KR20080100720A - A colored photosensitive resin composition, color filter, liquid crystal display device having the same - Google Patents

Abstract

A colored photocurable resin composition is provided to ensure excellent adhesion even if a coloring material is contained and the little exposure dose is applied, and excellent sensitivity, and not to generate the developed residue or the surface fault on the substrate. A colored photocurable resin composition comprises a binder resin(A), photopolymerizable compound(B), photopolymerization initiator(C), coloring material(D) and solvent(E). The photocurable acrylic copolymer(a-1) is characterized that the binder resin is a copolymer consisting of a compound(a1) having an unsaturated bond and an unsaturated carboxylic acid compound(a2), obtained by performing copolymerization, or a unsaturated group-containing resin obtained by reacting a compound(a3) having an unsaturated bond and epoxy group in one molecule to the obtained copolymer. The photocurable alkali soluble multi-functional oligomer(a-2) is obtained by polymerizing a monomer(a'1) containing hydroxy group, a monomer(a'2) containing at least one functional group selected from a halogen atom, -OH and carboxy group, a monomer(a'3) containing a glycidyl group, and a monomer(a'4) having -OH or carboxy group and an unsaturated bonding group. The colored photocurable resin composition is manufactured by adding, polymerizing or condensing the photocurable acrylic copolymer(a-1) and the photocurable alkali soluble multi-functional oligomer(a-2).

Description

Colored photosensitive resin composition, color filter and liquid crystal display device having the same {A COLORED PHOTOSENSITIVE RESIN COMPOSITION, COLOR FILTER, LIQUID CRYSTAL DISPLAY DEVICE HAVING THE SAME}

The present invention relates to a colored photosensitive resin composition, a color filter, and a liquid crystal display device having the same.

Color filters are widely used in liquid crystal displays (LCDs) and the like, and their application ranges are rapidly expanding. The color filter used for a color liquid crystal display device etc., after uniformly apply | coating the coloring photosensitive resin composition containing the pigment corresponding to each color of red, green, and blue on the board | substrate with which the black matrix was patterned uniformly by spin coating, The coating film formed by heating and drying (hereinafter sometimes referred to as preliminary firing) is exposed and developed, and if necessary, further heat curing (hereinafter sometimes referred to as postfiring) is repeated for each color to perform pixels of each color. It is manufactured by forming a.

As such a coloring photosensitive resin composition, the composition containing a photopolymerizable compound and a photoinitiator together with a pigment and binder resin is used abundantly, and the photosensitive resin composition containing a black pigment is used also for black matrix formation.

In recent years, in order to improve the yield in process, the coloring photosensitive resin composition is calculated | required the coloring photosensitive resin composition which has equivalent sensitivity and adhesiveness even with a small exposure amount.

In addition, recently, the coloring material of the coloring photosensitive resin composition has been further atomized in order to satisfy the required performance such as high color purity and high brightness. Therefore, the colored layer formed on the background when forming the pixel using this has a problem of developing residue that is not removed during development.

In order to increase the sensitivity, it may be considered to use a photosensitive resin composition using a reactive acrylic resin obtained by adding an unsaturated carboxylic acid to a polymer containing a monomer having an epoxy group and an unsaturated double bond, but there are limitations in the copolymerization reaction. Since the amount of introduction is limited, there is a limit to high sensitivity.

In addition, the conventional technique for improving the developability is generally the method of adjusting the acid value and molecular weight of the resin or the acid value of the binder resin and the composition, but the application range is limited, and when the acid value is too high, adhesion is insufficient or causes of surface defects. It is becoming.

It is an object of the present invention to provide good adhesion even at a low exposure amount even when it contains a coloring material, and does not cause development residues on the substrate or surface defects in the pixel portion when forming pixels, and has excellent sensitivity, resulting in problems during development. It is to provide a photosensitive resin composition.

Still another object of the present invention is to provide a color filter formed using the photosensitive resin composition and a liquid crystal display device having the same.

The present invention for achieving the above object,

A colored photosensitive resin composition containing a binder resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), a coloring material (D) and a solvent (E), wherein the binder resin (A) is a compound having an unsaturated bond ( a copolymer obtained by a copolymerization reaction containing a1) and an unsaturated carboxylic acid compound (a2) or an unsaturated group-containing resin obtained by further reacting a compound (a3) having an unsaturated bond and an epoxy group in one molecule of the copolymer obtained above. Photocurable acrylic copolymer (a-1); at least one functional group-containing monomer (a'2) selected from a hydroxy group-containing monomer (a'1), a halogen atom, a hydroxy group and a carboxyl group, and a glycidyl group-containing monomer (a '3) and a photocurable alkali-soluble polyfunctional oligomer (a-2) obtained by polymerizing a monomer (a'4) having a hydroxyl group or a carboxyl group and an unsaturated bond group together; It provides the coloring photosensitive resin composition characterized by the resin manufactured by carrying out reaction.

In addition, the photocurable acrylic copolymer (a-1) has an acid value of 40 to 300mgKOH / g, it provides a colored photosensitive resin composition, characterized in that the weight average molecular weight of the polystyrene conversion in the range of 3,000 to 100,000.

In addition, the photocurable alkali-soluble polyfunctional oligomer (a-2) has an acid value of 40 to 300 mgKOH / g, a hydroxyl value of 0 to 100, and a weight average molecular weight of its polystyrene equivalent in a range of 400 to 4,000. It provides the coloring photosensitive resin composition characterized by the above-mentioned.

Moreover, the ratio of the structural component guide | induced from each of said (a1)-(a2) is with respect to the total mole number of the said photocurable acrylic copolymer (a-1) structural component,

structural unit derived from (a1): 35 to 90 mol%,

structural unit derived from (a2): 10 to 65 mol%,

It is a range and when it reacts (a3) further, the coloring photosensitive resin composition characterized by reacting (a3) with 5 to 80 mol% with respect to the component derived from (a2) is provided.

Moreover, each ratio of the structural component guide | induced from (a-2) exists in the following range by molar fraction with respect to the total mole number of the structural component which comprises the copolymer of said (a-2), The coloring photosensitive property characterized by the above-mentioned. It provides a resin composition.

structural unit derived from (a'1): 2 to 40 mol%,

structural unit derived from (a'2): 2 to 60 mol%,

structural unit derived from (a'3): 2 to 50 mol%,

Structural units derived from (a'4): 2 to 40 mol%

The present invention further provides a color filter comprising a color layer formed by exposing and developing a colored photosensitive resin composition in a predetermined pattern, wherein the colored photosensitive resin composition is the colored photosensitive resin composition described above. To provide.

The present invention also provides a liquid crystal display device having the above-described color filter.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail. Since the following description is a detailed description of an embodiment, the scope of rights defined by the claims is not limited, even though there is a limiting and assertive expression.

The colored photosensitive resin composition of one Embodiment which concerns on this invention contains binder resin (A), a photopolymerizable compound (B), a photoinitiator (C), a coloring material (D), and a solvent (E). as,

The binder resin (A) is a copolymer obtained by a copolymerization reaction containing a compound (a1) having an unsaturated bond and an unsaturated carboxylic acid compound (a2) or a compound (a3) having an unsaturated bond and an epoxy group in one molecule of the obtained copolymer. Photocurable acrylic copolymer (a-1), characterized in that it is an unsaturated group-containing resin obtained by further reacting (); and

At least one functional group-containing monomer (a'2) selected from a hydroxyl group-containing monomer (a'1), a halogen atom, a hydroxyl group and a carboxyl group, a monomer having a glycidyl group-containing monomer (a'3) and a hydroxyl group or a carboxyl group together with an unsaturated bond group ( A photocurable alkali-soluble polyfunctional oligomer (a-2) obtained by polymerizing a'4); is a resin produced by mixing, polymerizing or condensing a reaction.

Binder Resin (A)

The binder resin (A) usually has reactivity and alkali solubility due to the action of light or heat, and acts as a dispersion medium of the coloring material.

