TWI668274B - Colored photosensitive resin composition, color filter and image display device produced using the same - Google Patents

Abstract

The coloring photosensitive resin composition according to the present invention includes a coloring agent containing a xanthene-based dye represented by Chemical Formula 1 and a compound represented by Chemical Formula 2.

Description

   Colored photosensitive resin composition, color filter and image display device manufactured by using same   

The present invention relates to a colored photosensitive resin composition, a color filter manufactured by using the same, and an image display device.

Since color filters are widely used in image display devices such as image pickup devices and liquid crystal display devices, their application range is rapidly expanding. A color filter used in a color liquid crystal display device, an image pickup element, and the like is generally manufactured by uniformly coating a coloring material containing red, green, and blue colors by spin coating on a substrate on which a black matrix pattern is formed. After coloring the photosensitive resin composition with an agent, it is heated and dried (hereinafter sometimes referred to as pre-firing), the formed coating film is exposed and developed, and further heat-cured if necessary (hereinafter sometimes referred to as post-firing). Repeat this operation for each color to form the primitive of each color.

The colored photosensitive resin composition is a photosensitive resin composition that contains a colorant and is colored, and can be used as a material for forming a colored pattern constituting a color filter. Among them, the color filter is an optical element built into a color liquid crystal display device, used to colorize a display image, or built into an imaging element, and used to obtain a color image.

Recently, in order to save power of a color liquid crystal display, a color filter with higher brightness is required. Generally, the color filter has a thinner film thickness and a higher brightness. At this time, in order to ensure high color reproduction, it is necessary to achieve a high pigment concentration. However, the increase in the concentration of the pigment further reduces the storage stability and coatability of the resist composition, and therefore it is difficult to produce a color filter having sufficient performance.

To achieve these goals, the application of dyes has been studied. However, compared with the case where a pigment is applied, problems of low reliability and low contrast often occur. Therefore, it is required to develop a technique for solving a problem existing when using a dye.

Korean Laid-Open Patent No. 2014-0115990 relates to a coloring composition, a coloring cured film, and a display element, and discloses the content related to the coloring composition. The coloring composition contains (A) A coloring composition of at least one of a compound, a coumarin compound, and a hydrazone compound, (B) a binder resin, and (C) a coloring composition of a polymerizable compound, further comprising (D) a transition metal compound (but not Including (A) component).

Korean Laid-Open Patent No. 2015-0101934 relates to a coloring composition, a coloring cured film, and a display element, and discloses a coloring composition which is a coloring combination containing (A) a colorant and (B) a polymerizable compound (A) The colorant contains a polymer having a site that emits fluorescence and a site that absorbs the fluorescence.

However, in the above-mentioned prior art, since an additive such as a transition metal or a color former such as an anthraquinone displays a unique color, brightness and reliability may be disadvantageous.

    Prior art literature         Patent literature    

(Patent Document 1) Korean Published Patent No. 2014-0115990 (2014.10.01.)

(Patent Document 2) Korean Published Patent No. 2015-0101934 (2015.09.04.)

The present invention is intended to solve the above-mentioned problems, and an object thereof is to provide a xanthene-based dye and a compound represented by a specific chemical formula so as to exhibit high reliability when applied to a color filter and an image display device including the same. Coloring photosensitive resin composition with high contrast characteristics.

The coloring photosensitive resin composition according to the present invention for achieving the above object includes a coloring agent containing a xanthene-based dye represented by the following Chemical Formula 1 and a compound represented by the following Chemical Formula 2.

[Chemical Formula 1]

In the above Chemical Formula 1, R ₁ to R ₄ are each independently a hydrogen atom, -R ₆ or an aromatic hydrocarbon group having 6 to 10 carbon atoms; or R ₁ and R ₂ and R ₃ and R ₄ can be combined with each other to form 6 members. ~ 10 member ring, the aromatic hydrocarbon group having 6 to 10 carbon atoms or the hydrogen atom contained in the above 6 member to 10 member ring is halogen atom, -R ₆ , -OH, -OR ₆ , -SO ₃ ^- ,- _{SO 3 Na, -CO 2 H,} -CO 2 R 6, -SO 3 H, -SO 3 R 6 -SO ₂ NHR _7, or a substituted or unsubstituted, R ₅ is ^{_{-SO 3 -, -SO 3 Na,}} - CO ₂ H, -CO ₂ R ₆ , -SO ₃ H or -SO ₂ NHR ₇ , R ₆ is a saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms is- OR ₆ or a halogen atom substituted or unsubstituted, R ₇ is a hydrogen atom, -R ₆ , -CO ₂ R ₆ , an aromatic hydrocarbon group having 6 to 10 carbon atoms, and the aromatic hydrocarbon group having 6 to 10 carbon atoms -R ₆ is a hydrogen atom or a substituted or unsubstituted, -OR _6, A is selected from the group consisting of a halogen ^{_{anion, ClO 4 -, BF 4 -}} , SbF 6 -, CF 3 CO 2 -, CF 3 SO 3 -, N (SO 2 CF ₃ ) ₂ ^- The ions in the group constituted, p is an integer of 1 to 5, but when p is an integer of 2 or more, a plurality of R ₅ are the same or different from each other, and q is 0 or 1 An integer, but the number of + charges and the number of-charges in the compound represented by the above Chemical Formula 1 are the same. [Chemical Formula 2] (X ⁺ ) _n (Y) ^{m-In the} above Chemical Formula 2, (X ⁺ ) is represented by the following chemical formula 3 to any of Chemical Formula 5, n is 1 to 10, m is the same as n, and (Y) ^m- has at least one element and an oxygen atom selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus Anion, In the above Chemical Formula 3, Z is carbon, nitrogen, sulfur, phosphorus, or iodine, and R ₈ , R ₉ , R _10, and R ₁₁ are each independently a hydrogen, a halogen atom, or a monovalent or divalent substitution of 1 to 30 carbon atoms. Or an unsubstituted hydrocarbon group, the carbon of -CH ₂ -constituting the above-mentioned hydrocarbon group may be converted with an oxygen atom, a sulfur atom, an amine group, or a carbonyl group, and a hydrogen atom contained in the above-mentioned hydrocarbon group may be a halogen atom, a cyano group, a nitro group, a carbonyl group, or a sulfonic acid group. Acid group, -SO ₃ M, -CO ₂ M, hydroxyl, formamyl or amine group conversion, may contain epoxy, acrylate reactive groups; can be selected from the group consisting of alkyl, halogen, CN, OR ₂₃ , SR ₂₄ , carbonyl, sulfonic group and NR ₂₅ R ₂₆ substituted with one or more substituents of phenyl or aromatic hydrocarbon, and R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ are hydrogen, halogen atom or carbon number A monovalent or divalent hydrocarbon group of 1 to 30, the carbon of -CH ₂ -constituting the above hydrocarbon group may be converted with an oxygen atom, a sulfur atom, an amine group, or a carbonyl group, and a hydrogen atom contained in the above hydrocarbon group may be a halogen atom, a cyano group, a nitro group, a carbonyl group, a sulfonic acid _{group, -SO 3 M, -CO 2 M} , hydroxy, methyl or acyl group conversion, may contain epoxy, acrylate reactive group; or a An alkenyl group having 1 to 30, selected from halogen atoms may include, a cyano group, a nitro group, a carbonyl group, a sulfonic acid _{group-containing, -SO 3 M, -CO 2 M} , hydroxy, methyl or acyl group of one or more R ₈ and R ₁₁ may be combined to form a nitrogen-containing heterocyclic ring having 5 to 7 members, or each independently is a cycloalkyl group, M is an alkali metal atom, and n is 0 to 5, In the above Chemical Formula 4, L is carbon or nitrogen, and R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R _16, and R ₁₇ are each independently a hydrogen, a halogen atom, or a monovalent or divalent substitution of 1 to 30 carbon atoms. Or an unsubstituted hydrocarbon group, the carbon of -CH ₂ -constituting the above hydrocarbon group may be converted with an oxygen atom, a sulfur atom, an amine amino group, or a carbonyl group, and a hydrogen atom contained in the above hydrocarbon group may be a halogen atom, a cyano group, a nitro group, a carbonyl group, Conversion of sulfonic acid group, -SO ₃ M, -CO ₂ M, hydroxyl group, formamyl group or amine group, and it may contain epoxy, acrylate reactive groups; it may be selected from the group consisting of alkyl, halogen, CN, OR ₂₃ , SR ₂₄ , carbonyl, sulfonic and NR ₂₅ R ₂₆ substituted with one or more substituents of phenyl or aromatic hydrocarbons, R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ are each independently hydrogen or halogen An atom or a monovalent or divalent hydrocarbon group having 1 to 30 carbon atoms. The -CH ₂ -carbon constituting the above hydrocarbon group may be converted with an oxygen atom, a sulfur atom, an amine group, or a carbonyl group. A hydrogen atom contained in the above hydrocarbon group may be a halogen atom. , a cyano group, a nitro group, a carbonyl group, a sulfonic acid _{group, -SO 3 M, -CO 2 M} , hydroxy, methyl or acyl group conversion, may contain epoxy, acrylate reaction Group; or an alkenyl group having a carbon number of 1 to 30, selected may contain a halogen atom, a cyano group, a nitro group, a carbonyl group, a sulfonic acid _{group-containing, -SO 3 M, -CO 2 M} , hydroxy, methyl or acyl amine A phenyl or aromatic hydrocarbon group having one or more substituents in the group, R ₁₃ and R ₁₄ may be combined to form a 5- to 7-membered nitrogen-containing heterocyclic ring, or each independently a cycloalkyl group, and M is an alkali metal atom , N is 0 ~ 5, In the above Chemical Formula 5, L is carbon, nitrogen, or sulfur, and R ₁₈ , R ₁₉ , R ₂₀ , R _21, and R ₂₂ are each independently a hydrogen, a halogen atom, or a monovalent or divalent substitution of 1 to 30 carbon atoms. Or an unsubstituted hydrocarbon group, the carbon of -CH ₂ -constituting the above-mentioned hydrocarbon group may be converted with an oxygen atom, a sulfur atom, an amine group, or a carbonyl group, and a hydrogen atom contained in the above-mentioned hydrocarbon group may be a halogen atom, a cyano group, a nitro group, a carbonyl group, or a sulfonic acid group. Acid group, -SO ₃ M, -CO ₂ M, hydroxyl, formamyl or amine group conversion, may contain epoxy, acrylate reactive groups; can be selected from the group consisting of alkyl, halogen, CN, OR ₂₃ , SR ₂₄ , carbonyl, sulfonic group and NR ₂₅ R ₂₆ substituted with one or more substituents of phenyl or aromatic hydrocarbon, and R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ are hydrogen, halogen atom or carbon number A monovalent or divalent hydrocarbon group of 1 to 30, the carbon of -CH ₂ ^- constituting the above hydrocarbon group may be converted with an oxygen atom, a sulfur atom, an amine group, or a carbonyl group, and a hydrogen atom contained in the above hydrocarbon group may be a halogen atom, a cyano group, Nitro, carbonyl, sulfonic, -SO ₃ M, -CO ₂ M, hydroxy, formamyl, or amine groups can contain epoxy, acrylate reactive groups; or The alkenyl group having 1 to 30 carbon atoms may include one selected from a halogen atom, a cyano group, a nitro group, a carbonyl group, a sulfonic group, -SO ₃ M, -CO ₂ M, a hydroxyl group, a methyl group, or an amine group. The phenyl or aromatic hydrocarbon group of the above substituents, R ₂₁ and R ₂₂ may be combined to form a 5- to 7-membered nitrogen-containing heterocyclic ring, or each independently a cycloalkyl group, M is an alkali metal atom, and n is 0 ~ 5.

