KR102055478B1 - Xanthene-based compound, colorant composition comprising the same and resin composition comprising the same - Google Patents

Abstract

The present specification relates to a novel xanthene-based compound, a colorant composition comprising the same, and a resin composition including the same.

Description

Xanthene-based compound, colorant composition comprising the same, and resin composition containing same {XANTHENE-BASED COMPOUND, COLORANT COMPOSITION COMPRISING THE SAME AND RESIN COMPOSITION COMPRISING THE SAME}

This application claims the benefit of the filing date of Korean Patent Application No. 10-2015-0133199 filed with the Korea Intellectual Property Office on September 21, 2015, the entire contents of which are incorporated herein.

The present specification relates to a novel xanthene-based compound, a colorant composition comprising the same, and a resin composition including the same.

Recently, as a light source of a liquid crystal display (LCD), in place of the conventional CCFL, LED or OLED devices that emit light by itself, not driving or liquid crystal, have been used. If LED or OLED is used as a light source, it emits red, green, and blue light by itself, and thus does not require a separate color filter.

However, in general, using the light from the LED or OLED light source, it is not easy to adjust or adjust the required color coordinates. In addition, a method for improving color purity, brightness, and contrast ratio in manufacturing a color filter using a pigment material dispersion method using a color material, especially a pigment, which has already been developed, has reached a limit point. In addition, it is necessary to reduce the amount of color materials used for thinning the color filter.

In order to overcome these problems and satisfy the requirements, the development of new color materials is required.

Korean Laid-Open Patent No. 2001-0009058

The present specification describes a novel xanthene-based compound, a colorant composition comprising the same, and a resin composition including the same.

According to an exemplary embodiment of the present specification, a compound represented by the following formula (1) is provided.

[Formula 1]

In Chemical Formula 1,

R ₁ and R ₃ are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted linear or branched alkyl group having 1 to 30 carbon atoms; A substituted or unsubstituted linear or branched alkenyl group having 2 to 30 carbon atoms; Substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms; And a substituted or unsubstituted monocyclic or polycyclic heteroaryl group having 2 to 30 carbon atoms,

R ₂ is a direct bond; Or a divalent linking group,

R ₄ to R ₁₃ are the same as or different from each other, and each independently hydrogen; heavy hydrogen; SO ₃ ^-; COOH; COO ^-; Hydroxyl group; A substituted or unsubstituted linear or branched alkyl group having 1 to 30 carbon atoms; Substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms; And a substituted or unsubstituted monocyclic or polycyclic heteroaryl group having 2 to 30 carbon atoms,

At least one of the R ₄ to R ₁₃ are SO ₃ ^-; COOH; Or COO ^- and,

R ₁₄ to R ₁₇ are the same as or different from each other, and each independently hydrogen; Or deuterium,

X ₁ to X ₄ are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted linear or branched alkyl group having 1 to 30 carbon atoms; A substituted or unsubstituted linear or branched alkenyl group having 2 to 30 carbon atoms; Substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms; And a substituted or unsubstituted monocyclic or polycyclic heteroaryl group having 2 to 30 carbon atoms,

r2, m, n, p and q are each an integer of 1 to 3,

when r2 is 2 or more, R ₂ is the same as or different from each other,

when m is 2 or more, R ₁₄ are the same as or different from each other,

when n is 2 or more, R ₁₅ is the same as or different from each other,

when p is 2 or more, R ₁₆ are the same as or different from each other,

When q is 2 or more, R ₁₇ is the same as or different from each other.

According to yet an embodiment of the present disclosure, it provides a color material composition comprising a compound represented by the formula (1).

According to yet an embodiment of the present disclosure, it provides a resin composition comprising the color material composition.

The compound according to one embodiment of the present specification may act as a dye, and thus may be used as a color filter material. Specifically, according to an exemplary embodiment of the present specification, the resin composition including the compound may obtain an absorption and transmission spectrum suitable for a desired light source, thereby achieving higher color reproducibility, higher brightness, and high contrast ratio. According to an exemplary embodiment of the present specification, the resin composition containing the compound has a high degree of crosslinking and is excellent in heat resistance and / or chemical resistance. Therefore, the resin composition according to one embodiment of the present specification has little change in color due to heat treatment, and little elution to a solvent.

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

According to an exemplary embodiment of the present specification, a compound represented by Formula 1 is provided.

Examples of substituents of the compound represented by Formula 1 are described below, but are not limited thereto.

As used herein, the term "substituted or unsubstituted" is deuterium; Halogen group; An alkyl group; Alkenyl groups; An alkoxy group; Cycloalkyl group; Silyl groups; Aryl alkenyl group; Aryloxy group; Alkyl thioxy group; Alkyl sulfoxy groups; Aryl sulfoxy group; Boron group; -NH ₂ ; Alkylamine group; Aralkyl amine groups; Arylamine group; Carbazole groups; Acryloyl group; Acrylate group; Ether group; Nitrile group; Nitro group; Hydroxyl group; Nitrile group; Epoxy groups; (Meth) acrylate group; Hydrocarbon ring group; And it is substituted with one or more substituents selected from the group consisting of a heterocyclic group containing one or more of N, O, S or P atoms or have no substituents.

 In the present specification, the alkyl group may be linear or branched chain, carbon number is not particularly limited, but is preferably 1 to 25. Specific examples include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl and heptyl groups.

