JPH04229865A - Manufacture of resin composition and color filter therewith, and color filter - Google Patents

Abstract

PURPOSE:To obtain a resin composition that is excellent in storage stability and a color filter therewith, by using an anionic dyable polymer and the resin composition inclusive of a specific bisazido compound. CONSTITUTION:It is a photosensitive resin composition containing an anionic dyable polymer (A) and a bisazido compound (B) with a structure expressed in a formula I. In the formula, R1, R2 shows a formula II independently, namely, n=1-2 and R3 is an alkyl group of carbon numbers from 1 to 4. In this connection, the polymer (A) is desirable to be a copolymer of those of dyable monomer, hydrophilic monomer and hydrophobic monomer. In addition, the azido compound (B) is desirable to use it as much as 2-15wt.% to the polymer (A).

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition, a method for producing a color filter using the same for use in color liquid crystal displays, color solid-state imaging devices, etc., and a color filter.

0002

[Prior Art] Conventionally, a method for manufacturing color filters used in color liquid crystal displays or color video cameras, etc., involves dyeing a resin layer in a relief pattern with a dye or the like on a substrate such as glass to form a colored resin layer. The general method is to repeat the forming process once or multiple times for the number of colors required by the filter, but the photosensitive resin used to form the resin layer is made of natural proteins such as casein and gelatin. Those containing dichromates such as potassium dichromate, sodium dichromate, and ammonium dichromate, and recently, synthetic polymers are being used.

0003

[Problems to be solved by the invention] When using casein, gelatin, etc., since they are natural products, they are easily perishable, their quality is inconsistent, and there are large variations depending on the raw material source, and color reproducibility is extremely poor. There are dyeing problems such as easy peeling in hot water, large deterioration of physical properties due to heat, and difficulty in obtaining deep colors due to restrictions on processing conditions.

Furthermore, when these casein, gelatin, etc. are used, ammonium dichromate or potassium dichromate, etc. are used as a photocuring agent, so it is necessary to solve the problem of pollution during the working process and during disposal. Must be. Furthermore, there is a problem that chromium incorporated into casein, gelatin, etc. is not completely removed, and the remaining chromium has an adverse effect.

The present inventors have investigated synthetic polymers in order to solve these problems. First, an azide compound is added as a crosslinking agent to a polymer having a basic group or a quaternary ammonium base that has an affinity for anionic dyes, and this photosensitive resin composition is coated on the surface of a substrate such as a glass plate.
It has been found that it is possible to create a resin film with good dyeability without film peeling by irradiating it with light, and it is now being put into practical use.

However, when using an azide compound, the azide compound is dissolved in a resin solution and stored in a cool, dark place below 5°C until use after production to avoid decomposition due to light or heat. When a known azide compound is used to increase the solution concentration of the azide compound, the azide compound tends to precipitate during storage, which is a practical problem.

Furthermore, when a resin and an azide compound are mixed and coated on a glass plate, etc., and then photocured and developed, there may be precipitation of unreacted photosensitizer (azide compound) during development, or the cured film may turn yellow. Due to these problems, there has been a demand for a dyeing resin film with less coloring.

[0008]

[Means for Solving the Problems] The present inventors have completed the present invention as a result of further studies to solve these problems.

That is, the present invention provides a photosensitive resin composition containing (1) an anionic dye-dyeable polymer (A) and an azide compound (B) having the structure of formula (1).

0010

[Chemical formula 3]

[0011] (In the formula, R1 and R2 are each independently

0012

[C4]

##STR2## where n=1 to 2, and R3 is an alkyl group having 1 to 4 carbon atoms. )

(2) Compound (C) having two or more acryloyl groups and/or methacryloyl groups in the same molecule
The resin composition according to (1) above, comprising:

(3) A color filter characterized in that a dyeable pattern is formed on a substrate using the resin composition described in (1) or (2) above, and the pattern is dyed with an anionic dye. Manufacturing method.

(4) In the manufacturing method described in (3) above,
After the first dyeing, the dyed film is treated with a dye fixing agent, a pattern is again formed on this substrate using the resin composition, a second color is dyed, and this process is repeated as many times as necessary. Characteristic color filter manufacturing method.

(5) A color filter obtained by the manufacturing method described in (3) or (4) above. Regarding.

When the azide compound (B) of formula (1) is used, it has good solubility in various resin solutions and does not generate precipitates even when stored at 5° C. or lower for a long period of time. Furthermore, it is less likely to precipitate during water development and less likely to cause defects due to foreign substances. Furthermore, since the resin film produced using this azide compound (B) has less coloration than conventionally known products, a color filter having high color purity can be obtained after dyeing.

