JP5772122B2 - Dye, colored resin composition, color filter, liquid crystal display device and organic EL display device - Google Patents

Description

  The present invention resides in a dye, a colored resin composition, a color filter, a liquid crystal display device, and an organic EL display device.

In recent years, color liquid crystal display devices and organic EL displays have attracted attention as flat displays, and color filters are used for 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 has an organic EL element having a structure in which an organic EL light emitting layer is sandwiched between an anode and a cathode. However, in practice, color display is possible using the organic EL element. In order to obtain an organic EL display, (1) a method of arranging organic EL elements that emit light of each of the three primary colors, (2) a method of combining an organic EL element that emits white light with a color filter layer of the three primary colors, and ( 3) There is a CCM method 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. Therefore, 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. .
In addition, the combination method of the white organic EL and the color filter in (2) and the CCM method in (3) may use only one type of organic EL element that emits light of the same color. Unlike the EL display, it is not necessary to align the characteristics of the organic EL elements of each color, and the number of processes and materials can be reduced.

  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 that require high-definition images, color filters created by the pigment dispersion method are the mainstream, and red, blue, or green pigments in the photosensitive resin solution have a particle size of 1 μm or less. After the finely dispersed material is applied on a glass substrate, pixels are formed in a desired pattern by photolithography.

For 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 in the photosensitive resin in the image forming material has been 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 1 describes a color filter provided with a blue filter layer having C-I Acid Blue 83 (triallylamine dye) and C-I Solvent Blue 67 (copper phthalocyanine dye). ing.

  Patent Document 2 describes a color filter using a polymer containing a polymerizable triphenylmethane dye represented by the following formula.

(At least one of R _{1 in} the above formula is a specific polymerizable group containing a carbon-carbon double bond)
Furthermore, Patent Document 3 also describes a color resin composition for a color filter containing a compound (pigment) represented by a specific structure.

Japanese Patent Laid-Open No. 2002-14222 JP 2000-162429 A JP 2009-235392 A

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

However, the color filters using the dyes described in Patent Documents 2 and 3 sometimes have insufficient brightness and solvent resistance.
Then, this invention makes it a subject to provide the dye which can obtain the color filter which made the brightness | luminance and solvent resistance compatible, and a colored resin composition.
Furthermore, this invention makes it a subject to provide the color filter formed using the said colored resin composition, a high quality liquid crystal display device, and an organic electroluminescent display device.

As a result of intensive studies, the present inventors have found that the above problems can be solved by further having a crosslinkable group in a dye containing a specific anion, and have reached the present invention.
That is, the present invention resides in a dye, a colored resin composition, a color filter, a liquid crystal display device, and an organic EL display device characterized by comprising a compound represented by the following formula (IV) .

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, “total solid content” means all components of the colored resin composition for color filter of the present invention other than the solvent components described later.
Furthermore, “aromatic ring” means both “aromatic hydrocarbon ring” and “aromatic heterocycle”.
C. I. Means a color index.

The present invention is a dye comprising the compound represented by the formula (I).
Further, the colored resin composition of the present invention comprises (A) the dye as the colorant, (B) a solvent, (C) a binder resin, (D) a monomer, (E) a photopolymerization initiation system, and further necessary. Contains other ingredients formulated accordingly.
First, the dye of the present invention will be described.

<Dye>
The dye of the present invention is a dye comprising a compound represented by the following formula (I).
Z ⁻ A ⁺ (I)
(In the above formula (I), Z ⁻ represents a disulfonylimide anion. A ⁺ represents a cationic dye.

However, at least one of Z ⁻ and A ⁺ has a crosslinkable group. )
(About A ⁺ )
A ⁺ represents a cationic dye.
The cationic dye is not particularly limited as long as it does not impair the effects of the present invention. For example, it is described in "Industrial Dyes -Chemistry, Properties, Applications- (Wiley-VCH, 2003, edited by Klaus Hunger)". Color materials that are present. More specifically, compounds having a colorant skeleton (Chromophore) such as triarylmethanes, cyanines, styryls, and azines can be mentioned, and can be appropriately selected depending on the desired color.

In particular, when blue is desired, triarylmethanes are preferable from the viewpoint of excellent color density, luminance, and heat resistance, and when purple is desired, color density, luminance, and From the viewpoint of excellent heat resistance, triarylmethanes and cyanines are particularly preferable.
(Z ^- About)
Z ⁻ represents a disulfonylimide 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, since the disulfonamide has a fluorine-containing substituent, 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 disulfonylimide anions absorbs in the visible region. Therefore, it hardly affects the color purity of the color material (particularly cationic dye), and hardly affects the color purity of the obtained pixel.

(About crosslinkable groups)
In the compound represented by the formula (I), the cationic dye or the anion has a crosslinkable group.
The crosslinkable group in the present invention refers to a group that reacts with the same or different groups of other molecules located nearby by irradiation with heat and / or active energy rays to form a new chemical bond.