The present invention also provides a color filter including the cured product of the colored photosensitive resin composition and an image display device including the same.

The colored photosensitive resin composition according to the present invention includes the dyes and compounds represented by specific chemical formulas, and thus has the advantages that when applied to a color filter and an image display device including the same, the brightness is not reduced and the display is high. Reliability and high contrast characteristics.

The present invention is described in further detail below.

In the present invention, when a component is "on" another component, it is not only the case where a component is in contact with another component, but also the case where there are other components between the two components.

In the present invention, when a certain part “contains” a certain constituent element, as long as there is no particular contrary description, it does not exclude other constituent elements, and means that other constituent elements can be further included.

<Colored photosensitive resin composition>

The coloring photosensitive resin composition according to the present invention includes: a coloring agent containing a xanthene-based dye represented by Chemical Formula 1; and a compound represented by Chemical Formula 2.

Xanthene dyes represented by chemical formula 1

The colorant according to the present invention includes a xanthene-based dye represented by the following Chemical Formula 1.

In the above Chemical Formula 1, R ₁ to R ₄ are each independently a hydrogen atom, -R ₆ or an aromatic hydrocarbon group having 6 to 10 carbon atoms; or R ₁ and R ₂ and R ₃ and R ₄ can be combined with each other to form 6 members. ~ 10 member ring, the aromatic hydrocarbon group having 6 to 10 carbon atoms or the hydrogen atom contained in the above 6 member to 10 member ring is halogen atom, -R ₆ , -OH, -OR ₆ , -SO ₃ ^- ,- _{SO 3 Na, -CO 2 H,} -CO 2 R 6, -SO 3 H, -SO 3 R 6 -SO ₂ NHR _7, or a substituted or unsubstituted, R ₅ is ^{_{-SO 3 -, -SO 3 Na,}} - CO ₂ H, -CO ₂ R ₆ , -SO ₃ H or -SO ₂ NHR ₇ , R ₆ is a saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms is- OR ₆ or a halogen atom substituted or unsubstituted, R ₇ is a hydrogen atom, -R ₆ , -CO ₂ R ₆ , an aromatic hydrocarbon group having 6 to 10 carbon atoms, and the aromatic hydrocarbon group having 6 to 10 carbon atoms -R ₆ is a hydrogen atom or a substituted or unsubstituted, -OR _6, A is selected from the group consisting of a halogen ^{_{anion, ClO 4 -, BF 4 -}} , SbF 6 -, CF 3 CO 2 -, CF 3 SO 3 -, N (SO 2 CF ₃ ) ₂ ^- An ion in the group consisting of p, which is an integer of 1 to 5. However, when p is an integer of 2 or more, a plurality of R ₅ are the same or different from each other, and q is 0 or 1. An integer, but the number of + charges and the number of-charges in the compound represented by the above Chemical Formula 1 are the same.

Commercially available xanthene dyes can be used, for example, "Chugai Aminol Fast Pink R-H / C" manufactured by Sinowac Corporation, and "Rhodamine 6G" manufactured by Taoka Chemical Industry Co., Ltd. Moreover, it can synthesize | combine using a commercially available xanthene dye as a starting material. In addition, rhodamine B and the like can be purchased and used.

In the present invention, the xanthene dye represented by the above Chemical Formula 1 can be expressed by any one of the following structural formulas.

The R ₆ may be a branched alkyl group having 6 to 12 carbon atoms, but is not limited thereto.

When the colorant contains a xanthene dye represented by the above Chemical Formula 1 and a compound represented by the above Chemical Formula 2, there is an advantage that a colored photosensitive resin composition having excellent reliability and contrast can be provided.

