JP2018112736A - Coloring photosensitive resin composition, color filter produced therewith and image display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring photosensitive resin composition expressing high reliability and high contrast characteristics when applied to a color filter and an image display device therewith by containing a xanthene-based dye and compound.SOLUTION: A colorant containing a xanthene-based dye and a coloring photosensitive resin composition containing a compound represented by a chemical formula 2. (Chemical formula 2.)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 are usually spin-coated with 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 is patterned. After coating uniformly, the coating film formed by heating and drying (hereinafter sometimes referred to as pre-baking) is exposed and developed, and further heat-cured (hereinafter also referred to as post-baking) as necessary. It is manufactured by repeating the operation 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 incorporated in the color liquid crystal display device and used to color a display image, or is incorporated in the imaging device and is used to acquire a color image.

  Recently, a color filter with higher luminance has been demanded for power saving of a color liquid crystal display. Generally, 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 coatability 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, problems with low reliability and contrast often occur compared to the case where pigments are usually applied. Therefore, development of a technique for solving the problems when using dyes is required.

  Korean Patent No. 2014-0115990 relates to a colored composition, a colored cured film, and a display element. (A) At least one compound selected from the group consisting of a xanthene compound, a polymethine compound, a coumarin compound and a perylene compound is used. A coloring composition comprising a coloring agent comprising (B) a binder resin and (C) a polymerizable compound, the content relating to the coloring composition further comprising (D) a transition metal compound (excluding the component (A)) Disclosure.

  Korean Patent No. 2015-0101934 relates to a colored composition, a colored cured film, and a display element, and is a colored composition containing (A) a colorant and (B) a polymerizable compound, and (A) the colorant is The content regarding the coloring composition containing the polymer which has the site | part which emits fluorescence, and the site | part which absorbs the fluorescence concerned is disclosed.

  However, the prior art may have disadvantages in luminance and reliability due to the unique color exhibited 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.)

  The present invention is intended to solve the above-described problems, and includes a xanthene dye and a compound expressed by a specific chemical formula, so that when applied to a color filter and an image display device including the same. The object is to provide a colored photosensitive resin composition exhibiting high reliability and 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 xanthene dye represented by the following chemical formula 1; and a compound represented by the following chemical formula 2. And

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

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

[Chemical formula 3]
In Formula 3,
Z is carbon, nitrogen, sulfur, phosphorus or iodine;
R ₈ , R ₉ , R ₁₀ and R ₁₁ are each independently hydrogen, a halogen atom, or a monovalent or divalent hydrocarbon group having 1 to 30 carbon atoms, which is substituted or unsubstituted,
The —CH ₂ — constituting the hydrocarbon group is a carbon atom converted by an oxygen atom, sulfur atom, amino group or carbonyl group, or a hydrogen atom contained in the hydrocarbon group is a halogen atom, a cyano group, a nitro group, group, a carbonyl group, a sulfonic acid _{group, -SO 3 M, -CO 2 M} , hydroxy group, or is transformed with a formyl group or an amino group, an epoxy, or contains a reactive group of acrylates;
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 ₂₃ , SR ₂₄ , carbonyl group, sulfonic acid group and NR ₂₅ R ₂₆ Can be a thing,
R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ are hydrogen, a halogen atom or a monovalent or divalent hydrocarbon group having 1 to 30 carbon atoms,
The —CH ₂ — constituting the hydrocarbon group is carbon converted by 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 group or amino group, or containing reactive group of epoxy, acrylate;
Is an alkenyl having 1 to 30 carbon atoms, or 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 group, or an amino group. A phenyl or aromatic hydrocarbon group containing one or more substituents,
R ₈ and R ₁₁ can 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,
L is carbon or nitrogen;
R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ are each independently hydrogen, a halogen atom, or a monovalent or divalent hydrocarbon group having 1 to 30 carbon atoms, which is substituted or unsubstituted. ,
The —CH ₂ — constituting the hydrocarbon group is carbon converted by 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 group or amino group, or containing reactive group of epoxy, acrylate;
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 ₂₃ , SR ₂₄ , carbonyl group, sulfonic acid group and NR ₂₅ R ₂₆ Can be a thing,
R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ are each independently hydrogen, a halogen atom or a monovalent or divalent hydrocarbon group having 1 to 30 carbon atoms,
The —CH ₂ — constituting the hydrocarbon group is carbon converted by 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 group or amino group, or containing reactive group of epoxy, acrylate;
Is an alkenyl having 1 to 30 carbon atoms, or 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 group, or an amino group. A phenyl or aromatic hydrocarbon group containing one or more substituents,
R ₁₃ and R ₁₄ 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 5]
In Formula 5,
L is carbon, nitrogen or sulfur;
R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ and R ₂₂ are each independently hydrogen, a halogen atom or a monovalent or divalent hydrocarbon group having 1 to 30 carbon atoms, which is substituted or unsubstituted,
The —CH ₂ — constituting the hydrocarbon group is carbon converted by 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 group or amino group, or containing reactive group of epoxy, acrylate;
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 ₂₃ , SR ₂₄ , carbonyl group, sulfonic acid group and NR ₂₅ R ₂₆ Can be a thing,
R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ are hydrogen, a halogen atom or a monovalent or divalent hydrocarbon group having 1 to 30 carbon atoms,
The —CH ₂ — constituting the hydrocarbon group is carbon converted by 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 group or amino group, or containing reactive group of epoxy, acrylate;
Is an alkenyl having 1 to 30 carbon atoms, or 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 group, or an amino group. A phenyl or aromatic hydrocarbon group containing one or more substituents,
R ₂₁ and R ₂₂ 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.

