KR102383519B1 - A green photosensitive resin composition, color filter and display device comprising the same - Google Patents

Abstract

(상기 화학식 1에서,
상기 A₁ 내지 A₁₆은 각각 독립적으로 수소, 브롬, 또는 염소이며,
상기 A₁ 내지 A₁₆ 중 수소는 1 내지 6개이고, 염소는 0 내지 5개이며, 브롬은 5 내지 13개이다).The present invention includes a colorant containing a green pigment in which the weight ratio of the compound represented by the following formula (1) to the aluminum phthalocyanine compound is 20:80 to 80:20, so that high color reproduction is possible due to high transmittance, and liquid crystal according to ion elution It relates to a green photosensitive resin composition capable of preventing the generation of an afterimage due to contamination, a color filter including the same, and an image display device.
[Formula 1]

(In Formula 1,
The A ₁ to A ₁₆ are each independently hydrogen, bromine, or chlorine,
Among A ₁ to A ₁₆ , hydrogen is 1 to 6, chlorine is 0 to 5, and bromine is 5 to 13).

Description

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

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

A color filter is a member used for a solid-state image sensor or a liquid crystal display device, and is generally produced by forming a coloring pattern (red, green, blue) using a coloring photosensitive resin composition on a support body.

In recent years, there is a tendency for image display devices to become thinner, and color filters included in image display devices also tend to become thinner, and accordingly, the size of the coloring pattern is becoming more miniaturized. appears conspicuously.

According to the miniaturization of the coloring pattern, the impreciseness of the colored pattern tip portion and the development residue of the unexposed portion are more problematic than before.

In addition, in the thin-layered color filter, the composition ratio of the colorant in the colored photosensitive resin composition increases in order to obtain spectral sensitivity equivalent to that of the conventional color filter. In this case, components other than the colorant (components contributing to photolithography performance) are relatively decreased, and thus the deterioration of durability is a problem.

Therefore, it is necessary to develop a colored photosensitive resin composition capable of maintaining photolithography performance of a conventional level even if a component contributing to photolithography performance is relatively reduced, or capable of high color reproduction despite using a small amount of colorant.

In this regard, Japanese Patent Application Laid-Open No. 2012-155231 describes a color filter that contains a specific phthalocyanine compound, which has excellent heat resistance and light resistance, and is capable of high brightness and a wide color reproduction area. There is a problem that an afterimage occurs on the liquid crystal.

Japanese Patent Laid-Open No. 2012-155231 (2012.08.16.)

The present invention is to solve the above problems, a green photosensitive resin composition capable of high color reproduction due to high transmittance and preventing the occurrence of an afterimage due to liquid crystal contamination due to ion elution, a color filter comprising the same, and An object of the present invention is to provide an image display device.

The green photosensitive resin composition of the present invention for achieving the above object is characterized in that it comprises a colorant containing a green pigment in which the weight ratio of the compound represented by the following formula (1) to the aluminum phthalocyanine compound is 20:80 to 80:20:

[Formula 1]

(In Formula 1,

The A ₁ to A ₁₆ are each independently hydrogen, bromine, or chlorine,

Among A ₁ to A ₁₆ , hydrogen is 1 to 6, chlorine is 0 to 5, and bromine is 5 to 13).

In addition, the color filter of the present invention is characterized in that it comprises a cured product of the above-described green photosensitive resin composition.

In addition, the image display apparatus of the present invention is characterized in that it includes the above-described color filter.

The green photosensitive resin composition of the present invention has the advantage of being able to reproduce high color due to high transmittance and prevent the occurrence of an afterimage due to liquid crystal contamination due to ion elution.

The color filter of the present invention has the same advantages as described above by including a cured product of the above-described green photosensitive resin composition.

The image display apparatus of the present invention has the same advantages as described above by including the color filter described above.

In the present invention, when a member is said to be located "on" another member, this includes not only a case in which a member is in contact with another member but also a case in which another member is present between the two members.

In the present invention, when a part "includes" a certain component, it means that other components may be further included, rather than excluding other components, unless otherwise stated.

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

<Green photosensitive resin composition>

By including a colorant containing a green pigment in which the weight ratio of the compound represented by Formula 1 to the aluminum phthalocyanine compound according to one embodiment of the present invention is 20:80 to 80:20, preferably 30:70 to 70:30, High color reproduction is possible due to high transmittance, and there is an advantage in that it is possible to prevent the occurrence of an afterimage due to liquid crystal contamination due to ion elution.

[Formula 1]

(In Formula 1,

The A ₁ to A ₁₆ are each independently hydrogen, bromine, or chlorine,

Among A ₁ to A ₁₆ , hydrogen is 1 to 6, chlorine is 0 to 5, and bromine is 5 to 13).

coloring agent

The green photosensitive resin composition according to an embodiment of the present invention includes a colorant including a green pigment, wherein the green pigment is a compound represented by the following Chemical Formula 1 and an aluminum phthalocyanine compound in a weight ratio of 20:80 to 80:20 By being included, high color reproduction is possible due to high transmittance, and there is an advantage in that it is possible to improve an afterimage phenomenon occurring in a color filter (liquid crystal panel) made of a cured product of a green photosensitive resin composition including the same.

A compound represented by Formula 1

The compound represented by Chemical Formula 1 is a compound having a structure of ZnPc (Zinc Phthalocyanine), and has the advantage of enabling high color reproduction by realizing high transmittance.

According to an embodiment of the present invention, the compound represented by Formula 1 is C.I. Pigment Green 58 or C.I. Pigment Green 59 may be included.

aluminum phthalocyanine compound

The aluminum phthalocyanine compound is a compound having a structure in which trivalent aluminum is disposed at the center of a phthalocyanine ring, and the aluminum is bonded to a nitrogen atom in the phthalocyanine ring. In the aluminum phthalocyanine compound, an additional bond other than the bond with the nitrogen atom in the phthalocyanine ring is possible. In addition, various chemical modifications of the phthalocyanine ring of the aluminum phthalocyanine compound are possible. The aluminum phthalocyanine compound can be multimerized into a dimer, a trimer, etc. in addition to a monomer.

According to an embodiment of the present invention, the aluminum phthalocyanine compound may include a compound represented by the following Chemical Formula 2 or Chemical Formula 3.

[Formula 2]

(In Formula 2,

R ¹ to R ¹⁶ are each independently hydrogen, a halogen atom, a nitro group, a substitutable phthalimidemethyl group, a substitutable sulfamoyl group, a C1 to C18 substitutable alkyl group, a C6 to C14 substitutable aryl group, C5 to C10 of a substitutable cycloalkyl group, a C5 to C14 heterocyclic group, a C1 to C18 substitutable alkoxy group, a C6 to C14 substitutable aryloxy group, a C1 to C18 substitutable alkylthio group, or a C6 to C14 substitutable aryl group It's Tigi,

Z is -OP(=O)X ₁ X ₂ ,

wherein X ₁ and X ₂ are each independently hydrogen, a hydroxyl group, a C1 to C18 substitutable alkyl group, a C6 to C14 substitutable aryl group, a C1 to C18 substitutable alkoxy group, or a C6 to C14 substitutable aryloxy group, ,

X ₁ and X ₂ may form a heterocycle together with the bonded phosphorus atom).

In the present invention, 'substitutable' means substituted or unsubstituted with a substituent, and the substituents may be different or the same, and specifically, halogen groups such as fluorine, chlorine, bromine, amino groups, hydroxyl groups, nitro In addition to characteristic groups such as a group, an alkyl group, an aryl group, a cycloalkyl group, an aryloxy group, an alkylthio group, an arylthio group, etc. may be mentioned, but are not limited thereto.

In Formula 2, the halogen atom may include fluorine, chlorine, and bromine. For example, when R ¹ to R ¹⁶ in Formula 2 includes hydrogen, chlorine and bromine, the number of hydrogens may be 1 to 6 The number of dogs and chlorine may be 3 to 9, and the number of bromine may be 2 to 7, or R ¹ to R ¹⁶ may be all hydrogen, but are not limited thereto.

