KR102028479B1 - A colored photosensitive resin composition, color filter and display device comprising the same - Google Patents

Abstract

The present invention is used in combination with a blue backlight unit (BLU), and includes (A) a colorant, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, and (E) a solvent. The content of the (A) coloring agent is 0.5-25 weight% with respect to the total weight of solid content in a coloring photosensitive resin composition, It is related with the coloring photosensitive resin composition.

Description

Colored photosensitive resin composition, color filter and display device comprising the same

The present invention relates to a colored photosensitive resin composition, a color filter and a display device including the same.

The color filter may be embedded in a color photographing apparatus of an image sensor such as a complementary metal oxide semiconductor (CMOS), a charge coupled device (CCD), or the like to be used to actually obtain a color image. . In addition, color filters are widely used in imaging devices, plasma display panels (PDPs), liquid crystal displays (LCDs), field emission displays (FELs), light emitting displays (LEDs), and the like, and their application ranges are rapidly expanding. In particular, in recent years, the use of LCDs has been further expanded. Accordingly, color filters have been recognized as one of the most important components in reproducing the color tone of LCDs.

The color filter used for a color liquid crystal display device, an imaging device, etc. is uniformly uniformly by spin-coating the coloring photosensitive resin composition containing the coloring material corresponding to each color of red, green, and blue on the board | substrate with which the black matrix was formed in pattern shape. After coating, it is heated and dried (hereinafter sometimes referred to as 'preliminary firing') to form a coating film, the formed coating film is exposed and developed, and further heat-cured as necessary (hereinafter referred to as 'post firing'). The same operation) is repeated for each color to form pixels of each color. Here, the coloring matrix formed in a pattern shape is normally formed from a black photosensitive resin composition.

In general, for the purpose of the color gamut, a color filter is used in the white back light unit (BLU) to display the colors of red, green, and blue, and the area of the dots is called a color reproduction area. In a typical display, the display is composed of a combination of a white BLU and a color filter having red, green, and blue colors as described above, and a white BLU is a commonly known CCFL (Cold Cathode Fluorescent Lamp) and LED (Light). Emitting Diodes (OLEDs) to OLEDs (Organic Light-Emitting Diodes).

In recent years, as the size of the display is rapidly progressing and high contrast ratio is continuously demanded, a method of using a dye or a dye and a pigment at the same time instead of a pigment dispersion method, which is conventionally used as a method of coloring a photosensitive resin composition, is adopted. It is becoming. By the way, the coloring photosensitive resin composition for a color filter using a dye as described above and the coloring photosensitive resin composition for a hybrid type color filter using a dye and a pigment simultaneously can provide a color filter with excellent transmittance, but the dye and photoinitiator used Depending on the type of sensitivity deterioration may occur. Therefore, researches are being actively conducted to solve the above problems and prevent a decrease in the sensitivity of the color filter.

It is an object of the present invention to provide a colored photosensitive resin composition which is used in combination with a blue backlight unit (BLU) and which contains a very low content of colorant and exhibits high luminance.

Another object of the present invention is to provide a color filter including a blue pattern formed of the colored photosensitive resin composition, and a display device including the color pulp and a blue backlight unit (BLU).

The present invention to achieve the above object

(A) colorant, (B) alkali-soluble resin, (C) photopolymerizable compound, (D) photoinitiator and (E) solvent, as used in combination with a blue backlight unit (BLU), wherein (A) It provides the coloring photosensitive resin composition characterized in that the content of the coloring agent is 0.5 to 25% by weight based on the total weight of solids in the coloring photosensitive resin composition.

In addition, the present invention provides a color filter comprising a color pattern made of the colored photosensitive resin composition.

The present invention also provides a display device including the color filter and the blue backlight unit (BLU).

The colored photosensitive resin composition of the present invention is used in combination with a blue backlight unit (BLU) and thus exhibits a high luminance value in spite of the low colorant content. In addition, a display device including a color filter and a blue backlight unit (BLU) manufactured using the colored photosensitive resin composition may provide a high quality display device having high energy efficiency and low power consumption.

1 is a graph illustrating a measurement of the wavelength of a blue backlight unit BLU.
2 is a graph illustrating the measurement of the wavelength of the white backlight unit (BLU).

Hereinafter, the present invention will be described in more detail.

The colored photosensitive resin composition of this invention is used in combination with a blue backlight unit (BLU), and is (A) coloring agent, (B) alkali-soluble resin, (C) photopolymerizable compound, (D) photoinitiator, and (E) solvent And (A) the content of the coloring agent is 0.5 to 25% by weight, preferably 1 to 20% by weight, more preferably 2 to 15% by weight, based on the total weight of solids in the colored photosensitive resin composition. do.

Since the luminance of the pattern of the colored photosensitive resin composition is 50 or more, and the wavelength of 580 nm or less has 90% or more by the blue backlight unit (BLU), and the blue wavelength is mainly, the colored photosensitive resin composition of the present invention has a fine color. Can act as a control

(A) colorant

As the colorant, organic pigments, inorganic pigments, and dyes generally used in the art may be used.

