JP5689851B2 - Colored curable composition, colored cured film, color filter and method for producing the same, display device, and novel compound - Google Patents

Description

  The present invention relates to a colored curable composition, a colored cured film using the same, a color filter provided with the colored cured film, a method for producing the color filter, and a display device including the color filter. The present invention also relates to a novel compound useful as a colorant contained in the colored curable composition.

  Conventionally, color filters are colored curable compositions by containing a pigment dispersion composition in which an organic pigment or an inorganic pigment is dispersed, a polyfunctional monomer, a polymerization initiator, an alkali-soluble resin, and other components as required. It is manufactured by forming a colored pattern by using a photolithography method, an ink jet method or the like.

  In recent years, color filters tend to be used not only for monitors but also for televisions (TVs) in liquid crystal display (LCD) applications. Along with this trend of expanding applications, color filters are required to have high color characteristics in terms of chromaticity and contrast. Similarly, color filters for image sensors (solid-state imaging devices) are required to further improve color characteristics such as reduction of color unevenness and improvement of color resolution.

  However, in the conventional pigment dispersion system, problems such as the occurrence of scattering due to coarse particles of the pigment and the increase in viscosity due to poor dispersion stability are likely to occur, and it is often difficult to further improve the contrast and brightness.

  Therefore, conventionally, as a colorant, it has been studied to use not only a pigment but also a dye (for example, see Patent Document 1). When a dye is used as a colorant, the hue and brightness of a display image when an image is displayed can be increased due to the color purity of the dye itself and the vividness of the hue, and contrast can be improved because coarse particles are eliminated. It is useful in terms.

  Examples of dyes include triarylmethane dyes and various colored compounds having a wide variety of dye bases such as pyridone azo dyes, dipyrromethene dyes, pyrimidine azo dyes, pyrazole azo dyes, xanthene dyes (for example, patent documents). 1-6).

JP 2010-168531 A JP-A-6-75375 JP 2008-292970 A JP 2007-039478 A Japanese Patent Laid-Open No. 06-230210 JP 2010-256598 A

  However, since the above known dyes have undesired absorption on the short wavelength side or long wavelength side of the absorption band, the color filter prepared using a colored curable composition containing such a dye is There has been a problem that the color purity and the luminance are lowered. Furthermore, since the above-mentioned known dyes are also inferior in heat resistance, there has been a problem that sufficient heat resistance cannot be obtained, for example, when post-baking is performed in the color filter production process.

The present invention has been made in view of the above-described problems, and the problem is to produce a color filter having a color pixel with good color purity, high luminance, and excellent heat resistance. It is to provide a colored curable composition that is suitably used.
Another object of the present invention is to provide a colored cured film having excellent color characteristics and heat resistance, a color filter provided with the colored cured film, a method for producing the color filter, and a display device including the color filter. Is to provide.
Furthermore, another object of the present invention is to provide a novel compound that is useful as a colorant, has small undesired absorption on the long wavelength side of the absorption band, and has heat resistance.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by the following means, and have reached the present invention.

<1> A colored curable composition containing the following component (A), component (B) and component (C).
(A) A colorant selected from compounds represented by the following general formula (I A-2 )

In General Formula (IA -2), R ¹ represents a t-butyl group. R ⁴ represents a hydrogen atom, an alkyl group, an aryl group, or a cyano group. R ⁵ represents an aryl group having a substituent. R ⁶ represents a hydrogen atom, an alkyl group, or an aryl group. Cy2 represents a ring structure containing a 5-membered ring or a 6-membered ring formed with adjacent carbon atoms .
(B) Colorant having a hue different from the colorant (A) (C) Polymerizable compound

<2> The colored curable composition according to <1>, wherein the (B) colorant is a colorant having a maximum absorption peak wavelength in a wavelength range of 380 nm to 800 nm in a range of 500 nm to 800 nm.

<3> The colored curable composition according to <1> or <2>, wherein the (B) colorant is a zinc phthalocyanine compound represented by the following general formula (II).

In the general formula ^{(II), A 1, A} 2, A 3, A 4, A 5, A 6, A 7, A 8, A 9, A 10, A 11, A 12, A 13, A 14, A ¹⁵ and A ¹⁶ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or a thioalkoxy group.

<4> The colored curable composition <5> according to any one of <1> to <3>, wherein the colorant (B) is a halogenated zinc phthalocyanine compound. (D) Photopolymerization The colored curable composition according to any one of <1> to <4>, which contains an initiator.
<6> The colored curable composition according to <5>, wherein the photopolymerization initiator is an oxime compound.
<7> The colored curable composition according to any one of <1> to <6>, further containing an aliphatic polyfunctional mercapto compound.

< 8 > The colored curable composition according to any one of <1> to < 7 >, which is for a color filter.
< 9 > A colored cured film formed from the colored curable composition according to any one of <1> to < 8 >.
<1 0 ><1> to < 8 > The colored curable composition according to any one of < 8 > is applied on a substrate to form a colored curable composition layer, and the formed colored curable composition is formed. And a step of exposing and developing the composition layer in a pattern, and a method for producing a color filter.
<1 1 > A color filter comprising the colored cured film according to < 9 >.
<1 2 > A color filter produced by the method for producing a color filter according to <1 0 >.
<1 3 > A display device comprising the color filter according to <1 1 > or <1 2 >.

<1 4 > A compound represented by the following general formula (IA -2 ).

In the general formula (I A-2), in the general formula (IA-2), ^{R 1} represents a t- butyl group. R ⁴ represents a hydrogen atom, an alkyl group, an aryl group, or a cyano group. R ⁵ represents an aryl group having a substituent. R ⁶ represents a hydrogen atom, an alkyl group, or an aryl group. Cy2 represents a ring structure containing a 5-membered ring or a 6-membered ring formed with adjacent carbon atoms .

In the present invention, the colorant includes a colorant selected from the compounds represented by the following general formula (I) (hereinafter referred to as “(A) specific colorant” as appropriate). .
The specific colorant (A), which is a new compound, has a yellow hue and has a steep absorption spectrum at 450 nm to 500 nm. Therefore, it has characteristics that can form a color filter that exhibits high color purity and luminance. Have. This characteristic is presumed to be an effect due to (A) the molecular structure having high rigidity that the specific colorant has.

Furthermore, the (A) specific colorant in the present invention has a steep absorption spectrum derived from its rigid structure, but has a low fluorescence intensity and can realize a high contrast. In general, when a steep absorption spectrum is given due to the rigid structure of the dye, it is predicted that the fluorescence intensity increases due to the rigidity. On the other hand, since the specific colorant (A) in the present invention has an NN hetero bond in the molecule, excitation energy can be deactivated efficiently due to thermal vibration of the NN bond. It has the characteristic of low fluorescence intensity while having an absorption spectrum, and exhibits excellent performance that combines high brightness and high contrast.
Further, (A) the specific colorant has high heat resistance of the compound itself because of its high structural rigidity, and can sufficiently withstand high-temperature treatment steps such as post-baking treatment in color filter production.

ADVANTAGE OF THE INVENTION According to this invention, the color curable composition used suitably for preparation of the color filter which has a color pixel with favorable color purity, high brightness | luminance, and excellent heat resistance can be provided.
The present invention also provides a colored cured film having excellent color characteristics and heat resistance, a color filter including the colored cured film, a method for producing the color filter, and a display device including the color filter. be able to.
Furthermore, according to the present invention, it is possible to provide a novel compound that is useful as a colorant, has small undesired absorption on the long wavelength side of the absorption band, and has heat resistance.

Hereinafter, a colored curable composition of the present invention, a colored cured film using the same, a color filter provided with the colored cured film, a method for producing the color filter, a display device including the color filter, and the present invention The novel compound will be described in detail.
The novel compound of the present invention will be described together in the description of the components contained in the colored curable composition.

  In the present specification, in the notation of substituents (atomic groups), the notation that does not indicate substitution and non-substitution includes those having further substituents as well as unsubstituted ones unless otherwise specified. Used to mean. For example, when describing as an “alkyl group”, the alkyl group is used in a meaning including an unsubstituted alkyl group and an alkyl group further having a substituent. The same applies to other substituents (atomic groups).

  In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

  In this specification, the total solid content refers to the total mass of components excluding the solvent from the total composition of the colored curable composition.

  Further, in this specification, “(meth) acrylate” represents both and / or acrylate and methacrylate, “(meth) acryl” represents both and / or acryl and “meth”. ) "Acryloyl" represents both and / or acryloyl and methacryloyl.

  In the present specification, “monomer” and “monomer” are synonymous. The monomer in this specification is distinguished from an oligomer and a polymer, and refers to a compound having a weight average molecular weight of 2,000 or less. In the present specification, the polymerizable compound means a compound having a polymerizable functional group, and may be a monomer or a polymer. The polymerizable functional group refers to a group that participates in a polymerization reaction.

  In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .

<Colored photosensitive composition>
The colored curable composition of the present invention contains the following component (A), component (B) and component (C), and may contain other components as necessary (hereinafter, It is appropriately referred to as “colored curable composition”) .
(A) Colorant selected from compounds represented by the following general formula (I) (B) Colorant having a hue different from the colorant (A) (C) Polymerizable compound

  Hereinafter, each component contained in the colored curable composition of the present invention will be described.

<Component (A): Colorant selected from compounds represented by formula (I) (specific colorant)>
Wearing color curable composition contains a colorant selected from compounds represented by the following general formula (I) ((A) specific colorant). The (A) specific colorant is a colorant having a yellow hue. The colored curable composition of the present invention is a compound represented by the following general formula (IA-2) among (A) specific colorants, R ¹ represents a t-butyl group, and R ⁴ represents hydrogen. An atom, an alkyl group, an aryl group, or a cyano group, R ⁵ represents an aryl group having a substituent, R ⁶ represents a hydrogen atom, an alkyl group, or an aryl group, and Cy2 is formed together with an adjacent carbon atom. And a compound representing a ring structure containing a 5-membered ring or a 6-membered ring.

Compound represented by the general formula (I) are novel compounds and are for chromatic as a colorant.