In embodiment of this invention, as a compound (a1) which has an unsaturated bond, if it is a compound which has a unsaturated double bond which can superpose | polymerize, it will not restrict | limit, As a specific example, methyl (meth) acrylate, ethyl (meth) acrylate, Unsubstituted or substituted alkyl ester compounds of unsaturated carboxylic acids such as butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, aminoethyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (Meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylate, menthyl (meth) acrylate, cyclopentenyl (meth) acrylate, cyclohexenyl (Meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, mentadienyl (meth) acrylate, isobornyl (meth Unsaturated carboxylic acid ester containing alicyclic substituents, such as) acrylate, pinanyl (meth) acrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate, and pineneyl (meth) acrylate Unsaturation including substituents having aromatic rings, such as monosaturated carboxylic acid ester compounds of glycols such as compounds and oligoethylene glycol monoalkyl (meth) acrylates, benzyl (meth) acrylates and phenoxy (meth) acrylates Aromatic vinyl compounds, such as a carboxylic acid ester compound, styrene, (alpha) -methylstyrene, and vinyltoluene, carboxylic acid vinyl esters, such as vinyl acetate and a vinyl propionate, cyanation, such as (meth) acrylonitrile and the (alpha)-chloro acrylonitrile Vinyl compound, phenyl maleimide, benzyl maleimide, naphthyl maleimide, cyclohexyl maleimide, methyl maleimide, ethyl maleimide There may be mentioned maleimide compounds such as maleimide profile. These can be used individually or in combination of 2 types or more, respectively.

In embodiment of this invention, as said unsaturated carboxylic acid (a2), if it is a carboxylic acid compound which has a unsaturated double bond which can superpose | polymerize, it will not restrict | limit, Acrylic acid, methacrylic acid, etc. are mentioned as a specific example. Acrylic acid and methacrylic acid can be used individually or in combination of 2 types or more, respectively. In addition to these acrylic acid and methacrylic acid, one or more other acids may be used. As another acid, it is also possible to specifically use together the carboxylic acid chosen from 1 type or more of other unsaturated carboxylic acids, such as crotonic acid, itaconic acid, maleic acid, and fumaric acid. Moreover, you may use together the monomer containing a hydroxyl group and a carboxyl group in the same molecule, such as (alpha)-(hydroxymethyl) acrylic acid.

In embodiment of this invention, as a specific example of the compound (a3) which has an unsaturated bond and an epoxy group in 1 molecule, glycidyl (meth) acrylate, 3, 4- epoxycyclohexyl (meth) acrylate, 3,4 -Epoxycyclohexyl methyl (meth) acrylate, methylglycidyl (meth) acrylate, etc. are mentioned. Among these, glycidyl (meth) acrylate is preferably used. These can be used individually or in combination of 2 types or more, respectively.

In an embodiment of the present invention, the monomer (a'1) having a hydroxy group has a reactive site which reacts well with the monomer (a'2) in the photocurable alkali-soluble polyfunctional oligomer, and such a monomer (a'1) Examples of the polyhydric alcohols include monohydric alcohols, dihydric alcohols, and trihydric alcohols. More specifically, 1,3-butylene glycol, 1,4-butylene glycol, diethylene glycol, ethylene glycol, 1,6 -Hexanediol, 2-methyl 1,3-propanediol, neopentylglycol, propylene glycol, triethylene glycol, trimethylolpropane, pentaerythritol and the like, but are not limited to these, these alone or two It can mix and use the above.

In an embodiment of the invention, the monomer (a'2) having at least one functional group selected from halogen atoms, hydroxy groups and carboxyl groups determines the overall physical properties, including the elasticity and hardness of the final cured product in the photocurable alkali soluble polyfunctional oligomer composition. It plays a role. As such a monomer (a'2), polyhydric carboxylic acids, such as an acid anhydride, a divalent carboxylic acid, and a trivalent carboxylic acid, etc. are mentioned, More specifically, a naphthalic anhydride, a phosphate anhydride, 3-fluoro Phthalate anhydride, butyric anhydride, hexahydro-4-methylphthalic anhydride, trifluoroacetic anhydride, hexahydrophthalic anhydride, phthalic anhydride, maleic anhydride, tetrahydrophthalic anhydride, acetic anhydride, trimellitic anhydride, itaconic anhydride , Neodecanoic acid oxiranylmethyl ester, chloric acid anhydride, succinic anhydride, tetrabromophthalic anhydride, dodecenyl succinic anhydride, nonenyl succinic anhydride, boric anhydride or methyl-5-norbornene-2 , 3-dicarboxylic acid anhydride and the like, but is not limited thereto, and these may be used alone or in combination of two or more thereof.

In an embodiment of the present invention, the monomer having a glycidyl group (a'3) serves as a linkage for imparting a final curing functional group in preparing a polyfunctional oligomer, selected from the halogen atom, hydroxy group and carboxyl group. Like the monomer (a'2) having at least one functional group, the photocurable alkali-soluble polyfunctional oligomer plays a role in determining physical properties such as elasticity and hardness of the final cured product.

Examples of such glycidyl group-containing monomer (a'3) include glycidyl group-containing ether compounds, glycidyl group-containing ester compounds, glycidyl group-containing unsaturated esters, and the like, and more specifically butyl glycidyl ether. Resorcinol diglycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, S-trityl glycidyl ether, glycerol triglycidyl ether, 2,6- Diglycidylphenylglycidyl ether, diglycidyl ether of 1,4-cyclohexanedimethanol, R-benzyl glycidyl ether, S-benzyl glycidyl ether, diglycidyl ether of bisphenol A, Neopentyl glycol diglycidyl ether, triethylene glycol diglycidyl ether, p-cresyl glycidyl ether, guacol glycidyl ether, o-cresyl glycidyl ether (o -cresyl glycidyl ether), p-chlorophenylglycidyl Ether, ethylene glycol diglycidyl ether, diglycidyl ether, hydroquinone diglycidyl ether, 1,4-butanediol diglycidyl ether, n-butylglycidyl ether, glycidyl neodecanoate, 2-ethylhexyl glycidyl ether, lauryl glycidyl ether, glycerol polyglycidyl ether, cresyl glycidyl ether, aryl glycidyl ether, 3,4-epoxycyclohexyl methyl methacrylate, glycy Dimethyl methacrylate, glycidyl acrylate and the like, but is not limited to these, these may be used alone or in combination of two or more.

 Of the monomers constituting the oligomer according to the present invention, a monomer (a'4) having a hydroxyl group or a carboxyl group and an unsaturated bond group together serves to provide a final curing functional group in the photocurable alkali-soluble polyfunctional oligomer composition. As such a monomer (a'4), an unsaturated carboxylic ester compound, an unsaturated carboxylic acid, its anhydride, an unsaturated hydroxy ester compound, etc. are mentioned, for example, 2-hydroxyethyl methacrylate, 2-hydroxyethyl Unsaturated carboxylic ester compounds of hydroxyalkyl esters such as acrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, etc. Unsaturated carboxyl such as acrylic acid, methacrylic acid, etc. Acid esters, maleic acid, fumaric acid, maleic anhydride, tetrahydrophthalic anhydride, and the like, and these may be used alone or in combination of two or more thereof.

Moreover, the ratio of the structural component guide | induced from each of said (a1)-(a2) is with respect to the total mole number of the said photocurable acrylic copolymer (a-1) structural component,

structural unit derived from (a1): 35 to 90 mol%,

structural unit derived from (a2): 10 to 65 mol%,

It is a range, and when making (a3) react further, it is good to make 5 to 80 mol% of (a3) react with the component derived from (a2).

In particular, it is more preferable that the ratio of said structural component is the following ranges.

structural unit derived from (a1): 50 to 85 mol%,

Structural units derived from (a2): 15 to 50 mol%

If said composition ratio is in the said range, since the balance of developability, solubility, and heat resistance is favorable, a preferable copolymer can be obtained.

In addition, the compound (a3) having the unsaturated bond and the epoxy group is preferably reacted 5 to 80 mol% with respect to the number of moles of the unsaturated carboxylic acid compound (a2) contained in the copolymer (a-1), particularly 10 to 80 Mole% is good. If the composition ratio of (a3) is in the said range, since sufficient photocurability and thermosetting are obtained, a sensitivity and pencil hardness are compatible, and since it is excellent in reliability, it is preferable.

Moreover, each ratio of the structural component guide | induced from (a-2) exists in the following range by molar fraction with respect to the total mole number of the structural component which comprises the copolymer of said (a-2), The coloring photosensitive property characterized by the above-mentioned. It provides a resin composition.

structural unit derived from (a'1): 2 to 40 mol%,

structural unit derived from (a'2): 2 to 60 mol%,

structural unit derived from (a'3): 2 to 50 mol%,

Structural units derived from (a'4): 2 to 40 mol%

That is, in the binder resin (A), a monomer (a'1) having a hydroxy group and a monomer (a'2) having at least one functional group selected from a halogen atom, a hydroxy group and a carboxy group constituting (a-2), a glyc The photocurable alkali-soluble polyfunctional oligomer (a-2) obtained by polymerizing a monomer (a'3) having a cylyl group, a hydroxyl group or a monomer (a'4) having an unsaturated bond group together with a total moles of components (A'1), (a'2), (a'3), and (a'4) monomers are not limited, but 2 to 40 mol%, 2 to 60 mol%, 2 to 50 mol%, It is preferably included in the range of 2 to 40 mol%.