( a1 Pigment

Pigment (a1) contains an organic pigment and an inorganic pigment.

As the organic pigment, various pigments used in printing ink, inkjet ink, and the like may be used. Specifically, phthalocyanine (aqueous azo pigment, insoluble azo pigment), phthalocyanine pigment, quinacridone pigment, isoin Dolanone pigments, isoindolin pigments, perylene pigments, perinone pigments, dioxazine pigments, anthraquinone pigments, dianthhraquinonyl pigments, anthrapyrimidine pigments, ananthrone pigments, indanthrone pigments, Pravantron pigments, pyranthrone pigments or diketopyrrolopyrrole pigments and the like.

Examples of the inorganic pigment include metal compounds such as metal oxides and metal complex salts, and specifically, metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony or carbon black Oxides or composite metal oxides;

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

As the pigment used in the pigment dispersion composition according to the present invention, an organic pigment or an inorganic pigment generally used in the art may be used, and these may be used alone or in combination of two or more kinds.

If necessary, the pigment may be a resin treatment, a surface treatment using a pigment derivative having an acidic group or a basic group introduced therein, a graft treatment on the surface of the pigment with a high molecular compound or the like, an atomization treatment by a sulfate atomization method or the like to remove impurities. Washing treatment with an organic solvent, water, or the like, removing ionic impurities by an ion exchange method, or the like can also be performed.

Specific examples of the pigment include 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;

CI Pigment Brown 28;

CI pigment black 1, 7, etc. are mentioned.

C.I. exemplified above. Among pigment pigments, C.I. Pigment yellow 138, 139, 150, and 185, C.I. Pigment Orange 38, C.I. Pigment Violet 23, C.I. Pigment Blue 15: 6, C.I. Pigments selected from Pigment Green 7, 36 and 58 can preferably be used.

It is preferable to use the pigment dispersion liquid which the said particle size disperse | distributed uniformly. As an example of the method for uniformly dispersing the particle size of the pigment, a method of containing and dispersing the pigment dispersant may be used. According to this method, a pigment dispersion in which the pigment is uniformly dispersed in a solution can be obtained.

In the coloring photosensitive resin composition of this invention, the said (a1) pigment can be contained in the form of a pigment dispersion composition.

The pigment dispersion composition includes (a1) a pigment, (a2) a dispersant, (a3) a dispersing aid, and (a4) a dispersing solvent, and (a5) a dispersing resin may be added to facilitate storage stability and dispersion.

In addition, the pigment (a1) may be included in the range of 20 to 90% by weight, preferably 30 to 70% by weight based on the total weight of the solid content in the pigment dispersion composition. If the content of the pigment is not included in the above range is high viscosity, poor storage stability, low dispersion efficiency adversely affects the contrast ratio.

( a2 ) Dispersant

The dispersant is added to maintain the stability of the pigment and deagglomeration can be used without limitation to those commonly used in the art. The dispersant preferably includes an acrylate dispersant (hereinafter referred to as an acrylate dispersant) including butyl methacrylate (BMA) or N, N-dimethylaminoethyl methacrylate (DMAEMA). Commercially available products of the acrylate-based dispersant include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, or DISPER BYK-2150, and the like. Each of the acrylate-based dispersants may be used alone or in combination of two or more thereof. Can be.

The dispersant according to the present invention may use a pigment dispersant of another resin type in addition to the acrylate-based dispersant. The other resin type pigment dispersants include known resin type pigment dispersants, in particular polycarboxylic acid esters represented by polyurethanes, polyacrylates, unsaturated polyamides, polycarboxylic acids, amine salts of polycarboxylic acids, Ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long chain polyaminoamide phosphate salts, esters of polycarboxylic acids substituted with hydroxyl groups and modified products thereof, free carboxyl groups Amides or salts thereof formed by the reaction of polyesters with poly (lower alkyleneimines), (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylate ester copolymers, styrene-maleic acid copolymers Water-soluble resins or water-soluble polymer compounds such as polymers, polyvinyl alcohol, polyvinyl pyrrolidone; Polyester; Modified polyacrylates; Adducts of ethylene oxide / propylene oxide and phosphate esters.

Commercially available products of the resin type pigment dispersant include cationic resin dispersants, for example, the trade names of BYK (BIC) Chemisa: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK. -164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; Product name of BASF Corporation: EFKA-44, EFKA-46, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA- 4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; Trade names: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204 / 10; Kawaken Fine Chemical's trade names: HINOACT T-6000, Hinoact T-7000, Hinoact T-8000; Trade names: AJISPUR PB-821, Azisper PB-822, Azisper PB-823; The brand names of Kyoeisha Chemical Co., Ltd. are: FLORENE DOPA-17HF, FLORENE DOPA-15BHF, FLORON DOPA-33, FLORON DOPA-44, and the like.

