JP2000321417A - Radiation-sensitive composition for color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a radiation-sensitive compsn. for a color filter which does not cause dropping or peeling of a pixel pattern during development, which does not produce display failure such as burning when a display panel is formed thereof, which has excellent mechanical strength after a film is formed and which gives good adhesion properties of pixels with a substrate and a good pattern profile. SOLUTION: The radiation-sensitive compsn. for a color filter contains components of (A) a coloring agent, (B) an alkali soluble resin, (C) a polyfunctional monomer and (D) a photopolymn. initiator. In this method, the component (A) contains a green org, pigment. When the amts. of tetrachlorophthalic acid, tetrachlorophthalic acid anhydride and tetrachlorophthalimide in the component (A) are analyzed, the total is specified to <=500 ppm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a radiation-sensitive composition for a color filter used for producing a color filter used for a color image pickup tube device, a color liquid crystal display device and the like.

[0002]

2. Description of the Related Art A color filter used in a color image pickup tube element, a color liquid crystal display device, or the like irradiates radiation (hereinafter, referred to as "exposure") to a coating film of a photosensitive resin through a photomask to form an exposure portion. Is cured and then subjected to a development treatment to remove unexposed portions of the coating film to form a pixel pattern, and then dye (a dyeing method) or a composition in which a colorant is dispersed or dissolved in a photosensitive resin. It is manufactured by a method such as a photolithography method of performing coating film formation, exposure and development processing in the same manner as described above, and the colorants of these color filters include three primary colors of red, green and blue. In addition, especially in the case of a color image pickup tube, a combination of complementary colors of cyan, magenta and yellow is used. In addition, a color liquid crystal display device generally has a
A transparent electrode made of, for example, indium oxide or tin oxide is formed on a color filter by, for example, vapor deposition or sputtering, and an alignment film for aligning liquid crystals in a certain direction is further formed thereon. In order to obtain an alignment film, it is generally necessary to form 2
High temperatures of at least 00 ° C, preferably at least 250 ° C, are required. And, among the color filters manufactured by the above method, the color filter using a dye has high transparency to radiation, but has insufficient heat resistance.
There is a problem that the formation of the transparent electrode and the alignment film must be performed at a temperature of less than 200 ° C., and the performance of the transparent electrode and the alignment film cannot be sufficiently secured. Further, color filters using dyes have poor light fastness and are not suitable for outdoor use. Therefore, in recent years, pigments, especially organic pigments, have been used instead of dyes as colorants from the viewpoints of heat resistance and light resistance.
However, colorants such as organic pigments used for color filters often contain various impurities, and the impurities in the colorant contained in the pixel array gradually elute or bleed into the liquid crystal, and thus the colorants are mixed. Since the liquid crystal is contaminated, the function as a liquid crystal display element, particularly the display performance, is gradually deteriorated due to burn-in and the like, which has been a problem in terms of reliability. In addition, the types of such impurities and their effects have not been sufficiently elucidated, and evaluation criteria for ensuring high reliability of the color filters have not been clarified.
In addition, in recent years, reflecting the high quality of color imaging tube elements, color liquid crystal display devices and the like and the expansion of applications, the radiation-sensitive composition used for the color filter has a developing property,
Characteristics such as adhesion to a substrate, a pattern shape, and mechanical strength after film formation are also important. However, such characteristics are often affected by impurities in a colorant. Therefore, regarding the radiation-sensitive composition used for the color filter, it is possible to avoid the influence of impurities contained in the colorant, particularly display defects due to burn-in, etc., and also to obtain the adhesion to the substrate, the pattern shape, and the mechanical properties after film formation. There is a need for the development of radiation-sensitive compositions for color filters that are also excellent in strength and the like.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to prevent a pixel pattern from being lost or peeled off during development.
Moreover, when a display panel is formed, display defects such as image sticking do not occur, and the mechanical strength after film formation is excellent.
Another object of the present invention is to provide a radiation-sensitive composition for a color filter having good adhesion between a pixel and a substrate and a good pattern shape.

[0004]

SUMMARY OF THE INVENTION The present invention is directed to a color filter containing (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a photopolymerization initiator. A radiation-sensitive composition, wherein the component (A) contains a green organic pigment, and the amounts of tetrachlorophthalic acid, tetrachlorophthalic anhydride and tetrachlorophthalimide in the component (A) are analyzed, and the total thereof is analyzed. Is 50
A radiation-sensitive composition for a color filter, wherein the composition is 0 ppm or less.

Hereinafter, the present invention will be described in detail. (A) Colorant The colorant in the present invention contains a green organic pigment, and includes, in the colorant, tetrachlorophthalic acid, tetrachlorophthalic anhydride and tetrachlorophthalimide (hereinafter collectively referred to as “tetrachlorophthalic acid-based The amount of impurities is referred to as "impurities"), and the total thereof is not more than 500 ppm. Hereinafter, a green organic pigment having a total of tetrachlorophthalic acid-based impurities of 500 ppm or less is referred to as “green organic pigment (a)”. The present inventors have studied the radiation-sensitive composition for a color filter in which the colorant contains a green organic pigment, with particular emphasis on the display performance of a liquid crystal display element, and as a result, tetrachlorophthalate contained in the green organic pigment. Acid-based impurities have a significant effect on display performance.If the total amount of tetrachlorophthalic acid-based impurities in the colorant exceeds a certain level, display defects such as burn-in when a display panel is formed will be significant. I found it. That is, the colorant in the present invention must have a total amount of tetrachlorophthalic acid-based impurities of 500 ppm or less, preferably 400 ppm or less, more preferably 300 ppm or less, particularly preferably 200 ppm or less.
Hereinafter, it is particularly desirable that the content be 150 ppm or less. In this case, when the total amount of the tetrachlorophthalic acid-based impurities exceeds 500 ppm, display defects such as burn-in occur when the display panel is formed.

The pigment component used as the green organic pigment (a) includes, for example, a color index (CI; Th;
CI Pigment Green 7, CI Pigment Green 36, and the like can be cited as color index (CI) numbers in e Society of Dyers and Colorists.

In the present invention, the colorant containing a green organic pigment is analyzed in advance for the total amount of tetrachlorophthalic acid-based impurities, and the green organic pigment is selected and used so that the value becomes 500 ppm or less. Is done. In this case, the analysis of the total amount of tetrachlorophthalic acid-based impurities was performed on the green organic pigment, and the analysis value was converted to a value for the colorant containing the green organic pigment, and also for the colorant containing the green organic pigment. May go. When the total amount of the coloring agent exceeds 500 ppm, the corresponding green organic pigment (hereinafter, referred to as “crude green organic pigment”) is subjected to, for example, a purification treatment by a method described later, and then renewed. The total amount is analyzed or converted and the value is 5
Only colorants that are below 00 ppm are used. The total amount of tetrachlorophthalic acid-based impurities in the colorant can be determined by selecting an appropriate purification method for the crude green organic pigment, repeating the purification method, or appropriately combining two or more purification methods. The following is also possible.

Hereinafter, the crude green organic pigment is purified, and the total amount of tetrachlorophthalic acid-based impurities in the colorant is reduced to 50%.
A method for obtaining a green organic pigment (a) having a concentration of 0 ppm or less will be described in detail. In addition, such a purification method can be applied to the green organic pigment (a) having the total amount of 500 ppm or less, if desired. (A) Recrystallization method In the recrystallization method, an appropriate solvent that can dissolve the pigment component and does not react with the pigment component is selected, and a saturated solution in which the crude green organic pigment is dissolved in this solvent while heating is cooled. And recrystallize and purify the pigment component. The solvent used in the recrystallization method varies depending on the type of the pigment component.
CI Pigment Green 7 and CI Pigment Green 3
In the case of a copper phthalocyanine green pigment such as 6, concentrated sulfuric acid, chlorosulfonic acid and the like are preferable. In this case, the amount of the solvent used is usually 5 times by weight or more, preferably 10 times by weight or more of the crude green organic pigment in order to completely dissolve the pigment component. On the other hand, if the dissolution temperature of the crude green organic pigment is too high, the pigment component may be decomposed. , Usually 30-500 ° C, preferably 50-250.
C. is desirable. If the dissolution time of the crude green organic pigment is too short, the total amount of tetrachlorophthalic acid-based impurities in the obtained pigment may not be able to be 500 ppm or less, while if too long, the pigment component may be decomposed. , Preferably 5 seconds to 5 hours, more preferably 3
0 seconds to 2 hours are desirable. After the crude green organic pigment is recrystallized under such processing conditions, a predetermined green organic pigment (a) can be obtained by filtering.