In particular, it is more preferable that the ratio of said structural component is the following ranges.

structural unit derived from (a'1): 2-25 mol%,

structural unit derived from (a'2): 10 to 60 mol%,

structural unit derived from (a'3): 10 to 45 mol%,

Structural units derived from (a'4): 5 to 40 mol%

If said composition ratio is in the said range, since the balance of developability, solubility, and heat resistance is favorable, a preferable copolymer can be obtained.

In the embodiment of the present invention, the binder resin (A) is prepared by adding, polymerizing or condensing a photocurable alkali-soluble polyfunctional oligomer (a-2) to a photocurable acrylic copolymer (a-1).

In the embodiment of the present invention, first, the method of preparing the photocurable acrylic copolymer (a-1) is not particularly limited when it is obtained by copolymerizing (a1) to (a2), and various conventionally known polymerization methods may be employed. Particularly preferred is solution polymerization. The polymerization temperature and the polymerization time vary depending on the type and ratio of the monomer component to be introduced, the target binder resin molecular weight and the acid value, and preferably can be polymerized at 60 to 130 ° C. for about 1 to 10 hours.

In addition, one part or whole quantity of a polymerization initiator may be put in a flask at the said process, and a part or whole quantity of (a1)-(a2) may be put in a flask.

In addition, when using a solvent in the said process, the solvent used at the time of a normal radical polymerization reaction can be used as a solvent, For example, tetrahydrofuran, dioxane, ethylene glycol dimethylethyl, diethylene glycol Dimethylethyl, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, propylene glycol monomethyl ethyl acetate, 3-methoxybutyl acetate, methanol, ethanol, propanol, n-butanol, Ethylene glycol monomethyl ether, propylene glycol monomethyl ether, toluene, xylene, ethylbenzene, chloroform, dimethyl sulfoxide and the like. These solvents may be used alone or in combination of two or more thereof.

In addition, the polymerization initiator used for the said process can add the polymerization initiator normally used, and is not specifically limited. Specific examples include diisopropylbenzenehydroperoxide, di-t-butylperoxide, benzoyl peroxide, t-butylteroxyisopropylcarbonate, t-amylperoxy-2-ethylhexanoate, t Organic peroxides such as -butyl teroxy-2-ethylhexanoate; 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylbareronitoryl), dimethyl 2,2'-azobis (2-methylpropionate), etc. Nitrogen compounds; Etc. can be mentioned. These may be used alone or in combination of two or more thereof.

Moreover, in order to control molecular weight and molecular weight distribution, mercapto system chain transfer agents, such as n-dodecyl mercapto, mercaptoacetic acid, and mercaptoacetic acid methyl, alpha-methylstyrene dimer, etc. can also be used as a chain transfer agent. The usage-amount of (alpha) -methylstyrene dimer and a mercapto compound is 0.005 to 5% on a mass basis with respect to the total amount of (a1)-(a2). In addition, the said polymerization conditions can also adjust an input method and reaction temperature suitably in consideration of the amount of heat generation by a manufacturing facility, superposition | polymerization, etc ..

In embodiment of this invention, in said binder resin (A), (a-1) can be manufactured by making said copolymer and (a3) react by the following methods, for example.

Reaction catalyst of 5 to 80 mol% of (a3), a carboxyl group and an epoxy group by molar fraction with respect to the structural unit derived from the unsaturated carboxylic acid compound (a2) which comprises the said copolymer, replacing atmosphere in a flask with nitrogen from air. For example, trisdimethylaminomethylphenol is 0.01 to 5% by mass relative to the total amount of (a1) to (a2) and as a polymerization inhibitor, for example, hydroquinone is added to the total amount of (a1) to (a2). The copolymer and (a3) can be reacted by adding 0.001 to 5% in a flask on a mass basis and reacting at 60 to 130 ° C for 1 to 10 hours. In addition, similarly to the polymerization conditions, the charging method and the reaction temperature may be appropriately adjusted in consideration of the amount of heat generated by the production equipment, the polymerization and the like.

In embodiment of this invention, it is preferable that it is 40-300 mgKOH / g, and, as for the acid value of a photocurable acrylic copolymer (a-1), it is more preferable that it is 60-150 mgKOH / g. In the above range, the problem of development failure, the pattern damage by the developer, and the like do not occur. In addition, the weight average molecular weight thereof in terms of polystyrene is preferably in the range of 3,000 to 100,000, and more preferably in the range of 5,000 to 50,000. When the weight average molecular weight of the photocurable acrylic copolymer (a-1) is in the range of 3,000 to 100,000, film reduction is unlikely to occur at the time of development, and it is preferable because the missing property of the non-pixel portion at the time of development tends to be good.

It is preferable that it is 1.5-6.0, and, as for the molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of a photocurable acrylic copolymer (a-1), it is more preferable that it is 1.8-4.0. If molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] is 1.5-6.0, since developability is excellent, it is preferable.

In the embodiment of the present invention, the method for producing a photocurable alkali-soluble polyfunctional oligomer (a-2) having an unsaturated bond group and a carboxyl group according to the present invention comprises a monomer (a'1) having a hydroxy group, a halogen atom and a hydroxy group. And an A'1-1 reaction in which the monomer (a'2) having a functional group selected from carboxyl groups is polymerized to obtain a first intermediate (A'1) having a hydroxy group and an ester group.

In such a first reaction, the polymerization is preferably performed at 40 to 160 ° C., and if the polymerization temperature is less than 40 ° C., a sufficient reaction may not proceed and the conversion may be lowered. It may gel or seriously affect physical properties. In addition, the A'1-1 order reaction is preferably terminated at an acid value of 50 to 300 mgKOH / g of the intermediate (A'1), which is the property of application of the final oligomer including developability in the lithographic process in the above range This is because it exhibits the best physical properties.

Meanwhile, the intermediate (A'1) produced by the A'1-1 order reaction has a hydroxyl group and an ester bond at the same time, and reacts with a monomer (a'3) having a glycidyl group in the subsequent reaction to A'1-. 2 to produce an intermediate (A'2). Specifically, the A'1-secondary reaction is polymerized by dropwise adding the monomer (a'3) having a glycidyl group to the intermediate (A'1) which is the A'1-first reaction product for 1 to 5 hours. The intermediate (A'2) is prepared, and the intermediate (A'2) has a hydroxyl group or a carboxy group as a residual functional group.

In the A′1-2 reaction, the reaction temperature is preferably 60 to 170 ° C., and if the temperature is less than 60 ° C., there is a concern that the formation of a desired residual functional group may not be sufficient. It is not preferable because the reactant may gel. In the A'1-2 secondary reaction, it is preferable to terminate the reaction at an acid value of 0 to 100 mgKOH / g, since the application properties of the final oligomer including developability in lithographic processes exhibit the best physical properties in the above range. .

A'1-3rd reaction by dropping a monomer (a'4) having a hydroxy group or a carboxyl group and an unsaturated bond group together for 1 to 5 hours to intermediate (A'2) which is the A'1-2nd reaction product prepared as described above. Finally, a photocurable alkali-soluble polyfunctional oligomer according to the present invention having an unsaturated bond group and a carboxyl group together is prepared. In the A′1-3rd reaction, the reaction temperature is preferably 60 to 200 ° C., when the temperature is less than 60 ° C., it is difficult to produce the desired carboxyl group. When the temperature is above 200 ° C., the appearance and color of the resin become poor. And side reactions may cause an increase in resin molecular weight and gelation. In addition, the A'1-3rd reaction is preferably terminated at an acid value of 40 to 300 mgKOH / g, since the application properties of the final oligomer including developability in lithographic processes exhibit the best physical properties in the above range.

