KR20120046462A - A colored photosensitive resin composition, color filter and liquid crystal display device having the same - Google Patents

Abstract

PURPOSE: Colored photo-sensitive resin compositions, color filters including the same, and liquid crystal display devices including the same are provided to reduce the generation of pattern exfoliation during a developing process and a compressing process. CONSTITUTION: Colored photo-sensitive resin compositions include coloring agents, alkali soluble resins, photopolymerizable compounds, photopolymerizable initiators, and solvents. The photopolymerizable compounds include fluorene-based acrylate monomers represented by chemical formula 1. In chemical formula 1, n and m are identical or different; and the sum of n and m is between 1 and 30. The content of the photopolymerizable compounds is 5 to 40 parts by weight based on the solid materials of the compositions. The content of the fluorene-based acrylate monomer is 10 to 100 parts by weight based on the photopolymerizable compounds.

Description

A colored photosensitive resin composition, a color filter and a liquid crystal display including 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 and a color filter and a liquid crystal display device including the same.

Color filters are manufactured by dyeing, printing, electrodeposition, pigment dispersion, film transfer, etc., and are not only used in liquid crystal display panels (LCDs) but also charge coupled devices (CCDs). ) And liquid crystal shutters are widely used. In particular, since color filters are one of the most important parts for reproducing color tones in LCDs, research on the manufacturing method of color filters with excellent processability and product reliability has been continued in the LCD manufacturing process.

Recently, materials for color filters have high sensitivity, excellent reliability in forming patterns and high color reproducibility of high transmittance. Accordingly, the pigment concentration of the colored photosensitive resin composition used to manufacture the color filter is continuously increasing, and in order to improve the productivity and yield in process, a colored photosensitive resin composition having an equivalent sensitivity and reliability even at a low exposure amount is required. However, the colored layer formed on the base when forming a pixel using the conventional colored photosensitive resin composition has a disadvantage in that the pattern cannot be maintained at a low exposure amount due to the pigment of high concentration.

An object of the present invention for solving the above problems is to provide a coloring photosensitive resin composition that is excellent in sensitivity and resolution at low exposure amount, and excellent adhesion to the substrate, without peeling of the pattern during the development process.

Another object of the present invention is to provide a color filter manufactured using the colored photosensitive resin composition.

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

According to an aspect of the present invention,

In the coloring photosensitive resin composition containing (A) a coloring agent, (B) alkali-soluble resin, (C) photopolymerizable compound, (D) photoinitiator, and (E) solvent,

The said (C) photopolymerizable compound relates to the coloring photosensitive resin composition containing the fluorene type acrylate monomer represented by following formula (1).

[Formula 1]

(In Formula 1, n and m are integers that are different or the same as each other, and n + m is 1 <n + m <30.)

The (C) photopolymerizable compound may be included in an amount of 5 to 40 parts by weight based on the solids of the colored photosensitive resin composition. In addition, the fluorene-based acrylate monomer may be included in an amount of 10 to 100 parts by weight based on the (C) photopolymerizable compound.

The colored photosensitive resin composition may further include a curable monomer having a bifunctional or higher functional group as the (C) photopolymerizable compound.

Another aspect of the present invention relates to a color filter made of the colored photosensitive resin composition.

Another aspect of the present invention relates to a liquid crystal display device having the color filter.

The colored photosensitive resin composition according to the present invention may exhibit excellent sensitivity and resolution at a low exposure amount at the time of pattern formation even when a pigment of high concentration is included.

Colored photosensitive resin composition according to the present invention can provide a pattern excellent in adhesion with the substrate, there is no peeling of the pattern during the development process can improve the productivity and yield in the process.

The colored photosensitive resin composition according to the present invention provides a liquid crystal display device in which surface defects and the like do not occur in the pixel portion, and can be very preferably used for manufacturing various high quality color filters.

Hereinafter, the present invention will be described in detail so that those skilled in the art can easily practice.

This invention provides the coloring photosensitive resin composition containing (A) coloring agent, (B) alkali-soluble resin, (C) photopolymerizable compound, (D) photoinitiator, and (E) solvent.

(A) Colorant

The said coloring agent (A) is not limited in color tone, A color tone can be selected according to the use of a color filter.

The (A) coloring agent may be used without limitation as long as it is used in the art, and specifically, may be used alone or in combination of two or more in pigments, dyes and natural dyes.

The pigments include organic pigments, compounds which are classified as pigments in the Color Index (Published by The Society of Dyers and Colourists), inorganic pigments such as inorganic salts such as metal oxides, metal complex salts and barium sulfate, or mixtures thereof. It is possible to use, preferably organic dyes exhibiting excellent heat resistance and color development.

