JP2003167339A - Radiation sensitive coloring composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation sensitive coloring composition that ensures satisfactory curing of exposed portions even at a high concentration of a pigment, has good developability, is excellent in solubility of a photopolymerization initiator, has high sensitivity and is excellent also in storage stability. <P>SOLUTION: In the radiation sensitive coloring composition having a radiation sensitive compound, a bonding resin, a colorant and a solvent, the radiation sensitive compound contains a photopolymerization initiator having a specified structure. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a radiation-sensitive coloring composition, and more particularly to a radiation-sensitive coloring composition suitable for producing a color filter used in a liquid crystal display device or a solid-state image pickup device.

[0002]

2. Description of the Related Art As a method for producing a color filter used in a liquid crystal display device or a solid-state image pickup device, a dyeing method,
Printing methods, electrodeposition methods and pigment dispersion methods are known.

Among these, the pigment dispersion method is a photolithography method using a radiation-sensitive coloring composition in which pigment particles are dispersed or dissolved in a component solution mainly composed of a radiation-sensitive compound and a binder resin. This is a method of producing a color filter. Since this method is relatively stable to light and heat due to the use of pigments and is patterned by the photolithography method, it has sufficient positional accuracy and is suitable for the production of color filters for large screens and high-definition color displays. Is the way.

On the other hand, various photopolymerization initiators have been proposed as the radiation-sensitive component of the radiation-sensitive composition for resists. Among these, photopolymerization initiators that are widely used in radiation-sensitive coloring compositions for producing color filters include (4-morpholinophenyl) benzylbutanone (see JP-A-4-340965), 2-
(P-Methoxystyryl) -4,6-bis (trichloromethyl) -S-triazine (see JP-A-6-201913), diethylthioxanthone (JP-A-6-51).
499), Irgacure-369, -65
Examples thereof include benzoyl compounds such as 1, and -907 (trade names, manufactured by Ciba-Geigy).

In particular, many photosensitive compositions containing a triazine compound as a photopolymerization initiator have been known so far, for example, JP-A-9-203806 and 11-.
No. 38613, No. 11-109614, No. 1
Nos. 1-258790, 11-326624, and 2000-47022 are mentioned. Among them, JP-A-11-38613 discloses s-triazine-based photopolymerization having a specific structure. Radiation-sensitive coloring compositions containing an initiator are disclosed.

In order to secure high color purity in recent years, it has been desired to develop a color filter having a high pigment concentration, and therefore, a radiation-sensitive coloring composition which gives a sufficiently cured resist even when the pigment concentration is high has been developed. Is desired. Also,
There is a demand for a radiation-sensitive coloring composition having excellent solubility as a photopolymerization initiator, high sensitivity, and excellent storage stability. However, under the present circumstances, the photopolymerization initiators that are generally used for producing color filters cannot sufficiently meet the above demands and it is not clear what kind of photopolymerization initiator should be used.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a radiation-sensitive coloring composition that is suitable for use in manufacturing color filters. More specifically, the object of the present invention is to provide a radiation-sensitive coloring composition in which the exposed portion is sufficiently cured even at a high pigment concentration and which has good developability. Another object of the present invention is to provide a radiation-sensitive coloring composition having excellent solubility as a photopolymerization initiator, high sensitivity, and excellent storage stability.

[0008]

DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted research to achieve the above-mentioned object, and have studied a radiation-sensitive coloring composition, particularly a radiation-sensitive coloring composition for producing a color filter by a pigment dispersion method. As a result of extensive studies as a photopolymerization initiator,
It was found that a novel halogenated triazine compound as a photopolymerization initiator having a specific structure can effectively achieve the object of the present invention. That is, according to the present invention, it was found that the above object of the present invention can be achieved by the following constitution.

(1) In a radiation-sensitive coloring composition containing a radiation-sensitive compound, a binder resin, a colorant, and a solvent, the radiation-sensitive compound is represented by the following formulas (I) and (II).
A radiation-sensitive coloring composition comprising at least one photopolymerization initiator selected from the group consisting of compounds represented by:

[0010]

[Chemical 2]

[Wherein R ₁ is a hydrogen atom or a carbon number of 1 to 4]
Represents an alkyl group, X represents F, Cl, Br or I, n represents an integer of 1 to 5, and m represents 2 or 3. (2) The colorant is a pigment, the average particle size of which is 0.01 μm to 0.1 μm, and the concentration of the colorant in the radiation-sensitive coloring composition is 30% by mass in terms of solid content. The radiation-sensitive coloring composition according to (1) above, which is as described above. (3) The binder resin has a carboxyl group and is 30 to 2
The radiation-sensitive coloring composition according to the above (1) or (2), which has an acid value of 00.

The halogenated triazine-based photopolymerization initiator having the specific structure represented by the above (I) to (II) is
The radiation-sensitive coloring composition, particularly the radiation-sensitive coloring composition for producing a color filter by a pigment dispersion method has not been used so far, and by using the photopolymerization initiator, the above-mentioned object of the present invention, For example, even at a high pigment concentration, the radiation-sensitive coloring composition of the present invention is sufficiently cured by exposure, has sufficient developability, and has excellent solubility as a photopolymerization initiator. Further, since it can be evenly distributed at a higher concentration in the coating film, the sensitivity becomes higher, and even when stored at a low temperature such as 5 to 10 ° C., crystals do not precipitate and the storage stability (pot life) is also improved. Excel. Further, since a black colorant such as carbon black which easily absorbs the irradiated radiation is used in the black matrix, it has been necessary to add a large amount of the conventional photopolymerization initiator to the composition. When the halogenated triazine compound having the specific structure of the present invention is used, sufficient sensitivity can be obtained even when the amount used is smaller than before, and further higher sensitivity can be achieved. Further, the halogenated triazine compound of the present invention, when used as a photopolymerization initiator of the radiation-sensitive coloring composition, its maximum absorption is on the shorter wavelength side than conventionally known photopolymerization initiators, so that it is a color filter. Since it can be activated by the shortest-wavelength emission line (j-line) of a high-pressure mercury lamp, which is an exposure light source generally used in the industry, the near-ultraviolet region (g
High sensitivity can be maintained even with a composition in which a pigment such as carbon black that strongly shields the bright lines of the lines (h-line, i-line) is used as a colorant.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The radiation-sensitive coloring composition of the present invention comprises a radiation-sensitive compound, a binder resin, a pigment, and a solvent. The radiation-sensitive compound contains a photopolymerization initiator and a radiation-sensitive polymerization component.

