WO2018203641A2 - Colorant compound and coloring composition comprising same - Google Patents

Abstract

The present invention relates to a colorant and a coloring composition comprising same. In particular, the present invention relates to a colorant having a novel structure and a coloring composition comprising same, the colorant exhibiting excellent color properties and thermal resistance and thus being usable for color filter production.

Description

 [Name of invention]

 Colorant Compound and Coloring Composition Comprising the Same

Technical Field

 Cross Citation with Related Application (s)

 This application claims the benefit of priority based on Korean Patent Application No. 10-2017-0056456 dated May 2, 2017, and all content disclosed in the literature of that Korean patent application is incorporated as part of this specification.

 The present invention relates to a colorant compound and a coloring composition comprising the same. More specifically, the present invention relates to a colorant compound having a novel structure exhibiting excellent color characteristics and heat resistance, and a coloring composition comprising the same.

[Technique to become background of invention]

 Color filters used in liquid crystal displays (LCDs) and organic light emitting diodes (OLEDs) are used to implement color images in display devices. It can be produced through the process of oxidization.

 The color filter is formed of three pixel portions of red, green, and blue on a transparent substrate such as glass, and color filters used in an image display device or a solid state image pickup device are typically red (R), green (G), and It has a coloring pattern of three primary colors of blue (B), and serves to color the light passing through or to separate it into three primary colors.

 The red, green, and blue pigments are composed of fine particles, that is, pigments or dyes, and these pigments are mixed with pigments having similar colors rather than being used alone to obtain color display characteristics of desired areas. Red, green and blue will be displayed.

 The material used as a dye is required to have a color absorption property desirable ¾ absorption properties, and to be resistant to oxidizing gases such as light resistance, heat resistance and ozone under the conditions used.

In recent years, the technology development of the large screen and high definition of a liquid crystal display is progressing. In such a situation, the color filter used for a liquid crystal display etc. is high It is required to have color purity. Various pigments or colorants that can be used in the production of color filters are known, but methods for improving color purity, brightness, and contrast ratio using only known color materials are gradually reaching their limit points.

 In addition, there is a method of increasing the content of the pigment to the solid content of the photosensitive resin composition for color filters in order to improve the color purity, but in order to thin the color filter is required to reduce the amount of the dye used, to overcome the above problems, the large screen There is a demand for the development of new pigments to meet the requirements for high resolution and high definition. [Invention and contents]

 Problem to be solved

 The present invention is to solve the above problems, to provide a colorant compound having a novel structure that can be used as a color filter colorant excellent in color reproducibility, color characteristics, heat resistance, light resistance, etc. and a coloring composition comprising the same. .

[Measures of problem]

 In order to solve the above problems of the present invention

It provides a colorant compound represented by the following formula (1).

 [Formula 1]

 In Chemical Formula 1,

R ¹ is —S0 ₃ M (M is hydrogen, an alkali metal, or a quaternary ammonium salt) or

-S0 ₂ NHR '(R' is hydrogen or an alkyl group having 1 to 20 carbon atoms), _n represents an integer of o to 4, when n is an integer of 2 or more, a plurality of R ¹ may be the same or different,

At least one of 2 to R ⁵ is represented by the following formula la,

The remainder of R ² to R ⁵ , which are not represented by the following formula la, independently represent hydrogen, a substituted or unsubstituted C 1 -C 20 alkyl group; A substituted or unsubstituted C1-C20 alkoxy group; A substituted or unsubstituted C1-C20 hydroxyalkyl group; Substituted or unsubstituted C6-C30 aryl group; A substituted or unsubstituted C7-C30 arylalkyl group; A substituted or unsubstituted C7-C30 alkylaryl group; Or a substituted or unsubstituted C2-C30 heteroaryl group,

 [Formula la] In Formula la,

R ^{1 1} is a direct bond or a C 1 -C 10 alkylene group; Q is -COO-, or -OCO-; R ¹² is a direct bond or a C1-C 10 alkylene group; A is a C6-C30 aryl group substituted with one or more hydroxy groups, or a C7-C30 alkylaryl group substituted with one or more hydroxy groups. Furthermore, this invention provides the coloring composition containing the said coloring agent compound, binder resin, a polymeric compound, and a photoinitiator.

【Effects of the Invention】

 The colorant compound for a color filter of the present invention is a compound of a novel structure which is not known in the art, and includes a specific group and may exhibit stable color reproducibility and excellent heat resistance and light resistance.

 Thus, a color filter can be prepared using a coloring composition comprising the coloring agent compound of the present invention. In this case, a high-resolution color filter exhibiting excellent color reproducibility, color characteristics, heat resistance, and light resistance may be manufactured.

【Brief Description of Drawings】

1 is a color pattern using a resin composition according to an embodiment of the present invention It is a graph showing the transmittance spectrum according to the wavelength of the substrate.

 2 is a graph showing a transmittance spectrum according to a wavelength of a color pattern substrate using a resin composition according to an embodiment of the present invention.

 3 is a graph showing a transmittance spectrum according to a wavelength of a color pattern substrate using a resin composition according to an embodiment of the present invention.

 4 is a graph showing a transmittance spectrum according to a wavelength of a color pattern substrate using a resin composition according to an embodiment of the present invention.

 5 is a graph showing a transmittance spectrum according to a wavelength of a color pattern substrate using a resin composition according to a comparative example of the present invention.

 6 is a graph showing a transmittance spectrum according to a wavelength of a color pattern substrate using a resin composition according to a comparative example of the present invention.

[Specific contents to carry out invention]

 As the invention allows for various changes and numerous embodiments, particular embodiments will be illustrated and described in detail below. However, this is not intended to limit the present invention to the specific disclosed form, it should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.

