TW201825575A - Colored photosensitive resin composition, color filter and image display device produced using the same - Google Patents

Abstract

The present invention relates to a colored photosensitive resin composition, which is characterized by containing: a coloring agent including a dye, and a compound represented by formula 1.

Description

   Color photosensitive resin composition, color filter manufactured using the same, and image display device   

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

Color filters are widely used in image display devices such as image pickup devices and liquid crystal display devices, and their applications are 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 substrate containing a black matrix pattern with a coloring agent corresponding to each of red, green, and cyan by spin coating. After the color photosensitive resin composition is heated and dried (hereinafter sometimes referred to as pre-firing), the formed coating film is exposed, developed, and further heat-cured if necessary (hereinafter also referred to as post-firing). This operation is repeated for each color to form pixels of each color.

The color photosensitive resin composition is a photosensitive resin composition that is colored by containing a colorant, and is used as a material for forming a colored pattern constituting a color filter. Among them, a color filter is an optical element that is built in a color liquid crystal display device to colorize a display image or is built in an imaging element 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. In general, the color filter tends to have a higher brightness as the film thickness becomes thinner. 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 this, research into dye applications has been performed. However, compared with a case where a pigment is generally used, problems of low reliability and contrast often occur. Therefore, it is necessary to develop a technique for solving a problem when using a dye.

Korean Published Patent No. 2014-0115990 relates to a coloring composition, a coloring cured film, and a display element, and discloses content related to the coloring composition. The coloring composition contains (A) a compound selected from xanthene, multiple times, A coloring composition of at least one of a methyl compound, a coumarin compound, and a fluorene compound, (B) a binder resin, and (C) a coloring composition of a polymerizable compound, further including (D) a transition metal compound (however, (Excluding component (A)).

Korean Laid-Open Patent No. 2015-0101934 relates to a coloring composition, a coloring cured film, and a display element, and discloses content related to a coloring composition which is a coloring composition 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.

In addition, Japanese Laid-Open Patent No. 2013-028764 relates to a colored curable composition, a colored cured film, a color filter, a method for forming a pattern, a method for manufacturing a color filter, a solid-state imaging element, and an image display device, and discloses colored curing The content of the sexual composition which contains (A) a pigment polymer having a polymerizable group, (B) a pigment, (C) a polymerizable compound, and (D) a photopolymerization initiator.

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

    [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.)

(Patent Document 3) Japanese Laid-Open Patent No. 2013-028764 (2013.02.07.)

The present invention is intended to solve the above-mentioned problems, and an object thereof is to provide a color photosensitive resin composition, which includes a dye and a compound represented by a specific chemical formula, and is used in a color filter and the color filter. Image display device, it exhibits high reliability and high contrast characteristics.

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

[Chemical Formula 1] (x ⁺ ) _n (Y) ^m-

(In the above Chemical Formula 1, (X ⁺ ) is represented by any one of Chemical Formulas 2 to 4 below, n is 1 to 10, and (Y) ^m- is at least one selected from tungsten, molybdenum, silicon, and phosphorus 1 element and an anion of an oxygen atom).

(In the above Chemical Formula 2, Z is carbon, nitrogen, sulfur, phosphorus, or iodine, and R ₁ , R ₂ , R _3, and R ₄ are each independently hydrogen, a halogen atom, or a monovalent or divalent carbon number of 1 to 30. A substituted or unsubstituted hydrocarbon group, the carbon of -CH ₂ -constituting the above hydrocarbon group may be converted into an oxygen atom, a sulfur atom, an amino group, or a carbonyl group, and a hydrogen atom contained in the above hydrocarbon group may be converted into a halogen atom, a cyano group , Nitro, carbonyl, sulfonic, -SO ₃ M, -CO ₂ M, hydroxyl, formamyl, or amino, and may include epoxy, acrylate reactive groups; R ₁ , R ₂ , R ₃ and R ₄ may be selected from phenyl or aromatic hydrocarbons which may be substituted with one or more substituents selected from alkyl, halogen, CN, OR ₁₆ , SR ₁₇ , carbonyl, sulfonic group, and NR ₁₈ R ₁₉ , R ₁₆ , R ₁₇ , R _18, and R ₁₉ are each independently hydrogen, a halogen atom, or a monovalent or divalent hydrocarbon group having 1 to 30 carbon atoms, and the -CH ₂ -carbon constituting the above hydrocarbon group can be converted into an oxygen atom and sulfur atom, an amino group or a carbonyl group, a hydrogen atom in the hydrocarbon group contained may be 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, may contain epoxy, acrylate reactive group; or R _1, R _2, R ₃ and R ₄ is alkenyl having 1 to 30, comprising a comprising a halogen atom selected from, cyano, nitro, A phenyl or aromatic hydrocarbon group having one or more substituents of a carbonyl group, a sulfonic group, -SO ₃ M, -CO ₂ M, a hydroxyl group, a methyl group, or an amino group, and R ₁ and R ₄ may be combined to form 5 to 7 The membered ring nitrogen-containing heterocyclic ring or each independently is a cycloalkyl group, and n is 0 to 5).

