KR20130014390A - Colored curable resin composition - Google Patents

Abstract

PURPOSE: A colored curable resin composition is provided to have excellent development property, and to optimize transmission spectrum of a color filter. CONSTITUTION: A colored curable resin composition comprises a fluorescent dye(A1), a coloring agent(a2), a polymerizable compound(C), and a polymerization initiator(D). When manufacturing first, second, and third compositions by using a raw material, optical properties of a layer formed of the compositions satisfies formula: F3/F1≤Te×Tf. In the formula, F1 and F3 are a maximum fluorescent strength of the first and third compositions at the maximum excitation wavelength(λ3), F3<F1, Te is a transmittance of the layer of the second composition at λ1, and Tf is a transmittance of the layer of the second composition at the wavelength of F1.

Description

Colored curable resin composition {COLORED CURABLE RESIN COMPOSITION}

The present invention relates to a colored curable resin composition.

In order to realize the high color reproducibility of a liquid crystal display panel, the high contrast of a color filter is calculated | required. Then, the colored curable resin composition which can manufacture such a color filter is proposed (nonpatent literature 1). The contrast of the color filter is an index indicating how large the difference in brightness between the light and dark areas is caused by the liquid crystal display panel. Contrast measures the brightness when the transmission axes of the two polarizing plates are parallel to each other and the brightness when they are orthogonal to each other when the color filters are irradiated with light from the sandwiching side of the two polarizing plates, and are represented by their ratios. Lose.

 Yoichi Kimura and four others, `` Contrast color filter resist for liquid crystal TV '', Hitachi Kasei Technical Report, Hitachi Kasei Senior High School, Ltd., January 2005, No. 44, p.17-20

The development of the colored curable resin composition which can manufacture the high contrast color filter is desired.

This invention provides the following [1]-[12].

[1] A fluorescent composition (A1), a coloring agent (A2) different from the fluorescent pigment, a resin (B), a polymerizable compound (C) and a polymerization initiator (D), the first composition using each of the above raw materials The colored curable resin composition in which the optical characteristic of the coating film formed from these compositions satisfy | fills Formula (X) when the 2nd composition and the 3rd composition are prepared.

F ₃ / F _One ≤T _e × T _f  (X)

Wherein (X) of the, F ₃ represents the maximum fluorescence intensity in the maximum excitation wavelength (λ ₃₎ of the coating (thickness is 3㎛) formed of a third composition; F ₁ represents the maximum fluorescence intensity at the maximum excitation wavelength λ ₁ of the coating film (thickness: 3 μm) formed of the first composition; Provided that F ₃ <F ₁ ; T _e represents a transmittance of a coating film (thickness: 3 µm) formed of the second composition in the lambda ₁ ;

T _f represents a transmittance of a coating film (thickness: 3 μm) formed of the second composition at the wavelength λ _{f1 at} which F ₁ is measured; The first composition comprises a fluorescent dye (A1), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), and the content of the fluorescent dye (A1) is a fluorescent dye (A1) and a resin (B). 2 mass% with respect to the total amount of the polymerizable compound (C) and the polymerization initiator (D); The said 2nd composition contains a coloring agent (A2), resin (B), a polymeric compound (C), and a polymerization initiator (D), and content of a coloring agent (A2) has a coloring agent (A2), resin (B), and a polymeric property. It is 2 mass% with respect to the total amount of a compound (C) and a polymerization initiator (D); The third composition comprises a fluorescent dye (A1), a coloring agent (A2), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), and the content of the fluorescent dye (A1) and the coloring agent (A2) 2 mass% with respect to the total amount of a fluorescent dye (A1), a coloring agent (A2), a resin (B), a polymerizable compound (C), and a polymerization initiator (D).]

[2] The colored curable resin composition according to [1], wherein F ₃ / F ₁ is 0.01 to 0.6.

[3] × T _e T _f is less than or equal to 0.7 [1] or colored curable resin composition according to [2].

[4] The colored curable resin composition according to any one of [1] to [3], wherein the fluorescent dye is a carbonium dye.

[5] The colored curable resin composition according to any one of [1] to [4], wherein the fluorescent dye is xanthene dye.

[6] The colored curable resin composition according to any one of [1] to [5], wherein the colorant (A2) has a maximum absorption wavelength in a range of 490 nm to 780 nm.

[7] The colored curable resin composition according to any one of [1] to [6], wherein the total content of the fluorescent dye (A1) and the coloring agent (A2) are 5-65 mass% with respect to the solid content of the colored curable resin composition.

[8] The colored curable resin composition according to any one of [1] to [7], wherein the content of the fluorescent dye (A1) is 1 to 99 mass% with respect to the total amount of the fluorescent dye (A1) and the coloring agent (A2).

[9] The colored curable resin composition according to any one of [1] to [8], wherein the coloring agent (A2) is a pigment and contains a pigment dispersant together with the pigment.

[10] The colored curable resin composition according to [9], wherein the amount of the pigment dispersant is 0.1 to 100 parts by mass with respect to 100 parts by mass of the pigment.

[11] A color filter formed of the colored curable resin composition according to any one of [1] to [10].

[12] A display device comprising the color filter according to [11].

(Effects of the Invention)

According to the colored curable resin composition of this invention, the color filter which is high contrast can be manufactured.

The colored curable resin composition of this invention contains fluorescent dye (A1), the coloring agent (A2) different from the said fluorescent dye, resin (B), a polymeric compound (C), and a polymerization initiator (D). And when the said colored curable resin composition prepares the 1st composition, 2nd composition, and 3rd composition using each said raw material, the optical characteristic of the coating film formed from these compositions satisfy | fills Formula (X), It is characterized by the above-mentioned. .

F ₃ / F _One ≤T _e × T _f  (X)

Wherein (X) of the, F ₃ represents the maximum fluorescence intensity in the maximum excitation wavelength (λ ₃₎ of the coating (thickness is 3㎛) formed of a third composition; F ₁ represents the maximum fluorescence intensity at the maximum excitation wavelength λ ₁ of the coating film (thickness: 3 μm) formed of the first composition; Provided that F ₃ <F ₁ ; T _e represents a transmittance of a coating film (thickness: 3 µm) formed of the second composition in the lambda ₁ ; T _f represents a transmittance of a coating film (thickness: 3 μm) formed of the second composition at the wavelength λ _{f1 at} which F ₁ is measured; The first composition comprises a fluorescent dye (A1), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), and the content of the fluorescent dye (A1) is a fluorescent dye (A1) and a resin (B). 2 mass% with respect to the total amount of the polymerizable compound (C) and the polymerization initiator (D); The said 2nd composition contains a coloring agent (A2), resin (B), a polymeric compound (C), and a polymerization initiator (D), and content of a coloring agent (A2) has a coloring agent (A2), resin (B), and a polymeric property. It is 2 mass% with respect to the total amount of a compound (C) and a polymerization initiator (D); The third composition comprises a fluorescent dye (A1), a coloring agent (A2), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), and the content of the fluorescent dye (A1) and the coloring agent (A2) 2 mass% with respect to the total amount of a fluorescent dye (A1), a coloring agent (A2), a resin (B), a polymerizable compound (C), and a polymerization initiator (D).]

In the color filter containing fluorescent dye, when used for a liquid crystal display device, the fluorescent dye in a color filter excites and fluoresces by the polarization which entered the color filter, for example. Therefore, in the color filter formed with the conventional colored curable resin composition, the phenomenon that the polarization emitted from the color filter is disturbed by the fluorescence generated from the fluorescent dye, the so-called depolarization of the polarization occurs, and the problem that contrast decreases have. In contrast, in the colored curable resin composition of the present invention, by using the fluorescent dye (A1) and the coloring agent (A2) in combination so as to satisfy the predetermined conditions, the fluorescence generated from the fluorescent dye (A1) by the coloring agent (A2) is reduced. Therefore, it can be set as the colored curable resin composition which can manufacture the color filter which is high contrast by using the colored curable resin composition of this invention.

In Formula (X), it means that the fluorescence derived from fluorescent dye (A1) is suppressed by the coloring agent (A2), so that F <_3> / F <_1> is small. In addition, when the fluorescence F ₃ emitted from the third composition is weak, "high contrast" is achieved. However, since the fluorescence intensity is a relative value, it was defined as the ratio with the fluorescence (F ₁ ) coming out of the first composition. In addition, in order to achieve high contrast, it is necessary to satisfy the maximum fluorescence intensity F ₃ of the third composition to be lower than the maximum fluorescence intensity F ₁ of the first composition, that is, F ₃ <F ₁ .

The value of F ₃ / F ₁ is not particularly limited as long as it satisfies the formula (X), but is preferably 0.6 or less, more preferably 0.4 or less, and still more preferably 0.2 or less. Contrast of the color filter obtained from colored curable resin composition becomes it still higher that F <_3> / F <_1> is in the said range. F ₃ / F ₁ is smaller the more preferable, the lower limit is, for example approximately 0.01, in particular may be 0.1 or so.

In Formula (X), when T _e is small, the excitation light of the fluorescent dye (A1) is absorbed by the colorant (A2) and the excitation of the fluorescent dye (A1) is suppressed, so that the fluorescence emitted from the coating film formed by the third composition is It will weaken. In addition, when T _f is small, the fluorescence emitted from the fluorescent dye (A1) is absorbed by the colorant (A2), so that the fluorescence emitted from the coating film formed by the third composition is weakened. Moreover, when either one of these was achieved, since the fluorescence emitted from the coating film formed by the 3rd composition was suppressed as a result, the product _Te * _Tf was prescribed | regulated.

The value of T _e × T _f is not particularly limited if satisfying the formula (X), is 0.7 or less and more preferably 0.6 or less, more preferably 0.5 or less. The value of T _e is preferably 0.95 or less, more preferably 0.9 or less, and still more preferably 0.85 or less. The value of T _f is preferably 0.9 or less, more preferably 0.7 or less, and still more preferably 0.5 or less.

Then, the contrast of the color filters obtained from the colored curable resin composition increases by the value of the T _e × _f T beyond the value of the F ₃ / F _1. The T _e × because the value of T _f to the F ₃ / F is fluorescence generated from the _first fluorescence dye (A1) in the colored curable resin is less than the color filter obtained from the composition value of the polarization extinction discarded blossomed lower the contrast.

