KR20160064393A - 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 colored photosensitive resin composition of the present invention comprises: (A) an alkali soluble resin; (B) a coloring agent; (C) a photopolymerizable compound; (D) a photopolymerization initiator; and (E) a solvent. The alkali soluble resin includes a monomer derived from a compound represented by chemical formula 1; and a monomer having an aliphatic polycyclic epoxy group. The colored photosensitive resin composition extends the chain of carboxylic groups on the side chains, thereby having excellent storage stability, reactivity, chemical resistance, and alkali solubility.

Description

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

The present invention relates to a colored photosensitive resin composition, a color filter including the same and a liquid crystal display device, and more particularly to a colored photosensitive resin composition having excellent adhesion and chemical resistance, a color filter manufactured using the same, .

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.

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)

A monomer derived from a compound represented by the following formula (1); And

Monomers having an aliphatic polycyclic epoxy group; Wherein the photosensitive resin composition is a photosensitive resin composition.

[Chemical Formula 1]

In Formula 1,

R is a C2-C6 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 photosensitive resin composition of the present invention can provide properties of excellent alkali solubility, storage stability, chemical resistance and heat resistance by including an alkali-soluble resin having a carboxyl group and a polyvalent aliphatic polycyclic group. 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)

A monomer derived from a compound represented by the following formula (1); And

Monomers having an aliphatic polycyclic epoxy group; The present invention provides a photosensitive resin composition.

[Chemical Formula 1]

In Formula 1,

R is a C2-C6 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, when the amount of the reactive group introduced is large, the alkali solubility is lowered and the developability is deteriorated.

In order to solve such a problem,

A monomer derived from a compound represented by the following formula (1); And

Monomers having an aliphatic polycyclic epoxy group; An alkali-soluble resin.

[Chemical Formula 1]

In Formula 1,

R is a C2-C6 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 (A) may contain the reactive alkali-soluble resin (A ') and the non-reactive alkali-soluble resin (A ") either singly or in combination.

(A ') and the non-reactive alkali-soluble resin (A'') is preferably in a weight ratio of 9: 1 to 1: 9, 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 formed by polymerization of a compound containing the compounds (A1), (A2), (A3) and (A4) ) And (A3) with (A4). Also included in the scope of the present invention is the case where other monomers are included and polymerized in addition to the monomers derived from the compounds (A1) to (A4).

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 C2-C6 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 compound (A2) contained in the reactive alkali-soluble resin (A ') is preferably a compound having an aliphatic polycyclic epoxy group and a polymerizable unsaturated double bond, and is preferably at least one selected from the following formulas (I) to (II).

(I)

≪ RTI ID = 0.0 &

In the above general formulas (I) to (II)

R is independently hydrogen or a C1-C4 alkyl group, and the alkyl group may include a hydroxyl group,

X is a C1-C6 alkylene group which may contain at least one member selected from N, O, S and P in a single bond or a chain.

The above-mentioned (A2) is contained in the reactive alkali-soluble resin (A ') and plays a role of improving heat resistance and permeability.

The (A3) contained in the reactive alkali-soluble resin (A ') is not limited as long as it is a compound having an unsaturated bond polymerizable with (A1) and (A2)

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 An unsaturated carboxylic acid ester compound containing an alicyclic substituent group such as a phenanthryl (meth) acrylate, adamanthyl (meth) acrylate, norbornyl (meth) acrylate or pinenyl (meth) acrylate;

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.

(A4) contained in the reactive alkali-soluble resin (A ') is not 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 (A4) having an unsaturated bond and an epoxy group in the molecule has a molar ratio of 5 to 5 based on the number of moles of the compound (A1) contained in the copolymer by polymerization of the compounds containing (A1), (A2) To 80 mol%, and more preferably from 10 to 80 mol%. (A4) is within the above-mentioned range, it has an advantage of excellent exposure sensitivity and developability.

The reactive alkali-soluble resin (A ') may include a monomer represented by the following formula (5) as a copolymer obtained by the reaction of the compounds (A1), (A2), (A3) and (A4)

[Chemical Formula 5]

In Formula 5,

R is a C2-C6 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.

