JP6160076B2 - Dye for color filter, colored resin composition, color filter, liquid crystal display device and organic EL display device - Google Patents

Description

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

Flat panel displays such as liquid crystal display devices and organic EL display devices are widely used, and color filters are used for these displays.
With the trend of energy saving, color filters are required to have higher brightness and higher contrast.
For the color filter, a colored resin composition using a pigment is mainly used. In order to obtain high brightness and high contrast, for example, in Non-Patent Document 1, the particle diameter of pigment particles is set to 1 of the coloration wavelength. Disclosed is a method of finely dispersing to / 2 or less.

However, since the blue pigment has a shorter coloration wavelength than other red and green pigments in particular, further fine dispersion is required in this case, which causes a problem of cost increase and stability after dispersion.
On the other hand, dyes have been developed as coloring materials.
For example, Patent Documents 1 and 2 disclose using a triarylmethane derivative having an indole ring as a dye.

JP 2011-070172 A JP 2011-068866 A

Kiyoshi Hashizume, “Color Material Association”, December 1967, p608

However, in Patent Documents 1 and 2, although the luminance is improved as compared with the case of using a blue pigment, the intermolecular counter ion dye with an anion having a dye skeleton has absorption derived from the anion at 400 nm to 500 nm. There was a problem that the transmittance of the liquid crystal was lowered.
In addition, when the dyes described in Patent Documents 1 and 2 are used, the present inventors may have insufficient voltage holding ratio of the obtained pixel when compared with the pigment. In some cases, the liquid crystal display device includes display unevenness or alignment failure. The reason why the voltage holding ratio of the obtained pixel is insufficient when the dyes described in Patent Documents 1 and 2 are used is estimated as follows.

As disclosed in Patent Documents 1 and 2, when the dye has a counterion structure between molecules, particularly when a liquid crystal phase is laminated on a pixel formed using a colored resin composition, There is a possibility of elution more easily than nonionic dyes.
As a factor that the voltage holding ratio is lowered, the dye and / or ions derived from the dye are eluted into the liquid crystal by the heat treatment in the element manufacturing process.

In addition, as an example of the structure of the element, when the element is formed in the order of the pixel, the electrode, and the liquid crystal phase, there is a defect in the electrode film laminated on the pixel, and the curable property of the pixel corresponding to the defective part is For example, the dye in the pixel and ions derived from the dye may elute into the liquid crystal because of low reason.
In order to support this presumption, the present inventors have further studied the present invention in the following two steps.

As the first step, whether or not the dye is dissolved in the liquid crystal was examined by mixing the colored resin composition containing the dye and the liquid crystal and coloring the dye color. Here, when the dye is colored, it means that the dye is easily dissolved in the liquid crystal.
In a further study, as a second step, with respect to the dye not colored in the first step, parameters calculated from waveform analysis obtained by ion density measurement, movement of the liquid crystal while applying a specific electric field at a certain frequency to the liquid crystal cell. Examination was conducted with a polarizing microscope.

The reason for this is that the amount of ions that affect electrical reliability depends on the state of ions when dissolved, that is, the charge density and charge distribution, the type of substituents that the ions have, the degree of fluorine atom content, etc. This is because it was supposed to depend.
Therefore, an object of the present invention is to provide a colored resin composition capable of obtaining a color filter with improved luminance and a good voltage holding ratio as compared with the case where a pigment is used as a coloring material.

  Another object of the present invention is to provide a color filter having pixels formed using the colored resin composition, a high-quality liquid crystal display device, and an organic EL display device.

As a result of intensive studies by the present inventors based on the above assumption, it has been found that the above problems can be solved by using a dye having a specific structure, and the present invention has been completed.
That is, the present invention includes a color filter dye represented by the following formula (I) (hereinafter sometimes referred to as “the dye (I) of the present invention”) and the color filter dye. It exists in a colored resin composition, a color filter, a liquid crystal display device, and an organic EL display device.

(In the above formula, R ^{1 to} R ⁶ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
Adjacent R ^{1 to} R ⁶ may be connected to each other to form a ring, and the ring may have a substituent.

R ⁷ and R ⁸ each independently represents a hydrogen atom or an arbitrary substituent.
R ⁷ and R ⁸ may be connected to each other to form a ring, and the ring may have a substituent.
Further, the benzene ring and indole ring in the above formula (I) may further have an arbitrary substituent.

M ⁺ represents a hydrogen ion, an alkali metal cation, an alkaline earth metal cation, an ammonium cation or a quaternary ammonium cation.
n represents an integer of 0 to 4. )

According to the present invention, the luminance of the obtained pixel is improved as compared with the case where a pigment is used as a coloring material, and the luminance of the obtained pixel is maintained or improved when a dye is used, and the voltage holding ratio is increased. It becomes possible to provide a colored resin composition capable of forming a high-quality pixel.
Furthermore, the color filter of the present invention is excellent in luminance, heat resistance and voltage holding ratio, and the liquid crystal display device and organic EL display device of the present invention are of high quality.

It is a section schematic diagram showing an example of an organic EL device which has a color filter of the present invention. 1 represents a modeling diagram for Compound A-1. It is a direct peak figure which appears by the orientation of a liquid crystal in an Example.

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 of the present invention other than the solvent components described later.
Furthermore, “aromatic ring” means both “aromatic hydrocarbon ring” and “aromatic heterocycle”.
Moreover, terms such as “CI Pigment Green” mean a color index (CI).
First, the dye (I) of the present invention will be described in detail.
[Dye (I) of the present invention]

(In the above formula, R ^{1 to} R ⁶ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
Adjacent R ^{1 to} R ⁶ may be connected to each other to form a ring, and the ring may have a substituent.

R ⁷ and R ⁸ each independently represents a hydrogen atom or an arbitrary substituent.
R ⁷ and R ⁸ may be connected to each other to form a ring, and the ring may have a substituent.
Further, the benzene ring and indole ring in the above formula (I) may further have an arbitrary substituent.
M ⁺ represents a hydrogen ion, an alkali metal cation, an alkaline earth metal cation, an ammonium cation or a quaternary ammonium cation.
n represents an integer of 0 to 4. )

[Structural features and molecular design]
The dye (I) is a triarylmethane dye having one or more sulfo groups in the molecule and an indole ring.
The characteristics of the dye (I) will be described below.
First, the dye (I) can form a salt only with the structure represented by the formula (I) and can exist as a dye. In a conventional triarylmethane dye having an indole ring of an intermolecular salt, it is known that a dye having a different skeleton is used as an anion in order to enhance durability (heat resistance and light resistance). However, in this case, the transmittance decreases due to absorption of the visible part of the anionic dye. On the other hand, since the dye (I) can exist only in the structure represented by the formula (I), the spectral characteristics of the triarylmethane dye having a steep absorption spectrum shape can be fully utilized. As a result, a color filter made of a colored resin composition having high transmittance, that is, high luminance is obtained.

From the viewpoint of voltage holding ratio, it is preferable to form a salt only with the structure represented by (I). For this reason, when n is 0 in (I), (I) is neutral in charge, and does not move even if eluted in hydrophobic liquid crystal. When n is 1 or more, there are n groups represented by sulfo groups in the form of a free acid, and if they are eluted into the liquid crystal, they are present as ions, which may reduce the voltage holding ratio. Therefore, as for the ion binding energy of the counter ion dye, comparison was made between the ion binding energy of the intermolecular counter ion dye and the ion binding energy of the intramolecular counter ion dye in which n is 1 and the sulfo group is a sodium salt. In addition, the following ion bond energy is calculated | required with the calculation tool described below. Ion bond energy (E _{ion bond} ) was calculated according to the following definition.

E _{ion bond} = E (counter ion)-(E (cation) + E (anion))
Here, E (counter ion), E (cation), and E (anion) are total energies in the stable structure of the counter-ion, cation, and anion, respectively, and calculated at the B3LYP level, which is a kind of hybrid density functional theory. It is the value. The basis set used for the calculation was 6-31G (d), and Gaussian 03 was used as a tool.
As an example, the ion binding energy of the following intermolecular counter ion dye was 64.4 kcal / mol.

  On the other hand, the ion binding energy was calculated in the same manner for the dye (I) of the present invention, that is, the intramolecular counter ion dye. For example, the ion bond energy of a compound represented by the following structure (hereinafter sometimes referred to as “compound (A)”) was 120.2 kcal / mol (in this case, the calculated ion bond energy is This is the dissociation of O-Na.)

In the case of the triarylmethane structure, if it is a sufficiently small anion, it is considered that it is located in the gap between the central carbon cation portions and can form a strong bond even between molecules.
From the simulation by calculation, when the intermolecular counter ionic dye is used, stabilization by sufficient ionic bond energy cannot be secured, and ions are affected by the effects of solvation, interaction with surrounding resin, heat, electric field, etc. They may dissociate and may dissolve or be compatible with the liquid crystal. That is, in the dye (I) in which n is 1 or more, the ionic bond of the dye (I) is sufficiently larger than the ionic bond between the central carbon cation and the anion between the molecules, and the ions from the dye (I) The possibility of elution into the liquid crystal is considered to be small.

From the above, in terms of molecular design, the ion binding energy of the dye (I) is 80 KCal / mol or more, more preferably 100 KCal / mol or more, and still more preferably 120 KC.
Al / mol is suggested.
Also, in the case of the following structure, it is possible to approximately calculate the electrostatic interaction (ion bond energy) between the triarylmethane cation and the sulfo group introduced as a substituent in the molecule. In that case, a result that an energy of about 100 kcal / mol, which is close to the result of the dissociation of O-Na, is obtained is obtained, and a more stable structural energy is obtained for the intermolecular ionic dye. You can see that it has.

  Further, the dye (I) is expected to have a strong ionic bond within the molecule or between the molecules. The central carbocation portion of the dye (I) has a relatively high charge density, and forms a salt when a sulfo group enters the gap between three aryl groups arranged around it. When the cation moiety and the sulfo group form a salt in one dye molecule, it is considered that a strong salt can be formed by arranging the anion portion and the cation portion close to each other. On the other hand, when a salt is formed between two molecules, it is considered that a cation site and an anion site of each molecule form a salt at two points, and a stronger salt can be formed than when the structures of the cation and anion are different. . In addition, when a salt is formed between multiple molecules, two points of salt can be formed per molecule, and the structure of the formed molecular assembly is expected to form a regular repeating unit. It is considered that they are arranged very close to each other and can form a strong salt as compared with the case where the structures of are different. On the other hand, regarding the number of sulfo groups in the dye (I), the greater the number of sulfo groups, the closer the positions of the anions and cations are, and thus it is considered that they have a strong bond.

  The following can be considered as an effect by having a strong ionic bond. In the dye (I), since the cation and the anion are difficult to separate, the cation and the anion are difficult to move even in an electric field, and the voltage holding ratio of the obtained pixel is increased. In addition, the voltage holding ratio of the pixel is increased by suppressing the dissociation of the counter ions and the decomposition of the dye during the heat treatment or the application of an electric field in the element manufacturing process. Moreover, durability (heat resistance, light resistance, etc.) is improved by strong intermolecular forces, dyes are difficult to decompose during firing, and a decrease in transmittance is avoided, and from a colored resin composition having high transmittance, that is, high luminance. A color filter is obtained.

In the dye (I) of the present invention, the ionic bond strength is estimated by the ionic bond energy, and the ionic bond energy varies depending on the distance between the “cation” of the central carbon atom and the “anion” of the sulfo group. It is considered a thing.
In the dye (I) of the present invention, the distance between “cation” and “anion” includes the following two points.
(1) In one molecule of dye (I), the distance between the cation (C ⁺ ) of the central carbon atom and the anion (O ⁻ ) of the sulfo group (hereinafter referred to as “distance (1) of the present invention”) There is)
(2) Between two or more molecules of the dye (I), for example, the distance between the cation (C ⁺ ) of the central carbon atom of one dye molecule and the anion (O ⁻ ) of the sulfo group of another dye molecule ( Hereinafter, it may be referred to as “distance (2) of the present invention”)
For example, in the dye (I), the distance (1) of the present invention is different as follows. The distance (1) of the present invention is obtained by a calculation tool described below.

In this sense, the fact that the positional relationship between the cation and the anion can be greatly changed, and that the steric structure of the cation can be adjusted by the adjacent substituent, has been clarified by this study. This is a special effect of a combination of I) with an inner salt or a sulfo group.
The above calculation is a calculated value obtained by obtaining a stable structure by structure optimization calculation using the B3LYP method which is a kind of density functional calculation method.

The basis function system used for the calculation was 6-31G (d), and Gaussian 03 was used as a tool.
The above calculation method is not limited to the above calculation method, and other calculation methods may be used, but the above calculation method is preferably used.

(For ^R 1 ^{~R 6)}
R ^{1 to} R ⁶ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
Examples of the alkyl group in R ^{1 to} R ⁶ include linear, branched, or cyclic alkyl groups having 1 or more carbon atoms and usually 8 or less, preferably 5 or less carbon atoms. . Specific examples include methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group, isobutyl group, tert-butyl group, cyclohexyl group and the like.
Examples of the aromatic ring group in R ^{1 to} R ⁶ include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.