In Formula 2, the alkyl group refers to a straight-chain or branched hydrocarbon group, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, n- A hexyl group, n-octyl group, stearyl group, 2-ethylhexyl group, etc. may be included, and the alkyl group may include a substituent, for example, a trichloromethyl group, a trifluoromethyl group, 2,2,2 -trifluoroethyl group, 2,2-dibromoethyl group, 2,2,3,3-tetrafluoropropyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-nitropropyl group, benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group, 2,4-dichlorobenzyl group, etc. are mentioned.

In Formula 2, the aryl group may include, for example, a phenyl group, a naphthyl group, and an anthryl group, and these may include a substituent, for example, p-methylphenyl group, p-bromophenyl group, p- Nitrophenyl group, p-methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2-aminophenyl group, 2-methyl-4-chlorophenyl group, 4-hydroxy-1-naphthyl group, 6-methyl-2 -naphthyl group, 4,5,8-trichloro-2-naphthyl group, anthraquinolyl group, 2-aminoanthraquinoryl group, etc. are mentioned.

In Formula 2, the cycloalkyl group includes, for example, a cyclopentyl group, a cyclohexyl group, and an adamantyl group, and these may include a substituent, for example, a 2,5-dimethylcyclopentyl group, A 4-tert- butylcyclohexyl group etc. are mentioned.

In Formula 2, the heterocyclic group includes, for example, a pyridyl group, a pyrazyl group, a piperidino group, a pyranyl group, a morpholino group, and an acridinyl group.

In Formula 2, the alkoxy group may be linear or branched, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group, neopentylox group, 2,3-dimethyl-3-pentyloxy group, n-hexyloxy group, n-octyloxy group, stearyloxy group, 2-ethylhexyloxy group, etc., which may include a substituent. For example, trichloromethoxy group, trifluoromethoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropoxy group, 2,2-ditrifluoro and a romethyl propoxy group, a 2-ethoxyethoxy group, a 2-butoxyethoxy group, a 2-nitropropoxy group, and a benzyloxy group.

In Formula 2, the aryloxy group may include, for example, a phenoxy group, a naphthoxy group, an anthryloxy group, and the like, and these may include a substituent, for example, p-methylphenoxy group, p-nitrophenoxy group. group, p-methoxyphenoxy group, 2,4-dichlorophenoxy group, pentafluorophenoxy group, 2-methyl-4-chlorophenoxy group, and the like.

In Formula 2, the alkyl thio group is, for example, a methyl thio group, an ethyl thio group, a propyl thio group, a butyl thio group, a phenylthio group, a hexyl thio group, an octyl thio group, a decyl thio group, a dodecyl thio group, an octa decylthio group, etc., which may have a substituent, for example, methoxyethylthio group, aminoethylthio group, benzyl aminoethylthio group, methylcarbonylamino ethylthio group, phenylcarbonylaminoethylthio group Ogi, etc. are mentioned.

In Formula 2, the aryl thio group may include, for example, a phenyl thio group, a 1-naphthyl thio group, a 2-naphthyl thio group, a 9-anthryl thio group, etc., which may include a substituent. Examples thereof include a chlorophenyl thio group, a trifluoromethyl phenyl thio group, a cyanophenyl thio group, a nitrophenyl thio group, a 2-aminophenyl thio group, and a 2-hydroxyphenyl thio group.

[Formula 3]

(In Formula 3,

wherein R ¹⁷ to R ³² are each independently hydrogen, a halogen atom, a nitro group, a substitutable phthalimidemethyl group, a substitutable sulfamoyl group, a C1 to C18 substitutable alkyl group, a C6 to C14 substitutable aryl group, C5 to C10 substitutable cycloalkyl group, C5 to C14 heterocyclic group, C1 to C18 substitutable alkoxy group, C6 to C14 substitutable aryloxy group, C1 to C18 substitutable alkylthio group or C6 to C14 substitutable an arylthio group,

또는

이며, The L is

or

is,

In this case, X ₃ to X ₇ are each independently a C1 to C18 substitutable alkyl group or a C6 to C14 substitutable aryl group).

In Formula 3, the meanings of a halogen atom, an alkyl group, an aryl group, a cycloalkyl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylthio group, and an arylthio group are as defined in Formula 2 above.

According to one embodiment of the present invention, the aluminum phthalocyanine compound is C.I. Pigment Green 62 or C.I. Pigment Green 63 may be included.

In the green photosensitive resin composition according to an embodiment of the present invention, as described above, the weight ratio of the compound represented by Formula 1 and the aluminum phthalocyanine compound, which is a green pigment capable of high color reproduction due to high transmittance, is 20:80 to 80:20. By doing so, it is possible to reproduce high color due to high transmittance, as well as to prevent the occurrence of an afterimage due to liquid crystal contamination due to ion elution.

According to one embodiment of the present invention, the colorant may further include one or more kinds of pigments or dyes other than the above-described green pigment.

pigment

The pigment may include an organic pigment or an inorganic pigment, which may be used alone or in combination of two or more. It may be more preferable to use an organic pigment in terms of excellent heat resistance and color development.

The organic pigment may be treated with rosin, if necessary; surface treatment using a pigment derivative into which an acidic group or a basic group is introduced; graft treatment to the surface of the pigment using a polymer compound or the like; fine-graining treatment by a sulfuric acid fine-graining method or the like; or washing treatment with an organic solvent or water to remove impurities; it may have been

As a specific example of the pigment, more preferably a compound classified as a pigment in the Color Index (Publisher: The Society of Dyers and Colorists) may be mentioned, and more specifically, the following color index (C.I.) number Examples of pigments may be mentioned, but the present invention is not limited thereto, and one or more selected from them may be co-dispersed using a binder resin, a dispersant, etc. to match the desired chromaticity.

Specifically, 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, 214, 231;

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

C.I. Pigment Green 7, 36, and the like may be mentioned, but is not limited thereto.

According to one embodiment of the present invention, among the above-mentioned pigments, in that high color reproduction is possible due to high transmittance, C.I. Pigment Yellow 129, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 185, C.I. It may be preferable to include at least one selected from the group consisting of Pigment Yellow 231, more preferably C.I. Pigment Yellow 138, C.I. Pigment Yellow 150, C.I. Pigment Yellow 185, C.I. Pigment Yellow 231 may be included.

The weight ratio of the green pigment and other pigments may be 10:90 to 90:10, preferably 20:80 to 80:20. When the weight ratio of each pigment is adjusted within the above range, a green colored layer having a desired color tone while improving luminance can be formed. When the color filter is manufactured, the R, G, and B color balance is not matched, which may cause a defect in the finally produced image display device.

dispersant

The dispersant may be added to deagglomerate and maintain stability of insoluble colorants such as the pigment, and those generally used in the art may be used without limitation. Specifically, surfactants such as cationic, anionic, nonionic, amphoteric, polyester, and polyamine may be used, but preferably BMA (butyl methacrylate) or DMAEMA (N,N-dimethylamino An acrylate-based dispersing agent (hereinafter, sometimes referred to as an acrylic dispersing agent) containing ethyl methacrylate) can be used. At this time, it may be preferable to apply the acrylic dispersant prepared by the living control method as presented in Korean Patent Application Laid-Open No. 2004-0014311. BYK-2000, DISPER BYK-2001, DISPER BYK-2070, DISPER BYK-2150, etc. may be mentioned, but are not limited thereto, and these may be used alone or in combination of two or more.