Among them, the crosslinkable group includes the following <crosslinkable group group T> from the viewpoint of easy crosslinking.
<Crosslinkable group T>

^(Wherein, R 71 ^{to R 75} each independently represent a hydrogen atom or an alkyl group.
Ar ³³ represents an aromatic ring group which may have a substituent. )
Among them, the crosslinkable group is preferably a group that crosslinks by cationic polymerization such as a cyclic ether group such as an epoxy group or an oxetane group, or a vinyl ether group. This is because the reactivity is high and the solubility in a solvent can be easily lowered. Among them, an oxetane group is particularly preferable in terms of easy control of the rate of cationic polymerization, and a vinyl group is bonded via an oxygen atom in that it is difficult to generate hydroxyl groups that may cause deterioration of the device during cationic polymerization. Preferred are vinyl ether groups.

Among the crosslinkable groups, it is a crosslinkable group represented by the following <crosslinkable group group T ′> from the viewpoint of hardly affecting the color tone and easily improving the solvent resistance of the obtained pixel. Is particularly preferred.
<Crosslinkable group T '>

The crosslinkable group may be included in the cationic dye, may be included in the anion, or both may be included. Among them, after forming a pixel, the crosslinkable group is a cationic group because it has a greater influence on the color tone by eluting into the solvent than the anion because the cationic dye is more effective than the anion. It is preferable that the dye has.
<Reason for effect>
The reason why the effect of achieving both brightness and solvent resistance is obtained by using the configuration of the present invention is estimated as follows.

The dye represented by the formula (I) contains disulfonylimide as an anion. Since the disulfonylimide anion is not easily sublimated or decomposed by heat, the stability of the dye itself is enhanced.
For this reason, if the dye contains disulfonylimide as an anion and further has a crosslinkable group, there are many crosslinkable groups that work more effectively than the stability of the dye itself, and as a result, the effect of improving solvent resistance The width is large, that is, the brightness and the chemical resistance can be compatible.

[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, luminance, and heat resistance of the coloring material.

(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).

However, at least one of A ⁺ , R ¹¹ and R ¹² has a crosslinkable group. )
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, an alkylthio group having 1 to 8 carbon atoms, and a vinyl group formed by bonding an alkyl group having 1 to 4 carbon atoms.

Among these, in particular, as the substituent of the alkyl group, alkenyl group or cycloalkyl group in R ¹¹ and R ¹² , the anion charge is more delocalized, and the heat resistance of the coloring material is improved. It preferably has a fluorine atom as a substituent.
That is, R ¹¹ and R ¹² are preferably a C 1-8 perfluoroalkyl group 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).
However, A ⁺ has a crosslinkable group. )
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 (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 the above, for the reason that the anion is most stabilized, bis (n = n ′ = 2,
Pentafluoroethanesulfone) imide is particularly preferred.
A ⁺ has the crosslinkable group.
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).
However, A ⁺ has a crosslinkable group. )
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.

A ⁺ has the crosslinkable group.
Hereinafter, preferred specific examples of Z ⁻ in the formula (I), that is, the disulfonylimide anion are shown below, but the present invention is not limited thereto.
<Specific examples of disulfonylimide anion>

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 pixel.

(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, and the ring may have a substituent.

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.
Moreover, the benzene ring in the above formula (III) may further have an arbitrary substituent.
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 optionally substituted aryl group or fluorine atom.

Alternatively, R ¹⁰¹ and R ¹⁰² may be bonded to form a ring, and the ring may have a substituent.
The cationic structural formula of the above formula (III) has a crosslinkable group.
In addition, multiple molecules in one molecule

May be the same structure or different structures. )
(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 in R ^{1 to} R ⁶ include an aromatic hydrocarbon ring and an aromatic heterocyclic ring.
The aromatic hydrocarbon ring 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. For example, a benzene ring, a naphthalene ring, an anthracene And monovalent or higher-valent groups such as a ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.

  In addition, the aromatic heterocycle 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. For example, a furan ring, a benzofuran ring, a 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, fluropyrrole ring, furofuran ring , Thienofuran ring, benzisoxazole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxaline ring, phenanthridine ring, Benzimidazole ring, perimidine , Quinazoline ring, a quinazolinone ring, and a monovalent or polyvalent group 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. R
^{When 1 to} R ⁶ are phenyl groups that may have a substituent, it is presumed that the cation is stabilized by extending the conjugated system to disperse the charges in the cation. As described above, as a result of stabilization of the cation, the resulting color filter is more excellent in solvent resistance.

Examples of the substituent that the alkyl group and aromatic ring group in R ^{1 to} R ⁶ may have include those described above in (Substituent group W).
(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.

The alkyl group and the aromatic ring group are the same as 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.

From the viewpoint that the obtained color filter is blue and has high luminance, it is preferable that R ⁷ and R ⁸ are not connected to each other to form a ring.
In addition, it is preferable that the obtained color filters are purple and have high luminance, and are connected to each other to form a ring.
(About R ⁹ and R ¹⁰ )
R ⁹ and R ¹⁰ 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, and a substituent. Represents an optionally substituted aryl group or fluorine atom.

R ⁹ and R ¹⁰ may be bonded to form a ring.
Specific examples of the ring formed by combining R ⁹ and R ¹⁰ include the following.

The ring formed by combining R ⁹ and R ¹⁰ 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).

(Position including a crosslinkable group)
In the cation structure of the formula (III), the crosslinkable group may be contained in R ^{1 to} R ⁶ and may be included in the naphthalene ring as a substituent.
(About R ²¹ and R ²² )
R ²¹ and R ²² are each independently an alkyl group having 1 to 8 carbon atoms which may have a substituent, an alkenyl group having 2 to 6 carbon atoms which may have a substituent, or a substituent. The C3-C8 cycloalkyl group which may have is represented.