 Specific examples of the monomer represented by the formula (5) include monomers represented by the following formulas (6) to (9), but are not limited thereto.

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

In the present invention, the reactive alkali-soluble resin (A ') is obtained, for example, by copolymerizing the compounds (A1), (A2), (A3) and (A4) .

A solvent in an amount of 0.5 to 20 times the weight of (A1) to (A3) 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) to (A3), a solvent of 0 to 20 times the total weight of (A1) to (A3), and a solvent of azobisisobutyl A solution in which 0.1 to 10 mol% of a polymerization initiator such as nitrile or benzoyl peroxide is added to the total molar amount of (A1) to (A3) (stirring or dissolving at room temperature or under heating) is carried out for 0.1 to 8 hours And the mixture is stirred at 40 to 140 DEG C for 1 to 10 hours. (A4) in a proportion of 5 to 80% by mole with respect to the constitutional unit derived from (A1) in the copolymer by polymerization of the compounds including (A1) to (A3), 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 (A4), and 0.001 to 5% by weight of hydroquinone as a polymerization inhibitor, for example, (A) can be reacted with the above-mentioned copolymer by reacting at 60 to 130 ° 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 (A4). 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 photosensitive resin composition of the present invention is not particularly limited as long as another monomer is further contained in the copolymer resulting from the polymerization of the compounds (A1) to (A4) And are included in the scope of the invention.

That is, by adding other monomers to the copolymer by polymerization of the compounds including (A1) to (A4), 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 40,000, more preferably 5,000 to 30,000. When the weight average molecular weight of the reactive alkali-soluble resin (A ') is in the range of 3,000 to 40,000, film reduction of the exposed portion is unlikely to occur during 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 produced by polymerizing (A4) in (A1), (A2) and (A3), and the proportion of the components derived from the above- (A2), (A3) and (A4) in the following range.

(A1): 10 to 60 mol%

(A2): 20 to 70 mol%

(A3): 10 to 60 mol%

(A4): 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 to UV irradiation, and is obtained by polymerization of the compounds containing (A1) to (A3) 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.

In other words, the above-mentioned non-reactive alkali-soluble resin (A ") also includes other monomers which, after polymerization, do not have an unsaturated bond polymerizable in the chain and are polymerized.

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" (A4) included in the reactive alkali-soluble resin (A ') can not be included because the polymerization should be performed in the absence of an unsaturated double bond capable of causing photopolymerization by a radical photoinitiator. A2) and (A3). The method example is the same as the general synthesis example of the reactive alkali-soluble resin (A '). The above exemplified materials may be used for (A1), (A2) and (A3), 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 40,000, more preferably 5,000 to 30,000. When the weight average molecular weight of the non-reactive alkali-soluble resin (A ") is in the range of 3,000 to 40,000, 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.

 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.

Wherein the non-reactive alkali-soluble resin (A ") comprises (A1), (A2) and (A3) It is preferable that the number of moles is in the following range.

(A1): 10 to 70 mol%,

(A2): 20 to 80 mol%

(A3): 10 to 70 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 6 to 85% by weight, preferably 40 to 75% by weight based on the solid content in the colored photosensitive resin composition. When the content of the alkali-soluble resin (A) is 6 to 85% by weight based on the above criteria, solubility in a developing solution is sufficient, so that development residue does not easily occur on the substrate of the non-pixel portion and film reduction of the exposed portion is unlikely to occur , And the solubility of the unexposed portions 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 ensuring reliability such as 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 dye include trianti-methane-based dyes, xanthene-based dyes including rhodamine-based dyes, flaine dyes, aramine dyes, sapphanine dyes, flocine dyes and methylene blue dyes.

Specific examples of the triarylmethane 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 rhodamine 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 flavin-based dye, for example, CI Basic Yellow 1 can be mentioned. Examples of the oraminic dyes include CI Basic Yellow 2 and CI Basic Yellow 3. As the sapphanine dye, for example, CI Basic Red 2 can be mentioned. As the floc naphtho dye, for example, CI Basic Red 12 can be mentioned. Examples of methylene blue 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) But is not limited thereto.