As the inorganic pigment, metal compounds such as metal oxides and metal complex salts may be used. Specific examples thereof include oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, and carbon black. Or a composite metal oxide.

As the pigment, compounds classified as pigments in the color index (Published by The society of Dyers and Colourists) may be used. More specifically, pigments having the following color index (CI) numbers may be used. It is not limited to.

C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139 , 147, 148, 150, 153, 154, 166, 173, 180, 185, 194 and 214;

C.I. Pigment orange 13, 31, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71 and 73;

C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264 and 265;

C.I. Pigment blue 15, 15: 3, 15: 4, 15: 6, 21, 28, 64, 60 and 76;

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

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

C.I. Pigment brown 23, 25 and 28;

C.I. Pigment black 1 and 7 and the like.

Preferably, the organic pigments include CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 185, CI Pigment Red 177, CI Pigment Red 242, CI Pigment Red 254, CI pigment violet 23, CI pigment blue 15: 6, CI pigment green 7, CI pigment green 36, CI pigment green 58, etc. can be used.

The said (A) coloring agent can use the above-mentioned organic pigment individually or in combination of 2 or more types, respectively. For example, the coloring agent for forming a red pixel among the above-mentioned (A) coloring agents is C.I. Pigment Red 254 and C.I. Pigment red 177, wherein the colorant for forming the green pixel is C.I. Pigment Green 58, C.I. Pigment Yellow 150 or C.I. Pigment yellow 138, wherein the colorant for forming the blue pixel is C.I. Pigment Blue 15: 6 and C.I. Pigment Violet 23 may be combined.

It is preferable to use the said pigment that the particle size is uniform. As a method of making the particle diameter of the said pigment uniform, the method of containing a pigment dispersing agent and performing a dispersion process is mentioned, According to this method, the pigment dispersion liquid of the state in which the pigment was disperse | distributed uniformly in the solution can be obtained.

The said pigment dispersant can be used individually or in combination with 2 or more types of surfactant, such as cationic, anionic, nonionic, and amphoteric.

As the brand name of the surfactant, Megapack (manufactured by Dainippon Ink & Chemicals Co., Ltd.), BYK, Disperbyk (manufactured by Big Chemi Japan Co., Ltd.), Sol Spas (manufactured by Geneca Co., Ltd.), and the like can be used. .

The pigment dispersant may be used in an amount of 1 part by weight or less based on 1 part by weight of the colorant (A), and preferably in an amount of 0.05 to 0.5 parts by weight. When used in the above range, it is possible to obtain a pigment of uniform particle size.

The colorant (A) may be included in an amount of 5 to 70 parts by weight, and preferably 10 to 50 parts by weight, based on the solids of the colored photosensitive resin composition. When the (A) colorant is included in an amount of 5 to 70 parts by weight, even when a thin film is formed, the color density of the pixel is sufficient, and the omission of the non-pixel portion during development does not decrease, so that the occurrence of residue can be reduced.

Solid content in a coloring photosensitive resin composition in this invention means the total content of the remaining component except a solvent from a coloring photosensitive resin composition.

(B) alkali-soluble resin

The said (B) alkali-soluble resin melt | dissolves in the solvent of this invention, and functions as a binder resin with respect to the said (A) coloring agent.

As long as the said (B) alkali-soluble resin is resin which can melt | dissolve in an alkaline developing solution, it can be used, without restrict | limiting the kind in particular. Preferably, the copolymer (B-1) or the copolymer of the first monomer (b1) having a carboxyl group and an unsaturated bond and the second monomer (b2) having an unsaturated bond copolymerizable with the first monomer (b1) ( The polymer (B-2) containing the photopolymerizable unsaturated bond obtained by making B-1) react the compound (b3) which has an unsaturated bond and an epoxy group can be used.

Specific examples of the first monomer (b1) having the carboxyl group and the unsaturated bond include unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid; Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; And anhydrides of the above unsaturated dicarboxylic acids. The 1st monomer (b1) illustrated above can be used individually or in combination of 2 types or more, respectively. Moreover, the monomer containing a hydroxyl group and a carboxyl group can also be used together in the same molecule like (alpha)-(hydroxymethyl) acrylic acid.

Specific examples of the second monomer (b2) having an unsaturated bond copolymerizable with the first monomer (b1) include styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, and m-methoxy Styrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethyl ether, p-vinylbenzylmethyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinyl Aromatic vinyl compounds such as benzyl glycidyl ether; Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, alkyl (meth) acrylates such as sec-butyl (meth) acrylate and t-butyl (meth) acrylate; Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.02,6] decane-8-yl (meth) acrylate, 2-dish Alicyclic (meth) acrylates such as clofentanyloxyethyl (meth) acrylate and isobornyl (meth) acrylate; Aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate; Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm N-substituted maleimide compounds such as -methylphenylmaleimide, Np-methylphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, and Np-methoxyphenylmaleimide; Unsaturated amide compounds such as (meth) acrylamide and N, N-dimethyl (meth) acrylamide; 3- (methacryloyl oxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyl oxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, etc. And unsaturated oxetane compounds. (B2) illustrated above can be used individually or in combination of 2 types or more, respectively.

