KR20100067973A - A colored photosensitive resin composition, color filter and liquid crystal display device having the same - Google Patents

Abstract

PURPOSE: A colored photosensitive resin composition, a color filter including a pixel which is formed using the same, and a liquid crystal display device including the color filter are provided to obtain excellent chemical resistance while maintaining development and storage stability. CONSTITUTION: A colored photosensitive resin composition includes a binder resin, a photopolymerizable compound, a photopolymerization initiator, a coloring material, a solvent, and a block isocyanate compound. The binder resin includes a hydroxyl group. The block isocyanate compound is included with a equivalence ratio(NCO/OH) of 0.5 ~ 2.2 based on the hydroxyl group of the binder resin.

Description

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

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

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

Therefore, in order to manufacture a color filter using a coloring photosensitive resin composition and apply it to a liquid crystal display device, it exposes to many chemical | medical agents. Recently, in addition to forming a color filter on a substrate on which a black matrix is patterned, a color filter is directly applied to a substrate (hereinafter referred to as a TFT substrate) on which a thin film transistor element (hereinafter referred to as TFT) on which a switching element is formed is formed. More often than ever before. Thus, the color filter manufactured from the coloring photosensitive resin composition requires chemical resistance.

In the related art, Korean Patent No. 10-0359218 discloses the inclusion of an epoxide as a method for improving chemical resistance. Chemical resistance is improved by using such an epoxide, but a yellowing phenomenon occurs when used in excess for sufficient chemical resistance effect, and there is a problem in storage stability due to gradual curing reaction. It may also cause deterioration of developability.

An object of this invention is to provide the coloring photosensitive resin composition which is excellent in storage stability and developability, and shows the outstanding chemical resistance at the time of color filter formation.

It is another object of the present invention to provide a high quality color filter formed of the composition.

Another object of the present invention is to provide a liquid crystal display device having the color filter.

The present invention to achieve the above object, (A) binder resin; (B) photopolymerizable compound; (C) photoinitiator; (D) coloring materials; (E) solvents; And (F) a block isocyanate compound, wherein the (A) binder resin includes a hydroxyl group, and the (F) block isocyanate compound has an equivalent ratio of isocyanate to a hydroxyl group of the binder resin (NCO / OH). It provides a colored photosensitive resin composition characterized in that it is included in the range of 0.5 to 2.2.

In order to achieve the another object of this invention, this invention provides the color filter characterized by including the pixel formed using the coloring photosensitive resin composition which concerns on this invention mentioned above.

In order to achieve the another object of the present invention, the present invention provides a liquid crystal display device comprising the above-mentioned color filter.

The coloring photosensitive resin composition of this invention is stable at normal temperature, does not affect developability at the time of a developing process, has no yellowing, and has the effect which shows the outstanding chemical resistance by the urethane bond of binder resin and a block isocyanate compound at the time of post-firing.

In addition, a color filter including a pixel formed using the colored photosensitive resin composition of the present invention and a liquid crystal display including the same also have an effect of showing high quality.

The coloring photosensitive resin composition which concerns on this invention is (A) binder resin; (B) photopolymerizable compound; (C) photoinitiator; (D) coloring materials; (E) solvents; And (F) block isocyanate compounds.

(A) binder resin

The binder resin usually has reactivity and alkali solubility due to the action of light or heat and acts as a dispersion medium of the coloring material. The binder resin according to the present invention preferably contains a hydroxyl group, and particularly preferably a polymer containing an unsaturated double bond in one molecule.

More preferably, the binder resin has a compound (a1) having a hydroxyl group and an unsaturated bond, a compound having a carboxylic acid group and an unsaturated bond (a2) and a compound having an unsaturated bond copolymerizable with (a1) and (a2) Binder by making the copolymer obtained by copolymerizing (a3) or the copolymer containing (a1)-the copolymer obtained by copolymerizing (a3) to the copolymer containing the unsaturated group obtained by making the compound (a4) which has an epoxy group and an unsaturated bond further react. Light / thermosetting can be provided to resin. If necessary, in addition to the compounds of (a1) to (a3), other monomers may be further included and copolymerized. The copolymer is excellent in crosslinking density and developability.

(a1) a compound having a hydroxyl group and an unsaturated bond

As a compound which has a hydroxyl group and an unsaturated bond, the compound which has a hydroxyl group and a (meth) acryloyl group in a molecule | numerator is mentioned, for example. As such a compound, For example, ester compound of polyhydric alcohols, such as hydroxy (meth) acrylate, its caprolactone adduct or alkylene oxide adduct, and glycerin, and (meth) acrylic acid, and glycidyl (Meth) arylate acrylic acid adducts, and at least one selected from these can be used. As hydroxy (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate are mentioned, for example. As these caprolactone addition products, hydroxyethyl (meth) acrylate caprolactone addition product, hydroxypropyl (meth) acrylate caprolactone addition product, hydroxybutyl (meth) acrylate capro, for example And lactone adducts. Examples of the alkylene oxide adduct include hydroxyethyl (meth) acrylate and alkylene oxide adducts, hydroxypropyl (meth) acrylate and propylene oxide adducts, and hydroxyethyl (meth). And acrylate butylene oxide adducts. As an ester compound, For example, glycerin mono (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, and methirol propane mono (meth) The di (meth) acrylate of the ethylene oxide addition product of an acrylate, a ditrimetholpropane tri (meth) acrylate, and a trimetholpropane, and the di (meth) acrylate of the propylene oxide addition product of a trimetholpropane are mentioned. have. These can be used individually or in combination of 2 types or more, respectively.

(a2) Compound having a carboxylic acid group and an unsaturated bond

The compound having a carboxylic acid group and an unsaturated bond is not particularly limited, and may be used alone or in combination of two or more. Specific examples thereof include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; Dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid; And anhydrides of the dicarboxylic acids; and mono (meth) acrylates of polymers having carboxyl groups and hydroxyl groups at both ends thereof, such as? -carboxypolycaprolactone mono (meth) acrylate. Acrylic acid and methacrylic acid among the compounds are preferred because of their excellent copolymerization reactivity and solubility in a developing solution.

