JP2012215686A - Coloring composition, color filter, liquid crystal display device and organic el display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a coloring composition which is capable of providing a pixel for a color filter having excellent transmittance (luminance) and contrast and satisfies heat resistance required in a color display manufacturing step; a color filter excellent in color purity of a blue pixel and transmittance by using such a coloring composition; and an organic EL display device and a liquid crystal display device achieving both high color reproducibility and high luminance by using such a color filter.SOLUTION: There is provided a coloring composition containing a color material (A), a solvent (B), a binder resin (C), a compound represented by the following formula (I) as the color material (A) and a copper phthalocyanine pigment and/or a dioxazine pigment. ZA(I)(where Zrepresents a disulfonylimide anion and Arepresents a cationic dye.)

Description

  The present invention provides a coloring composition capable of providing a pixel of a color filter excellent in transmittance (luminance) and contrast, a color filter having a pixel formed using the same, and the color filter formed using the color filter The present invention relates to a liquid crystal display device and an organic EL display device.

In recent years, color liquid crystal display devices and organic EL display devices have attracted attention as flat panel displays, and color filters are used in these displays.
For example, a color liquid crystal display device includes, as an example, a black matrix, a colored layer composed of a plurality of colors (usually three primary colors of red (R), green (G), and blue (B)), a transparent electrode, and an alignment layer. The provided color filter substrate, a thin film transistor (TFT element), a counter electrode substrate provided with a pixel electrode and an alignment layer, and these substrates are opposed to each other with a predetermined gap, sealed with a sealing member, and liquid crystal is placed in the gap. There is a transmissive liquid crystal display device that is roughly configured from a liquid crystal layer formed by injecting a material. There is also a reflective liquid crystal display device in which a reflective layer is provided between the color filter substrate and the colored layer.

  In principle, an organic EL display device has an organic EL element having a structure in which an organic EL light-emitting layer is sandwiched between an anode and a cathode, but in fact, color display is possible using the organic EL element. To make an organic EL display device, (1) a method of arranging organic EL elements that emit light of each of the three primary colors, and (2) a method of combining organic EL elements that emit white light with a color filter layer of the three primary colors, And (3) a CCM system that combines an organic EL element that emits blue light and a color conversion layer (CCM layer) that performs color conversion from blue to green and blue to red, respectively.

Needless to say, the method of (1) is characterized in that high color reproducibility can be exhibited because organic EL elements of each color are used. By placing color filters corresponding to the organic EL elements of each color, improvement in color reproducibility and improvement in contrast by absorbing reflected light can be expected, which is one of the promising methods.
Further, in the combination method of the white organic EL and the color filter in (2) and the CCM method in (3), it is only necessary to use one type of organic EL element that emits light of the same color. As in the EL display device, it is not necessary to make the characteristics of the organic EL elements of each color uniform, and the number of processes and materials can be reduced in terms of manufacturing cost.

In an organic EL device using a color filter and a color conversion method comprising a color conversion filter and an organic light emitter as constituent elements, heat resistance required in the color display manufacturing process, weather resistance when used as a display, and For those requiring high-definition images, it is the mainstream to use color filters created by the pigment dispersion method.
As a method for producing a color filter by such a pigment dispersion method, a photolithography method is applied after applying a fine dispersion of a red, blue or green pigment in a photosensitive resin solution to a particle size of 1 μm or less on a glass substrate. Thus, a method of forming pixels in a desired pattern is generally used (Patent Documents 1 and 2).

  With respect to color filters, improvements in color purity, saturation, and light transmission are required. Conventionally, for the purpose of improving light transmission, the content of the color pigment relative to the photosensitive resin in the image forming material is reduced. A method has been adopted in which the thickness of the pixel formed by the image forming material is reduced or the pixel formed is made thinner. However, in these methods, the saturation of the color filter itself is lowered, the entire display becomes whitish, and the vividness of the color necessary for display is sacrificed. When it is increased, the entire display becomes dark, and in this case, the amount of light of the backlight must be increased in order to ensure brightness, leading to an increase in power consumption of the display.

  On the other hand, for the purpose of improving the light transmission amount, a method of finely dispersing the particle size of pigment particles to 1/2 or less of the coloration wavelength is known (Non-patent Document 1). Is shorter in coloration wavelength than other red and green pigments, and in this case, further fine dispersion is required, resulting in problems of cost increase and stability after dispersion.

On the other hand, color filters using dyes as colorants are still being developed. For example, Patent Document 3 describes a color filter provided with a blue filter layer containing C.I. Acid Blue 83 (triallylamine dye) and C.I.Solvent Blue 67 (copper phthalocyanine dye). ing.
However, the color filter using the dye described in this document has a problem that the transmittance (brightness) and heat resistance are insufficient.

Patent Document 4 describes a color filter using a polymer containing a polymerizable triphenylmethane dye represented by the following formula.
However, the color filter using the dye described in the document has a problem of insufficient heat resistance although it is excellent in transmittance (brightness) and contrast.

(At least one of R _{1 in} the above formula is a specific polymerizable group containing a carbon-carbon double bond)

Patent Documents 5 to 7 describe a color composition for a color filter comprising a mixture of a dye containing at least one of oil-soluble dyes, disperse dyes and basic dyes and a copper phthalocyanine pigment.
However, the color filters using the dyes described in these documents have a problem of insufficient heat resistance although they are excellent in transmittance (brightness) and contrast.

Patent Document 8 describes a colorant containing an anthraquinone dye and a pigment.
However, although the color filter using the composition described in the document has excellent contrast, there is a problem that transmittance (luminance) and heat resistance are insufficient.

JP 60-129739 A JP 60-129707 A Japanese Patent Laid-Open No. 2002-14222 JP 2000-162429 A JP 2001-124915 A JP 2001-290019 A JP 2001-305521 A JP 2008-15530 A

Kiyoshi Hashizume “Journal of Color Material Association” (December 1967, p608)

An object of the present invention is to provide a color composition that can provide a pixel of a color filter excellent in transmittance (brightness) and contrast, and that also satisfies the heat resistance required in the color display manufacturing process described above. And
The present invention also provides a color filter particularly excellent in color purity and transmittance of a blue pixel by using such a coloring composition, and by using such a color filter, high color reproducibility and An object of the present invention is to provide an organic EL display device and a liquid crystal display device compatible with high luminance.

As a result of intensive studies, the present inventors have found that the above problem can be solved by using a salt composed of a specific compound and a specific pigment as a coloring composition for forming a pixel of a color filter. Invented.
That is, the gist of the present invention includes (A) a coloring material, (B) a solvent, and (C) a binder resin, and the (A) coloring material represented by the following formula (I), a copper phthalocyanine pigment, And / or a coloring composition, a color filter, a liquid crystal display device, and an organic EL display device containing a dioxazine pigment.
Z ⁻ A ⁺ (I)
(In the above formula (I), Z ⁻ represents a disulfonylimide anion.
A ⁺ represents a cationic dye. )

  According to the present invention, it is possible to obtain a color filter that satisfies the heat resistance required in the color display manufacturing process and is excellent in the transmittance (brightness) of blue pixels, and by using such a color filter, Light emission from the organic EL display device and light emission from the backlight of the liquid crystal display device can be efficiently extracted. This makes it possible to obtain a high-quality liquid crystal display device and organic EL display device.

It is a section schematic diagram showing an example of an organic EL device which has a color filter of the present invention.

  Embodiments of the present invention will be described in detail below, but the following description is an example of embodiments of the present invention, and the present invention is not limited to these contents.

In the present invention, “(meth) acryl”, “(meth) acrylate” and the like mean “acryl and / or methacryl”, “acrylate and / or methacrylate” and the like, for example, “(meth) acrylic acid” "Means" acrylic acid and / or methacrylic acid ".
Further, the “total solid content” means all components of the colored composition of the present invention other than the solvent component described later.
C. I. Means a color index.

  In the present invention, the weight average molecular weight refers to a polystyrene equivalent weight average molecular weight (Mw) by GPC (gel permeation chromatography).

The coloring composition of the present invention contains (A) a color material, (B) a solvent, and (C) a binder resin. The compound represented by the following formula (I) as the (A) color material, and a copper phthalocyanine pigment And / or a coloring composition containing a dioxazine pigment.
Z ⁻ A ⁺ (I)
(In the above formula (I), Z ⁻ represents a disulfonylimide anion.
A ⁺ represents a cationic dye. )
[Color material]
The coloring composition of the present invention contains, as a coloring material, a compound represented by the formula (I) (hereinafter sometimes referred to as compound (I)), a copper phthalocyanine pigment and / or a dioxazine pigment.
That is, the coloring composition of the present invention is a combination of the compound (I) that is a dye and the copper phthalocyanine pigment and / or dioxazine pigment that is a pigment as a coloring material.

By using a combination of such a dye (that is, compound (I)) and a copper phthalocyanine pigment and / or a dioxazine pigment, the color tone can be freely adjusted from blue to red, and the dye There is an effect that heat resistance, light resistance and the like are improved as compared with the case of using alone.
(Compound represented by formula (I))
In compound (I), A represents a cationic dye.
The cationic dye is not particularly limited as long as the effect of the present invention is not performed. For example, it is described in "Industrial Dyes -Chemistry, Properties, Applications- (Wiley-VCH, 2003, edited by Klaus Hunger)" Pigments. More specifically, compounds having a dye skeleton (Chromophore) such as triarylmethanes, cyanines, styryls and azines can be mentioned, and can be appropriately selected depending on a desired color.
In particular, when blue is desired, triarylmethanes are preferable from the viewpoint of excellent color density, luminance, and heat resistance. When purple is desired, color density, luminance, and heat resistance are excellent. From the viewpoint, triarylmethanes and cyanines are particularly preferable.
The cationic dye used in the present invention is preferably soluble in an organic solvent.

[Structural features]
The compound represented by the formula (I) in the present invention forms a counter ion.
In a color material forming counter ions, the properties of cations and anions affect physical properties, particularly heat resistance. This is due to the higher reactivity of cations and anions having a bias in charge than neutral molecules.
Therefore, it is presumed that the heat resistance of the coloring material can be improved by reducing the reactivity of the cation and the anion. That is, in the cation and the anion, it is considered that the reactivity is lowered by delocalizing the electric charge and the heat resistance is improved.
Here, the compound represented by the formula (I) includes a disulfonylimide anion as an anion.
The disulfonylimide anion is easy to produce because the ionic species is a sulfonamide group. In addition, since the negative charge is delocalized, the anion is relatively stable. Furthermore, by having a fluorine-containing substituent in the disulfonamide, it is considered that the anion is pulled toward the fluorine-containing substituent, whereby the charge is dispersed as a whole molecule and a more stable structure is obtained.
In addition, none of the anions in the present invention has absorption in the visible light wavelength region. Therefore, the color purity of the obtained pixel is not affected.

[Regarding Compound Represented by Formula (II)]
The compound represented by the formula (I) is preferably a compound represented by the following formula (II) from the viewpoint of excellent color density, brightness and heat resistance of the dye.

(In said formula (II), R < ¹¹ > and R < ¹² > are respectively independently the C1-C8 alkyl group which may have a substituent, and C2-C2 which may have a substituent. 6 represents an alkenyl group having 6 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms which may have a substituent.
R ¹¹ and R ¹² may be bonded to each other to form a ring.
A ⁺ has the same meaning as in formula (I). )

R ¹¹ and R ¹² have an optionally substituted alkyl group having 1 to 8 carbon atoms, an optionally substituted alkenyl group having 2 to 6 carbon atoms, and a substituent. Or a C3-C8 cycloalkyl group.
Examples of the substituent include those described in the following (Substituent group W).

(Substituent group W)
Fluorine atom, chlorine atom, alkyl group having 1 to 8 carbon atoms, alkenyl group having 2 to 8 carbon atoms, alkoxyl group having 1 to 8 carbon atoms, phenyl group, mesityl group, tolyl group, naphthyl group, cyano group, acetyloxy Group, alkyl carboxyl group having 2 to 9 carbon atoms, sulfonic acid amide group, sulfone alkylamide group having 2 to 9 carbon atoms, alkylcarbonyl group having 2 to 9 carbon atoms, phenethyl group, hydroxyethyl group, acetylamide group, carbon A dialkylaminoethyl group, a trifluoromethyl group, a trialkylsilyl group having 1 to 8 carbon atoms, a nitro group, or an alkylthio group having 1 to 8 carbon atoms, which is formed by bonding an alkyl group having 1 to 4 carbon atoms.
Among these, in particular, at least one of the alkyl group, alkenyl group or cycloalkyl group in R ¹¹ and R ¹² is a fluorine atom in that the anion charge is more delocalized and the heat resistance of the coloring material is improved. It is preferable to have as a substituent.
R ¹¹ and R ¹² are particularly preferably a perfluoroalkyl group having 1 to 8 carbon atoms in that the anion charge is dispersed and the anion is stabilized.
More specifically, the compound represented by the formula (II) is preferably a compound represented by the following formula (II-1).

