KR102001710B1 - Colored photosensitive resin composition - Google Patents

Abstract

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

Description

COLORED PHOTOSENSITIVE RESIN COMPOSITION [0002]

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

The large-sized display is proceeding at a high speed, and the market demand for high-quality display with high coloring power is increasing. The power consumption of the panel due to the enlargement is increasing and the content of the coloring material and the thickness of the coating film of the colored photosensitive resin composition used for manufacturing the color filter are continuously increasing for the high color reproducibility. In order to improve the energy efficiency through the improvement of the light efficiency, high-throughput development of the color filter has been continuously carried out. However, since the conventional pigment dispersing system has reached the limit of atomization of the pigment, a method of simultaneously using the pigment and the dye as the coloring agent has been examined .

However, when a color filter is produced using a colored photosensitive resin composition containing a dye as a coloring agent, the developing speed is low and the sensitivity is insufficient, thereby causing a problem that the pattern formed in the developing process by the alkali developing solution is peeled off. In addition, when a dye is used, there arises a problem that luminance and color characteristics are deteriorated after a high temperature process.

Korean Patent Laid-Open Publication No. 2012-80123 discloses a colored photosensitive composition, a method of manufacturing a color filter, a color filter, a liquid crystal display, and an organic EL display device, but does not provide an alternative to the above problem.

Korean Patent Publication No. 2012-80123

An object of the present invention is to provide a colored photosensitive composition which exhibits a very high development speed in the development process and exhibits excellent adhesion.

It is another object of the present invention to provide a colored photosensitive composition which does not deteriorate brightness and color characteristics even after a high temperature process due to additional curing. Further, it is an object of the present invention to provide a colored photosensitive resin composition suitable for producing a high-quality color filter.

Another object of the present invention is to provide a color filter made of the above colored photosensitive resin composition. It is still another object of the present invention to provide a liquid crystal display device having the color filter of the present invention.

The present invention relates to a photosensitive resin composition comprising an alkali soluble resin (A), a thermally crosslinkable novolak alicyclic epoxy resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), a colorant (E) The alkali-soluble resin (A) contains a repeating unit represented by the following formula (1), and the alkali-soluble resin (A) has a glass transition temperature of less than 0 ° C.

[Chemical Formula 1]

In Formula 1, R ₁ and R ₂ are each independently a hydrogen atom or a methyl group, and R ₃ is a residue containing a carboxylic acid derived by an acid anhydride.

According to a preferred embodiment of the present invention, the thermally crosslinkable novolak alicyclic epoxy resin (B) comprises a polymer prepared from at least one monomer selected from the following formulas (2) to (14).

(2)

 (3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

,

,

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

Wherein R ₁ is a hydrogen atom or a methyl group, R ₄ is a C ₁ to C ₂₀ aliphatic or aromatic hydrocarbon containing a simple bond or a hetero atom, and R ₁ in the general formulas (3) to (14) R ₂ is a divalent aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms, R ₃ is a divalent aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 0 to 10.

Another aspect of the present invention provides a color filter manufactured using the colored photosensitive resin composition. Further, a liquid crystal display device including the color filter of the present invention is provided.

The colored photosensitive resin composition of the present invention exhibits excellent adhesion even when the developing speed is very high. Further, it is excellent in heat resistance even with additional curing, and has an advantage suitable for manufacturing a high-quality color filter. In addition to this, it also has high chemical resistance and high brightness.

Hereinafter, the present invention will be described in more detail.

The conventional colored photosensitive composition has a problem in that the development speed and adhesion at the time of development are not improved.

In order to solve this problem, the present inventors have found that the above-mentioned problems can be solved by including a specific alkali-soluble binder resin and a specific heat-crosslinkable novolak alicyclic epoxy resin in a colored photosensitive composition, and have completed the present invention.

That is, the present invention includes an alkali-soluble resin (A), a heat-crosslinkable novolak alicyclic epoxy resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), a colorant (E) , The alkali-soluble resin (A) contains a repeating unit represented by the following formula (1), and the alkali-soluble resin (A) has a glass transition temperature of less than 0 ° C.

[Chemical Formula 1]

In Formula 1, R ₁ and R ₂ are each independently a hydrogen atom or a methyl group, and R ₃ is a residue containing a carboxylic acid derived by an acid anhydride.

According to a preferred embodiment of the present invention, R ₃ in the formula (1) may be selected from the group consisting of phthalic anhydride, (2-dodecen-1-yl) succinic anhydride, Maleic anhydride, succinic anhydride, citraconic anhydride, glutaric anhydride, methylsuccinic anhydride, 3,3-dimethylglutaric anhydride, (3,3-Dimethylglutaric anhydride), phenylsuccinic anhydride, itaconic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, , A carboxylic acid derived from at least one acid anhydride selected from the group consisting of trimellitic anhydride, hexahydrophthalic anhydride and carbamic anhydride. . Most preferably a residue comprising a carboxylic acid derived from phthalic anhydride, succinic anhydride or maleic anhydride.

The heat-crosslinkable novolac alicyclic epoxy resin (B) may include a polymer prepared from at least one monomer selected from the following formulas (2) to (14).

(2)

 (3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

,

,

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

Wherein R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a divalent aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms, R ₃ represents a divalent aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 0 to 10 And R ₄ is a divalent C ₁ to C ₂₀ aliphatic or aromatic hydrocarbon containing a simple bond or a hetero atom.

According to a preferred embodiment of the present invention, the weight ratio of the alkali-soluble resin (A) and the heat-crosslinkable novolak alicyclic epoxy resin (B) is 10:90 to 90:10, preferably 20:80 to 80: 20, and more preferably from 30:70 to 70:30.

If the weight ratio of the alkali-soluble resin is less than 10, there may be a problem of discoloration in the yield due to pattern loss and color change during the additional heat processing. And if it exceeds 90, there may be a problem of a decrease in yield due to pattern shortage and insufficient solvent resistance, so the above range is preferable.

Hereinafter, the contents of the present invention will be described in detail for each constitution.

The alkali-soluble resin (A)

The alkali-soluble resin (A) of the present invention has a glass transition temperature of less than 0 占 폚, and may specifically include a repeating unit represented by the following general formula (1).

[Chemical Formula 1]

In Formula 1, R ₁ and R ₂ are each independently a hydrogen atom or a methyl group, and R ₃ is a residue containing a carboxylic acid derived by an acid anhydride.

