JPH1062986A - Radiation sensitive colored composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a radiation sensitive colored compsn. contg. a radiation sensitive polymerizable component having improved compatibility with a bonding resin in the compsn., excellent in film forming property and capable of giving a color filter excellent in transmissivity and image adhesion by incorporating a specified (meth)acrylate compd. as a polymerizable component into a radiation sensitive component. SOLUTION: This radiation sensitive colored compsn. contains a radiation sensitive component, a bonding resin, a pigment and a solvent, and the radiation sensitive component contains a (meth)acrylate compd. selected from among compds. represented by formulae I, II as a polymerizable component. In the formulae I, II, B is -(CH2 CH2 O)- or -[CH2 CH(CH3 )O]-, X is acryloyl, methacryloyl or H, the total number of acryloyl and methacryloyl groups is 5 or 6 in the formula I and 3 or 4 in the formula II, (n) is an integer of 0-6, the sum of (n) is 3-24, (m) is an integer of 0-6 and the sum of (m) is 2-16.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a radiation-sensitive colored composition suitable for producing a color filter used for a liquid crystal display device or a solid-state imaging device.
The present invention relates to a radiation-sensitive colored composition having excellent compatibility between a polymerizable component of the radiation-sensitive component and a binder resin, and excellent developability.

[0002]

2. Description of the Related Art As a method for producing a color filter used for a liquid crystal display device or a solid-state imaging device, a dyeing method,
Printing, electrodeposition and pigment dispersion methods are known. The dyeing method is a method of producing a color filter by dyeing a dyeing substrate made of a natural resin such as gelatin, glue, casein or the like or a synthetic resin such as amine-modified polyvinyl alcohol with a dye such as an acid dye. In the dyeing method, there is a problem in light fastness, heat resistance, moisture resistance, etc. due to the use of a dye, and it is difficult to uniformly control the dyeing and fixing properties on a large screen, and color unevenness is likely to occur. In this case, there is a problem that an anti-dyeing layer is required and the process is complicated.

In the electrodeposition method, a transparent electrode is formed in a predetermined pattern in advance, a resin containing a pigment dissolved or dispersed in a solvent is ionized, and a voltage is applied to form a colored image in a pattern. This is a method for producing a color filter. The electrodeposition method requires a photolithography process including a film formation and an etching process of a transparent electrode for forming a color filter in addition to a transparent electrode for display. At this time, if there is a short circuit, a line defect occurs and the yield decreases. In addition, there is a problem that it is difficult to apply to a mosaic arrangement other than the stripe arrangement in principle, and it is difficult to manage the transparent electrodes.

[0004] The printing method is a simple method for producing a color filter by printing such as offset printing using an ink in which a pigment is dispersed in a thermosetting resin or an ultraviolet curable resin. However, there is a problem in that defects are likely to occur due to dust, foreign matters, and gelled portions of the ink binder, and there are problems in positional accuracy, line width accuracy, and planar smoothness associated with printing accuracy.

[0005] The pigment dispersion method is a method of producing a color filter by a photolithography method using a radiation-sensitive coloring composition in which a pigment is dispersed in various radiation-sensitive components. This method is stable to light and heat due to the use of pigments and is patterned by the photolithographic method, so it has a sufficient positional accuracy and is a method suitable for producing color filters for large screen and high definition color displays. is there.

As the radiation-sensitive polymerization component of the radiation-sensitive coloring composition used in the pigment dispersion method, conventionally, dipentaerythritol hexaacrylate, dipentaerythritol
Acrylic esters of dipentaerythritol, such as rupentaacrylate, have been used. However, this compound had many disadvantages as follows. Low solubility in aqueous alkali developer, high alkalinity is required to remove unexposed parts,
A surfactant must be added to the developer to make it hydrophilic. The binder resin that disperses the pigment in order to dissolve the unexposed parts in the developer must be hydrophilic, but the compatibility between the hydrophilic polymer and the photopolymerizable crosslinking agent is small, and the surfactant is used for preparing the pigment coating liquid. Agent is needed. Since the compatibility with the binder resin polymer was small, the viscosity of the coating material became high, so that a thin layer could not be applied and the transmittance as a color filter was low. In addition, since coating unevenness is likely to occur, color unevenness is likely to occur, so that color reproducibility is low. The mechanical properties of the coating film were hardened by exposure to light and became hard, the adhesion to the glass substrate was reduced, and a desired pattern could not be obtained or lacked during development.

In particular, the lack of compatibility between this compound and the binder resin results in an increase in the viscosity of the coating solution, making it impossible to apply a thin film, lowering the transmittance of the color filter and reducing the coating unevenness ( (Uniformity of the coating liquid) occurs, causing color unevenness, resulting in poor color reproducibility. These are fatal drawbacks when the size of the color filter is increased.