As the dispersant, a pigment dispersant of a resin type other than the above-mentioned acrylic dispersant may be used. The pigment dispersants of the other resin types include known resin type pigment dispersants, in particular polyurethanes, polycarboxylic acid esters typified by polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acids (partially) amine salts, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminoamide phosphate salts, esters of hydroxyl-containing polycarboxylic acids and modified products thereof, or free ) oily dispersants such as amides or salts thereof formed by the reaction of a polyester having a carboxyl group with poly(lower alkyleneimine); water-soluble resins or water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylate ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinyl pyrrolidone; Polyester; modified polyacrylates; adducts of ethylene oxide/propylene oxide and phosphate esters; and the like. As a commercially available product of the above-mentioned resin type dispersant, as a cationic resin dispersant, for example, BYK (Big) Chemi Corporation's trade names: 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 brand 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; Trade names from Lubirzol: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10; Trade names of Kawaken Fine Chemicals: HINOACT T-6000, HINOACT T-7000, HINOACT T-8000; Trade names of Ajinomoto Corporation: AJISPUR PB-821, AJISPUR PB-822, AJISPUR PB-823; Kyoeisha Chemical Company's trade name: FLORENE DOPA-17HF, fluorene DOPA-15BHF, fluorene DOPA-33, fluorene DOPA-44, etc. may be mentioned, but are not limited thereto, and these are each independently Or it can be used in combination of 2 or more types, and can also be used in combination with an acrylic dispersing agent.

The content of the dispersant may be included in an amount of 5 to 60 parts by weight, more preferably 15 to 50 parts by weight, based on 100 parts by weight of the total solid content of the pigment included together. If the content of the dispersant exceeds the above range, the viscosity may increase and process problems may occur.

dyes

The dye may be used without limitation as long as it has solubility in organic solvents or is dispersible. Preferably, it is preferable to use a dye that has solubility in organic solvents and can secure reliability such as solubility in alkali developer, heat resistance and solvent resistance. In the case of dyes that are not soluble in organic solvents, it is also possible to disperse them and use them.

As the dye, at least one selected from acid dyes having an acid group such as sulfonic acid or carboxylic acid, salts of acid dyes and nitrogen-containing compounds, sulfonamides of acid dyes, and derivatives thereof may be used. In addition, azo, xanthene, and phthalocyanine acid dyes and derivatives thereof may be selected.

Preferred examples of the dye include compounds classified as dyes in the color index (published by The Society of Dyers and Colorists), and well-known dyes described in the dyeing notes (color dyes).

Specific examples of the dye include,

C.I. Solvent Yellow No. 2, C.I. Solvent Yellow No. 14, C.I. Solvent Yellow No. 16, C.I. Solvent Yellow No. 33, C.I. Solvent Yellow No. 34, C.I. Solvent Yellow No. 44, C.I. Solvent Yellow No. 56, C.I. Solvent Yellow No. 82, C.I. Solvent Yellow No. 93, C.I. Solvent Yellow No. 94, C.I. Solvent Yellow No. 98, C.I. Solvent Yellow No. 116, C.I. Solvent Yellow No. 135;

C.I. Solvent Orange No. 1, C.I. Solvent Orange No. 3, C.I. Solvent Orange No. 7, C.I. Solvent Orange No. 63;

C.I. Solvent Blue No. 4, C.I. Solvent Blue No. 5, C.I. Solvent Blue No. 25, C.I. Solvent Blue No. 35, C.I. Solvent Blue No. 36, C.I. Solvent Blue No. 38, C.I. Solvent Blue No. 70;

C.I. Solvent Green No. 3, C.I. Solvent Green No. 5, C.I. Solvent Green No. 7, etc. may be mentioned, but the present invention is not limited thereto, and these may be used alone or in combination of two or more.

Also, C.I. as an acid dye

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

and green dyes such as C.I. Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109, etc., preferably in an organic solvent. C.I. Acid Yellow 42, which has excellent solubility in water; C.I. Acid Green 27 may be used, but is not limited thereto, and these may be used alone or in combination of two or more.

Also as a C.I. direct dye,

C.I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129 , 136, 138, 141 and other yellow dyes;

green dyes such as C.I. direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82;

Also, C.I. As modanto dye

yellow dyes such as C.I. modanto yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

Green dyes such as C.I. modanto green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53, and the like, but are not limited thereto, and these Each can be used individually or in mixture of 2 or more types.

According to an embodiment of the present invention, the content of the total colorant included in the green photosensitive resin of the present invention is 5 to 70% by weight, preferably 10 to 50% by weight, based on 100% by weight of the total solid content in the green photosensitive resin composition % may be included. If the total content of the colorant is less than the above range, the color separation ability of the formed pattern may be reduced, and if it exceeds the above range, lithography performance may be deteriorated to cause problems such as residues or non-development.

In the present invention, the solid content in the green photosensitive resin composition means the total content of the remaining components excluding all solvents included in the green photosensitive resin composition.

A green photosensitive resin composition according to an embodiment of the present invention includes an alkali-soluble resin; photopolymerizable compounds; photoinitiator; And solvent; may further include one or more selected from the group consisting of.

Alkali-soluble resin

The alkali-soluble resin is a condition for being soluble in the alkali developer used in the developing step of the color filter manufacturing step, and it may be preferable to use one having alkali solubility along with reactivity to light or heat.

According to one embodiment of the present invention, the alkali-soluble resin is a copolymer of a first monomer having an unsaturated bond and an epoxy group in a molecule and a second monomer having an unsaturated bond in a molecule, a third monomer having an unsaturated double bond and a carboxyl group, and a polybasic acid It may be an unsaturated group-containing resin formed by sequentially reacting with an anhydride.

Looking more specifically, the alkali-soluble resin is a polymerization step; unsaturated group addition step; and a reaction step with a polybasic acid anhydride.

The polymerization step is a step of forming a copolymer by polymerizing the first monomer and the second monomer.

Specifically, a solvent is introduced into a flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel, and a nitrogen introduction tube, and the atmosphere in the flask is replaced with nitrogen from air. After that, the solvent is heated to 40 ° C. to 140 ° C., and the first monomer, the second monomer, and the polymerization initiator are added and stirred and dissolved at room temperature or under heating. From the dropping funnel, over 0.1 to 8 hours from the flask It is dripped and stirred at 40 degreeC - 140 degreeC for 1 hour - 10 hours, and a copolymer is obtained.

The first monomer may be used without limitation as long as it is a compound having an unsaturated bond and an epoxy group in one molecule, and specifically, glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 3,4- Epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxytricyclodecan-8-yl (meth) acrylate and methyl glycidyl (meth) acrylate may be used alone or a mixture thereof there is. Preferably, glycidyl (meth) acrylate can be used.

The second monomer may be used without limitation as long as it is a compound having an unsaturated bond polymerizable with the first monomer, and specifically, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxy Unsubstituted or substituted alkyl ester compounds of unsaturated carboxylic acids such as oxyethyl (meth) acrylate and aminoethyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl ( Meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylate, menthyl (meth) acrylate, cyclopentenyl (meth) acrylate, cyclohexenyl (meth) acrylate, cycloheptenyl ( Meth) acrylate, cyclooctenyl (meth) acrylate, menthadienyl (meth) acrylate, isobornyl (meth) acrylate, pinanyl (meth) acrylate, adamantyl (meth) acrylate, nor Monosaturated carboxylic acids of glycols such as unsaturated carboxylic acid ester compounds containing alicyclic substituents such as bornyl (meth) acrylate and pinenyl (meth) acrylate, and oligoethylene glycol monoalkyl (meth) acrylate Unsaturated carboxylic acid ester compound containing a substituent having an aromatic ring, such as an ester compound, benzyl (meth) acrylate, phenoxy (meth) acrylate, rosin (meth) acrylate, styrene, α-methylstyrene, vinyltoluene Aromatic vinyl compounds, such as vinyl acetate, carboxylate vinyl esters, such as vinyl propionate, (meth)acrylonitrile, vinyl cyanide compounds, such as α-chloroacrylonitrile, N-cyclohexylmaleimide, N-phenylmaleimide It is possible to use alone or a mixture thereof selected from the group consisting of maleimide compounds such as

The solvent may be added in an amount of 0.5 to 20 parts by weight based on the content of the first monomer and the second monomer, and specifically, tetrahydrofuran, dioxane, ethylene glycol dimethyl ethyl, diethylene glycol dimethyl ethyl, acetone, methyl ethyl ketone , methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, propylene glycol monomethyl ethyl acetate, 3-methoxybutyl acetate, methanol, ethanol, propanol, n-butanol, ethylene glycol monomethyl ether, propylene glycol monomethyl It may be used alone or a mixture thereof selected from the group consisting of ether, toluene, xylene, ethylbenzene, chloroform and dimethyl sulfoxide, but is not limited thereto.

