JP2020504833A - Colorant composition, colorant dispersion, photosensitive resin composition, color filter and liquid crystal display - Google Patents

Abstract

The present invention relates to a first xanthene dye having the same number of positive charges and negative charges; and a second xanthene dye having at least one more negative charge than the number of positive charges, and an amine value of 0 to 200 mgKOH / g. The present invention relates to a colorant composition, a colorant dispersion, a photosensitive resin composition, a color filter, and a liquid crystal display device each including a complex in which a dispersant having an ammonium structure is ion-bonded.

Description

  This application claims the benefit of the filing date of Korean Patent Application No. 10-2017-0160315 filed with the Korea Patent Office on November 28, 2017, the entire contents of which are incorporated herein.

  The present invention relates to a colorant composition, a colorant dispersion, a photosensitive resin composition, a color filter, and a liquid crystal display.

  Recently, as a light source of a liquid crystal display (LCD), instead of the existing CCFL, an LED or an OLED element which emits light without being driven or liquid crystal is often used. When an LED or an OLED is used as a light source, red, green and blue light is emitted by itself, so that another color filter is not required.

  However, in general, it is not easy to match or adjust the required color coordinates using light emitted from an LED or OLED light source.

  On the other hand, at present, a pigment dispersion method using a pigment as a colorant is generally applied to realize a color filter. However, in the case of a pigment dispersion, not only does the pigment exist in a particle state and scatters light, but also the pigment surface area increases sharply due to the refinement of the pigment. Is generated. Therefore, the use of dyes instead of pigments as colorants has been studied in order to achieve the recently required high brightness, high contrast ratio and high resolution.

  However, in general, since the dye has low solubility, dispersion is not successful, and the brightness of the color filter cannot be sufficiently satisfied.

  The present invention seeks to provide a colorant composition capable of providing a colorant dispersion having an excellent degree of dispersion, a colorant dispersion manufactured using the same, and a photosensitive resin composition. The present invention also provides a color filter manufactured using the above-described photosensitive resin composition and a liquid crystal display device including the same.

One embodiment of the present invention is:
A first xanthene dye having the same number of positive and negative charges; and a second xanthene dye having at least one more negative charge than the number of positive charges, an amine value of 0 to 200 mgKOH / g, and an ammonium structure A colorant composition comprising a complex ionically bonded to a dispersant comprising:

  Another embodiment of the present invention provides a colorant dispersion comprising the colorant composition; a dispersant; a binder resin; and a solvent.

  Another embodiment of the present invention provides a photosensitive resin composition comprising the colorant dispersion, a binder resin, a polyfunctional monomer, and a photopolymerization initiator.

  Another embodiment of the present invention is a color filter including a transparent substrate and a colored layer provided on the transparent substrate, wherein the colored layer includes a cured product of the photosensitive resin composition. Provide a color filter.

  Another embodiment of the present invention provides a liquid crystal display including the color filter.

  According to the embodiment of the present invention, re-aggregation of the dye can be prevented to improve the dispersibility, whereby a colorant dispersion having high brightness and stability can be obtained. Further, when the colorant composition and the colorant dispersion according to some embodiments of the present invention are used, they have excellent storage stability, transmittance and heat resistance, and are excellent for use in color filter applications. .

  One embodiment of the present invention comprises a first xanthene-based dye having the same number of positive and negative charges; and a second xanthene-based dye having one or more negative charges greater than the number of positive charges; The present invention provides a colorant composition containing 200 mgKOH / g and a complex in which a dispersant having an ammonium structure is ion-bonded.

  Conventionally, when two or more kinds of dyes are mixed, it is usually to adjust the color to be realized, but the above embodiment relates to a combination of a dye and a dispersant capable of maximizing dispersion stability. Specifically, according to the embodiment, the first xanthene dye and the second xanthene dye are all xanthene dyes and have similar structures. Also, the first xanthene dye has the same number of positive and negative charges, while the second xanthene dye has one or more negative charges than the number of positive charges.

  However, when only the first xanthene dye is present, dispersion stability may decrease due to reaggregation between particles due to pi-pi interaction of the xanthene dye. However, according to the embodiment, by including the first xanthene-based dye and the second xanthene-based dye having the above-described properties, a part or the entirety of the second xanthene-based dye is adjacent to two or three adjacent xanthene dyes. It may be located between more than one first xanthene dye or adjacent to the end of the first xanthene dye.

  Accordingly, the primary role of the first xanthene dye is to develop a color as a xanthene dye, whereas the second xanthene dye disperses the first xanthene dye in addition to developing the color. By playing a role in the dispersion, the dispersion stability can be increased.

  In particular, since the dispersant has an ammonium structure, the dispersant has a cationic property, whereby the negative charge of the second xanthene-based dye can be ionic-bonded with the dispersant to form a complex. The dispersion stability can be greatly improved by the presence of such a second xanthene dye. This can prevent re-aggregation of the first xanthene-based dye, and provide a colorant dispersion having small dispersed particles, good brightness, and excellent dispersion stability.

  According to another embodiment of the present invention, the first xanthene dye has a maximum absorption wavelength between 500 and 580 nm, and a maximum absorption wavelength of the first xanthene dye and the second xanthene dye. Is 100 nm or less.

  According to another embodiment of the present invention, the first xanthene dye has a maximum absorption wavelength between 500 and 580 nm, and a maximum absorption wavelength of the first xanthene dye and the second xanthene dye. Is greater than 0 and not more than 100 nm. More than 0 and 50 nm or less is preferable, and more than 0 and 20 nm or less is most preferable. According to the embodiment, when only the first xanthene dye is present, the dispersion stability is not good, but by mixing and using the second xanthene dye having similar chemical structure and absorption characteristics, the first xanthene dye is originally used. Dispersion stability can be greatly improved while achieving the color to be achieved with xanthene dyes.

  In this specification, the first xanthene dye is described as a first dye, and the second xanthene dye is described as a second dye.

  In this specification, the amine value of the dispersant having an ammonium structure is 0 to 200 mgKOH / g. Preferably, the amine value may be 0 to 100 mgKOH / g, or more than 0 and 100 mgKOH / g or less. According to one example, the amine value of the dispersant comprising an ammonium structure may be greater than 0 and no greater than 160 mg KOH / g.

前記化学式１において、
Ｒ_１〜Ｒ_４は、互いに同一または異なり、それぞれ独立に、水素；重水素；陰イオン性基；ヒドロキシ基；スルホンアミド基；スルホン酸塩基；置換もしくは非置換のアルキル基；置換もしくは非置換のアリール基；置換もしくは非置換のヘテロアリール基；および窒素原子を含む二無水物基からなる群より選択され、
Ｒ_５〜Ｒ_９は、互いに同一または異なり、それぞれ独立に、水素；重水素；陰イオン性基；ヒドロキシ基；スルホンアミド基；スルホン酸塩基；置換もしくは非置換のアルキル基；置換もしくは非置換のアリール基；および置換もしくは非置換のヘテロアリール基からなる群より選択され、ただし、前記Ｒ_５〜Ｒ_９のうちの少なくとも１つは、陰イオン性基；スルホン酸塩基；またはスルホンアミド基であり、
Ｒ_１０およびＲ_１１は、互いに同一または異なり、それぞれ独立に、水素；重水素；ハロゲン基；ニトロ基；または置換もしくは非置換のアルキル基であり、ｒ_１０およびｒ_１１は、０〜３の整数であり、前記ｒ_１０およびｒ_１１がそれぞれ２以上の場合、括弧内の構造は、互いに同一または異なる。
［化学式２］

前記化学式２において、
Ｒ_２１〜Ｒ_２４は、互いに同一または異なり、それぞれ独立に、水素；重水素；陰イオン性基；ヒドロキシ基；スルホンアミド基；スルホン酸塩基；置換もしくは非置換のアルキル基；置換もしくは非置換のアリール基；置換もしくは非置換のヘテロアリール基；および窒素原子を含む二無水物基からなる群より選択され、Ｒ_２１〜Ｒ_２４のうちの少なくとも１つは、陰イオン性基、スルホン酸塩基、またはスルホンアミド基で置換もしくは非置換のアルキル基；陰イオン性基、スルホン酸塩基、またはスルホンアミド基で置換されたアリール基；または陰イオン性基、スルホン酸塩基、またはスルホンアミド基で置換されたヘテロアリール基であり、
Ｒ_２５〜Ｒ_２９は、互いに同一または異なり、それぞれ独立に、水素；重水素；陰イオン性基；ヒドロキシ基；スルホンアミド基；スルホン酸塩基；置換もしくは非置換の炭素数１〜３０の直鎖または分枝鎖のアルキル基；置換もしくは非置換のアリール基；および置換もしくは非置換のヘテロアリール基からなる群より選択され、ただし、前記Ｒ_２５〜Ｒ_２９のうちの少なくとも１つは、陰イオン性基；スルホン酸塩基；またはスルホンアミド基であり、
Ｒ_３０およびＲ_３１は、互いに同一または異なり、それぞれ独立に、水素；重水素；ハロゲン基；ニトロ基；または置換もしくは非置換のアルキル基であり、ｒ_３０およびｒ_３１は、０〜３の整数であり、前記ｒ_３０およびｒ_３１がそれぞれ２以上の場合、括弧内の構造は、互いに同一または異なる。 According to another embodiment of the present invention, the first xanthene-based dye includes a dye having the same number of positive and negative charges represented by the following Chemical Formula 1, and the second xanthene-based dye includes: It includes a dye represented by Formula 2 and having one or more negative charges than positive charges.
[Chemical formula 1]