 Hereinafter, the colored crab compound of the present invention and the colored composition including the same will be described in more detail. Colorant compound

 The colorant compound according to one embodiment of the present invention is represented by the following formula (I).

[Formula 1]

 In Chemical Formula 1,

R 'is -S0 ₃ M (M is hydrogen, alkali metal, or quaternary ammonium salt) or -S0 ₂ NHR' (R 'is hydrogen or an alkyl group having 1 to 20 carbon atoms),

 n represents an integer of 0 to 4, and when n is an integer of 2 or more, a plurality of

R ¹ may be the same or different,

At least one of R ² to R ⁵ is represented by the formula la,

The remainder of R ² to R ⁵ , which are not represented by the following formula la, each independently represent hydrogen, a substituted or unsubstituted C 1 -C 20 alkyl group; A substituted or unsubstituted C 1 -C 20 alkoxy group; A substituted or unsubstituted C1-C20 hydroxyoxyalkyl group; Substituted or unsubstituted C6-C30 aryl group; A substituted or unsubstituted C7-C30 arylalkyl group; A substituted or unsubstituted C7-C30 alkylaryl group; Or a substituted or unsubstituted C2-C30 heteroaryl group,

 [Formula la]

* ― R ¹¹ —— Q― R ¹² — A

 In the formula la,

RN is a direct bond or a ci-c io alkylene group; Q is -COO-, or -OCO-; R ¹² is a direct bond or a C1-C10 alkylene group; A is a C6-C30 aryl group substituted with one or more hydroxy groups, or a C7-C30 alkylaryl group substituted with one or more hydroxy groups.

 Meanwhile, in the present specification, * ᅳ means a bond connected to another substituent.

As used herein, the term "substituted or unsubstituted" is deuterium; Halogen group; Nitrile group; Nitro group; Hydroxy group; Carbonyl group; Ester group; Imide group; Amino group; Phosphine oxide groups; An alkoxy group; Aryloxy group; Alkyl thioxy group; Arylthioxy group alkyl sulfoxy group; Aryl sulfoxy group; Aryl sulfoxy group; Silyl groups; Boron group; Alkyl group cycloalkyl group; Alkenyl groups; Aryl group; Aralkyl group; Ar alkenyl group; Alkylaryl group alkylamine group; Aralkyl amine groups; Heteroarylamine group; Arylamine group; Aryl phosphine group; -S0 ₃ H, -S0 ₃ X, wherein X is a metal cation, or onium cation, -S0 ₂ NHR, wherein R is H or an alkyl group having 1 to 20 carbon atoms; Or substituted or unsubstituted with one or more substituents selected from the group consisting of heterocyclic groups including one or more of N, 0 and S atoms, or two or more substituents of the above-described substituents connected or substituted. . For example, "a substituent to which two or more substituents are linked" may be a biphenyl group. That is, the biphenyl group may be an aryl group and can be interpreted as a substituent to which two phenyl groups are linked.

According to an embodiment of the present invention, the substituent may be -S0 ₃ X, where X is a metal cation, or an onium cation. As a metal cation, bivalent metal cations, such as monovalent metal cations, such as lithium ion, sodium ion, and potassium ion, magnesium ion, calcium ion, are mentioned, for example. As an onium cation, an ammonium cation, a phosphonium cation, etc. are mentioned. As said ammonium cation, for example, tetramethylammonium, tetraethylammonium monostearyltrimethylammonium, distearyldimethylammonium tristearyl monomethylammonium, cetyltrimethylammonium, trioctylmethylammonium dioctyldimethylammonium, monolauryl Trimethylammonium, dilauryldimethylammonium trilaurylmethylammonium, triamylbenzylammonium, trinuxylbenzylammonium trioctylbenzylammonium, trilaurylbenzylammonium, benzyldimethylstearylammonium benzyldimethyloctylammonium, dialkyl (alkyl is C14 to C18) dimethyl ammonium, etc. are mentioned. As said phosphonium cation, tetraalkyl phosphonium, benzyl, such as methyl trioctyl phosphonium, octyl tributyl phosphonium, dodecyl tributyl phosphonium, nuxadecyl tributyl phosphonium, dinuxyl dioxyl phosphonium, etc., for example. Tetraaryl phosphates, such as aryl trialkyl phosphonium, such as tributyl phosphonium, dialkyl diaryl phosphonium, such as dibutyl diphenyl phosphonium, alkyl triphenyl phosphonium, such as butyl triphenyl phosphonium, and benzyl triphenyl phosphonium Phosphium etc. are mentioned.

In the present specification, the aryl group has 6 to 30 carbon atoms, or 6 to 30 carbon atoms 20 or C6-C12 monocyclic aryl group or polycyclic aryl group. The monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc., but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, and the like, but is not limited thereto.

 In the present specification, the heteroaryl group is a heteroaryl group containing one or more of 0, N, and S as heterologous elements, and the carbon number is not particularly limited, but is preferably 2 to 30 carbon atoms. Examples of the heteroaryl group include thiophene group, furan group, pyr group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, triazole group , Aridyl, pyridazine, pyrazinyl, quinolinyl, quinazolin, quinoxalinyl, phthalazinyl, pyrido pyrimidinyl, pyrido pyrazinyl, pyrazino pyrazinyl, isoquinoline Group, indole group, carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthrolin group (phenanthrolhie), thiazolyl group , Isooxazolyl group, oxdiazolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group, dibenzofuranyl group, and the like, but is not limited thereto.