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

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 acrylate-based dispersant prepared by a living control method as disclosed in Korean Patent Publication No. 2004-0014311. DISCLOSURE OF THE INVENTION The present invention relates to an acrylate- BYK-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 10 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 formula (10) may be mentioned.

[Chemical formula 10]

In Formula 10,

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 10 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 (11), (12) and (13).

(11)

[Chemical Formula 12]

[Chemical Formula 13]

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 60 to 90% by weight, preferably 70 to 85% 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 60 to 90% by weight on the basis of the above 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, drying may be performed at 150 to 230 ° C for 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 : Reactive alkali-soluble resin ( A ' ) Synthesis of

A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube was provided with 60 parts by weight of phthalic acid mono (2-acroyloxy) ethyl ether, 60 parts by weight of 3,4- 30 parts by weight of tricyclo [5.2.1.0 2,6] decane (EDCPA), 10 parts by weight of N-benzylmaleimide, 4 parts by weight of t-butylperoxy-2-ethylhexanoate, (Hereinafter referred to as "PGMEA") were charged, stirred and mixed to prepare a monomer dropping tank. 6 parts by weight of n-dodecanethiol and 24 parts by weight of PGMEA were added and stirred to prepare a chain transfer agent dropwise .

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 temperature was raised to 110 DEG C for 1 hour and maintained at 90 DEG C for 2 hours while maintaining the temperature at 90 DEG C. The temperature was raised to 110 DEG C for 3 hours and then a gas introduction tube was introduced to perform bubbling of an oxygen / nitrogen gas mixture of 5/95 (v / v) . Subsequently, 30 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 reactive alkali-soluble resin having a solid content of 29.1 wt% and a weight average molecular weight of 23,000 and an acid value of 120 mgKOH / g.

Synthetic example  2 to 6: Synthesis of Reactive Alkali-Soluble Resin (A ')

A reactive alkali-soluble resin was obtained in the same manner as in Synthesis Example 1 except that each component and ratio were changed as shown in Table 1 below.

Synthetic example  7: Non-reactive  Synthesis of alkali-soluble resin (A ")

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was prepared, and 300 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) was added and heated to 75 DEG C with stirring. 30 parts by weight of phthalic acid mono (2-acroyloxy) ethyl ether, 60 parts by weight of 3,4-epoxy-8- (acryloyloxy) tricyclo [5.2.1.02,6] decane (EDCPA) -Cyclohexylmaleimide in 170 parts by weight of PGMEA was added dropwise over 5 hours using a dropping funnel.

On the other hand, a solution prepared by dissolving 30 parts by weight of azobisisobutyronitrile as a polymerization initiator in 200 parts by weight of PGMEA was added dropwise over 5 hours using a separate dropping funnel. After the dropping of the polymerization initiator was completed, the temperature was maintained for about 4 hours while cooling to room temperature to obtain a non-reactive alkali-soluble resin having a solid content of 37.6% by weight and a weight average molecular weight of 23,000 and an acid value of 130 mgKOH / g.

Synthetic example  8-11: Non-reactive  Synthesis of alkali-soluble resin (A ")

A non-reactive alkali-soluble resin was obtained in the same manner as in Synthesis Example 7 except that each component and ratio were changed as shown in Table 1 below.

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.

                                                 (weight) Constituent Synthetic example One 2 3 4 5 6 7 8 9 10 11 A1 Phthalic acid mono- (2-methyl-acryloyloxymethyl) ester 20 20 30 30 Cyclohexane-1,2-dicarboxylic acid mono- (2-methyl-acryloyloxymethyl) ester 20 30 Naphthalene-2,3-dicarboxylic acid mono- (2-methyl-acryloyloxymethyl) ester 20 Decahydro-naphthalene-2,3-dicarboxylic acid mono- (2-methyl-acryloyloxymethyl) ester 20 A1 ' 메acrylacrylic acid 20 20 acrylic acid 20 A2 3, 4-epoxy-8- (acryloyloxy) tricyclo [5.2.1.0 2,6] decane 40 40 40 40 40 40 60 60 60 70 70 A3 N-benzyl maleimide 10 10 10 10 10 N-cyclohexylmaleimide 10 10 10 10 10 10 A4 Glycidyl methacrylate 30 30 30 30 30 30 Acid value (mg KOH / g) 120 130 128 132 120 68 130 130 128 135 120 Molecular weight (M _w ) 23,000 25,000 23,000 23,000 23,000 45,000 23,000 23,000 23,000 23,000 23,000 Molecular weight distribution (M _w / M _n ) 1.8 2.0 1.9 1.8 2.2 6.5 1.9 1.8 2.1 2.2 2.3