In general formula (I), R ¹ and R ⁴ each independently represent a hydrogen atom, an alkyl group, an aryl group, or a cyano group. R ² and R ³ each independently represent a substituent and may be linked to each other to form a ring structure. However, at least one of R ² and R ³ contains an XY bond, or R ³ contains Y and is linked to an adjacent nitrogen atom by Y. X and Y each independently represent an oxygen atom, a nitrogen atom, or a sulfur atom. Cy1 represents a ring structure containing a 5-membered ring or a 6-membered ring formed with adjacent carbon atoms.

The general formula (1) will be described in detail.
In General Formula (1), R ¹ and R ⁴ each independently represent a hydrogen atom, an alkyl group, an aryl group, or a cyano group.

The alkyl group represented by R ¹ or R ⁴ is preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an i-propyl group, a t-butyl group, an s-butyl group, or a cyclohexyl group. Etc.
The alkyl group represented by R ¹ or R ⁴ may further have a substituent. Examples of the substituent that can be introduced into the alkyl group include an alkoxy group, a thioalkoxy group, an ester group, a hydroxyl group, a cyano group, a carbonylamino group, and a sulfonylamino group.

The aryl group represented by R ¹ or R ⁴ is preferably an aryl group having 6 to 12 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.
The aryl group represented by R ¹ or R ⁴ may further have a substituent. Examples of the substituent that can be introduced into the aryl group include an alkyl group, an alkoxy group, a thioalkoxy group, a halogen, a hydroxyl group, a cyano group, a carbonylamino group, and a sulfonylamino group.

R ¹ in the general formula (I) is preferably an alkyl group which may have a substituent, an aryl group which may have a substituent, or a cyano group, more preferably a t-butyl group, a phenyl group, An o-methylphenyl group or an o, o′-dimethylphenyl group, more preferably a t-butyl group.

R ⁴ in the general formula (I) is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom.

In general formula (I), R ² and R ³ each independently represent a substituent, and may be linked to each other to form a ring structure. However, at least one of R ² and R ³ contains an XY bond, or R ³ contains Y and is linked to an adjacent nitrogen atom by Y.
X and Y each independently represent an oxygen atom, a nitrogen atom, or a sulfur atom.

It is more preferably R ² and R ^3, linked R ² and R ³ together form a ring structure, a and embodiments having X-Y bond in the ring structure. At this time, X and Y are each independently an oxygen atom, a nitrogen atom, or a sulfur atom, and it is most preferable that both X and Y are nitrogen atoms.

Examples of suitable ring structures formed by connecting R ² and R ³ to each other include pyrazolotriazole ring structures.

  In general formula (I), Cy1 represents a ring structure including a 5-membered ring or a 6-membered ring formed with an adjacent carbon atom, and is preferably a ring structure including a 6-membered ring.

Examples of the ring structure containing a 5-membered ring represented by Cy1 include pyrazolone, pyrazolidinedione, oxazolidinedione, thioxazolidinedione, indandione, indanone, and derivatives thereof.
Examples of the ring structure containing a 6-membered ring represented by Cy1 include pyridone, barbituric acid, thiobarbituric acid, quinolone, dimedone, meldrum acid, naphthindanedione, and derivatives thereof.

  The compound represented by the general formula (I) is more preferably a compound represented by the following general formula (IA) or a compound represented by the general formula (IB).

In General Formula (IA), R ¹ , R ⁴ , and Cy 1 have the same meanings as R ¹ , R ⁴ , and Cy ¹ in General Formula (I). R ⁵ and R ⁶ each independently represents a hydrogen atom, an alkyl group, or an aryl group.
In the general formula (IB), R ¹ , R ⁴ , and Cy1 are synonymous with R ¹ , R ⁴ , and Cy1 in the general formula (I). R ⁷ and R ⁸ each independently represents a hydrogen atom, an alkyl group, an aryl group, a sulfonylamino group, or a carbonylamino group.

General formulas (IA) and (IB) will be further described.
^R 1, ^{R 4} and Cy1 in the general formula (IA) or (IB) has the same meaning as ^R 1, ^{R 4} and Cy1 in formula (I), and preferred ranges are also the same.

In general formula (IA) or (IB), the alkyl group represented by R ⁵ , R ⁶ , R ⁷ , or R ⁸ is preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group or an ethyl group. I-propyl group, t-butyl group, s-butyl group, cyclohexyl group and the like.
In general formula (IA) or (IB), the alkyl group represented by R ⁵ , R ⁶ , R ⁷ , or R ⁸ may further have a substituent. Examples of the substituent that can be introduced into the alkyl group include an alkoxy group, a thioalkoxy group, an ester group, a hydroxyl group, a cyano group, a carbonylamino group, and a sulfonylamino group.

As the aryl group represented by R ⁵ , R ⁶ , R ⁷ , or R ⁸ , an aryl group having 6 to 12 carbon atoms is preferable, and examples thereof include a phenyl group and a naphthyl group.
The aryl group represented by R ⁵ , R ⁶ , R ⁷ , or R ⁸ may further have a substituent. Examples of the substituent that can be introduced into the aryl group include a substituted or unsubstituted alkyl group, a substituted or unsubstituted carbonylamino group, a substituted or unsubstituted sulfonylamino group, an alkoxy group, and a thioalkoxy group. .

In the general formula (IB), examples of the carbonylamino group represented by R ⁷ or R ⁸ include a substituted or unsubstituted alkyl or arylcarbonylamino group.

In the general formula (IB), examples of the sulfonylamino group represented by R ⁷ or R ⁸ include a substituted or unsubstituted alkyl or arylsulfonylamino group.

R ⁶ in the general formula (IA) is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom. R ⁷ in the general formula (IB) is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom.

R ⁵ in the general formula (IA) is a partial structure selected from a substituted or unsubstituted alkyl group, a PEO chain (polyethylene glycol), a PPO chain (polypropylene glycol), an ammonium salt, and a polymerizable group in the structure. It is preferably an alkyl group or an aryl group having a carbonylamino group or a sulfonylamino group as a substituent, and more preferably a substituted or unsubstituted alkyl group, PEO chain (polyethylene glycol), PPO in the structure An alkyl group or an aryl group having a sulfonylamino group having a partial structure selected from a chain (polypropylene glycol), an ammonium salt, and a polymerizable group as a substituent, and more preferably a substituted alkyl group, PEO in the structure Chain (polyethylene glycol), PP An aryl group having a sulfonylamino group having a partial structure selected from an O chain (polypropylene glycol), an ammonium salt, and a polymerizable group as a substituent.

R ⁸ in the general formula (IB) is a partial structure selected from a substituted or unsubstituted alkyl group, a PEO chain (polyethylene glycol), a PPO chain (polypropylene glycol), an ammonium salt, and a polymerizable group in the structure. Preferred are sulfonylamino groups having

  The compound represented by the general formula (IA) is more preferably a compound represented by the following general formula (IA-2). The compound represented by the general formula (IB) is more preferably a compound represented by the following general formula (IB-2).

In general formula (IA-2), R ¹ , R ⁴ , R ⁵ and R ⁶ have the same meanings as R ¹ , R ⁴ , R ⁵ and R ⁶ in general formula (IA). Cy2 represents a ring structure containing a 5-membered ring or a 6-membered ring formed with adjacent carbon atoms.
In general formula (IB-2), R ¹ , R ⁴ , R ⁷ and R ⁸ have the same meanings as R ¹ , R ⁴ , R ⁷ and R ⁸ in general formula (IB). Cy2 represents a ring structure containing a 5-membered ring or a 6-membered ring formed with adjacent carbon atoms.

General formulas (IA-2) and (IB-2) will be further described.
^{R 1,} R 4, ^{R 5} and ^{R 6} in the general formula (IA-2) ^{is, R} 1, ^R 4 in the general formula (IA), have the same meanings as ^{R 5} and ^{R 6,} a preferred range is also the same.
^{R 1,} R 4 in the general formula (IB-2), ^{R 7} and ^{R 8, R} 1, ^R 4 in the general formula (IB), have the same meanings as ^{R 7} and ^{R 8,} the preferred range is also the same.

In general formula (IA-2) or (IB-2), examples of the ring structure containing a 5-membered ring represented by Cy2 include pyrazolidinedione, oxazolidinedione, thioxazolidinedione, indandione, and indanone. And derivatives thereof.
In general formula (IA-2) or (IB-2), examples of the ring structure containing a 6-membered ring represented by Cy2 include barbituric acid, thiobarbituric acid, dimedone, meldrum acid, naphthindanedione, and the like. Derivatives.

  Illustrative compounds of the compounds represented by formula (I) and preferred embodiments thereof, which are the formulas (IA), (IB), (IA-2) and (IB-2) are shown below. . However, the present invention is not limited to these.

  The compound represented by the general formula (I) has a maximum absorption peak wavelength (λmax) at 420 nm to 480 nm.

The compound represented by the general formula (I) can be synthesized by the following method.
Hereinafter, the method for synthesizing the compound represented by the general formula (I) will be described in detail with reference to the synthesis example of the compound A-1 described above as an exemplary compound.

<Synthesis Example of Compound A-1>

First, according to the method described in Japanese Patent No. 2670943, pyrazolotriazole body a-1 which is a precursor structure of Compound A-1 was obtained (20.4 g).
Next, pyrazolotriazole compound a-1 (20.4 g) is dissolved in pyridine: 80 ml (manufactured by Wako Pure Chemical Industries, Ltd.), and octanesulfonic acid chloride: 17.9 g (Tokyo Kasei) in an ice bath. Kogyo Co., Ltd.) was added dropwise and reacted at room temperature for 1 hour. Next, 200 ml of ethyl acetate and 300 ml of water were added, and the target product was extracted into the ethyl acetate layer. Furthermore, dilute hydrochloric acid (300 ml) was added to the ethyl acetate layer, and the mixture was stirred at room temperature for 1 hour. Thereafter, the obtained precipitate was filtered, washed with 500 ml of a hexane / isopyropanol (1: 1) solvent, and then dried in a vacuum at 50 ° C. to obtain an intermediate a-2. (21.1g)

  Next, the obtained intermediate a-2 (3.0 g) was dissolved in dimethylformamide: 10 ml (manufactured by Wako Pure Chemical Industries, Ltd.), and phosphoric oxychloride: 1.6 g (Wako Pure Chemical Industries, Ltd.) in an ice bath. Kogyo Co., Ltd.) was added dropwise. After completion of the dropwise addition, the internal temperature was raised to 80 ° C. and stirred for 2 hours. The reaction was stopped by adding to 100 ml of water, followed by extraction with 200 ml of ethyl acetate, neutralization washing with an aqueous sodium bicarbonate solution, and concentration of the solvent to dryness to obtain intermediate a-3. (2.8g)

  Next, intermediate a-3 (1.5 g) and indaneone: 0.5 g (manufactured by Tokyo Chemical Industry Co., Ltd.) were put into 5 ml of methanol and 5 ml of acetic acid, and stirred at an internal temperature of 80 ° C. for 2 hours. . After the reaction, 20 ml of methanol was added, and the precipitate was filtered and dried. Furthermore, the target compound A-1 (0.5 g) was obtained by recrystallizing the precipitate with 50 ml of methyl ethyl ketone.