(In said formula (II-1), n and n 'represent the integer of 1-8 each independently.
A ⁺ has the same meaning as in formula (II). )
n and n ′ are generally an integer of 1 to 8, preferably 1 to 4.
n and n ′ may be the same or different.
Specific examples of the sulfonylimide anion when n and n ′ are the same include bis (trifluoromethanesulfone) imide, bis (pentafluoroethanesulfone) imide, bis (pentafluorobutanesulfone) imide, and the like.
Specific examples of the sulfonylimide anion when n and n ′ are different include pentafluoroethanesulfone trifluoromethanesulfonimide, trifluoromethanesulfone heptafluoropropanesulfonimide, fluorobutanesulfone trifluoromethanesulfonimide, and the like.
Among these, bis (pentafluoroethanesulfone) imide, where n = n ′ = 2, is particularly preferable because the anion is most stabilized.
On the other hand, R ¹¹ and R ¹² may be bonded to each other to form a ring.
In the case of forming a ring, R ¹¹ and R ¹² are particularly preferably a fluoroalkylene group having 2 to 12 carbon atoms.
That is, the compound represented by the formula (II) is preferably a compound represented by the following formula (II-2).

(In said formula (II-2), n '' represents the integer of 2-12.
A has the same meaning as in formula (II). )
n ″ is preferably 2 to 8 and more preferably 3 in terms of heat resistance.
The smaller the number of n ″, the smaller the effect of steric repulsion and the stronger the interaction. That is, it is presumed that the smaller n ″, the greater the interaction between the anion and cation, and the more stable the ion pair and the better the heat resistance.
Hereinafter, preferred specific examples of the anion in Formula (I), that is, Z ⁻ are shown below, but the present invention is not limited thereto.
<Specific examples of anions>

また、前記式（ＩＩ）で表される化合物は、カチオン、つまり式（ＩＩ）中のＡ^＋からリンカーを伸ばして、２量体や３量体などを形成していてもよい。
［式（ＩＩＩ）で表される化合物について］
前記式（ＩＩ）で表される化合物は、耐熱性に優れ、また得られるカラーフィルタの、特に青色純度及び透過率が優れる点で、下記式（ＩＩＩ）で表される化合物であることが好ましい。

In addition, the compound represented by the formula (II) may form a dimer or trimer by extending a linker from a cation, that is, A ⁺ in the formula (II).
[Compound represented by formula (III)]
The compound represented by the formula (II) is preferably a compound represented by the following formula (III) from the viewpoint of excellent heat resistance and particularly excellent blue purity and transmittance of the obtained color filter. .

(In the formula ^{(III), R 21} and ^{R 22} are each the same meaning as ^{R 11} and ^{R 12} in Formula (II).
R ^{1 to} R ⁶ each independently represent a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or an aromatic ring group optionally having a substituent. Adjacent R ^{1 to} R ⁶ may be bonded to form a ring.
R ⁷ and R ⁸ represent a hydrogen atom or an arbitrary substituent. R ⁷ and R ⁸ may be connected to each other to form a ring.
R ¹⁰¹ and R ¹⁰² have a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, an optionally substituted alkenyl group having 2 to 6 carbon atoms, or a substituent. Represents an aromatic ring group which may be substituted, or a fluorine atom. R ¹⁰¹ and R ¹⁰² may be bonded to form a ring.
Moreover, the benzene ring in the above formula (III) may further have an arbitrary substituent. )

(For ^R 1 ^{~R 6)}
R ^{1 to} R ⁶ each independently represent a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or an aromatic ring group optionally having a substituent.
Examples of the alkyl group in R ^{1 to} R ⁶ include linear, branched, or cyclic alkyl groups having 1 or more carbon atoms and usually 8 or less, preferably 5 or less carbon atoms. . Specific examples include methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group, isobutyl group, tert-butyl group, cyclohexyl group and the like.
Examples of the aromatic ring group in R ^{1 to} R ⁶ include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
The aromatic hydrocarbon ring group may be a single ring or a condensed ring, and is not particularly limited as long as the number of carbon atoms forming the ring is 5 to 18, but for example, one free valence Benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring and the like.
In addition, the aromatic heterocyclic group may be a single ring or a condensed ring, and is not particularly limited as long as the number of carbon atoms forming the ring is 3 to 10, but for example, one free atom Having a valence, furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole Ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, Synoline ring, quinoxaline ring, phenanthridine ring, Zone imidazole ring, perimidine ring, a quinazoline ring, a quinazolinone ring, groups such as azulene ring.
Adjacent R ^{1 to} R ⁶ may be bonded to form a ring, and the ring may have a substituent.
When adjacent R < ¹ > -R < ⁶ > couple | bonds together and forms a ring, the ring bridge | crosslinked by the hetero atom may be sufficient as these. Specific examples of this ring include the following. These rings may have a substituent.

From the viewpoint of chemical stability, R ^{1 to} R ⁶ are preferably each independently a hydrogen atom, a C 1-8 alkyl group which may have a substituent, or a substituent. It is a case where it is a good phenyl group or adjacent R ^{1 to} R ⁶ are bonded to each other to form a ring, which improves the heat resistance of the coloring material and is excellent in the light resistance of the resulting color filter. Preferably they are the C1-C8 alkyl group which may have a substituent, or the phenyl group which may have a substituent.
When R ^{1 to} R ⁶ are an optionally substituted alkyl group having 1 to 8 carbon atoms, it is presumed that the charges in the cation are dispersed by hyperconjugation and the cation is stabilized.
Further, when R ^{1 to} R ⁶ are phenyl groups which may have a substituent, it is assumed that the cation is stabilized by extending the conjugated system and dispersing the charge in the cation. Is done. As described above, it can be considered that the light resistance of the obtained color filter becomes more excellent as a result of stabilization of the cation.
The R ¹ alkyl group in to R ^6, an aromatic hydrocarbon ring group and an adjacent R ¹ to R ⁶ are bonded to each other ring substituents which may have formed by, for example, the following (substituted And those of the base group W).

(Substituent group W)
Fluorine atom, chlorine atom, alkyl group having 1 to 8 carbon atoms, alkenyl group having 2 to 8 carbon atoms, alkoxyl group having 1 to 8 carbon atoms, phenyl group, mesityl group, tolyl group, naphthyl group, cyano group, acetyloxy Group, alkyl carboxyl group having 2 to 9 carbon atoms, sulfonic acid amide group, sulfone alkylamide group having 2 to 9 carbon atoms, alkylcarbonyl group having 2 to 9 carbon atoms, phenethyl group, hydroxyethyl group, acetylamide group, carbon A dialkylaminoethyl group, a trifluoromethyl group, a trialkylsilyl group having 1 to 8 carbon atoms, a nitro group, or an alkylthio group having 1 to 8 carbon atoms, which is formed by bonding an alkyl group having 1 to 4 carbon atoms.

(About R ⁷ and R ⁸ )
R ⁷ and R ⁸ represent a hydrogen atom or an arbitrary substituent. As this arbitrary substituent, the C1-C8 alkyl group which may have a halogen atom, a substituent, the aromatic ring group which may have a substituent, etc. are mentioned, for example.
Examples of the alkyl group and the aromatic ring group include those described in the above section (for R ^{1 to} R ⁶ ).
R ⁷ and R ⁸ may be connected to each other to form a ring.
When R ⁷ and R ⁸ are bonded to each other to form a ring, these may be a ring bridged with a heteroatom. Specific examples of this ring include the following. These rings may have a substituent.

When a blue dye is desired, it is preferable that R ⁷ and R ⁸ are not connected to each other to form a ring from the viewpoint of high color purity and high brightness.
Moreover, when a purple dye is desired, it is preferable that they are connected to each other to form a ring from the viewpoint of high color purity and high brightness.

(About R ¹⁰¹ and R ¹⁰² )
R ¹⁰¹ and R ¹⁰² have a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, an optionally substituted alkenyl group having 2 to 6 carbon atoms, or a substituent. Represents an aromatic ring group which may be substituted, or a fluorine atom.
Examples of the alkyl group and the aromatic ring group include those described in the above section (for R ^{1 to} R ⁶ ).
Examples of the alkenyl group include those having usually 2 or more and usually 6 or less carbon atoms. Specific examples include a vinyl group, an allyl group, and a 1-butenyl group.
R ¹⁰¹ and R ¹⁰² may be bonded to form a ring.
Specific examples of the ring formed by combining R ¹⁰¹ and R ¹⁰² include the following.

The ring formed by combining R ¹⁰¹ and R ¹⁰² may also have a substituent.
Examples of the substituent include those described in the above section (Substituent group W).
Moreover, the benzene ring in the above formula (III) may further have an arbitrary substituent.
Examples of the substituent that the benzene ring may have include those described in the above section (Substituent group W).

(About R ²¹ and R ²² )
R ²¹ and R ²² are the same as R ¹¹ and R ¹² in the formula (II), respectively. The preferred embodiment is also the same.
That is, in the formula (III), the anion of the compound represented by the formula (II-1) or the anion of the compound represented by the formula (II-2) is similarly used. preferable.
The compound represented by the formula (III) are, for ^example, from R 1 to R ⁶ and ^{R 101} and ^{R 102,} stretched a linker, may form a like a dimer or trimer.

(Synthesis method)
The compound represented by the formula (III) is, for example, according to the method described in J. Chem. Soc., PerkinTrans. 1998, 2,297., International Publication No. 2006/120205 and International Publication No. 2009/107734. Can be synthesized.
(Specific examples of compounds represented by formula (III))
Among the compounds represented by the formula (III), preferred specific examples are shown below, but the present invention is not limited thereto.

[Compound represented by formula (IV)]
The compound represented by the formula (II) is preferably a compound represented by the following formula (IV) from the viewpoint of having light resistance, heat resistance, and high transmittance.

(In said formula (IV), R <^31> and R ^<32 > is synonymous with R < ¹¹ > and R < ¹² > in said Formula (II) respectively.

R ^{41 to} R ⁴⁶ each independently represent a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or an optionally substituted aromatic ring group. Adjacent R ^{41 to} R ⁴⁶ may be bonded to each other to form a ring.
R ⁴⁷ and R ⁴⁸ each independently represents a hydrogen atom or an arbitrary substituent. R ⁴⁷ and R ⁴⁸ may be bonded to each other to form a ring.
Further, the benzene ring and indole ring in the above formula (III) may further have an arbitrary substituent. )

(About R ^{41 to} R ⁴⁶ )
R ^{41 to} R ⁴⁶ each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or an optionally substituted aromatic ring group.
Examples of the alkyl group having 1 to 8 carbon atoms and the aromatic ring group are the same as those described in the above section (for R ^{1 to} R ⁶ ).
Further, adjacent R ^{41 to} R ⁴⁶ , that is, R ⁴¹ and R ⁴² , R ⁴³ and R ^44, and R ⁴⁵ and R ⁴⁶ may be bonded to each other to form a ring structure. May have a substituent.
When adjacent R ^{41 to} R ⁴⁴ are bonded to form a ring, these may be a ring bridged with a heteroatom. Specific examples of this ring include the following. These rings may have a substituent.

From the viewpoint of chemical stability, R ^{41 to} R ⁴⁶ are preferably each independently a hydrogen atom, a C 1-8 alkyl group which may have a substituent, or a substituent. It is a case where it is a good phenyl group or adjacent R ^{41 to} R ⁴⁶ are bonded to each other to form a ring, which improves the heat resistance of the color material and is superior in light resistance of the resulting color filter. Preferably they are the C1-C8 alkyl group which may have a substituent, or the phenyl group which may have a substituent.
R ⁴¹ to R ⁴⁶ is optionally substituted alkyl group which may 1 to 8 carbon atoms, the charge in the cation is dispersed by hyperconjugative, cations are assumed to be stabilized. Further, presumed R ⁴¹ to R ⁴⁶ is, when it is a phenyl group which may have a substituent group, is to extend the conjugated system, that charge in the cation are dispersed, and that the cation is stabilized Is done. As described above, it can be considered that the light resistance of the obtained color filter becomes more excellent as a result of stabilization of the cation.
Alkyl group or aromatic ring group in R ⁴¹ to R ^46, and, as the adjacent R ⁴¹ to R ⁴⁶ are bonded to each other ring substituents which may have formed by, for example, the (substituent Those described in the section of group W) can be mentioned.

