JPS58204042A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To provide a photosensitive compsn. which has high dyeability and good rosultion, by adding a photosensitizer to a copolymer of vinylpyrrolidone with a specified monomer. CONSTITUTION:A photosensitizer such as 4'-azido-4-adido benzalacetophenone-2- sulfonic acid is added to a copolymer obtd. by copolymerizing vinylpyrrolidone and a monomer having an ammonium salt type nitrogen atom and a polymerizable unsaurated bond, such as 3-methacryloxypropyltrimethylammonium chloride. A glass plate is coated with this photosensitive compsn., irradiated with ultraviolet light and dyed at 30 deg.C. EFFECT:The compsn. can be stored for one year or longer when preserved in a dark place. USE:Color separation filter for television camera using a solid image pickup element.

Description

DETAILED DESCRIPTION OF THE INVENTION A photosensitive composition having the Q-L dyeing 1) of the present invention, especially a color component *I: used in the production of ITJ dyeing 1) The present invention relates to a composition.

Color separation ((1 filter) For colorization of color television cameras that use solid-state image sensors as an example,
Color elements are arranged in a mosaic or stripe pattern on the light-receiving element surface of the solid-state image sensor. The most common (needle [l'j
' + red and green. Traditional color separation filters
! 1" L resin is used, and ammonium dichromate or potassium dichromate is added to proteins such as gelatin or casein as a photocrosslinking agent. A photosensitive composition containing additives such as chromium is used.A general method for manufacturing color separation filters is to apply gelatin or casein (containing hexavalent chromium) to a glass plate using a spin cord method.
A latent image of the color element dyed layer is formed by irradiating ultraviolet rays through a mask 7, and the color element dyed layer is exposed by development. Next, there is a method of dyeing this with a dye. In order to form the red, green, and g color concave element layers, lamination is repeated three times to form a color separation filter, which is then used by adhering it to the surface of the solid-state image sensor.

Therefore, through this process, the color 4I produced
y (III) The performance required for the photosensitive +!1 resin with dyeing 4f used in filters is firstly good resolution, secondly good storage 1"1-, and thirdly dyeing... The photosensitive resins made from casein and ceratin, which are currently widely used11, have high resolution. However, since alkali is used to increase the solubility in water, the hydrolysis of the resin proceeds even in the dark due to dark reaction, resulting in gradual deterioration. In addition, since it contains hexavalent chromium such as ammonium east chromate and potassium dichromate as a photocrosslinking agent, wastewater treatment equipment is required for disposal. Furthermore, dyeing (r) depends greatly on the film thickness, and the dyeing conditions require high temperatures and long periods of time.The thicker the resin film, the greater the amount of time required to harden the resin, and the irradiation of ultraviolet rays. Not only does the amount of light (exposure) increase, but also the light is irradiated onto the areas where the mask blocks the light due to diffraction due to the trenches, resulting in a decrease in the R degree. Therefore, the film thickness of the resin is required to be as thin as possible.Therefore, for the dyeability of the resin, a thin film thickness is required, and the dyeing risk concentration is kept at room temperature and at a level sufficient to obtain the desired properties.
It is also necessary to attack the resin film at a temperature of 1 mz near neutrality (11 under difficult staining conditions).

Therefore, resins such as casein and gelatin that require a film thickness of 0.8 μm or more and that require high-temperature and long-term dyeing conditions are unsuitable.

The present invention was made in order to eliminate the above-mentioned conventional drawbacks, and provides a photosensitive composition that has good dyeability and good resolution.

The photosensitive composition of the present invention is based on the following molecular film concept. That is, photosensitive function and dyeing 1. Neutralize resin with the following functions. Specifically, the above photosensitive composition is prepared by adding a photosensitive agent to a copolymer of vinylpyrrolidone and a monomer having an ammonium salt type nitrogen atom and an unsaturated bond capable of polymerization. Able to achieve purpose. In the photosensitive composition having such a structure, several types of monomers having an ammonium salt type nitrogen atom and a polymerizable unsaturated bond are listed below.