The said 1st composition contains fluorescent dye (A1), resin (B), a polymeric compound (C), and a polymerization initiator (D). Content of fluorescent dye (A1) in the said 1st composition is 2 mass% in 100 mass% of total of fluorescent dye (A1), resin (B), a polymeric compound (C), and a polymerization initiator (D). The said 2nd composition contains a coloring agent (A2), resin (B), a polymeric compound (C), and a polymerization initiator (D). Content of a coloring agent (A2) in the said 2nd composition is 2 mass% in 100 mass% of total of a coloring agent (A2), resin (B), a polymeric compound (C), and a polymerization initiator (D). The third composition comprises a fluorescent dye (A1), a colorant (A2), a resin (B), a polymerizable compound (C) and a polymerization initiator (D). Content of fluorescent dye (A1) in the said 3rd composition is 2 mass in 100 mass% of total of fluorescent dye (A1), a coloring agent (A2), resin (B), a polymeric compound (C), and a polymerization initiator (D). %to be. In addition, in the said 3rd composition, content of a coloring agent (A2) is 2 in 100 mass% of total of fluorescent dye (A1), a coloring agent (A2), resin (B), a polymeric compound (C), and a polymerization initiator (D). Mass%.

The ratio of the resin (B), the polymerizable compound (C) or the polymerization initiator (D) to the total amount of the resin (B), the polymerizable compound (C) and the polymerization initiator (D) in the second composition is the first composition. The same thing as ratio in is preferable. In the third composition, the ratio of the resin (B), the polymerizable compound (C), or the polymerization initiator (D) to the total amount of the resin (B), the polymerizable compound (C), and the polymerization initiator (D) is determined. The same thing as the ratio in 1 composition is preferable.

It is preferable that content of resin (B) in the sum total of resin (B), a polymeric compound (C), and a polymerization initiator (D) in a 1st composition, a 2nd composition, and a 3rd composition is the same in all compositions. It is preferable that it is the ratio similar to the Example mentioned later specifically ,.

It is preferable that content of the polymeric compound (C) in the sum total of resin (B), a polymeric compound (C), and a polymerization initiator (D) in a 1st composition, a 2nd composition, and a 3rd composition is the same in all compositions. Do. It is preferable that it is the ratio similar to the Example mentioned later specifically ,.

It is preferable that content of the polymerization initiator (D) in the sum total of resin (B), a polymeric compound (C), and a polymerization initiator (D) in a 1st composition, a 2nd composition, and a 3rd composition is the same in all compositions. . It is preferable that it is the ratio similar to the Example mentioned later specifically ,.

Moreover, it is preferable that the said 1st composition, the 2nd composition, and the 3rd composition all contain the same solvent.

As a method of forming a coating film from the said 1st composition, the 2nd composition, and the 3rd composition, when using a photoinitiator as a polymerization initiator (D), for example, the thickness after postbaking a composition on a glass substrate will be set to 3 micrometers. The method of forming by spin-coating, prebaking, exposing, and postbaking is mentioned. Specifically, the method as described in the Example mentioned later is preferable.

The maximum fluorescence intensity is the maximum value of the fluorescence intensity in the fluorescence spectrum measured using light having a predetermined wavelength as excitation light. The maximum excitation wavelength is a wavelength of the excitation light whose maximum fluorescence intensity is the largest when the fluorescence spectrum is measured by shaking the wavelength of the excitation light and the maximum fluorescence intensity in each fluorescence spectrum is measured. These maximum excitation wavelengths and the maximum fluorescence intensity can be measured by a fluorescence spectrophotometer, and the detail of a measuring method is mentioned later.

Here, the fluorescence intensity is susceptible to the device. Therefore, under the same conditions as in the F ₁ and F ₃ is used for such apparatus, it is also preferable to measure in succession in order to reduce the measurement error.

The transmittance is the ratio (I / I ₀ ) of the intensity I of light passing through the coating film and the intensity I _{0 of} incident light. Transmittance can be measured with a colorimeter and a spectrophotometer, and the detail of a measuring method is mentioned later.

The fluorescent dye (A1) is not particularly limited as long as it is a dye that generates fluorescence by irradiating light. Fluorescent dyes and fluorescent pigments are mentioned as said fluorescent dye (A1), and fluorescent dye is preferable.

Examples of the fluorescent dyes include carbonium dyes, azo dyes, coumarin dyes, naphthalimide dyes, and the like. Specific examples of the carbonium dyes include diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, and acridine dyes. Among these, carbonium dye is preferable, and triphenylmethane dye and xanthene dye are more preferable.

As said fluorescent dye, the compound classified as dye in the color index (The Society of Dyers and Colorists publication), and the well-known dye described in the dyeing note (Shiksensha) are mentioned, for example.

Specific examples of such compounds include C.I. Acid yellow 3 (hereinafter, the description of C.I.Solvent Yellow is omitted, and description is based on the number only), 7, 250; C.I. Acid red 77; C.I. Acid blue 9; C.I. Basic yellow 1, 35, 40, 95; C.I. Basic red 1-1, 13; C.I. Basic violet 7, 11: 1; C.I. Basic orange 22; C.I. Basic blue 7; C.I. Basic Green 1; C.I. Disperse yellow 121, 82; C.I. Disperse orange 11; C.I. Disperse red 58; C.I. Disperse blue 7; C.I. Direct yellow 11, 24, 26, 85, 100, 147; C.I. Direct orange 8, 13, 26, 29: 1, 46; C.I. Direct red 1, 9, 17, 239, 240, 242, 254; C.I. Direct blue 22; C.I. Direct green 6; C.I. Solvent yellow 7, 44; C.I. Solvent red 49; C.I. Solvent blue 5; C.I. Solvent green 7 and the like.

Commercially available products of such compounds include Fluorescent series [Arimoto Kagaku Co., Ltd.], Rhodamine B, Rhodamine 6GCP [manufactured by Taoka Kagaku Kogyo Co., Ltd.], Quinoline Yellow SS-5G, Quinoline Yellow GC [Chuo Kosei Kagaku Co., Ltd.], Azosol Brilliant Yellow 4GF, Azosol Fast Blue GLA, Celliton Pink 3B, Fast Yellow YL, Victoria Blue FN, Brilliant Sulfo Flavin FF, Thioflavin, Basic Yellow HG, Fluorescein , Eosin and the like.

Moreover, xanthene dye (A11) which has a compound which has a xanthene skeleton in a molecule as a main component as said fluorescent dye is mentioned.

As said xanthene dye (A11), it is C.I. Acid red 51, 52 [formula (A1-2)], 87, 92, 94 (rose bengal), 289 [formula (A1-3)], 388, C.I. Acid violet 9, 30, 102, C.I. Basic Red 1 (Rhodamine 6G) [Formula (A1-4)], 8, C.I. Basic Violet 10 (Rhodamine B), C.I. Solvent Red 218, C.I. Modern Red 27, C.I. Reactive red 36 (rose bengal B), sulfo rhodamine G, the xanthene dye of Unexamined-Japanese-Patent No. 2010-32999, the xanthene dye of Unexamined-Japanese-Patent No. 4452760, etc. are mentioned.

Among these, as xanthene dye (A11), the dye containing the compound represented by Formula (1) (Hereinafter, it may be called "compound (1).") Is preferable. When using the said compound (1), 50 mass% or more of content of the compound (1) in xanthene dye is preferable, More preferably, it is 70 mass% or more, More preferably, it is 90 mass% or more. In particular, it is preferable to use only compound (1) as xanthene dye.

[In formula (1), R <^1> -R <^4> respectively independently represents a hydrogen atom and -R <^8> represents a C6-C10 monovalent aromatic hydrocarbon group.

R ⁵ is _{^{-OH, -SO 3 -, -SO 3}} H, -SO 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -SO 3 R 8 or -SO ₂ NR ⁹ R ¹⁰ is shown.

R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

m represents the integer of 0-5. When m is an integer of 2 or more, a plurality of R ⁵ are the same or different.

a represents the integer of 0 or 1.

X represents a halogen atom.

R <^8> represents a C1-C20 monovalent saturated hydrocarbon group, and the hydrogen atom contained in the said saturated hydrocarbon group may be substituted by the halogen atom.

Z ⁺ represents ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ .

R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and R ⁹ and R ¹⁰ may be bonded to each other to form a 3 to 10 membered heterocycle including a nitrogen atom.

R ¹¹ each independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.]

As a C6-C10 monovalent aromatic hydrocarbon group represented by R <^1> -R <^4> , a phenyl group, toluyl group, xylyl group, mesityl group, propylphenyl group, butylphenyl group, etc. are mentioned, for example.

R ¹ ~ R ⁴ group having a carbon number of the monovalent aromatic hydrocarbon group of 6 to 10 represented by a hydrogen atom is a halogen atom which comprises the aromatic hydrocarbon ^{groups, -R 8, -OH, -OR 8} , -SO 3 -, -SO 3 H, It may be substituted by -SO ₃ ^- Z ⁺ , -CO ₂ H, -CO ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ¹⁰ . Among these substituents _{^{-SO 3 -, -SO 3 H,}} -SO 3 - Z + and -SO ₂ NR ⁹ R ¹⁰ preferably at least one member selected from the group consisting of, and -SO ₃ ^- Z ⁺ and -SO ₂ NR R ⁹ is more preferably at least one member selected from the group consisting of ^10. As -SO ₃ ^- Z ^{+ in} this case, -SO _3- ⁺ N (R ¹¹ ) ₄ is preferable. When R <^1> -R <^4> is these groups, the colored curable resin composition containing a compound (1) can form the color filter which is less likely to generate | occur | produce foreign matter and is excellent in heat resistance.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ⁸ to R ¹¹ are methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, Linear alkyl groups such as hexadecyl group and isocyl group; Branched alkyl groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group and 2-ethylhexyl group; C3-C20 alicyclic saturated hydrocarbon groups, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a tricyclodecyl group, are mentioned.

Is - -CH ₂ also included R ^9, 1-valent saturated hydrocarbon group of 1 to 20 carbon atoms represented by the R ¹⁰ group may be substituted by hydrogen atoms are -OH, or a halogen atom contained to said saturated hydrocarbon, the saturated aliphatic hydrocarbon groups - O-, -CO-, -NH- or -NR ⁸ -may be substituted.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ⁶ and R ⁷ include those having 1 to 6 carbon atoms among the alkyl groups exemplified above.

Examples of the aralkyl group having 7 to 10 carbon atoms represented by R ¹¹ include a benzyl group, a phenylethyl group and a phenylbutyl group.

Z ⁺ is ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N (R ¹¹ ) ₄ .

As said ⁺ N (R <^11> ) _4, it is preferable that at least 2 of four R <^11> is a C5-C20 monovalent saturated hydrocarbon group. Moreover, 20-80 are preferable and, as for the total carbon number of four R <^11> , 20-60 are more preferable. If R <^11> is these groups, the colored curable resin composition containing a compound (1) can form a coating film and a pattern with few foreign substances.