In the above chemical formula 1,
R _{1 to} R ₄ are the same or different and are each independently hydrogen, deuterium, anionic group, hydroxy group, sulfonamide group, sulfonate group, substituted or unsubstituted alkyl group, substituted or unsubstituted An aryl group; a substituted or unsubstituted heteroaryl group; and a dianhydride group containing a nitrogen atom,
R _{5 to} R ₉ are the same or different and are each independently hydrogen, deuterium, anionic group, hydroxy group, sulfonamide group, sulfonate group, substituted or unsubstituted alkyl group, substituted or unsubstituted Selected from the group consisting of an aryl group; and a substituted or unsubstituted heteroaryl group, provided that at least one of R _{5 to} R ₉ is an anionic group; a sulfonate group; or a sulfonamide group. ,
R ₁₀ and R ₁₁ are the same or different and are each independently hydrogen; deuterium; a halogen group; a nitro group; or a substituted or unsubstituted alkyl group, and r ₁₀ and r ₁₁ are integers of 0 to 3 When each of r ₁₀ and r ₁₁ is 2 or more, the structures in parentheses are the same or different from each other.
[Chemical formula 2]

In the above chemical formula 2,
R _{21 to} R ₂₄ are the same or different and are each independently hydrogen, deuterium, anionic group, hydroxy group, sulfonamide group, sulfonate group, substituted or unsubstituted alkyl group, substituted or unsubstituted An aryl group; a substituted or unsubstituted heteroaryl group; and a dianhydride group containing a nitrogen atom, wherein at least one of R _{21 to} R ₂₄ is an anionic group, a sulfonate group, Or an alkyl group substituted or unsubstituted with a sulfonamide group; an aryl group substituted with an anionic group, a sulfonate group, or a sulfonamide group; or substituted with an anionic group, a sulfonate group, or a sulfonamide group Is a heteroaryl group,
R _{25 to} R ₂₉ are the same or different and are each independently hydrogen, deuterium, anionic group, hydroxy group, sulfonamide group, sulfonate group, substituted or unsubstituted straight chain having 1 to 30 carbon atoms. Or a branched alkyl group; a substituted or unsubstituted aryl group; and a substituted or unsubstituted heteroaryl group, provided that at least one of R _{25 to} R ₂₉ is an anion. A sulfonate group; or a sulfonamide group,
R ₃₀ and R ₃₁ are the same or different and are each independently hydrogen; deuterium; a halogen group; a nitro group; or a substituted or unsubstituted alkyl group, and r ₃₀ and r ₃₁ are an integer of 0 to 3 When each of r ₃₀ and r ₃₁ is 2 or more, the structures in parentheses are the same or different from each other.

In one embodiment of the present specification, R _{1 to} R ₄ are the same or different and are each independently hydrogen; deuterium; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; R _{21 to} R ₂₄ are the same or different from each other and are each independently hydrogen; deuterium; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group And a dianhydride group containing a nitrogen atom; the remaining substituents are as defined above.

In Formula 1 of the present specification, R _{1 to} R ₄ are the same or different and are each independently hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; or a dianhydride containing a nitrogen atom. Material group.

In Formula 1 of the present specification, R _{1 to} R ₄ are the same or different and are each independently hydrogen; an aryl group substituted with an anionic group or an alkyl group; or a dianhydride group containing a nitrogen atom. Is a substituted or unsubstituted alkyl group.

In Chemical Formula 1 of the present specification, R _{1 to} R ₄ are the same or different and are each independently at least one member selected from the group consisting of hydrogen; a phenyl group substituted with a methyl group; a methyl group and an anionic group. A phenyl group substituted with a selected one; an ethyl group; a propyl group; or a propyl group substituted with a dianhydride group containing a nitrogen atom.

In Formula 1 of the present specification, R _{5 to} R ₉ are the same or different from each other, and each independently represents hydrogen; or an anionic group.

In Formula 1 of the present specification, R _{5 to} R ₉ are the same or different from each other, and are each independently hydrogen; or SO ₃ ^— .

In Formula 1 of the present specification, R ₁₀ and R ₁₁ are the same or different and are each independently hydrogen; or deuterium; r ₁₀ and r ₁₁ are integers of 0 to 3; _When each of ₁₀ and r ₁₁ is 2 or more, the structures in parentheses are the same or different from each other.

In Formula 2 of the present specification, R _{21 to} R ₂₄ are the same or different and are each independently a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; or a dianhydride group containing a nitrogen atom. It is.

In the above Chemical Formula 2 of the present specification, R _{21 to} R ₂₄ are the same or different from each other and are each independently an alkyl group substituted or unsubstituted with a dianhydride group containing a nitrogen atom; or an anionic group and an alkyl group And an aryl group substituted with at least one selected from the group consisting of

In Formula 2 of the present specification, R _{21 to} R ₂₄ are the same or different and are each independently an ethyl group; a propyl group; a propyl group substituted with a dianhydride group containing a nitrogen atom; Or a phenyl group substituted with one or more selected from the group consisting of a methyl group and an anionic group.

  As used herein, the term “substituted or unsubstituted” refers to deuterium; halogen; alkyl; alkenyl; alkoxy; cycloalkyl; arylalkenyl; aryl; aryloxy; Alkylamine group; aralkylamine group; arylamine group; heteroaryl group; hydroxy group; cyano group; heterocyclic group containing at least one of N, O, S or P atoms; A sulfonate group; means substituted with one or more substituents selected from the group comprising a sulfonamide group and an anionic group, or having no substituent. In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but preferably 1 to 30. Specific examples include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, and heptyl.

  In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 30. Specific examples include, but are not limited to, an alkenyl group substituted with an aryl group such as a stilbenyl group (stylbenzyl) and a styrenyl group (styrenyl).

  In the present specification, the alkoxy group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30.

  In the present specification, the alkenyloxy group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 30.

  In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 20 carbon atoms, and particularly preferably a cyclopentyl group or a cyclohexyl group.

  In this specification, examples of the halogen group include a fluorine group, a chlorine group, a bromine group, and an iodine group.

  In the present specification, specifically, in the arylalkyl group, the aryl portion has 6 to 30 carbon atoms, and the alkyl portion has 1 to 30 carbon atoms. Specific examples include benzyl, p-methylbenzyl, m-methylbenzyl, p-ethylbenzyl, m-ethylbenzyl, 3,5-dimethylbenzyl, α-methylbenzyl, α, α- Dimethylbenzyl group, α, α-methylphenylbenzyl group, 1-naphthylbenzyl group, 2-naphthylbenzyl group, p-fluorobenzyl group, 3,5-difluorobenzyl group, α, α-ditrifluoromethylbenzyl group, p -Methoxybenzyl group, m-methoxybenzyl group, α-phenoxybenzyl group, α-benzyl group oxybenzyl group, naphthylmethyl group, naphthylethyl group, naphthylisopropyl group, pyrrolylmethyl group, pyrrolylethyl group, aminobenzyl group, nitrobenzyl group , Cyanobenzyl group, 1-hydroxy-2-phenylisopropyl group, 1 And the like chloro-2-phenylisopropyl group, but not limited thereto.

  In the present specification, for the aryl portion of the arylalkenyl group, the description regarding aryl described below is applicable, and for the alkenyl portion, the description regarding the above-described alkenyl group is applicable.

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

  When the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but preferably has 6 to 30 carbon atoms. Specifically, the monocyclic aryl group may be, but is not limited to, a phenyl group, a biphenyl group, a terphenyl group, and the like.

  When the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited, but preferably has 10 to 30 carbon atoms. Specifically, the polycyclic aryl group may be a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, or the like, but is not limited thereto.

  In the present specification, the fluorenyl group may have a substituent, or the substituent may combine to form a spiro structure.

  In the present specification, the heterocyclic group is a heterocyclic group containing O, N, or S as a hetero atom, and the number of carbon atoms is not particularly limited, but preferably has 2 to 30 carbon atoms. Examples of heterocyclic groups include thiophene, furan, pyrrole, imidazole, thiazole, oxazole, oxadiazole, triazole, pyridyl, bipyridyl, triazine, acridyl, pyridazine, quinolinyl Group, isoquinoline group, indole group, carbazole group, benzoxazole group, benzimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, dibenzofuran group, etc., but are not limited thereto. Not something.

  In this specification, the carbon number of the dianhydride group containing a nitrogen atom is not particularly limited, but is preferably 4 to 20. For example, it may be isoindoline-1,3-dione.

  As used herein, an alkylene group refers to an alkane having two points of attachment. The alkylene group may be linear, branched or cyclic. Although the carbon number of the alkylene group is not particularly limited, for example, it has 1 to 30 carbon atoms.

