KR101051399B1 - Photosensitive resin composition and color filter using the same - Google Patents

Abstract

In the area | region containing a coloring agent of a high concentration, it provides the photosensitive resin composition for color filters with little heat-sulfur resistance, high color purity, and high sensitivity.

As an essential component, (A) component; Unsaturated group-containing alkali-soluble resins obtained by reacting a reaction product of an epoxy compound having two glycidyl ether groups derived from bisphenols with (meth) acrylic acid with a polybasic carboxylic acid or anhydride thereof, (B) component; Photopolymerizable monomer which has one or more ethylenically unsaturated bond, (C) component; A compound having one or more epoxy groups, (D) component; Photoinitiators containing the compound represented by general formula (I), and (E) component; The photosensitive resin composition for curling filters whose ratio (E) / (R) of (E) with respect to the gross weight (R) of a resin component is 0.5-2.5 as a coloring agent containing one or more organic pigments as an essential component.

[Tue 1]

Description

Photosensitive resin composition and the color filter using the same {PHOTOSENSITIVE RESIN COMPOSITION AND COLOR FILTER USING THE SAME}

The present invention relates to a photocurable composition and a color filter using the same, and more particularly, to a photosensitive resin composition suitable for a resist for color filters.

The color liquid crystal display device includes a liquid crystal unit for controlling the amount of light transmission or reflection and a color filter, but the manufacturing method of the color filter generally forms a black matrix on the surface of a transparent substrate such as glass or plastic sheet. Subsequently, a method of forming different colors of red, green, and blue into color patterns such as sequential, striped, or mosaic forms is used. In recent years, color liquid crystal display devices have been used in all fields such as liquid crystal televisions, liquid crystal monitors, and color liquid crystal cell phones, and color filters are one of the important members that influence the visibility of these color liquid crystal display devices. The pattern size is different depending on the use of the color filter and the respective colors, but the red, green, and blue pixels are thinned at 200 to 300 µm, so that the dimensional accuracy is high for the photosensitive resin material (also called photosensitive resin composition or photocurable composition). Is required.

Moreover, in recent color liquid crystal displays, although high color purity and a bright display are calculated | required, there exists a tendency for the content rate of the coloring agent in a photocurable composition to increase accordingly. However, when the content of the colorant increases, light in the ultraviolet region is hard to reach the coating film core portion during the formation of the color filter, resulting in poor adhesion of the pattern or pattern peeling at the time of development due to poor curing in the photocurable composition, and sharp edge shape. The problem of sex loss occurs. In order to improve the curing failure, the addition of the photopolymerization initiator or the sensitizer until the deep curing is sufficiently progressed without surface roughness results in a decrease in the brightness of the color filter due to coloration of the photoinitiator or discoloration after heat treatment, in particular, the transmittance of the blue color filter. It also causes a decrease.

Therefore, even when a large amount of photoinitiator is added so that a curing failure in a photocurable composition does not arise, the kind of photoinitiator with little discoloration by the coloring and heat processing, and selection of a prescription are needed. At the same time, it is required to obtain a pattern having good pattern dimensional stability, pattern adhesion, and sharpness of a pattern edge shape at a low exposure amount with a wide development margin. For this purpose, high sensitivity of the photosensitive resin composition is indispensable.

[Patent Document 1] Japanese Patent Application Laid-Open No. Hei1-152449

[Patent Document 2] Japanese Patent Application Laid-Open No. 7-278214

[Patent Document 3] Japanese Patent Application Laid-Open No. 2001-264530

[Patent Document 4] Japanese Patent Application Laid-Open No. 2002-323762

[Patent Document 5] Japanese Patent Publication No. 2003-96118

[Patent Document 6] Japanese Patent Application Laid-Open No. 2004-10838

[Patent Document 7] Japanese Patent Laid-Open No. 2003-270785

[Patent Document 8] Japanese Patent Application Laid-Open No. 10-301276

[Patent Document 9] Japanese Patent Application Laid-Open No. 9-197663

[Patent Document 10] Japanese Patent Application Laid-Open No. 9-95638

[Patent Document 11] Japanese Patent Application Laid-Open No. 7-3122

Patent Literature 1 discloses examples of use of halomethyloxadiazole-based compounds and halomethyl-S-triazine-based compounds as high-sensitivity photopolymerization initiators in order to increase the pigment concentration and prevent deterioration of sensitivity while achieving good color reproducibility. However, these compounds have a reduction in surface flatness due to the inhibition of reaction with oxygen, but are still not satisfactory in terms of pattern dimension accuracy. Moreover, although patent documents 2-5 etc. disclose the example which used the oxime ester type photoinitiator for the photosensitive resin composition as a high-sensitivity photoinitiator, since the sensitivity and image development property of alkali-soluble resin used together are not enough, a high concentration coloring agent is disclosed. In the photosensitive resin composition containing, it is difficult to perform favorable pattern formation.

Moreover, although the Example of the photosensitive resin composition for color filters which has a bisphenol fluorene structure is shown by the said patent documents 6-11, since the comparatively usual photoinitiator is used, especially in the photosensitive resin composition containing a high concentration coloring agent, The amount of addition of the photopolymerization initiator increases, resulting in absorption of the photoinitiator and discoloration after heat treatment, and in particular, the transparency and color reproducibility of the blue color filter cannot be sufficiently obtained.

It is therefore an object of the present invention to solve the above problems and to provide a photosensitive resin composition for color filters having low heat sulfur denaturation, high color purity, and high sensitivity in a region containing a high concentration of colorant. Moreover, another object is to provide the coating film and color filter formed using this alkali image development type photosensitive resin composition.

MEANS TO SOLVE THE PROBLEM The present inventors conducted the examination in order to solve the said subject, and, as a result, it contains the unsaturated group containing compound obtained by making the reaction material of the aromatic epoxy compound and (meth) acrylic acid derived from bisphenols react with polybasic carboxylic acid or its anhydride. By mix | blending the oxime ester type photoinitiator which has a specific chemical structure as a photoinitiator to the said photosensitive resin composition, it discovered that the said problem was solved and completed this invention.

The present invention provides the following components (A) to (E) as essential components.