(A) Reprecipitation method In the reprecipitation method, a crude green organic pigment is dissolved by selecting an appropriate solvent which can dissolve the pigment component and does not react with the pigment component, and a poor solvent is added to this solution, or This is a method in which this solution is dropped into a poor solvent to precipitate a pigment component and to purify it.
The solvent used in this reprecipitation method varies depending on the type of the pigment component. For example, CI Pigment Green 7 and CI
In the case of a copper phthalocyanine-based green pigment such as Pigment Green 36, concentrated sulfuric acid, chlorosulfonic acid and the like are preferable. In this case, the amount of the solvent used is usually 5 times by weight or more, preferably 10 times by weight or more, in order to completely dissolve the pigment component. When the dissolving temperature of the crude green organic pigment is too high, the pigment component may be decomposed. On the other hand, when the dissolving temperature is too low, the solubility decreases, and the yield of the green organic pigment (a) deteriorates.
500 ° C, preferably in the range of room temperature to 250 ° C. If the dissolving time of the crude green organic pigment is too short, the total amount of tetrachlorophthalic acid-based impurities in the pigment obtained is 5%.
There is a possibility that the content may not be less than 00 ppm. On the other hand, if it is too long, the pigment component may be decomposed, and preferably 5 seconds to 5 hours, more preferably 30 seconds to 2 hours. Further, as the poor solvent, pure water, methanol, ethanol, an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution and the like are preferable. When using pure water or an aqueous solution as the poor solvent, the calorific value is large, so the amount used is
It is usually at least 10 parts by weight, preferably at least 15 parts by weight, more preferably at least 20 parts by weight of the crude green organic pigment. In this way, a predetermined green organic pigment (a) can be obtained by precipitating the pigment component from the solution of the crude green organic pigment using the poor solvent, followed by filtering and drying.

(C) Solvent washing method In the solvent washing method, the crude green organic pigment is washed by selecting an appropriate solvent which can disperse the crude green organic pigment, does not react with the pigment component, and has an appropriate volatility. And purify it.
The solvent used in the solvent washing method may be one that dissolves the pigment component to some extent as long as a sufficient amount of the pigment component can be left during the washing. Examples of the solvent used in the solvent washing method include pure water, an organic solvent, an acidic aqueous solution, an alkaline aqueous solution, and the like.

Examples of the organic solvent include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, and ethylene glycol mono-n-butyl ether; Ethylene glycol monoalkyl ether acetates such as ether acetate and ethylene glycol monoethyl ether acetate; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol Poly such as ethylene glycol monoethyl ether Tylene glycol monoalkyl ethers; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, and propylene glycol mono-n-butyl ether; dipropylene glycol monomethyl ether, dipropylene glycol Propylene glycol monoethyl ether, dipropylene glycol mono-n-
Propyl ether, dipropylene glycol mono-n-
Propylene glycol monoalkyl ethers such as butyl ether, tripropylene glycol monomethyl ether and tripropylene glycol monoethyl ether; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; diethyl ether, ethyl- other ethers such as i-propyl ether, di-i-propyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, 1,4-dioxane;

Acetone, methyl ethyl ketone, methyl
ketones such as i-butyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and diacetone alcohol; alkyl lactates such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate;
-Ethyl hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy- Methyl 3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3
-Methyl-3-methoxybutyl propionate, ethyl acetate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, butyric acid n-butyl, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate,
Other esters such as methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate, dimethyl carbonate; amides such as N-methylpyrrolidone, N, N-dimethylformamide, acetamide, N, N-dimethylacetamide; methanol; Alcohols such as ethanol, i-propanol, ethylene glycol, diethylene glycol and glycerin; other highly polar solvents such as dimethyl sulfoxide, acetonitrile and pyridine; aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane and cyclohexane Aromatic hydrocarbons such as toluene and xylene; methylene chloride, chloroform, carbon tetrachloride,
1,1-dichloroethane, 1,2-dichloroethane,
Examples thereof include halogenated hydrocarbons such as 1,1,1-trichloroethane, 1,1,2-trichloroethane, and hexachlorobenzene. These organic solvents can be used alone or in combination of two or more.

Further, together with the organic solvent, for example, benzyl ethyl ether, dihexyl ether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1-
Octanol, 1-nonanol, benzyl alcohol,
High boiling solvents such as benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and ethylene glycol monophenyl ether acetate can also be used in combination. These high-boiling solvents can be used alone or in combination of two or more.

The acid used in the acidic aqueous solution is
Organic acids or inorganic acids may be used. Examples of the organic acid include aliphatic monocarboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, and glutaric acid. Acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, 1,4-cyclohexanedicarboxylic acid, itacone Aliphatic dicarboxylic acids such as acid, citraconic acid, maleic acid, fumaric acid, and mesaconic acid;
Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, and camphoronic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, and mesitylene acid; aromatics such as phthalic acid, isophthalic acid, and terephthalic acid Dicarboxylic acids; trivalent or higher aromatic polycarboxylic acids such as trimellitic acid, trimesic acid, melophanic acid, and pyromellitic acid; glycolic acid, lactic acid, α-oxybutyric acid,
In addition to oxycarboxylic acids such as glyceric acid, tartronic acid, malic acid, tartaric acid, citric acid, salicylic acid, p-oxybenzoic acid, gallic acid, mandelic acid, tropic acid, coumaric acid, umbellic acid, phenylacetic acid, hydroatropic acid, Hydrocinnamic acid, phenylsuccinic acid, atropic acid,
Examples thereof include cinnamic acid and cinnamylidenic acid.
Examples of the inorganic acid include sulfuric acid, nitric acid, carbonic acid, chloric acid, perchloric acid, and the like. In this case, the aqueous solution of sulfuric acid can be used as concentrated sulfuric acid, hot concentrated sulfuric acid, dilute sulfuric acid, or the like. These acids can be used alone or in combination of two or more.

The alkali used in the alkaline aqueous solution may be an inorganic alkali or an organic alkali.
Examples of the inorganic alkali include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,
Examples thereof include sodium hydrogen carbonate, potassium hydrogen carbonate, calcium hydroxide, barium hydroxide and the like. As the organic alkali, for example, ethanolamine, 2-
Dimethylaminoethanol, 2-diethylaminoethanol, 2- (di-n-propylamino) ethanol, 2
-(Di-i-propylamino) ethanol, 2- (di-
n-butylamino) ethanol, 3-dimethylamino-
1-propanol, 3-diethylamino-1-propanol, 2-dimethylamino-1-propanol, 2-diethylamino-1-propanol, 4-dimethylamino-2-butanol, 4-diethylamino-2-butanol, 3-dimethylamino -2-butanol, 3-diethylamino-2-butanol, 5-dimethylamino-2-
Alkanolamines such as pentanol, 5-diethylamino-2-pentanol, 4-dimethylamino-2-pentanol, 4-diethylamino-2-pentanol; monomethylamine, dimethylamine, trimethylamine, tetramethylammonium hydroxide; Monoethylamine, diethylamine, triethylamine, tetraethylammonium hydroxide, mono-n-propylamine, di-n-propylamine, mono-i-propylamine, di-i-propylamine, mono-n-butylamine, di-n- Examples thereof include alkylamines such as butylamine. These alkalis can be used alone or in combination of two or more.

Among these solvents, from the viewpoints of detergency, affinity with pigment components, etc., in addition to pure water, organic solvents include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, tetrahydrofuran, acetone, cyclohexanone, and the like. Diacetone alcohol, dimethyl carbonate, N-methylpyrrolidone, N, N-dimethylformamide, dimethylsulfoxide, methanol, ethanol, i-propanol, n-hexane, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride and the like are preferable, As the high boiling point solvent, γ-butyrolactone and the like are preferable. Also,
As the acidic aqueous solution, a 1% by weight aqueous solution of oxalic acid, a 1% by weight aqueous solution of phthalic acid, a 1% by weight aqueous solution of citric acid, concentrated sulfuric acid, hot concentrated sulfuric acid, diluted sulfuric acid and the like are preferable. As the alkaline aqueous solution, an aqueous solution of an inorganic alkali such as sodium hydroxide and potassium hydroxide; and an aqueous solution of an organic alkali such as ethanolamine, 2-dimethylaminoethanol, trimethylamine and tetramethylammonium hydroxide are preferable.