The polymerization process as described above is not particularly limited as a solvent, but hydrocarbon-based mineral spirits, xylene, toluene, propylene glycol monomethyl ether acetate, ethoxyethyl propionate, ethyl cellosolve acetate, diisopropyl ether, and propyl acetate Solvents that do not contain reactive active hydrogen, such as n-butylpropionate, may be used, but are not limited thereto, and any solvent known in the art may be used without limitation. In addition, the reaction may employ a catalyst in order to shorten the reaction time and improve the yield, wherein the usable catalysts include metal catalysts such as zirconium octoate, dibutyl tin dilaurate, and tertiary such as triethylamine. Amines, ammonium salts and the like can be used, but are not limited to these, and they can be used in catalytic amounts.

The photocurable alkali-soluble polyfunctional oligomer (a-2) having an unsaturated bond group and a carboxyl group according to the present invention as described above has an acid value of 40 to 300 mgKOH / g, a hydroxyl value of 0 to 100, and a nonvolatile content. It is 60 mass% or more based on the total amount of oligomers containing this solvent, has a viscosity of 100 to 20,000 centipoise, a number average molecular weight of 400 to 4,000, a weight average molecular weight of 600 to 5,000, and has a molecular weight distribution of 2 or less. It is possible to obtain excellent physical properties in a photolithographic process including developability as desired in the present invention.

The oligomer (a-2) according to the present invention may be used alone or in the form of a mixture with other monomers, oligomers or binder resins, but in the present invention, addition, polymerization or condensation reaction with the binder resin in order to obtain a more uniform curing composition. It provides a method for pendant to the side chain of the binder resin skeleton through.

Next, using the alkali-soluble copolymer (a-1) and the photocurable alkali-soluble polyfunctional oligomer (a-2) containing one or more photopolymerizable unsaturated bond groups in the molecule, a poly excellent in developing characteristics in the negative photosensitive resin composition For example, a method for producing a binder resin (A), which is an ester-based photocurable alkali-soluble polyfunctional oligomer-modified acrylic copolymer, includes direct addition, polymerization or condensation reaction between functional groups contained in (a-1) and (a-2). It may be prepared by, but in this case, two or more reactors in the molecule can be reduced due to steric hindrance between (a-1) and (a-2) or viscosity increase and gelation may occur due to reaction between unsaturated bonds. More preferably, a process of bonding at a temperature of 130 ° C. or lower using a compound having an as a medium may be recommended.

In addition, in the manufacturing method of manufacturing binder resin (A), the reaction ratio of (a-1) and (a-2) is (a-2) 1-80 with respect to the component derived from (a-1). It can react with mol%, and it is more preferable to make it react 2-40 mol%. If it is in the said range, since there are few unreacted monomers after manufacture and it is excellent in stability, it is preferable.

Examples of the mechanism using a compound having two or more reactors in a molecule that can be used in the manufacturing process of the binder resin (A) include a compound containing a hydroxyl group such as ethylene glycol, diethylene glycol, and (a-1) and (a Semi-esterification according to the ring-opening reaction between -hydroxy groups, epoxy group-containing compound such as bisphenol-A epoxy compound and carboxylic acid esterification reaction between (a-1) and (a-2), hexamethylene di Isocyanate group containing compounds, such as isocyanate, and urethane bond reaction between the hydroxyl groups of (a-1) and (a-2), and acid anhydride containing compounds, such as tetracarboxylic dianhydride, (a-1) and (a-2) Semi-esterification due to ring-opening reaction between hydroxy groups may be recommended.

In the embodiment of the present invention, the binder resin (A), which is a polyester-based photocurable alkali-soluble polyfunctional oligomer-modified acrylic copolymer having excellent development characteristics, preferably has a weight average molecular weight in terms of polystyrene in the range of 3,000 to 100,000. More preferably in the range of 5,000 to 50,000. If the weight average molecular weight is in the range of 3,000 to 100,000, film reduction is unlikely to occur at the time of development, and it is preferable because the missing property of the non-pixel portion at the time of development tends to be good.

It is preferable that it is 1.5-6.0, and, as for the molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of binder resin (A), it is more preferable that it is 1.8-4.0. The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of 1.5 to 6.0 is preferable because of its developability.

In addition, the acid value of the binder resin (A) which is the copolymer is preferably in the range of 30 to 300 mgKOH / g, more preferably 60 to 150 mgKOH / g based on solid content. If the acid value is less than 30 mgKOH / g, developability to alkaline water is low and there is a risk of leaving a residue on the substrate, if the acid value exceeds 300 mgKOH / g is more likely to desorption of the pattern.

Photopolymerization  Compound (B)

The photopolymerizable compound (B) contained in the colored photosensitive resin composition of this invention is a compound which can superpose | polymerize by the action | action of light and the photoinitiator mentioned later, A monofunctional monomer, a bifunctional monomer, another polyfunctional monomer, etc. are mentioned. have.

The photopolymerizable compound (B) used in the present invention may be used by mixing two or more photopolymerizable compounds having different functional groups or functional groups in order to improve the developability, sensitivity, adhesion, and surface problems of the colored photosensitive resin composition. It does not limit the scope.

Specific examples of the monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl arcrate, and N-vinylpi A ralidone etc. are mentioned.

Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, etc. are mentioned.

Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, and pentaerythritol tree. (Meth) acrylate, pentaerythritol tetra (meth) acrylate, thipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol Hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned.

Of these, bifunctional or higher polyfunctional monomers are preferably used.

A photopolymerizable compound (B) is used normally in 1-60 mass parts with respect to a total of 100 mass parts of binder resin (A) and a photopolymerizable compound (B), Preferably it is used in the range of 5-50 mass parts. If the photopolymerizable compound (B) is in the range of 1 to 60 parts by mass based on the above criteria, the intensity and smoothness of the pixel portion tends to be good, and thus it is preferable.

Photopolymerization Initiator (C)

Although the photoinitiator (C) contained in the coloring photosensitive resin composition of this invention is not restrict | limited, It is 1 or more types of compounds chosen from the group which consists of a triazine type compound, an acetophenone type compound, a biimidazole type compound, and an oxime compound. The coloring photosensitive resin composition containing said photoinitiator (C) is highly sensitive, and the film | membrane formed using this composition becomes favorable the intensity | strength and surface smoothness of the pixel part.

Moreover, when photopolymerization start adjuvant (C-1) is used together with a photoinitiator (C), since the coloring photosensitive resin composition containing these becomes more sensitive and the productivity at the time of forming a color filter using this composition is preferable, it is preferable. .

As said triazine type compound, it is 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1, 3, 5- triazine, 2, 4-bis (trichloromethyl)-, for example. 6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4- Bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2 -Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-tri Azine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloro Methyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like.

Moreover, as said acetophenone type compound, diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane- 1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] Oligomer of propan-1-one, etc. are mentioned. As an acetophenone type compound, the compound represented by following formula (1) is mentioned, for example.

<Formula 1>

In Formula 1, R1 to R4 are each independently a hydrogen atom, a halogen atom, a hydroxy group, a phenyl group which may be substituted by an alkyl group having 1 to 12 carbon atoms, a benzyl group which may be substituted by an alkyl group having 1 to 12 carbon atoms, or The naphthyl group which may be substituted by the C1-C12 alkyl group is shown.

Specific examples of the compound represented by the formula (1) include 2-methyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-ethyl-2-amino (4-morpholinophenyl) ethane-1 -One, 2-propyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-butyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-methyl-2 -Amino (4-morpholinophenyl) propane-1-one, 2-methyl-2-amino (4-morpholinophenyl) butan-1-one, 2-ethyl-2-amino (4-morpholino Phenyl) propane-1-one, 2-ethyl-2-amino (4-morpholinophenyl) butan-1-one, 2-methyl-2-methylamino (4-morpholinophenyl) propane-1- On, 2-methyl-2-dimethylamino (4-morpholinophenyl) propan-1-one, 2-methyl-2-diethylamino (4-morpholinophenyl) propan-1-one, etc. may be mentioned. have.

As said biimidazole compound, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetraphenyl biimidazole, 2,2'-bis (2,3-, for example) Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimi Dazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, and a phenyl group at the 4,4', 5,5 'position is carbo The imidazole compound substituted with the alkoxy group etc. are mentioned. Among them, 2,2'bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole is preferably used.

As said oxime compound, 0-ethoxycarbonyl- (alpha)-oxyimino-1- phenyl propane- 1-one of following formula (2) is mentioned, for example.

<Formula 2>

 Moreover, as long as it does not impair the effect of this invention, other photoinitiators etc. which are normally used in this field can also be used together. As another photoinitiator, a benzoin compound, a benzophenone type compound, a thioxanthone type compound, an anthracene type compound etc. are mentioned, for example. These can be used individually or in combination of 2 or more types, respectively.