3-Methacryloyloxypropyltrimethylammonium chloride (NOF) (blank below) Methacryloyloxypropyltrimethylammonium chloride
Chloride (1-1 manufactured by Tokagaku) 3-acrylamide, 3
-Methylbutyltrimethylammoniuno, chloride (
11 Tokagaku Co., Ltd.) Next, as for cutting, diazide compound,
Using known energy-sensitive substances such as tetrazonate and salt, 1 = 11 can be obtained. Next, list the numbers (Φ class).

4'-azido 4-azidobenzalacetophenone 2-sulfonic acid 4.4'-azidostilbene 2,2'-disulfonic acid 4.4'-diazidostilbene carboxylic acid N5-Q
-C=CH-Q-N3 OOH diphenyl 4,4'-bisdiazonium chloride, zinc chloride double salt Cl1N29 N2Cj2- ZnCj223.3'-
Dimethyldiphenyl-4,4'-bisdiazonium chloride, zinc chloride double salt vinylpyrrolidone, etc.
The photosensitive composition iL, which is prepared by adding the exemplified photosensitizer to a copolymer of IL and II, is extremely stable and can be stored for more than a year without being stored in the dark. -This photosensitive tfJ
When the tl product is applied to a gelatin plate [7, dyeing is performed after UV irradiation, compared to gelatin or casein,
It was found that dyeing can be done at a low temperature of 3oC. Moreover, the dyeing speed (time required to obtain a certain dyeing density)
Protein-based substances such as L1 gelatin and tunosein and dichromate-based staining gel 1. Compared to a photosensitive composition having [7
It was found that the number of cases was twice as high.

Next, examples of dyes that can be used to dye this photosensitive composition will be given.

(1) The first red dyes are Suminol Mi IJ 7g Scarlet G (Sumikata Chemical Industries), Cibacuron Scarlenoto GP (Ciba Kaikey Co., Ltd.), and Chihaku.
N Pronto Scarenoto (Civar Geigy), Suminol Fast Red G (Sumikata Chemical), Sumilite Supra Φ Red 4BL (Sumikata Chemical),
Aminyl Red E-2BL (Suikata Chemical Industries).

Aminyl Red E-sBL (Suikata Chemical Industries).

Suminol Milling Scarlenoto FG (Sumikata Chemical Industries), Suminol Milling Orange SG (Sumikata Chemical Industries), Suminol Fast Orange PO (
Sumikata Chemical Industries).

Maxilon Red GRL (Ciba Kaiki).

Eriosin Scarenoto RE (Chihakaigi-71
), Mikawan Brilliant Red sBs (Mitsubishi Chemical), And Light Scalette GL 130
% (Mitsubishi Chemical), Kayanol Milling Red R5
125 (Mitsubishi Chemical), etc.

(2) As a green dye, Suminol Milling Brilliant Green 6G (Sukkata Chemical Industry).

Acid Brilliant Milling Green G (Shikata Chemical), and Brilliant Milling Green
B (Shikata Chemical Industry), Mication Olive Green 3GS (-: F-Ba Geigy), Kayanol Milling Green 5GW (1-1 bottle f drug), Sooliidazole Green, P-GG (Hoechst), Paper-Fast Green 5G (Pieher), etc.

(3) As a blue dye, Sumilite Spraer Turquoise Blue G (Sukkata Chemical Industry).

Cibacron, Blue-3G-A (Ciba, Geigy),
Cibachloran Blue 5G (fva Geigy 11)
, Prodione Turquoise H-A (CIC), Kayathion Turquoise P-A (11 Mulberry), Kayathion Turquoise P-NGF (14 Honka Shiba), Sumikalon Blue E-FBL (Sumikata Chemical) 21' Business), Sumikalon Brilliant Blue 5-BL (Sumikata Chemical Industry)
, Suminol Revalinda Jar Sky Blue R Extra Conch (fir: Yukagaku Kogyo) Orazole
Blue GN (Ciba Geigy God), Makizion Blue 3GS (Mitsubishi Chemical), Makizion Blue 2GS
(Mitsubishi Chemical), Kayanor Milling Blue GW (
Examples include Nippon Kayaku) and Kayable Sky Blue R (Nippon Kayaku).

Next, examples of the present invention will be specifically described.