The present invention uses an alkali-soluble resin having a glass transition temperature of less than 0 ° C, thereby significantly improving the developing speed of the composition and improving the adhesion, thereby suppressing the problem of the pattern falling due to an increase in the developing speed.

Further, in the case of forming a pattern using the composition containing the alkali-soluble resin (A), it is possible to minimize the step of the pattern that can be enlarged by the colorant in the composition, thereby significantly improving the smoothness and improving the transmittance, Thereby making it possible to manufacture a color filter.

The content of the repeating unit represented by the general formula (1) is not particularly limited and may be, for example, 50 to 90 mol%, preferably 60 to 75 mol% based on the total molar percentage of the alkali-soluble resin (A) . When the above range is satisfied, it may be more preferable that the glass transition temperature of the polymerized resin is lower than 0 ° C. When the repeating unit is contained in an amount of less than 50 mol%, the sensitivity may be lowered and shorting of the pattern may occur. When the repeating unit is contained in excess of 90 mol%, the storage stability of the resin is deteriorated .

On the other hand, when the glass transition temperature (Tg) of the polymerized alkali-soluble resin (A) is 0 deg. C or higher, a step may be generated depending on the content of the colorant in the composition and it may be difficult to ensure flatness.

According to a preferred embodiment of the present invention, the alkali-soluble resin (A) further comprises a monomer (a2) having a copolymerizable unsaturated double bond in addition to the monomer (a1) for realizing the repeating unit represented by the formula .

The kind of the monomer (a2) having a copolymerizable unsaturated double bond is not particularly limited. Specific examples thereof include styrene, vinyltoluene,? -Methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethylether, m- Aromatic vinyl compounds such as ether, p-vinylbenzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether or p-vinyl benzyl glycidyl ether;

N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm N-substituted maleimide-based compounds such as methylphenylmaleimide, Np-methylphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide or Np-methoxyphenylmaleimide;

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-methylhexyl (meth) acrylate, 2-methylcyclohexyl Alicyclic (meth) acrylates such as mono (meth) acrylate, 2-dicyclopentanyloxyethyl (meth) acrylate or 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 or 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. These monomers may be used alone or in combination of two or more.

The content of the compound having a copolymerizable unsaturated double bond is not particularly limited and may be, for example, 10 to 50 mol% based on the total molar percentage of the monomers for polymerizing the alkali-soluble resin (A) May be 25 to 40 mol%. When the above range is satisfied, the glass transition temperature of the resin is less than 0 DEG C, so that the step can be minimized.

Hereinafter, the method for producing the alkali-soluble resin (A) according to the present invention will be described in more detail.

Conventionally, an alkali-soluble resin of a colored photosensitive resin composition is prepared by copolymerizing an ethylenically unsaturated monomer having a carboxyl group as an essential component in order to have solubility in an alkali developing solution used in a development processing step for forming a pattern. However, the alkali-soluble resin formed by such a production method has a problem that a resin having a carboxyl group in its main chain and having a glass transition temperature of less than 0 캜 is difficult to produce.

However, the alkali-soluble resin (A) of the present invention is prepared so that the carboxyl group is contained in the side chain other than the main chain in which the polymerization reaction is carried out, thereby giving appropriate developing properties and exhibiting a glass transition temperature of less than 0 占 폚.

On the other hand, one embodiment of the production method of the present invention comprises: (S1) copolymerizing glycidyl (meth) acrylate (a1) and a monomer (a2) having an unsaturated double bond; (S2) reacting the prepared copolymer with an ethylenically unsaturated monomer having a carboxyl group; And (S3) reacting the reacted copolymer with an acid anhydride.

The step (S2) is a step for imparting photo-curability to the alkali-soluble resin (A) of the present invention. In the step (S2), the type of the ethylenically unsaturated monomer having a carboxyl group is not particularly limited But are not limited to, for example, (meth) acrylic acid, ethyl acrylate and / or butyl acrylate, and preferably methacrylate.

The step (S3) is a step for imparting an appropriate acid value to the alkali-soluble resin (A) of the present invention. More specifically, the step (S3) is a step of reacting a hydroxyl group derived from the glycidyl group of the alkali- And introducing a carboxyl group into the side chain of the resin.

The kind of the acid anhydride used in the step (S3) is not particularly limited as long as it is within the range of its function. For example, phthalic anhydride, (2-dodecen-1-yl) succinic anhydride (2-Dodecen-1-yl) succinic anhydride, maleic anhydride, succinic anhydride, citraconic anhydride, glutaric anhydride, methylsuccinic anhydride Methylsuccinic anhydride, 3,3-Dimethylglutaric anhydride, Phenylsuccinic anhydride, Itaconic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, Maleic anhydride, maleic anhydride, maleic anhydride, maleic anhydride, maleic anhydride, maleic anhydride, maleic anhydride, maleic anhydride, maleic anhydride, maleic anhydride, maleic anhydride, anhydride), phthalic anhydride A phthalic anhydride, a trimellitic anhydride, a succinic anhydride, a hexahydrophthalic anhydride and a carbic anhydride are preferable, and trimellitic anhydride, , Succinic anhydride and hexahydrophthalic anhydride are more preferable.

The acid value of the alkali-soluble resin (A) according to the present invention may be 30 to 150 mgKOH / g in order to ensure compatibility with the dye contained in the composition and storage stability of the composition. When the acid value of the alkali-soluble resin (A) is less than 30 mgKOH / g, it may be difficult to secure a sufficient developing rate of the colored photosensitive resin composition. When the acid value exceeds 150 mgKOH / g, There is a problem that compatibility with the dye occurs, so that the dye in the colored photosensitive resin composition is precipitated or the storage stability of the colored photosensitive resin composition is lowered, and the viscosity may increase.

The content of the alkali-soluble resin (A) according to the present invention is not particularly limited, but may be, for example, preferably 1 to 80% by weight, more preferably 10 to 70% by weight based on the total weight percentage of the solid content in the composition. % ≪ / RTI > When the above-mentioned range is satisfied, the solubility in the developing solution is sufficient, the pattern formation is easy, and the development is preferable because the decrease in film thickness of the pixel portion of the open-top tube portion is prevented, and the non-pixel portion is satisfactorily missed.

