JP2002350628A - Coloring composition for color filter and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To realize a color filter having high brightness, a wide color reproduction range and excellent color reproducibility. SOLUTION: This coloring composition contains a coloring agent, a dispersant, an auxiliary dispersant, a compound having a polymerizable group and a polymerization initiator. The auxiliary dispersant cotains at least one of a colorless polycyclic aromatic compound and a polycyclic heterocyclic compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color filter used in combination with a liquid crystal display device or a solid-state image sensor, and more particularly, to a composition used for manufacturing a color filter by a colorant dispersion method and a colorant dispersion method. The present invention relates to a manufactured color filter.

[0002]

2. Description of the Related Art Liquid crystal display devices are widely used in personal computers, word processors, and the like. However, with the advancement of information, conversion from monochrome display to color display is progressing. In recent years, color display has become widespread, and is not limited to notebook PC display, which is the main application in the past,
It is beginning to be used rapidly for monitors and televisions.

In a color display by a liquid crystal display device, light from a light source is modulated in accordance with display information by an optical shutter utilizing an electrochemical effect of liquid crystal, and has a wavelength selective transmittance in a visible light wavelength region. The visible light wavelength region component of the modulated light is separated by the color filter, and this is realized by being visually recognized.

As a configuration of a color liquid crystal display device, there are many transmissive types in which a light source is disposed behind a liquid crystal optical shutter, but a reflective type in which a light source is disposed in front of a liquid crystal optical shutter is also possible. In the case of the additive color mixture method, red (R), green (G), and blue (B) are arranged on a plane such that one pixel is composed of three pixels. Is arranged such that cyan (C), yellow (Y), and magenta (M) are overlapped. In either case, the light from the light source is modulated by a liquid crystal light shutter according to the display information, unnecessary wavelength regions are attenuated by color filters, and the display is synthesized by combining the spectrum corresponding to the color and brightness of the display information. Are common.

A color filter used in a liquid crystal display device is also used for a solid-state image pickup device or the like, and uses a method such as a dyeing method, a printing method, an electrodeposition method, an ink jet method, and a colorant dispersion method. It is manufactured by forming fine pixels such as red, green and blue on a transparent substrate such as glass or polymer.

Among these conventional color filter manufacturing methods, in the dyeing method, an image is formed using a photosensitive resin in which dichromate is mixed as a photosensitive agent in gelatin, polyvinyl alcohol, or the like, and then this is dyed. Thereby, a color filter is manufactured. The dyeing method is excellent in terms of color reproducibility, but has a problem that the anti-staining step is indispensable in order to form multiple colors on the same substrate, and the step becomes complicated. In addition, light resistance is poor because a dye is used. Further, since the use of dichromate is essential, it is not desirable from the viewpoint of preventing pollution.

In the printing method, a color filter is manufactured by transferring thermosetting or photocurable ink to a glass substrate using a method such as screen printing or flexographic printing. This method simplifies the process because image formation and dyeing are not required, but does not provide a high-definition image and has a problem in ink smoothness.

In the electrodeposition method, a color filter is manufactured by immersing a glass substrate provided with electrodes in a bath containing a coloring agent or a dye and performing electrophoresis. Although this method is excellent in smoothness, it is difficult to form a complicated pattern because an electrode must be formed on a glass substrate in advance.

On the other hand, in the production of color filters for liquid crystal display devices in recent years, a colorant dispersion method has become widespread. In this method, a composition in which a coloring agent is dispersed in a photosensitive resin is applied on a transparent substrate such as glass to form a coating film, which is exposed to radiation through a photomask, and exposed to light. Is removed by a development process to form a pattern, followed by baking to stabilize the pattern by repeating a series of operations, in the case of the additive color mixing method, three times of red, green, and blue to obtain color. A filter is manufactured. This method has high productivity, excellent fine processing,
In addition, since they have high durability against heat and light, they have become the mainstream in the production of color filters in recent years.

[Problems to be solved by the invention]

When a color filter is manufactured by a colorant dispersion method, as described above, a composition (photoresist composition) in which a colorant is dispersed in a photosensitive resin is used. In the case of the additive color mixing method, this is a negative photoresist containing a coloring material for complementary colors, yellow and violet, in addition to coloring materials for three primary colors, such as red, green, and blue.

In such a photoresist composition, a dispersant and a dispersing aid are used for dispersing and mixing an organic colorant. Examples of the dispersant include a polyurethane polymer dispersant, an acrylic polymer dispersant having an alkylamino group or an imidazole group described in JP-A-11-1515, a polyethyleneimine dispersant, and the like. Are known. Also, as a dispersing aid,
Japanese Patent No. 2891418 and JP-A-5-60127 disclose a coloring agent derivative obtained by introducing a substituent of an acidic group or a basic group into a compound having the same or similar structure as a coloring agent to be used. Have been.

Here, the dispersing aid functions to assist the dispersing of the colorant by the dispersing agent. The colorant derivative described in the above publication has a structure in which an acidic and / or basic substituent is introduced into a colorant mother skeleton having affinity for the colorant.

However, since the coloring agent derivative introduces a substituent into the mother skeleton of the coloring agent, its molecular structure and crystal structure are changed from that of the mother coloring agent, and as a result, the coloring agent derivative is different from the mother coloring agent. It emits a unique color. When such a colorant derivative is used as a colorant dispersant or a dispersing aid, the dispersibility of the organic colorant in the photoresist is improved. The hue of the composition changes. As a result, the transmitted light spectrum of the color filter changes, the color reproducibility of the color filter decreases, and the consistency with the backlight emission spectrum deteriorates, so that the brightness of the color filter decreases. There is.

The present invention has been made in view of the above problems. That is, the present invention provides a composition for a color filter which, by being used as a photoresist composition, has a high lightness, has a wide color reproduction range, and enables the production of a color filter having excellent color reproducibility, It is an object to provide a color filter using this.

[0015]

Means for Solving the Problems As a result of intensive studies, the present inventors have selected colorless polycyclic aromatic compounds and polycyclic heterocyclic compounds and used them as dispersion aids. As a result, the present inventors have found that the above objects can be achieved, and have accomplished the present invention.

That is, the gist of the present invention is a composition containing a coloring agent, a dispersant, a dispersing aid, a compound having a polymerizable group, and a polymerization initiator, But,
A color filter composition characterized by being at least one of a colorless polycyclic aromatic compound and a polycyclic heterocyclic compound.

Further, another object of the present invention is to provide a transparent substrate,
A color filter comprising a colored pixel provided on the transparent substrate, wherein the colored pixel contains the above-described composition for a color filter. In the present invention, “colorless” generally means that the light transmittance is 90% or more for all wavelengths in the visible light wavelength region of 380 to 780 nm.

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. In the following description, for example, the description “(meth) acrylic acid” means “acrylic acid or methacrylic acid”. The same applies to “(meth) acrylate”, “(meth) acryloyl group” and the like. Further, the term “(co) polymer” is used to include both a homopolymer and a copolymer.

(1) Composition for Color Filter The composition for color filter of the present invention contains a colorant, a dispersant, a dispersing aid, a compound having a polymerizable group, and a polymerization initiator. Wherein at least one of a colorless polycyclic aromatic compound and a polycyclic heterocyclic compound is used as a dispersing aid. Further, it is preferable to include other components such as a binder resin and a solvent as needed. Hereinafter, each component contained in the color filter composition of the present invention will be described in detail.

