KR20100022402A - A colored photo sensitive 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 the composition, and a liquid crystal display including the color filter are provided to control phenomenon that an overlap level difference seems black by respectively making the overlap level difference of a chromatic layer of R, G, and B pixel be smaller than 0.6μm. CONSTITUTION: A colored photosensitive resin composition comprises: a binder resin; a photopolymerization compound; a photopolymerization initiator; a coloring material; and a solvent. The colored photosensitive resin composition is coated corresponding to R, G, and B pixel on a TFT substrate(1). An average molecular weight(Mw) of the binder resin which is measured by GPC is 5,000 ~ 20,000. The chromatic layer including the colored photosensitive resin composition is formed to make an overlap level difference(Ra) of R, G, and B pixel be smaller than 0.6μm.

Description

Colored photosensitive resin composition, color filter, liquid crystal display device having the same {A COLORED PHOTO SENSITIVE 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, and a liquid crystal display device having the same.

In general, in a liquid crystal display device, in order to realize color image display, a color filter having a plurality of colored layers arranged to correspond to a plurality of pixels of the liquid crystal display element is used.

This color filter is formed on the side of the opposite substrate disposed opposite to the TFT substrate, not on the side of the substrate (hereinafter referred to as TFT substrate) on which the thin film transistor element (hereinafter referred to as TFT) on which the switching element is formed is formed.

However, when the color filter is arranged on the opposite substrate side, alignment with each pixel electrode on the TFT substrate is not easy, and the aperture ratio is small. In addition, since the distance between the color filter and the liquid crystal layer is relatively large, a problem arises in that the display quality resulting from light incident from the oblique direction is lowered. In order to solve this problem, Japanese Patent Laid-Open No. 09-73078 solves this problem by forming a color filter on a TFT substrate.

At this time, when forming the color filter through the conventional technology, there is an overcoat layer on the colored layer to solve the problem of overlap step occurring in the colored layer, when forming the color filter on the TFT substrate Since a contact hole must be formed in the process, it is not possible to use a thermosetting type overcoat layer used in the prior art. Therefore, the overlap step of the colored layer in the color filter layer is large, the opening between the TFT and the color filter is narrowed, and thus there is a problem that the overlap part is dark when the liquid crystal is driven.

In particular, in the liquid crystal display device of large size and high color purity, the above problem causes serious display defects such as visibility, and therefore, a solution for this problem is required.

SUMMARY OF THE INVENTION The present invention has been made to overcome the above-mentioned conventional problems, and an object of the present invention is that even if a color filter is formed on a TFT substrate without an overcoat layer, there is less overlap step of the colored layer for each of R, G, and B pixels, thereby increasing the size and high color purity. The present invention provides a colored photosensitive resin composition, a color filter, and a liquid crystal display device having the same, which are formed on a TFT substrate without problems of display defects such as visibility in a liquid crystal display device.

The present invention for achieving the above object

A coloring photosensitive composition consisting of a binder resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), a coloring material (D) and a solvent (E) and coated corresponding to R, G and B pixels on a TFT substrate, respectively. In the resin composition, the binder resin (A) has a weight average molecular weight (Mw) in terms of polystyrene measured by GPC of 5,000 to 20,000, and the colored layer formed of the colored photosensitive resin composition is R, G, and B pixels. Overlap step (Ra) is characterized in that each formed smaller than 0.6㎛.

The binder resin (A) may be an unsaturated group-containing resin obtained by further reacting the following (A3) with a copolymer obtained by copolymerizing the following (A1) and (A2) compounds.

(A1): vinyltoluene,

(A2): a compound having an unsaturated carboxyl group,

(A3): Compound which has an unsaturated bond and an epoxy group in 1 molecule.

The binder resin (A) obtained by copolymerizing the above (A1) and (A2) may have a ratio of 20 to 60 mol% based on the total moles of the components constituting the copolymer described above. have.

The said binder resin (A) is unsaturated group containing resin obtained by making the compound obtained by copolymerizing vinyltoluene (A1) and the compound (A2) which has an unsaturated carboxyl group further react with the compound (A3) which has an unsaturated bond and an epoxy group in 1 molecule. Other binder resin can be contained in 50 mass% or less with respect to all binder resin.

Moreover, this invention includes the color filter containing the coloring photosensitive resin composition formed on the said TFT substrate.

In addition, the present invention includes a liquid crystal display device including the color filter.

As described above, in the colored photosensitive resin composition, the color filter, and the liquid crystal display device having the same, the overlap step Ra of the colored layer formed for each of R, G, and B pixels is formed to be smaller than 0.6 μm, respectively. It is possible to suppress the phenomenon in which the overlap step portion appears black.

Furthermore, the present invention can be suitably used for a liquid crystal display device having a large size and high color purity by improving display defects such as visibility.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings such that those skilled in the art may easily implement the present invention.