1-4 are preferable and, as for m, 1 or 2 is more preferable.

As said xanthene dye (A11), the dye containing the compound represented by Formula (2) (hereinafter may be called "compound (2)") is more preferable. When using the said compound (2), 50 mass% or more of content of the compound (2) in xanthene dye is preferable, More preferably, it is 70 mass% or more, More preferably, it is 90 mass% or more. In particular, it is preferable to use only compound (2) as xanthene dye.

[Formula (2) of, R ²¹ ~ R ²⁴ each independently represents a monovalent aromatic hydrocarbon group of hydrogen, -R ^26, or 6 to 10 carbon atoms.

R ²⁵ represents —SO ₃ ^— , —SO ₃ H, —SO ₃ ^— Z 1 ^+, or —SO ₂ NHR ²⁶ .

m1 represents the integer of 0-5. When m1 is an integer of 2 or more, some R <^25> is the same or different.

a1 represents the integer of 0 or 1.

X1 represents a halogen atom.

R <^26> represents a C1-C20 monovalent saturated hydrocarbon group.

Z1 ⁺ represents ⁺ N (R ²⁷ ) ₄ , Na ⁺ or K ⁺ .

Each R ²⁷ independently represents a monovalent saturated hydrocarbon or benzyl group having 1 to 20 carbon atoms.]

As a C6-C10 monovalent aromatic hydrocarbon group represented by R <^21> -R <^24> , the group similar to what was illustrated as said aromatic hydrocarbon group in said R <^1> -R <^4> is mentioned. Hydrogen atoms contained to said aromatic hydrocarbon is -SO ₃ ^- may be substituted with Z1 ^+, -SO ₃ R ²⁶ or _{^{-SO 2 NHR 26 -, -SO 3}} H, -SO 3.

As a combination of R ²¹ to R ²⁴ , R ²¹ and R ²³ are hydrogen atoms, R ²² and R ²⁴ are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and the hydrogen atoms contained in the aromatic hydrocarbon group are -SO ₃ ^- ,- SO ₃ H, -SO ₃ ^- as Z1 ^+, -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ is preferably substituted. A more preferable combination is that R ²¹ and R ²³ are hydrogen atoms, R ²² and R ²⁴ are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and the hydrogen atoms contained in the aromatic hydrocarbon group are -SO ₃ ^- Z 1 ⁺ or -SO _2. It is substituted by NHR ²⁶ . If R <^21> -R <^24> is these groups, the colored curable resin composition containing a compound (2) can form the color filter excellent in heat resistance.

Examples of the C 1-20 monovalent saturated hydrocarbon group represented by R ²⁶ and R ²⁷ include the same groups as those exemplified as the saturated hydrocarbon group in R ⁸ to R ¹¹ .

R ²¹ ~ R ²⁴ -R in ²⁶ is preferably independently a hydrogen atom, methyl or ethyl. Further, as R ²⁶ in -SO ₃ R ^26, and -SO ₂ NHR ^26, and the branch chain alkyl group having 3 to 20 carbon atoms are preferred, the branched chain alkyl group having a carbon number of 6 to 12 and more preferably, the 2-ethylhexyl group, More preferred. When R <^26> is these groups, the colored curable resin composition containing a compound (2) can form the color filter with few generation | occurrence | production of a foreign material.

Z 1 ⁺ is ⁺ N (R ²⁷ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N (R ²⁷ ) ₄ .

The N ⁺ (R ²⁷⁾ R _4, as the four ²⁷ of the at least two of the monovalent saturated hydrocarbon group having a carbon number of 5-20 is preferable. Moreover, 20-80 are preferable and, as for the total carbon number of four R <^27> , 20-60 are more preferable. Colored curable resin composition in which R <^27> contains the compound (2) which is these groups can form the color filter with little generation | occurrence | production of a foreign material.

1-4 are preferable and, as for m1, 1 or 2 is more preferable.

As compound (2), the compound represented, for example by Formula (1-1)-Formula (1-23) is mentioned. In addition, in formula, R <^26> represents a C1-C20 monovalent saturated hydrocarbon group, Preferably it is a C6-C12 branched alkyl group, More preferably, it is a 2-ethylhexyl group. Among these, sulfonamides of CI acid red 289, quaternary ammonium salts of CI acid red 289, sulfonamides of CI acid violet 102 or quaternary ammonium salts of CI acid violet 102 are preferable. As such a compound, the compound etc. which are represented, for example by Formula (1-1)-Formula (1-8), Formula (1-11), and Formula (1-12) are mentioned.

It is preferable that the said xanthene dye (A11) has a maximum absorption wavelength in the range of 490 nm or more and 580 nm or less, More preferably, it is the range of 510 nm or more and 560 nm or less, More preferably, it is 520 nm or more and 540 nm or less Range. In addition, the maximum absorption wavelength can be calculated | required from the absorption spectrum which measured the solution which melt | dissolved dye in the solvent using the spectrophotometer.

The xanthene dye (A11) is a commercially available xanthene dye (for example, "Chugai Aminol Fast Pink RH / C" manufactured by Chuga Kasei Co., Ltd., "Rhodamin 6G" manufactured by Taoka Kagaku Kogyo Co., Ltd.). ) Can be used. In addition, commercially available xanthene dyes may be synthesized with reference to Japanese Patent Application Laid-Open No. 2010-32999.

As said fluorescent pigment, it is C.I. Pigment red 81, 173, 181, etc. are mentioned. In addition, the fluorescent pigment may be a pigment obtained by dyeing or dissolving the fluorescent dye in a synthetic resin or by pulverizing a solid solution which is the obtained colored agglomerate resin. Examples of the synthetic resins include acrylic resins, vinyl chloride resins, alkyd resins, aromatic sulfonamide resins, urea resins, melamine resins, and benzoguanamine resins.

Content of fluorescent dye (A1) is 0.1-60 mass% with respect to solid content of colored curable resin composition, More preferably, it is 0.2-35 mass%, More preferably, it is 0.5-25 mass%. Here, solid content in this specification means the total amount of the component remove | excluding the solvent from colored curable resin composition. Solid content can be measured by well-known analytical means, such as liquid chromatography or gas chromatography, for example.

The coloring agent (A2) different from the said fluorescent dye (A1) can be used even if it is a dye or a pigment, and a pigment is preferable.

As the dye (A21) used in the coloring agent (A2), for example, a compound classified as a dye in Color Index (The Society of Dyers and Colors published), or a known dye described in dyeing notes (Shikishensha) Can be mentioned.

Specific examples of such dyes (A21) include solvent dyes, acid dyes, direct dyes, mordant dyes, and the like. These dyes may be appropriately selected in accordance with the spectral spectrum of the desired color filter. These dyes may be used independently or may use 2 or more types together.

As the solvent dye, C.I. Solvent yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162; C.I. Solvent red 45, 125, 130; C.I. Solvent orange 2, 7, 11, 15, 26, 56; C.I. Solvent blue 35, 37, 59, 67; C.I. Solvent green 1, 3, 4, 5, 28, 29, 32, 33, 34, 35 and the like.

As the acid dye, C.I. Acid yellow 1, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251; C.I. Acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 57, 66, 73, 80, 88, 91, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, 426; C.I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173; C.I. Acid blue 1, 7, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 92, 96, 103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340;

C.I. Acid violet 6B, 7, 17, 19; C.I. Acid green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109 and the like.

As the direct dye, C.I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 136, 138, 141; C.I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250; C.I. Direct orange 34, 39, 41, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; C.I. Direct Blue 57, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293; C.I. Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; C.I. Direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 and the like.

As the mordant dye, C.I. Modern dyes such as C.I. Modern Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; C.I. Modern Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41 , 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95; C.I. Modern orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; C.I. 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43 , 44, 48, 49, 53, 61, 74, 77, 83, 84; C.I. Modern violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58; C.I. Modern Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53 and the like.

Examples of the pigment (A22) used in the coloring agent (A2) include compounds classified as pigments by Color Index (Published by The Society of Dyers and Colourists).

As a specific example of such a pigment (A22), it is C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139 , 147, 148, 150, 153, 154, 166, 173, 194 and 214; C.I. Pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and the like orange pigments; C.I. Red pigments such as Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, ; C.I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, and 60; C.I. Violet pigments such as Pigment Violet 1, 19, 23, 29, 32, 36, 38; C.I. Green pigments such as Pigment Green 7, 36, and 58; C.I. Brown pigments such as Pigment Brown 23 and 25; C.I. Pigment black 1, pigment black 7, and the like.

Among these, C.I. Pigment Yellow 138, 139, 150, C.I. Pigment Red 177, 209, 242, 254, C.I. Pigment Violet 23, C.I. Pigment Blue 15: 3, 15: 6 and C.I. Pigment greens 7, 36 and 58 are preferred. These pigments may be used independently or may use 2 or more types together.

When using the pigment (A22) as said coloring agent (A2), it is preferable to use it, after performing a dispersion process in the presence of a pigment dispersant to make the pigment dispersion liquid of the pigment uniformly disperse | distributed in the solvent. As said pigment dispersant, surfactant, such as cationic, anionic, nonionic, amphoteric, polyester, and polyamine type, etc. are mentioned, for example, These pigment dispersants are 2 or more types also independently. You may use in combination.

As a specific example of the said pigment dispersant, For example, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol diester, sorbitan fatty acid ester, fatty acid modified polyester, tertiary amine modified polyurethane And polyethyleneimines. Moreover, as a commercial item, it is a brand name by KP [made by Shin-Etsu Kagaku Kogyo Co., Ltd.], Floren (made by Kyoeisha Kagaku Co., Ltd.), Solsperth (registered trademark) [made by Geneka Co., Ltd.], EFKA ( CIBA company), Disperbyk (trademark) (made by BIC Chem Corporation), and Ajisper (registered trademark) (made by Ajinomoto Fine Techno Co., Ltd.) etc. are mentioned.

When using a pigment dispersant, the usage-amount is 0.1-100 mass parts with respect to 100 mass parts of pigments (A22), More preferably, it is 5-50 mass parts, Most preferably, it is 39-50 mass parts. When the usage-amount of a pigment dispersant exists in the said range, there exists a tendency which can obtain a uniform pigment dispersion liquid.

It is preferable that the said coloring agent (A2) has maximum absorption wavelength in the range of 490 nm or more and 780 nm or less, More preferably, it is the range of 520 nm or more and 740 nm or less, More preferably, it is the range of 550 nm or more and 700 nm or less. .