(1-1) Dispersing Aid A coloring agent derivative generally used as a dispersing aid is, as described above, a substance obtained by introducing an acidic group and a basic group into a coloring agent or a derivative thereof, and has an affinity for the coloring agent. The colorant mother skeleton is used as a structure having an affinity, and the acid and / or
Alternatively, a basic substituent is present in the same structure.

On the other hand, the dispersing aid used in the color filter composition of the present invention has a colorless polycyclic aromatic structure and / or polycyclic heterocyclic structure as a structure having an affinity for an organic colorant. Having. Here, “colorless” specifically refers to a visible light wavelength range of 380 to 380, as described above.
90% light transmittance for all wavelengths in the 780 nm region
It points out that it is above. In addition, as a structure having an affinity for the binder resin, an acidic and / or basic substituent is preferably introduced into the above-mentioned polycyclic aromatic structure and / or polycyclic heterocyclic structure.

Such a compound exhibits a high affinity for both the colorant and the binder resin, like the above-mentioned colorant derivative, and thus has a function of assisting the dispersing of the colorant by the dispersant. Furthermore, unlike the above-described colorant derivatives, they are colorless, so they do not affect the hue of the color filter composition. Therefore, when the composition for a color filter of the present invention is used as a photoresist composition, it is possible to suppress a change in hue of the color filter and a decrease in transmittance due to wavelength mismatch with a backlight accompanying the change. Consequently, it is possible to manufacture a color filter having a high brightness and a wide color reproduction range.

As the colorless polycyclic aromatic structure and / or polycyclic heterocyclic structure of the dispersing aid of the present invention, a colorless compound having two or more aromatic structures and / or heterocyclic structures in a molecule can be used. It is preferably used. These aromatic structures and / or heterocyclic structures are usually bonded in a conjugated system and / or a non-conjugated system. The number of aromatic structures and / or heterocyclic structures to be bonded is usually 2 to 20, preferably 2 to 10.

Here, as the aromatic structure and / or heterocyclic structure, if the conjugated system is too long, the absorption wavelength range may be lengthened and the absorption may be in the visible region. Short ones are preferred. Further, when these structures are bonded by a conjugated system, if the conjugated system is too long, the absorption wavelength range may be extended to have absorption in the visible region, and therefore, the aromatic structure to be bonded and / or Alternatively, the number of heterocyclic structures is naturally limited. The molecular weight of the dispersion aid of the present invention is usually from 100 to 1,000, preferably from 100 to 500.

Examples of the aromatic skeleton include benzene, naphthalene, anthracene, phenanthrene, pyrene, coronene, azulene, biphenyl, terphenyl and the like. Examples of the heterocyclic skeleton include furan, thiophene, pyrrole, oxazole, thiazole, imidazole, pyrazole, triazole, tetrazole, pyridine, pyridazine, pyrimidine, pyrazine, pyran, dithiazine and the like.

These aromatic and heterocyclic skeletons include a hydrogen atom, a hydroxyl group, a nitro group, an amino group, an alkylamino group, a cyano group, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, and an aryloxy group. , Arylthio, aralkyl, alkenyl, alkenyloxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, alkylaminocarbonyl, alkoxyalkyl, fluoroalkyl, fluoroalkoxy, fluoroalkylthio,
Substitution of carboxyl group, formyl group, sulfonic acid group, alkylsulfonyl group, alkylaminosulfonyl group, alkylaminosulfonic acid group, chlorosulfone group, carbamide group, sulfonamide group, aliphatic heterocyclic group, aromatic heterocyclic group, etc. A group may be introduced.

Examples of the alkyl group include those having 1 to 10 carbon atoms, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group and sec-butyl group. 1-4 linear or branched alkyl groups are used. Further, a cyclic alkyl group having 3 to 10 carbon atoms, preferably 3 to 6 carbon atoms, such as a cyclopropyl group and a cyclobutyl group, is also used.

Examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, sec-
C 1-10, preferably C 1, such as a butoxy group
4 to 4 linear or branched alkoxy groups are used. Further, a cyclic alkoxy group having 3 to 10 carbon atoms, preferably 3 to 6 carbon atoms, such as a cyclopropyloxy group and a cyclobutyloxy group, is also used.

Examples of the alkylthio group include those having 1 to 10 carbon atoms, such as methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, tert-butylthio group and sec-butylthio group. A linear or branched alkylthio group of the formulas 1 to 4 is used. Further, a cyclic alkylthio group having 3 to 10 carbon atoms, preferably 3 to 6 carbon atoms, such as a cyclopropylthio group and a cyclobutylthio group, is also used.

The alkylamino group includes, for example, a methylamino group, an ethylamino group, a dimethylamino group, a diethylamino group and the like, having 1 to 10 carbon atoms, preferably 1 carbon atom.
~ 6 alkylamino groups are used.

As the aryl group, for example, a phenyl group,
An aryl group having 6 to 10 carbon atoms such as a naphthyl group is used. As the aryloxy group, an aryloxy group having 6 to 10 carbon atoms such as a phenyloxy group and a naphthyloxy group is used. As the arylthio group, for example, a phenylthio group, a naphthylthio group or the like having 6 to 6 carbon atoms.
Ten arylthio groups are used.

As the aralkyl group, an aralkyl group having 7 to 14 carbon atoms such as a phenylmethyl group and a phenylethyl group is used. As the alkenyl group, a linear or branched alkenyl group having 2 to 11 carbon atoms, preferably 2 to 5 carbon atoms, such as a vinyl group, a propenyl group, a butenyl group, and a pentenyl group is used. Further, for example, a C3-C3 group such as a cyclopentenyl group and cyclohexenyl.
A cyclic alkenyl group having 10, preferably 3 to 6 carbon atoms is also used.

As the alkenyloxy group, a linear or branched alkenyloxy group having 3 to 11 carbon atoms, preferably 2 to 5 carbon atoms, such as a propenyloxy group, a butenyloxy group, and a pentenyloxy group is used. Examples of the alkylcarbonyl group include those having 2 carbon atoms such as an acetyl group, a propionyl group, a butyryl group and an isobutyryl group.
To 11, preferably a straight-chain or branched alkylcarbonyl group having 2 to 5 carbon atoms.

Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group,
carbon atoms such as n-butoxycarbonyl, tert-butoxycarbonyl, sec-butoxycarbonyl, etc.
To 11, preferably a straight-chain or branched alkoxycarbonyl group having 2 to 5 carbon atoms.

Examples of the alkylcarbonyloxy group include a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an isopropylcarbonyloxy group, an n-butylcarbonyloxy group,
A linear or branched alkylcarbonyloxy group having 2 to 11 carbon atoms, preferably 2 to 5 carbon atoms, such as a tert-butylcarbonyloxy group and a sec-butylcarbonyloxy group is used.

The alkylaminocarbonyl group includes, for example, a methylaminocarbonyl group, an ethylaminocarbonyl group, a dimethylaminocarbonyl group, a diethylaminocarbonyl group and the like, having 1 to 10 carbon atoms, preferably 1 carbon atom.
~ 6 alkylaminocarbonyl groups are used. Examples of the alkoxyalkyl group include a methoxymethyl group,
A linear or branched alkoxyalkyl group having 2 to 11 carbon atoms, preferably 2 to 5 carbon atoms, such as a methoxyethyl group, an ethoxymethyl group, and an ethoxyethyl group is used.

Examples of the fluoroalkyl group include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoro-n-propyl group, a heptafluoroisopropyl group, a perfluoro-n-butyl group and a perfluoro-te
A linear or branched fluoroalkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, such as an rt-butyl group and a perfluoro-sec-butyl group is used.

