JP6897907B2 - Colorant compounds and coloring compositions containing them - Google Patents

Description

[Cross-reference of related applications]

This application claims the benefit of priority under Korean Patent Application No. 10-2017-0056456 dated May 2, 2017, and all the contents disclosed in the literature of the Korean patent application are part of this specification. Included as a part.

The present invention relates to a colorant compound and a coloring composition containing 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 containing the same.

Color filters used in liquid crystal displays (LCDs) and organic light emitting diodes (OLEDs) are used to realize color images in display devices, and dyes are used on the basic substrate using various methods. It can be manufactured through the steps of coating, curing and patterning.

A color filter is a transparent substrate such as glass in which each pixel portion of three colors of red, green, and blue is formed, and a color filter used for an image display device or a solid-state image sensor is usually red ( It has a coloring pattern of the three primary colors of R), green (G), and blue (B), and plays a role of coloring the passing light and separating it into the three primary colors.

The red, green, and blue dyes consist of fine particles, i.e. pigments or dyes, which are more similar than used alone to obtain color display properties in the desired region. The pigments that indicate the colors to be used are mixed to display red, green, and blue.

Substances used as dyes are generally required to have preferable absorption characteristics in terms of color reproducibility, light resistance under the conditions of use, heat resistance, and good resistance to oxidizing gases such as ozone. To.

Recently, technological developments for larger screens and higher clarity of liquid crystal displays have been promoted. In such a situation, the color filter used for a liquid crystal display or the like is required to have high color purity. Although various pigments or colorants that can be used in the production of color filters are known, methods for improving color purity, brightness, and light-dark ratio using only known color materials gradually reach the limit. There is.

Further, in order to improve the color purity, there is a method of increasing the content of the dye in the solid content of the photosensitive resin composition for the color filter, but in order to make the color filter thinner, the amount of the dye used can be reduced. Therefore, it is required to develop a new dye to overcome such a problem and satisfy the requirements for large screen and high sharpening.

An object of the present invention is to solve the above-mentioned problems, and to color a novel structure which is excellent in color reproducibility, color characteristics, heat resistance, light resistance, etc. and can be used as a colorant for a color filter. An object of the present invention is to provide an agent compound and a coloring composition containing the same.

In order to solve the above problems, according to one embodiment of the present invention, a colorant compound represented by the following chemical formula 1 is provided.

[Chemical formula 1]

前記化学式１ａで、
Ｒ^１１は直接結合またはＣ１−Ｃ１０アルキレン基であり；
Ｑは−ＣＯＯ−、または−ＯＣＯ−であり；
Ｒ^１２は直接結合またはＣ１−Ｃ１０アルキレン基であり；
Ａは一つ以上のヒドロキシ基で置換されたＣ６−Ｃ３０アリール基、または一つ以上のヒドロキシ基で置換されたＣ７−Ｃ３０アルキルアリール基である。 With the above chemical formula 1,
R ¹ is -SO ₃ M (M is hydrogen, alkali metal, or quaternary ammonium salt) or -SO ₂ NHR'(R'is hydrogen or an alkyl group having 1 to 20 carbon atoms).
n indicates an integer from 0 to 4, and when n is an integer of 2 or more, a plurality of R ^1s may be the same or different.
Any one or more of R ² to R ⁵ is represented by the following chemical formula 1a.
The ^{rest of R 2} to R ⁵ not represented by the following chemical formula 1a are independent of each other, hydrogen, substituted or unsubstituted C1-C20 alkyl groups; substituted or unsubstituted C1-C20 alkoxy groups; substituted or unsubstituted. C1-C20 hydroxyalkyl group; substituted or unsubstituted C6-C30 aryl group; substituted or unsubstituted C7-C30 arylalkyl group; substituted or unsubstituted C7-C30 alkylaryl group; or substituted or unsubstituted C2-C30 heteroaryl group,
[Chemical formula 1a]

In the chemical formula 1a,
R ¹¹ is a direct bond or C1-C10 alkylene group;
Q is -COO-, or -OCO-;
R ¹² 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.

The present invention also provides a coloring composition containing the colorant compound, a binder resin, a polymerizable compound, and a photoinitiator.

The colorant compound for a color filter of the present invention is a compound having a novel structure that has not been known in the past, contains a specific group (moiety), and exhibits stable color reproducibility, excellent heat resistance, and light resistance. be able to.

Therefore, when a color filter is produced using a coloring composition containing the colorant compound of the present invention, it is possible to produce a high-resolution color filter exhibiting excellent color reproducibility, color characteristics, heat resistance, and light resistance. it can.