(a3) Compounds having unsaturated bonds copolymerizable with (a1) and (a2)

The compound having an unsaturated bond copolymerizable with (a1) and (a2) is not limited as long as it is a compound having an unsaturated bond capable of polymerization with the compounds (a1) and (a2). Specific examples thereof include unsaturated carboxylic acids such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate and aminoethyl (meth) acrylate. Unsubstituted or substituted alkyl ester compound of; Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylate, menthyl (meth) acrylate, cyclophene Tenyl (meth) acrylate, cyclohexenyl (meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, mentadienyl (meth) acrylate, isobornyl (meth) acrylic Unsaturated carboxylic acid ester compound containing alicyclic substituents, such as late, pinanyl (meth) acrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate, and pineneyl (meth) acrylate ; 3-((meth) acryloyloxymethyl) oxetane, 3-((meth) acryloyloxymethyl) -3-ethyloxetane, 3-((meth) acryloyloxymethyl) -2-methyl Unsaturated carboxylic ester compounds containing thermosetting substituents such as oxetane and 3-((meth) acryloyloxymethyl) -2-trifluoromethyloxetane; Unsaturated carboxyl containing substituents having aromatic rings, such as monosaturated carboxylic acid ester compounds of glycols, such as oligoethylene glycol monoalkyl (meth) acrylate, benzyl (meth) acrylate, and phenoxy (meth) acrylate Acid ester compounds; Carboxylic acid vinyl esters, such as aromatic vinyl compounds, such as styrene and vinyltoluene (alpha) -methylstyrene, vinyl acetate, and a vinyl propionate; Vinyl cyanide compounds, such as (meth) acrylonitrile and the (alpha)-chloro acrylonitrile, etc. are mentioned. Among these, aromatic vinyl compounds are preferred for improving sensitivity and reducing outgassing. These can be used individually or in combination of 2 types or more, respectively.

(a4) Compound having an epoxy group and an unsaturated bond

Compounds having an epoxy group and an unsaturated bond that can further react with a copolymer obtained by copolymerizing (a1) to (a3) to impart photo / thermosetting properties to the binder resin can be preferably used. Specific examples of the compound (a4) imparting the photo / thermosetting property include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and 3,4-epoxycyclohexylmethyl (meth) acrylate And methylglycidyl (meth) acrylate. Among these, glycidyl (meth) acrylate is preferably used. These can be used individually or in combination of 2 types or more, respectively.

As used herein, (meth) acrylate means acrylate and / or methacrylate.

As described above, the binder resin (A) according to the present invention has an epoxy group and a copolymer obtained by copolymerizing the above-mentioned compounds (a1) to (a3) or a copolymer obtained by copolymerizing (a1) to (a3). In the case of a copolymer containing an unsaturated group obtained by further reacting a compound (a4) having an unsaturated bond, the copolymer obtained by copolymerizing the compounds (a1) to (a3) with a monomer is the compound (a1) to (a3). It is preferable that the ratio of the structural unit derived from each is the following range in mole fraction with respect to the total mole of the structural units which comprise the said copolymer. In this case, in addition to the compounds (a1) to (a3), the copolymer may further include other monomers.

The ratio of the constituents derived from each of the above (a1) to (a3) is based on the total moles of the copolymer constituents,

2 to 60 mol% of structural units derived from the compound (a1),

2 to 70 mol% of structural units derived from the compound (a2),

2 to 95 mol% of structural units derived from the compound (a3),

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

10 to 50 mol% of structural units derived from the compound (a1),

5 to 65 mol% of structural units derived from the compound (a2),

5 to 80 mol% of structural units derived from the compound (a3)

When the above-mentioned composition ratio satisfies the above range, the balance of developability, solubility and heat resistance is good, and thus a more preferable copolymer can be obtained.

The compound (a4) is preferably reacted at 5 to 80 mol%, particularly preferably 10 to 80 mol%, based on the total moles of the structural units derived from the compound (a2). When the said (a4) compound exists in the said range, since it is excellent in a sensitivity and developability, it is preferable.

Unsaturation obtained by further reacting the compound (a4) with the copolymer obtained by copolymerizing the compound (a) to (a3) or the copolymer (a1) to the compound (a3). An example of the manufacturing method in the case of the copolymer containing group is as follows.

To the flask equipped with the stirrer, the thermometer, the reflux cooling tube, the dropping lot and the nitrogen introduction tube, 0.5 to 20 times the solvent was introduced on a mass basis with respect to the total amount of (a1) to (a3), and the atmosphere in the flask was purged with nitrogen in air. Replace with. Then, after heating a solvent to 40-140 degreeC, the solvent of 0-20 times on a mass basis with respect to the predetermined amount of said (a1)-(a3) compound, the total amount of said (a1)-(a3), and A solution obtained by adding 0.1 to 10 mol% of a polymerization initiator such as azobisisobutyronitrile or benzoyl peroxide with respect to the total number of moles of the compounds (a1) to (a3) (agitated and dissolved at room temperature or under heating) was added from the dropping lot. It is dripped at the said flask over 8 hours, and it stirred at 40-140 degreeC for 1 to 10 hours further.

In this process, part or all of the polymerization initiator may be put in the flask, or part or all of the compounds (a1) to (a3) may be put in the flask. Moreover, in order to control molecular weight or molecular weight distribution, (alpha) -methylstyrene dimer or a mercapto compound can also be used as a chain transfer agent. The use amount of the α-methylstyrene dimer or mercapto compound is 0.005 to 5% by mass based on the total amount of the above (a1) to (a3). In addition, the said polymerization conditions can also adjust an input method and reaction temperature suitably in consideration of the amount of heat generation by a manufacturing facility, superposition | polymerization, etc ..