On the other hand, conventionally, only the alkali-soluble resin (A) is included in the colored photosensitive composition, the smoothness of the pattern can be remarkably improved by minimizing the step of the pattern, but there is a problem in the color change and stability after the high temperature process. Accordingly, the present invention solves the above problems by including a thermally crosslinkable novolak alicyclic epoxy resin (B). That is, since the alkali-soluble resin (A) and the heat-crosslinkable novolak alicyclic epoxy resin (B) are contained at the same time, the chemical resistance to the solvent used in the color filter manufacturing process is excellent and the color change And can provide a colored photosensitive resin composition excellent in long-term storage stability.

Thermally crosslinked type Novolac Aliens  The epoxy resin (B)

The thermally crosslinkable novolak alicyclic epoxy resin (B) of the present invention may comprise a polymer prepared from at least one monomer selected from the following formulas (2) to (14). The polymer is preferably a copolymer prepared from two or more monomers selected from the following formulas (2) to (14).

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

,

,

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

Wherein R ₁ is a hydrogen atom or a methyl group, R ₂ is a divalent aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms, R ₃ is a divalent aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms, and n is 0 And R ₄ is a divalent C ₁ to C ₂₀ aliphatic or aromatic hydrocarbon containing a simple bond or a hetero atom.

The present invention uses a thermally crosslinkable novolac alicyclic epoxy resin (B) comprising a polymer prepared from at least one monomer selected from the above formulas (2) to (14), thereby improving the heat resistance of the composition, It is possible to provide a colored photosensitive composition which is excellent in chemical resistance to chemicals and has long-term storage stability.

According to a preferred embodiment of the present invention, the heat-crosslinkable novolak alicyclic epoxy resin (B) preferably has a weight average molecular weight in terms of polystyrene of 3,000 to 100,000, more preferably 5,000 to 50,000 More preferable. When the weight average molecular weight of the heat-crosslinkable novolac alicyclic epoxy resin (B) is in the range of 3,000 to 100,000, the storage stability is excellent and the film is hardly reduced at the time of development.

According to a preferred embodiment of the present invention, the content of the polymer prepared from one or more monomers selected from the above formulas (2) to (14) is not particularly limited. Preferably, however, the polymer prepared from one or more monomers selected from the above formulas (2) to (14) may be contained in an amount of 20 to 100 mol% based on the molar percentage of the thermally crosslinkable novolak alicyclic epoxy resin (B) And preferably 30 to 80 mol%. If it is less than 20 mol%, there may be a problem of insufficient solvent resistance.

According to a preferred embodiment of the present invention, the thermally crosslinkable novolak alicyclic epoxy resin (B) is obtained by reacting a monomer (b2) having an unsaturated double bond in addition to at least one monomer (b1) selected from the above formulas And further copolymerizing them.

In the embodiment of the present invention, the compound (b2) having an unsaturated bond is not limited as long as it is a compound having an unsaturated double bond capable of polymerization. Specific examples thereof include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl ) Unsaturated carboxylic acids such as acrylate and / or aminoethyl (meth) acrylate; (Meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (Meth) acrylate, cyclohexenyl (meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, mentadienyl (meth) acrylate, isobornyl Unsaturated carboxylic acid esters containing alicyclic substituents such as methacrylate, norbornyl (meth) acrylate, norbornyl (meth) acrylate and / or pinenyl (meth) compound; Mono-saturated carboxylic acid ester compounds of glycols such as oligoethylene glycol monoalkyl (meth) acrylate; Unsaturated carboxylic acid ester compounds containing a substituent having an aromatic ring such as benzyl (meth) acrylate and / or phenoxy (meth) acrylate; Aromatic vinyl compounds such as styrene,? -Methylstyrene and / or vinyltoluene; Carboxylic acid vinyl esters such as vinyl acetate and / or vinyl propionate; Vinyl cyanide compounds such as (meth) acrylonitrile and / or? -Chloroacrylonitrile; Maleimide compounds such as N-cyclohexylmaleimide and / or N-phenylmaleimide; And the like.

According to a preferred embodiment of the present invention, the total amount of the sum of the alkali-soluble resin (A) and the heat-crosslinkable novolak alicyclic epoxy resin (B) is 10 to 90 By weight, and preferably 20 to 80% by weight. If it is contained in an amount of less than 10% by weight, there may be a problem of reduction in yield due to insufficient adhesion and heat resistance. If the amount exceeds 90% by weight, The above range is preferable because there may be a problem that can be caused.

Photopolymerization  The compound (C)

The photopolymerizable compound (C) according to the present invention is a compound capable of polymerizing under the action of the photopolymerization initiator (D) described below, and a monofunctional monomer, a bifunctional monomer or a polyfunctional monomer can be used. Functional 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.

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) , Bis (acryloyloxyethyl) ether of bisphenol A or 3-methylpentanediol di (meth) acrylate, but are not limited thereto.

Specific examples of the polyfunctional monomer include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tri (Meth) 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 content of the photopolymerizable compound (C) is not particularly limited. For example, the content of the photopolymerizable compound (C) may be 5 to 45% by weight, preferably 7 to 45% by weight based on the total weight percentage of the solid content in the composition. When the above range is satisfied, it is preferable that the strength and smoothness of the pixel portion are improved.

Light curing Initiator (D)

The photopolymerization initiator (D) can be used without particular limitation as long as it can polymerize the photopolymerizable compound (C). In particular, the photopolymerization initiator (D) is preferably a photopolymerization initiator (D) which is selected from the group consisting of an acetophenone compound, a benzophenone compound, a triazine compound, a biimidazole compound, an oxime compound, and an oxime compound from the viewpoints of polymerization characteristics, initiation efficiency, absorption wavelength, availability, Or a thioxanthone compound is preferably used.

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 -One and / or 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 and 2,4,6-trimethylbenzophenone.

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 and / L-methylethyl) -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- , 5,5'-tetraphenylbiimidazole and / or 2,2-bis (2,6-dichlorophenyl) -4,4'5,5'-tetraphenyl-1,2'-biimidazole Lt; / RTI >

Specific examples of the oxime compounds include o-ethoxycarbonyl-α-oximino-1-phenylpropan-1-one and OXE01 and / or OXE02 of BASF Co., Ltd., which are commercially available.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone and / or 1-chloro- And Santon.

The photopolymerization initiator (D) may further comprise a photopolymerization initiator (d1) to improve the sensitivity of the colored photosensitive resin composition of the present invention. The colored photosensitive resin composition according to the present invention contains a photopolymerization initiation auxiliary (d1), so that the sensitivity is further increased and the productivity can be improved.

As the photopolymerization initiation assistant (d1), for example, 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 can be preferably used.

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 ) And / or 4,4'-bis (diethylamino) benzophenone.