The polymerization initiator is diisopropylbenzene hydroperoxide, di-t-butyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, t-amylperoxy-2-ethyl hexanoate, t- organic peroxides such as butylperoxy-2-ethylhexanoate, and 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl -2,2'-Azobis(2-methylpropionate) may be used alone or a mixture thereof selected from the group consisting of nitrogen compounds, but is not limited thereto.

In order to control molecular weight or molecular weight distribution in the polymerization step, a chain transfer agent may be further included, and as the chain transfer agent, α-methylstyrene dimer or a mercapto compound may be used, but is not limited thereto.

The chain transfer agent may be included in an amount of 0.005 to 5 parts by weight based on the first and second monomers.

As for the polymerization conditions, those skilled in the art can arbitrarily adjust the input method or reaction temperature appropriately in consideration of the production equipment or the amount of heat generated by polymerization.

The step of adding the unsaturated group is a step of adding an unsaturated double bond to the copolymer by reacting the copolymer of the first monomer and the second monomer with the third monomer.

The third monomer for adding an unsaturated double bond may preferably be acrylic acid or methacrylic acid. The third monomer may be used in combination with an unsaturated carboxylic acid or a monomer containing a hydroxyl group and a carboxyl group. Specifically, while using acrylic acid or methacrylic acid as the third monomer, an unsaturated carboxylic acid or a monomer containing a hydroxyl group and a carboxyl group may be used in addition to this. The unsaturated carboxylic acid may be alone or a mixture thereof selected from the group consisting of crotonic acid, itaconic acid, maleic acid and fumaric acid, and specific examples of the monomer containing the hydroxyl group and the carboxyl group include α-(hydroxymethyl)acrylic acid. etc.

The reaction step with the polybasic acid anhydride is a step of reacting the copolymer with the third monomer and then further reacting with the polybasic acid anhydride. Specifically, after the copolymer obtained in the polymerization step is reacted with the third monomer, the polybasic acid anhydride is added thereto, and the reaction is performed by heating at 50°C to 150°C, preferably at 80°C to 130°C. It is not necessary to specifically add a catalyst in the above reaction step.

The polybasic acid anhydride is specifically, cohaxic anhydride, maleic anhydride, cytoraconic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, and It is possible to use either alone or a mixture thereof selected from the group consisting of pyromellitic anhydride and the like, and preferably tetrahydrophthalic anhydride and cohaxic anhydride.

In the alkali-soluble resin, the amount of the repeating unit derived from the first monomer may be 2 to 80 mol%, preferably 5 to 80 mol%, based on the entire resin, and the repeating unit obtained from the second monomer may be 2 to 90 mol%, Preferably, it may be 5 to 90 mol%. In addition, the third monomer may be reacted in an amount of 2 to 100 mol%, preferably 5 to 100 mol%, based on the epoxy equivalent of the first monomer, and the polybasic acid anhydride is used in the reaction of the first monomer and the third monomer. The reaction may be carried out in an amount of 2 to 100 mol%, preferably 5 to 100 mol%, based on the equivalent of the hydroxyl group produced by the The alkali-soluble resin having a repeating unit within the above range may have improved developability, solubility, heat resistance, and the like.

According to one embodiment of the present invention, the alkali-soluble resin has a polystyrene equivalent weight average molecular weight (hereinafter referred to as 'weight average molecular weight') measured by gel permeation chromatography (GPC; using tetrahydrofuran as an elution solvent) It may be 3,000 to 100,000, preferably 5,000 to 50,000. When the weight average molecular weight of the alkali-soluble resin is within the above range, the hardness of the coating film is improved, the residual film ratio is high, the solubility of the non-exposed part in the developer is excellent, and the resolution can be improved.

The molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the alkali-soluble resin may be 1.5 to 6.0, preferably 1.8 to 4.0. If the molecular weight distribution is 1.5 to 6.0, developability may be excellent.

The alkali-soluble resin may have an acid value of 30 to 180 (mgKOH/g). If the acid value is less than 30 (mgKOH/g), the developability to the developer is lowered and there is a risk of leaving a residue on the substrate. there is. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer, and can be usually obtained by titration using an aqueous potassium hydroxide solution.

The alkali-soluble resin may be included in an amount of 5 to 90 parts by weight, preferably 10 to 70% by weight, based on 100% by weight of the total solid content of the green photosensitive resin composition including the same. When the alkali-soluble resin is included in the above range, the solubility in the developer is sufficient, so that it is difficult to generate a developing residue on the substrate of the non-pixel part, and it is difficult to reduce the film of the pixel part of the exposed part during development, so that the non-pixel part is omitted This has the advantage that it can be good.

photopolymerization compound

The photopolymerizable compound is a compound that can be polymerized by the action of a photopolymerization initiator to be described later, and may use a monofunctional monomer, a bifunctional monomer, or other polyfunctional monomer, preferably a polyfunctional monomer having a bifunctional or higher function. .

Specific examples of the monofunctional monomer include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate or N-vinyl p Rollidone, and the like, but is not limited thereto.

Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and triethylene glycol di (meth) acrylate. , bis(acryloyloxyethyl)ether of bisphenol A, or 3-methylpentanediol di(meth)acrylate, but is not limited thereto.

Specific examples of the other polyfunctional monomer include trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, penta Erythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa ( Meth) acrylate or dipentaerythritol hexa (meth) acrylate, but is not limited thereto.

The photopolymerizable compound may be included in an amount of 5 to 45% by weight, preferably 7 to 45% by weight, based on 100% by weight of the total solid content of the green photosensitive resin composition including the same. When the photopolymerizable compound is included in the above range, the intensity or smoothness of the pixel portion may be improved.

light curing initiator

The photopolymerization initiator may be a compound that generates a radical capable of initiating polymerization of the above-described photopolymerizable compound by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, or X-ray.

According to an embodiment of the present invention, the photopolymerization initiator may include an oxime ester compound having an excellent degree of curing.

As the oxime ester compound, 1,2-octanedione,1-[4-(phenylthio)phenyl]-,2-(O-benzoyloxime) (1,2-octanedione,1-[4-(phenylthio) phenyl]-,2-(O-benzoyloxime)), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime) (1 -[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime)) , Igacure OXE 03, and the like. Since each oxime ester compound has various absorbances and generated radical species, it is preferable to use a mixture of two or more types.

The oxime ester compound may be included in an amount of 10 to 100% by weight, preferably 20 to 100% by weight, based on 100% by weight of the total photopolymerization initiator. When the oxime ester compound is included in an amount of less than 10% by weight, the sensitivity may be decreased due to the dye, and a short circuit of the pattern may easily occur during the developing process.

Moreover, photoinitiators other than an oxime ester compound can also be used together further. Specifically, it is preferable to use at least one compound selected from the group consisting of an acetophenone-based compound, a benzophenone-based compound, a triazine-based compound, a biimidazole-based compound, and a thioxanthone-based compound.

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1-[4-(2-hydroxyl) oxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one; 2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane-1 -one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, etc. are mentioned.

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

Specific examples of the triazine-based 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-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2- yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine , 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl )-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine etc. are mentioned.