R ²¹ and R ²² may be bonded to each other to form a ring.
R ²¹ and R ²² in the formula (III) are respectively synonymous with R ¹¹ and R ¹² in the formula (II), and the aspect thereof is the above-mentioned [about formula (II)] (R ¹¹ and it is similar to those described in the section) for R ^12. The preferred embodiment is also the same.
Preferred specific examples of the compound represented by the formula (III) are shown below, but the present invention is not limited thereto.
<Specific example>

[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 represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. R ⁴¹ and R ⁴² , and R ⁴³ and R ⁴⁴ may be bonded to each other to form a ring structure.

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.
Moreover, the benzene ring and indole ring in the above formula (IV) may further have an arbitrary substituent.
The cationic structural formula of the above formula (IV) has a crosslinkable group.

  In addition, multiple molecules in one molecule

May be the same structure or different structures. )
(About R ^{41 to} R ⁴⁶ )
R ^{41 to} R ⁴⁶ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. R ⁴¹ and R ⁴² , and R ⁴³ and R ⁴⁴ may be bonded to each other to form a ring structure, and the ring 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 the ring is the same as when the formula (II) of ^(for R 1 to R ⁶⁾ term to be bonded to ^R 1 to R ⁶ each other according to form a ring. The preferred embodiment is also the same.
(About R ⁴⁷ and R ⁴⁸ )
R ⁴⁷ and R ⁴⁸ represent a hydrogen atom or an arbitrary substituent. Examples of the optional substituents include those described in the 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 those described above (for the compound represented by the formula (III)) ( As for R ⁴⁷ and R ⁴⁸ ). These rings may have a substituent.

From the viewpoint that the obtained color filter is purple and has high luminance, it is preferable that R ⁷ and R ⁸ are not connected to each other to form a ring.
In addition, it is preferable that the obtained color filters are red and have high luminance, so that they are connected to each other to form a ring.
(Position including a crosslinkable group)
In the cation structure of the formula (IV), the position containing a crosslinkable group is not particularly limited, but R ⁴⁵ and R ⁴⁶ are particularly preferable in terms of easy synthesis.

(About R ³¹ and R ³² )
R ³¹ and R ³² are each independently 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. The C3-C8 cycloalkyl group which may have is represented.
R ³¹ and R ³² may be bonded to each other to form a ring.

R ³¹ and R ³² in the formula (IV) are respectively synonymous with R ¹¹ and R ¹² in the formula (II), and the aspect thereof is the above [about formula (II)] (R ¹¹ and it is similar to those described in the section) for R ^12. The preferred embodiment is also the same.
Preferred specific examples of the compound represented by the formula (IV) are shown below, but the present invention is not limited thereto.
<Specific example>

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

(In the formula ^{(V), R 51} and ^{R 52} have the same meanings 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. )
(About Ar ¹ and Ar ² )
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 indole ring, benzoindole ring, indolenine ring, benzoindolenin ring, oxazole ring, benzoxazole ring, thiazole ring, benzothiazole ring, benzimidazole ring, and quinoline ring. Of these, indole ring, benzoindole ring, indolenine ring, and benzoindolenine ring are preferable, and indole ring and benzoindolenine ring are more preferable in terms of high luminance.

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 , Butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group and other aliphatic hydrocarbon groups; phenyl group, o-tolyl group, m-tolyl group , Aromatic hydrocarbon ring groups such as 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;

(About n)
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.
The compound represented by the formula (V) has a cis-trans isomer at the cation site, but may be any isomer.

  The compound represented by the formula (V) is more preferably a compound represented by the following formula (V-1) in terms of increasing the lightness and heat resistance of the coating film.

(In the formula ^{(V-1), R 51} and ^{R 52} are as defined as in the formula (II).
R ³⁰¹ and R ³⁰² each independently represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
R ⁵¹ and R ⁵² 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. 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. )
(About R ³⁰¹ and R ³⁰² )
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, o
An aromatic hydrocarbon ring group such as -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, 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 ⁶¹ and R ⁶² 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 ³¹ and R ³² 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 have the same meanings as R ¹¹ and R ¹² in the formula (II). The preferred embodiment is also the same.
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.
In addition, the compound represented by the above formula (V) has a cis-trans isomer in the cation moiety (partial structure represented in parentheses), but any isomer may be used.

(Content)
The content of the compound represented by the formula (I) in the colored resin composition of the present invention is preferably 1% by weight or more, more preferably 3% by weight or more, and particularly preferably 5% by weight in the total solid content. In addition, it is usually 50% by weight or less, more preferably 40% by weight or less, and particularly preferably 30% by weight or less.

Within the above range, the curability of the coating film is hardly lowered, the film strength is sufficient, the coloring power is hardly lowered, the chromaticity is obtained at a sufficient concentration, and the film thickness is further increased. It is preferable because it is difficult.
In the case where the solubility of the compound represented by the formula (I) in the colored resin composition (particularly the solvent contained in the composition) is low, as in the case of a pigment which is an optional component described later, You may use it disperse | distributing in a composition using a dispersing agent etc. However, from the viewpoint of high contrast when applied to a liquid crystal display device, the compound represented by the formula (I) is preferably present in a dissolved state in the colored resin composition.