In the present specification, the alkyl group may be a linear or branched alkyl group having 1 to 20 carbon atoms, or 1 to 10 carbon atoms, or 1 to 5 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, _n -Pentyl, isopentyl, neopentyl, tert-pentyl, nuclear chamber, H-nuclear chamber, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylnuclear, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylnuclear, 2-propylpentyl, a-nonyl, 2,2-dimethylheptyl, I-ethyl- Propyl, 1, 1-dimethyl-propyl, isonuclear chamber, 2-methylpentyl, 4-methylnuclear chamber, 5-methylnuclear chamber, and the like, but is not limited thereto.

 In the present specification, the aryl group in the arylalkyl group and the alkylaryl group is the same as the examples of the aryl group described above. In the present specification, the alkyl group of the arylalkyl group and the alkylaryl group is the same as the examples of the alkyl group described above.

The colorant compound of Formula 1 is a xanthene derivative compound, At least one of R ² to R ⁵ has a novel structure represented by the following formula la.

 [Formula la]

* — R ¹¹ —— Q— R ¹² ― A

 In the formula la,

R ^{1 1} is a direct bond or a C1-C10 alkylene group; Q is -COO-, or -OCO-; R ¹² is a direct bond or a C1-C 10 alkylene group; A is a C6-C30 aryl group substituted with one or more hydroxy groups, or a C7-C30 alkylaryl group substituted with one or more hydroxy groups.

According to an embodiment of the present invention, one or two of the R ² to R ⁵ may be represented by the formula la.

According to an embodiment of the present invention, in formula la, R ^{1 1} is a direct bond or a C1-C5 alkylene group; Q is -COO-, or -OCO-; R ¹² may be a direct bond or a C1-C5 alkylene group.

According to an embodiment of the present invention, in the general formula (I), the remainder not represented by the following formula la among R ² to R ⁵ is a methyl group, ethyl group, n-propyl group, iso-propyl group, 2-hydroxy ethyl group, 3- Hydroxypropyl group, benzyl group, methylbenzyl group, dimethylbenzyl group, trimethylbenzyl group, ethylbenzyl group, diethylbenzyl group, triethylbenzyl group ^' , propylbenzyl group, dipropylbenzyl group, tripropylbenzyl group It may be a oxybenzyl group, or an ethoxybenzyl group, but the present invention is not limited thereto.

 According to an embodiment of the present invention, A may be represented by the following formula lb.

 [

 In the formula lb,

At least one of R ^a , R ^b , ^c , R ^d , and R ^e is a hydroxy group (—OH), and the others are independently of each other hydrogen, a straight chain alkyl group of C 1 -C 20, or a branched chain of C 3 -C 20 It is an alkyl group.

According to an embodiment of the present invention, in the formula lb,！ is a hydroxyl group, R ^b , and R ^d are independently of each other a C3-C20, or C3-C10, or a branched alkyl group of C3-C6, R ^a And R ^e may be hydrogen.

 Due to the structure of Formula la as described above, the colorant compound of Formula 1 including the improved color purity compared to the conventional colorant compound or xanthene, it can exhibit excellent color reproducibility, high brightness, and high contrast ratio.

According to an embodiment of the present invention, in Formula 1, -S0 ₃ M (M is hydrogen, alkali metal, or quaternary ammonium salt) or -S0 ₂ NHR '(R' is hydrogen or an alkyl group having 1 to 20 carbon atoms) More specifically, R ¹ may be -S0 ₃ Li, -S0 ₃ Na, or -S0 ₃ K.

 According to one embodiment of the present invention, the compound represented by Formula I may be any one selected from the group consisting of, but the present invention is not limited thereto.

SZ0S00 / 8T0ZaM / X3d T1 ⁷ 9C0Z / 810Z OAV

In the above structural formulas, X is a metal cation or an onium cation, and R is H or an alkyl group having 1 to 20 carbon atoms. Detailed description of the X is as described above in -so ₃ x.

According to an embodiment of the present invention, R may be a straight chain alkyl group having 1 to 20 carbon atoms, or 1 to 10 carbon atoms, or a branched chain alkali group having 2 to 20 carbon atoms or 2 to 10 carbon atoms. More specifically, R is methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, ^ Ethyl-butyl, pentyl, _η -pentyl, isopentyl, neopentyl, tert-pentyl, nuclear chamber, _η -nuclear chamber, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethyl Butyl, 2-ethylbutyl, heptyl, η-heptyl, 1-methylnuclear, octyl, η-octyl, tert-octyl, 1-methylheptyl, 2-ethylnuclear, 2-ethylheptyl, 2-propylpentyl, etc. Or not limited to these.

 The colorant compound of Formula 1 may be prepared by esterification of the compound of Formula 2 with the compound of Formula 3. The manufacturing method may be more specific in the synthesis examples to be described later.

 [Formula 2]

 In the chemical cutting 2,

R 'is -S0 ₃ M (M is hydrogen, alkali metal, or quaternary ammonium salt) or -S0 ₂ NHR' (R 'is hydrogen or an alkyl group having 1 to 20 carbon atoms),

n represents an integer of 0 to 4, when n is an integer of 2 or more, a plurality of R ¹ may be the same or different,

At least one of R ²⁰ to R ⁵⁰ is —R ⁿ —OH, wherein R ^{1 1} is a direct bond or a C1-C10 alkylene group,

The remainder other than -ί ^ -ΟΗ of R ²⁰ to R ⁵⁰ is independently of each other hydrogen, a substituted or unsubstituted C 1 -C 20 alkyl group; A substituted or unsubstituted C 1 -C 20 alkoxy group; A substituted or unsubstituted C 1 -C 20 hydroxyalkyl group; Substituted or unsubstituted C6-C30 aryl group; A substituted or unsubstituted C7-C30 arylalkyl group; A substituted or unsubstituted C7-C30 alkylaryl group; Or a substituted or unsubstituted C2-C30 heteroaryl group.