(In the above Chemical Formula 3, L is carbon or nitrogen, and R ₅ , R ₆ , R ₇ , R ₈ , R _9, and R ₁₀ are each independently hydrogen, a halogen atom, or a monovalent or divalent carbon number of 1 to 30. A substituted or unsubstituted hydrocarbon group, the carbon of -CH ₂ -constituting the above hydrocarbon group may be converted into an oxygen atom, a sulfur atom, an amino group, or a carbonyl group, and a hydrogen atom contained in the above hydrocarbon group may be converted into a halogen atom, a cyano group , Nitro, carbonyl, sulfonic, -SO ₃ M, -CO ₂ M, hydroxyl, formamyl, or amino, and may include epoxy or acrylate reactive groups; R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ may be selected from a phenyl group which may be substituted with one or more substituents selected from alkyl, halogen, CN, OR ₁₆ , SR ₁₇ , carbonyl, sulfonic group, and NR ₁₈ R ₁₉ Aromatic hydrocarbons, R ₁₆ , R ₁₇ , R _18, and R ₁₉ are each independently hydrogen, a halogen atom, or a monovalent or divalent hydrocarbon group having 1 to 30 carbon atoms, and the -CH ₂ -carbon constituting the above hydrocarbon group may be Conversion to oxygen, sulfur, amino or carbonyl groups, and the hydrogen atoms contained in the above hydrocarbon groups can be converted to halogen atoms, cyano, nitro, carbonyl, sulfonic, -SO ₃ M, -CO ₂ M, hydroxyl , Acyl or amino group, may contain epoxy, acrylate reactive group; or _{R 5, R 6, R 7} , R 8, R 9 and R ₁₀ is alkenyl having 1 to 30, selected from the group comprising comprising A phenyl group or an aromatic hydrocarbon group having one or more substituents 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 amino group, R ₆ and R ₇ may be combined to form a 5- to 7-membered nitrogen-containing heterocyclic ring or each independently a cycloalkyl group, and n is 0 to 5).

(In the above Chemical Formula 4, L is carbon, nitrogen, or sulfur, and R ₁₁ , R ₁₂ , R ₁₃ , R _14, and R ₁₅ are each independently hydrogen, a halogen atom, or a monovalent or divalent chain having 1 to 30 carbon atoms. A substituted or unsubstituted hydrocarbon group, the carbon of -CH ₂ -constituting the above hydrocarbon group may be converted into an oxygen atom, a sulfur atom, an amino group, or a carbonyl group, and a hydrogen atom contained in the above hydrocarbon group may be converted into a halogen atom, a cyano group, Nitro, carbonyl, sulfonic, -SO ₃ M, -CO ₂ M, hydroxy, formamyl, or amino, which may contain epoxy or acrylate reactive groups; R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ and R ₁₅ may be selected from phenyl or aromatic hydrocarbons which may be substituted with one or more substituents selected from alkyl, halogen, CN, OR ₁₆ , SR ₁₇ , carbonyl, sulfonic group, and NR ₁₈ R ₁₉ , R ₁₆ , R ₁₇ , R _18, and R ₁₉ are each independently hydrogen, a halogen atom, or a monovalent or divalent hydrocarbon group having 1 to 30 carbon atoms, and the -CH ₂ -carbon constituting the above hydrocarbon group can be converted into an oxygen atom , a sulfur atom, a carbonyl group or an amino group, a hydrogen atom in the hydrocarbon group contained may be converted into a halogen atom, a cyano group, a nitro group, a carbonyl group, a sulfonic acid _{group, -SO 3 M, -CO 2 M} , a hydroxyl group, Acyl or amino group, may contain an epoxy group, the reaction acrylate groups; or _{R 11, R 12, R 13} , R 14 and R ₁₅ is alkenyl having 1 to 30, selected from the group comprising a halogen atom comprising, R ₁₄ and R ₁₅ may be a phenyl or aromatic hydrocarbon group having one or more substituents of cyano, nitro, carbonyl, sulfonic, -SO ₃ M, -CO ₂ M, hydroxy, formamyl, or amino. A nitrogen-containing heterocyclic ring which is bonded to form a 5- to 7-membered ring or each independently is a cycloalkyl group, and n is 0 to 5).

The present invention also provides a color filter including a cured product of the above-mentioned color photosensitive resin composition, and an image display device including the color filter.

The color photosensitive resin composition according to the present invention includes a dye and a compound represented by a specific chemical formula, and when applied to a color filter and an image display device including the same, the color photosensitive resin composition exhibits high reliability and high display without reducing brightness. Advantages of contrasting features.

In addition, a color filter manufactured using the above-mentioned color photosensitive resin composition and an image display device including the above-mentioned color filter have the advantage of being excellent in sensitivity.

The present invention is explained in more detail below.

In the present invention, when a component is “on” another component, it includes 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 portion “contains” a certain component, as long as there is no particularly contrary description, it means that other components can be included without excluding other components.

<Color photosensitive resin composition>

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

[Chemical Formula 1] (x ⁺ ) _n (Y) ^m-

(In the above Chemical Formula 1, (X ⁺ ) is represented by any one of Chemical Formulas 2 to 4 below, n is 1 to 10, and (Y) ^m- is at least one selected from tungsten, molybdenum, silicon, and phosphorus 1 element and an anion of an oxygen atom).

[Chemical Formula 2]