In the colored resin composition of the present invention, only one type of compound (dye) represented by formula (I) may be included as the color material (A), or two or more types may be included. Moreover, 1 type (s) or 2 or more types of the other coloring material may be contained.
The (A) color material contains, in addition to the compound represented by the formula (I), other dyes mentioned in the following [Other color material] and the (F) pigment described later. The content of all (A) coloring materials in the colored resin composition of the present invention is usually 1% by weight or more, preferably 3% by weight or more, more preferably 5% by weight or more, based on the total solid content. Moreover, it is 50 weight% or less normally, Preferably it is 40 weight% or less, More preferably, it is 30 weight% or less.

When it is within the above range, the film thickness is appropriate with respect to the color density, and it is easy to control the gap when forming a liquid crystal cell. Furthermore, the dispersion stability is high, and it is preferable because reaggregation and thickening hardly occur.
In the colored resin composition of the present invention, the content of the compound represented by the formula (I) is usually 5% by weight or more, preferably 20% by weight or more, more preferably, based on the total amount of the color material (A). It is 30% by weight or more, particularly preferably 40% by weight or more.

In addition, since it is preferable that all the (A) color materials are compounds represented by the formula (I), the upper limit is usually 100% by weight or less.
Within the above range, it is preferable in that the effect of the present invention can be obtained satisfactorily.
[Other color materials]
The colored resin composition of the present invention contains (A) the compound represented by the formula (I) as a color material, but may contain other dyes as long as the effects of the present invention are not impaired.

Examples of other dyes include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinone imine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes, cyanine dyes, triarylmethane dyes, and the like. Is preferred. These do not need to have a crosslinkable group.
Examples of the azo dye include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse Blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Molded Red 7, C.I. I. Moldant Yellow 5, C.I. I. Examples thereof include Moldant Black 7.

Examples of anthraquinone dyes include C.I. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disper thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 etc. are mentioned.
Other examples of the phthalocyanine dye include C.I. I. Pad Blue 5 and the like are quinone imine dyes such as C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are quinoline dyes such as C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like are nitro dyes such as C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like.

Examples of the triarylmethane dye include those described in International Publication No. 2009/107734 pamphlet.
Furthermore, examples of the cyanine dye include those described in Japanese Patent Application No. 2010-142748, and preferred embodiments thereof are also the same.
The colored resin composition of the present invention may contain only the compound represented by the formula (I) as the color material (A), and in addition to the other dyes, from the viewpoint of improving heat resistance and light resistance. (F) It is preferable to contain a pigment.

  As the (F) pigment in the present invention, various color pigments such as a blue pigment, a green pigment, a red pigment, a yellow pigment, a purple pigment, an orange pigment, a brown pigment, and a black pigment can be used. In addition to the organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindoline, quinophthalone, isoindolinone, dioxazine, indanthrene, perylene, etc. Other inorganic pigments can also be used.

As these usable (F) pigments, for example, pigments described in JP-A-2009-025813 can be used.
When the colored resin composition of the present invention is a blue colored resin composition, it is particularly preferable to use Color Index (CI) Pigment Blue 15: 6 as a pigment to be used.

In this case, the dye of the present invention contained is particularly preferably combined with the compound represented by the formula (IV).
[(B) Solvent]
The colored resin composition of the present invention contains (B) a solvent. The solvent has a function of dissolving or dispersing each component contained in the colored resin composition and adjusting the viscosity.

The solvent (B) may be any solvent as long as it can dissolve or disperse each component constituting the colored resin 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 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.
Further, for example, when the pigment (F) is included as an optional component, the coating properties, surface tension and the like are well balanced, and the glycol alkyl ether is further used as a solvent from the viewpoint of relatively high solubility of the constituent components in the composition. It is more preferable to use a mixture of acetates. In a composition containing a pigment, glycol monoalkyl ethers have a high polarity, tend to aggregate the pigment, and may reduce storage stability such as increasing the viscosity of the colored resin 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. .

Moreover, from the viewpoint of suitability for the slit coat method corresponding to the recent large substrates, etc., 1
It is also preferable to use a solvent having a boiling point of 50 ° C. or higher in combination. 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 resin composition of the present invention may be used for color filter production by the ink jet method, but in color filter production by the ink jet method, the ink emitted from the nozzle is very small, from several to several tens pL, There is a tendency for the solvent to evaporate and the ink to concentrate and dry before landing on the periphery of the nozzle opening or in the pixel bank. 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 resin 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.
[(C) Binder resin]
(C) The preferred resin for the binder resin differs depending on the curing means.
When the colored resin 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, 11-14144, JP-A No. 11-174224, JP-A No. 2000-56118, JP-A No. 2003-233179, and the like can be used. C-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 anything as long as they are dissolved in an alkaline developer and are soluble to the extent that the desired development processing is performed. It is the same as that described as the same item of 2009-025813 gazette. 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 resin composition can be improved. , Styrene, (n-butyl) (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, benzyl (meth) acrylate , (Meth) acrylic acid-2-hydroxyethyl, N-phenylmaleimide, N-cyclohexylmaleimide.