(About R ⁴⁷ and R ⁴⁸ )
R ⁴⁷ and R ⁴⁸ represent a hydrogen atom or an arbitrary substituent. Examples of the optional substituent are the same as those described above (following R ^{1 to} R ⁶ ).
R ⁴⁷ and R ⁴⁸ may be connected to each other to form a ring.
When R ⁴⁷ and R ⁴⁸ are bonded to each other to form a ring, these may be a ring bridged with a heteroatom, and specific examples thereof are the same as those described in the section (about R ⁷ and R ⁸ ). It is the same as that. These rings may have a substituent.
When a purple dye is desired, it is preferable that R ⁴⁷ and R ⁴⁸ are not connected to each other to form a ring from the viewpoint of high color purity and high brightness.
When a red dye is desired, R ⁴⁷ and R ⁴⁸ are preferably connected to each other to form a ring from the viewpoint of high color purity and high brightness.
^As the substituent R 41 ^{to R 48} have, include those described in the section of the (substituted group W).
In the present invention, it is particularly preferable that at least one of R ^{41 to} R ⁴⁸ is an alkyl group having 1 to 8 carbon atoms having a fluorine atom as a substituent, since the light resistance of the resulting color filter is excellent. preferable.
This is presumably due to the fact that the cation became more stable due to the electrostatic interaction in the molecule with the positively charged region in the molecule. This means that the fluorine atom, which is a group with high electronegativity, locally attracts the carbon atom to which it is bonded, resulting in a slightly positively charged carbon atom, destabilizing the cation. It is against the prediction.
As the substituent which the ring formed by bonding adjacent R ^{41 to} R ⁴⁸ has, preferably an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, a silyl group, a carboxyl group, cyano Group, sulfonic acid amide group and the like.

In the compound represented by formula (IV), the benzene ring and the indole ring may further have a substituent. That is, you may have a substituent other than having specified in Formula (IV) in the range which does not impair the effect of this invention.
Examples of such a substituent include the substituents described in the above section (Substituent Group W).
In the benzene ring in formula (IV), when a bulky group is bonded at the o-position to the carbon atom located at the center of the triarylmethine structure, the planarity of the molecule is inhibited, and the compound Color purity may be reduced. Accordingly, it is preferable that the o-position does not have a substituent or is substituted with a halogen atom or an alkyl group having 1 to 4 carbon atoms.
The compound represented by the formula (IV) are, for ^example, from R 41 ^{to R 48,} stretched a linker, may form a like a dimer or trimer.

(Synthesis method)
The compound represented by the formula (IV) is, for example, according to the method described in J. Chem. Soc., PerkinTrans. 1998, 2,297., International Publication No. 2006/120205 and International Publication No. 2009/107734. Can be synthesized.
(Concrete example)
Among the compounds represented by the formula (IV), preferred specific examples are shown below, but the present invention is not limited thereto.

[Regarding Compound Represented by Formula (V)]
In the present invention, the compound represented by the formula (II) is preferably a compound represented by the following formula (V) in terms of heat resistance, light resistance, and transmittance of the obtained pixel.

(In the formula ^{(V), R 51} and ^{R 52} are each the same meaning as ^{R 11} and ^{R 12} in Formula (II).
Ar ¹ and Ar ² each independently represent a nitrogen-containing heterocyclic group which may have a substituent.
n represents an integer of 1 to 5. )

n represents an integer of 1 to 5. n is preferably 1 to 5 and particularly preferably 1 to 3 in terms of heat resistance.
Ar ¹ and Ar ² each independently represent a nitrogen-containing heterocyclic group which may have a substituent.
Examples of the nitrogen-containing heterocyclic group include an indole ring, a benzoindole ring, an indolenine ring, a benzoindolenine ring, an oxazole ring, a benzoxazole ring, a thiazole ring, a benzothiazole ring, a benzo having one free valence. Examples include imidazole ring and quinoline ring groups.
Among them, an indole ring, a benzoindole ring, an indolenine ring, and a benzoindolenine ring having one free valence are preferable in terms of high luminance, and groups of an indole ring and a benzoindolenine ring are more preferable.

Further, the substituent that the nitrogen-containing heterocyclic ring in Ar ¹ and Ar ² may have is not particularly limited as long as the effects of the present invention are not impaired, but a methyl group, an ethyl group, a propyl group, an isopropyl group Aliphatic hydrocarbon groups such as butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl;
Aromatic hydrocarbon ring groups such as phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group, mesityl group, o-cumenyl group, m-cumenyl group, p-cumenyl group;
Alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group;
Aryloxy groups such as phenoxy groups;
An aralkyloxy group such as a benzyloxy group;
Groups having an ester bond such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, acetoxy group, benzoyloxy group;
Methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group, diethylsulfamoyl group, n-propylsulfamoyl group, di-n-propylsulfamoyl group, isopropylsulfamoyl group, diisopropylsulfamoyl group Alkylsulfamoyl groups such as a famoyl group, n-butylsulfamoyl group, di-n-butylsulfamoyl group;
Alkylsulfonyl groups such as methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, n-butylsulfonyl group, isobutylsulfonyl group, sec-butylsulfonyl group, tert-butylsulfonyl group;
Halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom;
Examples thereof include a nitro group and a cyano group.

When the substituent has a hydrogen atom, the hydrogen atom is, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, or a butoxy group. , Isobutoxy group, sec-butoxy group, tert-butoxy group, alkoxy group such as pentyloxy group; aryloxy group such as phenoxy group, benzyloxy group; phenyl group, o-tolyl group, m-tolyl group, p-tolyl group An aromatic hydrocarbon ring group such as a group, xylyl group, mesityl group, o-cumenyl group, m-cumenyl group, and p-cumenyl group; a carboxy group; a cyano group; a nitro group;
The compound represented by the formula (V) has a cis-trans isomer at the cation site, but may be any isomer.
R ⁵¹ and R ⁵² are respectively synonymous with R ¹¹ and R ¹² in the formula (II). The preferred embodiment is also the same.
The compound represented by the formula (V) is more preferably a compound represented by the following formula (V-1) in terms of high brightness and heat resistance.

(In the formula ^{(V-1), R 51} and ^{R 52} are each the same meaning as ^{R 11} and ^{R 12} in Formula (II).
N is as defined in the formula (V).
R ³⁰¹ and R ³⁰² each independently represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
R ⁶¹ and R ⁶² each independently represent —O—, —S—, —N—, —Se— or —CR ³⁰³ R ³⁰⁴ —.
R ³⁰³ and R ³⁰⁴ each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms.
However, when R ⁶¹ and R ⁶² are —CR ³⁰³ R ³⁰⁴ —, R ³⁰³ may be bonded to each other to form a ring. The ring may have a substituent.
Rings Y ¹ and Y ² each independently represent a benzene ring that may have a substituent or a naphthalene ring that may have a substituent. )

R ³⁰¹ and R ³⁰² each independently represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms, which may have a substituent.
Examples of the aliphatic hydrocarbon group include methyl group, ethyl group, vinyl group, ethynyl group, propyl group, isopropyl group, isopropenyl group, 1-propenyl group, 2-propenyl group, 2-propynyl group, butyl group, Isobutyl group, sec-butyl group, tert-butyl group, 2-butenyl group, 1,3-butadienyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylpentyl group, 2-methylpentyl group 2-pentene-4-ynyl group, hexyl group, isohexyl group, 5-methylhexyl group, heptyl group and octyl group.
Examples of the substituent that the aliphatic hydrocarbon group may have include, for example, a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a xylyl group, a mesityl group, an o-cumenyl group, aromatic hydrocarbon ring groups such as m-cumenyl group and p-cumenyl group;
Alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, phenoxy group, benzyloxy group;
Halogen groups such as fluoro, chloro, bromo and iodo groups;
Furthermore, a carboxy group, a nitro group, and a cyano group are mentioned.
R ³⁰¹ and R ³⁰² are each preferably an alkyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms.
R ⁶¹ and R ⁶² each independently represent —O—, —S—, —N—, —Se— or —CR ³⁰³ R ³⁰⁴ —.
R ³⁰³ and R ³⁰⁴ each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms.
However, when R ³¹ and R ³² are —CR ³⁰³ R ³⁰⁴ —, R ³⁰³ may be bonded to each other to form a ring.
Preferable specific examples of the ring that R ⁶¹ and R ⁶² may be bonded to each other include, for example, the following, but the present invention is not limited thereto.

Rings Y ¹ and Y ² each independently represent a benzene ring that may have a substituent or a naphthalene ring that may have a substituent.
The aliphatic hydrocarbon group in R ³⁰³ and R ³⁰⁴ , the ring that R ⁶¹ and R ⁶² may be bonded to each other, and the benzene ring and the naphthalene ring in rings Y ¹ and Y ² may have. As a substituent, the substituent which the aliphatic hydrocarbon group in said ^R301 and ^R302 may have is mentioned.
R ⁵¹ and R ⁵² are respectively synonymous with R ¹¹ and R ¹² in the formula (II). The preferred embodiment is also the same.
That is, the anion in the compound represented by the formula (V) is changed to the anion of the compound represented by the formula (II-1), or the anion of the compound represented by the formula (II-2). Those changed to are also preferred.
Further, the compound represented by the formula (V), for ^example, from R 301 ^{to R 302} and ^{R 61} and ^{R 62,} stretched a linker, may form a like a dimer or trimer.

(Synthesis method)
Examples of the compound represented by the formula (III) include J. Chem. Soc., PerkinTrans. 1998, 2,297., JP 2008-242324, JP 2009-235392, International Publication No. 2006/120205, and International Publication. It can be synthesized according to the method described in Japanese Patent Application Publication No. 2009/107734.
(Concrete example)
Among the compounds represented by the formula (V), preferred specific examples are shown below, but the present invention is not limited thereto.

{Pigment}
The coloring composition of the present invention uses a copper phthalocyanine pigment and / or a dioxazine pigment as the pigment.

Examples of the copper phthalocyanine pigment include the following.
C. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6
C. I. Pigment Green 7, 36

Moreover, as a dioxazine pigment, the following are mentioned, for example.
C. I. Pigment Violet 23, 37

  These may be used alone or in a combination of two or more in any combination and ratio.

  Copper phthalocyanine pigments have good color tone and transparency and are relatively easy to disperse. I. Pigment Blue 15: 6 is preferably used, and 80% by weight or more, particularly 90% by weight or more, particularly 95 to 100% by weight of the copper phthalocyanine pigment is C.I. I. Pigment Blue 15: 6 is preferable.

  Dioxazine pigments have good color tone and transparency and are relatively easy to disperse. I. Pigment Violet 23 is preferably used, and 80% by weight or more, particularly 90% by weight or more, particularly 95 to 100% by weight of the dioxazine pigment is C.I. I. Pigment Violet 23 is preferable.

  The pigment used in the coloring composition of the present invention preferably has a small average primary particle size from the viewpoint of forming a high-contrast pixel. Specifically, the average primary particle size is preferably 40 nm or less, and 35 nm. The following is more preferable.

  Similarly, the copper phthalocyanine pigment that is an essential component in the colored composition of the present invention preferably has an average primary particle size of 40 nm or less, more preferably 35 nm or less, and still more preferably 20 to 30 nm. For dioxazine pigments, the average primary particle size is preferably 40 nm or less, more preferably 25 to 35 nm. From the viewpoint that the pigments hardly aggregate in the coloring composition, it is preferable that the average primary particle size is not too small.

Here, the average primary particle diameter of the pigment is a value measured and calculated by the following method.
First, the pigment is ultrasonically dispersed in chloroform, dropped onto a collodion film-attached mesh, dried, and a primary particle image of the pigment is obtained by observation with a transmission electron microscope (TEM). From this image, the particle size of each pigment particle is determined for a plurality of (usually about 200 to 300) pigment particles, with the diameter corresponding to the area circle converted to the diameter of a circle having the same area.
Using the obtained primary particle size value, the number average value is calculated according to the following formula to obtain the average particle size.
The particle diameter of each pigment _{particle: X 1, X 2, X} 3, X 4, ····, X i, ······ X m

  In addition, as the pigment, a pigment other than the copper phthalocyanine pigment and / or the dioxazine pigment may be used, and in this case, as the other pigment, various kinds such as blue and purple, which are usually used for forming a pixel of a color filter. Colors of pigments can be used. Examples of the chemical structure include organic pigments such as quinacridone, benzimidazolone, indanthrene, and perylene. In addition, various inorganic pigments can be used. Hereinafter, specific examples of usable pigments are indicated by pigment numbers. The following “CI” means a color index (CI).