In the present specification, the alkenyl group may be linear or branched chain, carbon number is not particularly limited, but is preferably 2 to 25. Specific examples include, but are not limited to, alkenyl groups in which aryl groups such as stylbenyl and styrenyl groups are substituted.

In the present specification, the alkoxy group may be linear or branched chain, carbon number is not particularly limited, but is preferably 1 to 25.

In the present specification, the alkenyloxy group may be linear or branched chain, carbon number is not particularly limited, but is preferably 2 to 25.

In this specification, although a cycloalkyl group is not specifically limited, It is preferable that it is C3-C20, A cyclopentyl group and a cyclohexyl group are especially preferable.

In the present specification, examples of the halogen group include fluorine, chlorine, bromine or iodine.

In the present specification, the aralkyl group specifically has an aryl portion having 6 to 49 carbon atoms and an alkyl portion having 1 to 44 carbon atoms. Specific examples include benzyl group, p-methylbenzyl group, m-methylbenzyl group, p-ethylbenzyl group, m-ethylbenzyl group, 3,5-dimethylbenzyl group, α-methylbenzyl group, α, α-dimethylbenzyl Group, α, α-methylphenylbenzyl group, 1-naphthylbenzyl group, 2-naphthylbenzyl group, p-fluorobenzyl group, 3,5-difluorobenzyl group, α, α-ditrifluoromethylbenzyl group , p-methoxybenzyl group, m-methoxybenzyl group, α-phenoxybenzyl group, α-benzyl groupoxybenzyl group, naphthylmethyl group, naphthylethyl group, naphthylisopropyl group, pyrrolylmethyl group, pyrrole Ethyl group, aminobenzyl group, nitrobenzyl group, cyanobenzyl group, 1-hydroxy-2-phenyl isopropyl group, 1-chloro-2-phenyl isopropyl group and the like, but is not limited thereto.

In the present specification, the aryl portion of the aralkenyl group may be described below with respect to aryl, and the alkenyl portion may be applied with the description of the alkenyl group described above.

In the present specification, the aryl group may be a monocyclic aryl group or a polycyclic aryl group.

When the aryl group is a monocyclic aryl group, carbon number is not particularly limited, but is preferably 6 to 40 carbon atoms. Specifically, the monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc., but is not limited thereto.

Carbon number is not particularly limited when the aryl group is a polycyclic aryl group. It is preferable that it is C10-C40. Specifically, the polycyclic aryl group may be naphthyl group, anthryl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, etc., but is not limited thereto.

,

,

및

등이 있다. In the present specification, the fluorenyl group may have a substituent, and the substituents may combine to form a spiro structure. Examples of fluorenyl groups

,

,

And

Etc.

In the present specification, the heterocyclic group is a heterocyclic group containing O, N or S as a hetero atom, and the carbon number is not particularly limited, but is preferably 2-40 carbon atoms. Examples of the heterocyclic group include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, triazine group, acridil group, pyridazine group , Quinolinyl group, isoquinoline group, indole group, carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, dibenzofuran And the like, but are not limited thereto.

In the present specification, an example of a heterocyclic group may be applied to the heteroaryl group.

In the present specification, the hydrocarbon ring group may be an aromatic, aliphatic or a condensed ring group of aromatic and aliphatic, and may be selected from examples of the cycloalkyl group or aryl group.

In the present specification, the alkylene group means that there are two bonding positions in the alkyl group. The alkylene group may be straight, branched or cyclic. Although carbon number of an alkylene group is not specifically limited, For example, it is C2-C25, Except that it is a divalent group, the illustration of the said alkyl group can be applied.

In the present specification, the arylene group means that there are two bonding positions in the aryl group. The arylene group may be monocyclic or polycyclic, and examples of the aryl group may be applied except that the arylene group is a divalent group.

In this specification, an epoxy group is an alicyclic epoxy group and it is preferable that it is C2-C20.

According to yet an embodiment of the present disclosure, in the general formula 1, R _One And R _{3 Are} the same as or different from each other, and each independently hydrogen; heavy hydrogen; And a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 20 carbon atoms.

According to yet an embodiment of the present disclosure, in the general formula 1, R _One And R _{3 Are} the same as or different from each other, and each independently hydrogen; heavy hydrogen; And a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 15 carbon atoms.

According to yet an embodiment of the present disclosure, in the general formula 1, R _One And R _{3 Are} the same as or different from each other, and each independently hydrogen; heavy hydrogen; And a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 10 carbon atoms.

According to yet an embodiment of the present disclosure, in the general formula 1, R _One And R _{3 Are} the same as or different from each other, and each independently hydrogen; heavy hydrogen; And a substituted or unsubstituted phenyl group.

According to yet an embodiment of the present disclosure, in the general formula 1, R _One And R _{3 Are} the same as or different from each other, and each independently hydrogen; heavy hydrogen; And a phenyl group substituted with a methyl group.

According to an exemplary embodiment of the present specification, in the general formula 1, R _{2 It} is a direct bond; Or a divalent linking group.

