KR20170111912A - Colored photosensitive resin composition, color filter and image display device using the same - Google Patents

Abstract

The present invention relates to a colored photosensitive resin, a color filter including the same, and an image display device, which comprises an alkali-soluble resin (A-1) represented by the general formula (1); And a repeating unit derived from the compound (a1) represented by the general formula (2), a repeating unit derived from a compound (a2) containing an unsaturated bond copolymerizable with (a1) and (a3), a repeating unit derived from an unsaturated carboxylic acid Soluble resin (A-2) at a weight ratio of 2: 8 to 8: 2, a color filter comprising the same, and an image display device.

Description

TECHNICAL FIELD [0001] The present invention relates to a colored photosensitive resin composition, a color filter including the colored photosensitive resin composition,

The present invention relates to a colored photosensitive resin composition capable of improving chemical resistance and improving defective display due to residues in a contact hole, a color filter including the same, and an image display device.

BACKGROUND ART [0002] Color filters are widely used in various display devices such as an image pickup device and a liquid crystal display (LCD), and their application range is rapidly expanding. The color filter may be formed of three color patterns of red, green, and blue, or may be formed of three color patterns of yellow, magenta, and cyan, Lt; / RTI >

The coloring pattern of each of the color filters is generally formed using a colored photosensitive resin composition comprising a coloring agent such as pigment or dye, a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. The coloring pattern processing using the colored photosensitive resin composition is usually performed by a lithography process.

On the other hand, in a color liquid crystal display device using a thin film transistor (TFT) substrate, a color filter substrate for displaying a color image has conventionally been manufactured separately from a drive substrate on which a thin film transistor (TFT) Was bonded to the driving substrate. However, in this method, there is a disadvantage that it is difficult to increase the width of the black matrix and increase the aperture ratio (that is, the ratio of apertures through which light is transmitted) because the positioning accuracy at the time of bonding is low.

Korean Patent Publication No. 2010-0022402 discloses a colored photosensitive resin composition, a color filter, and a liquid crystal display device having the same, which comprises a binder resin, a photopolymerizable compound, a photopolymerization initiator, a coloring material and a solvent , And R, G, and B pixels on a TFT substrate, wherein the binder resin has a weight average molecular weight (Mw) in terms of polystyrene as measured by GPC of 5,000 to 20,000, and the colored photosensitive resin composition The coloring layer formed of the resin composition is formed so that the overlap step Ra formed for each pixel of R, G, and B is less than 0.6 탆. However, the coloring photosensitive resin composition may be etched or chemically treated It is somewhat insufficient to improve the defective pixel due to instability of the coating film.

Korean Patent Publication No. 2010-0022402 (2010.03.02, Dongwoo Fine-Chem Co., Ltd.)

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and it is an object of the present invention to provide a color filter of COA (Color Filter on Array) type which can increase the aperture ratio, And to provide a colored photosensitive resin composition capable of improving defective display due to residues in the colored photosensitive resin composition.

Another object of the present invention is to provide a color filter and an image display device including the colored photosensitive resin composition.

In order to achieve the above object, the colored photosensitive resin composition according to the present invention comprises an alkali-soluble resin (A-1) represented by the following general formula (1); And a repeating unit derived from a compound (a1) represented by the following formula (2), a repeating unit derived from a compound (a2) containing an unsaturated bond copolymerizable with the repeating unit (a1) Soluble resin (A-2) comprising the following units:

[Chemical Formula 1]

 (In the formula 1,

R1, R2 and R3 are each independently H or a C1 to C5 alkyl group,

n is an integer of 1 to 4,

x, y and z are mole% in the copolymer of each repeating unit,

x + y + z = 70 to 100 mol%

(2)

 (In the formula (2)

R4 is hydrogen or a methyl group,

R5 is a substituted or unsubstituted alkylene group or alkenylene group having 1 to 6 divalent carbon atoms,

A is a substituted or unsubstituted phenyl group, a cyclohexyl group, an alkyl group or an alkenyl group having 1 to 6 carbon atoms,

The substituents of R5 and A are each independently selected from the group consisting of fluorine, chlorine, bromine, iodine, alkyl having 1 to 6 carbon atoms, perhalogenated alkyl having 1 to 3 carbon atoms, hydroxyl, ketone having 1 to 6 carbon atoms, Ester group, N, N- (C1-C3) alkyl substituted amide group.

The colored photosensitive resin composition according to the present invention has the effect of improving the chemical resistance in the etching process and the chemical treatment and improving the defective display due to the residues in the contact holes.

The color filter and the image display apparatus according to the present invention also have the same effects as described above.

Whenever a part is referred to as "including " an element in the present invention, it is to be understood that it may include other elements as well, without departing from the other elements unless specifically stated otherwise.

Hereinafter, preferred embodiments of the present invention will be described in detail.

≪ Colored photosensitive resin composition &

The alkali-soluble resin (A)

The colored photosensitive resin composition according to one embodiment of the present invention comprises an alkali-soluble resin (A-1) represented by the following formula (1); And a repeating unit derived from a compound (a1) represented by the following formula (2), a repeating unit derived from a compound (a2) containing an unsaturated bond copolymerizable with the repeating units (a1) and (a3) And an alkali-soluble resin (A-2) containing a repeating unit:

[Chemical Formula 1]

(In the formula 1,

R1, R2 and R3 are each independently H or a C1 to C5 alkyl group,

n is an integer of 1 to 4,

x, y and z are mole% in the copolymer of each repeating unit,

x + y + z = 70 to 100 mol%

(2)

 (In the formula (2)

R4 is hydrogen or a methyl group,

R5 is a substituted or unsubstituted alkylene group or alkenylene group having 1 to 6 divalent carbon atoms,

A is a substituted or unsubstituted phenyl group, a cyclohexyl group, an alkyl group or an alkenyl group having 1 to 6 carbon atoms,

The substituents of R5 and A are each independently selected from the group consisting of fluorine, chlorine, bromine, iodine, alkyl having 1 to 6 carbon atoms, perhalogenated alkyl having 1 to 3 carbon atoms, hydroxyl, ketone having 1 to 6 carbon atoms, Ester group, N, N- (C1-C3) alkyl substituted amide group.

The copolymer of Formula 1 is composed of a terminal double bond-containing repeating unit (x), an epoxy ring-containing repeating unit (y), and an alkyl group-containing repeating unit (z). Specifically, the terminal double bond-containing repeating unit is derived from an acrylic monomer containing a hydroxyl methacrylate group, the repeating unit containing an epoxy ring from an acrylic monomer containing an epoxy group, the repeating unit containing an alkyl group is selected from ethylhexyl acrylate Containing monomer may be derived from an acrylic monomer.

The terminal double bond-containing repeating unit (x) is a moiety for functioning as a binder resin, and x is in the range of 15 to 50 (in terms of the total content of the repeating units constituting the alkali-soluble resin (A- Mol%. When x satisfies the above range, the development characteristics are prevented from deteriorating and the phenomenon of increase in viscosity due to hydrogen bonding is prevented, which facilitates handling.

The epoxy ring-containing repeating unit (y) may serve to lower the development speed of the colored photosensitive resin composition.

Ethylhexyl acrylate among the alkyl group-containing repeating units (z) can improve the flowability of the colored photosensitive resin composition by lowering the glass transition temperature (Tg) of the entire copolymer to improve flowability.