[Formula 3]

 In Chemical Formula 3,

 Is a direct bond- or C1-C10 alkylene group; A is a C6-C30 aryl group substituted with one or more hydroxy groups, or a C7-C30 alkylaryl group substituted with one or more hydroxy groups. Coloring composition

 According to another embodiment of the present invention, there is provided a colorant composition comprising a colorant compound of Formula 1, a binder resin, a polymerizable compound, and a photoinitiator.

 In Formula I,

R ¹ is —S0 ₃ M (M is hydrogen, an alkali metal, or a quaternary ammonium salt) or —S0 ₂ NHR ′ (R ′ is hydrogen or an alkyl group having 1 to 20 carbon atoms),

n represents an integer of 0 to 4, when n is an integer of 2 or more, a plurality of R ¹ may be the same or different,

At least one of R ² to R ⁵ is represented by the formula la,

The remaining ones of R ² to R ⁵ , which are not represented by the following formula la are independently of each other hydrogen, a substituted or unsubstituted C 1 -C 20 alkyl group; A substituted or unsubstituted CI-C20 alkoxy group; A substituted or unsubstituted C1 'C20 hydroxyalkyl group; Substituted or unsubstituted C6-C30 aryl group; A substituted or unsubstituted C7-C30 arylalkyl group; A substituted or unsubstituted C7-C30 alkylaryl group; Or substituted or unsubstituted C2-C30 Heteroaryl group,

 [Formula l a]

* — R ¹¹ —— Q— R ¹² — A

 In Formula l a,

 R ″ is a direct bond or a C1-C10 alkylene group; Q is -COO-, or

-OCO-; R ¹² is a direct bond or a C 1 -C 10 alkylene group; A is a C6-C30 aryl group substituted with one or more hydroxy groups, or a C7-C30 alkylaryl group substituted with one or more hydroxy groups.

 Detailed description and specific examples of the colorant compound of Formula 1 are as described above.

 The colorant compound is about 10 parts by weight or more, or about 15 parts by weight or more, or about 20 parts by weight or more, about 50 parts by weight or less, based on 100 parts by weight of solid contents included in the coloring composition, Or about 40 parts by weight, or about 30 parts by weight or less. When the content of the colorant compound is too small, the color purity may be lowered, and when too high, curing reaction of the resin composition may not occur properly, so it is preferably included in the above range.

 In the coloring composition of this invention, the coloring agent compound of the said General formula (1) can be used individually or in mixture of 2 or more types.

 In addition, the coloring composition of the present invention may optionally further include other known coloring agents in addition to the coloring compound of the formula (1) as needed.

 The polymer resin is not particularly limited, and those generally used in the art to which the present invention pertains may be used, and preferably an alkali-soluble resin may be used.

 Specifically, (meth) acrylic resins, acrylamide resins, novolac resins, and the like may be used as the alkali-soluble resin, and preferably, those having a weight average molecular weight (Mw) of 3,000 to 150,000 g / m may be used. The present invention is not limited thereto.

The content of the polymer resin is about 3 parts by weight or more, or about 5 parts by weight or more, or about 10 parts by weight based on 100 parts by weight of the solid content included in the coloring composition. It may be included by weight or more, about 30 parts by weight or less, or about 20 parts by weight, or about 15 parts by weight or less, but the present invention is not limited thereto.

 The polymerizable compound is not particularly limited, and those generally used in the art to which the present invention pertains may be used, and preferably compounds having an ethylenically unsaturated group may be used. The compound having an ethylenically unsaturated group may be an acrylate compound.

 More specifically, examples of the polymerizable compound include pentaerythri tri (meth) acrylate, dipentaerythri tri (meth) acrylate, pentaerythri tetra (meth) acrylate, dipentaerythri One or more compounds selected from nucleated (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and the like may be used, but the present invention is not limited thereto.

 The content of the polymerizable compound is about 30 parts by weight or more, or about 40 parts by weight, or about 50 parts by weight or more, about 80 parts by weight or less, or about 70 parts by weight of solids contained in the coloring composition. It may be included in parts by weight, or about 60 parts by weight or less, but the present invention is not limited thereto.

 According to the exemplary embodiment of the present specification, the photopolymerization initiator may be 2,4-trichloromethyl- (4'-methoxyphenyl) -6-triazine, 2,4-trichloromethyl- (4'-methic Cystyryl) -6-triazine,

2,4-trichloromethyl- (piflonil) 6-triazine, 1-hydroxycyclonucleosil phenyl ketone, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy) propyl ketone, benzophenone ，

One or more compounds selected from 2,4,6-trimethylaminobenzophenone and the like can be used, but are not limited thereto.

 The content of the photopolymerization initiator may be about 0.1 to about 10 parts by weight with respect to 100 parts by weight of the solid content included in the coloring composition, but the present invention is not limited thereto.

 The coloring composition of this invention may further contain a solvent in order to improve applicability | paintability and workability.

According to an embodiment of the present disclosure, the solvent is methyl ethyl cairn, methyl cellosolve, ethyl cellosolve, 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, 2-especial propanol, 2-methoxy propane, 3-methoxy Butanol, Cyclonuxanon, Cyclopentanone, Propylene glycol methyl ether acetate, Propylene glycol ethyl ether acetate, 3-methoxybutyl acetate, Ethyl 3-ethoxypropionate, ethyl cellosolve acetate, methyl cellosolve acetate, butyl acetate One or more compounds selected from dipropylene glycol monomethyl ether and the like may be used, but is not limited thereto.