For example, the divalent linking group is oxy group (-O-); Thio group (-S-); Carbonyl group (-CO-); Sulfonyl group (-SO _2- ) amino group; A substituted or unsubstituted linear or branched alkylene group having 1 to 30 carbon atoms; A substituted or unsubstituted linear or branched alkenylene group having 2 to 30 carbon atoms; A substituted or unsubstituted monocyclic or polycyclic cycloalkylene group having 3 to 30 carbon atoms; Substituted or unsubstituted monocyclic or polycyclic arylene group having 6 to 30 carbon atoms; And a substituted or unsubstituted monocyclic or polycyclic heteroarylene group having 2 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, in the general formula 1, R _{2 It} is a direct bond; A substituted or unsubstituted linear or branched alkylene group having 1 to 30 carbon atoms; Or a substituted or unsubstituted monocyclic or polycyclic arylene group having 6 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, in the general formula 1, R _{2 It} is a direct bond; A substituted or unsubstituted linear or branched alkylene group having 1 to 20 carbon atoms; Or a substituted or unsubstituted monocyclic or polycyclic arylene group having 6 to 20 carbon atoms.

According to an exemplary embodiment of the present specification, in the general formula 1, R _{2 It} is a direct bond; Substituted or unsubstituted linear or branched alkylene group having 1 to 10 carbon atoms; Or a substituted or unsubstituted monocyclic or polycyclic arylene group having 6 to 10 carbon atoms.

According to an exemplary embodiment of the present specification, in the general formula 1, R _{2 It} is a direct bond; Linear or branched alkylene groups having 1 to 10 carbon atoms; Or a monocyclic or polycyclic arylene group having 6 to 10 carbon atoms substituted or unsubstituted with a linear or branched alkyl group having 1 to 10 carbon atoms.

According to an exemplary embodiment of the present specification, in the general formula 1, R _{2 It} is a direct bond; Substituted or unsubstituted methylene group; Or a phenylene group unsubstituted or substituted with an alkyl group.

According to an exemplary embodiment of the present disclosure, r2 is three.

According to an exemplary embodiment of the present specification, in the general formula 1, R _{2 It} is a direct bond; Methylene group; Or a phenylene group unsubstituted or substituted with a methyl group or an ethyl group.

According to yet an embodiment of the present disclosure, in the general formula 1, X _{One To} X _{4 Are} the same as or different from each other, and each independently hydrogen; heavy hydrogen; And a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms.

According to yet an embodiment of the present disclosure, in the general formula 1, X _{One To} X _{4 Are} the same as or different from each other, and each independently hydrogen; heavy hydrogen; And a substituted or unsubstituted linear or branched alkyl group having 1 to 15 carbon atoms.

According to yet an embodiment of the present disclosure, in the general formula 1, X _{One To} X _{4 Are} the same as or different from each other, and each independently hydrogen; heavy hydrogen; And a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms.

According to yet an embodiment of the present disclosure, in the general formula 1, X _{One To} X _{4 Are} the same as or different from each other, and each independently hydrogen; And substituted or unsubstituted with a hydroxyl group, thiol group, nitrile group, -NH ₂ , epoxy group, (meth) acrylate group, dianhydride group containing nitrogen atom, monocyclic or polycyclic heterocyclic group, or monocyclic or polycyclic hydrocarbon ring. Selected from the group consisting of alkyl groups having 1 to 10 carbon atoms.

According to yet an embodiment of the present disclosure, in the general formula 1, X _{One To} X _{4 Are} the same as or different from each other, and each independently hydrogen; And substituted or unsubstituted with a hydroxy group, thiol group, nitrile group, -NH ₂ , epoxy group, (meth) acrylate group, dianhydride group containing nitrogen atom, monocyclic or polycyclic heterocyclic group, or monocyclic or polycyclic aryl group. It is selected from the group consisting of alkyl groups having 1 to 10 carbon atoms.

According to yet an embodiment of the present disclosure, in the general formula 1, X _{One To} X _{4 Are} the same as or different from each other, and each independently hydrogen; And hydroxyl group, thiol group, nitrile group, -NH ₂ , epoxy group, (meth) acrylate group, oxiranyl group, oxetanyl group, pyrrolidinyl group, imidazolidinyl group, pyrazolidinyl group, morpholinyl group, Theomorpholinyl group, piperidyl group, piperidino group, piperazinyl group, homopyrazinyl group, 1,3-dioxolan-2-yl group, pyridyl group, pyrazinyl group, pyrimidyl group, pyridazinyl group , Quinolyl group, isoquinolyl group, phthalazinyl group, naphthyridinyl group, quinoxalinyl group, imidazolyl group, pyrazolyl group, triazoyl group, tetrazolyl group, thiazolyl group, benzothiazolyl group, C1-C10 straight or branched chain unsubstituted or substituted with an oxazolyl group, indolyl group, indazolyl group, benzoimidazolyl group, phthalimide group, thienyl group, furyl group, pyranyl group, or furinyl group It is selected from the group consisting of alkyl groups.

According to yet an embodiment of the present disclosure, in the general formula 1, X _{One To} X _{4 Are} the same as or different from each other, and each independently hydrogen; And a straight or branched chain alkyl group having 1 to 10 carbon atoms unsubstituted or substituted with a hydroxy group, a thiol group, a nitrile group, a -NH ₂ , a phthalimide group, or a (meth) acrylate group.

According to yet an embodiment of the present disclosure, in the general formula 1, X _{One To} X _{4 Are} the same as or different from each other, and each independently hydrogen; Methyl group; Ethyl group; And an n-propyl group unsubstituted or substituted with a hydroxyl group, thiol group, nitrile group, -NH ₂ , phthalimide group, or methyl methacrylate group.

According to yet an embodiment of the present disclosure, the compound represented by Formula 1 may be represented by any one of the following compounds.

The compound of Chemical Formula 1 may be prepared by referring to the following Preparation Example.

Another embodiment of the present specification provides a color material composition comprising the compound of Formula 1.

