JPH0124289B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel photosensitive resin composition using a polymer obtained by ring-opening polymerization of a norbornene derivative having a polar substituent.

BACKGROUND ART In recent years, photosensitive resins have been widely applied to printing plates and resist materials, and the demand for them has increased, but at the same time, the performance required of photosensitive resins has also become stricter. Conventionally, known photosensitive resin compositions include photosensitive resin compositions comprising a polymer or oligomer having an ethylenic double bond, a polythiol, and a photosensitizer (e.g.
No. 29528, No. 46-33530, etc.). However, these photosensitive resin compositions have a slow photocuring speed, and still have problems in the adhesion between the resin and the substrate, the abrasion resistance of the photocured resin, the flexibility, etc.

An object of the present invention is to provide a photosensitive resin composition that has a fast curing speed, therefore short photoirradiation time, easy cleaning of unexposed areas after curing, and excellent properties of the cured resin. There is a particular thing.

The present invention achieves this objective by the general formula (In the formula, X and Y each represent a substituent selected from hydrogen, ester, nitrile, or carboxyl. However, one of X and Y is a substituent selected from ester, nitrile, or carboxyl.) This is a photosensitive resin composition characterized by containing a polymer containing a unit represented by: and a compound having at least two thiol groups in the molecule.

The above polymer used in the present invention can be produced by homopolymerization or copolymerization of norbornene derivatives. Such norbornene derivatives have the general formula In the compound represented by, X and Y are each a substituent selected from ester, nitrile, or carboxyl, and specifically, -(CH ₂ ) _o -COOR, -(CH ₂ ) _o -OCOR, -( _CH2 ） _o
-CN, -( _CH2 ) _o -COOH (n=0 to 10, R is an alkyl group having 1 to 10 carbon atoms).

The production of the polymer consists of a tungsten or molybdenum compound and an organoaluminium compound,
This can be carried out by ring-opening polymerization of the norbornene derivative monomer at room temperature to 200° C. in an organic solvent using a catalyst to which a third component is optionally added.

Typical examples of the above-mentioned tungsten and molybdenum compounds include tungsten hexachloride, molybdenum pentachloride, and tungsten trioxide. The organoaluminum compound has the general formula _{AlR 3} or AlR _o Typical examples include triethylaluminum, diethylaluminium chloride, and ethylaluminum sesquichloride. In addition, as the third component,
Among them, alcohol compounds such as n-butanol and acetal compounds such as acetaldehyde diethyl acetal are suitable. Representative examples of the organic solvent include aromatic hydrocarbons such as toluene, halogenated aromatic hydrocarbons such as chlorobenzene, and halogenated aliphatic hydrocarbons such as trichloroethylene.

Homopolymers or copolymers obtained by ring-opening polymerization are thermoplastic resins with excellent mechanical properties such as tensile strength, heat resistance, and impact resistance, and are soluble in organic solvents. Therefore, when used as a solution-developable photosensitive material, it is dissolved in an organic solvent and used as a printing plate,
Organic solvents can also be used in photoresists and the like to wash out unexposed areas. Examples of these solvents include alcohols having 1 to 4 carbon atoms, cyclic ethers such as dioxane, and tetrahydrofuran;
Aromatic hydrocarbons such as benzene, toluene and xylene, halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene, halogenated aliphatic hydrocarbons such as dichloroethane and carbon tetrachloride, acetone,
Examples include ketones such as methyl ethyl ketone and methyl isobutyl ketone, N,N-dimethylformamide, and dimethyl sulfoxide. Further, when the above substituents X and Y are acidic groups, they are water-soluble and dilute alkaline water can be used for washing out.

Polythiols used as crosslinking agents in photosensitive resin compositions in combination with polymers obtained by ring-opening polymerization or copolymerization of norbornene derivatives include mercaptocarboxylic acids such as thioglycolic acid and α-mercaptopropionic acid. and glycol,
Esterified products with polyols such as triols and tetraols, such as ethylene glycol dithioglycolate, trimethylolpropane trithioglycolate, pentaerythritol tetrathioglycolate, ethylene glycol di-β-mercaptopropionate, and tri-β-mercaptopropion. Acid trimethylolpropane, and reaction products of diglycidyl ethers such as pentaerythritol tetraβ-mercaptopropionate, polyethylene glycol, polypropylene glycol, and hydrogen sulfide, ethanedithiol, hexamethylenedithiol, tolylene-2,4dithiol, etc. be. Polythiol as a crosslinking agent is usually used in an amount equivalent to 0.01 to 1 thiol group in the polythiol per double bond in the norbornene derivative polymer. Ru.

By adding a sensitizer to the photosensitive resin composition of the present invention, the photosensitive range of the photosensitive resin composition can be adjusted and the curing speed can be accelerated. The amount of the sensitizer added is 0.01 to 15% by weight, preferably 0.05 to 10% by weight, based on the resin composition. Examples of the sensitizer include benzophenone, acetophenone, acenaphthene-quinone, methyl ethyl ketone, valefuenone, p-morpholipropiophenone, 4-morpholinobenzophenone, 9-acetylphenanthrene, 3-acetylindole, 9-fluorenone, etc. be able to.

