JP2018081302A - Coloring photosensitive resin composition, and color filter and image display device produced by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring photosensitive resin composition that shows the properties of high reliability and high contrast when applied to a color filter and an image display device having the same.SOLUTION: A coloring photosensitive resin composition contains: a colorant containing a dye; and a compound represented by the following chemical formula 1 (where, n is 1-10, (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).SELECTED DRAWING: None

Description

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

  Color filters are widely used in image display devices such as image sensors and liquid crystal display devices, and their application range is rapidly expanding. Color filters used in color liquid crystal display devices and image sensors usually spin a colored photosensitive resin composition containing a colorant corresponding to each color of red, green and blue on a substrate on which a black matrix pattern is formed. After coating uniformly by coating, the coating film formed by heating and drying (hereinafter sometimes referred to as pre-baking) is exposed and developed, and further heat-cured as necessary (hereinafter also referred to as post-baking). This operation is repeated for each color to form pixels of each color.

  The colored photosensitive resin composition is a photosensitive resin composition colored with a colorant, and is useful as a material for forming a colored pattern constituting a color filter. Here, the color filter is an optical element that is built in the color liquid crystal display device and used to color the display image, or is built in the image pickup device and used to acquire the color image.

  Recently, a color filter with higher luminance has been required to save power in color liquid crystal displays. In general, the color filter tends to have higher luminance when the film thickness is thinner. At this time, it is necessary to realize a high pigment concentration in order to ensure high color reproduction. However, increasing the concentration of the pigment further reduces the storage stability and coating properties of the resist composition, making it difficult to produce a color filter having sufficient performance.

  In order to realize these, application of dyes is being studied. However, in general, there are many problems that reliability and contrast are low as compared with the case where a pigment is applied. Therefore, development of a technique for solving the problems in the case of using a dye is required.

  Korean Patent No. 2014-0115990 relates to a colored composition, a colored cured film and a display element, and (A) at least one selected from the group consisting of xanthene compounds, polymethine compounds, coumarin compounds and perylene compounds. A coloring composition containing a compound of (B), (B) a binder resin and (C) a coloring composition containing a polymerizable compound, and further comprising (D) a transition metal compound (excluding the component (A)) The contents regarding are disclosed.

  Korean Patent No. 2015-0101934 relates to a colored composition, a colored cured film, and a display device, and is a colored composition containing (A) a colorant and (B) a polymerizable compound, and (A) coloring. The agent discloses a content relating to a colored composition containing a polymer having a site that emits fluorescence and a site that absorbs the corresponding fluorescence.

  Japanese Patent Publication No. 2013-028764 relates to a colored curable composition, a colored cured film, a color filter, a pattern forming method, a color filter manufacturing method, a body imaging device, and an image display device ( The content regarding the coloring curable composition containing the pigment | dye multimer which has A) polymeric group, (B) pigment, (C) polymeric compound, and (D) photoinitiator is disclosed.

  However, the prior art can be detrimental to brightness and reliability due to the unique colors represented by additives such as transition metals or color formers such as anthraquinone.

Republic of Korea Published Patent No. 2014-0115990 (2014. 10.01.) Republic of Korea Patent No. 2015-0101934 (2015.09.04.) Japanese Published Patent No. 2013-028764 (2013.02.07)

  The present invention is for solving the above-mentioned problems, and includes a dye and a compound represented by a specific chemical formula, so that when applied to a color filter and an image display device having the same, high reliability is achieved. It is another object of the present invention to provide a colored photosensitive resin composition exhibiting high contrast characteristics.

  In order to achieve the above object, a colored photosensitive resin composition according to the present invention comprises a colorant containing a dye; and a compound represented by the following chemical formula 1.

[Chemical Formula 1]
(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 tungsten, molybdenum, silicon, and An anion having at least one element selected from the group consisting of phosphorus and an oxygen atom).

[Chemical formula 2]
(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 group having 1 to 30 carbon atoms. Or a divalent substituted or unsubstituted hydrocarbon group, and —CH ₂ — constituting the hydrocarbon group is a hydrocarbon in which carbon is converted to an oxygen atom, a sulfur atom, an amino group or a carbonyl group, or The hydrogen atom contained in the group 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, a hydroxy group, a formyl basis or an amino group, or an epoxy, Contains an acrylate reactive group; selected from the group consisting of alkyl, halogen, CN, OR ₁₆ , SR ₁₇ , carbonyl group, sulfonic acid group and NR ₁₈ R ₁₉ R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ may each independently be hydrogen, halogen atom or carbon number 1 and may be selected from phenyl or aromatic hydrocarbon which may be substituted by one or more substituents. To 30 monovalent or divalent hydrocarbon group, and —CH ₂ — constituting the hydrocarbon group is a group in which carbon is converted into an oxygen atom, a sulfur atom, an amino group or a carbonyl group, or the hydrocarbon group The hydrogen atom contained in is converted to a halogen atom, a cyano group, a nitro group, a carbonyl group, a sulfonic acid group, —SO ₃ M, —CO ₂ M, a hydroxy group, a formyl base or an amino group, or an epoxy, acrylate reaction or containing groups; or an alkenyl having 1 to 30 carbon atoms, a halogen atom, a cyano group, a nitro group, a carbonyl group, a sulfonic acid _group, -SO 3 M, -CO M, hydroxy group include phenyl including one or more substituents selected from the group of formyl base or amino group, or an aromatic hydrocarbon group, R ₁ and R ₄ are bonded to 5- to 7-membered ring A nitrogen-containing heterocycle is formed, or each may independently be cycloalkyl, and n is 0-5).

[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, halogen atom, or monovalent having 1 to 30 carbon atoms. Or a divalent substituted or unsubstituted hydrocarbon group, and —CH ₂ — constituting the hydrocarbon group is a hydrocarbon in which carbon is converted to an oxygen atom, a sulfur atom, an amino group or a carbonyl group, or The hydrogen atom contained in the group 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, a hydroxy group, a formyl basis or an amino group, or an epoxy, it contains a reactive group of the acrylates, alkyl, _{halogen, CN,} oR 16, _{SR 17,} carbonyl group one of, selected from the group consisting of sulfonic acid group and _NR 18 _{R 19} More obtained is selected from a phenyl or aromatic hydrocarbons may be substituted by a _{substituent, R 16, R 17, R} 18 and _{R 19} are each independently hydrogen, halogen atom or C1-30 Or —CH ₂ — constituting the hydrocarbon group is converted into an oxygen atom, a sulfur atom, an amino group or a carbonyl group, or is included in the hydrocarbon group. The hydrogen atom 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, a hydroxy group, a formyl base or an amino group, or an epoxy or acrylate reaction. or containing groups; or an alkenyl having 1 to 30 carbon atoms, a halogen atom, a cyano group, a nitro group, a carbonyl group, a sulfonic acid _group, -SO 3 M, -CO ₂ , Hydroxy groups, include one or more containing a substituent phenyl or aromatic hydrocarbon radical selected from the group of formyl base or amino group, R ₆ and R ₇ are nitrogen bonded to 5- to 7-membered ring Form a heterocycle containing or each independently may be cycloalkyl, n is 0-5).