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 and / or naphthoxyacetic acid.

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 hexaquis (3-mercaptopropionate) and / or tetraethylene glycol bis (3-mercaptopropionate), etc. .

The photopolymerization initiator (D) may be contained in an amount of 0.1 to 10% by weight, preferably 0.1 to 5% by weight based on the total weight percentage of the solid content of the colored photosensitive resin composition of the present invention. When the photopolymerization initiator (D) is within the above-mentioned range, the colored photosensitive resin composition becomes highly sensitive and the exposure time is shortened, which is preferable because productivity can be improved and high resolution can be maintained. Further, the strength of the pixel portion formed using the composition of the above-described conditions and the smoothness of the surface of the pixel portion can be improved.

When the photopolymerization initiator (d1) is further used, the photopolymerization initiator (d1) is used in an amount of 0.1 to 40% by weight, preferably 1 to 40% by weight, based on the content of the alkali- To 30% by weight. When the amount of the photopolymerization initiator (d1) used is within the range of 0.1 to 40% by weight, the sensitivity of the colored photosensitive resin composition becomes higher and the productivity of the color filter formed using the composition is improved.

The colorant (E)

The colorant (E) preferably contains at least one dye (e1), and may further comprise a pigment (e2). Hereinafter, each configuration will be described.

dyes( e1 )

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, heat resistance and solvent resistance.

As the dye (e1), an acidic dye having an acidic group such as a sulfonic acid or a carboxylic acid, a salt of an acidic dye and a nitrogen-containing compound, a sulfonamide of an acidic dye or the like and derivatives thereof may be used. , Phthalocyanine-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. Red dyes such as Solvent Red 8, 45, 49, 89, 111, 122, 125, 130, 132, 146, 179;

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. Yellow dyes such as Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162;

C.I. Solvent Orange Orange dye such as 2, 7, 11, 15, 26, 56

C.I. Green dyes such as solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34,

C.I. Solvent dye having excellent solubility in an organic solvent. Solvent Red 8, 49, 89, 111, 122, 132, 146, 179; C.I. Solvent Blue 35, 36, 44, 45, 70; C.I. Solvent violet 13 is preferred, and C.I. Solvent Red 8, 122 and 132 are more preferred.

Also, C.I. As an acid dye

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;

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, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251

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,

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 color dyes such as C.I. Acid Violet 6B, 7, 9, 17, 19, 66

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

CI Acid Red 92, which is excellent in solubility in organic solvents in acid dyes; C. I. Acid Blue 80, 90; C.I. Acid Violet 66 is preferred.

As a C.I. direct dye,

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;

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;

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,

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 (e1) in the colorant (E) is preferably 0.5 to 80% by weight, more preferably 0.5 to 60% by weight, and more preferably 1 to 50% by weight based on the weight percentage of the total solid content in the colorant (E) %end Particularly preferred. If the content of the dye in the colorant (E) is in the above range, it is possible to prevent the problem of lowering the reliability of the dye to be eluted by the organic solvent after pattern formation.

Pigment ( e2 )

The pigment may be an organic pigment or an inorganic pigment generally used in the art. The above-mentioned pigments can be used in various kinds of pigments used in printing ink, ink jet ink and the like. Specific examples thereof include water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, And an anthanthrone pigment, an anthanthrone pigment, a pravanthrone pigment, a pyranthrone pigment, an anthanthrone pigment, an anthanthrone pigment, an anthanthrone pigment, an anthanthrone pigment, an anthanthrone pigment, a pyranthrone pigment, pyranthrone pigments, diketopyrrolopyrrole pigments, and the like. The arms can be exemplified by metal compounds such as the pigment as the metal oxides, metal complex salts, specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, an oxide of a metal such as carbon black Or composite metal oxides. In particular, the as organic pigments and inorganic pigments can include compounds that are classified as pigments in the particular color index (The society of Dyers and Colourists Publishing), more specifically, the color index (CI) numbers as described below 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, 58 and 59

C.I Pigment Brown 28

C.I Pigment Black 1 and 7, etc.

These pigments (e2) may be used alone or in combination of two or more.

The exemplified C.I. Among the pigment pigments, 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 Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 185, C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 58, C.I. Pigment Violet 23, C.I. Pigment Blue 15: 3, Pigment Blue 15: 6 can be preferably used.

It is preferable to use a pigment dispersion in which the particle diameter of the pigment is uniformly dispersed. As an example of a method for uniformly dispersing the particle size of the pigment, a method of dispersing the pigment by incorporating the pigment dispersant (e3) can be cited. According to this method, a pigment dispersion in which the pigment is uniformly dispersed in the solution can be obtained have.

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 singly or in combination of two or more thereof .

The content of the pigment (e2) is in the range of 20 to 90% by weight, preferably 30 to 70% by weight based on the total solid content in the pigment dispersion composition. When the content of the pigment is in the range of 20 to 90% by weight, the viscosity is low, the storage stability is excellent, and the dispersion efficiency is high, which is effective for increasing the contrast ratio.

As the dispersant (e3), other resin type pigment dispersants other than the acrylic 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., In addition to the acrylic dispersant, other resin type pigment dispersants may be used alone or in combination of two or more, or may be used in combination with acrylic dispersion.

The amount of the dispersant (e3) to be used is in the range of 5 to 60 parts by weight, more preferably 15 to 50 parts by weight, based on 100 parts by weight of the solid content of the pigment (e2). If the content of the dispersant (e3) exceeds 60 parts by weight, the viscosity may be increased. If the content of the dispersant (e3) is less than 5 parts by weight, it may be difficult to atomize the pigment or cause gelation after dispersion.

The colorant (E) may be contained in an amount of 1 to 60% by weight, preferably 10 to 50% by weight based on the total weight percentage of the solid content in the colored photosensitive resin composition of the present invention. When the colorant is included in the above-mentioned range, even if a thin film is formed, the color density of the pixel is sufficient, and the residue of the non-curing portion is not lowered during development, so that residue is less likely to occur.

Solvent (F)

The solvent (F) may be any solvent which is effective in dissolving the other components contained in the colored photosensitive resin composition, and is not particularly limited, and may be selected from ethers, aromatic hydrocarbons, ketones, Alcohols, esters, amides and the like are preferable.