When the sum of the repeating units represented by y and the repeating units represented by z is 50 mol% or more, specifically 50? Y + z? 85 mol% in the whole copolymer, the loss of fine patterns is small, Can be secured.

Specifically, in the case of using the dye as the coloring agent (D), the colored photosensitive resin is preferably used in order to prevent the loss of fine patterns during the development process and to improve the stability during pattern formation, It is preferable that the content is 50 mol% or more.

When the molar ratio of y + z is 50 mol% or more, it is easy to produce a glass transition temperature of 0 ° C or less, and the phenomenon that the flowability of the binder during the heat treatment process of the binder and the loss of fine patterns during the development process are prevented, There is an advantage that the phenomenon in which the stability is lost when the pattern is formed and the loss of the pattern is liable to occur can be prevented. The higher the content of the photo-curable reactive group of the above-mentioned formula (1) is, the lower the flowability of the binder during the heat treatment process of the colored photosensitive composition and the less the fine pattern is lost during the development process. The developability of the resin itself is remarkably reduced and it is not preferable.

Other monomers having a copolymerizable unsaturated bond other than the monomers of the above-mentioned repeating units x, y and z may be further added and copolymerized to the extent that the effect of the present invention is not impaired. The reactive monomer may be contained in an amount of 30 mol% or less in the alkali-soluble resin (A-1) represented by the general formula (1).

The additional monomers having the copolymerizable unsaturated bond are illustrated below but are not necessarily limited thereto. Specific examples of the additional monomer having a copolymerizable unsaturated bond include styrene, vinyltoluene,? -Methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o Aromatic vinyls such as vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m- vinyl benzyl glycidyl ether and p- compound; N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm N-substituted maleimide-based compounds such as methylphenyl maleimide, Np-methylphenyl maleimide, No-methoxyphenyl maleimide, Nm-methoxyphenyl maleimide and Np-methoxyphenyl maleimide; Propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, alkyl (meth) acrylates such as sec-butyl (meth) acrylate and t-butyl (meth) acrylate; (Meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 2,6] decan- Alicyclic (meth) acrylates such as dicyclopentanyloxyethyl (meth) acrylate and isobornyl (meth) acrylate; (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl Hydroxyethyl (meth) acrylates such as hydroxyethyl acrylamide; Aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate; 3- (methacryloyloxymethyl) -2-trifluoromethyl oxetane, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, and the like Unsaturated oxetane compounds. The above monomers may be used alone or in combination of two or more.

The weight-average molecular weight of the alkali-soluble resin (A-1) represented by the general formula (1) may be 5,000 to 50,000, specifically 10,000 to 30,000, and more specifically 10,000 to 20,000. The weight-average molecular weight of the alkali-soluble resin (A-1) represented by the formula (1) affects the developability and the acid value, and the weight average molecular weight of the alkali- When the range is satisfied, there is an effect that stability in developing property and pattern formation can be given.

The alkali-soluble resin (A-2) is a copolymer comprising constituent units obtainable by polymerization of the following compounds (a1), (a2) and (a3) do.

 (a1): a compound represented by the following formula (2)

(2)

 (In the formula (2)

R4 is hydrogen or a methyl group,

R5 is a substituted or unsubstituted alkylene group or alkenylene group having 1 to 6 divalent carbon atoms,

A is a substituted or unsubstituted phenyl group, a cyclohexyl group, an alkyl group or an alkenyl group having 1 to 6 carbon atoms,

The substituents of R5 and A are each independently selected from the group consisting of fluorine, chlorine, bromine, iodine, alkyl having 1 to 6 carbon atoms, perhalogenated alkyl having 1 to 3 carbon atoms, hydroxyl, ketone having 1 to 6 carbon atoms, An ester group of N, N- (C1-C3) alkyl substituted amide group.

 (a2): a compound containing an unsaturated bond copolymerizable with (a1) and (a3)

(a3): unsaturated carboxylic acid

The above-mentioned alkali-soluble resin (A-2) can be polymerized together with other monomers in addition to the above monomers. That is, the present invention encompasses the case where a monomer other than (a1) to (a3) is further copolymerized.

In some embodiments of the present invention, specific examples of the compound (a1) represented by the general formula (2) are as follows.

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

More specific examples of the compound (a1) include 2- (phenylthio) ethyl (meth) acrylate, hexylthioethyl (meth) acrylate and the like. These may be used alone or in combination of two or more.

As the compound (a2) having an unsaturated bond capable of copolymerizing with (a1) and (a3) in the present invention, an aromatic vinyl compound, an N-substituted maleimide compound, an unsubstituted or substituted alkyl ester of an unsaturated carboxylic acid, An unsaturated carboxylic acid ester compound containing a formula substituent, a carboxylic acid vinyl ester compound, and an unsaturated oxetanyl compound containing an oxetane group. Among these compounds, an aromatic vinyl compound and an N-substituted maleimide compound are more preferable in terms of improvement in sensitivity and adhesion. These may be used alone or in combination of two or more.

Examples of the aromatic vinyl compound in the compound (a2) include vinyltoluene, styrene,? -Methylstyrene,? -Chlorostyrene, divinylbenzene, etc. These may be used alone or in combination of two or more.

Examples of the N-substituted maleimide compound include compounds represented by the following formula (7): < EMI ID =

(7)

 (In the above formula (7)

And R < 6 > is an aliphatic or aromatic hydrocarbon having 1 to 20 carbon atoms with or without a hetero atom).

Specific examples of R 6 include a phenyl group, a benzyl group, a naphthyl group, a cyclohexyl group, a methyl group, an ethyl group and a propyl group, and particularly preferably a benzyl group and a cyclohexyl group. These may be used alone or in combination of two or more.

Examples of the unsubstituted or substituted alkyl ester compound system of the above unsaturated carboxylic acid include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl Aminoethyl (meth) acrylate, and the like. These may be used alone or in combination of two or more.

Examples of the unsaturated carboxylic acid ester compound system containing the alicyclic substituent include cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (Meth) acrylate, cyclopentenyl (meth) acrylate, cyclohexyl (meth) acrylate, cycloheptenyl (meth) acrylate, (Meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, pinanyl (meth) acrylate, adamantyl ) Acrylate, and the like. These may be used alone or in combination of two or more.

Examples of the carboxylic acid vinyl ester compound include vinyl acetate and vinyl propionate. These may be used alone or in combination of two or more.

Examples of the unsaturated oxetanyl compound containing oxetane group include 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-pentafluoroethylox Cetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 3- (methacryloyloxymethyl) -2,2-difluorooxetane, 3- (methacryloyloxymethyl) (Methacryloyloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (methacryloyloxyethyl) oxetane, 3- , 3- (methacryloyloxyethyl) -3-ethyloxetane, 2-ethyl-3- (methacryloyloxyethyl) oxetane, 3- (Methacryloyloxyethyl) -2-phenyloxetane, 2, 2-difluoro-2-methylpropane, 2- 3 - (methacryloyloxyethyl) oxetane, 3- (methacryloyloxyethyl) -2,2,4-trifluorooxetane, 3- (methacryloyloxyethyl) 4,4-tetrafluorooxetane and the like. These may be used alone or in combination of two or more.