Further, the anionic dye-dyeable polymer (A) used in the present invention is a copolymer of a dyeable monomer (a), a hydrophilic monomer (b), and a hydrophobic monomer (c). is preferred. This anionic dye-dyeable polymer (
A) can be produced by using a conventionally known polymerization method.

Examples of the dyeable monomer (a) include the following. (N,N-dimethylamino)ethyl acrylate, (N
, N-dimethylamino)ethyl methacrylate, (N,
N-diethylamino)ethyl acrylate, (N,N-
diethylamino)ethyl methacrylate,

[0021]
(N,N-dimethylamino)propylacrylamide, (N,N-dimethylamino)propylmethacrylamide, (N,N-diethylamino)ethyl vinyl ether, (
N,N-dimethylamino)propyl acrylate, (N
, N-dimethylamino)propyl methacrylate,

0
022: 4-vinylpyridine, diarylamine, 2-
Hydroxy-3-methacryloyloxypropyltrimethylammonium chloride, methacryloyloxyethyltrimethylammonium chloride

[0023] Examples of the hydrophilic monomer (b) include the following. Hydroxyethyl acrylate, hydroxyethyl methacrylate acrylamide, methacrylamide, vinylpyrrolidone, dimethylaminoacrylamide, methylaminoacrylamide,

Examples of the hydrophobic monomer (c) include the following. Methyl acrylate, methyl methacrylate, ethyl acrylate, styrene, p-methylstyrene, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate,

The blending ratio of the dyeable monomer (a), the hydrophilic monomer (b), and the hydrophobic monomer (c) is 10 to 80% by weight of the dyeable monomer (a), and 10 to 80% by weight of the hydrophilic monomer (b). 2-60% by weight, hydrophobic monomer (c) 5-50
Preferably, it is expressed as % by weight. Moreover, the molecular weight of the polymer (A) created in this way is 5,000 to 200,0
00 is preferred, and 10,000 to 100,000 is particularly preferred.

The azide compound (B) of formula (1) is contained in an amount of 2 to 15% by weight based on the anionic dye-dyeable polymer (A).
It is preferable to use it, particularly preferably in an amount of 3 to 8% by weight.

Examples of the compound (C) used in the present invention include the following. Spiroglycol diacrylate [3,9-bis(2-acryloyloxy-1,1-dimethyl)2,4,8,10-tetraoxaspiro[5,5]undecane]cyclohexanedimethylol diacrylate, ethylene glycol diacrylate ,

Diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, butylene glycol diacrylate, neopentyl glycol diacrylate,

1
, 4-butanediol diacrylate, 1,6-hexanediol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate,
Trimethylolpropane triacrylate, novolac epoxy acrylate,

Bisphenol A epoxy acrylate, alkylene glycol diepoxy acrylate, glycidyl ester acrylate, polyester diacrylate, bisphenol A diacrylate, urethane diacrylate, methylene bisacrylamide,

Ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, propylene glycol dimethacrylate,

Butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane trimethacrylate,

The amount of these compounds (C) used is 0.1 parts by weight per 100 parts by weight of the anionic dye-dyeable polymer (A).
-10 parts by weight is preferred, particularly 0.5-6 parts by weight. Also, conventionally known azide compounds, such as 4,4'
-Diazide chalcone etc. may be further used in combination.

The photosensitive resin composition having the above composition is as follows:
It is usually used after being diluted with an organic solvent. Examples of organic solvents include methyl cellosolve, ethyl cellosolve, ethylene glycol monoethyl ether acetate,
Diethylene glycol dimethyl ether, methyl ethyl ketone, etc. may be mentioned, but these may be used alone or in a mixed system of two or more.

[0035] The proportion of the organic solvent in this photosensitive resin liquid varies depending on the composition of these resin liquids, so it cannot be absolutely defined, but it is possible to make the resin liquid have a viscosity that allows it to be applied to the substrate surface. preferable.

In the present invention, the photosensitive resin liquid (resin composition of the present invention) is coated on the surface of a substrate such as glass, plastic, silicon, etc. using a spin coater, a roll coater, etc. to form a thin film. Next 60℃~100℃
Pre-dry at °C. Thereafter, it is photocured by irradiating ultraviolet rays or the like in a predetermined pattern through a mask in a conventional manner, and the unexposed areas are developed with an aqueous solution. Developing is usually at room temperature ~60℃
Preferably, it is carried out at °C.

Next, the cured film is heat treated at a temperature of 100°C to 160°C. The heat treatment time is not particularly limited, but it is usually sufficient to perform the heat treatment for about 15 to 50 minutes. The heat treatment may be performed by a known method using a hot plate, an oven, or the like. It is preferable that the thickness of the photocured film obtained is usually about 0.3 to 5 μm. Next, the substrate having the predetermined pattern is dyed with an anionic dye by a conventionally known method.

