KR101981373B1 - A green photosensitive resin composition, color filter and display device comprising the same - Google Patents

Abstract

SUMMARY Pigment Green 59, a thermosetting oxetane resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. The green photoresist composition has high color reproducibility and excellent solvent resistance and heat resistance.

Description

TECHNICAL FIELD [0001] The present invention relates to a green photosensitive resin composition, a color filter including the green photosensitive resin composition,

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

BACKGROUND ART [0002] Color filters are widely used in imaging elements, liquid crystal displays (LCDs), and the like, and their application range is rapidly expanding. A color filter used in a color liquid crystal display device, an image pickup device, or the like is a device in which a colored photosensitive resin composition containing a pigment corresponding to each color of red, green and blue is uniformly applied by spin coating on a substrate on which a black matrix is pattern- (Hereafter also referred to as "post-baking") is carried out for each color, if necessary, by exposing and developing the coating film formed by heating and drying And then repeatedly forming pixels of each color. Here, the black matrix on which the pattern is formed is usually formed of a black photosensitive resin composition.

The colored photosensitive resin composition usually contains a pigment, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, and a surfactant, an adhesion promoter, a residue reducing compound and the like are added thereto.

In recent years, there is an increasing demand for high-quality displays with high color reproducibility of displays. In addition, development of a pixel with high light transmittance and high contrast while expressing high color reproduction power is required.

Conventionally, C.I. Pigment Green 7 and C.I. Pigment Green 36 (a halogenated phthalocyanine compound containing copper as a central metal) was mainly used. However, the light transmittance and the contrast ratio of the pixel obtained from the colored photosensitive resin composition containing the pigment can not be said to be a sufficient level, and there is a limit in providing an image of higher image quality.

Japanese Patent Application No. 2002-296778 discloses a colored photosensitive resin composition capable of forming a pixel having excellent solvent resistance, but it has been proposed that the content of a coloring agent is high, and thus chemical resistance and heat resistance are insufficient in the production of a resist.

Japanese Patent Application Laid-Open No. 2002-296778

An object of the present invention is to provide a green photosensitive resin composition capable of forming pixels having high color reproduction power, high light transmittance and high contrast ratio.

It is another object of the present invention to provide a green photosensitive resin composition excellent in heat resistance and chemical resistance.

It is another object of the present invention to provide a color filter including the green photosensitive resin composition and a display device including the same.

In order to achieve the above object,

The present invention relates to a green photosensitive resin composition comprising a colorant, a heat-crosslinkable oxetane resin, a photopolymerizable compound, a photopolymerization initiator and a solvent,

The colorant may be C.I. Pigment Green 59, and at least one pigment selected from the group consisting of pigments and dyes,

Wherein the heat-crosslinkable oxetane resin comprises a monomer represented by the following formula (2).

(2)

X ₁ and X ₂ each independently represent an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms, a -O- group, a -CO- group, a -C (= O) O- group, - or a phenylene group,

R < _{1 >} is hydrogen or a methyl group.

The present invention also provides a color filter comprising the green photosensitive resin composition.

Further, the present invention provides a display device including the color filter.

The green photosensitive resin composition of the present invention can form pixels having high color reproduction power, high sensitivity, high light transmittance and high contrast ratio.

Further, the green photosensitive resin composition of the present invention has an excellent heat resistance and chemical resistance.

Further, the color filter including the green photosensitive resin composition of the present invention and the display device including the color filter have an excellent effect of high color reproduction.

Fig. Pigment Green 59 (G59), C.I. Pigment Green 7 (G7) and C.I. Pigment Green 58 (G58).

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

The present invention relates to a green photosensitive resin composition comprising a colorant, a heat-crosslinkable oxetane resin, a photopolymerizable compound, a photopolymerization initiator and a solvent,

The colorant may be C.I. Pigment Green 59, and at least one pigment selected from the group consisting of pigments and dyes,

Wherein the heat-crosslinkable oxetane resin comprises a monomer represented by the following formula (2).

(2)

X ₁ and X ₂ each independently represent an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms, a -O- group, a -CO- group, a -C (= O) O- group, - or a phenylene group,

R < _{1 >} is hydrogen or a methyl group.

In the green photosensitive resin composition of the present invention, the C.I. Pigment Green 59 is a kind of pigment. By including Pigment Green 59, a resist of high color reproduction can be produced even if the content of pigment is small.

Also, by using an oxetane resin containing the monomer of the above formula (1), it is possible to provide a green photosensitive resin composition excellent in light transmittance, contrast ratio, heat resistance and chemical resistance.

Hereinafter, the green photosensitive resin composition of the present invention will be described in detail for each component.

(A) Colorant

The colorant contained in the green photosensitive resin composition of the present invention expresses green.

Further, the colorant may be C.I. Pigment Green 59, and at least one selected from the group consisting of pigments and dyes.

(a1) C.I . Pigment  Green 59

The colorant is C.I. Pigment Green 59, and the C.I. Pigment Green 59 has a structure represented by the following formula (1). The C.I. Pigment Green 59 has a structure of ZnPc (Zinc Phthalocyanine), and C.I. If Pigment Green 59 is included, high color reproduction can be achieved using a small amount of pigment.

[Chemical Formula 1]

Each of A ¹ to A ¹⁶ is independently hydrogen, bromine, or chlorine,

The hydrogen of A ¹ to A ¹⁶ is 1 to 6,

Chlorine is 0 to 5,

Bromine is 5 to 13.

The compound of formula (1) is preferably 1 to 6 hydrogen atoms, 0 to 5 chlorine atoms and 7 to 13 bromine atoms among A ¹ to A ¹⁶ . More preferably, from 2 to 5 of the hydrogens of A ¹ to A ¹⁶ , from 0 to 3 chlorine and from 8 to 13 bromine.

C.I. which was used as a conventional green pigment. Pigment Green 58 (G58) has a high brightness, but in order to realize high color reproduction, a large amount of pigment has to be used. Accordingly, when the amount of the pigment is increased, the developability is lowered and the pattern formed by the composition can be peeled off , And the problem of lowering the sensitivity occurred.

However, the above C.I. Pigment Green 59 can be used to reduce the pigment content and realize a high color reproduction with a small amount of pigment.

Also, C.I. Pigment Green 7 (G7) can exhibit high coloring property even with a small content, but a low luminance problem occurs.

The C.I. Pigment Green 59 is a mixture of C.I. Pigment Green 7 exhibits similar transmittance spectra and color coordinates at wavelengths of 400 to 610 nm and has excellent brightness, so that the above problems can be solved.

In the present specification, Tmax means the wavelength at which the transmittance of the pigment is maximum, and T50 _% means the wavelength at which the pigment transmittance is 50% or more of the maximum value.

The CI Pigment Green 59 has a Tmax of 500 to 530 nm and a T _50% of 445 to 580 nm. The green color photosensitive resin composition of the present invention can realize a high color reproduction since it can exhibit higher coloring property in the above range.

The above C.I. Pigment Green 59 is contained in an amount of 0.05 to 30% by weight, preferably 0.1 to 25% by weight, more preferably 0.5 to 20% by weight based on the total weight of the green photosensitive resin composition of the present invention.

The C.I. When the Pigment Green 59 is contained in an amount ranging from 0.05% by weight to 30% by weight, the light transmittance and the contrast ratio are improved, and excellent developability can be exhibited.

The colorant may be the C.I. Pigment Green 59 and at least one pigment selected from the group consisting of pigments and dyes conventionally used in the art, and can be manufactured and used in the form of a mill base.

The C.I. Pigment Green 59 and at least one pigment selected from the group consisting of pigments and dyes are mixed in a weight ratio of 1: 0.05 to 1:18, preferably 1: 0.1 to 1: 9, more preferably 1: 0.2 To 1: 4 by weight.

Exhibits effects of high coloring property and high brightness in the weight ratio range, and the process margin can be improved and the sensitivity can be enhanced.

In this case, the colorant may have a color coordinate of x = 0.1 to 0.35 when y = 0.6 or more in the XYZ color system.

On the other hand, as an example, C.I. When Pigment Green 58 is used, x = about 0.2 to 0.35 color coordinates can be obtained when y = 0.6 or more in the XYZ color system. At this time, C.I. In order to have a value near x = 0.1 by using Pigment Green 58, it is necessary to color with blue. In this case, there is a problem of lowering the luminance, which is not preferable.

As another example, C.I. In the case of using Pigment Green 7, there is a problem that the area capable of emitting color is wide, but the luminance is low.

