JPS59204010A - Color filter - Google Patents

Abstract

PURPOSE:To improve the color reproducibility by using a mixture of specified coloring matters as coloring matter for each of red, blue and green filters after combining two or three kinds of colors. CONSTITUTION:A mixture of coloring matters represented by formulae I , IIas coloring matter for a red filter, coloring matter represented by formula IIIas coloring matter for a blue filter, and a mixture of coloring matters represented by formulae IV, V as coloring matter for a green filter are used after combining two or three kinds of colors. In the formula I , each of R1 and R2 is H, alkyl, alkoxy, halogen or the like, and R3 is H, alkyl, alkoxy or halogen. In the formula II, each of R4, R5, R6 and R7 is H, alkyl or halogen. In the formula III, each of R8 and R9 is alkyl or cyclohexyl. In the formula IV, each of R10 and R11 is H, alkyl, alkoxy, aryl, halogen, sulfonic acid or the like. In the formula V, each of R14 and R15 is alkyl or aryl, each of R16 and R17 is H, hydroxyl or sulfonic acid, and B is a benzene ring, a naphthalene ring or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a color filter for color separation used in solid-state imaging devices and the like.

A color camera configured using one or two solid-state imaging devices such as COD, J3BD, or Δi08 requires a mosaic or stripe-like color filter for color separation.

These color filters are red,? J% Three colors of confusion! It is constructed in a stripe-like or mosaic-like arrangement using a combination of two or three colors. These color image sensors are formed on a light-sensitive material such as glass, and are aligned and laminated with a color filter on each side of the solid-state image sensor, or a color filter is placed directly on the solid-state image sensor. is formed and used.

As dyeable resins for these color filters, resins such as L-containing fats such as protein and casein, polyvinyl alcohol, polyacrylic, polycarbonate, polyamide, polyester, and polyether sulfone are known.

Dyeing methods, transfer printing methods, and the like are known as dyeing methods for these dyeable resins, and a dyeing method suitable for the type of dye and dyeable resin used is selected.

As pigments, textile dyes such as acid dyes, direct dyes, reactive dyes, disperse dyes, and cationic dyes, and resin dyes such as oil-soluble dyes have been used.

However, it has been difficult to obtain the spectral characteristics necessary for color separation using existing textile dyes or resin dyes alone.

As a result of various studies on dyes for color filters, the present inventors discovered a dye having spectral characteristics necessary for color separation and completed the present invention.

That is, an object of the present invention is to provide a color filter with good color reproducibility.

That is, the present invention provides a color separation color filter formed by dyeing a dyeable resin layer, in which the following general formula (1) and general formula (] are used as red filter dyes.
A mixture of dyes represented by I), a dye represented by the following general formula (III) as a blue filter dye, and a mixture of the following general formula (g) and general formula (V) as a green filter dye.
) is a color filter that uses a mixture of two or three colors in combination.

几.

[In the formula, ■1. R2 is a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group or a halogen atom, R
3 represents a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom] [In the formula, R4, R5, R6, and R7 represent a hydrogen atom, an alkyl group, or a halogen atom] [In the formula, R8 and R9 are an alkyl group, or represents a cyclohexyl group] 12 [In the formula, 几. , in general, 1 represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an N7-substituted sulfonamide group, a)-rogen atom, or a sulfonic acid group, or the following general group at the p-position of the azo group: It may be a group represented by the formula.

Jt,'2 (wherein, X is an oxygen atom, a sulfur atom, or a
+3 represents the same meaning as above) A represents a benzene ring; A represents a naphthalene ring; R12° [t13 is a hydrogen atom, an alkyl group, )) a rogene atom and represents a sulfonic acid group. However, R1°.

