TWI636327B - A green photosensitive resin composition, color filter and display device comprising the same - Google Patents

Abstract

The present invention relates to a green photosensitive resin composition containing a coloring agent containing CI Pigment Green 59, a thermally crosslinked oxetane resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, a color filter including the same, and In the display device, the green photosensitive resin composition can perform high color reproduction, and has the effects of excellent solvent resistance and heat resistance.

Description

Green photosensitive resin composition, color filter and display device including the same

FIELD OF THE INVENTION The present invention relates to a green photosensitive resin composition, a color filter and a display device including the green photosensitive resin composition.

BACKGROUND OF THE INVENTION Color filters are widely used in imaging elements, liquid crystal display devices (LCD), and the like, and their application range is rapidly expanding. A color filter used in a color liquid crystal display device, an image pickup element, and the like is generally manufactured by uniformly coating a coloring sensitivity containing pigments corresponding to red, green, and cyan by spin coating on a substrate having a black matrix pattern formed thereon. After the resin composition is heated and dried (hereinafter sometimes referred to as "pre-firing"), the formed coating film is exposed and developed, and further heat-cured as necessary (hereinafter also referred to as "post-firing"). This operation is repeated for each color to form pixels of each color. Among them, the patterned black matrix is usually formed of a black photosensitive resin composition.

Such a coloring 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 as necessary.

Recently, market demand for high-quality displays with high display color reproducibility has increased. In addition, it is required to develop pixels that have high light transmission and high contrast while exhibiting high color reproducibility.

Conventionally, as green pigments, C.I. Pigment Green 7 and C.I. Pigment Green 36 (halogenated phthalocyanine compounds containing copper as a central metal) have been mainly used. However, the light transmittance and contrast of a pixel obtained from a colored photosensitive resin composition containing the above pigment cannot be said to sufficiently satisfy a required level, and there are limitations on providing a higher-quality image.

In addition, Japanese Patent No. 2002-296778 discloses a coloring photosensitive resin composition capable of forming a pixel having excellent solvent resistance. However, it is pointed out that the content of a colorant is high, and chemical resistance and heat resistance are insufficient during the production of a resist. The problem. Prior Art Literature Patent Literature

Patent Document 1: Japanese Patent Laid-Open No. 2002-296778

Summary of the Invention Problems to be Solved by the Invention

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

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

Furthermore, an object of the present invention is to provide a color filter including the green photosensitive resin composition and a display device including the same. Means to solve the problem

To achieve the above object, the present invention provides a green photosensitive resin composition, which is a green photosensitive resin composition including a colorant, a thermally crosslinked oxetane resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. The colorant includes CI Pigment Green 59 and one or more selected from pigments and dyes, and the thermally crosslinked oxetane resin includes a monomer of Chemical Formula 2 below. [Chemical Formula 2] X ₁ and X ₂ are each independently an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms, -O- group, -CO- group, -C (= O) O- group, -CONH- group, or phenylene group, and R ₁ is hydrogen or methyl.

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

Furthermore, the present invention provides a display device including the color filter. Effect of the invention

The green photosensitive resin composition of the present invention can form an excellent pixel having high color reproducibility, high sensitivity, high light transmittance, and high contrast.

Moreover, the green photosensitive resin composition of this invention has the effect which is excellent in heat resistance and chemical resistance.

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

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention is explained in more detail below.

The present invention relates to a green photosensitive resin composition, which is a green photosensitive resin composition containing a colorant, a thermally crosslinked oxetane resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, and is characterized in that: The colorant contains CI Pigment Green 59 and one or more selected from pigments and dyes. The thermally crosslinked oxetane resin includes a monomer of the following Chemical Formula 2. [Chemical Formula 2] X ₁ and X ₂ are each independently an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms, -O- group, -CO- group, -C (= O) O- group , -CONH-, or phenylene, wherein R ₁ is hydrogen or methyl.

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

In addition, by using an oxetane resin containing the monomer of the above Chemical Formula 2, a green photosensitive resin composition having excellent light transmittance, contrast, heat resistance, and chemical resistance can be provided.

Hereinafter, each component of the green photosensitive resin composition of this invention is demonstrated in detail. (A) Colorant

The coloring agent contained in the green photosensitive resin composition of the present invention appears green.

The colorant contains C.I. Pigment Green 59 and one or more selected from pigments and dyes. (a1) C.I.Pigment Green 59

The colorant contains CI Pigment Green 59, which has the structure of Chemical Formula 1 below. The CI Pigment Green 59 has a ZnPc (zinc phthalocyanine) structure. If the CI Pigment Green 59 is included, high color reproduction can be performed even with a small amount of pigment. [Chemical Formula 1] The A ¹ to A ¹⁶ are each independently hydrogen, bromine, or chlorine. Among the A ¹ to A ¹⁶ , hydrogen is 1 to 6, chlorine is 0 to 5, and bromine is 5 to 13.

Further, among the compounds of the above Chemical Formula 1, it is preferable that in A1 to A16, there are 1 to 6 hydrogens, 0 to 5 chlorines, and 7 to 13 bromines. More preferably, A1 to A16 have 2 to 5 hydrogens, 0 to 3 chlorines, and 8 to 13 bromines.

CI Pigment Green 58 (G58) used as a conventional green pigment has the advantage of high brightness. However, in order to achieve high color reproduction, a large amount must be used. Therefore, if the amount of the pigment is increased, the developability is lowered and sometimes As a result, the pattern formed by the composition is peeled off, which causes a problem of reduced sensitivity.

However, if the above C.I. Pigment Green 59 is used as a colorant, the content of the pigment can be reduced, and even if the content is small, high color reproduction can be achieved.

In addition, C.I. Pigment Green 7 (G7), which is used as a conventional green pigment, can display high coloring properties even if the content is small, but it has a problem of low brightness.

At a wavelength of 400 to 610 nm, the C.I. Pigment Green 59 exhibits a transmission spectrum and color coordinates similar to that of the C.I. Pigment Green 7, and has an excellent effect of brightness, which can solve the above problems.

In this specification, Tmax indicates the wavelength at which the transmittance of the pigment is maximum, and T _50% indicates the wavelength at which the transmittance of the pigment 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. Since higher coloring properties can be exhibited in the above range, the green photosensitive resin composition of the present invention can achieve high color reproduction.

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

When the C.I. Pigment Green 59 is contained in a content range of 0.05% to 30% by weight, the transmittance and contrast are improved, and excellent developability can be exhibited.

The colorant contains the C.I. Pigment Green 59 and one or more selected from pigments and dyes commonly used in the art, and is produced in the form of a color paste and used.

The CI Pigment Green 59 is mixed with one or more selected from pigments and dyes in a weight ratio of 1: 0.05 to 1:18, preferably 1: 0.1 to 1: 9, and more preferably 1: 0.2 to 1: 4 weight ratio mixed.

Within the range of the aforementioned weight ratio, the effects of high colorability and high brightness are exhibited, the process margin is improved, and the sensitivity can be made excellent.

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

In contrast, when C.I. Pigment Green 58 is used as an example, in the XYZ color system, y = 0.6 or more can have a color coordinate of x = about 0.2 to 0.35. At this time, in order to use C.I. Pigment Green 58 and also have a value near x = 0.1, it is necessary to be tinted to blue. In this case, there is a problem that the brightness is lowered, which is not preferable.

As another example, in the case where C.I. Pigment Green 7 is used, although the area where the color is developed is wide, there is a problem that the brightness is low. (a2) Pigment

The pigment can be an organic pigment or an inorganic pigment generally used in the art. In terms of heat resistance and color development, an organic pigment is preferably used, and the organic pigment may be a synthetic pigment or a natural pigment.

In addition, the above-mentioned pigments may be subjected to resin treatment, surface treatment using a pigment derivative introduced with an acidic group or a basic group, graft treatment on a pigment surface using a polymer compound, and the like, if necessary, using sulfuric acid. Methods, such as a micronization process, a cleaning process using an organic solvent, water, or the like for removing impurities, or a ionic impurity removal process using an ion exchange method, or the like.

As the organic pigment, various pigments used in printing inks, inkjet inks, and the like can be used. Specific examples include water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, and isoindolinone pigments. , Isoindoline pigment, osmium pigment, fluorenone pigment, dioxazine pigment, anthraquinone pigment, bi-anthraquinone pigment, anthracene pigment, anthrone pigment, indanthrone pigment, xanthones pigment, dermatanthone Pigments, diketopyrrolopyrrole pigments, and the like.