(a2) Pigment

The pigment may be an organic pigment or an inorganic pigment generally used in the art. It is preferable to use an organic pigment in terms of heat resistance and color development, and the organic pigment may be a synthetic pigment or a natural pigment.

The pigment may be subjected to a surface treatment using a pigment treatment, a pigment derivative into which an acidic group or a basic group is introduced, a graft treatment of the surface of the pigment with a polymer compound, an atomization treatment using a sulfuric acid atomization method or the like, A cleaning treatment with an organic solvent or water, or a treatment for removing ionic impurities by ion exchange or the like.

The organic pigments may be various pigments used in printing ink, ink jet ink, etc. Specific examples thereof include water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, A pyranthrone pigment, a diketopyrrolopyrrole pigment, an anthraquinone pigment, an anthraquinone pigment, an anthrone pigment, an anthrone pigment, an indanthrone pigment, a pravanthrone pigment, a pyranthrone pigment, a diketopyrrolopyrrole pigment And the like.

As the inorganic pigment, metal compounds such as metal oxides and metal complex salts can be used. Specific examples of the inorganic pigments include iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, A black pigment, a titanium black, and an oxide of a metal such as a pigment that mixes red, green, and blue to give a black color, or a composite metal oxide.

Particularly, the organic pigments and inorganic pigments may be specifically classified into pigments in the Society of Dyers and Colourists, and more specifically, those having a color index (CI) number Pigments, but are not limited thereto.

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, 129, 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 Violet 14, 19, 23, 29, 32 and 177;

C.I. Pigment Blue 15: 3, 15: 4, 15: 6, 16, 22, 28 and 60;

C.I. Pigment Green 7, 36 and 58; And the like.

These pigments may be used alone or in combination of two or more.

The exemplified C.I. Among the pigment pigments, C.I. Pigment Yellow 138, C.I. Pigment Yellow 129, C.I. Pigment Yellow 150 and C.I. It is preferable to use at least one pigment selected from the group consisting of Pigment Yellow 185 and the like.

The pigment is preferably a pigment dispersion in which the particle diameter of the pigment is uniformly dispersed. Examples of a method for uniformly dispersing the particle diameter of the pigment include a method of dispersing the pigment dispersion (a3) by containing the pigment dispersant (a3), and a pigment dispersion in which the pigment is uniformly dispersed in the solution can be obtained have.

(a3) Pigment dispersant

The pigment dispersant is added for deaggregation of the pigment and maintenance of stability. Specific examples of the pigment dispersant include a cationic surfactant, an anionic surfactant, a nonionic surfactant, a positive surfactant, a polyester surfactant, and a polyamine surfactant. , Which may be used alone or in combination of two or more.

Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, and quaternary ammonium salts.

Specific examples of the anionic surfactant include higher alcohol sulfuric acid ester salts such as sodium lauryl alcohol sulfate ester and sodium oleyl alcohol sulfate ester, alkylsulfates such as sodium laurylsulfate and ammonium laurylsulfate, sodium dodecylbenzenesulfonate, And alkylarylsulfonic acid salts such as sodium dodecylnaphthalenesulfonate.

Specific examples of the nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, Polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines.

In addition, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines have.

Also, the pigment dispersant preferably includes an acrylate-based dispersant (hereinafter referred to as an acrylate-based dispersant) containing butyl methacrylate (BMA) or N, N-dimethylaminoethyl methacrylate (DMAEMA). Examples of commercially available acrylate dispersants include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070 and DISPER BYK-2150. The acrylate dispersants may be used alone or in combination of two or more. .

As the pigment dispersant, other resin type pigment dispersants other than the acrylate dispersant may be used. The other resin type pigment dispersing agent may be a known resin type pigment dispersing agent, especially a polycarboxylic acid ester such as polyurethane, polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) Amine salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long chain polyaminoamide phosphate salts, esters of hydroxyl group-containing polycarboxylic acids and their modified products, or free ) Oil-based dispersants such as amides formed by reaction of a polyester having a carboxyl group with poly (lower alkyleneimine) or salts thereof; Soluble resin or water-soluble polymer compound such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylate ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinylpyrrolidone; Polyester; Modified polyacrylates; Adducts of ethylene oxide / propylene oxide; And phosphate esters.

DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, and DISPER BYK-160 available from BYK (Big) Chemie are examples of commercially available pigment dispersants of other resin types. BYK-164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; EFKA-4060, EFKA-4060, EFKA-4055, EFKA-4055, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA- 4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10 from Lubirzol; Hinoact T-6000, Hinoact T-7000, Hinoact T-8000; available from Kawaken Fine Chemicals; AJISPUR PB-821, Ajisper PB-822, Ajisper PB-823 manufactured by Ajinomoto; FLORENE DOPA-17HF, fluorene DOPA-15BHF, fluorene DOPA-33, and fluorene DOPA-44 are trade names of Kyoeisha Chemical Co.,

In addition to the acrylate-based dispersant, other resin-type pigment dispersants may be used alone or in combination of two or more, and may be used in combination with an acrylate-based dispersant.

The pigment dispersant is included in the pigment in an amount of 5 to 60% by weight, preferably 15 to 50% by weight based on the total weight of the solid content. When the pigment dispersant is contained in an amount of less than 5% by weight, it is difficult to atomize the pigment and problems such as gelation may occur after dispersion. When the pigment dispersant is contained in an amount exceeding 60% by weight, the viscosity may be increased.

(a4) Dye

The dye can be used without limitation as long as it has solubility in an organic solvent. It is preferable to use a dye which has solubility in an organic solvent and can ensure reliability such as solubility in an alkali developing solution, heat resistance and solvent resistance. It is also possible to use a dye which is not soluble in an organic solvent in dispersion.

Examples of the dye include acid dyes having an acidic group such as a sulfonic acid and a carboxylic acid, salts of an acidic dye and a nitrogen-containing compound, sulfonamides of an acidic dye and derivatives thereof, and azo, xanthate, phthalocyanine Based acid dyes and their derivatives can also be selected. Preferably, the dye is 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 dyeing).

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

C.I. Solvent Yellow 2, 14, 16, 33, 34, 44, 56, 82, 93, 94, 98, 116 and 135;

C.I. Solvent Red 1, 2, 3, 8, 18, 23, 24, 27, 35, 43, 45, 48, 49, 91: 1, 119, 135, 140, 196 and 197;

C.I. Solvent Blue 4, 5, 25, 35, 36, 38 and 70;

C.I. Solvent Violet 8, 9, 13, 26, 28, 31 and 59;

C.I. Solvent Orange 1, 3, 7 and 63;

C.I. Solvent Green 3, 5 and 7, and the like.

The colorant is contained in the green photosensitive resin composition of the present invention in an amount of 5 to 70% by weight, preferably 10 to 50% by weight based on the total weight of the solid content.

If the amount of the colorant is less than 5% by weight, the color separation performance of the flattened pattern may be deteriorated. If the amount exceeds 70% by weight, the lithographic performance may be deteriorated, and residues may not remain or develop.

In the present invention, the total solid weight refers to the content of the green photosensitive resin composition excluding the solvent.

(B) Thermally crosslinked type Oxetane  Suzy

The thermally crosslinkable oxetane resin contained in the green photosensitive resin composition of the present invention comprises a monomer represented by the following formula (2) and serves as a bonding agent for the pigment in a thermal process.

(2)

X ₁ and X ₂ each independently represent an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms, a -O- group, a -CO- group, a -C (= O) O- group, - or a phenylene group,

R < _{1 >} is hydrogen or a methyl group.

The thermally crosslinkable oxetane resin may be an oxetane resin composed only of the monomer (b1) of the formula (2), a copolymer of the monomer of the formula (2) and the unsaturated carboxylic acid monomer (b2), a monomer of the formula (B3) containing a carboxylic acid monomer and an unsaturated bond capable of copolymerization with the monomer of Formula 2 and the unsaturated carboxylic acid monomer.

By using an unsaturated carboxylic acid monomer together, it is possible to impart solubility to an alkali developer.