By doing in this way, the copolymer obtained by copolymerizing the said (a1)-(a3) compound is manufactured.

Subsequently, the atmosphere in the flask was replaced with nitrogen from air, and the molar fraction of the structural unit derived from the compound (a2) in the copolymer obtained by copolymerizing the compounds (a1) to (a3) was 5 to 80 mol% (a4). As a reaction catalyst of a compound, a carboxyl group and an epoxy group, for example, trisdimethylaminomethylphenol is 0.01 to 5% relative to the total mass of the compounds (a1) to (a4) and a polymerization inhibitor, for example, hydroquinone (a1). 0.001 to 5% of the total mass of the compound (a) to (a4) is placed in a flask and reacted at 60 to 130 ° C. for 1 to 10 hours.

At this time, in the same manner as the polymerization conditions, the addition method and the reaction temperature may be appropriately adjusted in consideration of the amount of heat generated by the production equipment, polymerization, and the like.

Thereby, it is a copolymer containing the unsaturated group obtained by making the said (a4) compound further react with the copolymer obtained by copolymerizing the said (a1)-(a3) compound, or the copolymer obtained by copolymerizing the (a1)-(a3) compound. (A) A binder resin is produced. The binder resin (A) preferably has a weight average molecular weight in the range of 3,000 to 100,000, more preferably in the range of 5,000 to 50,000, as converted into polystyrene and measured by gel permeation chromatography. When the weight average molecular weight satisfies the above-mentioned range, film reduction is unlikely to occur at the time of development, and it is preferable because the missing property of the non-pixel portion at the time of development tends to be good.

At this time, according to the present invention, the acid value of the binder resin (A) according to the present invention is preferably in the range of 30 to 150 mgKOH / g based on solid content. If the acid value is less than 30 mgKOH / g, there is a possibility that the developability to the alkaline water is lowered, leaving a residue on the substrate, and if the acid value exceeds 150 mgKOH / g, the possibility of desorption of the pattern is increased.

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

The content of the binder resin (A) is in the range of 5 to 85% by mass, preferably 10 to 70% by mass, with respect to the solid content in the colored photosensitive resin composition. When the content of the binder resin (A) is 5 to 85% by mass, the solubility in the developing solution is sufficient, and development residues are less likely to occur on the substrate of the non-pixel portion. It is preferable because the omission of the pixel portion tends to be good.

(B) photopolymerizable compound

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

Specific examples of the monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate and N-vinylpyrroli Money, etc.

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

Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate and pentaeryte. Lithitol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipenta Erythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned.

Of these, bifunctional or higher polyfunctional monomers are preferably used. Particularly preferably polyfunctional monomers of at least 5 functional groups can be used.

The said (B) photopolymerizable compound is 5-50 mass% in mass fraction with respect to solid content in a coloring photosensitive resin composition, Preferably it is used in the range of 7-45 mass%. Since the intensity | strength and smoothness of a pixel part tend to become favorable when the (B) photopolymerizable compound is the range of 5-50 mass% on the said reference | standard, it is preferable.

(C) photopolymerization initiator

Although the (C) photoinitiator contained in the coloring photosensitive resin composition of this invention is not restrict | limited, It is preferable to use at least 1 compound chosen from the group which consists of a triazine type compound, an acetophenone type compound, a biimidazole type compound, and an oxime compound. desirable. The colored photosensitive resin composition containing the above-mentioned (C) photoinitiator is high sensitivity, and the film | membrane formed using this composition becomes favorable the intensity | strength and surface smoothness of the pixel part.

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

As an acetophenone type compound, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4- (2 -Hydroxyethoxy) phenyl] -2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1- On, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] And oligomers of propane-1-one.

Moreover, it is preferable that the said acetophenone type compound contains the compound represented by following formula (1).

Wherein R 1 to R 4 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms, a benzyl group unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms, or It represents the naphthyl group unsubstituted or substituted by the C1-C12 alkyl group.

Specific examples of the compound represented by Formula 1 include 2-methyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-ethyl-2-amino (4-morpholinophenyl) ethane- 1-one, 2-propyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-butyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-methyl- 2-amino (4-morpholinophenyl) propane-1-one, 2-methyl-2-amino (4-morpholinophenyl) butan-1-one, 2-ethyl-2-amino (4-morpholin Nophenyl) propane-1-one, 2-ethyl-2-amino (4-morpholinophenyl) butan-1-one, 2-methyl-2-methylamino (4-morpholinophenyl) propane-1 -One, 2-methyl-2-dimethylamino (4-morpholinophenyl) propan-1-one, 2-methyl-2-diethylamino (4-morpholinophenyl) propan-1-one, etc. are mentioned. Can be.

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

As an oxime compound, the compound etc. which are represented by following General formula (2), 3, 4 are mentioned.

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

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

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

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

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

Other photopolymerization initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone and camphorquinone. And methyl phenyloxyoxylate, titanocene compound, and the like.

According to the present invention, the photopolymerization initiator (C) may be used in combination with a photopolymerization initiation aid, and the colored photosensitive resin composition containing these is more sensitive, and thus the productivity at the time of forming a color filter using the composition is preferable. Do.

As the photopolymerization initiation assistant that can be used in combination with the (C) photopolymerization initiator, one or more compounds selected from the group consisting of amine compounds and carboxylic acid compounds can be preferably used.

Specific examples of the amine compound in the photopolymerization initiation aid include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine; 4-Dimethylaminobenzoic acid methyl, 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid isoamyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N, N-dimethylparatoluidine, 4,4 Aromatic amine compounds, such as' -bis (dimethylamino) benzophenone (common name: Michler's ketone) and 4,4'-bis (diethylamino) benzophenone, are mentioned. As an amine compound, an aromatic amine compound is used preferably.

Specific examples of the carboxylic acid compound in the photopolymerization initiation aid include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chloro And aromatic heteroacetic acids such as phenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthoxyacetic acid.