  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 it has high reliability without being reduced in luminance when applied to a color filter and an image display device having the same. Have the advantage of exhibiting high contrast and high contrast properties.

  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 does not exclude other components unless specifically stated to the contrary, and may include other components. To do.

<Colored photosensitive resin composition>
The colored photosensitive resin composition according to the present invention is characterized by containing a colorant containing a xanthene dye represented by Chemical Formula 1; and a compound represented by Chemical Formula 2.

Xanthene Dye Represented by Chemical Formula 1 The colorant according to the present invention includes a xanthene dye represented by the following Chemical Formula 1.

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

  As the commercially available xanthene dye, for example, “Chugai Aminol Fast Pink R—H / C” manufactured by Chugai Kasei Co., Ltd., “Rhodamine 6G” manufactured by Taoka Chemical Co., Ltd.] can be used. It is also possible to synthesize a commercially available xanthene dye as a starting material. In addition, Rhodamine B can be purchased and used.

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

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

  When the colorant contains a xanthene dye represented by Chemical Formula 1 and a compound represented by Chemical Formula 2, there is an advantage that it is possible to provide a colored photosensitive resin composition excellent in reliability and contrast.

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

  Examples of the triarylmethane dye include basic blue 7 (solvent red 41), solvent violet 31 (solvent violet 31), solvent blue 5 (acid blue 90), and acid blue 90 (acid). blue 90) and solvent blue 128 may be used, but the present invention is not limited thereto.

  Examples of the phthalocyanine pigment include C.I. I. Pigment B15: 6, C.I. I. Pigment B16, C.I. I. Pigment B15: 3, C.I. I. Pigment B15: 4 can be used, but is not limited to this.

  Examples of the anthraquinone pigment include C.I. I. Pigment R177, C.I. I. Pigment R207, C.I. I. Pigment R172, C.I. I. Pigment R111, C.I. I. Pigment R119, C.I. I. Pigment R168, C.I. I. Pigment R172 or the like can be used, but is not limited thereto.

  Examples of the diketopyrrolopyrrole pigment include C.I. I. Pigment R254, C.I. I. Pigment R255, C.I. I. Pigment R264, C.I. I. Pigment R272 or the like can be used, but is not limited thereto.

  When the colorant according to the present invention further includes at least one selected from the group consisting of triarylmethane dyes, phthalocyanine pigments, anthraquinone pigments, and diketopyrrolopyrrole pigments, high reliability and high luminance characteristics There is an advantage that can be granted.

  The colorant according to the present invention may further contain a pigment known in the art. For example, color pigments classified as pigments by Color Index (published by The Society of Dyers and Colorists) can be mentioned.

  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 CI 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 color pigments such as CI Pigment Green 7, 19, 21, 26, 36, 58, and 59. 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 CI 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 a color pigment, the transmission spectrum can be easily optimized, and the light resistance and chemical resistance of the color filter are 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, cleaning treatment with an organic solvent or water for removing impurities, removal treatment by an ion exchange method of ionic impurities, or the like may be performed.

  In still another embodiment of the present invention, the colorant including the xanthene dye represented by Chemical Formula 1 is 0.1 to 30 parts by weight, preferably 100 parts by weight of the whole colored photosensitive resin composition, 1 to 15 parts by weight may be included.