In this specification, sulfonate group, _'it may be expressed as, X' -SO 3 X can be a hydrogen or a Group 1 element. For example, sulfonate group, there is _-SO 3 Na.

As used herein, a sulfonamide group _may be represented as -SO 2 NRxRy, for example, Rx and Ry are equal to or different from each other, each independently represent a substituted or unsubstituted C1-30 A substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms; or a substituted or unsubstituted monocyclic or polycyclic heterocyclic group having 2 to 30 carbon atoms An aryl group.

In the present specification, the anionic group has a chemical bond with the structure of Chemical Formula 1, and the anionic group is not particularly limited. For example, US Pat. No. 7,939,644, JP-A-2006 -003080, JP-A-2006-001917, JP-A-2005-159926, JP-A-2007-7028897, JP-A-2005-071680, Korean Application Publication No. 2007-700093, JP-A-2005-2005 The anionic groups described in JP-A-111696, JP-A-2008-24963, and JP-A-2014-199436 are applicable. Specific examples of the anionic group include a trifluoromethanesulfonic acid anion, a bis (trifluoromethylsulfonyl) amide anion, a bistrifluoromethanesulfonimide anion, a bisperfluoroethylsulfonimide anion, and a tetraphenylborate anion. ion, tetrakis (4-fluorophenyl) borate, tetrakis (pentafluorophenyl) borate, tris trifluoromethanesulfonyl ^{_{methide, SO 3 -, CO 2 -}} , SO 2 N - SO 2 CF 3, SO 2 N - SO 2 CF ₂ CF ₃ , a halogen group, for example, a fluorine group, an iodine group, a chlorine group, etc., are not limited thereto.

  As used herein, an anionic group may itself have an anion or may be present in the form of a complex with other cations. Therefore, the total charge of the entire compound molecule of the present invention can be changed according to the number of substituted anionic groups. Since one of the amine groups of the compound of the present invention has a cation, the total charge of the entire molecule is calculated by subtracting 1 from the number of the substituted anionic groups to the number of anions from 0 to 0. Can have a value.

  In the present specification, a monomer is a repeating unit constituting a polymer, and the monomer can be contained in a main chain in the polymer to constitute the polymer.

  In this specification, a unit is a repeating structure in which a monomer is contained in a polymer, and means a structure in which the monomer is bonded in the polymer by polymerization.

［化学式４］

化学式３および４において、
Ｒ_１２、Ｒ_１３、Ｒ_３２およびＲ_３３は、互いに同一または異なり、それぞれ独立に、水素；重水素；ハロゲン基；ニトロ基；置換もしくは非置換のアルキル基；陰イオン性基；スルホン酸塩基；またはスルホンアミド基であり、ｒ_１２およびｒ_１３は、０〜５の整数であり、ｒ_３２は、０〜５の整数であり、ｒ_３３は、０〜４の整数であり、ｒ_１２、ｒ_１３、ｒ_３２およびｒ_３３がそれぞれ２以上の場合、括弧内の構造は、互いに同一または異なり、
Ｒ_６１およびＲ_６２は、互いに同一または異なり、それぞれ独立に、水素；重水素；置換もしくは非置換のアルキル基；または窒素原子を含む二無水物基であり、
Ｘは、陰イオン性基；スルホン酸塩基；またはスルホンアミド基であり、
残りの置換基は、化学式１および２で定義した通りである。 According to another embodiment of the present invention, the first xanthene-based dye includes a dye having the same number of positive and negative charges represented by the following Chemical Formula 3, and the second xanthene-based dye includes: A dye represented by Formula 4 and having one or more negative charges than positive charges is included.
[Chemical formula 3]

[Chemical formula 4]

In chemical formulas 3 and 4,
R ₁₂ , R ₁₃ , R ₃₂ and R ₃₃ are the same or different and are each independently hydrogen, deuterium, halogen, nitro, substituted or unsubstituted alkyl, anionic, sulfonate; Or a sulfonamide group, r ₁₂ and r ₁₃ are integers from 0 to 5, r ₃₂ is an integer from 0 to 5, r ₃₃ is an integer from 0 to 4, r ₁₂ , r _{12 13} , when r ₃₂ and r ₃₃ are each 2 or more, the structures in parentheses are the same or different from each other;
R ₆₁ and R ₆₂ are the same or different and are each independently hydrogen; deuterium; a substituted or unsubstituted alkyl group; or a dianhydride group containing a nitrogen atom;
X is an anionic group; a sulfonate group; or a sulfonamide group;
The remaining substituents are as defined in Formulas 1 and 2.

According to one example, R ₆₁ and R ₆₂ can be hydrogen.

化学式４−１において、
Ｒ_５０〜Ｒ_５３は、互いに同一または異なり、それぞれ独立に、水素；重水素；ハロゲン基；ニトロ基；または置換もしくは非置換のアルキル基であり、ｒ_５０およびｒ_５１は、０〜４の整数であり、ｒ_５２およびｒ_５３は、０〜３の整数であり、ｒ_５０〜ｒ_５３がそれぞれ２以上の場合、括弧内の構造は、互いに同一または異なり、
ＸａおよびＸｂは、互いに同一または異なり、それぞれ独立に、陰イオン性基；スルホン酸塩基；またはスルホンアミド基であり、
Ｒ_４５〜Ｒ_４９は、互いに同一または異なり、それぞれ独立に、水素；重水素；陰イオン性基；ヒドロキシ基；スルホンアミド基；スルホン酸塩基；置換もしくは非置換の炭素数１〜３０の直鎖または分枝鎖のアルキル基；置換もしくは非置換のアリール基；および置換もしくは非置換のヘテロアリール基からなる群より選択され、ただし、前記Ｒ_４５〜Ｒ_５９のうちの少なくとも１つは、陰イオン性基；スルホン酸塩基；またはスルホンアミド基である。 When the second xanthene-based dye including the dye of Formula 4 is used, the colorant composition may further include a dye of Formula 4-1.
[Chemical formula 4-1]

In Chemical Formula 4-1,
R _{50 to} R ₅₃ are the same or different and are each independently hydrogen; deuterium; a halogen group; a nitro group; or a substituted or unsubstituted alkyl group, and r ₅₀ and r ₅₁ are integers of 0 to 4 And r ₅₂ and r ₅₃ are integers of 0 to 3, and when r _{50 to} r ₅₃ are each 2 or more, the structures in parentheses are the same or different from each other;
Xa and Xb are the same or different from each other, and each independently represents an anionic group; a sulfonate group; or a sulfonamide group;
R _{45 to} R ₄₉ are the same or different and are each independently hydrogen, deuterium, anionic group, hydroxy group, sulfonamide group, sulfonate group, substituted or unsubstituted straight chain having 1 to 30 carbon atoms. Or a branched alkyl group; a substituted or unsubstituted aryl group; and a substituted or unsubstituted heteroaryl group, provided that at least one of R _{45 to} R ₅₉ is an anion. A sulfonate group; or a sulfonamide group.

［化学式６］

化学式５および６において、
Ｒ_１４〜Ｒ_１７、およびＲ_３４〜Ｒ_３７は、互いに同一または異なり、それぞれ独立に、置換もしくは非置換のアルキル基であり、
Ｒ_６１およびＲ_６２は、互いに同一または異なり、それぞれ独立に、水素；重水素；置換もしくは非置換のアルキル基；または窒素原子を含む二無水物基であり、
Ｘ１〜Ｘ３は、互いに同一または異なり、それぞれ独立に、陰イオン性基；スルホン酸塩基；またはスルホンアミド基である。 According to another embodiment of the present invention, the first xanthene-based dye includes a dye having the same number of positive and negative charges represented by the following Chemical Formula 5, and the second xanthene-based dye includes: A dye represented by Formula 6 and having one or more negative charges than positive charges is included.
[Chemical formula 5]

[Chemical formula 6]

In chemical formulas 5 and 6,
R _{14 to} R ₁₇ and R _{34 to} R ₃₇ are the same or different from each other and are each independently a substituted or unsubstituted alkyl group;
R ₆₁ and R ₆₂ are the same or different and are each independently hydrogen; deuterium; a substituted or unsubstituted alkyl group; or a dianhydride group containing a nitrogen atom;
X1 to X3 are the same or different and are each independently an anionic group; a sulfonate group; or a sulfonamide group.

According to one example, R _{14 to} R ₁₇ and R _{34 to} R ₃₇ may be a methyl group.

According to one example, R ₆₁ and R ₆₂ can be hydrogen.

化学式６−１において、
Ｒ_３８〜Ｒ_４１は、互いに同一または異なり、それぞれ独立に、置換もしくは非置換のアルキル基であり、
Ｘ４〜Ｘ６は、互いに同一または異なり、それぞれ独立に、陰イオン性基；スルホン酸塩基；またはスルホンアミド基である。 According to an example, when a second xanthene-based dye including the dye of Formula 6 is used, the colorant composition may further include a dye of Formula 6-1.
[Chemical formula 6-1]

In chemical formula 6-1:
R _{38 to} R ₄₁ are the same or different and are each independently a substituted or unsubstituted alkyl group;
X4 to X6 are the same or different and are each independently an anionic group; a sulfonate group; or a sulfonamide group.