Binder Resin (A)

The binder resin (A) of the present invention may be an unsaturated group-containing resin obtained by further reacting the following (A3) with a copolymer obtained by copolymerizing the following (A1) and (A2) compounds.

(A1): vinyltoluene,

(A2): a compound having an unsaturated carboxyl group,

(A3): Compound which has an unsaturated bond and an epoxy group in 1 molecule.

(A2) component contained in the said binder resin (A) is a compound which has an unsaturated bond and a carboxyl group in 1 molecule, and if it is a carboxylic acid compound which has a unsaturated double bond which can superpose | polymerize, it will not restrict | limit, each independently or two types The above can be used in combination. Specific examples 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 a carboxyl group and a hydroxyl group at both terminals 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.

Any compound having an unsaturated bond polymerizable with (A1) and (A2) contained in the binder resin (A) may be added and used without limitation. For example, styrene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethyl ether, p-vinyl Aromatic vinyl compounds such as benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, and indene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxy Ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxy Hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl Relate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl Methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol meth Methacrylate, methoxy propylene glycol acrylate, methoxy propylene glycol methacrylate, methoxy dipropylene glycol acrylate, methoxy dipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclo Pentadienyl acrylate, dicyclopentadiethyl methacrylate, adamantyl (meth) Acrylate, norbornyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate, etc. Unsaturated carboxylic acid esters; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethyl Unsaturated carboxyl such as aminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate and 3-dimethylaminopropyl methacrylate Acid aminoalkyl esters; Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; Carboxylic acid vinyl esters, such as vinyl acetate, a vinyl propionate, a vinyl butyrate, and a vinyl benzoate; Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether; Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and vinylidene cyanide; Unsaturated amides such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide and N-2-hydroxyethyl methacrylamide; Maleimide, benzylmaleimide, N-phenylmaleimide. Unsaturated imides such as N-cyclohexylmaleimide; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; And monoacryloyl or monomethacryloyl groups at the terminal of the polymer molecular chain of polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate and polysiloxane. The macromonomers which have a etc. are mentioned. These monomers can be used individually or in mixture of 2 or more types, respectively.

  Among these, the 2-hydroxyethyl (meth) acrylate compound etc. which contain a hydrophilic group are preferable in order to improve adhesiveness and developability. These can be used individually or in combination of 2 types or more, respectively.

As used herein, (meth) acrylate means acrylate and / or methacrylate. In addition, when the polycyclic alicyclic compound is included in the above, an overlap step is not preferable because Ra * (µm) increases.

In embodiment of this invention, in binder resin (A) obtained by copolymerizing (A1) and (A2) used by this invention, the ratio of the structural component guide | induced from (A1) comprises said copolymer What is in the range of 20 to 60 mol% with respect to the total number of moles of a component, More preferably, being in the range of 30-50 mol% can obtain the outstanding binder resin with few overlapping steps.

In the embodiment of the present invention, when the copolymer is obtained by copolymerizing (A1) and (A2), there is no particular limitation, and various conventionally known polymerization methods can be employed, and particularly preferred is a solution polymerization method. Can be mentioned. Moreover, although superposition | polymerization temperature and superposition | polymerization time depend on the kind and ratio of the monomer component introduce | transduced, target copolymer molecular weight, and acid value, Preferably it can superpose | polymerize about 60 to 130 degreeC for about 1 to 10 hours. In the above step, part or all of the polymerization initiator may be put in the flask, or part or all of (A1) and (A2) may be put in the flask.

  In addition, when using a solvent in the said process, the solvent used at the time of a normal radical polymerization reaction can be used as a solvent, For example, tetrahydrofuran, dioxane, ethylene glycol dimethylethyl, diethylene glycol Dimethylethyl, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, propylene glycol monomethyl ethyl acetate, 3-methoxybutyl acetate, methanol, ethanol, propanol, n-butanol, Ethylene glycol monomethyl ether, propylene glycol monomethyl ether, toluene, xylene, ethylbenzene, chloroform, dimethyl sulfoxide and the like. These solvents may be used alone or in combination of two or more thereof.

In addition, the polymerization initiator used for the said process can add the polymerization initiator normally used, and is not specifically limited. Specific examples thereof include diisopropylbenzenehydroperoxide, di-t-butylperoxide, benzoyl peroxide, t-butylperoxyisopropylcarbonate, t-amylperoxy-2-ethylhexanoate, t-butyl Organic peroxides such as peroxy-2-ethylhexanoate; 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylbareronitrile), dimethyl 2,2'-azobis (2-methylpropionate) Nitrogen compounds; Etc. can be mentioned. These may be used alone or in combination of two or more thereof.

Moreover, in order to control molecular weight and molecular weight distribution, mercapto type chain transfer agents, such as n-dodecyl mercapto, mercapto acetic acid, and mercapto acetate, alpha -methylstyrene dimer, etc. can also be used as a chain transfer agent. The usage-amount of (alpha) -methylstyrene dimer and a mercapto compound is 0.005 to 5% on a mass basis with respect to the total amount of (A1), (A2)-(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 ..