Examples of the fluoroalkoxy group include a trifluoromethoxy group, a pentafluoroethoxy group, a heptafluoro-n-propoxy group, a heptafluoroisopropoxy group, a perfluoro-n-butoxy group, a perfluoro-tert-butoxy group, Perfluoro-sec
A linear or branched fluoroalkoxy group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, such as butoxy group, is used.

Examples of the fluoroalkylthio group include trifluoromethylthio, pentafluoroethylthio, heptafluoro-n-propylthio, heptafluoroisopropylthio, perfluoro-n-butylthio, and perfluoro-tert-butylthio. , A perfluoro-sec-butylthio group or the like, having 1 to 10 carbon atoms;
Preferably, a linear or branched fluoroalkylthio group having 1 to 4 carbon atoms is used.

Examples of the alkylsulfonyl group include methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, tert-butylsulfonyl, sec.
A linear or branched alkylsulfonyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, such as -butylsulfonyl group, is used.

The alkylaminosulfonyl group includes, for example, a methylaminosulfonyl group, an ethylaminosulfonyl group, a dimethylaminosulfonyl group, a diethylaminosulfonyl group and the like, having 1 to 10 carbon atoms, preferably 1 carbon atom.
~ 6 alkylaminosulfonyl groups are used. Examples of the alkylaminosulfonic acid group include alkylamino having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, such as methylaminosulfonic acid group, ethylaminosulfonic acid group, dimethylaminosulfonic acid group, and diethylaminosulfonic acid group. Sulfonate groups are used.

As the aliphatic heterocyclic group, for example, an aliphatic heterocyclic group such as a morpholine ring and a piperidine ring is used. Examples of the aromatic heterocyclic group include a pyrrole ring, a furan ring, a thiol ring, a pyridine ring, an oxazole ring, a thiazole ring, an imidazole ring, a triazole ring, a thiadiazole ring, a triazine ring, a benzoxazole ring, a benzothiazole ring, and a benzimidazole ring. And the like. Note that these substituents may further have the above-mentioned substituents.

The plurality of mother skeletons can be bonded to each other by a single bond, condensed cyclized, or bonded to each other by a conjugated and / or non-conjugated bond through a divalent or higher valent organic group. Examples of the divalent or higher valent organic group used as the bonding group include an alkyl group, a fluoroalkyl group, a cycloalkyl group, a fluorocycloalkyl group, an alkene group, an alkyne group, an aryl group, an ester group, an amide group, an imide group, Examples of the organic group include a diazo group, an azomethine group, and a combination of these groups. Also,
These bonding groups may be further substituted by the substituents exemplified as the substituents of the above-mentioned mother skeleton.

(1-2) Dispersant The dispersant used in the color filter composition of the present invention is not particularly limited, but may be at least one of an acidic group, a basic group and a quaternary ammonium base. It is preferable to use a colorless polymer compound having the same.

In the main chain structure of the polymer compound, polyaddition polymers such as polystyrene, polymethacrylate, polyacrylate, polyvinylalkyl, polyacrylamide, polyacrylonitrile, polyvinyl chloride, polyvinyl alcohol and the like are used. Vinyl polymers, polyethylene, polypropylene, polyolefin polymers such as polyisobutylene, polybutadiene, diene polymers such as polyisoprene, polyethyleneimine, etc., and condensation polymers such as polyester, polyamide, polyether, polyurethane resin, and epoxy resin. , Melamine resin and the like are used, respectively.

The various polymers described above can be copolymerized with various monomers in order to achieve the desired performance. Taking the vinyl polymer as an example, the monomers to be copolymerized are exemplified as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and isobutyl (meth) acrylate. ) Acrylate, tert-butyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, (Meth) acrylates such as tetrahydrofurfuryl (meth) acrylate, styrene and its derivatives, (anhydride) dicarboxylic acids such as maleic acid, itaconic acid and citraconic acid, α-methyls Ren, vinyl acetate,
N-vinylpyrrolidone, (meth) acrylonitrile,
Examples include various monomers such as (meth) acrylamide, macromonomers such as polymethyl methacrylate macromonomer, polystyrene macromonomer, and poly2-hydroxyethyl methacrylate macromonomer. In addition, you may use together these various copolymerized monomers two or more types.

The structure of the polymer compound formed by polymerization may be any of a random polymer, a block polymer and a graft polymer.

As an example of the condensation polymer, the structure of a urethane resin is exemplified. Tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and cyclized trimerized oligomers of these isocyanate groups, ethylene glycol, propylene glycol, tetramethylene glycol, hexane Diol, decanediol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polycaprolactone, etc. and hydroxy compounds at both ends of these copolymers, and methanol, ethanol, propanol, butanol, hexanol, decanol, methoxy polyethylene glycol, ethoxy Polyethylene glycol, methoxy polypropylene glycol, ethoxy polypropylene glycol Polymers of one terminal hydroxy compounds such Lumpur like.

Preferably, at least one of an acidic group, a basic group and a quaternary ammonium group is bonded to the above-mentioned polymer compound as a substituent. Examples of the acidic group include a carboxyl group, a phosphoric acid group, and a sulfonic acid group. Examples of the basic group include an amino group, an alkylamino group, an imidazole group, an oxazole group, a pyridine group, and a morpholino group. Examples of the alkyl group corresponding to the alkyl portion of the alkylamino group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group,
A linear or branched alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, such as an n-butyl group, an isobutyl group, and a tert-butyl group can be used. Further, for example, a compound having 3 carbon atoms such as a cyclopropyl group and a cyclobutyl group
A cyclic alkyl group having 10 to 10, preferably 3 to 6 carbon atoms can also be used. As the quaternary ammonium group, for example, a functional group obtained by quaternizing the alkylamino group with an alkyl halide is used. In this alkyl halide, as the halogen, for example, fluorine, chlorine, bromine, and iodine, and as the alkyl, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, etc., having 1 to 10 carbon atoms, Preferably 1 to 4 carbon atoms
Can be used, respectively.

(1-3) Binder Resin The color filter composition of the present invention may contain a binder resin as an optional component. As the binder resin, a dedicated compound may be prepared, or a compound having the function of a compound having a polymerizable group described later may be selected. In the former case, an appropriate one is selected in consideration of the desired image formability and performance, the manufacturing method to be adopted, and the like. On the other hand, in the latter case, the purpose is to modify the color filter composition and to improve the physical properties after photo-curing. The resin will be appropriately selected.

Examples of the binder resin which is usually used include, for example, (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylamide, maleic acid, (meth) acrylonitrile, styrene, vinyl acetate, vinylidene chloride, maleimide and the like. Alternatively, a copolymer, polyethylene oxide, polyvinyl pyrrolidone, polyamide, polyurethane, polyester, polyether, polyethylene terephthalate, acetyl cellulose, novolak resin, resole resin, polyvinyl phenol or polyvinyl butyral, and the like can be given.

Preferred among these binder resins are those having a carboxyl group or a phenolic hydroxyl group in the side chain or main chain. Use of a resin having these functional groups enables development with an alkaline solution. Among them, preferred are resins having a carboxyl group having high alkali developability, such as acrylic acid (co) polymer, styrene / maleic anhydride resin, and acid anhydride modified resin of novolak epoxy acrylate.

Particularly preferred is a (co) polymer containing (meth) acrylic acid or a (meth) acrylate having a carboxyl group (hereinafter referred to as an acrylic resin).
It is. This is because this resin is excellent in developability and transparency and can obtain various copolymers by selecting various monomers, so that the performance and the production method can be easily controlled.

