TWI588212B - Triarylmethane compound, colored resin composition, color filter, liquid crystal display and organic el display - Google Patents

Description

Triarylmethane-based compound, colored resin composition, color filter, liquid crystal display device, and organic EL display device

The present invention relates to a triarylmethane-based compound, a colored resin composition, a color filter, a liquid crystal display device, and an organic EL display device.

Flat panel displays typified by liquid crystal display devices and organic EL (Electroluminescence) display devices are widely used, and color filters are used in these displays. In view of the trend of energy saving, the industry is demanding further high brightness and high contrast. In the color filter, a pigmented resin composition is mainly used, but in order to achieve high brightness and high contrast, for example, Non-Patent Document 1 discloses that fine dispersion is performed until the particle diameter of the pigment particles becomes 1 of its color development wavelength. /2 or less.

On the other hand, as a coloring agent, the development of dyes is also carried out in the industry. For example, Patent Document 1 discloses a case where a triarylmethane derivative is used as a dye. Further, in Patent Documents 2 and 3, the case where the anion has a specific structure is revealed for the triarylmethane salt.

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open Publication No. 2008-304766

Patent Document 2: Japanese Patent Laid-Open Publication No. 2011-132492

Patent Document 3: Japanese Patent Laid-Open Publication No. 2011-133844

[Non-patent literature]

Non-Patent Document 1: Bridge Claw, "Color Materials Association", December 1967, p608

However, with respect to the method disclosed in Non-Patent Document 1, in particular, the blue pigment has a shorter color development wavelength than other red and green pigments, so further fine dispersion, cost increase, and dispersion are required in this case. Stability is a problem. Further, in Patent Documents 1 to 3 for improving triarylmethane salts, it has been found that it is difficult to simultaneously achieve the luminance and voltage holding ratio of the obtained pixels. Accordingly, an object of the present invention is to provide a novel triarylmethane-based compound which can obtain pixels which simultaneously achieve luminance and voltage retention. Further, an object of the present invention is to provide a colored resin composition containing a novel triarylmethane-based compound which can form a pixel having a high luminance and a high voltage holding ratio. Further, an object of the present invention is to provide a color filter including a pixel having a high luminance and a high voltage holding ratio, and a high-quality liquid crystal display device and an organic EL display device.

As a result of intensive studies, the inventors of the present invention have found that the above problems can be solved by using a novel triarylmethane-based compound having a specific structure, and have completed the present invention. In other words, the present invention relates to a triarylmethane-based compound (hereinafter, abbreviated as "the compound (I)") represented by the following formula (I), a colored resin composition containing the compound (I), and a color. A filter, a liquid crystal display device, and an organic EL display device.

[1] A triarylmethane-based compound represented by the following formula (I), [Chemical Formula 1]

(In the above formula (I), R ¹ to R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or an aromatic ring group which may have a substituent; adjacent R ¹ ~ R ⁶ may be bonded to each other to form a ring, and the ring may have a substituent; R ⁷ and R ⁸ each independently represent a hydrogen atom or an arbitrary substituent; wherein at least one of R ⁷ and R ⁸ is a halogen atom, Or an alkyl group having 1 to 10 carbon atoms which may have a substituent; M ⁺ represents a cation; n represents an integer of 0 to 4).

[2] The triarylmethane-based compound according to [1], wherein, in the above formula (I), R ⁷ is a hydrogen atom, and R ⁸ is a halogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent.

[3] The triarylmethane-based compound according to [1] or [2], wherein the compound represented by the above formula (I) is a compound represented by the following formula (II), [Chemical 2]

(In the above formula (II), n, M ⁺ , R ¹ to R ⁵ , R ⁷ and R ⁸ are the same as defined in the above formula (I); and R ¹¹ and R ¹² each independently represent a hydrogen atom or an arbitrary substitution. Base; m represents an integer from 1 to 8.)

[4] A colored resin composition comprising (A) a dye, (B) a solvent, and (C) a binder resin, and (A) the dye contains the triarylmethane according to any one of [1] to [3] a compound.

[5] The colored resin composition according to [4], which further contains (D) a polymerizable monomer.

[6] The colored resin composition according to [4] or [5], which further contains at least one of (E) a photopolymerization starting component and a thermal polymerization starting component.

[7] A color filter having a pixel formed using the colored resin composition according to any one of [4] to [6].

[8] A liquid crystal display device having the color filter of [7].

[9] An organic EL display device having the color filter of [7].

According to the present invention, it is possible to provide a novel triarylmethane-based compound which can obtain pixels which simultaneously achieve luminance and voltage retention. Further, according to the present invention, it is possible to provide a novel triarylmethane containing a pixel which can form a higher luminance and a higher voltage holding ratio. A colored resin composition of a compound. Moreover, the present invention can provide a color filter including a pixel having a high luminance and a high voltage holding ratio, and a high-quality liquid crystal display device and an organic EL display device.

10‧‧‧Transparent support substrate

20‧‧ ‧ pixels

30‧‧‧Organic protective layer

40‧‧‧Inorganic oxide film

50‧‧‧Transparent anode

51‧‧‧ hole injection layer

52‧‧‧ hole transport layer

53‧‧‧Lighting layer

54‧‧‧Electronic injection layer

55‧‧‧ cathode

100‧‧‧Organic EL components

500‧‧‧Organic emitters

A‧‧‧ impurity peak

B‧‧‧ impurity peak

c‧‧‧Maximum ion density

d‧‧‧Direct peak current of liquid crystal (polarity of impurity peak)

E‧‧‧ impurity peak current (the largest of the impurity peaks selected)

F‧‧‧ direct peak of liquid crystal

Fig. 1 is a schematic cross-sectional view showing an example of an organic EL device having a color filter of the present invention.

Figure 2 is a direct peak diagram of the alignment of liquid crystals in the examples.

Hereinafter, the embodiments of the present invention will be described in detail, but the following description is an example of the embodiment of the present invention, and the present invention is not limited to the contents. In the present invention, "(meth)acrylonitrile", "(meth)acrylate" and the like means "at least one of an acryloyl group and a methacryloyl group", and "acrylic acid ester" "At least one of methacrylate" or the like, for example, "(meth)acrylic acid" means "at least one of acrylic acid and methacrylic acid".

In addition, the "total solid content" means the total component of the colored resin composition of the present invention other than the solvent component described below. Further, the term "aromatic ring" means both "aromatic hydrocarbon ring" and "aromatic heterocyclic ring". Further, terms such as "C.I. Pigment Green" mean a color index (C.I.).

First, the compound (I) in the present invention will be described in detail.

[About Compound (I)]

The triarylmethane-based compound of the present invention is represented by the following formula (I).

