JP5785810B2 - Colored curable resin composition - Google Patents

Description

  The present invention relates to a colored curable resin composition.

  In order to realize the high color reproducibility of the liquid crystal display panel, it is required to increase the contrast of the color filter. Then, the coloring 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 much the brightness difference between the bright part and the dark part of the liquid crystal display panel can be increased. Contrast is measured by measuring the lightness when the transmission axes of two polarizing plates are parallel to each other and the lightness when they are orthogonal to each other when the color filter is sandwiched between two polarizing plates and light is irradiated from one side. It is expressed by the ratio of

Yoichi Kimura and 4 others, “Contrast Color Filter Resist for LCD TV”, Hitachi Chemical Technical Report, Hitachi Chemical Co., Ltd., January 2005, No. 44, p. 17-20

  Development of a colored curable resin composition capable of producing a high-contrast color filter is desired.

The present invention provides the following [1] to [3].
[1] A fluorescent dye (A1), a colorant (A2) different from the fluorescent dye, a resin (B), a polymerizable compound (C), and a polymerization initiator (D). A colored curable resin composition in which the optical properties of a coating film formed from these compositions satisfy Formula (X) when one composition, a second composition, and a third composition are prepared.
F ₃ / F ₁ ≦ T _e × T _f (X)
[In Formula (X), F ₃ represents the maximum fluorescence intensity at the maximum excitation wavelength λ ₃ of the coating film (thickness is 3 μm) formed from the third composition; F ₁ is formed from the first composition. Represents the maximum fluorescence intensity at the maximum excitation wavelength λ ₁ of the coating film (thickness is 3 μm); where F ₃ <F ₁ ; _Te is formed from the second composition at λ ₁ Represents the transmittance of the coating film (thickness is 3 μm); T _f represents the transmittance of the coating film (thickness is 3 μm) formed from the second composition at the wavelength λ _f1 at which F ₁ is measured; The first composition includes 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 the fluorescent dye (A1), 2% by mass based on the total amount of the resin (B), the polymerizable compound (C) and the polymerization initiator (D); the second composition is a colorant (A2), resin (B), polymerizable compound (C) and polymerization initiator (D), and the content of the colorant (A2) is the colorant (A2), resin (B), polymerizable compound ( C) and 2% by mass with respect to the total amount of the polymerization initiator (D); the third composition comprises a fluorescent dye (A1), a colorant (A2), a resin (B), and a polymerizable compound (C ) And a polymerization initiator (D), and the contents of the fluorescent dye (A1) and the colorant (A2) are the fluorescent dye (A1), the colorant (A2), the resin (B), and the polymerizable compound (C). And 2% by mass with respect to the total amount of the polymerization initiator (D). ]
[2] A color filter formed from the colored curable resin composition according to [1].
[3] A display device comprising the color filter according to [2].

  According to the colored curable resin composition of the present invention, a high-contrast color filter can be produced.

The colored curable resin composition of the present invention comprises a fluorescent dye (A1), a colorant (A2) different from the fluorescent dye, a resin (B), a polymerizable compound (C), and a polymerization initiator (D). . And when the said colored curable resin composition prepared the 1st composition, the 2nd composition, and the 3rd composition using the said each raw material, the optical characteristic of the coating film formed from these compositions is The expression (X) is satisfied.
F ₃ / F ₁ ≦ T _e × T _f (X)
[In Formula (X), F ₃ represents the maximum fluorescence intensity at the maximum excitation wavelength λ ₃ of the coating film (thickness: 3 μm) formed from the third composition; F ₁ is formed from the first composition Represents the maximum fluorescence intensity at the maximum excitation wavelength λ ₁ of the coating film (thickness 3 μm); where F ₃ <F ₁ ; _Te is formed from the second composition at λ ₁ T _f represents the transmittance of the coating film (thickness is 3 μm) formed from the second composition at the wavelength λ _f1 at which F ₁ is measured; The first composition includes 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 the fluorescent dye (A1), 2% by mass based on the total amount of the resin (B), the polymerizable compound (C) and the polymerization initiator (D); The product includes a colorant (A2), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), and the content of the colorant (A2) is the colorant (A2) and the resin (B). , 2% by mass based on the total amount of the polymerizable compound (C) and the polymerization initiator (D); the third composition comprises a fluorescent dye (A1), a colorant (A2), a resin (B), It contains a polymerizable compound (C) and a polymerization initiator (D), and the contents of the fluorescent dye (A1) and the colorant (A2) are the fluorescent dye (A1), the colorant (A2), the resin (B), and the polymerization. It is 2 mass% with respect to the total amount of an organic compound (C) and a polymerization initiator (D), respectively. ]

  In a color filter including a fluorescent dye, for example, when used in a liquid crystal display device, the fluorescent dye in the color filter is excited by the polarized light incident on the color filter to emit fluorescence. Therefore, in a color filter formed from a conventional colored curable resin composition, there is a problem that the polarization emitted from the color filter is disturbed by the fluorescence emitted from the fluorescent dye, so-called depolarization occurs, and the contrast is lowered. is there. On the other hand, in the colored curable resin composition of the present invention, the fluorescent dye (A1) and the colorant (A2) are used in combination so that the predetermined condition is satisfied, so that the fluorescent dye (A1) is used by the colorant (A2). ) Is reduced. Therefore, it can be set as the colored curable resin composition which can manufacture a high contrast color filter by using the colored curable resin composition of this invention.

In Formula (X), the smaller F ₃ / F ₁ means that the fluorescence derived from the fluorescent dye (A1) is suppressed by the colorant (A2). If the fluorescence (F ₃ ) emitted from the third composition is weak, “high contrast” will be achieved. However, since the fluorescence intensity is a relative value, it was defined by the ratio to the fluorescence (F ₁ ) emitted from the first composition. In order to increase the contrast, the maximum fluorescence intensity (F ₃ ) of the _third composition is reduced from the maximum fluorescence intensity (F ₁ ) of the first composition, that is, F ₃ <F ₁ . It is necessary to satisfy.
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. When F ₃ / F ₁ is within the above range, the contrast of the color filter obtained from the colored curable resin composition is further increased.

In formula (X), the smaller the T _e, the excitation light of the fluorescent dye (A1) is absorbed by the colorant (A2), because the excitation of the fluorescent dye (A1) is suppressed, it is formed by the third composition The fluorescence emitted from the coated film will be weakened. On the other hand, if 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. In addition, if either of these was achieved, as a result, the fluorescence emitted from the coating film formed by the third composition was suppressed, so the product _Te × _Tf was defined.
The value of _Te x _Tf is not particularly limited as long as it satisfies the formula (X), but is preferably 0.7 or less, more preferably 0.6 or less, and even more preferably 0.5 or less. The value of the T _e is preferably 0.95 or less, more preferably 0.9 or less, 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 value of the T _e × T _f, by said F ₃ / F ₁ of the value or more, the contrast of the color filter obtained from the colored curable resin composition is high. _If the value of T _e × T _f is less than the value of F ₃ / F ₁ , fluorescence is emitted from the fluorescent dye (A1) in the color filter obtained from the colored curable resin composition, and thus there is no bias. It will occur and the contrast will be low.

  The first composition includes a fluorescent dye (A1), a resin (B), a polymerizable compound (C), and a polymerization initiator (D). In the first composition, the content of the fluorescent dye (A1) is 2% in a total of 100% by mass of the fluorescent dye (A1), the resin (B), the polymerizable compound (C), and the polymerization initiator (D). %. The second composition contains a colorant (A2), a resin (B), a polymerizable compound (C), and a polymerization initiator (D). In the second composition, the content of the colorant (A2) is 2% in a total of 100% by mass of the colorant (A2), the resin (B), the polymerizable compound (C), and the polymerization initiator (D). %. The third composition includes a fluorescent dye (A1), a colorant (A2), a resin (B), a polymerizable compound (C), and a polymerization initiator (D). In the third composition, the content of the fluorescent dye (A1) is 100 in total of the fluorescent dye (A1), the colorant (A2), the resin (B), the polymerizable compound (C), and the polymerization initiator (D). It is 2 mass% in mass%. In the third composition, the content of the colorant (A2) is such that the fluorescent dye (A1), the colorant (A2), the resin (B), the polymerizable compound (C), and the polymerization initiator (D). It is 2 mass% in a total of 100 mass%.

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

The contents of the resin (B) in the total of the resin (B), the polymerizable compound (C) and the polymerization initiator (D) in the first composition, the second composition and the third composition are all compositions. It is preferable that it is the same in a thing.
The content of the polymerizable compound (C) in the total of the resin (B), the polymerizable compound (C) and the polymerization initiator (D) in the first composition, the second composition and the third composition is all It is preferable that they are the same in the composition.
The contents of the polymerization initiator (D) in the total of the resin (B), the polymerizable compound (C) and the polymerization initiator (D) in the first composition, the second composition and the third composition are all It is preferable that they are the same in the composition.
The first composition, the second composition and the third composition preferably all contain the same solvent.