  When the colorant is included in less than the above range, the coloring power may be slightly reduced. When the colorant is included in excess of the above range, the solvent resistance or adhesion may be decreased, which may be undesirable in terms of process. Therefore, it is preferably included within the above range.

Compound Represented by Chemical Formula 2 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 2.

[Chemical formula 2]
In Formula 2,
(X ⁺ ) is represented by any one of the following chemical formulas 3 to 5.
n is 1-10, m and n are the same,
(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.
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 3]
In Formula 3,
Z is carbon, nitrogen, sulfur, phosphorus or iodine;
R ₈ , R ₉ , R ₁₀ and R ₁₁ are each independently hydrogen, a halogen atom, or a monovalent or divalent hydrocarbon group having 1 to 30 carbon atoms, which is substituted or unsubstituted,
The —CH ₂ — constituting the hydrocarbon group is carbon converted by 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 group or amino group, or containing reactive group of epoxy, acrylate;
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 ₂₃ , SR ₂₄ , carbonyl group, sulfonic acid group and NR ₂₅ R ₂₆ Can be a thing,
R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ are each independently hydrogen, a halogen atom or a monovalent or divalent hydrocarbon group having 1 to 30 carbon atoms,
The —CH ₂ — constituting the hydrocarbon group is carbon converted by 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 group or amino group, or containing reactive group of epoxy, acrylate;
Is an alkenyl having 1 to 30 carbon atoms, or 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 group, or an amino group. A phenyl or aromatic hydrocarbon group containing one or more substituents,
R ₈ and R ₁₁ can 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 specific compound of Formula 3 may be expressed as follows:

[Chemical formula 4]
In Formula 4,
L is carbon or nitrogen;
R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ are each independently hydrogen, a halogen atom, or a monovalent or divalent hydrocarbon group having 1 to 30 carbon atoms, which is substituted or unsubstituted. ,
The —CH ₂ ^— constituting the hydrocarbon group is a carbon atom converted by an oxygen atom, sulfur atom, amino group or carbonyl group, or a hydrogen atom contained in the hydrocarbon group is a halogen atom, a cyano group, a nitro group, group, a carbonyl group, a sulfonic acid _{group, -SO 3 M, -CO 2 M} , hydroxy group, or is transformed with a formyl group or an amino group, an epoxy, or contains a reactive group of acrylates;
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 ₂₃ , SR ₂₄ , carbonyl group, sulfonic acid group and NR ₂₅ R ₂₆ Can be a thing,
R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ are each independently hydrogen, a halogen atom or a monovalent or divalent hydrocarbon group having 1 to 30 carbon atoms,
The —CH ₂ — constituting the hydrocarbon group is carbon converted by 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 group or amino group, or containing reactive group of epoxy, acrylate;
Is an alkenyl having 1 to 30 carbon atoms, or 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 group, or an amino group. A phenyl or aromatic hydrocarbon group containing one or more substituents,
R ₁₃ and R ₁₄ 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 specific compound of Formula 4 may be expressed as follows:

[Chemical formula 5]
In Formula 5,
L is carbon, nitrogen or sulfur;
R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ and R ₂₂ are each independently hydrogen, a halogen atom or a monovalent or divalent hydrocarbon group having 1 to 30 carbon atoms, which is substituted or unsubstituted,
The —CH ₂ — constituting the hydrocarbon group is carbon converted by 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 group or amino group, or containing reactive group of epoxy, acrylate;
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 ₂₃ , SR ₂₄ , carbonyl group, sulfonic acid group and NR ₂₅ R ₂₆ Can be a thing,
R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ are each independently hydrogen, a halogen atom or a monovalent or divalent hydrocarbon group having 1 to 30 carbon atoms,
The —CH ₂ — constituting the hydrocarbon group is carbon converted by 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 group or amino group, or containing reactive group of epoxy, acrylate;
Is an alkenyl having 1 to 30 carbon atoms, or 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 group, or an amino group. A phenyl or aromatic hydrocarbon group containing one or more substituents,
R ₂₁ and R ₂₂ 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 specific compound of Formula 5 may be expressed as follows:

  Although not wishing to be bound by theory, the compound having the structure of the chemical formula 2 is hardly absorbed in the visible light region (380 to 780 nm), so that it represents white so that a color filter and an image display device having the color filter are provided. When applied to the above, it is possible to show high reliability and high contrast characteristics without lowering the luminance due to the influence of the transmission spectrum.

