KR20130001938A - Colored photosensitive resin composition for color filter - Google Patents

Abstract

PURPOSE: A green photosensitive resin composition for color filters is provided to be effectively used for color filter manufacturing of liquid crystal display devices for light emitting diode type backlights. CONSTITUTION: A green photosensitive resin composition for color filters comprises a compound represented by chemical formula 1. In the chemical formula 1, Z indicates substituents represented by a halogen atom, an aliphatic group, an aryl group, a heterocyclic group, a cyano group, a carboxyl group, a carbamoyl, an aliphatic family oxycarbonyl group, an aryloxy carbonyl group, an acyl group, a hydroxy group, an aliphatic family oxy group, an aryloxy group, an acyloxy group, a carbamoyloxy group, a heterocyclic oxy group, an aliphatic family oxycarbonyl oxy group, an N- alkylacyl amino group, a carbamoyl amino group, a sulfamoyl amino group, an aliphatic family oxycarbonylamino group, an aryloxycarbonylamino-group, an aliphatic family sulfonylamino group, an arylsulfonylamino group, an aliphatic family thio group, an arylthio group, an aliphatic family sulfonyl group, an allylsulfone group, a sulfamoyl group, a sulfo group, an imide group, a heterocyclic thio, a nitro group, -OR1, -COR1, -COOR1, or NR1R2.

Description

Colored photosensitive resin composition for color filters {COLORED PHOTOSENSITIVE RESIN COMPOSITION FOR COLOR FILTER}

The present invention relates to a color filter coloring agent and a colored photosensitive resin composition having excellent transparency.

Color filters used in liquid crystal displays are manufactured by forming patterns of three primary colors, that is, red, green, and blue, on a glass substrate. The process of manufacturing a color pattern comprises the steps of uniformly applying a photosensitive coloring composition containing a colorant corresponding to each color pixel on a substrate, heat-drying the applied composition to form a film And developing the dried film using a mask having a desired shape and then developing the dried film, and curing the heated film by heating.

It is common to mainly use a pigment as a coloring agent of the photosensitive resin composition.

In particular, a coloring photosensitive resin composition using various phthalocyanine compounds as a pigment for green has been proposed.

Specific examples of green pigments include copper chloride phthalocyanine pigment CI pigment green 7 (hereinafter PG7) and copper bromide phthalocyanine pigment CI pigment 36 (hereinafter PG36), and zinc bromide phthalocyanine pigment CI pigment 58 (hereinafter PG58). It is proposed.

As the green pigment, one or two or more phthalocyanine-based compounds selected from the group consisting of phthalocyanine-based compounds having no central metal and phthalocyanine-based compounds including metals other than copper may be used. As the center metal other than copper, Mg, Al, Si, Ti, V, Mn, Fe, Co, Ni, Zn, Ge, and Sn may be used.

The green pigments exhibit high transparency and color clarity, but are insufficient to meet the demand for high transparency recently.

Therefore, the use of the dye excellent in transparency and color clarity as a coloring agent for color filters instead of a pigment was examined. However, dyes are not used due to low thermal stability and light stability due to the problem of decomposition or discoloration in the step of heating and curing the film during the color filter manufacturing process.

Therefore, the objective of this invention is providing the coloring photosensitive resin composition for color filters containing the coloring agent which has high transparency.

In order to achieve the above object, the present invention provides a colored photosensitive resin composition comprising a compound represented by the following formula (1) as a coloring agent.

That is, this invention relates to the coloring agent for color filters containing an aluminum phthalocyanine type compound.

Z is a halogen atom, aliphatic group, aryl group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, aliphatic oxycarbonyl group, aryloxycarbonyl group, acyl group, hydroxy group, aliphatic oxy group, aryloxy group, acyloxy group, carba Moyloxy group, heterocyclic oxy group, aliphatic oxycarbonyloxy group, N-alkylacylamino group, carbamoylamino group, sulfamoylamino group, aliphatic oxycarbonylamino group, aryloxycarbonylamino group, aliphatic sulfonylamino group, arylsulfonyl Substituent represented by amino group, aliphatic thio group, arylthio group, aliphatic sulfonyl group, arylsulfonyl group, sulfamoyl group, sulfo group, imide group, heterocyclic thi group, nitro group, -OR1, -COR1, -COOR1 or NR1R2 ,

Wherein, R1 and R2 are each independently a hydrogen atom, C _{1 -20} alkyl, C _{3 -6} cycloalkyl group, C _{6 -18} aryl group;

n is an integer from 0 to 16;

M is Si or Ge as the center metal;

X and Y each independently represent a substituent represented by the following formulas a to h;

(A)

[Formula b]

[Formula c]

[Chemical formula d]

(E)

[Formula f]

[Formula g]

[Formula h]

R3 to R8 in Formulas a to h are each independently a hydrogen atom, a halogen atom, an aliphatic group, an aryl group, a heterocyclic group, a cyano group, a carboxyl group, a carbamoyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, an acyl group, a hydroxyl group, Aliphatic oxy group, aryloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, aliphatic oxycarbonyloxy group, N-alkylacylamino group, carbamoylamino group, sulfamoylamino group, aliphatic oxycarbonylamino group, Aryloxycarbonylamino group, aliphatic sulfonylamino group, arylsulfonylamino group, aliphatic thio group, arylthio group, aliphatic sulfonyl group, arylsulfonyl group, sulfamoyl group, sulfo group, imide group or heterocyclic thio group, and Z is It represents an oxygen atom or a sulfur atom.