It is a graph which shows the transmittance spectrum by the wavelength of the color pattern substrate using the resin composition by one Example of this invention. It is a graph which shows the transmittance spectrum by the wavelength of the color pattern substrate using the resin composition by one Example of this invention. It is a graph which shows the transmittance spectrum by the wavelength of the color pattern substrate using the resin composition by one Example of this invention. It is a graph which shows the transmittance spectrum by the wavelength of the color pattern substrate using the resin composition by one Example of this invention. It is a graph which shows the transmittance spectrum by the wavelength of the color pattern substrate using the resin composition by the comparative example of this invention. It is a graph which shows the transmittance spectrum by the wavelength of the color pattern substrate using the resin composition by the comparative example of this invention.

The present invention can be modified in various ways and can have various forms. Specific examples will be illustrated below in detail. However, this does not attempt to limit the invention to any particular form of disclosure, but must be understood to include all modifications, equivalents or alternatives contained within the ideas and technical scope of the invention. ..

Hereinafter, the colorant compound of the present invention and the coloring composition containing 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 chemical formula 1.

[Chemical formula 1]

前記化学式１ａで、
Ｒ^１１は直接結合またはＣ１−Ｃ１０アルキレン基であり；
Ｑは−ＣＯＯ−、または−ＯＣＯ−であり；
Ｒ^１２は直接結合またはＣ１−Ｃ１０アルキレン基であり；
Ａは一つ以上のヒドロキシ基で置換されたＣ６−Ｃ３０アリール基、または一つ以上のヒドロキシ基で置換されたＣ７−Ｃ３０アルキルアリール基である。 With the above chemical formula 1,
R ¹ is -SO ₃ M (M is hydrogen, alkali metal, or quaternary ammonium salt) or -SO ₂ NHR'(R'is hydrogen or an alkyl group having 1 to 20 carbon atoms).
n indicates an integer from 0 to 4, and when n is an integer of 2 or more, a plurality of R ^1s may be the same or different.
Any one or more of R ² to R ⁵ is represented by the following chemical formula 1a.
The ^{rest of R 2} to R ⁵ not represented by the following chemical formula 1a are independent of each other, hydrogen, substituted or unsubstituted C1-C20 alkyl groups; substituted or unsubstituted C1-C20 alkoxy groups; substituted or unsubstituted. C1-C20 hydroxyalkyl group; substituted or unsubstituted C6-C30 aryl group; substituted or unsubstituted C7-C30 arylalkyl group; substituted or unsubstituted C7-C30 alkylaryl group; or substituted or unsubstituted C2- C30 heteroaryl group
[Chemical formula 1a]

In the chemical formula 1a,
R ¹¹ is a direct bond or C1-C10 alkylene group;
Q is -COO-, or -OCO-;
R ¹² 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.

は他の置換基に連結される結合を意味する。 On the other hand, in this specification,

Means a bond linked to another substituent.

The term "substituted or unsubstituted" as used herein refers to dehydrogen; halogen group; nitrile group; nitro group; hydroxy group; carbonyl group; ester group; imide group; amino group; phosphine oxide group; alkoxy group; Aryloxy group; Alkyltioxy group; Arylthioxy group; Alkylsulfoxy group; Arylsulfoxic group; Cyril group; Boron group; Alkyl group; Cycloalkyl group; Alkenyl group; Aryl group; Alalkyl group; Alalkenyl group; alkylaryl groups; alkylamine group; aralkyl amine groups; a heteroaryl amine groups; arylamine group; an aryl phosphine _{group; -SO 3 H, -SO 3 X} ( at this time, the X is a metal cation or an onium cation,) , -SO ₂ NHR (where R is an H or an alkyl group having 1 to 20 carbon atoms); or 1 selected from the group consisting of heterocyclic groups containing one or more of the N, O and S atoms. It means that it is substituted or unsubstituted with one or more substituents, or that two or more of the above-exemplified substituents are linked and substituted or unsubstituted. For example, the "substituent in which two or more substituents are linked" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent in which two phenyl groups are linked.

According to an embodiment of the present invention, the substituent may be a -SO 3 _X, when this, X is like a metal cation or an onium cation. Examples of the metal cation include monovalent metal cations such as lithium ion, sodium ion and potassium ion, and divalent metal cations such as magnesium ion and calcium ion. Examples of the onium cation include ammonium cation and phosphonium cation. Examples of the ammonium cation include tetramethylammonium, tetraethylammonium, monostearyltrimethylammonium, distearyldimethylammonium, tristearylmonomethylammonium, cetyltrimethylammonium, trioctylmethylammonium, dioctyldimethylammonium, monolauryltrimethylammonium, and dilauryltrimethylammonium. Lauryldimethylammonium, trilaurylmethylammonium, triamylbenzylammonium, trihexylbenzylammonium, trioctylbenzylammonium, trilaurylbenzylammonium, benzyldimethylstearylammonium, benzyldimethyloctylammonium, dialkyl (alkyl C14 to C18) dimethylammonium, etc. Can be mentioned. Examples of the phosphonium cation include methyltrioctylphosphonium, octyltributylphosphonium, dodecyltributylphosphonium, hexadecyltributylphosphonium, tetraalkylphosphonium such as dihexyldioctylphosphonium, aryltrialkylphosphonium such as benzyltributylphosphonium, and dibutyldiphenylphosphonium. Examples thereof include alkyltriphenylphosphonium such as dialkyldiarylphosphonium and butyltriphenylphosphonium, and tetraarylphosphonium such as benzyltriphenylphosphonium.