  Examples of blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and the like.

  Examples of purple pigments include C.I. I. Pigment violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 25, 27, 29, 31, 32, 39, 42, 44, 47, 49, 50 and the like.

  A plurality of the above-mentioned various pigments can be used in combination. For example, in order to adjust the chromaticity, a blue pigment and a violet pigment can be used in combination as the pigment.

  However, in the present invention, when these pigments other than copper phthalocyanine pigment and / or dioxazine pigment are used in combination, in order to effectively obtain the effects of the present invention by using copper phthalocyanine pigment and / or dioxazine pigment, copper phthalocyanine pigment And / or the amount of the pigment other than the dioxazine pigment is preferably 30% by weight or less with respect to the total weight of the copper phthalocyanine pigment and / or the dioxazine pigment. The particle diameter is 40 nm or less, preferably 35 nm or less, more preferably 20 to 30 nm.

  These pigments are used after being subjected to a dispersion treatment so that the average particle size in the coloring composition is usually 1 μm or less, preferably 0.5 μm or less, more preferably 0.3 μm or less.

{Blending amount}
In the present invention, the total content of the copper phthalocyanine pigment and the dioxazine pigment in the coloring composition is usually 5% by weight or more, preferably 10% by weight or more, more preferably 20% by weight or more of the total content of the compound (I). In addition, it is usually 2000% by weight or less, preferably 1000% by weight or less, more preferably 500% by weight or less.

  By making the total content of the copper phthalocyanine pigment and the dioxazine pigment not more than the above upper limit value, the effect of achieving both high transmittance and high contrast by the compound (I) appears more remarkably, and more than the above lower limit value. As a result, heat resistance and light resistance become better.

In the colored composition of the present invention, the total content of (A) the colorant, that is, the compound (I), the copper phthalocyanine pigment and / or the dioxazine pigment, and other pigments used as necessary is The total solid content in the product is usually 3% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, and usually 50% by weight or less, preferably 40% by weight or less, more preferably 30% by weight or less. It is.
By making the content of the color material (A) in the coloring composition not more than the above upper limit value, it is possible to suppress the generation of development residues and maintain good plate making properties while maintaining higher sensitivity. Become. In addition, by setting the value to the above lower limit or higher, a sufficient color density can be secured, so that even if the pixel film thickness is reduced, color reproducibility is improved, which is preferable.

[(B) Solvent]
The coloring composition of the present invention contains (B) a solvent. (B) A solvent has a function which adjusts a viscosity by melt | dissolving or disperse | distributing each component contained in a coloring composition.
The solvent (B) may be any solvent as long as it can dissolve or disperse each component constituting the colored composition, and a solvent having a boiling point in the range of 100 to 200 ° C. is preferably selected. More preferably, it has a boiling point of 120-170 ° C.

Examples of such solvents include the following.
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol-mono t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, methoxymethylpentanol, propylene Glycol monoalkyl ethers such as glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, tripropylene glycol monomethyl ether;
Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether;
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monoethyl Glycol alkyl ether acetates such as ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate;
Ethers such as diethyl ether, dipropyl ether, diisopropyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;
Ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone;
Mono- or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin;
aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;
Cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;
Aromatic hydrocarbons such as benzene, toluene, xylene, cumene;
Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionic acid Linear or cyclic esters such as butyl, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride and amyl chloride;
Ether ketones such as methoxymethylpentanone;
Nitriles such as acetonitrile and benzonitrile:

  Commercially available solvents corresponding to the above include mineral spirit, Barsol # 2, Apco # 18 Solvent, Apco thinner, Soal Solvent No. 1 and no. 2, Solvesso # 150, Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (all trade names) and the like.

  These solvents may be used alone or in combination of two or more.

  Among the above solvents, glycol monoalkyl ethers are preferable from the viewpoint of the solubility and dispersibility of the colorant (A) according to the present invention. Among these, propylene glycol monomethyl ether is particularly preferable from the viewpoint of the solubility of various components in the composition.

  In particular, in terms of including a copper phthalocyanine pigment and a dioxazine pigment contained as a colorant (A), the balance of coating properties, surface tension, etc. is good, and from the point that the solubility of the constituent components in the composition is relatively high, It is more preferable to use a mixture of glycol alkyl ether acetates. In a composition containing a pigment, glycol monoalkyl ethers are highly polar and tend to aggregate the pigment, which may reduce storage stability, such as increasing the viscosity of the colored composition. For this reason, it is preferable that the amount of the glycol monoalkyl ether used is not excessively large, and the proportion of the glycol monoalkyl ether in the solvent (B) is preferably 5 to 50% by weight, more preferably 5 to 30% by weight. .

  Further, from the viewpoint of suitability for a slit coat method corresponding to a recent large substrate or the like, it is also preferable to use a solvent having a boiling point of 150 ° C. or higher. In this case, the content of such a high boiling point solvent is preferably 3 to 50% by weight, more preferably 5 to 40% by weight, and particularly preferably 5 to 30% by weight based on the total amount of the solvent (B). If the amount of the high-boiling solvent is too small, for example, coloring material components may precipitate and solidify at the tip of the slit nozzle to cause foreign matter defects, and if too large, the drying speed of the composition will be slow, which will be described later. There is a concern that it may cause problems such as tact defects in the vacuum drying process and pre-baked pin marks in the color filter manufacturing process.

  The solvent having a boiling point of 150 ° C. or higher may be glycol alkyl ether acetates or glycol alkyl ethers. In this case, a solvent having a boiling point of 150 ° C. or higher may not be included separately. .

The colored composition of the present invention may be used for color filter production by the ink jet method, but in the color filter production by the ink jet method, the ink emitted from the nozzle is very small, from several to several tens of pL. Before landing on the periphery of the mouth or in the pixel bank, the solvent tends to evaporate and the ink tends to concentrate and dry. In order to avoid this, it is preferable that the solvent has a high boiling point. Specifically, it is preferable that the solvent (B) contains a solvent having a boiling point of 180 ° C. or higher. In particular, it is preferable to contain a solvent having a boiling point of 200 ° C. or higher, particularly 220 ° C. or higher. Moreover, it is preferable that the high boiling point solvent whose boiling point is 180 degreeC or more is 50 weight% or more in (B) solvent.
Within the above range, the effect of preventing evaporation of the solvent from the ink droplets is effectively exhibited, which is preferable.

In the colored composition of the present invention, the content of the (B) solvent is not particularly limited, but the upper limit is usually 99% by weight.
It is preferable for it to be within the above range because it is sufficient for forming a coating film.
In addition, the lower limit of the content of (B) the solvent is usually 75% by weight, preferably 80% by weight, and more preferably 82% by weight in consideration of the viscosity suitable for coating.

[(D) Dispersant]
The (D) dispersant in the present invention is not particularly limited as long as the pigment is dispersed and stable.
For example, cationic, anionic, nonionic or amphoteric dispersants can be used, but polymer dispersants are preferred. Specific examples include block copolymers, polyurethanes, polyesters, alkylammonium salts or phosphate esters of polymer copolymers, and cationic comb graft polymers. Of these dispersants, block copolymers, polyurethanes, and cationic comb graft polymers are preferred. In particular, a block copolymer is preferable, and among these, a block copolymer composed of an A block having solvophilicity and a B block having a functional group containing a nitrogen atom is preferable.
Specifically, the B block having a nitrogen atom-containing functional group includes a unit structure having a quaternary ammonium base and / or an amino group in the side chain, while the solvophilic A block includes a quaternary ammonium. Examples include a unit structure having no base and amino group.

The B block constituting the acrylic block copolymer has a unit structure having a quaternary ammonium base and / or an amino group, and has a pigment adsorption function.
Further, when the B block has a quaternary ammonium base, the quaternary ammonium base may be directly bonded to the main chain, but may be bonded to the main chain via a divalent linking group. Good. Moreover, as such a quaternary ammonium base, what contains the partial structure represented by following formula (VI) especially is preferable.

In the above formula (VI), R ⁵⁰⁴ represents a hydrogen atom or a methyl group. X ¹ represents a divalent linking group.
R ⁵⁰¹ , R ⁵⁰² and R ⁵⁰³ are each independently an alkyl group having 1 to 10 carbon atoms, an optionally substituted aromatic hydrocarbon ring group having 6 to 15 carbon atoms, or a substituted group. A good aralkyl group having 7 to 20 carbon atoms is preferred.

Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a benzyl group, and a phenyl group. Of these, methyl, ethyl, propyl, butyl, benzyl and the like are preferable.
In the formula (VI), examples of the divalent linking group X ¹ include an alkylene group having 1 to 10 carbon atoms, an arylene group, —CONH—R ⁵⁰⁵ —, —COO—R ⁵⁰⁶ — (provided that R ⁵⁰⁵ and R ⁵⁰⁶ are each independently a direct bond, an alkylene group having 1 to 10 carbon atoms, or an ether group having 1 to 10 carbon atoms (—R ⁵⁰⁷ —O—R ⁵⁰⁸ —: R ⁵⁰⁷ and R ⁵⁰⁸ are each Independently represents an alkylene group.) And the like, preferably —COO—R ⁵⁰⁶ —.

Examples of the counter anion M ⁻ include Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CH ₃ COO ⁻ , and PF ₆ ⁻ .
Moreover, the partial structure containing the said specific quaternary ammonium base may be contained 2 or more types in one B block. In that case, two or more quaternary ammonium base-containing partial structures may be contained in the B block in any form of random copolymerization or block copolymerization. Furthermore, the partial structure which does not contain the quaternary ammonium base may be contained in the B block, and examples of the partial structure include a partial structure derived from a (meth) acrylic acid ester monomer described later, etc. Is mentioned. The content of the partial structure containing no quaternary ammonium base in the B block is preferably 0 to 50% by weight, more preferably 0 to 20% by weight. It is most preferable that it is not contained in.

In addition, the B block of the acrylic block copolymer described above may have some tertiary amino groups. This remains when the quaternization reaction of the tertiary amino group is not completely completed, and its amine value is usually about 10 mgKOH / g or less.
On the other hand, when the B block constituting the acrylic block copolymer includes a primary to tertiary amino group, the content ratio of the monomer having the primary to tertiary amino group constitutes the copolymer. In the monomer composition, it is preferably 20 mol% or more, more preferably 50 mol% or more.

The primary to tertiary amino group is preferably —NR ⁶⁰¹ R ⁶⁰² (where R ⁶⁰¹ and R ⁶⁰² are each independently a cyclic or chain alkyl group optionally having a substituent, An aryl group which may have a substituent or an aralkyl group which may have a substituent is preferable. As a partial structure including this (repeating unit), preferred examples include the following: Examples include structures represented by the formulas.

(However, R ⁶⁰¹ and R ⁶⁰² have the same meanings as R ⁶⁰¹ and R ⁶⁰² above, R ⁶⁰³ represents an alkylene group having 1 or more carbon atoms, and R ⁶⁰⁴ represents a hydrogen atom or a methyl group.)
Among them, R ⁶⁰¹ and R ⁶⁰² are preferably methyl groups, R ⁶⁰³ is preferably a methylene group and an ethylene group, and R ⁶⁰⁴ is preferably a hydrogen atom or a methyl group. As such a partial structure, a structure derived from dimethylaminoethyl acrylate or dimethylaminoethyl methacrylate represented by the following formula is particularly preferably used.

(In the above formula, R ⁶⁰⁴ has the same ^meaning as described above.)
Furthermore, the partial structure containing the said amino group may be contained 2 or more types in one B block. In that case, two or more amino group-containing partial structures may be contained in the B block in any form of random copolymerization or block copolymerization. Moreover, a partial structure not containing an amino group may be partially contained in the B block, and examples of such a partial structure include a partial structure derived from a (meth) acrylate monomer. . The content of such a partial structure not containing an amino group in the B block is preferably 0 to 50% by weight, more preferably 0 to 20% by weight. Most preferably it is not included.

  Further, the solvophilic A block constituting the block copolymer of the dispersant does not have the above-described nitrogen atom-containing functional group such as an amino group, and can be copolymerized with the monomer constituting the B block. If it consists of a monomer, there will be no restriction | limiting in particular. The A block is a solvophilic site that does not have a nitrogen atom-containing functional group that serves as a pigment adsorbing group, and has an affinity for the solvent, and thus functions to stabilize the pigment adsorbed on the dispersant in the solvent. .