One of R1, R12, R, and 3 represents a sulfonic acid group. [In the formula, R, , 15 represents an alkyl group, an aralkyl group, or an aryl group, and R, 6, R, , represents a hydrogen atom, a hydroxyl group, or a sulfonic acid group. B represents a benzene ring or a naphthalene ring. However, the aryl ring of R14, 几, 5 and ring B have two or more sulfonic acid groups in total. ] In general formula (1), R1*R2
Examples include hydrogen atoms, substituted or unsubstituted alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, and trifluoromethyl groups, methoxy, ethoxy, propoxy, butoxy, and hexyloxy groups. , a substituted or unsubstituted alkoxy group such as a methoxyethoxy group,
Examples include substituted or unsubstituted alkoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, hexyloxycarbonyl group, and methoxyethoxycarbonyl group, and halogen atoms such as fluorine atom, chlorine atom, and bromine atom. It will be done.

■t is a hydrogen atom, a substituted or unsubstituted alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a trifluoromethyl group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, or a hexyl group. oxy group,
Typical substituents include substituted or unsubstituted alkoxy groups such as methoxyethoxy groups, and halogen atoms such as fluorine atoms, chlorine atoms, and bromine atoms.

-1・In the substituent formula (It), substituent 114 p R5e
R6; Typical substituents for "7" include a hydrogen atom, a substituted or unsubstituted alkyl group such as a methyl group, an ethyl group, and a butyl group, and a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom.

In the general volume 2, substituents R8 and R9 include substituted or unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, butyl group, amyl group, hexyl group, octyl group, methoxyethyl group, -chloroethyl group, A typical substituent is a cyclohexyl group.

On the general formula side, when the diazo component A in the general formula is a phenyl group, the substituent R10e RI+ is a hydrogen atom,
Substituted or unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, octyl group, and dodecyl group; substituted or unsubstituted alkoxy groups such as methoxy group, ethoxy group, butoxy group, and methoxyethoxy group; basis,
Substituted or unsubstituted aryl groups such as phenyl group and tolyl group; substituted or unsubstituted aryloxy groups such as phenoxy group, methylphenoxy group, and pentylphenoxy group;
N-substituted sulfonamide groups such as N-phenylsulfonamide group, N,N-ethyl phenylsulfonamide group, N,N-diethylsulfonamide group, halogen atom such as fluorine atom, chlorine atom, bromine atom, or sulfonic acid group , in the case of naphthyl group, ■-sulfonaphthyl group, 5-
Examples include sulfonaphthyl group.

The following kazo-style can be mentioned.

Substituents R, 2, R, and 3 of the coupler component include a hydrogen atom, a substituted or unsubstituted alkyl group such as a methyl group, an ethyl group, and a propyl group, a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom, or a sulfone atom. A typical substituent is an acid group.

In general 200, substituents R14 and R15 are:
Alkyl groups such as methyl, ethyl, and propyl groups; substituted or unsubstituted aralkyl groups such as benzyl, sulfobenzyl, and methylbenzyl; substituted or unsubstituted aryl such as phenyl, tolyl, and sulfophenyl; Typical substituents for the group R16, R, include a hydrogen atom, a hydroxyl group, and a sulfonic acid group.

In the present invention, the compound of general formula CI) is a yellow dye, the compound of general formula 1) is a red dye, and a mixture thereof is used as the red filter dye. The mixing ratio is preferably (I): G[)-(2-7):lO
(weight ratio).

The compound represented by the general formula (I[) is a blue pigment, and can be used alone or as a mixture of two or more within the range of the general formula @) as a dye for blue filters, but preferably 2 to 5 kinds of the compound can be used as a dye for a blue filter. A mixture is used.

The compound of general formula (V) is a yellow dye, the compound of general formula (V) is a green dye, and a mixture thereof is used as a dye for a green filter.

The mixing ratio is (V'):(V)-(4~14)
:10 (weight/degree ratio) is preferable.

According to the present invention, a color filter' with good color reproducibility can be obtained by using two or three of the dyes for the red filter, blue filter, and green filter.

In the present invention, the following filter dyes are particularly preferably used.