In addition, examples of the inorganic pigment include metal compounds such as metal oxides and metal complex salts. Specific examples include iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, and carbon black. , Organic black pigments, titanium black, and oxides of metals such as pigments mixed with red, green, and cyan to be black, or composite metal oxides.

In particular, as the above-mentioned organic pigments and inorganic pigments, specifically, compounds classified as pigments in the Outstanding Index (published by The Society of Dyers and Colourists) may be listed, and more specifically, pigments having the following color index (CI) numbers may be listed. , But not necessarily limited to these.

Examples include: CI 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; CI Pigment Orange 13, 31, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, and 73; CI 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; CI Pigment Violet 14, 19, 23, 29, 32, and 177; CI Pigment Blue 15: 3, 15: 4, 15: 6, 16, 22, 28, and 60; CI Pigment Green 7 , 36 and 58; and other pigments.

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

Among the C.I. pigments exemplified above, one or more pigments selected from C.I. Pigment Yellow 138, C.I. Pigment Yellow 129, C.I. Pigment Yellow 150, and C.I. Pigment Yellow 185 are preferably used.

As the pigment, a pigment dispersion liquid in which pigment particle diameters are uniformly dispersed is preferably used. Examples of the method for uniformly dispersing the particle diameter of the pigment include a method of dispersing treatment containing a pigment dispersant (a3), etc. According to the above method, pigment dispersion in a state where the pigment is uniformly dispersed in a solution can be obtained liquid. (a3) Pigment dispersant

The pigment dispersant is added in order to maintain the deagglomeration and stability of the pigment. Specific examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, and polyamine. These can be used individually or in combination of 2 or more types.

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 sulfate salts such as sodium lauryl sulfate and sodium oleyl sulfate, and alkyl sulfates such as sodium dodecyl sulfate and ammonium dodecyl sulfate. Salts, alkylaryl sulfonates such as sodium dodecylbenzenesulfonate and sodium dodecylnaphthalenesulfonate.

Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkylaryl ether, other polyoxyethylene derivatives, and ethylene oxide / Propylene oxide block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, and poly Oxyethylene alkylamine and the like.

In addition, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, and tertiary amine modifications are exemplified. Polyurethanes and polyethyleneimines.

The pigment dispersant preferably contains an acrylate dispersant (hereinafter referred to as an acrylate dispersant) containing butyl methacrylate (BMA) or N, N-dimethylaminoethyl methacrylate (DMAEMA). ). Examples of commercially available products of the acrylic dispersant include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, and DISPER BYK-2150. The acrylic dispersants can be used alone or in combination. More than one species is used.

The pigment dispersant may be other resin-based pigment dispersants in addition to the acrylate-based dispersant. Examples of the other resin-based pigment dispersants include known resin-based pigment dispersants, and in particular, polycarboxylic acid esters such as polyurethanes and polyacrylates, unsaturated polyamines, and polycarboxylic acids. Acids, (partial) amine salts of polycarboxylic acids, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminophosphonium phosphates, hydroxyl-containing polycarboxylic acids Esters and their modified products, or oily dispersants such as amidines or their salts formed by the reaction of a polyester having a free carboxyl group with poly (lower alkyleneimine); ( (Meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylate copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, or a water-soluble resin such as polyvinylpyrrolidone or a water-soluble resin Polymer compounds; polyesters; modified polyacrylates; ethylene oxide / propylene oxide addition products; and phosphate esters.

As a commercially available product of the other resin-based pigment dispersants, examples of the cationic resin dispersant include the trade names of BYK (ビ ッ ク) ケ ミ: 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; BASF's trade names: 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; The trade names of Lubirzol Company: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204 / 10; the trade names of Kawaken Fine Chemicals Co., Ltd .: Hinoact T-6000, Hector T-7000, Hector T-8000; Ajino The product names of Susuke: AJISPUR PB-821, ASA PB-822, ASA PB-823; the trade names of Kyoeisha Chemical Co., Ltd .: FLORENE DOPA-17HF, FLORONE DOPA-15BHF, FLORONE DOPA-33 , Florence DOPA-44, etc.

In addition to the above-mentioned acrylate-based dispersant, other resin-based pigment dispersants may be used alone or as a mixture of two or more kinds, and may be used in combination with an acrylate-based dispersant.

The pigment dispersant is contained in an amount of 5 to 60% by weight, preferably 15 to 50% by weight based on the total weight of the solid content in the pigment. If the pigment dispersant is contained in an amount of less than 5% by weight, micronization of the pigment may be difficult, and problems such as gelation may occur after dispersion. If the pigment dispersant is contained in an amount of more than 60% by weight, the viscosity may increase. (a4) Dye

The dye can be used without limitation as long as it has solubility in an organic solvent. Preferably, a dye having solubility in an organic solvent and capable of ensuring reliability in solubility and heat resistance, solvent resistance, and the like in an alkali developing solution is preferably used. In addition, a dye having no solubility in an organic solvent may be dispersed and used.

As the dye, a dye selected from the group consisting of an acidic dye having an acidic group such as a sulfonic acid and a carboxylic acid, a salt of an acidic dye and a nitrogen-containing compound, a sulfonamide body of the acidic dye, and the like, and a derivative thereof can be used. Acid dyes of the azo type, the ton type, and the phthalocyanine type and their derivatives can also be selected. Preferably, the dye may be a compound classified as a dye in a color index (published by The Society of Dyers and Colourists) or a publicly-known dye described in a dyeing note (color dyeing company).

As specific examples of the above dyes, CI solvent dyes include: CI solvent yellow 2, 14, 16, 33, 34, 44, 56, 82, 93, 94, 98, 116, and 135; CI solvent red 1 , 2, 3, 8, 18, 23, 24, 27, 35, 43, 45, 48, 49, 91: 1, 119, 135, 140, 196, and 197; CI Solvent Blue 4, 5, 25, 35, 36, 38, and 70; CI solvent violet 8, 9, 13, 26, 28, 31, and 59; CI solvent orange 1, 3, 7, and 63; CI solvent green 3, 5, and 7, and other dyes, but not limited to These ones.

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

If the colorant is less than 5% by weight, the color separation ability of the formed pattern may be reduced. If it exceeds 70% by weight, problems such as reduced lithographic performance, residual residue, and inability to develop may occur.

In the present invention, the total weight of the solid content means that the content of the solvent is not included in the green photosensitive resin composition. (B) Thermally crosslinked oxetane resin

The thermally crosslinked oxetane resin contained in the green photosensitive resin composition of the present invention contains a monomer of the following Chemical Formula 2, and functions as a binder for the pigment in a thermal process. [Chemical Formula 2] X ₁ and X ₂ are each independently an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms, -O- group, -CO- group, -C (= O) O- group, -CONH- group, or phenylene group, and R ₁ is hydrogen or methyl.

The thermally crosslinked oxetane resin may be an oxetane resin composed of only the monomer (b1) of the above Chemical Formula 2, a monomer of the above Chemical Formula 2 and an unsaturated carboxylic acid monomer (b2). ), Or a monomer of the above Chemical Formula 2, an unsaturated carboxylic acid monomer, and an unsaturated bond-containing monomer (b3) copolymerizable with the monomer of the Chemical Formula 2 and the unsaturated carboxylic acid monomer Copolymer.