Specific examples of the biimidazole-based compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3- Dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimi Dazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole, 2,2-bis(2,6-dichlorophenyl)-4 ,4',5,5'-tetraphenyl-1,2'-biimidazole or a biimidazole compound in which the phenyl group at the 4,4',5,5' position is substituted with a carboalkoxy group; there is. Among them, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4' ,5,5'-tetraphenylbiimidazole and 2,2-bis(2,6-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole are preferably used

Examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like. There is this.

In addition, the photopolymerization initiator may be used in combination with a photopolymerization initiator auxiliary in order to improve the sensitivity of the green photosensitive resin composition of the present invention. When the green photosensitive resin composition of this invention contains a photoinitiation adjuvant, a sensitivity further becomes high and it can improve productivity.

As the photopolymerization initiation adjuvant, for example, at least one compound selected from the group consisting of an amine compound, a carboxylic acid compound, and a polyfunctional thiol compound may be preferably used.

Examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine; 4-dimethylaminobenzoic acid methyl, 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid isoamyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N,N-dimethylparatoluidine, 4, Aromatic amine compounds such as 4'-bis(dimethylamino)benzophenone (common name: Michler's ketone) and 4,4'-bis(diethylamino)benzophenone can be used, and it is particularly preferable to use an aromatic amine compound. Do.

The carboxylic acid compound is preferably aromatic heteroacetic acid, specifically phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, and dimethoxyphenyl. Thioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc. are mentioned.

Examples of the polyfunctional thiol compound include tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, trimethylolpropane tris-3-mercaptopropionate), pentaerythritol tetrakis-3- mercaptopropionate), dipentaerythritol hexa-3-mercaptopropionate), and the like.

The photopolymerization initiator may be included in an amount of 0.1 to 40 parts by weight, preferably 1 to 30 parts by weight, based on 100 parts by weight of the total of the alkali-soluble resin and the photopolymerizable compound included together. When the photopolymerization initiator is included in the above range, it is preferable because the green photosensitive resin composition of the present invention is highly sensitive and the exposure time is shortened, so that productivity is improved and high resolution can be maintained. In addition, the strength and smoothness of the surface of the pixel portion formed by using the composition of the above-described conditions may be improved.

In addition, when the photopolymerization initiation adjuvant is further used, the photopolymerization initiation adjuvant is in an amount of 0.1 to 40 parts by weight, preferably 1 to 30 parts by weight, based on 100 parts by weight of the total of the alkali-soluble resin and the photopolymerizable compound included together. may be included as When the photopolymerization initiation adjuvant is included in the above range, the sensitivity of the green photosensitive resin composition may be increased, and productivity of a color filter formed using the composition may be improved.

solvent

The solvent is preferably propylene glycol monomethyl ether acetate, but as long as it is effective in dissolving other components included in the green photosensitive resin composition, the solvent used in the conventional green photosensitive resin composition is not particularly limited and may be additionally used. In particular, ethers, aromatic hydrocarbons, ketones, alcohols, esters or amides are preferable.

The solvent is specifically ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, di Ethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether and ethers such as dipropylene glycol dibutyl ether; aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin; 3-ethyl 3-ethoxypropionate, 3-methoxymethyl propionate, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, butyl lactate, 3-methyl Toxybutyl acetate, 3-methyl-3-methoxy-1-butyl acetate, methoxypentyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol Esters such as monoacetate, diethylene glycol diacetate, diethylene glycol monobutyl ether acetate, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monoethyl ether acetate, ethylene carbonate, propylene carbonate and γ-butyrolactone, etc. can be heard Each of the solvents may be used alone or in combination of two or more.

The solvent may be included in an amount of 60 to 90% by weight, preferably 70 to 87% by weight, based on 100% by weight of the total green photosensitive resin composition including the solvent. When the solvent is included in the above range, the coating property may be improved when applied with an application device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater), or an inkjet.

additive

The green photosensitive resin composition of the present invention may contain additives such as fillers, other polymer compounds, curing agents, adhesion promoters, ultraviolet absorbers, and anti-aggregation agents according to the needs of those skilled in the art in the range that does not impair the purpose of the present invention in addition to the above-mentioned components. may be

Specifically, the filler may be glass, silica, alumina, or the like, but is not limited thereto.

Specific examples of the other high molecular compounds include curable resins such as epoxy resins and maleimide resins, and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane. However, the present invention is not limited thereto.

The curing agent is used for deep curing and increasing mechanical strength, and specifically, an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, an oxetane compound, etc. may be used, but the present invention is not limited thereto. Specifically, the epoxy compound is a bisphenol A-based epoxy resin, a hydrogenated bisphenol A-based epoxy resin, a bisphenol F-based epoxy resin, a hydrogenated bisphenol F-based epoxy resin, a novolak-type epoxy resin, other aromatic epoxy resins, alicyclic epoxy resins, Glycidyl ester-based resins, glycidylamine-based resins, or brominated derivatives of these epoxy resins, aliphatic, alicyclic or aromatic epoxy compounds other than epoxy resins and brominated derivatives thereof, butadiene (co)polymer epoxide, isoprene (co) ) Polymer epoxide, glycidyl (meth) acrylate (co) polymer, triglycidyl isocyanurate, etc. may be used, but is not limited thereto. Specifically, the oxetane compound may include carbonate bisoxetane, xylenebisoxetane, adipate bisoxetane, terephthalate bisoxetane, cyclohexanedicarboxylic acid bisoxetane, and the like, but is limited thereto. it is not

The curing agent may be used 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 together with the curing agent. Specifically, as the curing auxiliary compound, polyhydric carboxylic acids, polyhydric carboxylic acid anhydrides, acid generators, and the like may be used. As the carboxylic acid anhydride, a commercially available epoxy resin curing agent may be used. The commercially available epoxy resin curing agent includes, for example, a trade name (Adecahadona EH-700) (manufactured by Adeka Industrial Co., Ltd.), a trade name (Rikasiddo HH) (manufactured by Shin-Nippon Ewha Co., Ltd.), trade name (MH-700) (manufactured by Nippon Ewha Co., Ltd.); and the like.

The curing agent and curing auxiliary compound exemplified above may be used alone or in combination of two or more.

The adhesion promoter is specifically, vinyltrimethoxysilane, vinyltriethoxysilane, vinyl tris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N -(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltri One or a mixture thereof selected from the group consisting of methoxysilane, 3-isocyanatepropyltrimethoxysilane and 3-isocyanatepropyltriethoxysilane may be used.

The adhesion promoter may be included in an amount of 0.01 to 10 wt%, preferably 0.05 to 2 wt%, based on 100 wt% of the total solid content in the green photosensitive resin composition.

Specifically, the ultraviolet absorber may be 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, alkoxybenzophenone, or the like, but is not limited thereto.

The aggregation inhibitor may be specifically sodium polyacrylate, but is not limited thereto.

The method for preparing the green photosensitive resin composition in the present invention is not particularly limited, and the manufacturing method used in the art may be used without limitation, but an example thereof is as follows.

First, the pigment among the colorants is mixed with a solvent and dispersed using a bead mill or the like until the average particle diameter of the pigment is about 0.2 μm or less. In this case, if necessary, a pigment dispersant, a part or all of the alkali-soluble resin, or a dye may be mixed with a solvent to be dissolved or dispersed. The green photosensitive resin composition according to the present invention can be prepared by adding the remainder of the alkali-soluble resin, a photopolymerization initiator, and a photopolymerizable compound to the mixed dispersion, and further adding additives and solvents to a predetermined concentration if necessary. It is not limited.

<Color filter>

Another aspect of the present invention relates to a color filter that includes a cured product of the above-described green photosensitive resin composition, thereby enabling high color reproduction due to high transmittance and preventing the occurrence of an afterimage due to liquid crystal contamination due to ion elution.