The content of the repeating unit 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 in the above range since the colored resin 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 the said 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. Within the above range, heat resistance, film strength, and solubility in a developing solution are preferable in terms of quantity.
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. If the acid value is too low, the solubility in the developer may be reduced. Conversely, if it is too high, film roughening may occur.
(C) Content of binder resin is 0.1-80 weight% normally in a total solid, Preferably it is 1-60 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.
[(D) Polymerizable monomer]
The colored resin composition of the present invention preferably contains (D) a polymerizable monomer.
(D) 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 a photopolymerization initiation system described later when the colored resin composition of the present invention is irradiated with actinic rays. In addition, the (D) 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.
(D) 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 (D) 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 resin composition of the present invention, the content of the polymerizable monomer (D) is usually 1% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more in the total solid content. Further, it is usually 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 (D) polymerizable monomer to the (A) 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. Moreover, it is 200 weight% or less normally, Preferably it is 100 weight% or less, More preferably, it is 80 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.
[(E) Photopolymerization initiation system and / or thermal polymerization initiation system]
The colored resin composition of the present invention preferably includes (E) 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 resin composition of the present invention includes a resin having an ethylenic double bond as the component (C), or includes an ethylenic compound as the component (D), it directly absorbs light, or It is preferable to contain a photopolymerization initiating system having a function of generating a polymerization active radical and / or a thermal polymerization initiating system for generating a polymerization active radical by heat. In the present invention, the (E) component as a photopolymerization initiation system is a photopolymerization initiator (hereinafter arbitrarily referred to as (E1) component) or a polymerization accelerator (hereinafter arbitrarily referred to as (E2) component). , Means a mixture in which an additive such as a sensitizing dye (hereinafter, arbitrarily referred to as component (E3)) is used in combination.

(Photopolymerization initiation system)
You may contain in the colored resin composition of this invention. The photopolymerization initiation system is usually used as a mixture of (E1) a photopolymerization initiator, and (E2) a polymerization accelerator and (E3) an additive such as a sensitizing dye, which are added as necessary. 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 (E1) include titanocene derivatives described in JP-A Nos. 59-152396 and 61-151197; 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 (E1) 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 (E2) 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.

Each of these (E1) photopolymerization initiator and (E2) polymerization accelerator may be used alone or in combination of two or more.
Further, (E3) 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.

(E3) A sensitizing dye may also be used alone or in combination of two or more.
In the colored resin composition of the present invention, the content of these (E) photopolymerization initiation systems is usually 0.1% by weight or more, preferably 0.2% by weight or more, more preferably 0.8% by weight in the total solid content. It is 5% by weight or more, usually 40% by weight or less, preferably 30% by weight or less, more preferably 20% by weight or less.

Within the above range, it is preferable in that the sensitivity to the exposure light is good and the solubility of the unexposed portion in the development is good.
(Thermal polymerization initiation system)
Specific examples of the thermal polymerization initiation system (thermal polymerization initiator) that may be contained in the colored resin 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 colored resin composition of the present invention comprises a surfactant, an organic carboxylic acid and / or an organic carboxylic acid anhydride, a thermosetting compound, a plasticizer, a thermal polymerization inhibitor, a storage stabilizer, a surface It may contain a protective agent, an adhesion improver, a development improver, and the like. Moreover, when a pigment is contained as a coloring material, a dispersant or a dispersion aid may be contained. As these optional components, for example, various compounds described in JP-A-2007-113000 can be used.

[Preparation Method of Colored Resin Composition]
In the present invention, the colored resin composition can be prepared by an appropriate method. For example, the (A) color material and (C) binder resin are mixed with the (B) solvent and other additives. Can be prepared.
In addition, as a preparation method in the case of containing (F) a pigment as (A) a coloring material, (F) presence of a dispersing agent and, if necessary, a dispersing aid for adding (A) a coloring material containing a pigment in a solvent Under (C) a part of the binder resin, optionally, for example, a paint dispersion, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, etc. To prepare. Additives such as (C) a binder resin, (A) a colorant, and (D) a polymerizable monomer, (E) a photopolymerization initiator and / or a thermal polymerization initiator, if necessary, to the colored dispersion. The method of preparing by adding and mixing can be mentioned.

[Application of colored resin composition]
The colored resin composition of the present invention is usually in a state where all the constituent components are dissolved or dispersed in a solvent. This colored resin 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 resin 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 the present invention has a pixel formed from the colored resin composition of the present 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 colored resin 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 pixels, and after applying the colored resin composition of the present invention on this substrate, pre-baking is performed. The 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 the colored resin composition to the 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.