(In the formula, present represents an alkoxycarbonyl group having 1 to 4 carbon atoms.) 1 Blue dye (In the formula, present represents an alkyl group having 4 to 7 carbon atoms.) Green pigment (as a free acid) (In the formula, , "; 4 * '65 represents methyl group or ethyl is 1;) The dyeable resin used in the present invention includes polyester resin, polyethersulfone resin; 1:1, acetate resin, casein, gelatin, or Examples include polyamide and eye oil.

Glass, CIC! The dyeable resin coated on D, BBD or MOS is dyed by a transfer printing method or a sublimation dyeing method using a transfer plate coated with pigment ink, or by a dip dyeing method in water.

The above pigment ink is composed of a pigment, a binder, and a solvent. Examples of the binder include natural resins such as dammar, gum arabic, gum tragacanth, dextrin, or casein, or modified resins thereof, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, or ethyl hydroxy. One or a mixture of two or more of cellulose resins such as ethyl cellulose, vinyl resins such as polyvinyl alcohol or polyvinyl acetate, etc. can be used as a binder if the resin has a relatively low affinity with the dye. Can be used.

As a solvent for dissolving or dispersing the dye and binder,
Alcohols such as ethanol, propatool, butanol, ketones such as acetone and methyl ethyl ketone,
Aromatic hydrocarbons such as toluene xylene and monochlorobenzene, trichlorethylene, perchlorethylene,
Chlorinated solvents such as ethylene dichloride, vinegar dredge esters such as ethyl acetate, butyl acetate, ethoxyethyl acetate, etc. may be used alone or in mixtures.

The pigment ink used above is prepared by thoroughly dispersing the pigment of the present invention and a binder together with a suitable solvent using a paint conditioner, a ball mill, stirring (A, etc.).The resulting ink is prepared using a bar coater, It is applied using a spin coater or screen printing onto a substrate with good thermal conductivity such as aluminum, paper, or silicon wafer, and then subjected to dyeing.

When using the dyeing method, dye the dye with acetic acid water, etc.
It is dissolved in outside water and used for dyeing.

For the t4s f73 method, select a preferred method according to the dye used in [11]. In the present invention, it is advantageous to prepare inks and use transfer printing or sublimation dyeing for red and blue dyes, and to use dip dyeing for green dyes.

In the present invention, patterning when creating a red or blue color filter is carried out using a known method, for example, using a stain-resistant resist made by adding dichromate or chromate to casein, gelatin, grue, polyvinyl alcohol, or polyvinyl pyrrolidone. This is done by forming a mask with a mask, etc., and sequentially dyeing predetermined areas with one or two colors. Patterning when creating a green color filter is done by forming a dyed layer in a predetermined location using a known method, such as a resist made by adding dichromate or chromate to casein, gelatin, gris, etc. This is done by

In this way, according to the present invention, a color filter with good color reproducibility can be obtained.

Next, the present invention will be explained in more detail with reference to Examples. In the text, parts and % do not represent parts by weight or % by weight.

Example 1 The following components were sufficiently kneaded in a ball mill to prepare a pigment ink, this ink was gravure coated on paper, and the bath agent was evaporated and dried to prepare red and blue transfer plates, respectively.

Red: 100 parts of ethyl cellulose (8%-toluene, ethanol mixture) Blue: 100 parts of ethyl cellulose (8%-toluene, ethanol mixture) 3. For the green dye, the following components were dissolved to prepare an aqueous dye solution.

100 parts of 6% aqueous acetic acid Next, a polyester solution was applied as a red and blue dyeing layer onto a glass substrate using a spin coater, and after drying, a film having a thickness of about 3 μm was formed. Next, a casein solution (product name G-9QS, manufactured by Tokyo Ohka Co., Ltd.) sensitized with ammonium dichromate is applied onto this dyed layer, and after drying, a mask having a mosaic pattern is aligned, and exposed. Developed and dried, a dye-resistant mask was formed except for the areas to be dyed. Next, the dye layer side and the dyeing layer side of the transfer plate containing the a-color dye were placed opposite each other, and the polyester resin layer was dyed by applying heat at 170 to 250°C to form dyed tube regions in eight colors. Next, the dye-resistant mask layer was peeled off and the same operation was performed to form a red dyed area. Next, add the above casein solution to 1. After the ζ cloth is dried, a mask with a mosaic pattern is aligned, exposed and developed to form a dyed layer in the area to be dyed red, and immersed in total color dye Mizugo solution at 60-90°. Heat to C to form a pale colored dyed layer.
child.