The washing operation using the solvent includes, for example, (C-1) a mixture of a crude green organic pigment and a solvent, a dissolver, a homomixer, a homogenizer, a paint shaker, three rolls, two rolls, a bead mill. Using a mixing device such as 1 minute to 70 hours, preferably 5 minutes to 24 hours, more preferably 10 minutes to 6 hours,
After separating the solvent by filtration, decantation, etc.,
(C-2) The mixture of the crude green organic pigment and the solvent is added to a mixture of the crude green organic pigment and a solvent in an ultrasonic mixer such as an ultrasonic dispersion homogenizer or an ultrasonic cleaner, usually at 1 to 300 KHz, preferably 2 to 300 KHz. 10
Ultrasonic cleaning operation of irradiating an ultrasonic wave having a frequency of 0 KHz usually for 30 seconds to 10 hours, preferably for 1 minute to 5 hours, separating a solvent by filtration, decantation or the like, and then drying; The mixture of the crude green organic pigment and the solvent is usually mixed with a bladed stirrer at a rotation speed of 50 to 15000 rpm, preferably 100 to 2,000 rpm, usually for 5 minutes to
After stirring for 10 hours, preferably for 10 minutes to 5 hours, separating the solvent by filtration, decantation or the like, a stirring and washing operation of drying and the like can be mentioned. The operations (C-1) to (C-3) may be performed individually or in combination of two or more. (C)
The concentration of the crude green organic pigment in performing the operations 1) to 3) is usually 0.1 to 70% by weight, preferably 1 to 5% by weight.
0% by weight. By such a solvent washing method, a predetermined green organic pigment (a) can be obtained.

(D) Sublimation method The sublimation method is a method in which a crude green organic pigment is heated under normal pressure or reduced pressure to sublimate and refine the pigment component. The heating temperature for sublimating the pigment component varies depending on the type and pressure of the pigment component.
When purifying copper phthalocyanine-based green pigments such as CI Pigment Green 36 and CI, usually under normal pressure,
300-800 ° C, preferably 400-600 ° C is desirable. By such a sublimation method, a predetermined green organic pigment (a) can be obtained.

(E) Vacuum heating method The vacuum heating method is a method in which a crude green organic pigment is placed in a pressure vessel, heated under vacuum, and impurities are removed by evaporation to purify. The heating temperature in the vacuum heating method varies depending on the type of the pigment component, but if it is too high, the pigment component may sublime, while if it is too low, the removal of impurities tends to be difficult. 300 ° C, preferably 1
The temperature is desirably set to 00 to 200 ° C. The degree of vacuum is
If it is too low, it tends to be difficult to remove impurities,
Usually, it is desirable that the pressure be 20 torr or less, preferably 10 torr or less. By such a vacuum heating method,
A predetermined green organic pigment (a) can be obtained.

In the present invention, each of the above-mentioned purification methods (A) to (E) may be repeated once or twice or more, or may be carried out individually or by combining any two or more methods. May be implemented. Examples of preferred combinations of the purification methods (A) to (E) include (A) a combination of a recrystallization method and (C) a solvent washing method (recrystallization / solvent washing method), and (B) a reprecipitation method. (C) Combination of solvent washing methods (reprecipitation / solvent washing method), (c) Combination of solvent washing method and (e) vacuum heating method (solvent washing / vacuum heating method),
(C) In the solvent washing method, a combination of washing two or more times by changing the solvent (multiple solvent washing method) and the like can be mentioned.
In the present invention, the green organic pigment (a) can be used alone or in combination of two or more. Also,
In the present invention, as long as the total amount of terephthalic acid-based impurities in the colorant is 500 ppm or less, the crude green organic pigment can be used in combination with the green organic pigment (a).

The colorant in the present invention contains a green organic pigment (a), but the color tone of the colorant as a whole is not particularly limited.
The other colorant (hereinafter referred to as “other colorant”) is appropriately selected depending on the use of the color filter, and may be any of a pigment, a dye, and a natural pigment. Since the color filter is required to have high-definition color development and heat resistance, as the other colorant in the present invention, a colorant having a high color development property, and a colorant having high heat resistance, particularly a colorant having high heat decomposition resistance is preferable. Usually, a pigment is used, and particularly preferably, an organic pigment (hereinafter, referred to as “another organic pigment”) is used.

Examples of other organic pigments include those having the following color index (CI) numbers. CI Pigment Yellow 1,
CI Pigment Yellow 3 and CI Pigment Yellow 1
2, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 15, CI Pigment Yellow 16, CI Pigment Yellow 17, CI Pigment Yellow 20, CI Pigment Yellow 24,
CI Pigment Yellow 31, CI Pigment Yellow 55, CI Pigment Yellow 60, CI Pigment Yellow 61, CI Pigment Yellow 65, CI Pigment Yellow 71, CI Pigment Yellow 73, CI
Pigment Yellow 74, CI Pigment Yellow 8
1, CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 95, CI Pigment Yellow 97, CI Pigment Yellow 98, CI Pigment Yellow 100, CI Pigment Yellow 10
1, CI Pigment Yellow 104, CI Pigment Yellow 106, CI Pigment Yellow 108, CI Pigment Yellow 109, CI Pigment Yellow 11
0, CI Pigment Yellow 113, CI Pigment Yellow 114, CI Pigment Yellow 116, CI Pigment Yellow 117, CI Pigment Yellow 11
9, CI Pigment Yellow 120, CI Pigment Yellow 126, CI Pigment Yellow 127, CI Pigment Yellow 128, CI Pigment Yellow 12
9, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 15
2, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 156, CI Pigment Yellow 16
6, CI Pigment Yellow 168, CI Pigment Yellow 175; CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 16,
CI Pigment Orange 17, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI
Pigment Orange 46, CI Pigment Orange 4
9, CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73;

CI Pigment Red 1, CI Pigment Red 2, CI Pigment Red 3, CI Pigment Red 4, CI Pigment Red 5, CI Pigment Red 6, CI Pigment Red 7, CI Pigment Red 8, CI Pigment Red 9, CI Pigment Red 1
0, CI Pigment Red 11, CI Pigment Red 12, CI Pigment Red 14, CI Pigment Red 15, CI Pigment Red 16, CI Pigment Red 17, CI Pigment Red 18, CI Pigment Red 19, CI Pigment Red 21, CI Pigment Red 22, CI Pigment Red 23, CI Pigment Red 30, CI Pigment Red 31, CI Pigment Red 32, CI Pigment Red 37, CI Pigment Red 38, CI Pigment Red 40, CI
Pigment Red 41, CI Pigment Red 42, C.I.
I. Pigment Red 48: 1, CI Pigment Red 4
8: 2, CI Pigment Red 48: 3, CI Pigment Red 48: 4, CI Pigment Red 49: 1, C.I.
I. Pigment Red 49: 2, CI Pigment Red 5
0: 1, CI Pigment Red 52: 1, CI Pigment Red 53: 1, CI Pigment Red 57, CI Pigment Red 57: 1, CI Pigment Red 57:
2, CI Pigment Red 58: 2, CI Pigment Red 58: 4, CI Pigment Red 60: 1, CI Pigment Red 63: 1, CI Pigment Red 63:
2, CI Pigment Red 64: 1, CI Pigment Red 81: 1, CI Pigment Red 83, CI Pigment Red 88, CI Pigment Red 90: 1, CI
Pigment Red 97, CI Pigment Red 101,
CI Pigment Red 102, CI Pigment Red 1
04, CI Pigment Red 105, CI Pigment Red 106, CI Pigment Red 108, CI Pigment Red 112, CI Pigment Red 113, CI
Pigment Red 114, CI Pigment Red 12
2, CI Pigment Red 123, CI Pigment Red 144, CI Pigment Red 146, CI Pigment Red 149, CI Pigment Red 150, CI Pigment Red 151, CI Pigment Red 166,
CI Pigment Red 168, CI Pigment Red 1
70, CI Pigment Red 171, CI Pigment Red 172, CI Pigment Red 174, CI Pigment Red 175, CI Pigment Red 176, CI
Pigment Red 177, CI Pigment Red 17
8, CI Pigment Red 179, CI Pigment Red 180, CI Pigment Red 185, CI Pigment Red 187, CI Pigment Red 188, CI Pigment Red 190, CI Pigment Red 193,
CI Pigment Red 194, CI Pigment Red 2
02, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 208, CI Pigment Red 209, CI Pigment Red 215, CI
Pigment Red 216, CI Pigment Red 22
0, CI Pigment Red 224, CI Pigment Red 226, CI Pigment Red 242, CI Pigment Red 243, CI Pigment Red 245, CI Pigment Red 254, CI Pigment Red 255,
CI Pigment Red 264, CI Pigment Red 2
65;

CI Pigment Violet 1, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 29, CI Pigment Violet 32, CI Pigment Violet 3
6, CI Pigment Violet 38; CI Pigment Blue 15, CI Pigment Blue 15: 3, CI Pigment Blue 15: 4, CI Pigment Blue 15:
6, CI Pigment Blue 60; CI Pigment Brown 23, CI Pigment Brown 25; CI Pigment Black 1, CI Pigment Black 7. These other organic pigments can be used alone or in combination of two or more.