The color material composition may further include at least one of dyes and pigments in addition to the compound of Formula 1. For example, the colorant composition may include only the compound of Formula 1, but may include the compound of Formula 1 and one or more dyes, or may include the compound of Formula 1 and one or more pigments, or the compound of Formula 1 And at least one dye and at least one pigment.

According to an exemplary embodiment of the present specification, a resin composition comprising the color material composition is provided.

According to an exemplary embodiment of the present specification, the resin composition is a compound represented by Formula 1; Binder resins; Polyfunctional monomers; Photoinitiators; And solvents.

The binder resin is not particularly limited as long as it can exhibit physical properties such as strength, developability, and the like of the film made of the resin composition.

The binder resin may use a copolymer resin of a polyfunctional monomer imparting mechanical strength and a monomer imparting alkali solubility, and may further include a binder generally used in the art.

Polyfunctional monomers to impart the mechanical strength of the membrane include unsaturated carboxylic acid esters; Aromatic vinyls; Unsaturated ethers; Unsaturated imides; And acid anhydrides.

Specific examples of the unsaturated carboxylic acid esters include benzyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and isobutyl ( Meta) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, ethylhexyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, tetra Hydroperpril (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 4-hydroxybutyl ( Meth) acrylate, acyloctyloxy-2-hydroxypropyl (meth) acrylate, glycerol (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethoxy CD-ethyleneglycol (Meth) acrylate, methoxy triethylene glycol (meth) acrylate, methoxy tripropylene glycol (meth) acrylate, poly (ethylene glycol) methyl ether (meth) acrylate, phenoxydiethylene glycol (meth) acrylate , p-nonylphenoxypolyethylene glycol (meth) acrylate, p-nonylphenoxypolypropylene glycol (meth) acrylate, glycidyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, 1,1 , 1,3,3,3-hexafluoroisopropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, tribromophenyl (meth) acrylate , Methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate, propyl α-hydroxymethyl acrylate and butyl α-hydroxymethyl acrylate It is, but is not limited thereto.

Specific examples of the aromatic vinyl monomers include styrene, α-methylstyrene, (o, m, p) -vinyl toluene, (o, m, p) -methoxy styrene, and (o, m, p) -chloro It may be selected from the group consisting of styrene, but is not limited thereto.

Specific examples of the unsaturated ethers may be selected from the group consisting of vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether, but are not limited thereto.

Specific examples of the unsaturated imides are selected from the group consisting of N-phenyl maleimide, N- (4-chlorophenyl) maleimide, N- (4-hydroxyphenyl) maleimide, and N-cyclohexyl maleimide It may be, but is not limited to these.

Examples of the acid anhydride include maleic anhydride, methyl maleic anhydride, tetrahydro phthalic anhydride, phthalimide, and the like, but are not limited thereto.

The monomer which imparts the alkali solubility is not particularly limited as long as it contains an acid group. For example, (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monomethyl maleic acid, 5-norbornene-2-carboxylic acid, mono 2-((meth) acryloyloxy) ethyl phthalate, mono-2-((meth) acryloyloxy) ethyl succinate, ω-carboxy polycaprolactone mono (meth) acrylate selected from the group consisting of Although it is preferable to use 1 or more types, it is not limited to these.

According to an exemplary embodiment of the present specification, the acid value of the binder resin is 50 to 130 KOH mg / g, the weight average molecular weight is 1,000 to 50,000.

The polyfunctional monomer is a monomer that forms a photoresist image by light, specifically, propylene glycol methacrylate, dipentaerythritol hexaacrylate, dipentaerythritol acrylate, neopentyl glycol di Acrylate, 6-hexanediol diacrylate, 1,6-hexanediol acrylate tetraethyleneglycol methacrylate, bisphenoxy ethylalcohol diacrylate, trishydroxyethylisocyanurate trimethacrylate, trimethyl 1 selected from the group consisting of propane trimethacrylate, diphenylpentaerythritol hexaacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate and dipentaerythritol hexamethacrylate Species or a mixture of two or more thereof.

The photoinitiator is not particularly limited as long as it is an initiator that generates radicals by light to trigger crosslinking. For example, the photoinitiator is selected from the group consisting of acetophenone compounds, biimidazole compounds, triazine compounds, and oxime compounds. It may be one or more kinds.

The acetophenone-based compound is 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, benzoin Butyl ether, 2,2-dimethoxy-2-phenylacetophenone, 2-methyl- (4-methylthio) phenyl-2-morpholino-1-propan-1-one, 2-benzyl-2-dimethylamino -1- (4-morpholinophenyl) -butan-1-one, 2- (4-bromo-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one or 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, and the like.

As the biimidazole-based compound, 2,2-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl biimidazole, 2,2'-bis (o-chlorophenyl) -4 , 4 ', 5,5'-tetrakis (3,4,5-trimethoxyphenyl) -1,2'-biimidazole, 2,2'-bis (2,3-dichlorophenyl) -4, 4 ', 5,5'-tetraphenyl biimidazole, 2,2'-bis (o-chlorophenyl) -4,4,5,5'-tetraphenyl-1,2'-biimidazole, It is not limited to this.