(Example 1) Polyvinylpyrrolidone...φ...15y Blemmer O
A (NOF: 3-methacryloxypropyltrimethylammonium chloride) ψ・・・γξ6y azobutyronitrile・轡・・・・Q5y methanol・
...-11,300 ml of the above-mentioned liquid was placed in a milling flask, the reaction vessel was purged with nitrogen for 1 hour, the temperature was raised to 60° C., and the mixture was left in the heating box for 4 hours to perform radical copolymerization. After the completion of polymerization, the methanol solution of the copolymer was reduced to about 100 m/m, and 1. ,
The mixture was added dropwise to acetone (11) to obtain a copolymer. The obtained copolymer was dried under reduced pressure to remove acetone, and a copolymer used in a photosensitive composition was obtained. The obtained copolymer 5y was dissolved in 100 m/' of oil at 80°C, and after cooling to room temperature, 4,4'-azidostilbene 2°2'-disulfonic acid Q5y was added as a photosensitizer to improve dyeability. A photosensitive composition comprising: This photosensitive composition was coated on a glass substrate to a film thickness of 0.5 /l by a spin code method.
．． Heat treatment was performed at 130°C for 50 minutes.

After that, the surface illuminance (38 mW/c
ti) UV irradiation, using water as a developer,
A color element dyed layer is obtained by carrying out a 2-minute drying process at 20°C. After that, dyeing is carried out using the following dye bath.

Dye: Suminol Milling Orange SG (Sumikata Chemical Co., Ltd.) Dyeing conditions = 201R intermittent dye aqueous solution dyeing pH: pH 70 Dyeing temperature: 30°C Dyeing IL, 'j1ffj: 5 min after staining, min i
Y = 't'! +ze1 measurement (-1 specific wavelength (550n)
The permeability 1Ir5 ratio was investigated in m). As a result, 660nm
The transmittance was 582.

For comparison, a conventionally used photosensitive composition, casein-ammonium dichromate, was used, and in the same manner,
In order to obtain the same dyeing density (same spectral characteristics), the film thickness is 1011, the dye concentration is the same, and the dyeing temperature is 8o.
℃, and the dyeing time was found to be longer than 3° min.

This comparison revealed that when producing filters with the same spectral characteristics, the photosensitive composition used in the present invention can be dyed in a much shorter time at room temperature. The same was true for other dyes.

(Example 2) Using the photosensitive composition of composition 2 shown below, a copolymer was polymerized by the method described in Example 1 to produce a monochromatic filter. In order to obtain the same spectral properties as in Example 1, the staining time was 6 minutes.

Composition 2 Vinylpyrrolidone-premer QA combined y 4'-azido 4-azidobenzalacetophenone 2-sulfonic acid Q5y water
1oo′ (Example 3
) Next, the photosensitive [1+ composition shown in Composition 3] was filled, and a copolymer was polymerized by the method described in Example 1 to produce a monochromatic filter. Same spectroscopy and characteristics as Example 1;
If, i: staining time was 6 minutes.

Composition 3 Vinylpyrrolidone-methacryloyloxytrimethylammonium co-iF combination 6y4.4'-acidostilbene 2,2'-disulfonic acid
015y water
1Qoy (Example 4
) Next, using the photosensitive composition shown in Composition 4, a copolymer was polymerized by the method described in Example 1 to produce a monochrome filter. The dyeing time was 7 minutes in order to obtain a staining time of 7 minutes) as in Example 1.

jl) IL composition vinylpyrrolidone-3-acrylamide 3-methylbutyltrimethylammonium chloride copolymer
6y4.4'acidostilbene 2,2'-disulfonic acid 6y water 1oo
As can be seen from the explanations from Y to L, the photosensitive composition of the present invention contains no harmful metal components in its composition 4A.
First, in terms of dyeing properties, compared to conventional casein-based products, it has a rl-ability of several degrees Δ, and in terms of stability, it is much more stable than casein-based products, making it suitable for industrial use. ) 11 High value.

Unfortunately, the present invention is applicable not only to filter manufacturing, but also to the printing industry and other various industries.

Claims (1)

[Claims] A photosensitizer (f) obtained by adding a photosensitizer to a copolymer of vinylpyrrolidone and a monomer having an ammonium salt type nitrogen atom and a polymerization i + a negative unsaturated bond.