(A) component; Unsaturated group-containing alkali-soluble resins obtained by reacting an epoxy compound having two glycidyl ether groups derived from bisphenols, a (meth) acrylic acid, and a reactant with a polybasic carboxylic acid or an anhydride thereof,

(B) component; Photopolymerizable monomers having at least one or more ethylenically unsaturated bonds,

(C) component; A compound having at least one or more epoxy groups,

(D) component; Photoinitiator which makes a compound represented by general formula (I) essential, and

(E) component; It contains a coloring agent containing at least one organic pigment,

The weight ratio (A) / (B) of (A) component and (B) component is 20/80-90/10, and with respect to the total weight (R) of the resin component which consists of the sum total of resin and a polymerizable component. 2-30 weight part of (D) component is contained with respect to a total of 100 weight part of (A) component and (B) component in the density | concentration area whose ratio (E) / (R) of (E) becomes 0.5-2.5. It is a photosensitive resin composition for color filters characterized by the above-mentioned.

[Tue 1]

However, R ₁ may be substituted with a phenyl group (may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), an alkyl group having 1 to 20 carbon atoms (may be substituted with one or more hydroxyl groups, and at least 1 oxygen in the middle of the alkyl chain). An atom), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or a benzoyl group (may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group);

R ₂ is an alkanoyl group having ₂ to 12 carbon atoms (may be substituted with one or more halogen atoms or a cyano group), an alkenoyl group having 4 to 6 carbon atoms in which the double bond is not conjugated with a carbonyl group, and a benzoyl group (with 1 carbon atom). Or an alkyl group, a halogen atom or a cyano group of 6 to 6), an alkoxycarbonyl group or phenoxycarbonyl group of 2 to 6 carbon atoms (which may be substituted with one or more alkyl groups or halogen atoms of 1 to 6 carbon atoms);

R ₃ , R ₄ , R ₅ , R ₆ and R ₇ are independent of each other and represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzoyl group and 2 carbon atoms. An alkanoyl group of -l2 and an alkoxycarbonyl group having 2 to 12 carbon atoms (when the carbon number of the alkyl group constituting the alkoxyl group is 2 or more, the alkyl group may be substituted with one or more hydroxyl groups, and one or more oxygen atoms in the middle of the alkyl chain) Or a phenylthio group (may be substituted with an alkyl group having 1 to 6 carbon atoms) or a phenoxycarbonyl group.

Moreover, this invention is the coating film which hardened | cured and formed said photosensitive resin composition for color filters. Moreover, this invention is a color filter formed with the coating film obtained by apply | coating and hardening said photosensitive resin composition for color filters.

In the photosensitive resin composition for color filters of this invention, (A) component is the reaction product of the epoxy compound which has two glycidyl ether groups derived from bisphenol, and (meth) acrylic acid, a) saturated dicarboxylic acid, or its It is obtained by making an acid anhydride and b) saturated tetracarboxylic acid or its acid anhydride react in the range whose molar ratio a / b becomes 0.1-10, and contains resin represented by following General formula (II) as a main component. It is preferable.

[Tue 2]

R ₁ , R ₂ , R ₃ and R ₄ independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, and R ₅ represents a hydrogen atom or a methyl group. In addition, A is -CO-, -S0 _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -0-, 9 , A 9-fluorenyl group or a direct bond, X represents a tetravalent carboxylic acid residue, Y ₁ , Y ₂ independently represent a hydrogen atom or -0C-Z-C00H (Z is a divalent carboxylic acid N represents a number from 1 to 20.

In the photosensitive resin composition for color filters of this invention, it is preferable that (D) component is a photoinitiator which makes the compound represented by following formula (III) essential.

[Tue 3]

Hereinafter, the photosensitive resin composition of this invention is demonstrated in detail.

The photosensitive resin composition of this invention is a resin composition which has alkali image development characteristic containing the said (A)-(E) component as an essential component.

At least each of dicarboxylic acids and tetracarboxylic acids which are polybasic acids to the compound which has a hydroxyl group obtained by making (metal) acrylic acid react with the epoxy compound which has two glycidyl ether groups derived from bisphenols (A) component (A) It is an epoxy (meth) acrylate acid addition product obtained by making it react with one type. Since the component (A) has an ethylenically unsaturated double bond and a carboxyl group together, the alkali-developing photosensitive resin composition gives excellent photocurability, positive developability, and patterning characteristics, resulting in improvement of physical properties of red, green, and auditory pixels.

That is, in addition to having polymerizability in order to have an unsaturated group derived from (meth) acrylic acid, (A) component is a) dicarboxylic acid or its acid anhydride (henceforth abbreviated as dicarboxylic acids), and b) It has alkali solubility in order to have acidic groups derived from polybasic carboxylic acids, such as tetracarboxylic acid or its acid dianhydride (henceforth abbreviated to tetracarboxylic acids).

In addition, in this specification, when it is polybasic carboxylic acid, it means polybasic carboxylic acid, such as the said dicarboxylic acid, tetracarboxylic acids, or these acid anhydrides, and (meth) acrylic acid is acrylic acid, meta Krylic acid or both.

As (A) component, although well-known alkali-soluble resin can be used by the said patent documents 6-11, etc., it is not limited to this. Preferably, it is alkali-soluble resin represented by general formula (II). This alkali-soluble resin is derived from the acrylate compound represented by the following general formula (VII), and this acrylate compound is derived from the epoxy compound represented by the corresponding general formula (IV) or (VI), and this epoxy compound Is derived from the corresponding bisphenols. Therefore, (A) component is understood by illustrating bisphenols.

In addition, although an epoxy compound is normally represented by general formula (IV), since a main component is a compound represented by general formula (VI), it may be represented by general formula (VI) for easy understanding. Similarly, an acrylate compound may be represented by the acrylate compound represented by general formula (i) corresponding to the epoxy compound represented by general formula (VI).

[Tue 4]

[Tue 5]

In formulas (II), (IV), (VI) and ( _iii ), R ₁ , R ₂ , R ₃ and R ₄ independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group. But preferably hydrogen atom, and A is -CO-, -SO _2- , -C (CF ₃ ) _2- , Si (CH ₃ ) _2- , -CH ₂ -,-(CH ₃ ) _2- , Although -O-, 9,9- fluorenyl group or absence is shown, Preferably it is 9,9- fluorenyl group. Although 1 is an integer of 0-10, Preferably it is the range of 0-2 as 0 or an average value. Here, 9, 9- fluorenyl group means group represented by following General formula (V).