[Chemical formula 4]
(In 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 group having 1 to 30 carbon atoms, or A hydrocarbon group that is a divalent substituted or unsubstituted hydrocarbon, and —CH ₂ — constituting the hydrocarbon group is such that carbon is converted to an oxygen atom, a sulfur atom, an amino group, or a carbonyl group, or the hydrocarbon group The hydrogen atom contained in is converted to a halogen atom, a cyano group, a nitro group, a carbonyl group, a sulfonic acid group, —SO ₃ M, —CO ₂ M, a hydroxy group, a formyl base or an amino group, or an epoxy, acrylate Or selected from the group consisting of alkyl, halogen, CN, OR ₁₆ , SR ₁₇ , carbonyl group, sulfonic acid group and NR ₁₈ R ₁₉ R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ are each independently hydrogen, halogen atom or carbon number, which may be selected from phenyl or aromatic hydrocarbon which may be substituted by one or more substituents 1 to 30 monovalent or divalent hydrocarbon group, and —CH ₂ — constituting the hydrocarbon group is carbon converted to an oxygen atom, a sulfur atom, an amino group or a carbonyl group, or the hydrocarbon The hydrogen atom contained in the group 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, a hydroxy group, a formyl basis or an amino group, or an epoxy, it contains a reactive group of the acrylate; or an alkenyl having 1 to 30 carbon atoms, a halogen atom, a cyano group, a nitro group, a carbonyl group, a sulfonic acid _group, -SO 3 M, -C _{2 M,} hydroxy group include phenyl including one or more substituents selected from the group of formyl base or amino group, or an aromatic hydrocarbon group, R ₁₄ and R ₁₅ are bonded to 5- to 7-membered ring Or each independently can be cycloalkyl, n is 0-5.

  Moreover, this invention provides the color filter containing the hardened | cured material of the colored photosensitive resin composition mentioned above, and an image display apparatus containing the same.

  The colored photosensitive resin composition according to the present invention includes a dye and a compound represented by a specific chemical formula, so that when applied to a color filter and an image display device equipped with the same, the luminance is not lowered and the reliability is high. And has the advantage of exhibiting high contrast characteristics.

  Moreover, the color filter manufactured with the above-mentioned colored photosensitive resin composition and the image display device including the color filter have an advantage of excellent sensitivity.

  Hereinafter, the present invention will be described in more detail.

  In the present invention, when a certain member is positioned “on” another member, this is not only when the certain member is in contact with the other member, but also when another member is interposed between the two members. Including the case where it exists.

  In the present invention, when a part “includes” a component, this means that the component can further include other components rather than excluding other components unless specifically stated to the contrary. To do.

<Colored photosensitive resin composition>
The colored photosensitive resin composition according to the present invention includes a colorant including a dye; and a compound represented by the following chemical formula 1.

[Chemical Formula 1]
(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 tungsten, molybdenum, silicon, and An anion having at least one element selected from the group consisting of phosphorus and an oxygen atom).

[Chemical formula 2]
(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 group having 1 to 30 carbon atoms. Or a divalent substituted or unsubstituted hydrocarbon group, and —CH ₂ — constituting the hydrocarbon group is a hydrocarbon in which carbon is converted to an oxygen atom, a sulfur atom, an amino group or a carbonyl group, or The hydrogen atom contained in the group 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, a hydroxy group, a formyl basis or an amino group, or an epoxy, Contains an acrylate reactive group; selected from the group consisting of alkyl, halogen, CN, OR ₁₆ , SR ₁₇ , carbonyl group, sulfonic acid group and NR ₁₈ R ₁₉ R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ may each independently be hydrogen, halogen atom or carbon number 1 and may be selected from phenyl or aromatic hydrocarbon which may be substituted by one or more substituents. To 30 monovalent or divalent hydrocarbon group, and —CH ₂ — constituting the hydrocarbon group is a group in which carbon is converted into an oxygen atom, a sulfur atom, an amino group or a carbonyl group, or the hydrocarbon group The hydrogen atom contained in is converted to a halogen atom, a cyano group, a nitro group, a carbonyl group, a sulfonic acid group, —SO ₃ M, —CO ₂ M, a hydroxy group, a formyl base or an amino group, or an epoxy, acrylate reaction or containing groups; or an alkenyl having 1 to 30 carbon atoms, a halogen atom, a cyano group, a nitro group, a carbonyl group, a sulfonic acid _group, -SO 3 M, -CO M, hydroxy group include phenyl including one or more substituents selected from the group of formyl base or amino group, or an aromatic hydrocarbon group, R ₁ and R ₄ are bonded to 5- to 7-membered ring A nitrogen-containing heterocycle may be formed or each may independently be cycloalkyl, M is an alkali metal atom and n is 0-5.

[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, halogen atom, or monovalent having 1 to 30 carbon atoms. Or a divalent substituted or unsubstituted hydrocarbon group, and —CH ₂ — constituting the hydrocarbon group is a hydrocarbon in which carbon is converted to an oxygen atom, a sulfur atom, an amino group or a carbonyl group, or The hydrogen atom contained in the group 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, a hydroxy group, a formyl basis or an amino group, or an epoxy, it contains a reactive group of the acrylates, alkyl, _{halogen, CN,} oR 16, _{SR 17,} carbonyl group one of, selected from the group consisting of sulfonic acid group and _NR 18 _{R 19} More obtained is selected from a phenyl or aromatic hydrocarbons may be substituted by a _{substituent, R 16, R 17, R} 18 and _{R 19} are each independently hydrogen, halogen atom or C1-30 Or —CH ₂ — constituting the hydrocarbon group is converted into an oxygen atom, a sulfur atom, an amino group or a carbonyl group, or is included in the hydrocarbon group. The hydrogen atom 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, a hydroxy group, a formyl base or an amino group, or an epoxy or acrylate reaction. or containing groups; or an alkenyl having 1 to 30 carbon atoms, a halogen atom, a cyano group, a nitro group, a carbonyl group, a sulfonic acid _group, -SO 3 M, -CO ₂ , Hydroxy groups, include one or more containing a substituent phenyl or aromatic hydrocarbon radical selected from the group of formyl base or amino group, R ₆ and R ₇ are nitrogen bonded to 5- to 7-membered ring Forming a heterocycle containing or each independently may be cycloalkyl, M is an alkali metal atom and n is 0-5).