As a result of identifying this compound A-1 by MS, it was confirmed that it was the target structure.
Moreover, the absorption wavelength in ethyl acetate of the obtained compound A-1 was 435 nm, and the extinction coefficient was 43500.

  The compound represented by the general formula (I) including other exemplary compounds can be appropriately synthesized by selecting a heterocycle to be combined with the compound a-3.

  In the colored curable composition of this invention, (A) 1 type of specific colorants may be contained, and 2 or more types may be used together.

  The content of the specific colorant (A) in the colored curable composition of the present invention is appropriately selected according to the purpose, and when used for the purpose of forming the colored pixels of the color filter, the total solid content of the colored curable composition It is preferable that it is 0.5 mass%-70 mass% with respect to a minute, and it is more preferable that it is 10 mass%-40 mass%.

<Component (B): Colorant having a different hue from the specific colorant (A)>
The colored curable composition of the present invention contains a colorant having a hue different from that of the specific colorant (A) (hereinafter referred to as “(B) other colorant” as appropriate).
(B) Other colorants may be selected from known dye compounds and pigment compounds.

  Since (A) the specific colorant has a maximum absorption peak wavelength (λmax) of 420 nm to 480 nm, (B) as the other colorant, the maximum absorption in the visible light wavelength range of 380 nm to 800 nm. It is necessary that the peak wavelength is less than 420 nm or the colorant exceeds 480 nm.

  In this specification, the maximum absorption peak wavelength is a solvent such that the dye solution or pigment dispersion containing the colorant to be measured has a measurable concentration (for example, a concentration at which the absorbance is 0.8 to 1.0). The value measured using a CARY5 / UV-visible spectrophotometer (commercial product: manufactured by Varian) is used.

  (B) The dye compound used as the other colorant may have any structure as long as it does not affect the hue of the colored image. For example, an anthraquinone compound (for example, JP-A-2001-2001) may be used. Anthraquinone compounds described in Japanese Patent No. 10881), phthalocyanine compounds (for example, phthalocyanine compounds described in US 2008 / 0076044A1), xanthene compounds (for example, CI Acid Red 289). , Triarylmethane-based compounds (for example, CI Acid Blue 7), CI Acid Blue 83, CI Acid Blue 90, CISolvent Blue 38, CIS Acid Violet 17 (C.I. Acid Violet 17), C.I. Acid Violet 49, C.I.Acid Green 3 and methine dye.

  (B) Examples of pigment compounds used as other colorants include perylene, perinone, quinacridone, quinacridonequinone, anthraquinone, anthanthrone, benzimidazolone, disazo condensation, disazo, azo, indanthrone, phthalocyanine, and triaryl carbo Ni, dioxazine, aminoanthraquinone, diketopyrrolopyrrole, indigo, thioindigo, isoindoline, isoindolinone, pyranthrone, or isoviolanthrone. More specifically, for example, perylene compound pigments such as Pigment Red 190, Pigment Red 224, and Pigment Violet 29, perinone compound pigments such as Pigment Orange 43, and Pigment Red 194, Pigment Violet 19, and Pigment Violet. 42, quinacridone such as Pigment Red 122, Pigment Red 192, Pigment Red 202, Pigment Red 207, or Pigment Red 209, quinacridone compound pigment, Pigment Red 206, Pigment Orange 48, or Pigment Orange 49 Quinone compound pigments, anthraquinone compound pigments such as pigment yellow 147, anthanthrone compound pigments such as pigment red 168, and pigments Benzimidazolone compound pigments such as Pigment 25, Pigment Violet 32, Pigment Orange 36, Pigment Yellow 120, Pigment Yellow 180, Pigment Yellow 181, Pigment Orange 62, or Pigment Red 185 Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 166, Pigment Orange 34, Pigment Orange 13, Pigment Orange 31, Pigment Red 144, Pigment Red 166, Pigment Red Red 220, Pigment Red 221, Pigment Red 242, Pigment Red 248, Pigment Red 262, or Pigment Red Disazo compound pigments, round 23 such as,

Pigment Yellow 13, Pigment Yellow 83, or Pigment Yellow 188 disazo compound pigments, Pigment Red 187, Pigment Red 170, Pigment Yellow 74, Pigment Yellow 150, Pigment Red 48, Pigment Red 53 Pigment Orange 64, Pigment Red 247 and other azo compound pigments, Pigment Blue 60 and other Indantron compound pigments, Pigment Green 7, Pigment Green 36, Pigment Green 37, Pigment Green 58, Pigment Green Phthalocyanine compound pigments such as Blue 16, Pigment Blue 75, and Pigment Blue 15; Tries such as Pigment Blue 56 or Pigment Blue 61 Reel carbonium compound pigments, dioxazine compound pigments such as Pigment Violet 23 or Pigment Violet 37, aminoanthraquinone compound pigments such as Pigment Red 177, Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Diketopyrrolopyrrole compound pigments such as Red 272, Pigment Orange 71, or Pigment Orange 73, thioindigo compound pigments such as Pigment Red 88, Isoindoline compound pigments such as Pigment Yellow 139 and Pigment Orange 66, Pigment Pigment Orange 40, Pigment Orange 40, Pigment Orange 61, Pigment Orange 61, etc. It includes a pyranthrone compound pigment or isoviolanthrone compound pigments, such as Pigment Violet 31,.

  The yellow hue, that is, the maximum absorption peak wavelength (λmax) at 420 nm to 480 nm is used in combination with (A) a specific colorant, and (B) other colorant is suitable for use in color filters. In the wavelength range of 380 nm to 800 nm, those having a maximum absorption peak wavelength in the wavelength range of 500 nm to 800 nm are preferred, those having the maximum absorption peak wavelength in the wavelength range of 550 nm to 700 nm are more preferred, and a green hue That is, the one having the maximum absorption peak wavelength in the long region of 600 nm to 700 nm is most preferable. Specific examples of the other colorant (B) having the maximum absorption peak wavelength in the wavelength range include Pigment Green 36 and Pigment Green 58.

  (B) If attention is paid to the structure of a compound that is preferable as another colorant, a zinc phthalocyanine compound represented by the following general formula (II) may be mentioned as one of preferable embodiments. Moreover, the suitable aspect includes a halogenated zinc phthalocyanine compound.

In the general formula ^{(II), A 1, A} 2, A 3, A 4, A 5, A 6, A 7, A 8, A 9, A 10, A 11, A 12, A 13, A 14, A ¹⁵ and A ¹⁶ each independently represent a halogen atom, an alkyl group, an alkoxy group, or a thioalkoxy group.
In general formula (II), A ^{1 to} A ¹⁶ preferably each independently represent a hydrogen atom, a chlorine atom, or a bromine atom, and at least eight of these are preferably bromine atoms.
In the zinc phthalocyanine compound, when eight or more of A ^{1 to} A ¹⁶ are bromine atoms, it exhibits a yellowish green color with high brightness, and is optimal for forming a green pixel portion of a color filter. As the other colorant (B) in the present invention, a zinc phthalocyanine compound having 10 or more bromine atoms is most preferable.

The average composition of the zinc phthalocyanine compound can be easily obtained from mass spectrometry based on mass spectroscopy and halogen content analysis by flask combustion ion chromatography.
The zinc phthalocyanine compound can be produced by a known production method such as a chlorosulfonic acid method, a halogenated phthalonitrile method, or a melting method. More specific production methods are described in detail in JP 2008-19383 A, JP 2007-320986 A, JP 2004-70342 A, and the like.
In addition, C.I. I. The pigment known as Pigment Green 58 is also a pigment included in the brominated phthalocyanine pigment in the present invention.
As a zinc phthalocyanine compound used for the colored curable composition for color filters, those having an average primary particle diameter in the range of 10 nm to 40 nm are preferable. By using a zinc phthalocyanine compound having an average primary particle diameter in this range and the specific colorant (A), the color curable composition for color filters having excellent dispersibility stability and coloring power, high brightness, and high contrast. A composition can be obtained.

  In addition, the average primary particle diameter in the present invention is a long one of 100 primary particles of zinc phthalocyanine pigment constituting the aggregate on a two-dimensional image obtained by photographing particles in the field of view with a transmission electron microscope. The average value of the diameter (major axis) and the shorter diameter (minor axis) is obtained and averaged.

  In obtaining a zinc phthalocyanine pigment having an average primary particle diameter in the range of 10 nm to 40 nm, it may be finely divided by any method, but it can easily suppress crystal growth and has a relatively high average primary particle diameter. In view of obtaining small pigment particles, it is preferable to employ a solvent salt milling treatment. A brominated zinc phthalocyanine pigment having an average primary particle size in the range of 10 nm to 40 nm is also available as a commercial product, and can also be purchased from DIC Corporation.

  When a pigment is used as the (B) other colorant, it is preferable to prepare and use a pigment dispersion in advance. The pigment dispersion can be prepared, for example, according to the descriptions in JP-A-9-197118 and JP-A-2000-239544.

  (B) Content of another coloring agent should just be a range which does not impair the effect of this invention, and is 0.5 mass%-70 mass% with respect to the total solid of the colored curable composition of this invention. It is preferable that

  Moreover, as a content rate of (A) specific colorant and (B) other colorant, (B) other colorant is 20 mass parts-500 masses with respect to 100 mass parts of (A) specific colorant. Part.

<Component (C): Polymerizable compound>
The colored curable composition of the present invention contains at least one polymerizable compound. Examples of the polymerizable compound include addition polymerizable compounds having at least one ethylenically unsaturated double bond.

