JPS59182437A - Photosensitive material for coloring - Google Patents

Abstract

PURPOSE:To obtain a photosensitive material for coloring capable of being directly colored with an org. dye, giving easily a polychromatic image with high resolution, and facilitating the control of the coloring stage by using a polymer of a monomer having a specified group as a polymerizable component. CONSTITUTION:A polymer of a monomer having a group represented by a formula -CO-X-R (where X is O or S, and R is a benzene ring or a naphthalene ring), e.g., phenyl acrylate or phenyl methacrylate as a polymerizable component or a copolymer of said monomer with methyl methacrylate, styrene or the like as a copolymerizable component is used as a photosensitive material for coloring. A film of said polymer or copolymer is formed on a glass slide, and it is selectively irradiated with light. Only the irradiated part becomes reactive with a dye, so partial coloring is easily carried out.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a photosensitive coloring material that is colored due to photochemical properties.

Structure of conventional examples 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 method.

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 amines
Diazo compounds generally absorb short wavelength light and cause a photodecomposition reaction, but in alkaline conditions, this compound combines with phenols and amines (color formers) to form azo dyes. 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 colored and used for image formation.

(2) Combination of 0-naphthoquinone diato and indicator; This material was developed for the purpose of making it possible to easily identify the exposure pattern in the production of printing plates that have been previously photosensitized with 0-naphthoquinone diato.

O-naphthoquino/diad is used as a positive resist, and when exposed to light it turns into indenecarboxylic acid and its pH changes.
2.5 to 6.5 and is alkali soluble.

This printing original plate is characterized in that the photosensitive layer contains an organic dye (pH indicator) that changes the 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 another color by the action of the Sil H indicator upon exposure, and the exposed areas can be identified.

■ Thiocyanatoazetyl styrene copolymer: This material was proposed by the present inventors in Japanese Patent Application No. 57-78957, and it can be copolymerized by irradiation with ultraviolet light with a wavelength shorter than 3501 m. In the presence of an alkali or a base such as ammonia, this isothiocyanatoacetylstyrene copolymer creates an anion seat as shown below, and a functional group that fixes a so-called dye is produced, resulting in the production of a cationic dye. It reacts and becomes dyeable.

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. With @), the entire area of the unexposed area is colored by one exposure to the diazo compound, so it is not possible to form a multicolor image. In (3), the pH is continuously changed from 6.5 to 2.5 by increasing the exposure amount, and the necessary color is colored with a pH indicator, but in general, pH indicators cannot change color continuously; It is extremely difficult to color a specific location with a color that has predetermined spectral characteristics.

Since (4) contains a thiocyanato group, the organic solvent that dissolves this copolymer is limited to dimethylformamide, 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 an organic dye, and can easily form two multicolored high-resolution images.The coloring process can also be easily controlled, and optically transparent and uniform images can be produced by using a general-purpose solvent. The object 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 is a polymer or copolymer having a monomer having the formula % (where X represents O or S and R represents a group represented by) as a polymerization component. It is characterized by becoming.

Said monomers are particularly those of the formula aH2=c 1 C;O, where R/ stands for H or CH3, such as 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 is exposed to ultraviolet light with a wavelength as short as 350 nm.The above phenol group forms an anionic seat in the coexistence of an alkali IJ4 or a base, and the cationic dye is fixed as above. The photosensitive coloring material of the present invention does not undergo any structural change when an anion seat is formed in the drying process, so that it 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. A film with a thickness of about 60 μm is made on a glass slide from a 7% by weight benzene solution of the obtained copolymer. This copolymer forms a colorless and transparent film. Then, apply a 100W high-pressure mercury lamp (Ushio UM) to this film.
IO2) and selectively irradiate light from a distance of 10 cTL.

On the other hand, 5% by weight of dye (Azure A) O-5 and 0.2% by weight of triethylamine were dissolved in a solvent containing methanol and dioxane mixed at a weight ratio of 5:1, and the above-mentioned film irradiated with light was placed in this solution for 1 minute. After immersing, when the surface is washed with methanol and dried, only the irradiated area becomes Azure A.
colored by.

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 8 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, Azulian was used as the cationic dye, but tsuksin 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 colored base material 2 made of a polymer of 7-enyl methacrylate, styrene ψ, and a polymer is placed on a glass substrate 1, which will be a transparent substrate, to a thickness of about 2 μm.
It is applied as a colorless and transparent film a), and the opaque part (
After selectively irradiating ultraviolet light 4 using a photomask 3 having a diagonal area (shaded area) and causing the reaction described above in the light irradiated area, for example, the substrate 1 is immersed in the dye bath described above to dye the material 2. Only the light irradiated area is dyed to form a red dyeing pattern 5 with a diameter of, for example, 10 μm (C).

Next, using another photomask 6, ultraviolet light 7 is selectively irradiated onto a portion of the material 2 other than the pattern 5 forming portion.
), after causing the above-mentioned reaction, the pattern 5 is dyed, for example, 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 6 is formed (
6). Similarly, after selectively irradiating ultraviolet light 10 using a mask 9 on parts other than patterns 5 and 8, (
f), Only the irradiated area is dyed to form, for example, a green dyeing pattern 11 (g).

Through such steps, color filters having dyed patterns 5, 8, and 11 for color filters are manufactured.

According to the method shown in Fig. 3, the base material for photosensitive coloring is selectively irradiated with light so that only the light irradiated area can be colored. 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 colored pattern of multiple colors, the method shown in FIG. High-precision color filters can be easily manufactured with a small number of steps. Also, cyan for dyeing,
Other colored patterns can be similarly formed using any dye such as magenta, yellow, etc.

Although color filters have been described above, the material of the present invention can also be applied to other optical filters.

Furthermore, when the photosensitive coloring material of the fourth aspect of the present invention is used for fabric or film, only the irradiated portion 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, it is possible to easily dye fabrics and form a membrane, which are performed using conventional textile printing techniques. As shown in FIG. 3, the combination of ultraviolet light and a mask makes it possible to color fine parts in the micron range.

Therefore, color filters (mosaic images of several colors) required for image pickup tubes or image pickup plates for color television cameras can be easily created on a flat plate. moreover,
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 invention is used,
By performing light irradiation using a mask, only the light irradiated areas can react with the dye, so partial coloring can be easily performed. 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. Further, by adjusting the amount of light irradiation, the coloring of the coloring base material 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 highly accurate light irradiation device, it is possible to form fine images with high resolution. Furthermore, since the material of the present invention does not undergo any structural changes during dyeing, the coloring process can be easily managed.

[Brief explanation of the drawing]

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. Figures 3 and 3 are process diagrams for manufacturing a color filter using the material of the present invention. Name of agent Patent attorney Satoshi Nakao and one other person Figure 1 Sagikenho T11 (System Figure 2 M, Shooting Figure 3)

Claims (1)

[Claims] 0) A photosensitive coloring material comprising a polymer or copolymer containing a monomer having a group represented by the formula -C-X-R 1 as a polymerization component. 2) The photosensitive coloring material according to claim 1, wherein the monomer is represented by the formula 0H2=G (where R' is H, C=O, or ρ representing CH3).