 The content of the solvent is not particularly limited because it can be adjusted in consideration of coating properties and workability, for example, may be included in about 50 to about 500 parts by weight based on 100 parts by weight of the solid content included in the coloring composition.

 According to an embodiment of the present invention, the coloring composition, in addition to the above-described components, the curing accelerator, heat polymerization inhibitor, dispersant, antioxidant, ultraviolet absorber, leveling agent, photosensitizer, plasticizer, adhesion promoter, layering agent, or It may further include an additive which may be included in a conventional color composition for color filters such as a surfactant.

 Examples of the curing accelerator include 2-mercaptobenzoimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2,5-dimercapto-1,3,4-thiadiazole,

2-mercapto-4,6-dimethylaminopyridine, pentaerythri tetrakis (3-mercaptopropionate), pentaerythri tris (3-mercaptopropionate), pentaerythri tetrakis (2-mergaptoacetate), pentaerythritol tris (2-mercaptoacetate), trimethylolpropane tris (2-mergaptoacetate), trimethyl to propane tris (3-mergaptopropionate), trimethylol Ethane tris (2-mergaptoacetate), and trimethyl may include one or more selected from the group consisting of ethane tris (3-mergaptopropionate), but is not limited thereto. It may include those generally known in. On the other hand, the coloring composition according to an embodiment of the present invention can be used to produce a color filter by a method generally known in the art, for example, a printing method or a photolithography method.

For example, according to the photolithography method, the coloring composition is transferred to a transparent substrate. It is apply | coated by the method of spray coating, spin coating, slit coating, roll coating, immersion, etc. on a surface. An exposure process is selectively performed through a mask having a predetermined pattern in the coating film. Meanwhile, the pre bake and / or post bake heat treatment may be further performed. After exposure, the coloring composition is developed to form a desired photoresist pattern. By washing and drying the developed substrate, a color filter in which a photoresist pattern of a desired shape is formed can be obtained.

 According to the colorant for color filters of the present invention described above and the coloring composition comprising the same, due to the novel structure of the colorant compound may have excellent color properties.

 In addition, the colorant for color filters of the present invention can improve heat resistance without deterioration in transmittance, color purity, and storage stability as compared with conventional colorant compounds.

 Therefore, when using the coloring composition of this invention, a highly reliable and high resolution color filter can be manufactured.

 Hereinafter, the operation and effects of the present invention will be described in more detail with reference to specific embodiments of the present invention. However, these embodiments are only presented as an example of the invention, whereby the scope of the invention is not determined.

<Example>

 Synthesis Example of Colorant Compound

1.084 g (4.330 mmol) of Compound B-1 were added to 50 g of A-1 B-1 mm 1 methylene chloride and stirred. Ice bath (ice bath) was set to 0 ^° C, then N- (3-Dimethylaminopropyl) -N'-ethylcarbodiimide hydi chloride (EDC-HCl)

0.830 g (4.330 mmol) was added and stirred for 15 minutes. Small amount of dimethylformamide ，

4-dimethylaminopyridine 0.141 g (1.155 mmol) was added, compound A-1 0.737 g (1.443 mmol) was added, reacted at 0 ^° C. for 2 hours, and reacted at room temperature overnight. 100 ml of distilled water and 50 ml of methylene chloride were further added, and the organic layer was passed through Na ₂ SO ₄ to remove moisture and the solvent was removed under reduced pressure. The precipitate was then separated via column chromatography (Eluent-methylenechloride: methanol). As a result, the title compound l (0.422 g, 0.433 mmol) was obtained and the yield was 30%.

 Ionization mode = ： APCI +: m / z = 975.4 [M + H] +, Exact Mass: 974.4

1.084 g (4.330 mmol) of Compound B-1 were added to 100 g of methylene chloride, followed by stirring. An ice bath was installed to make 0 ^° C., and then 0.830 g (4.330 mmol) of N- (3-DLmethylaminopiOpyl) -N'-ethylcarbodiimide hydrochloride (EDC-HCl) was added and stirred for 15 minutes. Add a small amount of dimethylformamide, 4-dimethylaminopyridine 0.141 g (1.155 mmol), add 2.2 l lg (4.330 mmol) of Compound A-1, react at 0 ^° C for 2 hours, and keep at room temperature overnight (overnight ). 100 ml of distilled water and 50 g of methylene chloride were further added, and the organic layer was passed through Na ₂ SO ₄ to remove moisture and the solvent was removed under reduced pressure. The precipitate was then separated by column chromatography. (Eluent-methylene chloride: methanol). As a result, the title compound 2 (0.804 g, 1.083 mmol) was obtained and a yield was 25%.

 Ionization Mode = ： APCI +: m / z = 743.3 [M + H] +, Exact Mass: 742.3

A-1 B-2 No. 3 Synthesis Example 1 was synthesized in the same manner as in Synthesis Example 1, except that Compound B-2 l.205 g (4.33 mmol) was used instead of Compound B-1. As a result, the title compound 3 (0.670 g, () .650 mmol) was obtained. The yield was 45%.

Ionization mode = ： APCI +: m / z = 1031.5 [M + H] +, Exact Mass: 1030.5 Synthesis Example 4 Synthesis of Compound 4

 Α-1 Β-2 Sum ¾ | 4 Synthesis Example 2 was synthesized in the same manner as in Synthesis Example 2, except that 1.205 g (4.330 mmol) of Compound B-2 was used instead of Compound B-1. As a result, the title compound 4 (U68g, 1.5l6mmol) was obtained, and a yield was 35%.