  The aromatic hydrocarbon ring group may be a single ring or a condensed ring, and is not particularly limited as long as the number of carbon atoms forming the ring is 5 to 18, but for example, one free valence Benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring and the like.

  In addition, the aromatic heterocyclic group may be a single ring or a condensed ring, and is not particularly limited as long as the number of carbon atoms forming the ring is 3 to 10, but for example, one free atom Having a valence, furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole Ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, Synoline ring, quinoxaline ring, phenanthridine ring, Zone imidazole ring, perimidine ring, a quinazoline ring, a quinazolinone ring, groups such as azulene ring.

The free valence in the present invention is based on the description in “Organic Chemistry / Biochemical Nomenclature” (Nanedo, published May 20, 1992, translated by Kenzo Hirayama and Kazuo Hirayama, pages 11-12). It is.
Adjacent R ^{1 to} R ⁶ may be connected to form a ring, and the ring 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 good aromatic hydrocarbon group having 6 to 10 carbon atoms.
It has the C1-C8 alkyl group or substituent which may have a substituent more preferably at the point which improves the heat resistance of dye (I) and the heat resistance of the color filter obtained is excellent. It may be an aromatic hydrocarbon group having 6 to 10 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms or a phenyl group which may have a substituent.

When at least one of R ^{1 to} R ⁴ is an optionally substituted alkyl group having 1 to 8 carbon atoms, it is presumed that the charge in the cation is dispersed by hyperconjugation and the cation is stabilized. Is done.
In addition, when at least one of R ^{1 to} R ⁴ is an optionally substituted aromatic hydrocarbon group having 6 to 10 carbon atoms, the conjugated system is extended, so that the charge in the cation is dispersed. Thus, the cation is stabilized. As described above, it can be considered that as a result of stabilization of the cation, the heat resistance of the obtained color filter is further improved.
That is, R ^{1 to} R ⁴ are each an optionally substituted alkyl group having 1 to 8 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 10 carbon atoms. Is preferred.
Examples of the substituent that the alkyl group, aromatic ring group, and ring formed by connecting to each other in R ^{1 to} R ⁶ may have include the following (substituent group W).

(Substituent group W)
C1-C8 alkyl group, C2-C8 alkenyl group, C1-C8 alkoxy group, C6-C15 aryl group, C2-C9 alkylcarbonyloxy group, C7 -16 arylcarbonyloxy group, C2-C9 alkoxycarbonyl group, C7-C16 aryloxycarbonyl group, carbamoyl group, C2-C9 alkylcarbamoyl group, C7-C16 arylcarbamoyl Group, sulfamoyl group, alkylsulfamoyl group having 1 to 8 carbon atoms, arylsulfamoyl group having 6 to 15 carbon atoms, alkylcarbonyl group having 2 to 9 carbon atoms, arylcarbonyl group having 7 to 16 carbon atoms, carbon An alkylsulfonyl group having 1 to 8 carbon atoms, an alkylsulfonylamino group having 1 to 8 carbon atoms, and an arylsulfonylamino group having 6 to 15 carbon atoms An amino group, an alkylamino group formed by bonding an alkyl group having 1 to 8 carbon atoms, a dialkylamino group formed by bonding an alkyl group having 1 to 4 carbon atoms, an arylamino group having 6 to 15 carbon atoms, or 6 carbon atoms An arylalkylamino group formed by bonding an aryl group having 15 to 15 carbon atoms and an alkyl group having 1 to 4 carbon atoms, a diarylamino group formed by bonding an aryl group having 6 to 15 carbon atoms, a phenethyl group, a hydroxyethyl group, 1 carbon atom ˜8 alkylcarbonylamino group, C7-16 arylcarbonylamino group, dialkylaminoethyl group formed by bonding of C1-4 alkyl group, trifluoromethyl group, C1-8 trialkyl Silyl group, alkylthio group having 1 to 8 carbon atoms, arylthio group having 6 to 15 carbon atoms, hydroxy group, nitro group, cyano group, carboxy group, sulfo group Group, a fluorine atom, a halogen atom such as a chlorine atom.

Specific examples of the aryl group in the substituent group W include those described as the aromatic ring groups in R ^{1 to} R ⁶ . The aryl group is a lower alkyl group such as a methyl group or an ethyl group, a lower alkoxy group such as a methoxy group or an ethoxy group, a nitro group, a trifluoromethyl group, a cyano group, a carbamoyl group, a sulfamoyl group, a fluorine atom, or a chlorine atom. May be further substituted as a substituent.

Especially, as a substituent which the alkyl group in R < ¹ > -R < ⁶ >, an aromatic ring group, and the ring formed by mutually connecting may have, Preferably it is a C1-C8 alkyl group, C1-C1 8 alkoxy group, phenyl group, tolyl group, alkylcarbonyloxy group having 2 to 9 carbon atoms, carbamoyl group, sulfamoyl group, alkylsulfamoyl group having 1 to 8 carbon atoms, trifluoromethyl group, cyano group, sulfo group And a fluorine atom.

(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.
In the benzene ring in the formula (I), when a bulky group is bonded at the o-position to the carbon atom located at the center of the triarylmethine structure, the planarity of the molecule is inhibited, and the dye (I) The color purity of the color may be reduced. Accordingly, it is preferable that the o-position does not have a substituent or is substituted with a halogen atom or an alkyl group having 1 to 8 carbon atoms.

In addition, it is preferable that this C1-C8 alkyl group is a C1-C4 alkyl from the point that steric hindrance is small and the heat resistance of dye (I) improves further.
R ⁷ and R ⁸ may be connected to each other to form a ring, and the ring may have a substituent. Examples of the substituent include those described in the above section (Substituent group W).

When R ⁷ and R ⁸ are linked to form a ring, these may be a ring bridged with a heteroatom.
Examples of the structure of the linking moiety of R ⁷ and R ⁸ include the following. The structure of these connecting portions may have a substituent.

(In the above, R ^1b and R ^2b each independently represent a hydrogen atom or an alkyl group.)
R ^1b and R ^2b are preferably a hydrogen atom or a methyl group from the viewpoint that the molecular planarity of (I) is high and the molecules easily associate with each other and have high heat resistance.
When the obtained color filter is purple, it is preferable that R ⁷ and R ⁸ are not connected to each other to form a ring from the viewpoint of high luminance.

In addition, when the color filter to be obtained is red, it is preferable that they are connected to each other to form a ring from the viewpoint of high luminance.
In addition, the benzene ring and indole ring in formula (I) may further have an arbitrary substituent. As the substituent that the benzene ring and indole ring in formula (I) may have, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, carbon A C1-C8 alkoxy group, a C1-C10 alkylamino group, etc. are mentioned.

(About M ⁺ and n)
M ⁺ represents a hydrogen ion, an alkali metal cation, an alkaline earth metal cation, an ammonium cation or a quaternary ammonium cation.
Examples of the alkali metal of the alkali metal cation include lithium, sodium, and potassium. Examples of the alkaline earth metal of the alkaline earth metal cation include magnesium, calcium, and barium.
The ammonium cation represents —N ⁺ HR ₃ (R represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. R may be the same or different.

Examples of the preferred carbon number of the alkyl group in R and the substituents that may be present are the same as those exemplified for the alkyl groups of R ^{1 to} R ⁶ . Examples of the preferable number of carbon atoms of the aromatic ring group and the substituents that may be included are the same as those exemplified for the aromatic ring groups of R ^{1 to} R ⁶ . Specifically, a lower alkyl ammonium cation having 1 to 6 carbon atoms (for example, methyl ammonium cation, ethyl ammonium cation, diethyl ammonium cation, triethyl ammonium cation, etc.), an alkyl ammonium cation having 1 to 6 carbon atoms substituted with a hydroxy group. (Eg, ethanolammonium cation, diethanolammonium cation, triethanolammonium cation, etc.), carboxy-substituted alkylammonium cations having 1 to 6 carbon atoms (eg, carboxymethylammonium cation, carboxyethylammonium cation, carboxypropylammonium cation, Carboxymethylammonium cation, etc.), ammonium cation substituted with an aromatic ring group and an alkyl group (for example, N N- diethyl-phenyl ammonium cation and the like) and the like.

The quaternary ammonium cation is represented by —N ⁺ R ₄ , and R represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent. A plurality of Rs may be the same or different. The preferred carbon number of the alkyl group and examples of the substituent which may be present are the same as those exemplified in the case of the alkyl group of R ^{1 to} R ⁶ . Examples of the preferable number of carbon atoms of the aromatic ring group and the substituents that may be included are the same as those exemplified for the aromatic ring groups of R ^{1 to} R ⁶ .

Specific examples include quaternary alkylammonium cations having 1 to 6 carbon atoms (for example, tetramethylammonium cation, tetraethylammonium cation, tetrabutylammonium cation, etc.).
In addition, the kind of the cation of M ⁺ is not limited to one kind, and a plurality of kinds may be mixed. Moreover, multiple types may be mixed in one molecule of a compound, and multiple types may be mixed in the colored resin composition.

Preferred as M ⁺ is a hydrogen ion, an alkali metal cation, an ammonium cation, or a quaternary ammonium cation from the viewpoint of solubility in an organic solvent used in the colored resin composition, and more preferably a lithium cation or a sodium cation. An unsubstituted ammonium cation and a tetrabutylammonium cation are preferable.
n represents an integer of 0 to 4.

The larger n is, the more the sulfo group of the dye (I) is substituted, and the heat resistance and light resistance are improved, and the solubility of the dye (I) in the hydrophobic liquid crystal is also reduced. Although the voltage holding ratio is also improved, the solubility in the organic solvent used for the colored resin composition may be reduced.
Further, when the number of substituted sulfo groups increases, the shape of the absorption spectrum of the dye becomes broad, and the luminance of the obtained pixel may be lowered.
Therefore, n is preferably 0 to 2 in consideration of the voltage holding ratio, the solubility in an organic solvent, and the luminance of the obtained pixel.

[Dye (I-1)]
The dye (I) of the present invention is a color filter dye represented by the following formula (I-1) (hereinafter referred to as “this”) in that the color purity and transmittance of the obtained pixel are excellent when used as a color filter. It may be referred to as “the dye (I-1) of the invention”).

(In the above formula, R ^{11 to} R ¹⁶ each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
Adjacent R ^{11 to} R ¹⁶ may be connected to each other to form a ring, and the ring may have a substituent.

R ¹⁷ and R ¹⁸ each independently represents a hydrogen atom or an arbitrary substituent.
R ¹⁷ and R ¹⁸ may be connected to each other to form a ring, and the ring may have a substituent.
Moreover, the benzene ring and indole ring in the above formula (I-1) may further have an arbitrary substituent. )
The above formula (I-1) SO ₃ shown in ^- group indicates that it is substituted on any carbon of the indole ring. Moreover, when the sulfo group is substituted in the benzene ring in the above formula (I-1) and R ^{11 to} R ¹⁸ described below, the sulfo group is M ⁺ represented by the above formula (I). A salt may be formed.

(About R ^{11 to} R ¹⁶ )
R ^{11 to} R ¹⁶ are respectively synonymous with R ^{1 to} R ⁶ in the dye (I). Specific examples and preferred embodiments are also the same.
(About R ¹⁷ and R ¹⁸ )
R ¹⁷ and R ¹⁸ are respectively synonymous with R ^{7 to} R ⁸ in the dye (I). Specific examples and preferred embodiments are also the same.

[Dye (I-2)]
The dye (I) of the present invention is a color filter dye represented by the following formula (I-2) (hereinafter referred to as “this”) in that the color purity and transmittance of the obtained pixel are excellent when used as a color filter. It may be referred to as “the dye (I-2) of the invention”).

(In the above formula, R ^{21 to} R ²⁵ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
Adjacent R ^{21 to} R ²⁵ may be linked to form a ring, and the ring may have a substituent.

R ²⁷ and R ²⁸ each independently represent a hydrogen atom or an arbitrary substituent.
R ²⁷ and R ²⁸ may be bonded to each other to form a ring, and the ring may have a substituent.
Q ² is a divalent aromatic ring group that may have a substituent, a divalent aliphatic hydrocarbon group that may have a substituent, or a divalent that may have a substituent. An aliphatic heterocyclic group, one group selected from the group consisting of —C (═O) —, —O—, —S— and —NH—, or a group formed by bonding two or more of these.

Moreover, the benzene ring and indole ring in the above formula (I-2) may further have an arbitrary substituent. )
When the sulfo group is substituted in the benzene ring, indole ring, Q ² , R ^{21 to} R ²⁵ and R ^{27 to} R ²⁸ described below in the formula (I-2), the sulfo group is A salt may be formed with M ⁺ shown in (I).