[Chemical 3]

(In the above formula (I), R ¹ to R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or an aromatic ring group which may have a substituent; adjacent R ¹ ~ R ⁶ may be bonded to each other to form a ring, and the ring may have a substituent; R ⁷ and R ⁸ each independently represent a hydrogen atom or an arbitrary substituent; wherein at least one of R ⁷ and R ⁸ is a halogen atom, Or an alkyl group having 1 to 10 carbon atoms which may have a substituent; M ⁺ represents a cation; n represents an integer of 0 to 4)

Further, in the above formula (I), the -SO ₃ ^- group and the -(SO ₃ ^- M ⁺ ) _n group shown outside [ ] represent an aromatic ring in [ ], R ¹ to R ⁸ , or R ¹ ~ The substituent of R ⁸ is substituted by -SO ₃ ^- group and -(SO ₃ ^- M ⁺ ) _n , respectively.

(About R ¹ ~R ⁶ )

R ¹ to R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or an aromatic ring group which may have a substituent. The alkyl group in R ¹ to R ⁶ may be a linear, branched or cyclic alkyl group having usually 1 or more carbon atoms, and usually 10 or less. Specific examples thereof include methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, tert-butyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl, and benzene. Ethyl 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 monocyclic 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, and examples thereof include a benzene ring having one free valence and naphthalene. Ring, anthracene ring, phenanthrene ring, anthracene ring, fused tetraphenyl ring, anthracene ring, benzofluorene ring, The ring, the benzene ring, the ethane naphthalene ring, the fluoranthene ring, the anthracene ring and the like.

Further, the aromatic heterocyclic group may be a monocyclic ring or a condensed ring, and is not particularly limited as long as the number of carbon atoms forming the ring is from 3 to 10, and examples thereof include a furan ring having one free valence. , benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, Diazole ring, anthracene ring, indazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furanfuran ring, thiophene Furan ring, benzopyrene Oxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyridyl Ring, 嗒 Ring, pyrimidine ring, three Ring, quinoline ring, isoquinoline ring, Porphyrin ring, quinolin a group of a phenyl ring, a phenazin ring, a benzimidazole ring, an acridine ring, a quinazoline ring, a quinazolinone ring, an anthracene ring or the like.

Adjacent R ¹ to R ⁶ may be bonded to each other (specifically, R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ ) to form a ring, and the ring may have a substituent. Further, the ring may be a ring bridged by a hetero atom, and specific examples thereof include the following structures.

In terms of chemical stability, R ¹ to R ^{6 are} preferably independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or a phenyl group which may have a substituent, or adjacent thereto. The case where R ¹ to R ⁶ are connected to each other to form a ring. These substituents are also preferred in terms of brightness. In terms of improving the heat resistance of the compound (I) and obtaining excellent heat resistance of the color filter, it is more preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or may have a substituent. Phenyl.

When R ¹ to R ⁶ are an alkyl group having 1 to 10 carbon atoms which may have a substituent, the charge in the cation is dispersed by the superconjugation to stabilize the cation. More specifically, regarding the carbon number of the alkyl group in R ¹ to R ⁴ , it is difficult to affect the configuration of the triarylmethane skeleton (the effect on the brightness is less) and the substituent on N is not easily separated. In the aspect (the compound (I) is relatively stable), it is preferably 8 or less, more preferably 4 or less, and still more preferably 2 or more. Further, with respect to R ⁵ and R ^6, it aspect Compound (I) is not easy and the color tone of decomposition (high luminance) of the viewpoint is preferably R ⁵ is a hydrogen atom, R ⁶ is alkyl. The number of carbon atoms of the alkyl group in R ⁶ is more preferably 8 or less, still more preferably 5 or less. Further, when R ¹ to R ⁶ adjacent to each other are bonded to each other to form a ring, the substituent on N is not easily detached, and therefore it is stable. In the case where R ¹ to R ⁶ are a phenyl group which may have a substituent, the conjugated system is elongated, so that the charge in the cation is dispersed to stabilize the cation. It is considered that the cation is stabilized as described above, and as a result, the heat resistance of the obtained color filter is further improved. R ¹ ~ R ring as in the alkyl group, aromatic ring group, and mutually connected to form the ⁶ may have a substituent group, and examples include the following (the substituent group W) by.

(substituent group W)

a fluorine atom, a chlorine atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a 2,4,6-trimethylphenyl group, a tolyl group, Naphthyl, cyano, ethoxycarbonyl, alkylcarbonyloxy having 2 to 9 carbons, sulfonyl group, alkylamine sulfonyl group having 2 to 9 carbon atoms, alkylcarbonyl group having 2 to 9 carbon atoms a dialkylaminoethyl group, a trifluoromethyl group, a carbon number of 1-8 alkane bonded by a phenethyl group, a hydroxyethyl group, an ethyl hydrazinium group, an alkyl group having 1 to 4 carbon atoms. An alkylthio group having an alkyl group, a nitro group and a carbon number of 1 to 8. In the above, the substituent which may be possessed by the alkyl group, the aromatic ring group and the ring which are bonded to each other in R ¹ to R ⁶ is preferably an alkyl group having 1 to 10 carbon atoms and an alkoxy group having 2 to 8 carbon atoms. A cyano group, a cyano group, an ethoxy group, an alkylcarboxy group having 2 to 8 carbon atoms, an amine sulfonyl group, an alkylamine sulfonyl group having 2 to 9 carbon atoms, and a fluorine atom.

(About R ⁷ and R ⁸ )

R ⁷ and R ⁸ represent a hydrogen atom or an arbitrary substituent. Examples of the above-mentioned substituent include a halogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, an aromatic ring group which may have a substituent, and the like. Here, at least one of R ⁷ and R ⁸ is a halogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent. That is, in the benzene ring in the formula (I), if a large volume group is bonded to the ortho position to the bond of the carbon atom at the center of the triarylmethane structure, the center of the triaryl methane structure is stereoscopically protected. Therefore, the heat resistance of the compound (I) is improved.

Further, the carbon number of the alkyl group in R ⁷ and R ⁸ in terms of the absorption spectrum change caused by the change in the molecular configuration of the compound (I) and the decrease in the brightness of the pixel obtained thereby It is preferably 8 or less, more preferably 6 or less, still more preferably 4 or less, and usually 1 or more. As a preferred aspect of R ⁷ and R ⁸ , R ⁷ is preferably a hydrogen atom, R ⁸ is an alkyl group, and particularly preferably R ⁷ is a hydrogen atom and R ⁸ is a methyl group. Further, R ⁷ and R ⁸ may be bonded to each other to form a ring, and the ring may have a substituent. Examples of the substituent include those described in the above (Substituent Group W). In the case where the alkyl group in R ⁷ and R ⁸ has a substituent, a halogen atom is preferred. That is, a fluoromethyl group such as a trifluoromethyl group or the like can be preferably used.

(about M ⁺ and n)

M ⁺ represents a cation, and examples thereof include a hydrogen ion, an alkali metal cation, an alkaline earth metal cation, a tertiary ammonium cation, or a quaternary ammonium cation.