As used herein, the aryl group may be a monocyclic aryl group or a polycyclic aryl group having 6 to 30 carbon atoms, 6 to 20 carbon atoms, or 6 to 12 carbon atoms. The monocyclic aryl group can be, but is not limited to, a phenyl group, a biphenyl group, a terphenyl group, or the like. The polycyclic aryl group can be, but is not limited to, a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenel group, a chrysenyl group, a fluorenyl group and the like.

In the present specification, the heteroaryl group is a heteroaryl group containing at least one of O, N, and S as a heterologous element, and the number of carbon atoms is not particularly limited, but the number of carbon atoms is 2 to 30. Is preferable. Examples of heteroaryl groups include thiophene group, furan group, pyrrol group, imidazole group, thiazole group, oxazole group, oxadiazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, triazole group, acrizyl group and pyridazine. Group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyridopyrimidinyl group, pyridopyrazinyl group, pyrazinopyrazinyl group, isoquinolin group, indol group, carbazole group, benzoxazole group, benzoimidazole group, benzo There are thiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthrolin group, thiazolyl group, isooxazolyl group, oxadiazolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group and dibenzofuranyl group However, it is not limited to these.

As used herein, 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 alkyl groups 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, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , N-Heptyl, 1-methylhexyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl , 1,1-Dimethyl-propyl, Isohexyl, 2-Methylpentyl, 4-Methylhexyl, 5-Methylhexyl and the like, but not limited to these.

In the present specification, the aryl group among the arylalkyl group and the alkylaryl group is as an example of the above-mentioned aryl group. In the present specification, the alkyl group among the arylalkyl group and the alkylaryl group is as an example of the above-mentioned alkyl group.

The colorant compound of the chemical formula 1 is a xanthene-based derivative compound, and ^{any one or more of R 2} to R ⁵ has a novel structure represented by the following chemical formula 1a.

[Chemical formula 1a]

In the chemical formula 1a,
R ¹¹ is a direct bond or C1-C10 alkylene group;
Q is -COO-, or -OCO-;
R ¹² 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.

According to one embodiment of the present invention, ^{one or two of R 2} to R ⁵ may be represented by the chemical formula 1a.

According to one embodiment of the invention, in said chemical formula 1a, R ¹¹ is a direct bond or C1-C5 alkylene group; Q is -COO-, or -OCO-; R ¹² is a direct bond or C1-C5. It may be an alkylene group.

According to one embodiment of the present invention, the ^{rest of R 2} to R ⁵ not represented by the following chemical formula 1a in the chemical formula 1 is a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, or 2-hydroxyethyl. Group, 3-hydroxypropyl group, benzyl group, methylbenzyl group, dimethylbenzyl group, trimethylbenzyl group, ethylbenzyl group, diethylbenzyl group, triethylbenzyl group, propylbenzyl group, dipropylbenzyl group, tripropylbenzyl group, methoxy It can be a benzyl group, an ethoxybenzyl group, etc., but the present invention is not limited thereto.

According to one embodiment of the present invention, the A may be represented by the following chemical formula 1b.

[Chemical formula 1b]

In the chemical formula 1b,
^{R a, R b, R c} , R d, and any one or more of ^{R e} is hydroxy (-OH), an the rest, independently of one another, hydrogen, straight chain alkyl group of C1-C20 , Or a branched-chain alkyl group of C3-C20.

According to one embodiment of the present invention, in the chemical formula 1b, R ^c is a hydroxy group, and R ^b and R ^d are independent branches of C3-C20, or C3-C10, or C3-C6. It is a chain alkyl group, and ^Ra and ^Re may be hydrogen.

Due to the structure of Chemical Formula 1a as described above, the colorant compound of Chemical Formula 1 containing the same has improved color purity as compared with the conventional colorant compound or xanthene, and has excellent color reproducibility, high brightness, and high brightness / darkness ratio. Can be shown.

According to an embodiment of the present invention, in the above chemical formula 1, R ¹ is -SO ₃ M (M is hydrogen, alkali metal, or quaternary ammonium salt) or -SO ₂ NHR'(R'is hydrogen or carbon number. Alkyl groups from 1 to 20), and more specifically, R ¹ may be -SO ₃ Li, -SO ₃ Na, or -SO ₃ K.

According to one embodiment of the present invention, the compound represented by the chemical formula 1 may be any one selected from the group consisting of the following, but the present invention is not limited thereto. Absent.