The dispersant is included in an amount of 5 to 60 parts by weight, more preferably 15 to 50 parts by weight, based on 100 parts by weight of the pigment in the colorant. If the dispersant exceeds 60 parts by weight, the viscosity may be increased. If the dispersant is less than 5 parts by weight, it may be difficult to atomize the pigment, or may cause problems such as gelation after dispersion.

In addition to the dispersant described above, surfactants such as cationic, anionic, nonionic, amphoteric, polyester, and polyamine based may be used as the dispersant, and these may be used alone or in combination of two or more.

Specific examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethanes, and polyethyleneimines. And KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by Tochem Products), Mega Pack (MEGAFAC) (manufactured by Dainippon Ink & Chemicals Co., Ltd.), Florard (manufactured by Sumitomo 3M Inc.), Asahi guard, Suflon (manufactured by Asahi Glass Co., Ltd.), SOLSPERSE ) (Manufactured by Geneva Co., Ltd.), EFKA (manufactured by EFKA Chemicals Co., Ltd.), PB 821 (manufactured by Ajinomoto Co., Ltd.), and the like.

( a3 Dispersion Aids

Dispersion aid refers to a formulation that serves to prevent reagglomeration by dispersing the pigment into fine particles. The dispersing aid is effective in constructing a color filter having a high contrast ratio and excellent transmittance.

Dispersion aid according to the present invention has a structure represented by the following formula (1).

[Formula 1]

R ₁ to R ₄ are each independently hydrogen, —OH, or —NH—R ₉ ,

R ₅ to R ₈ are each independently hydrogen, halogen, or SO ₃ ⁻ ,

R ₉ is hydrogen, a linear or nonlinear alkyl having 1 to 8 carbon atoms, and a substituent represented by the following [Formula 2],

[Formula 2]

R ₁₀ to R ₁₄ are each independently hydrogen, a linear or nonlinear alkyl having 1 to 4 carbon atoms, SO ₃ ^−, or a substituent represented by [Formula 3],

[Formula 3]

R ₁₅ is a hydrogen atom, COR ₁₆ , a linear or nonlinear alkyl, saturated or unsaturated ring having 1 to 8 carbon atoms,

R ₁₆ is hydrogen or alkyl having 1 to 8 carbons.

Specifically 1,8-diamino-4,5-dihydroxyanthraquinone, 1,5-bis {[2- (diethylamino) ethyl] amino} anthra-9,10-quinone, 1,8- Bis (benzamido) anthraquinone, 1,4-bis {[2- (4-hydroxyphenyl) ethyl] amino} anthra-9,10-quinone, 1,4-bis {[2- (dimethylamino ) Ethyl] amino} -5,8-dihydroxyanthra-9,10-quinone, 1,8-dihydroxy-4- [4- (2-hydroxyethyl) anilino] -5-nitroanthra -9,10-quinone, 1,4-dihydroxyanthraquinone, 1,4-bis (4-butylanilino) -5,8-dihydroxyanthraquinone, 4 '-(4-hydroxy-1 -Anthraquinonylamino) -acetanilide, 1,4-bis [(2,6-diethyl-4-methylphenyl) amino] anthraquinone, 1,4-bis (butylamino) -9,10-anthracene Ion, 1,4-bis (4-butylanilino) -5,8-dihydroxyanthraquinone, 1,5-bis [(3-methylphenyl) amino] -9,10-anthracenedione, 1,5 Dicyclohexylaminoant Quinone, 1,4-bis (isopropylamino) anthraquinone, 1,4-bis (methylamino) anthraquinone, 1,4-bis (2,6-diethyl-4-methylanilino) anthraquinone, 2 , 2 '-(9,10-dioxoanthracene-1,4-diyldiimino) bis (5-methylsulfonate), 1-anilino-4-hydroxyanthraquinone, 1-hydroxy-4- [(4-methylphenyl) amino] -9,10-anthracenedione, 1,4-bis (para-tolylamino) anthraquinone, 1-amino-4-fetylaminoanthraquinone, N- [4-[(4 -Hydroxy-anthraquino-1-yl) amino] phenyl] acetamide, 1- (methylamino) -4- (4-methylanilino) anthracene-9,10-dione and 1,4,5,8 Tetrahydroxyanthraquinone, and the like.

In addition to the dispersing aid, it may further comprise a commercially available dispersing aid. Specifically, the SOLSPERSE-5000, SOLSPERSE-12000, SOLSPERSE-22000 of Lubrizol, BYK-SYNERGIST 2100, BYK-SINERGIST 2105, BASF EFKA-6745 or EFKA-6750, etc. may be mentioned.

The dispersing aid comprises 1 to 30 parts by weight based on 100 parts by weight of the pigment in the colorant. If it exceeds 30 parts by weight of the dispersion aid, the color inherent in the colorant (A) may be changed, and the color may be discolored by hard baking during the color filter manufacturing process.

( a4 ) Dispersion solvent

The dispersion solvent is not particularly limited and various organic solvents used in the art may be used.