In one embodiment of the present specification, the first xanthene-based dye may have any one of the following structures.

In one embodiment of the present specification, the second xanthene-based dye may have any one of the following structures.

  According to an embodiment of the present invention, the dispersant may include 3 to 50 mol%, preferably 4 to 40 mol%, of the monomer units having an ammonium structure based on 100 mol% of the total monomer units. .

  According to one embodiment of the present invention, the second xanthene-based dye may further include a counter cation. The colorant composition according to an embodiment of the present invention may further include a number of counter cations corresponding to the number of negative charges greater than positive charges in the second xanthene-based dye. The counter cation may be a hydrogen ion, a sodium ion, or a cationic group. For example, 1 to 7 of these may be contained per molecule of the second xanthene dye.

According to another embodiment of the present invention, the dispersant may further include a counter anion. The counter anion may be an inorganic or organic anion, and specifically, may be a halogen group such as Cl ⁻ . The dispersant may include a counter anion in a number corresponding to the number of positive charges of the dispersant.

  The colorant composition according to an embodiment of the present invention may be washed as described below, in which case the counter cation or counter anion is removed, and the cationic structure contained in the dispersant is removed. Can serve as a counter cation of the second xanthene dye.

化学式７において、
Ｒａ〜Ｒｄは、互いに同一または異なり、それぞれ独立に、水素；置換もしくは非置換のアルキル基；置換もしくは非置換のアルケニル基；置換もしくは非置換のアリール基；置換もしくは非置換のアリールアルキル基；−Ｌ−ＮＨＣＯ−Ｒ；または−Ｌ−ＯＣＯ−Ｒであるか、Ｒａ〜Ｒｄのうち２個が互いに結合して置換もしくは非置換の環を形成し、
Ｒは、水素；置換もしくは非置換のアルキル基；置換もしくは非置換のアリール基；または置換もしくは非置換のアリールアルキル基であり、
Ｌは、置換もしくは非置換のアルキレン基である。 According to another embodiment of the present invention, the dispersant is represented by the following Chemical Formula 7.
[Chemical formula 7]

In chemical formula 7,
Ra to Rd are the same or different and are each independently hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted arylalkyl group; L-NHCO-R; or -L-OCO-R, or two of Ra to Rd are bonded to each other to form a substituted or unsubstituted ring;
R is hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted arylalkyl group;
L is a substituted or unsubstituted alkylene group.

  According to an example, in Formula 7, one or more, and more preferably, two or more of Ra to Rd include a long chain having 5 or more carbon atoms. In this case, the dispersion stability by the dispersant may be further increased.

化学式８において、
Ｒｂ〜Ｒｄは、互いに同一または異なり、それぞれ独立に、水素；置換もしくは非置換のアルキル基；置換もしくは非置換のアルケニル基；置換もしくは非置換のアリール基；または置換もしくは非置換のアリールアルキル基であるか、Ｒｂ〜Ｒｄのうちの２個が互いに結合して置換もしくは非置換の環を形成し、
Ｚは、アルキレン基；アリーレン基；−Ｌ−ＮＨＣＯ−；または−Ｌ−ＯＣＯ−であり、Ｌは、アルキレン基であり、
Ｒｅ〜Ｒｇは、互いに同一または異なり、それぞれ独立に、水素；またはアルキル基である。
本発明のもう一つの実施態様によれば、前記分散剤は、重量平均分子量が１，０００〜１０，０００である。好ましくは３，０００〜８，０００であり、さらに好ましくは５，０００〜７，０００である。 According to another embodiment of the present invention, the dispersant comprises a unit of Formula 8:
[Chemical formula 8]

In chemical formula 8,
Rb to Rd are the same or different and are each independently a hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted arylalkyl group. Or two of Rb to Rd combine with each other to form a substituted or unsubstituted ring,
Z is an alkylene group; an arylene group; -L-NHCO-; or -L-OCO-; L is an alkylene group;
Re to Rg are the same or different from each other and are each independently hydrogen; or an alkyl group.
According to another embodiment of the present invention, the dispersant has a weight average molecular weight of 1,000 to 10,000. It is preferably from 3,000 to 8,000, and more preferably from 5,000 to 7,000.

  According to one example, the terminal of the dispersant is a hydrogen, a halogen group, or an alkyl group.

［化学式１０］

［化学式１１］

［化学式１２］

化学式９〜１２において、
Ｒｈ、Ｒｉ、Ｒｊ、Ｒｌ、Ｒｍ、Ｒｎ、Ｒｐ、Ｒｑ、Ｒｒ、Ｒｔ、ＲｕおよびＲｖは、互いに同一または異なり、それぞれ独立に、水素または炭素数１〜２０のアルキル基であり、
ＲｋおよびＲｓは、互いに同一または異なり、それぞれ独立に、炭素数１〜２０のアルキル基であり、
Ｒｏは、炭素数７〜２０のアリールアルキル基であり、
ＲｗおよびＲｘは、互いに同一または異なり、それぞれ独立に、水素、炭素数１〜２０のアルキル基、または炭素数７〜２０のアリールアルキル基であり、
Ｌ_１およびＬ_２は、互いに同一または異なり、それぞれ独立に、炭素数１〜６のアルキレン基であり、ｍは、１〜６の整数である。 According to another embodiment of the present invention, the dispersant further includes at least one unit of the following Formulas 9 to 12 in addition to the unit of Formula 8:
[Chemical formula 9]

[Chemical formula 10]

[Chemical formula 11]

[Chemical formula 12]

In chemical formulas 9 to 12,
Rh, Ri, Rj, Rl, Rm, Rn, Rp, Rq, Rr, Rt, Ru and Rv are the same or different from each other, and each independently represents hydrogen or an alkyl group having 1 to 20 carbon atoms;
Rk and Rs are the same or different from each other, and are each independently an alkyl group having 1 to 20 carbon atoms;
Ro is an arylalkyl group having 7 to 20 carbon atoms,
Rw and Rx are the same or different and are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms;
L ₁ and L ₂ are the same or different and are each independently an alkylene group having 1 to 6 carbon atoms, and m is an integer of 1 to 6.

前記構造において、ａ〜ｇは、分散剤を構成する繰り返し単位全体を基準とするモル％であり、ａ：４０−５０ｍｏｌ％、ｂ：１０−２０ｍｏｌ％、ｃ：５−１０ｍｏｌ％、ｄ：３−６ｍｏｌ％、ｅ：１−５ｍｏｌ％、ｆ：１５−２０ｍｏｌ％、ｇ：２−６ｍｏｌ％であってもよいが、これにのみ限定されるものではない。 As a specific example, the dispersant may include the following units, of which the rightmost unit is essential.

In the above structure, a to g are mol% based on the entire repeating units constituting the dispersant, a: 40 to 50 mol%, b: 10 to 20 mol%, c: 5 to 10 mol%, d: 3 It may be -6 mol%, e: 1-5 mol%, f: 15-20 mol%, g: 2-6 mol%, but is not limited thereto.

  According to another embodiment of the present invention, the colorant composition further comprises a solvent.

  The solvent is acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether , Diethylene glycol methyl ethyl ether, chloroform, methylene chloride, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane, 1,1,2-trichloroethene, hexane, heptane, octane, cyclohexane, Benzene, toluene, xylene, methanol, ethanol, isopropanol Propanol, butanol, t-butanol, 2-ethoxypropanol, 2-methoxypropanol, 3-methoxybutanol, cyclohexanone, cyclopentanone, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, 3-methoxybutyl acetate, ethyl 3- It may be one or more selected from the group consisting of ethoxypropionate, ethyl cellosolve acetate, methyl cellosolve acetate, butyl acetate, propylene glycol monomethyl ether, and dipropylene glycol monomethyl ether, but is not limited thereto. Not something.

  If necessary, the colorant composition may further include a salt. This salt can play a role of miniaturizing the dispersed particles in the miniaturization step described below. The salt is not particularly limited as long as it is removed by washing using a solvent such as distilled water and is useful for miniaturization. For example, a material such as NaCl can be used. When a salt is used, the amount used can be determined as necessary, and is, for example, 2 to 8 times, preferably 3 to 5 times the total weight of the first and second xanthene dyes. It can be used about twice. The salt can be removed by washing as described above, and in this case, the solvent can be removed together. The washing is performed once, or two or more times as necessary.

  The second xanthene-based dye may be included in an amount of 3 to 30 parts by weight, preferably 5 to 50 parts by weight, based on 100 parts by weight of the first xanthene-based dye.

  The dispersant may be included in an amount of 1.5 to 8 times, preferably 2 to 6 times, the weight of the second xanthene dye.

  When a solvent is included, the solvent may be included in a weight of 1/15 to 1/5 of the solid content weight. Here, the solid content weight, when used with the first and second xanthene dyes, means the weight of the solid content including the salt content.