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

Specific examples of the monomer (b1) of the chemical formula 2 include 3- (vinyloxymethyl) -2-methyloxetane, and 3- (vinyloxymethyl) -3- Methyloxetane, 3- (vinyloxymethyl) -2-ethyloxetane, 3- (vinyloxymethyl) -3-ethyloxetane, 3- (Vinyloxyethyl) -2-methyloxetane, 3- (vinyloxyethyl) -3-methyloxetane, 3- (vinyloxyethyl) -2- Ethyloxetane, 3- (vinyloxyethyl) -3-ethyloxetane, 2- (vinyloxymethyl) -2-methyloxetane, 2- (Vinyloxymethyl) -3-methyloxetane, 2- (vinyloxymethyl) -2-ethyloxetane, 2- (vinyloxymethyl) -3- Ethyloxetane, 2- (vinyloxyethyl) -2-methyloxetane, 2- (vinyloxyethyl) -3-methyloxetane, 2- (Vinyloxyethyl) -2-ethyloxetane, and (vinyloxyalkyl) alkyloxanes such as 2- (vinyloxyethyl) -3-ethyloxetane Cyclobutane; 3-[(meth) acryloxymethyl] oxetane, 3- [2- (meth) acryloxyethyl] oxetane (Meth) acrylic acid such as 2-[(meth) acryloxymethyl] oxetane and 2- [2- (meth) acryloxyethyl] oxetane Alkylalkyloxetane; 3-[(meth) acryloxymethyl] -2-methyloxetane, 3-[(meth) acryloxymethyl] -3 -Methyloxetane, 3-[(meth) acryloxymethyl] -2-ethyloxetane, 3-[(meth) acryloxymethyl] -3 -Ethyloxetane, 3- [2- (meth) propenyloxyethyl] -2-methyloxetane, 3- [2- (meth) propenyloxyethyl Yl] -3-methyloxetane, 3- [2- (meth) propenyloxyethyl] -2-ethyloxetane, 3- [2- (meth) propene Ethoxyethyl] -3-ethyloxetane, 2-[(meth) propenyloxymethyl] -2-methyloxetane, 2-[(meth) propene Ethoxymethyl] -3-methyloxetane, 2-[(meth) propylene ethoxymethyl] -4-methyloxetane, 2-[(meth) propylene Ethoxymethyl] -2-ethyloxetane, 2-[(meth) propylene ethoxymethyl] -3-ethyloxetane, 2-[(meth) propylene Methoxymethyl] -4-ethyloxetan , 2- [2- (Meth) propenyloxyethyl] -2-methyloxetane, 2- [2- (meth) propenyloxyethyl] -3-methyloxy Heterocyclobutane, 2- [2- (meth) propenyloxyethyl] -4-methyloxetane, 2- [2- (meth) propenyloxyethyl] -2 -Ethyloxetane, 2- [2- (meth) propenyloxyethyl] -3-ethyloxetane, and 2- [2- (meth) propenyloxy Ethyl] -4-ethyloxetane and other [(meth) acryloxyalkyl] alkyloxetane; 3-[(meth) acryloxymethyl] -2 -Trifluoromethyloxetane, 3-[(meth) acryloxymethyl] -2-pentafluoroethyloxetane, 3-[(meth) acryloxymethyl Yl] -2-fluorooxetane, 3-[(meth) propenyloxymethyl] -2,2-difluorooxetane, 3-[(meth) propenyloxy Methyl] -2,2,4-trifluorooxetane, 3-[(meth) acryloxymethyl] -2,2,4,4-tetrafluorooxetane, 3 -[2- (meth) acryloxyethyl] -2-trifluoromethyloxetane, 3- [2- (meth) acryloxyethyl] -2-pentafluoroethyl Oxetane, 3- [2- (meth) propenyloxyethyl] -2-fluorooxy Cyclobutane, 3- [2- (meth) propenyloxyethyl] -2,2-difluorooxetane, 3- [2- (meth) propenyloxyethyl]- 2,2,4-trifluorooxetane, 3- [2- (meth) propenyloxyethyl] -2,2,4,4-tetrafluorooxetane, 2- [ (Meth) acryloxymethyl] -2-trifluoromethyloxetane, 2-[(meth) acryloxymethyl] -3-trifluoromethyloxetane , 2-[(Meth) propenyloxymethyl] -4-trifluoromethyloxetane, 2-[(meth) propenyloxymethyl] -2-pentafluoroethyloxy Heterocyclobutane, 2-[(meth) acryloxymethyl] -3-pentafluoroethyloxetane, 2-[(meth) acryloxymethyl] -4-penta Fluoroethyloxetane, 2-[(meth) acryloxymethyl] -2,3-difluorooxetane, 2-[(meth) acryloxymethyl] -2,4-difluorooxetane, 2-[(meth) acryloxymethyl] -3,3-difluorooxetane, 2-[(meth) acryloxy Methylmethyl] -3,4-difluorooxetane, 2-[(meth) propenyloxymethyl] -4,4-difluorooxetane, 2-[(methyl ) Acryloxymethyl] -3,3,4-trifluorooxetane, 2-[(methyl) propane Allyloxymethyl] -3,4,4-trifluorooxetane, 2-[(meth) propenyloxymethyl] -3,3,4,4-tetrafluorooxane Butane, 2- [2- (meth) propenyloxyethyl] -2-trifluoromethyloxetane, 2- [2- (meth) propenyloxyethyl] -3 -Trifluoromethyloxetane, 2- [2- (meth) propenyloxyethyl] -4-trifluoromethyloxetane, 2- [2- (meth) propene Ethoxyethyl] -2-pentafluoroethyloxetane, 2- [2- (meth) propylene ethoxyethyl] -3-pentafluoroethyloxetane, 2- [2- (Meth) acryloxyethyl] -4-pentafluoroethyloxetane, 2- [2- (meth) acryloxyethyl] -2,3-difluoro Oxetane, 2- [2- (meth) acryloxyethyl] -2,4-difluorooxetane, 2- [2- (meth) acryloxyethyl ] -3,3-difluorooxetane, 2- [2- (meth) propenyloxyethyl] -3,4-difluorooxetane, 2- [2- (methyl Propyl) propenyloxyethyl] -4,4-difluorooxetane, 2- [2- (meth) propenyloxyethyl] -3,3,4-trifluorooxane Butane, 2- [2- (meth) propenyloxyethyl] -3,4,4-trifluorooxetane, and 2- [2- (methyl) propane Ethoxyethyl] -3,3,4,4-tetrafluorooxetane etc. [(meth) acrylic alkoxyalkyl] fluorooxetane or [(meth) acrylic oxetane Alkyl] fluoroalkyloxetane; 2-[(meth) acryloxymethyl] -2-phenyloxetane, 2-[(meth) acryloxymethyl Yl] -3-phenyloxetane, 2-[(meth) propenyloxymethyl] -4-phenyloxetane, 2- [2- (meth) propenyloxy Ethylethyl] -2-phenyloxetane, 2- [2- (meth) propenyloxyethyl] -3-phenyloxetane, and 2- [2- (methyl (Propyl) propenyloxyethyl] -4-phenyloxetane, etc. [(meth) propenyloxyalkyl] phenyloxetane; 4- [3- (3-ethyl Oxetane-3-ylmethoxy) propoxy] styrene, 4- [4- (3-ethyloxetane-3-ylmethoxy) butoxy] styrene, 4- [5- (3-ethyloxetane-3-ylmethoxy) pentoxy] styrene, 4- [6- (3-ethyloxetane-3-ylmethyl) Oxy) hexyloxy] styrene and 4- [7- (3-ethyloxetane-3-ylmethoxy) heptyloxy] styrene-containing aromatics containing oxetanyl Vinyl compounds, etc.

Among the above-mentioned compounds, from the viewpoint of increasing the solvent resistance and heat resistance of the colored layer, it is more preferable to include a compound selected from 3- (vinyloxymethyl) -3-ethyloxetane and 3-[(methyl) Propylene methoxymethyl] oxetane, 3-[(meth) propylene methoxymethyl] -3-ethyloxetane, 3-[(meth) propylene methoxymethyl Yl] -2-trifluoromethyloxetane, 3-[(meth) propenyloxymethyl] -2-phenyloxetane, 2-[(meth) propenyloxy One or more of methylmethyl] oxetane and 2-[(meth) acryloxymethyl] -4-trifluoromethyloxetane.

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

The unsaturated carboxylic acid monomer (b2) may be used alone or in combination of two or more of acrylic acid and methacrylic acid.

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

As the other acid, specifically, one or more carboxylic acids selected from other unsaturated carboxylic acids such as crotonic acid, itaconic acid, maleic acid, and fumaric acid may be used together. In addition, monomers containing a hydroxyl group and a carboxyl group in the same molecule, such as α- (hydroxymethyl) acrylic acid, may be used together.

The unsaturated bond-containing monomer (b3) which can be copolymerized with the monomer of Chemical Formula 2 and the unsaturated carboxylic acid monomer is not limited as long as it is a compound having a polymerizable unsaturated double bond.

Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and amino (meth) acrylate Unsubstituted or substituted alkyl ester compounds of unsaturated carboxylic acids such as ethyl ester; cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, (meth) Cycloheptyl acrylate, cyclooctyl (meth) acrylate, methyl (meth) acrylate, cyclopentene (meth) acrylate, cyclohexene (meth) acrylate, cycloheptene (meth) acrylate Ester, cyclooctenyl (meth) acrylate, (meth) acrylic acid Diene ester ( ) ), Isobornyl (meth) acrylate, pinane (meth) acrylate, amantad (meth) acrylate, norbornyl (meth) acrylate, and pinene (meth) acrylate, etc. Unsaturated carboxylic acid ester compounds of cyclic substituents; diol monosaturated carboxylic acid ester compounds such as oligoethylene glycol monoalkyl (meth) acrylates; benzyl (meth) acrylate and phenoxy ( Unsaturated carboxylic acid ester compounds containing a substituent having an aromatic ring, such as (meth) acrylates; aromatic vinyl compounds such as styrene, α-methylstyrene, and vinyl toluene; vinyl acetate and vinyl propionate Vinyl carboxylates such as esters; vinyl cyanide compounds such as (meth) acrylonitrile and α-chloroacrylonitrile; maleimides such as N-cyclohexylmaleimide and N-phenylmaleimide Compounds etc.

