KR20160063616A - A color photosensitive resin composition - Google Patents

Abstract

The present invention relates to a colored photosensitive resin composition, a color filter and a liquid crystal display device manufactured using the same. The resin composition of the present invention comprises: (A) an alkali soluble resin including a monomer derived from a compound represented by chemical formula 1; (B) a coloring agent; (C) a photopolymerizable compound; (D) a photopolymerization initiator; and (E) a solvent. The resin composition elongates the chain of carboxyl groups on side chains, thereby having excellent alkali solubility, reactivity, chemical resistance, and thermal resistance.

Description

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

More particularly, the present invention relates to a colored photosensitive resin composition excellent in alkali solubility, curability, and chemical resistance, and a color filter and liquid crystal display fabricated using the same. And a display device.

BACKGROUND ART [0002] Color filters are widely used in imaging devices, liquid crystal display devices, and the like, and their application range is rapidly expanding. A color filter used for a color liquid crystal display device, an image pickup device, or the like is a device for uniformly applying a colored photosensitive resin composition containing a coloring agent corresponding to each color of red, green and blue on a substrate on which a black matrix is pattern- The coating film formed by heating and drying (hereinafter also referred to as preliminary firing) may be exposed and developed, and if necessary, further heat curing (hereinafter also referred to as post-firing) may be repeated for each color, Color pixels are formed.

The colored photosensitive resin composition is a colored photosensitive resin composition containing a colorant and is useful as a material for forming a colored pattern constituting a color filter. Here, the color filter is an optical element which is built in a color liquid crystal display device and is used for coloring a display image or embedded in an image pickup device and used for obtaining a color image.

Until now, dyeing method, printing method, electrodeposition method and pigment dispersion method have been used as a color filter manufacturing method of a liquid crystal display element. The pigment dispersion method is a method in which a photosensitive colored resin composition in which red, green or blue pigments are dispersed is applied to a substrate, exposed and developed by a conventional photolithography method to sequentially form red, green and blue color filters on a substrate . This method is superior in color purity, dimensional accuracy, porosity, heat resistance and durability, and has the advantage that the thickness of the film can be uniformly maintained, which is the most widely used in the manufacture of color filters. As the colored photosensitive resin composition, an acrylic resin having a carboxyl group in its side chain is used as a resin having excellent light resistance and little change in color.

Korean Patent No. 292634 discloses a colored photosensitive resin composition which provides a color filter excellent in adhesion to a substrate without causing contamination or residual film by an alkali aqueous solution using an alkali soluble block copolymer as a binder. However, the conventional colored photosensitive resin composition fails to meet the recent demands such as improving the image quality such as chromaticity and color reproducibility. When a coloring layer is formed by using a photosensitive resin composition having poor heat resistance, out of the photosensitive resin composition There is a problem that an image such as a residual image is generated by the gas OUTGAS and the purity is lowered. Further, even if the sensitivity and adhesiveness are improved by using an acrylate-based resin, there is a problem that the taper straightness and resolution are lowered due to the residue in the pattern.

Korea Public Release No. 2011-0085773

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems of the prior art,

It is an object of the present invention to provide a colored photosensitive resin composition which is obtained by branching a carboxyl group in an alkali-soluble resin and is excellent in alkali solubility, storage stability, reactivity and chemical resistance.

In addition,

And a color filter and a liquid crystal display device manufactured using the colored photosensitive resin composition.

According to the present invention,

(A), a colorant (B), a photopolymerizable compound (C), a photopolymerization initiator (D) and a solvent (E)

The alkali-soluble resin (A)

There is provided a colored photosensitive resin composition comprising a monomer derived from a compound represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

R is a C1 to C5 alkylene group which may contain a hydroxyl group at a single bond or side chain or may contain an atom of N, O, S or P in its chain,

R 'is hydrogen or methyl (-CH _3),

Y is a group selected from the groups represented by the following formulas (Y1 to Y4).

 (Y1)

[Y2]

[Y3]

[Y4]

In addition,

And a color filter formed using the colored photosensitive resin composition.

The colored photosensitive resin composition of the present invention contains an alkali-soluble resin into which a long-chain carboxyl group is introduced, thereby providing excellent alkali solubility, chemical resistance and heat resistance. Also, a color filter having improved processability using the colored photosensitive resin composition of the present invention, and a high-quality, high-resolution liquid crystal display device including the same can be provided.

1 is a process diagram for a method of manufacturing a color filter in which a color layer 11 made of the colored photosensitive resin composition of the present invention is formed on a substrate 10.
Fig. 2 is a process diagram for a method of manufacturing a color filter for irradiating the formed color layer 11 with light in a predetermined pattern.
3 is a process diagram for a method of manufacturing a color filter to be developed after light irradiation.

Hereinafter, the present invention will be described in more detail. The following detailed description is merely an example of the present invention, and therefore, the present invention is not limited thereto.

According to the present invention,

(A), a colorant (B), a photopolymerizable compound (C), a photopolymerization initiator (D) and a solvent (E)

The alkali-soluble resin (A)

There is provided a photosensitive resin composition comprising a monomer derived from a compound represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

R is a C1 to C5 alkylene group which may contain a hydroxyl group at a single bond or side chain or may contain an atom of N, O, S or P in its chain,

R 'is hydrogen or methyl (-CH _3),

Y is a group selected from the groups represented by the following formulas (Y1 to Y4).

(Y1)

[Y2]

[Y3]

[Y4]

Hereinafter, the constituent elements of the present invention will be described in detail.

(A) an alkali-soluble resin

The alkali-soluble resin (A) contained in the colored photosensitive resin composition of the present invention enables the unexposed portion of the colored photosensitive resin layer formed using the colored photosensitive resin composition of the present invention to be made alkali-soluble and removed, .

In the prior art, an alkali-soluble resin having a reactive group reactive with UV irradiation was polymerized and substituted with a glycidyl ether group by securing alkali solubility by introducing methacrylic acid or acrylic acid into an alkali-soluble resin. In this case, when the amount of the reactive group introduced into the reactive alkali-soluble resin is small, the reactivity with the photopolymer is reduced and the heat resistance and chemical resistance are deteriorated. On the other hand, if the amount of the reactive group introduced is large, the alkali solubility is lowered and the developability is lowered.

In order to solve such a problem,

There is provided an alkali-soluble resin characterized by containing a monomer derived from a compound represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

R is a C1 to C5 alkylene group which may contain a hydroxyl group at a single bond or side chain or may contain an atom of N, O, S or P in its chain,

R 'is hydrogen or methyl (-CH _3),

Y is a group selected from the groups represented by the following formulas (Y1 to Y4).

(Y1)

[Y2]

[Y3]

[Y4]

The alkali-soluble resin of the present invention contains an alkali-soluble resin capable of ensuring sufficient alkali solubility and at the same time securing solubility and reactivity by substituting a part with a glycidyl ether group by including a monomer derived from the compound represented by the formula The problem of the prior art can be solved.