1. Photopolymerization Initiator First, the photopolymerization initiator which is a radiation-sensitive component will be described. In the present invention, at least one of the compounds represented by the above formulas (I) and (II) is used as the photopolymerization initiator. In the general formulas (I) and (II), the alkyl group having 1 to 4 carbon atoms represented by R ₁ is methyl group, ethyl group, n- or i-propyl group, n-, i- or t-.
A butyl group etc. can be mentioned. R ₁ is preferably a hydrogen atom or a methyl group. X represents F, Cl, Br or I. n represents an integer of 1 to 5, preferably 1 or 2. m represents 2 or 3. The above formulas (I) and (I
Among I), the compound represented by the formula (I) is particularly preferable, and among them, a halogenated triazine compound in which X is Cl and R ₁ is H is particularly preferable for achieving the object of the present invention.

In the present invention, preferred examples of the above photopolymerization initiator include those shown by the following (1) to (3).

[0016]

[Chemical 3]

The above compounds can be used alone or in combination of two or more. The compounds represented by the above formulas (I) and (II) are known per se, but the radiation-sensitive coloring composition, particularly the radiation-sensitive coloring for producing a color filter by a pigment dispersion method. No example has ever been used in a composition.

In the present invention, it is essential to use at least one of the compounds represented by the above formulas (I) to (II) as a photopolymerization initiator. “Other photopolymerization initiator”) can be used together. The following may be mentioned as other photopolymerization initiators that may be used in combination. (A) at least one active halogen compound selected from halomethyloxadiazole compounds and halomethyl-s-triazine compounds (provided that the above formulas (I) to (II)
And a 3-aryl-substituted coumarin compound. (B) At least one loffin dimer.

As the halomethyl-s-triazine compound which can be used in combination with the photopolymerization initiator of the present invention, the following general formula (VIII) described in JP-B-59-1281 is used.
A vinyl-halomethyl-s-triazine compound represented by the formula: 2- (naphth-1-yl) -4,6- represented by the following general formula (IX) described in JP-A-53-133428.
A bis-halomethyl-s-triazine compound and 4- (p-aminophenyl) -2 represented by the following general formula (X),
6-di-halomethyl-s-triazine compounds can be mentioned.

[0020]

[Chemical 4]

In the formula (VIII), Q represents Br or Cl, and Y
Is _{-C (Q) 3, -NH 2} , -NHR, -N (R) 2 , or -OR (wherein, R is phenyl or an alkyl group, Q is as defined above.), W is optionally An aromatic or heterocyclic nucleus substituted by or a compound represented by the following general formula (VIIIA).

[0022]

[Chemical 5]

In formula (VIIIA), Z is --O-- or --S-- and R has the same meaning as above.

In the formula (IX), X represents --Br or --Cl,
m and n are integers of 0 to 3, and R'is represented by the following general formula (IXA).

[0025]

[Chemical 6]

In the formula (IXA), R ₁ is H or OR _c (R _c represents an alkyl, cycloalkyl, alkenyl or aryl group) and R ₂ is —Cl, —Br or alkyl, alkenyl, aryl or alkoxy. Represents a group.

In the formula (X), R ₁ and R ₂ are --H, an alkyl group,
It is represented by a substituted alkyl group, an aryl group, a substituted aryl group, or the following general formulas (XA) and (XB). R _3, R ₄ represents -H, a halogen atom, an alkyl group, an alkoxy group. X is-
Cl or -Br is shown, and m and n represent 0, 1 or 2.

[0028]

[Chemical 7]

In the above general formulas (XA) and (XB), R ₅ , R ₆ and R ₇
Represents an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group. Examples of the substituent in the substituted alkyl group and the substituted aryl group include an aryl group such as a phenyl group, a halogen atom, an alkoxy group, a carboalkoxy group, a carboaryloxy group, an acyl group, a nitro group, a dialkylamino group and a sulfonyl derivative. Is mentioned.

In the formula (X), R ₁ and R ₂ may form a heterocyclic ring composed of a non-metal atom together with the nitrogen atom to which it is bonded, and in this case, the heterocyclic ring is as shown below. Can be mentioned.

[0031]

[Chemical 8]

Specific examples of general formula (VIII) include:
4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl-1,3
-Butadienyl) -s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine and the like.

Specific examples of the general formula (IX) include 2-
(Naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-methoxy-naphth-1)
-Yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-ethoxy-naphth-1-yl)-
4,6-bis-trichloromethyl-s-triazine, 2
-(4-butoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2
-Methoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [4-
(2-Ethoxyethyl) -naphth-1-yl] -4,6
-Bis-trichloromethyl-s-triazine, 2- [4
-(2-butoxyethyl) -naphth-1-yl] -4,
6-bis-trichloromethyl-s-triazine, 2-
(2-Methoxy-naphth-1-yl) -4,6-bis-
Trichloromethyl-s-triazine, 2- (6-methoxy-5-methyl-naphth-2-yl) -4,6-bis-
Trichloromethyl-s-triazine, 2- (6-methoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (5-methoxy-naphtho-
1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- ( 6-ethoxy-naphth-2-yl) -4,6
-Bis-trichloromethyl-s-triazine, 2-
(4,5-Dimethoxy-naphth-1-yl) -4,6-
Examples thereof include bis-trichloromethyl-s-triazine.

Specific examples of the general formula (X) include 4- [p-
N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-p-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-Di (trichloromethyl) -s-triazine, 4- [p-N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o -Methyl-
p-N, N-di (chloroethyl) aminophenyl]-
2,6-di (trichloromethyl) -s-triazine, 4
-(P-N-chloroethylaminophenyl) -2,6-
Di (trichloromethyl) -s-triazine, 4- (p-
N-ethoxycarbonylmethylaminophenyl) -2,
6-di (trichloromethyl) -s-triazine, 4-
[P-N, N-di (phenyl) aminophenyl] -2,
6-di (trichloromethyl) -s-triazine, 4-
(P-N-chloroethylcarbonylaminophenyl)-
2,6-di (trichloromethyl) -s-triazine, 4
-[P-N- (p-methoxyphenyl) carbonylaminophenyl] 2,6-di (trichloromethyl) -s-triazine, 4- [m-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2 , 6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN,
N-di (ethoxycarbonylmethyl) aminophenyl]
-2,6-di (trichloromethyl) -s-triazine,
4- [m-chloro-p-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-p-
N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-p
-N, N-di (ethoxycarbonylmethyl) aminophenyl-2,6-di (trichloromethyl) -s-triazine, 4- [o-fluoro-p-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-p
-N, N-di (chloroethyl) aminophenyl] -2,
6-di (trichloromethyl) -s-triazine, 4-
[O-chloro-p-N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-fluoro-p-N, N-di (chloroethyl) Aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN,
N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-p-N, N-di (chloroethyl) aminophenyl] -2,6-di (Trichloromethyl) -s-triazine, 4- [m-fluoro-p-N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo -P-N-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-p-N-ethoxycarbonylmethylaminophenyl) -2,6-di ( Trichloromethyl) -s-triazine, 4- (m-fluoro-p-N-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4 (O-Bromo-p-N-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-chloro-p-N-ethoxycarbonylmethylaminophenyl) -2, 6-di (trichloromethyl) -s-triazine, 4- (o-fluoro-p-N-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo -P-N-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-p-N
-Chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro-p
-N-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-p-N-chloroethylaminophenyl) -2,6-di (trichloromethyl)- s-triazine, 4- (o-chloro-p-N-chloroethylaminophenyl) -2,6
-Di (trichloromethyl) -s-triazine, 4- (o
-Fluoro-p-N-chloroethylaminophenyl)-
2,6-di (trichloromethyl) -s-triazine and the like can be mentioned.