  Examples of the solvophilic A block include styrene monomers such as styrene and α-methylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate (propyl) (meth) acrylate, isopropyl (meth) acrylate, Butyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl ethyl acrylate, polyethylene glycol ( (Meth) acrylate monomers such as (meth) acrylate and polypropylene glycol (meth) acrylate; polyalkylene glycols such as polyethylene glycol (meth) acrylate and polypropylene glycol (meth) acrylate Vinyl acetate monomers; (meth) (meth) acrylate monomers such as acrylic acid chloride allyl glycidyl ether, polymer structure in which the comonomer is copolymerized, such as glycidyl ether monomers such as crotonic acid glycidyl ether.

  Among these, as the A block, those containing a (meth) acrylic acid ester monomer as a copolymerization component are preferable. Also preferred are those containing polyalkylene glycol (meth) acrylates such as polyethylene glycol (meth) acrylate and polypropylene glycol (meth) acrylate as copolymerization components (that is, containing a partial structure derived from polyalkylene glycol (meth) acrylate). . Furthermore, when the dispersant used in the composition for forming a color filter pixel of the present invention is a (meth) acrylic copolymer, an A block having a partial structure represented by the following formula (VIII) is particularly preferable.

(In the formula (VIII), n represents an integer of 1 to 5, but when there are a plurality of the units, that is, the formula (VIII) in one molecule, n may be the same or different. R ⁸¹ Represents a hydrogen atom or a methyl group, R ⁸² represents an alkyl group having 1 to 4 carbon atoms or a phenyl group, and R ⁸² is particularly preferably an ethyl group.)
The partial structure represented by the above formula (VIII) is preferably contained in an amount of 3 to 20 mol% in terms of monomers constituting the (meth) acrylic copolymer. Most preferably, it is contained in mol%.

Although the detailed mechanism of action is unknown, it has a partial structure derived from polyalkylene glycol (meth) acrylate, in particular, a partial structure represented by the above formula, so that it is possible to increase hydrogen bonding properties, It is thought that the affinity for the dispersion improves and the stability of the dispersion increases.
Two or more partial structures represented by the formula (VIII) may be contained in one A block. Of course, the A block may further contain a partial structure other than these. When partial structures derived from two or more types of monomers are present in the A block, each partial structure may be contained in the A block in any form of random copolymerization or block copolymerization.

The dispersant (D) that can be used in the coloring composition of the present invention is an AB block or ABA block copolymeric polymer compound composed of an A block and a B block as described above. Of these, AB block copolymers are preferred. Such a block copolymer is prepared, for example, by a living polymerization method.
The living polymerization method includes an anion living polymerization method, a cation living polymerization method, and a radical living polymerization method. Specifically, for example, a method described in JP-A-2007-270147 can be mentioned.

The amine value of 1 g of the above (D) dispersant is usually about 1 to 300 mgKOH / g in terms of effective solid content, but the preferred range is when the B block has a quaternary ammonium base and when it does not. It is different.
That is, when the B block of the AB block copolymer and the ABA block copolymer of the (D) dispersant has a quaternary ammonium base, the amount of the quaternary ammonium base in 1 g of the copolymer is 0.1 It is preferable that it is -10 mmol. Outside this range, it may not be possible to combine good heat resistance and dispersibility. In such a block copolymer, an amino group generated in the production process may be contained, and its amine value is usually about 1 to 100 mgKOH / g, preferably 1 to 50 mgKOH per 1 g of the copolymer. / G, more preferably 1 to 30 mg KOH / g.

  When the quaternary ammonium base is not included in the B block, the amine value of the copolymer is usually about 50 to 300 mgKOH / g, preferably 50 to 200 mgKOH / g, more preferably 80 mgKOH / g or more and 150 mgKOH. / G or less, more preferably 90 to 150 mgKOH / g, and most preferably 100 to 140 mgKOH / g.

If the number of functional groups containing nitrogen atoms is too small, the adsorptive power of the dispersant molecules on the pigment surface may be insufficient, and it may be difficult to obtain sufficient dispersion stability. On the other hand, if the amine value is too high, the molecular weight of the A block becomes relatively small, and the dispersion stability may be insufficient.
The acid value of the block copolymer depends on the presence and type of the acid group that is the basis of the acid value, but is generally preferably lower, usually 100 mgKOH / g or less, preferably 50 mgKOH / g or less. , More preferably 40 mgKOH / g or less, most preferably 30 mgKOH / g or less. The molecular weight is usually in the range of 1000 or more and 100,000 or less in terms of polystyrene-equivalent weight average molecular weight (Mw) measured by GPC.

  In the present invention, a commercially available (meth) acrylic block copolymer having the same structure as that described above can also be used.

In addition, the (D) dispersant contained in the colored composition of the present invention is usually 2% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more of the total content of the compound (I). It is 2000 weight% or less, Preferably it is 500 weight% or less, More preferably, it is 250 weight% or less.
By making the content of the dispersant not more than the above upper limit value, good pigment dispersibility can be secured without affecting the heat resistance of the compound (I), and not less than the above lower limit value. As a result, the dispersion stability becomes better.
Further, in the colored composition of the present invention, the content of the dispersant is preferably 5% by weight or more based on the total amount of the pigment because the dispersibility of the pigment and the alkali developability of the colored composition can be compatible. It is preferably 10% by weight or more, usually 200% by weight or less, more preferably 100% by weight or less.
In addition, it is preferable not to exceed the content range with respect to the compound (I).

[Dispersion aid]
The coloring composition of the present invention may contain a dispersion aid. The dispersion aid here may be a pigment derivative. Examples of the pigment derivative include JP-A Nos. 2001-220520, 2001-271004, 2002-179976, and 2007-. Various compounds described in Japanese Patent Application Publication No. 113000 and Japanese Patent Application Publication No. 2007-186681 can be used.

The content of the dispersion aid in the colored composition of the present invention is usually 0.1% by weight or more, usually 30% by weight or less, preferably 20% by weight with respect to the pigment contained as the colorant (A). % Or less, more preferably 10% by weight or less, still more preferably 5% by weight or less.
Within the above range, the effect as a dispersion aid is effectively obtained, and this is preferable in terms of good dispersibility and dispersion stability.
Even when other dispersion aids are contained, the total amount of the dispersion aids is set within the above range.
In addition, when the coloring composition of this invention contains a dispersing aid, it is preferable that this dispersing aid is contained from the additive of this invention.

[Dispersion resin]
The colored composition of the present invention may contain a part or all of a resin selected from (C) binder resin or other binder resin described later as the following dispersion resin.
Specifically, in the dispersion treatment step to be described later, the (C) binder resin is added to the (D) dispersant by adding the (C) binder resin together with the components such as the (D) dispersant described above. It contributes to the dispersion stability of the pigment contained as the colorant (A) by a synergistic effect. As a result, there is a possibility that the amount of (D) dispersant added can be reduced, which is preferable. Further, it is preferable because the developability is improved, the undissolved matter does not remain in the non-pixel portion of the substrate, and the adhesion of the pixel to the substrate is improved.

Thus, the (C) binder resin used in the dispersion treatment step may be referred to as a dispersion resin. The dispersion resin is preferably used in an amount of about 0 to 200% by weight, more preferably about 10 to 100% by weight, based on the total amount of the pigment in the coloring composition.
As the dispersion resin, various (C) binder resins described later can be used.
The acid value of the dispersion resin is preferably 0.5 mgKOH / g or more, more preferably 1 mgKOH / g or more, most preferably 5 mgKOH / g or more, more preferably 300 mgKOH / g or less, more preferably 200 mgKOH / g or less, and 150 mgKOH / g. The following are most preferred. By controlling the acid value within the above range, the alkali developability is improved, and the handling becomes easy in synthesis and the like.

  The weight average molecular weight in terms of polystyrene measured by GPC of the dispersion resin is preferably 1000 or more, more preferably 1500 or more, most preferably 2000 or more, more preferably 200000 or less, more preferably 50000 or less, and 30000 or less. Most preferred. By controlling the molecular weight within the above range, the alkali developability can be improved and the dispersion stability can be prevented from being lowered.

[(C) Binder resin]
(C) The preferred resin for the binder resin differs depending on the curing means.
When the coloring composition of the present invention is a photopolymerizable resin composition, examples of the (C) binder resin include JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, and JP-A-11. The polymer compounds described in JP-A No. 140144, JP-A No. 11-174224, JP-A No. 2000-56118, JP-A No. 2003-233179, and the like can be used. -1) to (C-5) resins and the like.

(C-1): With respect to a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer, an unsaturated monobasic acid is added to at least a part of the epoxy group of the copolymer. Resin to be added, or an alkali-soluble resin (hereinafter referred to as “resin (C-1)”) obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction. .)
(C-2): Carboxyl group-containing linear alkali-soluble resin (C-2) (hereinafter sometimes referred to as “resin (C-2)”)
(C-3): a resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group portion of the resin (C-2) (hereinafter sometimes referred to as “resin (C-3)”).
(C-4): (Meth) acrylic resin (hereinafter sometimes referred to as “resin (C-4)”)
(C-5): Epoxy acrylate resin having a carboxyl group (hereinafter sometimes referred to as “resin (C-5)”)
Of these, the resin (C-1) is particularly preferable, and the resin will be described below.

  The resins (C-2) to (C-5) may be any ones that are dissolved in an alkaline developer and have solubility to the extent that the desired development processing is performed. This is the same as that described as the same item in Japanese Patent No. 025813. The preferred embodiment is also the same.

(C-1): With respect to a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer, an unsaturated monobasic acid is added to at least a part of the epoxy group of the copolymer. As one of particularly preferable resins of the alkali-soluble resin resin (C-1) obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction, or an epoxy group, Unsaturated in 10 to 100 mol% of the epoxy group of the copolymer with respect to the copolymer of 5 to 90 mol% of (meth) acrylate and 10 to 95 mol% of other radical polymerizable monomer Examples thereof include a resin obtained by adding a monobasic acid, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to 10 to 100 mol% of a hydroxyl group generated by the addition reaction.

  Examples of the epoxy group-containing (meth) acrylate include glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. ) Acrylate glycidyl ether and the like. Of these, glycidyl (meth) acrylate is preferred. These epoxy group-containing (meth) acrylates may be used alone or in combination of two or more.

The other radical polymerizable monomer copolymerized with the epoxy group-containing (meth) acrylate is not particularly limited as long as the effects of the present invention are not impaired. For example, vinyl aromatics, dienes, (meth) Examples include acrylic acid esters, (meth) acrylic acid amides, vinyl compounds, unsaturated dicarboxylic acid diesters, monomaleimides, and the like, and in particular, mono (meth) having a structure represented by the following formula (7) Acrylate is preferred.
The repeating unit derived from the mono (meth) acrylate having the structure represented by the following formula (7) contains 5 to 90 mol% among the repeating units derived from “other radical polymerizable monomers”. The content is preferably 10 to 70 mol%, more preferably 15 to 50 mol%.

In the above formula (7), R ⁸⁹ represents a hydrogen atom or a methyl group, and R ⁹⁰ represents a structure represented by the following formula (8).

The formula ^{(8), R} 91 ~R ⁹⁸ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ⁹⁶ and R ⁹⁸ may be connected to each other to form a ring.
The ring formed by connecting R ⁹⁶ and R ⁹⁸ is preferably an aliphatic ring, may be saturated or unsaturated, and preferably has 5 to 6 carbon atoms.

  Among these, among the structures represented by the formula (8), those represented by the following structural formulas (8a), (8b), or (8c) are particularly preferable.

  In addition, the mono (meth) acrylate which has a structure represented by the said Formula (8) may be used individually by 1 type, and may use 2 or more types together.

  As "other radical polymerizable monomers" other than the mono (meth) acrylate having the structure represented by the formula (8), the heat resistance and strength excellent in the colored composition can be improved. Styrene, (meth) acrylate-n-butyl, (meth) acrylate-tert-butyl, (meth) acrylate cyclohexyl, (meth) acrylate isobornyl, (meth) acrylate adamantyl, (meth) acrylate benzyl, (Meth) acrylic acid-2-hydroxyethyl, N-phenylmaleimide, and N-cyclohexylmaleimide.

  The content ratio of repeating units derived from at least one selected from the above monomer group is preferably 1 to 70 mol%, more preferably 3 to 50 mol%.