The color filter includes a green pattern made of a cured product of a green photosensitive resin composition, and the green pattern is formed by applying the above-described photosensitive resin composition on a substrate, and exposing and developing the photosensitive resin composition in a predetermined pattern. Cargo may be included. The substrate is a transparent material, and a material having sufficient strength and support for the stability of the color filter may be used. Preferably, glass having excellent chemical stability and high strength may be used, but is not limited thereto.

A method of forming a pattern using the green photosensitive resin composition of the present invention may use a method known in the art, but typically a coating step; exposure step; and a removing step. By coating the green photosensitive resin composition of the present invention on a substrate, photocuring and developing to form a pattern, it can be used as a green pixel (green image).

Specifically, the green photosensitive resin composition of the present invention is applied to an uncoated glass substrate and a glass substrate on which SiNx (protective film) is applied to a thickness of 500 to 1,500 Å using a suitable method such as spin coating or slit coating, It is applied to a thickness of 2.0 to 3.4 μm. After application, light is irradiated to form a pattern required for the color filter. After irradiating the light, if the coating layer is treated with an alkali developer, the unirradiated portion of the coating layer is dissolved and a pattern required for the color filter is formed. By repeating this process according to the required number of R, G, and B colors, a color filter having a desired pattern can be obtained. Further, in the above process, crack resistance, solvent resistance, and the like can be further improved by heating the image pattern obtained by development again or curing it by irradiation with actinic rays or the like.

image display device

Another aspect of the present invention relates to a color filter in which high color reproduction is possible due to high transmittance by including the above-described color filter and generation of an afterimage due to liquid crystal contamination caused by ion elution is prevented.

Specifically, the image display device may include other components that can be typically included in an image display device, such as a light emitting device such as a light source, a light guide plate, and a liquid crystal display including a color filter according to the present invention. It does not limit this.

The image display device includes, for example, not only a liquid crystal display device (LCD), but also various images such as an electroluminescence display device (EL), a plasma display device (PDP), a field emission display device (FED), an organic light emitting device (OLED), etc. a display device, but is not limited thereto.

In addition, the image display device of the present invention includes, if necessary, a red pattern layer containing red quantum dot particles, a green pattern layer containing green quantum dot particles, and a blue pattern layer containing blue quantum dot particles in addition to the color filter described above. A color filter may be additionally provided. In such a case, the emitted light of the light source applied to the image display apparatus is not particularly limited, but a light source emitting blue light may be preferably used in terms of superior color reproducibility.

The image display device may further include a color filter including only two color pattern layers among a red pattern layer, a green pattern layer, and a blue pattern layer in addition to the color filter described above. In such a case, the color filter may further include a transparent pattern layer that does not contain quantum dot particles. As such, when only the pattern layers of two colors are provided, a light source emitting light of a wavelength representing the remaining colors that is not included may be used. For example, when only the red pattern layer and the green pattern layer are included, a light source emitting blue light may be used. In such a case, the red quantum dot particles emit red light, the green quantum dot particles emit green light, and the transparent pattern layer transmits the blue light as it is to display blue color.

Hereinafter, preferred examples are presented to help the understanding of the present invention, but the following examples are merely illustrative of the present invention, and it will be apparent to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present invention. , it is natural that such variations and modifications fall within the scope of the appended claims. In the following Examples and Comparative Examples, "%" and "part" indicating the content are by weight unless otherwise specified.

Synthesis Example: Synthesis of alkali-soluble resin

Synthesis Example 1.

182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel and a nitrogen introduction tube, the atmosphere in the flask was replaced with nitrogen, and the temperature was raised to 80 ° C. A solution in which 3.6 g of azobisisobutyronitrile was added to a mixture containing 82.5 g (0.6 mol) of acrylate, 35.40 g (0.4 mol) of vinyltoluene and 136 g of propylene glycol monomethyl ether acetate was added from the dropping funnel over 2 hours. It was dripped at the flask and stirring was continued at 80 degreeC for 5 more hours. Next, the atmosphere in the flask was changed from nitrogen to air, and 43.2 g of acrylic acid [0.6 mol (100 mol% with respect to the epoxy group of glycidyl methacrylate used in this reaction)], 0.9 g of trisdimethylaminomethylphenol and 0.145 g of hydroquinone was put into the flask and the reaction was continued at 110°C for 4 hours, then 45.6 g (0.3 mol) of THPA (tetrahydrophthalic anhydride) was added, and then the reaction was continued at 110°C for 2 hours, and the solid content acid value Alkaline-soluble resin B-1 of 100 mgKOH/g was obtained.

The weight average molecular weight in terms of polystyrene measured by GPC was 17,000, and molecular weight distribution (Mw/Mn) was 2.3.

Synthesis Example 2.

A flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel and a nitrogen introduction tube was prepared, and on the other hand, as a monomer dropping funnel, benzyl methacrylate 176 g (1.00 mole), methacrylic acid 35.4 g (0.30 mole), vinyl 82.6 g (0.70 mol) of toluene, 4 g of t-butylperoxy-2-ethylhexanoate, and 40 g of propylene glycol monomethyl ether acetate were added and stirred and mixed, and 6 g of n-dodecanthiol as a chain transfer agent dropping tank , PGMEA 24g was added and stirred and mixed. Then, 395 g of propylene glycol monomethyl ether acetate was introduced into the flask, the atmosphere in the flask was changed from air to nitrogen, and the temperature of the flask was raised to 90° C. while stirring. Then, the monomer and the chain transfer agent were started dripping from the dropping lot. The dropping was carried out for 2 hours while maintaining 90° C., and after 1 hour, the temperature was raised to 110° C. and the reaction proceeded for 8 hours to obtain alkali-soluble resin B-2 having a solid content acid value of 70 mgKOH/g. The polystyrene conversion weight average molecular weight measured by GPC was 21,000, and molecular weight distribution (Mw/Mn) was 2.2.

Examples and Comparative Examples: Preparation of green photosensitive resin composition

The green photosensitive resin composition of Examples satisfying the conditions of the present invention was prepared with the composition and content of Table 1 below, and the green photosensitive resin composition of the Comparative Example that did not satisfy the conditions of the present invention with the composition and content of Table 2 below was prepared. .

(Unit: % by weight) coloring agent Alkali-soluble resin photopolymerizable compound photopolymerization initiator solvent additive A-1 A-2 A-3 A-4 A-5 A-6 A-7 A-8 B-1 C D E F-1 F-2 Example 1 2.4 - 0.6 - 3.0 - - - 6.5 3.5 0.6 76.7 6.6 0.1 Example 2 1.7 - 1.7 - 2.6 - - - 6.5 3.5 0.6 76.7 6.6 0.1 Example 3 0.8 - 3.2 - 2.0 - - - 6.5 3.5 0.6 76.7 6.6 0.1 Example 4 2.1 - - 0.6 3.3 - - - 6.5 3.5 0.6 76.7 6.6 0.1 Example 5 - 2.4 0.6 - 3.0 - - - 6.5 3.5 0.6 76.7 6.6 0.1 Example 6 - 1.7 1.7 - 2.6 - - - 6.5 3.5 0.6 76.7 6.6 0.1 Example 7 - 0.8 3.2 - 2.0 - - - 6.5 3.5 0.6 76.7 6.6 0.1 Example 8 - 2.1 - 0.6 3.3 - - - 6.5 3.5 0.6 76.7 6.6 0.1 Example 9 - 1.3 - 1.3 3.4 - - - 6.5 3.5 0.6 76.7 6.6 0.1 Example 10 - 2.4 0.6 - 2.7 - 0.3 - 6.5 3.5 0.6 76.7 6.6 0.1 Example 11 - 2.7 0.7 - 2.3 - - 0.3 6.5 3.5 0.6 76.7 6.6 0.1 Example 12 2.5 - - 0.7 - 2.8 - - 6.5 3.5 0.6 76.7 6.6 0.1 Example 13 1.6 - - 1.6 - 2.8 - - 6.5 3.5 0.6 76.7 6.6 0.1 Example 14 0.6 - - 2.4 - 3.0 - - 6.5 3.5 0.6 76.7 6.6 0.1 Example 15 - 2.6 - 0.7 - 2.7 - - 6.5 3.5 0.6 76.7 6.6 0.1 Example 16 - 1.6 - 1.6 - 2.8 - - 6.5 3.5 0.6 76.7 6.6 0.1 Example 17 - 0.7 - 2.4 - 2.9 - - 6.5 3.5 0.6 76.7 6.6 0.1 Example 18 - 2.6 - 0.7 - 2.4 0.3 - 6.5 3.5 0.6 76.7 6.6 0.1 Example 19 - 2.7 - 0.7 - 2.3 - 0.3 6.5 3.5 0.6 76.7 6.6 0.1 A-1: CI Pigment Green 62
A-2: CI Pigment Green 63
A-3: CI Pigment Green 58
A-4: CI Pigment Green 59
A-5: CI Pigment Yellow 138
A-6: CI Pigment Yellow 231
A-7: CI Pigment Yellow 150
A-8: CI Pigment Yellow 185
B-1: Alkali-soluble resin of Synthesis Example 1
C: dipentaerythritol hexaacrylate (KAYARAD DPHA, Kayaku, Japan)
D: IRGACURE OXE01 (Chiba Specialty Chemicals)
E: propylene glycol methyl ether acetate
F-1: BYK2001 (solid content concentration: 45.1%, BYK)
F-2: SH-8400 (Dow Corning Toray)

