JPH10316667A - Photosensitive compound and photosensitive resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound being a photosensitive compound usable for cathode-ray tubes, screen printing, other display tubes, immobilized enzymes, PS plates, etching resist, etc. SOLUTION: This compound is such one expressed by formula I [R is a <=6C alkyl or -(CH2 )m - formed by joining of 2 of the Rs into one group (m) is 2 or 3}; (n) is 1-3; Rx is a group expressed by formula II or III (X is a water- soluble group; Y is H, NO2 , OCH3 Cl or Br), etc.], e.g. 3-(2-dimethoxybutyl) rhodanine. The compound of formula I is obtained by, e.g. condensation reaction between a rhodanine compound, having an acetal group, expressed by formula IV, and a water-soluble benzaldehyde expressed buy formula V, etc., an allylaldehyde derivative or an aldehyde compound having a heterocycle. The rhodanine compound having an acetal group is obtained by reacting an acetal compound having an amino group with carbon disulfide in the presence of a base to produce a dithiocarbamate, followed by reaction of the dithiocarbamate with ethyl chloroacetate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel photosensitive compound and photosensitive resin, and more particularly, for example, for cathode ray tubes, screen printing, other display tubes, immobilized enzymes, PS plates, etching resists, and the like. The present invention relates to a photosensitive compound and a photosensitive resin that can be used in the above-mentioned applications.

[0002]

2. Description of the Related Art Conventionally, a photosensitive unit containing a photosensitive resin obtained by subjecting unmodified polyvinyl alcohol to a condensation reaction with a quaternary ammonium salt such as a styrylpyridium salt compound or a styrylquinolium salt compound (P)
VA-SbQ-based resists) are known (JP-B-56-5761, JP-B-56-5762, and JP-A-56-11906).

[0003]

SUMMARY OF THE INVENTION Such PVA-SbQ
The system resist has advantages such as a high photosensitivity, but is limited to cationic ones in terms of ionicity, which limits the application and composition. In addition, since a metal halide (400 nm) light source besides a mercury lamp (365 nm) is used as an exposure light source, it is necessary to use 4-methylquinoline or the like in order to set the photosensitive wavelength to a long wavelength, which increases costs. There is a disadvantage that.

[0004] Therefore, for example, for cathode ray tubes, screen printing, and other uses for display tubes, 40
There is a demand for a material having good photosensitivity at a long wavelength of 0 nm and which can be dissolved or dispersed in an aqueous solvent. In particular, polyvinyl alcohol (PVA) is excellent as a binder polymer for use in forming a phosphor pattern.
There is a demand for a PVA-based resist having a longer photosensitive wavelength than that of a PVA-SbQ-based resist, and also being able to use cations, anions, and nonions depending on the application in terms of ionicity.

In view of such circumstances, an object of the present invention is to provide a photosensitive compound capable of preparing a novel photosensitive resin and a photosensitive resin using the same.

[0006]

Means for Solving the Problems A photosensitive compound according to the present invention for solving the above-mentioned problems is a photosensitive compound represented by the following general formula.

[0007]

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Here, R is an alkyl group up to C6 and-(CH ₂ ) _m- (m
Is selected from 2 or 3). N is 1, 2 or 3. Further, Rx is selected from the following Rx1 to Rx9, X in Rx1 to Rx9 is a water-soluble group, and Y is H, N
Ry is an alkyl group, Y ^- is an anion such as phosphoric acid, methanesulfonic acid, monomethylsulfuric acid, chlorine, bromine, oxalic acid, p-toluenesulfonic acid, etc., selected from O ₂ , OCH ₃ , Cl, and Br.

[0009]

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Here, X is selected, for example, from the following X1 to X13.

[0011]

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[0012] Here, Q is represents lithium, sodium, potassium, ammonium, monoalkyl ammonium, dialkyl ammonium, trialkylammonium, or tetraalkylammonium, Y ^- is phosphate,
Anions such as methanesulfonic acid, monomethylsulfuric acid, chlorine, bromine, oxalic acid and p-toluenesulfonic acid.

Further, the photosensitive resin of the present invention is characterized by having a structural unit represented by the following general formula.

[0014]

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Here, n is 1, 2 or 3. Also,
Rx is selected from the above Rx1 to Rx9. Further, R
X in x1 to Rx9 is a water-soluble group, and Y is H, NO ₂ , O
CH ₃ , Cr, and Br are selected, Ry is an alkyl group, and Y ⁻ is an anion such as phosphoric acid, methanesulfonic acid, monomethyl sulfate, chlorine, bromine, oxalic acid, and p-toluenesulfonic acid.

Here, X is selected, for example, from the above X1 to X13.

Further, the photosensitive composition of the present invention is characterized by containing the above-mentioned photosensitive resin.

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, a novel rhodanine skeleton was obtained by condensing a rhodanine compound having an acetal group with a water-soluble aldehyde or an aldehyde having a heterocyclic ring. The present invention has been completed by developing a novel compound capable of performing long-wavelength photosensitization.