  In still another embodiment of the present invention, the compound represented by Chemical Formula 2 is 0.01 to 50 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 Chemical Formula 2 is included within the above range, there is an advantage that reliability and high contrast characteristics can be imparted without lowering the luminance due to the influence of the spectrum. In particular, the colored photosensitive resin composition according to the present invention has advantages of excellent reliability and contrast when used together with the xanthene-based dye represented by Formula 1 that has absorption or fluorescence in the visible light region of 380 to 780 nm. is there.

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

[Mathematical Formula 1]
0.4 ≦ weight of the compound represented by Formula 2 / weight of the xanthene dye represented by Formula 1 ≦ 20

  When the weight ratio of the xanthene dye represented by the chemical formula 1 and the compound represented by the chemical formula 2 satisfies the mathematical formula 1, it is excellent in terms of high CR (Contrast), high reliability, and processability. There is. When the weight ratio is less than the mathematical formula, satisfaction of high CR may be somewhat difficult, and when it exceeds the range, the processability may be somewhat disadvantageous. Therefore, it is preferable to satisfy the range.

  In still another embodiment of the present invention, the colored photosensitive resin composition further includes one or more 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 and 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), 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 ends, 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. Other monomers copolymerizable with the carboxy group-containing monomer include, for example, styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o -Methoxy styrene, m-methoxy styrene, p-methoxy styrene, 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-pro 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-hydroxy Butyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate Rate, 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 Isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadiethyl methacrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3 -Unsaturated carboxylic acid esters such as phenoxypropyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-amino Propyl 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, benzyl 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. The body is preferred because it tends to lower the non-dielectric constant value.

  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 in order to improve the retaining ratio. Here, the acid value is a value measured as 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. it can.

  Further, the polystyrene-equivalent 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, Binder resins that are from 000 to 100,000 are preferred. When the molecular weight is in the above range, the hardness of the coating film is improved, the remaining 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, 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 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 within the above range, the development residue is hardly generated on the substrate of the non-pixel portion because the solubility in the developer is sufficient, and the film thickness of the pixel portion of the exposed portion is reduced during development. Therefore, the non-pixel portion tends to drop off easily.

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, polyfunctional monomers having two or more functional groups are 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.

  In addition, when 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. 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- ( 4-morpholinophenyl) butan-1-one, oligomers of 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one, and the like.

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,3-dichlorophenyl) -4, 4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-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. Of 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, anthracene compounds, and the like. These may 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). Examples include benzophenone, 2,4,6-trimethylbenzophenone, 4,4′-di (N, N′-dimethylamino) -benzophenone. 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. Can be mentioned 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. An aromatic amine compound is preferably used as the amine compound.

  Examples of carboxylic acid compounds include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthio Aromatic heteroacetic acids such as acetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, nabutylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like 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 becomes highly sensitive and is excellent in the intensity | strength of a pixel part, and the smoothness on this pixel part surface.

  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 become higher, and the productivity of the color filter formed using this composition may improve.

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-ethoxypropionic acid, in terms of coating properties and drying properties. And esters such as ethyl and methyl 3-methoxypropionate, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate and the like. Can be mentioned. 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 preferably 65 to 85 parts by weight with respect to 100 parts by weight of the entire colored photosensitive resin composition. More preferred. When the content of the solvent is within the above range, the coatability is good when applied by a coating device such as a roll coater, a spin coater, a slit and spin coater, a 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, but is not limited thereto. It is not something.

  The adhesion promoter may be added to enhance adhesion to the substrate and has a reactive substituent selected from the group consisting of a carboxy group, a methacryloyl group, an isocyanate group, an epoxy group, and combinations thereof. A silane coupling agent may be included, but is not limited thereto. For example, the silane coupling agent may be trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane. , Β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like, and these 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), Florard FC-135 / FC-170C / FC-430 (Sumitomo 3M), SH-28PA / -190 / SZ-. A fluorine-based surfactant such as 6032 (Toray Silicon 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, and 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 the xanthene dye represented by the chemical formula 1 and the compound represented by the structure of the chemical formula 2 and thereby has an advantage of excellent reliability and contrast ratio without lowering luminance. is there.

  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, a glass having excellent chemical stability and high strength can be used. A partition wall may be further formed between the colored patterns, and a black matrix may 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 color filter is provided.

  Hereinafter, the present specification will be described in detail by way of examples in order to specifically describe the present specification. However, the examples according to the present specification may be modified in various other forms, and the scope of the present specification is not construed to be limited to the examples described in detail 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: 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 introduction 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 temperature of the reaction solution was raised to 80 ° C. while stirring and reacted for 4 hours.