[Tue 6]

In General Formula (II), X represents a tetravalent carboxylic acid residue, and Y ₁ and Y ₂ independently represent a hydrogen atom and a carboxylic acid residue represented by -OC-Z- (COOH) m (m). Represents a number of 1 to 3), and n represents a number of 1 to 20, but the average repeating number is preferably in the range of 1 to 10.

As bisphenol which gives alkali-soluble resin of a preferable (A) component, the following are mentioned. Bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3,5-dimethylphenyl) ketone, bis (4-hydroxy-3,5-dichlorophenyl) ketone, bis (4-hydroxyphenyl) Sulfone, bis (4-hydroxy-3,5-dimethylphenyl) sulfone, bis (4-hydroxy-3,5-dichlorophenyl) sulfone, bis (4-hydroxyphenyl) hexafluoropropane, bis (4 -Hydroxy-3,5-dimethylphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dichlorophenyl) hexafluoropropane, bis (4-hydroxyphenyl) dimethylsilane, bis (4- Hydroxy-3,5-dimethylphenyl) dimethylsilane, bis (4-hydroxy-3,5-dichlorophenyl) dimethylsilane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5 -Dichlorophenyl) methane, bis (4-hydroxy-3,5-dibromophenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3 , 5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3,5-dimethylphenyl) ether, bis (4-hydroxy -3,5-dichlorophenyl) ether and the like. Or 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (A is a 9,9-fluorenyl group) 4-hydroxy-3-chlorophenyl) fluorene, 9,9-bis (4-hydroxy-3-bromophenyl) fluorene, 9,9-bis (4-hydroxy-3-fluorophenyl) Fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dichlorophenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dibromophenyl) fluorene etc. are mentioned preferably. Moreover, 4,4'-biphenol, 3,3'-biphenol etc. are mentioned preferably.

The component (A) can be obtained from the above-described epoxy compounds derived from bisphenols, but in addition to the epoxy compound, a phenol novolak-type epoxy compound, a cresol novolak-type epoxy compound, and the like have a compound having two glycidyl ether groups. If it contains usefully, it can be used. In addition, when glycidyl etherification of bisphenols, an oligomer unit will mix, but if the average value of 1 in Formula (IV) is 0-10, Preferably it is the range of 0-2, the performance of this resin composition will There is no problem.

Although reaction of such an epoxy compound and (meth) acrylic acid is performed using about 2 mol of (meth) acrylic acid with respect to 1 mol of epoxy compounds, the reaction is well-known in the said patent documents 6-11. This reaction method and a reactant are described in the said patent document.

The reactant obtained by reaction of an epoxy compound and (meth) acrylic acid, and polyhydric carboxylic acid are made to react, and alkali-soluble resin of (A) component is obtained. As polyhydric carboxylic acid, the combination of a) dicarboxylic acid and b) tetracarboxylic acid obtained by reacting with the hydroxyl group in an epoxy (meth) acrylate compound molecule is preferable.

Here, as dicarboxylic acid, chain hydrocarbon dicarboxylic acid or its acid anhydride, alicyclic dicarboxylic acid or its acid anhydride, aromatic dicarboxylic acid or its acid anhydride is used.

Examples of the chain hydrocarbon dicarboxylic acid or its acid anhydride include succinic acid, acetyl succinic acid, maleic acid, adipic acid, itaconic acid, azaline acid, citramalic acid, malonic acid, glutaric acid and citric acid. , Tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid, and the like, and dicarboxylic acids introduced with an optional substituent, or It may be an acid anhydride.

Moreover, as alicyclic dicarboxylic acid or its acid anhydride, there exist compounds, such as hexa hydrophthalic acid, cyclobutane dicarboxylic acid, cyclopentane dicarboxylic acid, norbornane dicarboxylic acid, for example, Or dicarboxylic acids introduced with arbitrary substituents or acid anhydrides thereof.

Moreover, as aromatic dicarboxylic acid and its acid anhydride, there exist compounds, such as a phthalic acid and an isophthalic acid, for example, and the dicarboxylic acid in which arbitrary substituents were introduced, or its acid anhydride may be sufficient.

B) As tetracarboxylic acids, a linear hydrocarbon tetracarboxylic acid or an acid dianhydride thereof, an alicyclic tetracarboxylic acid or an acid dianhydride thereof, or an aromatic polyvalent carboxylic acid or an acid dianhydride is used.

Here, as chain | strand tetracarboxylic acid or its acid anhydride, butane tetracarboxylic acid, a pentane tetracarboxylic acid, hexane tetracarboxylic acid, etc. are mentioned, for example, the tetracarboxylic acids or its acid which were introduce | transduced by a substituent. Anhydrides may be used. Moreover, as alicyclic tetracarboxylic acid or its acid anhydride, For example, cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, cycloheptane tetracarboxylic acid norbornane tetracarbox Acid and the like, or tetracarboxylic acids introduced with a substituent or an acid anhydride thereof may be used.

Moreover, as aromatic tetracarboxylic acid or its acid anhydride, pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid, or its acid anhydride, for example These may be mentioned, and tetracarboxylic acids of the substituent or the acid anhydride thereof may be used.

The a) dicarboxylic acid and b) tetracarboxylic acid can be used 1 or more types, respectively, and the usage ratio of a) dicarboxylic acid and b) tetracarboxylic acid is 0.1-0.1 as molar ratio a / b of both. It is a range used as 10, Preferably it is a range used as 0.2-1. Although the ratio is suitable for the optimum molecular weight, alkali developability, light transmittance, heat resistance, solvent resistance, and pattern shape effect, the ratio of tetracarboxylic acids used increases alkali solubility and tends to increase molecular weight. do.

Moreover, when a) saturated dicarboxylic acid and its acid anhydride are used as a) dicarboxylic acids, and b) tetracarboxylic acid and its acid anhydride are used as tetracarboxylic acids, pattern dimensional stability, pattern adhesiveness, and pattern Sharpness of the edge shape may be better, and patterning at a wider development margin may be possible.

The method for producing the component (A) by reacting the reactant obtained by the reaction of the epoxy compound with (meth) acrylic acid and the acid component is not particularly limited, and the known methods as described in the Patent Documents 6 to 11 are used. It can be adopted.

