid, those having a substituent such as a cyano group, methyl group, or phenyl group at their alpha position, and furyl acrylic acid. The main component is an ester compound with an acid having a selected photosensitive group, and the ester compound is a polymer with a high degree of esterification that is insoluble in aqueous alkaline solutions and soluble in organic solvents, and a polymer with a low degree of esterification that is soluble in aqueous alkaline solutions. A photosensitive resin composition that is a mixture and is developable with an alkaline aqueous solution.