Specific examples of the compound (A3) having an unsaturated bond and an epoxy group in one molecule include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and 3,4-epoxycyclohexylmethyl (meth). Acrylate, methylglycidyl (meth) acrylate, and the like. Among these, glycidyl (meth) acrylate is preferably used. These can be used individually or in combination of 2 types or more, respectively.

The compound having the unsaturated bond and the epoxy group is preferably reacted with 5 to 80 mol%, particularly preferably 10 to 80 mol%, based on the number of moles of the compound (A2) having an unsaturated carboxyl group contained in the copolymer. If the composition ratio of (A3) is in the said range, since sufficient photocurability and thermosetting are obtained, a sensitivity and pencil hardness are compatible, and also excellent in developability, it is preferable.

In this invention, binder resin (A) can be manufactured by making the said copolymer and (A3) react by the following methods, for example.

The reaction atmosphere of the carboxyl group and the epoxy group of 5 to 80 mol% (A3) in molar fraction with respect to the component derived from the compound (A2) which has the said unsaturated carboxyl group is substituted for the atmosphere in a flask by nitrogen to air, for example 0.01 to 5% of trisdimethylaminomethylphenol by mass relative to the total amount of (A1) to (A3) and a polymerization inhibitor, for example, hydroquinone to 0.001 by mass relative to the total amount of (A1) to (A3) The copolymer and (A3) can be reacted by adding 5% to 5% in a flask and reacting at 60 to 130 ° C for 1 to 10 hours.

In addition, similarly to the polymerization conditions, the charging method and the reaction temperature may be appropriately adjusted in consideration of the amount of heat generated by the production equipment, the polymerization and the like.

In addition, the binder resin (A) of the present invention is obtained by further reacting a compound obtained by copolymerizing vinyltoluene (A1) and a compound (A2) having an unsaturated carboxyl group (A3) having an unsaturated bond and an epoxy group in one molecule. In addition to the unsaturated group-containing resin, a known binder resin used in the production of the colored photosensitive resin composition may be contained in an amount of 50% by mass or less based on the total binder resin in order to reduce film reduction or color change during development.

 In the embodiment of the present invention, the binder resin (A) preferably has a weight average molecular weight in terms of polystyrene thereof in the range of 5,000 to 20,000, and in the range of 6,000 to 20,000, film reduction hardly occurs during development. The missing property of the non-pixel portion tends to be good, and is particularly preferable because it reduces the overlap step.

 It is preferable that it is 1.5-4.0, and, as for the molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of binder resin (A), it is more preferable that it is 1.8-3.5.

If molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] is 1.5-4.0, since it is excellent in acid resistance, it is preferable.

Content of binder resin (A) is 5 to 85 mass% normally with respect to the total solid in colored photosensitive resin composition, Preferably it is the range of 10-70 mass%. When the content of the binder resin (A) is 5 to 85% by mass based on the above criteria, the solubility in the developing solution is sufficient, and development residues are less likely to occur on the substrate of the non-pixel portion, and the film reduction of the pixel portion of the exposed portion at the time of development is reduced. It is preferable because it is hard to occur and the omission of the non-pixel portion tends to be good.

Photopolymerizable Compound (B)

The photopolymerizable compound (B) contained in the colored 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-methylpentane diol di (meth) acrylate, etc. are mentioned.

Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and di Pentaerythritol hexa (meth) acrylate etc. are mentioned. Of these, bifunctional or higher polyfunctional monomers are preferably used.

A photopolymerizable compound (B) is used in 5-50 mass% normally with respect to solid content in colored photosensitive resin composition, Preferably it is used in the range of 7-45 mass%. If the photopolymerizable compound (B) is in the range of 5 to 50% by mass based on the above criteria, the strength and smoothness of the pixel portion tend to be good, and therefore it is preferable.

Photoinitiator (C)

Although the photoinitiator (C) contained in the coloring photosensitive resin composition of this invention is not restrict | limited, It is 1 or more types of compounds chosen from the group which consists of a triazine type compound, an acetophenone type compound, a biimidazole type compound, and an oxime compound. The coloring photosensitive resin composition containing said photoinitiator (C) is highly sensitive, and the film | membrane formed using this composition becomes favorable the intensity | strength and surface smoothness of the pixel part.

Moreover, when photopolymerization start adjuvant (C-1) is used together with a photoinitiator (C), since the coloring photosensitive resin composition containing these becomes more sensitive and the productivity at the time of forming a color filter using this composition is preferable, it is preferable. .

As a triazine type compound, it is 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1, 3, 5- triazine, 2, 4-bis (trichloromethyl) -6, for example. -(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-triazine , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl ) -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-morpholinopropan-1-one , 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane- 1-one oligomer etc. are mentioned. As an acetophenone type compound, the compound represented by following formula (1) is mentioned, for example.