Specifically, for example, ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether Diethylene glycol dialkyl ethers such as diethylene glycol dipropyl ether and diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, and propylene glycol monomethyl ether acetate , Alkylene glycol alkyl ether acetates such as propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxypentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene, methyl ethyl Ketone, ace Ketones such as methyl amyl ketone, methyl isobutyl ketone and 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. Preferably, alkylene glycol alkyl ether acetates, ketones, esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate can be used, and more preferably propylene glycol monomethyl ether acetate and propylene glycol mono Ethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like can be used.

The said dispersion solvent can be used individually or in mixture of 2 or more types, respectively.

The dispersion solvent is included 60 to 90% by weight, preferably 70 to 85% by weight based on the total weight of the pigment dispersion composition. Outside the above range may cause a disadvantage in that the storage stability of the pigment dispersion composition is poor.

( a5 Dispersion resin

The dispersion resin may be selectively added to act as a dispersion medium of the colorant (A), and the mixture of the dispersion resin (a5) may be used to prepare a better pigment dispersion composition than the use of the dispersion agent (a2) alone. In the case of the dispersion resin, it can be used without limitation as long as it can function as a dispersion medium, but it is preferable to have an acid value in order to have solubility in an alkaline developer in consideration of the developability of the colored photosensitive resin composition prepared from the pigment dispersion composition.

The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer, and can be determined by titration using an aqueous potassium hydroxide solution.

In the case of the acid-containing dispersion resin, the compound (b1) having an unsaturated bond with the carboxyl group and the compound (b2) having an unsaturated bond copolymerizable with the compound (b1) may be prepared by copolymerizing.

Specific examples of the compound (b1) having a carboxylic acid group and an unsaturated bond 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; mono (meth) acrylates of polymers having a carboxyl group and a hydroxyl group at both terminals such as? -carboxypolycaprolactone mono (meth) acrylate, and the like, and acrylic acid and methacrylic acid are preferred.

The compound illustrated by the said compound (b1) can be used individually or in combination of 2 or more types, respectively. Compound (b2) having an unsaturated bond copolymerizable with the compound (b1) may be, for example, styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p -Methoxystyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethyl ether, p-vinylbenzylmethyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether or p-vinylbenzyl glycid Aromatic vinyl compounds such as dil 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 or t-butyl (meth) acrylate; Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 2,6] decane-8-yl (meth) acrylate, 2- Alicyclic (meth) acrylates such as dicyclopentanyloxyethyl (meth) acrylate or isobornyl (meth) acrylate; Aryl (meth) acrylates such as phenyl (meth) acrylate or benzyl (meth) acrylate; Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate or 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- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane or 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, etc. Unsaturated oxetane compounds, and the like, but are not limited thereto.

The compound illustrated by the said compound (b2) can be used individually or in combination of 2 types or more, respectively.

The dispersion resin is included in an amount of 5 to 60 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the pigment solids in the colorant. When the dispersion resin exceeds 60 parts by weight, the viscosity may be increased by the dispersion resin, and when the dispersion resin is less than 5 parts by weight, the amount of the dispersion resin is insufficient to obtain an atomized pigment dispersion composition.

( a6 )dyes

The dye can be used without limitation so long as it has solubility in an organic solvent. Preferably, it is preferable to use a dye having solubility in an organic solvent and ensuring reliability such as solubility in an alkali developer, heat resistance and solvent resistance.

The dye may be selected from acid dyes having acidic groups such as sulfonic acid and carboxylic acid, salts of acid dyes and nitrogen-containing compounds, sulfonamides of acid dyes, and derivatives thereof, and azo, xanthene, and phthalocyanines. Acid dyes and derivatives thereof can also be selected.

Preferably, the dye may be a compound classified as a dye in the color index (Published by The Society of Dyers and Colourists), or a known dye described in a dyeing note (color dyed yarn).

Specific examples of the dye include C.I. As solvent dyes,

C.I. Solvent yellow 4, 14, 15, 21, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, and 162;

C.I. Solvent red 8, 45, 49, 122, 125 and 130;

C.I. Solvent oranges 2, 7, 11, 15, 26 and 56;

C.I. Solvent blue 35, 37, 59 and 67;

C.I. Green dyes, such as solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, and 35, etc. are mentioned.

See also C.I. As an acid dye

CI acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112 , 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184 , 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243 and 251;

CI acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88 , 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217 , 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349 , 382, 383, 394, 401, 412, 417, 418, 422 and 426;

C.I. acid oranges 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169 and 173;

CI acid blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 92, 96, 103 , 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324: 1 , 335 and 340;

C.I. Acid Violet 6B, 7, 9, 17 and 19;

And dyes such as C.I. acid green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106 and 109.

Also as a C.I. direct dye

CI direct yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129 , 136, 138, and 141;

CI Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246 and 250;

C.I. direct oranges 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106 and 107;

CI direct blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113 , 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189 , 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248 , 250, 251, 252, 256, 257, 259, 260, 268, 274, 275 and 293;

C.I. direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103 and 104;

And dyes such as C.I.Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79 and 82.