The photosensitive resin having a rhodanine skeleton is disclosed in US Pat. No. 2,828,087. However, this photosensitive resin is completely different from the present invention because the photosensitive group itself is hydrophobic and not water-soluble, but is soluble in alkali water by a carboxyl group of the polymer.

The compound represented by the above general formula (I) according to the present invention is basically water-soluble, has photodimerization type photosensitivity, and can be easily converted into a photosensitive resin by acetalization into PVA. Can be prepared.

The compound represented by the above general formula (I) according to the present invention is obtained by condensing a rhodanine compound having an acetal group with a water-soluble benzaldehyde or allylaldehyde derivative or an aldehyde compound having a heterocyclic ring. be able to.

Here, the rhodanine compound having an acetal group is represented by the following formula.

[0023]

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The rhodanine compound having an acetal group is, for example, an acetal compound having an amino group,
It can be obtained by synthesizing dithiocarbamate with carbon disulfide in the presence of a base such as ammonia, triethylamine, NaOH, or KOH, followed by reaction with ethyl chloroacetate. In this case, the reaction solvent can be selected from water, ether, DMF and the like depending on the amine compound used, but is not limited thereto.

The benzaldehyde aldehyde or allyl aldehyde derivative condensable with the rhodanin compound having an acetal group is represented by the following formulas (1) and (2). Further, the aldehyde compound having a heterocyclic ring is represented by the following formulas (3) to (9). These compounds impart water solubility to the photosensitive compound of the present invention, and therefore have water solubility.

[0026]

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[0027]

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Here, in equations (1) and (2), X
And Y are as described above.

The photosensitive compound represented by the above formula (I) of the present invention can be reacted with a saponified polyvinyl acetate or a water-soluble copolymer of vinyl alcohol and another vinyl compound in the presence of an acid catalyst. And the photosensitive resin represented by the above formula (II) of the present invention.

As the saponified polyvinyl acetate used herein, for example, those having an average degree of polymerization of 200 to 5000 and a degree of saponification of 60 to 100% are preferable. As the saponified polyvinyl acetate, for example, hydrophilic group modification,
A modified vinyl acetate saponified by anionic modification, cationic modification, or modification of a reactive group such as an acetoacetyl group can be used.

If the average degree of polymerization is less than 200, it is difficult to obtain a sufficient sensitivity. If the average degree of polymerization is more than 5,000, the viscosity of the photosensitive resin solution increases, and In addition, when the concentration is lowered to lower the viscosity, it becomes difficult to obtain a desired coating film thickness. On the other hand, if the saponification degree is lower than 60%, it is difficult to obtain sufficient water solubility and water developability.

On the other hand, as a copolymer of vinyl alcohol and another vinyl compound, for example, an average degree of polymerization of 200 to 200
5000 can be used. In addition, as a vinyl monomer copolymerizable with vinyl alcohol, for example, N
-Vinylpyrrolidone, acrylamide and the like.

Such saponified polyvinyl acetates,
When the photosensitive compound represented by the above formula (I) is reacted with the photosensitive compound represented by the above formula (I) in the presence of an acid catalyst to obtain a photosensitive resin represented by the above formula (II), for example, formaldehyde, acetaldehyde,
Aldehydes such as propionaldehyde, butyraldehyde, and benzaldehyde, or their acetals can be reacted simultaneously.

The introduction ratio of the photosensitive compound of the general formula (I) to the saponified polyvinyl acetate is preferably about 0.3 to 5 mol% per monomer unit.

[0035]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail based on embodiments.

Example 1 Preparation of 3- (2-dimethoxybutyl) rhodanine 67 g of aminobutyraldehyde dimethyl acetal and 51 g of triethylamine were dissolved in 300 g of diethyl ether and cooled to 10 ° C. . 38 g of carbon disulfide under stirring
Was added dropwise over 60 minutes, and then reacted at 20 ° C. for 24 hours. Next, 84 g of ethyl bromoacetate was added dropwise over 15 minutes and reacted at room temperature for 48 hours. Triethylamine / hydrobromide was removed by filtration, and diethyl ether was removed by an evaporator to obtain an oily liquid containing the target compound represented by the following formula.

[0037]

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(Example 2) [Synthesis example of 3- (2-dimethoxybutyl)-(4-pyridylidene) rhodanine] 54 g of 4-pyridinealdehyde, 2 g of sodium hydroxide
Was dissolved in 100 g of water and 100 g of methanol.
Cooled to 0 ° C. and added slowly to the oil of Example 1. Although the target product was precipitated according to the reaction, stirring was continued as it was, and the reaction was performed for 5 hours. It was separated by filtration, washed with water and dried to obtain the target product represented by the following formula.

The purity of the liquid chromatography was 98%. Further, the absorption maximum was 370 nm.

[0040]

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Further, 65 g of dimethyl sulfate was added to 160 g of this compound and 200 g of methanol.
It was quaternized by reacting for hours. After cooling, acetone was added to precipitate the desired product represented by the following formula, which was separated by filtration. The absorption maximum was 384 nm.