  As a method for forming a coating film from the first composition, the second composition and the third composition, for example, when a photopolymerization initiator is used as the polymerization initiator (D), the composition is formed on a glass substrate. Examples of the method include spin coating so that the thickness after post-baking is 3 μm, pre-baking, exposure, and post-baking. Specifically, the method described in Examples described later is preferable.

The maximum fluorescence intensity is a maximum value of fluorescence intensity in a fluorescence spectrum measured using light of a certain wavelength as excitation light. The maximum excitation wavelength is the wavelength of the excitation light that gives the maximum maximum fluorescence intensity when the fluorescence spectrum is measured by varying the wavelength of the excitation light and the maximum fluorescence intensity in each fluorescence spectrum is measured. These maximum excitation wavelength and maximum fluorescence intensity can be measured with a fluorescence spectrophotometer, and details of the measurement method will be described later.
Here, the fluorescence intensity is easily affected by the apparatus. Therefore, in order to reduce a measurement error, it is preferable that F ₁ and F ₃ are continuously measured using the same apparatus under the same conditions.

The transmittance is a ratio (I / I ₀ ) between the intensity (I) of light transmitted through the coating film and the intensity (I ₀ ) of incident light. The transmittance can be measured with a colorimeter or a spectrophotometer, and details of the measuring method will be described later.

  The fluorescent dye (A1) is not particularly limited as long as it is a dye that generates fluorescence when irradiated with light. Examples of the fluorescent dye (A1) include fluorescent dyes and fluorescent pigments, and fluorescent dyes are preferred.

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

Examples of the fluorescent dye include compounds classified as dyes according to a color index (published by The Society of Dyers and Colorists), and known dyes described in dyeing notes (color dyeing company).
Specific examples of such compounds include C.I. I. Acid Yellow 3 (hereinafter, CI Solvent Yellow is omitted and only the number is described), 7, 250; I. Acid Red 77; I. Acid Blue 9; I. Basic yellow 1, 35, 40, 95; I. B. Basic Red 1-1, 13; I. B. Basic violet 7, 11: 1; I. B. Basic Orange 22; I. Basic Blue 7; C.I. I. Basic Green 1; C.I. I. Disperse yellow 121, 82; C.I. I. Disperse orange 11; C.I. I. Disper thread 58; C.I. I. Disperse blue 7; C.I. I. Direct yellow 11, 24, 26, 85, 100, 147; I. Direct orange 8, 13, 26, 29: 1, 46; I. Direct Red 1, 9, 17, 239, 240, 242, 254; C.I. I. Direct Blue 22; C.I. I. Direct Green 6; C.I. I. Solvent Yellow 7, 44; I. Solvent Red 49; I. Solvent Blue 5; C.I. I. Solvent Green 7 etc. are mentioned.

  Commercially available products of such compounds include Fluorescent series (Arimoto Chemical Co., Ltd.), rhodamine B, rhodamine 6 GCP (manufactured by Taoka Chemical Co., Ltd.), quinoline yellow SS-5G, quinoline yellow GC (central synthetic chemistry ( Azosol brilliant yellow 4GF, azosol fast blue GLA, seriton pink 3B, fast yellow YL, Victoria blue FN, brilliant sulfoflavin FF, thioflavine, basic yellow HG, fluorescein, eosin and the like.

Moreover, as said fluorescent dye, the xanthene dye (A11) which has as a main component the compound which has a xanthene skeleton in a molecule | numerator is mentioned.
Examples of the xanthene dye (A11) include C.I. I. Acid Red 51, 52 (Formula (A1-2)), 87, 92, 94 (Rose Bengal), 289 (Formula (A1-3)), 388, C.I. I. Acid Violet 9, 30, 102, C.I. I. Basic Red 1 (Rhodamine 6G) (Formula (A1-4)), 8, C.I. I. Basic Violet 10 (Rhodamine B), C.I. I. Solvent Red 218, C.I. I. Modern Tread 27, C.I. I. Reactive red 36 (rose bengal B), sulforhodamine G, xanthene dyes described in JP 2010-32999 A, xanthene dyes described in Japanese Patent No. 4492760, and the like.

  Among these, as the xanthene dye (A11), a dye containing a compound represented by the formula (1) (hereinafter sometimes referred to as “compound (1)”) is preferable. When using the said compound (1), 50 mass% or more is preferable, as for content of the compound (1) in a xanthene dye, More preferably, it is 70 mass% or more, More preferably, it is 90 mass% or more. In particular, it is preferable to use only the compound (1) as the xanthene dye.

［式（１）中、Ｒ¹〜Ｒ⁴は、それぞれ独立に、水素原子、−Ｒ⁸又は炭素数６〜１０の１価の芳香族炭化水素基を表す。
Ｒ⁵は、−ＯＨ、−ＳＯ₃ ^-、−ＳＯ₃Ｈ、−ＳＯ₃ ^-Ｚ⁺、−ＣＯ₂Ｈ、−ＣＯ₂ ^-Ｚ⁺、−ＣＯ₂Ｒ⁸、−ＳＯ₃Ｒ⁸又は−ＳＯ₂ＮＲ⁹Ｒ¹⁰を表す。
Ｒ⁶及びＲ⁷は、それぞれ独立に、水素原子又は炭素数１〜６のアルキル基を表す。
ｍは、０〜５の整数を表す。ｍが２以上の整数である場合、複数のＲ⁵は同一であるか相異なる。
ａは、０又は１の整数を表す。
Ｘは、ハロゲン原子を表す。
Ｒ⁸は、炭素数１〜２０の１価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、ハロゲン原子で置換されていてもよい。
Ｚ⁺は、⁺Ｎ（Ｒ¹¹）₄、Ｎａ⁺又はＫ⁺を表す。
Ｒ⁹及びＲ¹⁰は、それぞれ独立に、水素原子又は炭素数１〜２０の１価の飽和炭化水素基を表し、Ｒ⁹及びＲ¹⁰は、互いに結合して窒素原子を含んだ３〜１０員環の複素環を形成していてもよい。
Ｒ¹¹は、それぞれ独立に、水素原子、炭素数１〜２０の１価の飽和炭化水素基又は炭素数７〜１０のアラルキル基を表す。］

In Expression (1), R ¹ to R ⁴ each independently represents a monovalent aromatic hydrocarbon radical of hydrogen, -R ⁸ or 6 to 10 carbon atoms.
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 represents NR ⁹ R ¹⁰
R ⁶ and R ⁷ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
m represents an integer of 0 to 5. When m is an integer of 2 or more, the plurality of R ⁵ are the same or different.
a represents an integer of 0 or 1.
X represents a halogen atom.
R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a 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 are bonded to each other to contain a nitrogen atom and a 3 to 10 member A heterocyclic ring may be formed.
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. ]

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms represented by R ^{1 to} R ⁴ include a phenyl group, a toluyl group, a xylyl group, a mesityl group, a propylphenyl group, and a butylphenyl group. It is done.

In the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms represented by R ^{1 to} R ⁴ , the hydrogen atom contained in the aromatic hydrocarbon group is a halogen atom, —R ⁸ , —OH, —OR. ⁸ , —SO ₃ ⁻ , —SO ₃ H, —SO ₃ ^— Z ⁺ , —CO ₂ H, —CO ₂ R ⁸ , —SO ₃ R ^8, or —SO ₂ NR ⁹ R ¹⁰ may be substituted. . Among these _{^{substituents, -SO 3 -, -SO 3 H}} , -SO 3 - is preferably at least one selected from Z ⁺ and the group consisting of _{^{-SO 2 NR 9 R 10, -SO}} 3 - Z + and More preferred is at least one selected from the group consisting of —SO ₂ NR ⁹ R ¹⁰ . In this case, —SO ₃ ^{− +} N (R ¹¹ ) ₄ is preferable as —SO ₃ ⁻ Z ⁺ . When R ^{1 to} R ⁴ are these groups, the colored curable resin composition containing the compound (1) can form a color filter with less generation of foreign matters and excellent heat resistance.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ^{8 to} R ¹¹ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a nonyl group. Group, decyl group, dodecyl group, hexadecyl group, icosyl group and other linear alkyl groups; isopropyl group, isobutyl group, isopentyl group, neopentyl group, 2-ethylhexyl group and other branched chain alkyl groups; cyclopropyl group, cyclopentyl And an alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as a group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a tricyclodecyl group.