< Example  And Comparative Example >

Example  1 to 9 and Comparative Example  1 to 4: Preparation of colored photosensitive resin composition

20 parts by weight (in terms of 100 parts by weight) of the pigment, the pigment dispersant and the mixture of the pigment dispersant and the propylene glycol monomethyl ether acetate, the sum of the pigment as the coloring agent (B) and the pigment dispersant as the additive (F) .

Thereafter, the pigment was sufficiently dispersed using a bead mill, and then the bead mill was separated. 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 2 below. The units in Table 2 are parts by weight.

Item Example Comparative Example One 2 3 4 One 2 3 4 Alkali solubility
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 6 6.03 4.02 2.01 5.82 Synthesis Example 10 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) CI Pigment
Red 254 4.69 CI Pigment
Red 177 6.75 Item Example Comparative Example 5 6 7 8 5 6 7 8 Alkali availability
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 6 0.95 1.89 2.84 4.29 Synthesis Example 10 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) CI Pigment
Green 58 10.99 C.I Pigment Yellow 138 3.10 Item Example Comparative Example 9 10 11 12 9 10 11 12 Alkali availability
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 6 15.22 10.87 6.52 13.68 Synthesis Example 10 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) CI 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 Chemical)

(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 at a light intensity of 100 mJ / cm ² using a 1 kW high pressure mercury lamp containing g, h and i lines, and no special optical filter was used.

The thin film irradiated with ultraviolet rays was immersed 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 described below, and the results are shown in Table 3 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

X: When the value of DELTA E * ab is 3 or more

Coated  Surface property Development speed (s) Residue Heat resistance NMP  Chemical resistance Example 1 O 16 O O O Example 2 O 17 O O O Example 3 O 18 O O O Example 4 O 18 O O O Example 5 O 13 O O O Example 6 O 14 O O O Example 7 O 10 O O O Example 8 O 16 O O O Example 9 O 13 O O O Example 10 O 14 O O O Example 11 O 12 O O O Example 12 O 16 O O O Comparative Example 1 X 17 O X O Comparative Example 2 △ 22 X △ X Comparative Example 3 X 35 △ X △ Comparative Example 4 X 45 △ X △ Comparative Example 5 X 20 O X O Comparative Example 6 △ 25 X X X Comparative Example 7 X 28 △ X △ Comparative Example 8 X 40 △ X △ Comparative Example 9 X 24 O X O Comparative Example 10 X 29 X X X Comparative Example 11 △ 34 △ X △ Comparative Example 12 X 45 △ X △

As can be seen from Table 3, the color filters prepared by using the colored photosensitive resin compositions of Examples 1 to 12 are excellent in the surface properties of the coating film and superior 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 monomer derived from a compound represented by the following formula (1); And
Monomers having an aliphatic polycyclic epoxy group; Wherein the coloring photosensitive resin composition comprises:
[Chemical Formula 1]

In Formula 1,
R is a C2-C6 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 monomer having an aliphatic polycyclic epoxy group comprises at least one member selected from the group consisting of the following formulas (I) to (II).
(I)

&Lt; RTI ID = 0.0 &

In the above general formulas (I) to (II)
R is independently hydrogen or a C1-C4 alkyl group,
X is a C1-C6 alkylene group which may contain at least one member selected from N, O, S and P in a single bond or a chain. The method according to claim 1,
Wherein the alkali-soluble resin is a copolymer further comprising a monomer represented by the following formula (5).
[Chemical Formula 5]

In Formula 5,
R is a C2-C6 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 3,
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,
6 to 85% by weight of an alkali-soluble resin;
10 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 60 to 90% by weight of a solvent. 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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