Examples of the inorganic pigments include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, ultramarine blue, navy blue, Chromium oxide green, cobalt green,
Amber, titanium black, synthetic iron black, carbon black and the like can be mentioned. These inorganic pigments can be used alone or in combination of two or more. In addition, each of the pigments may be used after modifying the surface of the pigment particles with a polymer. As the colorant in the present invention, only the green organic pigment containing the green organic pigment (a) or a mixture of the green organic pigment containing the green organic pigment (a) and another colorant can be used. The content of the green organic pigment including the green organic pigment (a) in the colorant in the present invention varies depending on the color tone of the colorant, the use of the obtained color filter, and the like.
100% by weight, preferably 20 to 100% by weight, more preferably 30 to 100% by weight, particularly preferably 50 to 100% by weight.
100% by weight.

The colorant in the present invention can be used together with a dispersant, if desired. Examples of the dispersant include surfactants such as cationic, anionic, nonionic, amphoteric, silicone, and fluorine-based surfactants. Such surfactants include, for example,
Polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether;
Polyoxyethylene alkyl phenyl ethers such as polyoxyethylene n-octyl phenyl ether and polyoxyethylene n-nonyl phenyl ether; polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; Polyesters; tertiary amine-modified polyurethanes; polyethylene imines, etc., and trade names include, for example, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (Manufactured by Tochem Products), Megafac (Dainippon Ink and Chemicals, Inc.)
), Florard (manufactured by Sumitomo 3M Limited), Asahi Guard, Surflon (all manufactured by Asahi Glass Co., Ltd.), EFK
A (manufactured by F-Car Chemicals Beef (EFKA))
Disparon (manufactured by Kusumoto Kasei Co., Ltd.), Disperbyk (manufactured by Big Chemie), Solsperse (manufactured by ZENEKA) and the like can be mentioned. These surfactants are
They can be used alone or in combination of two or more. The amount of the surfactant to be used is generally 50 parts by weight or less, preferably 0 to 30 parts by weight, based on 100 parts by weight of the colorant.

(B) Alkali-Soluble Resin As the alkali-soluble resin in the present invention, (A) acts as a binder for a colorant and is soluble in an alkali developing solution used in a developing step in the production of a color filter. As long as it is, an appropriate polymer can be used. Examples of such an alkali-soluble resin include polymers having an acidic functional group such as a carboxyl group and a phenolic hydroxyl group.
Among the alkali-soluble resins, the carboxyl group-containing alkali-soluble resin includes, for example, (co) -weight of an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter, simply referred to as “carboxyl group-containing unsaturated monomer”). Examples of the (co) polymer of the carboxyl group-containing unsaturated monomer include a carboxyl group-containing unsaturated monomer and another copolymerizable ethylenically unsaturated monomer (hereinafter simply referred to as “other unsaturated monomer”). (Hereinafter referred to as “carboxyl group-containing copolymer (b)”). Examples of the carboxyl group-containing unsaturated monomer include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; maleic acid, maleic anhydride, fumaric acid, itaconic acid Dicarboxylic acids (anhydrides) such as itaconic anhydride, citraconic acid, citraconic anhydride, and mesaconic acid; tri- or higher unsaturated polycarboxylic acids (anhydrides); monosuccinic acid (2-acryloyloxy) Ethyl), mono (2- (meth) yl) of non-polymerizable dicarboxylic acids such as mono (2-methacryloyloxyethyl) succinate, mono (2-acryloyloxyethyl) phthalate and mono (2-methacryloyloxyethyl) phthalate Acryloyloxyethyl) esters, ω-carboxypolycaprolactone monoacrylate, ω-carbo Shi polycaprolactone monomethacrylate, and the like. Of these carboxyl group-containing unsaturated monomers, mono (2-acryloyloxyethyl) succinate and mono (2-acryloyloxyethyl) phthalate are trade names of M-5300 and M-5400, respectively (Toa Gosei Co., Ltd. )). The carboxyl group-containing unsaturated monomers can be used alone or in combination of two or more.

The other unsaturated monomers include:
For example, styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, o
-Chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, aromatic vinyl compounds such as o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether and p-vinylbenzyl glycidyl ether; indenes such as indene and 1-methylindene; methyl acrylate, methyl methacrylate;
Ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-
Propyl acrylate, i-propyl methacrylate,
n-butyl acrylate, n-butyl methacrylate,
i-butyl acrylate, i-butyl methacrylate,
sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3
-Hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxy Ethyl acrylate, 2-methoxyethyl methacrylate, 2
-Phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene Glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate, 2
-Hydroxy-3-phenoxypropyl acrylate,
Unsaturated carboxylic esters such as 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate;
Aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-
Dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, Unsaturated carboxylic acid aminoalkyl esters such as 3-dimethylaminopropyl methacrylate; unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; vinyl carboxylate such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate Esters: unsaturated esters such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether and methallyl glycidyl ether Le acids; acrylonitrile, methacrylonitrile, alpha-chloro acrylonitrile, vinyl cyanide compounds such as vinylidene cyanide; acrylamide, methacrylamide, alpha-chloro acrylamide,
N- (2-hydroxyethyl) acrylamide, N-
Unsaturated amides such as (2-hydroxyethyl) methacrylamide, N-methylolacrylamide and N-methylolmethacrylamide; unsaturated imides such as maleimide, N-cyclohexylmaleimide and N-phenylmaleimide; 1,3-butadiene; Aliphatic conjugated dienes such as isoprene and chloroprene; polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate,
Macromonomers having a monoacryloyl group or a monomethacryloyl group at the terminal of a polymer molecular chain such as polysiloxane can be exemplified. These other unsaturated monomers can be used alone or in combination of two or more.

As the carboxyl group-containing copolymer (b), acrylic acid and / or methacrylic acid are essential. In some cases, mono (2-acryloyloxyethyl) succinate and mono (2-methacryloyloxyethyl) succinate are used. A carboxyl group-containing unsaturated monomer further containing at least one selected from the group of ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate, and styrene, methyl acrylate, methyl methacrylate,
Selected from the group of 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate, N-phenylmaleimide, polystyrene macromonomer and polymethyl methacrylate macromonomer (Hereinafter, referred to as “carboxyl group-containing copolymer (I)”) with at least one other unsaturated monomer.

Specific examples of the carboxyl group-containing copolymer (I) include (meth) acrylic acid / methyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate copolymer, and (meth) ) Acrylic acid / styrene / methyl (meth) acrylate copolymer, (meth)
Acrylic acid / styrene / benzyl (meth) acrylate copolymer, (meth) acrylic acid / methyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / methyl (meth) acrylate / polymethyl methacrylate macromonomer Copolymer, (meta)
Acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer, (meth)
Acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / 2-
Hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (Meth) acrylic acid / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / monosuccinic acid [2- (meth) acryloyloxyethyl] / styrene / benzyl (meth) acrylate /
N-phenylmaleimide copolymer, (meth) acrylic acid / mono [2- (meth) acryloyloxyethyl] succinate / styrene / allyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / Ω-
Carboxypolycaprolactone mono (meth) acrylate / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / succinic mono [2
-(Meth) acryloyloxyethyl] / ω-carboxypolycaprolactone mono (meth) acrylate / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / Succinic acid mono [2- (meta)
[Acryloyloxyethyl] / ω-carboxypolycaprolactone mono (meth) acrylate / styrene / allyl (meth) acrylate / glycerol mono (meth) acrylate / N-phenylmaleimide copolymer.