The aliphatic and aliphatic groups may be linear, branched, or cyclic and may be either saturated or unsaturated. The aliphatic may include, for example, an alkyl group, an alkenyl group, a cycloalkyl group or a cycloalkenyl group, and may be substituted or unsubstituted. The aliphatic group is preferably an aliphatic group having 1 to 15 carbon atoms in total, for example, methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, isopropyl, isobutyl, sec-butyl, tert-butyl group, 1-ethylpentyl group, trifluoromethyl group, cyclopentyl group, cyclohexyl group, vinyl group, allyl group, ethynyl group, isopropenyl group, 2-ethylhexyl group, etc. are mentioned.

The aryl may be monocyclic and condensed, and may be substituted or unsubstituted.

The aryl group may be substituted or unsubstituted, preferably an aryl group having 6 to 16 carbon atoms in total, and more preferably an aryl group having 6 to 12 carbon atoms in total. For example, a phenyl group, 4-nitrophenyl group, 2-nitrophenyl group, 2-chlorophenyl group, 2,4-dichlorophenyl group, 2,4-dimethylphenyl group, 2-methylphenyl group, 4-methoxyphenyl group, 2-methoxyphenyl group, 2-methoxycarbonyl-4-nitrophenyl group biphenyl group, o-, m-, and p- xylene group, naphthalene group, anthracene group, etc. are mentioned.

The heterocyclic ring and the heterocyclic group have a hetero atom (eg, nitrogen atom, sulfur atom, oxygen atom) in the ring, and may be a saturated ring or an unsaturated ring. The heterocyclic ring may be a monocyclic ring or a condensed ring, and may be substituted or unsubstituted. The heterocyclic group is preferably a heterocyclic group having 1 to 15 carbon atoms in total, and more preferably a heterocyclic group having 3 to 10 carbon atoms in total, and for example, 3-pyridyl group, 2-pyridyl group, 2-pyrimidinyl group, and 2-pyrady. And a 1-piperidyl group. It may also have additional substituents.

The substituent refers to a substitutable group.

As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, etc. are mentioned.

The carbamoyl group may be substituted or unsubstituted. The carbamoyl group is preferably a carbamoyl group having 1 to 16 carbon atoms, more preferably a carbamoyl group having 1 to 12 carbon atoms, and for example, a carbamoyl group, a dimethylcarbamoyl group, or a dimethoxyethyl carbamoyl group. Can be mentioned.

The aliphatic oxycarbonyl group may be substituted or unsubstituted. The aliphatic oxycarbonyl group may be saturated or unsaturated, or may be cyclic. The aliphatic oxycarbonyl group is preferably an aliphatic oxycarbonyl group having 2 to 16 carbon atoms, more preferably an aliphatic oxycarbonyl group having 2 to 10 carbon atoms, and examples thereof include a methoxycarbonyl group and a butoxycarbonyl group.

The aryloxycarbonyl group may be substituted or unsubstituted. The aryloxycarbonyl group is preferably an aryloxycarbonyl group having 7 to 17 carbon atoms in total, more preferably an aryloxycarbonyl group having 7 to 15 carbon atoms in total, and examples thereof include a phenoxycarbonyl group.

The acyl group may be an aliphatic carbonyl group or an arylcarbonyl group. When the acyl group is an aliphatic carbonyl group or an arylcarbonyl group, it may further have a substituent. The acyl group may be saturated or unsaturated, or may be cyclic. The acyl group is preferably an acyl group having 2 to 15 carbon atoms, more preferably an acyl group having 2 to 10 carbon atoms, and examples thereof include an acetyl group, pivaloyl group, and a benzoyl group. It may also have additional substituents.

The aliphatic oxy group may be substituted or unsubstituted. The aliphatic oxy group may be saturated or unsaturated, or may be cyclic. As said aliphatic oxy group, a C1-C12 aliphatic oxy group is preferable, A C1-C10 aliphatic oxy group is more preferable, For example, a methoxy group, an ethoxyethoxy group, a phenoxy ethoxy group, or thiophenoxy Ethoxy group etc. are mentioned.

The aryloxy group may be substituted or unsubstituted. The aryloxy group is preferably an aryloxy group having 6 to 18 carbon atoms in total, and more preferably an aryloxy group having 6 to 14 carbon atoms, and examples thereof include phenoxy group and 4-methylphenoxy group. The acyloxy group may be substituted or unsubstituted. The acyloxy group is preferably an acyloxy group having 2 to 14 carbon atoms, more preferably an acyloxy group having 2 to 10 carbon atoms, and examples thereof include an acetoxy group, a methoxyacetoxy group and a benzoyloxy group.

The carbamoyloxy group may be substituted or unsubstituted. The carbamoyloxy group is preferably a carbamoyloxy group having 1 to 16 carbon atoms in total, more preferably a carbamoyloxy group having 1 to 12 carbon atoms in total, and for example, a dimethylcarbamoyloxy group or a diisopropylcarbamoyloxy group. Can be mentioned.

The heterocyclic oxy group may be substituted or unsubstituted. The heterocyclic oxy group is preferably a heterocyclic oxy group having 1 to 15 carbon atoms in total, and more preferably a heterocyclic oxy group having 3 to 10 carbon atoms in total, such as 3-furyloxy group, 3-pyridyloxy group, and N-methyl-2. -Piperidyloxy group, etc. are mentioned.