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

According to one embodiment of the present invention, R is a straight chain alkyl group having 1 to 20 carbon atoms or 1 to 10 carbon atoms, or a branched alkaline group having 2 to 20 carbon atoms or 2 to 10 carbon atoms. You may. More specifically, the R is 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, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n It may be, but is not limited to, −heptyl, 1-methylhexyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-ethylheptyl, 2-propylpentyl and the like.

The colorant compound of the chemical formula 1 can be produced by an esterification reaction of the compound of the following chemical formula 2 and the compound of the chemical formula 3. The production method can be further embodied in a synthetic example described later.

[Chemical formula 2]

In the chemical formula 2,
R ¹ is -SO ₃ M (M is hydrogen, alkali metal, or quaternary ammonium salt) or -SO ₂ NHR'(R'is hydrogen or an alkyl group having 1 to 20 carbon atoms).
n indicates an integer from 0 to 4, and when n is an integer of 2 or more, a plurality of R ^1s may be the same or different.
One or more of R ²⁰ to R ^{50 is -R 11-} OH, where R ¹¹ is a direct bond or a C1-C10 alkylene group.
The ^{rest of R 20} to R ⁵⁰ that are not -R ^11- OH are independent of each other, hydrogen, substituted or unsubstituted C1-C20 alkyl groups; substituted or unsubstituted C1-C20 alkoxy groups; substituted or unsubstituted. C1-C20 hydroxyalkyl group; substituted or unsubstituted C6-C30 aryl group; substituted or unsubstituted C7-C30 arylalkyl group; substituted or unsubstituted C7-C30 alkylaryl group; or substituted or unsubstituted C2 -C30 heteroaryl group.

[Chemical formula 3]

In the chemical formula 3,
R ¹² 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 containing the colorant compound of the following chemical formula 1, a binder resin, a polymerizable compound, and a photoinitiator.

[Chemical formula 1]

前記化学式１ａで、
Ｒ^１１は直接結合またはＣ１−Ｃ１０アルキレン基であり；
Ｑは−ＣＯＯ−、または−ＯＣＯ−であり；
Ｒ^１２は直接結合またはＣ１−Ｃ１０アルキレン基であり；
Ａは一つ以上のヒドロキシ基で置換されたＣ６−Ｃ３０アリール基、または一つ以上のヒドロキシ基で置換されたＣ７−Ｃ３０アルキルアリール基である。 With the above chemical formula 1,
R ¹ is -SO ₃ M (M is hydrogen, alkali metal, or quaternary ammonium salt) or -SO ₂ NHR'(R'is hydrogen or an alkyl group having 1 to 20 carbon atoms).
n indicates an integer from 0 to 4, and when n is an integer of 2 or more, a plurality of R ^1s may be the same or different.
Any one or more of R ² to R ⁵ is represented by the following chemical formula 1a.
The ^{rest of R 2} to R ⁵ not represented by the following chemical formula 1a are independent of each other, hydrogen, substituted or unsubstituted C1-C20 alkyl groups; substituted or unsubstituted C1-C20 alkoxy groups; substituted or unsubstituted. C1-C20 hydroxyalkyl group; substituted or unsubstituted C6-C30 aryl group; substituted or unsubstituted C7-C30 arylalkyl group; substituted or unsubstituted C7-C30 alkylaryl group; or substituted or unsubstituted C2- C30 heteroaryl group
[Chemical formula 1a]

In the chemical formula 1a,
R ¹¹ is a direct bond or C1-C10 alkylene group;
Q is -COO-, or -OCO-;
R ¹² 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.

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

The colorant compound is about 10 parts by weight or more, about 15 parts by weight or more, or about 20 parts by weight or more with respect to 100 parts by weight of solid contents contained in the coloring composition. It may be contained in an amount of about 50 parts by weight or less, or about 40 parts by weight, or about 30 parts by weight or less. If the content of the colorant compound is excessively small, the color purity may decrease, and if it is excessively high, the curing reaction of the resin composition may not occur well. It is preferably contained.

In the coloring composition of the present invention, the coloring agent compound of Chemical Formula 1 can be used alone or in combination of two or more.

Further, the coloring composition of the present invention may optionally further contain other known coloring agents in addition to the coloring agent compound of Chemical Formula 1, if necessary.

The polymer resin is not particularly limited, and a resin generally used in the technical field to which the present invention belongs can be used, and an alkali-soluble resin can be preferably used.

Specifically, (meth) acrylic resin, acrylamide resin, novolak resin and the like can be used as the alkali-soluble resin, and the weight average molecular weight (Mw) is preferably 3,000 to 150,000 g / mol. However, the present invention is not limited to this.

The content of the polymer resin is about 3 parts by weight or more, about 5 parts by weight or more, or about 10 parts by weight or more, and about 30 parts by weight, based on 100 parts by weight of the solid content contained in the coloring composition. It may be contained in parts 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 a compound generally used in the technical field to which the present invention belongs can be used, and a compound having an ethylenically unsaturated group can be preferably used. The compound having an ethylenically unsaturated group may be an acrylate-based compound.