<Formula 1>

In Formula 1, R1 to R4 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group which may be substituted by an alkyl group having 1 to 12 carbon atoms, a benzyl group or carbon number which may be substituted by an alkyl group having 1 to 12 carbon atoms. The naphthyl group which may be substituted by the alkyl group of 1-12 is shown.

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- On, 2-methyl-2-dimethylamino (4-morpholinophenyl) propan-1-one, 2-methyl-2-diethylamino (4-morpholinophenyl) propan-1-one, etc. may be mentioned. have.

As a biimidazole compound, it is 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetraphenyl biimidazole, 2,2'-bis (2,3-dichloro, for example. Phenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimidazole , 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, phenyl group in 4,4', 5,5 'position And imidazole compounds substituted with groups. Among them, 2,2'bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole is preferably used.

Examples of the oxime compound include the following formulas (2), (3) and (4).

<Formula 2>

<Formula 3>

<Formula 4>

Moreover, as long as it does not impair the effect of this invention, the other photoinitiator 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) -Butyl peroxycarbonyl) benzophenone, 2,4, 6-trimethyl benzophenone, 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.

Other 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenylclioxylic acid Methyl, a titanocene compound, etc. are mentioned as another photoinitiator.

In addition, you may use combining a photoinitiator (C-1) with a photoinitiator (C).

As the photopolymerization initiation assistant (C-1), an amine compound and a carboxylic acid compound are preferably used.

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

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 amount of the photopolymerization initiator (C) to be used is usually 0.1 to 40% by mass, preferably 1 to 30% by mass, based on the solids content, based on the total amount of the (A) binder resin and the (B) photopolymerizable compound. The usage-amount of an adjuvant (C-1) is 0.1-50 mass% normally on the said reference | standard, Preferably it is 1-40 mass%.

When the usage-amount of a photoinitiator (C) 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 auxiliary (C-1) exists 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.

Coloring material (D)

It is preferable that a coloring material (D) is an organic pigment or inorganic pigment normally used for a pigment dispersion resist as a pigment normally. If necessary, 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 complex metal oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc and antimony Etc. can be mentioned.

 Specific examples of the organic pigment and inorganic pigment 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.

 These coloring materials (D) can be used individually or in combination of 2 or more types, respectively. Content of a coloring material (D) is 3-60 mass% normally on the basis of the total solid content in a coloring photosensitive resin composition, Preferably it is the range of 5-55 mass%. If the content of the coloring material (D) is in the range of 3 to 60% by 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 does not decrease during development. It is preferable because it tends to.

Solvent (E) and Additives (F)

The solvent (E) contained in the colored photosensitive resin composition of this invention is not specifically limited, Various organic solvents used in the field of colored 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 dimethyl ether, diethylene glycol diethyl ether, and diethylene. Diethylene glycol dialkyl ethers such as glycol dipropyl ether and diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, and propylene glycol Alkylene glycol alkyl ether acetates such as monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxy butyl acetate and methoxy pentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, methyl ethyl ketone, acetone , Ketones such as methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, ethyl 3-ethoxypropionate, 3-methoxy Ester, such as methyl propionate, Cyclic ester, such as (gamma) -butyrolactone, etc. are mentioned.

Among the solvents described above, organic solvents having a boiling point of 100 ° C. to 200 ° C. in the coating properties and drying properties are preferable, and alkylene glycol alkyl ether acetates, ketones, and 3-ethoxy are more preferable. Ester, such as ethyl propionate and the methyl 3-methoxypropionate, is mentioned, More preferably, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxy propionate, 3- Methyl methoxy propionate etc. are mentioned. These solvents (E) can be used individually or in mixture of 2 or more types, respectively.

Content of the solvent (E) in the coloring photosensitive resin composition of this invention is 60-90 mass% normally with a mass fraction with respect to the coloring photosensitive resin composition whole quantity containing it, Preferably it is 70-85 mass%. When the content of the solvent (E) 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, or the like. Since coating property tends to become favorable at the time, it is preferable.

In the coloring photosensitive resin composition of this invention, it is also possible to add additives (F), 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.

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

Specific examples of other high molecular compounds include curable resins such as epoxy resins and maleimide resins, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ethers, polyfluoroalkyl acrylates, polyesters, and thermoplastic resins such as polyurethanes. have.

Commercially available surfactants can 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, For example, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol diester, sorbitan fatty ester, fatty acid modified polyester, tertiary amine modified polyurethane , Polyethylenimine, etc., trade names include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by Tochem Products), MEGAFAC (manufactured by Dainippon Ink & Chemicals Co., Ltd.), Florard (manufactured by Sumitomo 3M Inc.), Asahi guard, Suflon (manufactured by Asahi Glass Co., Ltd.), SOLSPERSE (made by Genka Corporation), EFKA (made by EFKA Chemicals), PB 821 (made by Ajinomoto Co., Ltd.), etc. are mentioned.

