JPH0134370B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a coloring method, which uses changes in the photochemical reaction of a photosensitive organic coloring base material to achieve partial coloring.
The purpose is to provide a method that can be easily performed with good reproducibility, fineness, and high precision.

Coloring methods for forming images by partial coloring can be classified according to the process of latent image formation: methods using photochemical reactions such as diazonium photographs and blueprints;
Physical changes such as silver halide photography and magnetic recording, shapes such as pressure printing using convex, flat, concave, and stencils, and coloring of patterns formed with photosensitive materials, and Carlson electrophotographic processes. It can be broadly classified into those based on static electricity, such as corona charged latent images and electrostatic recording.

The principle of the blueprint method is that among iron compounds, ferric salts change to ferrous salts when exposed to light, and this photochemical property is utilized in the photographic method. There is a law. In the blue-on-white line method, ferric salt and red blood salt are used, and the ferric salt turns into ferrous salt when exposed to light, and the coexisting red blood salt converts Felician ferrous (Turnbull blue). Generates and turns blue. The white-on-blue line method uses ferric salt as a photosensitive component, but after exposure, it reacts with yellow blood salt to become soluble ferrous ferrous iron, which flows out during development, and the ferric salt in unexposed areas becomes yellow. It reacts with blood salts to produce ferric ferrocyan, ie, Plassian blue, resulting in a blue image. However, with this method, coloring other than blue is not possible in any case.

Diazotype method. Diazo compounds generally absorb short wavelength light to cause a photodecomposition reaction, and in alkaline conditions, these compounds combine with phenols and aminos (color formers) to form azo dyes. Positive photosensitive paper utilizes this, and has been developed using the conventional blue photography method. The color can be changed by changing the type of coloring agent. However, it is possible to color only a single color with one exposure, and it is impossible to color multiple colors.

On the other hand, when coloring a flat plate with several colors in fine patterns in micron units, a method is used in which a fine pattern is created using a photosensitive material such as resist and coloring is performed one color at a time. That is, this is a method of creating a latent image based on shape and coloring it.

For example, when making a color filter for a television camera, it is necessary to dye an area several tens of micrometers square with a color that exhibits the necessary spectral characteristics. In order to make this possible, the following methods are being considered.

The first method uses casein, which can be dyed, as a dyeing base material, imparts negative photosensitivity to the casein, and microfabricates the base material to form a dyed pattern that becomes the color of the color filter. It is something that is repeated. When three colors of red, green, and blue are formed using this method, three times of base material formation, three times of dyeing shape processing, and intermediate film formation between dyeing patterns are required in addition to the dyeing process, and fine color This is disadvantageous for manufacturing filters.

The second method is to apply a positive resist onto the dyed substrate, remove the resist in the dyed portion by exposure and development, and selectively dye the dyed substrate. This method also requires three times of resist application and three times of resist processing to manufacture a three-color color filter, and it is difficult to form a fine dyed pattern due to the diffusion of the dye.

Still another method is to use a color-forming base material (silver salt), but there are few color-forming materials that exhibit the necessary spectral characteristics, and it is not easy to form a color filter.

In partial coloring, the present invention selectively colors a photosensitive organic coloring substrate containing a thiocyanatoacetyl group directly in, for example, a micron region by light irradiation using a photomask and a dyeing operation with a colored material, and dyeing density is controlled by the amount of light irradiated onto the photosensitive organic coloring substrate, thereby making it possible to easily perform coloring with good reproducibility. Furthermore, the present invention provides a method that allows selective coloring of a wide variety of colors to be easily performed with high precision, and is suitable for forming fine images.

A specific implementation method of the present invention and its principle will be described below.

As an example of a photosensitive organic coloring material containing a thiocyanatoacetyl group, a thiocyanatoacetyl styrene copolymer is irradiated with ultraviolet light with a wavelength shorter than 350 nm, and the thiocyanatoacetyl group of the copolymer is treated as follows. It rearranges to become an isothiocyanatoacetyl group.

It has been found that this isothiocyanatoacetylstyrene copolymer can be dyed with a colored substance, that is, a cationic dye, in the presence of an alkali or base. The mechanism is thought to be as follows.

That is, with alkali or base, isothiocyanatoacetylstyrene creates anionic sites that serve as functional groups for fixing cationic dyes, and reacts with cationic dyes to dye.