More specifically, examples of the polymerizable compound include pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and ethylene glycol. One or more compounds selected from 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, about 40 parts by weight or more, or about 50 parts by weight or more, and about 80 parts by weight, based on 100 parts by weight of the solid content contained in the coloring composition. It may be included in less than a few parts, or about 70 parts by weight, or less than about 60 parts by weight, but the present invention is not limited thereto.

According to one embodiment of the present specification, the photopolymerization initiator includes 2,4-trichloromethyl- (4'-methoxyphenyl) -6-triazine and 2,4-trichloromethyl- (4'-methoxystyryl). ) -6-Triazine, 2,4-trichloromethyl- (fipronyl) 6-triazine, 1-hydroxycyclohexylphenyl ketone, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy) propyl ketone, benzophenone, 2,4 , 6-trimethylaminobenzophenone, etc., one or more compounds selected from, but not limited to, may be used.

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 contained in the coloring composition, but the present invention is limited thereto. Not.

The coloring composition of the present invention may further contain a solvent in order to improve coatability and workability.

According to one embodiment of the present specification, the solvent includes methyl ethyl ketone, 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, and diethylene glycol methyl. Ethylene ether, 2-ethoxypropanol, 2-methoxypropanol, 3-methoxybutanol, cyclohexanone, cyclopentanone, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, 3-methoxybutyl acetate, ethyl 3-ethoxypropionate, One or more compounds selected from, but not limited to, ethyl cellosolve acetate, methyl cellosolve acetate, butyl acetate, dipropylene glycol monomethyl ether, and the like may be used.

The content of the solvent is not particularly limited because it can be adjusted in consideration of coatability and workability, but is, for example, about 50 to about 500 weight by weight with respect to 100 parts by weight of the solid content contained in the coloring composition. It may be included in the part.

According to one embodiment of the present invention, in addition to the above-mentioned components, the coloring composition comprises a curing accelerator, a thermal polymerization inhibitor, a dispersant, an antioxidant, an ultraviolet absorber, a leveling agent, a photosensitizer, and the like. Additives such as plasticizers, adhesion promoters, fillers, or surfactants that may be included in conventional color filter colored compositions can be further included.

Examples of the curing accelerator include 2-mercaptobenzoimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2,5-dimercapto-1,3,4-thiadiazol, 2-mercapto-4,6-dimethylamino. Ppyridine, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tris (2-mercaptoacetate), trimethylolpropane tris Selected from the group consisting of (2-mocaptoacetate), trimethylolpropanetris (3-mercaptopropionate), trimethylolethaneethanol (2-mercaptoacetate), and trimethylolethaneethanol (3-mercaptopropionate). However, it is not limited to these, and can include generally known ones in the technical field to which the present invention belongs.

On the other hand, the coloring composition according to one embodiment of the present invention may be used for producing a color filter by a method generally known in the technical field to which the present invention belongs, for example, a printing method or a photolithography method.

For example, according to a photolithography method, the coloring composition is applied onto a transparent substrate by a method such as spray coating, spin coating, slit coating, roll coating, or dipping. The exposure step is selectively performed through a mask having a predetermined pattern on the coating film. On the other hand, the pre-exposure heat treatment (pre-bake) and / or the post-exposure heat treatment (post-bake) step can be further performed. After exposure, the colored composition is developed to form the desired photoresist pattern. When the developed substrate is washed and dried, a color filter having a photoresist pattern of a desired form can be obtained.

According to the colorant for color filters of the present invention and the coloring composition containing the same as described above, it is possible to have excellent color characteristics due to the novel structure of the colorant compound.

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

Therefore, when the coloring composition of the present invention is used, a highly reliable and high resolution color filter can be produced.

Hereinafter, the actions and effects of the invention will be described in more detail through specific examples of the present invention. However, such an embodiment is merely presented as an example of the invention, and the scope of rights of the invention is not determined by this.

<Example>

<Example of Synthesis of Colorant Compound>

Synthesis Example 1: Synthesis of Compound 1

1.084 g (4.330 mmol) of compound B-1 was added to 50 g of methylene chloride and stirred. An ice bath is installed to make the temperature at 0 ° C., and then 0.830 g (4.330 mmol) of N- (3-Dimethyllaminoppil) -N'-ethylcarbodiimide (EDC-HCl) is added and stirred for 15 minutes. did. Add 0.141 g (1.155 mmol) of 4-dimethylaminopyridine, a small amount of dimethylformamide, add 0.737 g (1.443 mmol) of compound A-1, react at 0 ° C. for 2 hours, and overnight at room temperature (overnight). ) Reacted. Distilled water (100 ml) and methylene chloride (50 ml) were additionally added for extraction, and the organic layer _{was passed through Na 2} SO ₄ to remove water and the solvent was removed under reduced pressure. Subsequently, the precipitate was separated by column chromatography (Eluent-methylene chloride: methanol). As a result, the title compound 1 (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