Advantageously, it is preferred to react quantitatively so that the acid component per mole of hydroxy group in the epoxy (meth) acrylate compound molecule is 1/2 mole. Moreover, as reaction temperature, it is 90-130 degreeC, Preferably it is 95-125 degreeC.

When an example of the method of manufacturing (A) component is shown about the case where 9, 9-bis (4-hydroxyphenyl) fluorene is used as a starting raw material, it is as follows.

First, 9,9-bis (4-hydroxyphenyl) fluorene and epichlorohydrin are reacted to synthesize a bisphenol fluorene type epoxy compound represented by the general formula (VI), and the bisphenol fluorene type epoxy compound Reacting (meth) acrylic acid represented by CH ₂ = CR ₅ -COOH to synthesize a bisphenol fluorene type epoxy acrylate resin represented by the general formula (VIII), and then in a propylene glycol monomethyl solvent, a bisphenol flu Orene type epoxy acrylate resin and the said acid component are reacted under heating, and alkali-soluble resin of fluorene type represented by the said General formula (II) which is (A) component is obtained.

The photosensitive resin composition of this invention contains the said (A) component as an essential component of a resin component. Here, a resin component means the component which becomes a resin by superposing | polymerizing or hardening, and contains an oligomer and a monomer other than resin. The component (A) is preferably 10 wt% or more, preferably 20 wt% or more, and more preferably 30 wt% or more.

The photosensitive resin composition of this invention contains an effective amount of following (B)-(D) component other than (A) component.

(B) component; Photopolymerizable monomers having at least one ethylenically unsaturated bond

(C) component; Compound having at least one kind or more epoxy group

(D) component; Photoinitiators containing an effective amount of the compound represented by general formula (I)

As a photopolymerizable monomer which has at least 1 or more ethylenically unsaturated bond of (B) component, For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl Monomers having hydroxyl groups such as (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acryl Rate, tetramethylene glycol di (meth) acrylate, trimetholpropane tri (meth) acrylate, trimetholethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylic Elate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol (meth) a (Meth) acrylic acid esters, such as a acrylate, are mentioned, These compounds can use 1 type (s) or 2 or more types.

The compounding ratio of these (A) component and (B) component is 20 / 80-90 / 10 in weight ratio (A) / (B), Preferably it is 40 / 60-80 / 20. When the blending ratio of the component (A) is small, the cured product after the photocuring is receded, and since the acid value of the coating film is low in the unexposed part, the solubility in the alkaline developer is lowered, and the edge of the pattern does not become mushy and sharp. A problem arises, and formation of a crosslinked structure with a small proportion of photoreactive functional groups occupying a resin is not sufficient, and the acid value in the resin component is too high, so that the solubility in the alkaline developer in the exposed portion is high. From the high point, there exists a possibility that a problem may arise that the formed pattern becomes thinner than the target line width, or the fall of a pattern becomes easy to occur.

The epoxy compound of (C) component is mix | blended for the purpose of further improving adhesiveness and alkali resistance. Examples of the compound having an epoxy group include phenol noblock type epoxy resins, cresol noblock type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenyl type epoxy resins, and alicyclic epoxy resins. Epoxy resins, phenylglycidyl ether, p-butylphenol glycidyl ether, triglycidyl isocyanurate, diglycidyl isocyanurate, allyl glycidyl ether, glycidyl methacrylate, and the like. The compound etc. which have at least one group are mentioned.

It is preferable to mix | blend the compounding quantity of this epoxy compound in the range of 10-30 weight part with respect to a total of 100 weight part of said (A) component and (B) component.

Moreover, although the oxime ester type photoinitiator represented by General formula (I) is used as photoinitiator of (D) component, in order to raise a sensitivity and to raise hardening density of photosensitive resin, other types of initiators, sensitizers, etc. Can be used in combination. In general formula (I), although R <_1> -R <_8> has the meaning as mentioned above, Preferably R <_6> is a phenylthio group, R <_1> is a C2-C6 alkyl group, and R <_2> has a substituent It may be a benzoyl group, and the guitar is H. More preferable oxime ester type photoinitiator is a compound represented by general formula (III). The photoinitiators mentioned in this invention are used by the meaning containing a sensitizer other than a photoinitiator.

Moreover, as a photoinitiator or sensitizer which can be used together, for example, acetophenone, 2,2- diethoxy acetophenone, p-dimethyl acetophenone, p-dimethyl amino propiophenone, dichloro acetophenone, trichloro acetophenone, p acetophenones such as -tert-butyl acetophenone, benzophenones such as benzophenone, 2-chloro benzophenone, p, p'-bisdimethylamino benzophenone, benzyl, benzoin, benzoin methyl ether, benzoin iso Benzoyl ethers such as propyl ether, benzoin isobutyl ether, 2- (o-chloro phenyl) -4,5-phenylbiimidazole, 2- (o-chlorophenyl) -4,5-di (m-meth Methoxyphenyl) biimidazole, 2- (o-fluorophenyl) -4,5-diphenylbiimidazole, 2- (o-methoxyphenyl) -4,5-diphenylbiimidazole, 2,4 Biimidazole-based compounds such as, 5-triarylbiimidazole, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-sia Nothryl) -1,3,4-oxadi Halomethylthiazole compounds such as sol and 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole, 2,4,6-tris (trichloromethyl)- 1,3,5-triazine, 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2-phenyl-4,6-bis (trichloromethyl) -1, 3,5-triazine, 2- (4-chlorophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxyphenyl) -4,6- Bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloroRmethyl) -1,3,5-triazine, 2- (4-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (3,4,5-trimethoxystyryl) -4,6-bis Halomethyl- such as (trichloromethyl) -1,3,5-triazine and 2- (4-methylthiostyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine S-triazine compounds, 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), 1- (4-phenylsulfanylphenyl) butane-1, 2-dione-2-oxime-0-benzoate, 1- (4-methylsulfate) O-acyl oxime compounds such as panylphenyl) butane-1,2-dione-2-oxime-0-acetate and 1- (4-methylsulfanylphenyl) butan-1-one oxime-0-acetate, benzyl Sulfur compounds, such as dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethyl thioxanthone, 2-methyl thioxanthone, and 2-isopropyl thioxanthone, 2-ethyl anthraquinone, and octane Anthraquinones such as methyl anthraquinone, 1,2-benzanthraquinone, and 2,3-diphenylanthydranone, organic peroxides such as azobisisobutylnitrile, benzoyl peroxide, cumene peroxide, and 2-mercapto Thiol compounds such as benzoimidazole, 2-mercaptobenzoxazole and 2-mercaptobenzothiazole, and tertiary amines such as triethanolamine and triethylamine.