When the thermally crosslinked oxetane resin of the present invention is a copolymer of the monomer of the above Chemical Formula 2 and an unsaturated carboxylic acid monomer, it is relative to the total mole of the thermally crosslinked oxetane resin. It is composed of 5 to 95 mole% of the monomer of the above Chemical Formula 2 and 5 to 95 mole% of the unsaturated carboxylic acid monomer.

If the monomer of the above Chemical Formula 2 is less than 5 mol%, reliability is insufficient, and if it exceeds 95 mol%, the developability of the lower substrate is disadvantageous.

If the unsaturated carboxylic acid monomer is less than 5 mol%, a residue may be generated after development, and if it exceeds 95 mol%, the adhesion of the pattern may be deteriorated.

The thermally crosslinked oxetane resin of the present invention is a monomer of the above Chemical Formula 2, an unsaturated carboxylic acid monomer, and an unsaturated bond containing a copolymerizable with the monomer of the Chemical Formula 2 and the unsaturated carboxylic acid monomer. In the case of a copolymer of monomers, 5 to 90 mole% of the monomer of the above Chemical Formula 2 and 5 to 5 moles of the unsaturated carboxylic acid monomer relative to the total mole number of the thermally crosslinked oxetane resin. 90 mol% and 5 to 70 mol% of an unsaturated bond-containing monomer copolymerizable with the monomer of the above Chemical Formula 2 and an unsaturated carboxylic acid monomer.

If the monomer of the above Chemical Formula 2 is less than 5 mol%, the reliability is insufficient, and if it exceeds 90 mol%, it is detrimental to developability and residue.

In addition, if the unsaturated carboxylic acid monomer is less than 5 mol%, it is unfavorable to developability, and if it exceeds 90 mol%, reliability may be insufficient.

Furthermore, if the unsaturated bond-containing monomer that can be copolymerized with the monomer of Chemical Formula 2 and the unsaturated carboxylic acid monomer is less than 5 mole%, the reliability is insufficient, and if it exceeds 90 mole%, the adhesion of the pattern may Become bad.

In one embodiment of the present invention, as an example of a method for producing the thermally crosslinked oxetane resin, the monomer (b1), unsaturated carboxylic acid monomer (b2), and In the case of a copolymer of the monomer (b3) containing an unsaturated bond in which the monomer of the above Chemical Formula 2 and the unsaturated carboxylic acid monomer are copolymerized, it can be produced by copolymerizing the monomer by the following method.

In a flask including a stirrer, a thermometer, a reflux cooling tube, a dropping funnel, and a nitrogen introduction tube, the monomer (b1), unsaturated carboxylic acid monomer (b2), and The total weight of the unsaturated bond-containing monomer (b3) copolymerized with the monomers and unsaturated carboxylic acid monomers was added together with a solvent of 0.5 to 20 times, and the atmosphere in the flask was replaced by air with nitrogen.

Then, after the solvent is heated to 40 to 140 ° C, an unsaturated bond monomer (b2) and an unsaturated bond-containing monomer copolymerizable with the monomer of the above Chemical Formula 2 and the unsaturated carboxylic acid monomer are added. A predetermined amount of (b3), based on the total weight of the unsaturated carboxylic acid monomer (b2) and the unsaturated bond-containing monomer (b3) copolymerizable with the monomer of the above Chemical Formula 2 and the unsaturated carboxylic acid monomer The solvent is 0 to 20 times, and contains a monomer (b1), an unsaturated carboxylic acid monomer (b2), and a monomer copolymerizable with the monomer of the chemical formula 2 and the unsaturated carboxylic acid monomer. A solution obtained by using a polymerization initiator such as azobisisobutyronitrile, peroxy 2-ethylhexylcarboxylic acid tert-butyl ester, etc., in which the total molar number of the unsaturated monomer (b3) is 0.1 to 10 mol%. Stir and dissolve with warming or heating) Add 0.1 to 8 hours from the dropping funnel into the flask and stir at 40 to 140 ° C for 1 to 10 hours.

In addition, in the above step, a part or the entire amount of the polymerization initiator may be charged into a flask, and the monomer (b1), unsaturated carboxylic acid monomer (b2), and A part or all of the unsaturated bond-containing monomer (b3) copolymerized with the monomer and the unsaturated carboxylic acid monomer was charged into a flask.

Furthermore, in order to control molecular weight and molecular weight distribution, α-methylstyrene dimer and mercapto compound can be used as a chain transfer agent. The monomer (b1), the unsaturated carboxylic acid monomer (b2), and the monomer (b3) containing an unsaturated bond that can be copolymerized with the monomer (b1), the unsaturated carboxylic acid monomer (b2), and the monomer of the chemical formula 2 The total weight of the α-methylstyrene dimer and mercapto compound is 0.005 to 5% by weight.

In addition, regarding the above-mentioned polymerization conditions, it is possible to appropriately adjust a charging method and a reaction temperature in consideration of production equipment, an amount of heat generated during polymerization, and the like.

The heat-crosslinkable oxetane resin has a polystyrene equivalent weight average molecular weight of 3,000 to 100,000, and more preferably 5,000 to 50,000. If the weight average molecular weight of the thermally crosslinked oxetane resin is in the range of 3000 to 100,000, the storage stability will be excellent, and film reduction will not occur easily during development.

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

If the thermally crosslinked oxetane resin is less than 5% by weight, the reliability is insufficient, and if it exceeds 80% by weight, the developability and residue of the lower substrate are disadvantageous. (C) Photopolymerizable compound

The photopolymerizable compound contained in the green photosensitive resin composition of the present invention must be a polymerizable compound under the action of a photopolymerization initiator (D) described later. Examples include, but are not limited to, monofunctional photopolymerizable compounds, bifunctional photopolymerizable compounds, and trifunctional photopolymerizable compounds.

Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, and acrylic acid 2 -Hydroxyethyl ester, N-vinylpyrrolidone and the like. As commercially available products, Alonics M-101 (East Asia Synthetic), KAYARAD TC-110S (Nippon Kayakushin), or コ ス コ ー ト 158 (Osaka Organic Chemical Industry) and the like can be mentioned.

Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, and neopentyl glycol di (meth) acrylate. , Triethylene glycol di (meth) acrylate, bis (acryloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like. As commercially available products, there is Alonics. M-210, M-1100, 1200 (East Asia Synthetic), KAYARAD HDDA (Nippon Kayaku), ビ ス コ ー ト 260 (Osaka Organic Chemical Industry), AH-600, AT-600, or UA-306H (Kyoeisha Chemical Co., Ltd.) Wait.

Specific examples of the trifunctional or higher polyfunctional photopolymerizable compound include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, and propoxylation. Trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (methyl) Acrylate), propoxylated dipentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. As commercially available products, there are Aronix M-309, TO-1382 (East Asia Synthesis), KAYARAD TMPTA, KAYARAD DPHA, or KAYARAD DPHA-40H (Japanese chemical).

Among the photopolymerizable compounds exemplified above, tri- or higher-functional (meth) acrylates and urethane (meth) acrylates are excellent in polymerizability, and can be improved in strength, which is preferable.

The photopolymerizable compound is contained in an amount of 5 to 45% by weight, and preferably 10 to 35% by weight based on the total weight of the solid content in the colored photosensitive resin composition for an organic light emitting diode of the present invention. The said photopolymerizable compound can improve the intensity | strength and flatness of a pixel part in the said range of 5 to 45 weight%. (D) Photopolymerization initiator

As long as the photopolymerization initiator contained in the green photosensitive resin composition of the present invention can polymerize the photopolymerizable compound (C) by exposure to radiation such as visible rays, ultraviolet rays, extreme ultraviolet rays, electron beams, and X-rays, There may be no particular limitation on its kind.

The type of the photopolymerization initiator is not particularly limited, but from the viewpoints of polymerization characteristics, initiation efficiency, absorption wavelength, availability, and price, it is preferred to use a compound selected from oxime-based compounds, acetophenone-based compounds, One or more of a benzoin-based compound, a biimidazole-based compound, a triazine-based compound, a thioxanthone-based compound, and an anthracene-based compound, and more preferably an oxime-based compound.