  A known solution polymerization method is applied to the copolymerization reaction between the epoxy group-containing (meth) acrylate and the other radical polymerizable monomer.

  In the present invention, as a copolymer of the epoxy group-containing (meth) acrylate and the other radical polymerizable monomer, 5 to 90 mol% of repeating units derived from the epoxy group-containing (meth) acrylate, and others Is preferably composed of 10 to 95 mol% of repeating units derived from the radically polymerizable monomer, more preferably composed of 20 to 80 mol% of the former and 80 to 20 mol% of the latter. What consists of 70 mol% and the latter 70-30 mol% is especially preferable.

  Within the above range, the addition amount of the polymerizable component and alkali-soluble component described later is sufficient, and the heat resistance and strength are sufficient, which is preferable.

  The epoxy group portion of the epoxy group-containing copolymer synthesized as described above is reacted with an unsaturated monobasic acid (polymerizable component) and a polybasic acid anhydride (alkali-soluble component).

Here, as an unsaturated monobasic acid added to an epoxy group, a well-known thing can be used, For example, unsaturated carboxylic acid which has an ethylenically unsaturated double bond is mentioned.
Specific examples include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position substituted with a haloalkyl group, an alkoxyl group, a halogen atom, a nitro group, or a cyano group. And monocarboxylic acids such as (meth) acrylic acid. Of these, (meth) acrylic acid is preferred. These may be used alone or in combination of two or more.
By adding such components, polymerizability can be imparted to the binder resin used in the present invention.

  These unsaturated monobasic acids are usually added to 10 to 100 mol% of the epoxy group of the copolymer, preferably 30 to 100 mol%, more preferably 50 to 100 mol%. It is preferable for it to be within the above range since the colored composition is excellent in stability over time. In addition, a well-known method is employable as a method of adding unsaturated monobasic acid to the epoxy group of a copolymer.

Furthermore, a well-known thing can be used as a polybasic acid anhydride added to the hydroxyl group produced when an unsaturated monobasic acid is added to the epoxy group of a copolymer.
For example, dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride; trimellitic anhydride, pyromellitic anhydride, benzophenone Examples thereof include anhydrides of three or more bases such as tetracarboxylic acid anhydride and biphenyltetracarboxylic acid anhydride. Of these, succinic anhydride and tetrahydrophthalic anhydride are preferred. These polybasic acid anhydrides may be used individually by 1 type, and may use 2 or more types together.
By adding such a component, alkali solubility can be imparted to the binder resin used in the present invention.

These polybasic acid anhydrides are usually added to 10 to 100 mol% of the hydroxyl group generated by adding an unsaturated monobasic acid to the epoxy group of the copolymer, preferably 20 to 90 mol. %, More preferably 30 to 80 mol%.
Within the above range, the remaining film ratio and solubility during development are sufficient, which is preferable.
In addition, a well-known method is employable as a method of adding a polybasic acid anhydride to this hydroxyl group.

  Furthermore, in order to improve photosensitivity, after adding the above-mentioned polybasic acid anhydride, glycidyl (meth) acrylate or a glycidyl ether compound having a polymerizable unsaturated group is added to a part of the generated carboxyl group. May be. Such a resin structure is described in, for example, Japanese Patent Application Laid-Open Nos. 8-297366 and 2001-89533.

The polystyrene-reduced weight average molecular weight (Mw) of the above-described binder resin (C-1) measured by GPC (gel permeation chromatography) is preferably 3000 to 100,000, and particularly preferably 5000 to 50000. If the molecular weight is less than 3000, heat resistance and film strength may be inferior, and if it exceeds 100,000, the solubility in a developer tends to be insufficient. Moreover, as a standard of molecular weight distribution, the ratio of weight average molecular weight (Mw) / number average molecular weight (Mn) is preferably 2.0 to 5.0.
In addition, the acid value of binder resin (C-1) is 10-200 mg-KOH / g normally, Preferably it is 15-150 mg-KOH / g, More preferably, it is 25-100 mg-KOH / g.
Within the above range, the solubility in a developer is good and film roughness is not likely to occur, which is preferable.
Moreover, content of (C) binder resin is 0.1 to 80 weight% normally in a total solid, Preferably it is 1 to 60 weight%.
Within the above range, the adhesion to the substrate is good, the permeability of the developer to the exposed area is moderate, and the surface smoothness and sensitivity of the pixels are good.
[(E) Polymerizable monomer]
The colored composition of the present invention preferably contains (E) a polymerizable monomer. (E) The polymerizable monomer is not particularly limited as long as it is a polymerizable low molecular compound, but it may be an addition-polymerizable compound having at least one ethylenic double bond (hereinafter referred to as “ethylenic compound”). Is preferred).

  The ethylenic compound is a compound having an ethylenic double bond that undergoes addition polymerization and cures by the action of the photopolymerization initiation system when the colored composition of the present invention is irradiated with actinic rays. In addition, the (E) polymerizable monomer in this invention means the concept opposite to what is called a polymeric substance, and also includes a dimer, a trimer, and an oligomer other than a monomer in a narrow sense.

  (E) Examples of the ethylenic compound in the polymerizable monomer include unsaturated carboxylic acids such as (meth) acrylic acid; esters of monohydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds and unsaturated carboxylic acids; Esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; Esterification of unsaturated carboxylic acids with polyvalent carboxylic acids and polyhydric hydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds described above An ester obtained by the reaction; an ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound and a (meth) acryloyl group-containing hydroxy compound;

  Esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate , Pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) Examples include (meth) acrylic acid esters such as acrylate and glycerol (meth) acrylate. In addition, the (meth) acrylic acid portion of these (meth) acrylic acid esters is replaced with an itaconic acid portion, a crotonic acid portion replaced with a crotonic acid portion, or a maleic acid ester replaced with a maleic acid portion, etc. Is mentioned.

  Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone di (meth) acrylate, resorcin di (meth) acrylate, pyrogallol tri (meth) acrylate, and the like.

  The ester obtained by the esterification reaction of an unsaturated carboxylic acid with a polyvalent carboxylic acid and a polyvalent hydroxy compound is not necessarily a single substance but may be a mixture. Representative examples are condensates of (meth) acrylic acid, phthalic acid, and ethylene glycol; condensates of (meth) acrylic acid, maleic acid, and diethylene glycol; condensation of (meth) acrylic acid, terephthalic acid, and pentaerythritol A condensate of (meth) acrylic acid, adipic acid, butanediol, and glycerin.

  Examples of the ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound and a (meth) acryloyl group-containing hydroxy compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; alicyclic rings such as cyclohexane diisocyanate and isophorone diisocyanate. Formula diisocyanates; aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate, and (meth) acryloyl such as 2-hydroxyethyl (meth) acrylate and 3-hydroxy [1,1,1-tri (meth) acryloyloxymethyl] propane A reaction product with a group-containing hydroxy compound is exemplified.

  In addition, examples of the ethylenic compound used in the present invention include (meth) acrylamides such as ethylene bis (meth) acrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate. .

  Among these, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids are preferred, pentaerythritol or (meth) acrylic acid esters of dipentaerythritol are more preferred, and dipentaerythritol hexa (meth) acrylate is particularly preferred.

The ethylenic compound may be a monomer having an acid value. The monomer having an acid value is, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A polyfunctional monomer having a group is preferable, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol.
These monomers may be used alone, but since it is difficult to obtain a single compound in production, a mixture of two or more kinds may be used.
Moreover, you may use together the polyfunctional monomer which does not have an acid group, and the polyfunctional monomer which has an acid group as (E) polymeric monomer as needed.

A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mg-KOH / g, and particularly preferably 5 to 30 mg-KOH / g.
When it is within the above range, the development and dissolution characteristics are hardly deteriorated, and the production and handling are easy. Furthermore, it is preferable because the photopolymerization performance is hardly lowered and the curability such as the surface smoothness of the pixel is good.

  In the present invention, a more preferred polyfunctional monomer having an acid group is, for example, a mixture containing succinic acid ester of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentaacrylate as a main component. It is also possible to use this polyfunctional monomer in combination with another polyfunctional monomer.

In the colored composition of the present invention, the content of these (E) polymerizable monomers is usually 1% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, based on the total solid content. Usually, it is 80% by weight or less, preferably 70% by weight or less, more preferably 50% by weight or less, and particularly preferably 40% by weight or less.
The ratio of the (E) polymerizable monomer to the total colorant is usually 1% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, and particularly preferably 20% by weight or more. It is 200% by weight or less, preferably 150% by weight or less, more preferably 110% by weight or less.

Within the above range, photocuring is appropriate, poor adhesion during development is difficult to place, the cross-section after development is difficult to reverse taper, and further, peeling phenomenon and omission failure due to lower solubility are difficult to place. preferable.
[(F) Photopolymerization initiation system and / or thermal polymerization initiation system]
The colored composition of the present invention preferably contains (F) a photopolymerization initiation system and / or a thermal polymerization initiation system for the purpose of curing the coating film. However, the curing method may be other than those using these initiators.

  In particular, when the colored composition of the present invention contains a resin having an ethylenic double bond as the component (C) or an ethylenic compound as the component (E), it directly absorbs light or It is preferable to contain a photopolymerization initiating system that has a function of generating a polymerization active radical and / or a heat polymerization initiating system that generates a polymerization active radical by heat. In the present invention, the component (F) as the photopolymerization initiation system is a photopolymerization initiator (hereinafter arbitrarily referred to as (F1) component) to a polymerization accelerator (hereinafter arbitrarily referred to as (F2) component). , Means a mixture in which an additive such as a sensitizing dye (hereinafter, arbitrarily referred to as component (F3)) is used in combination.

(Photopolymerization initiation system)
The colored composition of the present invention preferably contains a photopolymerization initiation system. The photopolymerization initiation system is usually used as a mixture of (F1) a photopolymerization initiator, and (F2) a polymerization accelerator added as necessary, (F3) an additive such as a sensitizing dye, and the like. It is a component having a function of generating a polymerization active radical by directly absorbing or photosensitizing to cause a decomposition reaction or a hydrogen abstraction reaction.

  Examples of the photopolymerization initiator constituting the photopolymerization initiation system (F1) include titanocene derivatives described in JP-A Nos. 59-152396 and 61-151197, etc .; JP-A-10-300922 Hexaarylbiimidazole derivatives described in JP-A-11-174224, JP-A-2000-56118, etc .; halomethylated oxadiazole derivatives described in JP-A-10-39503, etc., halomethyl-s -Radical activators such as triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives And oxime ester derivatives described in JP-A No. 2000-80068 and the like.

Specific examples include photopolymerization initiators described in International Publication No. 2009/107734 pamphlet and the like.
Among these photopolymerization initiators, α-aminoalkylphenone derivatives, oxime ester derivatives, biimidazole derivatives, acetophenone derivatives, and thioxanthone derivatives are more preferable.

  The oxime ester derivatives include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (o-benzoyloxime), ethanone, 1- [9-ethyl-6- ( 2-methylbenzoyl) -9H-carbazol-3-yl], 1- (o-acetyloxime), and the like.

  In addition, benzoin alkyl ethers, anthraquinone derivatives; acetophenone derivatives such as 2-methyl- (4′-methylthiophenyl) -2-morpholino-1-propanone, 2-ethylthioxanthone, 2,4-diethylthioxanthone, etc. Examples also include thioxanthone derivatives, benzoate derivatives, acridine derivatives, phenazine derivatives, anthrone derivatives and the like.

  Among these photopolymerization initiators, α-aminoalkylphenone derivatives, thioxanthone derivatives, and oxime ester derivatives are more preferable. In particular, oxime ester derivatives are preferable.

  Examples of the (F2) polymerization accelerator used as necessary include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester; 2-mercaptobenzothiazole, 2-mercapto Examples thereof include mercapto compounds having a heterocyclic ring such as benzoxazole and 2-mercaptobenzimidazole; mercapto compounds such as aliphatic polyfunctional mercapto compounds.

  These (F1) photopolymerization initiators and (F2) polymerization accelerators may be used alone or in combination of two or more.

  Further, (F3) sensitizing dye is used for the purpose of increasing the sensitivity as required. As the sensitizing dye, an appropriate one is used according to the wavelength of the image exposure light source. For example, xanthene dyes described in JP-A-4-221958 and JP-A-4-219756; No. 239703, JP-A-5-289335, etc. Coumarin dyes having a heterocyclic ring; JP-A-3-239703, JP-A-5-289335, etc .; 3-ketocoumarin dyes; Pyrromethene dyes described in JP-A-6-19240 and the like; JP-A-47-2528, JP-A-54-155292, JP-B-45-37377, JP-A-48-84183, JP-A-52-112681 JP, 58-15503, JP 60-88005, JP 59-56403, JP 2-69, JP 57-168088, JP 5-10. 761 No., JP-A-5-210240, dyes having a dialkyl aminobenzene skeleton described in JP-A 4-288818 Patent JP-like.