As the adhesion promoter, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyl tris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N -(2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltri Methoxysilane, etc. are mentioned.

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

Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole, alkoxybenzophenone and the like. Specific examples of the aggregation inhibitor include sodium polyacrylate and the like.

 The coloring photosensitive resin composition of this invention can be manufactured by the following methods, for example. The coloring material (D) 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 (D) is about 0.2 µm or less. At this time, a pigment dispersant is used as needed, and some or all of binder resin (A) may be mix | blended. The remainder of binder resin (A), the photopolymerizable compound (B), the photoinitiator (C), the other components used as needed, and the additional solvent as needed in the obtained dispersion liquid (henceforth a mill base). Is further added to a predetermined concentration to obtain a desired colored photosensitive resin composition.

1A to 1H, a process chart of forming a color filter using a color filter on array (COA) method using the colored photosensitive resin composition of the present invention is illustrated.

When manufacturing the color filter by the COA (Color Filter on Array) method using the colored photosensitive resin composition according to the present invention, as shown in Figure 1a, using the colored photosensitive resin composition directly to the TFT substrate (1) Each pixel pattern 2 of red (R), green (G), and blue (B) is formed on the TFT element 3 with a predetermined thickness. In the figure, reference numeral 4 denotes a nitride film (SiNx).

For example, the red pixel pattern is completed by coating, exposing, developing and curing the red photosensitive resin composition on the red pixel. Next, the green pixel pattern is completed by coating, exposing, developing and curing the green photosensitive resin composition on the green pixel. At this time, since the green pixel pattern overlaps the red pixel pattern by a predetermined width, an overlap step occurs. Finally, the blue pixel pattern is completed by coating, exposing, developing and curing the blue photosensitive resin composition on the blue pixel. In this case, the blue pixel pattern overlaps the green pixel pattern and the red pixel pattern by a predetermined width, thereby causing an overlap step.

In fact, referring to FIG. 2, a photograph showing an overlap step formed by application of the colored photosensitive resin composition is shown.

As shown in the drawing, as the boundary of the red pixel pattern and the boundary of the blue pixel pattern overlap each other, an overlap step of a predetermined height is formed on the boundary. Of course, as described above, the larger the overlap step, the darker this part appears. However, since the overlap step is all controlled to a value smaller than 0.6 µm by the characteristics of the colored photosensitive resin composition according to the present invention, such a dark appearance phenomenon hardly occurs in the liquid crystal display device according to the present invention.

Here, the measurement of the overlap step will be described below, but since the laboratory is not easy to reproduce, it is measured by the value on the black matrix.

Meanwhile, although not shown, the black matrix for preventing color mixing may be formed of a resin or a metal separately from the formation of the colored photosensitive resin composition, and may also be formed through the lamination of the colored photosensitive resin composition.

In addition, after this process, the colored photosensitive resin composition in the region corresponding to the source / drain electrodes is removed by a conventional photolithography process so that the source / drain electrodes of the TFT elements are exposed.

In FIG. 1A, a predetermined portion of the colored photosensitive resin composition corresponding to the source / drain electrodes of the TFT element is shown in an etched state. However, the nitride film 4 is not yet etched.

As shown in FIG. 1B, in the process of forming an electrical contact hole between the TFT element 3 and the electrode (IZO layer), the positive photosensitive resin film 5 is patterned using a mask to remove the nitride film.

As illustrated in FIG. 1C, a contact hole is formed by dry etching (dry etching) the insulating film 4 located on the lower surface (electrically conductive path) of the positive photosensitive resin film 5.

As shown in Fig. 1D, the positive photosensitive resin film 5 remaining on each pixel pattern 2 is removed using a stripper developer.

As shown in Fig. 1E, an IZO layer 6, which will be used as a common electrode with the TFT element 3, is deposited on the entire upper surface.

As shown in FIG. 1F, a positive photosensitive resin film 7 is formed on the common electrode (IZO layer) 6 to form the common electrode (IZO layer) 6.

As shown in FIG. 1G, all of the common electrode (IZO layer) 6 of the exposed portion (the portion where the Izo layer is exposed) of the positive photosensitive resin film 7 is removed by wet etching (wet etching).

As shown in FIG. 1H, the COA method color filter is completed by removing the remaining positive photosensitive resin film 7 on the IZO layer 6 with a stripper developer.

The present invention also includes a liquid crystal display device having the color filter.

The liquid crystal display device of the present invention includes all the configurations known in the art, except that the 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. For example, a transmissive liquid crystal display device in which a counter electrode substrate including a thin film transistor (TFT element), a pixel electrode, and an alignment layer is faced at predetermined intervals, and a liquid crystal material is injected into the gap to form a liquid crystal layer. Can be. Moreover, the present invention can also be applied to a reflective liquid crystal display device. Of course, the present invention includes a liquid crystal display including a backlight.