As a benzoin type compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. are mentioned, for example.

As a benzophenone type compound, for example, benzophenone, methyl 0- benzoyl benzoate, 4-phenyl benzophenone, 4-benzoyl-4'- methyl diphenyl sulfide, 3, 3 ', 4, 4'- tetra (tert) -Butyl peroxycarbonyl) benzophenone, 2,4, 6-trimethyl benzophenone, etc. are mentioned.

As a thioxanthone type compound, 2-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-4- propoxy thioxanthone, etc. are mentioned, for example. Can be mentioned.

Examples of the anthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like. Can be.

Other 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenylclioxylic acid Methyl, a titanocene compound, etc. are mentioned as another photoinitiator.

Moreover, the photoinitiator which has group which can cause chain transfer can also be used, As this photoinitiator, what is described in Unexamined-Japanese-Patent No. 2002-544205 is mentioned, for example. As a photoinitiator which has the group which can cause the said chain transfer, the compound represented by following formula (3)-8 is mentioned, for example.

<Formula 3>

<Formula 4>

<Formula 5>

<Formula 6>

<Formula 7>

<Formula 8>

In addition, you may use combining a photoinitiator (C-1) with a photoinitiator (C). As the photopolymerization initiation assistant (C-1), an amine compound and a carboxylic acid compound are preferably used. Specific examples of the amine compound in the photopolymerization start adjuvant include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 4 -Dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N, N-dimethyl paratoluidine, 4,4'-bis (dimethylamino) benzophenone (common name: Michler's ketone), 4,4'-bis Aromatic amine compounds, such as (diethylamino) benzophenone, are mentioned. As an amine compound, an aromatic amine compound is used preferably.

Specific examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenyl And aromatic heteroacetic acids such as thioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

The usage-amount of a photoinitiator (C) is 0.1-40 mass parts normally with respect to a total of 100 mass parts of binder resin (A) and a photopolymerizable compound (B), Preferably it is 1-30 mass parts, A photoinitiator adjuvant (C) The usage-amount of -1) is 0.1-50 mass parts normally on the said reference | standard, Preferably it is 1-40 mass parts. When the usage-amount of a photoinitiator (C) exists in the said range, since the coloring photosensitive resin composition becomes high sensitivity and the intensity | strength of the pixel part formed using this composition and the smoothness in the surface of this pixel part tend to become favorable, it is preferable. . Moreover, when the usage-amount of a photoinitiator auxiliary (C-1) exists in the said range, since the sensitivity of a coloring photosensitive resin composition becomes higher and the productivity of the color filter formed using this composition tends to improve, it is preferable.

Coloring material (D)

It is preferable that the coloring material (D) used by this invention is an organic pigment or inorganic pigment normally used for a pigment dispersion resist as a pigment normally. If necessary, dyes may be used and are included in the present invention.

Examples of the inorganic pigments include metal compounds such as metal oxides and metal complex salts. Specifically, oxides or complex metal oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc and antimony Etc. can be mentioned.

Specific examples of the organic pigment and inorganic pigment include compounds classified as pigments in the Color Index (published by The society of Dyers and Colorists), and more specifically, pigments having the following color index (CI) numbers. Although these are mentioned, It is not necessarily limited to these.

C.I. Pigment Yellow 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180 and 185

C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, and 71

C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 215, 216, 224, 242, 254, 255 and 264

C.I. Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37 and 38

C.I. Pigment Blue 15 (15: 3, 15: 4, 15: 6, etc.), 21, 28, 60, 64, and 76

C.I. Pigment Green 7, 10, 15, 25, 36 and 47

C.I Pigment Brown 28

C.I pigment black 1 and 7, etc.

These coloring materials (D) can be used individually or in combination of 2 or more types, respectively. Content of a coloring material (D) is 3-60 mass% normally on the basis of the total solid content in a coloring photosensitive resin composition, Preferably it is the range of 5-55 mass%. If the content of the coloring material (D) is in the range of 5 to 60% by mass based on the above criteria, even when a thin film is formed, the color density of the pixel is sufficient, and residues are less likely to occur because the omission of the non-pixel portion during development is not lowered. It is preferable because it tends to.

Solvent (E)

The solvent (E) contained in the colored photosensitive resin composition of this invention is not specifically limited, Various organic solvents used in the field of colored photosensitive resin composition can be used.

Specific examples thereof include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene. Diethylene glycol dialkyl ethers such as glycol dipropyl ether and diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, and propylene glycol Alkylene glycol alkyl ether acetates such as monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxy butyl acetate, and methoxy pentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, methyl ethyl ketone, Acetone, Ketones such as methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate Ester, such as these, Cyclic ester, such as (gamma) -butyrolactone, etc. are mentioned.

Among the solvents described above, organic solvents having a boiling point of 100 to 200 ° C in the solvents are preferable in terms of coating properties and drying properties, and more preferably alkylene glycol alkyl ether acetates, ketones and 3-ethoxypropionic acid. Ester, such as ethyl and 3-methoxy propionate, is mentioned, More preferably, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxy propionate, 3-methoxy Methyl oxypropionate etc. are mentioned.

These solvents (E) can be used individually or in mixture of 2 or more types, respectively.

Content of the solvent (E) in the colored photosensitive resin composition of this invention is 60-90 mass% normally with a mass fraction with respect to the coloring photosensitive resin composition whole quantity containing it, Preferably it is 70-85 mass%. When the content of the solvent (E) is in the range of 60 to 90% by mass based on the above criteria, it is applied with a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes referred to as die coater), inkjet, or the like. It is preferable because the coating property tends to be good at the time.

Other additives

In the coloring photosensitive resin composition of this invention, it is also possible to add additives (F), such as a filler, another high molecular compound, a hardening | curing agent, a pigment dispersing agent, an adhesion promoter, antioxidant, a ultraviolet absorber, and an aggregation inhibitor, as needed.

Specific examples of the filler include glass, silica, alumina and the like.

Specific examples of other polymer compounds include curable resins such as epoxy resins and maleimide resins, thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ethers, polyfluoroalkyl acrylates, polyesters, polyurethanes, and the like. have.

A hardening | curing agent is used in order to raise a deep part hardening and mechanical strength, As a hardening | curing agent, an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, an oxetane compound, etc. are mentioned.

Examples of the epoxy compound in the curing agent include bisphenol A epoxy resins, hydrogenated bisphenol A epoxy resins, bisphenol F epoxy resins, hydrogenated bisphenol F epoxy resins, noblock type epoxy resins and other aromatic epoxy resins and alicyclic compounds. Epoxy resins, glycidyl ester resins, glycidylamine resins, or brominated derivatives of such epoxy resins, aliphatic, alicyclic or aromatic epoxy compounds other than epoxy resins and their brominated derivatives, butadiene (co) polymer epoxides, Isoprene (co) polymer epoxide, glycidyl (meth) acrylate (co) polymer, triglycidyl isocyanurate and the like.

Examples of the oxetane compound in the curing agent include carbonate bis oxetane, xylene bis oxetane, adipate bis oxetane, terephthalate bis oxetane and cyclohexane dicarboxylic acid bis oxetane.

The curing agent may include a curing aid compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound with the curing agent. As a hardening auxiliary compound, polyhydric carboxylic acids, polyhydric carboxylic anhydrides, an acid generator, etc. are mentioned, for example.

As carboxylic acid anhydrides, what is marketed can be used as an epoxy resin hardening | curing agent. As this epoxy resin hardening | curing agent, a brand name (Adekahadona EH-700) (made by Adeka Industrial Co., Ltd.), a brand name (Rikaditdo HH) (made by Nippon Ewha Co., Ltd.), a brand name (MH-700) ( New Japan Ewha Co., Ltd.). The said hardening | curing agent can be used individually or in mixture of 2 or more types.

Commercially available surfactants can be used as the pigment dispersant, and examples thereof include surfactants such as silicone, fluorine, ester, cationic, anionic, nonionic and amphoteric. These can be used individually or in combination of 2 types or more, respectively. As said surfactant, For example, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol diester, sorbitan fatty ester, fatty acid modified polyester, tertiary amine modified polyurethane , Polyethyleneimine, and the like, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by Tochem Products), MEGAFAC (manufactured by Dainippon Ink Chemical Industries, Ltd.), Florard (manufactured by Sumitomo 3M), Asahi guard, Suflon (manufactured by Asahi Glass), SOLSPERSE (made by Genka Corporation), EFKA (made by EFKA Chemicals), PB 821 (made by Ajinomoto Co., Ltd.), etc. are mentioned.