The specific coloring (staining) conditions are 7 wt% of thiocyanatoacetylstyrene and acetylstyrene copolymer (20 mol% of thiocyanatoacetylstyrene).
Make a colorless transparent film (approximately 40 μm thick) on a glass slide from the THF solution. This film is irradiated with light for a predetermined time using a Ushio UM102 high-pressure mercury lamp (utilizing 310 nm light using a UV31 filter) while maintaining a distance of 10 cm. Note that it is appropriate that the irradiation light has a wavelength of 350 nm or less.

The irradiated film was mixed with 50 ml of a 0.5 wt% methanol-dioxane solution of fuchsin (volume ratio of methanol and dioxane 3:1) and triethylamine.
Dip in a 0.3ml dye bath for 10 seconds, then wash with water and dry. As a result, only the exposed areas are colored red by fuchsin.

The relationship between irradiation time and isothiocyanate group formation is
As shown in Figure 1. A2045 in the figure is the absorbance at 2045 cm ^-1 of the infrared absorption spectrum, -N =
It shows the absorption intensity based on the formation of C=S.
A1560 also has an infrared absorption spectrum of 1560 cm ^-1
(based on benzene rings) and is used as a standard for the amount (thickness) of the film substrate. From the data in FIG. 1, the amount of light-induced rearrangement of thiocyanatoacetyl groups to isothiocyanatoacetyl groups is proportional to the irradiation time.

The amount of isothiocyanate groups and the dyeing density of the dyed film were measured by absorbance at 555 nm (A555).
The relationship is shown in FIG. This result shows that the staining density increases in proportion to the content of isothiocyanate groups.

From these data, the dyeing density of the thiocyanatoacetylstyrene copolymer can be controlled by the amount of light irradiation. Of course, the dyeing time and dye concentration can also be adjusted, but the final density can be determined by the amount of light irradiation regardless of these conditions.

As a cationic dye, It could also be dyed.

In addition, examples of compounds containing thiocyanatoacetyl groups that can be used as photosensitive coloring materials include (a) to (d).
These include compounds and their derivatives as shown below. Derivatives include polymers or copolymers.

In addition, when the compounds (a) to (d) are used as a photosensitive film, they may be dispersed in a binder. Further, when the photosensitive coloring material is in a polymeric form such as a polymer or a copolymer, it can be used as a photosensitive coloring base material having film-forming properties.

In this way, if the above-mentioned photosensitive organic coloring material is used as a coloring base material, a functional group capable of fixing a colored substance, that is, a dye, will be generated based on light irradiation, and the reaction between the colored substance and the functional group will result in the formation of a functional group that can fix a colored substance and a functional group. Only parts can be colored. Therefore, partial coloring can be easily performed by simply irradiating the coloring substrate multiple times with light and repeating dyeing, and a fine dyed pattern in multiple colors can be easily formed. Also,
Since the coloring density can be controlled by the amount of light irradiation, reproducible coloring can be easily performed. moreover,
By using a high-precision light irradiation device, it is possible to form fine images with high resolution.

FIG. 3 shows a method of manufacturing a color filter for a television camera using the coloring method according to the present invention.

First, a photosensitive organic coloring base material 2 made of a thiocyanatoacetylstyrene copolymer is coated on a glass substrate 1, which will serve as a transparent base, to form a colorless and transparent film with a thickness of about 40 μm (a). After selectively irradiating ultraviolet light 4 using a photomask 3 having a shaded area (shaded area) to cause the above-mentioned reaction in the light-irradiated area, the substrate 1 is immersed in a dye bath containing the above-mentioned dye. dye only the light irradiated part of material 2, for example 10μ
A red dyeing pattern 5 of m□ is formed (c).

Thereafter, using another photomask 6, ultraviolet light 7 is selectively irradiated to a part of the material 2 different from the pattern 5 (d), and after the above reaction occurs, a part of the material 2 different from the pattern 5 is selectively irradiated (d). Dye another color using a dye bath of one color. In this way, a dyed pattern 8 different from the pattern 5, eg, blue, is formed (e).