In the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ⁹ and R ¹⁰ , a hydrogen atom contained in the saturated hydrocarbon group may be substituted with —OH or a halogen atom, —CH ₂ — contained in the saturated aliphatic hydrocarbon group may be replaced by —O—, —CO—, —NH— or —NR ⁸ —.

The alkyl group having 1 to 6 carbon atoms represented by R ⁶ and R ^7, among the alkyl groups listed above, include those having 1 to 6 carbon atoms.

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 the ⁺ N (R ¹¹ ) ₄ , at least two of the four R ¹¹ are preferably monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. The total number of carbon atoms of the four R ¹¹ is preferably 20 to 80, 20 to 60 is more preferable. When R ¹¹ is these groups, the colored curable resin composition containing the compound (1) can form a coating film or a pattern with few foreign matters.

  m is preferably 1 to 4, and more preferably 1 or 2.

  As said xanthene dye (A11), the dye containing the compound (henceforth "compound (2)") represented by Formula (2) is more preferable. When the compound (2) is used, the content of the compound (2) in the xanthene dye is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more. In particular, it is preferable to use only the compound (2) as the xanthene dye.

［式（２）中、Ｒ²¹〜Ｒ²⁴は、それぞれ独立に、水素原子、−Ｒ²⁶又は炭素数６〜１０の１価の芳香族炭化水素基を表す。
Ｒ²⁵は、−ＳＯ₃ ^-、−ＳＯ₃Ｈ、−ＳＯ₃ ^-Ｚ１⁺又は−ＳＯ₂ＮＨＲ²⁶を表す。
ｍ１は、０〜５の整数を表す。ｍ１が２以上の整数である場合、複数のＲ²⁵は同一であるか相異なる。
ａ１は、０又は１の整数を表す。
Ｘ１は、ハロゲン原子を表す。
Ｒ²⁶は、炭素数１〜２０の１価の飽和炭化水素基を表す。
Ｚ１⁺は、⁺Ｎ（Ｒ²⁷）₄、Ｎａ⁺又はＫ⁺を表す。
Ｒ²⁷は、それぞれ独立に、炭素数１〜２０の１価の飽和炭化水素基又はベンジル基を表す。］

Wherein (2), R ²¹ ~R ²⁴ each independently represent a hydrogen atom, a monovalent aromatic hydrocarbon group -R ²⁶ or 6 to 10 carbon atoms.
R ²⁵ is, -SO ₃ ^- represents a Z1 ⁺ or _{^{-SO 2 NHR 26 -, -SO 3}} H, -SO 3.
m1 represents the integer of 0-5. When m1 is an integer of 2 or more, the plurality of R ²⁵ are the same or different.
a1 represents an integer of 0 or 1.
X1 represents a halogen atom.
R ²⁶ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.
Z1 ⁺ represents ⁺ N (R ²⁷ ) ₄ , Na ⁺ or K ⁺ .
R ²⁷ each independently represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a benzyl group. ]

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms represented by R ^{21 to} R ²⁴ include the same groups as those exemplified as the aromatic hydrocarbon group in R ^{1 to} R ⁴ . Hydrogen atoms contained in the aromatic hydrocarbon _{^{group, -SO 3 -, -SO 3 H}} , -SO 3 - Z1 +, may be substituted by -SO ₃ R ²⁶ or -SO ₂ NHR ^26.
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 aromatic hydrocarbons hydrogen atoms contained in the _{^{groups, -SO 3 -, -SO 3 H}} , -SO 3 - Z1 +, those substituted by -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ preferred. A more preferred 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 hydrogen contained in the aromatic hydrocarbon group atom, -SO ₃ ^- in which are substituted with Z1 ⁺ or -SO ₂ NHR ^26. When R ^{21 to} R ²⁴ are these groups, the colored curable resin composition containing the compound (2) can form a color filter having excellent heat resistance.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms 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 ²⁶ in R ²¹ to R ²⁴ each independently represent a hydrogen atom, a methyl group or an ethyl group. As the R ²⁶ in -SO ₃ R ²⁶ and -SO ₂ NHR ^26, preferably branched alkyl group having 3 to 20 carbon atoms, more preferably a branched alkyl group having 6 to 12 carbon atoms, A 2-ethylhexyl group is more preferred. When R ²⁶ is these groups, the colored curable resin composition containing the compound (2) can form a color filter with less generation of foreign matters.

Z1 ⁺ is ⁺ N (R ²⁷ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N (R ²⁷ ) ₄ .
As the ⁺ N (R ²⁷ ) ₄ , at least two of the four R ²⁷ are preferably monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. The total number of carbon atoms of the four R ²⁷ is preferably 20 to 80, 20 to 60 is more preferable. The colored curable resin composition containing the compound (2) in which R ²⁷ is any of these groups can form a color filter with less generation of foreign matters.

  m1 is preferably 1 to 4, and more preferably 1 or 2.

Examples of the compound (2) include compounds represented by the formulas (1-1) to (1-23). In the formula, R ²⁶ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched alkyl group having 6 to 12 carbon atoms, and more preferably a 2-ethylhexyl group. Among these, C.I. I. Acid red 289 sulfonamidation product, C.I. I. Quaternary ammonium salt of Acid Red 289, C.I. I. Acid violet 102 sulfonamidate or C.I. I. The quaternary ammonium salt of Acid Violet 102 is preferred. Examples of such a compound include compounds represented by formula (1-1) to formula (1-8), formula (1-11), and formula (1-12).

  The xanthene dye (A11) preferably has a maximum absorption wavelength in the range of 490 nm to 580 nm, more preferably in the range of 510 nm to 560 nm, and still more preferably in the range of 520 nm to 540 nm. The maximum absorption wavelength can be obtained from an absorption spectrum obtained by measuring a solution obtained by dissolving a dye in a solvent using a spectrophotometer.

  As the xanthene dye (A11), a commercially available xanthene dye (for example, “Chugai Aminol Fast Pink RH / C” manufactured by Chugai Kasei Co., Ltd., “Rhodamin 6G” manufactured by Taoka Chemical Industry Co., Ltd.) should be used. Can do. Moreover, it can also synthesize | combine with reference to Unexamined-Japanese-Patent No. 2010-32999 using the commercially available xanthene dye as a starting material.

  Examples of the fluorescent pigment include C.I. I. Pigment red 81, 173, 181 and the like. The fluorescent pigment may be a pigment obtained by dyeing or dissolving the fluorescent dye in a synthetic resin and pulverizing a solid solution that is the obtained colored bulk resin. Examples of the synthetic resin include acrylic resin, vinyl chloride resin, alkyd resin, aromatic sulfonamide resin, urea resin, melamine resin, and benzoguanamine resin.

  The content of the fluorescent dye (A1) is preferably 0.1 to 60% by mass, more preferably 0.2 to 35% by mass, and still more preferably 0.5% with respect to the solid content of the colored curable resin composition. -25% by mass. Here, solid content in this specification means the total amount of the component except a solvent from colored curable resin composition. Solid content can be measured by well-known analysis means, such as a liquid chromatography or a gas chromatography, for example.

The colorant (A2) different from the fluorescent dye (A1) can be used as a dye or a pigment, and a pigment is preferred.
Examples of the dye (A21) used in the colorant (A2) include compounds classified as dyes in the Color Index (published by The Society of Dyers and Colorists) and dyeing notes (color dyeing company). And known dyes.
Specific examples of such a dye (A21) include solvent dyes, acid dyes, direct dyes, and mordant dyes. These dyes may be appropriately selected according to the desired spectral spectrum of the color filter. These dyes may be used alone or in combination of two or more.

  As the solvent dye, C.I. I. Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162; C.I. I. Solvent Red 45, 125, 130; C.I. I. Solvent Orange 2, 7, 11, 15, 26, 56; C.I. I. Solvent Blue 35, 37, 59, 67; C.I. I. Solvent green 1, 3, 4, 5, 28, 29, 32, 33, 34, 35 etc. are mentioned.

As the acid dye, C.I. 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; 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; I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173; 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. 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. I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141; C.I. 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, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250; I. Direct orange 34, 39, 41, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; 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; I. Direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; I. Direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 etc. are mentioned.

  As the mordant dye, C.I. I. Modern dyes such as C.I. I. Modern yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; C.I. 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; 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. I. Modern Blue 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; I. Modern violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58; I. Modern green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53 etc. are mentioned.

Examples of the pigment (A22) used in the colorant (A2) include compounds classified as pigments according to a color index (published by The Society of Dyers and Colorists).
Specific examples of such pigment (A22) include C.I. 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, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214; I. C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments; I. Red pigments such as CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265; C. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60; I. Violet pigments such as C.I. Pigment Violet 1, 19, 23, 29, 32, 36, 38; I. Green pigments such as CI Pigment Green 7, 36, 58; I. C.I. brown pigments such as CI Pigment Brown 23 and 25; I. And black pigments such as CI Pigment Black 1 and 7.