The total content of the fluorescent dye (A1) and the coloring agent (A2) is preferably 5 to 65% by mass, more preferably 8 to 60% by mass, still more preferably 10 to 55% by mass, based on the solid content of the colored curable resin composition. to be. When the total content of the fluorescent dye (A1) and the coloring agent (A2) is in the above range, the pattern obtained tends to be excellent in contrast, brightness, heat resistance, and chemical resistance.

The content of the fluorescent dye (A1) is preferably 1 to 99% by mass, more preferably 3 to 60% by mass, still more preferably 5 to 40% by mass relative to the total amount of the fluorescent dye (A1) and the coloring agent (A2). to be.

The content of the colorant (A2) is preferably 1 to 99% by mass, more preferably 40 to 97% by mass, still more preferably 60 to 95% by mass relative to the total amount of the fluorescent dye (A1) and the coloring agent (A2). .

When colored curable resin composition contains dye (A21), content of dye (A21) becomes like this. Preferably it is 0.1-50 mass%, More preferably, it is 0.1-30 mass% with respect to solid content of a colored curable resin composition. By containing dye (A21) in the said content, optimization of the transmission spectrum of the color filter obtained becomes easy, and it becomes the colored curable resin composition excellent in developability.

When the colored curable resin composition contains a fluorescent dye (A1) and a pigment (A22), the content of the fluorescent dye (A1) is preferably 1 to 99% by mass relative to the total amount of the fluorescent dye (A1) and the pigment (A22). More preferably, it is 1-70 mass%, More preferably, it is 1-50 mass%. The content of the pigment (A22) is preferably 1 to 99% by mass, more preferably 30 to 99% by mass, still more preferably 50 to 99% by mass based on the total amount of the fluorescent dye (A1) and the pigment (A22). %to be.

When the colored curable resin composition contains the xanthene dye (A11) and the pigment (A22), the content of the xanthene dye (A11) is preferably from 1 to the total amount of the xanthene dye (A11) and the pigment (A22). 70 mass%, More preferably, it is 1-60 mass%, More preferably, it is 1-50 mass%. The content of the pigment (A22) is preferably 30 to 99% by mass, more preferably 40 to 99% by mass, still more preferably 50 to 99 to the total amount of the xanthene dye (A11) and the pigment (A2). Mass%. When content of xanthene dye (A11) and pigment (A22) exists in the said range, the pattern obtained tends to be excellent in contrast, lightness, heat resistance, and chemical resistance.

Moreover, when colored curable resin composition contains xanthene dye (A11) and dye (A21), content of xanthene dye (A1) becomes like this. Preferably it is 1-100 mass% with respect to dye (A21), More preferably, Is 30-100 mass%.

The colored curable resin composition of this invention contains binder resin (B). Although it does not specifically limit as said binder resin (B), It is preferable that it is alkali-soluble resin. As binder resin (B), the following resin [K1]-[K6], etc. are mentioned, for example.

[K1] at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter may be referred to as "(a)"), a cyclic ether structure having 2 to 4 carbon atoms, and ethylene The copolymer of the monomer (b) (Hereinafter, it may be called "(b)") which has a sex unsaturated bond.

[K2] of (a) and (b) and the monomer (c) copolymerizable with (a), but different from (a) and (b) (hereinafter may be referred to as "(c)"). Copolymer.

[K3] The copolymer of (a) and (c).

[K4] A resin obtained by reacting (b) with a copolymer of (a) and (c).

[K5] A resin obtained by reacting (a) with a copolymer of (b) and (c).

Resin obtained by making (a) react with the copolymer of (b) and (c), and making carboxylic anhydride further react.

Specific examples of the above (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m- and p-vinylbenzoic acid; Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, Unsaturated dicarboxylic acids such as dimethyltetrahydrophthalic acid and 1,4-cyclohexenedicarboxylic acid; Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hepto-2-ene, 5,6-dicarboxybicyclo [2.2.1] hepto-2-ene , 5-carboxy-5-methylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-6-methylbicyclo Bicyclo unsaturated compounds containing carboxyl groups, such as [2.2.1] hepto-2-ene and 5-carboxy-6-ethylbicyclo [2.2.1] hepto-2-ene; Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride Unsaturated dicarboxylic acid anhydrides such as dimethyl tetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2.2.1] hepto-2-ene anhydride (hemic acid anhydride); Unsaturated mono [(meth) acryloyloxyalkyl of a divalent or higher polyhydric carboxylic acid such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] ] Esters; and unsaturated acrylates containing a hydroxyl group and a carboxyl group in the same molecule such as α- (hydroxymethyl) acrylic acid. These (a) may be used independently and may use 2 or more types together.

Among these, acrylic acid, methacrylic acid, maleic anhydride, etc. are preferable from the point of copolymerization reactivity or the solubility to aqueous alkali solution.

The said (b) is a C2-C4 cyclic ether structure (for example, at least 1 sort (s) chosen from the group which consists of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring (oxolan ring)) and ethylene It is a polymeric compound which has a sex unsaturated bond. As said (b), the monomer which has a C2-C4 cyclic ether and a (meth) acryloyloxy group is preferable.

In addition, in this specification, "(meth) acrylic acid" shows at least 1 sort (s) chosen from the group which consists of acrylic acid and methacrylic acid. Notation, such as "(meth) acryloyl" and "(meth) acrylate", has the same meaning.

As said (b), for example, the monomer (b1) which has an oxiranyl group and ethylenically unsaturated bond (henceforth "(b1)"), and the monomer (b2) which has an oxetanyl group and ethylenically unsaturated bond (Hereinafter, it may be called "(b2).") The monomer (b3) (Hereinafter, it may be called "(b3)") which has a tetrahydrofuryl group and ethylenically unsaturated bond, etc. are mentioned.

As said (b1), the monomer (b1-1) which has a structure which epoxidized unsaturated aliphatic hydrocarbon (it may be called "(b1-1)" hereafter), and the structure which epoxidized unsaturated alicyclic hydrocarbon, for example The monomer (b1-2) (Hereinafter, it may be called "(b1-2)"), etc. are mentioned.

As said (b1-1), glycidyl (meth) acrylate, (beta) -methyl glycidyl (meth) acrylate, (beta) -ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinyl benzyl Glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α -Methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxy Methyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6-tris (glycidyloxymethyl) styrene, etc. Can be.

As said (b1-2), vinylcyclohexene monooxide and 1,2-epoxy-4- vinylcyclohexane [for example, ceoxide 2000; Daicel Kagaku Kogyo Co., Ltd. product, 3, 4- epoxycyclohexyl methyl (meth) acrylate [for example, cyclomer A400; Daicel Kagaku Kogyo Co., Ltd. product, 3, 4- epoxycyclohexyl methyl (meth) acrylate [for example, cyclomer M100; Daicel Kagaku Kogyo Co., Ltd.], the compound represented by Formula (I), the compound represented by Formula (II), etc. are mentioned.

[In formula (I) and (II), R <^b1> and R <^b2> represent a hydrogen atom or a C1-C4 alkyl group independently of each other, and the hydrogen atom contained in the said alkyl group may be substituted by the hydroxy group.

L ¹ and L ² independently represent a single bond, -R ^b3- , * -R ^b3 -O-, * -R ^b3 -S-, and * -R ^b3 -NH-. R ^b3 represents a C1-C6 alkanediyl group. * Represents a bond with O.]

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ^b1 or R ^b2 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group.

Examples of the alkyl group having 1 to 4 carbon atoms and a hydrogen atom substituted with hydroxy include, for example, a hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3 -Hydroxypropyl group, 1-hydroxy-1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxy A oxybutyl group etc. are mentioned.

R ^b1 and R ^b2 are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, or a 2-hydroxyethyl group, and more preferably a hydrogen atom or a methyl group.

^Examples of the alkanediyl group represented by R ^b3 include a methylene group, an ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group and pentane-1,5-diyl group And hexane-1,6-diyl group.

L ¹ and L ² preferably include a single bond, a methylene group, an ethylene group, * -CH ₂ -O- (* represents a bond with O), and a * -CH ₂ CH ₂ -O- group. , and more preferably there may be mentioned a single bond, * -CH ₂ CH ₂ -O- group.

As a compound represented by Formula (I), the compound etc. which are represented by Formula (I-1)-Formula (I-15) are mentioned. Preferably formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9), formula (I-11) to formula (I-15) ). More preferably, Formula (I-1), Formula (I-7), Formula (I-9), and Formula (I-15) are mentioned.

As a compound represented by Formula (II), the compound etc. which are represented by Formula (II-1)-Formula (II-15) are mentioned. Preferably formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9), formula (II-11) to formula (II-15) ). More preferably, Formula (II-1), Formula (II-7), Formula (II-9), and Formula (II-15) are mentioned.

The compound represented by formula (I) and the compound represented by formula (II) can be used independently, respectively. In addition, they can be mixed in any ratio. In the case of mixing, the mixing ratio is preferably in a molar ratio of 5:95 to 95: 5, more preferably 10:90 to 90:10, and more preferably 20:80 in the formula (I): formula (II). ～ 80: 20.

As a monomer (b2) which has an oxetanyl group and ethylenically unsaturated bond, the monomer which has an oxetanyl group and a (meth) acryloyloxy group is more preferable. As said (b2), 3-methyl-3-methacryloyloxy methyl oxetane, 3-methyl-3- acryloyloxy methyl oxetane, 3-ethyl-3- methacryloyloxy methyl oxetane, 3 -Ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacryl Royloxyethyl oxetane, 3-ethyl-3-acryloyloxyethyl oxetane, etc. are mentioned.

As a monomer (b3) which has a tetrahydrofuryl group and ethylenically unsaturated bond, the monomer which has a tetrahydrofuryl group and a (meth) acryloyloxy group is more preferable. Specifically as said (b3), tetrahydrofurfuryl acrylate [For example, biscoat V # 150, the Osaka Yuki Kagaku Kogyo Co., Ltd. product], tetrahydrofurfuryl methacrylate, etc. are mentioned.

As said (b), it is preferable that it is a monomer (b1) which has an oxiranyl group and ethylenically unsaturated bond from the point which can make reliability, such as heat resistance and chemical resistance, of a color filter obtained. Moreover, the monomer (b1-2) which has a structure which epoxidized unsaturated alicyclic hydrocarbon is more preferable at the point which is excellent in the storage stability of colored curable resin composition.

As said (c) [polymerizable monomer different from said (a), (b)], for example, (meth) acrylic acid ester, dicarboxylic acid diester, bicyclo unsaturated compounds, dicarbonyl imide derivation. Retention, styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide And vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.