In the present invention, the compound (a3) having an unsaturated carboxyl group is not limited as long as it is a carboxylic acid compound having an unsaturated double bond capable of being polymerized, and each may be used alone or in combination of two or more. Specific examples thereof include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; Dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid; And anhydrides of these dicarboxylic acids; (meth) acrylates of a polymer having a carboxyl group and a hydroxyl group at both terminals such as? -carboxypolycaprolactone mono (meth) acrylate, and the like. Among these, acrylic acid and methacrylic acid are preferred because of their excellent copolymerization reactivity and solubility in a developing solution.

The proportion of the component derived from each of (a1) to (a3) in the copolymer obtained by copolymerizing (a1) to (a3) used in the present invention, that is, the alkali-soluble resin (A- It is preferable that the molar fraction is in the following range with respect to the total number of moles of constituent components constituting the coalescence.

(a1): 2 to 50% by mole,

(a2): 2 to 50% by mole,

(a3): 2 to 70 mol%

In the embodiment of the present invention, the method for producing the copolymer is not particularly limited as far as it is obtained by copolymerizing (a1) to (a3), and various conventionally known polymerization methods can be used, The solution polymerization method is more preferable. The polymerization temperature and the polymerization time vary depending on the type and ratio of the monomers to be introduced, the molecular weight of the target binder resin, and the acid value, but preferably polymerization is carried out at 60 ° C to 130 ° C for 1 to 10 hours.

In the above process, a part or all of the polymerization initiator may be put into a flask, or a part or all of (a1), (a2) and (a3) may be put into a flask.

When a solvent is used in the above step, a solvent used in a conventional radical polymerization reaction may be used. Specific examples thereof include tetrahydrofuran, dioxane, dimethyl glycol dimethyl ether, diethylene glycol dimethylethyl, acetone, Methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, propyleneglycol monomethylethylacetate, 3-methoxybutyl acetate, methanol, ethanol, propanol, n-butanol, ethylene glycol monomethyl ether, propylene Glycol monomethyl ether, toluene, xylene, ethylbenzene, chloroform, dimethylsulfoxide and the like. These solvents may be used alone or in combination of two or more.

As the polymerization initiator to be used in the above step, a commonly used polymerization initiator may be added and is not particularly limited. Specific examples thereof include diisopropylbenzene hydroperoxide, di-t-butyl peroxide, benzoyl peroxide, t-butyl peroxyisopropyl carbonate, t-amyl peroxy-2-ethylhexanoate, Organic peroxides such as peroxy-2-ethylhexanoate; Azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylbareronitolyl), dimethyl 2,2'-azobis (2-methylpropionate), etc. Of nitrogen compounds. These may be used alone or in combination of two or more.

In order to control the molecular weight and the molecular weight distribution, for example, mercapto-series chain transfer agents such as n-dodecyl mercapto, mercaptoacetic acid and methyl mercaptoacetate,? -Methylstyrene dimer and the like may be used as a chain transfer agent. The amount of the? -Methylstyrene dimer or mercapto compound to be used is 0.005 to 5% by mass relative to the total amount of (a1), (a2) and (a3).

In addition, the above-mentioned polymerization conditions may be appropriately adjusted depending on the production equipment or the amount of heat generated by polymerization, and the method of addition and the reaction temperature.

The alkali-soluble resin (A-2) contained in the colored photosensitive resin composition of one embodiment of the present invention is a copolymer obtained by copolymerizing (a1), (a2) and (a3) Can be obtained by further reacting the compound (a4).

By adding (a4) to the above copolymer, light / heat curability can be imparted to the binder resin.

Specific examples of the compound (a4) having an unsaturated bond and an epoxy group in the molecule of the present invention include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (Meth) acrylate, methylglycidyl (meth) acrylate, and the like. Of these, glycidyl (meth) acrylate is more preferably used. These may be used alone or in combination of two or more.

The proportion of the constituent unit derived from (a4) in the alkali-soluble resin (A-2) is preferably 5 to 80 mol% based on the number of moles of the constituent component derived from (a3) in the alkali- , More preferably from 10 to 70 mol%. When the composition ratio of (a4) is within the above range, sufficient photo-curability and thermosetting property are obtained, and both sensitivity and pencil hardness are compatible and reliability is preferable.

The weight average molecular weight of the alkali-soluble resin (A-2) in the present invention is not particularly limited, but is preferably in the range of 3,000 to 100,000, more preferably in the range of 5,000 to 50,000. When the weight average molecular weight of the alkali-soluble resin (A-2) is within the above range, film reduction during development is unlikely to occur, and the non-pixel portion tends to have a good dropout.

The content ratio of the alkali-soluble resin (A-1) to the alkali-soluble resin (A-2) represented by the general formula (1) is preferably in the range of 2: 8 to 8: 2. When the content ratio of the alkali-soluble resin (A-1) to the alkali-soluble resin (A-2) represented by the above formula (1) satisfies the above range, the chemical resistance required in the etching process and the chemical treatment is improved, There is an advantage that residue can be prevented.

In the case of the colored photosensitive resin composition comprising the alkali-soluble resin (A-1) and the alkali-soluble resin (A-2) represented by the above formula (1), it is possible to prevent the loss of fine patterns during the development process, The stability of the pattern can be secured. Further, in the liquid crystal display device of the color filter on array (COA) structure, contact holes having excellent alignment accuracy can be formed in the RGB resin film, and the resin film, that is, the electrical connection between the pixel electrode and the active element It is possible to improve the pixel defect due to the disconnection of RGB for securing the high aperture ratio in securing the pattern stability of the RGB resin film at the time of IZO deposition for the formation of the contact hole by the columnar etching and the IZO deposition to be used as the pixel electrode.

The content of the alkali-soluble resin (A) may be 10 to 80% by weight, specifically 10 to 70% by weight, based on the total solid content of the colored photosensitive resin composition. When the content of the alkali-soluble resin (A) is in the above range, solubility in a developing solution is sufficient, pattern formation is easy, reduction of the film of the pixel portion of the exposed portion is prevented, and the non- There is an advantage.

The photopolymerizable compound (B)

The colored photosensitive resin composition of the present invention may further comprise a photopolymerizable compound (B).

The photopolymerizable compound (B) of the present invention is a compound capable of polymerizing under the action of a photopolymerization initiator (C) to be described later, and a monofunctional monomer, a bifunctional monomer or a polyfunctional monomer can be used. Specifically, Monomers can be used.

Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate or N- But are not limited thereto.

The bifunctional monomers include, but are not limited to, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di Acrylate, bis (acryloyloxyethyl) ether of bisphenol A or 3-methylpentanediol di (meth) acrylate.

Examples of the polyfunctional monomer include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tri (Meta) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa Acrylate or dipentaerythritol hexa (meth) acrylate, but are not limited thereto.

The photopolymerizable compound (B) may be contained in an amount of 5 to 45% by weight, specifically 7 to 45% by weight based on 100% by weight of the total solid content of the colored photosensitive resin composition, but is not limited thereto. When the photopolymerizable compound (B) is contained within the above-described range with respect to the total solid content of the colored photosensitive resin composition, the strength and smoothness of the pixel portion are improved.

Light curing Initiator (C)

The colored photosensitive resin composition of the present invention may further comprise a photopolymerization initiator (C).