In addition, C.I. As modanto dye

C.I. Modanto Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62 and 65;

CI Modanto Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94 and 95;

C.I. modanto orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47 and 48;

CI Modanto Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83 and 84;

C.I. modanto violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53 and 58;

And dyes such as C.I. modanto green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43 and 53.

The colorant (A) may be used in combination of one or more pigments or dyes, respectively. In addition, 0.5 to 25% by weight relative to the total weight of solids in the colored photosensitive resin composition of the present invention, preferably 1 to 20% by weight, more preferably 2 to 15% by weight.

(B) alkali-soluble resin

The alkali-soluble resin may be one known in the art. In particular, it is preferable to include at least one of the compounds consisting of the following formulas 4 to 7, wherein the compounds of formulas 4 to 7 are each 3 to 80 mol%, preferably 5, in mole fraction with respect to the total number of moles of alkali-soluble resin, respectively. To 70 mol%. When at least one of the compounds of Formulas 4 to 7 is included within the mole fraction range, the sensitivity and adhesion of the colored photosensitive resin composition are excellent, so that peeling of the pattern does not occur during the developing process, and solvent resistance is excellent.

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

An alkali-soluble resin having at least one unit selected from the group consisting of Chemical Formulas 4 to 7 may be prepared by polymerizing with a polymerizable compound.

Specific examples of the unsaturated bond copolymerizable with the chemical formulas 4 to 7 of the alkali-soluble resin include styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, and p-methoxy Styrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, and the like. Aromatic vinyl compounds; 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 [5.2.1.0 2,6] decane-8-yl (meth) acrylate, 2- Alicyclic (meth) acrylates such as dicyclopentanyloxyethyl (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; (meth) acrylamide, Unsaturated amide compounds such as N, N-dimethyl (meth) acrylamide; 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, etc. And unsaturated oxetane compounds.

The compounds exemplified above may be used alone or in combination of two or more thereof.

The alkali-soluble resin of the present invention may be used by further mixing various known alkali-soluble resins commonly used in the art as needed.

The alkali-soluble resin has a weight average molecular weight in terms of polystyrene of 3,000 to 100,000, preferably 5,000 to 50,000. If the weight average molecular weight of the alkali-soluble resin is outside the above range, the film reduction is not prevented at the time of development, causing a problem that the omission of the pattern portion may occur.

The acid value of the alkali-soluble resin is 50 to 150 (KOH mg / g), preferably 60 to 140 (KOH mg / g), more preferably 80 to 135 (KOH mg / g), most preferably Is 80 to 130 (KOH mg / g). When the acid value of the said alkali-soluble resin is 50-150 (KOHmg / g), solubility to a developing solution improves and a residual film rate improves.

The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer, and can be determined by titration using an aqueous potassium hydroxide solution.

The alkali-soluble resin includes 10 to 80% by weight, preferably 10 to 70% by weight based on the total weight of solids in the colored photosensitive resin composition of the present invention. In the above range, the solubility of the developing solution 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 non-pixel portion has good omission.

(C) Photopolymerizable  compound

The photopolymerizable compound is not particularly limited as long as it is a compound that can be polymerized by the action of a photopolymerization initiator (D) described later, but is preferably a monofunctional photopolymerizable compound, a bifunctional photopolymerizable compound, or a trifunctional or higher polyfunctional photopolymerizable compound. Etc. can be mentioned.

Specific examples of the monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, and N-vinyl py. Commercially available products include Aronix M-101 (Toagosei), KAYARAD TC-110S (Nipbon Kayaku), or Biscotti 158 (Osaka Yuki Kagaku High School).

Specific examples of the bifunctional monomers include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like; commercially available products such as Aronix M-210, M-1100, 1200 (Doagosei), KAYARAD HDDA (Nipbon Kayaku), Biscot 260 (Osaka Yuki Kagaku High School), AH-600, AT-600 or UA-306H (Kyoeisha Kagakusa).

Specific examples of the trifunctional or higher polyfunctional photopolymerizable compound include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, and propoxylated trimethylolpropane tri (meth) acrylate. , Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, tipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxysilane Tied dipentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are commercially available products such as Aronix M-309, TO-1382 (Doagosei), KAYARAD TMPTA, KAYARAD DPHA, or KAYARAD. DPHA-40H (Nippon Kayaku).

Among the photopolymerizable compounds exemplified above, trifunctional or more than trifunctional (meth) acrylic acid esters and urethane (meth) acrylates are particularly preferable in terms of excellent polymerizability and improving strength.

Said photopolymerizable compound can be used individually or in combination of 2 or more types, respectively.

The photopolymerizable compound is preferably contained in 5 to 50% by weight, 7 to 48% by weight relative to the total weight of solids in the colored photosensitive resin composition of the present invention. When the photopolymerizable compound is included in the above range, the intensity and smoothness of the pixel portion are good.