The solvent (F) specifically includes ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and / or ethylene glycol monobutyl ether;

Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and / or diethylene glycol dibutyl ether;

Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and / or ethyl cellosolve acetate;

Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monopropyl ether acetate, methoxybutyl acetate and / or methoxypentyl acetate;

Aromatic hydrocarbons such as benzene, toluene, xylene and / or mesitylene;

Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and / or cyclohexanone;

Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin and / or 4-hydroxy-4-methyl-2-pentanone;

Esters such as ethyl 3-ethoxypropionate and / or methyl 3-methoxypropionate; and cyclic esters such as? -butyrolactone; and the like.

The solvent (F) is preferably an organic solvent having a boiling point of 100 ° C to 200 ° C in terms of coatability and drying property, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate , Butalactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like. Hydroxy-4-methyl-2-pentanone or the like which can improve the storage stability by inhibiting the precipitation of the dye.

The solvent (F) may be used alone or in admixture of two or more. The solvent (F) is used in an amount of 1 to 90% by weight, preferably 1 to 60% by weight, based on the total weight percentage of the color photosensitive resin composition of the present invention %. ≪ / RTI > When it is contained in the above-mentioned contents, it provides the effect of improving the coating property when applied with a coating apparatus such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater) .

Additive (G)

The additive (G) may be optionally added, for example, other polymer compounds, a curing agent, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber and / or an antiflocculant.

Specific examples of the other polymer compound include a curable resin such as maleimide resin, a thermoplastic resin such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester and / or polyurethane .

The curing agent is used for increasing the cure depth and mechanical strength. Specific examples of the curing agent include a polyfunctional isocyanate compound, a melamine compound and / or an oxetane compound.

Specific examples of the oxetane compound in the curing agent include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane and / or cyclohexanedicarboxylic acid bisoxetane, and the like .

The curing agent may be used in combination with a curing agent.

The curing auxiliary compound includes, for example, polyvalent carboxylic acids, polyvalent carboxylic anhydrides and / or acid generators. The polyvalent carboxylic acid anhydrides may be those commercially available as an epoxy resin curing agent. Specific examples of the above-mentioned epoxy resin curing agent include a resin (trade name: ADEKA HARDONE EH-700) (ADEKA INDUSTRIAL CO., LTD.), A trade name (RICACIDO HH) (Manufactured by Shin-Etsu Chemical Co., Ltd.). The curing agents exemplified above may be used alone or in combination of two or more.

The surfactant may be used to further improve film-forming properties of the photosensitive resin composition, and a fluorine-based surfactant and / or a silicon-based surfactant may be preferably used.

Examples of the silicone surfactants include DC3PA, DC7PA, SH11PA, SH21PA and / or SH8400 of Dow Corning Toray Silicone Co., Ltd., which are commercially available. And TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460 and / or TSF-4452 of GE Toshiba Silicones. Examples of the fluorine-based surfactant include Megapis F-470, F-471, F-475, F-482 and / or F-489 commercially available from Dainippon Ink and Chemicals, Incorporated. The above-exemplified surfactants may be used alone or in combination of two or more.

Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- ( 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- 3-isocyanatopropyltrimethoxysilane and / or 3-isocyanatepropyltriethoxysilane, and the like. The adhesion promoters exemplified above may be used alone or in combination of two or more. The adhesion promoter may be contained in an amount of usually 0.01 to 10% by weight, preferably 0.05 to 2% by weight based on the solid content of the colored photosensitive resin composition.

Specific examples of the antioxidant include 2,2'-thiobis (4-methyl-6-t-butylphenol) and / or 2,6-di-t-butyl-4-methylphenol.

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

Specific examples of the anti-aggregation agent include sodium polyacrylate and the like.

The process for producing the colored photosensitive resin composition of the present invention will be described as follows.

First, the pigment (e2) in the colorant (E) is mixed with the solvent (F) and dispersed using a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 μm or less. At this time, the pigment dispersant (e3), part or all of the alkali-soluble resin (A), or the dye (e2) may be mixed with the solvent (F) to dissolve or disperse it.

(B) a photopolymerizable compound (C), a photopolymerization initiator (D) and, if necessary, an additive (G), and the dye (e1), the remainder of the alkali- ) And the solvent (F) are added so as to have a predetermined concentration to prepare the colored photosensitive resin composition according to the present invention.

Another aspect of the present invention is a method for manufacturing a color filter, comprising: applying the colored photosensitive resin composition of the present invention; Selectively exposing a part of the colored photosensitive resin composition; And removing the exposed region or the non-exposed region of the colored photosensitive resin composition. The present invention also provides a method for forming a pattern of a colored photosensitive resin composition.

The present invention also provides a color filter including a color layer formed by exposing and developing the colored photosensitive resin composition of the present invention in a predetermined pattern, and a liquid crystal display device provided with the color filter.

The color filter and the liquid crystal display may be manufactured by a known method.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the embodiments of the present invention described below are illustrative only and the scope of the present invention is not limited to these embodiments. The scope of the present invention is indicated in the claims, and moreover, includes all changes within the meaning and range of equivalency of the claims. In the following Examples and Comparative Examples, "%" and "part" representing the content are based on weight unless otherwise specified.

Synthetic example  1: Synthesis of colorant composition

(1) Colorant composition (Pigment dispersion composition M1)

C.I. , 4.0 parts by mass of DISPERBYK-2001 (manufactured by BYK) as a pigment dispersing agent, 1.2 parts by mass of Acid Red 52 as a dye, 44 parts by mass of propylene glycol methyl ether acetate as a solvent and 12.0 parts by mass of Pigment Red 177 and 4 parts by mass of 4-hydroxy- And 20 parts by mass of methyl-2-pentanone were mixed / dispersed by a bead mill for 12 hours to prepare a pigment dispersion (M1).

(2) Colorant composition (Pigment dispersion composition M2)

, 13.2 parts by mass of CI Pigment Red 177 as a pigment, 4.0 parts by mass of DISPERBYK-2001 (manufactured by BYK) as a pigment dispersant, 44 parts by mass of propylene glycol methyl ether acetate as a solvent and 4 parts by mass of 4-hydroxy- Were mixed / dispersed by a bead mill for 12 hours to prepare a pigment dispersion (M2).