  Among these, C.I. I. Pigment yellow 138, 139, 150, C.I. I. Pigment red 177, 209, 242, 254, C.I. I. Pigment violet 23, C.I. I. Pigment blue 15: 3, 15: 6 and C.I. I. Pigment Green 7, 36, and 58 are preferable. These pigments may be used alone or in combination of two or more.

  When the pigment (A22) is used as the colorant (A2), it is used after being subjected to a dispersion treatment in the presence of a pigment dispersant to obtain a pigment dispersion in which the pigment is uniformly dispersed in a solvent. preferable. Examples of the pigment dispersant include surfactants such as cationic, anionic, nonionic, amphoteric, polyester and polyamine. These pigment dispersants may be used alone or in combination of two or more. It may be used.

  Specific examples of the pigment dispersant include, for example, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, polyethylene Examples include imines. As commercial products, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Geneca Co., Ltd.), EFKA (manufactured by CIBA) Disperbyk (registered trademark) (manufactured by Big Chemie) and Azisper (registered trademark) (manufactured by Ajinomoto Fine Techno Co., Ltd.).

  When a pigment dispersant is used, the amount used is preferably 0.1 to 100 parts by mass, more preferably 5 to 50 parts by mass with respect to 100 parts by mass of the pigment (A22). When the amount of the pigment dispersant used is in the above range, a uniform pigment dispersion tends to be obtained.

  The colorant (A2) preferably has a maximum absorption wavelength in the range of 490 nm to 780 nm, more preferably in the range of 520 nm to 740 nm, and still more preferably in the range of 550 nm to 700 nm.

  The total content of the fluorescent dye (A1) and the colorant (A2) is preferably 5 to 65% by mass, more preferably 8 to 60% by mass, and still more preferably based on the solid content of the colored curable resin composition. Is 10-55 mass%. When the total content of the fluorescent dye (A1) and the colorant (A2) is in the above range, the resulting pattern 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, and still more preferably 5 to 5%, based on the total amount of the fluorescent dye (A1) and the colorant (A2). 40% by mass.
The content of the colorant (A2) is preferably 1 to 99% by mass, more preferably 40 to 97% by mass, and even more preferably 60 to 60% by mass with respect to the total amount of the fluorescent dye (A1) and the colorant (A2). 95% by mass.

  When the colored curable resin composition contains a dye (A21), the content of the dye (A21) is preferably 0.1 to 50% by mass, more preferably based on the solid content of the colored curable resin composition. Is 0.1-30 mass%. By containing the dye (A21) in the above content, the transmission spectrum of the obtained color filter can be easily optimized, and a colored curable resin composition having excellent developability can be obtained.

  When the colored curable resin composition contains the fluorescent dye (A1) and the pigment (A22), the content of the fluorescent dye (A1) is preferably relative to the total amount of the fluorescent dye (A1) and the pigment (A22). Is 1 to 99% by mass, more preferably 1 to 70% by mass, and still more preferably 1 to 50% by mass. Further, the content of the pigment (A22) is preferably 1 to 99% by mass, more preferably 30 to 99% by mass, and still more preferably 50 to the total amount of the fluorescent dye (A1) and the pigment (A22). 99% by mass.

  When the colored curable resin composition contains a xanthene dye (A11) and a pigment (A22), the content of the xanthene dye (A11) is preferably relative to the total amount of the xanthene dye (A11) and the pigment (A22). Is 1 to 70% by mass, more preferably 1 to 60% by mass, and still more preferably 1 to 50% by mass. The content of the pigment (A22) is preferably 30 to 99% by mass, more preferably 40 to 99% by mass, and still more preferably 50 to 100% by mass with respect to the total amount of the xanthene dye (A11) and the pigment (A2). 99% by mass. When the content of the xanthene dye (A11) and the pigment (A22) is in the above range, the resulting pattern tends to be excellent in contrast, brightness, heat resistance, and chemical resistance.

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

The colored curable resin composition of the present invention contains a binder resin (B). The binder resin (B) is not particularly limited, but is preferably an alkali-soluble resin. Examples of the binder resin (B) include the following resins [K1] to [K6].
[K1] at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (a) (hereinafter sometimes referred to as “(a)”), a cyclic ether structure having 2 to 4 carbon atoms, A copolymer with a monomer (b) having an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b)”).
[K2] (a), (b), and monomer (c) copolymerizable with (a) (however, different from (a) and (b)) (hereinafter referred to as “(c)”) Copolymer).
[K3] A 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).
[K6] A resin obtained by reacting a copolymer of (b) and (c) with (a) and further reacting with a carboxylic acid anhydride.

Specific examples of (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, dimethyltetrahydrophthalic acid, 1,4- Unsaturated dicarboxylic acids such as cyclohexene dicarboxylic acid; methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2. 2.1] Hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [ 2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2 Bicyclounsaturated compounds containing a carboxy group such as 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, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride ( Unsaturated dicarboxylic acid anhydrides such as hydric acid anhydride; succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], etc. Unsaturated mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids having two or more valences; unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid And the like. These (a) may be used independently and may use 2 or more types together.
Among these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoint of copolymerization reactivity and solubility in an aqueous alkali solution.

The (b) includes, for example, a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring (oxolane ring)) and an ethylenically unsaturated bond. It is a polymerizable compound having. As said (b), the monomer which has C2-C4 cyclic ether and (meth) acryloyloxy group is preferable.
In the present specification, “(meth) acrylic acid” represents at least one selected from the group consisting of acrylic acid and methacrylic acid. Notations such as “(meth) acryloyl” and “(meth) acrylate” have the same meaning.

  Examples of (b) include a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1)”), and an oxetanyl group and an ethylenically unsaturated bond. Monomer (b2) (hereinafter sometimes referred to as “(b2)”), monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b3)”), etc. Is mentioned.

  Examples of the (b1) include a monomer (b1-1) having a structure obtained by epoxidizing an unsaturated aliphatic hydrocarbon (hereinafter sometimes referred to as “(b1-1)”), an unsaturated alicyclic group. And a monomer (b1-2) having a structure obtained by epoxidizing a hydrocarbon (hereinafter sometimes referred to as “(b1-2)”).

  Examples of (b1-1) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl 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 (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) The Tylene, 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6- Examples include tris (glycidyloxymethyl) styrene.

  Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate. (For example, Cyclomer A400; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100; manufactured by Daicel Chemical Industries, Ltd.), represented by Formula (I) And compounds represented by formula (II).

［式（Ｉ）及び式（II）中、Ｒ^b1及びＲ^b2は、互いに独立に、水素原子、又は炭素数１〜４のアルキル基を表し、該アルキル基に含まれる水素原子は、ヒドロキシ基で置換されていてもよい。
Ｌ¹及びＬ²は、互いに独立に、単結合、−Ｒ^b3−、＊−Ｒ^b3−Ｏ−、＊−Ｒ^b3−Ｓ−、＊−Ｒ^b3−ＮＨ−を表す。Ｒ^b3は、炭素数１〜６のアルカンジイル基を表す。＊は、Ｏとの結合手を表す。］

[In Formula (I) and Formula (II), R ^b1 and R ^b2 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is a hydroxy group May be substituted.
L ¹ and L ² each independently represent a single bond, —R ^b3 —, * —R ^b3 —O—, * —R ^b3 —S—, * —R ^b3 —NH—. R ^b3 represents an alkanediyl group having 1 to 6 carbon atoms. * 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 having a hydrogen atom substituted with hydroxy include, for example, a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, and a 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-hydroxybutyl group Etc.
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 methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5- Examples thereof include a diyl group and a hexane-1,6-diyl group.
L ¹ and L ² are preferably a single bond, a methylene group, an ethylene group, * —CH ₂ —O— (* represents a bond to O) group, or * —CH ₂ CH ₂ —O— group. More preferably, a single bond and a * —CH ₂ CH ₂ —O— group are mentioned.

  Examples of the compound represented by the formula (I) include compounds represented by the formula (I-1) to the formula (I-15). Preferably Formula (I-1), Formula (I-3), Formula (I-5), Formula (I-7), Formula (I-9), Formula (I-11) to Formula (I-15) Is mentioned. More preferably, Formula (I-1), Formula (I-7), Formula (I-9), and Formula (I-15) are mentioned.

  Examples of the compound represented by the formula (II) include compounds represented by the formula (II-1) to the formula (II-15). Preferably Formula (II-1), Formula (II-3), Formula (II-5), Formula (II-7), Formula (II-9), Formula (II-11) to Formula (II-15) Is mentioned. More preferably, Formula (II-1), Formula (II-7), Formula (II-9), and Formula (II-15) are mentioned.