  (F3) A sensitizing dye may also be used alone or in combination of two or more.

  In the colored composition of the present invention, the content of these (F) photopolymerization initiation systems is usually 0.1% by weight or more, preferably 0.2% by weight or more, more preferably 0.5% in the total solid content. It is in the range of not less than wt%, usually not more than 40 wt%, preferably not more than 30 wt%, more preferably not more than 20 wt%. If this content is extremely low, the sensitivity to exposure light may be reduced. On the other hand, if it is extremely high, the solubility of the unexposed portion in the developer may be reduced, leading to development failure.

(Thermal polymerization initiation system)
Specific examples of the thermal polymerization initiation system (thermal polymerization initiator) that may be contained in the colored composition of the present invention include azo compounds, organic peroxides, and hydrogen peroxide. Of these, azo compounds are preferably used. More specifically, for example, a thermal polymerization initiator described in International Publication No. 2009/107734 pamphlet or the like can be used.
These thermal polymerization initiators may be used individually by 1 type, and may use 2 or more types together.

[Optional ingredients]
In addition to the above components, the coloring composition of the present invention includes a surfactant, an organic carboxylic acid and / or an organic carboxylic acid anhydride, a plasticizer, a dye other than the colorant according to the present invention, a thermal polymerization inhibitor, It may contain a storage stabilizer, a surface protective agent, an adhesion improver, a development improver and the like. As these optional components, for example, various compounds described in JP-A-2007-113000 can be used.

[Method for Preparing Colored Composition]
Next, a method for preparing the colored composition of the present invention will be described.
First, the coloring material includes a binder resin and a solvent which are essential components, and in some cases, a dispersant and a monomer which are optional components, a photopolymerization initiation system and / or a thermal polymerization initiation system, a surfactant, and other components. By mixing to obtain a uniform solution, a colored composition is obtained. In mixing, it is preferable to stir until the dye such as compound (I) is sufficiently dissolved. In addition, since fine dust may be mixed in each step such as mixing, it is preferable to filter the obtained ink-like liquid with a filter or the like.

When the solubility of the compound (I) in the solvent is low, first, a predetermined amount of the solvent, a dispersant, a dispersion aid, etc. are weighed in the compound (I), and the compound (I) is dispersed in the dispersion treatment step. Ink-like liquid. In this dispersion treatment step, a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like can be used. By carrying out this dispersion treatment, the compound (I) is made into fine particles, so that the coating characteristics are improved and the transmittance of the color filter substrate and the like is improved.
However, it is preferable that compound (I) exists in a dissolved state in the colored composition of the present invention.

  Also, with copper phthalocyanine pigments and / or dioxazine pigments, the coating properties are improved by carrying out the same dispersion treatment process as described above, so that the coating characteristics are improved and the transmittance of the product color filter substrate is improved. To do. The copper phthalocyanine pigment and / or dioxazine pigment and the compound (I) may be dispersed in a mixed state, or may be mixed after being individually dispersed. Even when the solubility of the compound (I) is sufficient and a solution can be formed, the copper phthalocyanine pigment and / or the dioxazine pigment and the compound (I) may be mixed in advance and the dispersion treatment may be performed. After carrying out alone, you may mix with a compound (I) solution.

  When these color materials are subjected to a dispersion treatment, it is preferable to use a part of the binder resin and a dispersion aid as appropriate. Moreover, when performing a dispersion process using a sand grinder, it is preferable to use glass beads or zirconia beads having a diameter of 0.1 to several mm. The temperature during the dispersion treatment is usually set to 0 ° C. or higher, preferably room temperature or higher, and usually 100 ° C. or lower, preferably 80 ° C. or lower. The dispersion time needs to be appropriately adjusted because the appropriate time varies depending on the composition of the ink-like liquid and the size of the sand grinder apparatus.

  In addition to the ink-like liquid obtained by the dispersion treatment, (C) a binder resin, and (B) a solvent, and in some cases, an optional component (E) a polymerizable monomer and (F) a photopolymerization initiation system and / or The thermal polymerization initiating system, the surfactant, and other components are mixed to obtain a uniform dispersion solution. In addition, in each process of a dispersion | distribution process and mixing, since fine refuse may mix, it is preferable to filter the obtained ink-like liquid with a filter etc.

[Application of coloring composition]
The colored composition of the present invention is usually in a state where all the constituent components are dissolved or dispersed in a solvent. This colored composition is supplied onto the substrate to form components such as a color filter, a liquid crystal display device, and an organic EL display device.
Hereinafter, as an application example of the colored composition of the present invention, an application as a color filter, and a liquid crystal display device (panel) and an organic EL display device using them will be described.

<Color filter>
The color filter of this invention has a pixel formed from the coloring composition of this invention.
The method for forming the color filter of the present invention will be described below.
The pixel of the color filter can be formed by various methods. Here, although the case where it forms by the photolithographic method using a photopolymerizable coloring composition is demonstrated to an example, a manufacturing method is not limited to this.
First, on the surface of the substrate, if necessary, a black matrix is formed so as to partition a portion for forming a pixel, and after applying the coloring composition of the present invention on this substrate, pre-baking is performed to obtain a solvent. Is evaporated to form a coating film. Then, after exposing this coating film through a photomask, developing with an alkali developer, dissolving and removing the unexposed portion of the coating film, and then post-baking, each of red, green, and blue A color filter can be manufactured by forming a pixel pattern.

The substrate used for forming the pixel is not particularly limited as long as it is transparent and has an appropriate strength. For example, a polyester resin, a polyolefin resin, a polycarbonate resin, an acrylic resin, or a thermoplastic resin is used. A sheet, an epoxy resin, a thermosetting resin, various glass, etc. are mentioned.
In addition, these substrates may be appropriately subjected to pretreatment as desired, such as thin film formation treatment with a silane coupling agent or urethane resin, surface treatment such as corona discharge treatment or ozone treatment, if desired.
When applying a coloring composition to a substrate, a spinner method, a wire bar method, a flow coating method, a slit and spin method, a die coating method, a roll coating method, a spray coating method, and the like can be given. Of these, the slit and spin method and the die coating method are preferable.
The thickness of the coating film is usually 0.2 to 20 μm, preferably 0.5 to 10 μm, particularly preferably 0.8 to 5.0 μm as the film thickness after drying.
Within the above range, it is preferable in that the gap can be easily adjusted in the pattern development or liquid crystal cell forming step, and a desired color can be easily expressed.

For example, visible rays, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, and the like can be used as the radiation used when forming the pixels, but radiation having a wavelength in the range of 190 to 450 nm is preferable.
A light source for using radiation having a wavelength of 190 to 450 nm used for image exposure is not particularly limited. For example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, Lamp light sources such as medium pressure mercury lamp, low pressure mercury lamp, carbon arc, fluorescent lamp; laser light sources such as argon ion laser, YAG laser, excimer laser, nitrogen laser, helium cadmium laser, semiconductor laser, and the like. An optical filter can also be used when used by irradiating light of a specific wavelength.
Exposure of radiation, 10~10,000J / ^{m 2} is preferred.
Examples of the alkaline developer include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, Inorganic alkaline compounds such as potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide; mono-di- or tri-ethanolamine, mono-di-, or tri -Methylamine, mono-, di-, or tri-ethylamine, mono-, or di-isopropylamine, n-butylamine, mono-, di-, or tri-isopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium Hydroxide (TMAH) Aqueous solution of an organic alkaline compound choline are preferred.
An appropriate amount of a water-soluble organic solvent such as isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol, or the like can be added to the alkali developer. In addition, it is usually washed with water after alkali development.
As the development processing method, any method such as an immersion development method, a spray development method, a brush development method, and an ultrasonic development method can be used. The development conditions are preferably 5 to 300 seconds at room temperature (23 ° C.).

  There are no particular restrictions on the conditions of the development processing, but the development temperature is usually 10 ° C. or higher, especially 15 ° C. or higher, more preferably 20 ° C. or higher, and usually 50 ° C. or lower, especially 45 ° C. or lower, more preferably 40 ° C. or lower. Is preferred.

  The developing method can be any one of immersion developing method, spray developing method, brush developing method, ultrasonic developing method and the like.

  When the color filter thus produced is used in a liquid crystal display device, a transparent electrode such as ITO is formed on the image as it is and used as a part of a color display, a liquid crystal display device, or the like. Although used, in order to improve surface smoothness and durability, a top coat layer such as polyamide or polyimide can be provided on the image as necessary. Further, in some applications such as a planar alignment type drive system (IPS mode), the transparent electrode may not be formed. In the vertical alignment type driving method (MVA mode), ribs may be formed. Also, a column structure (photo spacer) made of photolithography may be formed instead of the bead dispersion type spacer.

<Liquid crystal display device>
The liquid crystal display device of the present invention uses the above-described color filter of the present invention. There is no restriction | limiting in particular about the model and structure of the liquid crystal display device of this invention, It can assemble according to a conventional method using the color filter of this invention.
For example, the liquid crystal display device of the present invention can be formed by the method described in “Liquid Crystal Device Handbook” (Nikkan Kogyo Shimbun, September 29, 1989, Japan Society for the Promotion of Science 142nd Committee).

<Organic EL display device>
When producing an organic EL display device including the color filter of the present invention, for example, as shown in FIG. 1, the organic EL display device is organically formed on a transparent support substrate 10 and on a blue color filter in which pixels 20 are formed by the colored composition of the present invention. A multicolor organic EL element is produced by laminating the organic light-emitting body 500 through the protective layer 30 and the inorganic oxide film 40.
As a method for laminating the organic light emitter 500, a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 are sequentially formed on the upper surface of the color filter. For example, a method of adhering the organic light-emitting body 500 formed on another substrate onto the inorganic oxide film 40 can be used. The organic EL element 100 manufactured as described above can be applied to both a passive drive type organic EL display device and an active drive type organic EL display device.

Next, although a synthesis example, an Example, and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to a following example, unless the summary is exceeded.
<Synthesis of dyes>
[Synthesis of Dye (A)]

  Compound 1 (6.0 g, 25 mmol: synthesized by the method described in International Publication No. 2008/003604 pamphlet), Compound 2 (6.4 ml, 50 mmol: manufactured by Tokyo Chemical Industry Co., Ltd.), potassium carbonate (6.9 g, 50 mmol) , N-methyl-2-pyrrolidone (25 ml) was stirred with heating at 110 to 125 ° C. for 4 hours. After cooling to room temperature, water was added and extracted with toluene. The toluene layer was washed with dilute hydrochloric acid and saturated brine, and dried over anhydrous sodium sulfate. Concentration under reduced pressure gave a light brown oil (9.2 g). This was dissolved in ethanol (40 ml), a solution of sodium hydroxide (2 g, 52.3 mmol) in water (25 ml) was added, and the mixture was stirred at 85 ° C. for 1 hour. The mixture was allowed to cool and extracted with toluene, and the toluene layer was washed with saturated brine and dried over anhydrous sodium sulfate. After concentration under reduced pressure, the residue was purified by silica gel column chromatography (hexane / ethyl acetate = 3/1) to obtain compound 3 (5.95 g, yield 94%) as a white powder.

  Compound 4 (1.47 g, 4.34 mmol: synthesized by the method described in International Publication No. 2009107734), Compound 3 (1.1 g, 4.34 mmol), toluene (30 ml), phosphorus oxychloride (0. 6 ml) was heated to reflux for 4 hours, cooled to room temperature, water was added, and the mixture was extracted with chloroform. The chloroform layer was concentrated under reduced pressure and purified by silica gel column chromatography (developing solvent: chloroform / methanol = 15/1 to 10/1), and the resulting solid was washed with hexane to give compound 5 (1.32 g, yield). 50%).