Synthetic example  2: Synthesis of alkali-soluble resin

(1) Synthesis of alkali-soluble resin (A-1)

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 100 g of propylene glycol monomethyl ether acetate, 100 g of propylene glycol monomethyl ether, 8.2 g of AIBN, 73.6 g of 2-ethylhexyl acrylate, , 78.1 g of glycidyl methacrylate and 6.1 g of n-dodecanethiol were charged and replaced with nitrogen. Thereafter, the temperature of the reaction solution was raised to 80 DEG C with stirring, and the reaction was carried out for 4 hours. Subsequently, the temperature of the reaction solution was lowered to room temperature, the atmosphere of the flask was replaced with air, and then 0.2 g of triethylamine, 0.1 g of 4-methoxyphenol and 39.6 g of acrylic acid were added thereto and reacted at 100 ° C for 6 hours. Thereafter, the temperature of the reaction solution was lowered to room temperature, 6.0 g of succinic anhydride was added, and the mixture was reacted at 80 DEG C for 6 hours.

The alkali-soluble resin thus synthesized had a solid dispersion value of 32.8 mgKOH / g and a weight average molecular weight Mw of about 6230 as measured by GPC. The glass transition temperature was measured with a differential scanning calorimeter and found to be -21.0 ° C.

(2) Synthesis of alkali-soluble resin (A-2)

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 100 g of propylene glycol monomethyl ether acetate, 100 g of propylene glycol monomethyl ether, 8.2 g of AIBN, 73.6 g of 2-ethylhexyl acrylate, , 78.1 g of glycidyl methacrylate and 6.1 g of n-dodecanethiol were charged and replaced with nitrogen. Thereafter, the temperature of the reaction solution was raised to 80 DEG C with stirring, and the reaction was carried out for 4 hours. Subsequently, the temperature of the reaction solution was lowered to room temperature, the atmosphere of the flask was replaced with nitrogen, and then 0.2 g of triethylamine, 0.1 g of 4-methoxyphenol and 21.7 g of acrylic acid were added and reacted at 100 ° C for 6 hours. Thereafter, the temperature of the reaction solution was lowered to room temperature, 12.5 g of succinic anhydride was added, and the mixture was reacted at 80 ° C for 6 hours.

The alkali-soluble resin thus synthesized had a solid dispersion value of 68.6 mgKOH / g and a weight-average molecular weight Mw of about 5870 as measured by GPC. The glass transition temperature was measured with a differential scanning calorimeter and found to be -27.3 ° C.

(3) Synthesis of alkali-soluble resin (A-3)

100 g of propylene glycol monomethyl ether acetate, 100 g of propylene glycol monomethyl ether, 8.2 g of AIBN, 55.2 g of 2-ethylhexyl acrylate, 10 g of 4-methylstyrene , 92.3 g of glycidyl methacrylate and 6.1 g of n-dodecanethiol were charged and replaced with nitrogen. Thereafter, the temperature of the reaction solution was raised to 80 DEG C with stirring, and the reaction was carried out for 4 hours. Subsequently, the temperature of the reaction solution was lowered to room temperature, the atmosphere of the flask was replaced with air with nitrogen, and then 0.2 g of triethylamine, 0.1 g of 4-methoxyphenol and 46.8 g of acrylic acid were added and reacted at 100 ° C for 6 hours. Thereafter, the temperature of the reaction solution was lowered to room temperature, 12.5 g of succinic anhydride was added, and the mixture was reacted at 80 ° C for 6 hours.

The alkali-soluble resin thus synthesized had a solid dispersion value of 70.2 mgKOH / g and a weight-average molecular weight Mw of about 6350 as measured by GPC. The glass transition temperature was measured by differential scanning calorimetry and found to be -28.6 ℃.

Synthetic example  3: Novolac Aliens  Synthesis of epoxy resin

(One) Novolac Aliens  Synthesis of epoxy resin (B-1)

137 g of propylene glycol monomethyl ether acetate and 45 g of propylene glycol monomethyl ether were introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube. After elevating the temperature to 110 캜, 3,4-epoxytricyclodecane-8 A mixture of 234.1 g of a mixture of (meth) acrylate and 3,4-epoxytricyclodecan-9-yl (meth) acrylate (50:50 molar ratio) and 136 g of propylene glycol monomethyl ether acetate, 2.9 g of pin and 1.3 g of methylhydroquinone were added and reacted at 100 ° C for 8 hours. The reaction was carried out in a mixed atmosphere of air / nitrogen. Thus, an epoxy resin B-1 was obtained.

The weight average molecular weight in terms of polystyrene measured by GPC was 10,100 and the molecular weight distribution (Mw / Mn) was 2.6.

(2) Novolac Aliens  Synthesis of epoxy resin (B-2)

137 g of propylene glycol monomethyl ether acetate and 45 g of propylene glycol monomethyl ether were introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube, and after heating to 110 DEG C, 10.8 g of acrylic acid and 0.15 g of propylene glycol monomethyl ether acetate Butylperoxy 2-ethylhexylcarbonate was added dropwise to the flask over 3 hours from the dropping funnel, and stirring was further continued at 110 ° C for 3 hours. Then, 199.0 g of a mixture of 3,4-epoxytricyclodecan-8-yl (meth) acrylate and 3,4-epoxytricyclodecan-9-yl (meth) acrylate (50:50 molar ratio) and propylene glycol monomethyl , 2.9 g of triphenylphosphine and 1.3 g of methylhydroquinone were added to the mixture, and the mixture was reacted at 100 DEG C for 6 hours.

The reaction was carried out in a mixed atmosphere of air / nitrogen. Thus, an epoxy resin B-2 having a solid dispersion value of 89 mgKOH / g was obtained. The weight average molecular weight measured by GPC in terms of polystyrene was 13,000 and the molecular weight distribution (Mw / Mn) was 2.5.

(3) Novolac Aliens  Synthesis of epoxy resin (B-3)

After introducing 137 g of propylene glycol monomethyl ether acetate and 45 g of propylene glycol monomethyl ether into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube, 23.6 g of vinyltoluene, 10.8 g of acrylic acid, Butyl peroxy-2-ethylhexylcarbonate was added dropwise to the flask over 3 hours from the dropping funnel, and stirring was further continued at 110 ° C for 3 hours . Next, 152.2 g of a mixture of 3,4-epoxytricyclodecan-8-yl (meth) acrylate and 3,4-epoxytricyclodecan-9-yl (meth) acrylate (50:50 molar ratio) and propylene glycol monomethyl , 2.9 g of triphenylphosphine and 1.3 g of methylhydroquinone were added to the mixture, and the mixture was reacted at 100 DEG C for 6 hours. The reaction was carried out in a mixed atmosphere of air / nitrogen. Thus, an epoxy resin B-3 having a solid acid value of 87 mgKOH / g was obtained.