  The compound represented by the formula (I) and the compound represented by the formula (II) can be used alone. They can also be mixed in any ratio. When mixing, the mixing ratio is a molar ratio, preferably 5:95 to 95: 5, more preferably 10:90 to 90:10, and still more preferably 20:80 in formula (I): formula (II). ~ 80: 20.

  As the monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond, a monomer having an oxetanyl group and a (meth) acryloyloxy group is more preferable. Examples of (b2) include 3-methyl-3-methacryloyloxymethyl oxetane, 3-methyl-3-acryloyloxymethyl oxetane, 3-ethyl-3-methacryloyloxymethyl oxetane, and 3-ethyl-3-acryloyloxymethyl. Examples thereof include oxetane, 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, and 3-ethyl-3-acryloyloxyethyl oxetane.

  As the monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond, a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group is more preferable. Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, Biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

  (B) is a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond in that the reliability of the obtained color filter such as heat resistance and chemical resistance can be further increased. Preferably there is. Furthermore, the monomer (b1-2) which has the structure which epoxidized unsaturated alicyclic hydrocarbon is more preferable at the point that the storage stability of colored curable resin composition is excellent.

  Examples of (c) (a polymerizable monomer different from the above (a) and (b)) include, for example, (meth) acrylic acid esters, dicarboxylic acid diesters, bicyclounsaturated compounds, and dicarbonylimide derivatives. , Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3- Examples thereof include butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.

Examples of the (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) 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 ] decan-8-yl (meth) acrylate (in the art, it is referred to as “dicyclopentanyl (meth) acrylate” as a common name. In addition, “tricyclodecyl (meth) Acrylate " Sometimes referred.), Tricyclo (Meta) acrylate (the art, "dicyclopentenyl (meth acrylate as trivial name)" [5.2.1.0 ^{2, 6]} decene-8-yl is said to Dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate And (meth) acrylic acid esters such as benzyl (meth) acrylate; hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate.

  Examples of the dicarboxylic acid diester include diethyl maleate, diethyl fumarate, diethyl itaconate and the like.

  Examples of the bicyclo unsaturated compounds include bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, and 5-ethylbicyclo [2.2. .1] Hept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2′- Hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene 5,6-dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2 '-Hydroxyethyl) bicyclo [2.2.1] hept 2-ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methyl Bicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] ] Hept-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonyl Bicyclo [2.2.1] hept-2-ene, 5,6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbo) Le) bicyclo [2.2.1] hept-2-ene, and the like.

  Examples of the dicarbonylimide derivatives include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, and N-succinimidyl-6. -Maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N- (9-acridinyl) maleimide and the like.

  Said (c) may be used independently and may use 2 or more types together. Among these, as the component (c), from the viewpoint of copolymerization reactivity and heat resistance, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept- 2-ene and the like are preferable.

In the resin [K1], the ratio of the structural units derived from each is preferably in the following range among all the structural units constituting the resin [K1].
Structural unit derived from (a); 2 to 50 mol% (more preferably 10 to 45 mol%)
Structural unit derived from (b); 50 to 98 mol% (more preferably 55 to 90 mol%)
When the ratio of the structural unit of the resin [K1] is in the above range, the storage stability, developability, and solvent resistance of the resulting pattern tend to be excellent.

  The resin [K1] is, for example, a method described in the document “Experimental Method for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., First Edition, First Edition, issued March 1, 1972) and the document Can be produced with reference to the cited references described in 1.

  Specifically, a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are charged into a reaction vessel, and stirred, heated, and kept warm in a deoxygenated atmosphere. In addition, the polymerization initiator, the solvent, and the like used here are not particularly limited, and any of those usually used in the field can be used. For example, as polymerization initiators, azo compounds (2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.) Any solvent may be used as long as it dissolves each monomer, and a solvent (E) described later can be used as a solvent for the colored curable resin composition.

  In addition, the obtained copolymer may use the solution after reaction as it is, a concentrated or diluted solution may be used, and it took out as solid (powder) by methods, such as reprecipitation. Things may be used. In particular, by using a solvent (E) described later as a solvent in the polymerization, the solution after the reaction can be used as it is, and the manufacturing process can be simplified.

In the resin [K2], the ratio of the structural units derived from each is preferably within the following range among all the structural units constituting the resin [K2].
Structural unit derived from (a); 4-45 mol% (more preferably 10-30 mol%)
Structural unit derived from (b); 2-95 mol% (more preferably 5-80 mol%)
Structural unit derived from (c); 1 to 65 mol% (more preferably 5 to 60 mol%)
When the ratio of the structural unit of the resin [K2] is in the above range, the storage stability, developability, solvent resistance of the resulting pattern, heat resistance, and mechanical strength tend to be excellent.

Resin [K2] can be produced, for example, in the same manner as the method described as the production method of resin [K1].
Specifically, a predetermined amount of (a), (b) and (c), a polymerization initiator, and a solvent are charged into a reaction vessel, and the mixture is stirred, heated and kept warm in a deoxygenated atmosphere. As the obtained copolymer, the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, or a solid (powder) taken out by a method such as reprecipitation. May be used.

In the resin [K3], the ratio of the structural unit derived from each is preferably in the following range among all the structural units constituting the resin [K3].
Structural unit derived from (a); 2-55 mol%, more preferably 10-50 mol%
Structural unit derived from (c); 45 to 98 mol%, more preferably 50 to 90 mol%
Resin [K3] can be produced, for example, in the same manner as described for the production method of resin [K1].

Resin [K4] obtains a copolymer of (a) and (c), and (a) has a carboxylic acid and / or carboxylic acid anhydride having (a) a cyclic ether having 2 to 4 carbon atoms that (b) has It can manufacture by adding to.
First, a copolymer of (a) and (c) is produced in the same manner as the method described as the production method of [K1]. In this case, the ratio of the structural units derived from each is preferably in the following range among all the structural units constituting the copolymer of (a) and (c).
Structural unit derived from (a); 5-50 mol% (more preferably 10-45 mol%)
Structural unit derived from (c); 50 to 95 mol% (more preferably 55 to 90 mol%)

Next, the C2-C4 cyclic ether which (b) has is reacted with a part of the carboxylic acid and / or carboxylic anhydride derived from (a) in the copolymer.
Subsequent to the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced from nitrogen to air, and (b) a reaction catalyst of carboxylic acid or carboxylic anhydride and cyclic ether (for example, tris ( (Dimethylaminomethyl) phenol and the like) and a polymerization inhibitor (for example, hydroquinone and the like) are placed in a flask and reacted at, for example, 60 to 130 ° C. for 1 to 10 hours to obtain a resin [K4]. .
The amount of (b) used is preferably 5 to 80 mol, more preferably 10 to 75 mol, per 100 mol of (a). By setting it as this range, there exists a tendency for the balance of storage stability, developability, solvent resistance, heat resistance, mechanical strength, and sensitivity to become favorable. Since the reactivity of the cyclic ether is high and unreacted (b) hardly remains, (b1) is preferable as (b) used for the resin [K4], and (b1-1) is more preferable.
The amount of the reaction catalyst used is preferably 0.001 to 5 mass% with respect to the total amount of (a), (b) and (c). The amount of the polymerization inhibitor used is preferably 0.001 to 5% by mass with respect to the total amount of (a), (b) and (c).
The reaction conditions such as the charging method, reaction temperature, and time can be appropriately adjusted in consideration of the production equipment and the amount of heat generated by polymerization. In addition, like the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.

Resin [K5] obtains a copolymer of (b) and (c) as a first step in the same manner as in the method for producing resin [K1] described above. Similarly to the above, the obtained copolymer may be used as it is after the reaction, or may be a concentrated or diluted solution, or may be solid (powder) by a method such as reprecipitation. You may use what was taken out as.
The ratio of the structural units derived from (b) and (c) is preferably in the following range with respect to the total number of moles of all structural units constituting the copolymer.
Structural unit derived from (b); 5-95 mol% (more preferably 10-90 mol%)
Structural unit derived from (c); 5-95 mol% (more preferably 10-90 mol%)

Further, under the same conditions as in the method for producing the resin [K4], the cyclic ether derived from (b) of the copolymer of (b) and (c) is added to the carboxylic acid or carboxylic acid anhydride of (a). Resin [K5] can be obtained by reacting the product.
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 the reactivity of the cyclic ether is high and unreacted (b) hardly remains, (b1) is preferable as (b) used for the resin [K5], and (b1-1) is more preferable.