(About R ^{21 to} R ²⁵ )
R ^{21 to} R ²⁵ are respectively synonymous with R ^{1 to} R ⁶ in the dye (I). Specific examples and preferred embodiments are also the same.
(For ^{R 27} and ^{R 28)}
R <^27> and R < ²⁸ > are synonymous with R < ⁷ > -R < ⁸ > in dye (I), respectively. Specific examples and preferred embodiments are also the same.

(For ^{Q 2)}
Q ² is a divalent aromatic ring group that may have a substituent, a divalent aliphatic hydrocarbon group that may have a substituent, or a divalent that may have a substituent. An aliphatic heterocyclic group, one group selected from the group consisting of —C (═O) —, —O—, —S— and —NH—, or a group formed by bonding two or more of these.

The divalent aromatic ring group shall have two free valences in the aromatic ring having one free valence described in the above section (for R ^{1 to} R ⁶ ), and Examples include groups having 2 to 14 carbon atoms. Examples of the substituent that these groups may have include those described above in (Substituent group W).
The divalent aliphatic hydrocarbon group is a linear, branched or cyclic group and is an aliphatic hydrocarbon group, the carbon number of which is usually 1 or more, and usually 8 or less, preferably Is 6 or less. Specific examples include an alkylene group having 1 to 8 carbon atoms, a cyclopentanediyl group, and a cyclohexanediyl group. Examples of the substituent that these groups may have include those described above in (Substituent group W).

  Examples of the divalent aliphatic heterocyclic group include piperidinyl group, pyrrolidinyl group, imidazolidinyl group, pyrazolidinyl group, piperazinyl group, morpholinyl group, indolinyl group, isoindolinyl group and the like. Examples of the substituent that these groups may have include those described above in (Substituent group W).

[Dye (I-3)]
The dye (I) of the present invention is a color filter dye represented by the following formula (I-3) (hereinafter referred to as “present”) in that the color purity and transmittance of the obtained pixel are excellent when used as a color filter. It may be referred to as “the inventive dye (I-3)”.

(In the above formula, R ^{31 to} R ³³ and R ^{35 to} R ³⁶ are each independently a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. Indicates.
Q ³ is a divalent aromatic ring group that may have a substituent, a divalent aliphatic hydrocarbon group that may have a substituent, or a divalent that may have a substituent. An aliphatic heterocyclic group, one group selected from the group consisting of —C (═O) —, —O—, —S— and —NH—, or a group formed by bonding two or more of these.

Adjacent R ³¹ and R ³² , R ³³ and Ar ^1, and R ³⁵ and R ³⁶ may be linked to each other to form a ring, and the ring may have a substituent.
R ³⁷ and R ³⁸ each independently represents a hydrogen atom or an arbitrary substituent.
R ³⁷ and R ³⁸ may be connected to each other to form a ring, and the ring may have a substituent.

Moreover, the benzene ring and indole ring in the above formula (I-3) may further have an arbitrary substituent. )
When a sulfo group is substituted in the benzene ring, indole ring, Q ³ , R ^{21 to} R ²⁵ and R ^{27 to} R ²⁸ described below in the above formula (I-3), the sulfo group has the above formula. A salt may be formed with M ⁺ shown in (I).

(About R ^{21 to} R ²⁵ )
R ^{21 to} R ²⁵ are respectively synonymous with R ^{1 to} R ⁶ in the dye (I). Specific examples and preferred embodiments are also the same.
(For ^{R 27} and ^{R 28)}
R <^27> and R < ²⁸ > are synonymous with R < ⁷ > -R < ⁸ > in dye (I), respectively. Specific examples and preferred embodiments are also the same.

(For ^{Q 3)}
Q ³ is a divalent aromatic ring group that may have a substituent, a divalent aliphatic hydrocarbon group that may have a substituent, or a divalent that may have a substituent. An aliphatic heterocyclic group, one group selected from the group consisting of —C (═O) —, —O—, —S— and —NH—, or a group formed by bonding two or more of these.

The divalent aromatic ring group shall have two free valences in the aromatic ring having one free valence described in the above section (for R ^{1 to} R ⁶ ), and Examples include groups having 2 to 14 carbon atoms. Examples of the substituent that these groups may have include those described above in (Substituent group W).
The divalent aliphatic hydrocarbon group is a linear, branched or cyclic group and is an aliphatic hydrocarbon group, the carbon number of which is usually 1 or more, and usually 8 or less, preferably Is 6 or less. Specific examples include an alkylene group having 1 to 8 carbon atoms, a cyclopentanediyl group, and a cyclohexanediyl group. Examples of the substituent that these groups may have include those described above in (Substituent group W).

  Examples of the divalent aliphatic heterocyclic group include piperidinyl group, pyrrolidinyl group, imidazolidinyl group, pyrazolidinyl group, piperazinyl group, morpholinyl group, indolinyl group, isoindolinyl group and the like. Examples of the substituent that these groups may have include those described above in (Substituent group W).

[Molecular weight]
The molecular weight of the dye (I) of the present invention is usually 500 or more, preferably 600 or more, and usually 5000 or less, preferably 2000 or less.
It is preferable that it is within the above-mentioned range in terms of good solubility in a solvent and easy production.
The preferred specific examples of the dye (I) of the present invention are shown below, but the present invention is not limited thereto.
[Specific Examples of Dye (I)]

The dye (I) of the present invention is preferably the dye (I-1) or the dye (I-2) in that the obtained pixel has high luminance and high voltage holding ratio.
[Synthesis method]
The compound represented by the dye (I) is, for example, J. Chem. Soc., PerkinTrans. 1998, 2,297.
It can be synthesized according to the method described in International Publication No. 2006/120205, “Review Review Synthetic Dyes” (Horiguchi Hiroshi, Sankyo Publishing, 1968).

(Content)
The colored resin composition of the present invention contains the dye (I) in the total solid content, preferably 0.01% by weight or more, more preferably 0.1% by weight or more, particularly preferably 1% by weight or more, and preferably It is contained in a proportion of not more than 50% by weight, more preferably not more than 40% by weight, particularly preferably not more than 30% by weight.

It is preferable for it to be less than or equal to the above upper limit because the curability of the coating film is unlikely to decrease and the film strength is sufficient. Moreover, since it is sufficient for coloring power to be more than the said minimum, since the chromaticity of a desired density | concentration is easy to be obtained and it is hard to become thick, it is preferable.
In the colored resin composition of this invention, only 1 type of dye (I) may be contained as (A) dye, and 2 or more types may be contained.

Furthermore, 1 type (s) or 2 or more types of other dyes other than dye (I) may be contained. Further, the content of all (A) dyes in the colored resin composition is preferably 0.1% by weight or more, or preferably 50% by weight or less, more preferably 40% by weight or less, in the colored resin composition. .
In the colored resin composition of the present invention, the content of the dye (I) is preferably 5% by weight or more, more preferably 10% by weight or more in the solid content of the total (A) dye.

[(B) Solvent]
The solvent (B) contained in the colored resin composition of the present invention has a function of adjusting the viscosity by dissolving or dispersing each component contained in the colored resin composition.
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, cyclohexyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, isobutyric acid Methyl, ethyl caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3- Linear or cyclic esters such as butyl methoxypropionate, 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:
These solvents may be used alone or in combination of two or more.

Of these solvents, glycol monoalkyl ethers are preferred from the viewpoint of the solubility of the dye (A) in the present invention. Among these, propylene glycol monomethyl ether is particularly preferable from the viewpoint of solubility of various components in the colored resin composition.
In addition, for example, in the case of containing a pigment (F) described later as an optional component, the balance of coatability, surface tension, etc. is good, and from the viewpoint that the solubility of the constituent components in the colored resin composition is relatively high, It is more preferable to use a mixture of glycol alkyl ether acetates. In addition, in colored resin compositions containing pigments, glycol monoalkyl ethers are highly polar and tend to aggregate the pigment, which may reduce storage stability, such as increasing the viscosity of the colored 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. .

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

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. When the ratio of such a high boiling point solvent is less than 50% by weight, the effect of preventing evaporation of the solvent from the ink droplets may not be sufficiently exhibited.

  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. When the content of the (B) solvent in the composition exceeds 99% by weight, the concentration of each component excluding the (B) solvent becomes too small and may be inappropriate for forming a coating film. . On the other hand, the lower limit of the content of the solvent (B) is usually 75% by weight, preferably 80% by weight, and more preferably 82% by weight in consideration of viscosity suitable for coating.

[(C) Binder resin]
(C) What preferable binder resin changes with the hardening means of a colored resin composition.
When the colored resin composition of the present invention is a photopolymerizable resin composition, examples of the (C) binder resin include JP-A-7-2072111, JP-A-8-259876, and JP-A-10-300922. The polymer compounds described in JP-A-11-140144, JP-A-11-174224, JP-A-2000-56118, JP-A-2003-233179, and the like can be used. However, among them, the following resins (C-1) to (C-5) are preferable.

(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 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 the strength of the film 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 developer are preferable.
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.
Content of (C) binder resin in a colored resin composition is 0.1 to 80 weight% normally in a total solid, Preferably it is 1 to 60 weight%.
Within the above range, the adhesion to the substrate is good, the permeability of the developer to the exposed area is moderate, and the surface smoothness and sensitivity of the pixels are good.

[(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 component 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 may be a single substance or 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) dye 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 component and / or thermal polymerization initiation component]
The colored resin composition of the present invention preferably contains (E) a photopolymerization initiation component and / or a thermal polymerization initiation component 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 component that has a function of generating a polymerization active radical and / or a thermal polymerization initiating component that generates a polymerization active radical by heat. In the present invention, the component (E) as a photopolymerization initiation component refers to a photopolymerization initiator (hereinafter also referred to as “(E1) component”), a polymerization accelerator (hereinafter, optionally referred to as “(E2) component”). ")" And a sensitizing dye (hereinafter also referred to as "(E3) component").

[(E) Photopolymerization initiation component]
The (E) photopolymerization initiating component in the present invention is usually a mixture of (E1) a photopolymerization initiator and, if necessary, (E2) a polymerization accelerator and (E3) an additive such as a sensitizing dye. And is a component having a function of generating a polymerization active radical by directly absorbing light or being photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction.

  Examples of (E1) photopolymerization initiator constituting the photopolymerization initiating component include titanocene derivatives described in JP-A Nos. 59-152396 and 61-151197, etc .; JP-A-10-300922 Hexaarylbiimidazole derivatives described in JP-A-11-174224, JP-A-2000-56118, etc .; halomethylated oxadiazole derivatives described in JP-A-10-39503, etc., halomethyl-s -Radical activators such as triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives And oxime ester derivatives described in JP-A No. 2000-80068 and the like.

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

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

(In the above formula (XI),
Z represents an aromatic ring group which may have a substituent.
p represents an integer of 0 or 1.
q represents the integer of 0-20.
X ^{is, -CR 54 R 55 -, -} C (= CR 56 R 57) -, - CR 58 = CR 59 - and one group, or selected from the group consisting of -C≡C- these bound 2 or more Represents a group consisting of

R ^{56 to} R ⁵⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
R ⁵⁴ , R ⁵⁵ and R ¹⁰¹ are each independently a hydrogen atom, a halogen atom, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, or a carbon atom, each of which may have a substituent. C2-C20 monovalent non-aromatic heterocyclic group, C1-C20 alkoxy group, C6-C20 aryloxy group, C2-C20 acyl group, C2-C20 acyloxy Group, N-substituted amino group having 1 to 20 carbon atoms, cycloalkyl group having 3 to 20 carbon atoms, carbamoyl group, alkylcarbamoyl group having 2 to 20 carbon atoms, arylcarbamoyl group having 7 to 20 carbon atoms, carbon number 1 -20 aminooxycarbonyl group, cyano group, nitro group, C1-C12 alkylsulfanyl group, C2-C12 alkoxycarbonyl group, C3-C12 alkenyloxy. A cicarbonyl group, an alkynyloxycarbonyl group having 3 to 12 carbon atoms, an aryloxycarbonyl group having 7 to 12 carbon atoms, a heteroaryloxycarbonyl group having 3 to 12 carbon atoms, or a group represented by the following formula (2): Represent.

(R ³⁰ and R ³¹ each independently represents an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 20 carbon atoms, which may have a substituent.)
R ¹⁰¹ may be bonded to Z to form a ring, and the ring may have a substituent.
R ¹⁰² may have a substituent, which may have a substituent, an alkylcarbonyl group having 2 to 20 carbon atoms, an alkenylcarbonyl group having 3 to 25 carbon atoms, a cycloalkylcarbonyl group having 4 to 8 carbon atoms, or a carbon number having 7 to 20 carbon atoms. An arylcarbonyl group, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, a heteroarylcarbonyl group group having 3 to 20 carbon atoms, or a carbon number Represents 2-20 alkylaminocarbonyl groups.

R ¹⁰³ represents an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 5 carbon atoms, or an aryl group having 6 to 20 carbon atoms,
R ^{104 to} R ¹⁰⁹ each independently represent a hydrogen atom, a halogen atom, a nitro group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. )
(About Z)
Z represents an aromatic ring group which may have a substituent.

Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
The aromatic hydrocarbon ring group may be a single ring or a condensed ring, and preferably has 5 to 18 carbon atoms forming the ring and has one free valence. Examples include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring, and indene ring.

In addition, the aromatic heterocyclic group may be a monocyclic ring or a condensed ring, and preferably has 3 to 10 carbon atoms to form the ring. Furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring , Thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline Ring, quinoxaline ring, phenanthridine ring, Zone imidazole ring, perimidine ring, a quinazoline ring, a quinazolinone ring, azulene ring, an acridine ring, a xanthene ring, a phenazine ring, a phenothiazine ring, a phenoxazine ring, groups such as a benzothiazole ring.
In addition, as a substituent which the aromatic ring group in Z may have, the thing as described in the term of the following (substituent group W) is mentioned, for example.

(Substituent group W)
C1-C8 alkyl group, C1-C8 alkoxy group, hydroxyl group, amino group, dimethylamino group, diethylamino group, halogen atom, sulfo group and carboxy group (about p)
p represents an integer of 0 or 1.

(About q)
q represents the integer of 0-20.
Q is preferably 0 to 5 in that the amount of radically active species generated per gram is high and the production is simple.
(About X and R ¹⁰¹ )
X ^{is, -CR 54 R 55 -, -} C (= CR 56 R 57) -, - CR 58 = CR 59 - and one group, or selected from the group consisting of -C≡C- these bound 2 or more Represents a group consisting of

When q is 2 or more, a plurality of X contained in one molecule may be the same or different.
R ^{56 to} R ⁵⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
R ⁵⁴ , R ⁵⁵ and R ¹⁰¹ are each independently a hydrogen atom, a halogen atom, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, or a carbon atom, each of which may have a substituent. C2-C20 monovalent non-aromatic heterocyclic group, C1-C20 alkoxy group, C6-C20 aryloxy group, C2-C20 acyl group, C2-C20 acyloxy Group, N-substituted amino group having 1 to 20 carbon atoms, cycloalkyl group having 3 to 20 carbon atoms, carbamoyl group, alkylcarbamoyl group having 2 to 20 carbon atoms, arylcarbamoyl group having 7 to 20 carbon atoms, carbon number 1 -20 aminooxycarbonyl group, cyano group, nitro group, C1-C12 alkylsulfanyl group, C2-C12 alkoxycarbonyl group, C3-C12 alkenyloxy. It represents a group represented by a cicarbonyl group, an alkynyloxycarbonyl group having 3 to 12 carbon atoms, an aryloxycarbonyl group having 7 to 12 carbon atoms, a heteroaryloxycarbonyl group having 3 to 12 carbon atoms, or the following formula (2). .

(R ³⁰ and R ³¹ each independently represents an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 20 carbon atoms, which may have a substituent.)
R ¹⁰¹ may be bonded to Z to form a ring, and the ring may have a substituent.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom, a chlorine atom, and a bromine atom that are relatively stable against a nucleophilic substitution reaction are preferable.

  The aryl group having 6 to 20 carbon atoms which may have a substituent preferably has 6 to 12 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthracenyl group. Examples of the group which may be substituted on the aryl group include an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, a halogen atom, a cyano group, A sulfo group, a carboxy group, etc. are mentioned. Specific examples of the aryl group include a phenyl group, a p-tolyl group, an m-tolyl group, a p-methoxyphenyl group, a mesityl group, a naphthyl group, and an anthracenyl group.

  The heteroaryl group having 2 to 20 carbon atoms which may have a substituent is an aromatic ring group containing any one of a nitrogen atom, a sulfur atom and an oxygen atom as a heteroatom, preferably having a carbon number. The thing of 2 or more and 12 or less is mentioned. When the heteroaryl group has a plurality of heteroatoms constituting a ring other than a carbon atom, these may be the same or different. The heteroaryl group may be a single ring or a condensed ring, and may be a pyrrolyl group, imidazolyl group, pyrazolyl group, thiazolyl group, oxazolyl group, triazolyl group, thiadiazolyl group, pyridinyl group, pyrimidinyl group, triazinyl group. Quinolinyl group, isoquinolinyl group, benzothiazolinyl group, phthalimidoyl group, benzimidazolonyl group, furyl group, thiophenyl group, pyranyl group, indolinyl group, isoindolinyl group and the like. Examples of the group that may be substituted on the heteroaryl group include an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, a halogen atom, and a sulfo group. And a carboxy group. Specific examples of the heteroaryl group include 2-pyrrolyl group, 2-imidazolyl group, 1-pyrazolyl group, 2-thiazolyl group, 2-oxazolyl group, 1,2,4-triazol-1-yl group, and 4-pyridinyl. Group, 2-pyrimidinyl group, 4,6-diamino-2-triazinyl group, 8-quinolinyl group, 8-isoquinolinyl group, 2-benzothiazolinyl group, 6-methyl-7-sulfo-2-benzothiazolinyl Group, 1,3-dihydro-1,3-dioxo-2H-isoindol-2-yl group, 1H-benzimidazol-2-yl group, 2-furyl group, 2-thiophenyl group, 1-indolinyl group, 2 -An isoindolinyl group is mentioned.

The monovalent non-aromatic heterocyclic group having 2 to 20 carbon atoms which may have a substituent is a non-aromatic cyclic group containing any one of a nitrogen atom, a sulfur atom and an oxygen atom as a hetero atom. Yes, preferably those having 2 to 12 carbon atoms. When the monovalent non-aromatic heterocyclic group has a plurality of heteroatoms constituting a ring other than a carbon atom, these may be the same or different. The monovalent non-aromatic heterocyclic group may be a single ring or a condensed ring, and examples thereof include a piperidinyl group, a pyrrolidinyl group, an imidazolidinyl group, a pyrazolidinyl group, a piperazinyl group, and a morpholinyl group. Examples of the substituent that the monovalent non-aromatic heterocyclic group may have include an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a hydroxyl group, an amino group, a dimethylamino group, and diethylamino. Group, halogen atom, sulfo group and carboxy group. Specific examples of the monovalent non-aromatic heterocyclic group include 1-piperidinyl group, 1-pyrrolidinyl group, 1-imidazolidinyl group, 1-pyrazolidinyl group, 1-piperazinyl group and 1-morpholinyl group.

  The alkoxy group having 1 to 20 carbon atoms which may have a substituent is preferably an alkoxy group having 1 to 10 carbon atoms. Examples of the substituent that the alkoxy group may have include an alkoxy group having 1 to 10 carbon atoms, a phenyl group, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, a halogen atom, a cyano group, a sulfo group, and a carboxy group. Etc. Specific examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, s-butoxy group, t-butoxy group, n-amyloxy group, t-amyloxy group, n- Hexyloxy group, n-heptyloxy group, n-octyloxy group, hydroxyethoxy group, 1,2-dihydroxypropoxy group, 2-methoxyethoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2- (2 -Methoxyethoxy) ethoxy group, 2- (2-ethoxyethoxy) ethoxy group, 2- (2-butoxyethoxy) ethoxy group, benzyloxy group, phenethyloxy group, etc., linear or branched alkoxy having 1 to 18 carbon atoms Groups.

  The aryloxy group having 6 to 20 carbon atoms which may have a substituent is preferably an aryloxy group having 6 to 14 carbon atoms. Examples of the aryloxy group include a phenoxy group, a naphthoxy group, and an anthracenyloxy group. Examples of the substituent that the aryloxy group may have include an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, a halogen atom, and cyano. Group, sulfo group, carboxy group and the like. Specific examples of the aryloxy group include aryls optionally having a substituent such as a phenoxy group, a 1-naphthoxy group, a 2-naphthoxy group, a 3-tolyloxy group, a 4-methoxyphenoxy group, and a 4-cyclohexylphenoxy group. An oxy group is mentioned.

Which may have a substituent alkylcarbamoyl group having 2 to 20 carbon atoms ^is represented by ^{-CO-NR 11b R 12b, R} 11 is an optionally substituted alkyl radical, R ^12b represents a hydrogen atom or an alkyl group which may have a substituent. The alkyl group usually has 1 or more carbon atoms and usually 19 or less, preferably 12 or less. Examples of the group that may be substituted with the alkyl group include an alkoxy group having 1 to 10 carbon atoms, a phenyl group, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, a halogen atom, a cyano group, a sulfo group, and a carboxy group. Is mentioned. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, n-butyl group, cyclohexyl group, hydroxyethyl group, 1,2-dihydroxypropyl group, 2-methoxyethyl group, 2-ethoxyethyl group. 2-butoxyethyl group, 2- (2-methoxyethoxy) ethyl group, 2- (2-ethoxyethoxy) ethyl group, 2- (2-butoxyethoxy) ethyl group, benzyl group, phenethyl group and the like. Specific examples of the alkylamino group include an ethylamino group, a dimethylamino group, a diethylamino group, a dibutylamino group, a di (2-ethoxyethyl) amino group, a diphenethylethylamino group, and a cyclohexylethyl group. Specific examples of the alkylcarbamoyl group include a methylcarbamoyl group, an ethylcarbamoyl group, a phenethylcarbamoyl group, a 2-ethylhexylcarbamoyl group, a 2-ethoxyethylcarbamoyl group, a 2- (2-ethoxyethoxy) ethylcarbamoyl group, and a dimethylcarbamoyl group. Etc.

The arylcarbamoyl group having 7 to 20 carbon atoms which may have a substituent is represented by —CO—NR ^13b R ^14b , and R ^13b represents an aryl group which may have a substituent. R ^1
4b represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. The preferred carbon number of the alkyl group and examples of the substituent which may be present are the same as those exemplified for the alkyl groups of R ^11b and R ^12b . The aryl group usually has 6 or more carbon atoms, usually 19 or less, preferably 12 or less, and examples thereof include a phenyl group, a naphthyl group, and an anthracenyl group. Examples of the group which may be substituted on the aryl group include an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, a halogen atom, a cyano group, A sulfo group, a carboxy group, etc. are mentioned. Specific examples of the aryl group include a phenyl group, a p-tolyl group, an m-tolyl group, a p-methoxyphenyl group, a naphthyl group, and an anthracenyl group. Specific examples of the arylcarbamoyl group include a phenylcarbamoyl group, a naphthylcarbamoyl group, a p-tolylcarbamoyl group, a p-methoxyphenylcarbamoyl group, and a phenylmethylcarbamoyl group.

Optionally substituted acyl group having 2 to 20 carbon atoms is represented by ^{-COR 15b,} R ^15b may have an optionally substituted alkyl group or a substituted group Represents an aryl group. The preferred carbon number of the alkyl group and examples of the substituent which may be present are the same as those exemplified for the alkyl groups of R ^11b and R ^12b . Examples of the preferable number of carbon atoms of the aryl group and the substituent which may be included are the same as those exemplified for the aryl group of R ⁴⁸ . Specific examples of the acyl group include acetyl group, ethylcarbonyl group, n-butylcarbonyl group, benzoyl group, p-tolylcarbonyl group, m-tolylcarbonyl group, p-methoxyphenylcarbonyl group and the like.

The acyloxy group having 2 to 20 carbon atoms that may have a substituent is represented by -O-COR ^16b , and R ^16b has an alkyl group or a substituent that may have a substituent. Represents a good aryl group. The preferred carbon number of the alkyl group and examples of the substituent which may be present are the same as those exemplified for the alkyl groups of R ^11b and R ^12b . Examples of the preferable carbon number of the aryl group and the substituent which may be included are the same as those exemplified for the aryl group of R ^13b . Specific examples of the acyl group include an acetoxy group, an ethylcarbonyloxy group, an n-butylcarbonyloxy group, a benzoyloxy group, a p-tolylcarbonyloxy group, an m-tolylcarbonyloxy group, and a p-methoxyphenylcarbonyloxy group. Is mentioned.

The optionally substituted N-substituted amino group having 1 to 20 carbon atoms is represented by —NR ^17b R ^18b , where R ^17b is a hydrogen atom, an ^optionally substituted alkyl group, a substituted group. An aryl group which may have a group is represented. R ^18b represents an alkyl group which may have a substituent and an aryl group which may have a substituent. The preferred carbon number of the alkyl group and examples of the substituent which may be present are the same as those exemplified for the alkyl groups of R ^11b and R ^12b . Examples of the preferable carbon number of the aryl group and the substituent which may be included are the same as those exemplified for the aryl group of R ^13b . Specific examples of the N-substituted amino group include an ethylamino group, a dimethylamino group, a diethylamino group, a dibutylamino group, a di (2-ethoxyethyl) amino group, a diphenethylethylamino group, a cyclohexylethyl group, and a phenylamino group. , Diphenylamino group, di (p-tolyl) amino group, di (p-methoxyphenyl) amino group, ethylphenylamino group, n-butylphenylamino group and the like.