The content of the (C) photoinitiator in the colored photosensitive resin composition of the present invention is 0.1 to 40% by mass, preferably 1 to 1, based on the solids, based on the total amount of the (A) binder resin and (B) the photopolymerizable compound. 30 mass%. The content of the photopolymerization initiation aid is 0.1 to 50% by mass, preferably 1 to 40% by mass, based on the solids content, based on the total amount of the (A) binder resin and the (B) photopolymerizable compound. (C) When the usage-amount of a photoinitiator exists in the said range, since the coloring photosensitive resin composition becomes high sensitivity and the intensity | strength of the pixel part formed using this composition and the smoothness in the surface of this pixel part tend to become favorable, it is preferable. . Moreover, when the usage-amount of a photoinitiator is in the said range, since the sensitivity of a coloring photosensitive resin composition becomes higher and the productivity of the color filter formed using this composition tends to improve, it is preferable.

(D) coloring material

It is preferable that the (D) coloring material used for the coloring photosensitive resin composition of this invention is an organic pigment or an inorganic pigment used for a pigment dispersion resist as a normal pigment. If desired, dyes may be used and are included in the present invention.

Examples of the inorganic pigments include metal compounds such as metal oxides and metal complex salts. Specifically, oxides or composite metals of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc and antimony Oxides; and the like.

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

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

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

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

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

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

C.I. Pigment Green 7, 10, 15, 25, 36, 47 and 58

C.I Pigment Brown 28

C.I pigment black 1 and 7, etc.

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

(E) Solvent

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

Specific examples thereof include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; Diethylene glycol 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, cyclohexanone, ethylene glycol and glycerin; Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; Cyclic ester, such as (gamma) -butyrolactone, etc. are mentioned.

Among the above-mentioned (E) solvents, preferred examples of coating properties and drying properties include organic solvents having a boiling point of 100 ° C. to 200 ° C., and more preferably alkylene glycol alkyl ether acetates, ketones, and 3-e. Ester, such as ethyl oxypropionate and methyl 3-methoxy propionate, is mentioned, More preferably, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3- Ethyl ethoxypropionate, methyl 3-methoxypropionate, and the like.

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

The content of the solvent (E) in the colored photosensitive resin composition of the present invention is usually 60 to 90% by mass, preferably 70 to 85% by mass, based on the mass fraction of the total amount of the colored photosensitive resin composition including the same. (E) When the content of the solvent is in the range of 60 to 90% by mass based on the above criteria, it is applied with a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes referred to as die coater), inkjet, etc. It is preferable because the coating property tends to be good at the time.

(F) Block Isocyanate Compounds

The colored photosensitive resin composition of this invention contains the (F) block isocyanate compound. Although the said (F) block isocyanate compound is obtained by making an isocyanate compound and a blocking agent react, it is also preferable to make it react by adding a polymerization inhibitor at the time of reaction. Herein, the polymerization inhibitor may rapidly react with free radicals generated from the monomers by free radical polymerization, thereby stabilizing the reaction system so that free radical polymerization does not proceed.

As an isocyanate compound used for manufacture of the said (F) block isocyanate compound, Aliphatic diisocyanate compound which has bivalent aliphatic groups, such as an alkylene group, Alicyclic diisocyanate compound which has bivalent alicyclic group, such as cycloalkylene, and aromatic di Isocyanate compounds, these isocyanurated modified compounds, carbodiimide-ized modified compounds, and biuret modified compounds are mentioned.

Specific examples of the aliphatic diisocyanate compound include hexamethylene diisocyanate and trimethylhexamethylene diisocyanate. As an alicyclic diisocyanate compound, isophorone diisocyanate, methylenebis (cyclohexyl) diisocyanate, 1, 3- or 1, 4-bis (isocyanate methyl) cyclohexane is mentioned. As an aromatic diisocyanate compound, a dimerization polymer of 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate or 2,6-toluene diisocyanate, (o, p or m) -Xylene diisocyanate, diphenylmethane diisocyanate, and 1, 5- naphthalene diisocyanate are mentioned. These can be used individually by 1 type or in combination of 2 or more types.

As the blocking agent used in the preparation of the (F) block isocyanate compound, a compound having only one active hydrogen in one molecule reacting with an isocyanate group is used as alcohols, phenols, lactams, oximes, acetoacetic acid alkyl esters and malonic acid. Alkyl esters, phthalimides, imidazoles, hydrogen chloride, hydrogen cyanide, sodium hydrogen sulfite and the like. Among these, substituted phenols, oximes, acetoacetic acid alkyl esters, malonic acid alkyl esters, phthalimides, imidazoles, hydrogen chloride, hydrogen cyanide or sodium hydrogen sulfate can be preferably used.

Specific examples include phenol, 2-pyridinol, 3-hydroxypyridine, 8-hydroxyquinoline, trihaloethyl alcohol, n-butyl alcohol, 2-ethylhexyl alcohol, furfuryl alcohol, cyclohexyl alcohol, 2-e Toxyhexyl alcohol, N-hydroxysuccinimide, N-morpholinoethanol, 3-oxazolidineethanol, hexyl mecapcaptan, methyl acetamide, acetanilide, thiophenol, mercaptopyridine, 2-ethylhexylhydride Oxybenzoate, p-cresol formaldehyde, 2-[(dimethylamino) methyl] phenol, pyrazole, 3-methylpyrazole, 1,2,4-triazole, aminocaproic acid, imidazoline, formi Eight, dicetone, benzyl methacrylhydramate, 2-benzooxazolone, ureddione, carbodiimide, urettonimine, β-caprolactam, diethylmalonate, ethyl acetoacetate, acetoxime, methyl ethyl ketoxime Etc. can be mentioned. These can be used individually by 1 type or in combination of 2 or more types.

