JPS58194030A - Photosensitive material for coloring - Google Patents

Abstract

PURPOSE:To obtain an image of high chroma, by using a compound contg. a thiocyanatoacetyl group as a photosensitive agent. CONSTITUTION:A compound contg. a thiocyanatoacetyl group or a deriv. of the compound such as a polymer or a copolymer contg. thiocyanatoacetylstyrene is used.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photosensitive coloring material that is colored based on photochemical properties.

Conventionally, photosensitive colorants based on photochemical properties include: ■ ferric salt and coloring agent (blush salt or yellow blood salt);
Diazo compounds and coloring agents (phenols and amines),
(2) O-naphthoquinonediazide and a coloring material (pH-indicator) are included. The coloring mechanism of these 4,1 ingredients is explained in detail: ■ Ferric salt and blush salt or yellow blood salt.

This combination of monthly interest rates is the material used in Sesha Teiho. This principle is based on the fact that among iron compounds, ferric salt d: The original irradiation transforms it into ferrous salt.

This photochemical property is utilized in photographic methods, including the blue-on-white line method and the white-on-blue line method.

In the blue-on-white line method, ferric salt and red blood salt are used, and when exposed to light, the ferric salt turns into ferrous salt, and the coexisting red blood salt produces ferric ferrous iron (turnpull blue). and turns blue. The reaction at this time is similar to Tsuki.

Fe”-N Fe2” Fe2+10KaFe (cy)6→FeaCFe(CN
) 6] 2 (Turnpull Blue) The white-on-blue line method uses ferric salt as a photosensitive component, but after exposure, it reacts with yellow blood salt to form soluble ferrous ferrocyanate, which flows out during development and remains unused. Ferric salt C at the base of the dew: Reacts with yellow blood salt to produce Ferron ferric, ie, Plan Anne blue, resulting in a Vlt color image.

・ Scolding Fe −・ Fe2+ Fe −1−K4Fe(CN)6−+ Fe4(:
Fe(CN)6]3(brush γ) blue) Fe, 1K4Fe(CN)6-+Fe2Fe(CM
)6 (Leaked) Ordinary 〃ko/)'Tea photosensitive paper f-, f-Fe (OH)a
Foil with whole citric acid, add ammonium citrate to it, and apply the liquid to the whole paper. This photosensitive coloring material is entirely composed of the inorganic material t1.

■ Diazo compounds, phenols and aminos.

Diazo compounds t and j generally absorb short-wavelength light and produce a light fraction W
(The reaction occurs 1-1, but this compound is 77' in alkaline conditions and combines with phenols and amines (coloring agent).
See and form dyeing. The kimono using this method is Y-paper (positive image), which is more advanced than the blueprint method described in 11t1. An example of the reaction mechanism is shown below.

C6H3-N2N” Cll −+ c6H6cg
+ In the unexposed area of N2, the color changes depending on the type of color former.

In the case of this material, the unexposed areas are colored and used for image formation.

■ 0-Naphthoquinonediazide and pH-indicator.

The purpose of this monthly charge is to make it possible to easily identify the exposure pattern in the production of printing plates that have been made photosensitive with O-naphthoquinone diazide.

O-naphthoquinonediazide is used as a positive resist, and when exposed to light, it becomes a J:Li/denecarboxylic acid, exhibiting a pH of 2.5 to 6.6, and becomes soluble in L-fluorocarbon. The structural changes are described below.

o o
c.

O-naph I-gynonindenecarboxylic acid This printing plate contains in the photosensitive layer an organic dye (pH indicator) that changes its color tone in the pH range of 2.6 to 6.5 in the form of homogeneous granules. It is a feature. Originally F1. When a yellow printing original plate is exposed to light, it is dyed in another color by the action of a pH-indicator, and the exposed areas can be identified.

The conventional example described above has its own problems.

For example, in case of ■, it is impossible to color other than blue in any case. ■ is diazo compound VC71
Since the entire area of the unexposed area is colored in one exposure, it is not possible to form a multicolor image. ■ Increase the exposure meter to continuously change the pH from 6.5 to 2.6,
A pH indicator is used to color the desired color, but since pH indicators generally change color continuously, it is very difficult to color a specific location with a color that has predetermined spectral characteristics.