The composition of the present invention is dissolved in the above-mentioned solvent together with a sensitizer if necessary, and applied onto a substrate to form a thin coating film. When this is irradiated with light, a cross-linking reaction occurs, resulting in insoluble in the solvent. It becomes a coating film. This coating film has good adhesion to the substrate, excellent impact resistance and strength, and good transparency. Therefore, when a coating film of the photosensitive resin composition of the present invention is irradiated, a specific image is irradiated and the unexposed area is washed out, thereby allowing the photocured area to remain as an image. This allows it to be used for printing plates, photoresists, etc.

Since the photosensitive resin composition of the present invention uses polythiols as a crosslinking agent, it is highly safe to handle, and is also resistant to dark reactions and is thermally stable, so it has good storage stability. .

The present invention will be explained below using specific examples, but the present invention is not limited thereto.

Reference Example 1 Methyl 5-norbornene-2-carboxylate ring-opening polymer 45.6 g of methyl 5-norbornene-2-carboxylate monomer was charged into a well-dried four-necked flask under a N ₂ stream. Next, 190ml of toluene, 1.2g
of tungsten hexachloride, 1.1 g of diethylaluminum chloride, and 0.44 g of n-butanol were added, and the polymerization was continued at 15° C. for 6 hours. After the reaction is completed, a mixed solvent of hydrochloric acid and methanol is added to the 400 ml system to precipitate the product. acetone polymer
Dissolve in 200 ml and purify by reprecipitation using the aforementioned hydrochloric acid-methanol mixed solvent. A white powder was obtained, and the yield was 45.0 g.

Reference Example 2 Production of 5-norbornene-2-carboxylic acid ring-opening polymer 15 parts by weight of methyl 5-norbornene-2-carboxylic acid ring-opening polymer pellets were placed in a dry flask, then 100 parts by weight of acetone was added, and the temperature of
Raise the temperature to 56°C and stir to completely dissolve the polymer.

Next, 4.0 parts by weight of caustic soda (equivalent moles to the ring-opened polymer) was dissolved in 15 parts of water based on 100 parts by weight of acetone charged, and this was dissolved into the ring-opened polymer. Add to the acetone solution one by one while keeping the system homogeneous. As ester hydrolysis progresses, the ring-opened polymer precipitates in the system.
After 2 hours of reaction, the product is separated off.

The precipitated ring-opened polymer was placed in 150 parts by weight of water,
After the ring-opening polymer is dissolved under stirring, 9.8 parts by weight of concentrated hydrochloric acid is diluted with 50 parts by weight of water, added to the aqueous solution of the ring-opening polymer, and stirred at room temperature. As the side chain changes from carboxylate to carboxylic acid, the ring-opening polymer precipitates as a white powder, which is separated and dried to form the desired ring-opening polymer of 5-norbornene-2-carboxylic acid. A combination was obtained.

Reference Example 3 Production of 2-cyano-5-norbornene ring-opening polymer Same as Reference Example 1 except that 40.2 g of 2-cyano-5-norbornene was used instead of 45.6 g of methyl 5-norbornene-2-carboxylate monomer. A ring-opened 2-cyano-5-norbornene polymer was obtained.

Example 1 2.5 g of the ring-opened methyl 5-norbornene-2-carboxylate polymer obtained in Reference Example 1 was dissolved in 16 ml of tetrachlorethylene along with 2.1 g of pentaerythritol tetrakis (mercaptopropionate) and 0.13 g of benzophenone. Then, the obtained photosensitive resin composition solution was placed on an aluminum plate.
It was applied to a thickness of 100μ, and after the coating had dried, it was irradiated with a 1KW high-pressure mercury lamp and photocured. A good cured film was obtained with an irradiation time of 30 seconds.

Example 2 The same coating surface as in Example 1 was prepared, a part of the coating surface was shielded from light with a black film having several circular light-transmitting parts, and irradiation was performed in the same manner as in Example 1. After photocuring, the unexposed areas were washed out with tetrachloroethylene. A good image line was obtained due to the boundary with the light-shielding area and the circular exposed area.

Example 3 Instead of the methyl 5-norbornene-2-carboxylic acid ring-opened polymer, 2.2 g of the 5-norbornene-2-carboxylic acid ring-opened polymer obtained in Reference Example 2 was used,
The rest was carried out in the same manner as in Example 1, and a good cured film was obtained with an irradiation time of 30 seconds.

Example 4 A part of the coated surface of Example 3 was irradiated with light shielded, and after photocuring, the unexposed area was washed out with dilute alkaline water.
A good drawing line was obtained.

Example 5 The same procedure as in Example 1 was carried out using 2.0 g of the 2-cyano-5-norbornene ring-opening polymer obtained in Reference Example 3 instead of the methyl 5-norbornene-2-carboxylate ring-opening polymer. Ivy. A good cured film was obtained with an irradiation time of 30 seconds.

Claims (1)

[Claims] 1. General formula (In the formula, X and Y each represent a substituent selected from hydrogen, ester, nitrile, or carboxyl. However, one of X and Y is a substituent selected from ester, nitrile, or carboxyl.) A photosensitive resin composition comprising a polymer containing a unit represented by the above formula and a compound having at least two thiol groups in the molecule.