The alkali-soluble resin (A) may contain the reactive alkali-soluble resin (A ') and the non-reactive alkali-soluble resin (A "

Soluble resin (A ') and the non-reactive alkali-soluble resin (A' ') are preferably in a weight ratio of 8: 2 to 2: 8, more preferably 7: 3 to 3: 7 When the weight ratio is the same as above, the residual film ratio and the degree of curing are excellent, and the taper attraction in the column spacer can be reduced.

The reactive alkali-soluble resin (A ') contained in the alkali-soluble resin (A) exhibits reactivity to the photopolymerization initiator or UV irradiation.

The reactive alkali-soluble resin (A ') may be a copolymer obtained by polymerization of a compound containing the compounds (A1), (A2) and (A3) With (A3) in the presence of a catalyst. Also included in the scope of the present invention is the case where other monomers other than the monomers derived from the compounds (A1) to (A3) are further contained and polymerized.

The compound (A1) contained in the reactive alkali-soluble resin (A ') may be a compound of the following formula (1) or a combination of a compound of the following formula (1) and one or more compounds containing an unsaturated bond and a carboxylic acid group in one molecule .

[Chemical Formula 1]

In Formula 1,

R is a C1 to C5 alkylene group which may contain a hydroxyl group at a single bond or side chain or may contain an atom of N, O, S or P in its chain,

R 'is hydrogen or methyl (-CH _3),

Y is a group selected from the groups represented by the following formulas (Y1 to Y4).

(Y1)

[Y2]

[Y3]

[Y4]

Specific examples of the compound represented by the formula (1) include compounds represented by the following formulas (1-1) to (1-4), but are not limited thereto.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In the above formulas 1-1 to 1-4, R 'may be hydrogen or methyl (-CH ₃ ), but is not limited thereto.

Specific examples of the compound containing an unsaturated bond and a carboxylic acid group within one molecule include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid;

Dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid;

Anhydrides of the dicarboxylic acids;

ω-carboxypolycaprolactone mono (meth) acrylate, and other mono (meth) acrylates of a polymer having a carboxyl group and a hydroxyl group at both terminals, but are not limited thereto.

The (A2) contained in the reactive alkali-soluble resin (A ') is not limited as long as it is a compound having an unsaturated bond polymerizable with the above-mentioned (A1)

Specific examples of the unsaturated carboxylic acid include unsaturated carboxylic acids such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) Unsubstituted or substituted alkyl ester compounds;

(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 (Meth) acrylate, norbornyl (meth) acrylate, pinenyl (meth) acrylate, and tricyclodecyl methacrylate, Unsaturated carboxylic acid ester compounds;

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, phenoxy (meth) acrylate and the like;

Aromatic vinyl compounds such as styrene,? -Methylstyrene, and vinyltoluene;

Carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate, vinyl cyanide compounds such as (meth) acrylonitrile and? -Chloroacrylonitrile;

Maleimide compounds such as N-cyclohexylmaleimide, N-phenylmaleimide and N-benzylmaleimide.

These may be used alone or in combination of two or more. Of these, aromatic vinyl compounds are preferred for improvement of sensitivity and loss of outgas, and they may be used alone or in combination of two or more.

The (meth) acrylate recorded in this specification means acrylate and / or methacrylate.

The (A3) contained in the reactive alkali-soluble resin (A ') is not particularly limited as long as it is a compound having an unsaturated bond and an epoxy group in one molecule, and specific examples thereof include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (Meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, methylglycidyl (meth) acrylate and the like, more preferably glycidyl These may be used alone or in combination of two or more.

The compound (A3) having an unsaturated bond and an epoxy group in one molecule is preferably reacted in an amount of 5 to 80 mol%, more preferably 10 to 80 mol%, based on the molar amount of the compound (A1). (A3) is within the above range, it has an advantage of excellent exposure sensitivity and developability.

The reactive alkali-soluble resin (A ') is a copolymer obtained by reacting the above compounds (A1), (A2) and (A3), and may include a monomer represented by the following formula (2).

 (2)

In Formula 2,

R is a C1 to C5 alkylene group which may contain a hydroxyl group at a single bond or side chain or may contain an atom of N, O, S or P in its chain,

R 'is hydrogen or methyl (-CH _3),

Y is a group selected from the groups represented by the following formulas (Y1 to Y4)

 (Y1)

[Y2]

[Y3]

[Y4]

Z is a C1-C60 alkyl group containing a reactive group, and the alkyl group may include a hydroxyl group and the like.

The reactive group is preferably an acrylate group, but is not limited thereto.

The monomer represented by the formula (2) may preferably include monomers represented by the following formulas (3) to (6), but is not limited thereto.

 (3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

In the present invention, when the (A ') reactive alkali-soluble resin is obtained by copolymerizing the compounds (A1), (A2) and (A3) as an example, for example, the following method can be used.

A solvent in an amount of 0.5 to 20 times the weight of (A1) to (A2) is introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introducing tube, and the atmosphere in the flask is replaced with nitrogen in air. Thereafter, after raising the temperature of the solvent to 40 to 140 캜, a predetermined amount of (A1) and (A2), a solvent of 0 to 20 times the total weight of (A1) and (A2), and a solvent of azobisisobutyl (Solution or solution under stirring at room temperature or under heating) in which 0.1 to 10 mol% of a polymerization initiator such as nitrile or benzoyl peroxide is added relative to the total molar amount of (A1) and (A2) is added over a period of 0.1 to 8 hours And the mixture is stirred at 40 to 140 DEG C for 1 to 10 hours. (A3) in a proportion of 5 to 80 mol% based on the constitutional unit derived from (A1) in the copolymer by polymerization of the compounds containing the above-mentioned (A1) to (A2), as a reaction catalyst of a carboxyl group and an epoxy group, For example, tris-dimethylaminomethylphenol is added in an amount of 0.01 to 5% by weight based on the total weight of (A1) to (A3) and 0.001 to 5% by weight of hydroquinone as a polymerization inhibitor, (A3) can be reacted by reacting the copolymer at 60 to 130 DEG C for 1 to 10 hours.

Further, alpha -methylstyrene dimer or mercapto compound may be used as a chain transfer agent to control molecular weight or molecular weight distribution. The amount of the? -methylstyrene dimer or mercapto compound to be used is 0.005 to 5% by weight based on the total weight of (A1) to (A3). The above-mentioned polymerization conditions may be appropriately adjusted depending on the production equipment or the amount of heat generated by polymerization and the like.

On the other hand, the reactive alkali-soluble resin (A ') contained in the colored photosensitive resin composition of the present invention is not particularly limited as long as other monomers are further polymerized in the copolymer resulting from polymerization of the compounds containing (A1) to (A3) And are included in the scope of the present invention.

That is, by adding other monomers to the copolymer by polymerization of the compounds including (A1) to (A3), light / thermosetting property can be imparted to the alkali-soluble resin to improve heat resistance and chemical resistance.

In the present invention, the reactive alkali-soluble resin (A ') preferably has a weight average molecular weight in terms of polystyrene of 3,000 to 100,000, more preferably 5,000 to 50,000. When the weight average molecular weight of the reactive alkali-soluble resin (A ') is in the range of 3,000 to 100,000, film reduction of the exposed portion is unlikely to occur at the time of development and the solubility of the unexposed portion tends to be good.