[Chemical formula 4]
(In 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 group having 1 to 30 carbon atoms, or A hydrocarbon group that is a divalent substituted or unsubstituted hydrocarbon, and —CH ₂ — constituting the hydrocarbon group is such that carbon is converted to an oxygen atom, a sulfur atom, an amino group, or a carbonyl group, or the hydrocarbon group The hydrogen atom contained in is converted to a halogen atom, a cyano group, a nitro group, a carbonyl group, a sulfonic acid group, —SO ₃ M, —CO ₂ M, a hydroxy group, a formyl base or an amino group, or an epoxy, acrylate Or selected from the group consisting of alkyl, halogen, CN, OR ₁₆ , SR ₁₇ , carbonyl group, sulfonic acid group and NR ₁₈ R ₁₉ R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ are each independently hydrogen, halogen atom or carbon number, which may be selected from phenyl or aromatic hydrocarbon which may be substituted by one or more substituents 1 to 30 monovalent or divalent hydrocarbon group, and —CH ₂ — constituting the hydrocarbon group is carbon converted to an oxygen atom, a sulfur atom, an amino group or a carbonyl group, or the hydrocarbon The hydrogen atom contained in the group 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, a hydroxy group, a formyl basis or an amino group, or an epoxy, it contains a reactive group of the acrylate; or an alkenyl having 1 to 30 carbon atoms, a halogen atom, a cyano group, a nitro group, a carbonyl group, a sulfonic acid _group, -SO 3 M, -C _{2 M,} hydroxy group include phenyl including one or more substituents selected from the group of formyl base or amino group, or an aromatic hydrocarbon group, R ₁₄ and R ₁₅ are bonded to 5- to 7-membered ring Or each independently may be cycloalkyl, M is an alkali metal atom and n is 0-5.

Colorant

  The colorant according to the present invention contains a dye.

  In one embodiment of the present invention, the dye may include one or more compounds selected from the group consisting of xanthene, triarylmethane, coumarin and perylene compounds.

  The colored photosensitive resin composition according to the present invention includes a colorant containing the dye, specifically, a dye containing one or more compounds selected from the group consisting of xanthene, triarylmethane, coumarin and perylene compounds, and the above When the compound represented by Chemical Formula 1 is included, there is an advantage that a colored photosensitive resin composition having excellent reliability and contrast can be provided.

  Examples of the dye containing the xanthene compound include xanthene such as rhodamine B, rhodamine 6G, acid red 52, solvent red 49, and basic violet 21. ) Based dyes.

  Examples of the dye containing the triarylmethane-based compound include basic blue 7, solvent red 41, solvent violet 31, solvent blue 5 and acid blue. 90 (Acid blue 90), Solvent blue 128, and the like.

  Examples of the dye containing the coumarin compound include 3- (2-benzothiazolyl) -7-diethylaminocoumarin (coumarin 6) and 3- (2-benzimidazolyl) -7-diethylaminocoumarin ( It may be a coumarin dye such as coumarin 7), coumarin 135, coumarin 153 and the like.

  Examples of the dye containing the perylene compound include 4,4-difluoro-1,3,5,7-tetraphenyl-4-bora-3a, 4a-diaza-s-indacene (IV), lumogen F red, lumogen ( It may be a perillin pigment such as Lumogen F orange or Lumogen F yellow.

  The colored photosensitive resin composition according to the present invention may further include a dye commonly used in the art in addition to the dye described above. For example, Color Index [The Society of Diers and Colorist Publishing], Solvent, Acid, Basic, Reactive, Direct, Disperse. Or the dye etc. which are classified into vat are mentioned. More specifically, the following dyes having a color intex (CI) number may be mentioned, but the dye is not limited thereto.

C. I. Solvent Yellow 25, 79, 81, 82, 83, 89;
C. I. Acid Yellow 7, 23, 25, 42, 65, 76;
C. I. Reactive Yellow 2, 76, 116;
C. I. Direct yellow 4, 28, 44, 86, 132;
C. I. Disperse Yellow 54, 76;
C. I. Solvent orange 41, 54, 56, 99;
C. I. Acid Orange 56, 74, 95, 108, 149, 162;
C. I. Reactive Orange 16;
C. I. Direct orange 26;
C. I. Solvent Red 24, 49, 90, 91, 118, 119, 122, 124, 125, 127, 130, 132, 160, 218;
C. I. Acid Red 73, 91, 92, 97, 138, 151, 211, 274, 289;
C. I. Acid Violet 102;
C. I. Solvent Green 1, 5;
C. I. Acid Green 3, 5, 9, 25, 28;
C. I. Basic Green 1;
C. I. Bat Green 1 etc.

  The colorant may be included in an amount of 0.1 to 30 parts by weight, preferably 1 to 15 parts by weight, based on 100 parts by weight of the entire colored photosensitive resin composition.

  When the colorant is contained in less than the above range, the coloring power may be somewhat reduced. When the colorant is contained in excess of the above range, solvent resistance or adhesion may be reduced, which is not preferable in terms of process. Therefore, it is preferably included within the above range.

  In still another embodiment of the present invention, the colorant may further include a pigment. The pigment is not particularly limited in the present invention, and a known color pigment can be used. For example, the pigment may be a color pigment classified by pigment in the color index (published by The Society of Dyers and Colorists).

  Examples of the color pigment include C.I. I. 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, etc. Pigments; C.I. I. Blue pigments such as C.I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, 16, 60; I. Violet color pigments such as C.I. Pigment Violet 1, 19, 23, 29, 32, 36, 38; I. Orange pigments such as CI Pigment Orange 13, 31, 38, 41, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73; I. And green pigments such as CI Pigment Green 7, 19, 21, 26, 36, 58, 59, 62, and 63.

  Specifically, examples of the color pigment include C.I. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60; I. Violet color pigments such as C.I. Pigment Violet 1, 19, 23, 29, 32, 36, 38; I. Green pigments such as CI Pigment Green 7, 36, 58 and 59 are preferred; I. Pigment blue 15: 3, 15: 6, C.I. I. Pigment violet 23 and C.I. I. Pigment Green 7 and 58 are more preferable, and C.I. I. Pigment blue 15: 6 and C.I. I. Pigment Green 7 is more preferable. By further including the color pigment, it is easy to optimize the transmission spectrum, and there is an advantage that the light resistance and chemical resistance of the color filter can be improved.