  The polymerizable compound having at least one ethylenically unsaturated double bond can be selected from known components, specifically, paragraph numbers [0010] to [0010] of JP-A-2006-23696. And the components described in paragraph numbers [0027] to [0053] of JP-A-2006-64921.

  About the polymerizable compound, the details of the structure, usage method such as single use or combination, addition amount and the like can be arbitrarily set in accordance with the final performance design of the colored curable composition. For example, from the viewpoint of sensitivity, a structure having a high unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Also, from the viewpoint of increasing the strength of the colored cured film, those having three or more functionalities are preferable, and those having different functional numbers and different polymerizable groups (for example, acrylic acid esters, methacrylic acid esters, styrene compounds, vinyl ether compounds). It is also effective to adjust both sensitivity and intensity by using together. In addition, the selection of the polymerizable compound is also possible with respect to the compatibility and dispersibility with other components (for example, photopolymerization initiator, colorant (pigment), binder polymer, etc.) contained in the colored curable composition. The method of use is an important factor. For example, compatibility may be improved by using a low-purity compound or using two or more kinds in combination. In addition, a specific structure may be selected from the viewpoint of improving adhesion to a hard surface such as a substrate.

As the polymerizable compound, a urethane addition polymerizable compound produced by using an addition reaction of an isocyanate and a hydroxyl group is also suitable. JP-A-51-37193, JP-B-2-32293, JP-B-2-16765 Urethane acrylates such as those described in Japanese Patent Publication No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418. Urethane compounds having a skeleton are also suitable.
Other examples include polyester acrylates, epoxy resins and (meth) described in JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates obtained by reacting with acrylic acid. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

  Specific examples include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri ((meth) acryloyloxyethyl) isocyanurate. , Pentaerythritol tetra (meth) acrylate EO modified product, dipentaerythritol hexa (meth) acrylate EO modified product, etc., and commercially available products include NK ester A-TMMT, NK ester A-TMM-3, NK oligo UA -32P, NK Oligo UA-7200 (above, manufactured by Shin-Nakamura Chemical Co., Ltd.), Aronix M-305, Aronix M-306, Aronix M-309, Aronix M-450, Aronic M-402, TO-1382 (above, manufactured by Toagosei Co., Ltd.), V # 802 (produced by Osaka Organic Chemical Industry Co., Ltd.), Kayarad D-330, Kayarad D-320, Kayarad D-310, Kayarad DPHA ( As mentioned above, Nippon Kayaku Co., Ltd.) etc. can be mentioned as a preferable example.

  Also, from the viewpoint of curing exposure sensitivity and developability adjustment, dipentaerythritol hexaacrylate is combined with EO-modified products such as pentaerythritol tetra (meth) acrylate EO-modified products and dipentaerythritol hexa (meth) acrylate EO-modified products. Is also preferable.

  Only one type of polymerizable compound may be included in the colored curable composition, or two or more types may be used in combination depending on the purpose.

  The content of the polymerizable compound (C) in the total solid content of the colored curable composition and the total content (when using two or more polymerizable compounds) are not particularly limited and are appropriately selected. However, from the viewpoint of obtaining the effects of the present invention more remarkably, 10% by mass to 80% by mass is preferable, 15% by mass to 75% by mass is more preferable, and 20% by mass to 60% by mass is particularly preferable.

  If necessary, the colored curable composition of the present invention may further include a photopolymerization initiator, a chain transfer agent, a polymerization inhibitor, an organic solvent, a crosslinking agent, a surfactant, an adhesion improver, a development accelerator, and other additives. Various other components such as a product (filler, polymer compound, ultraviolet absorber, antioxidant, aggregation inhibitor, sensitizer, light stabilizer, etc.) may be included. Hereinafter, other components will be described.

<Component (D): Photopolymerization initiator>
The colored curable composition of the present invention preferably contains at least one photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it can polymerize the polymerizable compound (C), and is selected in consideration of characteristics, generation efficiency of starting species, absorption wavelength, availability, cost, and the like. Is preferred.

  Examples of the photopolymerization initiator include at least one active halogen compound selected from a halomethyloxadiazole compound and a halomethyl-s-triazine compound, a 3-aryl-substituted coumarin compound, a lophine dimer, a benzophenone compound, and an acetophenone compound. And derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, oxime compounds, and the like. Specific examples of the photopolymerization initiator include those described in paragraphs [0070] to [0077] of JP-A No. 2004-295116. Among these, an oxime compound is preferable from the viewpoint of rapid polymerization reaction.

The oxime-based compound (hereinafter also referred to as “oxime-based photopolymerization initiator”) is not particularly limited. For example, JP-A-2000-80068, WO02 / 100903A1, JP-A-2001-233842, etc. The described oxime compounds are mentioned.
Specific examples of the oxime compound include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4. -(Phenylthio) phenyl] -1,2-pentanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-hexanedione, 2- (O-benzoyloxime)- 1- [4- (phenylthio) phenyl] -1,2-heptanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 2- (O— Benzoyloxime) -1- [4- (methylphenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (ethylphenylthio) Phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (butylphenylthio) phenyl] -1,2-butanedione, 1- (O-acetyloxime) -1- [9 -Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-methyl-6- (2-methylbenzoyl) -9H-carbazole -3-yl] ethanone, 1- (O-acetyloxime) -1- [9-propyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-Ethyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-ethyl-6- (2- Tylbenzoyl) -9H-carbazol-3-yl] ethanone, 2- (benzoyloxyimino) -1- [4- (phenylthio) phenyl] -1-octanone, 2- (acetoxyimino) -4- (4-chlorophenyl) Thio) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1-butanone and the like. However, it is not limited to these.

  In the present invention, from the viewpoint of sensitivity, stability over time, and coloring during post-heating, the compound represented by the following general formula (A) and the compound represented by the following general formula (B) are used as the oxime compounds. A compound selected from is more preferable.

  In general formula (A), R and X each represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. n is an integer of 0-5.

  In general formula (A), R is preferably an acyl group from the viewpoint of increasing sensitivity, and specifically, an acetyl group, a propionyl group, a benzoyl group, and a toluyl group are preferable.

  In the general formula (A), A is an unsubstituted alkylene group or alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, or a dodecyl group) from the viewpoint of increasing sensitivity and suppressing coloring over time. Alkylene group substituted with alkenyl group (for example, vinyl group, allyl group), aryl group (for example, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, An alkylene group substituted with a phenanthryl group or a styryl group is preferred.

  Ar is preferably a substituted or unsubstituted phenyl group from the viewpoint of increasing sensitivity and suppressing coloring due to heating. In the case of a substituted phenyl group, the substituent is preferably a halogen group such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

X is an alkyl group that may have a substituent, an aryl group that may have a substituent, or an alkenyl that may have a substituent from the viewpoint of improving solvent solubility and absorption efficiency in the long wavelength region. Group, an alkynyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthioxy group which may have a substituent, a substituent An arylthioxy group which may have an amino group and an amino group which may have a substituent are preferable.
Moreover, n in the general formula (A) is preferably an integer of 0 to 2.

  Examples of the compound represented by the general formula (A) include compounds having a structure represented by the following (D-2).

In the general formula (B), X ¹ , X ² , and X ³ each independently represent a hydrogen atom, a halogen atom, or an alkyl group, and R ¹ represents —R, —OR, —COR, —SR, -CONRR ', or represents -CN, each ^{R 2} and ^{R 3} independently, -R, -OR, -COR, -SR , or -NRR' represents a. R and R ′ each independently represents an alkyl group, an aryl group, an aralkyl group, or a heterocyclic group, and these groups are substituted with one or more selected from the group consisting of a halogen atom and a heterocyclic group. One or more of carbon atoms constituting the alkyl chain in the alkyl group and the aralkyl group may be replaced with an unsaturated bond, an ether bond, or an ester bond, and R and R ′ are bonded to each other. A ring may be formed.

  Examples of the compound represented by the general formula (B) include a compound having a structure represented by the following (D-3).

  In addition to the above photopolymerization initiator, other known photopolymerization initiators described in paragraph No. 0079 of JP-A No. 2004-295116 may be used in the colored curable composition of the present invention. Good.

A photoinitiator can be contained individually by 1 type or in combination of 2 or more types.
The content of the photopolymerization initiator in the total solid content of the colored curable composition (when two or more photopolymerization initiators are contained, the total content thereof) is said to obtain the effects of the present invention more remarkably. From a viewpoint, 3 mass%-20 mass% are preferable, 4 mass%-19 mass% are more preferable, and 5 mass%-18 mass% are especially preferable.

<Ingredient (E): Other ingredients>
(E-1: Binder polymer)
In the colored curable composition of the present invention, it is preferable to further use a binder polymer from the viewpoint of improving the film properties.
As the binder polymer, it is preferable to contain a linear organic polymer. As such a “linear organic polymer”, any compound may be used, but preferably water or weak alkaline water soluble or swellable to enable water development or weak alkaline water development. A linear organic polymer is selected. The linear organic high molecular polymer is selected and used not only as a film-forming agent for the composition but also according to its use as water, weak alkaline water or an organic solvent developer. For example, when a water-soluble organic polymer is used, water development is possible. Examples of such linear organic high molecular polymers include addition polymers having a carboxylic acid group in the side chain, such as JP 59-44615, JP-B 54-34327, JP-B 58-12777, and JP-B. 54-25957, JP-A-54-92723, JP-A-59-53836, JP-A-59-71048, ie, methacrylic acid copolymer, acrylic acid copolymer , Itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, and partially esterified maleic acid copolymer. Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. In addition, those obtained by adding a cyclic acid anhydride to an addition polymer having a hydroxyl group are useful.

  Among these, [benzyl (meth) acrylate / (meth) acrylic acid / other addition polymerizable vinyl monomers as required] copolymer and [allyl (meth) acrylate / (meth) acrylic acid / as required Other addition-polymerizable vinyl monomers] are preferred because they are excellent in the balance of film strength, sensitivity and developability.