The aliphatic oxycarbonyloxy group may be substituted or unsubstituted. The aliphatic oxycarbonyl oxy group may be saturated or unsaturated, or may be cyclic. The aliphatic oxycarbonyloxy group is preferably an aliphatic oxycarbonyloxy group having 2 to 16 carbon atoms in total, and more preferably an aliphatic oxycarbonyloxy group having 2 to 10 carbon atoms in total, such as a methoxycarbonyloxy group or t-part. A oxycarbonyloxy group etc. are mentioned.

The N-alkylacylamino group may be substituted or unsubstituted. The N-alkylacylamino group is preferably an N-alkylacylamino group having 3 to 15 carbon atoms in total, and more preferably an N-alkylacylamino group having 3 to 12 carbon atoms in total. For example, N-methylacetylamino group and N-ethoxyethyl A benzoylamino group, N-methylmethoxyacetylamino group, etc. are mentioned.

The carbamoylamino group may be substituted or unsubstituted. The carbamoylamino group is preferably a carbamoylamino group having 1 to 16 carbon atoms in total, and more preferably a carbamoylamino group having 1 to 12 carbon atoms in total, such as N, N-dimethylcarbamoylamino group or N-methyl-N. -Methoxyethylcarbamoylamino group, etc. are mentioned.

The sulfamoylamino group may be substituted or unsubstituted. The sulfamoylamino group is preferably a sulfamoylamino group having 0 to 16 carbon atoms, more preferably a sulfamoylamino group having 0 to 12 carbon atoms, such as N, N-dimethylsulfamoylamino group or N, N-diethylsulfamoyl. An amino group etc. are mentioned.

The aliphatic oxycarbonylamino group may be substituted or unsubstituted. The aliphatic oxycarbonylamino group is preferably an aliphatic oxycarbonylamino group having 2 to 15 carbon atoms in total, and more preferably an aliphatic oxycarbonylamino group having 2 to 10 carbon atoms in total, such as a methoxycarbonylamino group or methoxyethoxycarbon. And a carbonylamino group. The aryloxycarbonylamino group may be substituted or unsubstituted. The aryloxycarbonyl amino group is preferably an aryloxycarbonylamino group having 7 to 17 carbon atoms in total, more preferably an aryloxycarbonylamino group having 7 to 15 carbon atoms in total, for example, a phenoxycarbonylamino group or 4-methoxy Carbonylamino group etc. are mentioned.

The aliphatic sulfonylamino group may be substituted or unsubstituted. The aliphatic sulfonylamino group may be saturated or unsaturated, or may be cyclic. The aliphatic sulfonylamino group is preferably an aliphatic sulfonylamino group having 1 to 12 carbon atoms, more preferably an aliphatic sulfonylamino group having 1 to 8 carbon atoms, and examples thereof include a methanesulfonylamino group and a butanesulfonylamino group. .

The arylsulfonylamino group may be substituted or unsubstituted. The arylsulfonylamino group is preferably an arylsulfonylamino group having 6 to 15 carbon atoms in total, and more preferably an arylsulfonylamino group having 6 to 12 carbon atoms, such as a benzenesulfonylamino group or 4-toluenesulfonylamino group. Can be.

The aliphatic thio group may be substituted or unsubstituted. The aliphatic thio group may be saturated or unsaturated, or may be cyclic. As said aliphatic thi group, the aliphatic thi group of 1-16 total carbons is preferable, The aliphatic thi group of 1-10 total carbons is more preferable, For example, a methylthio group, an ethylthio group, an ethoxy ethylthio group, etc. are mentioned.

The arylthio group may be substituted or unsubstituted. The arylthio group is preferably an arylthio group having 6 to 22 carbon atoms in total, and an arylthio group having 6 to 14 carbon atoms in total, and examples thereof include a phenylthio group and a 2-t-butylthio group.

The aliphatic sulfonyl group may be substituted or unsubstituted. The aliphatic sulfonyl group is preferably an aliphatic sulfonyl group having 1 to 15 carbon atoms, more preferably an aliphatic sulfonyl group having 1 to 8 carbon atoms, and examples thereof include a methanesulfonyl group, butanesulfonyl group, and methoxyethanesulfonyl group. have.

The arylsulfonyl group may be substituted or unsubstituted. The arylsulfonyl group is preferably an arylsulfonyl group having 6 to 16 carbon atoms in total, and more preferably an arylsulfonyl group having 6 to 12 carbon atoms in total. For example, a benzenesulfonyl group, 4-t-butylbenzenesulfonyl group, and 4-toluenesulfo And a silyl group or 2-toluenesulfonyl group.

The sulfamoyl group may be substituted or unsubstituted. The sulfamoyl group is preferably a sulfamoyl group having 0 to 16 carbon atoms, more preferably a sulfamoyl group having 0 to 12 carbon atoms, and examples thereof include a sulfamoyl group, a dimethyl sulfamoyl group, and the like.

The imide group may be condensed, preferably an imide group having 3 to 22 carbon atoms, more preferably an imide group having 3 to 15 carbon atoms, and examples thereof include succinimide group and phthalic imide group. .

The heterocyclic thio group may be substituted or unsubstituted. The heterocyclic thio group is preferably a 5-7 membered ring and a heterocyclic thio group having 1 to 20 carbon atoms, more preferably a 5-7 membered heterocyclic thio group having 1 to 12 carbon atoms, for example, 3-furylthio group or 3 -A pyridylthio group, etc. are mentioned.

Since the green photosensitive resin composition for a colorant and a color filter according to the present invention has excellent transparency, it can be usefully used for the production of color filters, especially color filters of light emitting diode (LED) type liquid crystal display devices for backlights.

The coloring photosensitive resin composition of this invention can contain 1 or more types of compounds of the following general formula (1) as a coloring agent.