  The light source used for image exposure for using radiation having a wavelength of 190 to 450 nm is not particularly limited. 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 is 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. Further, a column structure (photo spacer) by a photolithography method 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 in accordance with 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, on a blue color filter in which pixels 20 are formed on a transparent support substrate 10 by the colored resin composition of the present invention. A multicolor organic EL element is manufactured by laminating the organic light-emitting body 500 through the organic 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 Compound A)

(Reaction 1)
Compound 2 (5.02 g, 20 mmol), Compound 1 (14 ml, 80 mmol), sodium t-butoxy (7.53 g, 80 mmol), toluene (100 ml), palladium (II) acetate (0.55 g, 2.45 mmol), Tri-t-butylphosphine (1
A mixture of 0% hexane solution, 10 g, 4.94 mmol) was heated to reflux under nitrogen for 10 hours. After cooling to room temperature, water was added and the mixture was filtered through celite. The filtrate was extracted with toluene and washed with water. The toluene layer was concentrated under reduced pressure, purified by silica gel column chromatography (silica gel 500 g, hexane / ethyl acetate 10 / 1-8 / 1-6 / 1), and the resulting powder was washed with cold methanol to give compound A (4 .59, 53% yield).
(Synthesis of Compound B)

(Reaction 2)
A mixture of compound 3 (5.8 g, 30 mmol) and N, N-dimethylformamide (50 ml) was cooled in an ice bath, 60% sodium hydride (1.57 g, 36 mmol) was added, and the mixture was stirred for 10 minutes. Compound 4 (5.1 ml, 36 mmol) was added dropwise and stirred as such for 30 minutes. The mixture was stirred for 2 hours while returning to room temperature. The mixture was heated and stirred at 45 ° C. for 1 hour. The mixture was cooled with ice, quenched with water, extracted with toluene, and the organic layer was washed twice with saturated brine. The extract was dried over anhydrous sodium sulfate and concentrated under reduced pressure. Hexane was added and the resulting crystals were collected by filtration to give Compound B (7.16 g, yield 77.1%) as a white powder.
(Synthesis of Compound C)

(Reaction 3)
A mixture of compound 3 (6 g, 31.1 mmol) and N, N-dimethylformamide (85 ml) was cooled in an ice bath, 60% sodium hydride (1.63 g, 37.3 mmol) was added, and the mixture was stirred for 10 minutes. Compound 5 (5.65 ml, 37.3 mmol) was added dropwise and stirred as such for 10 minutes. The mixture was stirred for 1 hour while returning to room temperature. The mixture was stirred at 40 ° C. for 3 hours. Water was added after cooling with ice, extracted with toluene, and dried over anhydrous sodium sulfate. Concentrated under reduced pressure. The product was purified by silica gel column chromatography (hexane / ethyl acetate = 4/1). The obtained crystals were washed with heptane to obtain compound 6 (9.1 g, yield 91%) as a white powder.

(Reaction 4)
Compound 6 (6.5 g, 0.02 mol) and methanol (200 ml) were placed in a container, and heated to 50 ° C. to dissolve. A 1 mol / l HCL aqueous solution (20 ml, 0.02 mol) was added dropwise. After 1 hour, the deprotection check was confirmed by TLC and the mixture was allowed to cool. The solution was added dropwise to an aqueous sodium hydrogen carbonate solution and extracted with methylene chloride. The solution was concentrated to about half amount (85 ml) and added to 1N / NaOH (10 ml) and water (250 ml). Further, methylene chloride (100 ml) was added, extracted and concentrated. Purification by column chromatography (silica gel 60 acidity (210 g), chloroform developing solvent) was performed to obtain Compound 7 (4.805 g, yield 100%).

(Reaction 5)
Compound 7 (2.55 g, 0.0107 mol) and tetrahydrofuran (50 ml) were placed in a container, and the inside of the system was adjusted to 5 ° C. or less with ice cooling. Triethylamine (2.17 g, 0.0215 mol) was added dropwise over 5 minutes. Further, methacryl chloride (2.23 g, 0.0215 mol, TCI) was added dropwise over 12 minutes. When the system was dripped, it became cloudy and triethylamine hydrochloride was precipitated. After 3 hours, the salt was removed by filtration, and the THF solution side was concentrated without applying heat. Column chromatography (silica gel 60 acid ethyl acetate / hexane = 3/7 dry
The oily compound C (2.7 g, yield 82.8%) was obtained.
(Synthesis of Compound D)

(Reaction 6)
Compound 3 (5.8 g, 30 mmol) and N, N-dimethylformamide (50 ml)
The mixture was cooled in an ice bath and 60% sodium hydride (1.57 g, 36 mmol) was added and stirred for 10 minutes. Compound 8 (6.5 ml, 36 mmol) was added dropwise and stirred as such for 30 minutes. The mixture was stirred for 1 hour while returning to room temperature. The mixture was heated and stirred at 45 ° C. for 2 hours. The mixture was extracted with toluene after cooling with ice, and the organic layer was washed twice with saturated brine. The extract was dried over anhydrous sodium sulfate and concentrated under reduced pressure. Purification by silica gel column chromatography (hexane / chloroform = 3/1-1/1) gave Compound 9 (2.19 g, 20.9% yield) as a pale yellow oil.

(Reaction 7)
Compound 9 (2.11 g, 5.7 mmol) and methanol (50 ml) were placed in a reaction vessel, and the mixture was heated and stirred at 50 ° C. in a water bath. 1 mol / L hydrochloric acid (5.72 ml, 5.7 mmol) was added dropwise and reacted for 2 hours. Added to saturated NaHCO ₃ (200 ml). Since it became alkaline to pH 9, it was adjusted to pH 6 by adding 1 mol / l hydrochloric acid. Extracted with chloroform and concentrated. Thereafter, it was purified by column chromatography (silica gel 60 acidic 100 g, chloroform) to obtain compound 10 (yield 1.063 g, yield 70.35%).