The cycloalkyl group having 3 to 20 carbon atoms which may have a substituent is preferably a cycloalkyl group having 3 to 12 carbon atoms. Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, and a decalinyl group. Examples of the group which may be substituted on the cycloalkyl group include an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, a halogen atom, and a cyano group. , Sulfo group and carboxy group. Specific examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, and a decalinyl group.

The C2-C12 alkoxycarbonyl group which may have a substituent is represented by -CO-OR ^24b , and R ^24b represents an alkyl group which may have a substituent. The preferred carbon number of the alkyl group and examples of the substituent which may be present are the same as those exemplified for the alkyl groups of R ^11b and R ^12b . Specific examples of the alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-butoxycarbonyl group, phenethyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, 2-ethoxyethoxycarbonyl group and the like.

The alkenyloxycarbonyl group having 3 to 12 carbon atoms which may have a substituent is represented by —CO—OR ^25b , and R ^25b represents an alkenyl group which may have a substituent. The alkenyl group usually has 1 or more carbon atoms and usually 11 or less, preferably 8 or less. Examples of the group that may be substituted with the alkenyl group include an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, a halogen atom, a cyano group, a sulfo group, and a carboxy group. Is mentioned. Specific examples of the alkenyl group include a vinyl group, an allyl group, and a methanyl group. Specific examples of the alkenyloxycarbonyl group include alkenyloxycarbonyl groups having 3 to 12 carbon atoms such as vinyloxycarbonyl group and allyloxycarbonyl group.

Which may have a substituent alkynyloxy group having 3 to 12 carbon atoms is represented by ^{-CO-OR 26b, R 26b} represents an alkynyl group which may have a substituent. The alkynyl group usually has 1 or more carbon atoms and usually 11 or less, preferably 8 or less. Examples of the group which may be substituted on the alkynyl group include an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, a halogen atom, a cyano group, a sulfo group and a carboxy group. Is mentioned. Specific examples of the alkynyl group include a methynyl group, a propynyl group, and a butynyl group. Specific examples of the alkynyloxycarbonyl group include alkynyloxycarbonyl groups having 3 to 12 carbon atoms such as methynyloxycarbonyl group and propynyloxycarbonyl group.

The aryloxycarbonyl group having 7 to 12 carbon atoms which may have a substituent is represented by —CO—OR ^27b , and R ^27b represents an aryl group which may have a substituent. Examples of the preferable carbon number of the aryl group and the substituent which may be included are the same as those exemplified for the aryl group of R ^13b . Specific examples of the aryloxycarbonyl group include those having 7 to 12 carbon atoms such as phenyloxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, p-tolyloxycarbonyl group, p-methoxyphenyloxycarbonyl group and the like. An aryloxycarbonyl group is mentioned.

Which may have a substituent heteroaryloxy group having 3 to 12 carbon atoms is represented by ^{-CO-OR 28b,} R ^28b represents a heteroaryl group which may have a substituent. Examples of the preferable carbon number of the heteroaryl group and an optionally substituted substituent are the same as those of the preferable carbon number of the heteroaryl group in R ⁵⁴ , R ⁵⁵ and R ^{101 and} an optionally substituted substituent. is there. Specific examples of the heteroaryloxycarbonyl group include 8-quinolinyloxycarbonyl group, 2-furanyloxycarbonyl group, 3-furanyloxycarbonyl group, 2-pyridyloxycarbonyl group, 3-pyridyloxycarbonyl group, 4 -Heteroaryloxycarbonyl groups having 3 to 12 carbon atoms such as a pyridyloxycarbonyl group and a 2-benzothiazolyloxycarbonyl group.

Examples of the alkyl group having 1 to 12 carbon atoms which may have a substituent of R ³⁰ and R ³¹ are the same as those exemplified in the case of the alkyl group of R ^11b and R ^12b . Examples of the aryl group having 6 to 20 carbon atoms which may have a substituent are the same as those exemplified for the aryl group of R ^13b .
R ¹⁰¹ may be bonded to Z to form a ring, and the ring may have a substituent.

<About ^{R 102>}
R ¹⁰² may have a substituent, which may have a substituent, an alkylcarbonyl group having 2 to 20 carbon atoms, an alkenylcarbonyl group having 3 to 25 carbon atoms, a cycloalkylcarbonyl group having 4 to 8 carbon atoms, or a carbon number having 7 to 20 carbon atoms. An arylcarbonyl group, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, a heteroarylcarbonyl group having 3 to 20 carbon atoms, or 2 carbon atoms Represents an alkylaminocarbonyl group of ˜20.

Examples of the alkylcarbonyl group having 2 to 20 carbon atoms which may have a substituent include an acetyl group, a propanoyl group, a butanoyl group, and the like, and preferably an acetyl group. Carbon number becomes like this. Preferably it is 2-10, More preferably, it is 2-7.
Examples of the alkenylcarbonyl group having 3 to 25 carbon atoms which may have a substituent include a crotonoyl group and an acryloyl group, and a crotonoyl group is preferable. Carbon number becomes like this. Preferably it is 3-12, More preferably, it is 3-7.

Examples of the cycloalkylcarbonyl group having 4 to 8 carbon atoms which may have a substituent include a cyclohexylcarbonyl group, a methylcyclohexylcarbonyl group and a cyclopentylcarbonyl group, and a cyclohexylcarbonyl group is preferable. The number of carbon atoms is preferably 4-7.
Examples of the arylcarbonyl group having 7 to 20 carbon atoms which may have a substituent include a benzoyl group, a methylbenzoyl group, and a naphthoyl group, and a benzoyl group is preferable. Carbon number becomes like this. Preferably it is 7-12, More preferably, it is 7-10.

Examples of the C2-C10 alkoxycarbonyl group which may have a substituent include a methoxycarbonyl group, an ethoxycarbonyl group, and a propoxycarbonyl group, and a methoxycarbonyl group is preferable. The number of carbon atoms is preferably 2-8.
Examples of the aryloxycarbonyl group having 7 to 20 carbon atoms which may have a substituent include a phenoxycarbonyl group, a p-methylphenoxycarbonyl group, and a naphthoxycarbonyl group, and a phenoxycarbonyl group is preferable. Carbon number becomes like this. Preferably it is 7-15, More preferably, it is 7-10.

Examples of the heteroaryl group having 2 to 20 carbon atoms which may have a substituent include a thienyl group, a pyrrolyl group, and a pyridyl group, and a thienyl group is preferable. Carbon number becomes like this. Preferably it is 2-12, More preferably, it is 2-7.
Examples of the heteroarylcarbonyl group having 3 to 20 carbon atoms which may have a substituent include a thiophenecarbonyl group, a pyrrolylcarbonyl group, a pyridinecarbonyl group, and the like, and preferably a thiophenecarbonyl group. Carbon number becomes like this. Preferably it is 5-15, More preferably, it is 7-10.

Examples of the alkylaminocarbonyl group having 2 to 20 carbon atoms which may have a substituent include a morpholinocarbonyl group, a dimethylaminocarbonyl group, and a methylaminocarbonyl group, and a dimethylaminocarbonyl group is preferable. Carbon number becomes like this. Preferably it is 2-12, More preferably, it is 2-10.
Of the above groups, from the viewpoint of exposure sensitivity, R ¹⁰² is preferably an alkylcarbonyl group, a cycloalkylcarbonyl group, or an arylcarbonyl group, and more preferably an alkylcarbonyl group or an arylcarbonyl group.
Examples of the substituent that each group described above as R ¹⁰² may have include those described in the following (Substituent group W ¹ ) section, and each group described above has a substituent. Those that do not are particularly preferred.

(Substituent group W ¹ )
C1-C8 alkyl group, C1-C10 alkoxy group, phenyl group, hydroxyl group, amino group, dimethylamino group, diethylamino group, halogen atom, cyano group, sulfo group and carboxy group <Regarding ^R103 >
R ¹⁰³ represents an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 5 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

  Examples of the alkyl group include methyl group, ethyl group, n-propyl group, n-butyl group, cyclohexyl group, hydroxyethyl group, 1,2-dihydroxypropyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2 -Butoxyethyl group, 2- (2-methoxyethoxy) ethyl group, 2- (2-ethoxyethoxy) ethyl group, 2- (2-butoxyethoxy) ethyl group, benzyl group, phenethyl group and the like can be mentioned. Carbon number becomes like this. Preferably it is 1-10, More preferably, it is 1-6.

Examples of the alkenyl group include allyl group and methanyl group. The number of carbon atoms is preferably 3-4.
The aryl group is the same as that described in the section <About X and R ¹⁰¹ >.
Examples of the substituent that each group described above as R ¹⁰³ may have include those described in the above section (Substituent group W ¹ ), and each group described above has a substituent. Those that do not are particularly preferred.
R ¹⁰³ is preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably an ethyl group, from the viewpoint that the generation amount of radical active species per gram is high and the production is simple.

<Regarding ^R 104 ^{to R 109>}
R ^{104 to} R ¹⁰⁹ each independently represent a hydrogen atom, a halogen atom, a nitro group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.
R ^{104 to} R ¹⁰⁹ are particularly preferably hydrogen atoms from the viewpoint that the generation amount of radical active species per gram is high and the production is simple.

  Commercial products may be used as the oxime initiator. Examples of commercial products include OXE-01, OXE-02 (BASF), TRONLYTR-PBG-304, TRONLYTR-PBG-309, TRONLYTR-PBG-305 (CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD)).

  Other photopolymerization initiators include benzoin alkyl ethers, anthraquinone derivatives; acetophenone derivatives such as 2-methyl- (4′-methylthiophenyl) -2-morpholino-1-propanone, 2-ethylthioxanthone, 2 Thioxanthone derivatives such as 1,4-diethylthioxanthone, benzoic acid ester derivatives, acridine derivatives, phenazine derivatives, anthrone derivatives and the like. Commercial products may be used as these initiators.

Examples of commercially available products include IRGACURE 651, IRGACURE 184, D
AROCUR 1173, IRGACURE 2959, IRGACURE 127, IRGACURE 907, IRGACURE 369, IRGACURE 379EG, LUCIRIN TPO, IRGACURE 819, IRGACURE 784 (all manufactured by BASF).

Among these photopolymerization initiators, α-aminoalkylphenone derivatives, thioxanthone derivatives, and oxime ester derivatives are more preferable, and oxime ester derivatives are particularly 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 initiating components 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, and more preferably 20% by weight or less. When the content of the (E) photopolymerization initiating component in the colored resin composition of the present invention is within the above range, the sensitivity to the exposure light is good, and the solubility of the unexposed part in the developer is also good. This is preferable in that it is difficult to induce defects.

[(E) Thermal polymerization starting component]
Specific examples of the (E) thermal polymerization initiating component 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 initiating component described in International Publication No. 2009/107734 can be used.
These thermal polymerization initiating components may be used alone or in combination of two or more.

[Other 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 it contains the below-mentioned (F) pigment, you may contain a dispersing agent and a dispersing aid. As these optional components, for example, various compounds described in JP-A-2007-113000 can be used.

[(F) Pigment]
The colored resin composition of the present invention may contain (F) a pigment within a range not impairing the effects of the present invention for the purpose of improving the heat resistance of the obtained color filter.
(F) As a pigment, for example, when forming a pixel of a color filter, pigments of various colors such as blue and purple can be used. Examples of the chemical structure include organic pigments such as phthalocyanine, quinacridone, benzimidazolone, dioxazine, indanthrene, and perylene. In addition, various inorganic pigments can be used. Hereinafter, specific examples of usable pigments are indicated by pigment numbers.

  Examples of blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and the like.

Among these, a blue copper phthalocyanine pigment is preferable, and examples of the copper phthalocyanine pigment include C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6 and the like are preferable, and C.I. I. Pigment Blue 15: 6.
For this reason, when the colored resin composition of this invention contains a blue pigment, it is 80 weight% or more with respect to the total content of a blue pigment, Especially 90 weight% or more, Especially 95-100 weight% is C.I. I. Pigment Blue 15: 6 is preferable.

Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like.
Among these, a purple dioxazine pigment is preferable, and as the dioxazine pigment, C.I. I. Pigment Violet 19 and 23 are preferable, and C.I. I. Pigment Violet 23.

For this reason, when the colored resin composition of this invention contains a purple pigment, it is 80 weight% or more with respect to the total content of a purple pigment, Especially 90 weight% or more, Especially 95-100 weight% is C.I. I. Pigment Violet 23 is preferable.
These may be used alone or in a combination of two or more in any combination and ratio.

The (F) pigment used in the colored resin composition of the present invention preferably has a small average primary particle diameter from the viewpoint of forming a high-contrast pixel. Specifically, the average primary particle diameter is 40 nm or less. Is preferable, and it is more preferable that it is 35 nm or less.
Particularly for the blue copper phthalocyanine pigment, the average primary particle size is preferably 40 nm or less, more preferably 35 nm or less, and still more preferably 20 to 30 nm.