[Formula 1]

The coloring photosensitive resin composition of the present invention may use the compound of Formula 1 as a green colorant, and may further include a commercially available organic-inorganic dye, and may use a mixture obtained by mixing it with the compound of Formula 1 as a colorant.

The content of the colorant included in the colored photosensitive resin composition of the present invention may be 0.1 to 40% by weight, more preferably 0.1 to 20% by weight.

Preferably, the compositions of the present invention may further comprise auxiliary colorants, dispersants, alkali-soluble resins, photoinitiators, crosslinkers and solvents. The auxiliary colorant, dispersant, alkali-soluble resin, photoinitiator, crosslinking agent and solvent are 0.1-20 wt%, 1-20 wt%, 1-50 wt%, 0.1-5 wt%, 0.5-10 wt% and 40-90, respectively. It may be included in an amount by weight.

Specific examples of the formula (1) used as the green colorant are shown below.

[Formula 2]

(3)

[Formula 4]

[Chemical Formula 5]

[Formula 6]

[Formula 7]

In the above Chemical Formulas 2 to 7, SiPC represents silicon phthalocyanine.

Formulas 2 to 7 represent preferred examples of X or Y, which are substituents of Formula 1, preferably n is 2.

Auxiliary colorant

The colorants of the formula (1) may be used alone or in combination of two or more, and may also be used with other auxiliary colorants. Yellow dyes may be used as auxiliary colorants. Specific examples of the yellow dye include Acid Yellow 1, 3, 5, 7, 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, 134, 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;

Solvent Yellow 14, 23, 38, 62, 63, 64, 68, 78, 82, 89, 90, 91, 92, 94, 98, 99, 104, 105, 106, 126, 128, 129, 130, 132, 133, 134, 138, 139, 140, 144, 145, 156, 160, 161, 162, 163, 164, 165, 168, 169, 170, 171 and the like.

As the pigment used with the colorant of Formula 1, any organic pigment having high transparency, color clarity and heat resistance may be used without particular limitation. Specific examples of the organic pigments include CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34 , 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93 , 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138 , 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179 , 180, 181, 182, 185, 187, 188, 193, 194, 199, 198, 213, and 214.

Particularly preferred are C. I. Pigment Yellow 138 (hereinafter referred to as PY138) and C. I. Pigment Yellow 150 (hereinafter referred to as PY150). The said organic pigment can be used individually or in combination of 2 or more types, respectively.

In addition, for the purpose of color adjustment, green pigments other than the compound of Formula 1, for example, green pigments such as C. I. Pigment Green 7, 36, 37 and 58 may be used.

The colorant of the formula (1) may be used as a color filter colorant by miniaturizing the particles by a method such as solvent salt milling, dry milling, acid paste, if necessary.

For example, when the organic pigment is refined by solvent salt milling, a mixture of the organic pigment, the water soluble inorganic salt and the water soluble organic solvent is milled with a strong shear force using a kneader. Thereafter, the milled mixture is poured into water and stirred with various stirrers to obtain a slurry state, which is filtered to remove inorganic salts and solvents. Through the above steps, a micronized organic pigment can be obtained. In the pigment refinement as described above, the pigment may be one kind or a mixture of two or more kinds.

In such a refinement process, sodium chloride or potassium chloride may be used as the water-soluble inorganic salt. The inorganic salt is used in the range of 1 to 30 times the weight of the organic pigment. If the inorganic salt is less than 1 times the weight of the organic pigment, sufficient refinement is not achieved. If the inorganic salt is more than 30 times the weight of the organic pigment, an effort is required to remove the inorganic salt, resulting in a decrease in treatment efficiency. Therefore, it is not preferable in terms of productivity.

As a water-soluble organic solvent, it is preferable to use the solvent which has a boiling point from 120-250 degreeC from a safety point of view. Specific examples of the water-soluble organic solvent include glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol dimethyl ether; And propylene glycol monoalkyl ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, and propylene glycol butyl ether.

Dispersant

The dispersing agent used for this invention is a thing normally used for manufacture of the colored resin for color filters. For example, it is suitable to include an amine group or an ammonium salt group as a pigment affinity group, and preferable examples thereof include acrylic copolymers, polyurethanes, polyethyleneimines, and mixtures thereof. Commercially available dispersants include BYK-Chemie's Disperbyk-160, Dispervic-161, Dispervic-165, Dispervic-168, Dispervic-170, Dispervic-171, and Dispervic- 2000, Dispervic-2001; Dispervic-LN21116 and dispervic-LN6919; EFKA-4046, EFKA-4047 and EFKA-4340 from EFKA; Solsperse-5000, Solsperth-12000, Solsperth-22000, Solsperth-24000, and Solsperth-32500 from AVECIA; And PB-821, PB-822, PB-824, and PB-827 from AJINOMOTO. These dispersants can be used individually or in combination of 2 or more types, respectively.

The dispersant may be used in an amount of preferably 1 to 20% by weight, more preferably 1 to 10% by weight, based on the total weight of the composition.

Alkali-soluble resin

Alkali-soluble resin used for this invention is normally used for the colored resin composition for color filters, and acrylic resin which is soluble in an organic solvent as a linear high polymer is preferable.

