JPH035738B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to a photosensitive coloring material that is colored due to photochemical properties. Conventional configurations and their problems Conventionally, there are the following photosensitive coloring materials due to photochemical properties. Combination of ferric salt and red blood salt or yellow blood salt; This combination of materials is the material used in the blueprint process. This principle utilizes the photochemical property of ferric salts changing into ferrous salts when exposed to light, and includes the blue-on-white line method and the white-on-blue line method. Combination of diazo compounds and phenols and aminos; Diazo compounds generally absorb short wavelength light and cause a photodecomposition reaction, but this compound combines with phenols and aminos (color formers) in alkaline conditions to form azo dyes. Form. Positive photosensitive paper utilizes this. The color changes by changing the type of coloring agent.
In the case of this material, the unexposed areas are used to color and form images. Combination of o-naphthoquinone diad and PH indicator: The purpose is to easily identify the exposure pattern in the production of printing plates that have been previously photosensitized with this material o-naphthoquinone diad. O-naphthoquinone diad is used as a positive resist, and when exposed to light, it turns into indenecarboxylic acid, exhibits a pH of 2.5 to 6.5, and becomes alkali-soluble. This printing plate is characterized by containing in the photosensitive layer an organic material (PH indicator) that changes its color tone in the PH range of 2.5 to 6.5 in the form of homogeneous particles. The original printing plate, which is originally yellow, is dyed in other colors by the action of the PH indicator when exposed to light, making it possible to identify the exposure. Thiocyanatoacetylstyrene copolymer: This material was proposed by the present inventors in Japanese Patent Application No. 78957/1983, and the thiocyanatoacetyl styrene copolymer was irradiated with ultraviolet light with a wavelength shorter than 350 nm. The toacetyl group is rearranged to become an isocyanatoacetyl group as follows. In the presence of an alkali or a base such as ammonia, this isothiocyanatoacetylstyrene copolymer creates an anion seat as shown below, and a so-called dye-fixing functional group is generated, which reacts with a cationic dye Dye X and dyes. becomes possible. Each of the conventional examples described above has its own problems. For example, in (1), it is impossible to color other than blue in any case. In method (2), the entire unexposed area of the diazo compound is colored by one exposure, and therefore multicolor image formation cannot be performed. (3) Increases the exposure amount and changes the pH from 6.5
2.5, and the required color is colored with a PH indicator. However, since PH indicators generally change color continuously, it is very difficult to color a specific location with a color with predetermined spectral characteristics. Have difficulty. Since (4) contains a thiocyanato group, the organic solvents for dissolving this copolymer are limited to dimethyl formamide, tetrahydrofuran, etc., and it may be difficult to form an optically transparent thin film. In addition, since coloring occurs after a two-step reaction of structural change due to exposure to light and structural change in the dye bath, it is necessary to control the concentration of alkali or base. Purpose of the Invention The present invention is colorless and can be directly colored with organic dyes, and can easily form multicolor high-resolution images.The coloring process is easy to control, and by using a general-purpose solvent, it is optically transparent and uniform. The purpose of the present invention is to provide a photosensitive coloring material that can form a thin film. Structure of the Invention The photosensitive coloring material of the present invention has the formula (However, X represents O or S, and R is

[expression] or

Represents [formula]. ) It is characterized by consisting of a polymer or copolymer containing a monomer having a group represented by the following as a polymerization component. In particular, the monomer has the formula (However, R' represents H or CH _3. ) For example, phenyl acrylate,
Phenyl methacrylate is used, and methyl methacrylate, styrene, etc. are used as copolymerization components. The coloring principle and coloring conditions of the photosensitive coloring material of the present invention will be described below. As an example of a photosensitive coloring material, polyphenyl methacrylate undergoes the following rearrangement when irradiated with ultraviolet light having a wavelength shorter than 350 nm.