As anionic dyes, Color Index (Society of Dyers and Co.
published by C.Lour-ists). I. Acid dyes listed as Acid, also C.I. I. Dir-ec
Direct dyes listed as C.t and also C.t. I.
Examples include reactive dyes described as "Reactive", and acid dyes are particularly preferred.

As the acid dye, C.I. I. Acid Ye
low 17, 49, 67, 72, 127, 110, 135, 16
1.C. I. Acid Red 37, Acid Red 50,
111, 114, 257, 2
66, 317, C. I. Acid Blue
41, 83, 90, 113, 4
129, 182, 125, C. I. Acid
Orange 7, 56, C. I. Acid
Green 25, 41, C. I. Acid Vi
olet 97, 27, 28, 48
, and Nippon Kayaku Co., Ltd. color filter dye Red
136P, Red 127P, Blue-e 43P, C
Examples include FG 51P.

The dyeing method using these dyes is dye 0.0
1 to 200 parts by weight are dissolved in 1000 parts by weight of water. At this time, the pH of the liquid may range from weakly alkaline to acidic. Dyeing is carried out with this dye solution at a temperature ranging from room temperature to 100°C. It is preferable to carry out dyeing at a high temperature because it is possible to obtain a dyed product in a short time. After dyeing in this manner, the dyed product is taken out and dried to obtain a dyed substrate (color filter) with a dyed resin film.

When a dyed film of another color (colored resin film) is provided on the obtained dyed substrate, the dyed film on the dyed substrate is first treated with a dye fixing agent. As the dye fixing agent, a dye fixing agent such as tannic acid is used. These treatments are performed by conventionally known methods.

For example, 1 to 10 g of tannic acid, 0 to 5 g of acetic acid
Dissolve g in 1 liter of water and heat at 50 to 80℃ with this solution.
After treatment for 0.5 to 10 minutes at 50 to 80° C., it is preferable to treat with an aqueous solution of antimonyl potassium tartrate at 0.5 to 5 g/l for 0.5 to 10 minutes. high temperature treatment,
Long-term treatment is not preferable as the dye may fall off. After drying, this is heat-treated at 120 to 160°C if necessary.

On the substrate thus obtained, a pattern is formed using the resin composition of the present invention in the same manner as described above, dyed with a second color, and further treated with a dye fixing agent and subjected to pattern formation, if necessary. By repeating the formation and dyeing, color filters dyed with multiple colors can be obtained.

[0043]

[Examples] The present invention will be specifically explained below with reference to Examples. Example 1 Dimethylaminopropylacrylamide 40 parts 2-hydroxyethyl methacrylate 15
Vinylpyrrolidone
15 parts methyl methacrylate
8-part methyl acrylate
12 parts dimethylamino acrylamide
7th part

The monomers of the above formulation are polymerized by a known solution polymerization method, poured into a large amount of isopropyl ether to precipitate the polymer, and then the polymer (average molecular weight 90,000) is taken out and dried.

To 100 parts of this polymer, 2 parts of 4,4'-diazide chalcone, 6 parts of bisazide compound (b) [a compound in which R1 = R2, n = 1, and R3 = ethyl group in formula (1)], A photosensitive resin liquid was prepared by mixing and dissolving 2 parts of silane coupler KBM603 (Shin-Etsu Chemical Co., Ltd.), 450 parts of ethyl cellosolve, and 450 parts of diethylene glycol diethyl ether.

This photosensitive resin liquid was coated on a glass plate by spin coating, and after preliminary drying at 80°C for 20 minutes, a surface illuminance of 8 mW was applied through a mask having a predetermined pattern.
/cm2 of UV irradiation for 10 seconds, and 0% polyethylene glycol nonyl phenyl ether was added to 1 liter of water.
．． When development was carried out for 5 minutes with a 25° C. developer containing 5 g dissolved therein, a glass plate having a resin film only on the irradiated area was obtained.

After heat treating this glass plate at 150°C for 30 minutes, it was dyed with a 0.2% solution of Red 137P (color filter dye manufactured by Nippon Kayaku Co., Ltd.) at 65°C for 20 minutes, resulting in a deep red pattern. A glass plate was obtained. The thickness of this dyed film was 1.5 microns.

Next, as a dye fixation treatment, this glass plate was treated with a solution containing 3 g of tannin and 3 g of acetic acid in 1 liter of water for 7 hours.
After treatment at 0℃ for 7 minutes, treated with a solution containing 1g of tartar in 1 liter of water at 70℃ for 5 minutes, washed with water, air-dried, and then dried at 150℃.
, heat treatment for 20 minutes.