  In addition, polyvinyl pyrrolidone, polyethylene oxide, and the like are also useful as water-soluble linear organic polymers. In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful. These linear organic high molecular polymers can be mixed in an arbitrary amount in the entire composition. From the viewpoint of the image strength to be formed, it is preferably 30 to 85% by mass. Further, the polymerizable compound and the linear organic polymer are preferably in the range of 1/9 to 7/3 by mass ratio. In a preferred embodiment, a binder polymer that does not require water and is soluble in alkali is used. By doing so, an organic solvent that is not environmentally preferable is not used as the developer, or the amount can be limited to a very small amount. In such a method of use, the acid value of the binder polymer (the acid content per gram of polymer expressed as a chemical equivalent number) and the molecular weight are appropriately selected from the viewpoint of image strength and developability. The preferred acid value is 3 to 200 mgKOH / g, the preferred molecular weight is in the range of 3000 to 100,000 in terms of mass average molecular weight, more preferably the acid value is 50 to 150 mgKOH / g, and the molecular weight is 10,000 to 50,000. It is a range.

(E-2: sensitizer)
The colored curable composition of the present invention may contain a sensitizer. Typical sensitizers used in the present invention include those disclosed in Crivello [JVCrivello, Adv. In Polymer Sci, 62, 1 (1984)], specifically pyrene, perylene, acridine. Thioxanthone, 2-chlorothioxanthone, benzoflavine, N-vinylcarbazole, 9,10-dibutoxyanthracene, anthraquinone, benzophenone, coumarin, ketocoumarin, phenanthrene, camphorquinone, phenothiazine derivatives and the like. The sensitizer is preferably added in a proportion of 50 to 200% by mass with respect to the photopolymerization initiator.
The sensitizer improves the sensitivity of the coexisting photopolymerization initiator. Furthermore, when an appropriate sensitizer is used in combination, even when a photopolymerization initiator that does not directly respond to the exposure wavelength is used, it has an advantage that it can be applied to the colored curable composition of the present invention. .

(E-3: Chain transfer agent)
A chain transfer agent may be used in the colored curable composition of the present invention.
Examples of the chain transfer agent used in the present invention include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, and 2-mercapto. Benzimidazole, N-phenylmercaptobenzimidazole, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, etc. And an aliphatic polyfunctional mercapto compound such as pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, and the like.

A chain transfer agent may be used individually by 1 type, and may use 2 or more types together.
The addition amount of the chain transfer agent is preferably in the range of 0.01 to 15% by mass with respect to the total solid content of the colored curable composition of the present invention, from the viewpoint of reducing sensitivity variation. 1-10 mass% is more preferable, and 0.5-5 mass% is especially preferable.

(E-4: polymerization inhibitor)
The colored curable composition of the present invention may contain a polymerization inhibitor.
The polymerization inhibitor means hydrogen donation (or hydrogen donation), energy donation (or energy donation), electron donation (or electron donation) to polymerization initiation species such as radicals generated in the colored curable composition by light or heat. , Electron donation) and the like to deactivate the polymerization initiating species and to prevent unintentional initiation of polymerization. The polymerization inhibitors described in paragraphs 0154 to 0173 of JP 2007-334322 A can be used.
Among these, p-methoxyphenol is preferably exemplified as the polymerization inhibitor.
The content of the polymerization inhibitor in the colored curable composition of the present invention is preferably 0.0001 to 5% by mass, more preferably 0.001 to 5% by mass with respect to the total mass of the polymerizable compound. 001 to 1% by mass is particularly preferable.

(E-5: Organic solvent)
The colored curable composition of the present invention can contain at least one organic solvent.
The organic solvent is basically not particularly limited as long as it can satisfy the solubility of each of the coexisting components and the coating property when the colored curable composition is used, and in particular, the solubility of the binder, the coating property, It is preferable to select in consideration of safety.

  Examples of the organic solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, and ethyl lactate. Oxyacetic acid alkyl esters (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (specific examples include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate). )), 3-oxypropionic acid alkyl esters (eg, methyl 3-oxypropionate, ethyl 3-oxypropionate and the like (specifically, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3- Methyl ethoxypropionate, 3-ethoxy Ethyl propionate, etc.)), 2-oxypropionic acid alkyl esters (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (specifically, 2 -Methyl methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, etc.)), 2-oxy-2-methylpropionic acid Methyl, ethyl 2-oxy-2-methylpropionate (specifically, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, Ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate , Methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like.

Examples of ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether. Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like.
Examples of ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone.
Preferable examples of aromatic hydrocarbons include toluene and xylene.

  It is also preferable to mix two or more of these organic solvents from the viewpoints of the solubility of each of the above-described components, and the solubility of the above-described components and the improvement of the coating surface state when an alkali-soluble polymer is included. In this case, particularly preferably, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol It is a mixed solution composed of two or more selected from acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

  The content of the organic solvent in the colored curable composition is preferably such that the total solid concentration in the composition is 10% by mass to 80% by mass, and more preferably 15% by mass to 60% by mass. .

(E-6: Crosslinking agent)
The colored curable composition of the present invention can be supplemented with a crosslinking agent to further increase the hardness of the colored cured film obtained by curing the colored curable composition.
The crosslinking agent is not particularly limited as long as the film can be cured by a crosslinking reaction. For example, at least selected from (a) an epoxy resin, (b) a methylol group, an alkoxymethyl group, and an acyloxymethyl group. Substituted with at least one substituent selected from a melamine compound, a guanamine compound, a glycoluril compound or a urea compound, (c) a methylol group, an alkoxymethyl group, and an acyloxymethyl group, which is substituted with one substituent; Phenol compounds, naphthol compounds or hydroxyanthracene compounds are mentioned. Of these, polyfunctional epoxy resins are preferred.
For details such as specific examples of the crosslinking agent, reference can be made to the descriptions in paragraph numbers 0134 to 0147 of JP-A No. 2004-295116.

(E-7: Surfactant)
The colored curable composition of the present invention may contain a surfactant.
As the surfactant, any of anionic, cationic, nonionic, or amphoteric surfactants can be used, but a preferred surfactant is a nonionic surfactant.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants. .
Further, as surfactants that can be used in the present invention, surfactants marketed under the following trade names, for example, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.) , F Top (manufactured by JEMCO), Mega Fuck (manufactured by DIC Corporation), Florard (manufactured by Sumitomo 3M Corporation), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), PolyFox (manufactured by OMNOVA), etc. Can be mentioned.

  Moreover, as a surfactant, the structural unit A and the structural unit B represented by the following general formula (1) are included, and the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography is 1,000 or more and 10 A copolymer having a molecular weight of 1,000 or less can be cited as a preferred example.

In general formula (1), R ¹ and R ³ each independently represent a hydrogen atom or a methyl group, R ² represents a linear alkylene group having 1 to 4 carbon atoms, and R ⁴ represents a hydrogen atom or carbon number. 1 represents an alkyl group having 1 to 4 carbon atoms, L represents an alkylene group having 3 to 6 carbon atoms, p and q are percentages based on mass representing a polymerization ratio, and p is 10% by mass to 80% by mass. Q represents a numerical value of 20% by mass or more and 90% by mass or less, r represents an integer of 1 to 18 and n represents an integer of 1 to 10; )
L in the general formula (1) is preferably a branched alkylene group represented by the following general formula (2).

In general formula (2), R ⁵ represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability to the coated surface. 2 or more and 3 or less alkyl groups are more preferable.

The weight average molecular weight (Mw) of the copolymer represented by the general formula (1) is more preferably 1,500 or more and 5,000 or less.
These surfactants can be used individually by 1 type or in mixture of 2 or more types.

  The addition amount of the surfactant in the colored curable composition of the present invention is preferably 10 parts by mass or less, more preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the binder polymer. More preferably, it is 0.01-1 mass part.

(E-8: adhesion improver)
The colored curable composition of the present invention may contain an adhesion improving agent.
The adhesion improver is a compound that improves the adhesion between a cured film and an inorganic substance serving as a substrate, for example, a silicon compound such as glass, silicon, silicon oxide, or silicon nitride, gold, copper, aluminum, or the like. Specific examples include silane coupling agents and thiol compounds. The silane coupling agent as the adhesion improving agent is for the purpose of modifying the interface, and any known silane coupling agent can be used without any particular limitation.
As the silane coupling agent, a silane coupling agent described in paragraph 0048 of JP-A-2009-98616 is preferable, and among them, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable. These can be used alone or in combination of two or more.
The content of the adhesion improving agent in the colored curable composition of the present invention is preferably from 0.1 to 20 mass%, more preferably from 0.2 to 5 mass%, based on the total solid content of the colored curable composition. .

(E-9: Development accelerator)
A development accelerator can be added in order to promote alkali solubility in the non-exposed area and further improve the developability of the colored curable composition. The development accelerator is preferably a low molecular weight organic carboxylic acid compound having a molecular weight of 1000 or less and a low molecular weight phenol compound having a molecular weight of 1000 or less.
Specifically, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Aromatic polycarboxylic acids such as trimesic acid, melophanoic acid, pyromellitic acid; phenylacetic acid Hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, and umbellic acid.

(E-10: Other additives)
If necessary, the colored curable composition of the present invention is blended with other various additives such as fillers, polymer compounds other than those described above, ultraviolet absorbers, antioxidants, anti-aggregation agents, and the like. be able to. Examples of these additives include those described in paragraphs [0155] to [0156] of JP-A No. 2004-295116.
The colored curable composition of the present invention can contain the light stabilizer described in paragraph [0078] of JP-A No. 2004-295116 and the thermal polymerization inhibitor described in paragraph [0081] of the same publication. .

<Preparation of colored curable composition>
Although it does not restrict | limit in particular about the preparation aspect of the colored curable composition of this invention, For example, (A) Specific coloring agent, (B) Other coloring agents, (C) Polymerizable compound, It is used together as needed. D) It is prepared by mixing other components such as a photopolymerization initiator.

In preparing the colored curable composition of the present invention, it is preferable to mix each component and then filter through a filter for the purpose of removing foreign substances and reducing defects. As the filter, those conventionally used for filtration and the like are not particularly limited. Specifically, for example, fluororesins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon-6 and nylon-6,6, polyolefin resins such as polyethylene and polypropylene (PP) (high density, ultrahigh And a filter formed by using a resin material selected from (including molecular weight). Among these filter materials, polyamide resins such as nylon-6 and nylon-6, 6 and polypropylene (including high density polypropylene) are preferable.
The pore size of the filter is suitably about 0.01 μm to 7.0 μm, preferably about 0.01 μm to 2.5 μm, more preferably about 0.01 μm to 2.0 μm. By setting the pore size of the filter within this range, fine foreign matters that obstruct the preparation of a uniform colored curable composition are surely removed, and a colored and curable composition that can form a uniform and smooth colored curable composition layer can be formed. It becomes a composition.