The photopolymerization initiator (C) can be used without particular limitation as long as it can polymerize the photopolymerizable compound (B). Specifically, the photopolymerization initiator (C) is preferably at least one selected from the group consisting of an acetophenone-based compound, a benzophenone-based compound, a triazine-based compound, a nonimidazole-based compound, an oxime compound, and an oxime compound from the viewpoints of polymerization characteristics, initiation efficiency, absorption wavelength, availability, And at least one compound selected from the group consisting of an oxalic acid compound and an oxalic acid compound, but is not limited thereto.

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy- 1- [4- 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2-methylcyclohexyl phenyl ketone, 2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1-one 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.

Examples of the benzophenone compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Specific examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6 - (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, (Trichloromethyl) -6- [2- (5-methylfuran-2- (4-methoxystyryl) -1,3,5-triazine, Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan- , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- ) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

Specific examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbimidazole, 2,2'-bis (2,3- Phenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) , 2,2'-bis (2,6-dichlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) Imidazole compounds in which 4'5,5'-tetraphenyl-1,2'-biimidazole or phenyl groups at 4,4 ', 5,5' positions are substituted by carboalkoxy groups. Among them, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- , 2,2-bis (2,6-dichlorophenyl) -4,4'5,5'-tetraphenyl-1,2'-biimidazole is preferably used do.

Specific examples of the oxime compounds include o-ethoxycarbonyl-α-oximino-1-phenylpropan-1-one and commercially available products such as OXE01 and OXE02 from BASF.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4- .

The photopolymerization initiator (C) is used in an amount of 0.1 to 40% by weight, more preferably 1 to 30% by weight, based on the total amount of the alkali-soluble resin (A) and the photopolymerizable compound (B), based on the solid weight of the colored photosensitive resin composition %. ≪ / RTI > When the photopolymerization initiator (C) is within the above range, the colored photosensitive resin composition becomes highly sensitive and the exposure time is shortened, so that the productivity is improved and high resolution can be maintained. Further, there is an advantage that the strength of the pixel portion formed using the colored photosensitive resin composition and the smoothness of the surface of the pixel portion are improved.

The photopolymerization initiator (C) may further include a photopolymerization initiator to improve the sensitivity of the colored photosensitive resin composition. When the colored photosensitive resin composition further contains the photopolymerization initiator, there is an advantage that the sensitivity is further increased and the productivity is improved.

The photopolymerization initiator may include at least one compound selected from the group consisting of an amine compound, a carboxylic acid compound, and an organic sulfur compound having a thiol group, but is not limited thereto.

As the amine compound, an aromatic amine compound is preferably used. Specific examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4- Dimethylaminobenzoic acid, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone ), 4,4'-bis (diethylamino) benzophenone, and the like.

The carboxylic acid compound is preferably an aromatic heteroacetic acid, and more specifically, it is preferably an aromatic heteroaromatic acid such as phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthio Acetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like.

Specific examples of the organic sulfur compound having a thiol group include 2-mercaptobenzothiazole, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) 1,3,5-triazine-2,4,6 (1H, 3H, 5H) -thione, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexacis (3-mercaptopropionate), and tetraethylene glycol bis (3-mercaptopropionate) .

When the photopolymerization initiator is further used, the amount of the photopolymerization initiator is preferably 0.1 to 40% by weight, more preferably 1 to 40% by weight, based on the total weight of the solid components of the colored photosensitive resin composition, To 30% by weight. When the content of the photopolymerization initiator is within the above range, the sensitivity of the colored photosensitive resin composition becomes higher, and the productivity of the color filter formed using the colored photosensitive resin composition can be improved.

The colorant (D)

The colored photosensitive resin composition of the present invention may further comprise a colorant (D).

In the present invention, the colorant (D) may include at least one of a pigment and a dye.

The colorant (D) may be contained in an amount of 5 to 60 parts by weight, specifically 10 to 45 parts by weight, based on the total solid content of the colored photosensitive resin composition, but is not limited thereto. When the colorant (D) is contained within the above range, the color density of the pixel is sufficient even when a thin film is formed, and the dropout of the non-curing portion during development is not lowered.

The pigment may be an organic pigment or an inorganic pigment generally used in the art.

Examples of the organic pigment include various pigments used in printing ink, ink jet ink, etc. Specific examples thereof include water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, Anthanthrone pigments, indanthrone pigments, pravanthrone pigments, anthraquinone pigments, anthraquinone pigments, anthanthrone pigments, anthanthrone pigments, indanthrone pigments, indanthrone pigments, Pyranthrone pigments, diketopyrrolopyrrole pigments, and the like.

Examples of the inorganic pigments include metallic compounds such as metal oxides and metal complex salts. Specific examples of the inorganic pigments include metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony and carbon black Oxides or composite metal oxides.

Particularly, the organic pigments and inorganic pigments may be specifically classified into pigments in the Society of Dyers and Colourists, and more specifically, those having a color index (CI) number Pigments, but are not limited thereto.

C.I. Pigment Yellow 13, 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, 208, 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, 47 and 58;

C.I. Pigment Brown 28;

C.I Pigment Black 1 and 7, etc.

The above-mentioned pigments may be organic pigments or inorganic pigments generally used in the art. These pigments may be used alone or in combination of two or more.

The exemplified C.I. Among the pigment pigments, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 185, C.I. Pigment Orange 38, C.I. Pigment Red 122, C.I. Pigment Red 166, C.I. Pigment Red 177, C.I. Pigment Red 208, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Violet 23, C.I. Pigment Blue 15: 3, Pigment Blue 15: 6, C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment selected from Pigment Green 58 can be preferably used.

The content of the pigment may be 3 to 60% by weight, specifically 5 to 55% by weight based on the total solid content in the colored photosensitive resin composition. When the content of the pigment satisfies the above range, the color density of the pixel is sufficient at the time of forming the thin film, and the dropping property of the non-oxide part at the time of development is not lowered, thereby preventing the residue from being formed.

It is preferable to use a pigment dispersion in which the particle diameter of the pigment is uniformly dispersed. An example of a method for uniformly dispersing the particle diameter of the pigment includes a method of dispersing the pigment by adding a pigment dispersant. According to this method, a pigment dispersion in which the pigment is uniformly dispersed in a solution can be obtained.

Specific examples of the pigment dispersant include cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, polyester surfactants, and polyamine surfactants. These surfactants may be used alone or in combination of two or more. have.

The pigment dispersant is added for maintenance of deagglomeration and stability of the pigment, and any of those generally used in the art can be used without limitation. Specifically, an acrylate-based dispersant containing BMA (butyl methacrylate) or DMAEMA (N, N-dimethylaminoethyl methacrylate) may be used. In this case, it is preferable to apply the acrylate-based dispersing agent prepared by the living control method as disclosed in Korean Patent Laid-Open Publication No. 2004-0014311. DISCLOSURE OF THE INVENTION [0004] BYK-2000, DISPER BYK-2001, DISPER BYK-2070 and DISPER BYK-2150.

The above-mentioned acrylate dispersants may be used alone or in combination of two or more.