Examples of the acrylic resin include (meth) acrylic acid and / or succinic acid (2- (meth) acryloyloxyethyl) ester, adipic acid (2-acryloyloxyethyl) ester, and phthalic acid ( 2- (meth) acryloyloxyethyl) ester, hexahydrophthalic acid (2- (meth) acryloyloxyethyl) ester, maleic acid (2- (meth) acryloyloxyethyl) ester, succinic acid (2- ( (Meth) acryloyloxypropyl) ester, adipic acid (2-
(Meth) acryloyloxypropyl) ester, hexahydrophthalic acid (2- (meth) acryloyloxypropyl) ester, phthalic acid (2- (meth) acryloyloxypropyl) ester, maleic acid (2- (meth) (Acryloyloxypropyl) ester, succinic acid (2- (meth) acryloyloxybutyl) ester, adipic acid (2- (meth) acryloyloxybutyl) ester, hexahydrophthalic acid (2- (meth) acryloyloxy) Butyl) ester, phthalic acid (2- (meth) acryloyloxybutyl) ester, maleic acid (2- (meth) acryloyloxybutyl) ester, etc., to hydroxyalkyl (meth) acrylate and (anhydride) succinic acid, Acids (anhydrides) such as (anhydride) phthalic acid and (anhydride) maleic acid
Is added as an essential component, and if necessary, styrene-based monomers such as styrene, α-methyl-styrene and vinyltoluene; unsaturated groups such as cinnamic acid, maleic acid, fumaric acid, maleic anhydride and itaconic acid Containing carboxylic acid;
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, allyl (meth)
Acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, hydroxyphenyl (meth) acrylate, methoxyphenyl (meth) acrylate, etc. (Meth) acrylic acid ester; a compound obtained by adding a lactone such as ε-caprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone to (meth) acrylic acid; acrylonitrile; ) Acrylamide, N-methylolacrylamide, N, N-dimethylacrylamide, N-methacryloylmorpholine, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminoethylacrylamide Acrylamide and the like; vinyl acetate, vinyl versatate, vinyl propionate,
Examples include resins obtained by copolymerizing various monomers such as vinyl cinnamate and vinyl acid such as vinyl pivalate.

For the purpose of increasing the strength of the coating film, styrene, α-methylstyrene, benzyl (meth) acrylate, hydroxyphenyl (meth) acrylate, methoxyphenyl (meth) acrylate, hydroxyphenyl (meth) acrylamide, hydroxyphenyl (Meta)
10 to 98 mol%, preferably 20 to 80 mol%, more preferably 30 to 70 mol% of a monomer having a phenyl group such as acrylsulfonamide, and (meth) acrylic acid or succinic acid (2- (meth) ) Acryloyloxyethyl) ester, adipic acid (2-acryloyloxyethyl) ester, phthalic acid (2- (meth) acryloyloxyethyl) ester, hexahydrophthalic acid (2-
At least one polymerizable group selected from the group consisting of (meth) acrylic esters having a carboxyl group such as (meth) acryloyloxyethyl) ester and maleic acid (2- (meth) acryloyloxyethyl) ester; From 2 to 90 mol%, preferably from 20 to
An acrylic resin copolymerized at a ratio of 80 mol%, more preferably 30 to 70 mol% is also preferably used.

It is preferable that these resins have an ethylenic double bond in a side chain. By using a binder resin having a double bond in a side chain, the photocurability of the composition for a color filter according to the present invention is increased, so that the resolution and adhesion can be further improved. Means for introducing an ethylenic double bond into the binder resin include, for example, Japanese Patent Publication No. 50-34443 and Japanese Patent Publication No.
No. 0-34444, that is, a method in which a carboxyl group of a resin is reacted with a compound having a glycidyl group or an epoxycyclohexyl group and a (meth) acryloyl group, or an acrylic acid chloride is added to a hydroxyl group of the resin. And the like.

For example, glycidyl (meth) acrylate,
Allyl glycidyl ether, α-ethyl glycidyl acrylate, crotonyl glycidyl ether, glycidyl ether of (iso) crotonic acid, (3,4-epoxycyclohexyl) methyl (meth) acrylate, (meth) acrylic chloride, (meth) allyl chloride By reacting such a compound with a resin having a carboxyl group or a hydroxyl group, a binder resin having an ethylenic double bond group in a side chain can be obtained. In particular, a resin obtained by reacting an alicyclic epoxy compound such as (3,4-epoxycyclohexyl) methyl (meth) acrylate is preferable as the binder resin.

As described above, when an ethylenic double bond is introduced into a resin having a carboxylic acid group or a hydroxyl group in advance, 2 to 50 mol% of the carboxyl group or the hydroxyl group of the resin is used.
Preferably, a compound having an ethylenic double bond is bonded to 5 to 40 mol%. The preferred range of the weight average molecular weight of these acrylic resins measured by GPC is 1,000 to 100,000. If the weight average molecular weight is less than 1,000, it is difficult to obtain a uniform coating film, and if it exceeds 100,000, the developability tends to be reduced. The preferred range of the content of the carboxyl group is 5 to 200 in terms of acid value.
When the acid value is 5 or less, it becomes insoluble in an alkali developing solution, and when it exceeds 200, the sensitivity may decrease.

These binder resins are contained in an amount of 10 to 80% by weight, preferably 20 to 70% by weight, based on the total solid content of the composition for a color filter of the present invention.

(1-4) Compound Having a Polymerizable Group The compound having a polymerizable group used in the composition for a color filter of the present invention is a low molecular compound having any polymerizable group. Although there is no particular limitation, a compound capable of addition polymerization having at least one ethylenic double bond (hereinafter abbreviated as “ethylenic compound”) is preferable. The ethylenic compound has an ethylenic double bond such that when the composition for a color filter of the present invention is irradiated with actinic rays, it undergoes addition polymerization by the action of a photopolymerization initiation system (described later) and cures. Compound. In this specification, the term "low molecular weight compound" is a term corresponding to a so-called high molecular weight substance and refers to a concept containing not only monomers in a narrow sense but also dimers, trimers and oligomers.

Examples of the ethylenic compound include unsaturated carboxylic acids, esters of monohydroxy compounds and unsaturated carboxylic acids, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids, and aromatic polyhydroxy compounds and unsaturated polyhydroxy compounds. An ester obtained from an ester with a carboxylic acid, an ester obtained by an esterification reaction with an unsaturated carboxylic acid and a polyvalent carboxylic acid, and a polyvalent hydroxy compound such as the above-mentioned aliphatic polyhydroxy compound and aromatic polyhydroxy compound; An ethylenic compound having a urethane skeleton obtained by reacting a (meth) acryloyl-containing hydroxy compound is exemplified.

Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate,
Acrylics such as trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate Acid esters. In addition, the acrylic acid portion of these acrylates is replaced with a methacrylic acid portion, a methacrylic acid ester, an itaconic acid ester, instead of an itaconic acid portion, a crotonic acid ester, instead of a crotonic acid portion, or a maleic acid, which is replaced with a maleic acid portion Esters and the like.

Examples of the ester of the aromatic polyhydroxy compound and the unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, pyrogallol triacrylate and the like. The ester obtained by the esterification reaction of the unsaturated carboxylic acid with the polyvalent carboxylic acid and the polyvalent hydroxy compound is not necessarily a single substance, but may be a mixture. Representative examples include condensates of acrylic acid, phthalic acid and ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, acrylic acid, adipic acid, butanediol and glycerin And the like.