Among these carboxyl group-containing copolymers (I), particularly, methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / polystyrene Macromonomer copolymer, methacrylic acid / benzyl methacrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / styrene / benzyl methacrylate / N-phenylmaleimide copolymer, methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polystyrene Macromonomer copolymer, methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polymethyl methacrylate macromonomer copolymer, Methacrylic acid / amber Sanmono (2
-Acryloyloxyethyl) / styrene / benzyl methacrylate / N-phenylmaleimide copolymer, methacrylic acid / M-5300 / styrene / benzyl methacrylate / N-phenylmaleimide copolymer, methacrylic acid / styrene / benzyl methacrylate / glycerol mono Methacrylate / N-phenylmaleimide copolymer is preferred.

The copolymerization ratio of the carboxyl group-containing unsaturated monomer in the carboxyl group-containing copolymer (b) is as follows:
Usually, it is 5 to 50% by weight, preferably 10 to 40% by weight. In this case, if the copolymerization ratio of the carboxyl group-containing unsaturated monomer is less than 5% by weight, the solubility of the obtained radiation-sensitive composition in an alkali developing solution tends to decrease. During development with a developing solution, the formed pixels tend to fall off the substrate or the surface of the pixels becomes rough. In particular, the carboxyl group-containing copolymer (b) containing the carboxyl group-containing unsaturated monomer at the specific copolymerization ratio has excellent solubility in an alkali developer, and the copolymer is used as a binder. The radiation-sensitive composition used as the non-dissolved material is very unlikely to remain after development with an alkaline developer, and it is difficult to cause background fouling, film residue, and the like in a region other than a portion where a pixel is formed on a substrate, Moreover, the pixel obtained from the composition does not dissolve excessively in the alkali developing solution, has excellent adhesion to the substrate, and does not have a risk of falling off the substrate. The weight average molecular weight in terms of polystyrene (hereinafter, referred to as “Mw”) of the carboxyl group-containing copolymer (b) measured by gel permeation chromatography (GPC; elution solvent: tetrahydrofuran) is preferably from 3,000 to 3.
00,000, more preferably 5,000-100,
000.

Further, an alkali-soluble polyester resin can be used as the alkali-soluble resin.
As such a polyester resin, polylactic acid having a relatively low molecular weight is particularly preferable. The Mw of the polylactic acid is usually 3,000 to 300,000, preferably 5,000.
0 to 100,000. Examples of the phenolic hydroxyl group-containing alkali-soluble resin include a (co) polymer of a phenolic hydroxyl group-containing vinyl aromatic compound and a phenol novolak resin. Examples of the phenolic hydroxyl group-containing vinyl aromatic compound include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxy-α-methylstyrene, m-hydroxy-α-methylstyrene,
p-hydroxy-α-methylstyrene and the like. These phenolic hydroxyl group-containing vinyl aromatic compounds can be used alone or in combination of two or more. The phenolic hydroxyl-containing vinyl aromatic compound can optionally be copolymerized with one or more other copolymerizable ethylenically unsaturated monomers, such as the other unsaturated monomers. Examples of the phenol used in the phenol novolak resin include o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol,
2,5-xylenol, 3,4-xylenol, 3,5
-Xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol and the like. Examples of the aldehyde include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde and phenyl. Examples thereof include acetaldehyde, glyoxal, glutaraldehyde, terephthalaldehyde, and isophthalaldehyde. These phenols and aldehydes can be used alone or in combination of two or more. Mw of the (co) polymer of the phenolic hydroxyl group-containing vinyl aromatic compound is preferably 1,000 to 150,000, and more preferably 3,000 to 100,000. The Mw of the phenol novolak resin is preferably 1,000 to 1
50,000, more preferably 1,500 to 80,0
00.

In the present invention, the alkali-soluble resin is
They can be used alone or in combination of two or more. The amount of the alkali-soluble resin used in the present invention is
(A) Usually, 10 to 1, based on 100 parts by weight of the coloring agent.
000 parts by weight, preferably 20 to 500 parts by weight.
In this case, if the use amount of the alkali-soluble resin is less than 10 parts by weight, for example, alkali developability may be reduced, and background contamination or film residue may occur in a region other than a portion where a pixel is formed. If the amount exceeds 1,000 parts by weight, the concentration of the colorant relatively decreases, so that it may be difficult to achieve the desired color density as a thin film.

(C) Polyfunctional Monomer The polyfunctional monomer in the present invention comprises a monomer having two or more polymerizable ethylenically unsaturated bonds. Examples of such polyfunctional monomers include diacrylates or dimethacrylates of alkylene glycols such as ethylene glycol and propylene glycol; diacrylates and dimethacrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol; Polyacrylates or polymethacrylates of trihydric or higher polyhydric alcohols such as methylolpropane, pentaerythritol and dipentaerythritol, and modified dicarboxylic acids thereof;
Oligoacrylates or oligomethacrylates such as polyester, epoxy resin, urethane resin, alkyd resin, silicone resin, and spirane resin; both ends hydroxyhydroxy-1,3-butadiene, both ends hydroxypolyisoprene, both ends hydroxypolycaprolactone In addition to diacrylates or dimethacrylates of terminal hydroxylated polymers, trisacryloyloxyethyl phosphate, trismethacryloyloxyethyl phosphate and the like can be mentioned.

Of these polyfunctional monomers, polyacrylates or polymethacrylates of trihydric or higher polyhydric alcohols and modified products of dicarboxylic acids thereof are preferred. Specifically, trimethylolpropane triacrylate, trimethylolpropane Trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate,
Dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, succinic acid-modified pentaerythritol triacrylate, succinic acid-modified pentaerythritol trimethacrylate, and the like are particularly preferable.
Trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and succinic acid-modified pentaerythritol triacrylate have high pixel strength, excellent pixel surface smoothness, and pixel formation. This is preferable in that it is unlikely to cause soiling, film residue, and the like in a region other than the portion shown in FIG.

In the present invention, the polyfunctional monomers can be used alone or as a mixture of two or more.
The amount of the polyfunctional monomer used in the present invention is usually 5 to 5 based on 100 parts by weight of the alkali-soluble resin (B).
00 parts by weight, preferably 20 to 300 parts by weight. In this case, if the amount of the polyfunctional monomer used is less than 5 parts by weight, the pixel strength or the smoothness of the pixel surface tends to be insufficient. In addition, there is a tendency that background contamination and film residue occur easily in a region other than the portion where the pixel is formed.

In the present invention, a part of the polyfunctional monomer may be replaced with a monofunctional monomer having one polymerizable ethylenically unsaturated bond. Examples of the monofunctional monomer include the carboxyl group-containing unsaturated monomer exemplified for the carboxyl group-containing copolymer (b) and other unsaturated monomers. These monofunctional monomers can be used alone or in combination of two or more. The proportion of the monofunctional monomer used is usually 40% by weight or less, preferably 20% by weight or less, based on the total of the polyfunctional monomer and the monofunctional monomer.

(D) Photopolymerization Initiator The photopolymerization initiator according to the present invention can be obtained by irradiating radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, etc. It consists of a compound capable of generating an active species which can initiate the polymerization of the monofunctional monomer used. Examples of such a photopolymerization initiator include a biimidazole compound having at least one main skeleton represented by the following formula (1), formula (2) or formula (3), a benzoin compound, or an acetophenone compound. A benzophenone compound, an α-diketone compound, a polynuclear quinone compound, a xanthone compound, a diazo compound, a triazine compound, and the like.
Of these, biimidazole compounds are preferred.