Japanese Patent Application Laid-Open No. 1-126345 discloses a photopolymerizable composition containing a polyfunctional acrylate such as polypentaerythritol polyacrylate. However, there is no description for use in a color filter and no description for introducing a ring-opened structure such as ethylene oxide or propylene oxide to the above acrylate. In addition, Japanese Unexamined Patent Publication
JP-B-38471 discloses a tetrafunctional acrylate monomer.
Discloses a composition for a photopolymerizable solder-resist using an acryloyl group linked by a ring-opening structure such as ethylene oxide or propylene oxide. However, there is no description used for color filters and no description of pentafunctional or hexafunctional acrylate monomers. JP-A-64-25147 also discloses a photosensitive resin composition similar to that of JP-A-2-38471, and there is no description for use in a color filter.

To prepare a color filter, a radiation-sensitive colored composition is applied on a glass substrate by a spin coater or a roll coater and dried to form a coating film, which is then exposed and developed to obtain colored pixels. This operation is performed for each color to obtain a color filter.However, the pixels formed by the conventional radiation-sensitive coloring composition are liable to peel off from the substrate during development or washing with water and to cause defects in the color filters, while the adhesion of the pixels is poor. When the value of is improved, the solubility of the non-image portion is reduced at the time of development, and there is a problem that background stain on the non-image portion easily occurs.

[0010]

SUMMARY OF THE INVENTION The present invention has been made in order to improve the above-mentioned drawbacks of the prior art, and has as its object to improve the compatibility between a radiation-sensitive polymerization component and a binder resin. Another object of the present invention is to provide a radiation-sensitive colored composition, particularly a composition for a color filter. Another object of the present invention is to provide a novel radiation-sensitive colored composition which has excellent coating properties and can provide a color filter having improved transmittance and image adhesion.

[0011]

As a result of various studies, the present inventors have found that the above object can be achieved by a radiation-sensitive coloring composition having the following constitution. Radiation-sensitive components,
In a radiation-curable coloring composition containing a binder resin, a pigment, and a solvent, the radiation-sensitive component is at least one selected from the group of compounds represented by the following general formulas (1) and (2) as a polymerizable component. A radiation-sensitive coloring composition comprising one kind of (meth) acrylate compound.

[0012]

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(Where B is each independently-(CH ₂
X independently represents any one of an acryloyl group, a methacryloyl group, and a hydrogen atom, and further represents a compound represented by the formula (1): CH ₂ O) — or — (CH ₂ CH (CH ₃ ) O) —; )), The total of the acryloyl group and the methacryloyl group is 5 or 6, and that in the formula (2) is 3 or 4, and n independently represents an integer of 0 to 6; The sum of n is from 3 to 24; m each independently represents an integer from 0 to 6, and the sum of each m is from 2 to
Sixteen. )

The present invention relates to a radiation-sensitive colored composition, in particular, as a polymerizable component of the radiation-sensitive component (hereinafter also referred to as a radiation-sensitive polymerization component), a (meth) acryloyl group and dipentaerythritol or pentane. By using a specific structure having a ring-opening chain of ethylene oxide or propylene oxide introduced between the erythritol skeletons, the hydrophilicity of the radiation-sensitive polymer component is improved, and the hydrophilic binder resin is used. With improved compatibility.
As a result, the viscosity of the coating liquid of the radiation-sensitive coloring composition is reduced, and a thin film can be applied, the transmittance of the color filter is improved, and the coating unevenness (uniformity of the coating liquid) is eliminated and the color unevenness is reduced. The color reproducibility is improved with a decrease. This means that
This is an advantageous advantage when the size of the color filter is increased. Furthermore, it has become possible to provide a color filter with improved image adhesion.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The radiation-sensitive colored composition of the present invention comprises a radiation-sensitive component, a binder resin, a pigment, and a solvent.

The radiation-sensitive component used in the present invention is represented by the general formulas (1) and (2).
An acrylate monomer is contained as a polymerization component. As the (meth) acrylate monomer represented by the general formula (1), n independently represents an integer of 0 to 6, preferably 0 to 4, and the total of each n is 3 to 24, preferably Is 6-1
2 is represented. (Meta) represented by the general formula (2)
As the acrylate monomer, m is each independently 0
To 6, preferably 0 to 4, and the sum of each m is 2
~ 16, preferably 4 ~ 8.

The (meth) acrylate monomers represented by the general formulas (1) and (2) are used alone or in combination of two or more. In particular, in the general formula (1), it is preferable to use an acrylate monomer in which all six Xs are an acroyl group. In the radiation-sensitive polymerizable component of the composition of the present invention, 20% by weight of the acrylate monomer is contained. More preferably, it is preferably present in an amount of 50% by weight or more.

The (meth) acrylate monomer used in the radiation-sensitive coloring composition of the present invention is obtained by diluting ethylene oxide or propylene oxide with dipentaerythritol or pentaerythritol, which is a conventionally known method. It can be produced from a step of bonding a ring-opening skeleton by a cycloaddition reaction and a step of introducing a (meth) acryloyl group by reacting, for example, (meth) acryloyl chloride with a terminal hydroxyl group of the ring-opening skeleton. Each step is a well-known step, and a person skilled in the art can easily synthesize the above (meth) acrylate monomer.