In one embodiment of the present invention, the colorant may further include one or more selected from the group consisting of a triarylmethane dye, a phthalocyanine pigment, an anthraquinone pigment, and a diketopyrrolopyrrole pigment.

The triarylmethane-based dye can be, for example, basic blue 7 (solvent red 41), solvent violet 31 (solvent violet 31), solvent blue 5 (solvent blue 5), or acid blue 90 ( Acid blue 90), solvent blue 128, etc., but it is not limited to this.

The phthalocyanine pigment can be, for example, C.I. pigment B15: 6, C.I. pigment B16, C.I. pigment B15: 3, C.I. pigment B15: 4, and the like, but is not limited thereto.

The anthraquinone pigment can be, for example, C.I. pigment R177, C.I. pigment R207, C.I. pigment R172, C.I. pigment R111, C.I. pigment R119, C.I. pigment R168, C.I. pigment R172, and the like, but is not limited thereto.

The diketopyrrolopyrrole-based pigment may be, for example, C.I. pigment R254, C.I. pigment R255, C.I. pigment R264, C.I. pigment R272, and the like, but is not limited thereto.

When the coloring agent according to the present invention further contains one or more selected from the group consisting of a triarylmethane dye, a phthalocyanine pigment, an anthraquinone pigment, and a diketopyrrolopyrrole pigment, it is capable of imparting high reliability and Advantages of high brightness characteristics.

The coloring agent according to the present invention can further contain a pigment known in the art. For example, colored pigments classified as pigments in the Color Index (published by The Society of Dyers and Colourists) can be cited.

Examples of the color pigment include CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255 , 264, 265, 269 and other red pigments; CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 16, 60 and other blue pigments; CI Pigment Violet 1, 19, 23, 29, 32, 36, 38 and other purple pigments; CI pigment orange 13, 31, 38, 41, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments; CI pigment green 7, 19, 21, 26, 36, 58, 59 and other green pigments. Examples of the coloring pigment include blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, and 60; purple pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, and 38; CI Pigment Green 7, 36, 58, 59 and other green pigments, more preferably CI Pigment Blue 15: 3, 15: 6, CI Pigment Violet 23 and CI Pigment Green 7,58, and more preferably CI Pigment Blue 15: 6 and CI Pigment green 7. By further including a coloring pigment, optimization of a transmission spectrum becomes easy, and light resistance and chemical resistance of a color filter become good.

Regarding the above-mentioned coloring pigment, if necessary, rosin treatment, surface treatment using a pigment derivative introduced with an acidic group or a basic group, etc., grafting treatment on the surface of the pigment with a polymer compound, and sulfuric acid may be performed. A micronization process such as a micronization method, a cleaning process using an organic solvent, water or the like for removing impurities, a ionic impurity removal process using an ion exchange method, or the like.

In another embodiment of the present invention, the colorant containing the xanthene-based dye represented by the above Chemical Formula 1 may contain 0.1 to 30 parts by weight based on 100 parts by weight of the entire colored photosensitive resin composition. It is preferably 1 to 15 parts by weight.

When the content of the colorant is less than the above range, the tinting power may be slightly reduced. When the content exceeds the above range, the solvent resistance or the adhesion force may be reduced, which may be disadvantageous in terms of process. Therefore, the preferred content is Within the above range.

    [Compound represented by Chemical Formula 2]    

The coloring photosensitive resin composition according to the present invention includes a coloring agent containing a dye and a compound represented by the following Chemical Formula 2.

[Chemical Formula 2] (X ⁺ ) _n (Y) ^{m-In the} above Chemical Formula 2, (X ⁺ ) is represented by any one of the following Chemical Formulas 3 to 5, n is 1 to 10, and m is the same as n, ( Y) ^m- is an anion having at least one element and an oxygen atom selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus.

On the other hand, when the anion is an anion of a heteropolyacid or an isopolyacid containing tungsten as an essential element, an anion including phosphotungstic acid, silicotungstic acid, and a tungsten homopolyacid may be used. For example, it may be a Keggin-type phosphorous tungsten. Acid ion α- [PW ₁₂ O ₄₀ ] ^3- , Dawson type phosphotungstic acid ion α- [P ₂ W ₁₈ O ₆₂ ] ^6- , β- [P ₂ W ₁₈ O ₆₂ ] ^6- , Keggin type silicotungstic acid Ions α- [SiW ₁₂ O ₄₀ ] ^4- , β- [SiW ₁₂ O ₄₀ ] ^4- , γ- [SiW ₁₂ O ₄₀ ] ^4- , [P ₂ W ₁₇ O ₆₁ ] ^10- , [P ₂ W ₁₅ O ₅₆ ] ^12- , [H ₂ P ₂ W ₁₂ O ₄₈ ] ^12- , [NaP ₅ W ₃₀ O ₁₁₀ ] ^14- , α- [SiW ₉ O ₃₄ ] ^10- , γ- [SiW ₁₀ O ₃₆ ] ^{8 -} , Α- [SiW ₁₁ O ₃₉ ] ^8- , β- [SiW ₁₁ O ₃₉ ] ^8- , [W ₆ O ₁₉ ] ^2- and mixtures thereof.

In the above Chemical Formula 3, Z is carbon, nitrogen, sulfur, phosphorus, or iodine, and R ₈ , R ₉ , R _10, and R ₁₁ are each independently a hydrogen, a halogen atom, or a monovalent or divalent substitution of 1 to 30 carbon atoms. Or an unsubstituted hydrocarbon group, or the -CH ₂ -carbon constituting the above hydrocarbon group is converted into an oxygen atom, a sulfur atom, an amine group or a carbonyl group, or a hydrogen atom contained in the above hydrocarbon group is converted into a halogen atom, a cyano group, a nitrate Group, carbonyl group, sulfonic group, -SO ₃ M, -CO ₂ M, hydroxy, methyl or amine group, or reactive group containing epoxy, acrylate; may be selected from the group consisting of alkyl, halogen , CN, OR ₂₃ , SR ₂₄ , carbonyl, sulfonic and NR ₂₅ R ₂₆ substituted with one or more substituents of phenyl or aromatic hydrocarbon, R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ are each independently Is hydrogen, a halogen atom, or a monovalent or divalent hydrocarbon group having 1 to 30 carbon atoms, or the -CH ₂ -carbon constituting the above hydrocarbon group is converted into an oxygen atom, a sulfur atom, an amine group, or a carbonyl group, or the above hydrocarbon group hydrogen atoms contained is converted into a halogen atom, a cyano group, a nitro group, a carbonyl group, a sulfonic acid _{group, -SO 3 M, -CO 2 M} , hydroxy, methyl or acyl group, or a package Epoxy, acrylate reactive group; or an alkenyl group having a carbon number of 1 to 30, selected may contain a halogen atom, a cyano group, a nitro group, a carbonyl group, a sulfonic acid group-containing, -SO ₃ M, -CO ₂ M Or a phenyl or aromatic hydrocarbon group having one or more substituents in the group of hydroxy, methyl, methyl, or amine groups, or nitrogen-containing heterocycles in which R ₈ and R _{11 are} combined to form a 5- to 7-membered ring, or may be independent of each other Ground is cycloalkyl, M is an alkali metal atom, and n is 0-5.

The specific compound of the said Chemical Formula 3 can be represented as follows.