Ionization mode = ： APC ^[ +: ml z = 74l.3 [M + H] +, Exact Mass: 740.3

 A-2 Compound Module 5

 Synthesis Example 1 was synthesized in the same manner as in Synthesis Example 1, except that 0.996 g (1.443 mmol) of Compound A-2 was used instead of Compound A-1. As a result, the title compound 5 (0.41 lg, 0.361 mmol) was obtained and the yield was 21.5%.

Ionization mode = ： APCi +: m / z = l 139.5 [M + H] +, Exact Mass: 1138.5

 A-2 B—1 Compound 6 Synthesis Example 2 was synthesized in the same manner as in Synthesis Example 2 except for using 2.991 g (4.33 mmol) of Compound A-2 instead of Compound A-1. As a result, the title compound

6 (0.720 g, 0.792 mmol) was obtained and the yield was 18.3%.

 Ionization mode = ： APCI +: m / z = 909.4 [M + H] +, Exact Mass: 908.4

 A-2 B-2 Compound 7 In Synthesis Example 1, except that Compound A-2 0.996 g (1.443 mmol) was used instead of Compound A-1, and Compound B-2 1.205 g (4.330 mmol) was used instead of Compound B-. Was synthesized in the same manner as in Synthesis example I. As a result, the title compound 7 (0.320 g, 0.264 mmol) was obtained, and the yield was 18.3%.

Ionization mode = ： APCI +: m / z = 909.4 [M + H] +, Exact Mass: 908.4

 A-2 8-2

 Synthesis Example 2 was used in the same manner as in Synthesis Example 2 except that Compound A-2 2.99 lg (4.33 mmol) was used instead of Compound A-1, and Compound B-2 1.205 g (4.330 mmol) was used instead of Compound B-1. And synthesized. As a result, the title compound 8 (0.437 g, 0.459 mmol) was obtained and the yield was 10.6%.

 Ionization mode = ： APCI +: m / z = 909.4 [M + H] +, Exact Mass: 908.4

 Except for using the compound A-3 instead of compound A-1 in Synthesis Example 1 and was synthesized in the same manner as in Synthesis Example 1 to obtain the title compound 9.

 Ionization mode = ： APCI +: ml z = 1211.6 [M + H] +, Exact Mass: 1210.6

A-3 B-1 Compound 10 Synthesis Example 2 except that Compound A-3 was used instead of Compound A-1 Synthesis was performed in the same manner as in Synthesis example 2 to obtain the title compound 10. Ionization mode = ： APCI +: m / z = 979.4 [M + H] +, Exact Mass: 978.4

 A-3 B-2 compound was synthesized in the same manner as in Synthesis Example 3 except that Compound A-3 was used instead of Compound A-2 in Synthesis Example 3 to obtain the title compound U.

Ionization mode = ： APCI +: m / z = 1267.6 [M + H] +, Exact Mass: 1266.6

 Synthesis Example 4 was obtained in the same manner as in Synthesis Example 4 except that Compound A-3 was used instead of Compound A-2 to obtain the title compound 12.

Ionization mode =: APCI +: nV z = 1007.5 [M + H] +, Exact Mass: 1006.5 Synthesis Example 13 Synthesis of Compound 13

 A-4 1

 Synthesis Example 1 Synthesis was carried out in the same manner as in Synthesis Example 1, except that Compound A-4 was used instead of Compound A-1 to obtain the title compound 13.

Ionization mode =: ᅀ 1 1+: 1/2 = 1099.5 [+ +, 5 3 & 85 ： 1098.5

 Synthesis Example 2 was used in the same manner as in Synthesis Example 2 except for using Compound A-4 instead of Compound A-1 to obtain the title compound 14.

 Ionization mode = ： APCI +: m / z = 895.3 [M + H] +, Exact Mass: 894.3 Synthesis Example 15 Synthesis of Compound 15

Compound 15 was obtained in the same manner as in Synthesis Example 3 except that Compound A-4 was used instead of Compound A-1 in Synthesis Example 3 to obtain the title compound 15.

 Ionization Mode =: APCI +: m / z = U55.5 [M + H] +, Exact Mass: 1154.5

 A-4 B-2

 Compound 16 was obtained in the same manner as in Synthesis 4 except that Compound A-4 was used instead of Compound A-1 to obtain the title compound 16.

 Ionization mode = ： APCI +: m / z = 895.3 [M + H] +, Exact Mass: 894.3

 A-5 B-1 ¾tS17 Compound 1-1 was synthesized in Synthesis Example 1, except that Compound A-5 was used, and was synthesized in the same manner as in Synthesis Example 1 to obtain the title compound 17.

Ionization mode = ： APCI +: ml z = 1267.6 [M + H] +, Exact Mass: 1266.6 Synthesis Example 18 Synthesis of Compound 18

 A-5 B-1 «¾ 18 Synthesis was carried out in the same manner as in Synthesis Example 2, except that Compound A-5 was used instead of Compound A-1 in Synthesis Example 2 to obtain the title compound 18.

 Ionization mode = ： APCI +: m / z = 1035.5 [M + H] +, Exact Mass: 1034.5

 Except for using the compound A-5 instead of compound A-1 in Synthesis Example 3 and was synthesized in the same manner as in Synthesis Example 3 to obtain the title compound 19.

Ionization mode = ： APCI +: m / z = 1323.7 [M + H] +, Exact Mass: 1322.7 Synthesis Example 20: Synthesis of Compound 20

 A -5 B-2 20 Synthesis was carried out in the same manner as in Synthesis Example 4, except that Compound A-5 was used instead of Compound A-1 in Synthesis Example 4 to obtain the title compound 20.