As the adhesion promoter, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyl tris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N -(2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltri A methoxysilane, 3-isocyanate propyl trimethoxysilane, 3-isocyanate profile triethoxysilane, etc. are mentioned.

These adhesion promoters can be used individually or in combination of 2 or more types, respectively. The concentration relative to the resist solid content is usually 0.01 to 10% by mass, preferably 0.05 to 2% by mass.

Specific examples of the anti-inflammatory agent include 2,2'-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butyl-4-methylphenol, and the like.

Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole, alkoxybenzophenone and the like.

Specific examples of the aggregation inhibitor include sodium polyacrylate and the like.

The coloring photosensitive resin composition of this invention can be manufactured by the following methods, for example. The coloring material (D) is previously mixed with the solvent (E) and dispersed using a bead mill or the like until the average particle diameter of the coloring material is about 0.2 µm or less. At this time, a pigment dispersant is used as needed, and some or all of binder resin (A) may be mix | blended. The remainder of binder resin (A), the photopolymerizable compound (B), the photoinitiator (C), the other components used as needed, and the additional solvent as needed in the obtained dispersion liquid (henceforth a mill base). Is further added to a predetermined concentration to obtain a desired colored photosensitive resin composition.

Hereinafter, the pattern formation method of the coloring photosensitive resin composition which concerns on this invention is demonstrated.

The pattern forming method of the colored photosensitive resin composition according to the present invention comprises the steps of applying the above-described colored photosensitive resin composition on a substrate, selectively exposing a portion of the colored photosensitive resin composition, and the colored photosensitive resin composition Removing the exposed or non-exposed areas.

As an example, it can apply | coat on a base material as follows, and perform a photocuring and image development to form a pattern, and can be used as a black matrix or a colored pixel (colored image).

First, the composition is applied onto a substrate (not limited, usually glass or silicon wafer) or a layer containing solids of the colored photosensitive resin composition formed first and preliminarily dried to remove volatile components such as solvents to obtain a smooth coating film. . The thickness of the coating film at this time is about 1-4 micrometers normally. In order to obtain the desired pattern to the coating film obtained in this way, an ultraviolet-ray is irradiated to a specific area | region through a mask. At this time, it is preferable to use apparatuses, such as a mask aligner and a stepper, so that a parallel light beam may be irradiated uniformly to the whole exposure part, and a mask and a board | substrate will be correctly aligned. In addition, a desired pattern can be produced by contacting the aqueous coating solution after completion of curing with an aqueous alkali solution to dissolve and develop the non-exposed areas. After image development, after-drying for about 10 to 60 minutes can be performed at 150-230 degreeC as needed.

The developing solution used for image development after patterned exposure is the aqueous solution containing an alkaline compound and surfactant normally.

The alkaline compound may be either an inorganic or organic alkaline compound.

Specific examples of the inorganic alkaline compounds include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, sodium bicarbonate And potassium hydrogen carbonate, sodium borate, potassium borate, ammonia and the like.

In addition, specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, mono Isopropylamine, diisopropylamine, ethanolamine, etc. are mentioned. These inorganic and organic alkaline compounds can be used individually or in combination of 2 or more types, respectively.

Preferable concentration of the alkaline compound in the alkaline developer is in the range of 0.01 to 10% by mass, more preferably 0.03 to 5% by mass.

Surfactant in alkaline developing solution can use all of a nonionic surfactant, anionic surfactant, or a cationic surfactant.

Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, poly Oxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine and the like.

Specific examples of the anionic surfactant include higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzene sulfonate, Alkyl aryl sulfonates, such as sodium dodecyl naphthalene sulfonate, etc. are mentioned.

Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryl trimethylammonium chloride, and quaternary ammonium salts.

These surfactant can be used individually or in combination of 2 or more types, respectively.

The concentration of the surfactant in the alkaline developer is usually 0.01 to 10% by mass, preferably 0.05 to 8% by mass, more preferably 0.1 to 5% by mass.

Hereinafter, the color filter according to the present invention will be described.

The color filter according to the present invention is characterized by comprising a color layer formed by exposing and developing the above-described colored photosensitive resin composition in a predetermined pattern.

The pattern formation method of a coloring photosensitive resin composition is based on the above-mentioned, and detailed description is abbreviate | omitted. As described above, a pixel or a black matrix corresponding to the color of the coloring material in the photosensitive resin composition is obtained through application of the colored photosensitive resin solution, drying, patterned exposure to the resulting dry coating film, and development. The color filter can be obtained by repeating such an operation by the number of colors required for the color filter. Since the configuration and manufacturing method of the color filter are well known in the art, detailed description thereof will be omitted.

The color filter is usually a black matrix and three primary color pixels of red, green and blue arranged on a substrate, but by performing the above operation using the colored photosensitive resin composition of the present invention containing a coloring material corresponding to a certain color. The black matrix and the three primary color pixels are disposed on a substrate by obtaining the black matrix or the pixel of the color and performing the same operation using the colored photosensitive resin composition of the present invention containing the coloring material corresponding to the desired color for other colors. can do. Of course, the photosensitive resin composition of this invention can also be apply | coated only to one color, two colors, or three colors of a black matrix and three primary colors.

In addition, although the black matrix which is a light shielding layer can also use the coloring (colored black) photosensitive resin of this invention, since it is formed by the chromium layer etc., for example, the coloring photosensitive resin composition of this invention for formation of a black matrix. There is no need to use.

The color filter manufactured using the coloring photosensitive resin composition of this invention has little in-plane film thickness difference, For example, it can make in-plane film thickness difference 0.15 micrometer or less and further 0.05 micrometer or less with the film thickness of 1-4 micrometers. . Therefore, the color filter obtained in this way is excellent in smoothness, and it can manufacture a liquid crystal display device of excellent quality by high yield by assembling this to a color liquid crystal display device.

The present invention also includes a liquid crystal display device provided with the color filter described above.

The liquid crystal display of the present invention includes a configuration known in the art, except that the above-described color filter is provided. That is, all of the liquid crystal display devices to which the color filter of the present invention can be applied are included in the present invention. For example, a transmissive liquid crystal display device in which a counter electrode substrate including a thin film transistor (TFT element), a pixel electrode, and an alignment layer is faced at predetermined intervals, and a liquid crystal material is injected into the gap to form a liquid crystal layer. Can be. There is also a reflective liquid crystal display device in which a reflective layer is provided between the substrate of the color filter and the colored layer.

As another example, a liquid crystal display device including a TFT (Thin Film Transistor) substrate joined on a transparent electrode of a color filter, and a backlight fixed at a position where the TFT substrate overlaps the color filter. The TFT substrate includes an outer frame made of light-proof resin surrounding a peripheral surface of a color filter, a liquid crystal layer made of nematic liquid crystals imposed in the outer frame, and a plurality of pixel electrodes provided for each region of the liquid crystal layer. , A transparent glass substrate on which the pixel electrode is formed, and a polarizing plate formed on the exposed surface of the transparent glass substrate.

The polarizing plate has a polarizing direction that traverses vertically and is made of an organic material such as polyvinyl alcohol. A plurality of pixel electrodes are connected to a plurality of thin film transistors each formed on a glass substrate of a TFT substrate. If a predetermined potential difference is applied to a specific pixel electrode, a predetermined voltage is applied between the specific pixel electrode and the transparent electrode. Therefore, the electric field formed according to the voltage changes the orientation of the region corresponding to the specific pixel electrode of the liquid crystal layer.

< Example >

As follows, the present invention will be described in more detail based on examples, but the embodiments of the present invention disclosed below are exemplified to the last, and the scope of the present invention is not limited to these embodiments. The scope of the invention is indicated in the appended claims, and moreover contains all changes within the meaning and range equivalent to the scope of the claims. Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited by an Example. In addition, "%" and "part" which show content in a following example and a comparative example are a mass reference | standard unless there is particular notice.