  After lowering the temperature of the reaction solution to room temperature and replacing the atmosphere of the flask with nitrogen to air, 0.2 g of triethylamine, 0.1 g of 4-methoxyphenol and 43.2 g of acrylic acid were added together with 136 g of propylene glycol monomethyl ether acetate from the dropping funnel. After dripping over 2 hours, it was made to react at 100 degreeC 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 mixture was reacted at 80 ° C. for 6 hours.

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

The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the alkali-soluble resin was performed using 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 determined. The molecular weight distribution (Mw / Mn) was used.
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 and 2 and Comparative Examples 1 to 5
The colored photosensitive resin compositions according to Examples and Comparative Examples were produced according to the compositions shown in Table 1 below. At this time, the solvent was included in the balance so that the colored photosensitive resin composition was 100 parts by weight as a whole.

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 so that the distance from the test photomask is 100 μm. And irradiated with ultraviolet rays. At this time, the ultraviolet light source was irradiated with an illuminance of 100 mJ / cm ² using a 1 kW high-pressure mercury lamp containing all of g, h, and i rays, and no special optical filter was used. The thin film irradiated with ultraviolet rays was immersed in a KOH aqueous solution developing solution having a pH of 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 produced 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 (kinematic viscosity) of each colored photosensitive resin composition after standing. B (mPa · s) was measured. The viscosity (kinematic viscosity) of the colored photosensitive resin composition is measured at 25 ° C. using an E-type viscometer (trade name: RE-01, product of Donggi Sangyo Co., Ltd.) in accordance with JIS Z8809. I went there. 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, and the initial viscosities of Examples 1 and 2 were expressed as relative values when the initial viscosity of the colored photosensitive resin composition of Comparative Example 1 was taken as the standard (100).

(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 in a spectrocolorimeter (trade name: CM-3700d, Konica Minolta Sensing Co., Ltd.), and the transmission chromaticity was measured on the X, Y, and Z coordinate axes at a C light source of 2 degrees (°). . 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 and 2 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 device is a color luminance meter (trade name: LS-100, Konica Minolta Sensing Co., Ltd. product), lamp (trade name: HF-SL-100 WLCG, product of Johnton Sangyo Co., Ltd.) and 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 was 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 in parallel. The brightness of the colored glass plate was measured at the position. The ratio (%) between the two was determined as contrast.

  The results are shown in Table 2 below. The contrast values of Examples 1 and 2 are relative values when the contrast 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.

(4) Measurement of heat resistance 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 (Showa 60) 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, the colored photosensitive resin compositions of Examples 1 and 2 mixed with the composition according to the present invention can provide a color filter having excellent luminance but also heat resistance and high contrast. Can be confirmed. In particular, in Comparative Examples 3, 4, and 5 that did not contain the xanthene dye according to the present invention, it was confirmed that the luminance was not excellent.

Claims (8)