(Unit: % by weight) coloring agent Alkali-soluble resin photopolymerizable compound photopolymerization initiator solvent additive A-1 A-2 A-3 A-4 A-5 A-6 B-1 B-2 C D E F-1 F-2 Comparative Example 1 2.8 - - - 3.3 - 6.4 - 3.5 0.6 76.7 6.6 0.1 Comparative Example 2 - 2.7 - - 3.3 - 6.5 - 3.5 0.6 76.7 6.6 0.1 Comparative Example 3 - 2.7 0.1 - 3.2 - 6.5 - 3.5 0.6 76.7 6.6 0.1 Comparative Example 4 - 0.2 4.3 - 1.5 - 6.5 - 3.5 0.6 76.7 6.6 0.1 Comparative Example 5 - - 4.6 - 1.4 - 6.5 - 3.5 0.6 76.7 6.6 0.1 Comparative Example 6 - - - 2.1 2.6 - 6.5 - 3.5 0.6 76.7 6.6 0.1 Comparative Example 7 3.3 - - - - 2.7 6.5 - 3.5 0.6 76.7 6.6 0.1 Comparative Example 8 - 3.3 - - - 2.7 6.5 - 3.5 0.6 76.7 6.6 0.1 Comparative Example 9 - 3.1 - 0.2 - 2.7 6.5 - 3.5 0.6 76.7 6.6 0.1 Comparative Example 10 - 0.2 - 2.9 - 2.9 6.5 - 3.5 0.6 76.7 6.6 0.1 Comparative Example 11 - - - 3.1 - 2.9 6.5 - 3.5 0.6 76.7 6.6 0.1 A-1: CI Pigment Green 62
A-2: CI Pigment Green 63
A-3: CI Pigment Green 58
A-4: CI Pigment Green 59
A-5: CI Pigment Yellow 138
A-6: CI Pigment Yellow 231
B-1: Alkali-soluble resin of Synthesis Example 1
B-2: Alkali-soluble resin of Synthesis Example 2
C: dipentaerythritol hexaacrylate (KAYARAD DPHA, Kayaku, Japan)
D: IRGACURE OXE01 (Chiba Specialty Chemicals)
E: propylene glycol methyl ether acetate
F-1: BYK2001 (solid content concentration: 45.1%, BYK)
F-2: SH-8400 (Dow Corning Toray)

production example : Manufacture of color filters

A 2-square-inch glass substrate (manufactured by Corning, #1737) was washed with a neutral detergent, water and alcohol, and then dried. Each of the green photosensitive resin compositions prepared in Examples and Comparative Examples was coated on this glass substrate and exposed at an exposure dose (365 nm) of 50 mJ/cm 2 so that the film thickness after firing when the development step was omitted was 2.6 It was spin-coated so that it might become micrometer, and it was then pre-dried in a clean oven at 100 degreeC for 3 minutes. After that, it is cooled to room temperature, and each green photosensitive resin composition is coated on the substrate and the quartz glass photomask (patterns that change the transmittance in steps in the range of 1 to 100% and lines/spaces from 1 µm to 50 µm) pattern) was set to 100 µm, and an ultra-high pressure mercury lamp (trade name: USH-250D) manufactured by Ushio Electric Co., Ltd. was used to irradiate light with an exposure dose (365 nm) of 50 mJ/cm 2 in an atmospheric atmosphere.

The thin film irradiated with ultraviolet light was developed by immersing it in a developing solution of an aqueous KOH solution having a pH of 10.5 for 2 minutes. The thin film-coated substrate was washed with distilled water, dried by blowing nitrogen gas, and dried at 220° C. for 30 minutes to prepare a color filter.

Experimental example One: color coordinates Measure

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

In Table 3 below, Examples and Comparative Examples of the present invention were adjusted to have different color coordinates in two groups, and the same color coordinates of Examples and Comparative Examples included in each group were produced in other experiments (especially in luminance or afterimage). evaluation) in order to equally control the experimental conditions that may affect the experimental results. To this end, by including a yellow pigment in addition to the green pigment, the color coordinates could be adjusted according to the conditions of each group.

Experimental example 2: Luminance measurement

The luminance of each color filter manufactured in the above Preparation Example was measured using a microscopic spectrometer OSP-SP2000, and the standard (Comparative Example 1 and Comparative Example 5) was determined for each color coordinate group, and the amount of luminance change therefrom was calculated in %. The results are shown in Table 3 below.

Experimental example 3: Afterimage evaluation

A measurement specimen was prepared in the following manner using the green photosensitive resin composition prepared in Examples and Comparative Examples.

A 25 cm 2 glass substrate (manufactured by Corning, #1737) was sequentially washed with a neutral detergent, water and alcohol, and then dried. The colored photosensitive resin compositions prepared in Examples and Comparative Examples were spin-coated on the substrate so that the film thickness after firing was 3.0±0.5 μm, and then pre-dried in a clean oven at 100° C. for 3 minutes. After cooling, the interval between the substrate coated with this colored photosensitive resin composition and a quartz glass photomask (exposed portion 30 mm × 30 mm) was set to 100 μm, and an ultra-high pressure mercury lamp (trade name USH-250D) manufactured by Ushio Denki Co., Ltd. was used to wait. It was irradiated with light at an exposure dose (365 nm) of 100 mJ/cm 2 in an atmosphere. Thereafter, the coating film was developed by immersing the coating film in an aqueous developer solution containing 0.12% of a nonionic surfactant and 0.06% of potassium hydroxide at 26°C for a predetermined time, and then washing with water in a heating oven at 200°C for 60 minutes to heat the colored layer. has formed The coating film of the colored substrate made through the above method was immersed in VA liquid crystal at a concentration of 0.5%, and then left in a clean oven at 110° C. for 24 hours. A liquid crystal sample from which impurities were removed was prepared by filtering the left sample with a 0.05 μm syringe filter. The prepared liquid crystal sample was injected into the cleaned VHR Cell (E.H.C Co., Ltd., trade name: KSRT-05/B111N/NTS05X) through the Keplery injection method. After the injection was completed, the VHR cell was sealed with a UV sealant, and an indium electrode was deposited and left for 24 hours to prepare a VHR specimen.

After leaving the VHR specimen obtained through the above method in a clean oven at 60° C. for 30 minutes, measurement was performed at an applied voltage of 1V using a VHR measuring device (TOYO Corporation Model 6254). After measuring through the above measurement method, the results were evaluated according to the following evaluation criteria, and the results are shown in Table 3 below.