 The acid value of the reactive alkali-soluble resin (A ') may preferably be in the range of 30 to 150 mgKOH / g on the solid basis. If the acid value is less than 30 mgKOH / g, the solubility in the alkaline developer may be lowered and the residue may be left on the substrate. If the acid value exceeds 150 mgKOH / g, the possibility of pattern peeling may increase.

The molecular weight distribution of the reactive alkali-soluble resin (A ') may preferably be 1.0 to 6.0, more preferably 1.5 to 4.0. When the molecular weight distribution is 1.0 to 6.0, it may be preferable since the developing property is excellent.

The reactive alkali-soluble resin (A ') can be prepared by polymerizing (A1), (A2) and (A3), and the proportion of the components derived from the compounds is (A1), (A3) is in the following molar ratio range with respect to the total number of moles of constituent components.

(A1): 10 to 60 mol%

(A2): 20 to 70 mol%

(A3): 10 to 60 mol%

When the composition ratio is within the above range, a good balance of alkali solubility and heat resistance is obtained, and thus a preferable copolymer can be obtained.

The non-reactive alkali-soluble resin (A ") which can be contained in the alkali-soluble resin (A) exhibits a photopolymerization initiator and non-reactivity with respect to UV irradiation, and is obtained by polymerization of the compounds including (A1) and But is a non-reactive alkali-soluble resin, which is a copolymer having no unsaturated double bond or triple bond polymerizable within the resin molecular chain after polymerization.

The above-mentioned non-reactive alkali-soluble resin (A ") is also included in the scope of the present invention when, after polymerization, other monomers which do not have an unsaturated bond polymerizable in the chain are further contained.

The (A ") non-reactive alkali-soluble resin used in the present invention can be produced in the same manner as the above-mentioned reactive alkali-soluble resin (A ') except that (A" (A3) contained in the reactive alkali-soluble resin (A3) can not be included because it is required to polymerize in the absence of an unsaturated double bond capable of photopolymerization by a radical photoinitiator. The method example is the same as the general synthesis example of the reactive alkali-soluble resin (A '). Further, the above exemplified materials can be used for (A1) and (A2), respectively.

In the present invention, the (A ") non-reactive alkali-soluble resin preferably has a weight average molecular weight in terms of polystyrene of 3,000 to 100,000, more preferably 5,000 to 40,000. When the weight average molecular weight of the (A ") non-reactive alkali-soluble resin is in the range of 3,000 to 100,000, film reduction of the exposed portion is unlikely to occur during development and the solubility of the unexposed portion tends to be good.

 If the acid value is less than 30 mgKOH / g, the solubility in an alkali developing solution is lowered, and if the acid value of the non-reactive alkali-soluble resin is lower than 30 mgKOH / g, If the acid value exceeds 150 mgKOH / g, there is a possibility that pattern peeling may occur.

The molecular weight distribution of the (A ") non-reactive alkali-soluble resin may be preferably 1.0 to 6.0, more preferably 1.5 to 4.0. If the molecular weight distribution is 1.0 to 6.0, have.

The non-reactive alkali-soluble resin (A ") is a copolymer obtained by polymerization of compounds containing (A1) and (A2) It is preferable that the number of moles is in the following range.

(A1): 2 to 70 mol%

(A2): 30 to 98 mol%

Particularly, it is more preferable that the ratio of the above components is in the following range.

(A1): 10 to 60 mol%

(A2): 40 to 90 mol%

When the composition ratio is within the above range, a good balance of alkali solubility and heat resistance is obtained, and thus a preferable copolymer can be obtained.

The alkali-soluble resin (A) is usually in the range of 7 to 85% by weight, preferably 30 to 75% by weight based on the solid content in the colored photosensitive resin composition. (A) the content of the alkali-soluble resin is 7 to 85 % By weight, the solubility in the developing solution is sufficient, so that development residue is not easily generated on the substrate of the non-pixel portion, the film thickness of the exposed portion is not easily reduced at the time of development, and the solubility of the unexposed portion tends to be good.

(B) Colorant

The colorant (B) contained in the colored photosensitive resin composition of the present invention may be used singly or in combination of two or more kinds selected from the dye (b1) and the pigment (b2).

( b1 ) Dye

The dye (b1) can be used without limitation as long as it has solubility in an organic solvent. However, it is preferable to use a dye having solubility in an organic solvent and securing reliability such as solubility in an alkali developing solution, heat resistance and solvent resistance. Such dyes include compounds classified as dyes in the color index (The Society of Dyers and Colourists), or known dyes described in the dyeing notes (color dyes).

Specific examples of the basic dyes include trianti-methane-based basic dyes, xanthene-based basic dyes including rhodamine-based basic dyes, flavone-based basic dyes, oramine-based basic dyes , A sapphanine-based basic dye, a flocine-based basic dye, and a methylene blue-based basic dye.

Specific examples of the triarylmethane-based basic dyes include C. I. basic violet 1 (methyl violet), C. I. basic violet 3 (crystal violet), and C. I. basic violet 14 (magenta); C. I. basic blue 1 (basic cyanide 6G), C. I. basic blue 5 (basic cyanine EX), C. I. basic blue 7 (victoria pure blue BO), and C.I. Basic Blue 26 (Victoria Blue B conc.); C. I. Basic Green 1 (Brilliant Green GX) and C. I. Basic Green 4 (Malachite Green).

Examples of the rhodamine-based basic dyes include CI Basic Red 1 (Rhodamine 6G, 6GCP) and CI Basic Red 8 (Rhodamine G); And CI basic violet 10 (rhodamine B). As the basic dye of the flavon base, for example, CI Basic Yellow 1 can be mentioned. Examples of the oraminic basic dyes include CI Basic Yellow 2 and CI Basic Yellow 3. As the saprinin basic dye, for example, CI Basic Red 2 can be mentioned. As the floc fresh basic dye, for example, CI Basic Red 12 can be mentioned. Examples of methylene blue basic dyes include CI Basic Blue 9 (methylene blue FZ, methylene blue B), CI Basic Blue 25 (Basic Blue GO), and CI Basic Blue 24 (N-methylene Blue NX) However, it is not limited thereto.

The basic dye may be contained in an amount of 1 to 70% by weight, and preferably 2 to 10% by weight based on the total weight of the solid content of the colored photosensitive resin composition. When the basic dye is included in the above range, there is an advantage that a color filter having excellent transmittance can be realized.

( b2 ) Pigment

The pigment (b2) which can be used as the colorant (B) may be an organic pigment or an inorganic pigment generally used in the art, and it may be preferable to use an organic pigment in view of excellent heat resistance and color development.

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.

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

Particularly, as the above organic pigments and inorganic pigments, compounds classified as pigments in the color index (The Society of Dyers and Colourists) can be used, and more specifically, Pigments, but are not limited thereto.