As the pigment dispersant, other resin type pigment dispersants other than the acrylate dispersant may be used. The other resin type pigment dispersing agent may be a known resin type pigment dispersing agent, especially a polycarboxylic acid ester such as polyurethane, polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) Amine salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long chain polyaminoamide phosphate salts, esters of hydroxyl group-containing polycarboxylic acids and their modified products, or free ) Oil-based dispersants such as amides formed by reaction of a polyester having a carboxyl group with poly (lower alkyleneimine) or salts thereof; Soluble resin or water-soluble polymer compound such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylate ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinylpyrrolidone; Polyester; Modified polyacrylates; Adducts of ethylene oxide / propylene oxide, and phosphate esters. DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK-160, BYK (trade name) 164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; EFKA-4060, EFKA-4060, EFKA-4055, EFKA-4055, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA- 4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10 from Lubirzol; Hinoact T-6000, Hinoact T-7000, Hinoact T-8000; available from Kawaken Fine Chemicals; AJISPUR PB-821, Ajisper PB-822, Ajisper PB-823 manufactured by Ajinomoto; FLORENE DOPA-17HF, fluorene DOPA-15BHF, fluorene DOPA-33, and fluorene DOPA-44 are trade names of Kyoeisha Chemical Co., The resin-type pigment dispersants other than the acrylate-based dispersant may be used alone or in combination of two or more, and may be used in combination with an acrylate-based dispersant.

The amount of the pigment dispersant may be in the range of 5 to 60% by weight, specifically 15 to 50% by weight based on 100% by weight of the total solid content of the pigment used. When the content of the pigment dispersant is within the above range, There is an advantage that the development is prevented, the pigment is easily atomized, and problems such as gelation after dispersion are prevented.

The dye can be used without limitation as long as it has solubility in an organic solvent. It is preferable to use a dye which has solubility in an organic solvent and can ensure reliability such as solubility in an alkali developing solution, solubility in solvent and stability with time.

Examples of the dye include acid dyes having an acidic group such as sulfonic acid and carboxylic acid, salts of an acidic dye and a nitrogen-containing compound, sulfonamides of an acidic dye and derivatives thereof, and azo, Based acid dyes and derivatives thereof.

Preferably, the dye is a compound classified as a dye in a color index (published by The Society of Dyers and Colourists), or a known dye described in a dyeing note (coloring yarn).

Specific examples of the dye include C.I. As solvent dyes,

C.I. Yellow dyes such as Solvent Yellow 4, 14, 15, 16, 21, 23, 24, 38, 56, 62, 63, 68, 79, 82, 93, 94, 98, 99, 151, 162, 163;

C.I. Red dyes such as Solvent Red 8, 45, 49, 89, 111, 122, 125, 130, 132, 146, 179;

C.I. Orange dyes such as solvent orange 2, 7, 11, 15, 26, 41, 45, 56, 62;

C.I. Blue dyes such as Solvent Blue 5, 35, 36, 37, 44, 59, 67 and 70;

C.I. Violet dyes such as solvent violet 8, 9, 13, 14, 36, 37, 47, 49;

C.I. Green dyes such as Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35 and the like.

The C.I. Solvent dye having excellent solubility in an organic solvent. Solvent Yellow 14, 16, 21, 56, 151, 79, 93; C.I. Solvent Red 8, 49, 89, 111, 122, 132, 146, 179; C.I. Solvent Orange 41, 45, 62; C.I. Solvent Blue 35, 36, 44, 45, 70; C.I. Solvent violet 13 is preferred, and C.I. Solvent Yellow 21, 79; C.I. Solvent Red 8, 122, 132; Is more preferable.

Also, C.I. As the acid dye,

CI Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112 , 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184 Yellow dyes such as 1,1,1,2,2,2,2,2,2,23,28, 240,242, 243,251 and the like, such as, for example, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, ;

CI Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88 , 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217 , 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349 Red dyes such as 382, 383, 394, 401, 412, 417, 418, 422, 426;

Orange dyes such as C.I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;

CI Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, , 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, , 335, 340 and the like;

Violet dyes such as C.I. Acid Violet 6B, 7, 9, 17, 19, 66 and the like;

Green dyes such as C.I. acid green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106,

C.I. Acid Yellow 42 having excellent solubility in an organic solvent in the above acid dye; C.I. Acid Red 92; C. I. Acid Blue 80, 90; C.I. Acid Violet 66; C.I. Acid Green 27 is preferred.

As a C.I. direct dye,

CI Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129 , Yellow dyes such as 136, 138, and 141;

CI Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211 , 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;

Orange dyes such as C.I. Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

CI Direct Blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113 , 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189 , 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248 , 250, 251, 252, 256, 257, 259, 260, 268, 274, 275 and 293;

Violet dyes such as C.I. Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

Green dyes such as C.I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79,

Also, C.I. As a modantoic dye

Yellow dyes such as C.I. Modatto Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

CI Modal Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, Red dyes such as 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;

CI Modanato Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, dyes;

CI Modanito Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 43, 44, 48, 49, 53, 61, 74, 77, 83, and 84;

Violet colored dyes such as C.I. Modanth violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;

Green dyes such as C.I. Modatto Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43,

These dyes may be used alone or in combination of two or more.

The content of the dye in the colorant (D) may be 0.5 to 80% by weight, specifically 0.5 to 60% by weight, more preferably 1 to 50% by weight, based on the solid content in the colorant (D). When the content of the dye in the colorant (D) is within the above-mentioned range, it is possible to prevent the problem of lowering the reliability of dye elution by organic solvent after pattern formation, and it is advantageous in sensitivity.

Solvent (E)

The colored photosensitive resin composition of the present invention may further comprise a solvent (E).

As long as the solvent (E) of the present invention is effective for dissolving the other components contained in the colored photosensitive resin composition, a solvent used in a conventional colored photosensitive resin composition can be used without particular limitation. Specifically, at least one selected from the group consisting of ethers, aromatic hydrocarbons, ketones, alcohols, esters and amides can be used.

The solvent (E) more specifically includes 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 Diethylene glycol dialkyl ethers such as diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol mono Alkylene glycol alkyl ether acetates such as methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene , Methyl ethyl ketone Ketones such as acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin, ethyl 3-ethoxypropionate, Esters such as methyl methoxypropionate, and cyclic esters such as? -Butyrolactone.

The solvent (E) may be a useful agent having a boiling point in the range of 100 ° C to 200 ° C in terms of coatability and drying property. Examples of the solvent include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, Decyltate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like.

The solvent (E) may be used alone or in admixture of two or more. The solvent (E) may be contained in an amount of 60 to 90% by weight, preferably 70 to 85% by weight based on 100% by weight of the total of the colored photosensitive resin composition. When the solvent is contained within the above range, the coating property is improved when applied with a coating apparatus such as a roll coater, a skin coater, a slit and spin coater, a slit coater (die coater), or an ink jet.

Additive (F)

The colored photosensitive resin composition according to the present invention may further contain an additive (F) as required.

Specifically, the colored photosensitive resin composition may further include at least one additive (F) selected from the group consisting of a dispersant, a wetting agent, a silane coupling agent and an anti-aggregation agent.

As the dispersing agent, a commercially available surfactant may be used. Examples of the surfactant include a silicone surfactant, a fluorinated surfactant, a silicon surfactant having a fluorine atom, and a mixture thereof.