Examples of the ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound with a (meth) acryloyl group-containing hydroxy compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; cyclohexane diisocyanate, isophorone diisocyanate and the like. Alicyclic diisocyanate, such as tolylene diisocyanate, diphenylmethane diisocyanate, etc .; 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy (1,1,1-triacryloyloxymethyl) propane, -Hydroxy compound containing (meth) acryloyl group such as -hydroxy (1,1,1-trimethacryloyloxymethyl) propane Reaction products of the like.

Other examples of the ethylenic compound used in the present invention include acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; and vinyl group-containing compounds such as divinyl phthalate. The mixing ratio of these ethylenic compounds is 10 to 80% by weight, preferably 20 to 70% by weight, based on the total solid content of the composition for a color filter of the present invention.

(1-5) Polymerization Initiator The polymerization initiator used in the color filter composition of the present invention is not particularly limited as long as it causes a polymerization reaction of the compound having a polymerizable group described above. Absent. However, when the composition for a color filter of the present invention contains an ethylenic compound as the compound having a polymerizable group described above, light is directly absorbed or photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction. A photopolymerization initiator which has a function of generating a polymerization active radical is required.

The photopolymerization initiator used in the present invention is usually composed of a system in which an additive such as an accelerator is used in combination with the polymerization initiator. As the polymerization initiator, for example, JP-A-59-1
No. 52396, metallocene compounds containing titanocene compounds described in JP-A-61-151197, hexaarylbiimidazole derivatives described in JP-A-10-39503, halomethyl-s-triazine derivatives,
N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-
Radical activators such as α-amino acid esters are included. As the accelerator, for example, a complex such as N, N-dialkylaminobenzoic acid alkyl ester such as N, N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, or 2-mercaptobenzimidazole is used. A mercapto compound having a ring or an aliphatic polyfunctional mercapto compound is used. The photopolymerization initiator and the additive may be used in combination of a plurality of types.

The compounding ratio of the photopolymerization initiator is from 0.1 to 30% by weight, preferably from 0.5 to 20% by weight, more preferably from 0.7 to 30% by weight, based on the total solid content of the composition for a color filter of the present invention.
-10% by weight. If the blending ratio is extremely low, the sensitivity is lowered. On the other hand, if the blending ratio is extremely high, the solubility of the unexposed portion in the developing solution is lowered, and poor development is likely to be induced.

In the composition for a color filter of the present invention,
If necessary, a sensitizing dye corresponding to the wavelength of the image exposure light source can be blended for the purpose of increasing the sensitivity of the color filter. Examples of these sensitizing dyes are disclosed in
Xanthene dyes described in JP-A-221958 and JP-A-4-219756, JP-A-3-239703 and JP-A-5-219756.
Coumarin dyes having a heterocyclic ring described in each of JP-A-289335, JP-A-3-239703 and JP-A-5-289335.
No. 3-ketocoumarin compounds described in
Pyrromethene dyes described in JP-A-19240, JP-A-47-2528, JP-A-54-155292, JP-B-45-37377, JP-A-48-84183, JP-A-52-112681, and JP-A-58-15503. No. 60
-88005, 59-56403, JP-A-2-6
9, JP-A-57-168088, JP-A-5-107
No. 761, JP-A-5-210240, JP-A-4-28
No. 8,818, each having a dialkylaminobenzene skeleton.

Preferred among these sensitizing dyes are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the same molecule. Particularly preferred are, for example, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone,
Benzophenone-based compounds such as 3,3′-diaminobenzophenone and 3,4-diaminobenzophenone; 2- (p
-Dimethylaminophenyl) benzoxazole, 2-
(P-diethylaminophenyl) benzoxazole,
2- (p-dimethylaminophenyl) benzo [4,5] benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) 1,3 , 4-oxazole, 2- (p-dimethylaminophenyl) benzothiazole, 2- (p-diethylaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole , 2,5-bis (p-diethylaminophenyl) 1,3,4-thiadiazole, (p-dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylamino) Phenyl) quinoline,
And p-dialkylaminophenyl group-containing compounds such as (p-dimethylaminophenyl) pyrimidine and (p-diethylaminophenyl) pyrimidine. Among these, the most preferred is 4,4'-dialkylaminobenzophenone.

The compounding ratio of the sensitizing dye is from 0 to 20% by weight, preferably from 0.2 to 15% by weight, more preferably from 0.5 to 10% by weight, based on the total solid content of the composition for color filter of the present invention. It is.

(1-6) Coloring Agent The coloring agent used in the composition for a color filter of the present invention includes:
There is no particular limitation, and various coloring agents, such as pigments and dyes, can be selected as long as they are colorants that can be used in ordinary color filter compositions. Among them, pigments are preferable from the viewpoint of heat resistance and light resistance of the color filter. As pigments, in addition to organic pigments such as azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindoline-based, dioxazine-based, indathrone-based, perylene-based, and diketopyrrolopyrrole-based, various inorganic pigments are also included. Available.

Specifically, for example, pigments having the following pigment numbers can be used. In addition, terms such as “CI Pigment Red 2” described below mean a color index (CI) number. Red colorant: C.I. I. Pigment Red 2, 3, 4, 5,
6,7,8,9,10,12,14,15,17,1
8, 22, 23, 31, 37, 38, 41, 42, 4
8: 1, 48: 2, 48: 3, 49, 50, 52, 5
3,54,57,58,60,63,64,68,8
1,88,90,97,112,114,115,12
2,123,133,139,144,146,14
7,149,150,151,166,168,17
0,171,175,176,177,178,17
9,180,185,187,188,190,19
2,194,202,207,208,209,21
4,215,216,217,220,221,22
3,224,226,227,228,240,24
2,243,245,246,247,254 Blue colorant: C.I. I. Pigment Blue 1, 15, 15:
1,15: 4,15: 6,16,17,19,22,5
6, 60, 61, 64 Green colorant: C.I. I. Pigment Green 2,7,8,1
0.36 yellow colorant: C.I. I. Pigment Yellow 1, 3, 4,
5, 6, 12, 13, 14, 16, 17, 18, 20,
24, 55, 65, 73, 74, 81, 83, 86, 8
7, 93, 94, 95, 97, 98, 100, 101,
108, 109, 110, 113, 116, 117, 1
20, 123, 125, 128, 129, 133, 13
7,138,139,147,148,150,15
1,153,154,155,156,166,16
8,169,170,171,172,173,17
5,180 Orange colorant: C.I. I. Pigment Orange 1, 2,
5,13,15,16,17,18,19,31,3
4,36,38,40,42,43,51,52,5
5,59,60,61,62 Violet colorant: C.I. I. Pigment Violet 1,2,3,5,19,23,29,30,31,3
2, 33, 36, 37, 38, 39, 40, 43, 50 Brown colorant: C.I. I. Pigment Brown 5, 23,
25, 26, 32 Black colorant: C.I. I. Pigment Black 7 Of course, other colorants can be used.

Further, as the inorganic colorant, for example, barium sulfate, lead sulfate, titanium oxide, yellow lead, red iron oxide, chromium oxide, carbon black and the like can be used.

On the other hand, examples of the dye include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinone imine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes, and the like. Examples of azo dyes include C.I. I. Acid Yellow 11, C.I. I.
Acid Orange 7, C.I. I. Acid Red 37,
C. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct yellow 12,
C. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I.
I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I.
I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I.
Disperse Blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Mordant Red 7, C.I. I. Mordant Yellow 5, C.I.
I. Mordant Black 7 and the like.

The anthraquinone dyes include, for example,
C. I. Bat Blue 4, C.I. I. Acid Blue 4
0, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49,
C. I. Disperse Red 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 and the like.