As said (meth) acrylic acid ester, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth), for example Acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) Acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate (in the art, the common name is “dicyclopentanyl (meth) acrylate In addition, it may be called "tricyclodecyl (meth) acrylate."), And tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate (the technical field) As a common name "dicyclopentenyl (meth) acrylate" Dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylic (Meth) acrylic acid esters such as late, phenyl (meth) acrylate, naphthyl (meth) acrylate and benzyl (meth) acrylate; Hydroxy-group containing (meth) acrylic acid ester, such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, is mentioned.

As said dicarboxylic acid diester, diethyl maleate, diethyl fumarate, diethyl itaconic acid, etc. are mentioned, for example.

Examples of the bicyclo unsaturated compounds include bicyclo [2.2.1] hepto-2-ene, 5-methylbicyclo [2.2.1] hepto-2-ene and 5-ethylbicyclo [2.2.1]. Hepto-2-ene, 5-hydroxybicyclo [2.2.1] hepto-2-ene, 5-hydroxymethylbicyclo [2.2.1] hepto-2-ene, 5- (2'-hydroxyethyl ) Bicyclo [2.2.1] hepto-2-ene, 5-methoxybicyclo [2.2.1] hepto-2-ene, 5-ethoxybicyclo [2.2.1] hepto-2-ene, 5,6- Dihydroxybicyclo [2.2.1] hepto-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hepto-2-ene, 5,6-di (2'-hydroxy Ethyl) bicyclo [2.2.1] hepto-2-ene, 5,6-dimethoxybicyclo [2.2.1] hepto-2-ene, 5,6-diethoxybicyclo [2.2.1] hepto-2 -Ene, 5-hydroxy-5-methylbicyclo [2.2.1] hepto-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hepto-2-ene, 5-hydroxymethyl -5-methylbicyclo [2.2.1] hepto-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hepto-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2. 1] hepto-2- , 5-phenoxycarbonylbicyclo [2.2.1] hepto-2-ene, 5,6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hepto-2-ene, 5,6-bis (Cyclohexyloxycarbonyl) bicyclo [2.2.1] hepto-2-ene, etc. are mentioned.

As said dicarbonyl imide derivatives, N-phenylmaleimide, N-cyclohexyl maleimide, N-benzyl maleimide, N-succinimidyl-3- maleimide benzoate, N-succinimidyl, for example 4-maleimide butyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3-maleimide propionate, N- (9-acridinyl) maleimide, and the like. have.

Said (c) may be used independently and may use 2 or more types together. Among these, as the component (c), styrene, N-phenylmaleimide, N-cyclohexyl maleimide, N-benzyl maleimide, bicyclo [2.2.1] hepto-2-ene, etc., may be used in view of copolymerization reactivity and heat resistance. This is preferred.

It is preferable that the ratio of the structural unit derived from each in resin [K1] exists in the following ranges among all the structural units which comprise resin [K1].

structural units derived from (a); 2-50 mol% (more preferably 10-45 mol%)

structural units derived from (b); 50-98 mol% (more preferably 55-90 mol%)

When the ratio of the structural unit of resin [K1] exists in the said range, it exists in the tendency which is excellent in storage stability, developability, and the solvent resistance of the pattern obtained.

The resin [K1] is, for example, the method described in the document "Experimental Method for Polymer Synthesis" (Osaka Yuki Hakkoso Co., Ltd. First Edition First Edition March 1, 1972) and the citation described in the above document. It can manufacture with reference to literature.

Specifically, a method of adding a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like into a reaction vessel and stirring, heating, and warming in a deoxygen atmosphere. In addition, the polymerization initiator, solvent, etc. which are used here are not specifically limited, Any of the thing normally used in the said field | area can be used. For example, as a polymerization initiator, an azo compound [2,2'- azobisisobutylonitrile, 2,2'- azobis (2, 4- dimethylvaleronitrile), etc.], an organic peroxide (benzoyl peroxide, etc.) As a solvent, what is necessary is just to melt | dissolve each monomer, and the solvent (E) mentioned later can be used as a solvent of a colored curable resin composition.

In addition, the obtained copolymer may use the solution after reaction as it is, the solution which concentrated or diluted may be used, and the thing taken out as solid (powder) by methods, such as reprecipitation, may be used. In particular, the solution after reaction can be used as it is by using the solvent (E) mentioned later as a solvent at the time of this superposition | polymerization, and a manufacturing process can be simplified.

It is preferable that the ratio of the structural unit derived from each in resin [K2] exists in the following ranges among all the structural units which comprise resin [K2].

structural units derived from (a); 4 to 45 mol% (more preferably 10 to 30 mol%)

structural units derived from (b); 2 to 95 mol% (more preferably 5 to 80 mol%)

structural units derived from (c); 1-65 mol% (more preferably 5-60 mol%)

When the proportion of the structural unit of the resin [K2] is in the above range, there is a tendency to be excellent in storage stability, developability, solvent resistance, heat resistance, and mechanical strength of the resulting pattern.

Resin [K2] can be manufactured similarly to the method described as a manufacturing method of resin [K1], for example.

Specifically, the method of adding the predetermined amount of (a), (b) and (c), a polymerization initiator, and a solvent in a reaction container, stirring, heating, and keeping warm in a deoxidation atmosphere is mentioned. The obtained copolymer may use the solution after reaction as it is, the solution which concentrated or diluted may be used, and the thing taken out as solid (powder) by methods, such as reprecipitation, may be used.

It is preferable that the ratio of the structural unit derived from each in resin [K3] exists in the following ranges among all the structural units which comprise resin [K3].

structural units derived from (a); 2 to 55 mol%, more preferably 10 to 50 mol%

structural units derived from (c); 45-98 mol%, More preferably, 50-90 mol%

Resin [K3] can be manufactured similarly to the method described as a manufacturing method of resin [K1], for example.

Resin [K4] is obtained by obtaining the copolymer of (a) and (c) and adding the C2-C4 cyclic ether which (b) has to the carboxylic acid and / or carboxylic anhydride which (a) has can do.

First, the copolymer of (a) and (c) is manufactured similarly to the method described as a manufacturing method of [K1]. In this case, it is preferable that the ratio of the structural unit derived from each exists in the following ranges among all the structural units which comprise the copolymer of (a) and (c).

structural units derived from (a); 5-50 mol% (more preferably 10-45 mol%)

structural units derived from (c); 50-95 mol% (more preferably 55-90 mol%)

Next, the C2-C4 cyclic ether which (b) has is made to react with a part of carboxylic acid and / or carboxylic anhydride derived from (a) in the said copolymer.

Subsequent to the preparation of the copolymers of (a) and (c), the atmosphere in the flask was replaced with nitrogen from air, and (b) the reaction catalyst of carboxylic acid or carboxylic anhydride and cyclic ether [for example, Resin [K4] can be obtained by putting tris (dimethylaminomethyl) phenol and the like and a polymerization inhibitor (for example, hydroquinone) in a flask and reacting at 60 to 130 ° C for 1 to 10 hours, for example. .

As for the usage-amount of (b), 5-80 mol is preferable with respect to 100 mol of (a), More preferably, it is 10-75 mol. By setting it as this range, there exists a tendency for the balance of storage stability, developability, solvent resistance, heat resistance, mechanical strength, and a sensitivity to become favorable. Since the reactivity of a cyclic ether is high and it is hard to remain unreacted (b), (b1) is preferable and (b1-1) is more preferable as (b) used for resin [K4].

As for the usage-amount of the said reaction catalyst, 0.001-5 mass% is preferable with respect to the total amount of (a), (b) and (c). As for the usage-amount of the said polymerization inhibitor, 0.001-5 mass% is preferable with respect to the total amount of (a), (b) and (c).

The reaction conditions such as the input method, the reaction temperature and the time can be appropriately adjusted in consideration of the amount of heat generated by the production equipment or polymerization. In addition, similarly to the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the amount of heat generated by the production equipment, the polymerization and the like.

Resin [K5] is obtained in the same manner as the method for producing resin [K1] described above as a first step to obtain a copolymer of (b) and (c). In the same manner as described above, the obtained copolymer may be used as it is, or a concentrated or diluted solution may be used, or one obtained as solid (powder) by a method such as reprecipitation may be used.

It is preferable that the ratio of the structural unit derived from (b) and (c) exists in the following ranges with respect to the total number of moles of all the structural units which comprise the said copolymer.

structural units derived from (b); 5 to 95 mol% (more preferably 10 to 90 mol%)

structural units derived from (c); 5 to 95 mol% (more preferably 10 to 90 mol%)

Moreover, the carboxylic acid or carboxylic anhydride which (a) has reacts with the cyclic ether derived from (b) which the copolymer of (b) and (c) has on the same conditions as the manufacturing method of resin [K4]. The resin [K5] can be obtained by doing this.

As for the usage-amount of (a) made to react with the said copolymer, 5-80 mol is preferable with respect to 100 mol of (b). Since reactivity of a cyclic ether is high and unreacted (b) hardly remains, (b1) is preferable and (b1-1) is more preferable as (b) used for resin [K5].

Resin [K6] is resin which made carboxylic anhydride further react with resin [K5]. The carboxylic acid anhydride is reacted with the hydroxy group generated by the reaction of the cyclic ether with the carboxylic acid or the carboxylic anhydride.

As carboxylic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6 -Tetrahydrophthalic anhydride, dimethyl tetrahydrophthalic anhydride, 5, 6- dicarboxy bicyclo [2.2.1] hepto-2-ene anhydride (hemic acid anhydride), etc. are mentioned.

Specific examples of the binder resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate / (meth Resins such as acrylic acid copolymers; Glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2 .1.0 ^2.6] decyl acrylate / (meth) resins such as acrylic acid / N- cyclohexyl maleimide copolymer, 3-methyl-3- (meth) acryloyloxyethyl-methyl oxetane / (meth) acrylic acid / styrene copolymer [K2]; Resins such as benzyl (meth) acrylate / (meth) acrylic acid copolymer and styrene / (meth) acrylic acid copolymer; Resin which glycidyl (meth) acrylate was added to the benzyl (meth) acrylate / (meth) acrylic acid copolymer, and glycidyl (meth) to the tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer Resin [K4], such as resin which added the acrylate, and resin which added glycidyl (meth) acrylate to the tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer; Of resin which made (meth) acrylic acid react with the copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate, and tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate Resins [K5], such as resin which made (meth) acrylic acid react with the copolymer; [K6], such as resin, in which tetrahydrophthalic anhydride is further reacted with a resin in which (meth) acrylic acid is reacted with a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate. .