(D) Photopolymerization Initiator

The photoinitiator can be used without particular limitation as long as it can polymerize the photopolymerizable compound (C).

In particular, the photopolymerization initiator may be an acetophenone compound, a benzophenone compound, a triazine compound, a biimidazole compound, an oxime compound, or a thioxanthone compound in view of polymerization characteristics, start efficiency, absorption wavelength, availability, or price. Preference is given to using at least one compound selected from the group consisting of compounds.

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-methylvinyl) phenyl] propane-1 -One or 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like.

As said benzophenone type compound, benzophenone, methyl 0- benzoyl benzoate, 4-phenylbenzo phenone, 4-benzoyl-4'- methyl diphenyl sulfide, 3,3 ', 4, 4'- tetra ( tert-butylperoxycarbonyl) benzophenone or 2,4,6-trimethylbenzophenone.

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-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 or 2,4-bis (trichloromethyl ) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine 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, The imidazole compound etc. which the phenyl group of a 4 ', 5,5'- tetraphenyl- 1,2'-biimidazole or a 4,4', 5,5 'position are substituted by the carboalkoxy group are mentioned. Among them, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4' , 5,5'-tetraphenylbiimidazole or 2,2-bis (2,6-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole is preferably Used.

Specific examples of the oxime compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one and the like, and OXE01 and OXE02 manufactured by BASF Corporation are typical examples of commercially available products.

As said thioxanthone type compound, 2-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-4- propoxy thioxanthone, etc. are mentioned, for example. There is this.

Moreover, photoinitiators other than the photoinitiator mentioned above can also be used within the range which does not impair the effect of this invention. For example, a benzoin type compound, an anthracene type compound, etc. are mentioned, These can be used individually or in combination of 2 or more types, respectively.

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

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

Other 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenylclioxylic acid Methyl or titanocene compounds, etc. can be used further as a photoinitiator.

In addition, the photopolymerization initiator may further include a photopolymerization initiation aid (D-1) in order to improve the sensitivity of the colored photosensitive resin composition of the present invention. The coloring photosensitive resin composition which concerns on this invention can contain a photoinitiation adjuvant (D-1), can improve a sensitivity and improve productivity.

As the photopolymerization initiation assistant (D-1), for example, one or more compounds selected from the group consisting of amine compounds, carboxylic acid compounds and organic sulfur compounds having thiol groups can be preferably used.

It is preferable to use an aromatic amine compound as the amine compound, and specifically, aliphatic amine compounds such as triethanolamine, methyl diethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4- Dimethylaminobenzoic acid isoamyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (common name: Michler's ketone ) Or 4,4'-bis (diethylamino) benzophenone can be used.

The carboxylic acid compound is preferably an aromatic heteroacetic acid, specifically, phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthio Acetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine or naphthoxyacetic acid, and the like.

Specific examples of the organic sulfur compound having the 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-mercaptopropionate), etc. are mentioned. Can be.

The 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 100 parts by weight of the total amount of the (B) alkali-soluble resin and (C) the photopolymerizable compound. When included in the above range, the colored photosensitive resin composition may be highly sensitive to shorten the exposure time, thereby improving productivity and maintaining high resolution. In addition, the strength of the pixel portion formed using the composition under the above-described conditions and smoothness on the surface of the pixel portion can be improved.

In addition, when the photopolymerization initiation aid (D-1) is further used, it is preferable to use the same content range as the photopolymerization initiator (D), and when used in the above range, the sensitivity of the colored photosensitive resin composition is increased, It is possible to provide an effect of improving the productivity of the color filter formed using the composition.

(E) Solvent

As long as the solvent is effective for dissolving the other components included in the colored photosensitive resin composition, the solvent used in the conventional colored photosensitive resin composition can be used without particular limitation, and especially ethers, aromatic hydrocarbons, ketones, alcohols, esters. Or amides are preferred.

Specifically, the solvent is ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, di Ethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, Ethers such as dipropylene glycol dibutyl ether; 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; Ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, butyl lactate, 3-meth Methoxybutyl acetate, 3-methyl-3-methoxy-1-butyl acetate, methoxypentyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol Monoacetate, diethylene glycol diacetate, diethylene glycol monobutyl ether acetate, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene carbonate, propylene carbonate or γ-buty Rockactone, etc. And esters thereof.

The solvent is preferably an organic solvent having a boiling point of 100 ℃ to 200 ℃ in terms of applicability and dryness, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butalac Tate, 3-ethoxy propionate, methyl 3-methoxypropionate, etc. can be used.

The solvents exemplified above may be used alone or in combination of two or more thereof.

The solvent may be included 60 to 90% by weight, preferably 70 to 85% by weight relative to the total weight of the colored photosensitive resin composition of the present invention. In the said range, when it apply | coats with coating apparatuses, such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes called a die coater), or an inkjet, the applicability | paintability becomes favorable.

The present invention provides a color filter made of the colored photosensitive resin composition and a display device including the color filter.