[0042]

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(Example 3) [Synthesis of photosensitive PVA] Polyvinyl alcohol (GH-24, manufactured by Nippon Gosei) 10
0 g was dissolved in 900 g of water. Compound of Example 2 was converted to 17
g and 3 g of phosphoric acid were added and reacted at 60 ° C. for 24 hours. The phosphoric acid is removed by ion exchange treatment, and the photosensitive group is added to PVA.
A photosensitive solution into which 6 mol% was introduced was prepared.

(Test Example 1) The photosensitive solution of Example 3 was diluted to 5%, coated on a glass plate with a film thickness of 1.0 μm, and applied with ultra-high pressure mercury or the like (ultraviolet illuminance 5 mW / cm ² : UV-35 (manufactured by Oak (Illuminometer)). Next, it was confirmed that a pattern was formed by developing with water.

Example 4 [Synthesis Example of 3- (2-dimethoxybutyl)-(benzylidene-4-carboxylate) rhodanine] An aqueous solution prepared by dissolving 75 g of terephthalaldehyde acid and 30 g of sodium hydroxide in 2000 g of water was prepared. C. and cooled with the compound of Example 2 (shown in Chemical Formula 15) 160
g. Although the target product was precipitated as the reaction proceeded, stirring was continued as it was, and the reaction was carried out for 24 hours. N
50 g of aCl was added, and the mixture was further stirred for 5 hours, filtered and washed with acetone.

The product represented by the following formula had a purity by liquid chromatography of 95%. The absorption maximum is 3
83 nm.

[0047]

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(Example 5) [Synthesis of photosensitive PVA] Polyvinyl alcohol (GH-24, manufactured by Nippon Gosei) 10
0 g was dissolved in 900 g of water. Compound of Example 4 was converted to 19
g and 3 g of phosphoric acid were added and reacted at 60 ° C. for 24 hours. Phosphoric acid is removed by ion exchange treatment, and the photosensitive group is added to PVA.
A photosensitive solution in which 0 mol% was introduced was prepared.

(Test Example 2) The photosensitive solution of Example 5 was diluted to 5%, coated on a glass plate to a thickness of 1.0 μm, and applied with ultra-high pressure mercury or the like (ultraviolet illuminance 5 mW / cm ² : UV-35 (manufactured by Oak) 20 mJ). It was confirmed that a pattern was formed by water development.

[0050]

As described above, according to the present invention,
By condensing a rhodanine compound having an acetal group with a water-soluble aldehyde or an aldehyde having a heterocyclic ring, it is possible to provide a novel compound having a novel rhodanine skeleton and capable of being exposed to light at a long wavelength.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09B 57/00 C09B 57/00 Z G03F 7/038 G03F 7/038

Claims (5)

[Claims] 1. A photosensitive compound represented by the following general formula: Embedded image Here, R represents an alkyl group of up to C6, and two R form together _{- (CH 2) m - (} m is 2 or 3) is selected from. N is 1, 2 or 3.
Further, Rx is selected from the following Rx1 to Rx9,
X in 1 to Rx9 is a water-soluble group, Y is H, NO ₂ , OC
H _3, Cl, and are selected from Br, Ry is an alkyl radical, Y ^- is phosphate, methanesulfonic acid, monomethyl sulfate, chlorine, bromine, oxalic acid, anions such p- toluenesulfonic acid. Embedded image 2. The method according to claim 1, wherein X is X1 to X13 below.
A photosensitive compound selected from the group consisting of: Embedded image Here, Q represents lithium, sodium, potassium, ammonium, monoalkylammonium, dialkylammonium, trialkylammonium, or tetraalkylammonium, and Y ⁻ represents phosphoric acid, methanesulfonic acid, monomethylsulfuric acid, chlorine, bromine, oxalic acid. , P-toluenesulfonic acid and the like. 3. A photosensitive resin having a structural unit represented by the following general formula. Embedded image Here, n is 1, 2 or 3. Rx is the following R
x1 to Rx9. Further, Rx1 to Rx9
X represents a water-soluble group, and Y represents H, NO ₂ , OCH ₃ , Cr,
Ry is an alkyl group, Y ^- is phosphoric acid, methanesulfonic acid, monomethyl sulfate, chlorine, bromine,
Anions such as oxalic acid and p-toluenesulfonic acid. Embedded image 4. The method according to claim 3, wherein X is the following X1 to X13.
A photosensitive compound selected from the group consisting of: Embedded image Here, Q represents lithium, sodium, potassium, ammonium, monoalkylammonium, dialkylammonium, trialkylammonium, or tetraalkylammonium, and Y ⁻ represents phosphoric acid, methanesulfonic acid, monomethylsulfuric acid, chlorine, bromine, oxalic acid. , P-toluenesulfonic acid and the like. 5. A photosensitive composition comprising the photosensitive resin according to claim 3 or 4.