These resin may be used independently or may use 2 or more types together.

Among these, as binder resin (B), resin [K1] and resin [K2] are preferable, and resin [K1] containing the structural unit derived from 3, 4- epoxy citricyclo [5.2.1.0 ^2.6 ] decyl acrylate. And Resin [K2] containing a structural unit derived from 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate is more preferable.

The weight average molecular weight of polystyrene conversion of the said binder resin (B) becomes like this. Preferably it is 3,000-100,000, More preferably, it is 5,000-50,000, More preferably, it is 5,000-30,000. When an average molecular weight exists in the said range, there exists a tendency for the solubility to the developing solution of an unexposed part to be high, and the residual film ratio and hardness of the pattern obtained also become high.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the said binder resin (B) becomes like this. Preferably it is 1.1-6, More preferably, it is 1.2-4.

The acid value of binder resin (B) becomes like this. Preferably it is 50-180 mg-KOH / g, More preferably, it is 60-150 mg-KOH / g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be obtained by, for example, titration using an aqueous potassium hydroxide solution.

Content of the said binder resin (B) becomes like this. Preferably it is 7-65 mass% with respect to solid content of colored curable resin composition, More preferably, it is 13-60 mass%, More preferably, it is 17-55 mass%. When content of binder resin (B) exists in the said range, there exists a tendency for the solubility to the developing solution of an unexposed part to be high.

The colored curable resin composition of this invention contains a polymeric compound (C). The polymerizable compound (C) is a compound which can be polymerized by active radicals and / or acids generated from the polymerization initiator (D) by the action of light or heat, and examples thereof include compounds having a polymerizable ethylenically unsaturated bond. And, preferably, a (meth) acrylic acid ester compound.

It is preferable that it is a polymeric compound which has 3 or more of ethylenically unsaturated bonds as said polymeric compound (C). As such a polymeric compound, for example, trimethol propane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tritree Pentaerythritol octa (meth) acrylate, tripentaerythritolhepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxy Ethyl) isocyanurate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol hexa (meth) acrylate, propylene glycol modified pentaerythritol tetra (meth) acrylate, propylene glycol modified dipentaerythritol Hexa (meth) acrylate, caprolactone modified pentaerythritol La (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate. Especially, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable. These polymeric compounds may be used independently or may use 2 or more types together.

Content of a polymeric compound (C) becomes like this. Preferably it is 7-65 mass% with respect to solid content of colored curable resin composition, More preferably, it is 13-60 mass%, More preferably, it is 17-55 mass%. When content of the said polymeric compound (C) exists in the said range, hardening arises enough, the film thickness ratio before and behind image development improves, it is preferable because it becomes difficult to undercut into a pattern, and adhesiveness tends to become favorable.

The colored curable resin composition of this invention contains a polymerization initiator (D). The polymerization initiator (D) is not particularly limited as long as it generates active radicals by the action of light or heat and can initiate polymerization of the polymerizable compound (C), and known radical polymerization initiators can be used.

As a polymerization initiator (D), the compound which generate | occur | produces an active radical by the action of light is preferable, An alkyl phenone compound, a triazine compound, an acyl phosphine oxide compound, an oxime compound, and a biimidazole compound are more preferable, and an oxime compound is included. The polymerization initiator to make is more preferable.

As said alkyl phenone compound, the (alpha)-aminoalkyl phenone compound, the (alpha)-alkoxy alkyl phenone compound, the (alpha)-hydroxyalkyl phenone compound, etc. are mentioned.

Examples of the α-aminoalkylphenone compound include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propane-1-one and 2-dimethylamino-1- (4-morpholinophenyl) -2 -Benzyl butan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2- (4-methylphenylmethyl) butan-1-one, and the like. Commercially available products include Ilgacure (registered trademark) 369, 379, 907 (above, manufactured by BASF Corporation), and the like.

Examples of the α-alkoxyalkylphenone compound include diethoxy acetophenone, benzyl dimethyl ketal, and the like.

Examples of the α-hydroxyalkylphenone compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] And oligomers of propane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one, and the like.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- (4 -Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloro To methyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) Tenyl] -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, 2,4-bis (trichloromethyl) -6 -[2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like.

2,4,6-trimethylbenzoyldiphenylphosphine oxide etc. are mentioned as said acylphosphine oxide compound. You may use commercially available products, such as Ilgacure (trademark) 819 (made by BASF Corporation).

O-acyl oxime compound is mentioned as said oxime compound, Specifically, N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one- 2-imine, N-benzoyloxy-1- ( 4-phenylsulfanylphenyl) octan-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethane-1 Imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazole- 3-yl] ethane-1-imine etc. are mentioned. You may use commercially available products, such as Ilgacure (trademark) OXE01, OXE02 (above, BASF Corporation), and N-1919 (ADEKA Corporation). Among them, N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2 -Imine is preferred. If it is these oxime compounds, there exists a tendency for a high brightness color filter to be obtained.

Examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,3-dichlorophenyl)- 4,4 ', 5,5'-tetraphenylbiimidazole (see, for example, Japanese Patent Application Laid-open No. Hei 6-75372, Japanese Patent Application Laid-open No. Hei 6-75373, etc.), 2,2'-bis (2-chlorophenyl) -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 (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole (see, for example, Japanese Patent Publication No. 48-38403, Japanese Patent Publication No. 62-174204, etc.), 4 The imidazole compound (For example, refer Unexamined-Japanese-Patent No. 7-10913 etc.) in which the phenyl group of the -4'5,5'-position is substituted by the carbo alkoxy group. Preferred are 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole.

As the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; Benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, Benzophenone compounds such as 2,4,6-trimethylbenzophenone; Quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone and camphor quinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compound and the like. It is preferable to use these in combination with the polymerization initiator (D1) (especially amines) mentioned later.

Content of a polymerization initiator (D) becomes like this. Preferably it is 0.1-30 mass parts with respect to 100 mass parts of total amounts of binder resin (B) and a polymeric compound (C), More preferably, it is 5-25 mass parts. When content of a polymerization initiator (D) exists in the said range, a pattern can be formed with high sensitivity and there exists a tendency for the color filter which is high brightness to be obtained.

It is preferable that the colored curable resin composition of this invention further contains a polymerization initiator (D1). When the polymerization initiator (D1) is included, it is usually used in combination with the polymerization initiator (D). The polymerization initiator (D1) is a compound or sensitizer used to promote the polymerization of the polymerizable compound in which polymerization is initiated by the polymerization initiator.

As polymerization initiator (D1), an amine compound, an alkoxy anthracene compound, a thioxanthone compound, a carboxylic acid compound, etc. are mentioned, Preferably it is a thioxanthone compound.

As the thioxanthone compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone, 1-chloro-4-propoxy city Orcanthone etc. are mentioned.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid isoamyl, benzoic acid 2-dimethylaminoethyl and 4-dimethylaminobenzoic acid 2-ethylhexyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (collectively, Michler's ketone), 4,4'-bis (diethylamino) benzophenone, 4,4 '-Bis (ethylmethylamino) benzophenone and the like can be cited, and among these, 4,4'-bis (diethylamino) benzophenone is preferable. You may use commercial items, such as EAB-F (made by Hodogaya Kagaku Kogyo Co., Ltd.).

Examples of the alkoxy anthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dibu Methoxy anthracene, 2-ethyl-9, 10-dibutoxy anthracene, etc. are mentioned.

Examples of the carboxylic acid compound include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid and chloro Phenyl sulfanyl acetic acid, dichlorophenyl sulfanyl acetic acid, N-phenylglycine, phenoxy acetic acid, naphthyl thioacetic acid, N-naphthyl glycine, naphthoxy acetic acid, etc. are mentioned.

These polymerization initiators may be used independently or may use 2 or more types together.

In addition, when using a polymerization initiator (D1), the usage-amount becomes like this. Preferably it is 0.1-30 mass parts with respect to 100 mass parts of total amounts of binder resin (B) and a polymeric compound (C), More preferably, it is 1-20. It is a mass part. Moreover, Preferably it is 20-100 mass parts, More preferably, it is 30-80 mass parts with respect to 100 mass parts of content of a polymerization initiator (D). If the amount of the polymerization initiator (D1) is in this range, there is a tendency to form a pattern with high sensitivity and to obtain a color filter having high brightness.

It is preferable that the colored curable resin composition of this invention contains a solvent (E).

Solvent (E) is not specifically limited, The solvent normally used in the said field | area can be used. For example, an ester solvent (a solvent containing -COO- in a molecule and not containing -O-), an ether solvent (a solvent containing -O- in a molecule and not containing -COO-) and an ether ester Solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- in the molecule and not containing -COO-), alcoholic solvents, aromatic hydrocarbon solvents, amide solvents, dimethyl It can select from sulfoxide, etc., and can use.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, Butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetic acid, ethyl acetoacetate, cyclohexanol acetate, gamma -butyrolactone, and the like.

As said ether solvent, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene Glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phentol, methyl anisole Etc. can be mentioned.

As said ether ester solvent, methyl methoxy acetate, ethyl methoxy acetate, methoxy acetate butyl, ethoxy acetate methyl, ethoxy acetate ethyl, 3-methoxy propionate methyl, 3-methoxy propionate ethyl, 3-ethoxy propionate methyl , Ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionic acid, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-methoxy-2- Methyl methyl propionate, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono Propyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoe Tyl ether acetate, diethylene glycol monobutyl ether acetate, etc. are mentioned.

As said ketone solvent, 4-hydroxy-4-methyl- 2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl- 2-pentanone, cyclo Pentanone, cyclohexanone, isophorone, etc. are mentioned.

Methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin, etc. are mentioned as said alcohol solvent.

Benzene, toluene, xylene, mesitylene, etc. are mentioned as said aromatic hydrocarbon solvent.

Examples of the amide solvents include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, and the like.

These solvents may be used independently or may use 2 or more types together.

The organic solvent whose boiling point in 1 atm (101.325 kPa) is 120 degreeC or more and 180 degrees C or less is preferable among the said solvents from an applicability | paintability and a drying point. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, 3-ethoxypropionate ethyl, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl Acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N, N-dimethylformamide, and the like are preferable, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, Dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate, and the like are more preferable.

Content of the solvent (E) in colored curable resin composition becomes like this. Preferably it is 70-95 mass% with respect to colored curable resin composition, More preferably, it is 75-92 mass%. In other words, solid content of colored curable resin composition becomes like this. Preferably it is 5-30 mass%, More preferably, it is 8-25 mass%. When content of a solvent (E) exists in the said range, flatness at the time of application | coating will become favorable, and when a color filter is formed, there exists a tendency for display characteristic to become favorable because color concentration does not run short.