(Reaction 8)
Compound 10 (1.0 g, 3.77 mmol) and tetrahydrofuran (25 ml) were placed in a container, and the inside of the system was cooled to 5 ° C. or less with ice cooling. Triethylamine (0.768g, 7.54mm
ol) was added dropwise over 5 minutes. Further, methacryl chloride (0.784 g, 7.54 mmol) was added dropwise over 5 minutes. When the system was dripped, it became cloudy and triethylamine hydrochloride was precipitated. After reacting at room temperature for 1.5 hours, the salt was removed by filtration, and the THF solution side was concentrated without applying heat. The compound D was confirmed by NMR. Oil-like compound D (1.55 g, yield 100%) was obtained.
(Synthesis Example 1: Synthesis of Color Material 1)

(Reaction 9)
To a mixture of Compound A (2.1 g, 6.46 mmol), Compound B (2.0 g, 6.46 mmol), 2,5-di-tert-butylhydroquinone (72 mg, 0.323 mmol) and toluene (35 ml) Phosphorus chloride (0.9 ml, 9.69 mmol) was added and heated to reflux for 5 hours. Water was added and the mixture was extracted with chloroform, and the organic layer was washed 3 times with saturated brine. Concentrate under reduced pressure and silica gel column chromatography (chloroform / methanol =
10 / 1-8 / 1) to obtain Compound E (3.06 g, yield 72.6%).

(Reaction 10)
A mixture of Compound E (365 mg, 0.56 mmol), lithium bis (trifluoromethanesulfonyl) imide (161 mg, 0.56 mmol) and methanol (25 ml) was stirred at 50 ° C. for 1 hour. After concentration under reduced pressure, the obtained solid was washed with methanol / water = 1/2 to obtain a coloring material 1 (410 mg, yield 81.6%).
(Synthesis Example 2: Synthesis of Color Material 2)

(Reaction 11)
Under pressure air blow, Compound A (1.6 g, 4.94 mmol), Compound C (1.5 g, 4.94 mmol), and toluene (10 ml) were placed in a reaction vessel, and cooled to 5 ° C. or less with ice cooling. When the internal temperature was 1-2 ° C., phosphorus oxychloride (0.98 g, 6.42 mmol) was added dropwise over 5 minutes. The mixture was stirred for 1 hour with cooling, and further reacted at room temperature for 5 hours. After the reaction, extracted with water and ethyl acetate. The organic layer was concentrated. Since it solidified, hexane washing was performed twice. Column chromatography (silica gel 60 acidic 100 g, methylene chloride → methylene chloride / methanol = 8 /
2 Developing solvent) Purification was carried out, concentrated and dried to obtain an oily compound F (1.03 g, yield 32.2%).

(Reaction 12)
A reaction vessel was charged with the aforementioned compound F (1.0 g, 1.545 mmol), bis (trifluoromethanesulfonyl) imidolithium (0.443 g, 1.545 mmol) methanol (30 ml), set to 50 ° C. with a water bath, 2 Stir for hours. Thereafter, the mixture was concentrated under reduced pressure, EtOH was added to the tar-like solid several times (about 40 ml each time), the concentration was repeated and further dried in a vacuum dryer at 40 ° C., and then the solid was scraped off. Washing with methanol / water = 1/2, filtration, and drying with hexane. Color material 2 (1.022 g, yield 74%) was obtained after vacuum drying.
(Synthesis Example 3: Synthesis of Color Material 3)

(Reaction 13)
Under pressure air blow, Compound A (1.46 g, 4.5 mmol, TCI), Compound D (1.5 g, 4.5 mmol), and toluene (10 ml) were placed in a reaction vessel, and cooled to 5 ° C. or less with ice cooling. When the internal temperature was 1-2 ° C., phosphorus oxychloride (1.035 g, 6.75 mmol) was added dropwise over 5 minutes. The mixture was stirred for 1 hour with cooling, and further reacted at room temperature for 2 hours. 80 ° C
And stirring was carried out for 5 hours. After completion of the reaction, extracted with water and chloroform. The organic layer was concentrated. Column chromatography (silica gel 60 acidic 150 g, chloroform → chloroform / methanol = 15/1 developing solvent) was purified, concentrated and dried. Compound G (0.92 g, yield 30.5%) was obtained in the form of an oil.

(Reaction 14)
A reaction vessel was charged with the aforementioned compound G (0.9 g, 1.33 mmol), bis (trifluoromethanesulfonyl) imidolithium (0.382 g, 1.33 mmol), methanol (30 ml), set to 50 ° C. with a water bath, Stir for 1.5 hours. After the reaction, the solvent was concentrated, and after sufficiently drying in vacuum, the solid content was scraped off to form a powder. After washing with methanol / water = 1/2 and filtering, dissolve the high-viscosity lump with ethanol, remove the solvent, dry it thoroughly, put it in the refrigerator for several tens of minutes, scrape the solid again, and powder The mixture was stirred with methanol / ice water = 1/2 and filtered while maintaining cooling. The resultant was vacuum-dried at 35 ° C. to obtain Coloring Material 3 (1.05 g, yield 85.7%).