The following sensitizers can be used in combination with these initiators. Specific examples thereof include benzoin, benzoin methyl ether, benzoin, 9-fluorenone,
2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone, 2-ethyl-9-anthrone, 9,10-anthraquinone, 2-ethyl-9,10-. Anthraquinone, 2-
t-Butyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone, xanthone, 2-methylxanthone, 2-methoxyxanthone, 2-methoxyxanthone, thioxanthone, benzyl, dibenzalacetone, p- (Dimethylamino) phenyl styryl ketone, p- (dimethylamino) phenyl-p-methylstyryl ketone, benzophenone, p- (dimethylamino) benzophenone (or Michler's ketone), p-
(Diethylamino) benzophenone, benzoanthrone and the like and benzothiazole compounds described in JP-B-51-48516.

The 3-aryl-substituted coumarin compound that can be used in combination with the photopolymerization initiator of the present invention is a compound represented by the following general formula (XI).

[0037]

[Chemical 9]

In the general formula (XI), R ₈ is a hydrogen atom and has 1 carbon atom.
~ 8 alkyl group, an aryl group having 6 to 10 carbon atoms (preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group), R ₉ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, carbon Formula 6-10 aryl group, group represented by the following general formula (XIA) (preferably methyl group, ethyl group, propyl group, butyl group, group represented by general formula (XIA), particularly preferably general formula (XIA) ) Represents a group).

[0039]

[Chemical 10]

R ₁₀ and R ₁₁ are each a hydrogen atom and have 1 carbon atom.
To 8 alkyl groups (eg, methyl group, ethyl group, propyl group, butyl group, octyl group), C1 to C8 haloalkyl groups (eg, chloromethyl group, fluoromethyl group, trifluoromethyl group, etc.), carbon number 1 To 8 alkoxy groups (eg, methoxy group, ethoxy group, butoxy group), optionally substituted aryl groups having 6 to 10 carbon atoms (eg, phenyl group), amino groups, —N (R ₁₆ ) (R ₁₇ ), Represents halogen (for example, -Cl, -Br, -F). Preferred are a hydrogen atom, a methyl group, an ethyl group, a methoxy group, a phenyl group, —N (R ₁₆ ) (R ₁₇ ), and —Cl. R ₁₂ represents an optionally substituted aryl group having 6 to 16 carbon atoms (eg, phenyl group, naphthyl group, tolyl group, cumyl group). As the substituent, an amino group, —N (R ₁₆ ) (R ₁₇ ), and a carbon number of 1 to
8 alkyl groups (eg methyl group, ethyl group, propyl group, butyl group, octyl group), haloalkyl groups having 1 to 8 carbon atoms (eg chloromethyl group, fluoromethyl group, trifluoromethyl group, etc.), 1 to carbon atoms 8 alkoxy group (eg, methoxy group, ethoxy group, butoxy group), hydroxy group, cyano group, halogen (eg, -Cl, -B)
r, -F). R ₁₃ , R ₁₄ , R ₁₆ and R ₁₇ each represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, octyl group). R ₁₃ and R ₁₄ and R ₁₆ and R ₁₇ are also bonded to each other with a nitrogen atom to form a heterocycle (eg piperidine ring,
A piperazine ring, a morpholine ring, a pyrazole ring, a diazole ring, a triazole ring, a benzotriazole ring, etc.) may be formed. R ₁₅ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, octyl group), an alkoxy group having 1 to 8 carbon atoms (eg, methoxy group, ethoxy group, butoxy group) ), An optionally substituted aryl group having 6 to 10 carbon atoms (for example, a phenyl group), an amino group, N (R ₁₆ ) (R ₁₇ ), and a halogen (for example, —Cl, —Br, —F). Zb represents = O, = S or = C (R ₁₈ ) (R ₁₉ ). Preferably = O, =
S, ═C (CN) ₂ , and particularly preferably ═O.
R ₁₈ and R ₁₉ are a cyano group, —COOR ₂₀ , and —C, respectively.
Represents OR ₂₁ . R ₂₀ and R ₂₁ are each an alkyl group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, octyl group), a haloalkyl group having 1 to 8 carbon atoms (eg, chloromethyl group, fluoromethyl group, Trifluoromethyl group) and an optionally substituted aryl group having 6 to 10 carbon atoms (eg, phenyl group).

A particularly preferred 3-aryl-substituted coumarin compound is represented by the general formula (XII) {(s-triazine-2
-Yl) amino} -3-arylcoumarin compounds.

[0042]

[Chemical 11]

In the general formula (XII), R _{12 to} R ₁₅ have the same meanings as described above.

The (b) loffin dimer means a 2,4,5-triphenylimidazolyl dimer composed of two loffin residues, and its basic structure is shown below.

[0045]

[Chemical 12]

Specific examples thereof include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2
-(O-Fluorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-methoxyphenyl) -4,
5-diphenylimidazolyl dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (2 , 4-Dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2
Examples include-(p-methylmercaptophenyl) -4,5-diphenylimidazolyl dimer.

In the present invention, other known ones can be used in addition to the above initiators. US Pat. No. 2,36
Vicinal polyketolualdonyl compounds disclosed in US Pat. No. 7,367,661.
And an alcohol compound having a carbonyl group at the α-position disclosed in US Pat. No. 2,367,670, an acyloin ether disclosed in US Pat. No. 2,448,828, US Pat. , 722, 512, and aromatic acyloin compounds substituted at the α-position with a hydrocarbon group, disclosed in U.S. Pat. Nos. 3,046,127 and 2,951,758. A polynuclear quinone compound, a combination of triallyl imidazole dimer / p-aminophenyl ketone disclosed in US Pat. No. 3,549,367, JP-B-51-4.
A benzothiazole-based compound / trihalomethyl-s-triazine-based compound disclosed in Japanese Patent No. 8516.