Binder Resin Synthesis Example

Resin (A-1)

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube was prepared, and as a monomer dropping lot, dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate 42.8 g (0.2 mol), benzyl maleimide 37.4 g (0.2 mol), 21.6 g (0.3 mol) acrylic acid, 35.4 g (0.3 mol) vinyltoluene, 4 g t-butylperoxy-2-ethylhexanoate, propylene glycol mono 40 g of methyl ether acetate (PGMEA) was added to the mixture, followed by stirring and preparation. As a chain transfer agent dropping tank, 6 g of n-dodecanethiol and 24 g of PGMEA were added and stirred and mixed. Thereafter, 395 g of PGMEA was introduced into the flask, and the atmosphere in the flask was changed to nitrogen from air, and then the temperature of the flask was raised to 90 ° C. while stirring. Subsequently, dropping of the monomer and the chain transfer agent was started from the dropping lot. The dropwise addition was carried out for 2 hours while maintaining 90 ° C, and after 1 hour, the temperature was raised to 110 ° C and maintained for 3 hours, and then a gas introduction tube was introduced to obtain oxygen / nitrogen = 5/95 (v / v) mixed gas. Bubbling was initiated. Subsequently, 14.2 g (0.1 mol) of glycidyl methacrylate, 0.4 g of 2,2'-methylenebis (4-methyl-6-t-butylphenol) and 0.8 g of triethylamine were added to the flask at 110 ° C. The reaction was continued for 8 hours to obtain Resin A-1 having a solid acid value of 71 mgKOH / g. The weight average molecular weight of polystyrene conversion measured by GPC was 17,000, and molecular weight distribution (Mw / Mn) was 2.3.

Resin (A-2)

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube was prepared, and as a monomer dropping lot, 37.4 g (0.2 mol) of benzyl maleimide, 21.6 g (0.3 mol) of acrylic acid, and 59.0 g of vinyltoluene (0.5 mol), 4 g of t-butylperoxy-2-ethylhexanoate and 40 g of propylene glycol monomethyl ether acetate were added thereto, followed by stirring and mixing. As a chain transfer agent dropping tank, 6 g of n-dodecanethiol and 24 g of PGMEA were added. Was prepared and stirred and mixed. Thereafter, 395 g of PGMEA was introduced into the flask, and the atmosphere in the flask was changed to nitrogen from air, and then the temperature of the flask was raised to 90 ° C. while stirring. Subsequently, dropping of the monomer and the chain transfer agent was started from the dropping lot. The dropwise addition was performed for 2 hours while maintaining 90 ° C, and after 1 hour, the temperature was raised to 110 ° C and maintained for 5 hours. Bubbling was initiated. Subsequently, 14.2 g (0.1 mol) of glycidyl methacrylate, 0.4 g of 2,2'-methylenebis (4-methyl-6-t-butylphenol) and 0.8 g of triethylamine were added to the flask at 110 ° C. The reaction was continued for 8 hours to obtain Resin A-2 having a solid acid value of 85 mgKOH / g. The weight average molecular weight of polystyrene conversion measured by GPC was 13,000, and molecular weight distribution (Mw / Mn) was 2.2.

Resin (A-3)

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube was prepared, and as the monomer dropping lot, 37.4 g (0.2 mol) of benzyl maleimide, 21.6 g (0.3 mol) of acrylic acid, and benzyl methacrylate were prepared. 88 g (0.5 mole), 4 g of t-butylperoxy-2-ethylhexanoate and 40 g of propylene glycol monomethyl ether acetate were added thereto, followed by stirring and mixing. As a chain transfer agent dropping tank, 6 g of n-dodecanethiol and PGMEA were added. 24g was prepared and the thing which stirred and mixed was prepared. Thereafter, 395 g of PGMEA was introduced into the flask, and the atmosphere in the flask was changed to nitrogen from air, and then the temperature of the flask was raised to 90 ° C. while stirring. Subsequently, dropping of the monomer and the chain transfer agent was started from the dropping lot. The dropwise addition was carried out for 2 hours while maintaining 90 ° C, and after 1 hour, the temperature was raised to 110 ° C and maintained for 3 hours, and then a gas introduction tube was introduced to obtain oxygen / nitrogen = 5/95 (v / v) mixed gas. Bubbling was initiated. Subsequently, 14.2 g (0.1 mol) of glycidyl methacrylate, 0.4 g of 2,2'-methylenebis (4-methyl-6-t-butylphenol) and 0.8 g of triethylamine were added to the flask at 110 ° C. The reaction was continued for 8 hours to obtain Resin A-3 having a solid acid value of 73 mgKOH / g. The weight average molecular weight of polystyrene conversion measured by GPC was 17,300, and molecular weight distribution (Mw / Mn) was 2.3.