<Evaluation criteria>

When the initial applied voltage of 1V passes through the liquid crystal contaminated by the green colored layer, when measured with the initial applied voltage of 1V is 100%. If only 0.9V is measured, it is displayed as 90%.

○ : VHR measurement ≥ 90%

△ : 80% ≤ VHR measurement < 90%

× : VHR measurement < 80%

Experimental example 4: Chemical resistance evaluation

A color filter was manufactured in the same manner as in Preparation Example except that a test photomask was not used when manufacturing the color filter in Preparation Example. After immersing the prepared color filter in an NMP (N-Methyl-2-pyrolidone) solution at 23° C. for 30 minutes, the color coordinates before and after immersion were measured, and then the color difference was calculated according to the following Equation 1 according to the following evaluation criteria Chemical resistance was evaluated.

[Equation 1]

(In Equation 1 above,

L ₁ ^* , a ₁ ^* , b ₁ ^* are color coordinates before immersion,

L ₂ ^* , a ₂ ^* , b ₂ ^* are the color coordinates after immersion.)

<Evaluation criteria>

○: The value of △E*ab is 3 or less

△: The numerical value of △E*ab is greater than 3 and less than or equal to 5

×: The numerical value of ΔE*ab exceeds 5

　
　 luminance afterimage evaluation chemical resistance Gx=0.255,
Gy=0.580 Example 1 58.2 104.1% ○ ○ Example 2 57.6 103.0% ○ ○ Example 3 57.1 102.1% ○ ○ Example 4 58.0 103.8% ○ ○ Example 5 58.3 104.3% ○ ○ Example 6 57.8 103.4% ○ ○ Example 7 57.1 102.1% ○ ○ Example 8 58.0 103.8% ○ ○ Example 9 57.3 102.5% ○ ○ Example 10 57.7 103.2% ○ ○ Example 11 57.5 102.9% ○ ○ Comparative Example 1 58.3 104.3% × △ Comparative Example 2 58.4 104.5% × △ Comparative Example 3 58.2 104.1% × △ Comparative Example 4 56.4 100.9% △ ○ Comparative Example 5 55.9 STD ○ ○ Comparative Example 6 55.5 99.3% ○ ○ Gx=0.255,
Gy=0.620 Example 12 53.2 104.5% ○ ○ Example 13 52.6 103.3% ○ ○ Example 14 52.0 102.2% ○ ○ Example 15 53.3 104.7% ○ ○ Example 16 52.6 103.3% ○ ○ Example 17 52.0 102.2% ○ ○ Example 18 53.0 104.1% ○ ○ Example 19 52.9 103.9% ○ ○ Comparative Example 7 53.4 104.9% × △ Comparative Example 8 53.4 104.9% × △ Comparative Example 9 53.3 104.7% △ △ Comparative Example 10 51.3 100.8% ○ ○ Comparative Example 11 50.9 STD ○ ○

Referring to Table 3, in the case of Examples 1 to 19 satisfying the conditions of the present invention within each same color coordinate group, the luminance is superior to those of Comparative Examples 1 to 11 which do not satisfy the conditions of the present invention, as well as the residue It was confirmed that no residue was left and the chemical resistance was also excellent.

Specifically, when only the aluminum phthalocyanine compound is included (Comparative Examples 1, 2, 7 and 8) and when the aluminum phthalocyanine compound is included more than the content ratio presented in the present invention (Comparative Example 3 and Comparative Example 9), the residue is It was confirmed that the chemical resistance was not good, and when only the compound of Formula 1 was included (Comparative Examples 5, 6 and 11) and when the compound of Formula 1 was included more than the content ratio presented in the present invention (Comparative Example) 4 and 10), it was confirmed that high color reproduction was difficult due to poor luminance.

Claims (13)

A colorant containing a green pigment having a weight ratio of the compound represented by the following Chemical Formula 1 to the aluminum phthalocyanine compound is 30:70 to 70:30,
The aluminum phthalocyanine compound includes CI Pigment Green 62 or CI Pigment Green 63,
The compound represented by Formula 1 is a green photosensitive resin composition comprising CI Pigment Green 58 or CI Pigment Green 59:
[Formula 1]

(In Formula 1,
The A ₁ to A ₁₆ are each independently hydrogen, bromine, or chlorine,
Among A ₁ to A ₁₆ , hydrogen is 1 to 6, chlorine is 0 to 5, and bromine is 5 to 13). The method of claim 1,
The aluminum phthalocyanine compound is a green photosensitive resin composition comprising a compound represented by the following Chemical Formula 2 or Chemical Formula 3:
[Formula 2]

(In Formula 2,
R ¹ to R ¹⁶ are each independently hydrogen, a halogen atom, a nitro group, a substitutable phthalimidemethyl group, a substitutable sulfamoyl group, a C1 to C18 substitutable alkyl group, a C6 to C14 substitutable aryl group, C5 to C10 of a substitutable cycloalkyl group, a C5 to C14 heterocyclic group, a C1 to C18 substitutable alkoxy group, a C6 to C14 substitutable aryloxy group, a C1 to C18 substitutable alkylthio group, or a C6 to C14 substitutable aryl group It's Tigi,
Z is -OP(=O)X ₁ X ₂ ,
wherein X ₁ and X ₂ are each independently hydrogen, a hydroxyl group, a C1 to C18 substitutable alkyl group, a C6 to C14 substitutable aryl group, a C1 to C18 substitutable alkoxy group, or a C6 to C14 substitutable aryloxy group, ,
X ₁ and X ₂ may form a heterocycle together with the bonded phosphorus atom)
[Formula 3]

(In Formula 3,
wherein R ¹⁷ to R ³² are each independently hydrogen, a halogen atom, a nitro group, a substitutable phthalimidemethyl group, a substitutable sulfamoyl group, a C1 to C18 substitutable alkyl group, a C6 to C14 substitutable aryl group, C5 to C10 substitutable cycloalkyl group, C5 to C14 heterocyclic group, C1 to C18 substitutable alkoxy group, C6 to C14 substitutable aryloxy group, C1 to C18 substitutable alkylthio group or C6 to C14 substitutable an arylthio group,
The L is

or

is,
In this case, X ₃ to X ₇ are each independently a C1 to C18 substitutable alkyl group or a C6 to C14 substitutable aryl group). delete delete The method of claim 1,
The green photosensitive resin composition is an alkali-soluble resin; photopolymerizable compounds; photoinitiator; And solvent; Green photosensitive resin composition, characterized in that it further comprises one or more selected from the group consisting of. 6. The method of claim 5,
The alkali-soluble resin is a copolymer of a first monomer having an unsaturated bond and an epoxy group and a second monomer having an unsaturated bond; a third monomer having an unsaturated double bond and a carboxyl group; And polybasic acid anhydride; Green photosensitive resin composition, characterized in that obtained by reacting sequentially. The green photosensitive resin composition according to claim 5, wherein the alkali-soluble resin has a weight average molecular weight of 3,000 to 100,000. The method of claim 1,
The colorant is a green photosensitive resin composition, characterized in that it further comprises one or more pigments or dyes. 9. The method of claim 8,
The pigment includes at least one selected from the group consisting of CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 129, CI Pigment Yellow 150, CI Pigment Yellow 231 and CI Pigment Yellow 185 A green photosensitive resin composition characterized in that. The method of claim 1,
The colorant is a green photosensitive resin composition, characterized in that it is contained in an amount of 5 to 70% by weight based on 100% by weight of the total solid content of the green photosensitive resin composition including the same. 6. The method of claim 5,
The photopolymerization initiator is a green photosensitive resin composition comprising an oxime-based compound. A color filter comprising the cured product of the green photosensitive resin composition according to any one of claims 1 to 2 and 5 to 11. An image display device comprising the color filter of claim 12 .