Synthesis Example 2: Synthesis of Compound 2

1.084 g (4.330 mmol) of compound B-1 was added to 100 g of methylene chloride and stirred. An ice bath is installed to make the temperature at 0 ° C., and then 0.830 g (4.330 mmol) of N- (3-Dimethyllaminoppil) -N'-ethylcarbodiimide (EDC-HCl) is added and stirred for 15 minutes. did. Add 0.141 g (1.155 mmol) of 4-dimethylaminopyridine, a small amount of dimethylformamide, add 2.211 g (4.330 mmol) of compound A-1, react at 0 ° C. for 2 hours, and overnight at room temperature (overnight). ) Reacted. Distilled water (100 ml) and methylene chloride (50 g) were additionally added for extraction, and the organic layer _{was passed through Na 2} SO ₄ to remove water and the solvent was removed under reduced pressure. After that, the precipitate was separated by column chromatography. (Eluent-methylene chloride: methanol). As a result, the title compound 2 (0.804 g, 1.083 mmol) was obtained, and the yield was 25%.

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

Synthesis example 3: Synthesis of compound 3

It was synthesized in the same manner as in Synthesis Example 1 except that 1.205 g (4.33 mmol) of Compound B-2 was used instead of Compound B-1 in Synthesis Example 1. As a result, the title compound 3 (0.670 g, 0.650 mmol) was obtained, and the yield was 45%.

Ionization mode =: APCI +: m / z = 1031.5 [M + H] +, Exact Mass: 1030.5

Synthesis Example 4: Synthesis of Compound 4

It was synthesized in the same manner as in Synthesis Example 2 except that 1.205 g (4.33 mmol) of Compound B-2 was used instead of Compound B-1 in Synthesis Example 2. As a result, the title compound 4 (1.168 g, 1.516 mmol) was obtained, and the yield was 35%.

Ionization mode =: APCI +: m / z = 741.3 [M + H] +, Exact Mass: 740.3

Synthesis Example 5: Synthesis of Compound 5

It 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 in Synthesis Example 1. As a result, the title compound 5 (0.411 g, 0.361 mmol) was obtained, and the yield was 21.5%.

Ionization mode =: APCI +: m / z = 1139.5 [M + H] +, Exact Mass: 1138.5

Synthesis Example 6: Synthesis of Compound 6

It was synthesized in the same manner as in Synthesis Example 2 except that 2.991 g (4.33 mmol) of Compound A-2 was used instead of Compound A-1 in Synthesis Example 2. 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

Synthesis Example 7: Synthesis of Compound 7

In Synthesis Example 1, 0.996 g (1.443 mmol) of compound A-2 was used in place of compound A-1, and 1.205 g (4.330 mmol) of compound B-2 was used in place of compound B-1. Except for this, it was synthesized in the same manner as in Synthesis Example 1. 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

Synthesis Example 8: Synthesis of Compound 8

In Synthesis Example 2, 2.991 g (4.33 mmol) of compound A-2 was used in place of compound A-1, and 1.205 g (4.33 mmol) of compound B-2 was used in place of compound B-1. Except for this, it was synthesized in the same manner as in Synthesis Example 2. 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

Synthesis Example 9: Synthesis of Compound 9

The title compound 9 was obtained by synthesizing in the same manner as in Synthesis Example 1, except that Compound A-3 was used instead of Compound A-1 in Synthesis Example 1.

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

Synthesis Example 10: Synthesis of Compound 10

The title compound 10 was obtained by synthesizing in the same manner as in Synthesis Example 2, except that Compound A-3 was used instead of Compound A-1 in Synthesis Example 2.

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

Synthesis Example 11: Synthesis of Compound 11

The title compound 11 was obtained by synthesizing 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.

Ionization mode =: APCI +: m / z = 1267.6 [M + H] +, Exact Mass: 2666.6

Synthesis Example 12: Synthesis of Compound 12

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

Ionization mode =: APCI +: m / z = 1007.5 [M + H] +, Exact Mass: 1006.5

Synthesis Example 13: Synthesis of Compound 13

The title compound 13 was obtained by synthesizing in the same manner as in Synthesis Example 1, except that Compound A-4 was used instead of Compound A-1 in Synthesis Example 1.

Ionization mode =: APCI +: m / z = 1099.5 [M + H] +, Exact Mass: 1098.5

Synthesis Example 14: Synthesis of Compound 14

The title compound 14 was obtained by synthesizing in the same manner as in Synthesis Example 2, except that Compound A-4 was used instead of Compound A-1 in Synthesis Example 2.

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

Synthesis Example 15: Synthesis of Compound 15

The title compound 15 was obtained by synthesizing 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.

Ionization mode =: APCI +: m / z = 1155.5 [M + H] +, Exact Mass: 1154.5

Synthesis Example 16: Synthesis of Compound 16

The title compound 16 was obtained by synthesizing in the same manner as in Synthesis Example 4, except that Compound A-4 was used instead of Compound A-1 in Synthesis Example 4.