  According to another embodiment of the present invention, the above-mentioned colorant composition may further include one or more of dyes and pigments. As an example, the colorant composition may further include a phthalocyanine pigment, or may include, for example, PB15: 6. Metal-free phthalocyanine-based pigments or dyes, metal-substituted phthalocyanine-based pigments or dyes, triarylmethane-based pigments or dyes, quinophthalone-based pigments or dyes, Indoline pigments or dyes, azo pigments or dyes, metal complex azo pigments or dyes, perylene pigments or dyes, diketopyrrolo-pyrroles ) Pigments or dyes, anthraquinone pigments or dyes, It is composed of a dipyrromethene pigment or dye, a porphyrin pigment or dye, a tetraazaporphyrin pigment or dye, a rhodamine pigment or dye, and a xanthene pigment or dye. One or more pigments or dyes selected from the group may be further included. One of the dyes and pigments additionally contained in the colorant composition may be 1 to 50 parts by weight, preferably 10 to 40 parts by weight based on 100 parts by weight of the colorant composition.

  Another embodiment of the present invention provides a colorant dispersion comprising a colorant composition as described above; a dispersant; a binder resin; and a solvent. In this specification, the colorant dispersion can be replaced by the term millbase. Here, the colorant composition contained in the colorant dispersion means a state in which the solvent has been removed. When a salt is used in the colorant composition, the salt is also removed by washing together with the solvent, and then included in the colorant dispersion.

  According to one embodiment, the colorant dispersion may further include beads. Beads having a particle size of 0.05 to 1.5 mm can be used. As a specific example, beads having a particle size of 0.1 mm, 0.3 mm, 0.5 mm, 0.8 mm, and / or 1 mm can be used. The material of the beads may be one or more of aluminum oxide, aluminum silicate, zirconium oxide, and / or silicon nitride. Although the use amount of the beads is not particularly limited, the beads can be used in an amount of 10 to 40 times the total weight of the colorant composition and the dispersant. Such beads can play a role of dispersing the composition contained in the colorant dispersion.

  According to another embodiment of the present invention, the above-mentioned colorant dispersion may further comprise one or more of dyes and pigments. Examples of the dyes and pigments additionally included are the same as those exemplified for the dyes and pigments additionally included in the colorant composition described above.

  Before the colorant composition is included in the colorant dispersion, the colorant composition may be subjected to a miniaturization step. The miniaturization step means a step of miniaturizing by applying a physical force. According to one example, the diameter of the particles dispersed in the colorant composition by the miniaturization process is 40 nm to 100 nm. Here, the diameter means the maximum length of the dispersed particles.

  The diameter of the particles after miniaturization can be measured with SEM or TEM equipment. A specific example using the SEM measurement method is as follows. First, 0.01 g of the colorant dispersion liquid containing the finely divided particles is placed in a chloroform solvent, and is treated for 10 minutes at an intermediate intensity by using KODO ultrasonic equipment JAC-5020, so that the space between the particles is reduced. Pull apart well. Then, after dropping about one drop on Glass, heat treatment is performed for 5 minutes on a hot plate at 50 degrees to remove the solvent. After coating on the particles so that the thickness of Pt is about 100 to 200 °, the diameter of the particles is observed by SEM.

  After preparing the colorant dispersion, a PGEMA (propylene glycol monomethyl ether acetate) solvent is added to a 1 cm × 5 cm cell at about 1/4 of the height, and about 1 to 2 drops of the dispersion (Millbase) are dropped into the cell. . After well diluting in solvent, the particle size was measured with a Malvern particle sizer. The particle size distribution is measured by measuring an angle change according to the intensity of light scattered while penetrating the fine particle sample in which the laser beam is dispersed.

  If the diameter of the particles dispersed in the colorant dispersion exceeds 100 nm, there is a problem that the contrast ratio decreases due to light scattering, and if the dispersed particle size is too small, the light-dark ratio ( Since the stability of the contrast ratio and the dispersion (Millbase) decrease, the range of 40 to 100 nm, more preferably 40 to 80 nm, is suitable.

  According to an example, the dispersed particle size of the colorant composition is 40 nm to 80 nm and the viscosity is 2.5 to 6.5 cP.

  The viscosity measurement method is as follows. About 1 mL of the manufactured colorant dispersion liquid (Millbase) is put into the chamber of the viscosity measurement device, and when the motor is turned on, the spindle rotates and reaches a steady flow while reaching a steady flow. Can be obtained.

  As the solvent, those exemplified above for the colorant composition can be used.

  The binder resin is not particularly limited as long as it can exhibit physical properties such as strength and developability of a film produced from the resin composition.

  As the binder resin, a copolymer resin of a polyfunctional monomer that imparts mechanical strength and a monomer that imparts alkali solubility can be used, and may further include a binder generally used in the art.

  The polyfunctional monomer that imparts mechanical strength to the film is at least one of unsaturated carboxylic esters, aromatic vinyls, unsaturated ethers, unsaturated imides, and acid anhydrides. There may be.

  Specific examples of the unsaturated carboxylic esters include benzyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and isobutyl (meth) acrylate. , T-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, ethylhexyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, hydroxyethyl (meth) acrylate , 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, acyloctyloxy-2- Droxypropyl (meth) acrylate, glycerol (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytri Propylene glycol (meth) acrylate, poly (ethylene glycol) methyl ether (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, p-nonylphenoxy polyethylene glycol (meth) acrylate, p-nonylphenoxy polypropylene glycol (meth) acrylate, glycidyl ( (Meth) acrylate, tetrafluoropropyl (meth) acrylate, 1,1,1,3,3,3-hexafluoro Isopropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, tribromophenyl (meth) acrylate, methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate, propyl α-hydroxymethyl It may be selected from the group consisting of acrylates and butyl α-hydroxymethyl acrylate, but is not limited thereto.

  Specific examples of the aromatic vinyl monomers include styrene, α-methylstyrene, (o, m, p) -vinyltoluene, (o, m, p) -methoxystyrene, and (o, m, p). ) -Chlorostyrene, but is not limited thereto.

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

  Specific examples of the unsaturated imides may be selected from the group consisting of N-phenylmaleimide, N- (4-chlorophenyl) maleimide, N- (4-hydroxyphenyl) maleimide, and N-cyclohexylmaleimide. However, the present invention is not limited to these.

  Examples of the acid anhydride include, but are not limited to, maleic anhydride, methylmaleic anhydride, and tetrahydrophthalic anhydride.

  The monomer imparting alkali solubility is not particularly limited as long as it contains an acid group. For example, (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monomethylmaleic acid, 5-norbornene-2- Selected from the group consisting of carboxylic acids, mono-2-((meth) acryloyloxy) ethyl phthalate, mono-2-((meth) acryloyloxy) ethyl succinate, and ω-carboxypolycaprolactone mono (meth) acrylate It is preferable to use one or more, but it is not limited thereto.

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

  The content of the colorant composition including the complex of the first xanthene dye and the second xanthene dye and the dispersant in the colorant dispersion may be 5 to 20% by weight. In the colorant dispersion, the binder resin may be 1 to 60% by weight, the dispersant may be 1 to 40% by weight, and the solvent may be 10 to 80% by weight.

  One embodiment of the present specification provides a photosensitive resin composition comprising the above-described colorant dispersion, a binder resin, a polyfunctional monomer, and a photopolymerization initiator.

  Here, as the binder resin and the solvent, those described in relation to the colorant dispersion and the colorant composition described above can be used.

  The polyfunctional monomer is a monomer that plays a role of forming a photoresist image by light, and specifically, propylene glycol methacrylate, dipentaerythritol hexaacrylate, dipentaerythritol acrylate, neopentyl glycol diacrylate, 6 -Hexanediol diacrylate, 1,6-hexanediol acrylate tetraethylene glycol methacrylate, bisphenoxyethyl alcohol diacrylate, trishydroxyethyl isocyanurate trimethacrylate, trimethylpropane trimethacrylate, diphenylpentaerythritol hexaacrylate, pentaerythritol trimethacrylate, penta Erythritol tetramethacrylate and dipentaerythritol May be one or a mixture of two or more selected from the group consisting of hexamethylene methacrylate.

  The photopolymerization initiator is not particularly limited as long as the initiator generates a radical by light to promote crosslinking, for example, an acetophenone-based compound, a biimidazole-based compound, a triazine-based compound, and an oxime-based compound. One or more selected types may be used.

  The acetophenone-based compound includes 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2- (Hydroxyethoxy) -phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, benzoin butyl ether, 2,2-dimethoxy-2-phenylacetophenone, 2-methyl- (4-methylthio) phenyl-2-morpholino-1-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- ( 4-bromo-benzyl-2-dimethylamino-1 (4-morpholinophenyl) - butan-1-one, or 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-one include, but are not limited to.

  Examples of the biimidazole-based compound include 2,2-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (o-chlorophenyl) -4,4 ′. , 5,5'-Tetrakis (3,4,5-trimethoxyphenyl) -1,2'-biimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4 ', 5,5' -Tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl) -4,4,5,5'-tetraphenyl-1,2'-biimidazole, and the like, but is not limited thereto.