Examples of the oxime-based compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropane-1-one, (Z) -2-((benzyloxy) imine ) -1- (4- (phenylthio) phenyl) octane-1-one, (E) -1-(((1- (9-ethyl-6- (2-methylbenzidine ) -9H-oxazol-3-yl) ethylene) amino) oxy) ethanone, and (E) -1-(((1- (6- (4-((2,2-dimethyl -1,3-dioxolane-4-yl) methoxy) -2-methylbenzyl) -9-ethyl-9H-carbazol-3-yl) ethylene) amino ) Oxygen) ethyl ketone and the like, and commercially available products include, but are not limited to, OXE-01, OXE-02, etc. of BASF Corporation.

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

Examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, benzophenone dimethyl ketal, and 2-acetophenone. Hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylsulfide Phenyl) -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1-one, 2-hydroxy 2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1-one, and 2- (4-methylbenzyl) -2- (dimethylamino)- 1- (4-morpholinophenyl) butane-1-one and the like.

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-based compound include benzophenone, 0-benzylmethylbenzoate, 4-phenylbenzophenone, and 4-benzophenyl-4'-methyl. Diphenyl sulfide, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, and 2,4,6-trimethylbenzophenone and the like.

Examples of the biimidazole-based compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2, 3-dichlorophenyl) -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'-tetrakis (trialkoxyphenyl) biimidazole, 2,2-bis (2,6-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, or 4,4', 5,5 'phenyl is alkoxy Carbonyl-substituted imidazole compounds and the like. Among these, more preferably, 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 and the like.

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-piperyl-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) vinyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2- (Yl) vinyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) vinyl ] -1,3,5-triazine, and 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) vinyl] -1,3,5 -Triazines and the like.

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

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

In addition, in addition, 2,4,6-trimethylbenzylidene diphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10 can be used. -Phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, and titanocene compounds and the like.

Furthermore, in order to improve the sensitivity of the green photosensitive resin composition of the present invention, the photopolymerization initiator may further include a photopolymerization initiation aid (d1). When the green photosensitive resin composition according to the present invention contains a photopolymerization initiation aid (d1), the sensitivity is further improved, and productivity can be improved.

As the photopolymerization initiation aid, for example, one or more compounds selected from the group consisting of an amine compound, a carboxylic acid compound, and an organic sulfur compound having a thiol group are preferably used.

As the amine compound, an aromatic amine compound is preferably used. Specific examples include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, and the like. 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid isoamyl ester, 4-dimethylaminobenzoic acid 2-ethylhexyl ester, benzoic acid 2-dimethylamino group Ethyl ester, N, N-dimethyl-p-toluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as melidone), and 4,4'-bis (diethyl Amino) benzophenone and the like.

The carboxylic acid compound is preferably an aromatic heteroacetic acid. Specific examples include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, and methylethylphenylthioacetic acid. , Dimethylphenyl thioacetic acid, methoxyphenyl thioacetic acid, dimethoxyphenyl thioacetic acid, chlorophenyl thioacetic acid, dichlorophenyl thioacetic acid, N-phenylglycine Acids, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycolic acid, and naphthyloxyacetic acid.

Specific examples of the organic sulfur compound having a thiol group include 2-mercaptobenzothiazole, 1,4-bis (3-mercaptobutyryloxy) butane, and 1,3,5-tris (3 -Mercaptobutoxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tri (3-mercaptopropionate), pentaerythritol Tetrakis (3-mercaptobutyrate), pentaerythritol tetra (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), and the like.

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

When the photopolymerization initiator is contained in the content in the above range, the green photosensitive resin composition is made more sensitive and the exposure time is shortened. Therefore, productivity is improved and high resolution can be maintained. Moreover, the intensity | strength of the pixel part formed using the said colored photosensitive resin composition, and the smoothness in the surface of the said pixel part became favorable.

When the photopolymerization initiation aid is additionally used, the photopolymerization initiator is used in an amount of 10 mol or less, preferably 0.01 to 5 mol, with respect to 1 mol of the photopolymerization initiator.

When the photopolymerization initiation aid is used within the above range, the sensitivity of the green photosensitive resin composition is improved, and the productivity of a color filter including the same can be improved. (E) Solvent

As long as the solvent is effective for dissolving other components contained in the green photosensitive resin composition, a solvent used in a general green photosensitive resin composition can be used without particular limitation, and ethers, acetates, and aromatics are particularly preferred. Groups of hydrocarbons, ketones, alcohols, esters, or amidines.

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. ; Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dialkyl ethers such as 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, and butyl lactate. Ester, 3-methoxybutyl acetate, 3-methyl-3-methoxy-1-butyl acetate, methoxypentyl acetate, ethylene glycol monoacetate, ethyl Glycol diacetate, methyl 3-methoxypropionate, propylene glycol methyl ether acetate, 3-methoxy-1-butyl acetate, 1,2-propylene glycol diacetate, Ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butanediol diacetate, diethylene glycol monobutyl ether Acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoacetate, diethylene glycol diacetate, diethylene glycol monobutyl ether ethyl Acid esters, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene carbonate, propylene carbonate, and the like.

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

Examples of the ketones include methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone.

Examples of the alcohols include ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerol, and 4-hydroxy-4-methyl-2-pentanone.

Examples of the esters include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and γ-butyrolactone.

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

These solvents can be used individually or in mixture of 2 or more types.

In terms of coating properties and drying properties, the solvent is preferably an organic solvent having a boiling point of 100 ° C to 200 ° C. Examples include alkylene glycol alkyl ether acetates, ketones, and 3-ethoxypropionic acid. Ester such as ethyl ester and methyl 3-methoxypropionate, more preferably, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, lactic acid Butyl, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate.

The solvent is contained in an amount of 60 to 90% by weight, and preferably 70 to 85% by weight based on the total weight of the green photosensitive resin composition. If the above-mentioned solvent is contained in the range of 60 to 90% by weight, a coating method such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater), and an inkjet coating is used. When the cloth device is applied, the applicability becomes good. (F) Alkali soluble resin

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

The said alkali-soluble resin normally makes the non-exposed part of the green photosensitive resin layer formed using a green photosensitive resin composition alkali-soluble, and functions for a pigment as a dispersion medium.

The type of the alkali-soluble resin is not particularly limited, and it can be selected from a variety of polymers used in the technical field, and preferably contains a carboxyl group-containing monomer (f1). As the polymer containing the carboxyl group-containing monomer, a copolymer obtained from a carboxyl group-containing monomer (f1) and another monomer (f2) copolymerizable with the carboxyl group-containing monomer is particularly preferably used.

The carboxyl group-containing monomer (f1) may be, for example, an unsaturated carboxylic acid having one or more carboxyl groups in the molecule, such as an unsaturated monocarboxylic acid and an unsaturated dicarboxylic acid.

More specifically, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid are mentioned. The aforementioned carboxylic acid-containing monomers can be used individually or in combination of two or more kinds.

In addition, the other monomer (f2) which can be copolymerized with the carboxyl group-containing monomer is a compound having a polymerizable carbon-carbon unsaturated bond. Specifically, for example, α-methylstyrene and vinyltoluene may be mentioned. And other aromatic vinyl compounds; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and benzyl (meth) acrylate Unsaturated carboxylic acid esters; Unsaturated carboxylic acid amino alkyl esters such as amino ethyl acrylate; Unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate; Carboxylic acids such as vinyl acetate and vinyl propionate Acid vinyl esters; vinyl cyanide compounds such as (meth) acrylonitrile and α-chloroacrylonitrile.

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

In addition, as preferable examples of the copolymer, benzyl methacrylate / methacrylic acid copolymer, benzyl methacrylate / methacrylic acid / styrene copolymer, and methyl methacrylate / methacrylic acid copolymer are exemplified. Materials, and methyl methacrylate / methacrylic acid / styrene copolymers.

In the case where the alkali-soluble resin is a copolymer obtained from the carboxyl group-containing monomer (f1) and other monomers (f2) copolymerizable with the carboxyl group-containing monomer, it is based on the total weight of the copolymer. 10 to 50% by weight, preferably 15 to 40% by weight, contains the carboxyl group-containing monomer (f1).

The weight-average molecular weight of the alkali-soluble resin measured by gel permeation chromatography in terms of polystyrene is preferably 3,000 to 100,000, and more preferably 5,000 to 50,000. If 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 non-pixel portion peeling properties tend to be good during development, which is preferable.

In addition, the molecular weight distribution of the alkali-soluble resin, that is, the number average molecular weight (weight average molecular weight (Mw) / number average molecular weight (Mn)) in weight average molecular weight ratio is preferably 1.5 to 6.0, and more preferably 1.8 to 4.0. Sexually is preferred.