The weight average molecular weight in terms of polystyrene measured by GPC was 13,200 and the molecular weight distribution (Mw / Mn) was 2.5.

compare Synthetic example : Synthesis of alkali-soluble resin

(1) Synthesis of alkali-soluble resin (A-4)

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 120 g of propylene glycol monomethyl ether acetate, 80 g of propylene glycol monomethyl ether, 3.3 g of AIBN, 9.4 g of acrylic acid, 17.6 g of benzyl methacrylate, -Methylstyrene, 20 g of methyl methacrylate and 6.1 g of n-dodecanethiol were charged and replaced with nitrogen.

Thereafter, the temperature of the reaction solution was raised to 80 DEG C with stirring, and the reaction was carried out for 8 hours. The alkali-soluble resin thus synthesized had a solid dispersion value of 77.2 mgKOH / g and a weight average molecular weight Mw of about 14950 as measured by GPC. The glass transition temperature was measured by a differential scanning calorimeter and found to be 93 ° C.

(2) Synthesis of alkali-soluble resin (A-5)

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 120 g of propylene glycol monomethyl ether acetate, 80 g of propylene glycol monomethyl ether, 3.3 g of AIBN, 9.4 g of acrylic acid, 17.6 g of benzyl methacrylate, -Methylstyrene, 10 g of methyl methacrylate and 6.1 g of n-dodecanethiol were charged and replaced with nitrogen. Thereafter, the temperature of the reaction solution was raised to 80 DEG C with stirring, and the reaction was carried out for 8 hours. The solid dispersion weight of the alkali-soluble resin thus synthesized was 72.6 mgKOH / g, and the weight average molecular weight Mw measured by GPC was about 16,310. The glass transition temperature was measured with a differential scanning calorimeter and found to be 87 ° C.

Example  And Comparative Example

(A), a heat-crosslinkable novolak alicyclic epoxy resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), a colorant (E) and a solvent (F) To prepare colored photosensitive resin compositions of Examples and Comparative Examples.

division A B C D E F weight% ingredient content Tg (占 폚) ingredient content content content ingredient content content Example 1 A-1 13.2 -21.0 B-1 3.3 3.6 0.9 M1 39.8 39.2 Example 2 A-1 13.2 -21.0 B-2 3.3 3.6 0.9 M1 39.8 39.2 Example 3 A-1 13.2 -21.0 B-3 3.3 3.6 0.9 M1 39.8 39.2 Example 4 A-1 3.3 -21.0 B-2 13.2 3.6 0.9 M1 39.8 39.2 Example 5 A-1 3.3 -21.0 B-3 13.2 3.6 0.9 M1 39.8 39.2 Example 6 A-1 8.3 -21.0 B-2 8.2 3.6 0.9 M1 39.8 39.2 Example 7 A-2 8.3 -27.3 B-2 8.2 3.6 0.9 M1 39.8 39.2 Example 8 A-3 8.3 -28.6 B-2 8.2 3.6 0.9 M1 39.8 39.2 Comparative Example 1 A-4 16.5 93.0 - - 3.6 0.9 M1 39.8 39.2 Comparative Example 2 A-5 16.5 87.0 - - 3.6 0.9 M1 39.8 39.2 Comparative Example 3 A-4 13.2 93.0 B-2 3.3 3.6 0.9 M1 39.8 39.2 Comparative Example 4 A-5 13.2 87.0 B-3 3.3 3.6 0.9 M1 39.8 39.2 Comparative Example 5 A-1 16.5 -23.0 - - 3.6 0.9 M1 39.8 39.2 Comparative Example 6 - - - B-2 16.5 3.6 0.9 M1 39.8 39.2 Comparative Example 7 A-1 16.5 -21.0 - - 3.6 0.9 M2 39.8 39.2 A-1: An alkali-soluble resin (1) of Synthesis Example 2- A-2: An alkali-soluble resin of Synthesis Example 2- (2) A-3: An alkali-soluble resin of Synthesis Example 2- (3) A-4: Alkali-soluble resin of Comparative Synthesis Example (1) A-5: Alkali-soluble resin of Comparative Synthesis Example (2) B-1: Synthesis of thermotropic novolac alicyclic epoxy resin (a) of Synthesis Example 3- (1) B-2: Thermotropic novolak alicyclic epoxy resin of Synthesis Example 3- (2) B-3: The thermograped novolac alicyclic epoxy resin (A-1) of Synthesis Example 3- (3) C: KAYADA DPHA (manufactured by Nippon Kayaku) D: PBG-305 (manufactured by TRON LISA) M1: Colorant composition of Synthesis Example 1- (1) M2: Colorant composition of Synthesis Example 1- (2) F: propylene glycol monomethyl ether acetate (27.8 wt%) + 4-hydroxy-4-methyl-2-pentanone (17.0 wt%

Experimental Example

Experimental Example  1: Manufacture of color filter and evaluation of development speed and adhesion

(1) Manufacture of color filters

A color filter was prepared using the colored photosensitive resin compositions prepared in the above Examples and Comparative Examples.

Specifically, each of the above colored photosensitive resin compositions was applied on a 2-inch-square glass substrate ("EAGLE XG", manufactured by Corning Inc.) by spin coating, then placed on a heating plate and held at a temperature of 100 ° C. for 3 minutes to form a thin film . Subsequently, a test photomask having a pattern for changing the transmittance in the range of 1 to 100% in a stepwise manner and a line / space pattern of 1 to 100 m was placed on the thin film, and the interval between the test photomask and the test photomask was set to 300 [ Respectively. At this time, the ultraviolet light source was irradiated with a high pressure mercury lamp of 1 KW containing g, h and i lines at an illuminance of 60 mJ / cm 2, 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. The glass plate coated with the thin film was washed with distilled water, and then blown with nitrogen gas, dried, and heated in a heating oven at 200 ° C for 25 minutes to prepare a color filter. The film thickness of the color filter prepared above was 2.4 占 퐉.

(2) Evaluation of development speed

The color filter was evaluated for the developing speed in the following manner.

The time (developing rate) required for the non-exposed portion to completely dissolve in the developer during development in the above process was measured and described in Table 2 below.

(3) Evaluation of adhesion

The color filter was evaluated for adhesion by the following method.

The resultant pattern was evaluated by an optical microscope, and the result was evaluated in terms of the degree of grazing phenomenon of the following 20 탆 pattern, and it is shown in Table 2 below.