[0040]

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[0041]

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[0042]

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Specific examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,
4 ′, 5,5′-tetrakis (4-methoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4 -Ethoxycarbonylphenyl) -1,2 '
-Biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-phenoxycarbonylphenyl) -1,2'-biimidazole,
2,2′-bis (2,4-dichlorophenyl) -4,
4 ', 5,5'-tetrakis (4-methoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5 '
-Tetrakis (4-ethoxycarbonylphenyl)-
1,2′-biimidazole, 2,2′-bis (2,4-
Dichlorophenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetrakis (4-
(Methoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1 , 2'-biimidazole,
2,2'-bis (2,4,6-trichlorophenyl)-
4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) -1,2′-biimidazole,

2,2'-bis (2-cyanophenyl)-
4,4 ′, 5.5′-tetrakis (4-methoxycarbonylphenyl) -1,2′-biimidazole, 2,2 ′
-Bis (2-cyanophenyl) -4,4 ', 5.5'-
Tetrakis (4-ethoxycarbonylphenyl) -1,
2′-biimidazole, 2,2′-bis (2-cyanophenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) -1,2′-biimidazole, 2,2 ′ -Bis (2-methylphenyl) -4,
4 ′, 5,5′-tetrakis (4-methoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2-methylphenyl) -4,4 ′, 5,5′-tetrakis ( 4-ethoxycarbonylphenyl) -1,2 '
-Biimidazole, 2,2'-bis (2-methylphenyl) -4,4 ', 5,5'-tetrakis (4-phenoxycarbonylphenyl) -1,2'-biimidazole,
2,2′-bis (2-ethylphenyl) -4,4 ′,
5,5′-tetrakis (4-methoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2
-Ethylphenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2-ethylphenyl)-
4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) -1,2′-biimidazole, 2,
2'-bis (2-phenylphenyl) -4,4 ', 5
5'-tetrakis (4-methoxycarbonylphenyl)
-1,2'-biimidazole, 2,2'-bis (2-phenylphenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, , 2'-bis (2-phenylphenyl)
-4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) -1,2′-biimidazole,

2,2'-bis (2-chlorophenyl)-
4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1, 2 '
-Biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2 −
Bromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,
4-dibromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-tribromophenyl) -4,4', 5,
5′-tetraphenyl-1,2′-biimidazole,
2,2′-bis (2-cyanophenyl) -4,4 ′,
5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dicyanophenyl)-
4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-tricyanophenyl) -4,4', 5,5'-tetra Phenyl-
1,2′-biimidazole,

2,2'-bis (2-methylphenyl)-
4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dimethylphenyl) -4,4', 5,5'-tetraphenyl-1 , 2 '
-Biimidazole, 2,2'-bis (2,4,6-trimethylphenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2 −
Ethylphenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,
4-diethylphenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-triethylphenyl) -4,4', 5 ,
5′-tetraphenyl-1,2′-biimidazole,
2,2′-bis (2-phenylphenyl) -4,4 ′,
5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-diphenylphenyl)-
4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-triphenylphenyl) -4,4', 5,5'-tetra Phenyl-
1,1'-biimidazole and the like can be mentioned.

Of these biimidazole compounds,
In particular, 2,2'-bis (2-chlorophenyl) -4,
4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetrakis ( 4-ethoxycarbonylphenyl) -1,2 '
-Biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-
1,2′-biimidazole, 2,2′-bis (2,4,
6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dibromophenyl) -4,4', 5,5 '
-Tetraphenyl-1,2'-biimidazole and 2,2'-bis (2,4,6-tribromophenyl)-
4,4 ', 5,5'-Tetraphenyl-1,2'-biimidazole is preferred. The biimidazole-based compound is excellent in solubility in a solvent, does not generate foreign matters such as undissolved substances and precipitates, and has high sensitivity. Since the curing reaction is not high in the unexposed areas, the exposed coating film clearly shows a cured part insoluble in the developing solution and an uncured part having high solubility in the developing solution. It is possible to form an excellent color filter which is divided and has no pattern missing, missing or undercut.

The benzoin-based compound includes
For example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, methyl-2-benzoylbenzoate, and the like can be given. As the acetophenone-based compound, for example, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-
2-methyl-1-phenylpropan-1-one, 1-
(4-i-propylphenyl) -2-hydroxy-2-
Methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2-methyl- (4- Methylthiophenyl) -2-morpholino-1-propane-1-
On, 2-benzyl-2-dimethylamino-1- (4-
Morpholinophenyl) butan-1-one, 1-hydroxycyclohexylphenyl ketone, 4-azidoacetophenone, 4-azidobenzalacetophenone and the like. Examples of the benzophenone-based compound include benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 3,3-dimethyl-4-methoxybenzophenone, and the like. .

Examples of the α-diketone compound include diacetyl, dibenzoyl, methylbenzoyl formate and the like. Examples of the polynuclear quinone-based compound include anthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1,4-
Naphthoquinone and the like can be mentioned. Examples of the xanthone-based compound include xanthone, thioxanthone, 2,4-diethylthioxanthone, and 2-chlorothioxanthone. Examples of the diazo compound include 4-diazodiphenylamine,
-Diazo-4'-methoxydiphenylamine, 4-diazo-3-methoxydiphenylamine and the like. Examples of the triazine-based compound include, for example, 2-
(2′-furylethylidene) -4,6-bis (trichloromethyl) -s-triazine, 2- (3 ′, 4′-dimethoxystyryl) -4,6-bis (trichloromethyl)
-S-triazine, 2- (4'-methoxynaphthyl)-
4,6-bis (trichloromethyl) -s-triazine,
2- (2'-bromo-4'-methylphenyl) -4,6
-Bis (trichloromethyl) -s-triazine, 2-
(2'-thiophenylethylidene) -4,6-bis (trichloromethyl) -s-triazine and the like. Further, as other photopolymerization initiators, 4-azidobenzaldehyde, azidopyrene, bis (2,6-
(Dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, N-phenylthioacridone, triphenylpyrylium perchlorate and the like can also be used.

In the present invention, the photopolymerization initiators can be used alone or in combination of two or more. The amount of the photopolymerization initiator used in the present invention is usually 0.01 to 200 parts by weight based on 100 parts by weight of the total of the polyfunctional monomer (C) and the optionally used monofunctional monomer.
Parts by weight, preferably 1 to 120 parts by weight, particularly preferably 1 to 50 parts by weight. In this case, if the amount of the photopolymerization initiator is less than 0.01 part by weight, curing by radiation irradiation becomes insufficient, and there is a possibility that a pattern may be missing, chipped or undercut, while if it exceeds 200 parts by weight,
The formed pattern easily falls off the substrate during development,
In addition, background contamination, film residue, and the like are likely to occur in a region other than the portion where the pattern is formed.

Further, in the present invention, one or more sensitizers, curing accelerators, polymer photocrosslinking / sensitizers and the like can be used in combination with the photopolymerization initiator. Examples of the sensitizer include 4-diethylaminoacetophenone,
-Dimethylaminopropiophenone, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis (4'-diethylaminobenzal) cyclohexanone, 7-diethylamino-3-
(4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone and the like can be mentioned. These sensitizers can be used alone or in combination of two or more. Examples of the curing accelerator include 2
-Mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole,
2,5-dimercapto-1,3,4-thiadiazole,
Chain transfer agents such as 2-mercapto-4,6-dimethylaminopyridine can be exemplified. These curing accelerators can be used alone or in combination of two or more. Further, the polymer photocrosslinking / sensitizer is a polymer compound having at least one kind of functional group capable of acting as a crosslinking agent and / or a sensitizer upon irradiation with radiation in a main chain and / or a side chain. Examples thereof include condensates of 4-azidobenzaldehyde and polyvinyl alcohol, condensates of 4-azidobenzaldehyde and phenol novolak resin, (co) polymers of 4-acryloylphenyl cinnamate, 1,4- Examples thereof include polybutadiene and 1,2-polybutadiene. These polymer photocrosslinking / sensitizers can be used alone or in combination of two or more. The total amount of the sensitizer, the curing accelerator and the polymer photocrosslinking / sensitizer in the present invention is usually 300 parts by weight or less, preferably 5 to 200 parts by weight, based on 100 parts by weight of the photopolymerization initiator. , More preferably 1
0 to 100 parts by weight.

In the present invention, as a photopolymerization initiator, a biimidazole compound, a benzophenone compound, an acetophenone compound and It is preferable to use in combination with at least one selected from the group of thiazole-based curing accelerators. In the present invention, when a biimidazole compound and another component are used in combination as the photopolymerization initiator, the amount of the other component used is preferably 80% by weight or less based on the entire photopolymerization initiator.