Polymerization inhibitors that may be added during the reaction of the above-mentioned isocyanate and blocking agent include phenolic compounds and phosphite compounds. Specific examples of the phenolic compound include 3,5-di-tert-butyl-4-hydroxytoluene (BHT), 4,4'-thio-bis (3-methyl-6-tert-butylphenol), 4, 4'-butylidene-bis (3-methyl-6-tert-butylphenol), 2,2'-methylene-bis (4-methyl-6-tert-butylphenol), 2,2'-methylene-bis (4-ethyl-6-tert-butylphenol), and 2,2'-dihydroxy-3,3'-di (?-Methyl-cyclohexyl) -5,5'-dimethyldiphenylmethane. The phosphite compound includes tris (nonylated phenyl) phosphite. The polymerization inhibitor exemplified above is known to be able to improve the transparency of the curable resin in the Republic of Korea Patent 10-0414478.

At this time, according to the present invention, the (F) block isocyanate compound is preferably used in the range of 0.5 to 2.2 equivalent ratio in the equivalent ratio (NCO / OH) of the isocyanate to the hydroxyl group of the (A) binder resin. More preferably, it is 0.6-2.0. If the equivalent ratio of NCO / OH is less than 0.5, there is no effect on the chemical resistance, if the equivalent ratio of NCO / OH is higher than 2.2, a large amount of reactive isocyanate remains, which adversely affects the chemical resistance and deteriorates the physical properties of the coating film There is this.

The (F) block isocyanate compound dissociates the blocking agent at about 130 to 250 ° C. during the firing process of the color filter, and the reactive isocyanate group formed at this time forms a urethane bond with the hydroxyl group of the binder resin (A), thereby developing and Excellent chemical resistance is achieved without affecting storage stability.

Other additives

The coloring photosensitive resin composition of this invention may further contain other additives, such as a filler, another high molecular compound, a pigment dispersing agent, an adhesion promoter, antioxidant, a ultraviolet absorber, and an aggregation inhibitor, as needed.

Examples of the filler include glass, silica, alumina, and the like.

Specific examples of the other high molecular compound include thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, polyurethane, and the like.

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

These pigment dispersants can be used individually or in combination of 2 or more types, respectively, and can be normally contained in 0.01-15 mass% with respect to solid content in a coloring photosensitive resin composition.

Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and N- ( 2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxy Silane, 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and the like.

These adhesion promoters can be used individually or in combination of 2 or more types, respectively. It is 0.01-10 mass% normally with respect to solid content in colored photosensitive resin composition, Preferably it can contain 0.05-2 mass%. Examples of the antioxidant include 2,2'-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butyl-4-methylphenol and the like.

As said ultraviolet absorber, 2- (3-tert- butyl- 2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole, alkoxy benzophenone, etc. are mentioned.

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

The coloring photosensitive resin composition of this invention mentioned above can be manufactured, for example by the following methods. (D) The coloring material is previously mixed with the solvent (E) and dispersed using a bead mill or the like until the average particle diameter of the coloring material is about 0.2 µm or less. At this time, a pigment dispersant is used as needed, and some or all of (A) binder resin may be mix | blended. In the resulting dispersion (hereinafter sometimes referred to as mill base), the remainder of the binder resin (A), (B) photopolymerizable compound, (C) photopolymerization initiator, (F) block isocyanate compound, other additives and additional (E) A solvent is further added so that it may become a predetermined | prescribed density | concentration, and a desired coloring photosensitive resin composition is obtained. However, the present invention does not limit this method.

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

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

As one example thereof, the colored photosensitive resin composition according to the present invention is applied onto a substrate as described below, and photocuring and development are performed to form a pattern, which can be used as a black matrix or a colored pixel (colored image). . The base material used for applying the composition is not limited, and is smoothed by removing volatile components such as solvents by applying a preliminary baking, for example, on a layer containing the solids of glass, silicon wafer, plastic or the previously formed colored photosensitive resin composition. One coat can be obtained. Amorphous polyolefin, polycarbonate, polyethylene terephthalate, polyethylene naphthalate, polynorbornene, polyether sulfone, polyether ketone, etc. are mentioned as a raw material of the said plastic used as a base material. The thickness of the coating film at this time is about 1-3 micrometers normally.

After the formation of the coating film, ultraviolet rays are irradiated to a specific area of the coating film through a mask to obtain a desired pattern. At this time, it is preferable to use apparatuses, such as a mask aligner and a stepper, so that a parallel light beam may be irradiated uniformly to the whole exposure part, and a mask and a board | substrate will be correctly aligned. In addition, a desired pattern can be produced by contacting the aqueous coating solution after completion of curing with an aqueous alkali solution to dissolve and develop the non-exposed areas. After image development, post-firing of about 10 to 120 minutes can be performed at 150 degrees C or less.

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

The alkaline compound may be either an inorganic or organic alkaline compound. Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, hydrogen carbonate Sodium, potassium hydrogen carbonate, sodium borate, potassium borate, ammonia and the like. Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, Monoisopropylamine, diisopropylamine, ethanolamine and the like. These inorganic and organic alkaline compounds can be used individually or in combination of 2 or more types, respectively.

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

Surfactant in alkaline developing solution can use all of a nonionic surfactant, anionic surfactant, or cationic surfactant. Specific examples of the non-ionic 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 ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine and the like. Specific examples of the anionic surfactant include higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfate salts such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzene sulfonate, Alkyl aryl sulfonic acid salts, such as sodium dodecyl naphthalene sulfonate, etc. are mentioned. Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryl trimethylammonium chloride, or quaternary ammonium salts. These surfactant can be used individually or in combination of 2 or more types, respectively.

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

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

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

Since the pattern formation method of a coloring photosensitive resin composition is as above-mentioned, detailed description is abbreviate | omitted. As described above, a pixel or a black matrix corresponding to the color of the coloring material in the photosensitive resin composition is obtained through the respective operations of patterning exposure and development in a dry coating film obtained by applying the coloring photosensitive resin composition to a substrate and then drying. Is repeated by the number of colors required by the color filter to obtain the color filter. Since the configuration and manufacturing method of the color filter are well known in the art, detailed description thereof will be omitted.