In addition, the copolymer (B-1) may be copolymerized by further including other monomers in addition to the first monomer (b1) and the second monomer (b2).

Specific examples of the compound (b3) having the unsaturated bond and the epoxy group further reacted with the copolymer (B-1) of the first monomer (b1) and the second monomer (b2) include glycidyl (meth) acrylate. , 3,4-epoxybutyl (meth) acrylate, 2,3-epoxycyclopentyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 6,7-epoxyheptyl (meth) acrylate , Methylglycidyl (meth) acrylate, 3,4-epoxytricyclo [5.2.1.02,6] decane-9-yl (meth) acrylate, and the like. (B3) illustrated above can be used individually or in combination of 2 types or more, respectively.

In the copolymer (B-1) of the first monomer (b1) and the second monomer (b2), the ratio of the structural units derived from the first monomer (b1) is the total mole number of the structural units constituting the copolymer. It may be in the range of 2 to 95 mol%, preferably 2 to 70 mol% in terms of mole fraction, and the ratio of the structural unit derived from the second monomer (b2) is 2 to 70 mol%, preferably 2 to 50 mol. Can be%. When the ratio of the structural unit derived from each of said (b1) and (b2) exists in the said range, since it is excellent in developability, solubility, and adhesiveness with a board | substrate, a preferable copolymer can be obtained.

The (b3) may be reacted with 2 to 80 mol%, preferably 2 to 50 mol% with respect to the total number of moles of the structural unit derived from (b1). When the (b3) is reacted in the above range, the crosslinking density is increased, so the sensitivity and developability are excellent.

An example of the manufacturing method of the copolymer (B-1) of said (b1) and (b2) is as follows. To the flask equipped with the stirrer, the thermometer, the reflux cooling tube, the dropping lot and the nitrogen inlet tube, 0.5 to 20 times the solvent was introduced on a weight basis with respect to the total amount of (b1) and (b2). Replace with Then, after heating a solvent at 40-140 degreeC, 0.5-20 times of a solvent and a polymerization initiator with respect to the predetermined amount of said (b1) and (b2) and the total amount of said (b1) and (b2) To the total moles of the above (b1) and (b2), a solution (agitated and dissolved under room temperature or heating) added 0.1 to 10 mol% was added dropwise to the flask over 0.1 to 8 hours from a dropping lot, and 40 to 140 ° C. Stir for 1 to 10 hours.

In the above process, a solvent may be used in the normal radical polymerization reaction, specific examples of the solvent may be tetrahydrofuran, dioxane, ethylene glycol dimethylethyl, diethylene glycol dimethylethyl, acetone, methyl ethyl ketone, methyl iso Butyl 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. The solvents exemplified above may be used alone or in combination of two or more thereof.

The polymerization initiator may be a polymerization initiator commonly used in the art, it is not particularly limited. Specific examples of the polymerization initiator include diisopropylbenzenehydroperoxide, di-t-butylperoxide, benzoyl peroxide, t-butylperoxyisopropylcarbonate, t-amylperoxy-2-ethylhexanoate, t- Organic peroxides such as butyl peroxy-2-ethylhexanoate; 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylbareronitrile), dimethyl 2,2'-azobis (2-methylpropionate) Nitrogen compounds; and the like. The polymerization initiators exemplified above may be used alone or in combination of two or more kinds.

In order to control the molecular weight in the process, α-methylstyrene dimer or mercapto compound may be used as a chain transfer agent. The α-methylstyrene dimer or mercapto compound may be used in an amount of 0.005 to 5 parts by weight based on the total amount of (b1) and (b2). The polymerization conditions described above may be appropriately adjusted in the input method and the reaction temperature in consideration of the amount of heat generated by the production facility, polymerization, and the like.

An example of the manufacturing method of the copolymer (B-2) obtained by making said (b3) further react with the copolymer (B-1) of said (b1) and (b2) is as follows.

(B1) in the copolymer obtained by preparing the copolymer of (b1) and (b2) in the same manner as above, then substituting the atmosphere in the flask with nitrogen for air and copolymerizing the (b1) and (b2). Reaction catalyst of carboxyl group and epoxy group of 0.01 to 5 parts by weight relative to the total amount of (b3), (b1) to (b3) of 2 to 80 mole%, based on the constitutional units derived from (e.g. trisdimethyl aminomethylphenol) And 0.001 to 5 parts by weight of a polymerization inhibitor (eg, hydroquinone) is added to the flask and reacted at 60 to 130 ° C. for 1 to 10 hours based on the total amount of (b1) to (b3) to obtain a copolymer (B-1). have. At this time, similarly to the copolymerization conditions described above, the charging 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.