The photosensitive coloring material of the present invention is colorless and can be directly colored by reacting with an organic dye, making it possible to form images with good color saturation. By using the photosensitive colored film of the present invention in the form of an organic polymer, it is possible to easily form a film with a homogeneous and uniform thickness from its solution or on a substrate, making it possible to form high-resolution images in the micron range. is possible. Furthermore, the abrasive material of the present invention enables the formation of multicolor images directly on a photosensitive colored substrate (without using a single plate, etc.) only by light irradiation using a mask and a dyeing operation.

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 organic coloring material, thiocyanatoacetylstyrene copolymer is 3! By irradiation with ultraviolet light having a wavelength shorter than On m, the thiocyanatoacetyl groups of the copolymer are rearranged to become isothio/anato γcetino ().

c=o C=0 1 CH2SCN CH2N-C2S
thiocyanatoacetylstyrene isothiocyanatoacetylstyrene copolymer copolymer thiocyanatoacetylstyrene] acetylstyrene copolymer d1
The present inventors have discovered that it is possible to dye with cationic dyes in the presence of one alkali and one base. The mechanism can be thought of as follows.

Below is the margin -CH2CH-alkali or base C=0 CH2N-C2S That is, isothiocyanatoacetylstyrene creates an anion seat with an alkali or base, so-called functional groups that fix the dye are generated, and react with the cationic dye. Can be dyed.

The specific coloring (staining) conditions were as follows: thiocyanatoacetylstyrene and acetylstyrene copolymer (thiocyanatoacetylstyrene 20 mol%) from a 7-wl% tetrasyl nitrofuran solution on a slide glass. (approximately 40 μm thick).

This copolymer d forms a colorless and transparent Filno.

17. A Ushio IIUM102 high-pressure mercury lamp (with a wavelength of 310 nm using a UV31 filter) is suitable for the film.

The irradiated film was mixed with 60 ml of a 0.5 wt% methanol-dioxane solution of Tsukusin (volume ratio of methanol and dioxane 3:1) and 0.5 wt% of triethylamine.
After immersing it in a 3 ml dye bath for 10 seconds, it is washed with water and dried. That is, dyeing is performed by a normal dyeing process.

As a result, only the irradiated area is colored red by Tsuksin.

The relationship between the irradiation time and the production of isothiocyanate groups is shown in FIG. A2045 in Figure 1 is the absorbance at 2045CnL""' VC of the infrared absorption spectrum, -
It shows the absorption intensity based on the formation of N=C-=S.

A1560 is also the absorbance at 1560 Cya in the infrared absorption spectrum (based on benzene rings), and is used as a standard for the amount (thickness) of the film base material.

From the data in FIG. 1, the amount of rearrangement of a thiocyanatoacetyl group into an inthiocyanadoacetyl group is proportional to the irradiation time.

The amount of inthiocyanate 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 dyeing density increases in proportion to the content of inthiocyanato groups.

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

Margins below 11 Kabuon Kan 11 Noni 1. (1) Tsukutsuno (to red R) (iii) Azure A (green) Can be dyed anywhere / 1 1, thio / Ana I / Sensitive with compounds containing acetyl groups) Y
The following substances (a) to
) and its derivatives. Derivatives include polymers or ←1 copolymers.

(In thiocyanatoacetylbenzene-H2SCN (in) Thiocyanatoacetylstyrene-H2SCN (c) In thionanadoacetylethylene H2SCN 3) Thio/ana-vinyl acetate CH 2= C H ■ ■ C? O CII2SCN In addition, when using the coloring film and (7), the compounds of (A) to (2) may be dispersed in the bond (2). In a polymeric form such as a small polymer or a copolymer, it can be used as a coloring group 4A that improves film-forming properties.