Resin (A-4)

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen introduction tube was prepared, and as a monomer dropping lot, 44.5 g (0.10 mole) of rosin acrylate, 23.6 g (0.20 mole) of vinyltoluene, and benzyl methacryl 52.8 g (0.3 mol) of rate, 34.4 g (0.4 mol) of methacrylic acid, 4 g of t-butylperoxy-2-ethylhexanoate and 40 g of propylene glycol monomethyl ether acetate were added thereto, followed by stirring and mixing to prepare a chain transfer agent. As the dripping tank, 6 g of n-dodecanethiol and 24 g of PGMEA were put, and the thing mixed with stirring was prepared. Thereafter, 395 g of PGMEA was introduced into the flask, and the atmosphere in the flask was changed to nitrogen from air, and then the temperature of the flask was raised to 90 ° C. while stirring. Subsequently, dropping of the monomer and the chain transfer agent was started from the dropping lot. The dropwise addition was carried out for 2 hours while maintaining 90 ° C, and after 1 hour, the temperature was raised to 110 ° C and maintained for 3 hours, and then a gas introduction tube was introduced to obtain oxygen / nitrogen = 5/95 (v / v) mixed gas. Bubbling was initiated. Subsequently, 14.2 g (0.1 mol) of glycidyl methacrylate, 0.4 g of 2,2'-methylenebis (4-methyl-6-t-butylphenol) and 0.8 g of triethylamine were added to the flask at 110 ° C. Reaction was continued for 8 hours and resin A-4 whose solid acid value is 99 mgKOH / g was obtained. The weight average molecular weight of polystyrene conversion measured by GPC was 28,000, and molecular weight distribution (Mw / Mn) was 2.6.

Resin (A-5)

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube was prepared, and as a monomer dropping lot, 37.4 g (0.2 mol) of benzyl maleimide, 14.4 g (0.2 mol) of acrylic acid, and 70.8 g of vinyltoluene (0.6 mol), 4 g of t-butylperoxy-2-ethylhexanoate and 40 g of propylene glycol monomethyl ether acetate were added thereto, followed by stirring and mixing. As a chain transfer agent dropping tank, 6 g of n-dodecanethiol and 24 g of PGMEA were added. Was prepared and stirred and mixed. Thereafter, 395 g of PGMEA was introduced into the flask, and the atmosphere in the flask was changed to nitrogen from air, and then the temperature of the flask was raised to 90 ° C. while stirring. Subsequently, dropping of the monomer and the chain transfer agent was started from the dropping lot. The dropwise addition was carried out for 2 hours each while maintaining 90 ° C, and after 1 hour, the reaction was continued at 110 ° C for 8 hours to obtain a resin A-5 having a solid acid value of 80 mgKOH / g. The weight average molecular weight of polystyrene conversion measured by GPC was 16,000, and molecular weight distribution (Mw / Mn) was 2.2.

About the measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) of said binder resin, it carried out on condition of the following using GPC method.

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

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

Column temperature: 40 ℃

Mobile phase solvent: tetrahydrofuran

Flow rate: 1.0 ml / min

Injection volume: 50µl

Detector: RI

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

Calibration standard: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)

The ratio of the weight average molecular weight and number average molecular weight obtained above was made into molecular weight distribution (Mw / Mn).

Example

As follows, the present invention will be described in more detail based on Examples. However, the scope of the present invention is not limited to these embodiments. The scope of the invention is indicated in the appended claims, and further includes all modifications within the meaning and range equivalent to those of the claims. In addition, "%" and "part" which show content below are mass references | standards unless there is particular notice.

Examples 1-5 and Comparative Examples 1-3

As shown in Table 1, Examples 1 to 5 and Comparative Examples 1 to 3 showed components and contents.

TABLE 1

TABLE 2

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

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

Photoinitiator (C-2): 4,4'-bis (diethylamino) benzophenone (EAB-F; manufactured by Hodogaya Kagaku Co., Ltd.)

Coloring material (D-1): C.I. Pigment Blue 15: 6

Coloring material (D-2): C.I. Pigment Blue PV23

Solvent (E): propylene glycol monomethyl ether acetate

Additive (F-1): Pigment Dispersant (Polyester)

Additive (F-2): 3-methacryloxypropyl trimethoxysilane

<Example 1>

In each component of the said Table 1, it mixes so that the total amount of the pigment which is a coloring material (D) and the pigment dispersant which is an additive (F) 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.

Thereafter, a glass substrate of 2 square inches (manufactured by Corning Corporation, E2K) was washed sequentially with a neutral detergent, water, and alcohol, and then dried. The above-mentioned colored photosensitive resin composition (Table 1) was exposed on the glass substrate at an exposure amount (365 nm) of 75 mJ / cm 2, and spin-coated so that the film thickness after post-firing when the developing step was omitted was 3.3 占 퐉. Pre-drying was carried out 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) Was made into 100 micrometers, and was irradiated with the exposure amount (365 nm) of 75 mJ / cm <2> in air | atmosphere using the ultra-high pressure mercury lamp (brand name USH-250D) by Ushio Denki Corporation. Thereafter, the coating film was immersed in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 26 ° C. for a predetermined time, and then dried at 230 ° C. for 30 minutes after washing with water.