Examples of the silicone surfactant include a surfactant having a siloxane bond. As commercially available products, Toray Silicon DC3PA, Toray Silicone SH7PA, Toray Silicon DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone 29SHPA, Toray Silicone SH30PA, Polyether Modified Silicone Oil SH8400 (Toray Silicone Co., Ltd.), KP321 (Manufactured by Shin-Etsu Silicones), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460, TSF4460, TSF4460 But is not limited thereto.

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain. Concretely, it is possible to use a propylene glycol (trade name) FC430, a prolineate FC431 (manufactured by Sumitomo 3M Ltd.), Megapack (trade name) F142D, Megapack F171, Megapack F172, Megafac F173, Megafac F177, (Trade name) EF301, Eftop EF303, Eftop EF351, and Eftop EF352 (manufactured by Shin-Aitaku Kasei Co., Ltd.), Megapack F183, Megapack R30 1000, BM-1100 (product name) S381, Surfron S382, Surfron SC101, Surfron SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Fine Chemical Co., Ltd.) Manufactured by BMChemie). Examples of the silicone surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain. Specific examples thereof include Megapac (trade name) R08, Megapack BL20, Megapack F475, Megapack F477, Megapack F443 (manufactured by Dainippon Ink and Chemicals, Incorporated).

Examples of the wetting agent include glycerin, diethylene glycol, ethylene glycol, and the like, and may include at least one selected from the group.

Examples of the silane coupling agent include aminopropyltriethoxysilane,? -Mercaptopropyltrimethoxysilane and? -Methacryloxypropyltrimethoxysilane, and commercially available products include SH6062, SZ6030 (Toray-Dow (Manufactured by Corning Silicon co., Ltd.), KBE903 and KBM803 (manufactured by Shin-Etsu silicone co., Ltd.).

The anti-flocculant includes, for example, sodium polyacrylate, but is not limited thereto, and an anti-flocculant commonly used in the art can be applied.

The additive (F) may be contained in an amount of 0.001 to 10% by weight, specifically 0.001 to 5% by weight, more specifically 0.001 to 1% by weight based on 100% by weight of the total of the colored photosensitive resin composition. When the additive (F) is contained in the above-mentioned range of the photosensitive resin composition, there is an advantage that the desired performance of each of the additives can be imparted without deteriorating the performance of the color filter made of the colored photosensitive resin composition.

<Color filter>

Another aspect of the present invention is a color filter comprising the above colored photosensitive resin composition.

The color filter can be produced by applying the above-mentioned colored photosensitive resin composition of the present invention on a substrate, and photo-curing and developing it to form a pattern.

First, the colored photosensitive resin composition is coated on a substrate and then heated and dried to remove volatile components such as a solvent to obtain a smooth coated film.

The coating method can be carried out by, for example, a spin coating method, a flexible coating method, a roll coating method, a slit and spin coating method, a slit coating method or the like. After application, heating and drying (prebaking), or drying under reduced pressure, volatile components such as solvents are volatilized. Here, the heating temperature is usually 70 to 200 占 폚, preferably 80 to 130 占 폚. The thickness of the coating film after heat drying is usually about 1 to 8 mu m. Ultraviolet rays are applied to the thus obtained coating film through a mask for forming a desired pattern. At this time, it is preferable to use an apparatus such as a mask aligner or a stepper so as to uniformly irradiate a parallel light beam onto the entire exposed portion and accurately align the mask and the substrate. When ultraviolet light is irradiated, the site irradiated with ultraviolet light is cured.

The ultraviolet rays may be g-line (wavelength: 436 nm), h-line, i-line (wavelength: 365 nm), or the like. The dose of ultraviolet rays can be appropriately selected according to need, and the present invention is not limited thereto. The desired pattern shape can be formed by dissolving the unexposed portion and developing the coated film after the hardening is brought into contact with the developing solution.

The developing method may be any of a liquid addition method, a dipping method, and a spraying method. Further, the substrate may be inclined at an arbitrary angle during development. The developer is usually an aqueous solution containing an alkaline compound and a surfactant. The alkaline compound may be either an inorganic or an organic alkaline compound. Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogenphosphate, sodium dihydrogenphosphate, ammonium dihydrogenphosphate, ammonium dihydrogenphosphate, potassium dihydrogenphosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate , Sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate, and ammonia. Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, Monoisopropylamine, diisopropylamine, ethanolamine, and the like.

These inorganic and organic alkaline compounds may be used alone or in combination of two or more. The concentration of the alkaline compound in the alkaline developer is preferably 0.01 to 10% by mass, and more preferably 0.03 to 5% by mass.

The surfactant in the alkali developer may be at least one selected from the group consisting of a nonionic surfactant, an anionic surfactant, and a cationic surfactant.

Specific examples of the nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, Polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines.

Specific examples of the anionic surfactant include higher alcohol sulfuric acid ester salts such as sodium stearate and oleyl alcohol sulfate ester to lauryl alcohol sulfate, alkylsulfates such as sodium laurylsulfate and ammonium laurylsulfate, dodecylbenzenesulfonic acid And alkylarylsulfonic acid salts such as sodium or sodium dodecylnaphthalenesulfonate.

Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, and quaternary ammonium salts. Each of these surfactants may be used alone or in combination of two or more.

The concentration of the surfactant in the developer is usually 0.01 to 10% by mass, preferably 0.05 to 8% by mass, and more preferably 0.1 to 5% by mass. After development, it may be washed with water and, if necessary, post-baking at 150 to 230 to 10 to 60 minutes may be performed.

<Image Display Device>

Yet another aspect of the present invention is an image display apparatus having the color filter described above.

The image display apparatus of the present invention is provided with the above-described color filter, and a specific example thereof is a liquid crystal display, an OLED, a flexible display, and the like, but is not limited thereto.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims. In the following Examples and Comparative Examples, "%" and "part" representing the contents are by weight unless otherwise specified.

Production Example 1: Preparation of pigment dispersion composition

11.3 parts by mass of C.I. DISPERBYK-2001 (manufactured by BYK) and 1.2 parts by mass of Acid Red 52 as a pigment dispersant, 72 parts by mass of propylene glycol methyl ether acetate and 8 parts by mass of propylene glycol monomethyl ether as a pigment dispersant, The mixture was mixed / dispersed by a mill for 12 hours to prepare a pigment dispersion M1.

Production Examples 2 and 3: Preparation of alkali-soluble resin

Production Example 2: Preparation of alkali-soluble resin (A-1)

Step 1: Preparation of 2-hydroxy-3- (vinyloxycarbonyloxy) propyl methacrylate

To the reactor was added 10.0 g (0.113 mole) of vinyl hydrogencarbonate to 100 mL of ethyl acetate. 14.66 g (0.103 mole) of glycidyl methacrylate and 0.83 g (0.005 mole) of FeCl ₃ were added, followed by stirring at room temperature for 3 hours. Purified water (100 mL) was added, stirred for 30 minutes, and the organic layer was recovered. After adding 3 g of anhydrous magnesium sulfate, the mixture was stirred for 30 minutes and filtered, and the filtrate was concentrated under reduced pressure. The concentrated residue was purified by silica gel column chromatography (ethyl acetate: n-hexane = 1: 4) to obtain 11.57 g (55.3% yield) of 2-hydroxy-3- (vinyloxycarbonyloxy) propyl methacrylate .