In the above Chemical Formula 4, L is carbon or nitrogen, and R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R _16, and R ₁₇ are each independently hydrogen, a halogen atom, or a monovalent or divalent bedding having 1 to 30 carbon atoms. A substituted or unsubstituted hydrocarbon group, or the -CH ₂ ^- carbon constituting the hydrocarbon group is converted into an oxygen atom, a sulfur atom, an amine group, or a carbonyl group, or a hydrogen atom contained in the hydrocarbon group is converted into a halogen atom, a cyano group, Nitro, carbonyl, sulfonic, -SO ₃ M, -CO ₂ M, hydroxyl, methyl or amine, or reactive groups containing epoxy or acrylate; can be selected from the group consisting of alkyl, Phenyl or aromatic hydrocarbon substituted with one or more substituents of the group of halogen, CN, OR ₂₃ , SR ₂₄ , carbonyl, sulfonic group and NR ₂₅ R ₂₆ , each of R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ Independently a hydrogen, a halogen atom, or a monovalent or divalent hydrocarbon group having 1 to 30 carbon atoms, or the -CH ₂ -carbon constituting the above hydrocarbon group is converted into an oxygen atom, a sulfur atom, an amine group, or a carbonyl group, or the above hydrocarbon group hydrogen atoms contained is converted into a halogen atom, a cyano group, a nitro group, a carbonyl group, a sulfonic acid _{group, -SO 3 M, -CO 2 M} , hydroxy, methyl or acyl group, or Epoxy, acrylate reactive group; or an alkenyl group having a carbon number of 1 to 30, and may comprise a halogen atom selected comprising, a cyano group, a nitro group, a carbonyl group, a sulfonic acid group, -SO ₃ M, -CO ₂ A phenyl group or an aromatic hydrocarbon group having one or more substituents in the group of M, a hydroxyl group, a methyl group, or an amine group, or a nitrogen-containing heterocyclic ring in which R ₁₃ and R _{14 are} combined to form a 5- to 7-membered ring, or It is independently a cycloalkyl group, M is an alkali metal atom, and n is 0 to 5.

The specific compound of the said Chemical Formula 4 can be represented as follows.

In the above Chemical Formula 5, L is carbon, nitrogen, or sulfur, and R ₁₈ , R ₁₉ , R ₂₀ , R _21, and R ₂₂ are each independently a hydrogen, a halogen atom, or a monovalent or divalent substitution of 1 to 30 carbon atoms. Or an unsubstituted hydrocarbon group, or the -CH ₂ ^- carbon constituting the above hydrocarbon group is converted into an oxygen atom, a sulfur atom, an amine group or a carbonyl group, or a hydrogen atom contained in the above hydrocarbon group is converted into a halogen atom, a cyano group, a nitrate Group, carbonyl group, sulfonic group, -SO ₃ M, -CO ₂ M, hydroxy, methyl or amine group, or reactive group containing epoxy, acrylate; can be selected from the group consisting of alkyl, halogen , CN, OR ₂₃ , SR ₂₄ , carbonyl, sulfonic and NR ₂₅ R ₂₆ substituted with one or more substituents of phenyl or aromatic hydrocarbon, R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ are each independently Is hydrogen, a halogen atom, or a monovalent or divalent hydrocarbon group having 1 to 30 carbon atoms, or the -CH ₂ ^- carbon constituting the above hydrocarbon group is converted into an oxygen atom, a sulfur atom, an amine group, or a carbonyl group, or the above hydrocarbon group hydrogen atoms contained is converted into a halogen atom, a cyano group, a nitro group, a carbonyl group, a sulfonic acid _{group, -SO 3 M, -CO 2 M} , hydroxy, methyl or acyl group, or Epoxy, acrylate reactive group; or an alkenyl group having a carbon number of 1 to 30, and may comprise a halogen atom selected comprising, a cyano group, a nitro group, a carbonyl group, a sulfonic acid group, -SO ₃ M, -CO ₂ A phenyl group or an aromatic hydrocarbon group having one or more substituents in the group of M, a hydroxyl group, a methyl group, or an amine group, or a nitrogen-containing heterocyclic ring in which R ₂₁ and R _{22 are} combined to form a 5- to 7-membered ring, or may be each It is independently a cycloalkyl group, M is an alkali metal atom, and n is 0 to 5.

The specific compound of the above Chemical Formula 5 can be represented as shown below.

Without wishing to be bound by theory, the compound having the structure of the above Chemical Formula 2 has almost no absorption in the visible light region (380 to 780 nm), and therefore displays white, and thus does not appear to be applied to a color filter and an image display device including the same. The brightness is reduced due to the influence of the transmission spectrum, and high reliability and high contrast characteristics can be displayed.

In another embodiment of the present invention, the compound represented by the above Chemical Formula 2 may contain 0.01 to 50 parts by weight, preferably 0.1 to 40 parts by weight, and more preferably 0.1 to 100 parts by weight of the entire colored photosensitive resin composition. 30 parts by weight.

When the compound represented by the above Chemical Formula 2 is contained within the above range, there is an advantage that the brightness is not reduced by the influence of the spectrum, and reliability and high contrast characteristics can be provided. In particular, when used together with a xanthene-based dye represented by the aforementioned Chemical Formula 1 having absorption or fluorescence in a visible light region of 380 to 780 nm, it has the reliability and contrast of the colored photosensitive resin composition according to the present invention. Excellent advantages.

In another embodiment of the present invention, the weight ratio of the xanthene dye represented by the above-mentioned chemical formula 1 and the compound represented by the above-mentioned chemical formula 2 can satisfy the following mathematical formula 1.

[Mathematical formula 1] 0.4 ≦ weight of the compound represented by the aforementioned chemical formula 2 / weight of xanthene-based dye represented by the aforementioned chemical formula 1 ≦ 20

When the weight ratio of the xanthene dye represented by the above-mentioned chemical formula 1 and the compound represented by the above-mentioned chemical formula 2 satisfies the above-mentioned mathematical formula 1, there is an advantage that it is excellent in high CR (contrast), high reliability, and processability. In the case where the weight ratio is less than the above-mentioned mathematical formula, it may be slightly difficult to satisfy a high CR, and in the case where the above-mentioned range is exceeded, the processability may be slightly disadvantageous, so it is preferable to satisfy the above-mentioned range.

In another embodiment of the present invention, the colored photosensitive resin composition further includes one or more selected from a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent.

[Binder resin]

The above-mentioned binder resin generally has reactivity and alkali solubility under the action of light and heat, and functions as a dispersion medium of a coloring material.

Examples of the binder resin include copolymers of a carboxyl group-containing monomer and other monomers copolymerizable with the monomer. Examples of the carboxyl group-containing monomer include unsaturated carboxylic acids such as unsaturated polycarboxylic acids having one or more carboxyl groups in molecules such as unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated tricarboxylic acids.

Among them, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and the like. The unsaturated polycarboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like.