  The colored pigment is optionally treated by rosin treatment, surface treatment using a pigment derivative having an acidic group or basic group introduced therein, graft treatment on the pigment surface with a polymer compound, or the like, sulfuric acid atomization method, etc. Atomization treatment, washing treatment with an organic solvent or water for removing impurities, removal treatment by ion exchange method of ionic impurities, etc. may be performed, but is not limited thereto. .

  The pigment may be included in an amount of 1 to 90 parts by weight, preferably 5 to 90 parts by weight, and more preferably 7 to 82 parts by weight with respect to 100 parts by weight of the entire colorant. When the pigment is further included in the colored photosensitive resin composition according to the present invention within the above range, it is easy to optimize the transmission spectrum, and when manufacturing a color filter, light resistance and chemical resistance can be improved. ,preferable.

Compound represented by Chemical Formula 1 The colored photosensitive resin composition according to the present invention includes a colorant containing a dye and a compound represented by the following Chemical Formula 1.

[Chemical Formula 1]
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 tungsten, molybdenum, silicon and phosphorus. An anion having at least one element selected from the group consisting of and an oxygen atom.

On the other hand, when the anion is an anion of heteropolyacid or isopolyacid containing tungsten as an essential element, it contains anions of phosphotungstic acid, silicotungstic acid and tungsten-based isopolyacid, for example, Keggin phosphotungstate ion α- [PW ₁₂ O ₄₀ ] ³⁻ , Dawson type phosphotungstate ion α- [P ₂ W ₁₈ O ₆₂ ] ⁶⁻ , β- [P ₂ W ₁₈ O ₆₂ ] ⁶⁻ , Keggin type silicotungstate ion α -[SiW ₁₂ O ₄₀ ] ⁴⁻ , β- [SiW ₁₂ O ₄₀ ] ⁴⁻ , γ- [SiW ₁₂ O ₄₀ ] ⁴⁻ , and other [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 ^{_{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 their It can be a mixture.

[Chemical formula 2]
In 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, a monovalent group having 1 to 30 carbon atoms, or A hydrocarbon group that is a divalent substituted or unsubstituted hydrocarbon, and —CH ₂ — constituting the hydrocarbon group is such that carbon is converted to an oxygen atom, a sulfur atom, an amino group, or a carbonyl group, or the hydrocarbon group The hydrogen atom contained in is converted to a halogen atom, a cyano group, a nitro group, a carbonyl group, a sulfonic acid group, —SO ₃ M, —CO ₂ M, a hydroxy group, a formyl base or an amino group, or an epoxy, acrylate One selected from the group consisting of alkyl, halogen, CN, OR ₁₆ , SR ₁₇ , carbonyl group, sulfonic acid group and NR ₁₈ R ₁₉ R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ may each independently be hydrogen, halogen atom or carbon number 1 to 1 and may be selected from phenyl or aromatic hydrocarbon which may be substituted by one or more substituents. 30 is a monovalent or divalent hydrocarbon group, and —CH ₂ — constituting the hydrocarbon group is converted into an oxygen atom, a sulfur atom, an amino group or a carbonyl group, or the hydrocarbon group The contained hydrogen atom 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, a hydroxy group, a formyl base or an amino group, or an epoxy or acrylate group. it contains a reactive group; or an alkenyl having 1 to 30 carbon atoms, a halogen atom, a cyano group, a nitro group, a carbonyl group, a sulfonic acid _group, -SO 3 M, -CO ₂ M, a hydroxy group, a formyl base, or a phenyl or aromatic hydrocarbon group containing one or more substituents selected from the group of amino groups, R ₁ and R ₄ are bonded to form a 5- to 7-membered ring A nitrogen-containing heterocycle may be formed or each may be independently cycloalkyl, M is an alkali metal atom, and n is 0-5.

The specific compound of Formula 2 may be expressed as follows:

[Chemical formula 3]
In 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 group having 1 to 30 carbon atoms, or A hydrocarbon group that is a divalent substituted or unsubstituted hydrocarbon, and —CH ₂ — constituting the hydrocarbon group is such that carbon is converted to an oxygen atom, a sulfur atom, an amino group, or a carbonyl group, or the hydrocarbon group The hydrogen atom contained in is converted to a halogen atom, a cyano group, a nitro group, a carbonyl group, a sulfonic acid group, —SO ₃ M, —CO ₂ M, a hydroxy group, a formyl base or an amino group, or an epoxy, acrylate one of alkyl, _{halogen, CN,} oR 16, _{SR 17,} a carbonyl group, selected from the group consisting of sulfonic acid group and _NR 18 _{R 19;} if containing a reactive group Obtained is selected from a phenyl or aromatic hydrocarbons may be substituted by the above _{substituents, R 16, R 17, R} 18 and _{R 19} are each independently hydrogen, halogen atom or C1-30 Or —CH ₂ — constituting the hydrocarbon group is converted into an oxygen atom, a sulfur atom, an amino group or a carbonyl group, or is included in the hydrocarbon group. The hydrogen atom 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, a hydroxy group, a formyl base or an amino group, or an epoxy or acrylate reaction. or containing groups; or an alkenyl having 1 to 30 carbon atoms, a halogen atom, a cyano group, a nitro group, a carbonyl group, a sulfonic acid _group, -SO 3 _{M, -CO} 2 M Hydroxy groups, include one or more containing a substituent phenyl or aromatic hydrocarbon radical selected from the group of formyl base or amino group, R ₆ and R ₇ are the nitrogen-containing bond to 5-7 membered ring It may form a heterocycle or may each independently be cycloalkyl, M is an alkali metal atom, and n is 0-5.

The specific compound of Formula 3 may be expressed as follows:

[Chemical formula 4]
In 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, C 1-30 monovalent or 2 Is a valently substituted or unsubstituted hydrocarbon group, and —CH ₂ — constituting the hydrocarbon group is converted to an oxygen atom, a sulfur atom, an amino group, or a carbonyl group, or the hydrocarbon group The contained hydrogen atom 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, a hydroxy group, a formyl base or an amino group, or an epoxy or acrylate group. Containing a reactive group; selected from the group consisting of alkyl, halogen, CN, OR ₁₆ , SR ₁₇ , carbonyl group, sulfonic acid group and NR ₁₈ R ₁₉ R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ may each independently be hydrogen, halogen atom or carbon number 1 and may be selected from phenyl or aromatic hydrocarbon which may be substituted by one or more substituents. To 30 monovalent or divalent hydrocarbon group, and —CH ₂ — constituting the hydrocarbon group is a group in which carbon is converted into an oxygen atom, a sulfur atom, an amino group or a carbonyl group, or the hydrocarbon group The hydrogen atom contained in is converted to a halogen atom, a cyano group, a nitro group, a carbonyl group, a sulfonic acid group, —SO ₃ M, —CO ₂ M, a hydroxy group, a formyl base or an amino group, or an epoxy, acrylate reaction or containing groups; or an alkenyl having 1 to 30 carbon atoms, a halogen atom, a cyano group, a nitro group, a carbonyl group, a sulfonic acid _group, -SO 3 M, -CO M, hydroxy groups, include one or more containing a substituent phenyl or aromatic hydrocarbon radical selected from the group of formyl base or amino group, R ₁₄ and R ₁₅ are 5- to 7-membered ring bonded A nitrogen-containing heterocycle may be formed or each may be independently cycloalkyl, M is an alkali metal atom, and n is 0-5.