  The triazine-based compound includes 3- {4- [2,4-bis (trichloromethyl) -s-triazin-6-yl] phenylthio} propionic acid, 1,1,1,3,3,3-hexafluoroisopropyl -3- {4- [2,4-bis (trichloromethyl) -s-triazin-6-yl] phenylthio} propionate, ethyl-2- {4- [2,4-bis (trichloromethyl) -s-triazine -6-yl] phenylthio} acetate, 2-epoxyethyl-2- {4- [2,4-bis (trichloromethyl) -s-triazin-6-yl] phenylthio} acetate, cyclohexyl-2- {4- [ 2,4-bis (trichloromethyl) -s-triazin-6-yl] phenylthio} acetate, benzyl-2- {4- [2,4-bis (trichloromethyl ) -S-Triazin-6-yl] phenylthio} acetate, 3- {chloro-4- [2,4-bis (trichloromethyl) -s-triazin-6-yl] phenylthio} propionic acid, 3- {4- [2,4-bis (trichloromethyl) -s-triazin-6-yl] phenylthio} propionamide, 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,4-bis (Trichloromethyl) -6- (1-p-dimethylaminophenyl) -1,3, -butadienyl-s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine and the like. However, the present invention is not limited to these.

  The oxime-based compounds include 1,2-octadione, 1- (4-phenylthio) phenyl, 2- (o-benzoyloxime) (Ciba Geigy, CGI124), and ethanone, 1- (9-ethyl) -6. -(2-methylbenzoyl-3-yl)-, 1- (O-acetyloxime) (CGI242), N-1919 (ADEKA), and the like, but are not limited thereto.

  According to one embodiment of the present specification, the content of the binder resin is 1 wt% to 60 wt%, preferably 10 to 25 wt%, based on the total weight of the solid content in the photosensitive resin composition. Wherein the content of the photopolymerization initiator is 0.1 wt% to 20 wt%, preferably 1 to 7 wt%, and the content of the polyfunctional monomer is 0.1 wt% to 50 wt%. , Preferably 5 to 20% by weight. The content of the solvent may be 10 to 85% by weight, preferably 35 to 65% by weight based on the total weight of the composition. The colorant dispersion is contained in an amount of 5 to 35% by weight based on the total weight of the composition, and the content of the first and second xanthene dyes and the dispersant in the colorant dispersion is 5 to 20%. % By weight.

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

  According to another embodiment of the present invention, the above-described photosensitive resin composition may further include at least one of a dye and a pigment. Examples of the dyes and pigments additionally included are the same as those exemplified for the dyes and pigments additionally included in the colorant composition described above.

  The photosensitive resin composition may further include a surface additive. Surface additives include curing accelerators, adhesion promoters, adhesion aids, surfactants, thermal polymerization inhibitors, ultraviolet absorbers, dispersants, leveling agents, antioxidants, photocrosslinking sensitizers, multithiol agents (Multi-thiol) can be used. The surface additive may be included in an amount of about 0.1 to 5% by weight, preferably about 0.5 to 1% by weight, based on the total amount of the photosensitive resin composition. The content of the surface additive may be 0.1% by weight to 20% by weight based on the total weight of the solid content in the photosensitive resin composition.

  The photocrosslinking sensitizer includes benzophenone, 4,4-bis (dimethylamino) benzophenone, 4,4-bis (diethylamino) benzophenone, 2,4,6-trimethylaminobenzophenone, methyl-o-benzoylbenzoate, Benzophenone-based compounds such as 3-dimethyl-4-methoxybenzophenone and 3,3,4,4-tetra (t-butylperoxycarbonyl) benzophenone; 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9 Fluorenone compounds such as fluorenone; thioxanthone compounds such as thioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 1-chloro-4-propyloxythioxanthone, isopropylthioxanthone and diisopropylthioxanthone; Xanthone compounds such as anthraquinone, 2-methylxanthone; anthraquinone-based compounds such as anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, t-butylanthraquinone, 2,6-dichloro-9,10-anthraquinone; 9-phenylacridine , 1,7-bis (9-acridinyl) heptane, 1,5-bis (9-acridinylpentane), 1,3-bis (9-acridinyl) propane and other acridine-based compounds; benzyl, 1,7, Dicarbonyl compounds such as 7-trimethyl-bicyclo [2,2,1] heptane-2,3-dione and 9,10-phenanthrenequinone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6- Dimethoxybenzoyl) -2,4,4-trimethylpentylpho Phosphine oxide compounds such as fin oxide; benzoate compounds such as methyl-4- (dimethylamino) benzoate, ethyl-4- (dimethylamino) benzoate, 2-n-butoxyethyl-4- (dimethylamino) benzoate; , 5-bis (4-diethylaminobenzal) cyclopentanone, 2,6-bis (4-diethylaminobenzal) cyclohexanone, 2,6-bis (4-diethylaminobenzal) -4-methyl-cyclopentanone 3,3-carbonylvinyl-7- (diethylamino) coumarin, 3- (2-benzothiazolyl) -7- (diethylamino) coumarin, 3-benzoyl-7- (diethylamino) coumarin, 3-benzoyl-7 -Methoxy-coumarin, 10,10-carboni Such as rubis [1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H, 5H, 11H-C1] -benzopyrano [6,7,8-ij] -quinolizin-11-one; Coumarin compounds; chalcone compounds such as 4-diethylaminochalcone and 4-azidobenzalacetophenone; and at least one selected from the group consisting of 2-benzoylmethylene and 3-methyl-b-naphthothiazoline can be used. .

  The curing accelerator is used to enhance curing and mechanical strength. Specifically, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2,5-dimercapto-1, 3,4-thiadiazole, 2-mercapto-4,6-dimethylaminopyridine, pentaerythritol-tetrakis (3-mercaptopropionate), pentaerythritol-tris (3-mercaptopropionate), pentaerythritol-tetrakis (2 -Mercaptoacetate), pentaerythritol-tris (2-mercaptoacetate), trimethylolpropane-tris (2-mercaptoacetate), and trimethylolpropane-tris (3-mercaptopropionate) It is possible to use one or more kinds-option.

  As the adhesion promoter used herein, methacryloyloxypropyltrimethoxysilane, methacryloyloxypropyldimethoxysilane, methacryloyloxypropyltriethoxysilane, methacryloylsilane coupling agents such as methacryloyloxypropyldimethoxysilane And at least one selected from the group consisting of octyltrimethoxysilane, dodecyltrimethoxysilane, octadecyltrimethoxysilane and the like as alkyltrimethoxysilane.

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

  The antioxidant is at least one selected from the group consisting of a hindered phenol antioxidant, an amine antioxidant, a thio antioxidant, and a phosphine antioxidant. However, the present invention is not limited to this.

  Specific examples of the antioxidant include phosphoric acid-based heat stabilizers such as phosphoric acid, trimethyl phosphate and triethyl phosphate; 2,6-di-t-butyl-p-cresol, octadecyl-3- (4-hydroxy -3,5-di-t-butylphenyl) propionate, tetrabis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, 1,3,5-trimethyl-2, 4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 3,5-di-t-butyl-4-hydroxybenzyl phosphite diethyl ester, 2,2-thiobis (4- Methyl-6-t-butylphenol), 2,6-g, t-butylphenol 4,4'-butylidene-bis (3-methyl-6-t-butylpheno) ), 4,4'-thiobis (3-methyl-6-t-butylphenol), or bis [3,3-bis- (4'-hydroxy-3'-tert-butylphenyl) butanoic acid] glycol ester A hindered phenol-based primary antioxidant such as (Bis [3,3-bis- (4′-hydroxy-3′-tert-butylphenyl) butanoic acid] glycol ester); phenyl-α-naphthylamine; Amine secondary antioxidants such as phenyl-β-naphthylamine, N, N′-diphenyl-p-phenylenediamine, or N, N′-di-β-naphthyl-p-phenylenediamine; dilauryl disulfide, diamine Lauryl thiopropionate, distearyl thiopropionate, mel Thio-based secondary antioxidants such as ptobenzothiazole or tetramethylthiuram disulfide tetrabis [methylene-3- (laurylthio) propionate] methane; or triphenyl phosphite, tris (nonylphenyl) phosphite, triisodecyl phosphite Phyte, bis (2,4-dibutylphenyl) pentaerythritol diphosphite (Bis (2,4-dibutylphenyl) pentaerythritol diphosphite), or tetrakis [1,1′-biphenyl) -4,4′-diylbisphosphonate [2 , 4-Bis (1,1-dimethylethyl) phenyl] ester ((1,1′-Biphenyl) -4,4′-phosphonic acid tetrakis [2,4-bis (1,1-dimethylethyl) Phosphite secondary antioxidant such as yl) phenyl] ester) and the like.

  Examples of the ultraviolet absorber include 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chloro-benzotriazole and alkoxybenzophenone, but are not limited thereto. All commonly used in the art can be used.

  Examples of the thermal polymerization inhibitor include p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, N-nitrosophenylhydroxyamine ammonium salt, and N-nitrosophenylhydroxyamine aluminum salt. , P-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, benzoquinone, 4,4-thiobis (3-methyl-6-t-butylphenol), 2,2-methylenebis (4-methyl-6-t -Butylphenol), 2-mercaptoimidazole, and phenothiazine, but are not limited thereto, and are generally known in the art. It can include those are.