As a specific example of the monomer which can be used for the said acrylic resin, The compound which has one or more carboxyl groups in a molecule | numerator (for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid); Aromatic vinyl compounds (eg, styrene, α-methylstyrene, vinyltoluene, vinylbenzylmethylether, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, etc.); Unsaturated carboxylate compounds (eg, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate); Compounds having a hydroxyl group (eg, 2-hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate); Hydrophilic compounds such as (meth) acrylamide, secondary or tertiary alkacrylamide, dialkylaminoalkyl (meth) acrylates, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, Vinyltriazole); Branched or straight chain butyl (meth) acrylate, ethylhexyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate; In addition, examples of the compound having the hydrophilicity include a monomer containing a tetrahydrofurfuryl group, a phosphoric acid site, a phosphate ester site, a quaternary ammonium salt site, an ethyleneoxy chain, a propyleneoxy chain, a sulfonic acid group and the like.

In order to increase the crosslinking efficiency, the resin may have a polymerizable group in the side chain.

The acrylic resin preferably has a weight average molecular weight (GPC method measurement, polystyrene conversion value) of 1,000 to 200,000, more preferably 2,000 to 50,000.

Alkali-soluble resins may be used in amounts of preferably 1 to 50% by weight, more preferably 1 to 10% by weight, based on the total weight of the composition.

Photoinitiator

As the photoinitiator used in the present invention, various conventionally known photoinitiator compounds may be used without particular limitation. Specific examples thereof include an iodine salt compound, a sulfonium salt compound, an organohalogen compound, an oxime compound and a mixture thereof. Commercially available photoinitiators include Irgacure-907, Irgacure-369, Irgacure OXE 01 and Irgacure OXE 02 from Ciba Geigy.

The photoinitiator may be used in an amount of preferably 0.1 to 5% by weight based on the total weight of the composition.

Cross-linking agent

The crosslinking agent used in the present invention can be used without any particular limitation to a variety of commonly known crosslinking compound. Specific examples include ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 2-trisacryloyloxymethylethylphthalic acid, propylene glycol di (meth) acrylate, polypropylene glycol di with 14 to 14 propylene groups (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned. These crosslinking agents can be used individually or in combination of 2 or more types, respectively.

The crosslinking agent may be used in an amount of preferably 0.5 to 10% by weight based on the total weight of the composition.

menstruum

As the solvent used in the present invention, various conventionally known solvents may be used without particular limitation. Specific examples include alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and the like. Ketones such as acetic acid esters, methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclohexanone, gamma-butyrolactone, ethyl lactate, butyl lactate and ethyl pyruvate. These solvents can be used individually or in combination of 2 or more types, respectively.

The solvent may be used in an amount of preferably 40 to 90% by weight, more preferably 60 to 80% by weight based on the total weight of the composition.

Surfactants

The composition of the present invention may include a surfactant as an additive as necessary in addition to the essential components described above. As the surfactant used in the present invention, various conventionally known surfactants may be used without particular limitation, and commercially available surfactants include Megapak R08 and Megapak F477 (manufactured by Dainippon Ink and Chemicals, Inc.). have.

The composition according to the invention can be prepared by dispersing and dissolving the colorant together with a dispersant, an acrylic resin or both in a solvent and then adding the remaining constituents (ie photoinitiator, crosslinker and optional additives).

Since the green photosensitive resin composition for colorants and color filters of the present invention prepared as described above has excellent transparency, it can be usefully used for the production of color filters, especially color filters of light emitting diode (LED) type liquid crystal display devices for backlights.

Example

Hereinafter, the present invention will be described in detail by way of examples. However, the following examples are illustrative of the present invention, and the present invention is not limited to the following examples.

Synthesis of Compound

Manufacturing example  1: Preparation of Compound of Formula 2

According to the nitrile method, dichlorosiliconphthalocyanine was obtained using phthalonitrile and anhydrous silicon chloride using DBU (1,8-diazabicyclo [5.4.0] undec-7-ene) as a catalyst. At room temperature, 200 g of dichlorosiliconphthalocyanine was slowly added to 6,000 g of an aqueous sulfuric acid solution, followed by stirring at about 10 ° C. for 2 hours. Then, sulfuric acid solution was added to 80,000 g of cold water at 5 ° C. to precipitate the powder, followed by washing with water and drying to obtain silicon hydroxide phthalocyanine. 100 g of the obtained silicon hydroxide phthalocyanine and 108 g of chlorotriphenylsilane were added to 500 g of toluene, followed by heating to reflux for 4 hours. The resulting material was filtered, washed with methanol and dried to obtain 130 g of the compound of formula (2).

[Formula 2]

.

Manufacturing example  2: Preparation of Compound of Formula 4

125 g of the compound of Formula 4 was obtained by the same method as Preparation Example 1, except that 110 g of diphenylchlorophosphate was used instead of chlorotriphenylsilane.

[Formula 4]

Manufacturing example  3: Preparation of Comparative Compound 1

According to the nitrile method, chloro aluminum phthalocyanine was obtained using phthalodinitrile and anhydrous aluminum chloride using DBU (1,8-diazabicyclo [5.4.0] undec-7-ene) as a catalyst. At room temperature, 100 g of chloro aluminum phthalocyanine was slowly added to 3,000 g of concentrated sulfuric acid. It stirred at 40 degreeC for 2 hours, and poured sulfuric acid solution into 80,000 g of cold water of 3 degreeC. The precipitated blue substance was filtered, washed with water and dried to obtain aluminum hydroxide phthalocyanine.

100 g of obtained aluminum hydroxide phthalocyanine and 60 g of triphenylsilane were added to 400 g of toluene, and heating and refluxing were continued for 4 hours. After completion of the reaction, the mixture was filtered, washed with methanol and dried to obtain 90 g of Comparative Compound 1 of the following Chemical Formula 8.