Examples of the alkali metal of the alkali metal cation include lithium, sodium, potassium, and the like. Moreover, examples of the alkaline earth metal as the alkaline earth metal cation include magnesium, calcium, barium, and the like. The tertiary ammonium cation is 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; further, the plurality of Rs may be the same, or Different) representation.

The preferred carbon number of the alkyl group in the above R and the substituent which the alkyl group may have are the same as those exemplified in the case of the above-mentioned alkyl group of R ¹ to R ⁶ . The preferred carbon number of the aromatic ring group and the substituent which the aromatic ring group may have are the same as those exemplified in the case of the above-mentioned aromatic ring group of R ¹ to R ⁶ . Specific examples thereof include a lower alkylammonium cation having 1 to 6 carbon atoms (for example, a methylammonium cation, an ethylammonium cation, a diethylammonium cation, a triethylammonium cation, etc.), which is substituted by a hydroxy group. An alkylammonium cation having 1 to 6 carbon atoms (for example, an ethanolammonium cation, a diethanolammonium cation, a triethanolammonium cation, etc.), an alkylammonium cation having a carbon number of 1 to 6 substituted with a carboxyl group (for example, carboxymethylammonium) a cationic cation, a carboxyethylammonium cation, a carboxypropylammonium cation, a dicarboxymethylammonium cation, or the like, an ammonium cation substituted with an aromatic ring group and an alkyl group (for example, N,N-diethylphenylammonium cation, etc.) )Wait.

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. Furthermore, the plurality of Rs contained 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 above-mentioned alkyl group of R ¹ to R ⁶ . The preferred carbon number of the aromatic ring group, and examples of the substituent which may be present, are the same as those exemplified in the case of the above-mentioned aromatic ring group of R ¹ to R ⁶ .

Specific examples thereof include a quaternary ammonium alkyl cation having 1 to 6 carbon atoms (for example, a tetramethylammonium cation, a tetraethylammonium cation, a tetrabutylammonium cation, etc.). Further, the type of the cation of M ⁺ is not limited to one type, and a plurality of types may be mixed. Further, a plurality of kinds may be mixed in one molecule of the compound, or a plurality of kinds may be mixed in the colored resin composition. With respect to M ⁺ , a hydrogen ion, an alkali metal cation, a tertiary ammonium cation, a quaternary ammonium cation is preferable from the viewpoint of solubility in an organic solvent used in the colored resin composition. Further preferred are lithium cations, sodium cations, unsubstituted ammonium cations, and tetrabutylammonium cations.

n represents an integer from 0 to 4. The larger the n is, the more the sulfo group of the hydrophilic group is substituted with the compound (I), the heat resistance and the light resistance are improved, and the solubility of the compound (I) in the hydrophobic liquid crystal is also lowered, so that the voltage holding ratio is also improved, but It is preferably 0 to 2 in terms of high solubility in the organic solvent used in the colored resin composition.

(About the substitution position of -SO ₃ ^- group)

In the compound (I), the -SO ₃ ^- group other than [ ] represents a substituent which is substituted with an aromatic ring, R ¹ to R ⁸ or R ¹ to R ⁸ in [ ]. A preferred substitution position of the -SO ₃ ^- group is a hydrogen atom forming a hydrogen atom on the naphthalene ring of the triarylmethane skeleton or a substituent on R ⁶ . Preferably, the -SO ₃ ^- group is substituted on the naphthalene ring forming the triarylmethane skeleton for the following reasons. When the compound (I) in which the -SO ₃ ^- group is substituted on the naphthalene ring is ionicly bonded to the nitrogen atom or the central carbon atom of another molecule, the compound (I) - The SO ₃ ^- group is located on the naphthalene ring, whereby the distance between the naphthalene ring of the compound (I) and the aromatic ring possessed by the other molecule becomes close. Therefore, in addition to the ionic bond between the two molecules, a π-π interaction is also generated, so that the intermolecular force is enhanced, and heat resistance and electrical reliability are improved. Further, by setting the -SO ₃ ^- group on the naphthalene ring, the position of the center carbon of the same molecule and the -SO ₃ ^- group become close, and the effect of solid salt formation in the molecule can be expected. Further, in particular, when the -SO ₃ ^- group is substituted on the naphthalene ring in which the nitrogen atom of the naphthalene ring is unsubstituted, the contribution to the conjugated system of the triarylmethane skeleton is small, and the influence on the color development is small. It is also better in terms of brightness. Next, it is preferred that the -SO ₃ ^- group is substituted on the substituent on R ⁶ for the following reason. The introduction of a -SO ₃ ^- group to the substituent on R ⁶ is less restrictive in synthesis than the case of introducing a substituent to R ¹ to R ⁴ , and is relatively easy, and -SO on the substituent of R ⁶ ₃ ^- Based on the formation of ionic bonds in or between molecules, a relatively free position can be obtained, which is easily disposed at a position where a strong ionic bond can be formed. In particular, when R ⁶ is an alkyl group, the degree of freedom of the substituent is high, and therefore the -SO ₃ ^- group is easily located at a position suitable for intramolecular and intermolecular ionic bonding, so that a strong ion can be formed. The key is therefore preferable in terms of heat resistance and electrical reliability. Further, the contribution to the conjugated system of the triarylmethane skeleton is small, and the influence on the color development is small, and the brightness of the obtained pixel is also preferable. Further, in the formula (I), the expression of the bond bond of the -SO ₃ ^- group or the -SO ₃ ^- M ⁺ group to [ ] means that there are a plurality of substitution positions or a substitution position in the synthesis. The form of the mixture of compounds is obtained and the like.

[Compound represented by formula (II)]

The compound (I) is preferably a compound represented by the following formula (II) (hereinafter referred to as "compound (II)") in terms of the brightness and voltage holding ratio of the obtained pixel.

(In the above formula (II), n, M ⁺ , R ¹ to R ⁵ , R ⁷ and R ⁸ are the same as defined in the above formula (I); and R ¹¹ and R ¹² each independently represent a hydrogen atom or an arbitrary substitution. Base; m means an integer from 1 to 8)

(About R ¹¹ and R ¹² )

Examples of the substituent of any of R ¹¹ and R ¹² include those described in the above (Substituent Group W). However, in terms of ease of synthesis, a hydrogen atom is preferred. Further, the plurality of R ¹¹ and R ¹² contained in one molecule may be the same or different from each other, but it is preferably the same in terms of ease of synthesis. Further, R ¹¹ and R ¹² may be the same or different, but are preferably the same in terms of ease of synthesis.