(In the above Chemical Formula 2, Z is carbon, nitrogen, sulfur, phosphorus, or iodine, and R ₁ , R ₂ , R _3, and R ₄ are each independently hydrogen, a halogen atom, or a monovalent or divalent carbon number of 1 to 30. A substituted or unsubstituted hydrocarbon group, the carbon of -CH ₂ -constituting the above hydrocarbon group may be converted into an oxygen atom, a sulfur atom, an amino group, or a carbonyl group, and a hydrogen atom contained in the above hydrocarbon group may be converted into a halogen atom, a cyano group , Nitro, carbonyl, sulfonic, -SO ₃ M, -CO ₂ M, hydroxyl, formamyl, or amino, and may include epoxy, acrylic reactive groups; R ₁ , R ₂ , R _3, and R ₄ may be selected from phenyl or aromatic hydrocarbons which may be substituted with one or more substituents selected from alkyl, halogen, CN, OR ₁₆ , SR ₁₇ , carbonyl, sulfonic group, and NR ₁₈ R ₁₉ , R ₁₆ , R ₁₇ , R _18, and R ₁₉ are each independently hydrogen, a halogen atom, or a monovalent or divalent hydrocarbon group having 1 to 30 carbon atoms, and the -CH ₂ -carbon constituting the above hydrocarbon group can be converted into an oxygen atom and a sulfur atom , an amino group or a carbonyl group, a hydrogen atom in the hydrocarbon group contained may be 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 amino acyl May contain epoxy, acrylate reactive group; or R _1, R _2, R ₃ and R ₄ is an alkenyl group having 1 to 30, selected from the group comprising a halogen atom, a cyano group, a nitro group, a carbonyl group-containing , Sulfonic acid group, -SO ₃ M, -CO ₂ M, hydroxy, formyl, or amino group of one or more substituents of phenyl or aromatic hydrocarbon group, R ₁ and R ₄ may be combined to form a 5 to 7 member The nitrogen-containing heterocyclic ring of the ring or each independently is a cycloalkyl group, M is an alkali metal atom, and n is 0 to 5).

(In the above Chemical Formula 3, L is carbon or nitrogen, and R ₅ , R ₆ , R ₇ , R ₈ , R _9, and R ₁₀ are each independently hydrogen, a halogen atom, or a monovalent or divalent carbon number of 1 to 30. A substituted or unsubstituted hydrocarbon group, the carbon of -CH ₂ -constituting the above hydrocarbon group may be converted into an oxygen atom, a sulfur atom, an amino group, or a carbonyl group, and a hydrogen atom contained in the above hydrocarbon group may be converted into a halogen atom, a cyano group , Nitro, carbonyl, sulfonic, -SO ₃ M, -CO ₂ M, hydroxyl, formamyl, or amino, and may include epoxy or acrylate reactive groups; R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ may be selected from a phenyl group which may be substituted with one or more substituents selected from alkyl, halogen, CN, OR ₁₆ , SR ₁₇ , carbonyl, sulfonic group, and NR ₁₈ R ₁₉ Aromatic hydrocarbons, R ₁₆ , R ₁₇ , R _18, and R ₁₉ are each independently hydrogen, a halogen atom, or a monovalent or divalent hydrocarbon group having 1 to 30 carbon atoms, and the -CH ₂ -carbon constituting the above hydrocarbon group may be Conversion to oxygen, sulfur, amino or carbonyl groups, and the hydrogen atoms contained in the above hydrocarbon groups can be converted to halogen atoms, cyano, nitro, carbonyl, sulfonic, -SO ₃ M, -CO ₂ M, hydroxyl , Acyl or amino group, may contain epoxy, acrylate reactive group; or _{R 5, R 6, R 7} , R 8, R 9 and R ₁₀ is alkenyl having 1 to 30, selected from the group comprising comprising A phenyl group or an aromatic hydrocarbon group having one or more substituents 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 amino group, R ₆ and R ₇ 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 the above Chemical Formula 4, L is carbon, nitrogen, or sulfur, and R ₁₁ , R ₁₂ , R ₁₃ , R _14, and R ₁₅ are each independently hydrogen, a halogen atom, or a monovalent or divalent chain having 1 to 30 carbon atoms. A substituted or unsubstituted hydrocarbon group, the carbon of -CH ₂ -constituting the above hydrocarbon group may be converted into an oxygen atom, a sulfur atom, an amino group, or a carbonyl group, and a hydrogen atom contained in the above hydrocarbon group may be converted into a halogen atom, a cyano group, Nitro, carbonyl, sulfonic, -SO ₃ M, -CO ₂ M, hydroxy, formamyl, or amino, and may include epoxy or acrylate reactive groups; R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ and R ₁₅ may be selected from phenyl or aromatic hydrocarbons which may be substituted with one or more substituents selected from alkyl, halogen, CN, OR ₁₆ , SR ₁₇ , carbonyl, sulfonic group, and NR ₁₈ R ₁₉ , R ₁₆ , R ₁₇ , R _18, and R ₁₉ are each independently hydrogen, a halogen atom, or a monovalent or divalent hydrocarbon group having 1 to 30 carbon atoms, and the -CH ₂ -carbon constituting the above hydrocarbon group can be converted into an oxygen atom , a sulfur atom, a carbonyl group or an amino group, a hydrogen atom in the hydrocarbon group contained may be converted into a halogen atom, a cyano group, a nitro group, a carbonyl group, a sulfonic acid _{group, -SO 3 M, -CO 2 M} , a hydroxyl group, Acyl or amino group, may contain an epoxy group, the reaction acrylate groups; or _{R 11, R 12, R 13} , R 14 and R ₁₅ is alkenyl having 1 to 30, selected from the group comprising a halogen atom comprising, R ₁₄ and R ₁₅ may be a phenyl or aromatic hydrocarbon group having one or more substituents of cyano, nitro, carbonyl, sulfonic, -SO ₃ M, -CO ₂ M, hydroxy, formamyl, or amino. Nitrogen-containing heterocycles which combine to form a 5- to 7-membered ring or are each independently cycloalkyl, M is an alkali metal atom, and n is 0 to 5).

Colorant

The colorant according to the present invention contains a dye.

In one embodiment of the present invention, the dye may contain one or more compounds selected from the group consisting of xanthene, triarylmethane, coumarin, and a sulfonium compound.

The color photosensitive resin composition according to the present invention includes a coloring agent containing the above dye, specifically a dye containing one or more compounds selected from the group consisting of xanthene, triarylmethane, coumarin, and fluorene compounds, and is represented by the above Chemical Formula 1 In the case of a compound, there is an advantage that a color photosensitive resin composition excellent in reliability and contrast can be provided.