Specific examples of preferable pigments that can be used in the present invention include

C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 63, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139 , 147, 148, 150, 153, 154, 166, 173, 194 and 214;

C.I. Orange pigments such as Pigment Orange 13, 31, 38, 41, 42, 43, 51, 55, 59, 61, 64, 65, 71 and 73;

C.I. Red pigments such as Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 264 and 265;

C.I. Pigment Blue 15, 15: 3, 15: 4, 15: 6 and 60;

C.I. Violet pigments such as Pigment Violet 1, 19, 23, 29, 32, 36 and 38;

C.I. Green pigments such as Pigment Green 7, 36 and 58;

C.I. Brown pigments such as Pigment Brown 23 and 25;

CI pigment black 1 and black pigment such as 7, and the like.

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 Red 177, C.I. Pigment Red 209, C.I. Pigment Red 254, C.I. Pigment Violet 23, C.I. Pigment Blue 15: 6 and C.I. Pigment Green 36 may be preferably used.

The above organic pigments and inorganic pigments may be used alone or in combination of two or more. For example, to form red pixels, CI Pigment Red 254 and CI Pigment Yellow 139 may be used. To form a green pixel, CI Pigment Green 58, CI Pigment Yellow 150, or CI Pigment Yellow 138 may be used. , And CI Pigment Blue 15: 6 in order to form a blue pixel, respectively.

The organic pigment in the pigment may be subjected to surface treatment using a pigment derivative or the like into which an acidic group or a basic group is introduced, graft treatment of the surface of the pigment with a polymer compound, atomization treatment such as sulfuric acid atomization method (refinement) A cleaning treatment with an organic solvent or water for removing the ionic impurities, or a removal treatment with an ion exchange method or the like of the ionic impurities.

The colorant contained in the colored photosensitive resin composition of the present invention preferably has a uniform particle size. In the case where the coloring agent is a pigment, as an example of a method for uniformly dispersing the particle diameter of the pigment, a pigment dispersing agent is further included and subjected to a dispersion treatment, whereby the pigment is uniformly dispersed in the solution, Can be obtained.

As the pigment dispersant, those generally used in the art can be used without limitation.

Examples of the surfactant include cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, polyester surfactants and polyamines surfactants. These surfactants may be used singly or in combination of two or more.

(Hereinafter referred to as an acrylic dispersant) containing BMA (butyl methacrylate) or DMAEMA (N, N-dimethylaminoethyl methacrylate). At this time, it is preferable to apply the acrylic dispersant prepared by a living control method as disclosed in Korean Patent Publication No. 2004-0014311. DISCLOSURE OF INVENTION It is an object of the present invention to provide an acrylic dispersant, 2000, DISPER BYK-2001, DISPER BYK-2070, and DISPER BYK-2150.

The acrylic dispersants exemplified above may be used alone or in combination of two or more.

The dispersing agent may be a pigment dispersing agent of a resin type other than the acrylic dispersing agent. 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 above acrylic dispersant, other resin type pigment dispersants may be used alone or in combination of two or more, and may be used in combination with an acrylic dispersant.

When a pigment dispersant is used, it is used in an amount of 1 part by weight or less, preferably 0.05 to 0.5 part by weight based on 1 part by weight of the colorant. When the pigment is used in such a content as mentioned above, a pigment in a uniformly dispersed state can be obtained. When the amount is less than 1 part by weight, it may be difficult to atomize the pigment, and gelation may occur after dispersion.

The colorant (B) of the present invention may be used alone or in combination of two or more. The content of the colorant may be 1 to 70% by weight, preferably 20 to 60% by weight based on the total weight of the solid content of the colored photosensitive resin composition. When the colorant is included in the above range, it has an advantage that a color density is sufficient when made into a color filter and a composition polymer can be contained in a required amount in the composition, so that the mechanical strength can form a sufficient pattern.

(C) Photopolymerization  compound

The photopolymerizable compound (C) contained in the colored photosensitive resin composition of the present invention is a compound capable of polymerizing under the action of light and a photopolymerization initiator described later, and includes monofunctional monomers, bifunctional monomers, and other polyfunctional monomers have.

Specific examples of monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone And the like.

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 A, and 3-methylpentanediol di (meth) acrylate.

Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol Acrylate, trimethylolpropane trimethacrylate, tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

Of these, polyfunctional monomers having two or more functionalities can be preferably used, and more preferably, polyfunctional monomers having five or more functionalities can be used.

The photopolymerizable compound (C) may be used in an amount of usually 10 to 60% by weight, preferably 20 to 50% by weight based on the solid content in the colored photosensitive resin composition. When the photopolymerizable compound (C) is in the range of 10 to 60% by weight based on the above-mentioned criteria, the strength of the pixel portion, the residual film ratio according to the progress of the process, and the contact hole characteristics tend to be favorable.

(D) Photopolymerization initiator

The photopolymerization initiator (D) contained in the colored photosensitive resin composition of the present invention is not particularly limited, but is at least one compound selected from the group consisting of triazine-based compounds, acetophenone-based compounds, nonimidazole-based compounds and oxime compounds. The colored photosensitive resin composition containing the photopolymerization initiator (D) described above has high sensitivity, and therefore, the film formed using this composition has good strength and contact hole characteristics of the pixel portion.

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.

Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2- (4-methylthioxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2- 2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1-one, 1-one oligomers and the like. Further, a compound represented by the following general formula (7) may be mentioned.

(7)

In Formula 7,

R 1 to R 4 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group substituted with an alkyl group having 1 to 12 carbon atoms, a benzyl group substituted or unsubstituted with an alkyl group having 1 to 12 carbon atoms, Or a naphthyl group substituted or unsubstituted with an alkyl group.

Specific examples of the compound represented by Formula 7 include 2-methyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-ethyl- 1-one, 2-propyl-2-amino (4-morpholinophenyl) ethan- (4-morpholinophenyl) propane-1-one, 2-amino-2- 2-methyl-2-methylamino (4-morpholinophenyl) propane-1-one, 1-one, 2-methyl-2-dimethylamino (4-morpholinophenyl) propan- have.

Examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis -Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4' Imidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, phenyl group at 4,4' An imidazole compound substituted by a haloalkoxy group, and the like. Of these, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- 5,5'-tetraphenylbiimidazole is preferably used.

Examples of the oxime compounds include the following chemical formulas (8), (9) and (10).

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

Further, as long as the effect of the present invention is not impaired, other photopolymerization initiators generally used in this field can be further used in combination. Examples of other photopolymerization initiators include benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and anthracene-based compounds. These may be used alone or in combination of two or more.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and the like.

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 4,4'-di (N, N'-dimethylamino) -benzophenone.

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

Examples of the anthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, .

Other examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenylclyoxylic acid Methyl, titanocene compounds and the like can be mentioned as other photopolymerization initiators.

According to a preferred embodiment of the present invention, when the photopolymerization initiator (D-1) is used in combination with the photopolymerization initiator (D-1), the colored photosensitive resin composition containing the photopolymerization initiator is more sensitive, The productivity can be improved.

The (D-1) photopolymerization initiation assistant which can be used in combination with the photopolymerization initiator (D) of the present invention is preferably at least one compound selected from the group consisting of an amine compound and a carboxylic acid compound.