Further, this glass plate was coated with a photosensitive resin liquid in the same manner as before, and after preliminary drying, UV irradiation, development, and heat treatment were performed through a mask having a predetermined pattern. After dyeing with a 0.2% solution (Dye for Color Filters, Inc.) at 60° C. for 10 minutes, heat treatment was performed with a fixing agent solution as before.

Further, this glass plate was coated with the same photosensitive resin liquid as before, and after preliminary drying, UV irradiation, development, and heat treatment were performed through a mask having a predetermined pattern.
Staining was performed at 60° C. for 10 minutes with a 0.1% solution of lue43P (color filter dye manufactured by Nippon Kayaku Co., Ltd.).

As a result of the above operations, a color filter having red, green, and blue patterns was obtained. The thickness of the green film was 1.4 microns, and the thickness of the blue film was 1.5 microns. Furthermore, no precipitate was generated in the photosensitive resin liquid when it was stored at 5° C. for 12 months.

Example 2 Dimethylaminopropylacrylamide 4
0 parts 2-hydroxyethyl methacrylate
15 parts vinylpyrrolidone
14 parts methyl methacrylate
8-part methyl acrylate
11 parts dimethylaminoacrylamide 8 parts

005
3) The monomers of the above formulation were polymerized and treated in the same manner as in Example 1 to obtain a dry polymer. To 100 parts of this polymer, 6 parts of the bisazide compound (b) used in Example 1, and 6 parts of cyclohexane dimethylol diacrylate.
A photosensitive resin liquid was prepared by mixing and dissolving 1 part of silane coupler KBM603, 450 parts of ethyl cellosolve, and 450 parts of diethylene glycol diethyl ether.

This photosensitive resin liquid was coated on a glass plate by spin coating in the same manner as in Example 1, and after preliminary drying, UV irradiation was performed for 20 seconds through a mask having a predetermined pattern, and a developing solution was applied. After development for 5 minutes and heat treatment, Re
When staining was carried out with a 0.19% solution of d137P at 70°C for 20 minutes, a glass plate stained in a deep red pattern was obtained. The thickness of this dyed film was 1.8 microns.

Next, this glass plate was subjected to fixing treatment and heat treatment in the same manner as in Example 1. Furthermore, this glass plate was coated with a photosensitive resin liquid in the same manner as before, and after preliminary drying, it was exposed to UV light through a mask with a predetermined pattern, developed, and
After heat treatment, 60% CFG51P 0.2% solution
After dyeing at 10° C. for 10 minutes, heat treatment was performed using a fixing agent solution as before.

Further, this glass plate was coated with the same photosensitive resin liquid as before, and after preliminary drying, UV irradiation, development, and heat treatment were performed through a mask having a predetermined pattern.
Staining was performed at 60° C. for 10 minutes with a 0.12% lue43P solution. As a result of performing the above operations,

A color filter having a pattern of red, green, and blue was obtained. The green film thickness was 1.7 microns, and the blue film thickness was 1.8 microns. Further, the photosensitive resin liquid did not generate any precipitates when stored at 5° C. for 12 months.

[0058]

[Comparative Examples] Comparative Examples 1 to 6 Photosensitive resin liquids were prepared using the same recipe as in Example 1 except that the bisazide compounds shown in Table 1 were used instead of the bisazide compound (b) in Example 1. When stored at 5°C for 3 months, precipitates were deposited due to poor solubility.

[0059]

[0060]

[Effects of the Invention] The resin composition of the present invention is more easily putrefied than conventional natural products such as gelatin and casein.
There is no problem with large variations due to raw materials. Furthermore, there is no problem of hexavalent chromium pollution caused by waste liquid.

Furthermore, since the azide compound (B) used in the present invention has good solubility in the resin solution, precipitation is unlikely to occur during low-temperature storage, and the azide compound does not precipitate even during water development, preventing foreign matter from forming. Since defects are less likely to occur, the resin composition and manufacturing method of the present invention are extremely useful in practice.

Claims (5)

[Claims] Claim 1: Anionic dye-dyeable polymer (A)
A photosensitive resin composition comprising an azide compound (B) having the structure of formula (1). [Formula 1] (In the formula, R1 and R2 each independently represent [Formula 2], n = 1 to 2, and R3 is an alkyl group having 1 to 4 carbon atoms.) [Claim 2] Acryloyl group or / in the same molecule
and a compound (C) having two or more methacryloyl groups. 3. A method for producing a color filter, comprising forming a dyeable pattern on a substrate using the resin composition according to claim 1 or claim 2, and dyeing the pattern with an anionic dye. . 4. In the manufacturing method according to claim 3, after the first dyeing, the dyed film is treated with a dye fixing agent,
A method for manufacturing a color filter, which comprises forming a pattern on this substrate again using a resin composition, dyeing it with a second color, and repeating this process as many times as necessary. 5. A color filter obtained by the manufacturing method according to claim 3 or 4.