(1H, dd), 6.20 (1H, dd), 7.15 (1H, dd) , m)

m / z: 230

Step 2: Preparation of 2-ethylhexyl acrylate

To the reactor was added 20.0 g (0.277 mole) of acrylic acid to 200 mL of ethyl acetate. 33.7 g (0.333 mole) of triethylamine was added and the mixture was stirred for 30 minutes. After adding 80.3 g (0.416 mole) of 3-bromo octane, the mixture was heated to 70 DEG C and stirred for 6 hours. After cooling to room temperature, purified water (200 mL) was added, stirred for 30 minutes, filtered, and the filtrate was concentrated under reduced pressure. The concentrated residue was purified by silica gel column chromatography (ethyl acetate: n-hexane = 1: 4) to obtain 30.8 g (60.3% yield) of 2-ethylhexyl acrylate.

(1H, dd), 6.20 (1H, dd), 6.55 (1H, m) (1 H, m)

m / z: 184

Step 3: Preparation of alkali-soluble resin (A-1)

50 parts by mass of glycidyl methacrylate, 100 parts by mass of 2-hydroxy-3- (vinyloxycarbonyloxy) propyl methacrylate and 100 parts by mass of 2-ethylhexyl acrylate were dissolved in chloroform Volume). 5 parts of AIBN were added and the mixture was stirred at 60 ° C for 3 hours and then at 80 ° C for 2 hours. The reaction was cooled to room temperature and further stirred for 2 hours.

The weight average molecular weight Mw of the thus synthesized alkali-soluble resin (A-1) measured by GPC was about 12,630, and the glass transition temperature measured by a differential scanning calorimeter was -7 ° C. The molar ratio of x, y and z was 40:20:40.

[A-1]

(R1: methyl group, R2: methyl group, R3: hydrogen

x: 40, y: 20, z: 40

n: 1)

Production Example 3: Preparation of alkali-soluble resin (A-2)

In preparing a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube, 52 g of 2-phenylthioethyl acrylate (0.25 mole), 44 g of benzyl methacrylate ), 12.9 g of methacrylic acid (0.15 mole), 41.3 g of vinyltoluene (0.35 mole), 4 g of t-butylperoxy-2-ethylhexanoate and 40 g of propylene glycol monomethyl ether acetate (PGMEA) And the mixture was stirred and mixed. Then, 6 g of n-dodecane thiol and 24 g of PGMEA were added as a chain transfer agent dropping vessel and stirred / mixed. Thereafter, 395 g of PGMEA was introduced into the flask, the atmosphere in the flask was replaced with nitrogen in air, and the temperature of the flask was raised to 90 DEG C with stirring. The monomer and the chain transfer agent were then added dropwise from the dropping funnel. The reaction was carried out for 2 hours while keeping the temperature at 90 캜 and elevated to 110 캜 for 1 hour. The reaction was carried out for 8 hours to obtain an alkali-soluble resin (A-2) having a solid acid value of 70 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 23,000 and the molecular weight distribution (Mw / Mn) was 2.4.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the alkali-soluble resin were measured by the GPC method under the following conditions.

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

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

Column temperature: 40 DEG C

Mobile phase solvent: tetrahydrofuran

Flow rate: 1.0 ml / min

Injection volume: 50 μl

Detector: RI

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

Standard materials for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500 and A-500 (manufactured by TOSOH CORPORATION)

Examples 1 to 4 and Comparative Examples 1 to 5

The components and contents in Table 1 below were used to prepare colored photosensitive resin compositions.

Classification (parts by weight) Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 alkali
Availability
Resin (A) A-1 1.92 2.50 3.08 3.85 - 3.46 0.39 - A-2 1.92 1.35 0.38 - 3.86 0.38 3.46 - A-3 - - - - - - - 3.85 Photopolymerizable compound
(B) B 4.93 Photopolymerization initiator
(C) C 0.99 coloring agent
(D) M1 27.15 Solvent (E) E-1 8.50 E-2 54.49 additive
(F) F 0.10 [A-1] An alkali-soluble resin
[A-2] The alkali-soluble resin of Production Example 3
[A-3] The ratio of glycidyl methacrylate to 2-hydroxy-3- (vinyloxycarbonyloxy) propyl methacrylate, octan-3-yl acrylate units was 20:40:20 , An average molecular weight of 12,600
[B] KAYARAD DPHA (manufactured by Nippon Kayaku)
[C] PBG-305 (manufactured by Tronis)
[D] Pigment dispersion composition M1
[E-1] 3-Ethoxypropionate
[E-2] Propylene glycol monomethyl ether acetate
[F] antioxidant F, pentaerythritol tetrakis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate) (manufactured by Aldrich) as a phenol antioxidant,

Manufacture of color filters

Color filters were prepared using the colored photosensitive resin compositions prepared according to Examples 1 to 3 and Comparative Examples 1 to 5.

The colored photosensitive resin compositions of Examples 1 to 3 and Comparative Examples 1 to 5 were coated on a glass substrate by spin coating and then placed on a heating plate and held at a temperature of 100 캜 for 3 minutes to form a thin film. Then, a test photomask having a pattern for changing the transmittance in the range of 1 to 100% to a step-like pattern and a line / space pattern of 1 to 50 μm was placed on the thin film, and the distance from the test photomask was set to 100 μm And irradiated with ultraviolet rays. At this time, the ultraviolet light source was irradiated at a light intensity of 100 mJ / cm ² using a 1 kw high pressure mercury lamp containing G, H and I lines, and no special optical filter was used. The thin film irradiated with ultraviolet rays was immersed in a KOH aqueous solution of pH 10.5 for 2 minutes to develop. Thereafter, the glass plate on which the thin film was coated was washed with distilled water, dried by blowing nitrogen gas, and heated in a 200 ° C heating oven for 30 minutes. It is preferable that the pattern shape (film) thickness of the color filter satisfies 1 to 5 탆, specifically 2 to 4 탆, and the pattern shape (film) thickness of the color filter according to the embodiment of the present invention obtained therefrom is all Respectively.

Experimental Example

Various experiments were carried out on the color filters made using the colored photosensitive resin compositions of Examples 1 to 3 and Comparative Examples 1 to 5 by the following methods, and the results are shown in Table 2 below. The measuring method and evaluation method used in the present invention are as follows.

EXPERIMENTAL EXAMPLE 1: Development Rate Experiment of Color Filter

The development speed test was performed on the color filter made of the colored photosensitive resin compositions of Examples 1 to 3 and Comparative Examples 1 to 5, and the review criteria for the development speed experiment were as follows: Developing <Spray Developer HPMJ method> Was determined as the time taken for the first dissolution in the developing solution. The results are shown in Table 2.

Experimental Example 2: Solvent resistance test of color filter

The solvent resistance measurement experiment was performed on the color filter made of the colored photosensitive resin composition according to Examples 1 to 3 and Comparative Examples 1 to 5 and the color filter was used in manufacturing the color filter or the liquid crystal display device The results are shown in Table 2 below. &Lt; tb &gt; &lt; TABLE &gt;

The color filters prepared from the colored photosensitive resin compositions according to Examples 1 to 3 and Comparative Examples 1 to 5 were immersed in respective solvents (NMP; 1-methyl-2-pyrolidinone) for 30 minutes, The equation used here was calculated by the following equation (1), which represents the color change in the three-dimensional colorimeter defined by L *, a *, b *.