Particularly preferred photopolymerization initiators in the present invention are shown below as combinations of the constituent components. That is, 2,2′-bis (2-
(Chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole / 4,4'-bis (diethylamino) benzophenone, 2,2'-bis (2- Chlorophenyl)-
4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole / 4,4'
-Bis (diethylamino) benzophenone / 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5, 5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole / 4,4'-bis (diethylamino) benzophenone / 1-hydroxycyclohexylphenyl ketone, 2,
2'-bis (2-chlorophenyl) -4,4 ', 5
5'-tetrakis (4-ethoxycarbonylphenyl)
-1,2'-biimidazole / 4,4'-bis (diethylamino) benzophenone / 1-hydroxycyclohexylphenyl ketone / 2-mercaptobenzothiazole, 2,2'-bis (2,4-dichlorophenyl)-
4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole / 4,4'-bis (diethylamino) benzophenone, 2,2'-bis (2,4-dibromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'
-Biimidazole / 4,4'-bis (diethylamino)
Benzophenone / 2-benzyl-2-dimethylamino-
1- (4-morpholinophenyl) butan-1-one,
2,2′-bis (2,4-dibromophenyl) -4,
4 ′, 5,5′-tetraphenyl-1,2′-biimidazole / 4,4′-bis (diethylamino) benzophenone / 1-hydroxycyclohexylphenyl ketone,
2,2'-bis (2,4,6-trichlorophenyl)-
4,4 ', 5,5'-Tetraphenyl-1,2'-biimidazole / 4,4'-bis (dimethylamino) benzophenone / 1-hydroxycyclohexylphenyl ketone / 2-mercaptobenzothiazole.

Solvent The radiation-sensitive composition for a color filter of the present invention may contain a solvent. As the solvent,
Dispersing or dissolving the components (A), (B), (C) and (D), and other additive components, if desired,
In addition, as long as it does not react with these components and has appropriate volatility, it can be appropriately selected and used.
Examples of such a solvent include glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, and ethylene glycol mono-n-butyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol Monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n
Ethylene glycol monoalkyl ether acetates such as -butyl ether acetate; diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether and diethylene glycol mono-n-butyl ether; propylene glycol monomethyl ether acetate; Propylene glycol monoalkyl ether acetates such as propylene glycol monoethyl ether acetate; other ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, and the like Ketones; alkyl lactates such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3- Methyl ethoxypropionate, ethyl 3-ethoxypropionate,
Ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-
Methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate , Ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyrate
Other esters such as butyl, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate and ethyl 2-oxobutanoate; and aromatic hydrocarbons such as toluene and xylene. it can. These solvents can be used alone or in combination of two or more.

Further, together with the solvent, benzyl ethyl ether, di-n-hexyl ether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, Diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate,
High boiling solvents such as propylene carbonate and ethylene glycol monophenyl ether acetate can also be used in combination. These high-boiling solvents can be used alone or in combination of two or more.

Among the above solvents, from the viewpoints of solubility, pigment dispersibility, coatability, etc., ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl 2-hydroxypropionate, 3-methyl-
3-methoxybutyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3
-Ethyl ethoxypropionate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, i-propyl butyrate, ethyl butyrate, n-butyl butyrate, ethyl pyruvate, etc. Γ-butyrolactone is preferred as the high boiling point solvent. The amount of the solvent to be used is generally 100 to 10,000 parts by weight, preferably 500 to 5,000 parts by weight, per 100 parts by weight of the alkali-soluble resin (B).

Other Additives The radiation-sensitive composition for a color filter of the present invention may further contain , if necessary, various additives other than the solvent. Examples of the additives include dispersing aids such as blue pigment derivatives and yellow pigment derivatives such as copper phthalocyanine derivatives; fillers such as glass and alumina; polyvinyl alcohol, polyethylene glycol monoalkyl ethers, and poly (fluoroalkyl acrylate). And the like; nonionic surfactants, cationic surfactants, anionic surfactants and other surfactants; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N -(2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane , 3-glycidoxypropyl meth Dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropyl methyl dimethoxy silane, 3-chloropropyl trimethoxysilane, 3
An adhesion promoter such as methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane;
Antioxidants such as 2,2-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butylphenol; 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) UV absorbers such as -5-chlorobenzotriazole and alkoxybenzophenone; and aggregation inhibitors such as sodium polyacrylate.

The method for forming a color filter Next, using the color filter radiation-sensitive composition of the present invention, a method for forming a color filter. First, a light-shielding layer is formed so as to partition a portion where a pixel pattern is formed on the surface of a transparent substrate, and on this substrate,
For example, after applying a radiation-sensitive composition in which a red (A) colorant is dispersed, pre-baking is performed to evaporate the solvent to form a coating film. Next, after this coating film is exposed through a photomask, development processing is performed with an alkali developing solution to dissolve and remove unexposed portions of the coating film, and thereafter, post-baking is performed, so that the red-colored pixels are formed. A pixel array arranged in a predetermined pattern is formed. Thereafter, if necessary, use each composition in which a colorant of another color (for example, green or blue) is dispersed, and apply, pre-bake, expose, develop, post-process each composition in the same manner as described above. A color filter is obtained by baking and sequentially forming a pixel array of each color on the same substrate. As a transparent substrate used when forming a color filter, for example,
Glass, silicon, polycarbonate, polyester,
Aromatic polyamide, polyamide imide, polyimide, norbornene-based ring-opening polymer or hydrogenated product thereof can be used. These transparent substrates may be subjected to an appropriate pretreatment such as a chemical treatment with a silane coupling agent or the like, a plasma treatment, an ion plating, a sputtering, a gas phase reaction method, or a vacuum deposition, if desired. When applying the radiation-sensitive composition for a color filter of the first invention to a transparent substrate, an appropriate coating method such as spin coating, casting coating, and roll coating can be employed. The coating thickness is usually 0.1 to 10 μm as a film thickness after drying.
m, preferably 0.2 to 1.5 μm. As the radiation used when forming the color filter, visible light, ultraviolet light, far ultraviolet light, an electron beam, X-ray, or the like can be used, and radiation having a wavelength in the range of 190 to 450 nm is preferable. The exposure energy amount of the radiation is preferably 1 to 1000 mJ / cm ² . Examples of the alkaline developer include sodium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8, and the like.
-Diazabicyclo- [5.4.0] -7-undecene,
An aqueous solution such as 1,5-diazabicyclo- [4.3.0] -5-nonene is preferred. For example, a suitable amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkali developer. After the alkali development, the film is usually washed with water. As the alkali developing method,
A shower developing method, a spray developing method, a dip (immersion) developing method, a paddle (liquid puddle) developing method and the like can be applied, and the developing condition is preferably 5 to 300 seconds at room temperature. The color filter of the second invention thus formed is particularly suitably used for a color image pickup tube element, and is also useful for a color liquid crystal display device, a color sensor and the like.

[0059]

BEST MODE FOR CARRYING OUT THE INVENTION The radiation-sensitive composition for a color filter of the present invention essentially comprises (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a photopolymerization initiator. Although it is contained as a component, the following (i) to () are specific examples of particularly preferable compositions. (I) The component (B) comprises the carboxyl group-containing copolymer (I), and the component (D) comprises 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4).
-Ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2-bromophenyl) -4,
4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5 '
-Tetraphenyl-1,2'-biimidazole, 2,
2'-bis (2,4,6-trichlorophenyl) -4,
4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dibromophenyl)
-4,4 ', 5,5'-Tetraphenyl-1,2'-biimidazole and 2,2'-bis (2,4,6-tribromophenyl) -4,4', 5,5'- A radiation-sensitive composition for a color filter, comprising at least one member selected from the group consisting of tetraphenyl-1,2'-biimidazole. (Ii) Component (D) further comprises a benzophenone-based compound,
The radiation-sensitive composition for a color filter according to the above (i), comprising one or more components selected from the group consisting of an acetophenone-based compound and a thiazole-based curing accelerator.

(Iii) Carboxyl group-containing copolymer (I) is methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / polystyrene macromonomer Copolymer, methacrylic acid / benzyl methacrylate /
Polymethyl methacrylate macromonomer copolymer, methacrylic acid / styrene / benzyl methacrylate / N-
Phenylmaleimide copolymer, methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polystyrene macromonomer copolymer, methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / amber Mono (2-acryloyloxyethyl) acid / styrene / benzyl methacrylate / N-phenylmaleimide copolymer, methacrylic acid / M
-5300 / styrene / benzyl methacrylate / N-
The color filter according to (i) or (ii), which is at least one copolymer selected from the group consisting of phenylmaleimide copolymer and methacrylic acid / styrene / benzyl methacrylate / glycerol monomethacrylate / N-phenylmaleimide copolymer. Radiation-sensitive composition for use. (Iv) Component (C) is trimethylolpropane triacrylate, pentaerythritol tetraacrylate,
(I), (ii) or (ii), which is at least one selected from the group consisting of dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate and succinic acid-modified pentaerythritol triacrylate.
i) The radiation-sensitive composition for a color filter.