Resin [K6] is a resin obtained by further reacting carboxylic anhydride with resin [K5]. Carboxylic anhydride is reacted with a hydroxy group generated by reaction of cyclic ether with carboxylic acid or carboxylic anhydride.
Carboxylic anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1 2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (highmic acid anhydride) and the like. It is done.

As the binder resin (B), specifically, 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] Resin such as decyl acrylate / (meth) acrylic acid copolymer [K1]; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meta ) Acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3-methyl-3- (meth) Resin [K2] such as acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer; benzyl (meth) acrylate Resin [K3] such as silicate / (meth) acrylic acid copolymer and styrene / (meth) acrylic acid copolymer; glycidyl (meth) acrylate in benzyl (meth) acrylate / (meth) acrylic acid copolymer Added resin, resin obtained by adding glycidyl (meth) acrylate to tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / ( Resin [K4] such as a resin in which glycidyl (meth) acrylate is added to a (meth) acrylic acid copolymer; (meth) acrylic acid is reacted with a tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate copolymer Resin, tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate Resin such as a resin obtained by reacting (meth) acrylic acid with a copolymer of [K5]; a resin obtained by reacting (meth) acrylic acid with a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate In addition, resin [K6] such as a resin obtained by further reacting with tetrahydrophthalic anhydride.
These resins may be used alone or in combination of two or more.

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

The polystyrene-reduced weight average molecular weight of the binder resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and further preferably 5,000 to 30,000. It is. When the average molecular weight is within the above range, the solubility of the unexposed area in the developer tends to be high, and the remaining film ratio and hardness of the resulting pattern tend to be high.
The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the binder resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.
The acid value of the binder resin (B) is preferably 50 to 180 mg-KOH / g, more preferably 60 to 150 mg-KOH / g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the resin, and can be determined by titration using, for example, an aqueous potassium hydroxide solution.

  The content of the binder resin (B) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 65% by mass with respect to the solid content of the colored curable resin composition. 55% by mass. When the content of the binder resin (B) is in the above range, the solubility of the unexposed area in the developer tends to be high.

  The colored curable resin composition of the present invention contains a polymerizable compound (C). The polymerizable compound (C) is a compound that can be polymerized by active radicals and / or acids generated from the polymerization initiator (D) by the action of light or heat, and includes, for example, a polymerizable ethylenically unsaturated bond. The compound etc. which have are mentioned, Preferably a (meth) acrylic acid ester compound is mentioned.

  The polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octane. (Meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, ethylene glycol modified penta Erythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol hexa (meth) acrylate, propylene glycol Le-modified pentaerythritol tetra (meth) acrylate, propylene glycol-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate. Of these, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable. These polymerizable compounds may be used alone or in combination of two or more.

  Content of polymeric compound (C) becomes like this. Preferably it is 7-65 mass% with respect to solid content of a colored curable resin composition, More preferably, it is 13-60 mass%, More preferably, 17- 55% by mass. When the content of the polymerizable compound (C) is within the above range, the curing is sufficiently performed, the film thickness ratio before and after the development is improved, the pattern is less likely to be undercut, and the adhesion is good. It is preferable because it tends to become.

The colored curable resin composition of the present invention contains a polymerization initiator (D). The polymerization initiator (D) is not particularly limited as long as it generates an active radical by the action of light or heat and can initiate polymerization of the polymerizable compound (C), and a known radical polymerization initiator can be used. Can be used.
The polymerization initiator (D) is preferably a compound that generates an active radical by the action of light, more preferably an alkylphenone compound, a triazine compound, an acyl phosphine oxide compound, an oxime compound, and a biimidazole compound, and a polymerization start containing an oxime compound. More preferred are agents.

Examples of the alkylphenone compounds include α-aminoalkylphenone compounds, α-alkoxyalkylphenone compounds, and α-hydroxyalkylphenone compounds.
Examples of the α-aminoalkylphenone compound include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutane. -1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2- (4-methylphenylmethyl) butan-1-one, and the like. Examples of commercially available products include Irgacure (registered trademark) 369, 379, and 907 (above, manufactured by BASF).
Examples of the α-alkoxyalkylphenone compound include diethoxyacetophenone and benzyldimethyl ketal.
Examples of the α-hydroxyalkylphenone compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propane-1 -One, 1-hydroxycyclohexyl phenyl ketone, oligomers of 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, 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl). ) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (Trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2- Methylphenyl) ete Le] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Commercial products such as Irgacure (registered trademark) 819 (manufactured by BASF) may be used.

  Examples of the oxime compound include O-acyl oxime compounds. Specifically, N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1 -(4-Phenylsulfanylphenyl) octane-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 and the like. Commercial products such as Irgacure (registered trademark) OXE01, OXE02 (above, manufactured by BASF), N-1919 (manufactured by ADEKA) may be used. Among them, N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine preferable. When these oxime compounds are used, a high brightness color filter tends to be obtained.

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,3-dichlorophenyl) -4, 4 ', 5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 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 (trialkoxy) Nyl) biimidazole (for example, see JP-B-48-38403, JP-A-62-174204, etc.), and the phenyl group at the 4,4′5,5′-position is substituted with a carboalkoxy group. Examples thereof include imidazole compounds (for example, see JP-A-7-10913). Preferably, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,3-dichlorophenyl) -4,4 ′, 5 Examples include 5'-tetraphenylbiimidazole and 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole.

  Furthermore, as the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl- Benzophenone compounds such as 4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, Examples include quinone compounds such as 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with a polymerization initiation assistant (D1) (particularly amines) described later.

  The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 5 to 100 parts by mass of the total amount of the binder resin (B) and the polymerizable compound (C). 25 parts by mass. When the content of the polymerization initiator (D) is in the above range, a pattern can be formed with high sensitivity, and a color filter with higher brightness tends to be obtained.

The colored curable resin composition of the present invention preferably further contains a polymerization initiation assistant (D1). When the polymerization initiation assistant (D1) is included, it is usually used in combination with the polymerization initiator (D). The polymerization initiation assistant (D1) is a compound or a sensitizer used for accelerating the polymerization of the polymerizable compound that has been polymerized by the polymerization initiator.
Examples of the polymerization initiation assistant (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, carboxylic acid compounds, and the like, and thioxanthone compounds are preferred.

  Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

  Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4 2-dimethylhexyl dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (Ethylmethylamino) benzophenone and the like can be mentioned, among which 4,4′-bis (diethylamino) benzophenone is preferable. Commercial products such as EAB-F (Hodogaya Chemical Co., Ltd.) may be used.

  Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-di. Examples include butoxyanthracene and 2-ethyl-9,10-dibutoxyanthracene.

  Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like can be mentioned.

These polymerization initiation assistants may be used alone or in combination of two or more.
Moreover, when using a polymerization start adjuvant (D1), the usage-amount is preferably 0.1-30 mass parts with respect to 100 mass parts of total amounts of binder resin (B) and polymeric compound (C), More preferably, it is 1-20 mass parts. Moreover, Preferably it is 20-100 mass parts with respect to 100 mass parts of content of a polymerization initiator (D), More preferably, it is 30-80 mass parts. When the amount of the polymerization initiation assistant (D1) is within this range, a pattern can be formed with high sensitivity, and a color filter with higher brightness tends to be obtained.

The colored curable resin composition of the present invention preferably contains a solvent (E).
A 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 the molecule and not containing —O—), an ether solvent (a solvent containing —O— in the molecule and not containing —COO—), an ether ester solvent (intramolecular) Solvent containing -COO- and -O-), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent, aromatic hydrocarbon solvent, amide solvent, dimethyl sulfoxide, etc. Can be selected and used.

  Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyric acid Examples include butyl, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

  Examples of the ether solvent include 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, di Chi glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, methyl anisole, and the like.

  Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3- Ethyl ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate , Ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ester Ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and the like.

  Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, Examples include isophorone.

  Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

  Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, mesitylene and the like.

Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.
These solvents may be used alone or in combination of two or more.

  Among the above-mentioned solvents, an organic solvent having a boiling point of 120 ° C. or more and 180 ° C. or less at 1 atm (101.325 kPa) is preferable from the viewpoints of coating properties and drying properties. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, 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, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, More preferred are 3-methoxy-1-butanol, ethyl 3-ethoxypropionate and the like.

  The content of the solvent (E) in the colored curable resin composition is preferably 70 to 95% by mass and more preferably 75 to 92% by mass with respect to the colored curable resin composition. In other words, the solid content of the colored curable resin composition is preferably 5 to 30% by mass, more preferably 8 to 25% by mass. When the content of the solvent (E) is in the above range, the flatness at the time of coating is good, and when the color filter is formed, the color density does not become insufficient and the display characteristics tend to be good.