In the radiation-sensitive coloring composition of the present invention,
The amount of the photopolymerization initiator represented by the formula (I) and / or (II), which is an essential component, is 5 to 100% by mass, particularly 20 to 10% by mass based on the total amount of the photopolymerization initiator. 100 mass% is preferable. Further, the total amount of the photopolymerization initiator used is preferably 1 to 30% by mass, more preferably 3 to 15% by mass, based on the radiation-sensitive polymerization component. The use of excess photopolymerization initiator lowers the molecular weight of the polymer formed by photopolymerization and weakens the film strength, and the initiator left in the film without being decomposed by exposure deteriorates the light resistance. It is not preferable.

2. Radiation-sensitive Polymerizable Component Next, the radiation-sensitive polymerizable component used in the radiation-sensitive colored composition of the present invention will be described. The radiation-sensitive polymerization component is preferably a compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher at normal pressure, and more preferably a tetrafunctional or higher functional acrylate compound. . It has at least one addition-polymerizable ethylenically unsaturated group and has a boiling point of 100 at normal pressure.
Examples of the compound having a temperature of ℃ or higher include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate,
Trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) Acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin,
A poly (meth) acrylate of pentaerythritol or dipentaerythritol obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as trimethylolethane or dipentaerythritol, or a poly (meth) acrylate of pentaerythritol, JP-B-48.
-41708, JP-B-50-6034, and JP-A-51-37193, urethane acrylates such as those described in JP-A-48-64183.
JP-B, JP-B-49-43191, JP-B-52-
Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates, which are reaction products of epoxy resin and (meth) acrylic acid, described in 30490 can be mentioned. Furthermore, the Journal of Japan Adhesion Association, Vol. 20, No. 7, 300-30
Those introduced as photocurable monomers and oligomers on page 8 can also be used.

Of these, a structure in which dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and their acryloyl groups have an ethylene glycol or propylene glycol residue therebetween is preferable. These radiation-sensitive polymerization components can be used alone or in combination of two or more. The amount of these radiation-sensitive polymerization components used is preferably 5 to 90% by mass, more preferably 10 to 50% by mass, based on the total solid content of the radiation-sensitive coloring composition.

The radiation-sensitive compound, including the photopolymerization initiator, the radiation-sensitive polymerization component, and the sensitizer optionally used, is contained in an amount of 10 to 90% by mass, particularly preferably 10 to 90% by mass, based on the solid content of the entire composition. The proportion is preferably 30 to 80% by mass.

3. Binder Resin Next, the binder resin blended in the radiation-sensitive coloring composition of the present invention will be described. The binder resin usable in the present invention is preferably a linear organic high molecular polymer, which is soluble in an organic solvent and can be developed with a weak alkaline aqueous solution. Examples of such a linear organic polymer include polymers having a carboxylic acid in the side chain, for example, JP-A-59-44615, JP-B-54-34327, and JP-B-58-12.
577, JP-B-54-25957, JP-A-59-53836, and JP-A-59-71048, a methacrylic acid copolymer, an acrylic acid copolymer, and itaconic acid. There are copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, and the like, and similarly, acidic cellulose derivatives having a carboxylic acid in the side chain. In addition to these, a polymer having an acid anhydride added to a polymer having a hydroxyl group is also useful. Among these, benzyl (meth) acrylate / (meth) acrylic acid copolymers and benzyl (meth) acrylate / (meth) acrylic acid / and multi-component copolymers with other monomers are particularly preferable. In addition, 2-hydroxyethyl methacrylate, polyvinylpyrrolidone, polyethylene oxide, polyvinyl alcohol and the like are also useful as the water-soluble polymer. In addition, alcohol-soluble nylon and polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin are also useful for increasing the strength of the cured film. These polymers can be mixed in any amount.

Further, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / described in JP-A-7-140654.
Methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer Examples thereof include polymers and 2-hydroxyethyl methacrylate / polystyrene macromonomers / benzyl methacrylate / methacrylic acid copolymers.

Further, as a binder resin which can be used, the following general formula described in JP-A-9-258445 is used.
The polyvinyl acetal resin or modified polyvinyl acetal resin represented by (XIII) can be mentioned.

[0055]

[Chemical 13]

However, in the general formula (XIII), R ₁ is an alkyl group which may have a substituent or a hydrogen atom, R ₂ is an alkyl group which does not have a substituent, and R ₃ is a fatty acid having a carboxylic acid group. Group or aromatic hydrocarbon group, R ₄ is at least 1
Shows an aliphatic or aromatic hydrocarbon group having one hydroxyl group or a nitrile group and optionally having another substituent, and n1, n2, n3, n4 and n5 are mol% of each repeating unit. The ranges are shown below. n1 = 5
85, n2 = 1-60, n3 = 1-20, n4 = 0-6
0, n5 = 0-10.

The binder resin preferred in the present invention has a carboxyl group, particularly in the side chain, and particularly benzyl methacrylate-methacrylic acid copolymer is preferred. From the viewpoint of maintaining good developability and coatability after exposure, those having an acid value of 30 to 200 are preferable.

The total amount of the binder resin of the present invention is 5 to 80% by mass based on the total solid components of the radiation-sensitive coloring composition. It is preferably 20 to 60% by mass. The total amount of binder resin is 5
If the amount is less than 80% by mass, the film strength will decrease,
If the amount is larger, the acid content is increased, so that it becomes difficult to control the solubility, and the pigment is relatively decreased, so that a sufficient image density cannot be obtained.

4. Colorant As the colorant contained in the radiation-sensitive coloring composition of the present invention, various pigments, dyes, and carbon black can be used alone or in combination of two or more.

As the pigment that can be used in the present invention, various conventionally known inorganic pigments or organic pigments can be used. Further, the pigment, whether it is an inorganic pigment or an organic pigment, preferably has a high transmittance in consideration of having a high transmittance, but in consideration of handling property, an average particle diameter of 0.01 μm is preferable.
To 0.1 μm, more preferably 0.01 μm to 0.05
A μm pigment is used. The inorganic pigment is a metal compound represented by a metal oxide, a metal complex salt or the like, and specifically, iron, cobalt, aluminum, cadmium, lead, copper,
Examples thereof include metal oxides such as titanium, magnesium, chromium, zinc and antimony, and complex oxides of the above metals.

Organic pigments include CIPigment Yellow 11, 24, 31, 53, 83, 93, 99, 10
8, 109, 110, 138, 139, 150, 151, 154, 167, 185, 19
9; CIPigment Orange 36, 38, 43; CIPigment Red 105, 122, 149, 150, 155, 171, 175,
176, 177,209, 224,254; CIPigment Violet 19, 23, 32, 39; CIPigment Blue 1, 2, 15, 16, 22, 60, 66; CIPigment Green 7, 36, 37; CIPigment Brown 25, 28; CIPigment Black 1, 7; and the like.