 [Equation 1]

? Eab * = (L *) ² + (a *) ² + (b *) ² ] ^1/2

?: Less than? Eab = 1,

?: Eab = 1 to 3,

×: Eab exceeded 3

Experimental Examples 1 and 2 describe experimental methods and evaluation criteria for physical properties required in the production of a general color filter. Experimental methods and evaluation criteria for physical properties required in each process step by the COA method are shown in Experimental Examples 3 and 4 Respectively.

Experimental Example  3: Color filter Stripper liquid  Tolerance and IZO Ethene fluid  Immunity experiment

 Using the color filter made of the colored photosensitive resin compositions of Examples 1 to 3 and Comparative Examples 1 to 5, the resistance to the stripper solution and the resistance to the etchant used in the etching process of the IZO (common electrode) film were evaluated And the results are shown in Table 2 below.

(MA-S03 / MASZ02-Dongwha Fine Chemical Co., Ltd.) was carried out in the same manner as the spray developer (HPMJ method) used in the above development. For the strip and IZO etching conditions, the IZO etching conditions were as follows: after immersion for 2 minutes at 35 ° C, the substrate was washed with water to confirm the stability of the coating film by the IZO etchant. The condition of the stripper solution was evaluated at 3-80 ° C for 3-5 minutes Respectively. The evaluation of the stripper solution also confirmed the stability of the coating film.

First, a positive PR <Clariant Co., Ltd. HKT-601> was coated on the R / G / B pattern coat, then placed on a heating plate and held at a temperature of 90 for 1 minute to form a thin film. Then, a test photomask having a pattern for changing the transmittance in the range of 1 to 100% to a step-like pattern and a line / space pattern of 1 to 50 μm was placed on the thin film, and the distance from the test photomask was set to 100 μm And irradiated with ultraviolet rays. At this time, the ultraviolet light source was irradiated at a light intensity of 100 mJ / cm 2 using a 1 kW high pressure mercury lamp containing g, h and i lines, and no special optical filter was used. The thin film irradiated with ultraviolet rays was further placed on a heating plate and held at a temperature of 110 ° C for 1 minute to further cure the thin film. The thin film irradiated with ultraviolet rays was immersed in a 2.38% aqueous solution of TMAH for 30 seconds to develop. Thereafter, the thin glass plate was rinsed with distilled water, blown with nitrogen gas, dried, and heated in a heating oven of 130 for 2 minutes. The thickness of a typical positive PR pattern shape (film) is 1 to 5 탆, more preferably about 2 to 4 탆, and the thickness of the produced positive PR pattern (film) satisfies all the above ranges. The deposition conditions of the IZO thin film were 500 ~ 2000 Å using a sputter, and more preferably about 500~1000 Å. The deposition of the IZO thin film was suitably performed within the above range. The review criteria for each experiment are as follows.

C / H Size (占 퐉): Size of the exposed line width of a 40 占 퐉 pattern of Contact Hole Mask.

C / H Form: Degree of implementation of 40 μm mask pattern on SEM image after exposure of 40 μm square pattern of C / H mask.

Stripper Resistance: Degree of pattern peeling after exposure of 100 mu m pattern of pattern mask

IZO Etchant Resistance: Degree of pattern erosion indicating the pattern stability after exposure of a pattern of 100 mu m of pattern mask.

The stripper resistance and IZO etchant resistance were confirmed on a three-dimensional surface type optical microscope.

○: Peeling off from pattern 1 to 3

X: Peeling in the pattern exceeded 3, and the degree of resistance can not be evaluated by the peeling of the pattern.

Experimental Example  4: Color filter Residue  Experiment

The patterned BM Glass was used to carry out the above-mentioned steps for the color filter manufacturing process and the development process, and thereafter the presence or absence of development residue on the substrate was visually observed and shown in Table 2 below.

?: No development residue on the substrate

X: Development residue on the substrate

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Development speed (sec) 18 20 23 28 14 26 15 12 NMP content ○ ○ ○ ○ × ○ × × Stripper Resistance ○ ○ ○ ○ × ○ × × IZO etching solution resistance ○ ○ ○ ○ × ○ × × Residue ○ ○ ○ × ○ × ○ ×

With reference to Table 2 above, it is understood that when using a colored photosensitive resin composition containing all of the alkali-soluble resins (A-1 and A-2) in the present invention (Examples 1 to 3), the alkali- (Comparative Examples 1 and 2) and the case of using the alkali-soluble resin of the present invention (Comparative Example 5) were superior in developing speed and solvent resistance, It was confirmed that the effect of preventing the residue on the substrate during the manufacturing process was excellent.

When the content ratio of the alkali-soluble resin in the present invention, that is, the content ratio of [A-1] to [A-2] satisfies the content ratio in the present invention of 2: 8 to 8: 3), and when the content ratio was not satisfied (Comparative Examples 3 and 4), the solvent resistance was excellent and the effect of preventing the residue on the substrate during the color filter manufacturing process was excellent.

Claims (7)

An alkali-soluble resin (A-1) represented by the following formula (1); And a repeating unit derived from a compound (a1) represented by the following formula (2), a repeating unit derived from a compound (a2) containing an unsaturated bond copolymerizable with the repeating unit (a1) Soluble resin (A) containing an alkali-soluble resin (A-2) in an amount of from 2: 8 to 8: 2 by weight,
[Chemical Formula 1]

(In the formula 1,
R1, R2 and R3 are each independently H or a C1 to C5 alkyl group,
n is an integer of 1 to 4,
x, y and z are mole% in the copolymer of each repeating unit,
x + y + z = 70 to 100 mol%

(2)

(In the formula (2)
R4 is hydrogen or a methyl group,
R5 is a substituted or unsubstituted alkylene group or alkenylene group having 1 to 6 divalent carbon atoms,
A is a substituted or unsubstituted phenyl group, a cyclohexyl group, an alkyl group or an alkenyl group having 1 to 6 carbon atoms,
The substituents on R 5 and A are each independently selected from the group consisting of fluorine, chlorine, bromine, iodine, alkyl having 1 to 6 carbon atoms, perhalogenated alkyl having 1 to 3 carbon atoms, hydroxyl, ketone having 1 to 6 carbon atoms, Ester group, N, N- (C1-C3) alkyl substituted amide group. The method according to claim 1,
Wherein the repeating unit represented by x is contained in an amount of 15 to 50 mol% based on the total amount of the repeating units constituting the alkali-soluble resin (A-1) represented by the formula (1). The method according to claim 1,
The sum of the repeating unit represented by y and the repeating unit represented by z is in the range of 50 to 85 mol% based on the total amount of the repeating units constituting the alkali-soluble resin (A-1) Wherein the coloring photosensitive resin composition is a colored photosensitive resin composition. The method according to claim 1,
Wherein the alkali-soluble resin (A) is contained in an amount of 10 to 80% by weight based on the total solid content of the colored photosensitive resin composition. The method according to claim 1,
Wherein the colored photosensitive resin composition further comprises at least one component selected from the group consisting of a photopolymerizable compound (B), a photopolymerization initiator (C), a colorant (D), and a solvent (E). A color filter formed from the colored photosensitive resin composition according to any one of claims 1 to 5. An image display device comprising the color filter of claim 6.