The weight average molecular weight (Mw) in terms of polystyrene of the (B) alkali-soluble resin may be 3,000 to 100,000, preferably 5,000 to 50,000. When the weight average molecular weight of the said (B) alkali-soluble resin exists in the range of 3,000-100,000, film | membrane reduction is prevented at the time of image development, and the omission property of a pattern part is favorable.

It is preferable that acid value of the said (B) alkali-soluble resin exists in the range of 30-150 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.

The alkali soluble resin (B) may be included in an amount of 5 to 90 parts by weight, and preferably 10 to 80 parts by weight, based on the solids in the photosensitive resin composition. When the alkali-soluble resin (B) is included in the above range, the solubility in the developer is sufficient, so that pattern formation is easy, and the film reduction of the pixel portion of the exposed portion is prevented at the time of development, so that the missing property of the non-pixel portion is improved. desirable.

(C) Photopolymerization  compound

The said (C) photopolymerizable compound means the compound which can be superposed | polymerized by active radical etc. which generate | occur | produce from (D) photoinitiator by irradiating light.

The (C) photopolymerizable compound may include a fluorene-based acrylate monomer represented by the following formula (1).

[Formula 1]

In Formula 1, n and m are different from each other or the same integer, n + m is 1 <n + m <30. When n + m is included in the above range, the sensitivity of the resin composition may be improved during pattern formation to provide a pattern shape having good adhesion and developing speed even at a low exposure amount.

The fluorene acrylate monomer represented by Chemical Formula 1 may be included in an amount of 10 to 100 parts by weight, and more preferably 40 to 100 parts by weight, based on the (C) photopolymerizable compound. When the fluorene-based acrylate monomer is included in an amount of 10 to 100 parts by weight based on the (C) photopolymerizable compound, it is excellent in sensitivity and resolution, so that a sufficient pattern shape can be provided even when a colorant is contained at a high concentration. Excellent adhesion, there is no peeling of the pattern during the development process and pressure washing process can provide a high quality color filter pattern.

The fluorene-based acrylate monomers may be used in combination with at least one selected from curable monomers having a bifunctional or higher functional group according to the purpose of use, and preferably, the curable monomer having a bifunctional or higher functional group is a bifunctional type or the like. It may be a six functional type curable monomer.

Specific examples of the bifunctional curable monomers include 1,6-hexanedioldiacrylate, 1,6-hexanedioldimethacrylate, 1,9-nonanedioldiacrylate, and 1,9-nonanedioldimethacryl. Rate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, di Ethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol methacrylate, tetramethylene glycol diacrylate, tetraethylene glycol diacrylate, 1,3-butylene glycol di Acrylate, 1,3-butylene glycol dimethacrylate, tripropylene glycol diacrylate, tripropylene glycol dimethacrylate, tricyclodecanedimethyroldi Acrylate, tricyclodecanedimethol dimethacrylate, polyethyleneglycol diacrylate, polypropylene glycol diacrylate, pentaerythritol diacrylate, bisphenol epoxy diacrylate, dimethol tricyclodecane diacrylate, dimethol dicycete Clopentanediacrylate, 2-n-butyl-2-ethyl-1,3-propanedioldiacrylate, cyclohexanedimethanoldiacrylate, cyclohexanedimethanoldimethacrylate, ethoxylated neopentylglycoldiacryl Ethoxylated neopentylglycol dimethacrylate, propoxylated neopentylglycol diacrylate, propoxylated neopentylglycol dimethacrylate, hydroxypivarine neopentylglycol diacrylate, ethoxylated bisphenol-A Diacrylate, ethoxylated bisphenol-A dimethacrylate, propoxylated bisphenol-A diacrylate, Propoxylated bisphenol-A dimethacrylate, dipentaerythritol diacrylate, dipentaerythritol dimethacrylate, propylene glycol diacrylate, dipropylene glycol diacrylate, hexamethylene glycol diacrylate, bisphenol-A di Acrylate, trimethol propanediacrylate, trimetholpropanedimethacrylate, propylene glycol dimethacrylate, dipropylene glycol dimethacrylate, hexanediacrylate, hexanedimethacrylate, glycerin diacrylate , Glycerin dimethacrylate, propylene glycol diacrylate, dicyclopentanyl diacrylate, triglycerol diacrylate, tetraethylene glycol dimethacrylate, propylene glycol dimethacrylate, tetrabromobisphenol-A dimethacryl Latex, dicyclopentanyldimethacrylate, article Liserol dimethacrylate, triglycerol dimethacrylate, etc. can be used.