The specific compound of Formula 4 may be expressed as follows:

  In still another embodiment of the present invention, the compound represented by Chemical Formula 1 is 0.01 to 40 parts by weight, preferably 0.1 to 40 parts by weight, based on 100 parts by weight of the whole colored photosensitive resin composition. More preferably, it may be contained at 0.1 to 30 parts by weight.

  When the compound represented by Formula 1 is included 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 colored photosensitive resin composition further includes at least one selected from the group consisting of a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent.

Binder Resin The binder resin usually has reactivity and alkali solubility due to the action of light or heat, and acts as a dispersion medium for the coloring material.

  Examples of the binder resin include a carboxy group-containing monomer and a copolymer with another monomer copolymerizable with this monomer. Examples of the carboxy group-containing monomer include unsaturated carboxylic acids such as unsaturated polycarboxylic acids having one or more carboxy groups in the molecule such as unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated tricarboxylic acids. An acid etc. are mentioned.

  Here, 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, and mesaconic acid. The unsaturated polyvalent carboxylic acid can be an acid anhydride, and specific examples include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like.

  Further, the unsaturated polyvalent carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester such as oxalic acid mono (2-acryloyloxyethyl), oxalic acid mono (2-methacryloyloxyethyl), or phthalic acid monoester. (2-acryloyloxyethyl), mono (2-methacryloyloxyethyl) phthalate and the like. The unsaturated polycarboxylic acid can be a mono (meth) acrylate of a dicarboxy polymer at both terminals, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. These carboxy group-containing monomers can be used alone or in admixture of two or more. Examples of other monomers copolymerizable with the carboxy group-containing monomer include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o- Methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p- Aromatic vinyl compounds such as vinyl benzyl glycidyl ether and indene; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propiyl Methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxyethyl acrylate, 2- Hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl Methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate , Allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol Acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, Sobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy- Unsaturated carboxylic acid esters such as 3-phenoxypropyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2- Aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopro Unsaturated carboxylic acid aminoalkyl esters such as dimethyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate and 3-dimethylaminopropyl methacrylate; unsaturated carboxylic acids such as glycidyl acrylate and glycidyl methacrylate Glycidyl esters; carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether; acrylonitrile, methacrylonitrile, α -Vinyl cyanide compounds such as chloroacrylonitrile and vinylidene cyanide; acrylamide, methacrylamide, α-chloroacrylamide, N-2 Unsaturated amides such as hydroxyethyl acrylamide, N-2-hydroxyethyl methacrylamide; maleimide, pen Jill maleimide, N- phenylmaleimide. Unsaturated imides such as N-cyclohexylmaleimide; aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene; and polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly Examples thereof include giant monomers having a monoacryloyl group or a monomethacryloyl group at the end of the polymer molecular chain of -n-butyl methacrylate and polysiloxane. These monomers can be used alone or in admixture of two or more. In particular, as other monomers copolymerizable with the carboxy group-containing monomer, a monomer having a norbornyl skeleton, a monomer having an adamantane skeleton, a monomer having a rosin skeleton, etc. Is preferable because it tends to lower the specific dielectric constant.

  The binder resin of the present invention preferably has an acid value in the range of 20 to 200 (KOH mg / g). When the acid value is within the above range, the solubility in the developer is improved, the unexposed portion is easily dissolved and the sensitivity is increased, and as a result, the pattern of the exposed portion remains at the time of development and the remaining film ratio (film This is preferable because it improves the (retaining ratio). Here, the acid value is a value measured by the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the acrylic polymer, and is usually obtained by titration using an aqueous potassium hydroxide solution. Can do.

  The polystyrene-converted weight average molecular weight (hereinafter simply referred to as “weight average molecular weight”) measured by gel permeation chromatography (GPC; tetrahydrofuran is used as an elution solvent) is 3,000 to 200,000, preferably 5,000. Binder resins that are ~ 100,000 are preferred. When the molecular weight is in the above range, the hardness of the coating film is improved, the residual film ratio is high, the solubility of the unexposed portion in the developer 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, 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 can be excellent.

  The content of the binder resin of the present invention is preferably 1 to 60 parts by weight with respect to 100 parts by weight as a whole of the solid content in the colored photosensitive resin composition. When the content of the binder resin is included within the above range, the solubility in the developer is sufficient, so that development residues are hardly generated on the non-pixel portion of the substrate, and the film portion of the exposed portion is reduced during development. Is less likely to occur, and there is a tendency for the non-pixel portion to drop off.

Photopolymerizable compound The photopolymerizable compound is a compound that can be polymerized by the action of light and a photopolymerization initiator described later, and examples thereof include a monofunctional monomer, a bifunctional monomer, and other polyfunctional monomers. It is done.

  Specific examples of the monofunctional monomer include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinyl pyrrolidone, 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, and triethylene glycol di (meth) acrylate. Bis (acryloyloxyethyl) 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, dipentaerythritol penta (meth) acrylate, di Examples include pentaerythritol hexa (meth) acrylate. Of these, a polyfunctional monomer having two or more functional groups is preferably used.

  The photopolymerizable compound is preferably contained in an amount of 5 to 50 parts by weight, 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 the content of the photopolymerizable compound is included within the above range, the strength and smoothness of the pixel portion can be improved.

Photopolymerization initiator The photopolymerization initiator is not limited, but is at least one compound selected from the group consisting of triazine compounds, acetophenone compounds, biimidazole compounds, and oxime compounds. The photosensitive resin composition containing the photopolymerization initiator has high sensitivity, and the pixel pixel formed using this composition has good strength and pattern characteristics of the pixel portion.

  Further, if a photopolymerization initiator auxiliary agent is used in combination with the photopolymerization initiator, the photosensitive resin composition containing them becomes more sensitive, and the productivity when forming a color filter using this composition is improved. Since it improves, it is preferable.

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxy Naphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) ) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4- Bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2) -Methylphenyl Ethenyl] -1,3,5-triazine, such as 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl]. 2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- And oligomers of (4-morpholinophenyl) butan-1-one and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one.