Furthermore, the acid value of the said alkali-soluble resin is 30-170 mgKOH / g on a solid content basis, More preferably, it is 50-150 mgKOH / g. When the acid value of the alkali-soluble resin is less than 30 mgKOH / g, it is difficult for the green photosensitive resin composition to ensure a sufficient development speed. When the acid value exceeds 170 mgKOH / g, the adhesiveness to the substrate is reduced, which may easily occur. The short circuit of the pattern causes problems with compatibility with the coloring agent, and the coloring agent in the green photosensitive resin composition may be precipitated, the storage stability of the green photosensitive resin composition may be decreased, and the viscosity may be increased, which is not preferable.

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

If the content of the alkali-soluble resin is 5 to 85% by weight, the solubility in the developing solution is sufficient, it is difficult to generate development residues on the substrate of the non-pixel portion, and the film of the pixel portion of the exposed portion is prevented from decreasing during development, and the non-pixel portion is reduced. The shedding property becomes good. (G) Additives

The additives are optionally added as necessary, and may include, for example, one or more selected from other polymer compounds, curing agents, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, and anticoagulants.

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

The curing agent is used to improve deep curing and mechanical strength. Specific examples of the curing agent include epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, and oxetane compounds.

Specific examples of the epoxy compound in the curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, and hydrogenated bisphenol F epoxy resin. Novolac epoxy resin, other aromatic epoxy resins, alicyclic epoxy resins, glycidyl ester resins, glycidylamine resins, or brominated derivatives of epoxy resins, epoxy resins , And aliphatic, cycloaliphatic or aromatic epoxy compounds other than their brominated derivatives, butadiene (co) polymer epoxide, isoprene (co) polymer epoxide, (methyl ) Glycidyl acrylate (co) polymer, and triglycidyl isocyanurate.

Specific examples of the oxetane compound in the curing agent include carbonate dioxetane, xylene dioxetane, adipate dioxetane, and Phthalate dioxetane, cyclohexanedicarboxylic acid dioxetane, and the like.

The said hardening | curing agent can use together with a hardening | curing agent the hardening auxiliary compound which can ring-open | polymerize the epoxy group of an epoxy compound and the oxetane skeleton of an oxetane compound, and can be used together.

Examples of the curing auxiliary compound include polycarboxylic acids, polycarboxylic anhydrides, and acid generators. As the polybasic carboxylic acid anhydride, a product commercially available as an epoxy resin curing agent can be used. Examples of the above-mentioned commercially available products include Akkaka EH-700 (manufactured by Aika Industry Co., Ltd.), Rikashi HH (manufactured by Shinnippon Rika Co., Ltd.), and MH-700 (manufactured by Shinnippon Rika Co., Ltd.). The curing agent exemplified above may be used alone or as a mixture of two or more kinds.

In order to further improve the film formation of the colored photosensitive resin composition, the above-mentioned surfactant can be used, and a silicone-based, fluorine-based, ester-based, cationic, anionic, non-ionic, amphoteric surfactant, or the like is preferably used.

The aforementioned silicone-based surfactants are, for example, commercially available products such as DC3PA, DC7PA, SH11PA, SH21PA, and SH8400 of Dow Corning Toray Silicone, and TSF-4440, TSF-4300, and TSF from GE Toshiba Silicone. -4445, TSF-4446, TSF-4460, and TSF-4452.

The above-mentioned fluorine-based surfactants are, for example, commercially available products such as Daishin Ink Chemical Industry Co., Ltd. F-470, F-471, F-475, F-482, and F-489.

In addition, as other commercially available products, KP (Shin-Etsu Chemical Industry Co., Ltd.), Polyflow (Kyoeisha Chemical Co., Ltd.), EFTOP (ト ー ケ ム プ ロ ダ ク ツ 社), MEGAFAC (Dai Nihon Ink Chemical Industry Co., Ltd.), Fluoro (Flourad) (Sumitomo Suriyo Co., Ltd.), Asahi Guard, Surfon (above, Asahi Glass Co., Ltd.), ソ ル ス パ ー ス ( SOLSPERSE) (Lubrisol), EFKA (EFKA ケ ミ カ ル ズ), PB821 (Ajinomoto Co., Ltd.), Disperbyk-series (BYK-chemi), and the like.

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

Examples of the anionic surfactant include higher alcohol sulfate salts such as sodium lauryl sulfate and sodium oleyl sulfate, alkyl sulfates such as sodium dodecyl sulfate and ammonium lauryl sulfate, and twelve Alkyl aryl sulfonates such as sodium alkylbenzenesulfonate and sodium dodecylnaphthalenesulfonate.

Examples of the non-ionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkylaryl ether, other polyoxyethylene derivatives, and ethylene oxide / propylene oxide blocks. Copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, and polyoxyethylene alkylamine Wait.

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

The kind of the adhesion promoter is not particularly limited, and specific examples of the adhesion promoter that can be used include vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltri (2-methyl). (Oxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyl Trimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxy Silyl, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane.

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

The kind of the antioxidant is not particularly limited, and examples thereof include 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenylacrylic acid. Ester, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 6- [3- ( 3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenzo [d, f] [1,3, 2] Dioxaphosphoheptene, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propanyloxy} -1,1 -Dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 2,2'-methylenebis (6-tert-butyl-4-methylphenol) , 4,4'-butylenebis (6-tert-butyl-3-methylphenol), 4,4'-thiobis (2-tert-butyl-5-methylphenol), 2,2 '-Thiobis (6-tert-butyl-4-methylphenol), 3,3'-thiodipropionate dilauryl, 3,3'-thiodipropionate dimyristate, 3 , 3'-Distearylthiopropionate, pentaerythritol tetrakis (3-laurylthiopropionate), 1,3,5-tris (3,5-di-tert-butyl-4-hydroxy Benzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 3,3 ', 3' ', 5,5', 5 ''-hexa-tert-ter -Butyl-a, a ', a' '-(mesitylene- 2,4,6-triyl) tri-p-cresol, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,6-di- Tert-butyl-4-methylphenol, and 2,2'-thiobis (4-methyl-6-tert-butylphenol), and 2,6-di-tert-butyl-4-methyl Phenol, etc.

The type of the ultraviolet absorber is not particularly limited, and specific examples of usable ultraviolet absorbers include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotris. Azole, alkoxybenzophenone and the like.

There is no particular limitation on the type of the above-mentioned anticoagulant, and specific examples of usable examples include sodium polyacrylate and the like.

Hereinafter, the manufacturing method of the green photosensitive resin composition of this invention is demonstrated to an example.

First, in the colorant (A), the compound (a1) or pigment (a2) of the above Chemical Formula 1 is mixed with a solvent (E), and dispersed using a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 μm or less. . In this case, if necessary, a part or all of the pigment dispersant (a3), the thermally crosslinked oxetane resin (B), or the dye (a4) may be mixed with the solvent (E) to dissolve or dispersion.

To the mixed dispersion, the dye (a4), the remainder of the thermally crosslinked oxetane resin (B), the photopolymerizable compound (C), and the photopolymerization initiator (D) are further added, and if necessary, The additive (G) and the solvent (E) are used so as to have a predetermined concentration, and the green photosensitive resin composition according to the present invention can be produced.

The present invention also includes a colored pattern produced using the green photosensitive resin composition. The colored pattern is produced by applying the green photosensitive resin composition of the present invention on a substrate, photocuring, and developing. The thickness of the colored pattern is not particularly limited, and may be, for example, 1 to 6 μm.

The colored pattern is formed by, for example, the following method.

First, the green photosensitive resin composition is coated on a substrate or a previously formed layer composed of a solid component of a green photosensitive resin composition, and the coated green photosensitive resin composition layer is pre-baked to evaporate a solvent or the like. The sexual components are removed to obtain a smooth coating film.

Examples of the coating method include spin coating, cast coating, roll coating, slit and spin coating, and slit coating.

After the coating is performed, pre-baking (heat-drying) or heating under reduced pressure is performed to volatilize a volatile component such as a solvent to form a green photosensitive resin composition layer. Among them, the heating temperature is usually 70 to 200 ° C, and preferably 80 to 130 ° C.

The coating film thus obtained was irradiated with ultraviolet rays through a mask for forming a target pattern. At this time, the entire exposure portion is uniformly irradiated with parallel light rays, and in order to accurately align the mask and the substrate, it is preferable to use a device such as a mask aligner and a stepper.

In addition, by contacting the cured coating film with an alkali developing solution, dissolving and exposing the non-exposed portion, the target pattern shape can be obtained. As the development method described above, a liquid addition method, a dipping method, a spray method, or the like can be implemented, and the substrate can be inclined at an arbitrary angle during development.