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

In addition, although the black matrix which is a light shielding layer can use the coloring (colored black) photosensitive resin of this invention, for example, it may be formed by the chromium layer etc., In this case, coloring of this invention is carried out in formation of a black matrix. It is not necessary to use the photosensitive resin composition.

The color filter manufactured using the coloring photosensitive resin composition of this invention has little in-plane film thickness difference, For example, it can make in-plane film thickness difference 0.15 micrometer or less and further 0.05 micrometer or less with the film thickness of 1-3 micrometers. .

Therefore, the color filter obtained in this way is excellent in smoothness, and it can manufacture a liquid crystal display device of excellent quality by high yield by assembling this to a color liquid crystal display device. In addition, by using the above-described color filter, it is possible to manufacture an image pickup device of excellent quality.

Therefore, the present invention also includes a liquid crystal display device having the color filter described above. The liquid crystal display of the present invention includes a configuration known in the art, except that the above-described color filter is provided. That is, all of the liquid crystal display devices to which the color filter of the present invention can be applied are included in the present invention.

Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited by an Example. In addition, "%" and "part" which show content in a following example and a comparative example are a mass reference | standard unless there is particular notice.

Production Example 1 Binder Resin Synthesis (A1)

40 parts by mass of propylene glycol monomethyl ether acetate and 140 parts by mass of propylene glycol monomethyl ether were introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube, and the atmosphere in the flask was nitrogen from air. After heating up at 100 degreeC, 7.47 mass parts (7.1 mol%) of cyclohexyl methacrylate, 30 mass parts (27.1 mol%) of benzyl methacrylate, 7.45 mass parts (5.3 mol%) of isobornyl methacrylate, and methyl methacryl A mixture containing 9.5 parts by mass (15.1 mole%), 19.58 parts by mass methacrylic acid (34.4 mole%), 10 parts by mass (4-1.0 mole%) 4-hydroxybutyl acrylate and 136 parts by mass propylene glycol monomethyl ether acetate The solution to which 4 mass parts of azobisisobutyronitrile was added was dripped at the flask over 2 hours from the dropping lot, and stirring was continued at 80 degreeC for 5 hours. Subsequently, the atmosphere in the flask was changed from nitrogen to air, 15 parts by mass of glycidyl (meth) acrylate (32.8 mol% of methacrylic acid), 0.5 parts by mass of trisdimethylaminomethylphenol, and 0.1 parts by mass of hydroquinone were introduced into the flask. The reaction was continued at 110 ° C. for 6 hours to obtain a (A1) binder resin having a solid acid value of 81 mg KOH / g. The weight average molecular weight of polystyrene conversion measured by GPC was 28,257, and molecular weight distribution (Mw / Mn) was 2.4. In addition, OH equivalent was 3,596 g / equivalent (solid component), and solid content was 39 mass%.

In this case, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the binder resin were measured by using an HLC-8120GPC (manufactured by Tosoh Corporation) apparatus, and the column was used by serially connecting TSK-GELG4000HXL and TSK-GELG2000HXL. The column temperature was 40 ° C, the mobile phase solvent was tetrahydrofuran, the flow rate was 1.0 ml / min, the injection amount was 50 µl, the detector RI was used, and the measurement sample concentration was 0.6 mass% (solvent = tetrahydrofuran), for calibration. TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation) was used as a standard material.

< Production Example  2> Binder Resin Synthesis (A2)

In the same manner as in Binder Resin Production Example 1, except that the secondary reaction of replacing 10 parts by mass of 4-hydroxybutyl acrylate with methyl methacrylate and adding glycidyl (meth) acrylate ( A2) A binder resin was prepared. As for the manufactured (A2) binder resin, the weight average molecular weight of polystyrene conversion measured by solid acid value of 82 mgKOH / g and GPC was 23,330, molecular weight distribution (Mw / Mn) was 2.4, and solid content was 40 mass%.

< Production Example  3> Block Isocyanate Compound Synthesis (F1)

In a 100 ml four-necked flask equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, 224 parts by mass of methyl ethyl ketoxime (manufactured by ICCCHEM) and 3,5-di-tert-butyl in 250 parts by mass of ethylene glycol acetate under a nitrogen atmosphere. 0.1 parts by mass of -4-hydroxytoluene (manufactured by Tohsei Chemical Co., Ltd.) was added and dissolved uniformly. When it became uniform, it heated up at 70 degreeC and stirred again, 357 mass parts of hexamethylene diisocyanate (made by RHODIA) was dripped over 2 hours, and it maintained at the same temperature for 1 hour. A small amount of sample was taken from the reaction system to measure the IR spectrum. As a result, it was confirmed that the absorption near 2270 cm −1 based on the NCO group was below the detection limit, and the reaction was terminated.

NCO equivalent weight of the prepared block isocyanate compound was 408g / equivalent (solid component), and solid content was 71.37 mass%.

< Production Example  4> Block Isocyanate Compound Synthesis (F2)

It progressed similarly except having changed the isocyanate compound into 370 mass parts of 2, 4- toluene diisocyanate (made by BASF) in manufacture example 3. The NCO equivalent of the prepared block isocyanate compound was 583 g / equivalent (solid component), and solid content was 68.3 mass%.

< Example  1 to 5 and Comparative example  1-6> Preparation of colored photosensitive resin composition

In each component shown in following Table 1 and Table 2, it mixes previously so that the total amount of the pigment dispersant which is a pigment and other additives (D) coloring material may be 20 mass% with respect to the mixture of a pigment, a pigment dispersant, and a propylene glycol monomethyl ether acetate. After the pigment was sufficiently dispersed using the bead mill, the bead mill was separated, and the remaining components including the remaining amount of propylene glycol monomethyl ether acetate were further added and mixed to obtain a colored photosensitive resin composition.