  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′-tetra (alkoxyphenyl) biimidazole, 2,2′-bis ( 2-chlorophenyl) -4,4 ′, 5,5′-tetra (trialkoxyphenyl) biimidazole, imidazole compounds in which the phenyl group at the 4,4 ′, 5,5 ′ position is substituted by a carboalkoxy group Can be mentioned. Among these, 2,2′bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,3-dichlorophenyl) -4,4 ′, 5 , 5'-tetraphenylbiimidazole is preferably used.

  Moreover, as long as the effect of the present invention is not damaged, other photopolymerization initiators usually used in this field can be further included. Examples of other photopolymerization initiators include benzoin compounds, benzophenone compounds, thioxanthone compounds, and anthracene compounds. These can be used alone or in combination of two or more.

  Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. Examples of the benzophenone compounds include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl). ) Benzophenone, 2,4,6-trimethylbenzophenone, 4,4′-di (N, N′-dimethylamino) -benzophenone, and the like. Examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like. Examples of the anthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene and the like. In addition, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compound, etc. Are listed as other photopolymerization initiators.

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

  Specific examples of the amine compound among the photopolymerization initiation assistants include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4- Isoamyl dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (common name: Michler's ketone), 4 , 4′-bis (diethylamino) benzophenone and the like. As the amine compound, an aromatic amine compound is preferably used.

  Examples of carboxylic acid compounds include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N- Aromatic heteroacetic acids such as phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthoxyacetic acid can be mentioned.

  The content of the photopolymerization initiator in the colored photosensitive resin composition of the present invention is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the entire solid content in the colored photosensitive resin composition. More preferably, it is contained in 10 to 10 parts by weight. When the usage-amount of the said photoinitiator is contained in the said range, the photosensitive resin composition is made highly sensitive and the intensity | strength of a pixel part and the smoothness on the surface of this pixel part are excellent.

  Moreover, it is preferable that the usage-amount of a photoinitiation adjuvant is contained in 0.1-20 weight part with respect to 100 weight part of solid content whole in the said photosensitive resin composition, and is contained in 1-10 weight part. More preferably. When the usage-amount of the said photoinitiation adjuvant is contained in the said range, the sensitivity efficiency of the photosensitive resin composition will further increase, and the productivity of the color filter formed using this composition may be improved.

Solvent The solvent is not particularly limited, and various organic solvents used in the field of colored 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, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol. Diethylene glycol dialkyl ethers such as dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether Alkylene glycol alkyl ether acetates such as acetate, methoxybutyl acetate and methoxypentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene, ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone , Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin, esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, and cyclic esters such as γ-butyrolactone It is done.

  The solvent is preferably an organic solvent having a boiling point of 100 to 200 ° C., more preferably alkylene glycol alkyl ether acetates, ketones, 3-ethoxy. Examples include esters such as ethyl propionate and methyl 3-methoxypropionate, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate. Etc. These solvents can be used alone or in admixture of two or more.

  The content of the solvent in the colored photosensitive resin composition of the present invention is preferably 60 to 90 parts by weight, and 65 to 85 parts by weight with respect to 100 parts by weight of the entire colored photosensitive resin composition. Is more preferable. When the content of the solvent is within the above range, the coatability when applied by a coater such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes referred to as a die coater), or an ink jet. Can be good.

The colored photosensitive resin composition according to the additive present invention include antioxidants to enhance coatability or adhesion, adhesion promoter may further contain additives such as surfactants.

  The antioxidant may be one selected from the group consisting of benzotriazole-based light stabilizers, triazine-based light stabilizers, benzophenone-based, Hals light stabilizers, and combinations thereof. Is not to be done.

  The adhesion promoter may be added to enhance adhesion with the substrate, and is a reactive substituent selected from the group consisting of a carboxy group, a methacryloyl group, an isocyanate group, an epoxy group, and a combination thereof. However, the present invention is not limited to this. For example, the silane coupling agent may be trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxy. Examples thereof include silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like, which can be used alone or in combination of two or more.

  When the colored photosensitive resin composition according to the present invention contains the surfactant, there is an advantage that the coating property can be improved. For example, the surfactant is BM-1000, BM-1100 (BM Chemie), FLUORAD FC-135 / FC-170C / FC-430 (Sumitomo 3M), SH-28PA / -190 / SZ-6032 A fluorine-based surfactant such as (Toray Silicone Co., Ltd.) can be used, but is not limited thereto.

  In addition to this, the colored photosensitive resin composition according to the present invention may further contain an additive such as an ultraviolet absorber and an aggregation inhibitor as long as the effects of the present invention are not impaired. Those skilled in the art can appropriately add and use them as long as they do not impair the effects. For example, the additive is 0.05 to 10 parts by weight, specifically 0.1 to 10 parts by weight, more specifically 0.1 to 5 parts by weight based on 100 parts by weight of the whole colored photosensitive resin composition. Although it can be used by weight part, it is not limited to this.

<Color filter>
The present invention provides a color filter including a colored pattern produced from the colored photosensitive resin composition. That is, this invention includes the color filter manufactured using the said colored photosensitive resin composition. The color filter according to the present invention includes both the dye and the compound represented by the structure of Chemical Formula 1, and thus has an advantage of excellent reliability and contrast ratio without lowering the luminance.

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

  As the method for producing the color filter, a common method widely 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, a display device for a portable terminal such as a mobile phone, a digital display. Examples include display devices such as camera display devices and car navigation display devices, but are not limited thereto.

  The image display device of the present invention can be manufactured by a method generally known in the technical field of the present invention except that the image display device includes the color filter.

  Hereinafter, the present specification will be described in detail by way of examples in order to specifically describe the present specification. However, the embodiment according to the present specification can be modified into various other forms, and the scope of the present specification is not limited to the embodiment described below. The examples herein are provided to more fully explain the present specification to those skilled in the art. In the following, “%” and “parts” representing the contents are based on weight unless otherwise specified.

Synthesis example 1
A solution of 6 g of phosphotungstic acid hydrate (Aldrich, P4006) in 25 g of water was slowly dissolved in a solution in which 30 g of methanol was completely dissolved by adding 2 g of dodecylpyridinium chloride to 2 g of dodecylpyridinium chloride. It was dripped. After dropping, the mixture was stirred at 25 to 50 ° C. for 4 hours, and then 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. (Synthesized with reference to Eur. J. Inorg. Chem. 2014, 21-35)

[Chemical Formula A-1]

Synthesis example 2
By using tetrapropylammonium hydroxide (TCI, product number T0171) in place of dodecylpyridinium chloride, 7.3 g of the chemical formula A-2 was obtained in the same manner as in Synthesis Example 1.