The triazine compound is 3- {4- [2,4-bis (trichloromethyl) -s-triazin-6-yl] phenylthio} propionic acid, 1,1,1,3,3,3- Hexafluoroisopropyl-3- {4- [2,4-bis (trichloromethyl) -s-triazin-6-yl] phenylthio} propionate, ethyl-2- {4- [2,4 -Bis (trichloromethyl) -s-triazin-6-yl] phenylthio} acetate, 2-epoxyethyl-2- {4- [2,4-bis (trichloromethyl) -s-triazine-6 -Yl] phenylthio} acetate, cyclohexyl-2- {4- [2,4-bis (trichloromethyl) -s-triazin-6-yl] phenylthio} acetate, benzyl-2- {4- [ 2,4-bis (trichloromethyl) -s-triazin-6-yl] phenylthio} acetate, 3- {chloro-4- [2,4-bis (trichloromethyl) -s-triazine-6 -Yl] phenylthio} propionic acid, 3- {4- [2,4-bis (trichloromethyl) -s-triazin-6-yl] phenylthio} propionamide, 2,4-bis (trichloro Methyl) -6-p-methoxystyryl-s-triazine, 2,4-bis (trichloromethyl) -6- (1-p-di Methylaminophenyl) -1,3, -butadienyl-s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine, and the like, but is not limited thereto. .

The oxime-based compound is 1,2-octadione, -1- (4-phenylthio) phenyl, -2- (o-benzoyloxime) (Shibagai Co., Shijiai 124), ethanone, -1- (9 -Ethyl) -6- (2-methylbenzoyl-3-yl)-, 1- (O-acetyloxime) (CGII242), N-1919 (Adeca Co.), and the like.

The solvent is acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether , Propylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, chloroform, methylene chloride, 1,2-dichloroethane, 1,1,1-trichloroethane, 1 , 1,2-trichloroethane, 1,1,2-trichloroethene, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, methanol, ethanol, isopropanol, propanol, butanol, t-butanol, 2 Ethoxy propanol, 2-methoxy propanol, 3-methoxy butanol, cyclohexanone, cyclopentanone, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, 3-methoxybutyl ah Cetate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, methyl cellosolve acetate, butyl acetate, propylene glycol monomethyl ether and dipropylene glycol monomethyl ether, but may be It is not limited only.

According to one embodiment of the present specification, based on the total weight of solids in the resin composition, the content of the compound represented by Formula 1 is 5% by weight to 60% by weight, and the content of the binder resin is 1% by weight to 60 wt%, the content of the photoinitiator is 0.1 wt% to 20 wt%, and the content of the multifunctional monomer is 0.1 wt% to 50 wt%.

The total weight of the solid content means the sum of the total weight of the components excluding the solvent in the resin composition. The weight percentages based on solids and solids of each component can be measured by common analytical means used in the art, such as liquid chromatography or gas chromatography.

According to an exemplary embodiment of the present specification, the resin composition may further include an antioxidant.

According to an exemplary embodiment of the present specification, the content of the antioxidant is 0.1% to 20% by weight based on the total weight of solids in the resin composition.

According to one embodiment of the present specification, the resin composition may include one or two or more additives selected from the group consisting of a photocrosslinking agent, a curing accelerator, an adhesion promoter, a surfactant, a thermal polymerization inhibitor, a UV absorber, a dispersant, and a leveling agent. It includes.

According to an exemplary embodiment of the present specification, the content of the additive is 0.1% by weight to 20% by weight based on the total weight of solids in the resin composition.

The photocrosslinking sensitizer is benzophenone, 4,4-bis (dimethylamino) benzophenone, 4,4-bis (diethylamino) benzophenone, 2,4,6-trimethylaminobenzophenone, methyl-o-benzoyl Benzophenone compounds such as benzoate, 3,3-dimethyl-4-methoxybenzophenone, 3,3,4,4-tetra (t-butylperoxycarbonyl) benzophenone; Fluorenone compounds such as 9-florenone, 2-chloro-9-prorenone, and 2-methyl-9-florenone; Thioxanthones such as thioxanthone, 2,4-diethyl thioxanthone, 2-chloro thioxanthone, 1-chloro-4-propyloxy thioxanthone, isopropyl thioxanthone and diisopropyl thioxanthone compound; Xanthone compounds such as xanthone and 2-methylxanthone; Anthraquinone compounds such as anthraquinone, 2-methyl anthraquinone, 2-ethyl anthraquinone, t-butyl anthraquinone and 2,6-dichloro-9,10-anthraquinone; 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, 1,5-bis (9-acridinylpentane), 1,3-bis (9-acridinyl) propane Acridine-based compounds; Dicarbonyl compounds such as benzyl, 1,7,7-trimethyl-bicyclo [2,2,1] heptane-2,3-dione, 9,10-phenanthrenequinone; Phosphine oxide compounds such as 2,4,6-trimethylbenzoyl diphenylphosphine oxide and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl phosphine oxide; Benzoate compounds such as methyl-4- (dimethylamino) benzoate, ethyl-4- (dimethylamino) benzoate and 2-n-butoxyethyl-4- (dimethylamino) benzoate; 2,5-bis (4-diethylaminobenzal) cyclopentanone, 2,6-bis (4-diethylaminobenzal) cyclohexanone, 2,6-bis (4-diethylaminobenzal) -4- Amino synergists such as methyl-cyclopentanone; 3,3-carbonylvinyl-7- (diethylamino) coumarin, 3- (2-benzothiazolyl) -7- (diethylamino) coumarin, 3-benzoyl-7- (diethylamino) coumarin, 3 -Benzoyl-7-methoxy-coumarin, 10,10-carbonylbis [1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H, 5H, 11H-C1] -benzo Coumarin-based compounds such as pyrano [6,7,8-ij] -quinolizine-11-one; Chalcone compounds such as 4-diethylamino chalcone and 4-azidebenzalacetophenone; 2-benzoylmethylene, 3-methyl-b-naphthothiazoline; one or more selected from the group consisting of can be used.