(Reference Synthesis Example 1: Synthesis of Resin A)
145 parts by weight of propylene glycol monomethyl ether acetate was stirred while purging with nitrogen, and the temperature was raised to 120 ° C. 10 parts by weight of styrene, 85.2 parts by weight of glycidyl methacrylate, and 66 parts by weight of monoacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were added dropwise thereto, and 2.2'-azobis-2-methyl 8.47 parts by weight of butyronitrile was added dropwise over 3 hours, and stirring was continued at 90 ° C. for 2 hours. Next, the inside of the reaction vessel was changed to air substitution, 0.7 part by weight of trisdimethylaminomethylphenol and 0.12 part by weight of hydroquinone were added to 43.2 parts by weight of acrylic acid, and the reaction was continued at 100 ° C. for 12 hours. Thereafter, 56.2 parts by weight of tetrahydrophthalic anhydride (THPA) and 0.7 parts by weight of triethylamine were added and reacted at 100 ° C. for 3.5 hours. The binder resin thus obtained had a weight average molecular weight Mw measured by GPC of about 8400, acid value of 80 mgKOH / g.

[Preparation of pigment dispersion]
(Preparation of blue pigment dispersion (1))
As a blue pigment, 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, 3.02 parts by weight of the above-mentioned dispersant “Disperbic 2000” in terms of solid content, and a diameter of 0. A stainless steel container was filled with 215.7 parts by weight of 5 mm zirconia beads and dispersed in a paint shaker for 6 hours to prepare a blue pigment dispersion (1).

(Preparation of blue pigment dispersion (2))
As a blue pigment, C.I. I. Pigment Blue 15: 6 and Violet 23 in a weight ratio of 9.20: 3.81, 11.36 parts by weight as a solvent, 57.5 parts by weight of propylene glycol monomethyl ether acetate as a solvent, the above-mentioned dispersant “Disperbic 2000” Was filled in a stainless steel container with 215.7 parts by weight of zirconia beads having a diameter of 0.5 mm in terms of solid content, and dispersed in a paint shaker for 6 hours to prepare a blue pigment dispersion.

[Preparation of colored resin composition]
Using the dye and blue pigment dispersion obtained in the above (Synthesis of dye), other components were mixed so as to have the composition described in Table 1 to prepare a colored resin composition.
In addition, all the numerical values in Table 1 represent parts by weight of each component to be added.
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 1 represent parts by weight of each component to be added.
Moreover, each compound in Table 1 is as follows.
PGMEA: Propylene glycol monomethyl ether acetate PGME: Propylene glycol monomethyl ether [Production of colored resin film and evaluation of solvent resistance]
Each colored resin composition is applied onto a glass substrate cut into 5 cm square by spin coating so that the y value after drying is 0.085, dried under reduced pressure, and then heated at 80 ° C. on a hot plate. Pre-baked for 3 minutes. Thereafter, the entire surface was exposed with an exposure amount of 60 mJ / cm ² and baked at 230 ° C. for 30 minutes in a clean oven. 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.
Subsequently, after the substrate was immersed in PGMEA for 30 minutes, the spectral transmittance was measured as described above, and the chromaticity (C light source) in the XYZ color system was calculated. Table 2 summarizes the results of measuring the color difference (ΔE * ab) from the chromaticity after immersion, that is, the solvent resistance.

As shown in Table 2, it can be seen that a pixel formed using the composition containing the dye of the present invention has high luminance and excellent solvent resistance.
More specifically, Comparative Example 1 uses pigments (CIPB15: 6 and CIPV23) as the main component of the color material, and the solvent resistance is 4 or less. However, the luminance has almost reached its peak, and it has not been possible to meet the demand for luminance enhancement.

On the other hand, in Examples 1 to 3, in addition to the solvent resistance being 4 or less, which is a practical level, it was possible to show a value higher than the luminance of the blue pigment.
That is, by using the dye of the present invention, it is possible to meet the demand for improvement in luminance.

Claims (9)

A dye comprising the compound represented by the following formula (IV):

(In the above formula (IV), R ³¹ and R ³² are each independently an alkyl group having 1 to 8 carbon atoms which may have a substituent, or 2 to 2 carbon atoms 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 ³¹ and R ³² may be bonded to each other to form a ring.
R ^{41 to} R ⁴⁶ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. R ⁴¹ and R ⁴² , and R ⁴³ and R ⁴⁴ may be bonded to each other to form a ring structure.
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.
Moreover, the benzene ring and indole ring in the above formula (IV) may further have an arbitrary substituent.
The cationic structural formula of the above formula (IV) has a crosslinkable group. ) The dye according to claim 1 , wherein the crosslinkable group is any one of the following <crosslinkable group group T '>.
<Crosslinkable group T '>

(A) a coloring material, (B) a solvent, and (C) a binder resin,
(A) The coloring material contains the dye according to claim 1 or 2 ,
Colored resin composition. The colored resin composition according to claim 3 , further comprising (D) a polymerizable monomer. The colored resin composition according to claim 3 or 4 , further comprising (E) a photopolymerization initiation system and / or a thermal polymerization initiation system. Furthermore, (A) a coloring material contains the (F) pigment, The colored resin composition as described in any one of Claims 3-5 characterized by the above-mentioned. It has a pixel formed using the colored resin composition as described in any one of Claims 3-6 , The color filter characterized by the above-mentioned. A liquid crystal display device comprising the color filter according to claim 7 . An organic EL display device comprising the color filter according to claim 7 .

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