(about m)

m is usually 1 or more, preferably 2 or more, and is usually 8 or less, preferably 5 or less. If it is within the above range, the degree of freedom of SO ₃ ^- at the end of the -(CR ¹¹ R ¹² ) _m - group becomes high, and ionic bonding between molecules becomes easy and with the central carbon atom in the molecule The ion bonding becomes easy, and the heat resistance and the voltage holding ratio become good, which is preferable in this respect.

[molecular weight]

The compound (I) in the present invention has a molecular weight of usually 450 or more, preferably 500 or more, and usually 5,000 or less, preferably 2,000 or less.

If it is in the above range, it is preferable in terms of ease of synthesis.

[Specific example]

[Chemical 6]

[Chemistry 7]

[Chemistry 9]

<About the synthesis method of the compound (I)>

The compound (I) can be synthesized, for example, according to the method described in "General Synthetic Dyes" (Sakaguchi, Sankyo, 1968), "Theory of Manufacturing Dyes Chemistry" (Hita Fumiko, Takubun, 1957), but It is not limited to this method. Specifically, there are (i) a method of constructing a triarylmethane skeleton from a compound having a sulfo group and (ii) a method of introducing a sulfo group after constructing a triarylmethane skeleton. In the case of (i), a benzene ring or a naphthalene ring directly substituted with a sulfo group or a benzene ring or a naphthalene ring which is a triarylmethane skeleton is substituted with a sulfonate. A method of constructing a triarylmethane skeleton by a conventional method. In the case of (ii), there are a method of constructing a triarylmethane skeleton by a conventional method, sulfonation using sulfuric acid, chlorosulfonic acid, fuming sulfuric acid, or the like, a method of introducing a sulfo group, and a compound having a triarylmethane skeleton. A method of introducing a substituent having a sulfo group by reacting with sodium hydroxymethanesulfonate, 1,3-propane sultone, 1,4-butane sultone or the like.

<Use of Compound (I)>

The use of the compound (I) of the present invention is not particularly limited and can be used for various purposes. Among them, the compound (I) of the present invention is preferably used for a color filter in terms of high luminance and voltage retention of the obtained pixel and further high heat resistance of the compound (I). That is, this hair The compound (I) is preferably used as a dye for color filters. Hereinafter, as a dye for a color filter, a coloring resin composition containing the compound (I) will be described.

<Colored resin composition>

The colored resin composition of the present invention contains (A) a dye, (B) a solvent, and (C) a binder resin, and (A) the dye contains the compound (I), and further preferably contains (D) a polymerizable monomer, E) at least one of a photopolymerization starting component and a thermal polymerization starting component, and if necessary, other components.

First, the (A) dye will be described in detail.

[About (A) Dyes]

The colored resin composition of the present invention contains the compound (I) in the dye (A). However, other dyes other than the compound (I) may be contained as long as the effects of the present invention are not impaired. Examples of the other dyes include an azo dye, an anthraquinone dye, a phthalocyanine dye, a quinone imine dye, a quinoline dye, a nitro dye, a carbonyl dye, and a methine group. Dyes, cyanine dyes, triarylmethane dyes, dipyrromethene dyes, Dyes and the like. Examples of the azo dye include CI Acid Yellow 11, CI Acid Orange 7, CI Acid Red 37, CI Acid Red 180, CI Acid Blue 29, CI Direct Red 28, CI Direct Red 83, and CI Direct Yellow 12 , CI Direct Orange 26, CI Direct Green 28, CI Direct Green 59, CI Reaction Yellow 2, CI Reaction Red 17, CI Reaction Red 120, CI Reaction Black 5, CI Disperse Orange 5, CI Disperse Red 58, CI Disperse Blue 165 , CI alkaline blue 41, CI alkaline red 18, CI mordant red 7, CI mordant yellow 5, CI mord black 7 and so on. Examples of the lanthanide dyes include CI Indigo 4, CI Acid Blue 25, CI Acid Blue 40, CI Acid Blue 80, CI Acid Green 25, CI Reaction Blue 19, CI Reaction Blue 49, and CI Disperse Red 60. , CI Disperse Blue 56, CI Disperse Blue 60, etc. In addition, examples of the phthalocyanine-based dye include CI Direct Blue 86, CI Direct Blue 199, CI Indigo 5, JP-A-2002-14222, JP-A-2005-134759, and JP-A-2010- In the case of the quinone imine dye, for example, CI basic blue 3, CI basic blue 9, etc., and the quinoline dye can be used, for example. For example, CI Solvent Yellow 33, CI Acid Yellow 3, CI Disperse Yellow 64, and the like; examples of the nitro dye include CI Acid Yellow 1, CI Acid Orange 3, and CI Disperse Yellow 42. In addition, examples of the triarylmethane dye include those described in CI Acid Blue 86, CI Acid Blue 88, CI Acid Blue 108, International Publication No. 2009/107734, and International Publication No. 2011/162217. Further, examples of the cyanine dye include those described in International Publication No. 2011/162217, and preferred embodiments are also the same. Examples of the dipyrromethene-based dyes include, for example, JP-A-2008-292970, JP-A-2010-84009, JP-A-2010-84141, JP-A-2010-85454, and JP-A-2010-85454 The person described in the Japanese Patent Publication No. 2012-224846, the Japanese Patent Publication No. 2012-224846, the Japanese Patent Application Publication No. 2012-224849 . As Examples of the dyes include CI Acid Red 50, CI Acid Red 52, CI Acid Red 289, Japanese Patent No. 3,837, 751, JP-A-2010-32999, No. 4,492,760, and "General Synthetic Dyes" ( Sakaguchi, the three publications, 1968, 326 pages ~ 348 pages, etc. Especially when forming a blue pixel, it is preferably A dye, a triarylmethane dye, an anthraquinone dye, an azo dye, a dipyrromethene dye, a cyanine dye, or a phthalocyanine dye. In the colored resin composition of the present invention, the (A) dye may contain only one kind of the compound (I), or may contain two or more kinds. Further, one or two or more kinds of other dyes other than the compound (I) may be contained.

(content)

The content of all (A) dyes in the colored resin composition of the present invention is preferably 0.01% by weight or more, and more preferably 50% by weight or less, based on the total solid content. Also, colored resin group The content of the compound (I) in the product is usually 0.01% by weight or more, preferably 0.1% by weight or more, more preferably 1% by weight or more, and usually 50% by weight or less, based on the total solid content. It is 40% by weight or less, more preferably 30% by weight or less. When it is at most the above upper limit, the hardenability of the coating film is not easily lowered, and the film strength is sufficient, which is preferable. Moreover, when it is more than the above lower limit, the coloring power is sufficient, so that the chromaticity of the desired concentration is easily obtained, and the film thickness is not easily increased, which is preferable.

Further, in the colored resin composition of the present invention, the content of the compound (I) is preferably 30% by weight or more based on the total solid content of the (A) dye.

[(B) Solvent]

The (B) solvent contained in the colored resin composition of the present invention has a function of dissolving or dispersing each component contained in the colored resin composition to adjust the viscosity.