Specific examples of the trifunctional curable monomers include trimetholpropane triacrylate, trimetholpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, tetramethylol methanetriacrylate, and tetramethyl. All propane triacrylate, tri (2-hydroxyethyl isocyanate) triacrylate, ethoxylated trimetholpropane triacrylate, propoxylated trimethol propane triacrylate, caprolactone modified trimethol propane triacrylate , Ethoxy isocyanuric acid triacrylate, propoxylate glycerin triacrylate, sorbitol triacrylate, sorbitol trimethacrylate, trimethyl propane triacrylate, trimethyl propane trimethacrylate, tris (hydroxyethyl) isocyanate Triacrylic Book, trimethylol ethane triacrylate, trimethylol ethane trimethacrylate, glycerin triacrylate, glycerin trimethacrylate, tetratrimethylolpropane triacrylate, tetratrimethylolpropane trimethacrylate, ethylene isocyanate Oxide modified triacrylate, isocyanate ethylene oxide modified trimethacrylate, etc. are mentioned.

Specific examples of the 4-functional curable monomers include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, ditrimethyrolpropane tetraacrylate, ditrimethyrolpropane tetramethacrylate, dipentaerythritol tetraacrylate, tetra Methylol methane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, glycerine tetraacrylate, glycerol tetramethacrylate, etc. are mentioned.

Specific examples of the 5-functional curable monomers include dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol monohydroxypentamethacrylate, and the like. .

Specific examples of the six-functional curable monomer include dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and the like.

The (C) photopolymerizable compound may be included in an amount of 5 to 40 parts by weight, and preferably 10 to 35 parts by weight, based on the solids of the colored photosensitive resin composition. When the (C) photopolymerizable compound is within the above range, it is possible to provide a pattern shape excellent in sensitivity and adhesion to the substrate, and at the same time, exhibit good strength or smoothness of the pixel portion.

(D) Light curing Initiator

The (D) photoinitiator can be used without particular limitation as long as it can polymerize the (B) alkali-soluble resin and (C) photopolymerizable compound.

More specifically, the (D) photopolymerization initiator may be used a triazine compound, acetophenone compound, biimidazole compound, oxime compound and the like from the viewpoint of polymerization characteristics, starting efficiency, absorption wavelength, availability, price, etc. These can be used individually or in combination of 2 types or more, respectively.

Specific examples of the triazine-based compound include 2,4-bis (trichloromethyl ) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6 -(4-methoxy naphthyl) -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.

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4- (2-hydroxy Hydroxyethoxy) phenyl] -2-methylpropan-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-methyl vinyl) phenyl] propane-1 -One, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholino phenyl) butan-1-one, and the like.

Specific examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichloro 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, 2,2'-bis (2,6-dichlorophenyl) -4 , 4 ', 5,5'-tetraphenyl-1,2'-biimidazole or a biimidazole compound in which a phenyl group at the 4,4', 5,5 'position is substituted by a carboalkoxy group, and the like can be used. have. Preferably, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4, 4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,6-dichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole Etc. can be mentioned.

Specific examples of the oxime compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one or compounds represented by the following Chemical Formulas 2 to 4:

[Formula 2]

(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. For example, a benzoin compound, a benzophenone type compound, a thioxanthone type compound, an anthracene type compound, etc. are mentioned, The said photoinitiator can be used individually or in combination of 2 or more types, respectively.

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

Specific examples of the benzophenone compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert -Butyl peroxycarbonyl) benzophenone, 2,4, 6-trimethyl benzophenone, etc. are mentioned.

Specific examples of the thioxanthone-based compound include 2-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone, 1-chloro-4-propoxy thioxanthone, and the like. Can be mentioned.

Specific 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.

In addition to 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methylphenylphenyloxylate , Titanocene compounds and the like can be used.

The (D) photopolymerization initiator may be included in an amount of 0.1 to 40 parts by weight, preferably 1 to 30 parts by weight, based on the total amount of the (B) alkali-soluble resin and (C) the photopolymerizable compound based on the solid content of the resin composition. When the (D) photoinitiator is in the above range, the colored photosensitive resin composition becomes highly sensitive and the exposure time is shortened, thereby improving productivity, maintaining high resolution, and intensities of the pixel portion formed using the composition, It is preferable because smoothness on the surface of this pixel portion becomes good.

(D-1) Starting adjuvant

It can also be used combining the (D-1) photoinitiator with the said (D) photoinitiator. When (D-1) photoinitiator adjuvant is used together with (D) photoinitiator, the photosensitive resin composition containing these will become more sensitive and can improve productivity.