The dye containing the xanthene-based compound may be, for example, rhodamine B, rhodamine 6G, acid red 52, solvent red 49, and basic violet 21 ) And other xanthene pigments.

The dye containing the above triarylmethane-based compound can contain, for example, basic blue 7 (solvent red 41), solvent violet 31 (solvent violet 31), solvent blue 5 (solvent blue 5), acidic Acid blue 90, solvent blue 128, and the like.

The dye containing the coumarin-based compound may be, for example, 3- (2-benzothiazolyl) -7-diethylamino coumarin (coumarin 6), 3- (2 -Benzimidazolyl) coumarin-based pigments such as coumarin (coumarin 7), coumarin 135, and coumarin 153.

The dye containing the fluorene-based compound may be, for example, 4,4-difluoro-1,3,5,7-tetraphenyl-4-boraza-3a, 4a-diaza-s-induction province (IV) , Lumajin F red, Lumagen F orange, Lumagen F yellow, and other actin pigments.

The color photosensitive resin composition according to the present invention can further include a dye generally used in the art in addition to the dye described above. For example, it can be classified as Solvent, Acid, Basic, Reactive, Direct, Disperse in the Colour Index [published by The Society of Dyers and Colourists]. ) Or reduced (Vat) dyes. More specifically, dyes having the following color index (C.I.) numbers may be mentioned, but they are not limited to these.

CI Solvent Yellow 25, 79, 81, 82, 83, 89; CI Acid Yellow 7, 23, 25, 42, 65, 76; CI Active Yellow 2, 76, 116; CI Direct Yellow 4, 28, 44, 86, 132; CI Disperse Yellow 54, 76; CI Solvent Orange 41, 54, 56, 99; CI Acid Orange 56, 74, 95, 108, 149, 162; CI Active Orange 16; CI Direct Orange 26; CI Solvent Red 24, 49, 90, 91, 118, 119, 122, 124, 125, 127, 130, 132, 160, 218; CI Acid Red 73, 91, 92, 97, 138, 151, 211, 274, 289; CI Acid Violet 102; CI solvent green 1, 5; CI acid green 3, 5, 9, 25, 28; CI basic green 1; CI reduced green 1 and the like.

The colorant may contain 0.1 to 30 parts by weight, and preferably 1 to 15 parts by weight, based on 100 parts by weight of the entire color photosensitive resin composition.

When the colorant is included in an amount less than the above range, the tinting strength may be slightly reduced. In the case where the colorant is contained in an amount exceeding the above range, the solvent resistance or adhesion may be reduced, which is not good from the engineering point of view. It is included in the above range.

In another embodiment of this invention, the said coloring agent can further contain a pigment. The said pigment is not specifically limited in this invention, A well-known coloring pigment can be used. For example, the above pigments can be colored pigments classified as pigments in the Color Index (published by The Society of Dyers and Colourists).

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 cyan 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, 62, 63 and other green pigments.

Specifically, as the above-mentioned coloring pigment, it is preferably a cyan pigment such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60; CI Pigment Violet 1, 19, 23, 29, 32, 36, 38, etc. Purple pigments; 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 even more preferably CI Pigment Blue 15: 6 and CI Pigment Green 7. By further including the above-mentioned colored pigment, there is an advantage that optimization of the transmission spectrum becomes easy, and light resistance and chemical resistance of the color filter can be improved.

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, surface treatment with a polymer compound, etc., and sulfuric acid can be used A micronization process such as a micronization method, a cleaning process using an organic solvent or water for removing impurities, a removal process using an ion exchange method, or the like for ionic impurities are not limited thereto.

The pigment may contain 1 to 90 parts by weight, preferably 5 to 90 parts by weight, and more preferably 7 to 82 parts by weight based on 100 parts by weight of the entire colorant. In the case where the pigment is further contained within the above range in the color photosensitive resin composition according to the present invention, optimization of the transmission spectrum becomes easy, and when a color filter is manufactured, light resistance and chemical resistance can become Good and therefore better.

Compound represented by Chemical Formula 1

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

[Chemical Formula 1] (x ⁺ ) _n (Y) ^m-

In the above Chemical Formula 1, (X ⁺ ) is represented by any one of the following Chemical Formula 2 to Chemical Formula 4, n is 1 to 10, and (Y) ^m- has at least 1 selected from tungsten, molybdenum, silicon, and phosphorus. Element and oxygen atom anionic compound.

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. 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- , and [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 2, Z is carbon, nitrogen, sulfur, phosphorus, or iodine, and R ₁ , R ₂ , R _3, and R ₄ are each independently hydrogen, a halogen atom, or a monovalent or divalent compound having 1 to 30 carbon atoms. A substituted or unsubstituted hydrocarbon group, the carbon of -CH ₂ -constituting the above hydrocarbon group may be converted into an oxygen atom, a sulfur atom, an amino group, or a carbonyl group, and a hydrogen atom contained in the above hydrocarbon group may be converted into a halogen atom, a cyano group, Nitro, carbonyl, sulfonic, -SO ₃ M, -CO ₂ M, hydroxy, formamyl or amino, which may contain epoxy, acrylic reactive groups; R ₁ , R ₂ , R ₃ and R ₄ It may be selected from phenyl or aromatic hydrocarbons which may be substituted with one or more substituents selected from the group consisting of alkyl, halogen, CN, OR ₁₆ , SR ₁₇ , carbonyl, sulfonic and NR ₁₈ R ₁₉ , R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ are each independently hydrogen, a halogen atom, or a monovalent or divalent hydrocarbon group having 1 to 30 carbon atoms, and the -CH ₂ -carbon constituting the above hydrocarbon group can be converted into an oxygen atom, a sulfur atom, Amino group or carbonyl group, and the hydrogen atom contained in the above hydrocarbon group can be converted into halogen atom, cyano group, nitro group, carbonyl group, sulfonic group, -SO ₃ M, -CO ₂ M, hydroxyl group, formamyl group or amino group , Which may contain epoxy groups, acrylate reactive groups; or R ₁ , R ₂ , R ₃ and R ₄ are alkenyl groups having 1 to 30 carbon atoms, containing a group selected from halogen atoms, cyano groups, nitro groups, and carbonyl groups , Sulfonic acid group, -SO ₃ M, -CO ₂ M, hydroxy, formyl, or amino group of one or more substituents of phenyl or aromatic hydrocarbon group, R ₁ and R ₄ may be combined to form a 5 to 7 member The nitrogen-containing heterocycle of the ring or each independently is a cycloalkyl group, M is an alkali metal atom, and n is 0 to 5.