[Chemical Formula A-2]

Synthesis Example 3: Synthesis of binder resin (B) 100 g of propylene glycol monomethyl ether acetate, 100 g of propylene glycol monomethyl ether and the atmosphere in the flask were added to a flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet tube. After changing from air to nitrogen, 8.2 g of azobisisobutyronitrile, 3.1 g of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.), 55.2 g of 2-ethylhexyl acrylate, 4-methyl Styrene 5.9 g, glycidyl methacrylate 85.2 g, and n-todecanethiol 6.0 g were added. Thereafter, the mixture was stirred to raise the temperature of the reaction solution to 80 ° C., and reacted for 4 hours.

  The temperature of the reaction solution was lowered to room temperature, and the atmosphere in the flask was replaced with air from nitrogen. Then, 0.2 g of triethylamine, 0.1 g of 4-methoxyphenol and 43.2 g of acrylic acid were added from the dropping funnel to 136 g of propylene glycol monomethyl ether acetate. And then dropped over 2 hours, followed by reaction at 100 ° C. for 6 hours. Thereafter, the temperature of the reaction solution was lowered to room temperature, 6.0 g of succinic anhydride was added, and the reaction was carried out at 80 ° C. for 6 hours.

  The acid value of the solid content 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 Tg was −12 ° C.

  The measurement of the weight average molecular weight (Mw) and horizontal bacterial molecular weight (Mn) of the alkali-soluble resin is performed under the following conditions using the GPC method. At this time, the obtained weight average molecular weight and horizontal bacterial molecular weight are measured. The ratio was the molecular weight distribution (Mw / Mn).

Equipment: HLC-8120GPC (manufactured by Tosoh Corporation)
Column: TSK-GELG4000HXL + TSK-GELG2000HXL (series connection)
Column temperature: 40 ° C
Moving bed solvent: Tetrahydrofuran Flow rate: 1.0 ml / min Injection volume: 50 μl
Detector: RI
Measurement sample concentration: 0.6% by weight (solvent = tetrahydrofuran)
Standard materials for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)

Production of colored photosensitive resin composition: Examples 1-3 and Comparative Examples 1-3
The colored photosensitive resin compositions according to Examples and Comparative Examples were produced as shown in Table 1 below. At this time, the solvent was contained in the balance so that the total amount of the colored photosensitive resin composition was 100 parts by weight. .

Color Filter (Glass Substrate) Production Example A color filter was produced using the colored photosensitive resin composition produced according to Examples and Comparative Examples. That is, each of the colored photosensitive resin compositions was applied onto a glass substrate by spin coating, and then placed on a heating plate and maintained at a temperature of 100 ° C. for 3 minutes to form a thin film. Subsequently, a test photomask having a pattern in which the transmittance is changed stepwise in the range of 1 to 100% and a line / space pattern of 1 μm to 50 μm is placed on the thin film, and the distance from the test photomask is set to 100 μm. And irradiated with ultraviolet rays. At this time, the ultraviolet light source is irradiated at an illuminance of 100 mJ / cm ² using a 1 kW high-pressure mercury lamp containing all g, h, and i rays, and no special optical filter is used. The thin film irradiated with ultraviolet rays was immersed in a KOH aqueous solution developing solution of pH 10.5 for 2 minutes for development. The glass plate covered with this thin film was washed with distilled water, dried by blowing nitrogen gas, 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 above was 2.0 μm.

Experimental example

(1) Thickening rate of colored photosensitive resin composition The initial viscosity (kinematic viscosity) A (mPa · s) of each colored photosensitive resin composition immediately after production according to Examples and Comparative Examples was measured.

  Thereafter, the colored photosensitive resin compositions according to Examples and Comparative Examples were allowed to stand for 1 day immediately after production in an environment of 25 ° C., and then the viscosity (dynamic viscosity) B ( mPa · s) was measured. The measurement of the viscosity (kinematic viscosity) of the colored photosensitive resin composition is based on JIS Z8809, using an E-type viscometer (trade name: RE-01, product of Donggi Sangyo Co., Ltd.) in an environment of 25 ° C. went. The thickening rate was calculated based on the following formula.

  Thickening rate = (viscosity after standing B) / (initial viscosity A)

  The results are shown in Table 2 below. The initial viscosities of Examples 1 to 3 are expressed as relative values when the initial viscosity of the colored photosensitive resin composition of Comparative Example 1 is defined as a standard (100), and the results are shown. It is shown in Table 2.

(2) Measurement of luminance (Y) The luminance (Y) of the colored glass plates according to Examples and Comparative Examples was measured as follows. The colored glass plate was set on a spectroscopic colorimeter (trade name: CM-3700d, Konica Minolta Sensing Co., Ltd.), and the transmission chromaticity at the X, Y, and Z coordinate axes at 2 degrees (°) of C light source was measured. . The Y value at this time was adopted as the luminance (Y). The results are shown in Table 2 below.

  In Table 2 below, the luminance values of Examples 1 to 3 are expressed as relative values when the luminance of the colored glass plate obtained using the colored photosensitive resin composition of Comparative Example 1 is standard (100). The results are shown in Table 2.

(3) Measurement of contrast The contrast of the colored glass plate (color filter) after post-baking according to Examples and Comparative Examples was measured using a contrast measuring device. Contrast measuring devices include a color luminance meter (trade name: LS-100, Konica Minolta Sensing Co., Ltd.), a lamp (trade name: HF-SL-100WLCG, a product of Johnton Sangyo Co., Ltd.) and a polarizing plate (trade name: POLAX-38S, Luceo product).

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

  A rotatable polarizing plate was installed on the top. After confirming that the brightness of the backlight is sufficiently stable, measure the brightness of the colored glass plate by adjusting the rotatable polarizing plate installed on the top to the crossed Nicol position, and then rotating it 90 degrees. The brightness of the colored glass plate was measured at the parallel position. The ratio (%) between the two was determined as contrast.

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

(4) Heat resistance measurement 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 required by the following saturation formula according to the CIE 1976 (L ^* , a ^* , b ^* ) space color system. The results are shown in Table 2. (New Color Science Handbook edited by Japanese Color Society (1985) p.266).

ΔE ^* _ab = {(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² } ^1/2

[Heat resistance evaluation criteria]
○: ΔE ^* _ab value: 3 or less Δ: ΔE ^* _ab value: 3 to 10 or less X: ΔE ^* _ab value: more than 10

  As shown in Table 2, it is confirmed that the colored photosensitive resin compositions of Examples 1 to 3 mixed with the composition according to the present invention can provide a heat-resistant and high-contrast color filter. be able to.