The photoinitiator of (D) component can use together 1 type (s) or 2 or more types. The compound represented by the general formula (I) is preferably contained in the photopolymerization initiators of the component (D) in an effective amount or more, preferably 50% by weight or more, and more preferably 80% by weight or more.

The total amount of photopolymerization initiators of component (D) is 2 to 50 parts by weight, and preferably 5 to 40 parts by weight based on 100 parts by weight in total for each component of (A) and (B). When the blending ratio of component (D) is small, the speed of photopolymerization is slowed down, and sensitivity is lowered. On the other hand, when the amount is too large, the sensitivity is too strong. Can't. In addition, there is a fear that a problem occurs that the pattern edge is not ragged and sharp.

In addition, the coloring agent of (E) component is not specifically limited in color tone, It selects suitably according to the use of the obtained color filter, Any of a pigment, dye, or a natural pigment may be sufficient. Since the color filter requires high color development and heat resistance, the thing containing an organic pigment, Preferably what contains 50-100 weight% is used.

As said organic pigment, a single red pigment system may be used for red use, and a yellow pigment system may be mixed with a red pigment system, and color tone may be performed. As the red pigment system, for example, anthraquinone pigments, quinacridone pigments, tiketopyrroro pigments, and perylene pigments, particularly preferably diketopyrrolopyrrole red (CI pigment red 254) or dianthra Quinone red (CI pigment red 177), and the like.

As a yellow pigment type | system | group, isoindolin yellow (C.I pigment yellow 139), nickel azo yellow (C.I pigment yellow 150), a diary lead yellow (C.I pigment yellow 83), etc. are mentioned, for example. These red pigment type and yellow pigment type can also mix and use 2 or more types, respectively. In addition, when mixing and using a red pigment system and a yellow pigment system, it is preferable to use a yellow pigment system at 90 weight part or less with respect to 100 weight part of total amounts of a red pigment system and a yellow pigment system.

A single green pigment system may be used for the green pigment, or a yellow pigment system may be mixed with the green pigment system to colorize. Examples of the red pigment system include chlorinated phthalocyanine green (C.I pigment green 7), brominated chlorinated phthalocyanine green (C.I pigment green 36), and the like. Examples of the yellow pigment include isoindolin yellow (C.I pigment yellow 139), nickel azo yellow (C.I pigment yellow 150), diaryrid yellow (C.I pigment yellow 83), and the like. These green pigments and yellow pigments may be used in combination of two or more kinds, respectively. In addition, when using a mixture of a green pigment system and a yellow pigment system, it is preferable to use a yellow pigment system at 90 weight part or less with respect to 100 weight part of total amounts of a green pigment system and a yellow pigment system.

As a blue pigment, a single blue pigment system may be used, and a purple pigment system may be mixed with a blue pigment system, and coloration may be performed. Examples of the blue pigments include phthalocyanine-based pigments and srenne-based pigments, and particularly preferably ε-phthalocyanine blue (C.I pigment blue 15: 6). Moreover, as a purple pigment type, dioxazine violet (C.I pigment violet 23) etc. are mentioned, for example. These blue pigments and purple pigments may be used in combination of two or more kinds, respectively. In addition, when mixing and using a blue pigment system and a purple pigment system, it is preferable to use a purple pigment system at 90 weight part or less with respect to 100 weight part of total amounts of a blue pigment system and a purple pigment system.

Moreover, the addition amount of the coloring agent of (E) component is 0.5-2.5, Preferably it is 1.0-2.0, More preferably, 1.5 (E) / (R) of (E) component with respect to gross weight (R) of a resin component. Mix it so that it may become -1.8. Here, the total weight (R) of the resin component refers to the sum of the resin in the composition and the polymerizable component (the component that is polymerized or cured with a monomer, oligomer, etc. to be a resin).

If this (E) / (R) ratio is low, color purity will become inadequate, and in order to obtain favorable contrast, a film thickness must be made thick and the surface smoothness of a color filter is hard to be obtained. On the contrary, when too high, dispersion stability of the photosensitive resin composition for color filters containing (E) component will fall, and content of the photosensitive resin used as an original binder will also fall, and it will impair development characteristics and a film forming ability. There is a fear that undesirable problems of damage occur.

Moreover, a dispersing agent may be used for the dispersion stabilization use of a coloring agent. The dispersant may be used together with a colorant, and examples of such dispersants include surfactants such as cationic, anionic, nonionic, amphoteric, silicone, and fluorine based. Specific examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene stearyl ether.

When using the photosensitive resin composition of this invention for color filters, it is preferable to use a solvent other than said (A)-(E) component. As a solvent, For example, alcohols, such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, telpens, such as (alpha)-or (beta)-tepineol, acetone, methyl ethyl ketone, cyclohexanone, N- Ketones such as methyl-2-pyrrolidone, aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methylcarbitol, ethylcarbitol, butylcarb Glycol ethers such as bitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethyl acetate, Butyl Acetate, Cellosolve Acetate, Ethyl Cellosolve Acetate, Butyl Cellosolve Acetate, Carbitol Acetate, Ethyl Carbitol Acetate, Butyl Acetate acetates, such as carbitol acetate, a propylene glycol monomethyl ether acetate, and a propylene glycol monoethyl ether acetate, etc. are mentioned, It can be set as a uniform solution composition by melt | dissolving and mixing using these.

Moreover, additives, such as a hardening accelerator, a thermal polymerization inhibitor, a plasticizer, a filler, a solvent, a leveling agent, an antifoamer, can be mix | blended with the photosensitive resin composition of this invention as needed. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butyl catechol, phenothiazine, and the like. As the plasticizer, dibutyl phthalate, dioctyl phthalate, and tricredyl may be mentioned. Examples of the filler include glass fiber, silica, mica, aluminum oxide, and the like, and examples of the antifoaming agent and the leveling agent include silicone, fluorine, and acrylic compounds.