【formula】

[Formula] The above phenol group forms an anionic seat in the presence of an alkali or base and fixes a cationic dye. As described above, the photosensitive coloring material of the present invention does not undergo structural changes when forming anion seats in a dye bath, and therefore can be dyed stably and efficiently. Description of Examples Example 1 A copolymer was obtained by radical copolymerization of 20 parts by weight of phenyl methacrylate (hereinafter simply expressed in parts) and 80 parts of methyl methacrylate using azoisobutyronitrile as an initiator. The resulting copolymer was deposited on a glass slide from a 7% by weight solution in benzene to a thickness of approximately
Make a 50μm film. This copolymer forms a colorless and transparent film. and this film
A 100W high-pressure mercury lamp (UMI02 manufactured by Ushio) is used to selectively irradiate light from a distance of 10cm. On the other hand, methanol and dioxane were polymerized at a polymerization ratio of 5:
0.5% by weight of the dye (Azure A) and 0.2% by weight of triethylamine were dissolved in the solvent mixed in step 1, and the above photoirradiated film was immersed in this solution for 1 minute, and the surface was washed with methanol and dried. Only the portion was colored with Azure A. The relationship between the irradiation time and the absorbance representing the amount of coloring was as shown in FIG. This result shows that the irradiation time and the amount of coloring are proportional. From this, the amount of coloring can be controlled by the irradiation time. Example 2 A copolymer was obtained by radical copolymerization of 20 parts of phenyl methacrylate and 80 parts of styrene using azoisobutyronitrile as an initiator. The obtained copolymer was colored with Azure A in the same manner as in Example 1, and the relationship between the irradiation time and the amount of coloring was measured. This is shown in Figure 2. This result shows that the irradiation time and the amount of coloring are proportional. From this, similarly to the copolymer of Example 1, the amount of coloring can be controlled by the irradiation time. In the above example, Azure A was used as the cationic dye, but fuchsin or methylene blue can also be used. Example 3 Next, as an application example of the photosensitive coloring material of the present invention, a method for making a color filter for a television camera will be described with reference to FIG. First, a photosensitive coloring base material 2 made of a copolymer of phenyl methacrylate and styrene is applied as a colorless and transparent film with a thickness of about 2 μm onto a glass substrate 1 that will serve as a transparent base.
(a) Photomask 3 with opaque areas (hatched areas)
After selectively irradiating the ultraviolet light 4 using a (b) to cause the above-mentioned reaction to occur in the light-irradiated area, for example, the substrate 1 is immersed in the dye bath described above to dye only the light-irradiated area of the material 2. For example, a red staining pattern 5 with a diameter of 10 μm is formed (c). Next, using another photomask 6, ultraviolet light 7 is selectively irradiated to a part other than the part where the pattern 5 of the material 2 is formed (d) to cause the above-mentioned reaction.
For example, the pattern 5 is dyed blue using a dye bath of a different color from that of the pattern 5. In this way, a blue dyeing pattern 8 different from pattern 5 is formed (e). Similarly, after selectively irradiating ultraviolet light 10 using a mask 9 on parts other than patterns 5 and 8, (f), a dye bath of a different color from patterns 5 and 8 is used to selectively irradiate ultraviolet light 10.
For example, a green dyeing pattern 11 is formed by dyeing only the irradiated area of 0 (g). Through these steps, a color filter having dyed patterns 5, 8, and 11 for color filters is manufactured. According to the method shown in Fig. 3, the base material for photosensitive coloring is selectively irradiated with light, and only the light irradiated area can be colored, and a colored pattern is formed in the light irradiated area, so that the base material is simply irradiated with light. A colored pattern on a filter can be formed simply by using selective exposure and dyeing steps. Therefore, when manufacturing a color filter having a multi-color coloring pattern, the method shown in Figure 3 requires multiple dyeing film coatings and processing, or multiple resist coatings, development, resist removal, etc. High-precision color filters can be easily manufactured in a few steps.
Further, other colored patterns can be similarly formed by using any dye such as cyan, magenta, yellow, etc. for dyeing. Although the above description has been made regarding color filters, the material of the present invention can also be applied to other optical filters. Furthermore, when the photosensitive coloring material of the present invention is used on fabric or film, only the irradiated areas can be easily colored by using it in combination with a photomask. By repeating light irradiation and dyeing, a wide variety of colors can be produced. Therefore, dyeing of fabric and film-like formation, which are carried out using conventional textile printing techniques, can be easily carried out. And the third
As shown in the figure, the combination of ultraviolet light and a mask makes it possible to color fine parts in the micron range. Therefore, a color filter (mosaic image of several colors) required for an image pickup tube or an image pickup plate for a color television camera can be easily created on a flat plate. Furthermore, the material of the present invention can also be used as a wet-development type recording material for color copying machine recording paper. Effects of the Invention As described above, when the photosensitive coloring material of the present invention is used, only the light irradiated area can react with the dye by performing light irradiation using a mask.
Partial coloring can be done easily. That is, image formation can be easily performed. Furthermore, in the present invention, many dyes can be applied to a colorless colored base material, many colors can be selected, and coloring can be performed with high precision in terms of color and tone.
Furthermore, by adjusting the amount of light irradiation, the coloring of the coloring substrate can be easily controlled. In the present invention, general-purpose solvents such as ester, ether, and aromatic solvents can be used, and an optically transparent thin film can be easily formed. By using a high-precision light irradiation device, it is possible to form fine images with high resolution. Furthermore, in the material of the present invention,
Since there is no structural change during dyeing, the coloring process can be easily managed.

[Brief explanation of drawings]

Figure 1 shows the relationship between irradiation time and coloring amount for a copolymer of phenyl methacrylate and methyl methacrylate, and Figure 2 shows the relationship between irradiation time and coloring amount for a copolymer of phenyl methacrylate and styrene. The figure shown in FIG. 3 is a manufacturing process diagram of a color filter using the material of the present invention.

Claims (1)

[Claims] 1 A polymer containing a monomer having a group represented by the formula [formula] (wherein, X represents O or S, and R represents [formula] or [formula]) as a polymerization component Or a photosensitive coloring material made of a copolymer. 2. The photosensitive coloring material according to claim 1, wherein the monomer is represented by the formula: (wherein R' represents H or CH ₃ ).