 Ionization mode = ： APCI +: m / z = l 063.5 [M + H] +, Exact Mass: 1062.5

AS _8- m 21

 Compound 1 was obtained in the same manner as in Synthesis 1 except that Compound A-6 was used instead of Compound A-1 to obtain the title compound 21.

Ionization mode =: ᅀ 1 1+: 111 /

£ ∑ 358 ： 1182.6

Synthesis Example 2 was used in the same manner as in Synthesis Example 2 except for using the compound A-6 instead of the compound A-1 to obtain the title compound 22.

 Ionization mode = ： APCI +: m / z = 95 1.4 [M + H] +, Exact Mass: 950.4

 Synthesis Example 3 was used in the same manner as in Synthesis Example 3 except that Compound A-6 was used instead of Compound A-1 to obtain the title compound 23.

 Eunhwa mode = ： APCI +: ml z = 1239.6 [M + H] +, Exact Mass: 1238.6

Synthesis Example 4 except that Compound A-6 was used instead of Compound A-1 '' was synthesized in the same manner as in Synthesis Example 4 to obtain the title compound 24.

 Ionization mode = ： APCI +: m / z = 979.4 [M + H] +, Exact Mass: 978.4

Compound 25 was obtained in the same manner as in Synthesis Example 1 except that Compound A-7 was used instead of Compound A-1 in Synthesis Example 1.

 Ionization mode =: ᅀ 1 1+: 1 ᄁ / 2 = 1159.5 [+ +, £ 3 ^ 333: 1158.

A-1 B ^w 1 m 26

 Synthesis Example 2 was obtained in the same manner as in Synthesis Example 2 except that Compound A-7 was used instead of Compound A-1 to obtain the title compound 26.

 Ionization mode = ： APCI +: ml z = 927.3 [+ H] +, Exact Mass: 926.3

 A-7 8-2 m 27

Synthesis Example 3 was used in the same manner as in Synthesis Example 3 except that Compound A-7 was used instead of Compound A-1 to obtain the title compound 27. Ionization Mode =: APCI +: m / z = 1215.5 [M + H] +, Exact Mass: 1214.5

 Synthesis Example 4 was used in the same manner as in Synthesis Example 4 except that Compound A-7 was used instead of Compound A-1 to obtain the title compound 28.

 Ionization mode = ： APCI +: m / z = 955.4 [M + H] +, Exact Mass: 954.4 Comparative Example Compound 1

 Colorant of the formula (Basic blue 7) was obtained from TCI Chemicals and used as Comparative Example I.

Comparative Compound 2

 Colorants of the formula (Rhodamine 6G) were obtained from Sigma-Aldrich.

Comparative Example 2 was used.

<Example of Preparation of Resin Composition>

 Example 1

5.554 g of the colorant compound of Synthesis Example 1, a copolymer of benzyl methacrylate and methacrylic acid with a binder resin (molar ratio 70:30, acid value is 1 13 OH mg / g, weight average molecular weight 20,000 g / mol measured by GPC, Molecular weight distribution (PDI) 2.0, solid content (SC) 25%, solvent PGMEA) I0.376 g, polymerizable compound DPHA (dipentaerythritol hexaacrylate) (Japanese gunpowder) Π. ⁴⁴ , a total of 100g of a resin composition was prepared by mixing 2.018g of I- ³⁶ 9 (BASF) as a photoinitiator, 1.013g of F-475 (DIC) as an additive, and 68.593g of solvent PGMEA (Propylene Glycol Monomethyl Ether Acetate). Example 2

Colorant compound of Synthesis Example 1 ₅ . _{55 A} resin composition was prepared in the same manner as in Example 1 except that 5.554 g of the colorant compound of Synthesis Example 5 was used instead of 4 g. Example 3

 A resin composition was prepared in the same manner as in Example 1 except that 5.554 g of the colorant compound of Synthesis Example 9 was used instead of 5.554 g of the colorant compound of Synthesis Example 1. Example 4

Advantageously same manner as in Example 1, except that the colorant compound in the synthesis instead of ₅ .554g colorant compound of Synthesis Example 1 to Example 17 5.554g of the resin composition was prepared. Comparative Example 1

A resin composition was prepared in the same manner as in Example 1 except that 5.554 g of Comparative Example Compound 1 was used instead of 5.554 g of the colorant compound of Synthesis Example 1. Comparative Example 2 A resin composition was prepared in the same manner as in Example 1 except that 5.554 _g of Comparative Example Compound 2 was used instead of 5.554 _g of the colorant compound of Synthesis Example 1.

Experimental Example

 5 Light transmittance and heat resistance evaluation

 About the coloring composition of the said Example and the comparative example, light transmittance and heat resistance were evaluated by the following method.

Specifically, the resin compositions of Examples 1 to 4 and Comparative Examples 1 and 2 were spin coated on glass (5 × 5 cm) and subjected to an electrothermal treatment (pre 10 bake, prB) for 100 seconds at 100 ^° C. Was formed. An interval between the substrate on which the film was formed and the photo mask was 300, and the exposure amount of 40 mJ / cm ² was irradiated on the entire surface of the substrate using an exposure machine.