<Example 2>

The same operation as in Example 1 was carried out except that the content in Example 1 was changed to the amount indicated in Table 1. The evaluation results are shown in Table 3.

<Example 3>

In Example 1, operation similar to Example 1 was performed except having changed resin A-1 into resin A-1 and A-3. The evaluation results are shown in Table 3.

<Example 4>

In Example 1, operation similar to Example 1 was performed except having changed resin A-1 into resin A-2. The evaluation results are shown in Table 3.

Example 5

In Example 1, operation similar to Example 1 was performed except having changed resin A-1 into resin A-2 and A-3. The evaluation results are shown in Table 3.

Comparative Example 1

Operation similar to Example 1 was performed except having changed resin A-1 into resin A-3 in Example 1. The evaluation results are shown in Table 3.

Comparative Example 2

In Example 1, operation similar to Example 1 was performed except having changed resin A-1 into resin A-4. The evaluation results are shown in Table 3.

Comparative Example 3

Operation similar to Example 1 was performed except having changed resin A-1 into resin A-5 in Example 1. The evaluation results are shown in Table 3.

TABLE 3

Overlap step evaluation is a specimen prepared in the same manner as in Example 1 on a 2 inch square inch BM (Black Matrix) glass substrate is obtained as shown in FIG. At this time, the step was measured for each step using a Veeco Dektek 6M Stylus Profiler, and then the overlap step was calculated by Equation 1.

As described above, in the COA color filter, the overlap step substantially occurs between the R, G, and B pixel patterns, but it is noted here that the overlap step is indirectly formed on the BM glass substrate for the convenience of experimentation.

 (Equation 1)

Ra * (μm) = a (height from glass substrate to colored layer on BM layer) -b (height of BM)

(1) ◎: Ra * (μm) <0.6um, X: Ra * (μm)> = 0.6um

In FIG. 3, 11 is a pixel pattern, 12 is a black matrix BM, and 13 is a glass substrate.

(2) ◎: No developing residue on substrate, X: Developing residue on substrate.

According to Table 3, the colored photosensitive resin compositions of Examples 1, 2, 3, 4, and 5 containing the binder resin of the present invention are excellent in overlap step and developing residue, and thus a color filter without opening ratio, visibility, and display defect is obtained. I could see that.

1A to 1H are process charts for forming a color filter using a color filter on array (COA) method using the colored photosensitive resin composition of the present invention.

2 is a photograph for showing an overlap step formed by application of the colored photosensitive resin composition.

FIG. 3 is a cross-sectional view in which an overlap step is formed by applying a colored photosensitive resin composition on a BM (Black Matrix) using the colored photosensitive resin composition of the present invention. FIG.

-Description of the main symbols in the drawing-

One; TFT substrate 2; Pixel pattern

3; TFT element 4; Nitride Film (SiNx)

5; Positive photosensitive resin film 6; IZO layer

7; Positive photosensitive resin film 11; Pixel Pattern (Color Layer)

12; Black matrix (BM) 13; Glass substrate

Claims (6)

Color photosensitive which consists of binder resin (A), a photopolymerizable compound (B), a photoinitiator (C), a coloring material (D), and a solvent (E), and coats corresponding to R, G, and B pixels on a TFT substrate, respectively. In the resin composition, The binder resin (A) has a weight average molecular weight (Mw) of 5,000 to 20,000 in terms of polystyrene measured by GPC, and the colored layer formed of the colored photosensitive resin composition is overlapped by R, G, and B pixels. ) The colored photosensitive resin composition characterized in that the step Ra is smaller than 0.6 µm, respectively. The method of claim 1, The said binder resin (A) is unsaturated group containing resin obtained by making the following (A3) further react with the copolymer obtained by copolymerizing the following (A1) and (A2) compounds, The coloring photosensitive resin composition characterized by the above-mentioned. (A1): vinyltoluene, (A2): a compound having an unsaturated carboxyl group, (A3): Compound which has an unsaturated bond and an epoxy group in 1 molecule. The method of claim 2, The binder resin (A) obtained by copolymerizing the above (A1) and (A2) has a ratio of 20 to 60 mol% based on the total moles of components constituting the copolymer described above. The coloring photosensitive resin composition characterized by the above-mentioned. The method of claim 2, The said binder resin (A) is unsaturated group containing resin obtained by making the compound obtained by copolymerizing vinyltoluene (A1) and the compound (A2) which has an unsaturated carboxyl group further react the compound (A3) which has an unsaturated bond and an epoxy group in 1 molecule. The coloring photosensitive resin composition containing other binder resin in 50 mass% or less with respect to all binder resin. The color filter containing the coloring photosensitive resin composition formed on the TFT substrate in any one of Claims 1-4. A liquid crystal display device comprising the color filter according to claim 5.

Images