The radiation-sensitive component of the present invention has the general formula (1)
(Meth) acrylate monomers represented by (2)
In addition, the following radiation-sensitive components (a), (b) and (c) can be contained. (A) A compound having at least one addition-polymerizable ethylene group and having an ethylenically unsaturated group having a boiling point of 100 ° C. or more under normal pressure. (B) at least one active halogen compound selected from a halomethyloxadiazole compound, a halomethyl-s-triazine compound, and a 3-aryl-substituted coumarin compound. (C) at least one lophine dimer; here,
(B) and (c) are photopolymerization initiators having an action of polymerizing the polymerization component of the radiation-sensitive component by light irradiation. Therefore, the radiation-sensitive component preferably contains at least one of (b) and (c). Also,
The radiation-sensitive component can contain (a) as a polymerization component in addition to the (meth) acrylate monomer represented by the general formulas (1) and (2).

(A) It has at least one ethylenically unsaturated group capable of addition polymerization and has a boiling point of 100 at normal pressure.
Examples of the compound having a temperature of not less than ° C 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 hexa (meth) acrylate, hexanediol (meth) acrylate, Trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin, trimethylolethane, and other polyfunctional alcohols added with ethylene oxide or propylene oxide and then (meth) acrylated, Japanese Patent Publication No. 48-41708
No., JP-B-50-6034, JP-A-51-37193.
Urethane acrylates described in JP-A-48-64183 and JP-B-49-4319.
And polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates which are reaction products of an epoxy resin and (meth) acrylic acid described in JP-A-52-30490. I can do it. Further, the Journal of the Adhesion Society of Japan, Vol. 20,
No. 7, pages 300 to 308, photocurable monomers and oligomers can also be used. These radiation-polymerizable monomers or oligomers may be used in any proportion as long as the composition of the present invention can form a coating film having adhesiveness by receiving irradiation with radiation, as long as the object and effects of the present invention are not impaired. it can. The amount used is 5 to 90% by weight, preferably 10 to 5% by weight, based on the total solid content of the radiation-sensitive composition.
0% by weight.

The active halogen compounds such as halomethyloxadiazole and halomethyl-s-triazine (b) include 2-halomethyl-5-vinyl represented by the following general formula IV described in JP-B-57-6096. -1, 3,
4-oxadiazole compounds are mentioned.

[0022]

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In the formula (IV), W is a substituted or unsubstituted aryl group, X is a hydrogen atom, an alkyl group or an aryl group, Y is a fluorine atom, a chlorine atom or a bromine atom, and n is 1 Represents an integer of ~ 3. Specific compounds include 2-
Trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p -Methoxystyryl) -1,
3,4-oxadiazole and the like. Examples of the photopolymerization initiator of the halomethyl-s-triazine-based compound include vinyl-halomethyl-s-triazine compounds represented by the following general formula V described in JP-B-59-1281 and JP-A-53-133428. 2- (naphth-1-yl) -4,6-bis-halomethyl-s-triazine compound represented by the following general formula VI and 4- (p-aminophenyl) -2,2 represented by the following general formula VII 6-di-halomethyl-s-triazine compounds.

[0024]

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In the formula (V), Q ₃ is Br, Cl, and P is -C
Q ₃ , —NH ₂ , —NHR, —N (R) ₂ , —OR (where R is a phenyl or alkyl group), W is an optionally substituted aromatic, heterocyclic nucleus or general formula VA. In the formula VA, Z is -O- or -S-, and R is as defined above.

[0026]

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In the formula (VI), X represents -Br, -Cl;
m and n are integers of 0 to 3, R ′ is represented by the general formula VIA,
R ₁ is H or OR _c (R _c is an alkyl, cycloalkyl, alkenyl, aryl group), and R ₂ is —Cl, —Br
Or an alkyl, alkenyl, aryl, or alkoxy group.

[0028]

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In the formula (VII), R ₁ and R ₂ are each represented by —H, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or the general formulas VIIA and VIIB. R ₃ and R ₄ are -H,
Represents a halogen atom, an alkyl group, or an alkoxy group. X,
Y represents -Cl, -Br, and m and n represent 0, 1 or 2.

[0030]

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In the formulas VII A and VII B, R ₅ , R ₆ and R ₇ represent 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 (VII), R ₁ and R ₂ may form a heterocyclic ring composed of a nonmetallic atom together with the nitrogen atom bonded thereto, in which case the heterocyclic ring may be one of the following: No.

[0033]

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As a specific example of the general formula V, 2,4-
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 VI 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-naphth-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-bis-trichloromethyl-s-triazine and the like.

Specific examples of the general formula VII include 4- [p-
N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, 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
-[PN- (p-methoxyphenyl) carbonylaminophenyl] 2,6-di (trichloromethyl) -s-triazine, 4- [mN, N-di (ethoxycarbonylmethyl) aminophenyl] -2 , 6-Di (trichloromethyl) -s-triazine, 4- [m-bromo-p-N,
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-pN, 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-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-fluoro-pN, 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-pN, N-di (chloroethyl) aminophenyl] -2,6-di (Trichloromethyl) -s-triazine, 4- [m-fluoro-pN, 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, (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.