When using filters, different filters may be combined. At that time, the filtering using the first filter may be performed only once or may be performed twice or more. Moreover, it is good also as a 1st filtering by combining the filter of a different hole diameter within the range mentioned above, and making a 1st filter into a some filter. The pore diameter here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, it can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Japan Microlith Co., Ltd.) or KITZ Micro Filter Co. .
As the second filter, a filter formed of the same material as the first filter described above can be used.
Further, for example, the filtering with the first filter is performed only on the pigment dispersion, and after mixing the other components with the pigment dispersion to obtain a colored curable composition, the second filtering is performed. Also good.

  The colored curable composition of this invention is applied suitably for formation of the colored pixel which the color filter with which display apparatuses, such as a solid-state image sensor, a liquid crystal display device, and an organic electroluminescent apparatus, etc. have. The colored curable composition of the present invention can also be applied to various uses such as printing ink and inkjet ink.

<Colored cured film>
The colored cured film obtained by curing the colored curable composition of the present invention has a high color purity, a high absorption coefficient in a thin layer, and excellent heat resistance, so that a solid-state imaging device, a liquid crystal display device, It is suitably used for forming colored pixels in a color filter for a display device such as an organic EL device.

  When forming the colored cured film of the present invention on an arbitrary substrate or substrate, the colored curable composition is applied, or the substrate or the like is immersed in the colored curable composition to form a colored curable composition. A physical layer may be formed and cured. Further, when forming a patterned colored cured film, it may be applied to a substrate or a substrate by an inkjet recording method, or a known printing method such as textile printing or offset printing may be applied. From the viewpoint that a pattern can be formed, a method of forming a colored curable composition layer on a substrate, which will be described later, exposing to a pattern, and developing to remove an unexposed portion of the colored curable composition layer Is preferred.

<Color filter and manufacturing method thereof>
The color filter of the present invention comprises a colored cured film formed of the colored curable composition of the present invention on a substrate.
That is, a color filter can be most suitably produced by forming a colored cured film (for example, colored pixels) of each color (for example, 3 colors or 4 colors) by a color filter manufacturing method described below. .
As a result, a color filter used in a display device such as a solid-state imaging device, a liquid crystal display device, or an organic EL display device can be manufactured with low process difficulty, high quality, and low cost.

The method for producing a color filter of the present invention comprises a step of forming a colored curable composition layer (colored layer) by applying the above-described colored curable composition of the present invention onto a substrate [hereinafter referred to as step (i). The colored curable composition layer (colored layer) is exposed in a pattern, and the uncured portion is developed and removed with a developer to form a patterned colored cured film [hereinafter referred to as step (ii). ))].
That is, the colored curable composition of the present invention is applied to a substrate such as glass directly or via another layer, for example, by a method such as spin coating, slit coating, casting coating, roll coating, or inkjet coating. Then, a colored layer is formed, and the formed colored layer is exposed by a method such as exposing through a predetermined mask pattern [step (i)], and the uncured portion is developed and removed with a developer after the exposure. A colored cured film is formed by [Step (ii)]. Pattern exposure may be performed by scanning exposure in addition to exposure through a mask pattern.
In the method for producing a color filter of the present invention, a step of irradiating the patterned colored region formed in the step (ii) with ultraviolet rays [hereinafter also referred to as step (iii). ] And a step of performing heat treatment on the colored region irradiated with ultraviolet rays [hereinafter also referred to as step (iv). The aspect which further has at least 1 process chosen from these is preferable.
Hereinafter, the manufacturing method of the color filter of the present invention will be described more specifically.

-Step (i)-
In the method for producing a color filter of the present invention, first, the above-described colored curable composition of the present invention is applied to the support directly or via another layer by a desired method, and the colored curable composition is provided. A coating film (colored curable composition layer) is formed, and then pre-cured (prebaked) as necessary, and the colored curable composition layer is dried.
As the support, for example, non-alkali glass, soda glass, Pyrex (registered trademark) glass, quartz glass, and those obtained by attaching a transparent conductive film to these, used for solid-state imaging devices, etc. Examples of the photoelectric conversion element substrate include a silicon substrate and a plastic substrate. Further, on these supports, a black matrix for isolating each pixel may be formed, or a transparent resin layer may be provided for promoting adhesion. Further, if necessary, an undercoat layer may be provided on the support for improving adhesion to the upper layer, preventing diffusion of substances, or flattening the surface.
The plastic substrate preferably further has at least one layer selected from a gas barrier layer and a solvent resistant layer on the surface thereof.

In addition, a driving substrate on which a thin film transistor (TFT) of a thin film transistor (TFT) type color liquid crystal display device is disposed (hereinafter referred to as “TFT type liquid crystal driving substrate”) is used as a support. A color filter using the colored curable composition of the present invention can also be formed on the substrate to produce a color filter.
Examples of the substrate in the TFT type liquid crystal driving substrate include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide. These substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired. For example, a substrate in which a passivation film such as a silicon nitride film is formed on the surface of the TFT liquid crystal driving substrate can be used.

  Examples of a method for applying the colored curable composition of the present invention on a support include spin coating, slit coating, cast coating, roll coating, bar coating, and inkjet coating methods.

In the step (i), the method for applying the colored curable composition of the present invention to the support is not particularly limited, but a slit nozzle such as a slit-and-spin method or a spinless coating method is used. A method (hereinafter referred to as slit nozzle coating method) is preferred.
In the slit nozzle coating method, the slit-and-spin coating method and the spinless coating method have different conditions depending on the size of the coated substrate. For example, the fifth generation glass substrate (1100 mm × 1250 mm) is colored and cured by the spinless coating method. When the curable composition is applied, the discharge amount of the colored curable composition from the slit nozzle is usually 500 microliter / second to 2000 microliter / second, preferably 800 microliter / second to 1500 microliter / second. In addition, the coating speed is usually 50 mm / second to 300 mm / second, preferably 100 mm / second to 200 mm / second.
The solid content concentration of the colored curable composition used in step (i) (solid content concentration in the colored curable composition coating solution) is usually 10% by mass to 20% by mass, preferably 13% by mass to 18% by mass.

In the step (i), usually, a prebaking treatment is performed after the colored curable composition layer is formed. If necessary, vacuum treatment can be performed before pre-baking. The vacuum drying condition is that the degree of vacuum is usually about 13.33 Pa (0.1 torr) to 133.32 Pa (1.0 torr), preferably about 26.66 Pa (0.2 torr) to 66.66 Pa (0.5 torr). It is.
The pre-bake treatment can be performed in a temperature range of 50 ° C. to 140 ° C., preferably in a temperature range of about 70 ° C. to 110 ° C. under conditions of 10 seconds to 300 seconds using a hot plate, oven, or the like. . Note that in the pre-bake treatment, a high-frequency treatment or the like may be used in combination with the heat treatment. Moreover, when drying a colored curable composition layer, it can replace with a prebaking process and can also perform a high frequency process independently.

The thickness of the colored curable composition layer formed from the colored curable composition is appropriately selected according to the purpose. In the color filter for liquid crystal display devices, the range of 0.2 μm to 5.0 μm is preferable, the range of 1.0 μm to 4.0 μm is more preferable, and the range of 1.5 μm to 3.5 μm is the most preferable. Moreover, in the color filter for solid-state image sensors, the range of 0.2 micrometer-5.0 micrometers is preferable, The range of 0.3 micrometer-2.5 micrometers is more preferable, The range of 0.3 micrometer-1.5 micrometers is the most preferable.
In addition, the thickness of the colored curable composition layer is a film thickness after pre-baking.

-Step (ii)-
Subsequently, pattern exposure is performed on the coating film (colored curable composition layer) formed of the colored curable composition formed on the support as described above. The pattern exposure is performed through, for example, a photomask. The exposure is performed.
As light or radiation applicable to exposure, g-line, h-line, i-line, j-line, KrF light and ArF light are preferable, and i-line is particularly preferable. When using the i-line to the irradiation light is ^preferably irradiated at an exposure dose of ^{100mJ / cm 2 ~10000mJ / cm 2} .

  Other exposure rays include ultra high pressure, high pressure, medium pressure and low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, various visible and ultraviolet laser light sources, fluorescent lamps, tungsten lamps, solar Light etc. can also be used.

~ Exposure process using laser light source ~
In an exposure method using a laser light source, it is preferable to use an ultraviolet laser as the light source.
The irradiation light is preferably an ultraviolet laser having a wavelength in the range of 300 nm to 380 nm, more preferably an ultraviolet laser having a wavelength in the range of 300 nm to 360 nm matches the photosensitive wavelength of the resist. Is preferable.
Specifically, the Nd: YAG laser third harmonic (355 nm), which is a relatively inexpensive solid output, and the excimer laser XeCl (308 nm), XeF (353 nm) can be suitably used. .
The exposure amount of the exposure object ^(pattern), in the range of ^{1mJ / cm 2 ~100mJ / cm 2} , the range of 1mJ / cm ² ~50mJ / cm 2 is more preferable. An exposure amount within this range is preferable from the viewpoint of pattern formation productivity.

The exposure apparatus that can be used in the present invention is not particularly limited, but commercially available exposure apparatuses include LE5565A (manufactured by Hitachi High-Technologies Corporation), Callisto (manufactured by Buoy Technology Co., Ltd.) and EGIS (manufactured by Buoy Technology Co., Ltd.). Or DF2200G (manufactured by Dainippon Screen Co., Ltd.) can be used. Further, devices other than those described above are also preferably used.
When the production method of the present invention is applied to the production of a color filter for a liquid crystal display device, exposure using mainly h-line and i-line is preferably used by a proximity exposure machine and a mirror projection exposure machine. Further, when manufacturing a color filter for a solid-state image sensor, it is preferable to mainly use i-line in a stepper exposure machine. When manufacturing a color filter using a TFT type liquid crystal driving substrate, the photomask used has a through hole or a U-shaped depression in addition to a pattern for forming a pixel (colored pattern). The thing in which the pattern for forming is provided is used.