The display device may be manufactured by coating the colored photosensitive resin composition on a substrate, photocuring and developing the same, and forming a pattern.

First, a coloring photosensitive resin composition is apply | coated on a board | substrate (usually glass) or the layer which consists of solid content of the coloring photosensitive resin composition formed previously, and heat-drying removes volatile components, such as a solvent, and obtains a smooth coating film.

As a coating method, it can carry out by a spin coat, cast coating method, the roll coating method, the slit and spin coat, the slit coat method, etc., for example. After coating, heating and drying (prebaking) or drying under reduced pressure are carried out to volatilize volatile components such as a solvent. Here, heating temperature is 70-200 degreeC normally, Preferably it is 80-130 degreeC. The coating film thickness after heat drying is about 1-8 micrometers normally. The coating film thus obtained is irradiated with ultraviolet rays through a mask for forming a target pattern. At this time, it is preferable to use apparatuses, such as a mask aligner and a stepper, so that the parallel light beam may be irradiated uniformly to the whole exposure part, and the exact alignment of a mask and a board | substrate is performed. When ultraviolet light is irradiated, curing of the site irradiated with ultraviolet light is performed.

G-rays (wavelength: 436 nm), h-rays, i-rays (wavelength: 365 nm) and the like can be used as the ultraviolet rays. The irradiation amount of ultraviolet rays may be appropriately selected as necessary, and the present invention is not limited thereto. When the coating film after hardening is contacted with a developing solution and the non-exposed part is melted and developed, the target pattern shape can be formed.

The developing method may be any of a liquid addition method, a dipping method, a spray method and the like. In addition, during development, the substrate may be tilted at an arbitrary angle. The developer is usually an aqueous solution containing an alkaline compound and a surfactant. The alkaline compound may be either an inorganic or organic alkaline compound. Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate And sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, ammonia and the like. Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, Monoisopropylamine, diisopropylamine, ethanolamine and the like.

These inorganic and organic alkaline compounds can be used individually or in combination of 2 or more types, respectively. The concentration of the alkaline compound in the alkaline developer is preferably 0.01 to 10% by weight, more preferably 0.03 to 5% by weight.

The surfactant in the alkaline developer may be at least one selected from the group consisting of nonionic surfactants, anionic surfactants or cationic surfactants.

Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine and the like.

Specific examples of the anionic surfactants include higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzene sulfonate, Alkyl aryl sulfonates, such as sodium dodecyl naphthalene sulfonate, etc. are mentioned.

Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryl trimethylammonium chloride, or quaternary ammonium salts. These surfactant can be used individually or in combination of 2 or more types, respectively.

The concentration of the surfactant in the developer is usually 0.01 to 10% by weight, preferably 0.05 to 8% by weight, more preferably 0.1 to 5% by weight. After image development, it is washed with water and also 10-60 minutes post-baking may be performed at 150-230 degreeC as needed.

Using the coloring photosensitive resin composition of this invention, a pattern can be formed on a board | substrate or a color filter substrate through each process as mentioned above. This pattern is useful as a photo spacer used in a display device.

Therefore, the pattern thus obtained can be usefully used in image display devices such as liquid crystal displays, and has excellent visible light shielding properties, high crosslinking density even at low exposure amounts, and excellent adhesion to substrates, thereby providing excellent heat resistance and chemical stability (contents). Attractiveness) and has high elastic recovery rate.

Hereinafter, the present invention will be described in detail with reference to Examples. However, embodiments according to the present invention can be modified in various other forms, the scope of the present invention is not limited to the following examples. The embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.

Synthesis Example  1. (B) Alkali Soluble Resin Preparation

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, 3,4-epoxytridecane-8-yl (meth) acrylate and 3,4-epoxytrile were prepared. 40 parts by weight of a mixture of cyclodecane-9-yl (meth) acrylate (50:50 molar ratio), 50 parts by weight of methyl methacrylate, 40 parts by weight of acrylic acid, 70 parts by weight of vinyltoluene, t-butylperoxy-2- 4 parts by weight of ethyl hexanoate and 40 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) were added and prepared by stirring, and as a chain transfer dropper, 6 parts by weight of n-dodecanethiol and 24 parts by weight of PGMEA were added and stirred. One was prepared. Thereafter, 395 parts by weight of PGMEA was introduced into the flask, and the atmosphere in the flask was changed to nitrogen in air, and then the temperature of the flask was raised to 90 ° C. while stirring. The monomer and chain transfer agent were then started dropping 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 to obtain an (B) alkali-soluble resin having a solid acid value of 75 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.

About the measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) of the said alkali-soluble 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: 50 μl

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  1-4. Preparation of colored photosensitive resin composition

To the components and compositions shown in Table 1 below, a colored photosensitive resin composition was prepared according to a conventional method.