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) phenylstyryl 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 are exemplified.

The 3-aryl-substituted coumarin compound is as follows:
Refers to a compound represented by the general formula VIII. R₈Is a hydrogen atom,
C1-C8 alkyl group, C6-C10 aryl
Group (preferably a hydrogen atom, a methyl group, an ethyl group,
Butyl group), R₉Is a hydrogen atom, having 1 to 8 carbon atoms
Alkyl group, aryl group having 6 to 10 carbon atoms, the following general formula
A group represented by VIIIA (preferably a methyl group, an ethyl group,
A propyl group, a butyl group, a group represented by the general formula VIIIA,
Preferably a group represented by the general formula VIIIA).
R_Ten, R₁₁Represents a hydrogen atom and an alkyl having 1 to 8 carbon atoms, respectively.
(Such as methyl, ethyl, propyl, butyl
Group, octyl group), haloalkyl group having 1 to 8 carbon atoms (eg,
For example, chloromethyl group, fluoromethyl group, trifluoromethy
And an alkoxy group having 1 to 8 carbon atoms (for example,
Xy, ethoxy, butoxy), which may be substituted
An aryl group having 6 to 10 carbon atoms (for example, a phenyl group);
Amino group, -N (R₁₆) (R₁₇), Halogen (eg, -C
1, -Br, -F). Preferably a hydrogen atom, methyl
Group, ethyl group, methoxy group, phenyl group, -N
(R₁₆) (R ₁₇), -Cl. R12 may be substituted
Aryl groups having 6 to 16 carbon atoms (e.g., phenyl,
Phenyl, tolyl, cumyl). As a substituent
Is an amino group, -N (R₁₆) (R₁₇), Al having 1 to 8 carbon atoms
Kill groups (eg, methyl, ethyl, propyl,
Octyl group), a haloalkyl group having 1 to 8 carbon atoms
(For example, chloromethyl, fluoromethyl, trifluoromethyl
A methyl group), an alkoxy group having 1 to 8 carbon atoms (for example,
Methoxy, ethoxy, butoxy), hydroxy
Group, cyano group, halogen (for example, -Cl, -Br,-
F). R ₁₃, R₁₄, R₁₆, R₁₇Are each
A hydrogen atom, an alkyl group having 1 to 8 carbon atoms (eg, methyl
Group, ethyl group, propyl group, butyl group, octyl group)
Represent. R₁₃And R₁₄And R₁₆And R₁₇Are also bonded to each other
Heterocycle (eg piperidine ring, piperazine
Ring, morpholine ring, pyrazole ring, diazole ring,
(Riazole ring, benzotriazole ring, etc.)
Good. R_FifteenIs a hydrogen atom, an alkyl group having 1 to 8 carbon atoms (eg,
For example, methyl, ethyl, propyl, butyl, octane
Tyl group), an alkoxy group having 1 to 8 carbon atoms (for example,
Group, ethoxy group, butoxy group), optionally substituted charcoal
Aryl groups having a prime number of 6 to 10 (for example, phenyl group),
Group, N (R₁₆) (R₁₇), Halogen (eg, -Cl,-
Br, -F). Zb is = O, = S or = C
(R₁₈) (R₁₉). Preferably = O, = S, = C
(CN)_TwoAnd particularly preferably 好 ま し く O. R₁₈, R
₁₉Is a cyano group, -COOR₂₀, -COR_{twenty one}To
Represent. R₂₀, R_{twenty one}Is an alkyl group having 1 to 8 carbon atoms
(E.g., methyl, ethyl, propyl, butyl,
Octyl group), a haloalkyl group having 1 to 8 carbon atoms (for example,
Chloromethyl group, fluoromethyl group, trifluoromethyl group
Etc.), an aryl group having 6 to 10 carbon atoms which may be substituted
(For example, a phenyl group).

Particularly preferred 3-aryl-substituted coumarin compounds are {(s-triazin-2-yl) amino} -3-arylcoumarin compounds of the general formula IX.

[0040]

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(C) Rofin dimer means 2,4,5-triphenylimidazolyl dimer consisting of two rofin residues, and its basic structure is shown below.

[0042]

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Specific examples thereof include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer,
-(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
-(P-methylmercaptophenyl) -4,5-diphenylimidazolyl dimer and the like.

In the present invention, other known initiators can be used in addition to the above initiators. US Patent No. 2,36
Bicinal polykettle aldonyl compounds disclosed in US Pat. No. 7,660, US Pat. No. 2,367,661.
-Carbonyl compounds disclosed in U.S. Pat. No. 2,448,82 and U.S. Pat. No. 2,448,82.
No. 8, disclosed in U.S. Pat. No. 2,722,512.
-Aromatic acyloin compounds substituted with hydrocarbons, U.S. Pat. Nos. 3,046,127 and 2,951,75
No. 8,491,367, and the combination of triallylimidazole dimer / p-aminophenyl ketone disclosed in U.S. Pat. No. 3,549,367, JP-B-51-48516. Disclosed benzothiazole compounds / trihalomethyl-
s-Triazine compounds.