The exposed substrate was developed for 60 seconds in a developing solution (KOH, 0.05%), followed by post heat treatment (post bake, PB) at 230 ^° C. for 20 minutes to obtain a substrate on which a color pattern was formed.

i5

 In order to evaluate light transmittance and heat resistance, an absorption spectrum of a visible light region in the range of 380 nm to 780 nm was obtained using a spectrometer (MCPD Otsuka Co., Ltd.) on a substrate subjected to electrothermal treatment (pre bake, prB). In addition, for the substrate subjected to post heat treatment (post bake, PB), a transmittance spectrum of 20 was obtained in the same equipment and measurement range.

 About the color pattern board | substrate formed using the resin composition of Example 1, the transmittance spectrum according to the wavelength measured after electrothermal processing (prB) and post-heat processing (PB), respectively is shown in FIG.

 About the color pattern board | substrate formed using the resin composition of Example 2, the transmittance | permeability spectrum according to the wavelength measured after 25 heat-transfer treatment (prB) and post-heat treatment (PB), respectively is shown in FIG.

 About the color pattern substrate formed using the resin composition of Example 3, the transmittance | permeability spectrum according to the wavelength measured after the electrothermal treatment (ρι * Β) and the post-heat treatment (ΡΒ), respectively, is shown in FIG.

30 With respect to the color pattern substrate formed using the resin composition of Example 4, The transmittance spectra according to the wavelengths measured after the heat treatment (prB) and the after heat treatment (PB), respectively, are shown in FIG. 4.

 About the color pattern board | substrate formed using the resin composition of the comparative example 1, the transmittance | permeability spectrum according to the wavelength measured after electrothermal treatment (prB) and post-heat treatment (PB), respectively is shown in FIG.

Comparative Example 2 with respect to the substrate color pattern is formed by using the resin composition, shown in Figure ₆ a transmission spectrum according to a wavelength measured after each heat treatment (prB) and post - treatment (PB).

 In addition, AEab was calculated according to the following Equation 1 using the absorption spectrum obtained during the electrothermal treatment and the post-heat treatment and the values E (L *, a *, b *) obtained using the C light source backlight, and the results are shown in Table 1.

 [Equation 1]

Ab Eab (L *, a *, b *) = {(AL *) ² + (ᅀ a *) ² + (Ab *) ² }

 Table 1

 Referring to FIGS. I to 6 and Table 1, the color pattern substrate formed using the resin composition of the embodiment of the present invention has a higher color stability than the color pattern substrate formed using a conventionally known pigment, and has a post heat treatment and a post heat treatment. The difference in post-transmission spectrum (ΔΕΛ) was very small, indicating excellent heat resistance.

Claims

[Claim]

 [Claim 1]

 Represented by the following formula (1). Colorant Compound:

 In Chemical Formula 1,

R ¹ is —S0 ₃ M (M is hydrogen, an alkali metal, or quaternary ammonium salt) or —S0 ₂ NHR ′ (R ′ is hydrogen or an alkyl group having 1 to 20 carbon atoms),

n represents an integer of 0 to 4, when n is an integer of 2 or more, a plurality of R ¹ may be the same or different,

At least one of R ² to R ⁵ is represented by the formula la,

The remainder of R ² to R ⁵ , which are not represented by the following formula la, independently represent hydrogen, a substituted or unsubstituted C 1 -C 20 alkyl group; Substituted or unsubstituted

C1-C20 alkoxy group; A substituted or unsubstituted C1-C20 hydroxyalkyl group; Substituted or unsubstituted C6-C30 aryl group; A substituted or unsubstituted C7-C30 arylalkyl group; A substituted or unsubstituted C7-C30 alkylaryl group; Or a substituted or unsubstituted C2-C30 heteroaryl group,

 [Formula la]

* —— R ¹¹ —— Q— R ¹² — A

 In the formula la,

R ^u is a direct bond or a C1-C10 alkylene group; Q is -COO-, or

-OCO-; R ¹² is a direct bond or a C 1 -C10 alkylene group; A is a C6-C30 aryl group substituted with one or more hydroxy groups, or a C7-C30 alkylaryl group substituted with one or more hydroxy groups.

[Claim 2]

 The method of claim 1,

 A is a colorant compound represented by the following formula lb:

 [

 In the formula lb,

At least one of R ^a , R ^b , R ^c , R ^d , and R ^e is a hydroxy group (-OH), and the others are independently of each other hydrogen, a straight chain alkyl group of C1-C20, or a branched alkyl group of C3-C20 .

[Claim 3]

 The method of claim 2,

And R ^a and ^' are hydrogen, 1 is a hydroxy group, and R ^L \ and R ^d are each independently a branched alkyl group of C 3 -C 20.

[Claim 4]

 The method of claim 1,

R ¹ is —S0 ₃ Li, —S0 ₃ Na, or —S0 ₃ K. A colorant compound.

[Claim 5]

 The method of claim 1,

The compound represented by Formula 1 is any one selected from the group consisting of, a colorant compound:

SJOSOO / 8lOZaMX3d OAV OAVd _/ l _/ SS _E sssoo _S

L

£ Z0S00 / 8T0rHM / X3d T1 ⁷ 9C0Z / 810Z OAV Of

SZ0S00 / 8l0ZHM / X3d lt'9C0Z / 8T0Z OAV

In the above structural formulas, X is a metal cation or an onium cation, and R is H or an alkyl group having 1 to 20 carbon atoms.

[Claim 6]

 The coloring composition containing the coloring agent compound of Claim 1, a binder resin, a polymeric compound, and a photoinitiator. [Claim 7]

 The method of claim 6,

 10 to 50 parts by weight of the colorant compound, 3 to 30 parts by weight of the binder resin, 30 to 80 parts by weight of the polymerizable compound, and the photopolymerization, based on 100 parts by weight of solid contents included in the coloring composition. The coloring composition containing 0.1-10 weight part of initiators.