The specific compound of the said Chemical Formula 2 can be represented as follows.

In the above Chemical Formula 3, L is carbon or nitrogen, and R ₅ , R ₆ , R ₇ , R ₈ , R _9, and R ₁₀ are each independently hydrogen, a halogen atom, or a monovalent or divalent warp of 1 to 30 carbon atoms. A substituted or unsubstituted hydrocarbon group, the carbon of -CH ₂ -constituting the above hydrocarbon group may be converted into an oxygen atom, a sulfur atom, an amino group, or a carbonyl group, and a hydrogen atom contained in the above hydrocarbon group may be converted into a halogen atom, a cyano group, Nitro, carbonyl, sulfonic, -SO ₃ M, -CO ₂ M, hydroxy, formamyl, or amino, and may include epoxy or acrylate reactive groups; R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ may be selected from phenyl or aromatic which may be substituted with one or more substituents selected from alkyl, halogen, CN, OR ₁₆ , SR ₁₇ , carbonyl, sulfonic and NR ₁₈ R ₁₉ Group hydrocarbons, R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ are each independently hydrogen, a halogen atom or a monovalent or divalent hydrocarbon group having 1 to 30 carbon atoms, and the carbon of -CH ₂ -constituting the above hydrocarbon group can be converted Is an oxygen atom, a sulfur atom, an amino group, or a carbonyl group, and the hydrogen atom contained in the above-mentioned hydrocarbon group can be converted into 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 Fluorenyl or amino, which may contain epoxy or acrylate reactive groups; or R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are alkenyl groups having 1 to 30 carbon atoms, A phenyl group or an aromatic hydrocarbon group having one or more substituents 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 amino group, R ₆ and R ₇ 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.

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

In the above Chemical Formula 4, L is carbon, nitrogen, or sulfur, and R ₁₁ , R ₁₂ , R ₁₃ , R _14, and R ₁₅ are each independently hydrogen, a halogen atom, or a monovalent or divalent substituted group having 1 to 30 carbon atoms. Or an unsubstituted hydrocarbon group, the carbon of -CH ₂ -constituting the above-mentioned hydrocarbon group may be converted into an oxygen atom, a sulfur atom, an amino group or a carbonyl group, and a hydrogen atom contained in the above-mentioned hydrocarbon group may be converted into a halogen atom, a cyano group, a nitrate Group, carbonyl group, sulfonic group, -SO ₃ M, -CO ₂ M, hydroxyl group, methyl group or amino group, and may include epoxy group, acrylate reactive group; R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ And R ₁₅ may be selected from phenyl or aromatic hydrocarbons which may be substituted with one or more substituents selected from alkyl, halogen, CN, OR ₁₆ , SR ₁₇ , carbonyl, sulfonic group, and NR ₁₈ R ₁₉ , R ₁₆ , R ₁₇ , R _18, and R ₁₉ are each independently hydrogen, a halogen atom, or a monovalent or divalent hydrocarbon group having 1 to 30 carbon atoms, and the -CH ₂ -carbon constituting the above hydrocarbon group can be converted into an oxygen atom, Sulfur atom, amino group or carbonyl group, and the hydrogen atom contained in the above-mentioned hydrocarbon group can be converted into halogen atom, cyano group, nitro group, carbonyl group, sulfonic group, -SO ₃ M, -CO ₂ M, hydroxyl group, methyl group The fluorenyl or amino group may contain an epoxy group or an acrylate reactive group; or R ₁₁ , R ₁₂ , R ₁₃ , R _14, and R ₁₅ are alkenyl groups having 1 to 30 carbon atoms, and contain a group selected from halogen atoms, R ₁₄ and R ₁₅ may be a phenyl or aromatic hydrocarbon group having one or more substituents of cyano, nitro, carbonyl, sulfonic, -SO ₃ M, -CO ₂ M, hydroxy, formamyl, or amino. The nitrogen-containing heterocyclic ring which is bonded to form a 5- to 7-membered ring or each independently is 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 still another embodiment of the present invention, it may contain 0.01 to 40 parts by weight, preferably 0.1 to 40 parts by weight, and more preferably 0.1 to 30 parts by weight based on 100 parts by weight of the entire color photosensitive resin composition. The compound represented by the above Chemical Formula 1.

When the compound represented by the above Chemical Formula 1 is contained within the above range, there is an advantage that reliability and high contrast characteristics can be imparted.

In still another embodiment of the present invention, the color 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 or 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 a molecule such as unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, and unsaturated tricarboxylic acid.