The monomer (b1) of the formula (2) is specifically, for example,

3- (vinyloxymethyl) -2-methyloxetane, 3- (vinyloxymethyl) -2-methyloxetane, 3- (vinyloxymethyl) 3- (vinyloxyethyl) -2-ethyloxetane, 3- (vinyloxyethyl) -2-methyloxetane, 3- (Vinyloxymethyl) -2-methyloxetane, 2- (vinyloxymethyl) -3-methyloxetane, 2- (vinyloxymethyl) Ethyloxetane, 2- (vinyloxyethyl) -3-ethyloxetane, 2- (vinyloxyethyl) -2-methyloxetane, 2- (Vinyloxyalkyl) alkyloxetanes such as 2-ethyloxetane and 2- (vinyloxyethyl) -3-ethyloxetane;

(Meth) acryloyloxymethyl] oxetane, 2- [(meth) acryloyloxyethyl] oxetane, 2- [ (Meth) acryloyloxyethyl] oxetane; a (meth) acryloyloxyalkyl oxetane such as 2- (meth) acryloyloxyethyl] oxetane;

3 - [(meth) acryloyloxymethyl] -2-methyloxetane, 3- [(meth) acryloyloxymethyl] Acryloyloxymethyl] -3-ethyloxetane, 3- [2- (meth) acryloyloxyethyl] -2-methyloxetane, 3- [ (Meth) acryloyloxyethyl] -3-methyloxetane, 3- [2- (meth) acryloyloxyethyl] (Meth) acryloyloxymethyl] -3-methyloxetane, 2- [(meth) acryloyloxymethyl] -2-methyloxetane, 2- [(Meth) acryloyloxymethyl] -4-methyloxetane, 2- [(meth) acryloyloxymethyl] -2-ethyl oxetane, 2- [ Acryloyloxymethyl] -4-ethyloxetane, 2- [2- (meth) acryloyloxyethyl] -2-methyloxetane, 2- [2- (Meth) acryloyloxyethyl] -3-methyloxetane, 2 (Meth) acryloyloxyethyl] -4-methyloxetane, 2- [2- (meth) acryloyloxyethyl] [(Meth) acryloyloxyalkyl] alkyl oxetane such as 2- [2- (meth) acryloyloxyethyl] -4-ethyl oxetane;

(Meth) acryloyloxymethyl] -2-trifluoromethyl oxetane, 3 - [(meth) acryloyloxymethyl] -2-pentafluoroethyl oxetane, 3- (Meth) acryloyloxymethyl] -2,2-difluorooxetane, 3 - [(meth) acryloyloxymethyl] (Meth) acryloyloxyethyl] -2,2,4,4-tetrafluorooxetane, 3- [2- (meth) acryloyloxyethyl] -2 (Meth) acryloyloxyethyl] -2-fluorooxetane, 3- [2- (meth) acryloyloxyethyl] , 3- [2- (meth) acryloyloxyethyl] -2,2-difluorooxetane, 3- [2- (meth) acryloyloxyethyl] -2,2,4- Cetane, 2- [(meth) acryloyloxyethyl] -2,2,4,4-tetrafluorooxetane, 2- [(meth) acryloyloxymethyl] Acryloyloxymethyl] -4-trifluoromethyloxetane, 2- [(meth) acryloyloxymethyl] -3-trifluoromethyloxetane, 2- [ (Meth) acryloyloxymethyl] -2-pentafluoroethyloxetane, 2- [(meth) acryloyloxymethyl] -3-pentafluoroethyloxetane, 2- [ ] - 4-pentafluoroethyloxetane, 2 - [(meth) acryloyloxymethyl] -2,3-difluorooxetane, 2- [ (Meth) acryloyloxymethyl] -3,3-difluorooxetane, 2- [(meth) acryloyloxymethyl] -3,4-difluorooxane, 2- Cetane, 2- [(meth) acryloyloxymethyl] -4,4-difluorooxetane, 2- [(meth) acryloyloxymethyl] -3,3,4-trifluorooxetane, 2 - [(meth) acryloyloxymethyl] -3,4,4-trifluoroxetane, 2- [(meth) acryloyloxymethyl] (Meth) acryloyloxyethyl] -2-trifluoromethyl oxetane, 2- [2- (meth) acryloyloxyethyl] (Meth) acryloyloxyethyl] -4-trifluoromethyloxetane, 2- [2- (meth) acryloyloxyethyl] -2-pentafluoroethyl Oxetane, 2- [2- (meth) acryloyloxyethyl] -4-pentafluoroethyloxetane, 2- [ - [2- (meth) acryloyloxyethyl] -2,4-difluorooxetane, 2 [2- (meth) acryloyloxyethyl] -2,3-difluorooxetane, 2- - [2- (meth) acryloyloxyethyl] -3,4-difluorooxetane, 2 - [(meth) acryloyloxyethyl] - [2- (meth) acryloyloxyethyl] -4,4-difluorooxetane, 2- [2- (meth) acryloyloxyethyl]Acryloyloxyethyl] -3,4,4-tetrafluorooxetane and 2- [2- (meth) acryloyloxyethyl] -3,3,4,4-tetra [(Meth) acryloyloxy] fluorooxetane or [(meth) acryloyloxyalkyl] fluoroalkyl oxetane such as fluorooxetane;

2 - [(meth) acryloyloxymethyl] -2-phenyloxetane, 2- [(meth) acryloyloxymethyl] (Meth) acryloyloxyethyl] -3-phenyloxetane and 2 [2- (meth) acryloyloxyethyl] - [(meth) acryloyloxyalkyl] phenyloxetane such as [2- (meth) acryloyloxyethyl] -4-phenyloxetane;

4- [3-ethyloxetane-3-ylmethoxy) propoxy] styrene, 4- [4- Hexyloxy] styrene and 4- [7- (3-ethylox [gamma] -methoxy) pentyloxy] styrene, 4- [6- (3-ethyloxetane- Cetane-3-ylmethoxy) heptyloxy] styrene; an aromatic vinyl compound containing an oxetanyl group; And the like.

(Meth) acryloyloxymethyl] -3-ethyloxetane, 3 - [(meth) acryloyloxymethyl] oxetane, 3- , [(Meth) acryloyloxymethyl] -2-trifluoromethyl oxetane, 3- [(meth) acryloyloxymethyl] Oxymethyl] oxetane and 2 - [(meth) acryloyloxymethyl] -4-trifluoromethyloxetane is preferable in terms of improving the solvent resistance and heat resistance of the colored layer .

These compounds may be used alone or in combination of two or more.

The unsaturated carboxylic acid monomer (b2) may be used either singly or in combination of acrylic acid and methacrylic acid.

In addition, one or more other acids may be added to acrylic acid or methacrylic acid.

As the other acid, it is possible to use concretely one or more carboxylic acids selected from other unsaturated carboxylic acids such as crotonic acid, itaconic acid, maleic acid and fumaric acid. In addition, a monomer containing a hydroxyl group and a carboxyl group may be used together in the same molecule such as? - (hydroxymethyl) acrylic acid.

The monomer (b3) containing an unsaturated bond capable of copolymerization with the monomer of Formula 2 and the unsaturated carboxylic acid monomer is not limited as long as it is a compound having an unsaturated double bond capable of polymerization.

Specific examples thereof include unsaturated carboxylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2- hydroxyethyl (meth) acrylate and aminoethyl Unsubstituted or substituted alkyl ester compounds;

(Meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (Meth) acrylate, cyclohexenyl (meth) acrylate, cyclohexenyl (meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl Unsaturated carboxylic acid ester compounds containing an alicyclic substituent such as a carboxylate, a carboxylate, a carboxylate, a pyranyl (meth) acrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate and pinenyl (meth) acrylate;

Mono-saturated carboxylic acid ester compounds of glycols such as oligoethylene glycol monoalkyl (meth) acrylate;

Unsaturated carboxylic acid ester compounds containing a substituent having an aromatic ring such as benzyl (meth) acrylate and phenoxy (meth) acrylate;

Aromatic vinyl compounds such as styrene,? -Methylstyrene, and vinyltoluene;

Carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate;

Vinyl cyanide compounds such as (meth) acrylonitrile and? -Chloroacrylonitrile;

And maleimide compounds such as N-cyclohexylmaleimide and N-phenylmaleimide.

When the thermally crosslinkable oxetane resin of the present invention is a copolymer of the monomer of the above formula (2) and the unsaturated carboxylic acid monomer, 5 to 95 mol% of the monomer of the above formula (2) And 5 to 95 mol% of a carboxylic acid monomer.

If the amount of the monomer of Formula 2 is less than 5 mol%, the reliability is insufficient. If the amount of the monomer is more than 95 mol%, the developability to the lower substrate may be deteriorated.

If the amount of the unsaturated carboxylic acid monomer is less than 5 mol%, residues may develop after development, and if it exceeds 95 mol%, adhesion of patterns may deteriorate.