A coloring agent comprising a xanthene dye represented by the following chemical formula 1; and a colored photosensitive resin composition comprising a compound represented by the following chemical formula 2:
[Chemical Formula 1]
In Formula 1,
Each of R _{1 to} R ₄ independently represents a hydrogen atom, —R _6, or an aromatic hydrocarbon group having 6 to 10 carbon atoms;
R ₁ and R ₂ and R ₃ and R ₄ can be bonded to each other to form a 6-membered to 10-membered ring,
The hydrogen atom contained in the aromatic hydrocarbon group having 6 to 10 carbon atoms or the 6 to 10 membered ring is a halogen atom, —R ₆ , —OH, —OR ₆ , —SO ₃ ^— or —SO ₃ Na. _{, -CO 2 H, -CO 2 R} 6, -SO 3 H, unsubstituted or substituted with _-SO 3 _{R 6,} or _-SO 2 NHR _7,
R ₅ is —SO ₃ ^— , —SO ₃ Na, —CO ₂ H, —CO ₂ R ₆ , —SO ₃ H or —SO ₂ NHR ₇ ;
R ₆ is a saturated hydrocarbon group having 1 to 10 carbon atoms,
The hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms is substituted or unsubstituted with -OR ₆ or a halogen atom,
R ₇ is a hydrogen atom, —R ₆ , —CO ₂ R ₆ , an aromatic hydrocarbon group having 6 to 10 carbon atoms,
The hydrogen atom contained in the aromatic hydrocarbon group having 6 to 10 carbon atoms is substituted or unsubstituted with —R ₆ or —OR ₆ ;
A is an ion selected from the group consisting of a halogen anion, ClO ₄ ⁻ , BF ₄ ⁻ , SbF ₆ ⁻ , CF ₃ CO ₂ ⁻ , CF ₃ SO ₃ ⁻ , and N (SO ₂ CF ₃ ) ₂ ^—. Yes,
p is an integer of 1 to 5, provided that when p is an integer of 2 or more, the plurality of R ₅ are the same or different from each other;
q is an integer of 0 or 1,
However, the number of + charges and the number of − charges in the compound represented by Formula 1 are the same,
[Chemical formula 2]
In Formula 2,
(X ⁺ ) is represented by any one of the following chemical formulas 3 to 5.
n is 1-10, m and n are the same,
(Y) ^m− is an anion having at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and an oxygen atom;
[Chemical formula 3]
In Formula 3,
Z is carbon, nitrogen, sulfur, phosphorus or iodine;
R ₈ , R ₉ , R ₁₀ and R ₁₁ are each independently hydrogen, a halogen atom, or a monovalent or divalent hydrocarbon group having 1 to 30 carbon atoms, which is substituted or unsubstituted,
The —CH ₂ — constituting the hydrocarbon group is carbon converted by 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 group or amino group, or containing reactive group of epoxy, acrylate;
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 ₂₃ , SR ₂₄ , carbonyl group, sulfonic acid group and NR ₂₅ R ₂₆ Can be a thing,
R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ are hydrogen, a halogen atom or a monovalent or divalent hydrocarbon group having 1 to 30 carbon atoms,
The —CH ₂ — constituting the hydrocarbon group is carbon converted by 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 group or amino group, or containing reactive group of epoxy, acrylate;
Is an alkenyl having 1 to 30 carbon atoms, or 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 group, or an amino group. A phenyl or aromatic hydrocarbon group containing one or more substituents,
R ₈ and R ₁₁ can 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,
L is carbon or nitrogen;
R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ are each independently hydrogen, a halogen atom, or a monovalent or divalent hydrocarbon group having 1 to 30 carbon atoms, which is substituted or unsubstituted. ,
The —CH ₂ — constituting the hydrocarbon group is carbon converted by 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 group or amino group, or containing reactive group of epoxy, acrylate;
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 ₂₃ , SR ₂₄ , carbonyl group, sulfonic acid group and NR ₂₅ R ₂₆ Can be a thing,
R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ are each independently hydrogen, a halogen atom or a monovalent or divalent hydrocarbon group having 1 to 30 carbon atoms,
The —CH ₂ — constituting the hydrocarbon group is carbon converted by 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 group or amino group, or containing reactive group of epoxy, acrylate;
Is an alkenyl having 1 to 30 carbon atoms, or 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 group, or an amino group. A phenyl or aromatic hydrocarbon group containing one or more substituents,
R ₁₃ and R ₁₄ 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 5]
In Formula 5,
L is carbon, nitrogen or sulfur;
R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ and R ₂₂ are each independently hydrogen, a halogen atom or a monovalent or divalent hydrocarbon group having 1 to 30 carbon atoms, which is substituted or unsubstituted,
The —CH ₂ ^— constituting the hydrocarbon group is carbon converted by 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 group or amino group, or containing reactive group of epoxy, acrylate;
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 ₂₃ , SR ₂₄ , carbonyl group, sulfonic acid group and NR ₂₅ R ₂₆ Can be a thing,
R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ are hydrogen, a halogen atom or a monovalent or divalent hydrocarbon group having 1 to 30 carbon atoms,
The —CH ₂ — constituting the hydrocarbon group is carbon converted by 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 group or amino group, or containing reactive group of epoxy, acrylate;
Is an alkenyl having 1 to 30 carbon atoms, or 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 group, or an amino group. A phenyl or aromatic hydrocarbon group containing one or more substituents,
R ₂₁ and R ₂₂ 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.   2. The colored photosensitive resin according to claim 1, wherein the colorant further contains at least one selected from the group consisting of triarylmethane dyes, phthalocyanine pigments, anthraquinone pigments, and diketopyrrolopyrrole pigments. Composition.   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.   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.   2. The colored photosensitive resin composition according to claim 1, wherein the compound represented by Chemical Formula 2 is contained in an amount of 0.01 to 50 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 weight ratio of the xanthene dye represented by the chemical formula 1 and the compound represented by the chemical formula 2 satisfies the following mathematical formula 1:
[Mathematical Formula 1]
0.4 ≦ weight of the compound represented by Formula 2 / weight of the xanthene dye represented by Formula 1 ≦ 20   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.