Specific examples of the (D-1) photopolymerization initiation aid include an amine compound, a carboxylic acid compound, an organic sulfur compound having a thiol group, and the like. The above can be used in combination.

Specific examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 4-dimethyl Aminobenzoic acid-2-ethylhexyl, benzoic acid-2-dimethylaminoethyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (collectively: Michler's ketone), 4,4'-bis Aromatic amine compounds, such as (diethyl amino) benzophenone, etc. are mentioned, Preferably an amine compound can be used.

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

Specific examples of the organic sulfur compound having a thiol group include 2-mercaptobenzothiazole, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropanetris (3-mergaptopropionate), pentaerythritol tetrakis (3-mercaptobutyl Late), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercapto propionate), etc. are mentioned. .

The photopolymerization initiation assistant (D-1) may be included in an amount of 0.1 to 50 parts by weight, preferably 1 to 40 parts by weight, based on the total amount of the (B) alkali-soluble resin and (C) the photopolymerizable compound. When the said photoinitiator adjuvant (D-1) exists in the said range, since the sensitivity of a coloring photosensitive resin composition becomes higher and productivity of a color filter improves, it is preferable.

(E) Solvent

The solvent (E) disperses or dissolves the other components included in the colored photosensitive resin composition.

The solvent (E) may be used without particular limitation as long as it is effective for dispersing or dissolving other components, and preferably ethers, aromatic hydrocarbons, ketones, alcohols, esters and amides, and the like. The solvents exemplified above may be used alone or in combination of two or more thereof.

Specific examples of the solvent (E) include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate; Aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone; Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin; Esters such as 3-ethoxypropionate, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; And cyclic esters such as γ-butyrolactone. The above-mentioned (E) solvent can be used individually or in mixture of 2 or more types, respectively.

Preferably, the (E) solvent may be an organic solvent having a boiling point of 100 ℃ to 200 ℃, because the organic solvent having a boiling point of the above range is excellent in coating properties and drying properties. As specific examples, esters such as alkylene glycol alkyl ether acetates, ketones, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate and 3-ethoxypropionate can be used, and more preferably propylene glycol Monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, 3-ethoxypropionate, and the like.

The solvent (E) may be included in an amount of 60 to 90 parts by weight, preferably 70 to 85 parts by weight based on the colored photosensitive resin composition. When the (E) solvent is in the above range, the coating composition may be further improved when the resin composition is applied using a coating apparatus such as a roll coater, a spin coater, a slit and spin coater, a slit coater (or a die coater), or an inkjet. Can be.

(F) additive

The coloring photosensitive resin composition of this invention can further contain (F) additives, such as a high molecular compound, a hardening | curing agent, surfactant, an adhesion promoter, antioxidant, a ultraviolet absorber, and an aggregation inhibitor, as needed.

Specific examples of the polymer compound include curable resins such as epoxy resins and maleimide resins, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ethers, thermoplastic resins such as polyfluoroalkyl acrylates, polyesters, polyurethanes, and the like. Can be.

The curing agent is used to increase the core hardening and mechanical strength, and specific examples of the curing agent include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, an oxetane compound, and the like.

Specific examples of the epoxy compound include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, noblock type epoxy resin, other aromatic epoxy resin, alicyclic epoxy resin, and glyc Cydyl ester resins, glycidylamine resins, brominated derivatives of such epoxy resins, aliphatic, cycloaliphatic or aromatic epoxy compounds other than epoxy resins and their brominated derivatives, butadiene (co) polymer epoxides, isoprene (co) polymers Epoxide, glycidyl (meth) acrylate (co) polymer, triglycidyl isocyanurate, etc. are mentioned.

Specific examples of the oxetane compound include carbonate bis oxetane, xylene bis oxetane, adipate bis oxetane, terephthalate bis oxetane and cyclohexane dicarboxylic acid bis oxetane.

The said hardening | curing agent can use together the hardening auxiliary compound which can make ring-opening-polymerize the epoxy group of an epoxy compound, and the oxetane skeleton of an oxetane compound with a hardening | curing agent. Specific examples of the curing aid compound include polyhydric carboxylic acids, polyhydric carboxylic anhydrides, acid generators, and the like.

The polyhydric carboxylic anhydrides may be commercially available as an epoxy resin curing agent, and specific examples of the epoxy resin curing agent may include trade names (Adecahadona EH-700) (manufactured by Adeka Industrial Co., Ltd.) ) (Manufactured by Nippon Ewha Co., Ltd.), trade name (MH-700) (manufactured by Nippon Ewha Co., Ltd.), and the like. The said hardening | curing agents can be used individually or in combination of 2 or more types, respectively.

The said surfactant is used in order to improve the film formability of the photosensitive resin composition further. Specific examples of the surfactant may include a fluorine-based surfactant or a silicone-based surfactant, and the above-described surfactants may be used alone or in combination of two or more thereof.