The amount of the initiator used is from 0.01% by weight to 100% by weight, preferably from 1% by weight to 50% by weight, based on the solid content of the radiation-sensitive polymerization component. The amount of the initiator used is 0.
When the amount is less than 01% by weight, the polymerization is difficult to proceed.
If the amount is more than 10% by weight, the polymerization rate increases, but the molecular weight decreases and the film strength decreases.

The radiation-sensitive component preferably accounts for 10 to 80% by weight, particularly 20 to 70% by weight, based on the solid content of the whole composition. The content of the (meth) acrylate compound represented by the general formulas (1) and (2) is 20 to 99% by weight, preferably 30 to 80% by weight, based on the solid content of the radiation-sensitive component. Is preferred.

The binder resin usable in the present invention is preferably a linear organic polymer which is soluble in an organic solvent and can be developed with a weak alkaline aqueous solution. Examples of such a linear organic high molecular polymer include a polymer having a carboxylic acid in a side chain, for example, JP-A-59-44615 and JP-B-54.
-34327, JP-B-58-12577, JP-B-5
Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer described in JP-A-4-25957, JP-A-59-53836 and JP-A-59-71048. There are polymers, maleic acid copolymers, partially esterified maleic acid copolymers, and the like. Similarly, there are acidic cellulose derivatives having a carboxylic acid in the side chain. In addition, those obtained by adding an acid anhydride to a polymer having a hydroxyl group are also useful. Among these, a benzyl (meth) acrylate / (meth) acrylic acid copolymer and a multi-component copolymer with benzyl (meth) acrylate / (meth) acrylic acid / and other monomers are particularly preferable. Other useful water-soluble polymers include 2-hydroxyethyl methacrylate, polyvinylpyrrolidone, polyethylene oxide, and polyvinyl alcohol. In order to increase the strength of the cured film, alcohol-soluble nylon and polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin are also useful. These polymers can be mixed in any amount.

Also, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl described in JP-A-7-140654 Methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer Polymers.

Further, as a binder resin that can be used, a polyvinyl acetal resin or a modified polyvinyl acetal resin represented by the following general formula (3) described in a patent application (Japanese Patent Application No. 8-64699) filed by the present applicant is used. Can be mentioned.

[0050]

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However, in the general formula (3), R ₁ is an alkyl group or hydrogen atom which may have a substituent, R ₂ is an alkyl group having no substituent, and R ₃ is a fatty acid having a carboxylic acid group. Group or aromatic hydrocarbon group, R ₄ is at least 1
An aliphatic or aromatic hydrocarbon group having two hydroxyl groups or nitrile groups and optionally having another substituent, wherein n1, n2, n3, n4, and n5 represent mol% of each repeating unit. And the following ranges. n1 = 5
85, n2 = 1-60, n3 = 1-20, n4 = 0-6
0, n5 = 0-10.

The total amount of the binder resin of the present invention is 5 to 90% by weight based on the total solid components of the radiation-sensitive coloring composition. Preferably it is 10 to 60% by weight. The total amount of binder resin is 5
If it is less than wt%, the film strength decreases, and 90 wt%
If the amount is larger than the above range, it becomes difficult to control the solubility due to an increase in the amount of the acidic component, and a sufficient image density cannot be obtained because the amount of the pigment is relatively small.

As the pigment that can be used in the present invention, various conventionally known inorganic or organic pigments can be used. Inorganic pigments include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony And a composite oxide of the metal.

As organic pigments, CI Pigment Yellow 11, 24, 31, 53, 83, 99, 108, 10
9, 110, 138, 139,151, 154, 167 CIPigment Orange 36, 38, 43 CIPigment Red 105, 122, 149, 150, 155, 171, 1
75, 176, 177, 209 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, etc. Can be mentioned.

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

Examples of these pigments include, but are not limited to, the following.

[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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These organic pigments are used alone or in various combinations in order to increase color purity. Specific examples are shown below.
As the red pigment, an anthraquinone pigment, a perylene pigment alone, or a mixture of at least one of them and a disazo yellow pigment or an isoindoline yellow pigment is used. For example, as anthraquinone pigments, C.I.
I. Pigment Red 177 and perylene pigments include C.I. I. Pigment Red 155, and C.I. I. Pigment Yellow 83 or C.I.
I. Pigment Yellow 139 was good. The weight ratio of the red pigment to the yellow pigment is from 100: 5 to 1
00:50 was good. 400 for 100: 4 or less
The light transmittance from nm to 500 nm could not be suppressed and the color purity could not be increased. At 100: 51 or more, the dominant wavelength became shorter and the deviation from the NTSC target hue increased. Especially from 100: 10 to 100: 30
Range was optimal.