When the thermally crosslinkable oxetane resin of the present invention is a copolymer of the monomer of Formula 2, the unsaturated carboxylic acid monomer, and the monomer containing unsaturated bond capable of copolymerization with the monomer of Formula 2 and the unsaturated carboxylic acid monomer , 5 to 90 mol% of the monomer of the formula (2), 5 to 90 mol% of the unsaturated carboxylic acid monomer and 5 to 90 mol% of the unsaturated carboxylic acid monomer, which are copolymerizable with the monomer and the unsaturated carboxylic acid monomer of the formula And 5 to 70 mol% of a monomer containing a bond.

If the amount of the monomer represented by the formula (2) is less than 5 mol%, the reliability is insufficient. If the amount exceeds 90 mol%, the developing property and the residue may be deteriorated.

If the amount of the unsaturated carboxylic acid monomer is less than 5 mol%, the developing performance is deteriorated. If the unsaturated carboxylic acid monomer is more than 90 mol%, the reliability may be insufficient.

If the amount of the monomer having an unsaturated bond capable of copolymerizing with the monomer represented by the formula (2) and the unsaturated carboxylic acid monomer is less than 5 mol%, the reliability is insufficient, and if it exceeds 90 mol%, the pattern adhesion may be poor.

In one embodiment of the present invention, the monomer (b1), the unsaturated carboxylic acid monomer (b2), the monomer of the formula (2) and the unsaturated carboxylic acid In the case of a copolymer of a monomer (b3) containing an unsaturated bond capable of copolymerization with a carboxylic acid monomer and a copolymerizable unsaturated monomer capable of copolymerization with a carboxylic acid monomer.

The monomer (b1), the unsaturated carboxylic acid monomer (b2), and the monomer and unsaturated carboxylic acid monomer of the above formula (2) and the monomer (b1) of the above formula (2) (B3) containing an unsaturated bond capable of copolymerization of 0.5 to 20 times with respect to the total weight of the monomer, and the atmosphere in the flask is replaced with nitrogen in air.

Thereafter, the temperature of the solvent is raised to 40 to 140 캜, and then the unsaturated carboxylic acid monomer (b2) and the monomer (b3) containing an unsaturated bond capable of copolymerizing with the monomer of the above formula (2) and the unsaturated carboxylic acid monomer (B3) containing an unsaturated bond capable of copolymerization with the monomer of the formula (2) and the unsaturated carboxylic acid monomer, and a solvent of 0 to 20 times the total weight of the unsaturated carboxylic acid monomer (b3) And a polymerization initiator such as azobisisobutyronitrile or tert-butyryl peroxy 2-ethylhexyl carbonate are reacted with the monomer (b1), the unsaturated carboxylic acid monomer (b2), the monomer of the above formula (2) (Solution or solution under stirring at room temperature or under heating) added in an amount of 0.1 to 10 mol% based on the total number of moles of the monomer (b3) containing an unsaturated bond capable of copolymerizing with the unsaturated carboxylic acid monomer Over 0.1 to 8 hours and added dropwise to the flask above and stirred for 1 to 10 hours at 40 to 140 ℃.

The monomer (b1), the unsaturated carboxylic acid monomer (b2), and the monomers and unsaturated carboxylic acid monomers of Formula 2 and the unsaturated carboxylic acid monomer Of the monomer (b3) containing an unsaturated bond capable of copolymerization can be added to the flask.

Further, an alpha -methylstyrene dimer or a mercapto compound may be used as a chain transfer agent to control the molecular weight or the molecular weight distribution. The amount of the? -methylstyrene dimer or mercapto compound to be used is not particularly limited as long as the amount of the monomer (b1), the unsaturated carboxylic acid monomer (b2), and the unsaturated carboxylic acid monomer Is 0.005 to 5% by weight based on the total weight of the monomer (b3).

In addition, the above-mentioned polymerization conditions may be appropriately controlled depending on the production equipment or the amount of heat generated by polymerization, and the method of addition and the reaction temperature.

The heat-crosslinkable oxetane resin has a weight average molecular weight in terms of polystyrene of 3,000 to 100,000, more preferably 5,000 to 50,000. When the weight average molecular weight of the heat-crosslinkable oxetane resin is in the range of 3,000 to 100,000, the storage stability is excellent and the film is hardly reduced during development.

The thermosetting oxetane resin is contained in an amount of 5 to 80% by weight, preferably 10 to 70% by weight based on the total solid weight of the green photosensitive resin composition of the present invention.

If the amount of the heat-crosslinkable oxetane resin is less than 5% by weight, the reliability is insufficient. If the amount of the thermosetting oxetane resin is more than 80% by weight, developability and residue of the base agent may be deteriorated.

(C) Photopolymerization  compound

The photopolymerizable compound contained in the green photosensitive resin composition of the present invention should be a compound capable of polymerizing under the action of the photopolymerization initiator (D) described later. A monofunctional photopolymerizable compound, a bifunctional photopolymerizable compound or a trifunctional photopolymerizable compound, and the like, but are not limited thereto.

Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N- And vinyl pyrrolidone. Commercially available products include Aronix M-101 (Toagosei), KAYARAD TC-110S (Nippon Kayaku), and Viscot 158 (Osaka Yuki Kagaku Kogyo).

Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di M-210, M-1100, and 1200 (Doagosei Co., Ltd.) as commercially available products, and the like. Examples of commercially available products include Aronix M-210, M- , KAYARAD HDDA (Nippon Kayaku), Biscoat 260 (Osaka Yuki Kagaku Kogyo), AH-600, AT-600 or UA-306H (Kyoeisha Chemical Co., Ltd.).

The polyfunctional photopolymerizable compound having three or more functional groups is specifically exemplified by trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, Propoxylated dipentaerythritol hexa (meth) acrylate and dipentaerythritol hexa (meth) acrylate. Commercially available products include Aronix M-309, TO-1382 (Toagosei), KAYARAD TMPTA, KAYARAD DPHA or KAYARAD DPHA-40H (Nippon Kayaku).

Of the photopolymerizable compounds exemplified above, trifunctional or higher (meth) acrylate esters and urethane (meth) acrylates are preferred because they have excellent polymerizability and can improve the strength.

The photopolymerizable compound is included in the colored photosensitive resin composition for an organic light emitting diode of the present invention in an amount of 5 to 45 wt%, preferably 10 to 35 wt%, based on the total weight of the solid content. The photopolymerizable compound can improve the strength and flatness of the pixel portion in the range of 5 to 45% by weight.

(D) Light curing Initiator

The photopolymerization initiator contained in the green photosensitive resin composition of the present invention is not particularly limited as long as it can polymerize the photopolymerizable compound (C) by radiation exposure such as visible light, ultraviolet light, deep ultraviolet light, electron beam and X- Can be used.

Although the kind of the photopolymerization initiator is not particularly limited, from the viewpoints of polymerization characteristics, initiation efficiency, absorption wavelength, availability and price, oxime compounds, acetophenone compounds, benzoin compounds, benzophenone compounds, It is preferable to use at least one compound selected from the group consisting of a perazine-based compound, a triazine-based compound, a thioxanthone-based compound, and an anthracene-based compound, more preferably an oxime-based compound.

Oximeimino-1-phenylpropan-1-one, (Z) -2 - ((benzoyloxy) imino) -1- (4- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl) ethylidene) amino ) Oxy) ethanone and (E) -1 - ((1- (6- (4 - ((2,2- dimethyl- 1, 3- dioxolan-4- yl) methoxy) ) -9-ethyl-9H-carbazol-3-yl) ethylidene) amino) oxy) ethanone and commercially available products include OXE-01 and OXE-02 of BASF Co., It is not.

The content of the oxime-based compound is not particularly limited as long as the function of the oxime-based compound is fulfilled. The content of the oxime-based compound is preferably 10 to 100% by weight, more preferably 20 to 100% by weight based on the total weight of the photopolymerization initiator . When the content of the oxime compound is within the above range, the brightness and sensitivity can be maximized.

Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2- 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1- (2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane -1-one and 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.

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

Examples of the benzophenone compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone and 2,4,6-trimethylbenzophenone.