  Further, a light emitting diode (LED) and a laser diode (LD) can be used as the active radiation source. In particular, when an ultraviolet light source is required, an ultraviolet LED and an ultraviolet LD can be used. For example, Nichia Corporation has introduced a purple LED whose main emission spectrum has a wavelength between 365 nm and 420 nm. When even shorter wavelengths are required, US Pat. No. 6,084,250 discloses an LED that can emit actinic radiation centered between 300 nm and 370 nm. Other ultraviolet LEDs are also available and can emit radiation in different ultraviolet bands. The actinic radiation source particularly preferred in the present invention is a UV-LED, particularly preferably a UV-LED having a peak wavelength at 340 to 370 m.

  Since the parallelism of the ultraviolet laser is good, the pattern can be exposed without using a mask at the time of exposure. However, it is more preferable to expose the pattern using a mask because the linearity of the pattern is further increased.

The colored curable composition layer exposed as described above can be heated.
The exposure can be performed while flowing nitrogen gas in the chamber in order to suppress oxidation fading of the coloring material in the colored curable composition layer.

Subsequently, the colored curable composition layer after exposure is developed with a developer. Thereby, a negative type or positive type coloring pattern (resist pattern) can be formed. In development, the uncured portion after exposure is eluted in the developer, and only the cured portion remains on the substrate.
Any developer can be used as long as it dissolves the coating film (colored curable composition layer) of the colored curable composition in the uncured portion while not dissolving the cured portion. For example, combinations of various organic solvents and alkaline aqueous solutions can be used.
Examples of the organic solvent used for development include the above-described solvents that can be used when preparing the colored curable composition of the present invention.

Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, Concentration of an alkaline compound such as tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene, in a concentration of 0.001 to 10% by mass, preferably 0.01 to An alkaline aqueous solution dissolved so as to be 1% by mass can be mentioned.
When the developer is an alkaline aqueous solution, the alkali concentration is preferably adjusted to be pH 11 to 13, more preferably pH 11.5 to 12.5.
An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline aqueous solution.

The development temperature is usually preferably carried out using a developer in the temperature range of 20 ° C. to 30 ° C., and the development time is preferably 20 seconds to 90 seconds.
For the development, the developer may be applied by any method such as a dip method, a shower method, or a spray method, and any stress is applied to the developer bath such as a swing method, a spin method, or an ultrasonic method. You may combine methods. It is also possible to take a method of preventing development unevenness by pre-wetting the surface to be developed with water or the like before touching the developer. Moreover, it can also develop by inclining the board | substrate provided with the colored curable composition layer after exposure.
In the case of producing a color filter for a solid-state image sensor, paddle development in which development is performed while stirring the developing bath may be used.

After the development process, a rinsing process for washing and removing excess developer is performed, followed by drying, followed by heat treatment (post-baking) to complete the curing.
The rinsing process is usually performed with pure water, but in order to save liquid, pure water is used in the final cleaning, and used pure water is used in the initial stage of cleaning, or the substrate is inclined and cleaned. Alternatively, a method of using ultrasonic irradiation together may be used.

  After the rinse treatment, after draining and drying, a heat treatment is preferably performed at 100 ° C. to 300 ° C., more preferably 150 ° C. to 250 ° C., as described in detail below. In this heat treatment (post-bake: step (iv)), the coating film after development is heated using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater or the like so as to satisfy the above-described conditions. It can be carried out continuously or batchwise.

  By sequentially repeating the above steps for each color according to the desired number of hues, it is possible to produce a color filter in which a cured film (colored pattern) colored in a plurality of colors is formed.

-Step (iii)-
In the method for producing a color filter of the present invention, in particular, post-exposure by ultraviolet irradiation can be performed on a patterned colored region (colored pixel) formed using a colored curable composition.

-Step (iv)-
It is preferable to further heat-treat the patterned colored region that has been post-exposed by ultraviolet irradiation as described above. The colored region can be further cured by subjecting the formed colored region to heat treatment (so-called post-bake treatment). This heat treatment can be performed by, for example, a hot plate, various heaters, an oven, or the like.
As temperature in the case of heat processing, it is preferable that it is 100 to 300 degreeC, More preferably, it is 150 to 250 degreeC. The heating time is preferably about 10 minutes to 120 minutes.

The patterned colored region (colored cured film) thus obtained constitutes a pixel in the color filter. In the production of a color filter having pixels of a plurality of hues, the above steps (i), (ii), and if necessary, the steps (iii) and (iv) are repeated according to the desired number of colors. Good.
Each time the formation, exposure, and development of the monochromatic colored curable composition layer are completed (for each color), at least one step selected from the step (iii) and the step (iv) may be performed. Then, after the formation, exposure, and development of all the colored curable composition layers having the desired number of colors are completed, at least one step selected from step (iii) and step (iv) is performed collectively. Also good.

A colored cured film obtained by the method for producing a color filter of the present invention or a color filter (color filter of the present invention) provided with a colored cured film formed of the colored curable composition of the present invention is colored according to the present invention. Since the curable composition is used, the color when the image is displayed is vivid, the contrast is high, and the fastness (particularly heat resistance and light resistance) is excellent. Furthermore, as will be described later, not only a known CCFL but also a white LED is used as a backlight, there is an excellent effect that a good hue can be reproduced.
The color filter of the present invention can be used for a liquid crystal display device or a solid-state imaging device, and is particularly suitable for use in a liquid crystal display device. When used in a liquid crystal display device, it is possible to display an image excellent in spectral characteristics and contrast while achieving a good hue by using a dye as a colorant, and further excellent in suitability for a white LED. .

As described above, the use of the colored curable composition of the present invention has been described mainly focusing on the formation of the color filter color pattern. However, the color curable composition of the present invention is used to form a black matrix that isolates the color pattern (pixels) constituting the color filter. Can also be applied.
The black matrix on the substrate is a colored curable composition containing a black pigment light-shielding pigment such as carbon black or titanium black, and is subjected to coating, exposure, and development steps. It can be formed by baking.

  When a colored layer is formed by applying the colored curable composition of the present invention on a substrate, the dry thickness of the colored layer is generally 0.3 μm to 5.0 μm, preferably 0.5 μm to 3.5 μm. And most desirably 1.0 μm to 2.5 μm.

<Display device (liquid crystal display device, organic EL display device)>
The color filter of the present invention is particularly suitable as a color filter for liquid crystal display devices and organic EL display devices. A liquid crystal display device and an organic EL display device provided with such a color filter can display a high-quality image.

  For the definition of display devices and explanation of each display device, refer to, for example, “Electronic Display Device (Akio Sasaki, published by Industrial Research Institute 1990)”, “Display Device (written by Junaki Ibuki, Industrial Book Co., Ltd.) Issue year)). The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next-generation liquid crystal display technology”.

  The color filter of the present invention is particularly effective when used in a color TFT liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Further, the color filter of the present invention is a liquid crystal display device with a wide viewing angle, such as a lateral electric field driving method such as IPS, a pixel division method such as MVA, STN, TN, VA, OCS, FFS, and R-OCB. Etc.

The color filter of the present invention is a bright and high-definition COA (Color-filter).
(On Array) method can also be used. In the case of a COA type liquid crystal display device, the required characteristics for the color filter layer must be the required characteristics for the interlayer insulating film, that is, the low dielectric constant and the resistance to the peeling solution, in addition to the normal required characteristics as described above. The color filter of the present invention is considered to enhance the transparency of the ultraviolet light laser that is the exposure light by selecting the hue and film thickness of the pixels defined by the present invention in addition to the exposure method using the ultraviolet light laser. As a result, the curability of the colored pixel is improved, and a pixel free from chipping, peeling, or twisting can be formed. Therefore, the resistance to the peeling liquid of the colored layer provided directly or indirectly on the TFT substrate is improved. Useful for liquid crystal display devices. In order to further improve the required characteristics of the low dielectric constant, a resin film may be further provided on the color filter layer.

The colored layer formed by the COA method has a rectangular shape with a side length of about 1 μm to 15 μm in order to connect the ITO electrode arranged on the colored layer and the terminal of the driving substrate below the colored layer. It is necessary to form a conduction path such as a through hole or a U-shaped depression, and the dimension of the conduction path (that is, the length of one side) is particularly preferably 5 μm or less, and the colored layer has good curability. It is also possible to form a conduction path of 5 μm or less by using the color filter of the present invention having
These image display methods are described, for example, on page 43 of "EL, PDP, LCD display-Technology and latest trends in the market (issued by Toray Research Center Research Division 2001)".

The liquid crystal display device and organic EL display device of the present invention are composed of various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film in addition to the color filter of the present invention. The color filter of the present invention can be applied to a liquid crystal display device and an organic EL display device composed of these known members.
Regarding these materials, for example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shima, CMC 1994)”, “2003 Liquid Crystal Related Markets Current Status and Future Prospects (Volume 2)” Fuji Chimera Research Institute, Ltd., 2003) ”.
and so on.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” and “%” are based on mass.

Example 1-1 Synthesis of Compound A-1
Compound A-1 described above as an exemplary compound was synthesized according to the synthesis examples described above.
As a result of identifying the obtained compound A-1 by MS, it was confirmed that it was the target structure. The absorption wavelength of the obtained compound A-1 in ethyl acetate was 435 nm, and the extinction coefficient was 43500.