Specific examples of the amine compound in the (D-1) photopolymerization initiation assistant include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine;

4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4- Aromatic amine compounds such as bis (dimethylamino) benzophenone (commonly known as Michler's ketone) and 4,4'-bis (diethylamino) benzophenone; And the like. As the amine compound, an aromatic amine compound is preferably used.

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

The content of the photopolymerization initiator (D) in the colored photosensitive resin composition of the present invention may be from 0.1 to 20% by weight, preferably from 1 to 10% by weight, based on the total solid content in the colored photosensitive resin composition, ) The amount of the photopolymerization initiator to be used is usually 0.1 to 20% by weight, preferably 1 to 10% by weight based on the above-mentioned criteria.

When the amount of the photopolymerization initiator (D) is in the above range, the colored photosensitive resin composition may be highly sensitized and the strength of the pixel portion and the smoothness on the surface of the pixel portion tend to be good. When the amount of the photopolymerization initiator (D-1) used is within the above range, the sensitivity of the colored photosensitive resin composition is further increased and the productivity of the color filter formed using the composition tends to be improved. have.

(E) Solvent

The solvent (E) contained in the colored photosensitive resin composition of the present invention is not particularly limited and various organic solvents used in the field of the photosensitive resin composition can be used.

Specific examples of the solvent (E) include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol 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 dialkyl ethers such as propylene glycol monomethyl ether; Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl 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; Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin; Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; cyclic esters such as? -butyrolactone; And the like.

Among the above-mentioned solvents, organic solvents having a boiling point of 100 to 200 DEG C in the solvent are preferably used from the viewpoint of coatability and dryness, more preferably alkylene glycol alkyl ether acetates, ketones, 3-ethoxy Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxypropionate, and the like, and more preferably, an ester such as ethyl propionate or methyl 3-methoxypropionate. More preferred examples thereof include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Ethyl methoxypropionate, methyl 3-methoxypropionate, and the like.

These (E) solvents may be used alone or in combination of two or more.

The content of the (E) solvent in the colored photosensitive resin composition of the present invention may be generally 30 to 90% by weight, preferably 30 to 80% by weight based on the total amount of the colored photosensitive resin composition containing the solvent. When the content of the solvent (E) is in the range of 30 to 90% by weight based on the above-mentioned criteria, it may be applied by a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater) It may be preferable since the coating property tends to be good.

(F) Additive

The colored photosensitive resin composition of the present invention may further include UV stabilizers, fillers, other polymer compounds, curing agents, dispersants, adhesion promoters, antioxidants, and anti-aggregation agents as necessary in addition to the above components.

The UV stabilizer is included in the colored photosensitive resin composition to ensure light resistance.

Specific examples of the UV stabilizer include benzophenone derivatives, benzoate derivatives, benzotriazole derivatives, triazine derivatives, benzothiazole derivatives, cinnamate derivatives, anthranilate derivatives and dibenzoylmethane derivatives.

Specific examples of the benzophenone derivative include 2-hydroxy-4-methoxy-benzophenone 2-hydroxy-4-methoxybenzophenone, 2-hydroxy- Dihydroxy-4-methoxybenzophenone, and 2,4-dihydroxybenzophenone.

Specific examples of the benzoate derivative include 2-ethylhexyl salicylate, phenyl salicylate, p-tart-butylphenyl salicylate, 2,4-di-tart- -4-hydroxybenzoate, and hexadecyl-3,5-di-tart-butyl-4-hydroxybenzoate.

Specific examples of the benzotriazole derivatives include 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- 5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di- Benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tart-amylphenyl) benzotriazole and the like .

Specific examples of the triazine derivatives include hydroxyphenyltriazine and bisethylhexyloxyphenol methoxyphenyltriazine.

The UV stabilizer may also be a commercially available one such as TINUVIN PS, TINUVIN 99-2, INUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 479, TINUVIN 1577 , CHIMASSORB81 (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name), and the like.

The UV stabilizer may preferably have a maximum absorption region at 350 nm or less (inclusive of j-line) in the wavelength region. A UV stabilizer having a maximum absorption region of 350 nm or more may weaken the irradiation intensity of i-line. From the viewpoint of the structure of the UV stabilizer, benzophenone derivatives and triazine derivatives have a good absorption region at 350 nm or less. Commercially available products include TINUVIN 400, TINUVIN 1577, CHIMASSORB81, and the like.

The above UV stabilizers can be used singly or in combination of two or more kinds, and the light resistance and yellowing of the colored photosensitive resin composition of the present invention can be prevented.

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

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

The curing agent is used for increasing the hardness of the deep portion and the mechanical strength. Examples of the curing agent include an epoxy compound, a polyfunctional isocyanate compound and an oxetane compound.

Examples of the epoxy compound in the curing agent include a bisphenol A epoxy resin, a hydrogenated bisphenol A epoxy resin, a bisphenol F epoxy resin, a hydrogenated bisphenol F epoxy resin, a Novolak epoxy resin, an aromatic epoxy resin, Based epoxy resins, glycidyl ester-based resins, glycidylamine-based resins, aliphatic, alicyclic or aromatic epoxy compounds other than the brominated derivatives, epoxy resins and brominated derivatives of such epoxy resins, butadiene (co) polymeric epoxides , Isoprene (co) polymer epoxides, glycidyl (meth) acrylate (co) polymers, and triglycidyl isocyanurate.

Examples of the oxetane compound in the curing agent include carbonates such as carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, cyclohexanedicarboxylic acid bisoxetane, and the like. have.

The curing agent may further comprise a curing auxiliary compound capable of ring-opening polymerization of an epoxy group of an epoxy compound and an oxetane skeleton of an oxetane compound together with a curing agent. Examples of the curing aid compound include polyvalent carboxylic acids, polyvalent carboxylic anhydrides, acid generators, and the like. As the carboxylic acid anhydrides, those commercially available as epoxy resin curing agents can be used. As the epoxy resin curing agent, for example, there may be mentioned epoxy resin curing agents such as trade name (ADEKA HARDONE EH-700) (ADEKA INDUSTRY CO., LTD.), Trade name (RICACIDO HH) Manufactured by Shin-Etsu Chemical Co., Ltd.). These curing agents may be used alone or in combination of two or more.

As the dispersing agent, a commercially available surfactant can be used, and examples thereof include surfactants such as silicone, fluorine, ester, cationic, anionic, nonionic, and amphoteric surfactants. These may be used alone or in combination of two or more. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethanes (Manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by TOKEM PRODUCTS CO., LTD.), And polyethyleneimine, (Manufactured by Asahi Glass Co., Ltd.), Surfon (manufactured by Asahi Glass Co., Ltd.), Mitsubishi Kasei Kogyo Co., Ltd., MEGAFAC (manufactured by Dainippon Ink and Chemicals Inc.), Flourad (manufactured by Sumitomo 3M Limited), Asahi guard, Surflon SOLSPERSE (manufactured by Genene), EFKA (manufactured by EFKA Chemical), PB 821 (manufactured by Ajinomoto), and the like.