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, acrylic acid 2 -Aminopropyl, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate Unsaturated carboxylic acid amino alkyl esters such as esters, 3-dimethylaminopropyl acrylate, 3-dimethylaminopropyl methacrylate, and the like; unsaturated carboxylic acids such as glycidyl acrylate and glycidyl methacrylate Glycidyl esters; vinyl carboxylates such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate; vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether, etc. Unsaturated ethers; acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, vinylidene, etc. Compounds; unsaturated amidamines such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide, N-2-hydroxyethylmethacrylamide; horses Unsaturated pyrimides such as lyme, benzylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, etc .; 1,3-butadiene, isoprene Diene, chloroprene and other aliphatic conjugated dienes; and polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, polysilicon Macromolecules having a monopropenyl group or a monomethacryl group at the end of a polymer molecular chain of an oxane. 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, a bulky monomer such as a monomer having a fluorenyl skeleton, a monomer having an adamantane skeleton, and a monomer having a rosin skeleton has a reduced ratio. The dielectric constant value is 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. good. 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 3,000 to 200,000, preferably 5,000 to 100,000. Binder 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 solid content in the color photosensitive resin composition. As for the content of the binder resin, if it is contained in the above range, the solubility in the developing solution is sufficient. Therefore, it is difficult to generate development residues on the substrate of the non-pixel portion, and it is difficult to cause the pixel portion of the exposed portion to develop during development. Since the number of films is reduced, the non-pixel portion 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 preferably contains 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 color photosensitive resin composition. When content of a photopolymerizable compound is contained in the said range, the intensity | strength and smoothness of a pixel part will become favorable.

Photopolymerization initiator

There is no limitation on the photopolymerization initiator, and it is selected from three One or more compounds among the compound, the acetophenone compound, the biimidazole compound, and the oxime compound. The photosensitive resin composition containing the above-mentioned photopolymerization initiator is highly sensitive, and a pixel formed using the composition has high strength and patternability of a pixel portion.

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

As three Compounds, for example, 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-tris , 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-tri , 2,4-bis (trichloromethyl) -6-piperyl-1,3,5-tri , 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) vinyl] -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) vinyl] -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) vinyl] -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) vinyl] -1,3,5-tris Wait.

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-2 -An oligomer of 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 and 2,2'-bis (2,3-di (Chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxy) (Phenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (trialkoxyphenyl) biimidazole, 4,4', 5,5 An imidazole compound in which a phenyl group is substituted with an alkoxycarbonyl group, and the like. Among these, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,3-dichloro) are preferably used. (Phenyl) -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 generally used in this field can be further included. Examples of other photopolymerization initiators include benzoin-based compounds, benzophenone-based compounds, thioxanthen-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'-tetra (t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, 4,4'-di (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, methyl phenylglyoxylate, titanocene compound, etc. as other photopolymerization initiators.

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

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- Ethyl dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N -Aromas such as dimethyl-p-toluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as linone), 4,4'-bis (diethylamino) benzophenone Group amine compounds. 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-naphthylglycine, naphthyloxy Aromatic heteroacetic acids such as acetic acid.

In the color photosensitive resin composition of the present invention, in terms of the content of the photopolymerization initiator, the color photosensitive resin composition preferably contains 0.1 to 20 parts by weight relative to 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 makes the photosensitive resin composition high sensitivity when it is contained in the said range, and the intensity | strength of a pixel part and the smoothness of the surface of a pixel part are excellent.

In addition, in terms of the amount of the photopolymerization initiation aid used, the photosensitive resin composition described above preferably contains 0.1 to 20 parts by weight, and more preferably 1 to 10 parts by weight based on 100 parts by weight of the entire solid content. Serving. When the usage-amount of the said photopolymerization start 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 color 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 Alkyl glycol alkyl ether acetates such as acetate and methoxypentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, methyl ethyl ketone, acetone, methylpentyl Ketones such as methyl ketone, methyl isobutyl ketone, cyclohexanone, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerol and other alcohols, ethyl 3-ethoxypropionate , Esters such as methyl 3-methoxypropionate, cyclic esters such as γ-butyrolactone, and the like.

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 glycols may be mentioned. Alkyl ether acetates, ketones, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate and the like, and more preferably, propylene glycol monomethyl ether acetate, Propylene glycol monoethyl 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 color photosensitive resin composition of the present invention is preferably 60 to 90 parts by weight, and more preferably 65 to 85 parts by weight based on 100 parts by weight of the entire color photosensitive resin composition. As for the content of the above-mentioned solvent, if it is contained within the above range, a roll coater, a spin coater, a slit and spin coater, a slit coater (also sometimes referred to as a die coater), The coating properties can be improved during coating by a coating device such as an inkjet.

Additives

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

The antioxidant can be selected from benzotriazole-based light stabilizers, One of the light stabilizer, benzophenone-based, Hals light stabilizer, and a combination thereof, but is not limited thereto.

The adhesion promoter is added to improve adhesion to the substrate, and can include a silane coupling agent having a reactive substituent selected from a carboxyl group, a methacryl group, an isocyanate group, an epoxy group, and a combination thereof. But it is 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., which can be used alone as well as Two or more kinds are used in combination.

When the color photosensitive resin composition according to the present invention contains the above-mentioned surfactant, there is an advantage that coating properties can be improved. For example, the above surfactants can be BM-1000, BM-1100 (BM Chemie), FLUORAD FC-135 / FC-170C / FC-430 (Sumitomo 3M (stock)), SH-28PA / -190 / SZ-6032 (Toray Organosilicon) is not limited thereto.

In addition, the color 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 that does not impair the effects of the present invention. The above-mentioned additives also do not impair the effects of the present invention. Within the scope, those skilled in the art can appropriately use it. For example, the above additives can be used in an amount of 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, based on 100 parts by weight of the entire color photosensitive resin composition as a basis, but Not limited to this.

<Color filter>

The present invention provides a color filter including a coloring pattern produced using the color photosensitive resin composition. That is, this invention includes the color filter manufactured using the said color photosensitive resin composition. The color filter according to the present invention has the advantages of excellent reliability and contrast ratio without lowering the brightness by containing both a dye and a compound represented by the structure of Chemical Formula 1 above.