In addition, the unsaturated polycarboxylic acid may be a mono (2-methacryloxyalkyl) ester thereof, and examples thereof include a mono (2-propenyloxyethyl) succinate and a mono (2-methacryloxyethyl) succinate. Methacryloxyethyl), mono (2-propenyloxyethyl) phthalate, mono (2-methacryloxyethyl) phthalate, and the like. The unsaturated polycarboxylic acid may be a mono (meth) acrylate of a dicarboxyl polymer at both ends thereof, and examples thereof include ω-carboxy polycaprolactone monoacrylate and ω-carboxy polycaprolactone monomethacrylate Wait. Each of these carboxyl group-containing monomers can be used alone or as a mixture of two or more. Examples of other monomers copolymerizable with the carboxyl group-containing monomer include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, and p-chlorine. Styrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-ethylene Aromatic vinyl compounds such as benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, indene, etc; Ester, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, methacrylic acid N-butyl, isobutyl acrylate, isobutyl methacrylate, second butyl acrylate, second butyl methacrylate, third butyl acrylate, third butyl methacrylate, 2-hydroxyethyl acrylate , 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, formazan 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, methacrylic acid 3 -Hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, methyl Cyclohexyl acrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-benzene methacrylate Ethoxyethyl ester, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxypropylene glycol acrylic acid Ester, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadiene acrylate, methyl Dicyclopentadiene acrylate, (meth) acrylic acid Amantadine, norbornyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, glycerol monomethyl Unsaturated carboxylic acid esters such as acrylate; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate Ester, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate Esters, unsaturated amino carboxylic acid alkyl esters such as 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, 3-dimethylaminopropyl methacrylate; glycidyl acrylate Esters, glycidyl methacrylate and other unsaturated carboxylic acid glycidyl esters; vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate and other carboxylic acid vinyl esters; vinyl methyl ether, ethylene Unsaturated ethers such as ethyl ethyl ether, allyl glycidyl ether; ethylene such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, vinylidene vinyl Cyanide compounds; unsaturated amidamines such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide, N-2-hydroxyethylmethacrylamide; Unsaturated pyrimides such as maleimide, benzylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, etc .; 1,3-butadiene, iso Aliphatic conjugated dienes such as pentadiene and chloroprene; and polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, poly Macromolecules of a polymer chain of a siloxane having a monoacrylfluorene group or a monomethacrylfluorene group, and the like. These monomers can be used individually or in mixture of 2 or more types. In particular, as other monomers that can be copolymerized with the carboxyl group-containing monomer, monomers having a norbornyl skeleton, monomers having an adamantane skeleton, and monomers having a rosin skeleton have a relatively low relative volume. Dielectric constant values tend to be preferred.

As the binder resin of the present invention, the acid value is preferably in the range of 20 to 200 (KOHmg / g). If the acid value is within the above range, the solubility in the developing solution is improved, the non-exposed portion is easily dissolved, and the sensitivity is increased. As a result, the pattern of the exposed portion remains during development, and the film remaining ratio is improved, which is preferable. Here, the acid value is a value measured by the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer, and can usually be determined by titration with an aqueous potassium hydroxide solution.

In addition, a polystyrene-equivalent weight average molecular weight (hereinafter referred to as "weight average molecular weight") measured by gel permeation chromatography (GPC; using tetrahydrofuran as a dissolution solvent) is preferably 3000 to 200000, and preferably 5000 to 100,000.剂 材料。 Resin. When the molecular weight is within the above range, the hardness of the coating film is increased, the residual film ratio is high, the solubility of the non-exposed portion in the developing solution is excellent, and the resolution tends to be improved, which is preferable.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the binder resin is preferably 1.5 to 6.0, and more preferably 1.8 to 4.0. When the molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] is within the above range, the developability is excellent.

The content of the binder resin of the present invention is preferably from 1 to 60 parts by weight based on 100 parts by weight of the entire solid content in the colored photosensitive resin composition. As for the content of the binder resin, if it is contained within the above range, the solubility in the developing solution is sufficient. Therefore, it is difficult to generate development residues on the substrate in the non-graphic portion, and it is difficult to generate the graphic elements of the exposed portion during development. Part of the film is reduced, and therefore the non-graphical part tends to have good peeling properties.

[Photopolymerizable compound]

The photopolymerizable compound is a compound capable of polymerizing under the action of light and a photopolymerization initiator described later, and examples thereof include monofunctional monomers, difunctional monomers, and other polyfunctional monomers.

Specific examples of the monofunctional monomer include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, and 2-hydroxy acrylate Ethyl ester, N-vinylpyrrolidone and the like.

Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Triethylene glycol di (meth) acrylate, bis (propylene ethoxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like.

Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol penta (methyl) ) Acrylate, dipentaerythritol hexa (meth) acrylate and the like. Among these, it is preferable to use a bifunctional or more polyfunctional monomer.

The photopolymerizable compound is preferably contained in an amount of 5 to 50 parts by weight, and more preferably 7 to 45 parts by weight based on 100 parts by weight of the entire solid content in the colored photosensitive resin composition. When content of a photopolymerizable compound is contained in the said range, the intensity | strength and smoothness of a graphic element part will become favorable.

[Photopolymerization initiator]

The photopolymerization initiator is not limited, and is one or more compounds selected from the group consisting of triazine-based compounds, acetophenone-based compounds, biimidazole-based compounds, and oxime compounds. The photosensitive resin composition containing the above-mentioned photopolymerization initiator has high sensitivity, and the graphic elements formed using the composition have high strength and patternability of the graphic element portions.

In addition, when a photopolymerization initiator is used in combination with a photopolymerization initiator, the photosensitive resin composition containing them is further highly sensitive, and the productivity when forming a color filter using this composition is improved.

Examples of the triazine-based compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (tri (Chloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperyl-1,3,5-tri Azine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) vinyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl ) Vinyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) vinyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) vinyl] -1,3,5-tri Hydrazine, etc.

Examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, benzophenone dimethyl ketal, and 2-hydroxy -1- [4- (2-hydroxyethoxy) phenyl] -2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthio (Phenyl) -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1-one, 2-hydroxy- An oligomer of 2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1-one and the like.

Examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetrakis (alkoxy) Phenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (trialkoxyphenyl) biimidazole, 4,4', 5, An imidazole compound in which the phenyl group at the 5 'position is substituted with an alkoxycarbonyl group and the like. Among these, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorobenzene) are preferably used. Group) -4,4 ', 5,5'-tetraphenylbiimidazole.

In addition, as long as the effect of the present invention is not impaired, other photopolymerization initiators and the like commonly used in this field can be further included. Examples of other photopolymerization initiators include benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and anthracene-based compounds. These can be used individually or in combination of 2 or more types.

Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. Examples of the benzophenone-based compound include benzophenone, 0-benzylmethylbenzoate, 4-phenylbenzophenone, and 4-benzophenyl-4'-methyldione. Phenyl sulfide, 3,3 ', 4,4'-tetrakis (third-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, 4,4'- Bis (N, N'-dimethylamino) -benzophenone and the like. Examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxy Thioxanthone and so on. Examples of the anthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9 , 10-diethoxyanthracene and the like. In addition, 2,4,6-trimethylbenzylidene diphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzoin, 9,10 -Phenanthrenequinone, camphorquinone, phenylglyoxylate, titanocene compound, etc. as other photopolymerization initiators.

In addition, as the photopolymerization initiation adjuvant that can be used in combination with a photopolymerization initiator in the present invention, one or more compounds selected from the group consisting of an amine compound and a carboxylic acid compound can be preferably used.

Specific examples of the amine compound in the photopolymerization initiation aid include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, and 4- Dimethylaminobenzoate, 4-dimethylaminobenzoate isoamyl, 2-dimethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate , N, N-dimethyl-p-toluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as melidone), 4,4'-bis (diethylamino) Aromatic amine compounds such as benzophenone. As the amine compound, an aromatic amine compound is preferably used.

Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, and methoxyphenylthio Acetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycolic acid And aromatic heteroacetic acids such as naphthyloxyacetic acid.

In the colored photosensitive resin composition of the present invention, the content of the photopolymerization initiator in the colored photosensitive resin composition is preferably 0.1 to 20 parts by weight based on 100 parts by weight of the entire solid content, and more preferably Contains 1 to 10 parts by weight. The usage-amount of the said photoinitiator raises the sensitivity of the photosensitive resin composition when it is contained in the said range, and the intensity | strength of a graphic element part and the smoothness of the surface of a graphic element part are excellent.

In addition, the used amount of the photopolymerization initiating adjuvant is preferably from 0.1 to 20 parts by weight, and more preferably from 1 to 10 parts by weight, based on 100 parts by weight of the entire solid content in the photosensitive resin composition. When the usage-amount of the said photoinitiation adjuvant is contained in the said range, the sensitivity efficiency of the photosensitive resin composition will improve further, and the productivity of the color filter formed using this composition can be improved.