Each of these dispersants may be used alone or in combination of two or more, and may be contained in an amount of usually 0.01 to 15% by weight based on the solid content in the colored photosensitive resin composition.

Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane , N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- Propyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and the like. These adhesion promoters may be used alone or in combination of two or more, and may contain 0.01 to 10% by weight, preferably 0.05 to 2% by weight, based on the solid content in the colored photosensitive resin composition.

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

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

The colored photosensitive resin composition for pixel formation of the present invention can be produced, for example, by the following method. (A) an alkali-soluble resin, (B) a colorant, (C) a photopolymerizable compound, (D) a photopolymerization initiator and (E) a solvent in appropriate proportions and further adding other components, A colored photosensitive resin composition can be obtained.

Hereinafter, a pattern forming method using the colored photosensitive resin composition according to the present invention will be described.

The method for forming a pattern of a colored photosensitive resin composition for forming a pixel according to the present invention includes the steps of applying the above-mentioned colored photosensitive resin composition for pixel formation onto a substrate, 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.

As an example thereof, it is coated on a substrate as follows to form a pattern by photo-curing and development, and it can be used in the production of a black matrix or a colored pixel.

More specifically, the composition is first applied on a substrate (not limited to a glass or silicon wafer in general) or a layer containing a solid component of a colored photosensitive resin composition formed in advance, and preliminarily dried to remove volatile components such as a solvent, To obtain a coated film. The thickness of the coating film at this time is usually about 1 to 3 mu m. Ultraviolet rays are applied to a specific region through a mask to obtain a desired pattern on the thus obtained coating film. At this time, it is preferable to use an apparatus such as a mask aligner or a stepper so that the entire exposed portion is uniformly irradiated with parallel rays, and the mask and the substrate are accurately positioned. Thereafter, the coated film after curing is brought into contact with the aqueous alkaline solution to dissolve and expose the non-exposed region, thereby making it possible to produce a desired pattern. After development, if necessary, post-drying may be performed at about 150 to 230 DEG C for about 10 to 60 minutes.

On the other hand, the developer used for development after patterned exposure may be 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 hydrogen phosphate, sodium dihydrogen phosphate, ammonium dihydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, Potassium hydrogen carbonate, 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, monoiso Propylamine, diisopropylamine, ethanolamine, and the like. These inorganic and organic alkaline compounds may be used alone or in combination of two or more.

The preferred concentration of the alkaline compound in the alkaline developer may be in the range of 0.01 to 10% by weight, more preferably 0.03 to 5% by weight.

The surfactant in the alkaline developer may be any of a nonionic surfactant, an anionic surfactant or 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 lauryl alcohol sulfate ester and sodium oleyl alcohol sulfate ester, alkylsulfates such as sodium laurylsulfate and ammonium laurylsulfate, sodium dodecylbenzenesulfonate And alkylarylsulfonic acid salts such as 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 alkali developer is usually 0.01 to 10% by weight, preferably 0.05 to 8% by weight, more preferably 0.1 to 5% by weight.

The present invention also provides a color filter formed using the colored photosensitive resin composition of the present invention and a liquid crystal display device including the color filter.

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

The present invention provides a color filter comprising a color layer formed by applying a colored photosensitive resin composition on a substrate and formed by exposure and development in a predetermined pattern, wherein the colored photosensitive resin composition is used do. A partition wall may be further formed between each coloring pattern, or a black matrix may be added. Further, a protective film may be further formed on the color filter shown. Figs. 1 to 3 are process drawings for a method of manufacturing a color filter using the above-mentioned colored photosensitive resin composition.

In order to form a colored pattern, the colored photosensitive resin composition of the present invention is patterned. Specifically, a color layer 11 composed of a colored photosensitive resin composition is formed on the substrate 10 (FIG. 1), the color layer 11 formed thereon is irradiated with a predetermined pattern (FIG. 2) (Fig. 3). The substrate 10 is not limited, and may be a substrate of the color filter itself, or may be a portion where a color filter is placed in a display device or the like.

The substrate may be a glass plate, a silicon wafer, a plastic plate such as PES (Polyether Sulfone), PC (Poly Carbonate) or the like. That is, the substrate may be silicon (Si), silicon oxide (SiO _x ), a glass substrate, or a polymer substrate. In order to form the layer 11 made of the colored photosensitive resin composition on the substrate 10, for example, a colored photosensitive resin composition diluted with a solvent may be spun, slit after spin, slit, roll, spray, After coating on a substrate by a coating method, volatile components such as solvents are volatilized. Thereby, a color layer 11 made of a colored photosensitive resin composition is formed, wherein the color layer is composed of solid components of the colored photosensitive resin composition and hardly contains volatile components. The thickness of the film surface is determined by the coating conditions such as the viscosity of the composition, the concentration of the solid content, the coating speed, and the like. When the composition of the present invention is used, the color layer 11 having a thickness of 0.5 to 5 탆 can be obtained.

Thereafter, the color layer 11 made of the colored photosensitive resin composition is exposed to light. In order to expose, for example, the color layer is irradiated with a predetermined pattern through the photomask 20. As the light, g-line (wavelength: 436 nm), h-line and i-line (wavelength: 365 nm) of ultraviolet rays are mainly used. The light rays pass according to the pattern of the photomask. The photomask provides a light-shielding layer for shielding a light beam on a surface of a glass plate in a predetermined pattern. The light beam is shielded by the shielding layer. The portion of the glass plate on which the light-shielding layer is not provided is a light-transmitting portion through which light rays pass. According to the pattern of the light transmitting portion, the color layer 11 is exposed. The irradiation dose of the light ray is appropriately selected according to the used colored photosensitive resin composition.

The portion irradiated with the light ray has a much lower solubility than the portion irradiated with no light ray, so that the difference in solubility between the two portions is maximized. Developed after exposure. For the development, for example, the colored photosensitive resin composition layer after exposure is immersed in a developer. As the developer, an alkaline compound such as an aqueous solution of sodium carbonate, sodium hydroxide, potassium hydroxide, potassium carbonate, tetramethylammonium hydroxide or the like is used. By the development, the light ray unirradiated region not irradiated with the light ray of the colored photosensitive resin composition layer is removed. On the contrary, the light-irradiated region irradiated by the light ray remains to constitute a coloring pattern.

After the development, the layer is washed with ordinary water and dried to obtain a predetermined coloring pattern. After drying, a heat treatment may be performed. The colored pattern formed by the heat treatment is cured and its mechanical strength is improved. Since the mechanical strength of the colored pattern can be improved by the heat treatment, it is preferable to use a colored photosensitive resin composition containing a curing agent. The heating temperature is usually 180 ° C or higher, preferably 200 to 250 ° C.

The color filter may be manufactured in the same manner as described above, but the present invention is not limited thereto, and the constitution and the manufacturing method may be applied using conventional methods well known in the art within the scope of the present invention.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the embodiments of the present invention described below are merely examples, and the scope of the present invention is not limited to these embodiments. The scope of the present invention includes all changes within the meaning and range of equivalence, as well as the scope of the claims.