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

Synthesis Example 17: Synthesis of Compound 17

The title compound 17 was obtained by synthesizing in the same manner as in Synthesis Example 1, except that Compound A-5 was used instead of Compound A-1 in Synthesis Example 1.

Ionization mode =: APCI +: m / z = 1267.6 [M + H] +, Exact Mass: 2666.6

Synthesis Example 18: Synthesis of Compound 18

The title compound 18 was obtained by synthesizing 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.

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

Synthesis Example 19: Synthesis of Compound 19

The title compound 19 was obtained by synthesizing in the same manner as in Synthesis Example 3, except that Compound A-5 was used instead of Compound A-1 in Synthesis Example 3.

Ionization mode =: APCI +: m / z = 1323.7 [M + H] +, Exact Mass: 1322.7

Synthesis Example 20: Synthesis of Compound 20

The title compound 20 was obtained by synthesizing 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.

Ionization mode =: APCI +: m / z = 1063.5 [M + H] +, Exact Mass: 1062.5

Synthesis Example 21: Synthesis of Compound 21

The title compound 21 was obtained by synthesizing in the same manner as in Synthesis Example 1, except that Compound A-6 was used instead of Compound A-1 in Synthesis Example 1.

Ionization mode =: APCI +: m / z = 1183.6 [M + H] +, Exact Mass: 1182.6

Synthesis Example 22: Synthesis of Compound 22

The title compound 22 was obtained by synthesizing in the same manner as in Synthesis Example 2, except that Compound A-6 was used instead of Compound A-1 in Synthesis Example 2.

Ionization mode =: APCI +: m / z = 951.4 [M + H] +, Exact Mass: 950.4

Synthesis Example 23: Synthesis of Compound 23

The title compound 23 was obtained by synthesizing in the same manner as in Synthesis Example 3, except that Compound A-6 was used instead of Compound A-1 in Synthesis Example 3.

Ionization mode =: APCI +: m / z = 1239.6 [M + H] +, Exact Mass: 1238.6

Synthesis Example 24: Synthesis of Compound 24

The title compound 24 was obtained by synthesizing in the same manner as in Synthesis Example 4, except that Compound A-6 was used instead of Compound A-1 in Synthesis Example 4.

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

Synthesis Example 25: Synthesis of Compound 25

The title compound 25 was obtained by synthesizing 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 =: APCI +: m / z = 1159.5 [M + H] +, Exact Mass: 1158.5

Synthesis Example 26: Synthesis of Compound 26

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

Ionization mode =: APCI +: m / z = 927.3 [M + H] +, Exact Mass: 926.3

Synthesis Example 27: Synthesis of Compound 27

The title compound 27 was obtained by synthesizing in the same manner as in Synthesis Example 3, except that Compound A-7 was used instead of Compound A-1 in Synthesis Example 3.

Ionization mode =: APCI +: m / z = 1215.5 [M + H] +, Exact Mass: 1214.5

Synthesis Example 28: Synthesis of Compound 28

The title compound 28 was obtained by synthesizing in the same manner as in Synthesis Example 4, except that Compound A-7 was used instead of Compound A-1 in Synthesis Example 4.

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

Comparative Example Compound 1

A colorant (Basic blue 7) having the following structural formula was obtained from TCI Chemicals and used as Comparative Example Compound 1.

Comparative Example Compound 2

A colorant (rhodamine 6G) having the following structural formula was obtained from Sigma-Aldrich and used as Comparative Example Compound 2.

<Example of manufacturing resin composition>

Example 1

5.554 g of the colorant compound of Synthesis Example 1, a copolymer of benzyl methacrylate and methacrylic acid as a binder resin (molar ratio 70:30, acid value 113 KOH 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 included) 10.376 g, DPHA (dipentaerythritol hexaacrylate) (Nippon Kayaku) as a polymerizable compound, 12.443 g, as a photoinitiator A total of 100 g of a resin composition is produced by mixing 2.018 g of I-369 (BASF), 1.013 g of F-475 (DIC) as an additive, and 68.593 g of the solvent PGMEA (Propyrene Glycol Polymer Ether Actate). did.

Example 2

A resin composition was produced 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 5.554 g of the colorant compound of Synthesis Example 1.

Example 3

A resin composition was produced 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

A resin composition was produced in the same manner as in Example 1 except that 5.554 g of the colorant compound of Synthesis Example 17 was used instead of 5.554 g of the colorant compound of Synthesis Example 1.

Comparative Example 1

A resin composition was produced 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 produced 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>

Light transmittance and heat resistance evaluation

The light transmittance and heat resistance of the colored compositions of the examples and comparative examples were evaluated by the following methods.