[Example 1-2: Synthesis of compound A-6]
The compound A-6 described above as an exemplary compound was synthesized according to the following synthesis example.
First, according to the method described in Japanese Patent No. 2670943, a pyrazolotriazole body a-1 which is a precursor structure of Compound A-6 was obtained (20.4 g). Next, a-1 (20.4 g) was dissolved in 80 ml of pyridine (manufactured by Wako Pure Chemical Industries, Ltd.), and o-methylbenzenesulfonic acid chloride: 16.8 g (Tokyo Chemical Industry Co., Ltd.) in an ice bath. )) Was added dropwise and reacted at room temperature for 1 hour. Next, 200 ml of ethyl acetate and 300 ml of water were added, and the target product was extracted into the ethyl acetate layer. The ethyl acetate layer was concentrated, and the target product was purified by column chromatography to obtain intermediate a-2-2. (24.3g)

  Next, the obtained intermediate a-2-2 (3.0 g) was dissolved in dimethylformamide: 10 ml (manufactured by Wako Pure Chemical Industries, Ltd.), and phosphorus oxychloride: 1.6 g (Wako Pure Chemical Industries, Ltd.) in an ice bath. (Made by Co., Ltd.) was dripped. After completion of the dropwise addition, the internal temperature was raised to 80 ° C. and stirred for 2 hours. The reaction was stopped by adding to 100 ml of water, followed by extraction with 200 ml of ethyl acetate, neutralization washing with an aqueous sodium bicarbonate solution, and concentration of the solvent to dryness to obtain intermediate a-3-2. (2.6g)

  Next, intermediate a-3 (1.5 g) and pyridone: 0.71 g (manufactured by Tokyo Chemical Industry Co., Ltd.) were put into 10 ml of acetic anhydride and stirred at an internal temperature of 80 ° C. for 2 hours. After the reaction, 20 ml of methanol was added, and the precipitate was filtered and dried.

As a result of identifying this compound A-6 by MS, it was confirmed that it was the target structure.
Moreover, the absorption wavelength in ethyl acetate of the obtained compound A-6 was 462 nm, and the extinction coefficient was 58000.

[Examples 2-1 to 2-7, Examples 3-1 to 3-4, Comparative Examples 1 and 2]
First, each component used for preparation of each colored curable composition of Examples 2-1 to 2-7, Examples 3-1 to 3-4, and Comparative Examples 1 and 2 is shown below.

(A1) (A) Specific colorant (component (A) ) or compound for comparison shown below
In addition, the Example using the following A-1, A-3, A-8, A-9, and A-11 as (A) specific colorant is an Example of the present invention, and the following A-14 Examples using A-16 and A-16 are reference examples of the present invention.
A-1: The exemplified compound (A-1)
A-3: The exemplified compound (A-3)
A-8: The exemplified compound (A-8)
A-9: Exemplified compound (A-9)
A-11: Exemplified compound (A-11)
A-14: The exemplified compound (A-14)
A-16: The exemplified compound (A-16)
A′-1: Compound shown below (Comparative compound)


A′-2: Compound shown below (Comparative compound)

(B1) C.I. I. 14.9 parts of Pigment Green 58 and 7.1 parts of an acrylic pigment dispersant [methyl methacrylate / methacrylic acid (80/20) [mass ratio] copolymer (weight average molecular weight: 12,000)] A pigment dispersion obtained by mixing with 78.0 parts of propylene glycol monomethyl ether acetate and sufficiently dispersing the pigment using a bead mill. [Component (B)]
The above C.I. I. The pigment dispersion of Pigment Green 58 is further diluted with propylene glycol monomethyl ether acetate (hereinafter also referred to as PGMEA), adjusted to a concentration of 0.8 to 1.0, and CARY5 / UV-visible spectrophotometry. When measured using a meter (commercially available product: manufactured by Varian), the maximum absorption peak wavelength was 661 nm.

(C1) Photopolymerizable compound: Kayrad DPHA (trade name, manufactured by Nippon Kayaku Co., Ltd.) [component (C)]
(D1) Photopolymerization initiator: 2- (benzoyloxyimino) -1- [4 ′-(phenylthio) phenyl] -1-octanone (manufactured by BASF; IRGACURE OXE 01) [Component (D)]
(D2) Photopolymerization initiator: the following compound [component (D)]

(D3) Photopolymerization initiator: the following compound [component (D)]

(D4) Photopolymerization initiator: IRGACURE 369 (manufactured by BASF: α-acylamino compound)
(E1) Propylene glycol monomethyl ether acetate [Solvent]
(E2) Ethyl 3-ethoxypropionate [Solvent]
(E3) 1,4-bis (3-mercaptobutyryloxy) butane (Karenz MTBD1 manufactured by Showa Denko KK)
(F1) Binder resin: Allyl methacrylate / methacrylic acid (80:20 (molar ratio))
(G1) 4-Methoxyphenol (H1) Surfactant: Megafac F781-F (trade name, manufactured by DIC Corporation)

-Preparation of colored curable composition-
Each component shown in the following Table 1 or 2 is blended in the amount shown in the following Table 1 or 2 (the numerical value indicates mass%), mixed at room temperature (25 ° C.) for 10 minutes, and then allowed to stand for 10 minutes. And filtering with HDC II (trade name, manufactured by Nippon Pole Co., Ltd.) to obtain colored curable compositions of Examples and Comparative Examples.

-Evaluation of colored curable composition-
The colored curable compositions of Examples and Comparative Examples obtained above were evaluated as follows. The results are shown in Tables 1 and 2.

1. Formation of colored cured film After applying the colored curable composition of Example 2-1 obtained above on glass (Corning Corp .; EAGLE-XG (0.7 mm)) by spin coating, The coating film 1 was formed by volatilizing volatile components in 2 minutes. After cooling, the coating film 1 was exposed by irradiating with i-line [wavelength 365 nm]. An ultra-high pressure mercury lamp was used as the i-line light source, and the light was irradiated after being converted into parallel light. The amount of irradiation light was 50 mJ / cm ² . Next, post-baking was performed at 230 ° C. for 20 minutes to obtain a colored cured film 1 having a thickness of 2 μm. Similarly to the colored cured film 1, the colored curable compositions of Examples 2-2 to 2-7, Examples 3-1 to 3-4, and Comparative Examples 1 and 2 were used in the same manner. A coating film was formed and exposed to produce colored cured film 2 to colored cured film 13.

2. Evaluation of chromaticity About each of the colored cured films 1-13 obtained above, chromaticity was evaluated by the following method.
CCFL backlight (LC-32GH5 adopted product, manufactured by Sharp Corporation) was used as a light source, and measurement was performed using a microspectrophotometer OSP-SP200 manufactured by Olympus Co., Ltd., and x and y were adjusted to targets. The brightness was evaluated by the Y value. x = 0.30 and y = 0.60 are the green chromaticity of the HDTV standard. When x and y are these numerical values, the higher the Y value, the better the performance as a liquid crystal display.

3. Contrast / luminance evaluation The obtained colored cured film is sandwiched between two polarizing films, and the luminance value when the polarization axes of the two polarizing films are parallel and perpendicular is measured with a color luminance meter (Topcon). Measured using a model number: BM-5A manufactured by Co., Ltd., and the brightness when the polarization axes of the two polarizing films are parallel divided by the brightness when vertical, the obtained value is used as the contrast. It was calculated | required (In Table 1 or Table 2, it describes as CR.). The higher the numerical value described in the column of contrast (CR), the better the performance as a color filter for a liquid crystal display.

4). Evaluation of heat resistance The sample used in the above "3. Evaluation of contrast and brightness" was forcibly heat-treated in an oven at 230 ° C for 1 hour, and the color difference before and after heating was measured to obtain an index of heat resistance. The chromaticity is measured with a microspectrophotometer (manufactured by Olympus Optical Co., Ltd .; OSP100 or 200), calculated as a result of the F10 light source field of view of 2 degrees, and expressed as an xyY value in the xyz color system. The difference in chromaticity is represented by the color difference of the La ^* b ^* color system. A smaller color difference means higher heat resistance.

  As apparent from the results shown in Tables 1 and 2, the colored cured film obtained using the compound represented by the general formula (I) ((A) specific colorant) is a conventionally known yellow dye. Compared with a colored cured film obtained by using a comparative compound, it shows the HDTV standard green chromaticity in combination with a CCFL backlight, with high brightness, excellent contrast, and heat resistance. It can be seen that it is excellent. This means that a color filter having a colored cured film formed using the colored curable composition of the example has a color pixel with good color purity, high luminance, and excellent heat resistance. Means a color filter.

Claims (14)

A colored curable composition containing the following component (A), component (B) and component (C).
(A) A colorant selected from compounds represented by the following general formula (I A-2 )

(In General Formula (IA-2), R ¹ represents a t-butyl group. R ⁴ represents a hydrogen atom, an alkyl group, an aryl group, or a cyano group. R ⁵ represents an aryl group having a substituent. R ⁶ represents a hydrogen atom, an alkyl group, or an aryl group, and Cy 2 represents a ring structure including a 5-membered ring or a 6-membered ring formed with an adjacent carbon atom.
(B) Colorant having a hue different from the colorant (A) (C) Polymerizable compound   The colored curable composition according to claim 1, wherein the (B) colorant is a colorant having a maximum absorption peak wavelength in a wavelength range of 380 nm to 800 nm in a range of 500 nm to 800 nm. The colored curable composition according to claim 1 or 2, wherein the (B) colorant is a zinc phthalocyanine compound represented by the following general formula (II).

(In the general formula ^{(II), A 1, A} 2, A 3, A 4, A 5, A 6, A 7, A 8, A 9, A 10, A 11, A 12, A 13, A 14, A ¹⁵ and A ¹⁶ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or a thioalkoxy group.) (B) the colorant, wearing color curable composition as claimed in any one of claims 3 is a zinc phthalocyanine compound halogenated.   The colored curable composition according to any one of claims 1 to 4, further comprising (D) a photopolymerization initiator.   The colored curable composition according to claim 5, wherein the photopolymerization initiator is an oxime compound.   Furthermore, the colored curable composition of any one of Claims 1-6 containing an aliphatic polyfunctional mercapto compound. The colored curable composition according to any one of claims 1 to 7 , which is used for a color filter. The colored cured film formed with the colored curable composition of any one of Claims 1-8 . A step of applying the colored curable composition according to any one of claims 1 to 8 on a substrate to form a colored curable composition layer, and the formed colored curable composition layer comprising: A method for producing a color filter, comprising exposing and developing in a pattern. A color filter comprising the colored cured film according to claim 9 . A color filter produced by the method for producing a color filter according to claim 10 . Display device comprising the color filter according to claim 11 or claim 12. The compound represented by the following general formula (IA -2 ).

(In General Formula (IA-2), R ¹ represents a t-butyl group. R ⁴ represents a hydrogen atom, an alkyl group, an aryl group, or a cyano group. R ⁵ represents an aryl group having a substituent. R ⁶ represents a hydrogen atom, an alkyl group, or an aryl group, and Cy 2 represents a ring structure including a 5-membered ring or a 6-membered ring formed with an adjacent carbon atom.