[Solvent]

The solvent is not particularly limited, and various organic solvents used in the field of coloring photosensitive resin compositions can be used.

Specific examples include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether. Diethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, methyl cellosolve acetate, ethyl Ethyl glycol ether ether acetates such as cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate Alkylene glycol alkyl ether acetates such as esters and methoxypentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, methyl ethyl ketone, acetone, methyl amyl ketone, methyl Ketones such as methyl isobutyl ketone, cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerol, ethyl 3-ethoxypropionate, 3-methyl Esters such as methyl oxypropionate, and cyclic esters such as γ-butyrolactone.

In terms of the above-mentioned solvents, from the aspects of coating properties and drying properties, preferably, organic solvents having a boiling point of 100 to 200 ° C. in the above-mentioned solvents may be mentioned, and more preferably, alkylene glycol alkyl groups may be mentioned. Ether acetates, ketones, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate and the like, more preferably, propylene glycol monomethyl ether acetate, propylene glycol monoester Ethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like. These solvents can be used individually or in mixture of 2 or more types.

The content of the solvent in the colored photosensitive resin composition of the present invention is preferably 60 to 90 parts by weight, and more preferably 70 to 85 parts by weight based on 100 parts by weight of the entire colored photosensitive resin composition. As for the content of the solvent, if it is contained within the above range, use a roll coater, spin coater, slit and spin coater, slit coater (also sometimes referred to as a die coater), inkjet, etc. When the coating device is applied, the applicability can be improved.

Additives

In order to promote coatability or adhesion, the coloring photosensitive resin composition according to the present invention may further contain additives such as an antioxidant, an adhesion promoter, and a surfactant.

As the antioxidant, one selected from benzotriazole-based light stabilizers, triazine-based light stabilizers, benzophenone-based, Hals light stabilizers, and combinations thereof can be used, but is not limited thereto.

In order to improve the adhesion to the substrate, the above-mentioned adhesion promoter may be added, and it may contain a silane coupling having a reactive substituent selected from a carboxyl group, a methacryl group, an isocyanate group, an epoxy group, and a combination thereof. Agent, but not limited to this. Examples of the silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. These can be used alone as well as Two or more kinds are used in combination.

When the coloring photosensitive resin composition which concerns on this invention contains the said surfactant, there exists an advantage that coating property can be improved. For example, as the surfactant, BM-1000, BM-1100 (BM Chemie), FC-135 / FC-170C / FC-430 (Sumitomo 3M Co., Ltd.), SH-28PA / -190 / SZ-6032 (Toray Silicone Co., Ltd.) and other fluorine-based surfactants, but not limited to them this.

In addition, the colored photosensitive resin composition according to the present invention may further include additives such as an ultraviolet absorber and an anti-agglomerating agent within a range not hindering the effects of the present invention, and the above-mentioned additives are also within a range not inhibiting the effects of the present invention. Those skilled in the art can appropriately add and use them. For example, as for the additive, based on 100 parts by weight of the entire colored photosensitive resin composition, 0.05 to 10 parts by weight, specifically 0.1 to 10 parts by weight, and more specifically 0.1 to 5 parts by weight can be used. But it is not limited to this.

<Color filter>

The present invention provides a color filter including a coloring pattern produced using the colored photosensitive resin composition. That is, this invention includes the color filter manufactured using the said coloring photosensitive resin composition. The color filter according to the present invention includes the xanthene dye represented by the above Chemical Formula 1 and the compound represented by the structure of the Chemical Formula 2 at the same time, and thus has the advantages of no decrease in brightness and excellent reliability and contrast.

The color filter of the present invention includes a substrate and a coloring pattern produced using the coloring photosensitive resin composition of the present invention on the substrate. The substrate is made of a transparent material. For the stability of the color filter, a material having sufficient strength and supporting force can be used. Preferably, glass having excellent chemical stability and high strength can be used. A partition wall may be further formed between each colored pattern, and a black matrix may be added.

As the method for manufacturing the color filter, a general method known in the art can be used.

<Image display device>

The present invention also provides an image display device including the color filter. Specific examples of the image display device include a liquid crystal display (liquid crystal display device; LCD), an organic EL display (organic EL display device), a liquid crystal projector, a display device for a game machine, and a display for a mobile terminal. Devices, display devices such as digital camera displays, display devices for car navigation, and the like are not limited thereto.

The image display device of the present invention may be manufactured by a method generally known in the technical field of the present invention, in addition to the color filter.

In order to explain the present specification in detail, examples will be described in detail below. However, the embodiments described in this specification can be modified into various other forms, and the scope of this specification should not be construed as being limited to the embodiments described in detail below. The embodiments of the present specification are provided to more completely explain the specification to those skilled in the art. In addition, "%" and "part" which show content below are a weight basis unless there is particular notice.

Synthesis Example 1

30 g of methanol was added to 2 g of dodecylpyridinium chloride, and 6 g of phosphotungstic acid hydrate (Aldrich, P4006) was slowly added dropwise to the completely dissolved solution. A solution in 25 g of water. After the dropwise stirring, the mixture was stirred at 25 to 50 ° C for 4 hours, and the precipitate was filtered and washed with water. After filtration, it was dried in a vacuum oven at 50 ° C. for 12 hours to obtain 8.5 g of the following chemical formula A-1 (see Eur. J. Inorg. Chem. 2014, 21-35).

Synthesis Example 2: Synthesis of Binder Resin (B)

Into a flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen introduction tube, 100 g of propylene glycol monomethyl ether acetate and 100 g of propylene glycol monomethyl ether were charged, and the atmosphere in the flask was changed from air to nitrogen. 8.2 g of azobisisobutyronitrile, 3.1 g of monomethacrylate (FA-513M, manufactured by Hitachi Chemical Co., Ltd.), 55.2 g of 2-ethylhexyl acrylate, and 4-methyl 5.9 g of styrene, 85.2 g of glycidyl methacrylate, and 6.0 g of n-dodecanethiol. Then, the temperature of the reaction solution was raised to 80 ° C. with stirring, and the reaction was performed for 4 hours.

The temperature of the reaction solution was lowered to normal temperature, and the atmosphere of the flask was replaced with nitrogen from air. Then, 2 g of triethylamine, 0.1 g of 4-methoxyphenol, 43.2 g of acrylic acid, and propylene glycol monomethyl were dropped from the dropping funnel over 2 hours. After 136 g of diethyl ether acetate was added together, the reaction was performed at 100 ° C. for 6 hours. Thereafter, the temperature of the reaction solution was lowered to normal temperature, 6.0 g of succinic anhydride was added, and the reaction was performed at 80 ° C. for 6 hours.

The solid content acid value of the alkali-soluble resin thus synthesized was 36.2 mgKOH / g, the weight-average molecular weight Mw measured by GPC was about 7,540, and the Tg was -12 ° C.

The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the alkali-soluble resin were measured by the GPC method under the following conditions, and the ratio of the weight-average molecular weight and the number-average molecular weight obtained at this time was used as the molecular weight distribution ( Mw / Mn).

Device: HLC-8120GPC (manufactured by Tosoh Corporation)

Column: TSK-GELG4000HXL + TSK-GELG2000HXL (connected in series)

Column temperature: 40 ° C

Moving bed solvent: tetrahydrofuran

Flow rate: 1.0ml / min

Injection volume: 50μl

Detector: RI

Measurement sample concentration: 0.6% by weight (solvent = tetrahydrofuran)

Calibration Standards: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)

Production of colored photosensitive resin composition: Examples 1, 2 and Comparative Examples 1 to 5

The colored photosensitive resin compositions according to the examples and comparative examples were produced as the composition in Table 1 below. At this time, the solvent was contained in the balance so that the entire colored photosensitive resin composition became 100 parts by weight.