The spectral characteristics of each color filter of the color filter thus obtained showed good spectral characteristics as shown in FIG. 1, and a color filter with good color reproducibility was obtained.

Example 2 In Example 1, a color filter was produced in the same manner as in Example 1, except that the following dye mixture was used as the blue filter dye. The color reproducibility of the obtained color filter was very good.

Goods.

H3CH3 Example 3 A silicon wafer on which a CCD image sensor was formed was used as the substrate, and polyether sulfone resin was used instead of polyester resin as the intermediate layer for red and blue dyeing JΔ, but otherwise the same as in Example 2. I created a color filter. The color reproducibility of the obtained color image sensor was very good.

Example 4 Create a pigment ink by thoroughly kneading the following ingredients with a paint conditioner, apply this ink on an aluminum plate with a bar coater, evaporate the solvent, and create red and blue transfer plates, respectively. did.

Red: Methyl cellulose (8% xylene, butanol mixture) Loo part Blue: Methyl cellulose (8% xylene, butanol mixture) 100 parts H3 CH3 For the green dye, the following components were dissolved to prepare an aqueous dye solution.

6% acetic acid water 100 parts 03 Next, the polyethersulfone resin solution was applied as red and blue dyeing layers and gelatin was used as a green dyeing layer, using a spin coater, on the silicon wafer provided with the solid-state image sensor, and other operations were performed. A color filter was prepared in the same manner as in Example 1. The color reproducibility of the obtained color image sensor was very good.

As described above, according to the present invention, a color filter with good color reproducibility suitable for solid-state imaging devices can be obtained.

[Brief explanation of the drawing]

FIG. 1 shows the spectral characteristic curve of the color filter of Example 1. Curve (1) is the red filter,
(2) shows a blue filter, and (3) shows a green filter.

Claims (1)

[Scope of Claims] In a color separation color filter formed by dyeing a dyeable resin layer, a mixture of dyes represented by the following general formula (I) and general formula (11) as a red filter dye, The following general formula (I
A car filter characterized in that a dye represented by II) and a mixture of dyes represented by the following general formulas (to) and general formula (V) are used in combination of two or three colors as a green filter dye. 1 [wherein R1j R1 is a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group or a halogen atom,
R3 represents a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom] [In the formula, "4*R5# R6*
R7 represents a hydrogen atom, an alkyl group, or a halogen atom] [In the formula, R8 and 几9 represent an alkyl group or a cyclohexyl group] [In the formula, R, o, and R1 represent a hydrogen atom, an alkyl group, and an alkoxy group. , aryl group, aryloxy group, N-substituted sulfonamide group, halogen atom may represent a sulfonic acid group, or may be represented by a group represented by the following general formula at the p-position of the azo group. . (In the formula, X is an oxygen atom, a sulfur atom, or 78fJBa
59-204 (110(2)) COD, n is 0 or 1
represents. Horse. . RI2. R13 represents the same meaning as above. ) A represents a benzene ring or a naphthalene ring. R, 2, g, and 3 each represent a hydrogen atom, an alkyl group, a halogen atom, or a sulfonic acid group. However, R,0,
One of R1, R12v■13 represents a sulfonic acid group. ] 16 [In the formula, R+5 represents an alkyl group, an aralkyl group, or an aryl group, and R1, R1, represents a hydrogen atom, a hydroxyl group, or a sulfonic acid group. B represents a benzene ring or a naphthalene ring. Tatashi, ”+4 s Ji,
The aryl ring of No. 5 and ring B have two or more sulfones FiiL4 in total. ]