Other phthalocyanine dyes include, for example, C.I. I. Pad Blue 5 and the like include quinone imine dyes such as C.I. I. Basic Blue 3, C.I.
I. Basic Blue 9 etc. are quinoline dyes,
For example, C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64
And the like, as nitro dyes, for example, C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like.

These colorants have an average particle size of 1 μm or less,
Preferably 0.5 μm or less, more preferably 0.25 μm
It is preferable to use it after dispersing it to m or less.

(1-7) Solvent The composition for a color filter of the present invention may be used by dissolving the above-mentioned components in a solvent in order to adjust the viscosity and dissolve additives such as a photopolymerization initiator. . This solvent can be appropriately selected in accordance with the selection of each component described above.

Specifically, for example, diisopropyl ether, mineral spirit, n-pentane, amyl ether, ethyl caprylate, n-hexane, diethyl ether, isoprene, ethyl isobutyl ether, butyl stearate, n-octane, valsol # 2 , Apco #
18 solvent, diisobutylene, amyl acetate,
Butyl acetate, apco thinner, butyl ether,
Diisobutyl ketone, methyl cyclohexene, methyl nonyl ketone, propyl ether, dodecane, Socal Solvent No. 1 and No. 2, amyl formate,
Dihexyl ether, diisopropyl ketone, Solvesso # 150, (n, sec, t-) butyl acetate, hexene, Shell TS28 solvent, butyl chloride,
Ethyl amyl ketone, ethyl benzoate, amyl chloride, ethylene glycol diethyl ether, ethyl orthoformate, methoxymethyl pentanone, methyl butyl ketone, methyl hexyl ketone, methyl isobutyrate, benzonitrile, ethyl propionate, methyl cellosolve acetate, Methyl isoamyl ketone, methyl isobutyl ketone, propyl acetate, amyl acetate, amyl formate, bicyclohexyl, diethylene glycol monoethyl ether acetate, dipentene, methoxymethyl pentanol, methyl amyl ketone, methyl isopropyl ketone, propyl propionate, propylene glycol t-butyl ether, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethyl cellosolve Acetate, carbitol, cyclohexanone, ethyl acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether , Dipropylene glycol monomethyl ether acetate, 3-methoxypropionic acid, 3-ethoxypropionic acid, methyl 3-ethoxypropionate, 3
-Ethyl ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, ethylene glycol acetate, ethyl carbitol, butyl carbitol, ethylene glycol Monobutyl ether, propylene glycol-t-butyl ether, 3-methyl-3-methoxybutanol, tripropylene glycol methyl ether,
3-methyl-3-methoxybutyl acetate and the like.

These solvents are capable of dissolving or dispersing the above-mentioned components, and have a boiling point of 100%.
It is preferable to select one in the range of -200 ° C. Especially, what has a boiling point in the range of 120-170 degreeC is more preferable. In addition, these solvents may be used alone or in combination of two or more.

(1-8) Other Ingredients The color filter composition of the present invention may further contain, if necessary, a thermal polymerization inhibitor, a plasticizer, a storage stabilizer, a surface protective agent, a smoothing agent, and a coating aid. And various additives can be added.

As the thermal polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-t-butyl-p-cresol, β-naphthol and the like are used. The amount of the thermal polymerization inhibitor is from 0 to the total solid content of the color filter composition of the present invention.
Preferably it is in the range of 3% by weight. As the plasticizer, for example, dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate,
Dioctyl adipate, dibutyl sebacate, triacetylglycerin and the like are used. The blending amount of these plasticizers is preferably within a range of 10% by weight or less based on the total solid content of the composition for a color filter of the present invention.

In addition to the above components, an adhesion improver, a coatability improver, a development improver and the like can be appropriately added as additives.

[0085]

(1-9) Production of Color Filter Composition Next, an example of a method for producing a color filter composition of the present invention using the above-described components will be described. First, the above-mentioned coloring agent, the dispersant, the dispersant,
Dispersion treatment is performed using a solvent to prepare an ink. The dispersion treatment is performed using a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like. Since the colorant becomes fine particles by the dispersion treatment, the transmittance of transmitted light and the coating properties are improved. In the process of the dispersion treatment, other auxiliaries such as a surfactant may be appropriately added.

As a specific dispersion processing method, for example, when the dispersion processing is performed using a sand grinder,
It is preferable to use glass beads or zirconia beads having a diameter of several millimeters. The temperature during the dispersion treatment is usually 0 to 10
The temperature is set at 0 ° C., preferably in the range of room temperature to 80 ° C. still,
Since the appropriate time varies depending on the adjusted ink composition (colorant, solvent, dispersant) and the size of the sand grinder, the dispersion treatment time needs to be adjusted as appropriate. Next, other components such as a binder resin, a compound having a polymerizable group, and a polymerization initiator are mixed with the colored ink obtained by the dispersion treatment to form a uniform solution. In addition, in each step of the dispersion treatment and the mixing, fine dust is often mixed, so that the obtained solution is preferably subjected to a filtration treatment using a filter or the like.

(2) Color Filter The color filter of the present invention comprises a transparent substrate and colored pixels provided on the transparent substrate. A colored pixel is usually composed of a black matrix and pixel images of red, green and blue. The color filter of the present invention can be manufactured by forming pixel images of usually three colors of red, green and blue on a transparent substrate provided with a black matrix. The above-described composition for a color filter of the present invention is generally used for three-color pixel images of red, green and blue, but can also be used for a black matrix.

The material of the transparent substrate is not particularly limited. For example, polyesters such as polyethylene terephthalate, polyolefins such as polypropylene and polyethylene, thermoplastics such as polycarbonate, polymethyl methacrylate, and polysulfone; epoxy resins; Thermosetting plastics such as saturated polyester resin and poly (meth) acrylic resin; various types of glass plates; Among these, a glass plate and a thermosetting plastic are preferable from the viewpoint of heat resistance.

The transparent substrate may be subjected to a corona discharge treatment, an ozone treatment, a thin film treatment of various polymers such as a silane coupling agent or a urethane polymer, etc. in order to improve physical properties such as surface adhesiveness. Good. On this transparent substrate, a black matrix is usually formed using a metal thin film or a colorant dispersion for a black matrix.

When a metal thin film is used, for example, a black matrix is formed using a metal thin film composed of a single layer of chromium or two layers of chromium and chromium oxide. First,
A thin film of such a metal or metal / metal oxide is formed on a transparent substrate by using a vapor deposition method, a sputtering method, or the like. Subsequently, after forming a photosensitive film thereon, the photosensitive film is exposed and developed using a photomask having a repetitive pattern of stripes, mosaics, triangles, etc., and the thin film is etched to form a black matrix. Form.

When a colorant dispersion for black matrix is used, a black matrix is formed using a photoresist composition containing a black colorant. For example, using a black colorant such as carbon black, bone black, graphite, iron black, aniline black, cyanine black, titanium black alone or in combination, or inorganic or organic colorants, dyes as appropriate Selected red,
A photoresist composition containing a black colorant prepared by mixing green, blue and the like can be used. When a colorant dispersion is used, a black matrix is usually formed in the same manner as the method for forming a red, green, and blue pixel image described below.

After a color filter composition containing a colorant of one of red, green and blue is applied on a transparent substrate provided with a black matrix and dried, then the color filter composition is coated on the transparent substrate. A photomask is placed, image exposure and development are performed through the photomask, and a pixel image is formed by heat curing or light curing as necessary. This operation is performed for each of the three color filter compositions of red, green, and blue to form pixel images of three colors of red, green, and blue.