Specifically, the resin compositions of Examples 1 to 4 and Comparative Examples 1 and 2 are spin-coated on glass (5 x 5 cm) and preheated (pre-bake, prB) at 100 ° C. for 100 seconds. This was carried out to form a film. The distance between the substrate on which the film was formed and the photomask (photomask) was set to 300 μm, and the front surface of the substrate was irradiated with an exposure amount of ^{40 mJ / cm 2 using an exposure device.}

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

In order to evaluate the light transmittance and heat resistance, the absorption spectrum in the visible light region in the range of 380 nm to 780 nm was obtained by using a spectroscope (MCPD OTSUKA) on the substrate in a state where the pre-heat treatment (pre-bake, prB) was performed. Obtained. Further, a transmittance spectrum was obtained with the same equipment and measurement range for the substrate subjected to the post-heat treatment (post bake, PB).

The transmittance spectra at wavelengths measured after the pre-heat treatment (prB) and the post-heat treatment (PB) for the color pattern substrate formed by using the resin composition of Example 1 are shown in FIG.

FIG. 2 shows the transmittance spectra of the color pattern substrate formed using the resin composition of Example 2 by wavelengths measured after the pre-heat treatment (prB) and the post-heat treatment (PB), respectively.

The transmittance spectra at wavelengths measured after the pre-heat treatment (prB) and the post-heat treatment (PB) for the color pattern substrate formed by using the resin composition of Example 3 are shown in FIG.

FIG. 4 shows the transmittance spectra of the color pattern substrate formed by using the resin composition of Example 4 at wavelengths measured after the pre-heat treatment (prB) and the post-heat treatment (PB), respectively.

FIG. 5 shows the transmittance spectra of the color pattern substrate formed by using the resin composition of Comparative Example 1 by wavelength measured after the pre-heat treatment (prB) and the post-heat treatment (PB), respectively.

FIG. 6 shows the transmittance spectra of the color pattern substrate formed by using the resin composition of Comparative Example 2 at wavelengths measured after the pre-heat treatment (prB) and the post-heat treatment (PB), respectively.

Further, ΔEab is calculated by the following equation 1 using the absorption spectrum obtained during the pre-heat treatment and the post-heat treatment and the value E (L *, a *, b *) obtained by using the C light source backlight. The results are shown in Table 1.

[Equation 1]

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

Referring to FIGS. 1 to 6 and Table 1, the color pattern substrate formed by using the resin composition of the embodiment of the present invention is more color stable than the color pattern substrate formed by using a conventionally known dye. It was shown that the difference in transmittance spectrum (ΔEab) between the post-heat treatment and the post-heat treatment was very small, and the heat resistance was excellent.

Claims (5)

Colorant compound represented by the following chemical formula 1:
[Chemical formula 1]

With the above chemical formula 1,
R ¹ is -SO ₃ M (M is hydrogen, alkali metal, or quaternary ammonium salt) or -SO ₂ NHR'(R'is hydrogen or an alkyl group having 1 to 20 carbon atoms).
n indicates an integer from 0 to 4, and when n is an integer of 2 or more, a plurality of R ^1s may be the same or different.
Any one or more of R ² to R ⁵ is represented by the following chemical formula 1a.
The ^{rest of R 2} to R ⁵ not represented by the following chemical formula 1a are independent of each other, hydrogen, substituted or unsubstituted C1-C20 alkyl groups; substituted or unsubstituted C1-C20 alkoxy groups; substituted or unsubstituted. C1-C20 hydroxyalkyl group; substituted or unsubstituted C6-C30 aryl group; substituted or unsubstituted C7-C30 arylalkyl group; substituted or unsubstituted C7-C30 alkylaryl group; or substituted or unsubstituted C2 -C30 heteroaryl group
[Chemical formula 1a]

In the chemical formula 1a,
R ¹¹ is a direct bond or C1-C10 alkylene group;
Q is -COO-, or -OCO-;
R ¹² is a direct bond or C1-C10 alkylene group;
A is represented by the following chemical formula 1b.
[Chemical formula 1b]

In the chemical formula 1b,
R ^c is a hydroxy group
R ^a , R ^b , R ^d , and ^Re are independent of each other, hydrogen, a linear alkyl group of C1-C20, or a branched-chain alkyl group of C3-C20.
One or more of R ^b and R ^d is a branched-chain alkyl group of C3-C20. R ¹ is -SO ₃ Li, -SO ₃ Na, or -SO ₃ K,
The colorant compound according to claim 1. The compound represented by the chemical formula 1 is
It is a compound represented by any one selected from the group composed of the following structural formulas.
The colorant compound according to claim 1:

With the above structural formula
X is a metal cation or an onium cation,
R is H or an alkyl group having 1 to 20 carbon atoms. The colorant compound according to any one of claims 1 to 3.
Binder resin,
A coloring composition containing a polymerizable compound and a photopolymerization initiator. With respect to 100 parts by weight of solid contents contained in the coloring composition.
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,
The photopolymerization initiator is contained in an amount of 0.1 to 10 parts by weight.
The coloring composition according to claim 4.

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