The curing accelerator is used to increase the curing and mechanical strength, specifically 2-mercaptobenzoimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2,5-dimercapto-1,3 , 4-thiadiazole, 2-mercapto-4,6-dimethylaminopyridine, pentaerythritol-tetrakis (3-mercaptopropionate), pentaerythritol-tris (3-mercaptopropionate), penta Erythritol-tetrakis (2-mercaptoacetate), pentaerythritol-tris (2-mercaptoacetate), trimethylolpropane-tris (2-mercaptoacetate), and trimethylolpropane-tris (3-mercaptopropio Nate) can be used one or more selected from the group consisting of.

As the adhesion promoter used in the present specification, methacryloyloxy propyltrimethoxy silane, methacryloyloxy propyldimethoxy silane, methacryloyloxy propyltriethoxy silane, methacryloyloxy propyldimethoxysilane One or more types of methacryloyl silane coupling agents, such as these, can be selected and used, and at least 1 type can be selected from octyl trimethoxy silane, dodecyl trimethoxy silane, and octadecyl trimethoxy silane as an alkyl trimethoxy silane. You can choose to use it.

The surfactant is a silicone-based surfactant or a fluorine-based surfactant, specifically, the silicone-based surfactant is BYK-Chemie's BYK-077, BYK-085, BYK-300, BYK-301, BYK-302, BYK-306, BYK-307 , BYK-310, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-335, BYK-341v344, BYK-345v346, BYK-348, BYK -354, BYK-355, BYK-356, BYK-358, BYK-361, BYK-370, BYK-371, BYK-375, BYK-380, BYK-390, and the like. (DaiNippon Ink & Chemicals) F-114, F-177, F-410, F-411, F-450, F-493, F-494, F-443, F-444, F-445, F-446 , F-470, F-471, F-472SF, F-474, F-475, F-477, F-478, F-479, F-480SF, F-482, F-483, F-484, F -486, F-487, F-172D, MCF-350SF, TF-1025SF, TF-1117SF, TF-1026SF, TF-1128, TF-1127, TF-1129, TF-1126, TF-1130, TF-1116SF , TF-1131, TF1132, TF1027SF, TF-1441, TF-1442, etc. may be used, but is not limited thereto.

The antioxidant may be one or more selected from the group consisting of hindered phenol antioxidants, amine antioxidants, thio antioxidants, and phosphine antioxidants, but is not limited thereto.

Specific examples of the antioxidant include phosphoric acid thermal stabilizers such as phosphoric acid, trimethyl phosphate or triethyl phosphate; 2,6-di-t-butyl-p-cresol, octadecyl-3- (4-hydroxy-3,5-di-t-butylphenyl) propionate, tetrabis [methylene-3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate] methane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxy Benzyl) benzene, 3,5-di-t-butyl-4-hydroxybenzylphosphite diethyl ester, 2,2-thiobis (4-methyl-6-t-butylphenol), 2,6-g, t-butylphenol 4,4'-butylidene-bis (3-methyl-6-t-butylphenol), 4,4'-thiobis (3-methyl-6-t-butylphenol) or bis [3 , 3-bis- (4'-hydroxy-3'-tert-butylphenyl) butanoic acid] glycol ester (Bis [3,3-bis- (4'-hydroxy-3'-tert-butylphenyl) butanoicacid] glycol hindered phenol-based primary antioxidants such as esters; Amines such as phenyl-α-naphthylamine, phenyl-β-naphthylamine, N, N'-diphenyl-p-phenylenediamine or N, N'-di-β-naphthyl-p-phenylenediamine System secondary antioxidants; Thio such as dilauryl disulfide, dilaurylthiopropionate, distearylthiopropionate, mercaptobenzothiazole or tetramethylthiuram disulfide tetrabis [methylene-3- (laurylthio) propionate] methane System secondary antioxidants; Or triphenyl phosphite, tris (nonylphenyl) phosphite, triisodecylphosphite, bis (2,4-dibutylphenyl) pentaerythritol diphosphite (Bis (2,4-ditbutylphenyl) Pentaerythritol Diphosphite or (1, 1'-biphenyl) -4,4'-diylbisphosphonoic acid tetrakis [2,4-bis (1,1-dimethylethyl) phenyl] ester ((1,1'-Biphenyl) -4,4 ' Phosphite-based secondary antioxidants such as -diylbisphosphonous acid tetrakis [2,4-bis (1,1-dimethylethyl) phenyl] ester).

As the ultraviolet absorber, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chloro-benzotriazole, alkoxy benzophenone, etc. may be used, but is not limited thereto. All commonly used ones can be used.

Examples of the thermal polymerization inhibitor include p-anisole, hydroquinone, pyrocatechol, t-butyl catechol, N-nitrosophenylhydroxyamine ammonium salt and N-nitrosophenylhydroxy Amine aluminum salt, p-methoxyphenol, di-t-butyl-p-cresol, pyroggarol, benzoquinone, 4,4-thiobis (3-methyl-6-t-butylphenol), 2,2- It may include one or more selected from the group consisting of methylenebis (4-methyl-6-t-butylphenol), 2-mercaptoimidazole and phenothiazine, but is not limited thereto. It may include those generally known in the art.