Claims (8)

Colored photosensitive resin composition comprising: a colorant comprising a dye; and a compound represented by the following chemical formula 1:
[Chemical Formula 1]
(In Formula 1 above,
(X ⁺ ) is represented by any one of the following chemical formulas 2 to 4.
n is 1-10,
(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 2]
(In Formula 2 above,
Z is carbon, nitrogen, sulfur, phosphorus or iodine;
R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen, a halogen atom, or a monovalent or divalent hydrocarbon group having 1 to 30 carbon atoms, or a hydrocarbon group,
The —CH ₂ — constituting the hydrocarbon group is carbon converted to an oxygen atom, sulfur atom, amino group or carbonyl group, or the hydrogen atom contained in the hydrocarbon group is a halogen atom, cyano group, nitro group Carbonyl group, sulfonic acid group, —SO ₃ M, —CO ₂ M, hydroxy group, formyl base or amino group, or containing epoxy, acrylate reactive group;
Selected from phenyl or aromatic hydrocarbons that may be substituted by one or more substituents selected from the group consisting of alkyl, halogen, CN, OR ₁₆ , SR ₁₇ , carbonyl group, sulfonic acid group and NR ₁₈ R ₁₉ Can be a thing,
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,
The —CH ₂ — constituting the hydrocarbon group is carbon converted to an oxygen atom, sulfur atom, amino group or carbonyl group, or the hydrogen atom contained in the hydrocarbon group is a halogen atom, cyano group, nitro group Carbonyl group, sulfonic acid group, —SO ₃ M, —CO ₂ M, hydroxy group, formyl base or amino group, or containing epoxy, acrylate reactive group;
Selected from the group consisting of a halogen atom, a cyano group, a nitro group, a carbonyl group, a sulfonic acid group, —SO ₃ M, —CO ₂ M, a hydroxy group, a formyl base, or an amino group. A phenyl or aromatic hydrocarbon group containing one or more substituents,
R ₁ and R ₄ may combine to form a 5- to 7-membered nitrogen-containing heterocycle, or each independently can be cycloalkyl;
M is an alkali metal atom,
n is 0-5).
[Chemical formula 3]
(In Formula 3 above,
L is carbon or nitrogen, and R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are each independently substituted with hydrogen, a halogen atom, or C 1-30 monovalent or divalent, or An unsubstituted hydrocarbon group,
The —CH ₂ — constituting the hydrocarbon group is carbon converted to an oxygen atom, sulfur atom, amino group or carbonyl group, or the hydrogen atom contained in the hydrocarbon group is a halogen atom, cyano group, nitro group Carbonyl group, sulfonic acid group, —SO ₃ M, —CO ₂ M, hydroxy group, formyl base or amino group, or containing epoxy, acrylate reactive group;
Selected from phenyl or aromatic hydrocarbons that may be substituted by one or more substituents selected from the group consisting of alkyl, halogen, CN, OR ₁₆ , SR ₁₇ , carbonyl group, sulfonic acid group and NR ₁₈ R ₁₉ Can be a thing,
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,
The —CH ₂ — constituting the hydrocarbon group is carbon converted to an oxygen atom, sulfur atom, amino group or carbonyl group, or the hydrogen atom contained in the hydrocarbon group is a halogen atom, cyano group, nitro group Carbonyl group, sulfonic acid group, —SO ₃ M, —CO ₂ M, hydroxy group, formyl base or amino group, or containing epoxy, acrylate reactive group;
Selected from the group consisting of a halogen atom, a cyano group, a nitro group, a carbonyl group, a sulfonic acid group, —SO ₃ M, —CO ₂ M, a hydroxy group, a formyl base, or an amino group. A phenyl or aromatic hydrocarbon group containing one or more substituents,
R ₆ and R ₇ may combine to form a 5- to 7-membered nitrogen-containing heterocycle, or each independently can be cycloalkyl;
M is an alkali metal atom,
n is 0-5).
[Chemical formula 4]
(In Formula 4 above,
L is carbon, nitrogen or sulfur;
R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ and R ₁₅ are each independently hydrogen, a halogen atom, or a monovalent or divalent hydrocarbon group having 1 to 30 carbon atoms, or a hydrocarbon group,
The —CH ₂ — constituting the hydrocarbon group is carbon converted to an oxygen atom, sulfur atom, amino group or carbonyl group, or the hydrogen atom contained in the hydrocarbon group is a halogen atom, cyano group, nitro group Carbonyl group, sulfonic acid group, —SO ₃ M, —CO ₂ M, hydroxy group, formyl base or amino group, or containing epoxy, acrylate reactive group;
Selected from phenyl or aromatic hydrocarbons that may be substituted by one or more substituents selected from the group consisting of alkyl, halogen, CN, OR ₁₆ , SR ₁₇ , carbonyl group, sulfonic acid group and NR ₁₈ R ₁₉ Can be a thing,
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,
The —CH ₂ — constituting the hydrocarbon group is carbon converted to an oxygen atom, sulfur atom, amino group or carbonyl group, or the hydrogen atom contained in the hydrocarbon group is a halogen atom, cyano group, nitro group Carbonyl group, sulfonic acid group, —SO ₃ M, —CO ₂ M, hydroxy group, formyl base or amino group, or containing epoxy, acrylate reactive group;
Selected from the group consisting of a halogen atom, a cyano group, a nitro group, a carbonyl group, a sulfonic acid group, —SO ₃ M, —CO ₂ M, a hydroxy group, a formyl base, or an amino group. A phenyl or aromatic hydrocarbon group containing one or more substituents,
R ₁₄ and R ₁₅ may combine to form a 5- to 7-membered nitrogen-containing heterocycle, or each independently can be cycloalkyl;
M is an alkali metal atom,
n is 0-5).   The colored photosensitive resin composition according to claim 1, wherein the dye contains one or more compounds selected from the group consisting of xanthene, triarylmethane, coumarin and perylene compounds.   The colored photosensitive resin composition according to claim 1, wherein the colorant further contains a pigment.   The colored photosensitive resin composition according to claim 1, further comprising at least one selected from the group consisting of a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent.   2. The colored photosensitive resin composition according to claim 1, wherein the compound represented by Chemical Formula 1 is contained in an amount of 0.01 to 40 parts by weight with respect to 100 parts by weight of the entire colored photosensitive resin composition. .   The colored photosensitive resin composition according to claim 1, wherein the colorant is contained in an amount of 0.1 to 30 parts by weight with respect to 100 parts by weight of the entire colored photosensitive resin composition.   The color filter containing the hardened | cured material of the coloring photosensitive resin composition as described in any one of Claims 1-6.   An image display device comprising the color filter according to claim 7.