The solvent (B) may be any component which can dissolve or disperse the constituent resin composition, and it is preferred to select a boiling point of 100 to 200 °C. More preferably, it has a boiling point of 120 to 170 °C. As such a solvent, the following are mentioned, for example. Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol a diol such as alcohol monoethyl ether, methoxymethylpentanol, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol or tripropylene glycol monomethyl ether Monoalkyl ethers; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether Glycol dialkyl ethers; 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 Ester, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl Glycol alkyl ether such as ether acetate or 3-methyl-3-methoxybutyl acetate Acid esters; ethers such as diethyl ether, dipropyl ether, diisopropyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether; acetone, methyl ethyl ketone, methyl amyl ketone, Isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl Ketones such as hexyl ketone and methyl decyl ketone; monovalent or divalent substances such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, and glycerin Alcohols; aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane; cyclohexane, methylcyclohexane, An alicyclic hydrocarbon such as methylcyclohexene or bicyclohexane; an aromatic hydrocarbon such as benzene, toluene, xylene or cumene; amyl formate, ethyl formate, ethyl acetate, acetic acid Butyl ester, propyl acetate, amyl acetate, cyclohexyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, Methyl isobutyrate, octanoic acid Ester, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, 3-methoxypropionic acid Chain or cyclic esters such as ethyl ester, propyl 3-methoxypropionate, butyl 3-methoxypropionate, γ-butyrolactone; 3-methoxypropionic acid, 3-ethyl Alkoxycarboxylic acids such as oxypropionic acid; halogenated hydrocarbons such as chlorobutane and chloropentane; ether ketones such as methoxymethylpentanone; and nitriles such as acetonitrile and benzonitrile The solvent may be used alone or in combination of two or more.

Among the above solvents, the diol monoalkyl ethers are preferred in terms of the solubility of the dye (A) in the present invention. Among them, propylene glycol monomethyl ether is particularly preferable in terms of solubility of various constituent components in the colored resin composition. In addition, when the following (F) pigment is contained as an optional component, the balance between coatability and surface tension is good, and the solubility of the component in the colored resin composition is relatively high. It is preferred to further use a glycol alkyl ether acetate as a solvent. Furthermore, in the pigmented resin composition containing the pigment, the diol monoalkyl ether has a higher polarity and has a pigment The tendency to agglomerate may be such that the viscosity of the colored resin composition is increased to lower the storage stability. Therefore, the amount of the diol monoalkyl ethers used is preferably not too much, and the ratio of the diol monoalkyl ethers in the solvent (B) is preferably from 5 to 50% by weight, more preferably from 5 to 30% by weight. .

Moreover, from the viewpoint of adaptability to the slit coating method corresponding to the recent large substrate or the like, it is also preferred to use a solvent having a boiling point of 150 ° C or higher. In this case, the content of the high boiling point solvent is preferably from 3 to 50% by weight, more preferably from 5 to 40% by weight, even more preferably from 5 to 30% by weight, based on the total of the solvent (B). When the amount of the high-boiling solvent is too small, for example, a dye component may be deposited and solidified at the tip end of the slit nozzle to cause foreign matter defects, and if too large, the drying speed of the composition may be slow, resulting in the following color. Problems such as poor contact in the vacuum drying process in the filter manufacturing step or traces of pre-baked pores.

Further, the solvent having a boiling point of 150 ° C or higher may be a glycol alkyl ether acetate or a glycol alkyl ether. In this case, a solvent having a boiling point of 150 ° C or higher may not be additionally contained. The colored resin composition of the present invention can also be used for the production of a color filter by an ink jet method, but in the manufacture of a color filter by an ink jet method, the ink ejected from the nozzle is a very small number. ~ tens of pL, so there is a tendency for the solvent to evaporate and the ink to concentrate and dry before being sprayed to the periphery of the nozzle opening or in the pixel array. In order to avoid the above, the higher the boiling point of the solvent, the better. Specifically, the solvent (B) preferably contains a solvent having a boiling point of 180 ° C or higher. More preferably, it contains a solvent having a boiling point of 200 ° C or higher, particularly a boiling point of 220 ° C or higher. Further, the high boiling point solvent having a boiling point of 180 ° C or higher is preferably 50% by weight or more in the solvent (B). 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 solvent (B) is not particularly limited, and the upper limit is usually set to 99% by weight. The content of the solvent (B) in the composition exceeds In the case of 99% by weight, the concentration of each component other than the solvent (B) is too small, and it may become difficult to form 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 view of viscosity or the like suitable for coating.

[(C) Binder Resin]

(C) The binder resin preferably differs depending on the hardening means of the colored resin composition. In the case where the coloring resin composition of the present invention is a photopolymerizable resin composition, as the (C) binder resin, for example, Japanese Patent Laid-Open No. Hei 7-207211, No. Hei 8-259876, and No. A polymer compound described in each of the publications of Japanese Patent Laid-Open Publication No. Hei. The following (C-1) to (C-5) resins and the like are preferable.

(C-1): a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer, wherein at least a part of the epoxy group of the copolymer is added with an unsaturated monobasic acid An alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of a hydroxyl group formed by the addition reaction (hereinafter referred to as "resin (C-1)")

(C-2): a linear alkali-soluble resin (C-2) having a carboxyl group (hereinafter referred to as "resin (C-2)")

(C-3): a resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group of the above resin (C-2) (hereinafter referred to as "resin (C-3)")

(C-4): (meth)acrylic resin (hereinafter referred to as "resin (C-4)")

(C-5): epoxy acrylate resin having a carboxyl group (hereinafter, referred to as "resin (C-5)" Situation)

Among them, the resin (C-1) can be preferably mentioned, and the resin will be described below. In addition, the resin (C-2) to (C-5) may be any one of those having a solubility which can be dissolved by an alkaline developer and can be subjected to a target development treatment. The same as that described in the item of the publication No. 2009-025813. The preferred form is also the same.

(C-1): a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer, wherein at least a part of the epoxy group of the copolymer is added with an unsaturated monobasic acid An alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of a hydroxyl group formed by the addition reaction

One of the resins which are particularly preferable as the resin (C-1) is 5 to 90 mol% of the epoxy group-containing (meth) acrylate and 10 to 95 mol of the other radical polymerizable monomer. a copolymer of %, a resin obtained by adding 10 to 100 mol% of the epoxy group of the copolymer to an unsaturated monobasic acid, or 10 to 100 moles of a hydroxyl group formed by the addition reaction An alkali-soluble resin obtained by adding a polybasic acid to the ear.

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

The other radical polymerizable monomer to be copolymerized with the epoxy group-containing (meth) acrylate is not particularly limited as long as the effects of the present invention are not impaired, and examples thereof include vinyl aromatics. , dienes, (meth) acrylates, (meth) acrylamides, vinyl compounds, unsaturated dicarboxylic acid diesters, mono-n-butylene diimides In particular, a mono(meth)acrylate having a structure represented by the following formula (7) is particularly preferred.