< Production example of photocurable acrylic copolymer (a-1)>

Synthesis Example A-4

Propylene glycol monomethyl ether acetate (182 parts) was introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube, and the atmosphere in the flask was changed from nitrogen to air. To a mixture comprising methacrylate (95.5 parts), methacrylic acid (35.0 parts), and propylene glycol monomethyl ether acetate (136 parts), a solution of azobisisobutyronitrile (3.6 parts) was added dropwise from the lot. It was dripped at the flask over time, and stirring was continued for 5 hours at 100 degreeC. Subsequently, the atmosphere in the flask was changed from nitrogen to air, and glycidyl methacrylate (20.0 parts) [(50 mol% based on the carboxyl group of methacrylic acid used in this reaction)], trisdimethylaminomethylphenol (0.9 parts) And hydroquinone (0.145 parts) was put into the flask, the reaction was continued at 110 ° C for 6 hours to obtain a resin (a-1-1) having a solid acid value of 78 mgKOH / g.

It was confirmed that the photocurable alkali-soluble acrylic copolymer resin prepared had an acid value of 78 mgKOH / g and a weight average molecular weight of 24,000.

< Production example of photocurable alkali-soluble polyfunctional oligomer (a-2) >

Synthesis Example a-2-1

A four-necked flask equipped with a thermometer, condenser, dropping funnel and stirrer was used as the reaction vessel. First, propylene glycol (76.1 parts) and 3-fluorophthalic anhydride (365.4 parts) were added to the reaction vessel in the presence of propylene glycol monomethyl ether acetate (335.9 parts) and zirconium octoate catalyst (0.13 parts), followed by stirring. After the temperature was raised to 150 ° C., the acid value of the product was confirmed to determine the end point of the first reaction when the acid value was 250 mgKOH / g. After the completion of the first reaction, n-butylglycidyl ether (260.4 parts) was added dropwise to the reaction vessel at a uniform rate over 3 hours, and after completion of dropping, the reaction temperature was set at 160 ° C., and the acid value of the product was stirred. It was confirmed that when the acid value was 3.91mgKOH / g as the end of the secondary reaction was carried out the secondary reaction. After the completion of the secondary reaction, maleic anhydride (215.6 parts) was added dropwise to the reaction vessel at 120 ° C. at a uniform rate for 2 hours to carry out the tertiary reaction, finally bringing the acid value to 115 mgKOH / g as the end point. A chemically alkaline soluble polyfunctional oligomer was prepared.

The prepared polyester oligomer was confirmed to have a characteristic value of the acid value 115mgKOH / g, non-volatile content 75% by mass, viscosity 1,500cps, number average molecular weight 820, weight average molecular weight 1,100, molecular weight distribution 1.34.

Synthesis Example a-2-2

A four-necked flask equipped with a thermometer, condenser, dropping funnel and stirrer was used as the reaction vessel. First, in the presence of propylene glycol monomethyl ether acetate (150 parts) and ethoxyethyl propionate (176.6 parts), neopentyl glycol (104.1 parts), hexahydrophthalic anhydride (154.2 parts) and chloride anhydride (444.9) Part I) was added to the reaction vessel, and the temperature was raised to 140 ° C. while stirring. Then, the acid value of the product was confirmed to determine the end point of the first reaction when the acid value was 250 mgKOH / g. After completion of the first reaction, triethylene glycol diglycidyl ether (603.6 parts) was added dropwise to the reaction vessel at a uniform rate over 2 hours, and after completion of dropping, the acid value of the product was stirred with the reaction temperature of 120 ° C. It was confirmed that the acid value was 3.67mgKOH / g as the end of the secondary reaction was terminated the secondary reaction. After the completion of the secondary reaction, fumaric acid (298.9 parts) was added dropwise to the reaction vessel at a uniform rate for 2 hours to carry out the tertiary reaction, and finally the photocurable alkali having an acid value of 88 mgKOH / g as the end point. Soluble polyfunctional oligomers were prepared.

The prepared polyester oligomer was confirmed to have a characteristic value of the acid value 90mgKOH / g, nonvolatile content 83% by mass, viscosity 1,700cps, number average molecular weight 1,216, weight average molecular weight 1,520, molecular weight distribution 1.25.

Synthesis Example a-2-3

A four-necked flask equipped with a thermometer, condenser, dropping funnel and stirrer was used as the reaction vessel. First, neopentyl glycol (104.1 parts) and trimethylol propane (134.2 parts) in the presence of propylene glycol monomethyl ether acetate (300 parts), ethoxyethyl propionate (409.8 parts) and zirconium octoate catalyst (0.1 parts) Dodecenyl succinic anhydride (532.8 parts) and tetrabromophthalic anhydride (1,391.1 parts) were added to the reaction vessel, the temperature was raised to 130 ° C. while stirring, and the acid value of the product was confirmed. The end of the reaction was taken. After completion of the first reaction, n-butylglycidyl ether (676.9 parts) was added dropwise to the reaction vessel at a uniform rate over 2 hours, and after completion of the dropping, the reaction temperature was 110 ° C., and the acid value of the product was stirred. It was confirmed that when the acid value was 1.9mgKOH / g as the end of the secondary reaction was carried out the secondary reaction. After the completion of the secondary reaction, maleic acid (604 parts) was added dropwise to the reaction vessel at 170 ° C. at a uniform rate for 2 hours to carry out the tertiary reaction, and finally the photocurable alkali having an acid value of 88 mgKOH / g as the end point. Soluble polyfunctional oligomers were prepared.

It was confirmed that the polyester oligomer prepared above had characteristic values of an acid value of 87 mgKOH / g, a nonvolatile content of 80 mass%, a viscosity of 800 cps, a number average molecular weight of 2,116, a weight average molecular weight of 2,730, and a molecular weight distribution of 1.29.

<Of binder resin A Synthesis Example >

Synthesis Example A-1

A four-necked flask equipped with a thermometer, condenser, dropping funnel and stirrer was used as the reaction vessel. The polyfunctional oligomer (13 parts) prepared in Synthesis Example a-2-1 and the photocurable alkali-soluble acrylic copolymer resin (250 parts) prepared in Synthesis Example A-4 were added to the flask, followed by tetracarboxylic dianhydride. (2.2 parts) was added and maintained at 120 ° C. for 2 hours, and the binder resin (A) was a polyester-based photocurable alkali-soluble polyfunctional oligomer-modified acrylic copolymer having an acid value of 82-89 mgKOH / g based on resin solid content as a reaction termination point. -1) was prepared.

It was confirmed that the binder resin prepared above had an acid value of 85 mgKOH / g, a nonvolatile content of 42 mass%, a viscosity of 2,500 cps, and a weight average molecular weight of 55,000.

Synthesis Example A-2

A four-necked flask equipped with a thermometer, condenser, dropping funnel and stirrer was used as the reaction vessel. The polyfunctional oligomer (11 parts) prepared in Synthesis Example a-2-2 and the photocurable alkali-soluble acrylic copolymer resin (250 parts) prepared in Synthesis Example A-4 were added to the flask, followed by tetracarboxylic dianhydride. Binder resin (A), which is a polyester-based photocurable alkali-soluble polyfunctional oligomer-modified acrylic copolymer having an end point of the reaction when (1.6 parts) was added and held at 120 ° C for 2 hours and the acid value was 76-84 mgKOH / g based on resin solid content. -2) was prepared.

It was confirmed that the binder resin prepared above had an acid value of 80 mgKOH / g, a nonvolatile content of 42 mass%, a viscosity of 2,000 cps, and a weight average molecular weight of 40,000.

Synthesis Example A-3

A four-necked flask equipped with a thermometer, condenser, dropping funnel and stirrer was used as the reaction vessel. The polyfunctional oligomer (12 parts) prepared in Synthesis Example a-2-3 and the photocurable alkali-soluble acrylic copolymer resin (250 parts) prepared in Synthesis Example A-4 were added to the flask, followed by tetracarboxylic dianhydride. (1.6 parts) was added and maintained at 120 ° C. for 2 hours, and the binder resin (A) was a polyester-based photocurable alkali-soluble polyfunctional oligomer-modified acrylic copolymer having an acid value of 90-97 mgKOH / g based on resin solid content as a reaction end point. -3) was prepared.

It was confirmed that the binder resin prepared above had an acid value of 93 mgKOH / g, a nonvolatile content of 42 mass%, a viscosity of 6,000 cps, and a weight average molecular weight of 76,000.

The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the binder resin was carried out under the following conditions using the GPC method.