[Formula 8]

Manufacturing example  4: Preparation of Acrylic Resin Solution

450 g of cyclohexanone was added to the reaction vessel and heated to 80 ° C while injecting nitrogen gas into the vessel. At the same temperature, 20.0 g of methacrylic acid, 10.0 g of methyl methacrylate, 55.0 g of n-butylmethacrylate, and 2-hydro A mixture of 15.0 g of oxyethyl methacrylate and 4.0 g of 2,2'-azobisisobutylonitrile was added dropwise over 1 hour to conduct a polymerization reaction. After completion | finish of dripping, after making it react for 3 hours again at 80 degreeC, the thing which dissolved 1.0 g of azobisisobutylnitrile in 50 g of cyclohexanone was added, and reaction was continued for 1 hour at 80 degreeC, and the solution of acrylic resin was continued. Got it. The weight average molecular weight of the acrylic resin was about 40,000. After cooling to room temperature, about 2 g of the resin solution was sampled, dried by heating at 180 ° C. for 20 minutes to measure solid content, and cyclohexanone was added so that the solid content was 20% by weight or more to prepare an acrylic resin solution.

Manufacturing example  5: Processing of Colorant 1

36 g of the compound of formula 2, 360 g of sodium chloride and 46 g of diethylene glycol prepared in Preparation Example 1 were placed in a 1 L kneader (manufactured by Kyungin Precision Co., Ltd.), and then milled at 30 ° C. for 7 hours. The milled mixture was poured into 10 L of 70 DEG C warm water, stirred for 1 hour, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, dried at 80 DEG C for 24 hours to obtain 34 g of colorant 1. .

Manufacturing example  6: processing of colorant 2

36 g of the compound of formula 4, 360 g of sodium chloride and 46 g of diethylene glycol prepared in Preparation Example 2 were placed in a 1 L kneader (manufactured by Kyungin Precision Co., Ltd.), and then milled at 30 ° C. for 7 hours. The milled mixture was poured into 10 L of hot water at 70 ° C, stirred for 1 hour, filtered, washed with water repeatedly to remove sodium chloride and diethylene glycol, and dried at 80 ° C for 24 hours to obtain 34 g of colorant 5. .

<Production of Colored Photosensitive Resin Composition>

Example  One

1 6% by weight of the colorant prepared in Production Example 5, CI Pigment Yellow 150 (Yellow Pigment G04, LANXESS) 1.5% by weight, Dispervic-LN21116 (40% solids, BYK-Chemical) 6.25% by weight, acrylic resin (20% solids, Preparation Example 4), and 48.74% by weight propylene glycol monomethyl ether acetate (PGMEA) as a solvent were added, stirred and dispersed in a vertical bead mill. Next, 2% by weight of photoinitiator Irgacure-369, 3% by weight of dipentaerythritol hexaacrylate as a crosslinking agent, and 0.01% by weight of Megapak R08 (manufactured by Dainippon Ink and Chemicals) as a surfactant were added, followed by stirring and coloring the green. The photosensitive resin composition was obtained.

Example  2

A green colored photosensitive resin composition was obtained in the same manner as in Example 1 except that 6 wt% of the coloring agent 2 prepared in Preparation Example 6 was used.

Example  3

Green coloring photosensitive in the same manner as in Example 1, except that 5.25% by weight of the coloring agent 1 prepared in Preparation Example 5 and 2.25% by weight of CI Pigment Yellow 138 (Y-1010 manufactured by Toyo Ink Co., Ltd.) were used. The resin composition was obtained.

Example  4

A green colored photosensitive resin composition was obtained in the same manner as in Example 1, except that 5.25 wt% of the coloring agent 2 prepared in Preparation Example 6 and 2.25 wt% of CI Pigment Yellow 138 (Y-1010 manufactured by Toyo Ink Co., Ltd.) were used. .

Comparative example  One

A green colored photosensitive resin composition was obtained in the same manner as in Example 1 except that 6 wt% of Comparative Compound 1 prepared in Preparation Example 3 was used.

Comparative example  2

A green colored photosensitive resin composition was obtained in the same manner as in Example 1 except that 6 wt% of C. I. Pigment Green 58 (A110 manufactured by DIC Corporation) was used as the coloring agent.

Comparative example  3

Green coloring by the same method as Example 1 except having used 5.25 weight% of CI Pigment Green 36 (6YK by Toyo Ink Co., Ltd.) and 2.25 weight% of Pigment Yellow 138 (Y-1010 by Toyo Ink Co., Ltd.) as a coloring agent. The photosensitive resin composition was obtained.

Test Example : Luminance evaluation test of colored photosensitive resin composition

Using the spin coater to form a film of each of the colored photosensitive resin composition obtained in Examples 1 to 4 and Comparative Examples 1 to 3 and dried for 10 minutes in an oven at 80 ℃ to obtain a coating film. The obtained coating film was exposed with a light quantity of 100 mJ / cm ² using an ultrahigh pressure mercury lamp, developed with an alkaline developer, and washed with ultrapure water. The developed coating film was post-baked in an oven at 230 ° C. for 20 minutes to form a pattern for a color filter. The chromaticity (x, y, Y) of the thermosetting coating film was measured using a colorimeter MCPD-3000 (manufactured by Otsuka Co., Ltd.), and also Examples 1 to 4, based on the green colored photosensitive resin composition of Comparative Example 2. And the relative luminance values of the green-colored photosensitive resin compositions of Comparative Examples 1 and 3, and when the value is 3% or more, ◎, and less than 1%, Δ, the results are shown in Table 1 below.