The colored curable resin composition of this invention may further contain surfactant (F). Examples of the surfactant (F) include silicone-based surfactants, fluorine-based surfactants, and silicone-based surfactants having fluorine atoms. These may have a polymeric group in a side chain.

As said silicone type surfactant, surfactant etc. which have a siloxane bond are mentioned. Specifically, Toray silicon DC3PA, copper SH7PA, copper DC11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30PA, copper SH8400 (manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 [Shin-Etsu Kagaku Kogyo Co., Ltd.], TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (made by Momentive Performance Materials Japan Co., Ltd.), etc. are mentioned.

As said fluorine-type surfactant, surfactant etc. which have a fluorocarbon chain | strand are mentioned. Specifically, fluoride (trade name) FC430, copper FC431 (manufactured by Sumitomo 3M Co., Ltd.), megapack (registered trademark) F142D, copper F171, copper F172, copper F173, copper F177, copper F183, copper R30, copper RS-718-K [product made by DIC Corporation], F-top (registered trademark) EF301, copper EF303, copper EF351, copper EF352 (made by Mitsubishi Material Denshi Kasei Co., Ltd.), Suplon (registered trademark) S381, copper S382, the same SC101, the same SC105 (made by Asahi Glass Co., Ltd.), E5844 (made by Daikin Fine Chemical Kenkyu Sho) etc. are mentioned.

As a silicone type surfactant which has the said fluorine atom, surfactant etc. which have a siloxane bond and a fluorocarbon chain | strand are mentioned. Specifically, Mega Pack R08, BL20, F475, F477, F443 (manufactured by DIC Corporation), and the like can be given.

These surfactant may be used independently or may use 2 or more types together.

Content of surfactant (F) becomes like this. Preferably it is 0.001 mass% or more and 0.2 mass% or less with respect to colored curable resin composition, Preferably it is 0.002 mass% or more and 0.1 mass% or less, More preferably, 0.01 mass% or more and 0.05 mass% It is as follows. However, content of the said pigment dispersant is not contained in content of the said surfactant (F). If content of surfactant (F) exists in the said range, flatness of a coating film can be made favorable.

The colored curable resin composition of this invention may contain various additives, such as a filler, another high molecular compound, an adhesion promoter, antioxidant, a ultraviolet absorber, a light stabilizer, and a chain transfer agent as needed.

As a method of forming the pattern of a color filter using the colored curable resin composition of this invention, the photolithographic method, the inkjet method, the printing method, etc. are mentioned, for example, Photolithographic method is preferable among these. In order to form a pattern by the photolithographic method, it is applied on a substrate or another resin layer (for example, a separate colored curable resin composition layer formed first on the substrate), and volatile components such as a solvent are removed (dried). What is necessary is just to form a colored layer, and to expose and develop the said colored layer through a photomask. In the photolithographic method, a coating film having no pattern can be formed by not using a photomask during exposure and / or not developing.

The film thickness of the pattern to be produced or the coating film is not specifically limited, It can adjust suitably according to the material to be used, a use, etc., for example, 0.1-30 micrometers, Preferably it is 1-20 micrometers, More preferably, it is 1-. 6 micrometers.

As a board | substrate, Glass plates, such as quartz glass, borosilicate glass, alumina silicate glass, and soda-lime glass which silica-coated the surface; Resin plates such as polycarbonate, polymethyl methacrylate and polyethylene terephthalate; Silicon, silver, a silver / copper / palladium alloy thin film, etc. which were formed on the said board | substrate are used. Separate color filter layers, resin layers, transistors, circuits, and the like may be formed on these substrates.

Examples of the coating method include a spin coating method, a slit coating method, a slit and spin coating method, and the like.

As a method of forming each color pixel by the photolithographic method, a well-known or a conventional method can be used. For example, it can manufacture as follows.

A colored curable resin composition is apply | coated on a board | substrate, volatile components, such as a solvent, are removed by heat-drying (prebaking) and / or drying under reduced pressure, and a smooth coating film is obtained.

30-120 degreeC is preferable and, as for the temperature at the time of heat drying, 50-110 degreeC is more preferable. Moreover, as heating time, it is preferable that it is for 10 second-60 minutes, and it is more preferable that it is for 30 seconds-30 minutes.

When drying under reduced pressure, it is preferable to carry out in the temperature range of 20-25 degreeC under the pressure of 50-150 Pa.

The film thickness of the coating film after drying is not specifically limited, According to the material to be used, a use, etc., it can adjust suitably, For example, it is 0.1-20 micrometers, Preferably it is 0.5-6 micrometers.

After drying, the coating film is exposed through a photomask for forming a target pattern. The pattern shape on the photomask at this time is not specifically limited, The pattern shape according to the intended use is used.

As a light source used for exposure, the light source which produces the light of 250-450 nm wavelength is preferable. For example, light of less than 350 nm is blocked using a filter that blocks this wavelength region, or light around 436 nm, 408 nm, and 365 nm is used a band pass filter that extracts these wavelength regions. May be withdrawn selectively. Specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp etc. are mentioned.

It is preferable to use apparatuses, such as a mask aligner and a stepper, in order to irradiate a parallel light beam uniformly to the whole exposure surface, or to perform exact alignment of a mask and a base material.

A pattern can be obtained by making a predetermined part, for example, an unexposed part, melt and develop it by making it contact with a developing solution after exposure. As a developing solution, aqueous solution of alkaline compounds, such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, tetramethylammonium hydroxide, etc., is preferable, for example. The concentration in the aqueous solution of these alkaline compounds becomes like this. Preferably it is 0.01-10 mass%, More preferably, it is 0.03-5 mass%. In addition, the developing solution may contain surfactant.

The developing method may be any of paddle method, dipping method, spray method and the like. In addition, during development, the substrate may be tilted at an arbitrary angle.

It is preferable to wash with water after image development.

In addition, you may post-bake as needed. 150-250 degreeC is preferable and, as for a postbaking temperature, 160-235 degreeC is more preferable. 0.5-10 minutes is preferable and, as for a postbaking time, 1-5 minutes are more preferable.

The pattern obtained as mentioned above by the colored curable resin composition of this invention is useful as a color filter. The color filter can be used in a form known in the art relating to various colored images such as a display device (for example, a liquid crystal display device, an organic EL device, etc.), a solid-state image sensor, and an electronic paper.

[Example]

Although an Example is given to the following and this invention is demonstrated to it further more concretely, this invention is not limited to the following Example, It is also possible to change suitably and to implement in the range which may be suitable for the purpose of the previous and the latter, They are all included in the technical scope of this invention. In the examples, &quot;% &quot; and &quot; part &quot; are parts by mass and parts by mass unless otherwise specified.

Synthesis Example 1

A mixture of a compound represented by formula (A1-1a) and a compound represented by formula (A1-1b) (manufactured by Chugai Kasei Co., Ltd., product name: Chugai Aminol Fast Pink R) in a flask equipped with a cooling tube and a stirring device 15 parts, 150 parts of chloroform, and 8.9 parts of N, N-dimethylformamide were added, and 10.9 parts of thionyl chloride was added dropwise while maintaining the temperature at 20 ° C or lower while stirring. It heated up at 50 degreeC after completion | finish of dripping, hold | maintained at the same temperature for 5 hours, and made it react, and cooled at 20 degreeC after that. A mixture of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine was added dropwise while maintaining the reaction solution after cooling at 20 ° C. or less under stirring. Thereafter, the reaction was stirred at the same temperature for 5 hours. Subsequently, the solvent was distilled off from the reaction mixture obtained by the rotary evaporator, and a small amount of methanol was added and the mixture was stirred vigorously. This mixture was added to the liquid mixture of 375 parts of ion-exchange water, stirring, and the crystal | crystallization was deposited. The precipitated crystals were filtered out, washed well with ion-exchanged water, dried under reduced pressure at 60 ° C, and represented by xanthene dyes A1-1 [Formula (A1-1-1) to Formula (A1-1-8)]. Mixture] was obtained.

Synthesis Example 2

Into a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to make a nitrogen atmosphere, and 636 parts of ethyl lactate was added and heated to 70 ° C while stirring. Subsequently, 126 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate [compound represented by formula (I-1) and compound represented by formula (II-1) are molar ratios of 50:50. Mixed] 294 parts were dissolved in 405 parts of ethyl lactate to prepare a solution, and the dissolved solution was added dropwise into a flask kept at 70 ° C. over 4 hours using a dropping funnel. On the other hand, the solution which melt | dissolved 30 parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 274 parts of ethyl lactate was dripped in the flask over 4 hours using the other dropping funnel. After completion of the dropwise addition of the solution of the polymerization initiator, the mixture was kept at 70 ° C for 4 hours, and then cooled to room temperature. The weight average molecular weight (Mw) was 1.0 × 10 ⁴ , the molecular weight distribution was 2.1, the solid content was 26%, and the solution acid value. A resin B1 solution having a value of 31 mg-KOH / g was obtained. When the solid acid value is calculated from the solid content and the acid value of the solution, it is 122 mg-KOH / g.

The polystyrene conversion weight average molecular weight (Mw) and number average molecular weight (Mn) of resin obtained by the synthesis example were measured on condition of the following by GPC method. In addition, ratio (Mw / Mn) of a weight average molecular weight and a number average molecular weight was made into molecular weight distribution.

Device; HLC-8120GPC [product of Tosoh Corporation]

column; TSK-GELG2000HXL

Column temperature; 40 ℃

menstruum; THF

Flow rate; 1.0 mL / min

Test liquid solids concentration; 0.001-0.01 mass%

Dose; 50 μL

Detectors; RI

Calibration standards; TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 [product of Tosoh Corporation]

Examples and Comparative Examples

[Preparation of Pigment Dispersion 1]

The following components were mixed and the pigment dispersion 1 was obtained by fully disperse | distributing a pigment using the bead mill.

C.I. Pigment Blue 15: 6

Acrylic pigment dispersant 13.6 parts

Propylene glycol monomethyl ether acetate 194 parts

[Preparation of Pigment Dispersion 2]

The pigment component 2 was obtained by mixing the following components and fully disperse | distributing a pigment using the bead mill.

C.I. Pigment Blue Part 15: 6

Acrylic pigment dispersant 17.7 parts

Propylene glycol monomethyl ether acetate 228 parts

The following components were mixed and the pigment dispersion 3 was obtained by fully disperse | distributing a pigment using the bead mill.