The dispersant may be used as a method of internally adding to the pigment in the form of surface treatment of the pigment in advance or externally adding to the pigment. As the dispersant, a compound type, nonionic, anionic or cationic dispersant may be used, and examples thereof include fluorine, ester, cationic, anionic, nonionic and amphoteric surfactants. These can be used individually or in combination of 2 or more types.

Specifically, the dispersant may be polyalkylene glycol and esters thereof, polyoxyalkylene polyhydric alcohols, ester alkylene oxide adducts, alcohol alkylene oxide adducts, sulfonic acid esters, sulfonate salts, carboxylic acid esters, carboxylate salts, At least one selected from the group consisting of alkylamide alkylene oxide adducts and alkylamines is not limited thereto.

The leveling agent may be polymeric or nonpolymeric. Specific examples of polymeric leveling agents include polyethyleneimine, polyamideamine, reaction products of amines and epoxides, and specific examples of nonpolymeric leveling agents include non-polymeric sulfur-containing and non-polymeric nitrogen-containing. Including but not limited to the compounds, all generally used in the art can be used.

According to one embodiment of the present specification, a photosensitive material prepared from the resin composition is provided.

In more detail, the resin composition of this specification is apply | coated on a base material by a suitable method, and forms the photosensitive material of a thin film or a pattern form.

Although it does not restrict | limit especially as said coating method, A spray method, a roll coating method, a spin coating method, etc. can be used, Generally, a spin coating method is used widely. In addition, after forming a coating film, some residual solvent can be removed in some cases under reduced pressure.

As a light source for curing the resin composition according to the present specification, for example, mercury vapor arc (arc), carbon arc, Xe arc, etc., which emit light having a wavelength of 250 nm to 450 nm, but are not limited thereto.

The resin composition according to the present disclosure may be a pigment dispersion photosensitive material for manufacturing a thin film transistor liquid crystal display device (TFT LCD) color filter, a photosensitive material for forming a black matrix of a thin film transistor liquid crystal display device (TFT LCD) or an organic light emitting diode, It can be used for photosensitive material for forming overcoat layer, column spacer photosensitive material, photocurable paint, photocurable ink, photocurable adhesive, printing plate, photosensitive material for printed circuit board, photosensitive material for plasma display panel (PDP), and the like. There is no special place.

According to an exemplary embodiment of the present specification, a color filter including the photosensitive material is provided.

The color filter may be manufactured using a resin composition containing the compound represented by Chemical Formula 1. The resin composition may be applied onto a substrate to form a coating film, and the color filter may be formed by exposing, developing, and curing the coating film.

The resin composition according to the exemplary embodiment of the present specification is excellent in heat resistance, so that there is little change in color by heat treatment, thereby providing a color filter having a high color reproducibility and a high luminance and contrast ratio by the curing process during the manufacture of the color filter. have.

The substrate may be a glass plate, a silicon wafer, a plate of a plastic substrate such as polyethersulfone (PES), polycarbonate (PC), or the like, and the type thereof is not particularly limited.

The color filter may include a red pattern, a green pattern, a blue pattern, and a black matrix.

According to another exemplary embodiment, the color filter may further include an overcoat layer.

A black pattern on a lattice called a black matrix can be disposed between the color pixels of the color filter for the purpose of improving contrast. Chromium can be used as the material of the black matrix. In this case, a method of depositing chromium over the entire glass substrate and forming a pattern by etching may be used. However, in consideration of high process cost, high reflectance of chromium, and environmental pollution caused by chromium waste liquid, a resin black matrix by a pigment dispersion method capable of fine processing can be used.

The black matrix according to one embodiment of the present specification may use black pigment or black dye as a colorant. For example, carbon black may be used alone, or carbon black and coloring pigments may be used. At this time, since coloring pigments lacking light shielding properties may be mixed, even if the amount of colorant is increased, the strength of the film or the adhesion to the substrate may be reduced. There is no advantage.

Provided is a display device including a color filter according to the present specification.

The display device may be a plasma display panel (PDP), a light emitting diode (LED), an organic light emitting diode (OLED), a liquid crystal display (LCD), a thin film transistor. The liquid crystal display device may be any one of a liquid crystal display (LCD-TFT) and a cathode ray tube (CRT).

Hereinafter, the present specification will be described in detail with reference to Examples. The following examples are provided to illustrate the present specification, and the scope of the present specification includes the ranges described in the following claims, their substitutions and changes, and is not limited to the examples.

Preparation Example 1 Preparation of Compound 1

1) Preparation of Compound A-3

Under shading conditions, A-1 3.000 g (7.403 mmol) and A-2 0.753 g (2.96 mmol) were added to 30 g of N-Methylpyrrolidone (NMP) and reacted at 150 ° C. for 4 hours. The solvent was removed under reduced pressure, and the crude compound was obtained by column chromatography, obtaining 1.174 g (1.184 mmol) of compound A-3.

2) Preparation of Compound A-5

50 g of N-Methylpyrrolidone (NMP) was added 5.000 g (5.041 mmol) of Compound A-3 and 2.443 g (20.162 mmol) of Compound A-4. The reaction was carried out at 150 ° C. for 5 hours. After cooling to room temperature, 35% HCl was added and stirred. The solvent was removed under reduced pressure and Compound A-5, 1.756 g (1.512 mmol) was obtained through column chromatography.