Colorant type X y Luminance
(Y) Relative brightness evaluation Green Yellow Example 1 Colorants 1 Y150 0.2755 0.572 61.4 103.4% ◎ Example 2 Colorant 2 Y150 0.2762 0.572 61.6 103.7% ◎ Example 3 Colorants 1 Y138 0.2763 0.572 63.5 106.9% ◎ Example 4 Colorant 2 Y138 0.2754 0.572 63.2 106.4% ◎ Comparative Example 1 Comparative compound 1 Y150 0.2747 0.572 60.1 101.2% △ Comparative Example 2 G58 Y150 0.2754 0.572 59.4 100.0% △ Comparative Example 3 G36 Y138 0.2751 0.572 59.8 100.7% △

As shown in Table 1, the colored photosensitive resin composition of the present invention using the coloring agents 1 and 2 according to the present invention shows an excellent Y value (transmittance) compared to the colored photosensitive resin composition of the comparative example, and also has an excellent relative luminance value Could confirm.

Claims (10)

Colored photosensitive resin composition containing the compound represented by following General formula (1) as a coloring agent:
[Formula 1]

Z is a halogen atom, aliphatic group, aryl group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, aliphatic oxycarbonyl group, aryloxycarbonyl group, acyl group, hydroxy group, aliphatic oxy group, aryloxy group, acyloxy group, carba Moyloxy group, heterocyclic oxy group, aliphatic oxycarbonyloxy group, N-alkylacylamino group, carbamoylamino group, sulfamoylamino group, aliphatic oxycarbonylamino group, aryloxycarbonylamino group, aliphatic sulfonylamino group, arylsulfonyl Substituent represented by amino group, aliphatic thio group, arylthio group, aliphatic sulfonyl group, arylsulfonyl group, sulfamoyl group, sulfo group, imide group, heterocyclic thi group, nitro group, -OR1, -COR1, -COOR1 or NR1R2 ,
Wherein, R1 and R2 are each independently a hydrogen atom, C _{1 -20} alkyl, C _{3 -6} cycloalkyl group, C _{6 -18} aryl group;
n is an integer from 0 to 16;
M is Si or Ge as the center metal;
X and Y each independently represent a substituent represented by the following formulas a to h;
(A)

[Formula b]

[Formula c]

[Formula d]

[Formula e]

[Formula f]

[Formula g]

[Formula h]