Examples of the non-imidazole compound compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis , 3-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'- ) Diimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) ) -4,4'5,5'-tetraphenyl-1,2'-biimidazole or an imidazole compound in which the phenyl group at the 4,4 ', 5,5' position is substituted with a carboalkoxy group . Among them, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis 4,4 ', 5,5'-tetraphenylbiimidazole or 2,2-bis (2,6-dichlorophenyl) -4,4'5,5'-tetraphenyl- And the like.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4 Bis (trichloromethyl) -6- [2- (5-methylfuran-1-yl) Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan- Triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5- triazine and 2,4- L-methylethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone and 1-chloro-4- And the like.

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

In addition, in addition to the above, it is also possible to use 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethyl anthraquinone, 9,10-phenanthrenequinone, camphorquinone, phenylclyoxylic acid Methyl and titanocene compounds and the like can be used.

The photopolymerization initiator may further include a photopolymerization initiator (d1) to improve the sensitivity of the green photosensitive resin composition of the present invention. The green photosensitive resin composition according to the present invention contains the photopolymerization initiation auxiliary (d1), thereby further increasing the sensitivity and improving the productivity.

As the photopolymerization initiation auxiliary, for example, at least one compound selected from the group consisting of an amine compound, a carboxylic acid compound and an organic sulfur compound having a thiol group can be preferably used.

As the amine compound, an aromatic amine compound is preferably used. Specific examples thereof include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine, 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid Ethyl, 4-dimethylaminobenzoic acid isoamyl, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone : Michler's ketone) and 4,4'-bis (diethylamino) benzophenone.

The carboxylic acid compound is preferably an aromatic heteroacetic acid compound. Specific examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, Dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

The organic sulfur compound having a thiol group is specifically exemplified by 2-mercaptobenzothiazole, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyl Trimethylolpropane tris (3-mercaptopropionate), pentaerythritoltetrakis (3-hydroxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) (Mercaptobutylate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate) and tetraethylene glycol bis (3-mercaptopropionate ) And the like.

The photopolymerization initiator may be contained in an amount of 2 to 10% by weight, preferably 3 to 7% by weight based on the total weight of the solid content of the green photosensitive resin composition of the present invention.

When the photopolymerization initiator is included in the above range, the green photosensitive resin composition has high sensitivity and shortens the exposure time, thereby improving the productivity and maintaining high resolution. In addition, the strength of the pixel portion formed using the colored photosensitive resin composition and the smoothness of the surface of the pixel portion can be improved.

When the photopolymerization initiator is further used, it is used in an amount of 10 mol or less, preferably 0.01 to 5 mol per mol of the photopolymerization initiator.

When the photopolymerization initiator is used within the above range, the sensitivity of the green photosensitive resin composition is improved, and the productivity of the color filter including the green photosensitive resin composition can be improved.

(E) Solvent

The solvent used in the conventional green photosensitive resin composition is not particularly limited so long as it is effective to dissolve the other components contained in the green photosensitive resin composition. In particular, the solvent may be selected from ethers, acetates, aromatic hydrocarbons, ketones, Alcohols, esters, amides and the like are preferable.

Examples of the ethers include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether;

And diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether.

Examples of the acetates include methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, butyl lactate, 3-methoxybutyl acetate, 3 Methoxy-1-butylacetate, methoxypentyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, methyl 3-methoxypropionate, propylene glycol methyl ether acetate, 3-methoxy- Butyl acetate, 1,2-propylene glycol diacetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, diethylene glycol monobutyl ether Acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, di Ethylene 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 and propylene carbonate. .

Examples of the aromatic hydrocarbons include benzene, toluene, xylene, and mesitylene.

The ketones include, for example, methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone.

The alcohols include, for example, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin and 4-hydroxy-4-methyl-2-pentanone.

Examples of the esters include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate and? -Butyrolactone.

Examples of the amide include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.

These solvents may be used alone or in combination of two or more.

The solvent is preferably an organic solvent having a boiling point in the range of 100 ° C to 200 ° C in terms of coatability and dryness, and examples thereof include alkylene glycol alkyl ether acetates, ketones, ethyl 3-ethoxypropionate, Propyleneglycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butyl lactate, ethyl 3-ethoxypropionate, and 3-ethoxypropionate, and more preferably propyleneglycol monomethylether acetate, -Methoxypropionate, and the like.

The solvent is contained in an amount of 60 to 90% by weight, preferably 70 to 85% by weight based on the total weight of the green photosensitive resin composition. When the solvent is contained in the range of 60 to 90% by weight, when the solvent is applied by a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater) .

(F) an alkali-soluble resin

The green photosensitive resin composition of the present invention may further comprise an alkali-soluble resin.

The alkali-soluble resin usually makes the unexposed portion of the green photosensitive resin layer formed using the green photosensitive resin composition alkali-soluble and serves as a dispersion medium for the pigment.

The kind of the alkali-soluble resin is not particularly limited and may be selected from various polymers used in the technical field, and preferably includes a monomer (f1) containing a carboxyl group. As the polymer containing the carboxyl group-containing monomer, it is particularly preferable to use a copolymer obtained from a monomer (f1) containing a carboxyl group and another monomer (f2) copolymerizable with a monomer containing the carboxyl group.

The monomer (f1) containing a carboxyl group can be, for example, an unsaturated carboxylic acid having at least one carboxyl group in the molecule such as an unsaturated monocarboxylic acid and an unsaturated dicarboxylic acid.

More specifically, examples include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid and fumaric acid. The carboxylic acid-containing monomers may be used alone or in combination of two or more.

The other monomer (f2) copolymerizable with the monomer containing a carboxyl group is a compound having a polymerizable carbon-carbon unsaturated bond. Specifically, for example,

aromatic vinyl compounds such as? -methylstyrene and vinyltoluene;

Unsaturated carboxylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate and benzyl (meth) acrylate;

Unsaturated aminoalkyl carboxylates such as aminoethyl acrylate,

Unsaturated glycidyl carboxylates such as glycidyl (meth) acrylate;

Vinyl carboxylates such as vinyl acetate and vinyl propionate;

(Meth) acrylonitrile, and? -Chloroacrylonitrile.

These monomers may be used alone or in combination of two or more.

Preferred examples of the copolymer include benzyl methacrylate / methacrylic acid copolymer, benzyl methacrylate / methacrylic acid / styrene copolymer, methyl methacrylate / methacrylic acid copolymer, and methyl methacrylate / Methacrylic acid / styrene copolymer, and the like.

When the alkali-soluble resin is a copolymer obtained from the monomer (f1) containing the carboxyl group and the other monomer (f2) copolymerizable with the monomer containing the carboxyl group, the monomer (f1) containing the carboxyl group is a copolymer And may be contained in an amount of 10 to 50% by weight, preferably 15 to 40% by weight.

The alkali-soluble resin preferably has a weight average molecular weight of 3,000 to 100,000, more preferably 5,000 to 50,000, as measured by gel permeation chromatography in terms of polystyrene. When the weight average molecular weight of the alkali-soluble resin is in the range of 3,000 to 100,000, film reduction is unlikely to occur during development and leakage of the non-pixel portions tends to be favorable at the time of development.

The weight average molecular weight (weight average molecular weight (Mw) / number average molecular weight (Mn)) relative to the number average molecular weight of the alkali-soluble resin is preferably 1.5 to 6.0, more preferably 1.8 to 4.0 Is good in terms of developability.

The acid value of the alkali-soluble resin is preferably 30 to 170 mgKOH / g, more preferably 50 to 150 mgKOH / g, based on the solid content. When the acid value of the alkali-soluble resin is less than 30 mgKOH / g, it is difficult to ensure a sufficient developing rate of the green photosensitive resin composition. When the acid value exceeds 170 mgKOH / g, the adhesion with the substrate is reduced, And the compatibility with the coloring agent is liable to occur, so that the coloring agent in the green photosensitive resin composition is precipitated or the storage stability of the green photosensitive resin composition is lowered and the viscosity is increased, which is not preferable.

The alkali-soluble resin is contained in an amount of 5 to 85% by weight, preferably 10 to 70% by weight, based on the total solid weight of the green photosensitive resin composition of the present invention.

When the content of the alkali-soluble resin is 5 to 85% by weight, solubility in a developing solution is sufficient, so that development residue does not easily occur on the substrate of the non-pixel portion, and film reduction of the pixel portion of the exposure portion is prevented at the time of development, The missing part of the part can be improved.

(G) Additive

The additive may be optionally added as needed. For example, the additive may include at least one selected from the group consisting of another polymer compound, a hardener, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber and an anti- have.

Specific examples of the other polymer compound include a curable resin such as an epoxy resin and a maleimide resin, a thermoplastic resin such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester and polyurethane .