Equipment: HLC-8120GPC (manufactured by Tosoh Corporation)

Column: TSK-GELG4000HXL + TSK-GELG2000HXL (Serial Connection)

Column temperature: 40 ℃

Mobile phase solvent: tetrahydrofuran

Flow rate: 1.0 ml / min

Injection volume: 50µl

Detector: RI

Measurement sample concentration: 0.6 mass% (solvent = tetrahydrofuran)

Calibration standard: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)

The ratio of the weight average molecular weight and number average molecular weight obtained above was made into molecular weight distribution (Mw / Mn).

< Example  1>

In each component of the following Table 1, it mixes so that the total amount of the pigment which is a coloring material (D), and the pigment dispersant which is an additive (F) may be 20 mass% with respect to the mixture of a pigment, a pigment dispersant, and a propylene glycol monomethyl ether acetate. After the pigment was sufficiently dispersed using the bead mill, the bead mill was separated, and the remaining components including the remaining amount of propylene glycol monomethyl ether acetate were further added and mixed to obtain a colored photosensitive resin composition.

TABLE 1

Coloring material (D)  C.I. Pigment Green 36 Part 5.51  C.I. Pigment Yellow 150 Part 2.43 Binder Resin (A)  Resin A-1 (solid content calculation) Part 6.59 Photopolymerizable Compound (B)  Dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) Part 5.71 Photoinitiator (C) 2-benzyl-2-dimethylamino-1 (4-morpholinophenyl) butanone (Irgacure 369; manufactured by Ciba Specialty Chemical) Part 1.46  4,4'-di (N, N'-dimethylamino) -benzophenone (EAB-F; manufactured by Hodogaya Kagaku Co., Ltd.) 0.49part Solvent (E)  Propylene Glycol Monomethyl Ether Acetate 76.00part Additive (F)  Pigment Dispersant (Polyester) Part 1.20  Epoxy resin (SUMI-EPOXY ESCN-195XL; manufactured by Sumitomo Kagaku Kogyo Co., Ltd.) 0.51 parts  3-methacryloxypropyltrimethoxysilane 0.10part

A 2 square inch glass substrate (# 1737, manufactured by Corning) was washed sequentially with a neutral detergent, water, and alcohol and dried. The coated photosensitive resin composition (Table 1) was exposed on the glass substrate at an exposure amount (365 nm) of 100 mJ / cm 2, and spin-coated so that the film thickness after post-firing when the developing step was omitted was 3.0 µm, and then Preliminary drying was carried out at 100 ° C for 3 minutes in a clean oven. After cooling, the gap between the substrate coated with the colored photosensitive resin composition and a quartz glass photomask (having a pattern for changing the transmittance stepwise in the range of 1 to 100% and a line / space pattern from 1 µm to 50 µm) Was made into 100 micrometers, and it irradiated with the exposure amount (365 nm) of 100 mJ / cm <2> in air | atmosphere using the ultrahigh pressure mercury lamp (brand name USH-250D) by Ushio Denki Corporation. Thereafter, the coating film was immersed in a water-based developer containing 0.12% of a nonionic surfactant and 0.06% of potassium hydroxide at 26 ° C. for a predetermined time, and then dried at 220 ° C. for 30 minutes after washing with water. No surface roughness was found in the obtained pixel portion. In addition, developing residue and undeveloped defects did not occur in the non-pixel portion on the substrate. And even if it develops, the minimum required exposure amount required in order to form the pattern without surface roughness was 30 mJ / cm <2>.

< Example  2>

In Example 1, operation similar to Example 1 was performed except having changed resin A-1 into resin A-2. The evaluation results are shown in Table 2.

< Example  3>

Operation similar to Example 1 was performed except having changed resin A-1 into resin A-3 in Example 1. The evaluation results are shown in Table 2.

< Comparative example  1>

In Example 1, operation similar to Example 1 was performed except having changed resin A-1 into resin a-1-1. The evaluation results are shown in Table 2.

TABLE 2

Example 1 Example 2 Example 3 Comparative Example 1 Sensitivity * 1 (mJ / cm ² ) 40 45 45 60 Developing residue on board * 2 ○ ○ ○ ○ Section Shape * 3 ○ ○ ○ ○ Pencil Hardness * 4 5H 5H 5H 4H Developability * 5 ○ ○ ○ △

* 1: The minimum required exposure amount required for forming a pattern without surface roughness even when developed.

* 2: ○: no developing residue on the substrate, X ': developing residue on the substrate

* 3: The cross-sectional shape of the pixel edge part was observed using SEM.

 ○: Forward tapered, X ': Reverse tapered

* 4: The cured coating film was produced like Example except having not used a photomask. Measurement of the pencil hardness is in accordance with JIS K5600-5-4.

* 5: Developability is measured at 23 ℃ / 0.04% KOH

 ○: less than 30 seconds, Δ: 30 to 50 seconds X: 50 seconds or more.

From Table 2, the photosensitive resin compositions of Examples 1, 2 and 3 containing the binder resin of the present invention can form patterns without surface roughness at low exposure doses. In addition, it was found that a color filter having excellent film hardness and developing speed was obtained. The colored photosensitive resin composition of Comparative Example 1, which does not contain the photocurable alkali-soluble polyfunctional oligomer (a-2) of the present invention, lacks sensitivity and lacks a developing speed, thereby degrading the quality of the color filter and thus providing a high quality color filter. Can't get it.

According to the present invention, the binder resin, which is a polyester-based photocurable alkali-soluble polyfunctional oligomer-modified acrylic copolymer, has a pendant oligomer having a functional group rich in side chains compared to a photocurable acrylic copolymer used in a conventional photolithographic process. In addition to excellent developability peculiar to a polyester compound, a compact hardened structure can be realized. Therefore, the present invention containing the binder resin is excellent in adhesion even with a small exposure amount even if it contains a coloring material, and does not cause development residue on the substrate or surface defects in the pixel portion when forming pixels, It is excellent in providing the photosensitive resin composition which does not have a problem at the time of image development.

Claims (7)

As colored photosensitive resin composition containing binder resin (A), a photopolymerizable compound (B), a photoinitiator (C), a coloring material (D), and a solvent (E), The binder resin (A) is a copolymer obtained by a copolymerization reaction containing a compound (a1) having an unsaturated bond and an unsaturated carboxylic acid compound (a2) or a compound (a3) having an unsaturated bond and an epoxy group in one molecule of the obtained copolymer. Photocurable acrylic copolymer (a-1), characterized in that it is an unsaturated group-containing resin obtained by further reacting (); and At least one functional group-containing monomer (a'2) selected from a hydroxyl group-containing monomer (a'1), a halogen atom, a hydroxyl group and a carboxyl group, a monomer having a glycidyl group-containing monomer (a'3) and a hydroxyl group or a carboxyl group together with an unsaturated bond group ( It is resin produced by addition, superposition | polymerization, or condensation reaction of the photocurable alkali-soluble polyfunctional oligomer (a-2) obtained by superposing | polymerizing a'4). The coloring photosensitive resin composition characterized by the above-mentioned. The colored photosensitive resin composition according to claim 1, wherein the photocurable acrylic copolymer (a-1) has an acid value of 40 to 300 mgKOH / g, and a weight average molecular weight thereof in terms of polystyrene is in the range of 3,000 to 100,000. . The photocurable alkali-soluble polyfunctional oligomer (a-2) has an acid value of 40 to 300 mgKOH / g, a hydroxyl value of 0 to 100, and a weight average molecular weight of its polystyrene equivalent 400 It is in the range of 4,000 to 4,000, The coloring photosensitive resin composition characterized by the above-mentioned. The ratio of the component derived from each of said (a1)-(a2) with respect to the total number of moles of the said photocurable acrylic copolymer (a-1) component, structural unit derived from (a1): 35 to 90 mol%, structural unit derived from (a2): 10 to 65 mol%, It is a range and when it reacts (a3) further, the coloring photosensitive resin composition characterized by reacting (a3) with 5 to 80 mol% with respect to the component derived from (a2). The ratio of each of the components derived from (a-2) is in the following range in mole fraction with respect to the total number of moles of the components which comprise the copolymer of said (a-2). Colored photosensitive resin composition to be used. structural unit derived from (a'1): 2 to 40 mol%, structural unit derived from (a'2): 2 to 60 mol%, structural unit derived from (a'3): 2 to 50 mol%, Structural units derived from (a'4): 2 to 40 mol% A color filter comprising a color layer formed by exposing and developing a colored photosensitive resin composition in a predetermined pattern, The said colored photosensitive resin composition is the colored photosensitive resin composition of any one of Claims 1-5, The color filter characterized by the above-mentioned. The liquid crystal display device provided with the color filter of Claim 6.