The developing solution used in the development after the patterned exposure is usually an aqueous solution containing a basic compound and a surfactant. The basic compound may be any of inorganic and / or organic basic compounds.

Specific examples of the inorganic basic compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, Potassium silicate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium borate, potassium borate, and ammonia.

Specific examples of the organic basic compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, and diethylamine. Amine, triethylamine, monoisopropylamine, diisopropylamine, and ethanolamine.

The above-mentioned inorganic and organic basic compounds can be used individually or in combination of two or more kinds.

The concentration of the alkaline compound in the alkaline 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, or a cationic surfactant.

Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkylaryl ether, other polyoxyethylene derivatives, and ethylene oxide / Propylene oxide block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, and poly Oxyethylene alkylamine and the like.

Specific examples of the anionic surfactant include higher alcohol sulfate salts such as sodium lauryl sulfate and sodium oleyl sulfate; alkane such as sodium dodecyl sulfate and ammonium dodecyl sulfate. Alkyl sulfates; alkylaryl sulfonates such as sodium dodecylbenzenesulfonate and sodium dodecylnaphthalenesulfonate.

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

The said surfactant can be used individually or in mixture of 2 or more types.

The concentration of the surfactant in the rhenium 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 is washed with water, and after baking may be performed at 150 to 230 ° C. for 10 to 60 minutes, if necessary.

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

The color filter of the present invention includes a substrate and a colored pattern produced on the substrate using the green photosensitive resin composition of the present invention. The substrate is made of a transparent material, and for the stability of the color filter, a material having sufficient strength and support can be used. Preferably, glass having excellent chemical stability and high strength can be used.

As the method for manufacturing the color filter, a general method known in the art can be adopted.

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

Specific examples of the display device include a liquid crystal display (liquid crystal display device; LCD), an organic EL display (organic EL display device), a liquid crystal projector, a display device for a game machine, a display device for a portable terminal such as a mobile phone, A display device such as a display device for a digital camera and a display device for a car navigation system, etc., are particularly preferably a color display device.

The display device includes, in addition to the color filter, a configuration known to those skilled in the technical field of the present invention, 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 using examples and experimental examples. However, the following embodiments are used to illustrate the present invention, and the present invention is not limited to the following embodiments, and various modifications and variations can be made within the scope of the present invention. The scope of the present invention is determined by the technical idea of the scope of patent application described later. <Synthesis of thermally crosslinked oxetane resin> Synthesis Example 1.

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

Then, a mixture containing 110.5 g of 3-ethyl-3- (methacryloxy) methyloxetane, 14.4 g of acrylic acid, and 35.2 g of benzyl methacrylate was dissolved, and α-methylbenzene was added. After 5.0 g parts by weight of an ethylene dimer (chain transfer agent), 3.3 g of 2,2'-azobis (2,4-dimethyl) was added to 50 parts by weight of propylene glycol monomethyl ether acetate. A solution of valeronitrile) was dropped into the flask from the dropping funnel over 1 hour and stirred at 80 ° C. for 5 hours to obtain a thermally crosslinked oxetane resin B-1 having a solid acid value of 65 mgKOH / g.

The polystyrene equivalent weight average molecular weight measured by GPC was 10,100, and the molecular weight distribution (Mw / Mn) was 2.8. Synthesis Example 2.

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

Then, a mixture containing 110.5 g of 3-ethyl-3- (methacryloxy) methyloxetane, 17.2 g of methacrylic acid, and 23.6 g of 4-vinyltoluene was dissolved, and α-formaldehyde was added. After 5.0 g parts by weight of a styrene dimer (chain transfer agent), 3.3 g of 2,2'-azobis (2,4-di) was added to 50 parts by weight of propylene glycol monomethyl ether acetate. A solution of methylvaleronitrile) was dropped into the flask from the dropping funnel for 1 hour, and stirred at 80 ° C for 5 hours to obtain a thermally crosslinked oxetane resin B- with a solid content acid value of 68 mgKOH / g. 2.

The polystyrene equivalent weight average molecular weight measured by GPC was 12,300, and the molecular weight distribution (Mw / Mn) was 2.7. Synthesis Example 3.

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

Then, a mixture containing 102.1 g of 3-ethyl-3- (propenyloxy) methyloxetane, 21.6 g of acrylic acid, and 17.6 g of benzyl methacrylate was dissolved, and α-methylstyrenediamine was added. After 5.0 g parts by weight of a polymer (chain transfer agent), 3.3 g of 2,2'-azobis (2,4-dimethylvaleronitrile) was added to 50 parts by weight of propylene glycol monomethyl ether acetate. The solution of) was dropped into the flask from the dropping funnel over 1 hour, and stirred at 80 ° C. for 5 hours to obtain a thermally crosslinked oxetane resin B-3 having a solid content acid value of 95 mgKOH / g.

The polystyrene equivalent weight average molecular weight measured by GPC was 8,900, and the molecular weight distribution (Mw / Mn) was 2.9. Synthesis Example 4.

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

Then, a mixture containing 51.0 g of 3-ethyl-3- (propenyloxy) methyloxetane, 21.6 g of acrylic acid, 35.2 g of benzyl methacrylate, and 20.0 g of methyl methacrylate was dissolved, After adding 5.0 g parts by weight of α-methylstyrene dimer (chain transfer agent), 3.3 g of 2,2'-azobis (2) was added to 50 parts by weight of propylene glycol monomethyl ether acetate. (4-dimethylvaleronitrile) was dropped into the flask from the dropping funnel for 1 hour, and stirred at 80 ° C for 5 hours to obtain a thermally crosslinked oxetan with a solid content acid value of 90 mgKOH / g. Alk resin B-4.

The polystyrene equivalent weight average molecular weight measured by GPC was 11,300, and the molecular weight distribution (Mw / Mn) was 2.7. Synthesis Example 5.

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

Then, a mixture containing 17.0 g of 3-ethyl-3- (propenyloxy) methyloxetane, 21.6 g of acrylic acid, 35.2 g of benzyl methacrylate, and 40.0 g of methyl methacrylate was dissolved, After adding 5.0 g parts by weight of α-methylstyrene dimer (chain transfer agent), 3.3 g of 2,2'-azobis (2) was added to 50 parts by weight of propylene glycol monomethyl ether acetate. , 4-dimethylvaleronitrile) was dropped into the flask from the dropping funnel for 1 hour, and stirred at 80 ° C for 5 hours to obtain a thermally crosslinked oxetan with a solid content acid value of 105 mgKOH / g Alk resin B-5.

The polystyrene equivalent weight average molecular weight measured by GPC was 8,100, and the molecular weight distribution (Mw / Mn) was 2.8. <Synthesis of alkali-soluble resin> Synthesis Example 6.

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

Then, a mixture containing 21.6 g of acrylic acid, 70.4 g of benzyl methacrylate, and 30.0 g of methyl methacrylate was dissolved, and 5.0 g parts by weight of an α-methylstyrene dimer (chain transfer agent) was added. A solution in which 3.3 g of 2,2'-azobis (2,4-dimethylvaleronitrile) was added to 50 parts by weight of propylene glycol monomethyl ether acetate was dropped into the flask from the dropping funnel over 1 hour. It stirred at 80 degreeC for 5 hours, and obtained the fluorene soluble resin B-6 whose solid content acid ester was 103 mgKOH / g.

The polystyrene equivalent weight average molecular weight measured by GPC 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 resins produced in the above Synthesis Examples 1 to 6 were measured by the GPC method under the following conditions. Device: HLC-8120GPC (manufactured by Tosoh Corporation) Column: TSK-GELG4000HXL + TSK-GELG2000HXL (series connection) Column temperature: 40 ° C Mobile phase solvent: Tetrahydrofuran Flow rate: 1.0ml / min Injection volume: 50μl Detector: RI Measurement sample concentration: 0.6% by weight (solvent = tetrahydrofuran) Calibration standard material: 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 the number-average molecular weight obtained above was used as the molecular weight distribution (Mw / Mn). <Production of pigment dispersion liquid> Production Examples 1 to 4.

The pigment dispersions of Production Examples 1 to 4 were produced by the compositions shown in Table 1 below. [Table 1] (Unit:% by weight) Pigment 1: CI Pigment Green 59 Pigment 2: CI Pigment Yellow 185 Pigment 3: CI Pigment Yellow 150 Pigment 4: CI Pigment Green 7 Dispersant: BYK2001 (manufactured by ビ ー パ イ ケ ー (BYK), solid content concentration 45.1% by weight) Solvent: propylene glycol methyl ether acetate <manufacturing of green photosensitive resin composition> Examples 1 to 10 and Comparative Examples 1 to 3.