The composition for a color filter of the present invention can be applied by a coating apparatus such as a spinner, a wire bar, a flow coater, a die coater, a roll coater, and a spray. Drying after application may be performed using a hot plate, an IR oven, a convection oven, or the like. As for the drying temperature, the higher the temperature, the more the adhesion to the transparent substrate is improved. However, if the drying temperature is too high, the photopolymerization initiation system is decomposed and thermal polymerization is induced.
It is in the range of 0-200C, preferably 50-150C. The drying time is 10 seconds to 10 minutes, preferably 30 seconds.
The range is from seconds to 5 minutes.

The thickness of the dried color filter composition of the present invention is usually 0.5 to 3 μm, preferably 1 to 2 μm.
m. When the color filter composition of the present invention uses a binder resin and an ethylenic compound in combination, and the binder resin is an acrylic resin having an ethylenic double bond and a carboxyl group in a side chain. Since the color filter composition has very high sensitivity and high resolution, it is possible to form a colored pixel by performing exposure and development without providing an oxygen barrier layer such as polyvinyl alcohol, and That is preferred.

The exposure light source applicable to the color filter composition of the present invention is not particularly limited. For example, a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, Lamp light source such as high pressure mercury lamp, low pressure mercury lamp, carbon arc, fluorescent lamp, argon ion laser, YAG
Laser light sources such as lasers, excimer lasers, nitrogen lasers, helium cadmium lasers, and semiconductor lasers are used. When only a specific wavelength is used, an optical filter can be used.

The image for the color filter of the present invention is subjected to image exposure with the above-mentioned light source and then developed using an aqueous solution containing an alkali agent and a surfactant or an organic solvent. An image can be formed on a substrate. The former aqueous solution may further contain an organic solvent, a buffer, a dye or a coloring agent. Although there is no particular limitation on the method of the development treatment, a method such as immersion development, spray development, brush development, or ultrasonic development is usually used at a development temperature of 10 to 50 ° C., preferably 15 to 45 ° C. Is preferred.

Examples of the alkaline agent include sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, sodium carbonate, potassium carbonate and sodium bicarbonate. Examples thereof include inorganic alkali agents and organic amines such as trimethylamine, diethylamine, isopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, and tetraalkylammonium hydroxide. These may be used alone or in combination.

Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters;
Anionic surfactants such as alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfates, alkyl sulfonates, sulfosuccinate salts; and amphoteric surfactants such as alkyl betaines and amino acids can be used.

As the organic solvent, when used alone or in combination with an aqueous solution, for example, isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like can be used.

[0101]

EXAMPLES Next, the present invention will be described in detail with reference to examples. However, the present invention is not limited to the following examples, and various modifications may be made without departing from the scope of the invention. It is possible to First, substances and abbreviations used in the following examples are shown below. In the following examples, "parts" represents parts by weight.

· Binder resin. . . P-1

Embedded image

Compounds having a polymerizable group. . . DP
HA

Embedded image

-Polymerization initiator 1. . . BI

Embedded image

A polymerization initiator2. . . EABF

Embedded image

Polymerization initiator3. . . 2MBT

Embedded image

Reference Example 1 "Production of dispersant solution" Under a nitrogen atmosphere, a trimer of tolylene diisocyanate (Mitec GP7 manufactured by Mitsubishi Chemical Corporation)
70A, a resin solid content of 49% by weight, a butyl acetate solution, 440 g of an average isocyanate group per molecule (the isocyanate group content is 7.8% by weight), and 440 g of dibutyltin dioctoate as a catalyst. .1 g and 912 g of PGMEA (propylene glycol monomethyl ether acetate) sufficiently dehydrated as a solvent were added and mixed, and dissolved by heating at 70 ° C. for 30 minutes.

Next, under stirring, polyethylene glycol having a methoxy group at one end and having a number average molecular weight of 2,000 (Uniox M-200 manufactured by NOF Corporation) was used.
0) 400 g was added, and the reaction was carried out at 70 ° C. for 2 hours until the isocyanate group content reached 1.5% by weight of the theoretical remaining amount.

Subsequently, a polypropylene glycol having a number average molecular weight of 1,000 (manufactured by Sanyo Chemical Co.,
P-1000) at 80 ° C. until the isocyanate group content reaches 1.0% by weight of the theoretical residual amount.
A time reaction was performed.

Further, n-propanol (PrOH)
9.5 g was added, and the mixture was reacted at 40 ° C. for 1.5 hours until the isocyanate group content reached 0.6% by weight of the theoretical residual amount.

Finally, aminopropylimidazole (A
32.5 g of PI) was added thereto, and the mixture was reacted at 40 ° C. for 1 hour to react all remaining isocyanate groups.

From the above steps, a solution containing a polyisocyanate polyadduct having a solid content of 40% by weight, which is a colorless polymer dispersant solution, was obtained. The viscosity of this dispersant solution is 17
The polyisocyanate polyadduct contained in this dispersant solution had a number average molecular weight in terms of polystyrene of 7,800 mPa · sec.

Example 1 Production of Pigment Dispersion Green pigment C.I. I. Pigment Green 36 (brominated copper phthalocyanine) 1
0.0 g of 8-hydroxy-1,3,3 as a dispersing aid
Using 0.5 g of 6-pyrenetrisulfonic acid, these were mixed with 10.0 g of the colorless polymer dispersant solution produced in Reference Example 1 and 37.5 g of propylene glycol monomethyl ether acetate as a solvent, and the mixture was mixed. The mixture was placed in a paint shaker containing 180.0 g of zirconia beads having a diameter of 0.5 mm and dispersed for 10 hours to produce a green pigment dispersion. The viscosity of the obtained green pigment dispersion was 120 m · Pa · sec. Similarly, a yellow pigment C.I. I. Pigment Yellow 138
(Quinophthalone Yellow), S22000 manufactured by Avicia was used as a dispersing aid, and the dispersion was carried out under the same conditions as for the green pigment dispersion described above, thereby producing a yellow pigment dispersion (colorant dispersion). The viscosity of the resulting yellow pigment dispersion is 79
m · Pa · sec.

[Production of resist composition] 3.71 g of the above-mentioned green pigment dispersion and 2.7 of the yellow pigment dispersion obtained above.
In 8 g, 3.7 of the binder resin solution (solid content: 40.0%)
0 g and 1.48 g of an ethylenic compound, dipentaerythritol hexaacrylate (DPHA), as a compound having a polymerizable group, and 4,4′-bis (diethylamino) benzophenone (photopolymerization initiator) as a polymerization initiator. EABF) 0.0582 g, 2- (2'-chlorophenyl) -4,5-diphenylimidazole dimer (BI) 0.0832 g, 2-mercaptobenzothiazole (2MBT) 0.0166 g as a solvent, propylene glycol monomethyl ether Acetate 37.
5 g was added and mixed to prepare a resist composition (color filter composition) having a solid content concentration of 25%.

[Production of Color Filter] The prepared resist composition containing a green pigment and a yellow pigment was applied to a glass substrate by a spin coater so as to have a dry film thickness of 1.4 μm. Dry for 3 minutes. Next, using a photomask that repeats pixels having a width of 100 μm and a height of 300 μm, exposure was performed with an appropriate exposure amount (100 mj / cm ² ) using a 3 Kw ultra-high pressure mercury lamp.
Using a developer consisting of an aqueous solution containing 01% by weight of potassium hydroxide and 0.05% of a nonionic surfactant (Emulgen A-60 manufactured by Kao), shower-developed at 23 ° C.,
The development was stopped with pure water, followed by rinsing with a water spray to form green pixels. Thereafter, the sample was
Heat treatment was performed at 10 ° C. for 10 minutes to thermally cure. The obtained pixel reproduced the mask pattern, had a sharp edge shape, had no line width change during development, and no surface roughness due to the developer was observed.