Color filter (glass substrate) manufacturing example

A color filter was manufactured using the colored photosensitive resin composition manufactured by the Example and the comparative example. That is, each of the colored photosensitive resin compositions described above was coated on a glass substrate by a spin coating method, and then placed on a hot plate and maintained at a temperature of 100 ° C. for 3 minutes to form a thin film. Next, a test photomask having a pattern with a step change in transmittance in the range of 1 to 100% and a line / gap pattern of 1 μm to 50 μm was placed on the film, and the distance from the test photomask was 100 μm. Exposure to ultraviolet rays. At this time, as the ultraviolet light source, a 1 KW high-pressure mercury lamp including all g, h, and i rays was used, and the light was irradiated at an illumination intensity of 100 mJ / cm ² without using a special optical filter. The film irradiated with the ultraviolet ray was immersed in a KOH aqueous solution developing solution at pH 10.5 for 2 minutes to develop. After washing the thin-film-coated glass plate with distilled water, nitrogen was blown, dried, and heated in a heating oven at 220 ° C. for 1 hour to produce a color filter. The film thickness of the color filter manufactured as described above was 2.0 μm.

    [Experimental example]    

(1) Thickening ratio of colored photosensitive resin composition

The initial viscosity (kinematic viscosity) A (mPa · s) of each of the colored photosensitive resin compositions immediately after production in the examples and comparative examples was measured.

Then, each colored photosensitive resin composition according to the examples and comparative examples was left to stand for one day immediately after production in an environment of 25 ° C., and the viscosity (kinematic viscosity) of each colored photosensitive resin composition after standing was measured. ) B (mPa‧s). The viscosity (kinematic viscosity) of the colored photosensitive resin composition is measured in accordance with JIS Z8809 using an E-type viscometer (trade name: RE-01, Industrial Co., Ltd.) was performed in an environment of 25 ° C. The thickening ratio is calculated according to the following formula.

Thickening rate = (viscosity B after placing) / (initial viscosity A).

The results are shown in Table 2 below. The initial viscosity of Examples 1 to 2 is expressed as a relative value when the initial viscosity of the colored photosensitive resin composition of Comparative Example 1 is used as a standard (100).

(2) Measurement of brightness (Y)

The brightness (Y) of the colored glass plates according to the examples and comparative examples was measured as described below. Set the colored glass plate in a spectrophotometer (trade name: CM-3700d, Co., Ltd.), and measured the transmission chromaticity at the X, Y, and Z coordinate axes at 2 degrees (°) from the C light source. The Y value at this time is used as the brightness (Y). The results are shown in Table 2 below.

The brightness values of Examples 1 to 2 in the following Table 2 are shown as relative values when the brightness of a colored glass plate obtained by using the colored photosensitive resin composition of Comparative Example 1 as a standard (100), and the results are shown in FIG. In Table 2.

(3) Measurement of contrast

The contrast of the colored glass plate (color filter) after post-baking which concerns on an Example and a comparative example was measured using the contrast measuring apparatus. The contrast measuring device is a color brightness meter (trade name: LS-100, Co., Ltd.), lamps (trade name: HF-SL-100WLCG, Industry Co., Ltd.) and polarizers (trade name: POLAX-38S, Co., Ltd.) Products) composition.

A polarizing plate was provided on the backlight so that the distance between the polarizing plate (POLAX-38S) and the colored glass plate became 1 mm.

A rotatable polarizer is provided on the upper part. After confirming that the brightness of the backlight was sufficiently stable, the rotatable polarizer provided on the upper part was adjusted to the position of the crossed Nicols, and the brightness of the stained glass plate was measured. Then, it was rotated by 90 degrees and measured at a parallel position. The brightness of the stained glass plate. Find the ratio (%) of the two as the contrast.

The results are shown in Table 2 below, and the contrast values of Examples 1 to 2 are relative values when the contrast of a colored glass plate obtained using the colored photosensitive resin composition of Comparative Example 1 is used as a standard (100). The results are shown in Table 2.

(4) Measurement of heat resistance

The heat resistance was evaluated by measuring a color change value (ΔE ^* _ab ) after heating at 230 ° C for 120 minutes. ΔE ^* _ab is a value obtained by using the following chroma formula based on the CIE 1976 (L ^* , a ^* , b ^* ) spatial color system. The results are shown in Table 2. (New Color Handbook of Japan Color Society (Showa 60), p.266).

△ E ^* _ab = ((△ L ^* ) ² + (△ a ^* ) ² + (△ b ^* ) ² } ^1/2

[Heat resistance evaluation standard]

○: △ E ^* _ab value: 3 or less

△: △ E ^* _ab value: 3 ~ 10

×: △ E ^* _ab value: more than 10

As shown in Table 2 above, it can be confirmed that the colored photosensitive resin compositions of Examples 1 to 2 in which the above-mentioned composition is mixed according to the present invention can provide a color filter having excellent brightness while having heat resistance and high contrast. In particular, in Comparative Examples 3, 4, and 5 that did not contain the xanthene dye according to the present invention, it was confirmed that the brightness was poor.

Claims (6)