R3 to R8 in Formulas a to h are each independently a hydrogen atom, a halogen atom, an aliphatic group, an aryl group, a heterocyclic group, a cyano group, a carboxyl group, a carbamoyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, an acyl group, a hydroxyl group, Aliphatic oxy group, aryloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, aliphatic oxycarbonyloxy group, N-alkylacylamino group, carbamoylamino group, sulfamoylamino group, aliphatic oxycarbonylamino group, Aryloxycarbonylamino group, aliphatic sulfonylamino group, arylsulfonylamino group, aliphatic thio group, arylthio group, aliphatic sulfonyl group, arylsulfonyl group, sulfamoyl group, sulfo group, imide group or heterocyclic thio group, and Z is It represents an oxygen atom or a sulfur atom.
The method of claim 1,
The aliphatic group is an aliphatic group having 1 to 15 carbon atoms in total, the aryl group is an aryl group having 6 to 16 carbon atoms in total, the heterocyclic group is a heterocyclic group having 1 to 15 carbon atoms in total, and the carbamoyl group is 1 to 16 carbon atoms in total. Carbamoyl group, the aliphatic oxycarbonyl group is an aliphatic oxycarbonyl group having 2 to 16 carbon atoms in total, the aryloxycarbonyl group is an aryloxycarbonyl group having 7 to 17 carbon atoms in total, and the acyl group is an acyl group having 2 to 15 carbon atoms in total. Wherein the aliphatic oxy group is an aliphatic oxy group having 1 to 12 carbon atoms in total, the aryloxy group is an aryloxy group having 6 to 18 carbon atoms in total, the acyloxy group is an acyloxy group having 2 to 14 carbon atoms in total, and the carba The moyloxy group is a carbamoyloxy group having 1 to 16 carbon atoms in total, the heterocyclic oxy group is a heterocyclic oxy group having 1 to 15 carbon atoms in total, and the aliphatic oxycarbonyloxy group is It is a minority 2-16 aliphatic oxycarbonyloxy group, The said N-alkylacylamino group is a C3-C15 N-alkylacylamino group, The said carbamoylamino group is a C1-C16 carbamoylamino group And the sulfamoylamino group is a sulfamoylamino group having 0 to 16 carbon atoms in total, the aliphatic oxycarbonylamino group is an aliphatic oxycarbonylamino group having 2 to 15 carbon atoms in total, and the aryloxycarbonylamino group is 7 to 17 carbon atoms in total. Is an aryloxycarbonylamino group, the aliphatic sulfonylamino group is an aliphatic sulfonylamino group having 1 to 12 carbon atoms in total, the arylsulfonylamino group is an arylsulfonylamino group having 6 to 15 carbon atoms in total, and the aliphatic thi group is total carbon atoms An aliphatic thio group having 1 to 16 carbon atoms, the arylthio group being an arylthio group having 6 to 22 carbon atoms in total, and the aliphatic sulfonyl group having 1 to 15 carbon atoms in total An aliphatic sulfonyl group, the arylsulfonyl group is an arylsulfonyl group having 6 to 16 carbon atoms in total, the sulfamoyl group is a sulfamoyl group having 0 to 16 carbon atoms in total, and the imide group is an imide group having 3 to 22 carbon atoms in total The heterocyclic thi group is a 5 to 7 membered ring and is a heterocyclic thi group having 1 to 20 carbon atoms in total.
The method of claim 1,
The aliphatic group is methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, 1-ethylpentyl and tri Fluoromethyl group, cyclopentyl group, cyclohexyl group, vinyl group, allyl group, ethynyl group, isopropenyl group or 2-ethylhexyl group,
The aryl group is a phenyl group, 4-nitrophenyl group, 2-nitrophenyl group, 2-chlorophenyl group, 2,4-dichlorophenyl group, 2,4-dimethylphenyl group, 2-methylphenyl group, 4-methoxyphenyl group, 2-methoxyphenyl group , 2-methoxycarbonyl-4-nitrophenyl group biphenyl group, o-, m-, and p-xylene group, naphthalene group or anthracene group,
Single group heterocyclic group is 3-pyridyl group, 2-pyridyl group, 2-pyrimidinyl group, 2-pyridinyl group, 1-piperidyl group,
The halogen atom is a fluorine atom, a chlorine atom or a bromine atom,
The carbamoyl group is a carbamoyl group, a dimethylcarbamoyl group, a dimethoxyethylcarbamoyl group,
The aliphatic oxycarbonyl group is a methoxycarbonyl group or a butoxycarbonyl group,
The aryloxycarbonyl group is a phenoxycarbonyl group,
The acyl group is an acetyl group, pivaloyl group or benzoyl group,
The aliphatic oxy group is a methoxy group, an ethoxyethoxy group, a phenoxyethoxy group or a thiophenoxyethoxy group,
The aryloxy group is a phenoxy group or 4-methylphenoxy group,
The acyloxy group is an acetoxy group, a methoxyacetoxy group or a benzoyloxy group,
The carbamoyloxy group is a dimethylcarbamoyloxy group or a diisopropylcarbamoyloxy group,
The heterocyclic oxy group is a 3-furyloxy group, 3-pyridyloxy group or N-methyl-2-piperidyloxy group,
The aliphatic oxycarbonyloxy group is a methoxycarbonyloxy group or a t-butoxycarbonyloxy group,
The N-alkylacylamino group is an N-methylacetylamino group, an N-ethoxyethylbenzoylamino group, or an N-methylmethoxyacetylamino group,
The carbamoylamino group is an N, N-dimethylcarbamoylamino group or an N-methyl-N-methoxyethylcarbamoylamino group,
The sulfamoylamino group is an N, N-dimethylsulfamoylamino group or an N, N-diethylsulfamoylamino group,
The aliphatic oxycarbonylamino group is a methoxycarbonylamino group or a methoxyethoxycarbonylamino group,
The aryloxycarbonylamino group is a phenoxycarbonylamino group or 4-methoxycarbonylamino group,
The aliphatic sulfonylamino group is a methanesulfonylamino group or a butanesulfonylamino group,
The arylsulfonylamino group is a benzenesulfonylamino group or 4-toluenesulfonylamino group,
The aliphatic thio group is methylthio group, ethylthio group or ethoxyethylthio group,
The arylthio group is a phenylthio group or 2-t-butylthio group,
The aliphatic sulfonyl group is a methanesulfonyl group, a butanesulfonyl group or a methoxyethanesulfonyl group,
The arylsulfonyl group is a benzenesulfonyl group, 4-t-butylbenzenesulfonyl group, 4-toluenesulfonyl group or 2-toluenesulfonyl group,
The sulfamoyl group is a sulfamoyl group or a dimethyl sulfamoyl group,
The imide group is a succinimide group or a phthalimide group,
The heterocyclic thio group is a colored photosensitive resin composition, characterized in that 3-furylthio group or 3-pyridylthio group.
The method of claim 1,
Wherein the aliphatic group is C _{1 -6} alkyl group,
The cycloalkyl group is a cyclopentyl group, a cyclohexyl group,
The said aryl group is a phenyl group, 2-methylphenyl group, 4-methylphenyl group, 2, 4- dimethylphenyl group, 2, 6- dimethylphenyl group, or naphthalene group, The coloring photosensitive resin composition characterized by the above-mentioned.
The method of claim 1,
X and Y are each a substituent represented by the following formula (a) to (f) colored photosensitive resin composition.
(A)

[Formula b]

[Formula c]

[Formula d]

[Formula e]

[Formula f]

R3 to R5 are a phenyl group, a biphenyl group, 2-methylphenyl group, 4-methylphenyl group, 2,4-dimethylphenyl group, 2,6-dimethylphenyl group, or naphthalene group, respectively.
The method of claim 1,
The colored photosensitive resin composition further comprises an auxiliary colorant, a dispersant, an alkali-soluble resin, a photoinitiator, a crosslinking agent, and a solvent.
The method according to claim 6,
The coloring photosensitive resin composition, wherein the auxiliary colorant further comprises a yellow pigment or a dye.
The method of claim 1,
Coloring photosensitive resin composition, characterized in that it comprises the coloring agent in an amount of 0.1 to 40% by weight based on the total weight of the composition.
The method according to claim 6,
Coloring photosensitive resin composition, characterized in that the dispersant is selected from the group consisting of acrylic copolymers, polyurethanes, polyethyleneimines and mixtures thereof.
The method according to claim 6,
1 to 20% by weight of the dispersant, 1 to 50% by weight of the alkali-soluble resin, 0.1 to 5% by weight of the photoinitiator, 0.5 to 10% by weight of the crosslinking agent, and 40 to 90% by weight of the solvent, based on the total weight of the composition. The coloring photosensitive resin composition characterized by including.