In the present invention, particularly those having a basic N atom in the structural formula of the pigment can be preferably used. The pigments having these basic N atoms exhibit good dispersibility in the composition of the present invention. Although the cause has not been sufficiently clarified, it is presumed that the good affinity between the radiation-sensitive polymerization component and the pigment has an effect.

These organic pigments are used alone or in various combinations for increasing the color purity. A specific example is shown below.
As the red pigment, an anthraquinone pigment, a perylene pigment alone or a mixture of at least one of them with a disazo yellow pigment or an isoindoline yellow pigment is used. For example, as the anthraquinone pigment, C.I.
I. Pigment Red 177 and perylene pigments include C.I. I. Pigment Red 155, C.I. I. Pigment Red 224, and C.I. I.
Pigment Yellow 83 or C.I. I. Pigment Yellow 139 was mixed well. The mass ratio of the red pigment to the yellow pigment was 100: 5 to 100: 50. When the ratio is 100: 4 or less, the light transmittance from 400 nm to 500 nm cannot be suppressed and the color purity cannot be increased. When the ratio is 100: 51 or more, the dominant wavelength becomes shorter and the deviation from the NTSC target hue becomes large. In particular, the range from 100: 10 to 100: 30 was optimal.

As the green pigment, a halogenated phthalocyanine type pigment alone or a mixture with a disazo type yellow pigment or an isoindoline type yellow pigment may be used. I.
Pigment Green 7, 36, 37 and C.I. I. Pigment Yellow 83 or C.I. I. Pigment Yellow 13
Mixing with 9 was good. The mass ratio of the green pigment and the yellow pigment was 100: 40, which was better than 100: 5. 10
Below 0: 4, the light transmittance from 400 nm to 450 nm could not be suppressed and the color purity could not be increased. If the ratio is 100: 41 or more, the dominant wavelength becomes longer and NT
The deviation from the SC target hue became large. Especially 100:
The range of 100: 20 was optimal from 5.

As the blue pigment, a phthalocyanine pigment alone or a mixture with a dioxazine purple pigment is used. I. Pigment Blue 15: 6 and C.I.
I. Pigment Violet 23 was mixed well. The mass ratio of blue pigment to purple pigment is 1 from 100: 5.
00:50 was good. 400 below 100: 4
The light transmittance from nm to 420 nm could not be suppressed, and the color purity could not be increased. When it was 100: 51 or more, the dominant wavelength was longer and the deviation from the NTSC target hue was large. In particular, the range of 100: 5 to 100: 20 was optimal.

Further, by using a powdered processed pigment in which the above pigment is finely dispersed in an acrylic resin, a maleic acid resin, a vinyl chloride-vinyl acetate copolymer, an ethyl cellulose resin, etc., a pigment having good dispersibility and dispersion stability. A photosensitive resin containing can be obtained.

As the pigment for the black matrix,
Carbon black, titanium carbon, iron oxide, etc. may be used alone or in combination. Above all, when carbon black and titanium carbon are mixed and used, the mixing ratio is preferably in the range of 100: 5 to 100: 40 in terms of mass ratio. If it is less than 100: 5, the light transmittance in the long wavelength region becomes large, and if it exceeds 100: 40, there is a problem in the dispersibility of the composition.

The method of treating the pigment will be described below. Generally, these pigments are supplied after being dried by various methods after synthesis. Usually, it is dried from an aqueous medium and supplied as a powder body, but since water requires a large latent heat of vaporization to dry, a large amount of heat energy is applied to dry it into a powder. Therefore, the pigment usually forms an aggregate (secondary particle) in which primary particles are aggregated.

It is not easy to disperse the pigment forming such aggregates into fine particles. Therefore, it is preferable to treat the pigment with various resins in advance. Examples of these resins include the binder resins described above. As the treatment method, there are a flushing treatment and a kneading method using a kneader, an extruder, a ball mill, a two or three roll mill, or the like. Of these, the flushing process and the kneading method using a two- or three-roll mill are suitable for atomization.

The flushing treatment is usually a method in which an aqueous dispersion of a pigment and a resin solution dissolved in a solvent immiscible with water are mixed, the pigment is extracted from an aqueous medium into an organic medium, and the pigment is treated with a resin. . According to this method, since the pigment is not dried, aggregation of the pigment can be prevented and dispersion becomes easy. In a two- or three-roll mill, by mixing a pigment and a resin or a solution of a resin, and then applying a high shear (shearing force), the pigment and the resin are kneaded to coat the surface of the pigment with the resin. , A method of treating a pigment. The pigment particles aggregated in this process are dispersed from lower-order aggregates to primary particles.

In the present invention, a processed pigment previously treated with an acrylic resin, vinyl chloride-vinyl acetate resin, maleic acid resin, ethyl cellulose resin, nitrocellulose resin or the like can also be used conveniently. In the present invention, as a form of the processed pigment treated with the above various resins, a powder in which the resin and the pigment are uniformly dispersed,
A paste form, a pellet form, and a paste form are preferable. In addition, a gelled nonuniform mass of resin is not preferable. The colored dispersion thus obtained is mixed with a radiation-sensitive compound and provided as a radiation-sensitive coloring composition.

The concentration of the colorant in all solid components of the radiation-sensitive coloring composition of the present invention is not particularly limited, but is usually 5 to 80% by mass. In the case of the radiation-sensitive colored composition of the present invention, even if the colorant concentration is 30% by mass or more, sufficient curing proceeds by exposure, and the above effect is more apparent when the colorant concentration is 35% by mass or more. become. However, if it is used in an amount exceeding 80% by mass, another problem such as a background stain in the non-image area or a film residue is likely to occur.

In the present invention, conventionally known pigment dispersants and surfactants can be added for the purpose of improving the dispersibility of the pigment. Although many kinds of compounds are used as these dispersants, for example, a phthalocyanine derivative (commercial item EFKA-745 (manufactured by Efka)), Solsperse 5000 (manufactured by Zeneca); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) ), (Meth) acrylic acid-based (co) polymer polyflow No. 75, No. 90, No. 9
5 (manufactured by Kyoeisha Oil and Fat Chemical Co., Ltd.) and W001 (manufactured by Yusho); cationic surfactants; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxy Nonionic surfactants such as ethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester; F-top EF301, EF303, EF352 (manufactured by Shin-Akita Kasei), Megafac F171, F172, F173 (Dainippon Nihon) Ink), Florard FC430, FC431
(Manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S382, SC-101, SC-102, SC-
103, SC-104, SC-105, SC-1068
Fluorine-based surfactants such as (made by Asahi Glass); W004, W0
05, W017 (manufactured by Yusho) and the like anionic surfactants;
EFKA-46, EFKA-47, EFKA-47E
A, EFKA polymer 100, EFKA polymer 40
0, EFKA polymer 401, EFKA polymer 450
Polymer dispersants such as (made by Morishita Sangyo), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (manufactured by San Nopco); Solspers 3000, 5000, 9000, 1200
0, 13240, 13940, 17000, 2400
Various sol sparse dispersants such as 0, 26000 and 28000 (manufactured by Zeneca Corporation);
1, F38, L42, L44, L61, L64, F6
8, L72, P95, F77, P84, F87, P9
4, L101, P103, F108, L121, P-1
23 (manufactured by Asahi Denka Co., Ltd.) and ISONET S-20 (manufactured by Sanyo Kasei).