Specific examples of the fluorine-based surfactant include Megapieces F-470, F-471, F-475, F-482, and F-489 manufactured by Dainippon Ink Industries, Ltd. as commercially available products.

Specific examples of the silicone-based surfactants are commercially available products such as DC3PA, DC7PA, SH11PA, SH21PA, SH8400, and Toshiba Silicon TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF -4452, and the like.

Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N -(2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltri Methoxysilane, 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and the like. The adhesion promoter exemplified above can be used individually or in combination of 2 or more types, respectively.

The adhesion promoter may be included in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 2 parts by weight, based on the solids of the photosensitive resin composition.

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 method.

The coloring agent (A) 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. Under the present circumstances, a pigment dispersant is used as needed and one part or all part of (B) alkali-soluble resin may be mix | blended. The remaining dispersion of the alkali-soluble resin (B), (C) photopolymerizable compound and (D) photopolymerization initiator, other components used if necessary, and additional solvents as necessary, are further added to the obtained dispersion so as to obtain a desired concentration. The colored photosensitive resin composition can be obtained.

The present invention relates to a color filter manufactured using the colored photosensitive resin composition.

The color filter includes a substrate and a color layer formed on the substrate.

The substrate may be a substrate of the color filter itself, or may be a portion where the color filter is positioned in a display device or the like, and is not particularly limited. The substrate may be glass, silicon (Si), silicon oxide (SiO _x ) or a polymer substrate, and the polymer substrate may be polyethersulfone (PES) or polycarbonate (PC).

The color layer is a layer including the colored photosensitive resin composition of the present invention, and may be a layer formed by applying the colored photosensitive resin composition and exposing, developing, and thermosetting in a predetermined pattern.

The color filter including the substrate and the color layer as described above may further include a partition formed between each color pattern, and may further include a black matrix. In addition, a protective film formed on the color layer of the color filter may be further included.

The present invention relates to a liquid crystal display device having the color filter.

The liquid crystal display device of the present invention may include a configuration known to those skilled in the art except for providing the color filter, and is not particularly limited in the present invention.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.

< Example  And Comparative example  > Preparation of colored photosensitive resin composition

To prepare a colored photosensitive resin composition by a conventional method known in the art in the composition of Table 1.

(Unit: parts by weight) division Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 (A) Colorant (A-1) 3.920 3.920 3.920 3.920 3.920 3.920 3.920 (A-2) 2.614 2.614 2.614 2.614 2.614 2.614 2.614 (B) alkali availability
Suzy (B-1) 4.652 4.652 4.652 4.652 4.652 4.652 4.652 (C) photopolymerization
compound
(C-1) 4.652 2.326 (C-2) 4.652 2.326 (C-3) 4.652 (C-4) 4.652 (C-5) 2.326 2.326 4.652 (D) photoinitiator (D-1) 1.366 1.366 1.366 1.366 1.366 1.366 1.366 (D-2) 0.765 0.765 0.765 0.765 0.765 0.765 0.765 (E) Solvent (E-1) 7.659 7.659 7.659 7.659 7.659 7.659 7.659 (E-2) 72.259 72.259 72.259 72.259 72.259 72.259 72.259 (F) additive (F-1) 1.564 1.564 1.564 1.564 1.564 1.564 1.564 (F-2) 0.510 0.510 0.510 0.510 0.510 0.510 0.510 (F-3) 0.039 0.039 0.039 0.039 0.039 0.039 0.039

(A) Colorant

A-1: C.I. Pigment Red R254

A-2: C.I. Pigment Red R177

(B) alkali-soluble resin

B-1: Copolymer of methacrylic acid and benzyl methacrylate

(The ratio of the methacrylic acid unit and the benzyl methacrylate unit is 27:73 in molar ratio, the acid value is 83, and the weight average molecular weight in terms of polystyrene is 18,000.)

(C) Photopolymerization  compound

C-1: [Formula 1] (Miwon. HR6100 m + n = 10)

C-2: [Formula 1] (Miwon. HR6200 m + n = 20)

C-3: 1,6-hexadiol diacrylate

C-4: tri (2-hydroxyethyl) isocyanurate triacrylate

C-5: dipentaerythritol hexaacrylate

(D) Light curing Initiator

D-1: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one

D-2: 4,4'-bis (diethylamino) benzophenone

(E) Solvent

E-1: 3-ethoxypropionate

E-2: Propylene Glycol Monomethyl Ether Acetate

(F) additive

F-1: Pigment Dispersant (Polyester)

F-2: epoxy resin (SUMI-EPOXY ESCN-195XL)