  The leveling agent may be polymeric or non-polymeric. Specific examples of the polymeric leveling agent include polyethyleneimine, polyamidoamine, and a reaction product of an amine and an epoxide. Specific examples of the non-polymeric leveling agent include non-polymer sulfur- All but commonly used in the art, including but not limited to containing and non-polymeric nitrogen-containing compounds, can be used.

  Another embodiment of the present invention is a color filter including a transparent substrate and a colored layer provided on the transparent substrate, wherein the colored layer includes a cured product of the above-described photosensitive resin composition. A color filter.

  The color filter can be manufactured using the photosensitive resin composition. A color filter can be formed by applying the photosensitive resin composition on a substrate to form a coating film, and exposing, developing, and curing the coating film.

  The application method is not particularly limited, but a spray method, a roll coating method, a spin coating method, or the like can be used, and the spin coating method is generally widely used. After the formation of the coating film, the residual solvent can be partially removed under reduced pressure in some cases.

  The light source for curing the resin composition according to the present specification includes, for example, a mercury vapor arc (arc) that emits light having a wavelength of 250 nm to 450 nm, a carbon arc, a Xe arc, and the like, but is not necessarily limited thereto. Absent.

  The resin composition according to an embodiment of the present specification is excellent in heat resistance, has little change in color due to heat treatment, and has a high color reproducibility even during a curing process during the production of a color filter, and has a high luminance and contrast ratio. A high color filter can be provided.

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

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

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

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

  The black matrix according to one embodiment of the present specification can use a black pigment or a black dye as a coloring material. For example, carbon black can be used alone or a mixture of carbon black and a coloring pigment can be used. There is an advantage that the strength of the film or the adhesion to the substrate does not decrease even if it increases.

  Provided is a liquid crystal display device including the color filter according to the present specification. The liquid crystal display may have a configuration known in the art except for including the above-described color filter.

  Hereinafter, the present specification will be described in detail with reference to examples. The following examples are intended to illustrate the present specification, and the scope of the present specification includes the scope described in the following claims and substitutions and modifications thereof, and is not limited to the scope of the examples. .

  [Method for producing dispersant containing resin having cationic group in side chain]

(Production Example 1: Production of resin A-1 having a cationic group in a side chain)
In a four-neck separable flask equipped with a thermometer, a stirrer, a distillation tube, and a cooler, propylene glycol monomethyl ether acetate based on 100 parts by weight of the total weight of the dispersant containing the resin having a cationic group in the side chain After adding 56.7 parts by weight, the temperature was raised to 75 ° C. under a nitrogen stream. 45.8 parts by weight of methyl methacrylate, 14.8 parts by weight of n-butyl methacrylate, 7.8 parts by weight of 2-ethylhexyl methacrylate, 7.8 parts by weight of benzyl methacrylate, based on 100 parts by weight of the total weight of the monomer or polymerization initiator separately added After 5.0 parts by weight, 3.0 parts by weight of triethylene glycol methyl ether methacrylate, 18.9 parts by weight of 2-dimethylaminoethyl methacrylate, and 4.7 parts by weight of a benzyl chloride salt, the mixture was charged into a dropping funnel. The solution was attached to a four-neck separable flask and added dropwise over 2 hours. Two hours after the completion of the dropwise addition, it was confirmed that the polymerization yield was 98.7% or more and the weight average molecular weight (Mw) was 5,500 from the solid content, and the mixture was cooled to 50 ° C. Thereafter, 10 parts by weight of propylene glycol monomethyl ether based on 100 parts by weight of the total weight of the dispersant containing the resin having a cationic group in the side chain is added, and the cationic group is added to 5 mol% of the side chain of the resin component. Was produced. The amine value of the obtained resin was 30 mgKOH / g.

  The weight average molecular weight (Mw) of the resin having a cationic group in the side chain was measured by gel permeation chromatography (GPC) using polystyrene as a standard substance. The amine value was determined by potentiometric titration using a 0.1N aqueous hydrochloric acid solution, and then converted to an equivalent of potassium hydroxide.

(Production Examples 2 to 8: Production of Resins A-2 to A-8 Having a Cationic Group in the Side Chain)
Resins A-2 to A-8 having a cationic group in the side chain were obtained in the same manner as in Production Example 1, except that the monomers, the polymerization initiator, and the reaction temperature were changed to the compositions shown in Table 1.

  In the above Table 1, MMA is methyl methacrylate, nBMA is n-butyl methacrylate, EHMA is ethylhexyl methacrylate, BzMA is benzyl methacrylate, TEGMA is triethyleneaminoethyl methacrylate, DMAEMA is dimethylaminoethyl methacrylate, BC is benzyl chloride salt, and ST is benzyl chloride salt. Styrene, MDGMA means diethylene glycol methyl ether methacrylate, and EG means ethylene glycol methacrylate.

[Method for producing colorant complex]
The composition shown in Table 1 was put in a Bench Knader (Irie shokai co. Ltd. Model PBV-01) together with the solvent diethylene glycol (Diethylene Glycol) 7.5 g and pulverized salt (NaCl) 40 g, followed by miniaturization for 4 hours. Was. After 4 hours, the refined colorant composition was added to 1 L of distilled water at 60 ° C., stirred for 30 minutes, and then the pressure was reduced to remove distilled water. When the distilled water is removed by reducing the pressure, about 7 L of distilled water at 60 ° C. is additionally used to completely remove the salt (NaCl), thereby obtaining the complexes B-1 to B-21 shown in Table 2 below. Obtained. The following structures were used as the first and second xanthene dyes.

  In Table 2, the term "Mol ratio (%)" means the ratio of ammonium salt introduced by the ratio of EG (ethylene glycol methacrylate) in Table 1.

[Method for producing colorant dispersion]
The prepared composites B-1 to B-21 of the colorant composition were stirred so that a mixture of the composition shown in Table 3 below and 8.4 g of propylene glycol monomethyl ether acetate was uniformly mixed. Using a 0.3 mm zirconia bead, a dispersion treatment was performed for 2 hours with a Paint shaker. After that, the dispersion was switched to 0.1 mm zirconia beads, and the dispersion treatment was further allowed to proceed for 2 hours using a Paint shaker. After the dispersion treatment, 12.6 g of propylene glycol monomethyl ether acetate was added for each composition, and the mixture was filtered with a 1.0 μm filter to obtain a colorant dispersion.

  In Table 3, Binder A is a copolymer having a mass ratio of benzyl methacrylate: N-phenylmaleimide: styrene: methacrylic acid = 55: 9: 11: 25.

[Production of photosensitive coloring composition]
A photosensitive coloring composition was prepared by applying the components and the amounts shown in Table 4 below.
16.74 parts by weight of one of the previously prepared colorant dispersions C-1 to C-21 and phthalocyanine (PB15: 6) dispersion 22 based on 100 parts by weight of the total weight of the photosensitive coloring composition. 0.33 parts by weight, 11.73 parts by weight of binder A, 9.88 parts by weight of Mihon Trading's DPHA (DIPENTARYTHRITOL HEXACRYLATE), 1.16 parts by weight of initiator PBG-3057, 1.16 parts by weight of photosensitizer EMK (4,4'-Bis ( (diethylamino) benzophenone) 0.39 part by weight, surface additive B (leveling agent DIC F-554) 0.1 part by weight, surface additive C (adhesion aid KBM-503) 0.19 part by weight, surface additive 0.14 parts by weight D (antioxidant Songwon Industrial Songnox-1010), surface additive E (Muti- 0.44 parts by weight of thiol SQ-506), 29.5 parts by weight of a solvent PGMEA (propylene glycol monomethyl ether acetate), and 17.4 parts by weight of 3-MBA (3-methoxy butyl acetate).

  The same binder A was used as when the colorant dispersion was produced.

The binder A is a copolymer having a mass ratio of benzyl methacrylate: N-phenylmaleimide: styrene: methacrylic acid = 55: 9: 11: 25.

  In Table 4, in Comparative Examples 1 to 4 and 6 to 8, the colorant dispersion was gelled (Gel) and could not be evaluated.

[Evaluation of colorant dispersion]
The particle size and storage stability of the obtained colorant dispersions (C-1 to C-21) were evaluated by the following methods.

(Grain size evaluation method)
A 1 cm × 5 cm quartz cell was filled with PGMEA (propylene glycol monomethyl ether acetate) at about 1/4 of the height, and about 1 to 2 drops of the produced colorant dispersion were dropped. The particle size was measured using a particle size analyzer (Zetasizer nano-ZS90 from Malvern). The degree of miniaturization was evaluated based on the particle size measurement results. The results of the particle size measurement are shown in Table 5 below.

  Dispersions C-9 to C-21, which have been made finer by using a first xanthene dye, a second xanthene dye, and a dispersant having an ammonium structure, are not gelled, and have a particle size of 40 to 80 nm. Was obtained.