As the green pigment, a halogenated phthalocyanine pigment alone or a mixture with a disazo yellow pigment or an isoindoline yellow pigment is used. I.
Pigment Green 7, 36, 37 and C.I. I. Pigment Yellow 83 or C.I. I. Pigment Yellow 13
The mixture with No. 9 was good. The weight ratio of the green pigment to the yellow pigment was preferably from 100: 5 to 100: 40. 10
When the ratio is 0: 4 or less, the light transmittance from 400 nm to 450 nm cannot be suppressed, and the color purity cannot be increased. When the ratio is 100: 41 or more, the dominant wavelength becomes longer than the long wavelength, and NT
The deviation from the SC target hue has increased. Especially 100:
The range of 5: 100: 20 was optimal.

As the blue pigment, a phthalocyanine pigment alone or a mixture with a dioxazine purple pigment is used. I. Pigment Blue 15: 3 and C.I.
I. Pigment Violet 23 was good. The weight ratio of the blue pigment to the violet pigment is from 100: 5 to 1
00:50 was good. 400 for 100: 4 or less
The light transmittance from nm to 420 nm could not be suppressed, and the color purity could not be increased. At 100: 51 or more, the dominant wavelength became longer and the deviation from the NTSC target hue increased. In particular, the range of 100: 5 to 100: 20 was optimal.

Further, a pigment having good dispersibility and dispersion stability can be obtained by using a powdery pigment obtained by finely dispersing the above pigment in an acrylic resin, a maleic acid resin, a vinyl chloride-vinyl acetate copolymer, an ethyl cellulose resin or the like. Containing photosensitive resin can be obtained. As the pigment for the black matrix, carbon, titanium carbon, iron oxide alone or a mixture was used, and carbon and titanium carbon were good. The weight ratio ranges from 100: 5 to 10
The range of 0:40 was good. When the ratio was 100: 4 or less, the light transmittance of long wavelengths increased. Below 100: 41,
There was a problem with dispersion stability.

Pigment Processing Methods Generally, these pigments are supplied after being synthesized and dried by various methods. Usually, it is dried from an aqueous medium and supplied as a powder, 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 the primary particles are aggregated.

It is not easy to disperse the pigment forming such an aggregate into fine particles. Therefore, it is preferable that the pigment is previously treated with various resins. Examples of these resins include the binder resins described above. Examples of the treatment method include a flushing treatment and a kneading method using a kneader, an extruder, a ball mill, a two or three roll mill, or the like. Among them, a flushing treatment and a kneading method using a two- or three-roll mill are suitable for forming fine particles.

The flushing treatment is generally a method of mixing an aqueous dispersion of a pigment with a resin solution dissolved in a solvent immiscible with water, extracting the pigment from an aqueous medium into an organic medium, and treating the pigment with a resin. . According to this method, since the pigment does not undergo drying, aggregation of the pigment can be prevented and dispersion becomes easy. In kneading with two or three roll mills, a pigment and a resin or a solution of a resin are mixed, and then the pigment and the resin are kneaded while applying a high shear (shearing force) to coat the pigment surface with the resin. And a method of treating a pigment. The pigment particles that have 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, a vinyl chloride-vinyl acetate resin, a maleic acid resin, an ethylcellulose resin, a nitrocellulose resin or the like can also be conveniently used. In the present invention, the form of the processed pigment treated with the various resins described above includes a powder in which the resin and the pigment are uniformly dispersed,
Paste, pellet, and paste are preferred. In addition, a non-uniform lump having a gelled resin is not preferable. The colored dispersion thus obtained is mixed with a radiation-sensitive component to provide a radiation-sensitive colored composition.

The concentration of the pigment in all solid components of the radiation-sensitive colored composition of each color pigment is 5% by weight to 80% by weight. If the content is 5% by weight or less, the color purity does not increase unless the film thickness is 10 μm or more, which is a practical problem. 80% by weight
In the above, problems such as background contamination and film residue in the non-image portion are likely to occur. Preferably it is from 10% by weight to 60% by weight.

In the present invention, conventionally known pigment dispersants and surfactants can be added for the purpose of improving the dispersibility of the pigment. As these dispersants, many kinds of compounds are used. For example, phthalocyanine derivatives (commercially available EFKA-745 (manufactured by Morishita Sangyo)); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.);
(Meth) acrylic acid (co) polymer polyflow No.7
5, No. 90, No. 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo), W
Cationic surfactants such as 001 (manufactured by Yusho); polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, Nonionic surfactants such as polyethylene glycol distearate and sorbitan fatty acid ester; F-Top EF301, EF303, E
F352 (manufactured by Shin-Akita Kasei), Megafac F171, F
172, F173 (Dainippon Ink), Florard FC
430, FC431 (Sumitomo 3M), Asahigard AG710, Surflon S382, SC-101, S
C-102, SC-103, SC-104, SC-10
5, fluorinated surfactants such as SC-1068 (manufactured by Asahi Glass); anionic surfactants such as W004, W005, W017 (manufactured by Yusho); EFKA-46, EFKA-47;
EFKA-47EA, EFKA polymer 100, EFK
A polymer 400, EFKA polymer 401, EFKA
Polymer 450 (from Morishita Sangyo), Disperse Aid 6, Disperse Aid 8, Disperse Aid 1
5, a polymer dispersant such as Disperse Aid 9100 (manufactured by San Nopco); Solsperse 3000, 5000, 90
00, 12000, 13240, 13940, 1700
Various Solsperse dispersants such as 0, 24000, 26000 and 28000 (manufactured by Zeneca Corporation); Adecapluronic L31, F38, L42, L44, L61, L6
4, F68, L72, P95, F77, P84, F8
7, P94, L101, P103, F108, L12
1, P-123 (made by Asahi Denka) and Isonet S-20
(Manufactured by Sanyo Chemical Industries).