The green photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 to 3 were produced by the compositions in Table 2 below. [Table 2] (Unit:% by weight) M1: Pigment dispersion liquid produced in Production Example 1 M2: Pigment dispersion liquid produced in Production Example 2 M3: Pigment dispersion liquid produced in Production Example 3 M4: Pigment dispersion liquid produced in Production Example 4 B-1: Synthesis example Thermally crosslinked oxetane resin B-2 produced in 1: Thermally crosslinked oxetane resin B-3 produced in Synthesis Example 2: Thermally crosslinked oxetane produced in Synthesis Example 3 Cyclobutane resin B-4: Thermally crosslinked oxetane resin produced in Synthesis Example 4 B-5: Thermally crosslinked oxetane resin B-6 produced in Synthesis Example 5: Synthesis example Fluorene-soluble resin photopolymerizable compound produced in 6: dipentaerythritol hexaacrylate photopolymerization initiator: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 Solvent: propylene glycol monomethyl ether acetate Experimental example 1. Evaluation of physical properties of green photosensitive resin composition

A 2 square inch glass substrate (manufactured by Corning Corporation, # 1737) was sequentially washed with a neutral detergent, water, and alcohol, and then dried. The green photosensitive resin compositions of the above-mentioned Examples 1 to 10 and Comparative Examples 1 to 3 were spin-coated on the glass substrates, respectively, so as to be exposed at an exposure amount (365 nm) of 100 mJ / cm ² , and the development process was omitted. The film thickness after firing was 2.0 μm.

Next, it was pre-dried in a clean oven at 100 ° C for 3 minutes. After cooling, the substrate coated with the above-mentioned green photosensitive resin composition and a photomask made of quartz glass (having a pattern in which the transmittance is changed stepwise in the range of 1 to 100%, and a line / gap pattern of 1 to 50 μm are provided. ) Interval is 100μm, use An ultrahigh-pressure mercury lamp (trade name USH-250D) manufactured by Denki Co., Ltd. was irradiated with light at an exposure amount (365 nm) of 100 mJ / cm ² in an atmospheric atmosphere.

Then, the coating film was immersed in a water-based developer containing 0.12% of a nonionic surfactant and 0.06% of potassium hydroxide at 26 ° C for a predetermined time, developed, and then washed with water and dried at 220 ° C for 30 minutes. Color filter.

1-1. Measurement of brightness (Y)

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

1-2. Measurement of chromaticity (color coordinates)

The color coordinates of the color filters manufactured as described above were measured using a micro spectrometer OSP-SP2000, and the results are shown in Table 3 below.

1-3. Evaluation of solvent resistance

The color filters manufactured above were immersed in each solvent (NMP; 1-methyl-2-pyrrolidone, IPA; isopropyl alcohol, GBL; γ-butyrolactone) for 30 minutes, and the color change before and after the evaluation was calculated and compared. Evaluation.

The calculation formula used at this time is the following mathematical formula 1, which represents a color change using a three-dimensional colorimeter as defined by L *, a *, b *.

[Mathematical formula 1] △ E _ab ^* = [(△ L ^* ) ² + (△ a ^* ) ² + (△ b ^* ) ² ] ^1/2

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

<Evaluation criteria for solvent resistance> ○: △ Eab = less than 1 △: △ Eab = 1 ～ 3 X: △ Eab = more than 3 1-4. Evaluation of heat resistance

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

The color change was calculated by the above-mentioned mathematical formula 1, and the brightness change (ΔY) before and after the heat resistance evaluation was confirmed, and the presence or absence of the decrease in brightness due to the thermal yellowing was confirmed.

The evaluation criteria are as described below, and the results are described in Table 3 below. <Evaluation criteria for heat resistance> ○: △ Eab = less than 1 △: △ Eab = 1 to 3 X: △ Eab = more than 3 <Evaluation criteria for brightness change (ΔY)> ○: less than 0.3 △: 0.3 to 0.5 X: more than 0.5 [Table 3]

The color coordinates of the pigment containing C.I. Pigment Yellow 185 are x = 0.256 and y = 0.641, which appear in Examples 1 to 5 and Comparative Examples 1 to 2.

The color coordinates of the pigment containing C.I. Pigment Yellow 150 are x = 0.24 and y = 0.606, which appear in Examples 6 to 10 and Comparative Example 3.

In the above-mentioned color coordinates, Comparative Examples 1 and 3 including C.I. Pigment Yellow 185 or C.I. Pigment Yellow 150 and C.I. Pigment Green 7 serve as reference values for the color coordinates.

From the results of Table 3 above, it was confirmed that the green photosensitive resin composition of Examples 1 to 10 including the C.I. Pigment Green 59 of the present invention instead of C.I. Pigment Green 7 improved the chromaticity (Y) of 7 to 10%.

In addition, it was confirmed that the green photosensitive resin composition of Examples 1 to 10 including the thermally crosslinked oxetane resin containing the monomer of the above Chemical Formula 2 of the present invention was excellent in heat resistance and solvent resistance, It was confirmed that the green photosensitive resin composition of Comparative Example 2 not containing the monomer of Chemical Formula 2 was inferior in 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 a color filter including the green photosensitive resin composition can exhibit high color reproduction.

Figure 1 shows the transmission spectra of the above C.I. Pigment Green 59 (G59), C.I. Pigment Green 7 (G7), and C.I. Pigment Green 58 (G58).

Claims (10)

A green photosensitive resin composition comprising a colorant, a thermally crosslinked oxetane resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein the colorant includes CI Pigment Green 59 and a compound selected from CI Pigment Yellow 138, CI Pigment Yellow 129, CI Pigment Yellow 150, and CI Pigment Yellow 185. One or more members of this group. The thermally crosslinked oxetane resin includes a monomer of the following Chemical Formula 2, wherein The total solid weight of the green photosensitive resin composition. The green photosensitive resin composition includes 5 to 70% by weight of the colorant and 5 to 80% by weight of the thermally crosslinked oxetane resin. The CI pigment green 59 is mixed with one or more selected from the group consisting of CI pigment yellow 138, CI pigment yellow 129, CI pigment yellow 150, and CI pigment yellow 185 in a weight ratio of 1: 0.05 to 1:18; Wherein X ₁ is an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms, -O- group, -CO- group, -C (= O) O- group, -CONH- group, Or phenylene; X ₂ is an alkyl group having 1 to 4 carbon atoms or a perfluoroalkyl group having 1 to 4 carbon atoms; and R ₁ is hydrogen or methyl. The green photosensitive resin composition according to claim 1, wherein the thermally crosslinked oxetane resin comprises: a thermally crosslinked oxetane resin containing the monomer of Chemical Formula 2, A copolymer of a monomer and an unsaturated carboxylic acid monomer, or the monomer of the chemical formula 2, an unsaturated carboxylic acid monomer, and an unsaturated bond containing a copolymerizable with the monomer of the chemical formula 2 and the unsaturated carboxylic acid monomer Copolymer of monomers. For example, the green photosensitive resin composition according to claim 2, wherein 5 to 95 mol% of the monomer of the chemical formula 2 and 5 to 95 are included with respect to the total mole number of the thermally crosslinked oxetane resin. Mole% unsaturated carboxylic acid monomer. For example, the green photosensitive resin composition according to claim 2, wherein 5 to 90 mol% of the monomer of the chemical formula 2 and 5 to 90% of the total mole number of the thermally crosslinked oxetane resin are included. Molar% unsaturated carboxylic acid monomer, and 5 to 70 Molar% of monomers containing an unsaturated bond that can be copolymerized with the monomer of Chemical Formula 2 and the unsaturated carboxylic acid monomer. The green photosensitive resin composition according to claim 1, which contains 5 to 45% by weight of a photopolymerizable compound and 2 to 10% by weight of a photopolymerization initiator with respect to the total weight of the solid content in the green photosensitive resin composition. The solvent contains 60 to 90% by weight of the total weight of the green photosensitive resin composition. The green photosensitive resin composition according to claim 1, wherein the Tmax of the C.I. Pigment Green 59 is 500 to 530 nm. The green photosensitive resin composition according to claim 1, wherein the T _50% of the CI pigment green 59 is 445 to 580 nm. The green photosensitive resin composition according to claim 1, wherein, in the XYZ color system, the colorant has a color coordinate of x = 0.1 to 0.35 when y = 0.6 or more. A color filter comprising the green photosensitive resin composition according to any one of claims 1 to 8. A display device includes a color filter as claimed in claim 9.