The above-mentioned curing agent is used for enhancing deep curing and mechanical strength. Specific examples of the curing agent include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound and an oxetane compound.

Specific examples of the epoxy compound in the curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolak epoxy resin, other aromatic epoxy resin, alicyclic epoxy resin Aliphatic, alicyclic or aromatic epoxy compounds, butadiene (co) polymeric epoxides, isoprene (co) polymers other than the brominated derivatives, epoxy resins and brominated derivatives of the above epoxy resins, glycidyl ester resins, glycidyl amine resins, (Co) polymer epoxides, glycidyl (meth) acrylate (co) polymers and triglycidyl isocyanurate.

Specific examples of the oxetane compound in the curing agent include carbonates bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and cyclohexanedicarboxylic acid bisoxetane.

The curing agent may be used together with a curing agent in combination with a curing auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound.

The curing auxiliary compound includes, for example, polyvalent carboxylic acids, polyvalent carboxylic anhydrides and acid generators. The polyvalent carboxylic acid anhydrides may be those commercially available as an epoxy resin curing agent. Examples of the commercially available products include Adekahadona EH-700 (manufactured by Adeka Kogyo Co., Ltd.), Rikashido HH (manufactured by Shin-Nihon Ehwa Co., Ltd.), and MH-700 (manufactured by Shin-Etsu Chemical Co., Ltd.). The curing agents exemplified above may be used alone or in combination of two or more.

The surfactant can be used for further improving the film formation of the colored photosensitive resin composition, and silicon, fluorine, ester, cationic, anionic, nonionic, amphoteric surfactant and the like can be preferably used.

Examples of the silicone surfactant include DC3PA, DC7PA, SH11PA, SH21PA and SH8400 of Dow Corning Toray Silicone Co., Ltd. as commercial products, and TSF-4440, TSF-4300, TSF-4445, TSF- -4460 and TSF-4452.

Examples of the fluorine-based surfactant include Megapis F-470, F-471, F-475, F-482 and F-489 commercially available from Dainippon Ink and Chemicals, Incorporated.

Other commercially available products include KP (Shinetsugaku Kagaku Kogyo Co., Ltd.), POLYFLOW (Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by TOKEM PRODUCTS CO., LTD.), MEGAFAC Asoui guard, Surflon (available from Asahi Glass Co., Ltd.), SOLSPERSE (Lubrisol) (available from Dainippon Ink and Chemicals Inc.), Flourad (Sumitomo 3M Co., Ltd.) , EFKA (EFKA Chemical), PB 821 (Ajinomoto), and Disperbyk-series (BYK-chemi).

Examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, and quaternary ammonium salts.

Examples of the anionic surfactant include higher alcohol sulfuric acid ester salts such as sodium lauryl alcohol sulfate ester and sodium oleyl alcohol sulfate ester, alkylsulfates such as sodium laurylsulfate and ammonium laurylsulfate, sodium dodecylbenzenesulfonate And alkylarylsulfonic acid salts such as sodium dodecylnaphthalenesulfonate.

The nonionic surfactants include, for example, polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters , Polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines.

The above-exemplified surfactants may be used alone or in combination of two or more.

The type of the adhesion promoter is not particularly limited and specific examples of the adhesion promoter that can be used include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl Aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, -Glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxy Propyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane, and 3-isocyanatepropyltriethoxysilane.

The adhesion promoters exemplified above may be used alone or in combination of two or more. The adhesion promoter may be contained in an amount of usually 0.01 to 10% by weight, preferably 0.05 to 2% by weight based on the total weight of the solid content of the red photosensitive resin composition.

The type of the antioxidant is not particularly limited, and examples thereof include 2-tert-butyl-6- (3-tert-butyl-2-hydroxy- Tert-butyl-4-hydroxy-5-tert-butylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 6- [3- Methylphenyl) propoxy] - 2,4,8,10-tetra-tert-butyldibenz [d, f] [1,3,2] dioxaphosphepin, 3,9-bis [2- {3- 5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 2,2'- Methylenebis (6-tert-butyl-4-methylphenol), 4,4'-butylidenebis (6-tert- Methylphenol), 2,2'-thiobis (6-tert-butyl-4-methylphenol), dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodi Propionate, distearyl 3,3'-thiodipropionate, pentaerythrityl tetrakis (3-laurylthiopropionate), 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) 3 ', 3 ", 5,5', 5" -hexa-tert-butyl-a, a ', a " Cresol, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,6- '-Thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butyl-4-methylphenol.

The ultraviolet absorber is not particularly limited, but specific examples thereof include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole and alkoxybenzophenone .

The kind of the anti-aggregation agent is not particularly limited, but specific examples that can be used include sodium polyacrylate and the like.

A method of preparing the green photosensitive resin composition of the present invention will be described below.

First, the compound (a1) or the pigment (a2) of the formula (1) in the colorant (A) is mixed with the solvent (E) and dispersed using a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 탆 or less . At this time, if necessary, the pigment dispersant (a3), a part or all of the heat-crosslinkable oxetane resin (B), or the dye (a4) may be mixed and dissolved or dispersed with the solvent (E).

(C) and the photopolymerization initiator (D), and if necessary, the additive (G) and the solvent (E) are mixed with the predetermined dispersion Concentration, so that the green photosensitive resin composition according to the present invention can be prepared.

The present invention also includes a coloring pattern made of the green photosensitive resin composition. The coloring pattern can be prepared by applying the green photosensitive resin composition of the present invention onto a substrate, and by photo-curing and developing. The thickness of the coloring pattern is not particularly limited, and may be, for example, 1 to 6 탆.

The coloring pattern may be formed by, for example, the following method.

First, the green photosensitive resin composition is applied on a substrate or a layer composed of a solid component of a green photosensitive resin composition formed in advance, and pre-baked from the applied green photosensitive resin composition layer to remove volatile components such as a solvent to obtain a smooth coating film .

As the application method, for example, a spin coat, a flexible coating method, a roll coating method, a slit and spin coat method, a slit coat method and the like can be carried out.

After the application, the green photosensitive resin composition layer is formed by pre-baking (heating and drying) or drying after reduced pressure drying and volatilizing the volatile components such as a solvent. Here, the heating temperature is usually 70 to 200 占 폚, preferably 80 to 130 占 폚.

Ultraviolet rays are applied to the thus obtained coating film through a mask for forming a desired pattern. At this time, it is preferable to use an apparatus such as a mask aligner or a stepper so as to uniformly irradiate a parallel light beam onto the entire exposed portion and accurately align the mask and the substrate.

Further, the coating film after completion of the curing is contacted with an alkali developing solution to dissolve the non-visible portion and development, whereby a desired pattern shape can be obtained. As the developing method, a liquid addition method, a dipping method, a spraying method, or the like can be performed, and the substrate can be tilted at an arbitrary angle at the time of development.

The developer used for development after patterning exposure is usually an aqueous solution containing an alkaline compound and a surfactant. The alkaline compound may be any of inorganic and / or organic alkaline compounds.

Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogenphosphate, sodium dihydrogenphosphate, ammonium dihydrogenphosphate, ammonium dihydrogenphosphate, potassium dihydrogenphosphate, sodium silicate, potassium silicate, sodium carbonate, Potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate and ammonia.

Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, mono Isopropylamine, diisopropylamine, ethanolamine and the like.

The inorganic and organic alkaline compounds may be used alone or in combination of two or more.

The concentration of the alkaline compound in the alkali developer is, for example, 0.01 to 10% by weight, and more preferably 0.03 to 5% by weight.

The surfactant in the alkali developer may be any of a nonionic surfactant, an anionic surfactant, and a cationic surfactant.

Specific examples of the nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters , Polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines.

Specific examples of the anionic surfactant include higher alcohol sulfuric acid ester salts such as sodium lauryl alcohol sulfate ester and sodium oleyl alcohol sulfate ester; Alkyl sulfates such as sodium lauryl sulfate or ammonium lauryl sulfate; Alkylarylsulfonic acid salts such as sodium dodecylbenzenesulfonate and sodium dodecylnaphthalenesulfonate; And the like.

Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride or lauryltrimethylammonium chloride; Quaternary ammonium salts; And the like.

These surfactants may be used alone or in combination of two or more.

The concentration of the surfactant in the alkali developer is, for example, 0.01 to 10% by weight, preferably 0.05 to 8% by weight, and more preferably 0.1 to 5% by weight.