  The colored curable resin composition of the present invention may further contain a surfactant (F). Examples of the surfactant (F) include silicone surfactants, fluorine surfactants, and silicone surfactants having a fluorine atom. These may have a polymerizable group in the side chain.

  Examples of the silicone-based surfactant include surfactants having a siloxane bond. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH29PA, SH30PA, SH8400 (manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (made by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (made by Momentive Performance Materials Japan GK), etc. are mentioned.

  Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain. Specifically, Florard (trade name) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), MegaFac (registered trademark) F142D, F171, F172, F173, F177, F183, R183, R30, RS-718-K (manufactured by DIC Corporation), Ftop (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals), Surflon (registered trademark) S381, S382, SC101, SC105 (Asahi Glass Co., Ltd.), E5844 (Daikin Fine Chemical Laboratory Co., Ltd.) and the like.

Examples of the silicone-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain. Specifically, Megafac (registered trademark) R08, BL20, F475, F477, F443 (manufactured by DIC Corporation) and the like can be mentioned.
These surfactants may be used alone or in combination of two or more.

  The content of the surfactant (F) is preferably 0.001% by mass or more and 0.2% by mass or less, and preferably 0.002% by mass or more and 0.1% by mass with respect to the colored curable resin composition. Below, more preferably 0.01 mass% or more and 0.05 mass% or less. However, the content of the pigment dispersant is not included in the content of the surfactant (F). When the content of the surfactant (F) is in the above range, the flatness of the coating film can be improved.

  The colored curable resin composition of the present invention includes various additives such as fillers, other polymer compounds, adhesion promoters, antioxidants, ultraviolet absorbers, light stabilizers, chain transfer agents, and the like as necessary. May be included.

Examples of a method for forming a color filter pattern using the colored curable resin composition of the present invention include a photolithographic method, an ink jet method, a printing method, and the like. Among these, a photolithography method is preferable. In order to form a pattern by the photolithographic method, it is applied onto a substrate or another resin layer (for example, another colored curable resin composition layer previously formed on the substrate), and a volatile component such as a solvent. Is removed (dried) to form a colored layer, and the colored layer is exposed through a photomask and developed. In the photolithography method described above, a coating film having no pattern can be formed by not using a photomask and / or not developing during exposure.
The film thickness of the pattern or coating film to be produced is not particularly limited, and can be appropriately adjusted depending on the material used, application, etc. For example, 0.1-30 μm, preferably 1-20 μm, more preferably 1-6 μm is there.

As a substrate, glass plate such as quartz glass, borosilicate glass, alumina silicate glass, soda lime glass coated with silica on the surface; resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate; silicon, on the substrate Aluminum, silver, silver / copper / palladium alloy thin film, etc. are used. On these substrates, another color filter layer, a resin layer, a transistor, a circuit, and the like may be formed.
Examples of the coating method include spin coating, slit coating, and slit-and-spin coating.

  As a method of forming each color pixel by the photolithography method, a known or commonly used method can be used. For example, it can be produced as follows.

The colored curable resin composition is applied onto a substrate, and volatile components such as a solvent are removed by drying by heating (pre-baking) and / or drying under reduced pressure to obtain a smooth coating film.
30-120 degreeC is preferable and the temperature in the case of performing heat drying has more preferable 50-110 degreeC. In addition, the heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.
When performing vacuum drying, 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 particularly limited and can be appropriately adjusted depending on the material used, application, etc., and is, for example, 0.1 to 20 μm, preferably 0.5 to 6 μm.

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 particularly limited, and a pattern shape corresponding to the intended application is used.
The light source used for exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, light less than 350 nm can be cut using a filter that cuts this wavelength range, or light near 436 nm, 408 nm, and 365 nm can be selectively extracted using a bandpass filter that extracts these wavelength ranges. Or you may. Specific examples include mercury lamps, light emitting diodes, metal halide lamps, halogen lamps, and the like.
It is preferable to use an apparatus such as a mask aligner or a stepper because the entire exposed surface can be irradiated with parallel rays uniformly and accurate alignment between the mask and the substrate can be performed.

After exposure, a pattern can be obtained by contacting a developing solution to dissolve a predetermined portion, for example, an unexposed portion, and developing. As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, tetramethylammonium hydroxide and the like is preferable. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Further, the developer may contain a surfactant.
The developing method may be any of paddle method, dipping method, spray method and the like. Further, the substrate may be tilted at an arbitrary angle during development.
After development, it is preferable to wash with water.
Furthermore, you may post-bake as needed. The post-bake temperature is preferably 150 to 250 ° C, more preferably 160 to 235 ° C. The post-bake time is preferably 0.5 to 10 minutes, and more preferably 1 to 5 minutes.

  The pattern obtained as described above by the colored curable resin composition of the present invention is useful as a color filter. The color filter can be used in a known manner for devices related to various colored images such as a display device (for example, a liquid crystal display device, an organic EL device, etc.), a solid-state imaging device, and electronic paper.

  The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the following examples, and may be appropriately modified and implemented within a range that can meet the purpose described above and below. All of which are within the scope of the present invention. Unless otherwise specified, “%” and “parts” in the examples are% by mass and parts by mass.

Synthesis example 1
In a flask equipped with a condenser and a stirrer, a mixture of a compound represented by formula (A1-1a) and a compound represented by formula (A1-1b) (manufactured by Chugai Kasei Co., Ltd., trade name Chugai Aminol Fast Pink R 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 with stirring. After completion of the dropwise addition, the temperature was raised to 50 ° C., the reaction was continued for 5 hours at the same temperature, and then cooled to 20 ° C. While maintaining the reaction solution after cooling at 20 ° C. or lower with stirring, a mixed solution of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine was added dropwise. Then, it was made to react by stirring at the same temperature for 5 hours. Next, after the solvent of the obtained reaction mixture was distilled off with a rotary evaporator, a small amount of methanol was added and stirred vigorously. This mixture was added to a mixture of 375 parts of ion exchange water with stirring to precipitate crystals. The precipitated crystals were separated by filtration, washed well with ion-exchanged water, dried under reduced pressure at 60 ° C., and represented by xanthene dye A1-1 (formula (A1-1-1) to formula (A1-1-8). 11.3 parts of a mixture of the following compounds).

Synthesis example 2
Into a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was allowed to flow at 0.02 L / min to form a nitrogen atmosphere, 636 parts of ethyl lactate was added, and the mixture was heated to 70 ° C. with stirring. Next, 126 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (a compound represented by formula (I-1) and a compound represented by formula (II-1)) 294 parts were dissolved in 405 parts of ethyl lactate in a molar ratio of 50:50 to prepare a solution, and this solution was kept at 70 ° C. for 4 hours using a dropping funnel. It was dripped in. On the other hand, a solution obtained by dissolving 30 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 274 parts of ethyl lactate was dropped into the flask using another dropping funnel over 4 hours. After completion of the dropwise addition of the polymerization initiator solution, the temperature was maintained 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 A resin B1 solution having a content of 26% and a solution acid value of 31 mg-KOH / g was obtained. It is 122 mg-KOH / g when solid content acid value is calculated from said solid content and solution acid value.

The polystyrene-reduced weight average molecular weight (Mw) and number average molecular weight (Mn) of the resins obtained in the synthesis examples were measured by the GPC method under the following conditions. The ratio of the weight average molecular weight and the number average molecular weight (Mw / Mn) was defined as the molecular weight distribution.
Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)
Column; TSK-GELG2000HXL
Column temperature: 40 ° C
Solvent: THF
Flow rate: 1.0 mL / min
Test liquid solid content concentration: 0.001 to 0.01% by mass
Injection volume: 50 μL
Detector; RI
Reference material for calibration; TSK STANDARD POLYSTYRENE
F-40, F-4, F-288, A-2500, A-500
(Manufactured by Tosoh Corporation)

Examples and Comparative Examples [Preparation of Pigment Dispersion Liquid 1]
The following components were mixed and the pigment dispersion 1 was obtained by fully dispersing the pigment using a bead mill.
C. I. Pigment Blue 15: 6 34.7 parts Acrylic pigment dispersant 13.6 parts Propylene glycol monomethyl ether acetate 194 parts

[Preparation of pigment dispersion 2]
The following components were mixed and the pigment dispersion 2 was obtained by fully dispersing the pigment using a bead mill.
C. I. Pigment Blue 15: 6 33.3 parts 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 dispersing the pigment using a bead mill.
C. I. Pigment Blue 15: 6 31.9 parts Acrylic pigment dispersant 12.1 parts Propylene glycol monomethyl ether acetate 174 parts

C. used as colorant (A2) I. The maximum absorption wavelength of Pigment Blue 15: 6 is 600 nm. The maximum absorption wavelength of the colorant (A2) was measured as follows. Dissolve 0.35 g of colorant in ethyl lactate to a volume of 250 cm ³ , 2 cm ^{3 of} which is diluted with ethyl lactate to a volume of 100 cm ³ (concentration: 0.028 g / L), UV-visible near infrared spectroscopy The absorption spectrum at 400 to 700 nm was measured using a photometer (V-650; manufactured by JASCO Corporation) (quartz cell, optical path length: 1 cm). From the absorption spectrum, the wavelength at which the absorbance is maximized was determined and taken as the maximum absorption wavelength.