Example 1 Example 2 Example 3 Example 4 Example 5 (D1) coloring material 5.20 5.20 5.20 5.20 5.20 (D2) coloring material 1.40 1.40 1.40 1.40 1.40 (A1) binder resin 5.10 5.10 5.10 5.10 5.10 (A2) binder resin - - - - - (B) photopolymerizable compound 5.48 5.02 4.70 4.16 4.63 (C1) photoinitiator 0.70 0.70 0.70 0.70 0.70 (C2) photoinitiator 0.46 0.46 0.46 0.46 0.46 (C3) photoinitiator 0.70 0.70 0.70 0.70 0.70 (E) Solvent 80.00 80.00 80.00 80.00 80.00 (F1) Block Isocyanate Compounds 0.60 1.06 1.38 1.92 - (F2) Block Isocyanate Compounds - - - - 1.45 Other additives 0.36 0.36 0.36 0.36 0.36 Epoxy thermal crosslinking agent - - - - - NCO / OH equivalence ratio 0.60 1.00 1.30 1.80 1.00

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 (D1) coloring material 5.20 5.20 5.20 5.20 5.20 5.20 (D2) coloring material 1.40 1.40 1.40 1.40 1.40 1.40 (A1) binder resin - 5.10 5.10 5.10 5.10 5.10 (A2) binder resin 5.10 - - - - - (B) photopolymerizable compound 4.70 5.63 3.58 5.58 4.88 4.08 (C1) photoinitiator 0.70 0.70 0.70 0.70 0.70 0.70 (C2) photoinitiator 0.46 0.46 0.46 0.46 0.46 0.46 (C3) photoinitiator 0.70 0.70 0.70 0.70 0.70 0.70 (E) Solvent 80.00 80.00 80.00 80.00 80.00 80.00 (F1) Block Isocyanate Compounds 1.38 0.45 2.50 - - - (F2) Block Isocyanate Compounds - - - - - - Other additives 0.36 0.36 0.36 0.36 0.36 0.36 Epoxy thermal crosslinking agent - - - 0.50 1.20 2.00 NCO / OH equivalence ratio - 0.40 2.40 - - -

* Numerical values in Table 1 and Table 2 refer to parts by mass.

(A1) and (A2) Binder Resin: Binder Resin Synthesized in Preparation Examples 1 and 2

(B) photopolymerizable compound: dipentaerythritol hexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.)

(C1) photoinitiator: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one (Irgacure 369; manufactured by Ciba Specialty Chemical)

(C2) photoinitiator: 4,4'-bis (diethylamino) benzophenone (EAB-F; product made by Hodogaya Kagaku Co., Ltd.)

(C3) photoinitiator: ethanone-1- [9-ethyl-6- (2-methyl-4tetrahydropyranyloxybenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (Irgacure OXE02; manufactured by Ciba Specialty Chemical)

(D1) Coloring material: C.I. pigment red 254

(D2) Coloring material: C.I. pigment yellow 138

(E) Solvent: Propylene Glycol Monomethyl Ether Acetate

(F1) Block isocyanate compound prepared in Production Example 3

(F2) Block isocyanate compound prepared in Production Example 4

Other additives: pigment dispersant (polyester type)

Epoxy thermal crosslinking agent: NOBLOCK epoxy resin (SUMI-EPOXY ESCN-195XL; manufactured by Sumitomo Kagaku Kogyo Co., Ltd.)

<Test Example>

A 2 square inch glass substrate (# 1737, manufactured by Corning) was washed sequentially with a neutral detergent, water, and alcohol, and then dried. The coated photosensitive resin composition (Table 1) was exposed on the glass substrate at an exposure amount (365 nm) of 100 mJ / cm 2 and spin-coated so that the film thickness after post-firing when the developing step was omitted was 1.9 µm. Preliminary drying (preliminary baking) was performed at 100 degreeC for 3 minutes in the clean oven. After cooling, the gap between the substrate coated with the colored photosensitive resin composition and a quartz glass photomask (having a pattern for changing the transmittance stepwise in the range of 1 to 100% and a line / space pattern from 1 µm to 50 µm) It was made into 100 micrometers, and it irradiated at 100 mJ / cm <2> exposure amount (365 nm) in air | atmosphere using the ultrahigh pressure mercury lamp (brand name USH-250D) by Ushio Denki Corporation. Thereafter, the coating film was immersed in a water-based developing solution containing 0.12% of a nonionic surfactant and 0.06% of potassium hydroxide at 26 ° C. for a predetermined time, and then fired after washing at 220 ° C. for 30 minutes after washing with water. , Table 3 and Table 4 show the results of sensitivity, chemical resistance, storage stability and surface abnormalities.

Development speed (sec)

It represents the time taken for a non-exposed part to melt completely in a developing solution at the time of image development. ○: 10 seconds or more and 15 seconds or less, △: more than 15 seconds and 20 seconds or less, X: more than 20 seconds and 25 seconds or less

<Sensitivity (mJ / cm 2)>

Even if it develops, the minimum required exposure amount required in order to form the pattern without surface roughness is shown. (80 mJ / ㎠ or less good)

<Chemical Resistance>

Chemical resistance is evaluated by measuring color change (ΔEab) before and after precipitation for 23 ° C./40 minutes under NMP. ○: ΔEab = less than 1, △: ΔEab = 1 to 3, X: ΔEab = 3

<Storage stability>

Storage stability shows the viscosity change before and after storage after storing the coloring photosensitive resin composition of Examples 1-5 and Comparative Examples 1-6 for 2 weeks in 40 degreeC storage. ○: less than 10%, △: 10 to 20%, X: more than 20%

<Over surface>

Surface abnormalities indicate the presence or absence of surface abnormalities when observed under a 500x magnification microscope after baking for 30 minutes at 220 ° C. ○: no abnormality, X: sunspot, crater occurrence