(V) The total amount of tetrachlorophthalic acid-based impurities in the component (A) is 400 ppm or less, more preferably 300 ppm or less, and particularly preferably 200 ppm or less.
pm or less, especially 150 ppm or less,
(Ii) The radiation-sensitive composition for a color filter according to (iii) or (iv). (Vi) The above (i), (ii), (iii), (i) wherein the green organic pigment (a) in the component (A) contains Pigment Green 7
The radiation-sensitive composition for a color filter according to (v) or (v).

Hereinafter, embodiments of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these embodiments.

EXAMPLE 1 CI Pigment Green 7 was used as a green organic pigment (a).
(Commercially available product) was a pigment (hereinafter, referred to as "green organic pigment (a1)") purified by the above method (c) using pure water as a washing solvent. (A) 80 parts by weight of a 83/17 (weight ratio) mixture of a green organic pigment (a1) and CI Pigment Yellow 83 (commercially available) as a component;
50 parts by weight of a methacrylic acid / benzyl methacrylate / polystyrene macromonomer copolymer (copolymerization weight ratio = 25/65/10, Mw = 55,000) as the component (B), and dipentaerythritol pentaacrylate 40 as the component (C) Parts by weight, 10 parts by weight of 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 10 parts by weight of 4,4'-bis (diethylamino) benzophenone as component (D) And 800 parts by weight of ethylene glycol monoethyl ether acetate as a solvent, to prepare a solution of the radiation-sensitive composition. Next, a light-shielding layer is provided on the surface of a transparent substrate made of soda glass on which a silica (SiO ₂ ) film for preventing elution of sodium ions from being formed is formed so as to partition a portion where a pixel pattern is formed. The solution was applied using a coater, and prebaked at 90 ° C. for 2 minutes to form a coating film having a thickness of 2.0 μm. Then
After the substrate was cooled, the coating film was exposed to ultraviolet light of 100 mJ / cm ² including light of wavelengths of 365 nm, 405 nm and 436 nm through a photomask using a high-pressure mercury lamp. Thereafter, the substrate is immersed in a 0.1% by weight aqueous solution of tetramethylammonium hydroxide at 25 ° C. for 1 minute to perform a development process, washed with ultrapure water, air-dried, and further post-baked at 180 ° C. for 30 minutes. Was performed to produce a pixel array on which a green pixel pattern having a size of 20 μm × 20 μm on each side was formed. Evaluation Results Tetrachlorophthalic acid-based impurities in the coloring agent used here were measured by liquid chromatography, and the total of tetrachlorophthalic acid and tetrachlorophthalic anhydride was 56 ppm, and the amount of tetrachlorophthalimide was 3 ppm.
At 7 ppm, these totaled 93 ppm. Observation of the obtained pixel array with an optical microscope revealed that no dropout or peeling was observed in the pixel pattern, and that the mechanical strength after film formation was excellent, and that the obtained pixel had good adhesion to the substrate and pattern shape. It was good. Further, a display panel was manufactured using the obtained pixel array, and the burn-in was evaluated by the following procedure. No burn-in occurred.

Evaluation of Burn-in Liquid Crystal: A nematic liquid crystal (trade name: ZLI-5081, manufactured by Merck Japan Ltd.) composed of a fluorobiphenyl derivative was used. Production of liquid crystal display element: 1 cm ² patterned on one side of a glass substrate
Is formed, a commercially available liquid crystal aligning agent for active matrix is applied on the ITO film by using a spinner, and then dried at 180 ° C. for 1 hour to form a film having a thickness of 6 μm.
A 00 ° coating was formed. After a patterned 1 cm ² ITO film was formed on a color filter formed using the liquid composition of each example, a coating film of a liquid crystal aligning agent was formed on the ITO film in the same manner as described above. . After a patterned 1 cm ² ITO film was formed on a color filter formed using the liquid composition of each comparative example, a coating film of a liquid crystal aligning agent was formed on the ITO film in the same manner as described above. . After forming an ITO film (continuous film) on one side of a glass substrate, a coating film of a liquid crystal aligning agent was formed on the ITO film in the same manner as described above. Next, a rubbing treatment was performed on the surface of the coating film on each substrate obtained by using a rubbing machine provided with a roll wound with a rayon cloth to form a liquid crystal alignment film. The rubbing condition at that time was a roll rotation speed of 400
rpm, the stage movement speed was 3 cm / sec, and the push-in length of the hair foot was 0.4 mm. Of the substrates on which the liquid crystal alignment film has been formed in this way, or each of the substrates that have been subjected to the processing, are combined with the substrates that have been subjected to the processing to form a set of two substrates. After applying an epoxy resin-based adhesive containing a silica gel columnar spacer with a diameter of 5.5 μm to the part by screen printing, the gap between the two substrates is adjusted so that the rubbing directions of the liquid crystal alignment films cross at 90 degrees. The substrates were opened and opposed to each other, and were pressed so that the outer edges of the substrates were in contact with each other to cure the adhesive. Next, for each set, a nematic liquid crystal “ZLI-5081” is injected and filled into a cell gap defined by an inner surface of two substrates and a cured layer of an adhesive, and then the injection hole is sealed. A liquid crystal cell was manufactured. Thereafter, a polarizing plate was attached to the outer surface of the liquid crystal cell so that the polarization direction of the polarizing plate coincided with the rubbing direction of the liquid crystal alignment film on each substrate, thereby producing a liquid crystal display device.

Evaluation method for burn-in: Function generator WAVE
FACTRY (NF ELECTRONIC INSTRUMENT) is connected,
A rectangular wave voltage of AC 3 V and DC 1 V is applied, and the liquid crystal display element is heated at 70 ° C. for 1 hour in that state. After heating the liquid crystal display element, cut off the square wave voltage
After allowing to cool for 30 minutes, a rectangular wave voltage of 30 Hz and a halftone voltage is applied by the function generator. Using an LCD EVALUATION SYSTEM (manufactured by Photal), a flicker waveform obtained from the flicker appearance pulse data related to the display of the liquid crystal display element was converted to an oscilloscope 5460.
0A OSCILLOSCOPE (made by HEWLETT PACKARD)
FFT analyzer R9211C FFT SERVO ANALYZER (ADVANTES
(Company T) to measure the flicker strength. An offset voltage is applied by the function generator, and an offset voltage at a point where the flicker waveform completely disappears is measured to obtain a flicker elimination voltage (that is, a burn-in removal voltage). The degree of burn-in increases as the flicker elimination voltage increases. If the flicker elimination voltage is less than 50 mV, burn-in does not occur, but if it is 50 mV or more, burn-in occurs. Therefore, when the flicker elimination voltage is less than 50 mV, it is determined that no burn-in occurs and the flicker elimination voltage is 50 mV.
The above case was considered to cause image sticking.

[0065]

According to the radiation-sensitive composition for a color filter of the present invention, the pixel pattern does not drop or peel off at the time of development. It is possible to provide a color filter which has excellent mechanical strength after film formation, excellent adhesion to the substrate of the pixel, and favorable pattern shape. Therefore, the radiation-sensitive composition for a color filter of the present invention is suitably used particularly for a color image pickup tube element, and is also useful for a color liquid crystal display device, a color sensor and the like.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Takayoshi Koyama 2--11-24 Tsukiji, Chuo-ku, Tokyo Inside JSR Co., Ltd. (72) Inventor Takeshi Watanabe 2-11-24 Tsukiji, Chuo-ku, Tokyo JSR F term in the company (reference) 2H025 AA00 AA03 AA04 AA13 AA14 AB13 AC01 AD01 BC13 BC42 CA00 CC11 CC20 2H048 BA45 BA47 BA48 BB02 BB14 BB15 BB42 BB46

Claims (2)

[Claims] 1. A radiation-sensitive composition for a color filter, comprising (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a photopolymerization initiator. , The component (A) contains a green organic pigment, and the amounts of tetrachlorophthalic acid, tetrachlorophthalic anhydride and tetrachlorophthalimide in the component (A) are analyzed, and their total is 500 ppm or less. Radiation-sensitive composition for color filters. 2. The radiation-sensitive composition for a color filter according to claim 1, wherein the green organic pigment in the component (A) contains Pigment Green 7.