A coloring photosensitive resin composition comprising: a colorant containing a xanthene-based dye represented by the following Chemical Formula 1; and a compound represented by the following Chemical Formula 2: In the above Chemical Formula 1, R ₁ to R ₄ are each independently a hydrogen atom, -R ₆ or an aromatic hydrocarbon group having 6 to 10 carbon atoms; or R ₁ and R ₂ and R ₃ and R ₄ can be combined with each other to form 6 members. ~ 10 member ring, the aromatic hydrocarbon group having 6 to 10 carbon atoms or the hydrogen atom contained in the 6 member to 10 member ring is halogen atom, -R ₆ , -OH, -OR ₆ , -SO ₃ ^- ,- _{SO 3 Na, -CO 2 H,} -CO 2 R 6, -SO 3 H, -SO 3 R 6 -SO ₂ NHR _7, or a substituted or unsubstituted, R ₅ is ^{_{-SO 3 -, -SO 3 Na,}} - CO ₂ H, -CO ₂ R ₆ , -SO ₃ H, or -SO ₂ NHR ₇ , R ₆ is a saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms is- OR ₆ or halogen atom substituted or unsubstituted, R ₇ is a hydrogen atom, -R ₆ , -CO ₂ R ₆ , an aromatic hydrocarbon group having 6 to 10 carbon atoms, and an aromatic hydrocarbon group having 6 to 10 carbon atoms -R ₆ is a hydrogen atom or a substituted or unsubstituted, -OR _6, A is selected from the group consisting of a halogen ^{_{anion, ClO 4 -, BF 4 -}} , SbF 6 -, CF 3 CO 2 -, CF 3 SO 3 -, N (SO 2 CF _{3) 2} ^- in the case of the group consisting of an ion, p is an integer of 1 to 5, however, p is an integer of 2 or more, a plurality of R ₅ identical to or different from each other, q is an integer of 0 or 1, However, the + charge number of the compounds of the above Chemical Formula 1 - charge number the same, [Chemical Formula _{^{2] (X +) n (}} Y) m- in the chemical formula 2, (X ⁺⁾ by Chemical Formula 3 below ~ In any one of Chemical Formula 5, n is 1 to 10, m is the same as n, and (Y) ^m- is an anion having at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus and an oxygen atom. , [Chemical Formula 3] In Chemical Formula 3, Z is carbon, nitrogen, sulfur, phosphorus, or iodine, and R ₈ , R ₉ , R _10, and R ₁₁ are each independently a hydrogen, a halogen atom, or a monovalent or divalent substitution of 1 to 30 carbon atoms. Or an unsubstituted hydrocarbon group, the carbon of -CH ₂ ^- constituting the hydrocarbon group may be converted with an oxygen atom, a sulfur atom, an amine group, or a carbonyl group, and a hydrogen atom contained in the hydrocarbon group may be a halogen atom, a cyano group, a nitro group, a carbonyl group, or a sulfonic acid group. Acid group, -SO ₃ M, -CO ₂ M, hydroxyl group, methyl group or amine group conversion, the hydrocarbon group may contain epoxy group, acrylate reactive group; R ₈ , R ₉ , R ₁₀ and R ₁₁ may A phenyl or aromatic hydrocarbon selected from the group consisting of one or more substituents selected from the group consisting of alkyl, halogen, CN, OR ₂₃ , SR ₂₄ , carbonyl, sulfonic group, and NR ₂₅ R ₂₆ , R ₂₃ , R ₂₄ , R _25, and R ₂₆ are hydrogen, a halogen atom, or a monovalent or divalent hydrocarbon group having 1 to 30 carbon atoms. The -CH ₂ ^- carbon constituting the hydrocarbon group may be an oxygen atom, a sulfur atom, an amine group, or The carbonyl group can be converted. The hydrogen atom contained in the hydrocarbon group can be converted with a halogen atom, a cyano group, a nitro group, a carbonyl group, a sulfonic group, -SO ₃ M, -CO ₂ M, a hydroxyl group, a methyl group, or an amino group. Contains ring Oxygen, acrylate reactive groups; or R ₈ , R ₉ , R ₁₀ and R ₁₁ are alkenyl groups having 1 to 30 carbon atoms, which may contain a group selected from halogen atoms, cyano, nitro, carbonyl, and sulfonic acid Group, -SO ₃ M, -CO ₂ M, hydroxy, formamyl, or amine group of one or more substituents of phenyl or aromatic hydrocarbon group, R ₈ and R ₁₁ may be combined to form 5 to 7 members A nitrogen-containing heterocyclic ring, or each independently a cycloalkyl group, M is an alkali metal atom, and n is 0 to 5, In Chemical Formula 4, L is carbon or nitrogen, and R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R _16, and R ₁₇ are each independently a hydrogen, a halogen atom, or a monovalent or divalent substitution of 1 to 30 carbon atoms. Or an unsubstituted hydrocarbon group, the carbon of -CH ₂ ^- constituting the hydrocarbon group may be converted with an oxygen atom, a sulfur atom, an amine group, or a carbonyl group, and a hydrogen atom contained in the hydrocarbon group may be a halogen atom, a cyano group, a nitro group, a carbonyl group, or a sulfonic acid group. Acid group, -SO ₃ M, -CO ₂ M, hydroxyl group, methyl group or amino group conversion, the hydrocarbon group may contain epoxy group, acrylate reactive group; R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ may be selected from phenyl or aromatic which may be substituted by one or more substituents selected from the group consisting of alkyl, halogen, CN, OR ₂₃ , SR ₂₄ , carbonyl, sulfonic group, and NR ₂₅ R ₂₆ Group hydrocarbons, R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ are each independently hydrogen, a halogen atom or a monovalent or divalent hydrocarbon group having 1 to 30 carbon atoms, and a carbon atom of -CH ₂ ^- constituting the hydrocarbon group may be an oxygen atom , Sulfur atom, amine group or carbonyl group, the hydrogen atom contained in the hydrocarbon group can be a halogen atom, a cyano group, a nitro group, a carbonyl group, a sulfonic group, -SO ₃ M, -CO ₂ M, a hydroxyl group, a methyl group, or Amino group In other words, the hydrocarbon group may contain an epoxy group or an acrylate reactive group; or R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ are alkenyl groups having 1 to 30 carbon atoms, and may include a group containing A phenyl or aromatic hydrocarbon group having one or more substituents in the group of a halogen atom, a cyano group, a nitro group, a carbonyl group, a sulfonic group, -SO ₃ M, -CO ₂ M, a hydroxyl group, a methyl group, or an amine group, R ₁₃ and R ₁₄ may be combined to form a 5- to 7-membered nitrogen-containing heterocyclic ring, or each independently is a cycloalkyl group, M is an alkali metal atom, and n is 0 to 5, In Chemical Formula 5, L is carbon, nitrogen, or sulfur, and R ₁₈ , R ₁₉ , R ₂₀ , R _21, and R ₂₂ are each independently hydrogen, a halogen atom, or a monovalent or divalent substitution of 1 to 30 carbon atoms or An unsubstituted hydrocarbon group, the carbon of -CH ₂ ^- constituting the hydrocarbon group may be converted with an oxygen atom, a sulfur atom, an amine group or a carbonyl group, and a hydrogen atom contained in the hydrocarbon group may be a halogen atom, a cyano group, a nitro group, a carbonyl group, or a sulfonic acid. Group, -SO ₃ M, -CO ₂ M, hydroxyl, methyl group or amine group, the hydrocarbon group may contain epoxy group, acrylate reactive group; R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ and R ₂₂ may be selected from phenyl or aromatic hydrocarbons which may be substituted by one or more substituents selected from the group consisting of alkyl, halogen, CN, OR ₂₃ , SR ₂₄ , carbonyl, sulfonic group, and NR ₂₅ R ₂₆ , R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ are hydrogen, a halogen atom, or a monovalent or divalent hydrocarbon group having 1 to 30 carbon atoms, and a CH ₂ ^- carbon constituting the hydrocarbon group may be an oxygen atom, a sulfur atom, an amine group, or The carbonyl group can be converted. The hydrogen atom contained in the hydrocarbon group can be converted with a halogen atom, a cyano group, a nitro group, a carbonyl group, a sulfonic group, -SO ₃ M, -CO ₂ M, a hydroxyl group, a methyl group, or an amino group. With Epoxy, acrylate reactive groups; or _{R 18, R 19, R 20} , R 21 and R ₂₂ is alkenyl having 1 to 30, may comprise a gas such as a halogen atom, a cyano group, a nitro group, A phenyl group or an aromatic hydrocarbon group having one or more substituents in the group of a carbonyl group, a sulfonic group, -SO ₃ M, -CO ₂ M, a hydroxyl group, a methyl group, or an amine group, and R ₂₁ and R ₂₂ may be combined to form A nitrogen-containing heterocyclic ring of 5 to 7 members, or each independently is a cycloalkyl group, M is an alkali metal atom, and n is 0 to 5, which contains 0.1 parts by weight based on 100 parts by weight of the entire colored photosensitive resin composition. ~ 30 parts by weight of the colorant, the weight ratio of the xanthene dye represented by the chemical formula 1 and the compound represented by the chemical formula 2 satisfies the following mathematical formula 1: [Mathematical formula 1] 0.4 ≦ represented by the chemical formula 2 The weight of the compound / the weight of the xanthene-based dye represented by Chemical Formula 1 is ≦ 20. The coloring photosensitive resin composition according to item 1 of the patent application scope, wherein the colorant further comprises a pigment selected from the group consisting of a triarylmethane dye, a phthalocyanine pigment, an anthraquinone pigment, and a diketopyrrolopyrrole pigment More than one of them. The colored photosensitive resin composition according to item 1 of the scope of patent application, further comprising one or more selected from the group consisting of a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. The colored photosensitive resin composition according to item 1 of the patent application scope, which contains 0.01 to 50 parts by weight of the compound represented by the chemical formula 2 with respect to 100 parts by weight of the entire colored photosensitive resin composition. A color filter comprising a cured product of the colored photosensitive resin composition according to any one of claims 1 to 4 of the scope of patent application. An image display device includes the color filter described in item 5 of the scope of patent application.