The photosensitive resin composition of this invention contains the said (A)-(B) component or these and a solvent as a main component. Solid content excluding a solvent (solid content contains a monomer which becomes a solid content after curing) includes (A) to (E) components in total of 70 wt% or more, preferably 80 wt% or more, and more preferably 90 wt% or more. desirable. The amount of the solvent varies depending on the target viscosity, but is preferably in the range of 20 to 80 wt%.

The coating film of this invention can be obtained by apply | coating the solution of the said photosensitive resin composition to a board | substrate etc., for example, irradiating light (including ultraviolet rays, a radiation, etc.), and hardening this. If the part which does not touch the part which light contacts, is hardened | cured, and only the part which light hits is hardened and another part is melt | dissolved in alkaline solution, the coating film of a desired pattern can be obtained.

Next, the manufacturing method of the color filter using the photosensitive resin composition is demonstrated. First, on the surface of a board | substrate, a light shielding layer is formed so that the part which forms a pixel may be divided as needed, and for example, after apply | coating the liquid composition of the photosensitive resin composition in which the red pigment was disperse | distributed on this board | substrate, The solvent is evaporated by prebaking to form a coating film. Next, after exposing through a photomask to this coating film, it develops using alkaline developing solution, dissolves and removes the unexposed part of a coating film, and post-bakes, and the red pixel pattern was arrange | positioned in predetermined | prescribed arrangement. A pixel array is formed. Then, using the liquid composition of the photosensitive resin composition in which the green or blue pigment was disperse | distributed, apply | coating, prebaking, exposing, developing, and postbaking each liquid composition similarly to the above, and green pixel array and blue By sequentially forming pixel arrays on the same substrate, a pixel array of three primary colors of red, green, and blue is disposed on the substrate, and as a protective film thereon, the liquid composition of the photosensitive resin composition is prepared in the same manner as above. Application | coating, prebaking, exposure, image development, and postbaking of a liquid composition are performed, and the color filter in which the protective film was formed is obtained.

When apply | coating the liquid composition of the photosensitive resin composition to a board | substrate, in addition to a well-known solution immersion method and a spray method, any method, such as the method of using a roller coater, a land coater, or a spinner group, can be employ | adopted. By these methods, after apply | coating to desired thickness, a film is formed by removing a solvent (prebaking). Prebaking is performed by heating with an oven, a hot plate or the like, vacuum drying or a combination thereof. The heating temperature and the heating time in the prebaking are appropriately selected according to the solvent to be used, for example, performed at a temperature of 80 to 120 ° C. for 1 to 10 minutes.

As the radiation used when producing the color filter, for example, visible rays, ultraviolet rays, far ultraviolet rays, electron beams, X rays and the like can be used, but radiation having a wavelength in the range of 250 to 450 nm is preferable. Moreover, as a developer suitable for this alkali image development, although the aqueous solution of the carbonate of an alkali metal or alkaline-earth metal, the aqueous solution of the hydroxide of an alkali metal, etc. are mentioned, Especially, carbonates, such as sodium carbonate, potassium carbonate, lithium carbonate, etc., are mentioned, for example. It is good to develop at the temperature of 20-30 degreeC using the weakly alkaline aqueous solution containing 0.05-10 weight%, and a fine image can be formed precisely using a commercially available developer, an ultrasonic cleaner, and the like. In addition, after alkali image development, water washing is normally performed. As the developing treatment method, a shower developing method, a spray developing method, a dip (immersion) developing method, a paddle (liquid amount) developing method, or the like can be applied. As for image development conditions, 10 to 120 second is preferable at normal temperature.

After developing in this way, heat processing (post-baking) is performed on the temperature of 180-250 degreeC, and the conditions of 20-100 minutes. This post-baking is performed for the purpose of improving the adhesiveness of a patterned coating film and a board | substrate. This is done by heating with an oven, a hot plate or the like, like prebaking. The patterned coating film of this invention is formed through each process by the above photolithographic method.

As a substrate used when forming a color filter having a pixel and / or a black matrix, for example, ITO, gold, etc., on glass, transparent film (for example, polycarbonate, polyethylene terephthalate, polyether sulfone, etc.) A transparent electrode deposited or patterned is used. Further, these substrates may be subjected to a suitable pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, vapor phase reaction, vacuum deposition, or the like as desired.

Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples, Examples and Comparative Examples. In addition, evaluation of resin in the following synthesis examples is as follows unless there is a prior notice.

Solid content concentration: The resin solution was calculated | required by heating at 160 degreeC for 2 hours.

Acid value: titrated with 1 / 1ON-KOH ethanol (50%) aqueous solution, and calculated | required.

Molecular weight: It calculated | required by GPC. This molecular weight is the weight average molecular weight (Mw) of polystyrene conversion of (A) component except an unreacted raw material.

In addition, the symbol used by a synthesis example is as follows.

FHPA: Equivalent reactant of fluorene bisphenol-type epoxy resin and acrylic acid (Shin-Nitetsu Kagaku Co., ASF-400 solution: solid content concentration 50wt%, solid content equivalent 1.28mgKOH / g, epoxy equivalent 21300)

CHDA: cyclohexane carboxylic dianhydride

SA: succinic anhydride

TPP: Triphenylphosphine

PGMEA: Propylene Glycol Monomethyl Ether Acetate

Synthesis Example 1

238.0 g of 50% PGMEA solution of FHPA, 33.0 g of CHDA, 9.81 g of PGMEA, 46 g of PGMEA and 46 g of TPP0 were charged into four 50 mL flasks of reflux, and stirred for 1 hr under heating at 120 to 125 ° C. 6 hours of heating and stirring were performed at 80 degreeC, and the alkali-soluble resin solution was synthesize | combined. Solid content of the obtained resin solution was 53.5 wt%, acid value (solid content conversion) was 150 mgKOH / g, the area% of alkali-soluble resin (A) -2 in the resin solution by GPC analysis was 91%, and Mw was 10000.

[Example]

(A) -1: In the above Synthesis Example 1, benzophenone tetracarboxylic dianhydride (BTDA) is used to change CHDA, and 1,2,3,6-tetrahydrophthalic anhydride (THPA) is used to change SA. Alkali-soluble resin obtained by synthesizing similarly except using. Acid value (solid content conversion) 100 mgK0H / g, Mw 4000.