After the development, the substrate may be washed with water and, if necessary, subjected to post-baking at 150 to 230 ° C for 10 to 60 minutes.

The present invention also relates to a color filter comprising the green photosensitive resin composition.

The color filter of the present invention comprises a substrate and a coloring pattern made of the green photosensitive resin composition of the present invention on the substrate. The substrate may be made of a transparent material having sufficient strength and supporting force for the stability of the color filter. Preferably, a glass having excellent chemical stability and high strength can be used.

The color filter may be manufactured by a conventional method well known in the art.

The present invention also relates to a display device including the color filter.

Specific examples of the display device include a liquid crystal display (LCD), an organic EL display (organic EL display), a liquid crystal projector, a display device for a game machine, a display device for a portable terminal such as a mobile phone, And a display device such as a display device for a car navigation system. Particularly, a color display device is preferable.

The display device includes a configuration known to those skilled in the art, except for including the color filter, that is, the present invention includes a display device to which the color filter of the present invention can be applied.

Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples. However, it should be understood that the following examples are illustrative of the present invention, and the present invention is not limited by the following examples, and various modifications and changes may be made without departing from the scope of the present invention. The scope of the present invention will be determined by the technical idea of the following claims.

< Thermally crosslinked type Oxetane  Resin synthesis>

Synthetic example  One.

180 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube, and then the temperature was raised to 80 ° C.

Thereafter, a mixture containing 110.5 g of 3-ethyl-3- (methacryloyloxy) methyloxetane, 14.4 g of acrylic acid and 35.2 g of benzylmethacrylic acid was dissolved, and a solution of? -Methylstyrene dimer (chain transfer agent) , And then a solution prepared by adding 3.3 g of 2,2'-azobis (2,4-dimethylvaleronitrile) to 50 parts by weight of propylene glycol monomethyl ether acetate was added to a flask , And the mixture was stirred at 80 ° C for 5 hours to obtain a heat-crosslinkable oxetane resin B-1 having a solid acid value of 65 mgKOH / g.

The weight average molecular weight in terms of polystyrene measured by GPC was 10,100 and the molecular weight distribution (Mw / Mn) was 2.8.

Synthetic example  2.

180 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube, and then the temperature was raised to 80 ° C.

Thereafter, a mixture containing 110.5 g of 3-ethyl-3- (methacryloyloxy) methyloxetane, 17.2 g of methacrylic acid, and 23.6 g of 4-vinyltoluene was dissolved and a-methylstyrene dimer ) Was added, and then a solution prepared by adding 3.3 g of 2,2'-azobis (2,4-dimethylvaleronitrile) to 50 parts by weight of propylene glycol monomethyl ether acetate was added from the dropping funnel over 1 hour And the mixture was stirred at 80 캜 for 5 hours to obtain a thermally crosslinkable oxetane resin B-2 having a solid acid value of 68 mgKOH / g.

The weight average molecular weight in terms of polystyrene measured by GPC was 12,300 and the molecular weight distribution (Mw / Mn) was 2.7.

Synthetic example  3.

180 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube, and then the temperature was raised to 80 ° C.

Thereafter, a mixture containing 102.1 g of 3-ethyl-3- (acryloyloxy) methyloxetane, 21.6 g of acrylic acid and 17.6 g of benzylmethacrylic acid was dissolved and 5.0 g of? -Methylstyrene dimer (chain transfer agent) , And then a solution prepared by adding 3.3 g of 2,2'-azobis (2,4-dimethylvaleronitrile) to 50 parts by weight of propylene glycol monomethyl ether acetate was added dropwise to the flask over one hour from the dropping funnel And the mixture was stirred at 80 캜 for 5 hours to obtain a heat-crosslinkable oxetane resin B-3 having a solid acid value of 95 mgKOH / g.

The weight average molecular weight in terms of polystyrene measured by GPC was 8,900 and the molecular weight distribution (Mw / Mn) was 2.9.

Synthetic example  4.

180 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube, and then the temperature was raised to 80 ° C.

Thereafter, a mixture containing 51.0 g of 3-ethyl-3- (acryloyloxy) methyloxetane, 21.6 g of acrylic acid, 35.2 g of benzylmethacrylic acid and 20.0 g of methyl methacrylic acid was dissolved, (Chain transfer agent) was added, and then a solution prepared by adding 3.3 g of 2,2'-azobis (2,4-dimethylvaleronitrile) to 50 parts by weight of propylene glycol monomethyl ether acetate was added dropwise from a dropping funnel Was added dropwise to the flask over 1 hour, and the mixture was stirred at 80 DEG C for 5 hours to obtain a heat-crosslinkable oxetane resin B-4 having a solid acid value of 90 mgKOH / g.

The weight average molecular weight in terms of polystyrene measured by GPC was 11,300 and the molecular weight distribution (Mw / Mn) was 2.7.

Synthetic example  5.

180 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube, and then the temperature was raised to 80 캜.

Thereafter, a mixture containing 17.0 g of 3-ethyl-3- (acryloyloxy) methyloxetane, 21.6 g of acrylic acid, 35.2 g of benzyl methacrylic acid and 40.0 g of methyl methacrylic acid was dissolved, (Chain transfer agent) was added, and then a solution prepared by adding 3.3 g of 2,2'-azobis (2,4-dimethylvaleronitrile) to 50 parts by weight of propylene glycol monomethyl ether acetate was added dropwise from a dropping funnel The mixture was added dropwise to the flask over 1 hour, and the mixture was stirred at 80 DEG C for 5 hours to obtain thermally crosslinkable oxetane resin B-5 having a solid acid value of 105 mgKOH / g.

The weight average molecular weight in terms of polystyrene measured by GPC was 8,100 and the molecular weight distribution (Mw / Mn) was 2.8.

<Synthesis of alkali-soluble resin>

Synthetic example  6.

180 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube, and then the temperature was raised to 80 캜.

Thereafter, a mixture containing 21.6 g of acrylic acid, 70.4 g of benzylmethacrylic acid, and 30.0 g of methylmethacrylic acid was dissolved, and 5.0 g parts by weight of -methylstyrene dimer (chain transfer agent) was added and then propylene glycol monomethyl ether Azobis (2,4-dimethylvaleronitrile) in 50 parts by weight of acetic acid was added dropwise to the flask over 1 hour from the dropping funnel, followed by stirring at 80 ° C for 5 hours to obtain a solid content An alkali-soluble resin B-6 having a hydroxyl value of 103 mgKOH / g was obtained.

The weight average molecular weight measured by GPC in terms of polystyrene was 12,800 and the molecular weight distribution (Mw / Mn) was 2.4.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin prepared in Synthesis Examples 1 to 6 were measured by the GPC method under the following conditions.

Apparatus: HLC-8120GPC (manufactured by TOSOH CORPORATION)

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

Column temperature: 40 DEG C

Mobile phase solvent: tetrahydrofuran

Flow rate: 1.0 ml / min

Injection amount: 50 μl

Detector: RI

Measurement sample concentration: 0.6% by weight (solvent = tetrahydrofuran)

Standard materials for calibration: 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 to the number average molecular weight obtained above was defined as a molecular weight distribution (Mw / Mn).

<Preparation of Pigment Dispersion>

Manufacturing example  1-4.

The pigment dispersions of Production Examples 1 to 4 were prepared with the compositions shown in Table 1 below.

(Unit: wt%) division Preparation Example 1 (M1) Production Example 2 (M2) Production Example 3 (M3) Production Example 4 (M4) coloring agent Pigment 1 12 12 - - Pigment 2 8 - 8.8 - Pigment 3 - 8 - 8.8 Pigment 4 - - 11.2 11.2 Dispersant 12 12 12 12 solvent 68 68 68 68

Pigment 1: C.I. Pigment Green 59

Pigment 2: C.I. Pigment Yellow 185

Pigment 3: C.I. Pigment Yellow 150

Pigment 4: C.I. Pigment Green 7

Dispersant: BYK2001 (Dispersive: manufactured by BYK, solid concentration 45.1% by weight)

Solvent: Propylene glycol methyl ether acetate

&Lt; Preparation of green photosensitive resin composition &

Example  1 to 10 and Comparative Example  1-3.

The green photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 to 3 were prepared with the compositions shown in Table 2 below.