(Preparation of colored curable resin composition)
The components described in Table 1 were mixed to obtain a colored curable resin composition.

In Table 1, each component is as follows.
Fluorescent pigment (A1); Dye A1
Colorant (A2); C.I. I. Pigment Blue 15: 6 (included in each pigment dispersion)
Resin (B); Resin B1 (The content in Table 1 represents the value in terms of solid content.)
Polymerizable compound (C); dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Polymerization initiator (D); (D-1); N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF Corp .; Oxime Compound)
Polymerization initiator (D); (D-2); 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one (Irgacure 907; manufactured by BASF; alkylphenone compound)
Polymerization initiation aid (D1); 2,4-diethylthioxanthone (KAYACURE (registered trademark) DETX-S; manufactured by Nippon Kayaku Co., Ltd .; thioxanthone compound)
Solvent (E); (E-1); Ethyl lactate Surfactant (F); Polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.)
The surfactant was mixed so that the content in the colored curable resin composition was 0.05% by mass.

[Preparation of first to third compositions]
The components listed in Table 2 were mixed to obtain a composition. As shown in Table 3, these compositions correspond to the first to third compositions of the colored curable resin compositions 1 to 3 obtained above.

[Preparation of coating film]
About the composition of coloring curable resin compositions 1-3 and Table 2, the following operation was performed and the coating film was produced.
The composition was applied by spin coating on a 5 cm (2 inch) square glass substrate (Eagle XG; manufactured by Corning), and then pre-baked at 100 ° C. for 3 minutes. After standing to cool, using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.), it was irradiated with light at an exposure amount of 150 mJ / cm ² (based on 365 nm) in an air atmosphere. After light irradiation, post-baking was performed in an oven at 230 ° C. for 30 minutes to obtain a coating film. After standing to cool, the film thickness of the obtained coating film was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.), and found to be 3.0 μm.

[Measurement of maximum excitation wavelength and maximum fluorescence intensity]
The fluorescence spectrum was measured using a fluorescence spectrophotometer (FluoroMAX-3; manufactured by HORIBA, Ltd.) (excitation side slit 0.5, fluorescence side slit 2.5).
With respect to the coating film obtained from the composition (1-1), the excitation light wavelength is changed stepwise by 50 nm in the range of 400 to 700 nm, the fluorescence spectrum is measured, and the maximum fluorescence intensity of each fluorescence spectrum is determined. Asked. As a result, since the maximum fluorescence intensity showed the highest value at 550 nm, the excitation light wavelength was further changed step by step every 10 nm in the range of 500 to 600 nm, and the maximum fluorescence intensity was similarly determined. As a result, the maximum fluorescence intensity showed the largest value at 530 nm, and this was set as the maximum excitation wavelength λ ₁ (nm).
Further, when the maximum excitation wavelength was confirmed in the same manner as in the case of the maximum excitation wavelength λ ₁ for the coating film obtained from each third composition (1-3), the maximum fluorescence intensity was the highest value at 530 nm. Therefore, this was set to the maximum excitation wavelength λ ₃ (nm).
Then, the coating film obtained from the first composition (1-1), to measure the fluorescence spectrum at an excitation wavelength of 530 nm, was determined maximum fluorescence intensity F _1. At this time, the fluorescence wavelength λ _f1 (nm) at the maximum fluorescence intensity F ₁ was 575 nm. In addition, following this measurement, the fluorescence spectrum at an excitation wavelength of 530 nm was also measured for the coating film obtained from the third composition (1-3, 2-3, 3-3), and the maximum fluorescence intensity F _{3 was obtained.} Asked. From the obtained results, F ₃ / F ₁ was calculated and shown in Table 4.

(Measurement of transmittance)
For each coating film obtained from the second composition, the calorimeter; using (OSP-SP-200 manufactured by Olympus Corporation), the transmittance _{T e} and the maximum excitation wavelength lambda ₁ (nm) (530 nm) The transmittance T _f at the fluorescence wavelength λ _f1 (nm) (575 nm) was measured, and the product T _e × T _f of both was calculated. The results are shown in Table 4.

[Measurement of contrast]
About the coating film produced from the colored curable resin compositions 1-3, using a contrast meter (color difference meter BM-5A; manufactured by Topcon Corporation, light source: F-10, polarizing film; manufactured by Aisaka Electric Co., Ltd.). The contrast was measured. The blank value was 30000. The results are shown in Table 4.

[Pattern formation]
A colored curable resin composition is applied by spin coating on a 5 cm (2 inch) square glass substrate (Eagle XG; manufactured by Corning), and then pre-baked at 100 ° C. for 3 minutes to form a composition layer on the substrate. Formed. After cooling, the distance between the substrate on which the composition layer is formed and the quartz glass photomask having a pattern is set to 100 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Corp.) is used in an air atmosphere at 150 mJ. Light was irradiated with an exposure amount of / cm ² (based on 365 nm). As a photomask, a mask on which a 100 μm line and space pattern was formed was used. After the light irradiation, the composition layer was immersed and developed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 24 ° C. for 60 seconds, washed with water, Post-baking was carried out at 20 ° C. for 20 minutes to obtain a pattern.

[Film thickness measurement]
About the obtained pattern, the film thickness was measured using the film thickness measuring apparatus (DEKTAK3; Nippon Vacuum Technology Co., Ltd.). The results are shown in Table 4.

[Chromaticity evaluation]
About the obtained pattern, spectrum was measured using the colorimeter (OSP-SP-200; Olympus Co., Ltd.), and XYZ color system of CIE (International Lighting Commission) was used using the characteristic function of C light source. Xy chromaticity coordinates (x, y) and brightness Y were measured. The results are shown in Table 4.

  According to the colored curable resin composition of the present invention, a high-contrast color filter can be produced.

Claims (5)

Fluorescent dye (A1) which is a xanthene dye having a maximum absorption wavelength in the range of 490 nm to 580 nm, a colorant (A2) having a maximum absorption wavelength in the range of 490 nm to 780 nm and different from the fluorescent dye, resin (B ), A polymerizable compound (C) and a polymerization initiator (D),
When the first composition, the second composition, and the third composition are prepared using the respective raw materials, a colored curable resin that satisfies the formula (X) in the optical properties of the coating film formed from these compositions Composition.
F ₃ / F ₁ ≦ T _e × T _f (X)
Wherein (X), F ₃ represents a coating film formed from a third composition (3 [mu] m thickness), the maximum fluorescence intensity at the maximum excitation wavelength lambda _3;
F ₁ represents the maximum fluorescence intensity at the maximum excitation wavelength λ ₁ of the coating film (thickness: 3 μm) formed from the first composition; provided that F ₃ <F ₁ ;
T _e is in the lambda _1, (thickness 3 [mu] m) coating film formed from a second composition representing a transmittance;
T _f represents the transmittance of the coating film (thickness is 3 μm) formed from the second composition at the wavelength λ _f1 at which F ₁ is measured;
The first composition includes 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 the fluorescent dye (A1), 2% by mass based on the total amount of the resin (B), the polymerizable compound (C) and the polymerization initiator (D);
The second composition contains a colorant (A2), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), and the content of the colorant (A2) is the colorant (A2), 2% by mass based on the total amount of the resin (B), the polymerizable compound (C) and the polymerization initiator (D);
The third composition includes a fluorescent dye (A1), a colorant (A2), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and the fluorescent dye (A1) and the colorant (A2). ) Content is 2% by mass with respect to the total amount of the fluorescent dye (A1), the colorant (A2), the resin (B), the polymerizable compound (C) and the polymerization initiator (D). ] The colored curable resin according to claim 1, wherein the colorant is a pigment and further contains a pigment dispersant, and the amount of the pigment dispersant used is 39 parts by mass to 100 parts by mass with respect to 100 parts by mass of the pigment. Composition. F _Three / F ₁ Is 0.6 or less, T _e × T _f Is 0.7 or less, T _e Is 0.95 or less, T _f The colored curable resin composition according to claim 1, wherein is 0.9 or less. The color filter formed with the colored curable resin composition in any one of Claims 1-3. A display device comprising the color filter according to claim 4 .