(A) -2: alkali-soluble resin obtained in Synthesis Example 1

(A) -3: Propylene glycol monomethyl ether acetate solution of Mw8800, N-phenyl maleimide / methacrylic acid / benzyl methacrylate copolymer of acid value 130 (resin solid content concentration: 37.9 wt%) (N-phenyl maleimide Methacrylic acid: benzyl methacrylate = 26: 34: 40 mol%)

(B): A mixture of dipentaerythritol hexa acrylate and dipentaerythritol penta acrylate (Nihon Kayaku Co., Ltd. product name DPHA)

(C): fluorene-type epoxy resin (Shin-Nitetsu Kagaku Corporation make, brand name ESF-300)

(D) -1: 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (0-benzoyloxime); Compound represented by formula (III), (Chiba Specialty Product, CGI124)

(D) -2: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-one (available from Chiba-Geigi, Monocure 907)

(D) -3: the compound represented by chemical formula (i)

[Tue 7]

(E) -1: ε-phthalocyanine blue (C.I. Pigment Blue 15: 6)

(E) -2: brominated chlorinated phthalocyanine green (C.I. pigment green 36)

(E) -3: diketopyrrolopyrrole red (C.I. Pigment Red 254)

(E) -4: nickel azo yellow (C.I. pigment yellow 150)

(E) -5: Isoindorin Yellow (C.I. Pigment Yellow 139)

(E) -6: Dioxazine Violet (C.I. Pigment Violet 23)

Solvent-1: Propylene Glycol Monomethyl Ether Acetate

Solvent-2: ethyl lactate

Additive-1: Silane Coupling Agent

Additive-2: Surfactant

Examples 1-12 and Comparative Examples 1-15

The said compounding component was mix | blended in the ratio of Tables 1-3, and the resin composition of Examples 1-12 and Comparative Examples 1-15 was prepared. In Tables 1-3, the compounding quantity of the component without description and the component shown by-means that it is zero.

The photosensitive resin composition obtained by uniformly mixing the photosensitive resin compositions of Examples 1 to 12 and Comparative Examples 1 to 15 using a spin coater on a glass substrate of 125 mm x 125 mm has a post-baked film thickness of 2.O. After apply | coating so that it might become micrometer, and prebaking for 2 minutes at 90 degreeC, the ultraviolet-ray of 20Omj / cm <^2> was irradiated with the ultrahigh pressure mercury lamp of I-line roughness 30mW / cm <^2> , and the photocuring reaction of the photosensitive part was performed. Subsequently, the exposure finish plate was subjected to 0.1 MPa pressure shower development and spray washing at 0.5 MPa pressure for 60 seconds at 23 ° C. in 0.04% potassium hydroxide aqueous solution, and the unexposed part of the coating film was removed to evaluate developability. Thereafter, hot post-baking was carried out at 23O &lt; 0 &gt; C for 30 minutes using a hot air dryer to create a coating film for color filters, and evaluation of developability, pattern shape, or transmittance was performed.

In addition, the color filter preparation substrate at the end of post-baking was heat-treated at 250 ° C./60 minutes using a hot air dryer to evaluate heat discoloration resistance.

Tables 4 to 6 show evaluation results such as light transmittance in Examples and Comparative Examples. These evaluation methods are as follows.

Development: It evaluated whether the phenomenon of 100 micrometers patterning by alkali image development is (circle) <orable> or << impossible>.

Film thickness: It measured using the stylus type | mold step shape measuring apparatus (KLA Tencol Co., Ltd. brand name P-10).

Transmittance: The comparative evaluation of average transmittance was performed using the spectrophotometer. The one with the highest numerical value was determined to be &quot; better than &quot;, the next higher one was &quot; good &quot;, and the one with the lowest value was × <defect>.

Heat discoloration resistance: When measuring the average transmittance | permeability using a spectrophotometer, when the fall rate of the transmittance | permeability after heat processing was less than 1%, it determined as << good> and when it is 1% or more as x <defect>.

Pattern shape: Using the side microscope, the pixel pattern after image development was observed, and it was determined that (<good>) and (x) <(bad)> that the peeling with respect to a board | substrate and the groove | channel of a pattern edge part were not recognized.

Sensitivity: The line width of the remaining pattern at the time of exposing using a 100-micrometer pattern mask and performing alkali image development was evaluated using the measurement microscope (brand name XD-20 by Nikon Corporation). (Line width is thick It is thought that the higher the sensitivity.)

When <100 micrometers or less, when it is 100 micrometers or less, when it is (<good>) and when 105 or more, the time when it is 100-105 micrometers, it determined as (better than).

Table 4 shows the photosensitive resin composition for red color filters of Examples 1-4 and Comparative Examples 1-5 using (A) -1, (A) -2, and (A) -3 which are three different alkali-soluble resin. The example which prepared and carried out the physical property comparison is shown. As a result, when (A) -3 was used, pattern formation by development was not possible in (E) / (R) of 2.6.

Table 5 shows the photosensitive resin compositions for blue color filters of Examples 5 to 8 and Comparative Examples 6 to 10 using (A) -1, (A) -2 and (A) -3 which are three different alkali-soluble resins. The example which prepared and carried out the physical property comparison is shown. When (A) -3 was used, pattern formation by development was not possible and development was impossible at (E) / (R) of 2.6.

Table 6 shows the photosensitive resin compositions for green color filters of Examples 9 to 12 and Comparative Examples 11 to 15 using (A) -1, (A) -2 and (A) -3 which are three different alkali-soluble resins. The example which prepared and carried out the physical property comparison is shown. When (A) -3 was used, (E) / (R) peeled all the exposure part and the unexposed part at 1, 5, and image development was not possible. Moreover, the developability of (A) -2 was more favorable about (A) -1 and (A) -2.

In Tables 4-6, (-) means that evaluation was not possible because it was impossible to develop.

Examples 13 and 14 and Comparative Examples 16 and 17

The photoinitiator (D) component was mix | blended in the ratio of Table 7, it was mixed uniformly, and the photosensitive resin composition of Example 13, 14 and comparative examples 16 and 17 was prepared. About these photosensitive resin compositions, (E) / (R) was 1.5 and solid content concentration was 22%.