(Unit: wt%)

M1: The pigment dispersion prepared in Production Example 1

M2: The pigment dispersion prepared in Production Example 2

M3: The pigment dispersion prepared in Production Example 3

M4: The pigment dispersion prepared in Production Example 4

B-1: Heat-crosslinkable oxetane resin prepared in Synthesis Example 1

B-2: Heat-crosslinkable oxetane resin prepared in Synthesis Example 2

B-3: Heat-crosslinkable oxetane resin prepared in Synthesis Example 3

B-4: Heat-crosslinkable oxetane resin prepared in Synthesis Example 4

B-5: Heat-crosslinkable oxetane resin prepared in Synthesis Example 5

B-6: The alkali-soluble resin prepared in Synthesis Example 6

Photopolymerizable compound: dipentaerythritol hexaacrylate

Photopolymerization initiator: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)

Solvent: Propylene glycol monomethyl ether acetate

Experimental Example  1. Evaluation of physical properties of green photosensitive resin composition

A 2-inch square glass substrate (# 1737, manufactured by Corning Incorporated) was sequentially washed with a neutral detergent, water and alcohol, and then dried. When the green photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 to 3 were exposed on the glass substrate at an exposure amount (365 nm) of 100 mJ / cm 2 and the development step was omitted, the film thickness after the post- 2.0 &lt; / RTI &gt;

And then preliminarily dried in a clean oven at 100 DEG C for 3 minutes. After cooling, the distance between the substrate coated with the green photosensitive resin composition and a quartz glass photomask (having a pattern for changing the transmittance in a stepwise manner from 1 to 100% and a line / space pattern from 1 to 50 m) Was irradiated with light at an exposure dose (365 nm) of 100 mJ / cm 2 using an ultra-high pressure mercury lamp (trade name: USH-250D) manufactured by Ushio DENKI CO., LTD.

Thereafter, the coating film was immersed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.06% of potassium hydroxide at 26 캜 for a predetermined time, developed, washed with water and dried at 220 캜 for 30 minutes to prepare a color filter.

1-1. Measuring luminance (Y)

The brightness of the color filter prepared above was measured using a microscopic spectrometer OSP-SP2000, and the results are shown in Table 3 below.

1-2. Chromaticity ( Color coordinates ) Measure

The color coordinates of the color filter prepared above were measured using a microspectrophotometer OSP-SP2000, and the results are shown in Table 3 below.

1-3. Solvent resistance  evaluation

The color filter prepared above was immersed in each solvent (NMP; 1-methyl-2-pyrolidinone, IPA; isopropyl alcohol, GBL; gamma-butyryllactone) for 30 minutes to calculate the color change before and after the evaluation Respectively.

The equation used in this case represents the color change in the three-dimensional colorimetric system defined by L *, a *, b * in the following equation (1).

[Equation 1]

^{_{△ E ab * = [(△}} L *) 2 + (△ a *) 2 + (△ b *) 2] 1/2

The evaluation criteria are as follows, and the results are shown in Table 3 below.

<Evaluation criteria for solvent resistance>

?: Less than? Eab = 1,

?: Eab = 1 to 3,

X: exceeded Eab = 3

1-4. Heat resistance evaluation

The color filter prepared above was heated in a heating oven at 230 캜 for 2 hours, and the color change before and after heating was measured.

The color change was calculated by the above formula (1), and the change in brightness (? Y) before and after the evaluation of the heat resistance was confirmed, and it was confirmed whether or not the luminance was lowered due to thermal yellowing.

The evaluation criteria are as follows, and the results are shown in Table 3 below.

&Lt; Heat resistance evaluation standard &

?: Less than? Eab = 1,

?: Eab = 1 to 3,

X: exceeded Eab = 3

<Evaluation criteria of luminance change (? Y)>

○: less than 0.3

?: 0.3 to 0.5

X: greater than 0.5

C.I. The color coordinates including the pigment of Pigment Yellow 185 were found in Examples 1 to 5 and Comparative Examples 1 and 2 at x = 0.256, y = 0.641.

C.I. The color coordinates including the pigment of Pigment Yellow 150 appeared in Examples 6 to 10 and Comparative Example 3 with x = 0.24 and y = 0.606.

C.I. Pigment Yellow 185 or C.I. Pigment Yellow 150, and C.I. Comparative Example 1 and Comparative Example 3 including Pigment Green 7 are reference values of the color coordinates.

In the results of Table 2, C.I. Instead of Pigment Green 7, the above C.I. It was confirmed that the green photosensitive resin compositions of Examples 1 to 10 including the Pigment Green 59 had an improved chromaticity (Y) of 7 to 10%.

It was also confirmed that the green photosensitive resin compositions of Examples 1 to 10 including the thermally crosslinkable oxetane resin containing the monomer of Formula 2 of the present invention were excellent in both heat resistance and solvent resistance, It was confirmed that the green photosensitive resin composition of Comparative Example 2, which did not contain the curing agent, had poor heat resistance and solvent resistance.

Therefore, the green photosensitive resin composition of the present invention is excellent in chromaticity, heat resistance, and solvent resistance, and the color filter including the green photosensitive resin composition can exhibit high color reproduction.

Claims (11)

A green photosensitive resin composition comprising a colorant, a heat-crosslinkable oxetane resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent,
The colorant comprises at least one selected from the group consisting of CI Pigment Green 59, CI Pigment Yellow 185 and CI Pigment Yellow 150,
Wherein the thermally crosslinkable oxetane resin is at least one monomer selected from the group consisting of 3-ethyl-3- (methacryloyloxy) methyloxetane and 3-ethyl-3- (acryloyloxy) Wherein the green light-sensitive resin composition is a green light-sensitive resin composition. The method of claim 1, wherein the C.I. Pigment Green 59, and C.I. Pigment Yellow 185 and C.I. Pigment Yellow 150 is mixed in a weight ratio of 1: 0.05 to 1:18. The thermoplastic resin composition according to claim 1, wherein the heat-crosslinkable oxetane resin
Thermocrosslinked oxetane comprising at least one monomer selected from the group consisting of 3-ethyl-3- (methacryloyloxy) methyloxetane and 3-ethyl-3- (acryloyloxy) methyloxetane Suzy,
And at least one monomer selected from the group consisting of 3-ethyl-3- (methacryloyloxy) methyloxetane and 3-ethyl-3- (acryloyloxy) methyloxetane and an unsaturated carboxylic acid monomer Copolymer, or
And at least one monomer selected from the group consisting of 3-ethyl-3- (methacryloyloxy) methyloxetane and 3-ethyl-3- (acryloyloxy) methyloxetane, an unsaturated carboxylic acid monomer, And at least one monomer selected from the group consisting of 3-ethyl-3- (methacryloyloxy) methyloxetane and 3-ethyl-3- (acryloyloxy) methyloxetane and at least one monomer selected from the group consisting of an unsaturated carboxylic acid monomer Wherein the copolymer is a copolymer of a monomer containing an unsaturated bond capable of copolymerization with the monomer. 4. The thermoplastic resin composition according to claim 3, wherein the total amount of the 3-ethyl-3- (methacryloyloxy) methyloxetane and 3-ethyl-3- (acryloyloxy) methyloxetane And 5 to 95% by mole of an unsaturated carboxylic acid monomer. The green photosensitive resin composition according to claim 1, 4. The thermoplastic resin composition according to claim 3, wherein the total amount of the 3-ethyl-3- (methacryloyloxy) methyloxetane and 3-ethyl-3- (acryloyloxy) methyloxetane 5 to 90 mol% of at least one monomer selected from the group consisting of 3-ethyl-3- (methacryloyloxy) methyloxetane and 3-ethyl-3 - (acryloyloxy) methyloxetane, and from 5 to 70 mol% of a monomer containing an unsaturated bond copolymerizable with the unsaturated carboxylic acid monomer. Resin composition, The green photosensitive resin composition according to claim 1, wherein 5 to 70% by weight of a colorant, 5 to 80% by weight of a thermally crosslinkable oxetane resin, 5 to 45% by weight of a photopolymerizable compound and 2 to 10% by weight of a photopolymerization initiator % Based on the total weight of the green photosensitive resin composition, and 60 to 90% by weight of a solvent based on the total weight of the green photosensitive resin composition. The method of claim 1, wherein the C.I. And the Tmax of Pigment Green 59 is 500 to 530 nm. The green photosensitive resin composition according to claim 1, wherein T _50% of the CI pigment green 59 is 445 to 580 nm. The green photosensitive resin composition according to claim 1, wherein the colorant has a color coordinate of x = 0.1 to 0.35 when y = 0.6 or more in the XYZ color system. A color filter comprising the green photosensitive resin composition of claim 1. A display device comprising the color filter of claim 10.

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