The radiation-sensitive colored composition of the present invention may contain various additives, if necessary, such as a filler, a polymer compound other than the above binder resin, a surfactant, an adhesion promoter, an antioxidant, An ultraviolet absorber, an anti-agglomeration agent and the like can be added.

Specific examples of these additives include fillers such as glass and alumina; and high molecular compounds other than the binder polymer (A) such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether and polyfluoroalkyl acrylate. Surfactants such as nonionic, cationic and anionic 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) and 2,6-di-t-butylphenol: 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5- UV absorbers such as chlorobenzotriazole and alkoxybenzophenone; and aggregation inhibitors such as sodium polyacrylate.

When the alkali solubility of the non-irradiated portion is promoted to further improve the developability of the composition of the present invention, an organic carboxylic acid, preferably having a molecular weight of 1,000 or less, is added to the composition of the present invention. Can be added. Specifically, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, enanthic acid, and caprylic acid; oxalic acid, malonic acid, succinic acid, and glutaric acid Aliphatic dicarboxylic acids such as acids, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid and citraconic acid; 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, and mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesin Aromatic polycarboxylic acids such as acid, melophanic 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.

The radiation-sensitive coloring composition of the present invention preferably further contains a thermal polymerization inhibitor in addition to the above, 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 for preparing the radiation-sensitive colored composition of the present invention include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, and 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, ethoxyacetate Ethyl acetate,

Alkyl 3-oxypropionates such as methyl 3-hydroxypropionate 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, methyl 2-oxy-2-methylpropionate, 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; 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, 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 methyl ether acetate and the like are preferably used.

These solvents can be used alone or
It may be used in combination of more than one kind. The radiation-sensitive colored composition of the present invention is prepared by mixing the above main components and other additives used as necessary with a solvent, and mixing and dispersing the mixture using various mixers and dispersers. Can be.

The radiation-sensitive colored composition of the present invention is applied to a substrate by a coating method such as spin coating, casting coating, roll coating or the like to form a radiation-sensitive composition layer, and is applied via a predetermined mask pattern. By exposing and developing with a developer,
Form a colored pattern. As the radiation used at this time, ultraviolet rays such as g-rays, h-rays, and i-rays are particularly preferably used.

As the substrate, for example, soda glass, pyrex glass, quartz glass used for a liquid crystal display device or the like and a transparent conductive film adhered thereto, or a photoelectric conversion device substrate used for a solid-state imaging device or the like, for example, silicon Substrates and the like can be mentioned. These substrates are generally formed with black stripes for isolating each pixel.

Any developer can be used as long as it dissolves the radiation-sensitive colored composition of the present invention but does not dissolve the irradiated portion. Specifically, a combination of various organic solvents or 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.

As the alkali, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide , Choline, pyrrole, piperidine, an alkaline compound such as 1,8-diazabicyclo- [5,4,0] -7-undecene at a concentration of 0.001 to 0.001.
An alkaline aqueous solution dissolved to be 10% by weight, preferably 0.01 to 1% by weight is used. When a developer composed of such an alkaline aqueous solution is used, it is generally washed with water after development.

[0086]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist of the invention. Example 1 First, a polymer included in the general formula (3) was synthesized as a binder resin by the following method. (Synthesis Example of Binder Resin (1)) 60 g of polyvinyl butyral (Denka Butyral # 4000-1) in a 1-liter three-necked round bottom flask equipped with a thermometer, a reflux condenser, and a stirrer. Was dissolved in 720 ml of acetic acid by heating. After the reaction temperature was further raised to 100 ° C., phthalic anhydride 8
9.8 g and 60.5 g of sodium acetate were added and reacted for 3 hours. After the reaction, this solution was added little by little to a 10-liter solution of methanol-water 1: 3 to precipitate a polymer. The solid was dried under vacuum to obtain 64.8 g of a polymer (A). The acid content was 2.72 meq / g. GP
The molecular weight by the method C is 140,000 as a weight average molecular weight.
Met. -40 parts of the resin of Synthesis Example (1) (polymer (A))-C.I. I. Pigment Red 155 35 parts C.I. I. Pigment Yellow 83 15 parts ・ Propylene glycol monomethyl ether acetate 200 parts was dispersed in a sand mill for 24 hours.