A mixture of Compound 5 (8.9 g, 14.6 mmol), Compound 6 (4.2 g, 14.6 mmol: manufactured by Tokyo Chemical Industry Co., Ltd.) and methanol (50 ml) was stirred at 50 ° C. for 1.5 hours, and then concentrated under reduced pressure. The obtained solid was washed with methanol / water = 1/2 to obtain a dye (A) (11.5 g, yield 92.3%).
[Synthesis of Dye (B)]

A mixture of Compound 5 (4.27 g, 7.0 mmol), Compound 7 (2.32 g, 7.0 mmol: manufactured by Tokyo Chemical Industry Co., Ltd.) and methanol (200 ml) was stirred at 50 ° C. for 1.5 hours. After concentration under reduced pressure, the obtained solid was washed with methanol / water = 1/2 to obtain Dye (B) (5.42 g, yield 89%).
[Synthesis of Dye (C)]

Compound 5 (1.22 g, 2.0 mmol) and compound 8 (0.70 g, 1.03 mmol) were dissolved in methanol and then concentrated under reduced pressure. The obtained solid was washed with a solvent mixture of methanol / water (1/2) to obtain dye (C) (1.48 g, yield 83%).
[Synthesis of Dye (D)]

A mixture of Compound 9 (397 mg, 0.6 mmol: synthesized by the method described in International Publication No. 2009/107734), Compound 6 (172 mg, 0.6 mmol: manufactured by Tokyo Chemical Industry Co., Ltd.), and methanol (30 ml) was mixed with 50. After stirring at ° C for 1.5 hours, the mixture was concentrated under reduced pressure, and the resulting solid was washed with methanol / water = 1/2 to obtain Dye (D) (410 mg, yield 75.3%).
[Synthesis of Dye (E)]

A mixture of Compound 9 (397 mg, 0.6 mmol: synthesized by the method described in WO2009 / 107734), Compound 7 (200 mg, 0.6 mmol: purchased from Tokyo Kasei) and methanol (30 ml) at 50 ° C. After stirring for 1.5 hours, the solid obtained by concentration under reduced pressure was washed with methanol / water = 1/2 to obtain Dye (E) (450 mg, yield 81.6%).
[Synthesis of Dye (F)]

A mixture of compound 9 (5.00 g, 7.55 mmol: synthesized by the method described in WO200 / 07734), compound 8 (2.56 g, 3.77 mmol), and methanol (50 ml) was stirred at 40 ° C. for 1 hour. After that, it was concentrated under reduced pressure, water was added and the solid was collected by filtration. The solid was washed with methanol / water 1/3 (200 ml) and again with methanol / water = 1/3 (200 ml) to obtain dye (F) (5.90 g, yield 83%).
[Synthesis of Dye (G)]

A mixture of compound 10 (3.21 g, 5.9 mmol: manufactured by Hayashibara Biochemical Laboratories), compound 6 (1.70 g, 5.9 mmol: manufactured by Tokyo Chemical Industry Co., Ltd.), and methanol (200 ml) was mixed at 50 ° C. with 1.5. After stirring for hours, the mixture was concentrated under reduced pressure, and the resulting solid was washed with methanol / water = 1/2 to obtain Dye (G) (3.91 g, yield 95%).
[Synthesis of Dye (H)]

  A mixture of Compound 10 (5.41 g, 10 mmol: manufactured by Hayashibara Biochemical Laboratories), Compound 7 (3.31 g, 10 mmol: manufactured by Tokyo Chemical Industry Co., Ltd.) and methanol (200 ml) was stirred at 50 ° C. for 1.5 hours. Thereafter, the mixture was concentrated under reduced pressure, and the resulting solid was washed with methanol / water = 1/2 to obtain Dye (H) (6.65 g, yield 94%).

<Resin synthesis>
(Synthesis of Resin A)
Propylene glycol monomethyl ether acetate (145 parts by weight) was stirred while being purged with nitrogen, and the temperature was raised to 120 ° C. Styrene (10 parts by weight), glycidyl methacrylate (85.2 parts by weight) and monoacrylate (66 parts by weight) having a tricyclodecane skeleton (FA-513M: manufactured by Hitachi Chemical Co., Ltd.) were added dropwise thereto, and 2.2. '-Azobis-2-methylbutyronitrile (8.47 parts by weight) was added dropwise over 3 hours, and the mixture was further stirred at 90 ° C for 2 hours. Next, the inside of the reaction vessel was changed to air substitution, and trisdimethylaminomethylphenol (0.7 part by weight) and hydroquinone (0.12 part by weight) were added to acrylic acid (43.2 parts by weight). The reaction continued for hours. Thereafter, tetrahydrophthalic anhydride (THPA) (56.2 parts by weight) and triethylamine (0.7 parts by weight) were added and reacted at 100 ° C. for 3.5 hours. The binder resin thus obtained had a weight average molecular weight of about 8400 and an acid value of 80 mgKOH / g as measured by GPC.

<Preparation of pigment dispersion>
[1] Preparation of blue pigment dispersion (1) C.I. I. Pigment Blue 15: 6 is 11.36 parts by weight, 57.5 parts by weight of propylene glycol monomethyl ether acetate as a solvent, and “Disperbic 2000” (manufactured by BYK Chemie) as a dispersant is 3.02 parts by weight in terms of solid content. A stainless steel container was filled with 215.7 parts by weight of 0.5 mm zirconia beads and dispersed in a paint shaker for 6 hours to prepare a blue pigment dispersion (1).

[2] Preparation of blue pigment dispersion (2) C.I. I. Pigment Blue 15: 6 and Violet 23 in a weight ratio of 9.20: 3.81, 11.36 parts by weight, 57.5 parts by weight of propylene glycol monomethyl ether acetate as a solvent, and “Dispervik 2000” (Bic Chemie) as a dispersant A stainless steel container was filled with 3.02 parts by weight in terms of solid content and 215.7 parts by weight of zirconia beads having a diameter of 0.5 mm, and the mixture was dispersed with a paint shaker for 6 hours to prepare a blue pigment dispersion.
<Preparation of coloring composition>
Table 1 shows the dyes (pigments) used in Examples 1 to 6 and Comparative Examples 1 and 3.

上記各染料及びその他の成分を下記表２に記載の比率で混合して、着色組成物を調製した。
混合に際しては、各成分が十分に混合するまで１時間以上攪拌し、最後に５μｍの駒型フィルターによって濾過し、異物を取り除いた。
尚、表２中の数値は、いずれも添加する各成分の重量部を表す。

The above dyes and other components were mixed at the ratios shown in Table 2 below to prepare a colored composition.
In mixing, the components were stirred for 1 hour or more until they were sufficiently mixed, and finally filtered through a 5 μm piece filter to remove foreign matters.
In addition, all the numerical values in Table 2 represent parts by weight of each component to be added.

［３］着色樹脂膜の製造及び耐熱性の評価
５ｃｍ角に切断したガラス基板上に、上記各着色組成物をスピンコート法により乾燥後のy値が０．１２０となるように塗布し、減圧乾燥させた後、ホットプレート上にて８０℃３分間プリベークした。その後、６０ｍＪ／ｃｍ^２の露光量にて全面露光して、着色樹脂膜を作成した。
その後、分光光度計Ｕ−３３１０（日立製作所製）にて、分光透過率を測定し、ＸＹＺ表色系における色度（Ｃ光源）を算出した（加熱前の色特性）。
続いて、クリーンオーブンにて２３０℃３０分焼成し、分光光度計Ｕ−３３１０（日立製作所製）にて、同様に分光透過率を測定し、ＸＹＺ表色系における色度（Ｃ光源）を算出した（加熱後の色特性）。
この結果を、表３に示す。

[3] Production of colored resin film and evaluation of heat resistance On a glass substrate cut into 5 cm square, each colored composition was applied by spin coating so that the y value after drying was 0.120, and the pressure was reduced. After drying, it was prebaked on a hot plate at 80 ° C. for 3 minutes. Thereafter, the entire surface was exposed with an exposure amount of 60 mJ / cm ² to prepare a colored resin film.
Thereafter, the spectral transmittance was measured with a spectrophotometer U-3310 (manufactured by Hitachi, Ltd.), and the chromaticity (C light source) in the XYZ color system was calculated (color characteristics before heating).
Subsequently, baking was performed at 230 ° C. for 30 minutes in a clean oven, and the spectral transmittance was similarly measured with a spectrophotometer U-3310 (manufactured by Hitachi, Ltd.) to calculate chromaticity (C light source) in the XYZ color system. (Color characteristics after heating).
The results are shown in Table 3.

ΔY in Table 3 is the difference between Y (luminance) after heating and Y before heating.
As shown in Table 3, the pixel obtained using the colored composition of the present invention has a small decrease in luminance before and after heating and a high luminance. Accordingly, for example, since the luminance drop in the heating process when forming red, green, and blue pixels by photolithography is small, the liquid crystal display device and the organic EL display device having the color filter of the present invention are of high quality. It is.

DESCRIPTION OF SYMBOLS 100 Organic EL element 20 Pixel 30 Organic protective layer 40 Inorganic oxide film 500 Organic light-emitting body 51 Hole injection layer 54 Electron injection layer

Claims (12)

(A) a coloring material, (B) a solvent and (C) a binder resin,
As the colorant (A), a compound represented by the following formula (I):
A coloring composition comprising a copper phthalocyanine pigment and / or a dioxazine pigment.
Z ⁻ A ⁺ (I)
(In the above formula (I), Z ⁻ represents a disulfonylimide anion.
A ⁺ represents a cationic dye. ) The coloring composition according to claim 1, wherein the compound represented by the formula (I) is a compound represented by the following formula (II).

(In said formula (II), R < ¹¹ > and R < ¹² > are respectively independently the C1-C8 alkyl group which may have a substituent, and C2-C2 which may have a substituent. 6 represents an alkenyl group having 6 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms which may have a substituent.
R ¹¹ and R ¹² may be bonded to each other to form a ring.
A ⁺ has the same meaning as in formula (I). ) The coloring composition according to claim 2, wherein at least one of R ¹¹ and R ¹² is a group containing a fluorine atom. The colored composition according to claim 2 or 3, wherein the compound represented by the formula (II) is a compound represented by the following formula (III).

(In the formula ^{(III), R 21} and ^{R 22} are each the same meaning as ^{R 11} and ^{R 12} in Formula (II).
R ^{1 to} R ⁶ each independently represent a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or an aromatic ring group optionally having a substituent. Adjacent R ^{1 to} R ⁶ may be bonded to form a ring.
R ⁷ and R ⁸ represent a hydrogen atom or an arbitrary substituent. R ⁷ and R ⁸ may be connected to each other to form a ring.
R ¹⁰¹ and R ¹⁰² have a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, an optionally substituted alkenyl group having 2 to 6 carbon atoms, or a substituent. Represents an aromatic ring group which may be substituted, or a fluorine atom. R ¹⁰¹ and R ¹⁰² may be bonded to form a ring.
Moreover, the benzene ring in the above formula (III) may further have an arbitrary substituent. ) The colored composition according to claim 2 or 3, wherein the compound represented by the formula (II) is a compound represented by the following (IV).

(In said formula (IV), R <^31> and R ^<32 > is synonymous with R < ¹¹ > and R < ¹² > in said Formula (II) respectively.
R ^{41 to} R ⁴⁶ each independently represent a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or an optionally substituted aromatic ring group. Adjacent R ^{41 to} R ⁴⁶ may be bonded to each other to form a ring.
R ⁴⁷ and R ⁴⁸ each independently represents a hydrogen atom or an arbitrary substituent. R ⁴⁷ and R ⁴⁸ may be bonded to each other to form a ring.
Further, the benzene ring and indole ring in the above formula (III) may further have an arbitrary substituent. ) The colored composition according to claim 2 or 3, wherein the compound represented by the formula (II) is a compound represented by the following formula (V).

(In the formula ^{(V), R 51} and ^{R 52} are each the same meaning as ^{R 11} and ^{R 12} in Formula (II).
Ar ¹ and Ar ² each independently represent a nitrogen-containing heterocyclic group which may have a substituent.
n represents an integer of 1 to 5. )   The total content of the copper phthalocyanine pigment and the dioxazine pigment is 5% by weight or more and 2000% by weight or less of the total content of the compound represented by the formula (I). The coloring composition as described in any one.   A copper phthalocyanine pigment, wherein 80% by weight or more of the copper phthalocyanine pigment is C.I. I. The coloring composition according to any one of claims 1 to 8, which is CI Pigment Blue 15: 6.   A dioxazine pigment, wherein 80% by weight or more of the dioxazine pigment is C.I. I. It is pigment violet 23, The coloring composition as described in any one of Claims 1-9 characterized by the above-mentioned.   It has a pixel formed using the coloring composition as described in any one of Claims 1-9, The color filter characterized by the above-mentioned.   A liquid crystal display device comprising the color filter according to claim 10.   An organic EL display device comprising the color filter according to claim 10.

Images