<Evaluation Criteria>

○: No pattern peeling

△: 1 to 3 pattern peeling

X: Pattern peeling 4 or more

Experimental Example  2: Manufacture of color filter and evaluation of transmittance

Test A color filter was prepared in the same manner as in Experimental Example 1 except that the photomask was not used. Then, the transmittance (%) was measured in the following manner. Among the formed patterns, a line pattern portion of 100 mu m was measured using a colorimeter (OSP-200, manufactured by Olympus Corporation) and is shown in Table 2 below.

Experimental Example  3: Manufacture of color filter and evaluation of heat resistance

A color filter was prepared in the same manner as in Experimental Example 1. Thereafter, the heat resistance (DELTA E * ab) was measured in the following manner. The heat resistance of the prepared color filter was measured at 230 DEG C for 120 minutes, and the color change was measured.

Experimental Example  4: Manufacture of color filters and Solvent resistance  evaluation

A color filter was prepared in the same manner as in Experimental Example 1. Thereafter, the solvent resistance (DELTA E * ab) was measured in the following manner. The solvent resistance measurement was performed by immersing the prepared color filter in each solvent (NMP; 1-methyl-2-pyrrolidinone) for 30 minutes, and calculating the color change before and after the evaluation. The equation to be used at this time is calculated by the following equation (1) representing the color change in the three-dimensional colorimetric system defined by L *, a *, b *

[Equation 1]

? Eab * = [(? L *) 2+ (? A *) 2+ (? B *) 2] 1/2

?: Less than? Eab = 3,

DELTA: Eab = 3 to 5,

X: exceeded Eab = 5

division Development speed (s) Adhesiveness Transmittance Heat resistance (△ Eab *) Solvent resistance
(? Eab *) Example 1 17 ○ 13.90 ○ ○ Example 2 14 ○ 13.85 ○ ○ Example 3 12 ○ 13.84 ○ ○ Example 4 19 ○ 13.92 ○ ○ Example 5 18 ○ 13.87 ○ ○ Example 6 13 ○ 13.83 ○ ○ Example 7 13 ○ 13.84 ○ ○ Example 8 12 ○ 13.87 ○ ○ Comparative Example 1 60 X 13.60 X X Comparative Example 2 57 X 13.67 X X Comparative Example 3 51 X 13.64 X X Comparative Example 4 48 X 13.65 X X Comparative Example 5 11 △ 13.72 △ △ Comparative Example 6 39 △ 13.74 ○ △ Comparative Example 7 48 X 13.40 ○ △

Referring to Table 2, Examples 1 to 8 which are the colored photosensitive resin compositions according to the present invention exhibited excellent adhesion even though the developing speed was very fast. It is also confirmed that it is suitable for manufacturing a high quality color filter because of high transmittance and excellent heat resistance.

Particularly, when the developing speed is within 25 seconds, it is preferable to shorten the manufacturing time of the color filter, and if the number of pattern peelings is less than 3, it is preferable to improve the color filter yield. If the transmittance is 13.7 or more, a high-definition color filter can be manufactured. If the heat resistance is 2.5 or less, the occurrence of defects due to the color change in the additional thermal process can be minimized.

Therefore, even when the transmittance is only 1%, the improvement of the transmittance is a very important characteristic which shows the quality of the photosensitive resin composition by influencing the brightness of the color filter, and the composition of the present invention is 3% It was confirmed that the excellent transmittance was improved and the excellent effect was exhibited.

Claims (12)

(A), a thermally crosslinkable novolak alicyclic epoxy resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), a colorant (E) and a solvent (F)
The alkali-soluble resin (A) contains a repeating unit represented by the following formula (1)
Wherein the alkali-soluble resin (A) is synthesized by including acrylic acid and succinic anhydride, and has a glass transition temperature of less than 0 占 폚.
[Chemical Formula 1]

In Formula 1, R ₁ and R ₂ are each independently a hydrogen atom or a methyl group, and R ₃ is a residue containing a carboxylic acid derived by an acid anhydride. The method according to claim 1,
The thermosetting novolak alicyclic epoxy resin (B) comprises a polymer prepared from at least one monomer selected from the following formulas (2) to (14):
(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

,
[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

Wherein R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a divalent aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms, R ₃ represents a divalent aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 0 to 10 And R ₄ is a divalent C ₁ to C ₂₀ aliphatic or aromatic hydrocarbon containing a simple bond or a hetero atom. The method according to claim 1,
Wherein the weight ratio of the alkali-soluble resin (A) to the heat-crosslinkable novolak alicyclic epoxy resin (B) is 10:90 to 90:10. The method according to claim 1,
Wherein R ₃ is selected from the group consisting of phthalic anhydride, (2-dodecen-1-yl) succinic anhydride, maleic anhydride, succinic anhydride, anhydride, citraconic anhydride, glutaric anhydride, methylsuccinic anhydride, 3,3-dimethylglutaric anhydride, phenylsuccinic anhydride, Itaconic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, trimellitic anhydride, hexahydrophthalic anhydride, hexahydrophthalic anhydride, Wherein the resin is a residue comprising a carboxylic acid derived from at least one acid anhydride selected from the group consisting of Hexahydrophthalic anhydride and Carbic anhydride. The method according to claim 1,
Wherein the repeating unit represented by the formula (1) is contained in an amount of 50 to 90 mol% based on the total molar percentage of the alkali-soluble resin (A). The method according to claim 1,
Wherein the alkali-soluble resin (A) further comprises a monomer having an unsaturated double bond in addition to the monomer for implementing the repeating unit represented by the formula (1). The method according to claim 1,
Wherein the heat-crosslinkable novolac alicyclic epoxy resin (B) is further copolymerized with at least one monomer selected from the general formulas (2) to (14), further comprising a monomer having an unsaturated double bond. The method according to claim 1,
Wherein the total content of the sum of the alkali-soluble resin (A) and the heat-crosslinkable novolak alicyclic epoxy resin (B) is in the range of 10 to 90% by weight based on the total weight percentage of the total solid content in the composition. Composition. The method according to claim 1,
Wherein the colored photosensitive resin composition further comprises at least one additive selected from other polymer compounds, curing agents, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers and coagulation inhibitors. Applying the colored photosensitive resin composition of claim 1;
Selectively exposing a part of the colored photosensitive resin composition; And
And removing the exposed region or the non-exposed region of the colored photosensitive resin composition. A color filter comprising a color layer formed by exposing and developing the colored photosensitive resin composition of claim 1 in a predetermined pattern. A liquid crystal display device comprising the color filter of claim 11.