<Yellowing>

Yellowing is evaluated by color change value (ΔEab) measurement before and after baking at 230 ° C. for 120 minutes. ○: ΔEab = less than 1, △: ΔEab = 1 to 3, X: ΔEab = 3

division Example 1 Example 2 Example 3 Example 4 Example 5 Developing speed (sec) ○ ○ ○ ○ ○ Sensitivity (mJ / ㎠) 70.00 70.00 70.00 80.00 70.00 Chemical resistance ○ ○ ○ ○ ○ Storage stability ○ ○ ○ ○ ○ Over surface ○ ○ ○ ○ ○ Yellowing ○ ○ ○ ○ ○

division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Developing speed (sec) △ ○ ○ △ × × Sensitivity (mJ / ㎠) 80.00 80.00 80.00 70.00 70.00 80.00 Chemical resistance X △ △ × △ ○ Storage stability ○ ○ ○ △ × × Over surface ○ ○ X ○ ○ ○ Yellowing △ △ ○ △ X X

As a result of the test, in Comparative Example 1, when the A2 binder without a hydroxyl group was used in the binder resin, chemical resistance and developability were poor. In addition, Comparative Example 2 had a poor NCO / OH equivalent ratio of less than 0.5, the sufficient activity of the NCO did not achieve a good chemical resistance, Comparative Example 3 contains an excess of block isocyanate compound, poor chemical resistance, The surface abnormality by volatilization of the block agent generate | occur | produced in the baking process. Comparative Examples 4 to 6 can be improved in chemical resistance by including an epoxy heat crosslinking agent, but due to the increase in the content, due to poor storage stability and yellowing, the problem of the present invention could not be achieved.

As can be seen from the results of Examples 1 to 5, the colored photosensitive resin composition according to the present invention not only has excellent storage stability, but the pixels obtained by using the same have no problem of deterioration of developability, and have excellent chemical resistance, The minimum required exposure amount needed to form a pattern without surface roughness after development was excellent at 60 to 80 mJ / cm 2, and an excellent pixel without surface abnormality after post-firing was obtained. Therefore, the color filter obtained using the coloring photosensitive resin composition of this invention enjoys the outstanding physical property of a coloring photosensitive resin composition, and the liquid crystal display device containing this has a high quality effect.

Claims (7)

(A) binder resin, (B) photopolymerizable compound, (C) photoinitiator, (D) coloring material, (E) solvent, (F) block isocyanate compound, The binder resin (A) comprises a hydroxyl group, and the (F) block isocyanate compound is included in the range of 0.5 to 2.2 in the equivalent ratio (NCO / OH) of isocyanate to the hydroxyl group of the binder resin. Colored photosensitive resin composition to be used. The method of claim 1, The binder resin (A) is: a compound having a hydroxyl group and an unsaturated bond (a1), a compound having a carboxylic acid group and an unsaturated bond (a2) and a compound having an unsaturated bond copolymerizable with (a1) and (a2) A copolymer obtained by copolymerizing (a3) or a copolymer obtained by further reacting a compound (a4) having an epoxy group and an unsaturated bond with a copolymer obtained by copolymerizing (a1) to (a3). Colored photosensitive resin composition. The method of claim 2, The ratio of the constituents derived from each of the above (a1) to (a3) is based on the total moles of the copolymer constituents, 2 to 60 mol% of structural units derived from the compound (a1), 2 to 70 mol% of structural units derived from the compound (a2), 2 to 95 mol% of structural units derived from the compound (a3) It is a range and when it reacts (a4) further, the coloring photosensitive resin composition characterized by reacting (a4) with 5 to 80 mol% with respect to the component derived from (a2). The method of claim 1, The (F) block isocyanate compound is an aliphatic diisocyanate compound hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, an alicyclic diisocyanate compound isophorone diisocyanate, methylene bis (cyclohexyl) diisocyanate, 1,3- or 1 2,2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate or 2,6-toluene diisocyanate, which is a 4-4- (isocyanate methyl) cyclohexane, an aromatic diisocyanate compound At least one isocyanate compound selected from the group consisting of a polymerizing polymer, (o, p or m) -xylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, Phenol, 2-pyridinol, 3-hydroxypyridine, 8-hydroxyquinoline, trihaloethyl alcohol, n-butyl alcohol, 2-ethylhexyl alcohol, furfuryl alcohol, cyclohexyl alcohol, 2-ethoxyhexyl Alcohol, N-hydroxysuccinimide, N-morpholinoethanol, 3-oxazolidineethanol, hexyl mercaptan methylacetamide, acetanilide, thiophenol, mercaptopyridine, 2-ethylhexylhydroxybenzoate , p-cresolformaldehyde, 2-[(dimethylamino) methyl] phenol, pyrazole, 3-methylpyrazole, 1,2,4-triazole, aminocaproic acid, imidazoline, formiate, di From the group consisting of cetone, benzyl methacrylhydramate, 2-benzooxazolone, ureddione, carbodiimide, urettonimine, β-prolactam, diethylmalonate, ethyl acetoacetate, acetoxime, and methyl ethyl ketoxime Characterized in that it is obtained by reacting at least one selected blocking agent. Colored photosensitive resin composition. The method of claim 1, Said binder resin (A) is 5-85 mass% in mass fraction with respect to the total solid in a coloring photosensitive resin composition; The said (B) photopolymerizable compound is 5-50 mass% in mass fraction with respect to the total solid in a coloring photosensitive resin composition; The said (C) photoinitiator is 0.1-40 mass% in mass fraction with respect to the total amount of (A) binder resin and (B) photopolymerizable compound based on solid content; The said (D) coloring material is 3-60 mass% in mass fraction with respect to the total solid in a coloring photosensitive resin composition; And The said (E) solvent is contained by 60 to 90 mass% in mass fraction with respect to the coloring photosensitive resin composition whole quantity, The coloring photosensitive resin composition characterized by the above-mentioned. The pixel formed using the coloring photosensitive resin composition of any one of Claims 1-5, The color filter characterized by the above-mentioned. A liquid crystal display device comprising the color filter of claim 6.