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

The manufacturing method of the said color filter can use the usual method well-known in this field.

<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 portable terminal display such as a mobile phone. 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 described above.

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 is not limited to the embodiments described below. The embodiments of the present specification are intended to more completely explain to those skilled in the art what the present specification provides. 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 dripped into the completely dissolved solution, and dissolved in 6 g of A solution in 25 g of water. After stirring at 25 to 50 ° C for 4 hours after dropping, 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. (Refer to Eur. J. Inorg. Chem. 2014, 21-35.)

Synthesis Example 2

Tetrapropylammonium Hydroxide (TCI, product number T0171) was used in place of Dodecylpyridinium chloride, and chemical formula A-27.3 g was obtained by the same method as in Synthesis Example 1.

[Chemical Formula A-2]

Synthesis Example 3: 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 of the alkali-soluble resin thus synthesized had an acid value of 36.2 mgKOH / g, a weight-average molecular weight Mw measured by GPC of about 7,540, and a Tg of -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 ℃

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 color photosensitive resin composition: Examples 1 to 3 and Comparative Examples 1 to 3

The color photosensitive resin compositions according to the examples and comparative examples were produced in accordance with the composition of Table 1 below, and at this time, the solvent was contained so that the entire color photosensitive resin composition became 100 parts by weight.

Color filter (glass substrate) manufacturing example

A color filter was produced using the color photosensitive resin compositions produced in the examples and comparative examples. That is, each of the color 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 of the g, h, and i rays was used, and the light was irradiated at 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 thickness of the color filter manufactured as described above was 2.0 μm.

Experimental example

(1) Thickening rate of color photosensitive resin composition

The initial viscosity (kinematic viscosity) A (mPa · s) of each of the color photosensitive resin compositions which were obtained after the production of the examples and comparative examples was measured.

Then, each color photosensitive resin composition according to the examples and comparative examples was left to stand for one day immediately after manufacture in an environment of 25 ° C., and the viscosity (kinematic viscosity) of each color photosensitive resin composition after standing was measured. B (mPa‧s). The measurement of the viscosity (kinematic viscosity) of the color photosensitive resin composition was performed in an environment of 25 ° C. in accordance with JIS Z8809 using an E-type viscometer (trade name: RE-01, DONGGI Industries Co., Ltd. product). 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 viscosities of Examples 1 to 3 are shown as relative values when the initial viscosity of the color photosensitive resin composition of Comparative Example 1 is used as a standard (100), and the results are shown in the table. 2 in.

(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. The colored glass plate was set on a spectrophotometer (trade name: CM-3700d, a product of konicaminolta sensing) and the transmission chromaticity at the X, Y, and Z coordinate axes at 2 degrees (°) of the C light source was measured. 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 3 in the following Table 2 are expressed as relative values when the brightness of a colored glass plate obtained using the color photosensitive resin composition of Comparative Example 1 as a standard (100), and the results are shown in the table. 2 in.

(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 measurement device consists of a color brightness meter (trade name: LS-100, konicaminolta sensing (stock) product), a lamp (trade name: HF-SL-100WLCG, Johnson Industries (stock) product), and a polarizing plate (trade name) : POLAX-38S, (LUshare products)

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 to measure 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. The contrast values of Examples 1 to 3 are expressed as relative values when the contrast of a colored glass plate obtained by using the color photosensitive resin composition of Comparative Example 1 as a standard (100). The results are shown in Table 2.

(4) Heat resistance measurement

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 to 10

×: △ E ^* ab value: more than 10

As shown in Table 2 above, it was confirmed that the color photosensitive resin compositions of Examples 1 to 3 obtained by mixing the above-mentioned compositions according to the present invention can provide a color filter having heat resistance and high contrast.

Claims (8)