F-3: methacryloxypropyl trimethoxysilane

< Manufacturing example > Manufacturing of Color Filters

Color filters were prepared using the colored photosensitive resin compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 3. That is, each of the colored photosensitive resin composition was applied on a glass substrate by spin coating, and then placed on a heating plate and maintained at a temperature of 100 ° C. for 3 minutes to form a thin film. Subsequently, a test photomask having a pattern in which the transmittance is changed stepwise in the range of 1 to 100% and a line / space pattern of 1 to 50 µm is placed on the thin film, and the distance from the test photomask is 100 µm. Was investigated. At this time, the ultraviolet light source was irradiated with luminous intensity of 100 mJ / cm 2 using a 1KW high-pressure mercury lamp containing all g, h, and i rays, and no special optical filter was used. The thin film irradiated with ultraviolet rays was developed by soaking in a KOH aqueous solution developing solution of pH 10.5 for 2 minutes. The thin plate coated with the thin glass plate was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 200 ° C. for 1 hour to prepare a color filter. The film thickness of the color filter prepared above was 2.0 μm.

< Experimental Example  1> Solubility Measurement

The colored photosensitive resin composition prepared in Examples and Comparative Examples was prebaked at 100 ° C. for 3 minutes after slit coating on a 500 mm × 500 mm glass substrate. After soaking in 1% alkaline developer for 3 minutes, the solution was shaken and visually confirmed. The results are shown in Table 2 below.

division Example Comparative Example One 2 3 4 One 2 3 Solubility ○ ○ ○ ○ ○ ○ △

○: dissolution, △: peeling off, ×: peeling

As shown in Table 2, the coloring photosensitive resin composition of the Example was excellent in solubility, and the composition of the comparative example also showed good solubility similarly to the Example.

< Experimental Example  2> evaluation of sensitivity

The minimum exposure amount necessary to form a thin film without pattern tearing after development in manufacturing the color filters of Examples and Comparative Examples was measured and the results are shown in Table 3 below.

< Experimental Example  3> Evaluation of adhesion

The patterns generated in the color filters of the Examples and Comparative Examples were evaluated on the degree of tearing on the pattern based on the following criteria through an optical microscope, and the results are shown in Table 3 below.

○: No tearing on the pattern

△: 1 to 3 tears on the pattern

×: 4 or more tears on the pattern

< Experimental Example  4> Evaluation of Development Speed

The colored photosensitive resin composition prepared in Examples and Comparative Examples was prebaked at 100 ° C. for 3 minutes after slit coating on a 500 mm × 500 mm glass substrate. The produced substrate was supported on a 1% alkaline developer, the time for dissolving the formed coating film was measured, and evaluated according to the following evaluation criteria, and the results are shown in Table 3 below.

division Example Comparative example One 2 3 4 One 2 3 Sensitivity (mJ / cm ² ) 30 20 30 25 80 45 20 Adhesion O O O O X △ O Developing speed (sec) 8 6 10 8 8 10 15

As shown in Table 3, when the pattern is formed of the colored photosensitive resin composition of Examples 1 to 4 including the multifunctional monomer represented by Formula 1 according to the present invention, it can be confirmed that the sensitivity and the adhesion are excellent.

On the other hand, the photosensitive resin composition of the comparative example is inferior in sensitivity and adhesiveness compared with the Example, In particular, the photosensitive resin composition of the comparative example 3 provides the favorable sensitivity, but shows the result of falling in developing speed.

The colored photosensitive resin composition according to the present invention not only has excellent sensitivity and resolution even in solubility and low exposure amount, but also has excellent adhesion with a substrate, thereby eliminating pattern peeling during development, thereby improving process productivity and yield. It can be seen that a high quality color filter pattern with excellent sensitivity can be produced.

Claims (6)

In the coloring photosensitive resin composition containing (A) a coloring agent, (B) alkali-soluble resin, (C) photopolymerizable compound, (D) photoinitiator, and (E) solvent,
Colored photosensitive resin composition characterized in that the (C) photopolymerizable compound comprises a fluorene-based acrylate monomer represented by the following formula (1):
[Formula 1]

(In Formula 1, n and m are integers that are different or the same as each other, and n + m is 1 <n + m <30.) The method of claim 1,
The said (C) photopolymerizable compound is 5 to 40 weight part with respect to solid content of a coloring photosensitive resin composition, The coloring photosensitive resin composition characterized by the above-mentioned. The method of claim 1,
The fluorene-based acrylate monomers are contained in 10 to 100 parts by weight with respect to the (C) photopolymerizable compound. The method of claim 1,
The colored photosensitive resin composition further comprises a curable monomer having a 2 to 6 functional group as the (C) photopolymerizable compound. The color filter manufactured from the coloring photosensitive resin composition of any one of Claims 1-4. A liquid crystal display device comprising the color filter of claim 5.