3) Preparation of Compound 1

1.756 g (5.041 mmol) of Compound A-5, 3.427 g (20.162 mmol) of Compound A-6, and 2.786 g (20.162 mmol) of K ₂ CO ₃ were added to 50 g of N-Methylpyrrolidone (NMP) and reacted at 95 ° C. for 12 hours. . The solvent was removed under reduced pressure and Compound 1 (1,4141 g (1.008 mmol)) was obtained through column chromatography.

Ionization mode =: APCI +: m / z = 1329 [M + H] +, Exact Mass: 1328

Preparation Examples 2 to 10 Preparation of Compounds 2 to 10

Compounds 2 to 10 were prepared in the same manner except for applying the substituents differently in Preparation Example 1.

In Examples and Comparative Examples were prepared in the same ratio as in Table 1. The unit of addition of the compound is grams (g).

compound Binder Resin (g) Photoinitiator (g) Polyfunctional monomer (g) Additive (g) Solvent (g) Example 1 Compound 1 5.554 10.376 2.018 12.443 1.016 68.593 Example 2 Compound 2 Example 3 Compound 3 Example 4 Compound 4 Example 5 Compound 5 Example 6 Compound 6 Example 7 Compound 7 Example 8 Compound 8 Example 9 Compound 9 Example 10 Compound 10 Comparative Example 1 Comparative Compound 1 Comparative Example 2 Comparative Compound 2

Binder resin: copolymer of benzyl methacrylate and methacrylic acid (molar ratio 70:30, acid value is 113
KOH mg / g, weight average molecular weight 20,000 measured by GPC, molecular weight distribution (PDI) 2.0
25% solids (SC) with solvent PGMEA)
Photoinitiator: I-369 (BASF)
Polyfunctional Monomer: DPHA
Solvent: PGMEA (Propylene Glycol Mnomethyl Ether Acetate)
Additive: DIC Corporation F-475
* Evaluation after insoluble component filter
Comparative Example 1 Compound (Basic blue 7) Comparative Example 2 (Rhodamine 6G)

PCB Fabrication

The compound prepared by the synthesis was spincoated on glass (5 × 5 cm) and prebake at 100 ° C. for 100 seconds to form a film. The distance between the substrate on which the film was formed and the photo mask was set to 250 µm, and the exposure amount of 40 mJ / cm ² was irradiated on the entire surface of the substrate using an exposure machine. Thereafter, the exposed substrate was developed in a developer (KOH, 0.05%) for 60 seconds, and post-baked at 230 ° C. for 20 minutes to prepare a substrate.

Heat resistance rating

Using a spectrometer (MCPD-Otsuka Co., Ltd.), a prebake substrate prepared under the above conditions was used to obtain a transmittance spectrum of a visible light region in the range of 380 nm to 780 nm. In addition, the prebake substrate was further subjected to post bake at 230 ° C. for 20 minutes to obtain transmittance spectra in the same equipment and measurement range.

(DELTA) Eab was computed using the obtained transmittance spectrum and C light source backlight, and the obtained values E (L *, a *, b *) are shown in following Table 2.

ΔE (L *, a *, b *) = {(ΔL *) 2+ (Δa *) 2+ (Δb *) 2} 1/2

Small ΔE values indicate excellent color heat resistance.

The heat resistance measurement results of the color material compositions of Examples 1 to 10 and Comparative Examples 1 and 2 are shown in Table 2. As shown in Table 2, Examples 1 to 10 it was confirmed that the color change (ΔEab) is smaller than Comparative Examples 1 and 2.

ΔEab (PB-PrB) Example 1 2.86 Example 2 3.45 Example 3 3.24 Example 4 3.04 Example 5 2.98 Example 6 3.12 Example 7 3.05 Example 8 2.96 Example 9 3.01 Example 10 3.34 Comparative Example 1 26.52 Comparative Example 2 23.95

Claims (14)

Compound represented by the following formula (1):
[Formula 1]

In Chemical Formula 1,
R ₁ and R ₃ are the same as or different from each other, and each independently a phenyl group; Or a phenyl group substituted with a methyl group,
R ₂ is a methylene group; Or a phenylene group substituted with an ethyl group or a methyl group,
R ₄ and R ₉ is SO ₃ ^-, and
R ₅ to R ₈ and R ₁₀ to R ₁₇ are hydrogen,
X ₁ to X ₄ are the same as or different from each other, and each independently a methyl group; Ethyl group; And an n-propyl group unsubstituted or substituted with a hydroxy group, a thiol group, a nitrile group, a -NH ₂ , a phthalimide group, or a methyl methacrylate group,
m, n, p and q are each an integer of 3,
r2 is 3, R ₂ is the same as or different from each other. delete delete delete delete The compound of claim 1, wherein the compound represented by Chemical Formula 1 is represented by any one of the following compounds:

A color material composition comprising the compound of any one of claims 1 and 6. The color material composition according to claim 7, further comprising at least one of dyes and pigments. A compound represented by formula 1 according to claim 1; Binder resins; Polyfunctional monomers; Photoinitiators; And a solvent. The method according to claim 9,
Based on the total weight of solids in the resin composition
The content of the compound represented by Formula 1 is 5% by weight to 60% by weight,
The binder resin content is 1% by weight to 60% by weight,
The content of the photoinitiator is 0.1% by weight to 20% by weight,
The content of the multifunctional monomer is a resin composition of 0.1% by weight to 50% by weight. The resin composition of Claim 9 which further contains antioxidant. The photosensitive material manufactured using the resin composition of Claim 9. A color filter comprising the photosensitive material according to claim 12. Display device including a color filter according to claim 13.