"Measurement of Color Characteristics" For the measurement of color characteristics, a solid coating film using the above-described resist composition was prepared under the same conditions as the above-mentioned image forming conditions except that the mask exposure was omitted. The transmittance of the obtained resist solid coating film was measured with a glass reference using a spectrophotometer U-3500 manufactured by Hitachi, Ltd., and at the same time, color calculation was performed with a C light source. The measured chromaticity was x = 0.31, y = 0.52, and the Y value as an index of brightness was 72.

Comparative Example 1 In Example 1, when producing a green pigment dispersion, 0.5 g of 8-hydroxy-1,3,6-pyrenetrisulfonic acid was not used as a dispersing aid, and Dispersion treatment was performed under the same conditions as in Example 1 except that the dispersant BYK161 manufactured by BYK Chemie was used instead of the dispersant solution produced in Reference Example 1. Two hours after the start of dispersion, the dispersion solution stopped flowing, and dispersion was impossible.

Comparative Example 2 In Example 1, instead of 0.5 g of 8-hydroxy-1,3,6-pyrenetrisulfonic acid as a dispersing aid in producing a green pigment dispersion, a pigment manufactured by Avicia was used. Dispersing aid S5000 (alkyl amide of copper phthalocyanine having sulfonic acid: blue pigment derivative) 0.5
Dispersion processing was performed under the same conditions as in Example 1 except that g was used. The viscosity of the dispersion was 92 m · Pa · sec. Subsequently, the ratio between the green pigment dispersion and the yellow pigment dispersion was determined by performing computer color matching (CCM) so as to have the same chromaticity as in Example 1, and the other substances were blended so as to have the same ratio. To prepare a resist composition, and the color characteristics were measured. The Y value of the brightness index was 68.

Example 2 In Example 1, anthraquinone-2, 8-hydroxy-1,3,6-pyrenetrisulfonic acid was used instead of 8-hydroxy-1,3,6-pyrenetrisulfonic acid as a dispersing aid in producing a green pigment dispersion.
Dispersion treatment was performed under the same conditions as in Example 1 except that 6-disulfonic acid was used. The viscosity of the obtained green pigment dispersion was 230 m · Pa · sec, and the Y value when applied to a glass substrate was 69.

Example 3 In Example 1, 4-[(9,10) was used instead of 8-hydroxy-1,3,6-pyrenetrisulfonic acid as a dispersing aid when producing a green pigment dispersion. -Dioxo-2-anthryl) carbonylamino] benzene was subjected to dispersion treatment under the same conditions as in Example 1 except that benzenesulfonic acid was used. The viscosity of the obtained green pigment dispersion was 38 m · Pa · sec, and the Y value when applied to a glass substrate was 73.

Example 4 In Example 1, (9,10-dioxo () was used instead of 8-hydroxy-1,3,6-pyrenetrisulfonic acid as a dispersing aid when producing a green pigment dispersion. 2-anthryl) -4- [4- (dipropylamino)
Example 1 except that phenylcarboxamide was used.
Dispersion processing was performed under the same conditions as described above. The viscosity of the obtained green pigment dispersion was 93 m · Pa · sec, and the Y value when applied to a glass substrate was 75.

Example 5 In producing a pigment dispersion in Example 1, the green pigment C.I. I. Pigment Green 36 (brominated copper phthalocyanine) instead of blue pigment C.I. I. Pigment Blue 15: 6 as 8-hydroxy-1,3,3 as a dispersing aid.
6 instead of 6-pyrene trisulfonic acid
[(9,10-Dioxo-2-anthryl) carbonylamino] benzenesulfonic acid was used as a dispersant, except that the polymer dispersant BYK182 manufactured by Bikchemy was used instead of the dispersant solution prepared in Reference Example 1. Under the same conditions as in Example 1, a blue pigment dispersion was prepared instead of a green pigment dispersion. The viscosity of the obtained blue pigment dispersion was 28 m · Pa · sec.

To the obtained blue pigment dispersion, as in Example 1, a binder resin solution, an ethylenic compound DPHA, a photopolymerization initiator EABF, BI, 2M
BT and propylene glycol monomethyl ether acetate as a solvent were added and mixed to prepare a resist composition having a solid concentration of 25%. As in the case of Example 1, coating was performed on a glass substrate so as to have a dry film thickness of 1.4 μm, followed by drying, mask exposure, and development. The obtained pixels accurately reproduced the mask pattern and were sharp. It had an edge shape, no line width change during development, and no surface roughness due to the developer was observed. The color characteristics were (x, y) = (0.14, 0.15) and the Y value was 19.4.

Comparative Example 3 In Example 5, when preparing a blue pigment dispersion, Avivisia was used instead of 4-[(9,10-dioxo-2-anthryl) carbonylamino] benzenesulfonic acid as a dispersing aid. Pigment derivative dispersion aid S500
0 was performed in the same manner as in Example 1. The Y value as an index of brightness was 18.2.

[0125]

According to the composition for a color filter of the present invention and the color filter using the same, a colorant can be obtained by using a colorless polycyclic aromatic compound and / or a polycyclic heterocyclic compound as a dispersion aid. Can be faithfully reflected in the composition for a color filter, and as a result, a color filter having high lightness, a wide color reproduction range, and excellent color reproducibility is realized.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/038 501 G03F 7/038 501 (72) Inventor Tetsuo Kasai 1st Kurosaki Castle Stone, Yahatanishi-ku, Kitakyushu City, Fukuoka Prefecture No. 1 Kurosaki Plant of Mitsubishi Chemical Corporation (72) Inventor Hideshi Fujiwara 1000 Kamoshitacho, Aoba-ku, Yokohama-shi, Kanagawa Prefecture F-term in Yokohama Research Laboratory, Mitsubishi Chemical Corporation 2H025 AB13 AC01 AD01 BC32 BC42 BC53 BC85 BC92 CA28 CA30 CB43 CC11 CC20 2H048 BA02 BA11 BA45 BA48 BB03 BB14 BB15 BB42

Claims (10)

[Claims] 1. A composition comprising a coloring agent, a dispersing agent, a dispersing aid, a compound having a polymerizable group, and a polymerization initiator, wherein the dispersing aid is a colorless polycyclic resin. A composition for a color filter, which is at least one of an aromatic compound and a polycyclic heterocyclic compound. 2. The color filter composition according to claim 1, wherein said dispersing aid has an acidic group or a basic group. 3. The method according to claim 1, wherein the dispersant comprises an acidic group, a basic group and
The color filter composition according to claim 1, wherein the composition is a colorless polymer compound having at least one of a quaternary ammonium base. 4. The color filter composition according to claim 1, further comprising a binder resin. 5. The composition for a color filter according to claim 4, wherein said binder resin is a colorless high molecular compound having a carboxyl group in a side chain. 6. The color filter composition according to claim 4, wherein the binder resin is a colorless high molecular compound having an ethylenic double bond in a side chain. 7. The compound having a polymerizable group,
The color filter composition according to any one of claims 1 to 6, wherein the composition is a colorless compound having an ethylenic double bond. 8. The compound having a polymerizable group,
Molecular weight 300 having a plurality of ethylenic double bonds in the molecule
8. A colorless compound as described above, wherein:
The composition for a color filter according to the above. 9. The color filter composition according to claim 1, wherein the polymerization initiator initiates polymerization by light. 10. A composition for a color filter, comprising: a transparent substrate; and a colored pixel provided on the transparent substrate. A color filter characterized by containing.