A color photosensitive resin composition comprising: a coloring agent containing a dye; and a compound represented by the following Chemical Formula 1, [Chemical Formula 1] (x ⁺ ) _n (Y) ^{m- In} the Chemical Formula 1, (X ⁺ ) Is represented by any one of the following Chemical Formulas 2 to 4, n is 1 to 10, and (Y) ^m- is an anion having at least one element selected from tungsten, molybdenum, silicon, and phosphorus and an oxygen atom, In the chemical formula 2, Z is carbon, nitrogen, sulfur, phosphorus, or iodine, and R ₁ , R ₂ , R _3, and R ₄ are each independently hydrogen, a halogen atom, or a monovalent or divalent carbon number of 1 to 30. A substituted or unsubstituted hydrocarbon group, the -CH ₂ -carbon constituting the hydrocarbon group may be converted into an oxygen atom, a sulfur atom, an amino group, or a carbonyl group, and a hydrogen atom contained in the hydrocarbon group may be converted into a halogen atom, Cyano, nitro, carbonyl, sulfonic, -SO ₃ M, -CO ₂ M, hydroxy, formamyl or amino, and may contain epoxy or acrylate reactive groups; R ₁ , R ₂ , R ₃ and R ₄ may be selected from phenyl or aromatic hydrocarbons which may be substituted with one or more substituents selected from alkyl, halogen, CN, OR ₁₆ , SR ₁₇ , carbonyl, sulfonic group, and NR ₁₈ R ₁₉ , R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ are each independently hydrogen, a halogen atom or a monovalent or divalent hydrocarbon group having 1 to 30 carbon atoms, and the -CH ₂ -carbon constituting the hydrocarbon group may be converted into oxygen Atom, sulfur atom, amino group or carbonyl group, the hydrogen atom contained in the hydrocarbon group can be converted into halogen atom, cyano group, nitro group, carbonyl group, sulfonic group, -SO ₃ M, -CO ₂ M, hydroxyl group, methyl group醯 基 or Group, may contain epoxy, acrylate reactive group; or R _1, R _2, R ₃ and R ₄ is alkenyl having 1 to 30, comprising a comprising a halogen atom selected from, cyano, nitro, A phenyl or aromatic hydrocarbon group having one or more substituents of a carbonyl group, a sulfonic group, -SO ₃ M, -CO ₂ M, a hydroxyl group, a methyl group, or an amino group, and R ₁ and R ₄ may be combined to form 5 to 7 Nitrogen-containing heterocyclic ring or each independently cycloalkyl group, M is an alkali metal atom, n is 0 to 5, [Chemical Formula 3] In the chemical formula 3, L is carbon or nitrogen, and R ₅ , R ₆ , R ₇ , R ₈ , R _9, and R ₁₀ are each independently hydrogen, a halogen atom, or a monovalent or divalent carbon number of 1 to 30. A substituted or unsubstituted hydrocarbon group, the -CH ₂ -carbon constituting the hydrocarbon group may be converted into an oxygen atom, a sulfur atom, an amino group, or a carbonyl group, and a hydrogen atom contained in the hydrocarbon group may be converted into a halogen atom, Cyano, nitro, carbonyl, sulfonic, -SO ₃ M, -CO ₂ M, hydroxy, formamyl or amino, and may contain epoxy or acrylate reactive groups; R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ may be selected from benzenes which may be substituted with one or more substituents selected from alkyl, halogen, CN, OR ₁₆ , SR ₁₇ , carbonyl, sulfonic group, and NR ₁₈ R ₁₉ Or an aromatic hydrocarbon, R ₁₆ , R ₁₇ , R _18, and R ₁₉ are each independently hydrogen, a halogen atom, or a monovalent or divalent hydrocarbon group having 1 to 30 carbon atoms, and -CH _2- The carbon can be converted into an oxygen atom, a sulfur atom, an amino group or a carbonyl group, and the hydrogen atom contained in the hydrocarbon group can be converted into a halogen atom, a cyano group, a nitro group, a carbonyl group, a sulfonic group, -SO ₃ M, -CO ₂ M, hydroxyl, forma The fluorenyl or amino group may contain an epoxy group or an acrylate reactive group; or R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are alkenyl groups having 1 to 30 carbon atoms, A phenyl group or an aromatic hydrocarbon group having one or more substituents 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 amino group, R ₆ and R ₇ 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 to 5, In the chemical formula 4, L is carbon, nitrogen, or sulfur, and R ₁₁ , R ₁₂ , R ₁₃ , R _14, and R ₁₅ are each independently hydrogen, a halogen atom, or a monovalent or divalent warp of 1 to 30 carbon atoms. A substituted or unsubstituted hydrocarbon group, the -CH ₂ -carbon constituting the hydrocarbon group may be converted into an oxygen atom, a sulfur atom, an amino group, or a carbonyl group, and a hydrogen atom contained in the hydrocarbon group may be converted into a halogen atom, cyanide Group, nitro group, carbonyl group, sulfonic group, -SO ₃ M, -CO ₂ M, hydroxyl group, formamyl group or amino group, and may include epoxy group, acrylate reactive group; R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ and R ₁₅ may be selected from phenyl or aromatic which may be substituted by one or more substituents selected from alkyl, halogen, CN, OR ₁₆ , SR ₁₇ , carbonyl, sulfonic and NR ₁₈ R ₁₉ Hydrocarbon, R ₁₆ , R ₁₇ , R _18, and R ₁₉ are each independently hydrogen, a halogen atom, or a monovalent or divalent hydrocarbon group having 1 to 30 carbon atoms, and the -CH ₂ -carbon constituting the hydrocarbon group may be converted Is an oxygen atom, a sulfur atom, an amino group, or a carbonyl group, and the hydrogen atom contained in the hydrocarbon group can be converted into a halogen atom, a cyano group, a nitro group, a carbonyl group, a sulfonic group, -SO ₃ M, -CO ₂ M, hydroxyl A The fluorenyl or amino group may contain an epoxy group or an acrylate reactive group; or R ₁₁ , R ₁₂ , R ₁₃ , R _14, and R ₁₅ are alkenyl groups having 1 to 30 carbon atoms, and contain a group selected from halogen atoms, R ₁₄ and R ₁₅ may be a phenyl or aromatic hydrocarbon group having one or more substituents of cyano, nitro, carbonyl, sulfonic, -SO ₃ M, -CO ₂ M, hydroxy, formamyl, or amino. The nitrogen-containing heterocyclic ring which is bonded to form a 5- to 7-membered ring or each independently is a cycloalkyl group, M is an alkali metal atom, and n is 0 to 5.     The color photosensitive resin composition according to item 1 of the scope of patent application, wherein the dye contains one or more compounds selected from the group consisting of xanthene, triarylmethane, coumarin, and fluorene compounds.         The color photosensitive resin composition according to item 1 of the scope of patent application, wherein the colorant further comprises a pigment.         The color photosensitive resin composition according to item 1 of the patent application scope, further comprising one or more selected from the group consisting of a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent.         The color photosensitive resin composition according to item 1 of the patent application scope, which contains 0.01 to 40 parts by weight of the compound represented by the chemical formula 1 with respect to 100 parts by weight of the entire color photosensitive resin composition.         The color photosensitive resin composition according to item 1 of the scope of patent application, wherein the colorant is contained in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the entire color photosensitive resin composition.         A color filter includes a cured product of a color photosensitive resin composition according to any one of claims 1 to 6 of a patent application.         An image display device includes a color filter according to item 7 of the scope of patent application.