Next, the following components were added. 40 parts of acrylate monomer (1) 15% by weight of hexaacrylate having six ethylene oxides added to dipentaerythritol (2) 85% by weight of pentaacrylate having six ethylene oxides added to dipentaerythritol 4- [o-bromo-p-N, N-di (ethoxycarbonyl) 3 parts aminophenyl] 2,6-di (trichloromethyl) -S-triazine7-[{4-chloro-6- (diethylamino) ) -S-Triazine 2 parts -2-yl @ amino] -3-phenylcoumarin 0.01 parts hydroquinone monomethyl ether 150 parts propylene glycol monomethyl ether acetate

After mixing the above two components, the mixture was filtered with a filter having a pore size of 5 μm to obtain a radiation-sensitive colored composition of the present invention.
This composition was applied to a glass substrate for a color filter by a spin coater so as to have a dry film thickness of 1.5 μm, and dried at 100 ° C. for 2 minutes. As a result, a uniform red coating film was obtained.

An exposure amount of 200 mj / cm 2 was applied through a mask using an ultra-high pressure mercury lamp of 2.5 Kw. Next, 0.
It was immersed in a 1% aqueous solution of sodium carbonate for development. At this time, the number of seconds during which the unexposed portion peeled off with the developing solution and the number of seconds during which the exposed portion was peeled off with the developing solution were measured. Separately, 1 part by weight of the above acrylate monomer and 2 parts by weight of a methyl acrylate-acrylic acid copolymer (70/30 (molar ratio)) are dissolved in parts by weight of hexanone to form a film having a dry thickness of 2 μm. And turbidity was visually observed. The results are shown in Table 1.

Examples 2 to 6, Comparative Examples 1 and 2 Example 1 was repeated except that the acrylate monomer was changed as follows. The results are shown in Table 1. Example 2 (1) Ethylene oxide was added to dipentaerythritol
Hexaacrylate (25% by weight) (2) Ethylene oxide was added to dipentaerythritol
Example 3 (1) Ethylene oxide was added to dipentaerythritol by adding 6 parts by weight of pentaacrylate (75% by weight).
(6) ethylene oxide was added to dipentaerythritol.
Example 4 (1) Ethylene oxide was added to dipentaerythritol by adding 6 parts of pentaacrylate (40% by weight).
Hexaacrylate added (100% by weight)

Example 5 (1) Hexaacrylate in which six propylene oxides were added to dipentaerythritol (60% by weight) (2) Pentaacrylate in which six propylene oxides were added to dipentaerythritol Example 6 (1) Ethylene oxide was added to dipentaerythritol
(2) Hexaacrylate (60% by weight) added with two (2) ethylene oxide to dipentaerythritol
Example 7 (1) Ethylene oxide was added to dipentaerythritol with two pentaacrylates added (40% by weight).
Comparative Example 1 (1) Dipentaerythritol hexaacrylate (6% by weight)
(2%) dipentaerythritol pentaacrylate (4% by weight)
Comparative Example 2 (1) Pentaerythritol tetraacrylate (10
0% by weight)

[0092]

[Table 1]

From the above results, it can be seen that the developability of the unexposed portion is promoted by the present invention, and the exposed portion is less likely to be dissolved by the development, and the discrimination between the exposed portion and the unexposed portion is achieved.
(ion) is clear. This is because the binder resin made hydrophilic to ensure solubility in an alkali developer is selected from the specific (meth) acrylate monomer as the radiation-sensitive polymer component in the present invention, and the radiation-sensitive polymer component is selected. This is because they are easily compatible with each other, and the curability with ultraviolet light is improved.

[0094]

According to the present invention, a radiation-sensitive colored composition having improved compatibility between a radiation-sensitive polymer component and a binder resin, particularly a radiation-sensitive colored composition suitable for a color filter, is provided. You. The composition of the present invention has excellent coating properties and can provide a color filter having improved transmittance, uneven color and improved image adhesion.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location G03F 7/004 505 G03F 7/004 505

Claims (4)

[Claims] 1. A radiation-sensitive coloring composition containing a radiation-sensitive component, a binder resin, a pigment, and a solvent, wherein the radiation-sensitive component is a polymerizable component represented by the following general formulas (1) and (2). A radiation-sensitive coloring composition comprising at least one (meth) acrylate compound selected from the group of compounds represented by the formula: Embedded image (Where B represents, independently of one another, any of — (CH ₂ CH ₂ O) — and — (CH ₂ CH (CH ₃ ) O) —;
X independently represents any one of an acryloyl group, a methacryloyl group, and a hydrogen atom;
Where the total of acryloyl and methacryloyl groups is 5
Or six, and in equation (2), three or four
N is each independently an integer from 0 to 6, and the sum of each n is 3 to 24; m is each independently 0 to 6
6 represents an integer, and the sum of each m is 2 to 16. ) 2. The composition according to claim 1, wherein the polymerizable component contains at least 20% by weight of an acrylic compound of the general formula (1) wherein all six X's are acryloyl groups. 3. The composition according to claim 2, wherein the polymerizable component contains at least 50% by weight of an acrylic compound of the general formula (1) wherein all six X's are acryloyl groups. 4. The sum of n in the general formula (1) is 6 to 1
4. The composition according to claim 1, wherein the composition is 2.