C.I. Pigment Blue Part 15: 6

Acrylic pigment dispersant 12.1 parts

Propylene glycol monomethyl ether acetate 174 parts

C.I. used as colorant (A2). The maximum absorption wavelength of Pigment Blue 15: 6 is 600 nm. In addition, the maximum absorption wavelength of a coloring agent (A2) was measured as follows. An ultraviolet-visible near-infrared spectrophotometer [V-650] dissolved 0.35 g of a coloring agent in ethyl lactate to make a volume of 250 cm 3, of which 2 cm 3 was diluted with ethyl lactate to make a volume of 100 cm 3 (concentration: 0.028 g / L). ; The absorption spectrum in 400-700 nm was measured using Nippon Bunco Co., Ltd. product (quartz cell, optical path length; 1 cm). From the said absorption spectrum, the wavelength whose maximum absorbance is calculated | required was made into the maximum absorption wavelength.

[Preparation of Colored Curable Resin Composition]

The components of Table 1 were mixed to obtain a colored curable resin composition.

In Table 1, each component is as follows.

Fluorescent dyes (A1); Dye A1

Colorant (A2); C.I. Pigment Blue 15: 6 (included in each pigment dispersion)

Resin (B); Resin B1 (Content of Table 1 shows the value of solid content conversion.)

Polymerizable compound (C); Dipentaerythritol hexaacrylate [KAYARAD® DPHA; Nihon Kayaku Co., Ltd.]

Polymerization initiator (D); (D-1); N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine [Igurecure® OXE 01; Manufactured by BASF; Oxime compound]

Polymerization initiator (D); (D-2); 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one [ylcure 907; Manufactured by BASF; Alkylphenone Compound]

Polymerization initiator (D1); 2,4-diethyl thioxanthone [KAYAC® RE (TM) DETX-S; Nihon Kayaku Co., Ltd. product; Thioxanthone compound]

Solvent (E); (E-1); Ethyl lactate

Surfactant (F); Polyether modified silicone oils [Toray Silicone SH8400; Toray Dow Corning Co., Ltd.]

In addition, surfactant was mixed so that content in colored curable resin composition might be 0.05 mass%.

[Preparation of 1st-3rd Compositions]

The composition of Table 2 was mixed and the composition was obtained. As shown in Table 3, these compositions correspond to the 1st-3rd compositions of the colored curable resin compositions 1-3 obtained above.

[Production of coating]

The following operation was performed about the colored curable resin compositions 1-3 and the composition of Table 2, and the coating film was produced.

After apply | coating the composition on the glass substrate (Eagle XG; Corning Corporation make) of 5 cm (2 inches) * 5 cm by spin coating, it prebaked at 100 degreeC for 3 minutes. After cooling the exposure machine [TME-150RSK; Topcon Co., Ltd.] was irradiated with light at an exposure amount (365 nm standard) of 150 mJ / cm 2 under an air atmosphere. After light irradiation, it post-baked for 30 minutes in 230 degreeC in oven, and obtained the coating film. After cooling, the film thickness of the coating film obtained was measured by a film thickness measuring apparatus [DEKTAK3; It was 3.0 micrometers as a result of using Nihon Shinkogi Co., Ltd. product.

[Measurement of maximum excitation wavelength and maximum fluorescence intensity]

Fluorescence spectra were measured using a fluorescence spectrophotometer [FluoroMAX-3; It was measured using Horiba Seisakusho Co., Ltd. (excited side slit 0.5, fluorescent side slit 2.5).

About the coating film obtained from the composition (1-1), the excitation light wavelength was changed stepwise every 50 nm in the range of 400-700 nm, and the fluorescence spectrum was measured, respectively, and the maximum fluorescence intensity of each fluorescence spectrum was calculated | required. As a result, the maximum fluorescence intensity at 550 nm exhibited the greatest value, and the maximum fluorescence intensity was similarly determined by changing the excitation light wavelength stepwise for every 10 nm in the range of 500 to 600 nm. As a result, the maximum fluorescence intensity showed the largest value at 530 nm, so that this was set as the maximum excitation wavelength λ ₁ (nm).

In addition, as for the coating films obtained from the respective third compositions (1-3), the maximum excitation wavelength was confirmed in the same manner as in the case of the maximum excitation wavelength (λ ₁ ), the maximum fluorescence intensity was the highest at 530 nm. It was set as the maximum excitation wavelength (lambda) ₃ (nm).

The first composition (1-1) measures the fluorescence spectrum at the excitation wavelength 530㎚ respect to the coating film obtained from, and asked for the maximum fluorescence intensity F _1. The fluorescence wavelength lambda _f1 (nm) at the maximum fluorescence intensity F ₁ at this time was 575 nm. In addition, in succession in the measuring a third composition of measuring the fluorescence spectrum of the excitation wavelength 530㎚ even for the coating film obtained from (1-3, 2-3, 3-3), and fluorescence intensity was determined up to ₃ F, respectively. F ₃ / F ₁ was calculated from the obtained result and shown in Table 4.

[Measurement of transmittance]

For each coating film obtained from the second composition, a colorimeter [OSP-SP-200; Transmittance T _e at the maximum excitation wavelength λ ₁ (nm) (530 nm) and transmittance T _f at the fluorescence wavelength λ _f1 (nm) (575 nm) were measured using Olympus Co., Ltd. The product T _e × T _f was calculated. The results are shown in Table 4.

[Measurement of Contrast]

About the coating film produced from colored curable resin compositions 1-3, contrast type [color chrominance system BM-5A; Topcon Co., Light Source; F-10, polarizing film; The contrast was measured using Tsubosaka Denki Corporation. The blank value was 30000. The results are shown in Table 4.

[Pattern Formation]

After apply | coating the colored curable resin composition on the glass substrate (Eagle XG; Corning Corporation) of 5 cm (2 inch) x 5 cm by the spin coat method, it prebaked at 100 degreeC for 3 minutes, and formed the composition layer on the board | substrate. . After cooling, an exposure machine [TME-150RSK; Topcon Co., Ltd.] was irradiated with light at an exposure dose (365 nm standard) of 150 mJ / cm 2 under an air atmosphere. In addition, as a photomask, the mask in which the 100 micrometer line and space pattern was formed was used. After light irradiation, the composition layer was immersed in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 24 ° C. for 60 seconds, followed by post-baking at 220 ° C. for 20 minutes in an oven after washing with a pattern. Got.

[Measurement of film thickness]

The film thickness measuring apparatus [DEKTAK3; The film thickness was measured using Nihon Shinku Gijutsu Co., Ltd. product. The results are shown in Table 4.

[Color evaluation]

Colorimeter [OSP-SP-200; Spectroscopy was measured using Olympus Co., Ltd., and the x, y chromaticity coordinates (x, y) and brightness Y in the XYZ colorimeter of the CIE (International Lighting Commission) were measured using the characteristic function of the C light source. . The results are shown in Table 4.

According to the colored curable resin composition of this invention, the color filter which is high contrast can be manufactured.

Claims (12)

A fluorescent dye (A1), a coloring agent (A2) different from the fluorescent dye, a resin (B), a polymerizable compound (C) and a polymerization initiator (D),
When the 1st composition, 2nd composition, and 3rd composition are prepared using each said raw material, the optical property of the coating film formed from these compositions satisfy | fills Formula (X), The coloring curable resin composition characterized by the above-mentioned.
F ₃ / F ₁ ≤T _e × T _f （X)
Wherein (X) of the, F ₃ represents the maximum fluorescence intensity in the maximum excitation wavelength (λ ₃₎ of the coating (thickness is 3㎛) formed of a third composition;
F ₁ represents the maximum fluorescence intensity at the maximum excitation wavelength λ ₁ of the coating film (thickness: 3 μm) formed of the first composition; Provided that F ₃ <F ₁ ;
T _e represents a transmittance of a coating film (thickness: 3 µm) formed of the second composition in the lambda ₁ ;
T _f represents a transmittance of a coating film (thickness: 3 μm) formed of the second composition at the wavelength λ _{f1 at} which F ₁ is measured;
The first composition comprises a fluorescent dye (A1), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), and the content of the fluorescent dye (A1) is a fluorescent dye (A1) and a resin (B). 2 mass% with respect to the total amount of the polymerizable compound (C) and the polymerization initiator (D);
The said 2nd composition contains a coloring agent (A2), resin (B), a polymeric compound (C), and a polymerization initiator (D), and content of a coloring agent (A2) has a coloring agent (A2), resin (B), and a polymeric property. It is 2 mass% with respect to the total amount of a compound (C) and a polymerization initiator (D);
The third composition comprises a fluorescent dye (A1), a coloring agent (A2), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), and the content of the fluorescent dye (A1) and the coloring agent (A2) 2 mass% with respect to the total amount of fluorescent dye (A1), colorant (A2), resin (B), polymerizable compound (C) and polymerization initiator (D)] The method of claim 1,
Said F <_3> / F <_1> is 0.01-0.6, The colored curable resin composition characterized by the above-mentioned. The method of claim 1,
The T _e × _f T is colored curable resin composition according to claim 0.7 or less. The method according to any one of claims 1 to 3,
The fluorescent dye is a colored curable resin composition, characterized in that the carbonium dye. The method according to any one of claims 1 to 3,
The fluorescent pigment is colored curable resin composition, characterized in that xanthene dye. The method according to any one of claims 1 to 3,
The said coloring agent (A2) has maximum absorption wavelength in the range of 490 nm or more and 780 nm or less, The colored curable resin composition characterized by the above-mentioned. The method according to any one of claims 1 to 3,
The total content of the said fluorescent dye (A1) and the said coloring agent (A2) is 5-65 mass% with respect to solid content of the said colored curable resin composition, The colored curable resin composition characterized by the above-mentioned. The method according to any one of claims 1 to 3,
Content of the said fluorescent dye (A1) is 1-99 mass% with respect to the total amount of the said fluorescent dye (A1) and the said coloring agent (A2), The colored curable resin composition characterized by the above-mentioned. The method according to any one of claims 1 to 3,
The said coloring agent (A2) is a pigment, and also contains the pigment dispersant with this pigment, The colored curable resin composition characterized by the above-mentioned. The method of claim 9,
The quantity of the said pigment dispersant is 0.1-100 mass parts with respect to 100 mass parts of said pigments, The colored curable resin composition characterized by the above-mentioned. It formed with the colored curable resin composition in any one of Claims 1-3, The color filter characterized by the above-mentioned. A display device comprising the color filter according to claim 11.