Pigment dispersion composition Coloring photosensitive resin composition B15: 6 V23 Total Pigment Content alkali
Soluble resin Photopolymerizable compound Photopolymerization
Initiator solvent Example 1 5 0 5 45 50 5 200 Example 2 5 5 10 45 45 5 200 Example 3 10 0 10 45 45 5 200 Example 4 10 10 20 35 40 5 200

B15: 6 (A): C.I. Pigment Blue 15: 6

V23 (A): C.I. Pigment Violet 23

Alkali-soluble resin (B): Resin of the synthesis example 1

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

Photoinitiator (D): 1,2-octanedione-1- [4- (phenylthio) phenyl] -2-0-benzoyloxime (OXE-01; manufactured by BASF)

Photoinitiator (D-2): 2-methyl-1- [4- (methylthiophenyl) -2-morpholinopropane-1-one (Irgacure 907 (manufactured by Ciba Specialty Chemical))

Solvent (E): Propylene glycol monomethyl ether acetate

Example  5. Substrate Manufacturing

A glass substrate (Eagle 2000; manufactured by Corning Corporation) having a length and width of 2 inches was washed sequentially with a neutral detergent, water, and alcohol, and dried. Each of the colored photosensitive resin compositions prepared in Examples 1 to 4 was spin coated on the glass substrate and then prebaked at 90 ° C. for 3 minutes in a clean oven. After cooling the prebaked substrate to room temperature, the distance from the quartz glass photomask was set to 10 μm, and light was emitted at an exposure dose (365 nm standard) of 60 mJ / cm 2 using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.). Investigate. Radiation light from an ultrahigh pressure mercury lamp was used for irradiation to the polymeric resin composition at this time. In this case, a photomask in which the next pattern was formed on the same plane was used. One side has a square light-transmitting part (pattern) of 10 micrometers-100 micrometers, and the said space | interval is 100 micrometers. After irradiation with light, the coating film was immersed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25 ° C. for 100 seconds. After washing with water, post-baking was performed at 220 ° C. for 20 minutes in an oven. The substrate was made.

Experimental Example  1 to 4 and Comparative Experiment  1 to 4. Color and Luminance Measurement

Each board | substrate manufactured using the coloring photosensitive resin composition of the said Examples 1-4 was combined with blue BLU or white BLU, and color and brightness were measured.

Color results were measured by CIE 1931, and the results of color and brightness are shown in Table 2 below.

Color coordinates Luminance x y Y Experimental Example 1 Example 1 Substrate + Blue BLU 0.136 0.133 15.7 Experimental Example 2 Example 2 Substrate + Blue BLU 0.142 0.115 14.8 Experimental Example 3 Example 3 Substrate + Blue BLU 0.132 0.125 14.2 Experimental Example 4 Example 4 Substrate + Blue BLU 0.135 0.107 13.8 Comparative Experimental Example 1 Example 1 Substrate + White BLU 0.136 0.105 13.7 Comparative Experiment 2 Example 2 Substrate + White BLU 0.142 0.115 13.2 Comparative Experiment 3 Example 3 Substrate + White BLU 0.132 0.125 12.1 Comparative Experiment 4 Example 4 Substrate + White BLU 0.138 0.105 11.8

As shown in Table 2, in the case of a substrate combined with a blue BLU having a wavelength of 580 nm or less having 90% or more, it can be confirmed that the substrate has a higher luminance in the same color coordinate as compared with the case of combining with a white BLU representing white light. there was. Accordingly, from the above results, it was confirmed that the colored photosensitive resin composition of the present invention can have high luminance when it is combined with a blue BLU having a wavelength of 580 nm or less at 90% or more.

Claims (6)

As a coloring photosensitive resin composition for use in the color filter which uses a blue backlight unit (BLU) as a light source, (A) a coloring agent, (B) alkali-soluble resin, (C) photopolymerizable compound, (D) photoinitiator, and (E A solvent, wherein the content of the (A) coloring agent is 0.5 to 25% by weight based on the total weight of solids in the colored photosensitive resin composition,
The said blue back light unit has the wavelength of 580 nm or less in 90% or more, The coloring photosensitive resin composition. The method according to claim 1, 10 to 80% by weight of the (B) alkali-soluble resin, (C) 5 to 50% by weight of the photopolymerizable compound, (B) alkali-soluble resin and the solids based on the total weight of solids in the colored photosensitive resin composition (C) 0.1 to 40 parts by weight of the photopolymerization initiator (D) based on 100 parts by weight of the total of the photopolymerizable compound;
The coloring photosensitive resin composition containing 60-90 weight% of (E) solvent with respect to the total weight of coloring photosensitive resin composition. The colored photosensitive resin composition according to claim 1, wherein the alkali soluble resin (B) comprises at least one compound represented by the following Chemical Formulas 4 to 7:
[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

The colored photosensitive resin composition according to claim 1, wherein the (B) alkali-soluble resin has an acid value of 50 to 150 (KOH mg / g) and a polystyrene reduced weight average molecular weight of 3,000 to 100,000. The color filter characterized by including the color pattern manufactured from the coloring photosensitive resin composition of Claim 1. A display device comprising the color filter of claim 5 and a backlight unit (BLU).

Images