(Method of evaluating storage stability)
For the colorant dispersion, the initial viscosity at 25 ° C. on the day when the colorant dispersion was produced and the viscosity after storage at 40 ° C. in a reaction open for 7 days were measured using a viscometer (Toki Sangyo Viscometer TV-25). ) At 100 rpm. The rate of change in viscosity over time was calculated from the viscosity measured based on the following equation. The storage stability was evaluated according to the following criteria based on the calculated rate of change in viscosity over time. The evaluation results are shown in Table 6 below.
(Change in viscosity over time) = [{(initial viscosity) − (viscosity over time)} / (initial viscosity)] × 100
◎: less than 5%, Δ: less than 5 to 10%, X: 10% or more

  Dispersions C-9 and C- were prepared by forming a composite using the first xanthene dye, the second xanthene dye, and a dispersant having an ammonium structure, and applying a dispersant having an ammonium structure to form a dispersion. In the case of 12 to C-21, the viscosity stability was excellent and was in a range that could be preferably used as a color filter.

(Permeability evaluation method)
Comparative Example 5 and Examples 1 to 13 of the prepared photosensitive coloring composition were spin-coated on a 5 cm × 5 cm glass, and pre-baked at 110 ° C. for 75 seconds to form a film. . The distance between the substrate on which the film was formed and the photo mask was 250 μm, and an exposure amount of 40 mJ / cm ² was irradiated using an exposure device.

  The exposed substrate was developed in a developing solution (KOH, 0.05%) for 60 seconds, and post-heat treated at 230 ° C. for 20 minutes to obtain a color pattern. The color patterns were measured with a spectrophotometer (MCPD), and the transmittances of Comparative Examples 1 to 8 and Examples 1 to 13 were obtained. The transmittance value is a value obtained by comparison when By = 0.051.

(Heat resistance evaluation method)
A post-baking process was performed at 230 ° C. for 20 minutes, and the substrate whose color characteristics were confirmed using a spectrophotometer was further heated at 230 ° C. for 5 hours and 30 minutes. The color characteristics were confirmed again with a spectrophotometer, and the ΔEab value was confirmed.
Permeability improvement rate (%) = Permeability of composition / Permeability of Comparative Example 5 The results of the permeability and heat resistance evaluation are shown in Table 7 below.

  Examples 1 to 13 in which the first xanthene dye and the second xanthene dye were combined with a dispersant having an ammonium structure to achieve fineness were excellent in the transmittance improvement rate, and when producing a colorant dispersion, ammonium was used. A composition using a dispersant having a structure has excellent heat resistance.

  A complex in which a first xanthene dye having the same number of positive charges and negative charges, and a second xanthene dye having a number of negative charges greater than or equal to one more than the number of positive charges, and a dispersant having an ammonium structure are ion-bonded. When a colorant dispersion was produced by applying the above method, the dispersibility was enhanced, and the viscosity stability and the brightness of the coating film were high.

Claims (20)

A first xanthene dye having the same number of positive and negative charges; and a second xanthene dye having at least one more negative charge than the number of positive charges, an amine value of 0 to 200 mgKOH / g, and an ammonium structure A colorant composition comprising a complex in which a dispersant containing ionic bond is formed.   A part or all of the second xanthene dye is located between two or three or more adjacent first xanthene dyes or adjacent to an end of the first xanthene dye. 2. The colorant composition according to 1.   The first xanthene dye has a maximum absorption wavelength between 500 and 580 nm, and the difference between the maximum absorption wavelength of the first xanthene dye and the maximum absorption wavelength of the second xanthene dye is 100 nm or less. The colorant composition according to claim 1, wherein the colorant composition is provided. The first xanthene-based dye is represented by Formula 1 below and includes dyes having the same number of positive and negative charges, and the second xanthene-based dye is represented by Formula 2 below and is more negative than the number of positive charges. The colorant composition according to any one of claims 1 to 3, wherein the colorant composition comprises a dye having one or more charges.
[Chemical formula 1]

In the above chemical formula 1,
R _{1 to} R ₄ are the same or different and are each independently hydrogen, deuterium, anionic group, hydroxy group, sulfonamide group, sulfonate group, substituted or unsubstituted alkyl group, substituted or unsubstituted An aryl group; a substituted or unsubstituted heteroaryl group; and a dianhydride group containing a nitrogen atom,
R _{5 to} R ₉ are the same or different and are each independently hydrogen, deuterium, anionic group, hydroxy group, sulfonamide group, sulfonate group, substituted or unsubstituted alkyl group, substituted or unsubstituted Selected from the group consisting of an aryl group; and a substituted or unsubstituted heteroaryl group, provided that at least one of R _{5 to} R ₉ is an anionic group; a sulfonate group; or a sulfonamide group. ,
R ₁₀ and R ₁₁ are the same or different and are each independently hydrogen; deuterium; a halogen group; a nitro group; or a substituted or unsubstituted alkyl group, and r ₁₀ and r ₁₁ are integers of 0 to 3 And when each of r ₁₀ and r ₁₁ is 2 or more, the structures in parentheses are the same or different from each other;
[Chemical formula 2]

In the above chemical formula 2,
R _{21 to} R ₂₄ are the same or different and are each independently hydrogen, deuterium, anionic group, hydroxy group, sulfonamide group, sulfonate group, substituted or unsubstituted alkyl group, substituted or unsubstituted An aryl group; a substituted or unsubstituted heteroaryl group; and a dianhydride group containing a nitrogen atom, wherein at least one of R _{21 to} R ₂₄ is an anionic group, a sulfonate group, Or an alkyl group substituted or unsubstituted with a sulfonamide group; an aryl group substituted with an anionic group, a sulfonate group, or a sulfonamide group; or substituted with an anionic group, a sulfonate group, or a sulfonamide group Is a heteroaryl group,
R _{25 to} R ₂₉ are the same or different and are each independently hydrogen, deuterium, anionic group, hydroxy group, sulfonamide group, sulfonate group, substituted or unsubstituted straight chain having 1 to 30 carbon atoms. Or a branched alkyl group; a substituted or unsubstituted aryl group; and a substituted or unsubstituted heteroaryl group, provided that at least one of R _{25 to} R ₂₉ is an anion. A sulfonate group; or a sulfonamide group,
R ₃₀ and R ₃₁ are the same or different and are each independently hydrogen; deuterium; a halogen group; a nitro group; or a substituted or unsubstituted alkyl group, and r ₃₀ and r ₃₁ are an integer of 0 to 3 When each of r ₃₀ and r ₃₁ is 2 or more, the structures in parentheses are the same or different from each other. R _{1 to} R ₄ are the same or different and are each independently hydrogen, deuterium, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, and dianhydride group containing nitrogen atom. More selected,
R _{21 to} R ₂₄ are the same or different and are each independently hydrogen, deuterium, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a dianhydride group containing a nitrogen atom. More selected,
The colorant composition according to claim 4, wherein the remaining substituents are the same as defined in claim 4.   The colorant composition according to any one of claims 1 to 5, wherein the dispersant contains 3 to 50 mol% of a monomer unit having an ammonium structure based on 100 mol% of the total monomer units.   The colorant composition according to any one of claims 1 to 6, wherein the second xanthene-based dye further includes a counter cation.   The colorant composition according to any one of claims 1 to 7, wherein the dispersant further includes a counter anion. The colorant composition according to any one of claims 1 to 8, wherein the dispersant is represented by the following Chemical Formula 7:
[Chemical formula 7]

In chemical formula 7,
Ra to Rd are the same or different and are each independently hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted arylalkyl group; L-NHCO-R; or -L-OCO-R, or two of Ra to Rd are bonded to each other to form a substituted or unsubstituted ring;
R is hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted arylalkyl group;
L is a substituted or unsubstituted alkylene group. The colorant composition according to any one of claims 1 to 9, wherein the dispersant includes a unit represented by the following Chemical Formula 8.
[Chemical formula 8]

In chemical formula 8,
Rb to Rd are the same or different and are each independently a hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted arylalkyl group. Or two of Rb to Rd combine with each other to form a substituted or unsubstituted ring,
Z is an alkylene group; an arylene group; -L-NHCO-; or -L-OCO-; L is an alkylene group;
Re to Rg are the same or different from each other and are each independently hydrogen; or an alkyl group.   The colorant composition according to claim 10, wherein the dispersant has a weight average molecular weight of 1,000 to 10,000.   The colorant composition according to any one of claims 1 to 11, wherein the colorant composition further includes at least one of a dye and a pigment.   The colorant composition according to any one of claims 1 to 12, wherein particles dispersed in the colorant composition have a diameter of 40 nm to 100 nm.   The colorant composition according to any one of claims 1 to 13, wherein the colorant composition further comprises a solvent.   A colorant dispersion comprising the colorant composition according to any one of claims 1 to 13; a dispersant; a binder resin; and a solvent.   The colorant dispersion according to claim 15, wherein the diameter of the particles dispersed in the colorant dispersion is 40 to 80 nm, and the viscosity of the colorant dispersion is 2.5 to 6.5 cP.   A photosensitive resin composition comprising the colorant dispersion according to claim 15, a binder resin, a polyfunctional monomer, and a photopolymerization initiator.   The photosensitive resin composition according to claim 17, wherein the photosensitive resin composition further includes a surface additive.   A color filter comprising: a transparent substrate; and a coloring layer provided on the transparent substrate, wherein the coloring layer includes a cured product of the photosensitive resin composition according to claim 17.   A liquid crystal display device comprising the color filter according to claim 19.