Moreover, about a dioxazine pigment, an average primary particle diameter becomes like this. Preferably it is 40 nm or less, More preferably, it is 25-35 nm. From the viewpoint that the pigment is less likely to aggregate in the colored resin composition, it is preferable that the average primary particle size is not too small.
Here, the average primary particle size of the (F) pigment is a value measured and calculated by the following method.

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

{Blending amount}
In the present invention, when the pigment (F) is contained, the content of the pigment in the colored resin composition is usually 80% by weight or less, preferably 50% by weight or less in the total solid content.
Moreover, content with respect to 100 weight part of said (A) dye is 3000 weight part or less normally, Preferably it is 1000 weight part or less.
By setting it within the above range, it is preferable because the heat resistance of the obtained pixel is likely to be better without greatly affecting the transmittance of the dye (I).

[Dispersant]
When the colored resin composition of the present invention contains (F) a pigment, it is preferable to further contain a dispersant.
The dispersant in the present invention is not particularly limited as long as the pigment is dispersed and can maintain stability.

  For example, cationic, anionic, nonionic or amphoteric dispersants can be used, but polymer dispersants are preferred. Specific examples include block copolymers, polyurethanes, polyesters, alkylammonium salts or phosphate esters of polymer copolymers, and cationic comb graft polymers. Of these dispersants, block copolymers, polyurethanes, and cationic comb graft polymers are preferred. In particular, a block copolymer is preferable, and among these, a block copolymer composed of an A block having solvophilicity and a B block having a functional group containing a nitrogen atom is preferable.

Specifically, the B block having a nitrogen atom-containing functional group includes a unit structure having a quaternary ammonium base and / or an amino group in the side chain, while the solvophilic A block includes a quaternary ammonium. Examples include a unit structure having no base and amino group.
The B block constituting the acrylic block copolymer has a unit structure having a quaternary ammonium base and / or an amino group, and has a pigment adsorption function.

Further, when the B block has a quaternary ammonium base, the quaternary ammonium base may be directly bonded to the main chain, but may be bonded to the main chain via a divalent linking group. Good.
Examples of such block copolymers include those described in JP-A-2009-025813.

Moreover, the colored resin composition of the present invention may contain a dispersant other than those described above. Examples of other dispersants include those described in JP-A-2006-343648, for example.
When the colored resin composition of the present invention contains (F) a pigment, the content of the dispersant in the total solid content is 2 to 1000% by weight, particularly 5 to 500% by weight of the total content of (F) pigment. %, Particularly 10 to 250% by weight.
By setting it within the above range, it is preferable in that good pigment dispersibility can be ensured without affecting the heat resistance of the dye (I), and the pigment dispersion stability becomes better.

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

  The content of the dispersion aid in the colored resin composition of the present invention is usually 0.1% by weight or more, usually 30% by weight or less, preferably 20% by weight or less, based on the total solid content of the pigment. Preferably it is 10 weight% or less, More preferably, it is 5 weight% or less. By controlling the addition amount within the above range, it is preferable in that the effect as a dispersion aid is exhibited and the dispersibility and dispersion stability are better.

[Dispersion resin]
The colored resin composition of the present invention may contain a part or all of the resin selected from the (C) binder resin or other binder resins as the following dispersion resin.
Specifically, in [Preparation Method of Colored Resin Composition], which will be described later, by adding (C) binder resin together with the components such as the above-mentioned dispersant, the (C) binder resin is combined with the dispersant. It contributes to the dispersion stability of the pigment (F) by a synergistic effect. As a result, the amount of dispersant added may be reduced, which is preferable. Further, it is preferable because the developability is improved, the undissolved matter does not remain in the non-pixel portion of the substrate, and the adhesion of the pixel to the substrate is improved.
Thus, the (C) binder resin used in the dispersion treatment step may be referred to as a dispersion resin. The dispersion resin is preferably used in an amount of about 0 to 200% by weight, more preferably about 10 to 100% by weight, based on the total amount of the pigment in the colored resin composition.

[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) dye and the (C) binder resin containing the dye (I), the (B) solvent, and as necessary. It can prepare by mixing with the arbitrary component used.
In addition, as a preparation method in the case of containing (F) a pigment, in the solvent containing (F) pigment, in the presence of a dispersing agent and a dispersing aid to be added if necessary, (C) a binder resin may be used. A pigment dispersion liquid is prepared by mixing and dispersing together with the parts, for example, using a paint shaker, sand grinder, ball mill, roll mill, stone mill, jet mill, homogenizer, and the like. (A) dye containing dye (I), (C) binder resin, (D) polymerizable monomer, (E) photopolymerization initiating component and / or thermal polymerization initiating component, if necessary, in the pigment dispersion The method of preparing by adding etc. 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. Such a colored resin composition is supplied onto a 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 pixel of a color filter, 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 pixels is not particularly limited as long as it is transparent and has an appropriate strength. For example, polyester resin, polyolefin resin, polycarbonate resin, acrylic resin, thermoplastic resin Examples thereof include a sheet made, an epoxy resin, a thermosetting resin, and various glasses.
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.
As the radiation used in the exposure, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used, and radiation having a wavelength in the range of 190 to 450 nm is preferable.

  A light source for using radiation having a wavelength of 190 to 450 nm used for image exposure is not particularly limited. For example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, Lamp light sources such as medium pressure mercury lamp, low pressure mercury lamp, carbon arc, fluorescent lamp; laser light sources such as argon ion laser, YAG laser, excimer laser, nitrogen laser, helium cadmium laser, semiconductor laser, and the like. An optical filter can also be used when used by irradiating light of a specific wavelength.

Exposure of radiation, 10~10,000J / ^{m 2} is preferred.
Examples of the alkaline developer include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, Inorganic alkaline compounds such as potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide; mono-di- or tri-ethanolamine, mono-di-, or tri -Methylamine, mono-, di-, or tri-ethylamine, mono-, or di-isopropylamine, n-butylamine, mono-, di-, or tri-isopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium Hydroxide (TMAH) Aqueous solution of an organic alkaline compound choline are preferred.

An appropriate amount of a water-soluble organic solvent such as isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol, or the like can be added to the alkali developer. In addition, it is usually washed with water after alkali development.
As the development processing method, any method such as an immersion development method, a spray development method, a brush development method, and an ultrasonic development method can be used. The development conditions are preferably 5 to 300 seconds at room temperature (23 ° C.).

There are no particular restrictions on the conditions of the development processing, but the development temperature is usually 10 ° C. or higher, especially 15 ° C. or higher, more preferably 20 ° C. or higher, and usually 50 ° C. or lower, especially 45 ° C. or lower, further 40 ° C. or lower. Is preferred.
The developing method can be any one of immersion developing method, spray developing method, brush developing method, ultrasonic developing method and the like.

  When the color filter thus produced is used in a liquid crystal display device, a transparent electrode such as ITO is formed on the image as it is and used as a part of a component such as a color display or a liquid crystal display device. 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 having 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 Example 1: Synthesis of Dye 1)
(Synthesis of Intermediate B1)

N-ethyl-p-toluidine (Tokyo Chemical Industry Co., Ltd., 138 g) was dissolved in N, N-dimethylformamide (520 ml), cooled in an ice bath, and t-butoxypotassium (115 g) was added little by little. Furthermore, 4,4'-difluorobenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd., 3
A solution of 7 g) in N, N-dimethylformamide (180 ml) was added dropwise over 30 minutes with cooling in an ice bath, and the mixture was stirred at 50 ° C. for 3 hours. Water and toluene were added, the organic layer was separated, and the organic layer was washed with water. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. Purification by silica gel column chromatography (hexane / ethyl acetate 15/1 to 10/1) gave Intermediate B1 (63.6 g) as a pale yellow solid.
(Synthesis of Intermediate C1)

To a mixture of Intermediate B1 (24 g), 1-methyl-2-phenylindole (Tokyo Chemical Industry Co., Ltd., 11.1 g) and toluene (130 ml), phosphorus oxychloride (Wako Pure Chemical Industries, 7.3 ml) was added. ) And heated to reflux for 5 hours. After cooling to room temperature, water was added, extracted with chloroform, and the organic layer was washed 3 times with saturated brine. The extract was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and purified by silica gel column chromatography (chloroform / methanol = 12/1) to obtain Intermediate C1 (34.8 g).

A mixture of intermediate C1 (6.0 g) and 95% sulfuric acid (90 g) was stirred at 70 ° C. for 6 hours and at 80 ° C. for 4 hours, then poured into ice water, and the precipitate was collected by filtration. After dissolving in acetone and diluting with water, the pH is adjusted to 8 with 1N aqueous sodium hydroxide solution, the precipitate is filtered and dried, and dye 1 (5.4) is obtained.
g) was obtained. Dye 1 was a 64:36 mixture of Dye 1A and Dye 1B by ¹ H NMR analysis. The maximum absorption wavelength (λmax) of this compound in a 10 ppm propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 65/35 solution was 605 nm.

The results of ¹ H NMR and MS are shown below.
¹ H NMR (500 MHz, CD ₃ OD) δ 1.25 (t, H-4), 2.39 (s, H-1), 3.88 (m, H-5, H-11), 6.4 -6.8 (br, H-6), 7
. 00 (d, H-15), 7.12 (d, H-3), 7.23-7.38 (m, H-2, H-7, H-8, H-9, H-10) 7.60 (d, H-12), 7.63 (dd, H-16), 7.71 (d, H-14), 7.87 (dd, H-13), 8.11 (d , H-17). _{MS (LDI, posi) m /} z 718 (M + H, C 46 H 44 N 3 O 3 S), 740 (M + Na, C 46 H 43 N 3 NaO 3 S).

(Synthesis Example 2: Synthesis of Dye 2)
(Synthesis of Intermediate E2)

A solution of 2-phenylindole (19.3 g) in tetrahydrofuran (100 ml) was added dropwise to 60% sodium hydride (4.2 g) over 20 minutes with cooling in an ice bath, and 1,4-butane sultone (10 ml) was added. 0.7 ml) was added dropwise and then heated to reflux for 1.5 hours. After cooling to room temperature, the mixture was poured into isopropyl alcohol (300 ml), suction filtered, the cake was taken out and washed with isopropyl alcohol (300 ml) to obtain intermediate E2 (31.0 g) as a white solid.

  A mixture of bis (4-diethylaminophenyl) methanol (1.63 g, manufactured by Tokyo Chemical Industry Co., Ltd.), intermediate E2 (1.76 g), and acetic acid (20 ml) was stirred at 80 ° C. for 10 hours and then concentrated under reduced pressure to give a residue. Was dissolved in methanol (30 ml), chloranil (1.23 g) was added, the mixture was stirred at room temperature for 3 hours, concentrated under reduced pressure, and purified by silica gel column chromatography (chloroform / methanol = 30 / 1-15 / 1). The obtained solid was washed with hexane to obtain Dye 2 (1.85 g). The maximum absorption wavelength (λmax) of this compound in a 10 ppm propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 65/35 solution was 600 nm.

The result of ¹ H NMR is shown below. ¹ H NMR (400 MHz, CDCl ₃ ) δ 1.26 (12H, t), 1.75-1.86 (2H, m), 2.05-2.15 (2H, m), 2.77 (2H, t), 3.40-3.60 (8H, m), 4.26 (2H, t), 6.50-6.70 (4H, br), 7.04 (1H, d), 7.10 -7.40 (11H, m), 7.64 (1H, d)
(Synthesis Example 3: Synthesis of Dye 3)

Intermediate C1 (1 g) was dissolved in 10% fuming sulfuric acid, stirred at room temperature for 10 hours, poured into ice water, salted out with lithium chloride, and collected by filtration. The cake was dissolved in water, adjusted to pH 8 by adding an aqueous lithium hydroxide solution, salted out with lithium chloride, and the precipitate was collected by filtration and dried. The crude product (0.298 g) was purified by medium pressure column chromatography (Yamazen Hi-Flash column octadecyl C18 standard, eluent: methanol / water = 10 / 90-48 / 52), and dye 3 was (0 .153 g). Dye 3 was a 67:33 mixture of Dye 3A and Dye 3B from ¹ H NMR analysis. The maximum absorption wavelength (λmax) of this compound in a 10 ppm propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 65/35 solution was 604 nm.

The results of ¹ H NMR and MS are shown below. ¹ H NMR (500 MHz, CD ₃ OD) δ 1.29 (t, H-5), 2.73 (s, H-1), 3.90 (m, H-6, H-12), 6.4 -6.9 (br, H-7), 7.10 (D, H-16), 7.2-743 (m, H-3, H-8, H-9, H-10, H -11), 7.44 (d, H-2), 7.66 (d, H-13), 7.68 (dd, H-17), 7.74 (d, H-15), 7. 80 (d, H-4), 7.90 (dd, H-14), 8.14 (d, H-18). _{MS (MALDI Neg): m /} z 882 (M-Li, C 46 H 41 LiN 3 O 9 S 3)
.