Similarly, after selectively irradiating ultraviolet light 10 to parts of the material 2 other than patterns 5 and 8 using a mask 9 (f), ultraviolet light is applied using a dye bath of a different color from patterns 5 and 8. Only the irradiated areas 10 are dyed to form, for example, a green pattern 11 (g). Note that other colored patterns such as cyan, magenta, and yellow can be similarly formed.

In this way, a color filter having the dyeing patterns 5, 8, and 11 for color filters is manufactured. According to the method shown in Fig. 3, the base material for photosensitive organic coloring is selectively irradiated with light, so that 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. It is possible to form a colored pattern on a filter simply by using the selective exposure and dyeing steps. Therefore, when manufacturing a color filter having a coloring pattern of multiple colors, the method shown in FIG.
Alternatively, a highly accurate color filter can be easily manufactured with a small number of steps without requiring multiple steps of resist coating, development, resist removal, etc. Although the above description has been made regarding color filters, the material of the present invention can also be applied to other optical filters.

According to the present invention, by using a photosensitive organic coloring material that generates functional groups for fixing colored substances when irradiated with light, a substrate coated with this material is dyed after being irradiated with light using a mask. Dye the first color using a bath. Then, the same operation is repeated using another mask to dye other colors, creating a colored pattern such as a color filter using a simple method that does not require conventional positive resist coating, resist development, and resist removal operations. Easy to create. Further, as mentioned above, the ability to obtain a colorless and transparent base material is extremely advantageous for dyeing.

As described above, in the present invention, by performing light irradiation using a photomask, only the light irradiated area can react with the dye, so that partial coloring can be easily performed. In other words, image formation can be carried out within a certain range. In addition, many types of dyes can be used, colors with appropriate spectral characteristics can be selected, and coloring can be performed with high precision in terms of color and tone. Therefore, by using a high-precision light irradiation device,
It is possible to form fine images with high resolution.

Since the coloring density can be controlled by adjusting the amount of light irradiation, reproducible coloring can be easily achieved.

Furthermore, when the coloring method of the present invention and a photomask are used together on fabric or film, only the irradiated area can be easily colored, and by repeating light irradiation and dyeing, it is possible to color the fabric or film in a wide variety of colors. Therefore, dyeing and pattern formation of fabrics, etc., which are performed using conventional textile printing techniques, can be easily carried out. Furthermore, in the present invention, it is possible to form a uniform film of the coloring material itself from a solution, and by combining ultraviolet light and a mask, it is possible to color minute parts in the micron range, making it possible to apply color to image pickup tubes or image pickup plates for color television cameras. The required color filter (mosaic image of several colors) can be easily created on a flat plate, and it is highly effective for such applications.

[Brief explanation of drawings]

Figure 1 is a diagram showing the relationship between irradiation time and isothiocyanate group production, Figure 2 is a diagram showing the relationship between the amount of isothiocyanate groups and the dyeing density of the dyed film measured by absorbance at 555 nm (A555), and Figure 3 (a) -(g) are manufacturing process diagrams of a color filter according to an embodiment of the present invention. 1...Glass substrate, 2...Photosensitive organic colored base material, 3,6,9...Photomask, 4,7,1
0...Light, 5,8,11...Dyeing pattern.

Claims (1)

[Scope of Claims] 1. By irradiating a photosensitive organic coloring base material containing a thiocyanatoacetyl group with light, a functional group capable of fixing a colored substance is generated on the material itself in the light irradiated part, and the colored substance is A coloring method characterized by reacting a substance with the functional group to color only the light-irradiated portion. 2. The coloring material is made of a polymer or copolymer containing thiocyanatoacetylstyrene, and the polymer or copolymer is irradiated with light to remove the functional groups of the light-irradiated portion of the polymer or copolymer. The method for coloring according to claim 1, wherein the coloring method is performed by coloring with a colored material. 3 Claim 1 using ultraviolet light as light
Coloring method described in section. 4. The coloring method according to claim 2, wherein the coloring is carried out in the presence of an alkali or a base. 5. The coloring method according to claim 2, in which a cationic dye is used as the colored substance. 6. The coloring method according to claim 2, wherein a thin film made of a polymer or a copolymer is formed on a substrate, and the thin film is selectively irradiated with light. 7. The coloring method according to claim 2 or 6, wherein a cationic dye is used as the colored substance and the cationic dye is colored in the presence of an alkali or base.