In the following Examples and Comparative Examples, "%" and "part" representing the content are based on weight unless otherwise specified.

< Synthetic example >

Synthesis Example 1 : Alkali-soluble resin ( a1 ) Synthesis of

50 parts by weight of 2- (methacryloyloxy) ethyl phthalate mono, 40 parts by weight of N-benzylmaleimide, 40 parts by weight of tricyclo 10 parts by weight of decyl methacrylate, 4 parts by weight of t-butylperoxy-2-ethylhexanoate and 40 parts by weight of propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA") were added and stirred, A lot was prepared, 6 parts by weight of n-dodecanethiol and 24 parts by weight of PGMEA were added and stirred to prepare a chain transfer agent drop-lot.

Thereafter, 395 parts by weight of PGMEA was introduced into the flask, the atmosphere in the flask was changed to nitrogen in air, and the temperature of the flask was raised to 90 DEG C while stirring. Then, the monomer and the chain transfer agent were added dropwise from the dropping funnel. The mixture was heated to 110 ° C for 1 h and held at this temperature for 3 hours. After cooling to room temperature, a resin having a solid content of 29.1% by weight and a weight average molecular weight of 20,000 and an acid value of 100 mgKOH / g a1.

Synthetic example  2: Alkali-soluble resin ( a2 ) Synthesis of

An alkali-soluble resin was synthesized in the same manner as in Synthesis Example 1, and the temperature was maintained at 90 占 폚 for 2 hours, and the temperature was elevated to 110 占 폚 for 1 hour and maintained for 3 hours. Then, Bubbling of 5/95 (v / v) mixed gas was started. Subsequently, 25 parts by weight of glycidyl methacrylate, 0.4 part by weight of 2,2'-methylenebis (4-methyl-6-t-butylphenol) and 0.8 part by weight of triethylamine were charged into a flask, The reaction was continued and then cooled to room temperature to obtain a resin a2 having a solid content of 29.1 wt% and a weight average molecular weight of 23,000 and an acid value of 50 mgKOH / g.

Synthesis Example 3 : Alkali-soluble resin ( a3 ) Synthesis of

15 parts by weight of hydroxy methacrylate, 40 parts by weight of N-benzylmaleimide, 35 parts by weight of methacrylic acid, 0.1 part by weight of tri 10 parts by weight of cyclodecyl methacrylate, 4 parts by weight of t-butylperoxy-2-ethylhexanoate and 40 parts by weight of propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA") were added and stirred to obtain a monomer A dropping lot was prepared, 6 parts by weight of n-dodecanethiol and 24 parts by weight of PGMEA were added and stirred to prepare a chain transfer agent dropping lot.

Thereafter, an alkali-soluble photosensitive resin was synthesized in the same manner as in Synthesis Example 1. A resin a3 having a solid content of 29.1% by weight, a weight average molecular weight of 20,000 and an acid value of 110 mgKOH / g was obtained.

Synthesis Example 4 : Alkali-soluble resin ( a4 ) Synthesis of

An alkali-soluble resin was synthesized in the same manner as in Synthesis Example 3, and glycidyl methacrylate was added in the same manner as in Synthesis Example 2 to synthesize an alkali-soluble photosensitive resin. A resin a4 having a solid content of 29.1% by weight and a weight average molecular weight of 24,000 and an acid value of 80 mgKOH / g was obtained.

Molecular weight evaluation

The weight average molecular weight (Mw) of the alkali-soluble resin (A) was 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 amount: 50 μl

Detector: RI

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

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

Solids

The polymer solution was weighed in an amount of about 1 g into an aluminum cup, and about 3 g of acetone was added to dissolve it, followed by natural drying at room temperature. Using a hot-air drier (trade name: PHH-101, manufactured by Espec Co., Ltd.), it was dried in a vacuum at 160 ° C for 3 hours, and then cooled in a desiccator and its weight was measured. The solid content of the polymer solution was calculated from the weight reduction amount.

Acid value

3 g of the resin solution was subjected to crystallization and dissolved in a mixed solvent of 90 g of acetone and 10 g of water. Using an automatic titration apparatus (manufactured by Hiranuma Industrial Co., Ltd., trade name: COM- 555), and the acid value per 1 g of the solid content was determined from the acid value of the solution and the solid content of the solution.

< Example  And Comparative Example >

Example  1 to 12 and Comparative Example  1 to 12: Preparation of colored photosensitive resin composition

Of the components shown in Table 1 below, 20 parts by weight of the coloring agent (B) was mixed in advance with respect to 100 parts by weight of the mixture of the solvent propylene glycol monomethyl ether acetate.

Thereafter, the bead mill was sufficiently dispersed using a bead mill, and the remaining components including the remaining amount of propylene glycol monomethyl ether acetate were further added and mixed to obtain a colored photosensitive resin composition having the composition shown in Table 1 below. The units in Table 1 are parts by weight.

Item Example Comparative Example One 2 3 4 One 2 3 4 The alkali-soluble resin (A) Synthesis Example 1 6.03 4.02 2.01 5.82 Synthesis Example 2 2.01 4.02 6.03 5.82 Synthesis Example 3 6.03 4.02 2.01 5.82 Synthesis Example 4 2.01 4.02 6.03 5.82 The photopolymerizable compound (C) 14.38 10.78 14.38 10.785 Photopolymerization initiator (D) 3.59 Solvent (E) 62.55 The colorant (B) C. I. Pigment Red 254 4.69 C.I Pigment Red 177 6.75 Item Example Comparative Example 5 6 7 8 5 6 7 8 The alkali-soluble resin (A) Synthesis Example 1 0.95 1.89 2.84 4.29 Synthesis Example 2 2.84 1.89 0.95 4.29 Synthesis Example 3 0.95 1.89 2.84 4.29 Synthesis Example 4 2.84 1.89 0.95 4.29 The photopolymerizable compound (C) 28.71 23.93 28.71 23.93 Photopolymerization initiator (D) 5.62 Solvent (E) 47.79 The colorant (B) C.I Pigment Green 58 10.99 C.I Pigment Yellow 138 3.10 Item Example Comparative Example 9 10 11 12 9 10 11 12 The alkali-soluble resin (A) Synthesis Example 1 15.22 10.87 6.52 13.68 Synthesis Example 2 6.52 10.87 15.22 13.68 Synthesis Example 3 15.22 10.87 6.52 13.68 Synthesis Example 4 6.52 10.87 15.22 13.68 The photopolymerizable compound (C) 28.06 22.45 28.06 22.45 Photopolymerization initiator (D) 7.3 Solvent (E) 32.09 The colorant (B) C.I Pigment Blue 15: 6 9.07 C.I Pigment Violet 23 1.73

week)

(C) Photopolymerization  compound

Dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)

(D) Photopolymerization initiator

1,2-octanediol, 1- [4- (phenylthio) -, 2- (O-benzoyloxime)] (IRGACURE OXE01, manufactured by Ciba Specialty Chemicals)

(E) Solvent

Propylene glycol monomethyl ether acetate (PGMEA)

<Color filter Manufacturing example >

A color filter was prepared using the colored photosensitive resin compositions prepared in Examples 1 to 12 and Comparative Examples 1 to 12. Each of the colored photosensitive resin composition solutions was 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 line / space pattern of 1 μm to 50 μm was placed on the thin film and irradiated with ultraviolet rays at a distance of 100 μm from the test photomask. At this time, the ultraviolet light source was irradiated with a light pressure 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 and developed in a KOH aqueous solution of pH 10.5 for 1 minute. The glass plate coated with the thin film was washed with distilled water, dried by blowing nitrogen gas, and heated in a 220 ° C heating oven for 1 hour to prepare a color filter. The film thickness of the color filter prepared above was 2.4 mu m.