(Synthesis Example 4: Synthesis of Dye 4)
(Synthesis of Intermediate E4)

A solution of 2-phenylindole (19.3 g) in tetrahydrofuran (100 ml) was added dropwise to 60% sodium hydride (4.2 g) over 20 minutes while cooling in an ice bath. While cooling in an ice bath, a solution of 1,3-propane sultone (12.8 g) in tetrahydrofuran (20 ml) was added dropwise over 15 minutes, and the mixture was heated to reflux for 1 hour. After cooling to room temperature, the mixture was poured into isopropyl alcohol (350 ml), and the resulting solid was collected by filtration, washed with isopropyl alcohol, and dried under reduced pressure to obtain Intermediate E4 (28.2 g).

  A mixture of bis (4-diethylaminophenyl) methanol (1.63 g, manufactured by Tokyo Chemical Industry Co., Ltd.), intermediate E4 (1.69 g) and acetic acid (20 ml) was stirred at 80 ° C. for 2 hours, and then concentrated under reduced pressure. Methanol (30 ml) and chloranil (1.23 g) were added, and the mixture was stirred at room temperature for 1.5 hours and then at 50 ° C. for 5 hours. The mixture was concentrated under reduced pressure, purified by silica gel column chromatography (chloroform / methanol 1/0 to 20/1), and the obtained solid was washed with hexane to obtain Dye 4 (0.70 g). The maximum absorption wavelength (λmax) of this compound in a 10 ppm propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 65/35 solution was 598 nm.

The result of ¹ H NMR is shown below. ¹ H NMR (400 MHz, CDCl ₃ ) δ 1.26 (12H, t), 2.37-2.47 (2H, m), 2.80 (2H, t), 3.40-3.60 (8H, m), 4.47-4.54 (2H, m), 6.45-6.69 (4H, br), 7.02 (1H, d), 7.10-7.40 (11H, m). 7.86 (1H, d)
(Synthesis Example 5: Synthesis of Dye 5)
(Synthesis of Intermediate D5)

Under a nitrogen atmosphere, a 3 mol / l LiBH ₄ / tetrahydrofuran solution (17.1 mL, 51.2 mmol) was diluted with tetrahydrofuran (34 ml), and methanol (1.64 g, 51.2 mmol) was added little by little at room temperature. This was heated to 50 ° C. and intermediate B1
A solution of (11.51 g, 25.6 mmol) in tetrahydrofuran (40 ml) was added over 40 minutes, and the mixture was stirred as it was for 30 minutes. After completion of the reaction, the mixture was cooled to 3 ° C. with an ice bath, and 1N NaOH aqueous solution (20 ml) was added. The solvent was concentrated under reduced pressure and extracted with ethyl acetate. The organic layer was washed with water and brine and then dried over anhydrous sodium sulfate. After the desiccant was filtered off, the solvent was concentrated under reduced pressure to obtain Intermediate D5 as a pale yellow liquid. (11.62g)

Acetic acid (20 mL) was added to Intermediate D5 (12.25 g, 5.00 mmol) and Intermediate E2 (1.76 g, 5.00 mmol) and heated to 80 ° C. The mixture was stirred as it was for 4.5 hours and then concentrated under reduced pressure. The obtained oil was dissolved in methanol (30 mL), and chloranil (1.23 g, 5.00 mmol) was added. The mixture was stirred at room temperature for 3.5 hours and then left overnight. The reaction solution was filtered, concentrated under reduced pressure, and purified by silica gel column chromatography (chloroform / methanol = 30 / 1-15 / 1) to obtain Dye 5 (0.90 g). The maximum absorption wavelength (λmax) of this compound in a 10 ppm propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 65/35 solution was 598 nm.
The result of ¹ H NMR is shown below. ¹ H NMR (400 MHz, DMSO-d ⁶ ) δ 1.16 (t, 6H), 1.44 (quint, 2H), 1.79 (quint, 2H), 2.22 (t, 2H), 2.24 (S, 6H), 3.84 (q, 4H), 4.26 (t, 2H), 6.70 (br, 4H), 6.94 (d, 1H), 7.14-7.40 ( m, 19H), 7.88 (d, 1H)
(Synthesis Example 6: Synthesis of Dye 6)

A mixture of Intermediate D5 (1.07 g), Intermediate E4 (0.80 g) and acetic acid (20 mL) was stirred at 80 ° C. for 3 hours and then concentrated under reduced pressure. Methanol (30 mL) and chloranil (0.58 g) were added to the residue, stirred at room temperature for 4 hours, concentrated under reduced pressure, and purified by silica gel column chromatography (chloroform / methanol 15/1 to 10/1). The solid was washed with hexane to obtain Dye 6 (0.53 g).
The maximum absorption wavelength (λmax) of this compound in a 10 ppm propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 65/35 solution was 595 nm.

The result of ¹ H NMR is shown below. ¹ H NMR (400 MHz, CDCl ₃ ) δ 1.27 (6H, t), 2.41 (6H, t), 2.81 (2H, t), 3.75-3.90
(4H, m), 4.47-4.57 (2H, m), 6.40-6.65 (4H, br), 7.10-7.42 (20H, m), 7.87 (1H , D)
(Synthesis Example 7: Synthesis of Dye 7)
(Synthesis of Intermediate A7)

p-Toluidine (manufactured by Tokyo Chemical Industry Co., Ltd., 224 mmol, 24.0 g) and potassium carbonate (246 mmol, 34.1 g) were dissolved in NMP (200 ml) and heated to 70 ° C. 1-Bromo-3-methylbutane (manufactured by Kanto Chemical Co., Inc., 224 mmol, 33.8 g) diluted with NMP (50 ml) was added dropwise thereto over 1 hour, and the mixture was heated and stirred at 80 ° C. for 4 hours. After cooling to room temperature, toluene (300 ml) and distilled water (300 ml) were added, and the organic layer was washed with a saturated aqueous sodium chloride solution. The organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography (hexane: ethyl acetate = 6/1) to obtain intermediate A7 (16.4 g) as a pale yellow liquid. .
(Synthesis of Intermediate B7)

Dissolve in Intermediate A7 (15.0 g) and N, N-dimethylformamide (60 ml), add t-butoxypotassium (9.49 g) under cooling in an ice bath, and add 4,4 at 4 ° C. or lower. A solution of '-difluorobenzophenone (4.61 g, manufactured by Tokyo Chemical Industry Co., Ltd.) in N, N-dimethylformamide (15 ml) was added dropwise. After stirring as it was for 2 hours, the mixture was further stirred at 50 ° C. for 2.5 hours. The mixture was diluted with toluene, water was added to separate the organic layer, washed with saturated brine, and concentrated under reduced pressure. Purification by silica gel column chromatography (hexane / ethyl acetate 20/1) gave Intermediate B7 (2.32 g).
(Synthesis of Intermediate D7)

Under a nitrogen atmosphere, Intermediate B7 (3.90 g, 7.32 mmol) was dissolved in tetrahydrofuran (20 ml) and heated to 50 ° C. A 3 mol / L LiBH ₄ / tetrahydrofuran solution (2.44 mL, 7.32 mmol) was added little by little, and the reaction was allowed to proceed for 2.5 hours. After completion of the reaction, the mixture was cooled to 3 ° C. with an ice bath, and 1N NaOH aqueous solution (5 mL) was added. The solvent was concentrated under reduced pressure and extracted with ethyl acetate. The organic layer was washed with water and brine and then dried over anhydrous sodium sulfate. After the desiccant was filtered off, the solvent was concentrated under reduced pressure to obtain Intermediate D7 as a pale yellow liquid. (3.87 g)

  Acetic acid (5 mL) was added to Intermediate D7 (0.839 g, 1.56 mmol) and Intermediate E2 (0.535 g, 1.53 mmol) and heated to 80 ° C. After stirring for 3.5 hours as it was, it was concentrated under reduced pressure, and the resulting oil was dissolved in methanol (10 mL), and chloranil (0.376 g, 1.53 mmol) was added. The mixture was stirred at room temperature for 3.5 hours and then left overnight. The reaction solution was filtered, concentrated under reduced pressure, and purified by silica gel column chromatography (chloroform / methanol = 1 = 30 / 1-25 / 1) to obtain Dye 7 (0.366 g). The maximum absorption wavelength (λmax) of this compound in a 10 ppm propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 65/35 solution was 600 nm.

The result of ¹ H NMR is shown below. ¹ H NMR (400 MHz, DMSO-d ⁶ ) δ 0.85 (d, 12H), 1.46 (m, 6H), 1.60 (quint, 2H), 1.79 (quint, 2H), 2.23 (T, 2H), 2.50 (s, 6H), 3.79 (br, 4H), 4.27 (t, 2H), 6.70 (br, 4H), 6.94 (d, 1H) , 7.14-7.40 (m, 19H), 7.88 (d, 1H)
(Synthesis Example 8: Synthesis of Dye 8)
(Synthesis of Intermediate E8)

N, N-dimethylformamide (50 mL) was added to 60% sodium hydride (2.27 g), and a solution of 2-phenylindole (9.66 g) in N, N-dimethylformamide (35 ml) was cooled with an ice bath. The solution was added dropwise over a period of time and stirred for another 2 hours. Subsequently, a solution of 2-ethylhexyl bromide (11.6 g) in N, N-dimethylformamide (30 mL) was added dropwise over 2 hours while cooling with an ice bath, and the mixture was stirred at 20 ° C. for 4 hours and at 35 ° C. for 2 hours. After cooling in an ice bath, water (100 mL) was added, extracted with toluene (200 mL), the organic layer was washed twice with water (150 mL), and the organic layer was dried over anhydrous sodium sulfate. The desiccant was filtered off and concentrated under reduced pressure. The resulting brown liquid was purified by silica gel column chromatography (hexane / toluene = 95/5) to obtain Intermediate E8 (5.49 g) as a transparent liquid. .

The result of ¹ H NMR is shown below.
¹ H NMR (400 MHz, CDCl ₃ ) δ 7.62 (d, 2H, J = 7.6 Hz), 7.50-7.34 (m, 7H), 7.28-7.08 (m, 3H), 6.50 (s, 1H), 4.11 (dd, 2H, J = 7.2, 2.8 Hz), 1.76-1.62 (m, 1H), 1.15-0.95 (m , 8H), 0.75 (t, 3H, J = 7.2 Hz), 0.61 (t, 3H, J = 7.2 Hz)
(Synthesis of Intermediate C8)

Intermediate B1 (1.79 g) and intermediate E8 (1.22 g) were dissolved in toluene (11 mL), phosphorus oxychloride (1.51 g) was added, and the mixture was stirred at 95 ° C. for 6 hr. After cooling to room temperature, water (10 mL) was added, extracted with chloroform, washed twice with saturated brine, and the solvent was distilled off. The resulting crude product was purified by silica gel column chromatography (chloroform / methanol = 10/1) to obtain Intermediate C8 (2.76 g).
(Synthesis of Dye 8)

Intermediate C8 (1.0 g) was dissolved in 10% fuming sulfuric acid (15.0 g), stirred at room temperature for 5 hours, poured into ice water, salted out with lithium chloride, and collected by filtration. The cake was suspended in water, adjusted to pH 7 by adding an aqueous lithium hydroxide solution, filtered and dried. The crude product was purified by medium pressure column chromatography (Yamazen Hi-Flash column octadecyl C18 standard, eluent: methanol / water = 10 / 90-48 / 52) to obtain Dye 8 (0.86 g). .