The repeating unit derived from the mono(meth)acrylate having the structure represented by the following formula (7) is in a repeating unit derived from "other radical polymerizable monomer", preferably containing 5 to 90 moles. %, further preferably contains 10 to 70 mol%, and particularly 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).

In the above formula (8), R ⁹¹ to R ⁹⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Further, R ⁹⁶ and R ⁹⁸ may be bonded to each other to form a ring. The ring formed by linking R ⁹⁶ and R ^{98 is} preferably an aliphatic ring, and may be either saturated or unsaturated, and further preferably has a carbon number of 5 to 6. Among them, the structure represented by the formula (8) is particularly preferably represented by the following structural formulae (8a), (8b), or (8c).

[化12]

In addition, the mono(meth)acrylate having the structure represented by the above formula (8) may be used alone or in combination of two or more. As the "other radical polymerizable monomer" other than the mono(meth)acrylate having the structure represented by the above formula (8), the colored resin composition can have excellent heat resistance and strength. Examples thereof include styrene, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, and (meth)acrylic acid. Base ester, adamantyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N-phenyl maleimide, N-cyclohexyl cis Butylene diimine.

The content of the repeating unit derived from at least one selected from the above monomer groups is preferably from 1 to 70 mol%, more preferably from 3 to 50 mol%. Further, a known solution polymerization method can be applied to the copolymerization reaction of the above epoxy group-containing (meth) acrylate with the above other radical polymerizable monomer. In the present invention, the copolymer of the epoxy group-containing (meth) acrylate and the other radical polymerizable monomer preferably contains a repeat derived from an epoxy group-containing (meth) acrylate. 5 to 90 mol% of the unit and 10 to 95 mol% of the repeating unit derived from other radical polymerizable monomers, and more preferably 20 to 80 mol% of the former and 80 to 20 mol% of the latter. Youjia is 30~70% for the former and 70~30 for the latter. Mole%.

When it is in the above range, the addition amount of the polymerizable component and the alkali-soluble component described below is sufficient, and the heat resistance or the strength of the film is sufficient, which is preferable. The unsaturated monobasic acid (polymerizable component) and further the polybasic acid anhydride (alkali soluble component) are reacted with the epoxy group of the epoxy group-containing copolymer synthesized as described above. Here, as the unsaturated monobasic acid to be added to the epoxy group, a known one can be used, and examples thereof include an unsaturated carboxylic acid having an ethylenically unsaturated double bond.

Specific examples thereof include (meth)acrylic acid, crotonic acid, o/m/p-vinylbenzoic acid, α-position haloalkyl group, alkoxy group, halogen atom, nitro group, or cyano group. A monocarboxylic acid such as (meth)acrylic acid is substituted. Among them, (meth)acrylic acid is preferred. These may be used alone or in combination of two or more.

By adding such a component, the binder resin used in the present invention can be imparted with polymerizability. The unsaturated monobasic acid is usually added to 10 to 100 mol% of the epoxy group of the above copolymer, preferably 30 to 100 mol%, more preferably 50 to 100. Moer%. When it is in the above range, the colored resin composition is excellent in stability over time, which is preferable. Further, as a method of adding an unsaturated monobasic acid to the epoxy group of the copolymer, a known method can be employed.

Further, as the polybasic acid anhydride added to the hydroxyl group formed when the unsaturated monobasic acid is added to the epoxy group of the copolymer, a known one can be used. For example, a dibasic acid anhydride such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride or chloro-bridge anhydride; A trivalent or higher anhydride such as tricarboxylic anhydride, pyromellitic anhydride, diphenyl ketone tetracarboxylic anhydride or biphenyl tetracarboxylic anhydride. Among them, succinic anhydride and tetrahydrophthalic anhydride are preferred. These polybasic acid anhydrides may be used alone or in combination of two or more.

By adding such a component, the binder resin used in the present invention can be made alkali-soluble. The polybasic acid anhydride is usually added in an amount of 10 to 100 mol%, preferably 20 to 90 mol%, of a hydroxyl group formed by adding an unsaturated monobasic acid to the epoxy group of the above copolymer. %, more preferably added to 30~80 mol%.

When it is in the above range, the residual film ratio and solubility at the time of development are sufficient, which is preferable. Further, as a method of adding a polybasic acid anhydride to the hydroxyl group, a known method can be employed. Further, in order to increase the sensitivity, after the addition of the polybasic acid anhydride, a glycidyl (meth)acrylate or a glycidyl ether compound having a polymerizable unsaturated group may be added to a part of the generated carboxyl group. The structure of such a resin is described in, for example, Japanese Laid-Open Patent Publication No. Hei 8-297366 or JP-A-2001-89533.

The above-mentioned binder resin (C-1) preferably has a weight average molecular weight (Mw) in terms of polystyrene measured by GPC (gel permeation chromatography) of 3,000 to 100,000, particularly preferably 5,000 to 50,000. When it is in the above range, it is preferable in terms of heat resistance, film strength, and further solubility in a developing solution. Further, as a standard of the molecular weight distribution, the weight average molecular weight (Mw) / the number average molecular weight (Mn) is preferably from 2.0 to 5.0.

Further, the acid value of the binder resin (C-1) is usually 10 to 200 mg-KOH/g, preferably 15 to 150 mg-KOH/g, and more preferably 25 to 100 mg-KOH/g. If the acid value is too low, the solubility in the developer may be lowered. On the other hand, if it is too high, there is a case where the film is rough. The content of the (C) binder resin in the colored resin composition is usually from 0.1 to 80% by weight, preferably from 1 to 60% by weight, based on the total solids. When it is in the above range, the adhesion to the substrate is good, and the permeability of the developer to the exposed portion is moderate, and the surface smoothness or sensitivity of the pixel is good.

[(D) Polymerizable monomer]

The colored resin composition of the present invention preferably contains (D) a polymerizable monomer. (D) Polymeric sheet The body is not particularly limited as long as it is a polymerizable low molecular compound, and is preferably an addition polymerizable compound having at least one ethylenic double bond (hereinafter referred to as "ethylenic compound").

When the colored resin composition of the present invention is irradiated with active light, the ethylenic double-bonded compound which can be hardened by addition polymerization by the action of the photopolymerization starting component described below can be used. Further, the (D) polymerizable monomer in the present invention means a concept opposite to a so-called high molecular substance, and includes a dimer, a trimer, and an oligomer in addition to the narrowly defined monomer. Examples of the ethylenic compound in the (D) polymerizable monomer include unsaturated carboxylic acids such as (meth)acrylic acid; esters of monohydroxy compounds with unsaturated carboxylic acids; aliphatic polyhydroxy compounds and unsaturated carboxylic acids; An acid ester; an ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid; obtained by esterification reaction of an unsaturated carboxylic acid with a polyvalent carboxylic acid, a polyvalent hydroxy compound such as the above aliphatic polyhydroxy compound or an aromatic polyhydroxy compound; An ester; an ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound with a hydroxy compound containing a (meth) acrylonitrile group.

Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and trimethylolpropane tris(methyl). Acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(a) (meth) acrylate such as acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, or (meth) acrylate. Further, it is possible to replace the (meth)acrylic acid moiety of the (meth) acrylate with the itaconate of the itaconic acid moiety, the butyrate of the butenoic acid moiety, or replace it with a cis. a maleic acid moiety, maleic acid ester or the like.

Examples of the ester of the aromatic polyhydroxy compound and the unsaturated carboxylic acid include: Hydroquinone di(meth)acrylate, resorcinol di(meth)acrylate, pyrogallol tri(meth)acrylate, and the like. The ester obtained by esterification of an unsaturated carboxylic acid with a polyvalent carboxylic acid and a polyvalent hydroxy compound may be a single substance or a mixture. Typical examples include condensates of (meth)acrylic acid, phthalic acid, and ethylene glycol; condensates of (meth)acrylic acid, maleic acid, and diethylene glycol; a condensate of acrylic acid, terephthalic acid, and pentaerythritol; a condensate of (meth)acrylic acid, adipic acid, butylene glycol, and glycerin, and the like.

Examples of the ethylenic compound having a urethane skeleton formed by reacting a polyisocyanate compound with a hydroxy compound containing a (meth) acrylonitrile group include hexamethylene diisocyanate and trimethyl hexamethylene. Aliphatic diisocyanates such as bis-isocyanate, alicyclic diisocyanates such as cyclohexane diisocyanate and isophorone diisocyanate, aromatic diisocyanates such as toluene diisocyanate and diphenylmethane diisocyanate, and (meth)acrylic acid 2 a reaction product of a (meth) acrylonitrile-containing hydroxy compound such as hydroxyethyl ester or 3-hydroxy[1,1,1-tris(meth)acryloxymethyl]propane.

Further, examples of the ethylenic compound used in the present invention include (meth)acrylamide such as ethyl bis(meth)acrylamide; and alkene such as diallyl phthalate. Propyl esters; vinyl-containing compounds such as divinyl phthalate. Among these, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferable, a (meth) acrylate of pentaerythritol or dipentaerythritol is more preferable, and dipentaerythritol hexa (meth) acrylate is especially preferable.

Further, the ethylenic compound may also be a monomer having an acid value. As the monomer having an acid value, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, it is preferred to react a non-aromatic carboxylic anhydride with an unreacted hydroxyl group of the aliphatic polyhydroxy compound to have a large acid group. The functional monomer is particularly preferably a monomer in which the aliphatic polyhydroxy compound is at least one of pentaerythritol and dipentaerythritol.

These monomers may be used singly, but it is difficult to obtain a single compound in the production, and thus a mixture of two or more kinds may be used. Further, as the (D) polymerizable monomer, a polyfunctional monomer having no acid group and a polyfunctional monomer having an acid group may be used in combination as needed. The preferred 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.

If it is in the above range, the development and dissolution characteristics are not easily lowered, and it is easy to manufacture or handle. Further, the photopolymerization performance is not easily lowered, and the surface smoothness of the pixel is good, and the like. In the present invention, a more preferable polyfunctional monomer having an acid group is, for example, a mixture of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentaacrylate succinate as a main component. The polyfunctional monomer can also be used in combination with other polyfunctional monomers.

In the colored resin composition of the present invention, the content of the (D) polymerizable monomer is usually 1% by weight or more, preferably 5% by weight or more, and more preferably 10% by weight or more based on 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 still more preferably 40% by weight or less. Further, the ratio of the (D) polymerizable monomer to the dye (A) 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, and usually 200% by weight or less, preferably 100% by weight or less, and more preferably 80% by weight or less. When it is in the above range, the photohardening is moderate, and it is difficult to cause poor adhesion during development, and the cross section after development is less likely to be in the shape of an inverted cone, and it is less likely to cause peeling due to a decrease in solubility and poor removal. .

[(E) Photopolymerization starting component, thermal polymerization starting component]

In order to harden the coating film, the colored resin composition of the present invention preferably contains at least one of (E) a photopolymerization starting component and a thermal polymerization starting component. However, the hardening method can also be beneficial A method other than the method of using such an initiator. In particular, when the colored resin composition of the present invention contains a resin having an ethylenic double bond as the component (C) or a case where the ethylenic compound is contained as the component (D), it is preferred to contain a light having direct absorption or a light absorption. At least one of a photopolymerization starting component which causes a decomposition reaction or a hydrogen abstraction reaction to generate a function of polymerizing living radicals and a thermal polymerization starting component which generates a living radical by heat. In the present invention, the component (E) as a photopolymerization starting component means a polymerization accelerator (hereinafter, also referred to as "(E1) component arbitrarily"). Hereinafter, it is also arbitrarily referred to as a mixture of "(E2) component") and an additive such as a sensitizing dye (hereinafter, arbitrarily referred to as "(E3) component").

[(E) Photopolymerization starting ingredients]

The (E) photopolymerization starting component in the present invention is usually in the form of a mixture with an (E1) photopolymerization initiator, and optionally an (E2) polymerization accelerator and an (E3) sensitizing dye. It is used as a component which has a function of directly absorbing light or sensitizing light, causing a decomposition reaction or a hydrogen abstraction reaction, and generating a function of polymerizing active radicals.

The (E1) photopolymerization initiator which is a photopolymerization initiator is exemplified by the ferrocene derivative described in JP-A-59-152197, JP-A-61-151197, and the like. The hexaarylbiimidazole derivative described in the above-mentioned Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Halogen methylation Diazole derivatives, halomethyl groups Free derivatives such as N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, and N-aryl-α-amino acid esters The pharmaceutically acceptable agent, the α-aminoalkylphenone derivative, and the oxime ester derivative described in JP-A-2000-80068.

Specifically, for example, a photopolymerization initiator described in International Publication No. 2009/107734 or the like can be mentioned. Among the photopolymerization initiators, α-aminoalkylphenone derivatives, oxime ester derivatives, biimidazole derivatives, acetophenone derivatives, and 9-oxosulfuric acid are more preferred. Derivatives.

Further, examples of the oxime ester-derived derivatives include 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(o-benzoylhydrazine), and ethyl ketone- 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-1-(o-ethylindenyl), and represented by the following formula (XI) Compounds and the like.