As the colorant contained in the radiation-sensitive coloring composition of the present invention, a dye that colors the composition in a molecularly dissolved state in the composition can be selected. The dye that can be used in the present invention is not particularly limited, and conventionally known dyes for color filters can be used. For example, JP-A-64-
No. 90403, No. 64-91102, No. 1-94301, No. 6-11614, No. 2592207, U.S. Pat. No. 4,808,5.
No. 01, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5
-333207, JP-A-6-35183,
JP-A-6-51115, JP-A-6-194828
The dyes disclosed in Japanese Unexamined Patent Publications can be used. As the chemical structure, pyrazole azo type, anilino azo type, triphenyl methane type, anthraquinone type, benzylidene type,
Dyes of oxonol type, pyrazolotriazole azo type, pyridone azo type, cyanine type, phenothiazine type, pyrrolopyrazole azomethine type and the like can be used. In particular, since the curable composition can be cured at a relatively low temperature, even a dye having a lower heat resistance than a pigment can be cured at a high temperature during post baking to impart durability to the cured film. Even when exposed to water, problems such as decomposition can be reduced.

The carbon black that can be used in the composition of the present invention is, for example, carbon black # 2400, # 2350, # 230 manufactured by Mitsubishi Chemical Corporation.
0, # 2200, # 1000, # 980, # 970, #
960, # 950, # 900, # 850, MCF88,
# 650, MA600, MA7, MA8, MA11, M
A100, MA220, IL30B, IL31B, IL
7B, IL11B, IL52B, # 4000, # 401
0, # 55, # 52, # 50, # 47, # 45, # 4
4, # 40, # 33, # 32, # 30, # 20, # 1
0, # 5, CF9, # 3050, # 3150, # 325
0, # 3750, # 3950, Diamond Black A, Diamond Black N220M, Diamond Black N234, Diamond Black I, Diamond Black LI, Diamond Black I
I, diamond black N339, diamond black SH, diamond black SHA, diamond black LH, diamond black H, diamond black HA, diamond black SF, diamond black N550M, diamond black E, diamond black G, diamond black R, diamond black N760
M, diamond black LP. Carbon black Thermax N990, N991, N907, manufactured by Cancarb
N908, N990, N991, N908. Asahi Carbon Carbon Black Asahi # 80, Asahi # 70, Asahi # 70
L, Asahi F-200, Asahi # 66, Asahi # 66HN, Asahi # 60
H, Asahi # 60U, Asahi # 60, Asahi # 55, Asahi # 50H, Asahi # 51, Asahi # 50U, Asahi # 50, Asahi # 35, Asahi # 15,
Asahi Thermal, Degussa carbon black Col
orBlack Fw200, ColorBlack
Fw2, ColorBlack Fw2V, Color
Black Fw1, ColorBlack Fw1
8, ColorBlack S170, ColorBl
ack S160, SpecialBlack6, Sp
economicBlack5, SpecialBlack
4, SpecialBlack4A, Printex
U, PrintexV, Printex140U, Pr
For example, the index 140V can be used.

Insulating carbon black can also be used in the composition of the present invention. Insulating carbon black, for example, having an organic compound on the surface of the carbon black particles, such as organic matter is adsorbed, coated or chemically bonded (grafted) on the surface of the carbon black particles, and Carbon black that exhibits insulating properties when the volume resistance as powder is measured by the following method.

The insulating carbon black was dispersed in propylene glycol monomethyl ether so that the molar ratio of the benzyl methacrylate and the methacrylic acid was 70:30 and the copolymer (mass average molecular weight 30,000) was 20:30. To prepare a coating solution, thickness 1.1 mm, 10 cm
It is applied on a × 10 cm chrome substrate to prepare a coating film with a dry film thickness of 3 μm, and the coating film is further heated in an oven at 200 ° C.
High-resistivity meter, Hiresta UP manufactured by Mitsubishi Chemical Co., Ltd. according to JISK6911 after heat treatment for 1 hour.
(MCP-HT450) to apply a volume resistance value of 23
Measured in an environment of ℃ and 65% relative humidity. The volume resistance value is 10 ⁶ Ω · cm or more, more preferably 10 ⁸ Ω · cm or more, and particularly preferably 10 ⁹ Ω · cm.
The insulating carbon blacks shown above are preferable.

As the insulating carbon black, for example,
JP-A-11-60988, JP-A-11-60989
JP-A-10-330643 and JP-A-11-805.
83, JP-A-11-80584, and JP-A-9-124.
The resin-coated carbon black disclosed in Japanese Patent No. 969 and JP-A No. 9-95625 can be used.

In addition, carbon black coated with a resin may be used. To coat carbon black with a resin (coating resin), a coating base and a solvent are added to carbon black to prepare a mill base, which is subjected to a flushing treatment, a kneader, a ball mill, a sand mill, a bead mill, a two or three roll mill, an extruder. The dispersion treatment is performed by a method such as a paint shaker, ultrasonic wave, or homogenizer. Two or more of these processing methods can be combined. If necessary, a dispersant can be used to uniformly disperse the carbon black.

Examples of the coating resin include the following. 1) Polyolefin polymer polyethylene, polypropylene, polyisobutylene, etc. 2) Diene polymer polybutadiene, polyisoprene, etc. 3) Polymer having a conjugated polyene structure Polyacetylene polymer, polyphenylene polymer, etc. 4) Vinyl polymer Polyvinyl chloride, polystyrene, vinyl acetate , Polyvinyl alcohol, poly (meth) acrylic acid, poly (meth)
Acrylic ester, polyacrylamide, polyacrylonitrile, polyvinylphenol, etc. 5) Polyether polyphenylene ether, polyoxirane, polyoxetane, polytetrahydrofuran, polyether ketone,
Polyether ether ketone, polyacetal, etc. 6) Phenolic resin Novolak resin, resole resin, etc. 7) Polyester polyethylene terephthalate, polyphenolphthalein terephthalate, polycarbonate, alkyd resin, unsaturated polyester resin, etc. 8) Polyamide nylon-6, nylon 66, water-soluble Nylon, polyphenylene amide, etc. 9) Polypeptide gelatin, casein, etc. 10) Epoxy resin and its modified products Novolac epoxy resin, bisphenol epoxy resin, novolac epoxy acrylate and modified resin with acid anhydride 11) Other polyurethane, polyimide, melamine resin, Urea resin,
Polyimidazole, polyoxazole, polypyrrole,
Polyaniline, polysulfide, polysulfone, celluloses, etc.