The maximum absorption wavelength (λmax) of this compound in a 10 ppm propylene glycol monomethyl ether acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 65/35 solution was 612 nm. The results of MS are shown below.
LCMS (EI, posi) m / z 976 (M + 2H-2Li, C 53 H 57 N 3 O 9 S 3) ( Synthesis Example 9: Synthesis of Dye 9)
(Synthesis of Intermediate A9)

p-Toluidine (25.0 g) and potassium carbonate (34.1 g) were added to NMP (200 mL) and heated to 80 ° C. 1-bromobutane (30.7 g) dissolved in NMP (50 mL) was added dropwise thereto over 1 hour, and the mixture was heated and stirred at 80 ° C. for 1 hour. After standing to cool to room temperature, toluene (200 mL) and distilled water (200 mL) were added for extraction, and distilled water (200 mL) was extracted.
And the organic layer was washed with a saturated aqueous sodium chloride solution. The organic layer was dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure, followed by silica gel column chromatography (hexane: ethyl acetate = 6/1) to obtain Intermediate A9 (15.0 g) as a pale yellow liquid. .
(Synthesis of Intermediate B9)

Intermediate A9 (10.0 g) was dissolved in N, N-dimethylformamide (20 mL), cooled in an ice bath, and potassium t-butoxy (6.88 g) was added in small portions. Further, a solution of 4,4′-difluorobenzophenone (3.34 g) in N, N-dimethylformamide (20 mL) was added dropwise over 30 minutes with cooling in an ice bath, and the mixture was stirred at 50 ° C. for 3 hours. After cooling to room temperature, water and toluene were added, the organic layer was separated, and the organic layer was washed with water. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. Purification by silica gel column chromatography (hexane / ethyl acetate 10/1 to 5/1) gave Intermediate B9 (1.94 g) as a pale yellow solid.
(Synthesis of Intermediate C9)

To a mixture of Intermediate B9 (5.05 g), 1-methyl-2-phenylindole (2.48 g) and toluene (40 mL) was added phosphorus oxychloride (3.83 g), and 7.
Heated for 5 hours. After cooling to room temperature, water was added, extracted with chloroform, and the organic layer was washed 3 times with saturated brine. The organic layer was concentrated under reduced pressure and purified by silica gel column chromatography (chloroform / methanol = 20/1 to 10/1) to obtain Intermediate C9 (5.37 g).
(Synthesis of Dye 9)

A mixture of intermediate C9 (1.0 g) and 95% sulfuric acid (15.0 g) was stirred at 75 ° C. for 5 hours. After cooling to room temperature, it was discharged into ice water, and the precipitate was collected by filtration. This cake was dissolved in acetone (20 mL), diluted with water (100 mL), acetone was distilled off, and the precipitate was filtered and dried to obtain Dye 9 (0.73 g). The maximum absorption wavelength (λmax) in a 10 ppm propylene glycol monomethyl ether acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 65/35 solution of this compound was 608 nm. The results of MS are shown below.
LCMS (EI, posi) m / z 773 (M, C ₅₀ H ₅₁ N ₃ O ₃ S) (Reference Synthesis Example 1: Synthesis of Comparative Dye)

The comparative dye was synthesized by the method described in JP2011-70172.
(Reference Synthesis Example 2: 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. Here, 5.2 parts by weight of styrene, 132 parts by weight of glycidyl methacrylate, and 4.4 parts by weight of monoacrylate FA-513M (manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton were added dropwise, and 2.2′-azobis-2 -8.47 weight part of methylbutyronitrile was dripped over 3 hours, and also it stirred at 90 degreeC for 2 hours. Next, the inside of the reaction vessel was changed to air substitution, 1.1 parts by weight of trisdimethylaminomethylphenol and 0.19 parts by weight of hydroquinone were added to 67.0 parts by weight of acrylic acid, and the reaction was continued at 100 ° C. for 12 hours. Thereafter, 15.2 parts by weight of tetrahydrophthalic anhydride (THPA) and 0.2 parts by weight of triethylamine were added and reacted at 100 ° C. for 3.5 hours. The weight average molecular weight Mw measured by GPC of the binder resin thus obtained was about 9000, with an acid value of 25 mg-KOH / g.

(Reference Synthesis Example 3: Synthesis of Resin B)
“NC3000H” (epoxy equivalent 288, softening point 69 ° C.) (manufactured by Nippon Kayaku Co., Ltd.) 400 parts by weight, acrylic acid 102 parts by weight, p-methoxyphenol 0.3 part by weight, triphenylphosphine 5 parts by weight, and propylene glycol The reaction vessel was charged with 264 parts by weight of monomethyl ether acetate and stirred at 95 ° C. until the acid value became 3 mg-KOH / g or less. It took 9 hours for the acid value to reach the target (acid value 2.2 mg-KOH / g). Subsequently, 151 parts by weight of tetrahydrophthalic anhydride was further added and reacted at 95 ° C. for 4 hours to obtain a resin B having an acid value of 102 mg-KOH / g and a polystyrene-reduced weight average molecular weight (Mw) of 3900 measured by GPC. .

[Preparation of blue pigment dispersion]
As a blue pigment, C.I. I. Pigment Blue 15: 6 11.36 parts by weight, 57.5 parts by weight of propylene glycol monomethyl ether acetate as a solvent, 3.02 parts by weight, 0.5 mm in diameter, in terms of solid content, a dispersant “Dispervic 2000” manufactured by Big Chemie 215.7 parts by weight of zirconia beads were filled in a stainless steel container and dispersed in a paint shaker for 6 hours to prepare a blue pigment dispersion.

[Preparation 1 of colored resin composition]
The other components were mixed with the dyes 1 to 9 obtained in Synthesis Examples 1 to 9, the comparative dye, and the resins A and B obtained in Reference Synthesis Examples 2 and 3 so as to have the composition described in Table 1 below. Thus, colored resin compositions were prepared (Examples 1 to 7, Examples 9 to 10, and Comparative Example 1).
In addition, the numerical value of Table 1 represents the weight part of each component to add.

  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 [Preparation 2 of colored resin composition]
A colored resin composition is prepared by mixing the other components of the dye A obtained in the synthesis example, the comparative dye, and the resin A obtained in the reference synthesis example 2 so as to have the composition described in Table 2 below. did. In Example 8, Dye 1 was used, and in Comparative Example 2, a comparative dye was used.

In addition, the numerical value of Table 2 represents the weight part of each component to add.
In mixing, the components were stirred for 1 hour or more until they were sufficiently mixed, and finally filtered through a 5 μm piece filter to remove foreign matters.

In addition, all the numerical values in Table 2 represent parts by weight of each component to be added.
[Production of colored resin film and evaluation of brightness]
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 0.120, dried under reduced pressure, and then heated on a hot plate at 80 ° C. And pre-baked for 3 minutes. Thereafter, the entire surface was exposed with an exposure amount of 60 mJ / cm ² .

Subsequently, baking was performed at 230 ° C. for 30 minutes in a clean oven, 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.
The evaluation results (Examples 1-7, Examples 9-10, Comparative Example 1) using the compositions prepared according to [Preparation 1 of colored resin composition] are shown in Table 3, and [Preparation 2 of colored resin composition] Table 4 shows the evaluation results (Example 8, Comparative Example 2) using the compositions prepared according to the above.

As shown in Tables 3 and 4, pixels formed using the colored resin composition containing the color filter dye of the present invention have high luminance.
[Liquid crystal evaluation (voltage holding ratio and ion density)]
A colored resin composition prepared with the above-described ratio and composition containing the dyes of Examples and Comparative Examples was formed on a glass substrate on which an ITO (indium-tin oxide alloy) electrode was vapor-deposited on the entire surface so that the film thickness was about 2 μm. The number of revolutions was set so as to be (300 rpm to 700 rpm), and coating was performed using a spin coater. Next, using a high-pressure mercury lamp, a photomask is applied to the outer periphery to be an electrode, and radiation (20 mW) including each wavelength of 365 nm, 405 nm, and 436 nm is applied to the coating film to 50 m.
The coated substrate was cut out to a large size so as to be exposed at an exposure amount of J / cm ² and opposed to an electrode substrate for a partner described later.

Thereafter, post baking was performed at 230 ° C. for 60 minutes to cure the coating film, and blue pixels were formed on the substrate.
After the substrate on which the blue pixel is formed and the electrode substrate on which ITO electrodes are simply deposited in a predetermined shape are bonded with a sealant mixed with 5 μm glass beads (gap is 5 μm), liquid crystal MLC6846 or liquid crystal MLC7024 (both are Merck & Co., Inc.) was injected, and the injection-side end portion and the opposite-side end portion were sealed by photocuring an ultraviolet curable resin to produce a liquid crystal cell. The electrode area was 0.5 cm ² .

  Next, the voltage holding ratio of the liquid crystal cell was measured at 25 ° C. using a liquid crystal physical property evaluation system 6254 type (manufactured by Toyo Technica Co., Ltd.). The applied voltage at this time is a square wave of 5.0 V, and the measurement frequencies are 60 Hz and 2 Hz. Here, the voltage holding ratio is usually expressed in two ways: area ratio and voltage ratio. In this case, the value of the area ratio is adopted (voltage of 0 milliseconds is observed time 16.7 mm). Voltage trajectory from 0 milliseconds to 16.7 milliseconds relative to the area obtained by maintaining the second (in the case of 60 Hz measurement) or the observation time of 0.5 seconds (in the case of 2 Hz measurement). The ratio of the area surrounded by the zero voltage level).

  The ion density was measured using the same apparatus as the voltage holding ratio. A triangular wave having a frequency of 0.1 Hz and ± 10 V was applied, and a waveform obtained by calculating the time change of current was obtained. The director peak of the liquid crystal in the waveform is measured in advance in the above-mentioned cell containing only the liquid crystal, and then measured for the liquid crystal cell of each example. Table 5 shows the director peak and impurity ion peak of the liquid crystal, the maximum impurity ion density, and the ratio between the director peak current value and the impurity ion peak current value of the liquid crystal.

In addition, the solubility test in liquid crystal was conducted by dropping the colored resin composition into a glass sample bottle having a capacity of 5 ml, and dropping the liquid crystal in a volume 10 to 20 times the dropped volume. A solubility test liquid was prepared by dispersing for 1 hour with an ultrasonic disperser. The supernatant was sucked up with a micropipette tip using capillary action, and the sucked liquid crystal was examined for coloring.
As a result, it can be seen that if the liquid crystal is colored even slightly, the dye is dissolved or compatible with the liquid crystal.
In addition, when a strong ionic bond is formed even if it is compatible with the liquid crystal, the voltage holding ratio tends not to decrease. Further, when the waveform obtained by measuring the ion density is examined, not only the current peak area due to the migration adsorption of the impurity ions to the electrode but also the current value of the impurity with respect to the current value of the director peak (shown in FIG. 3) appearing due to the orientation of the liquid crystal. The magnitude of the ratio of the ion peak current value was also found to be an effective evaluation criterion for the quality of the liquid crystal alignment behavior of the cell, which cannot be measured only by the voltage holding ratio.

The above evaluation results are shown in Table 5.
Table 5 Evaluation results (voltage holding ratio, solubility test in liquid crystal, ion density, ratio of director peak current of liquid crystal to impurity ion peak current)

Although the difference in voltage holding ratio between Example 7 and Comparative Example 1 is small, the difference in maximum ion density is large. In Comparative Example 1, since the current due to the ionic substance is extremely large, neither the maximum ion density nor the director peak of the liquid crystal can be measured, and the good alignment of the liquid crystal tends to be inhibited.
In addition, Example 2 has a large maximum ion density but a low impurity ion peak voltage (the ratio of the impurity ion peak current to the director peak current of the liquid crystal is small, and it is understood that the liquid crystal orientation is hardly disturbed. As a result, the voltage holding ratio can maintain a large value.

  In addition, although the difference in voltage holding ratio at 2 Hz is small between Example 5 and Comparative Example 1, in Example 5, the voltage holding ratio at 60 Hz is still high, and a liquid crystal director peak is observed (a liquid crystal director). Since the ratio of impurity ion peak current to peak current can be measured), it is superior to Comparative Example 1. In Example 5, the voltage holding ratio at 60 Hz is large, and the impurity concentration that can be estimated from the ion density is not more than the picomolar concentration, which is negligibly small from the amount of dye 5 in the colored composition resin. Since it is estimated that it is a component, it is estimated that the ionic component of Example 5 is a factor different from the origin derived from the dye itself.

The voltage holding ratio is 80% or more at 60 Hz, preferably 90% or more, and more preferably 95% or more. In addition, the voltage holding ratio of 2 Hz needs to be considered in conjunction with ion density measurement results (ion density, liquid crystal director peak current / impurity ion peak current) and liquid crystal behavior observation, such as ionic intervention. Preferably it is 50% or more, More preferably, it is 60% or more, More preferably, it is 70% or more.

As described above, a pixel formed using the colored resin composition containing the dye (I) of the present invention has high luminance and high voltage holding ratio.
From this, the color filter which has the pixel formed using the colored resin composition of this invention, and the liquid crystal display device and organic electroluminescence display which have this color filter are high quality.

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

Claims (8)

A dye for a color filter, which is represented by the following formula (I):
(The formula R ¹ to R ⁴ are, each independently represents, an alkyl group which may have a location substituent, or an aromatic ring group which may have a substituent.
R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
Adjacent R ^{1 to} R ⁶ may be connected to form a ring, and the ring may have a substituent.
R ⁷ and R ⁸ each independently represents a hydrogen atom or an arbitrary substituent.
R ⁷ and R ⁸ may be connected to each other to form a ring, and the ring may have a substituent.
Further, the benzene ring and indole ring in the above formula (I) may further have an arbitrary substituent.
M ⁺ represents a hydrogen ion, an alkali metal cation, an alkaline earth metal cation, an ammonium cation or a quaternary ammonium cation.
n represents an integer of 0 to 4. ) (A) a dye, (B) a solvent and (C) a binder resin,
A colored resin composition , wherein the dye (A) contains a dye for a color filter represented by the formula (I) according to claim 1 . The colored resin composition according to claim 2 , further comprising (D) a polymerizable monomer. The colored resin composition according to claim 2 , further comprising (E) a photopolymerization initiation component and / or a thermal polymerization initiation component. The colored resin composition according to any one of claims 2 to 4, further comprising (F) a pigment. It characterized by having a pixel formed by using a colored resin composition according to any one of claims 2-5, color filters.   A liquid crystal display device comprising the color filter according to claim 6.   An organic EL display device comprising the color filter according to claim 6.