Next, using the characteristics of the photosensitive coloring abrasive of Fudo Ichitano,
A method for making a color filter for a television camera will be explained with reference to FIG. 1. Apply a colorless and transparent film with a thickness of about 40 μm consisting of a photosensitive organic coloring group H2 of a thionanadoacetyl styrene copolymer to the glass substrate which will serve as a transparent substrate.a) Opaque areas (hatched areas) Selectively irradiate ultraviolet light 4 using a four mask 3 having a
After causing the light irradiated part to undergo the above-mentioned reaction, the substrate 1 is immersed in, for example, the above-mentioned dye bath 4, and only the light irradiated part of the material 2 is dyed to form a red dyeing pattern 6 of, for example, 10 μm 11. do(
C).

Afterwards, using another photomask 6, pattern 5 is formed.
Selectively irradiate ultraviolet light 7 to 20 parts of the material other than (d)
After causing the above-mentioned reaction, the pattern 6 is dyed with a different color, for example, blue, using a dye bath of a different color. In this way, another blue dyeing pattern 8 different from pattern 6 is formed (e).

Similarly, after selectively irradiating ultraviolet light 10 on parts of the material 2 other than the patterns 5 and 8 using a mask 9 (
f), Only the irradiated area of the ultraviolet light 10 is dyed with a dye bath of a color different from that of patterns 5 and 8 to form, for example, a green dyeing pattern 11 (q).

In this way, dyeing patterns 5, 8 for color filters.
A color filter having 11 is manufactured. According to the method shown in Fig. 3, the base material for photosensitive organic coloring is selectively irradiated, 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. Selective exposure and dyeing process 15.

It is possible to form a colored pattern on a filter simply by combining them. IJ-When manufacturing a Cassie filter having a multi-colored coloring pattern, the method shown in Fig. 3 was used.
1 Multiple times of dyeing film application, processing or CJ, several times of coating/strike coating II, development, resist removal, etc.]: Requires culm [No, high precision with few steps. Color filters can be easily manufactured. t & Q for dyeing
Other colored patterns can be similarly formed using any dye such as cyan, macenta, yellow, etc.

Although the above description has been made regarding the 1-Kashi filter, the present invention can also be applied to other 1-Kashi filters, both old and new. In addition, the effect of the present invention on the base film
[: When using the old 'v JA' in combination with a photomask, it is possible to easily color only the irradiation 17/141X. By repeating light irradiation and dyeing, a wide variety of colors can be produced. Therefore, the dyeing and pattern formation of fabrics, etc., which are performed by conventional textile printing techniques, can be easily performed using VC. As shown in FIG. 3, the combination of ultraviolet light and a mask enables fine local coloring in the micron range. Therefore, color filters (mosaic images of several colors) necessary 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 coating material of the present invention can be used as a wet-development type recording material as cutting paper for a color copying machine.

As described above, when the photosensitive coloring material of the present 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 performed immediately. The problem is that in the present invention, many dyes can be applied to a colorless colored base material, a wide variety of colors can be selected, and coloring can be performed with high precision in terms of color and tone.

However, by adjusting the amount of light irradiation, the coloring of the colored substrate can be easily controlled. Furthermore, the present invention has excellent industrial value in applications that require coloring, such as the ability to form a uniform photoresist film and the ability to form fine images with high resolution by using a high-precision light irradiation device. It is something.

17 part

[Brief explanation of the drawings] Figure 1 shows the relationship between irradiation time and soothiocyanate group production. ')Y
4 degrees < A355 ) - ril + 1 constant/column relationship diagram, Figures 3 (a) to (q) k1 Manufacture of a color filter according to the present invention - "This is a process diagram. 2... ...C' cimanatoacetylstyrene copolymer 31: Colored group A'A4A old. Agent's name j [Rito Toshio Nakao and 1 other person Figure 1

Claims (3)

[Claims] (1) A compound containing a thiocyanatoacetyl group or d
: A photosensitive coloring material consisting of a derivative thereof. (2) The photosensitive coloring material according to claim 1, wherein the derivative is a polymer or copolymer containing thiocyanatoacetylstyrene. (3) The photosensitive coloring material according to claim 2, wherein the copolymer is a copolymer of thiocyanatoacetylstyrene and acetylstyrene.