< Experimental Example > Characterization of color filters

The surface characteristics, development speed, NMP chemical resistance, residue, heat resistance, etc. of the color filter prepared in the above production example were measured and evaluated as follows, and the results are shown in Table 2 below.

Coating film  Evaluation of surface characteristics

Each of the colored photosensitive resin compositions of Examples 1 to 12 and Comparative Examples 1 to 12 was coated on a glass substrate and allowed to stand at 230 占 폚 for 10 minutes to confirm the surface of the coated film by an optical microscope.

[Evaluation criteria for surface characteristics]

O: No foreign matter

Δ: When the surface is opaque

X: Foreign body

Development speed and Residue  evaluation

Each of the colored photosensitive resin compositions of Examples 1 to 12 and Comparative Examples 1 to 12 was coated on a glass substrate by a spin coating method and then placed on a heating plate and maintained at a temperature of 100 캜 for 3 minutes to form a thin film. After irradiating ultraviolet rays of 50 mJ / cm ^{2 with} the front exposure, the film thickness of the pattern was measured using a film thickness measuring apparatus (DEKTAK 6M; Veeco). The substrate having undergone the thickness measurement was again immersed in a KOH aqueous solution of pH 10.5 for 80 seconds to develop and then the presence of the colored photosensitive resin composition was confirmed in the unexposed portion.

[Development rate evaluation criteria]

The time taken for the unexposed area to completely dissolve in the developing solution was measured and shown. And the case where the development can not be performed is represented by 'x'.

[Residue evaluation criteria]

O: If not remaining

?: Remained above 0% to below 20%

X: 20% or more remains

Heat resistance evaluation

The heat resistance was evaluated by measuring the color change value (ΔEab) after heating at 230 ° C. for 120 minutes. △ Eab is the value required by the following saturation formula by the CIE 1976 (L *, a *, b *) spatial colorimetric system (New Color Science Handbook (1986) p.266).

? E * ab = {(? L) 2 + (? A) 2+ (? B) 2} 1/2

[Criteria for evaluation of heat resistance]

?:? E * ab = less than 3

Δ: ΔE * ab = 3 or more to 5 or less

X: DELTA E * ab exceeding 5

NMP  Chemical resistance evaluation

The color filter prepared in the above Preparation Example was immersed in N-methyl-2-pyrolidone (NMP) solution at 80 ° C for 30 minutes, and color difference before and after immersion was confirmed.

[Evaluation Criteria for NMP Chemical Resistance]

When the value of O: DELTA E * ab is 3 or less

If X: ΔE * ab is greater than 3

Coated  Surface property Development speed (s) Residue Heat resistance NMP  Chemical resistance Example 1 O 13 O O O Example 2 O 16 O O O Example 3 O 20 O O O Example 4 O 18 O O O Example 5 O 15 O O O Example 6 O 19 O O O Example 7 O 24 O O O Example 8 O 21 O O O Example 9 O 9 O O O Example 10 O 14 O O O Example 11 O 19 O O O Example 12 O 16 O O O Comparative Example 1 X 20 O X X Comparative Example 2 △ 26 △ △ X Comparative Example 3 X 39 X X △ Comparative Example 4 X 34 X X △ Comparative Example 5 △ 26 O △ X Comparative Example 6 △ 29 △ X X Comparative Example 7 X 41 X X △ Comparative Example 8 X 36 X X △ Comparative Example 9 X 21 O X O Comparative Example 10 X 29 X X △ Comparative Example 11 △ 38 △ X X Comparative Example 12 X 33 △ X X

As can be seen from Table 2, the color filters prepared by using the colored photosensitive resin compositions of Examples 1 to 12 were excellent in surface characteristics of the coating film, excellent in the developing speed, chemical resistance of NMP, residual residue and heat resistance I could confirm. On the other hand, the color filters prepared by using the colored photosensitive resin compositions of Comparative Examples 1 to 12 showed that no foreign matter was generated or developed on the surface of the coating film, or residues were formed after development, and the chemical characteristics in the NMP were poor .

11: Color layer
10: substrate
20: Photomask
30: Light
11R: formed color layer

Claims (8)

(A), a colorant (B), a photopolymerizable compound (C), a photopolymerization initiator (D) and a solvent (E)
The alkali-soluble resin (A)
A colored photosensitive resin composition comprising a monomer derived from a compound represented by the following formula (1).
[Chemical Formula 1]

In Formula 1,
R is a C1 to C5 alkylene group which may contain a hydroxyl group at a single bond or side chain or may contain an atom of N, O, S or P in its chain,
R 'is hydrogen or methyl (-CH _3),
Y is a group selected from the groups represented by the following formulas (Y1 to Y4).
(Y1)

[Y2]

[Y3]

[Y4]

The method according to claim 1,
Wherein the alkali-soluble resin is a copolymer further comprising a monomer represented by the following formula (2).
(2)

In Formula 2,
R is a C1 to C5 alkylene group which may contain a hydroxyl group at a single bond or side chain or may contain an atom of N, O, S or P in its chain,
R 'is hydrogen or methyl (-CH _3),
Y is a group selected from the groups represented by the following formulas (Y1 to Y4)
(Y1)

[Y2]

[Y3]

[Y4]

Z is a C1-C60 alkyl group containing a reactive group.
The method according to claim 1,
Wherein the compound of Formula 1 is at least one selected from the group consisting of the following Formulas 1-1 to 1-4.
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In the above Chemical Formulas 1-1 to 1-4, R 'is hydrogen or methyl (-CH ₃ ).
The method of claim 2,
Wherein the reactive group is an acrylate group. The method according to claim 1,
As to the solid content in the colored photosensitive resin composition,
7 to 85% by weight of an alkali-soluble resin;
1 to 70% by weight of a colorant;
10 to 60% by weight of photopolymerizable compound; And
0.1 to 20% by weight of a photopolymerization initiator; / RTI &gt;
Based on the total weight of the colored photosensitive resin composition,
And 30 to 90% by weight of a solvent. The method according to claim 1,
The alkali-soluble resin (A) may be a photopolymerization initiator or a reactive alkali-soluble resin (A ') exhibiting reactivity against UV irradiation; And
A photopolymerization initiator, and a non-reactive alkali-soluble resin (A ") which exhibits non-reactivity to UV irradiation. A color filter formed using the colored photosensitive resin composition according to any one of claims 1 to 6. A liquid crystal display device comprising the color filter of claim 7.

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