This resin composition was applied onto a glass substrate of 125 mm x 125 mm using a spin coater so that the film thickness after post-baking was 2.0 µm, and after pre-baking at 90 ° C. for 2 minutes, an ultra-high pressure of 30 mW / cm ² of I-ray roughness was applied. Ultraviolet rays of 200mj / cm ² were irradiated with a mercury lamp and the photocuring reaction of the photosensitive part was performed. Subsequently, this exposure finish plate was subjected to 60 MPa of 0.1 MPa pressure showering and 0.5 MPa pressure spray washing at 23 ° C. in 0.04% potassium hydroxide aqueous solution, to remove unexposed portions of the coating film, and to evaluate developability. . Thereafter, hot post-baking was performed at 230 ° C. for 30 minutes using a hot air dryer to prepare a color filter coating film, and evaluation of the transmittance, sensitivity (100 μm pattern) and brightness (Y value) of the film was performed. Table 7 shows the composition and evaluation results.

In Example 13 using the photoinitiator (D) -1, the physical properties were balanced, and even if the amount of addition was a little, the decrease in brightness (Y value) was hardly seen, but in Comparative Example 16 using (D) -2 In the case of addition amount similar to Example 13, the fall of brightness (Y value) was seen. Moreover, when (D) -3 was used, sensitivity was low and it peeled in the density | concentration area of (E) / (R) = 1.5. On the other hand, in Example 14 which used (D) -1 and (D) -3 together, the fall of the brightness (Y value) was hardly seen, and also the pattern shape etc. could obtain the best result.

Photosensitive composition containing unsaturated group containing alkali-soluble resin obtained by reacting the reaction compound of the epoxy compound which has two glycidyl ether groups derived from bisphenol, and (meth) acrylic acid with polybasic carboxylic acid or its anhydride, and a large amount of coloring agent. By photocuring a resin composition with the oxime ester type photoinitiator which has a specific chemical structure, even if it contains a large amount of initiator, the resin composition for color filters which has little heat-sulfur resistance and good image development characteristics can be obtained. Moreover, control of a pattern shape was also possible by using together 1 type or more photoinitiators other than an oxime ester system. In addition, by forming the resin composition for color filters, it is possible to create a color filter having high color purity and high reliability, and used for various multicolor displays such as color liquid crystal display devices, color facsimile machines, image sensors, optical devices, and the like. It can be used suitably for the color filter which has the coloring ink for color filters used, and the black matrix formed by these, a television, a video monitor, or a display of a computer. In addition, the color filter thus obtained is extremely useful, for example, in a transmissive or reflective color liquid crystal display device, a color imaging tube element, a color sensor, and the like.

Claims (5)

The following (A)-(E) component as an essential component (A) component; Unsaturated group-containing alkali-soluble resins obtained by reacting a reaction product of an epoxy compound having two glycidyl ether groups derived from bisphenols with (meth) acrylic acid with a polybasic carboxylic acid or anhydride thereof, (B) component; Photopolymerizable monomers having at least one ethylenically unsaturated bond, (C) component; A compound having at least one epoxy group, (D) component; Photoinitiators which make the compound represented by general formula (I) essential, and (E) component; Colorants containing at least one organic pigment The weight ratio (A) / (B) of (A) component and (B) component is 20/80-90/10, and the total weight of the resin component which consists of the sum total of resin and a polymeric component ( In the concentration range where the ratio (E) / (R) of (E) to R) is from 0.5 to 2.5, (D) component is added to 100 parts by weight of the total of (A) component and (B) component. It contains-50 weight part, The photosensitive resin composition for color filters characterized by the above-mentioned. [Tue 1]

However, in general formula (I), R ₁ may be substituted with a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), an alkyl group having 1 to 20 carbon atoms (may be substituted with one or more hydroxyl groups, and one or more oxygen atoms in the middle of the alkyl chain; Or a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or a benzoyl group (may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group); R <_2> is a C2-C2 alkanoyl group (it may be substituted by 1 or more halogen atoms or a cyano group), C4-C6 alkenoyl group and benzoyl group whose double bond does not conjugate with a carbonyl group (C1) It may be substituted with an alkyl group, a halogen atom or a cyano group of -6), an alkoxycarbonyl group or a phenoxycarbonyl group of 2 to 6 carbon atoms (may be substituted with one or more alkyl groups or halogen atoms of 1 to 6 carbon atoms), R ₃ , R ₄ , R ₅ , R ₆ and R ₇ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzoyl group and 2 carbon atoms. An alkanoyl group of 12 to 12 and an alkoxycarbonyl group of 2 to 12 carbon atoms (when the carbon number of the alkyl group constituting the alkoxyl group is 2 or more, the alkyl group may be substituted with one or more hydroxyl groups and one or more oxygen atoms in the middle of the alkyl chain). Or a phenylthio group (may be substituted with an alkyl group having 1 to 6 carbon atoms) or a phenoxycarbonyl group. The reaction product of (1) the epoxy compound which has two glycidyl ether groups derived from bisphenols, (meth) acrylic acid, a) saturated dicarboxylic acid or its acid anhydride, and b) saturated For a color filter comprising a resin represented by the following general formula (II) obtained by reacting a tetracarboxylic acid or its acid anhydride in a range in which its molar ratio a / b is from 0.1 to 10 as a main component. Photosensitive resin composition. [Tue 2]

(Wherein R ₁ , R ₂ , R ₃ , R ₄ independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, and R ₅ represents a hydrogen atom or a methyl group. A represents -C0 -, -S0 _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O-, 9,9-fluorenyl group Or represents a direct bond, X represents a tetravalent carboxylic acid residue, Y ₁ , Y ₂ independently represent a hydrogen atom or -OC-Z-COOH (Z represents a divalent carboxylic acid residue), n Represents a number from 1 to 20.) The photosensitive resin composition for color filters of Claim 1 or 2 whose (D) component is a photoinitiator which makes the compound represented by following formula (III) essential. [Tue 3]

The coating film which hardened and formed the photosensitive resin composition for color filters of Claim 1 or 2 characterized by the above-mentioned. It is formed of the coating film obtained by apply | coating and hardening the photosensitive resin composition of Claim 1 or 2, The color filter characterized by the above-mentioned.