The amount of carbon black (including insulating carbon black) added is usually 10 to 60% by mass, preferably 20 to 55% by mass, and particularly preferably 25% in the composition.
Is about 50% by mass.

In the radiation-sensitive coloring composition of the present invention, various additives such as a filler, a polymer compound other than the above-mentioned binder resin, a surfactant, an adhesion promoter, an antioxidant are added, if necessary. An ultraviolet absorber, an anti-aggregation agent, etc. can be added.

Specific examples of these additives include fillers such as glass and alumina; polymer compounds other than the binder polymer (A) such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate. Nonionic, cationic, anionic and other surfactants; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane ,
N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3
-Glycidoxypropylmethyldimethoxysilane, 2-
Adhesion promoters such as (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane ; 2,2
-Antioxidants such as thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol: 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5- Examples thereof include ultraviolet absorbers such as chlorobenzotriazole and alkoxybenzophenone; and aggregation inhibitors such as sodium polyacrylate.

When the alkali solubility of the unirradiated area is promoted and the developability of the composition of the present invention is further improved, an organic carboxylic acid, preferably a molecular weight of 1,000 or less is added to the composition of the present invention. The low molecular weight organic carboxylic acid can be added. Specifically, for example, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid and other aliphatic monocarboxylic acids; oxalic acid, malonic acid, succinic acid, glutaric acid. Acids, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid and other aliphatic dicarboxylic acids; tri Aliphatic tricarboxylic acids such as carballylic acid, aconitic acid and camphoronic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesin Aromatic polycarboxylic acids such as acids, melophanoic acid and pyromellitic acid; phenylacetic acid, Doroatoropa acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.

In addition to the above, it is preferable to add a thermal polymerization inhibitor to the radiation-sensitive coloring composition of the present invention, for example, hydroquinone, p-methoxyphenol, di-t-butyl-p-. Cresol, pyrogallol,
t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,
2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole and the like are useful.

Solvents used in preparing the radiation-sensitive coloring composition of the present invention include esters such as ethyl acetate, -n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, propionic acid. Butyl, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethoxy Ethyl acetate,

3-Oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate; methyl 3-methoxypropionate,
Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 2-
Methyl oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxy Ethyl propionate, 2-oxy-2-methyl methyl propionate, 2-
Ethyl oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-
Ethyl methyl propionate,

Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .; ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether,

Propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate etc .; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone etc .; aromatic hydrocarbons such as toluene, xylesi etc. Is mentioned.

Of these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate (EEP),
Ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimeter ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate (PGMEA), etc. are preferably used. To be

These solvents may be used alone or in a mixture of 2
You may use it in combination of 2 or more types. The radiation-sensitive coloring composition of the present invention is prepared by mixing the above-mentioned main components, and other additives used as necessary with a solvent, and mixing and dispersing using various mixers and dispersers. You can

The radiation-sensitive coloring composition of the present invention is coated on a substrate by a coating method such as spin coating, slit coating, cast coating, roll coating or the like to coat the radiation-sensitive composition layer. A film is formed. Among the coating methods,
Spin coating and slit coating are preferred. The spin coating is a spin coater in which a radiation-sensitive composition is dropped as a coating solution onto the center of a rotated substrate, and the coating solution is cast on the entire surface of the substrate to form a uniform coating film. Is the way. According to this method, a thin film having a uniform thickness of several microns to 1 μm or less can be accurately obtained with relatively simple equipment. For slit application, width (tens of microns),
A coating jig (slit head) having a slit (length of one side of the coating area) and a slit having a gap between the substrate and the substrate set to several tens of microns are used to coat the radiation-sensitive coloring composition and slit. In this coating method, the coating film of the radiation-sensitive coloring composition is formed on the substrate by moving the head. Compared to spin coating, slit coating can form a coating film with a small amount of coating liquid (about 1/10 of spin coating).
The film thickness distribution is relatively good, and a uniform coating film can be obtained. The coating film formed on the substrate by the above coating method is dried, and then the coating film is exposed through a predetermined mask pattern and developed with a developing solution to form a colored pattern. . Ultraviolet rays such as g-rays, h-rays and i-rays are preferably used as the radiation used in this case.

As the substrate, for example, soda glass, Pyrex (registered trademark) glass, quartz glass used for liquid crystal display elements and the like, a transparent conductive film attached to these, or a photoelectric conversion element used for a solid-state image pickup element or the like is used. A substrate such as a silicon substrate may be used. These substrates are generally formed with black stripes that separate each pixel.

As the developing solution, any composition can be used as long as it is a composition that dissolves the radiation-sensitive coloring composition of the present invention but does not dissolve the radiation-irradiated portion. Specifically, a combination of various organic solvents and an alkaline aqueous solution can be used. Examples of the organic solvent include the above-mentioned solvents used when preparing the composition of the present invention.

Examples of the alkali include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide. , Choline, pyrrole, piperidine, 1,8-diazabicyclo- [5.4.0] -7-undecene and other alkaline compounds at a concentration of 0.001-
An alkaline aqueous solution is used which is dissolved so as to be 10% by mass, preferably 0.01 to 1% by mass. When a developer containing such an alkaline aqueous solution is used, it is generally washed with water after development.

[0096]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited to the following examples. Reference Example Regarding the exemplified photopolymerization initiator (1) of the present invention and the following photopolymerization initiator (1) described in JP-A No. 11-38613, 10 g of the solvent (PGMEA and EEP) at 25 ° C. The saturated solubility (the amount of dissolution until precipitation as crystals) was measured. The results are shown in Table 1.

[0097]

[Chemical 14]

[0098]

[Table 1]

[0099] (Example 1) Binder resin: benzyl methacrylate / methacrylic acid 40 parts Copolymer (molar ratio 70/30; mass average molecular weight 30,000; acid value 120) -C. I. Pigment Blue # 15: 650 50 parts ・ Propylene glycol monomethyl ether acetate 200 parts Was dispersed all day and night with a sand mill.

Then, the following ingredients were added. -Acrylate monomer 40 parts (1) Hexaacrylate containing 6 ethylene oxides added to dipentaerythritol 15 mass% (2) Pentaacrylate containing 5 ethylene oxides added to dipentaerythritol 85 mass% -Exemplary photopolymerization initiator (1) of the present invention 3 parts-Hydroquinone monomethyl ether 0.01 part-Propylene glycol monomethyl ether acetate 150 parts

After uniformly mixing the above components, the mixture was filtered through a filter having a pore size of 1 μm to obtain the radiation-sensitive coloring composition of the present invention (color filter coating composition).

(Examples 2 to 3 and Comparative Examples 1 and 2) Radiation sensitivity was the same as in Example 1 except that the kind and blending ratio of the photopolymerization initiator were changed as follows. A colored composition was obtained. Example 2 Photopolymerization initiator represented by the formula (2) 3 parts Example 3 Photopolymerization initiator represented by the formula (3) 3 parts Comparative Example 1 Photopolymerization initiator having the following structure (Comparative Compound A) 3 Part Comparative Example 2 Photopolymerization initiator having the following structure (Comparative Compound B) 3 parts

[0103]

[Chemical 15]

[Evaluation of sensitivity (residual film rate)] The composition prepared as described above was applied to a glass substrate for a color filter by a spin coater so that the dry film thickness was 1.5 μm,
It was dried at 90 ° C. for 2 minutes to obtain a uniform coating film. The pigment concentration at this time was 37% by mass in terms of solid content. Furthermore, using a 2.5 Kw ultra-high pressure mercury lamp, 100 mj / cm ² , 150 mj / cm ² through a mask of 20 μm width.
Irradiation doses of ² and 200 mj / cm ² were applied. Then, it was immersed in a 0.1% sodium carbonate aqueous solution for development.
After development, post-baking was performed in a convection oven at 220 ° C. for 30 minutes to measure the residual film rate. Regarding the residual film rate, the film thickness before development was 100%.

[Evaluation of Storage Stability] Approximately 3.8 ml of the radiation-sensitive coloring compositions of Examples 1 to 3 and Comparative Examples 1 and 2 were put in a brown glass bottle for storage and put in a storage kept at 5 ° C. 10
After storage for 30 days and 30 days, the composition was sampled from the upper layer, the middle layer, and the lower layer of the glass bottle, and each of the two compositions was applied onto a 10 cm square glass substrate in a thickness of 1.5 μm. After drying, the coating film surface was thoroughly observed with an optical microscope of 300 magnification to check the presence of foreign matters such as aggregates, precipitates, and precipitates. The results are shown in Table 2.

[0106]

[Table 2]

As is clear from the results shown in Table 2, the composition of the present invention has high sensitivity and excellent storage stability.

[0108] (Example 4) Binder resin: benzyl methacrylate / methacrylic acid 24 parts Copolymer (molar ratio 70/30; mass average molecular weight 30,000; acid value 120) ・ Carbon black 63 parts ・ Propylene glycol monomethyl ether acetate 162 parts Was dispersed all day and night with a sand mill.

Then, the following ingredients were added. ・ Dipentaerythritol hexaacrylate 34 parts ・ 10 parts of the above binder resin ・ Propylene glycol monomethyl ether acetate 362 parts 11 parts of the exemplified photopolymerization initiator (1) of the present invention

After uniformly mixing the above components, the mixture was filtered with a filter having a pore size of 1 μm to obtain a radiation-sensitive black composition.

(Examples 5 to 6 and Comparative Examples 3 to 4) Radiation sensitivity was the same as in Example 4 except that the type and blending ratio of the photopolymerization initiator were changed as follows. A black composition was obtained. Example 5 11 parts of the photopolymerization initiator represented by the formula (2) Example 6 11 parts of the photopolymerization initiator represented by the formula (3) Comparative Example 3 11 parts of the comparative compound A Comparative example 4 The comparative compound B 11 copies

[Evaluation of Sensitivity (Remaining Film Ratio)] The composition prepared as described above was applied to a glass substrate for a color filter by a spin coater so that the dry film thickness would be 1.2 μm,
It was dried at 90 ° C. for 2 minutes to obtain a uniform coating film. The pigment concentration at this time was 44 mass% in terms of solid content. Furthermore, using a 2.5 Kw ultra-high pressure mercury lamp, through a mask of 20 μm width, 100 mj / cm ² , 200 mj / cm 2.
Irradiation doses of ² and 300 mj / cm ² were applied. Next, it was immersed in a 0.05% aqueous solution of potassium hydroxide for development. After development, 220 ° C in convection oven, 3
After post-baking for 0 minutes, the residual film rate was measured. Regarding the residual film rate, the film thickness before development was 100%.

[Evaluation of Storage Stability] The radiation-sensitive black compositions of Examples 5 to 6 and Comparative Examples 3 to 4 were put into a brown glass bottle for storage, and stored in a storage kept at 5 ° C. for 10 days and 30 days. After storage, the composition was sampled from the upper layer, the middle layer and the lower layer of the bottle, and applied on a glass substrate in a dry film thickness of 1.2 μm. This was observed with an optical microscope at 300 magnifications, and the presence or absence of aggregates, precipitates, and precipitates was inspected. Sensitivity (residual film rate)
Table 3 shows the results of the evaluation and the storage stability evaluation.

[0114]

[Table 3]

[0115]

INDUSTRIAL APPLICABILITY The radiation-sensitive coloring composition of the present invention is highly sensitive and excellent in storage stability by using a photopolymerization initiator having a specific structure which is excellent in solubility.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2H025 AA01 AA04 AA11 AB13 AC01                       AD01 BC13 BC42 CA14 CA28                       CB43 CC03 CC12 FA17                 2H048 BA02 BA11 BA45 BA48 BA58                       BB02 BB14 BB15 BB42 BB46                       CA04 CA05 CA14 CA19 CA29                 4J011 AC04 QA03 QA13 QA22 QA23                       QA24 QA25 QB16 SA78 TA03                       UA01 VA01 WA01

Claims (3)

[Claims] 1. A radiation-sensitive coloring composition containing a radiation-sensitive compound, a binder resin, a colorant, and a solvent, wherein the radiation-sensitive compound is represented by the following formulas (I) and (II). A radiation-sensitive coloring composition comprising at least one photopolymerization initiator selected from the group consisting of compounds. [Chemical 1] [In the formula, R ₁ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, X represents F, Cl, Br or I, and n is 1 to 5
Represents the integer, and m represents 2 or 3. ] 2. The colorant is a pigment, the average particle diameter is 0.01 μm to 0.1 μm, and the concentration of the colorant in the radiation-sensitive coloring composition is 30 in terms of solid content.
The radiation-sensitive coloring composition according to claim 1, which is contained in an amount of not less than mass%. 3. The binder resin has a carboxyl group, and 3
The radiation-sensitive coloring composition according to claim 1, which has an acid value of 0 to 200.