(In the formula (XI), R ¹⁰¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms or a heteroaryl group having 4 to 25 carbon atoms. Or an alkyl group, which may have a substituent. Alternatively, R ¹⁰¹ may be bonded to X or Z to form a ring. R ¹⁰² represents an alkylene group having 2 to 20 carbon atoms and an olefin group having 3 to 25 carbon atoms. 4 to 8 cycloalkyl fluorenyl groups, 7 to 20 aryl fluorenyl groups, 2 to 10 carbon alkoxycarbonyl groups, 7 to 20 carbon aryloxycarbonyl groups, carbon number 2 to 20 An aryl group, a heteroaryl group having 3 to 20 carbon atoms or an alkylaminocarbonyl group having 2 to 20 carbon atoms, which may have a substituent. X represents a condensation of two or more rings which may have a substituent. At least one of a divalent aromatic hydrocarbon ring group and an aromatic heterocyclic group. Z represents an aromatic ring group which may have a substituent)

In addition, among the compounds represented by the above formula (XI), X is a compound of a carbazole ring which may have a substituent, and specifically, a compound represented by the following formula (XII), etc. Among them, a compound represented by the following formula (XIII) is particularly preferred.

[Chemistry 14]

(wherein R ¹⁰¹ , R ¹⁰² and Z are the same as defined in the above formula (XI). R ¹⁰³ to R ¹⁰⁹ each independently represent a hydrogen atom or an arbitrary substituent)

(In the formula, R ^101a represents an alkyl group having 1 to 3 carbon atoms or a group represented by the following formula (XIIIa).

(wherein R ¹⁰³ and R ¹⁰⁴ each independently represent a hydrogen atom, a phenyl group or an N-ethylindenyl-N-acetoxyamino group. * indicates a bonding site)

R ^102a represents an alkanoyl group having 2 to 4 carbon atoms, and X ^a represents ^a 3,6-carbazolyl group in which ^a nitrogen atom may be substituted with an alkyl group having 1 to 4 carbon atoms. Z ^a represents a phenyl group which may be substituted by an alkyl group or may be Polinyl substituted naphthyl)

As the oxime-based initiator, a commercially available product can also be used. Examples of commercially available products include OXE-01, OXE-02 (manufactured by BASF Corporation), and TRONLYTR-PBG-304. TRONLYTR-PBG-309, TRONLYTR-PBG-305 (manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD).

Further, as a photopolymerization initiator, benzoin alkyl ethers and anthracene derivatives; 2-methyl-(4'-methylthiophenyl)-2- Acetophenone derivatives such as phenyl-1-propanone; 2-ethyl 9-oxosulfur 2,4-diethyl 9-oxosulfur 9-oxosulfur Derivatives; benzoate derivatives; acridine derivatives, brown Derivatives, anthrone derivatives, and the like. As such an initiator, a commercially available product can also be used.

Examples of commercially available products include IRGACURE 651, IRGACURE 184, DAROCURE 1173, IRGACURE 2959, IRGACURE 127, IRGACURE 907, IRGACURE 369, IRGACURE 379EG, LUGIRIN TPO, IRGACURE 819, and IRGACURE 784 (all manufactured by BASF Corporation). .

Among the photopolymerization initiators, α-aminoalkylphenone derivatives and 9-oxosulfuric acid are more preferred. Derivatives, oxime ester derivatives. It is especially preferred to be an oxime ester derivative. Examples of the (E2) polymerization accelerator to be used, for example, N,N-dialkylaminobenzoic acid alkyl esters such as N,N-dimethylaminobenzoic acid ethyl ester; 2-mercapto Benzothiazole, 2-mercaptobenzophenone a mercapto compound having a heterocyclic ring such as an azole or a 2-mercaptobenzimidazole; or a mercapto compound such as an aliphatic polyfunctional mercapto compound.

These (E1) photopolymerization initiators and (E2) polymerization accelerators may be used alone or in combination of two or more. Further, (E3) a sensitizing dye is used as needed in order to improve the sensitivity. The sensitizing dye can be used in accordance with the wavelength of the image-exposure light source, and is described in, for example, JP-A-4-221958, JP-A-4-219756, and the like. A coumarin-based dye having a heterocyclic ring as described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The 3-keto coumarin dye described in the Japanese Patent Laid-Open Publication No. Hei 6-19240, and the like. Japanese Unexamined Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Publication No. Hei 59-56403, Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A dye having a dialkylamino benzene skeleton described in the publication or the like.

Further, the (E3) sensitizing dye may be used singly or in combination of two or more kinds. In the colored resin composition of the present invention, the content of the (E) photopolymerization starting component is usually 0.1% by weight or more, preferably 0.2% by weight or more, and further preferably 0.5% by weight based on the total solid content. The above is usually 40% by weight or less, preferably 30% by weight or less, and more preferably 20% by weight or less. When it is in the above range, the sensitivity to the exposure light is good, and the solubility of the unexposed portion to the developer is also good, which is preferable because it is less likely to cause development failure or the like.

[(E) Thermal polymerization starting component]

Specific examples of the (E) thermal polymerization starting component which can be contained in the colored resin composition of the present invention include an azo compound, an organic peroxide, and hydrogen peroxide. Among these, an azo compound can be preferably used. More specifically, for example, a thermal polymerization starting component described in International Publication No. 2009/107734 or the like can be used. These thermal polymerization starting components may be used alone or in combination of two or more.

[Other optional ingredients]

The colored resin composition of the present invention may contain, in addition to the above components, at least one of a surfactant, an organic carboxylic acid, and an organic carboxylic anhydride, a thermosetting compound, a plasticizer, A thermal polymerization inhibitor, a storage stabilizer, a surface protective agent, a adhesion improving agent, a development improving agent, and the like. As the optional components, for example, various compounds described in JP-A-2007-113000 can be used. Further, in the case of containing the (F) pigment described below, a dispersing agent or a dispersing aid may be contained.

[(F) pigment]

In order to improve the heat resistance and the like of the obtained color filter, the colored resin composition of the present invention may contain (F) a pigment within a range not impairing the effects of the present invention. As the (F) pigment, for example, in the case of forming a pixel of a color filter or the like, a pigment of various colors such as blue or purple can be used. Moreover, examples of the chemical structure include a phthalocyanine system, a quinophthalone type, a benzimidazolone type, and Organic pigments such as linden, indanthrene, and lanthanide. Further, various inorganic pigments and the like can also be used. Hereinafter, specific examples of the pigment which can be used are exemplified by the pigment number.

As the blue pigment, for example, CI 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, etc.

Among these, a blue copper phthalocyanine pigment is preferable, and as the copper phthalocyanine pigment, CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4 is preferably used. 15:6, etc., and further preferably CI Pigment Blue 15:6. Therefore, in the case where the colored resin composition of the present invention contains a blue pigment, it is preferably 80% by weight or more, particularly 90% by weight or more, particularly 95 to 100% by weight based on the total content of the blue pigment. CI Pigment Blue 15:6.

Examples of the violet pigment include CI 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, etc. Among these, it is preferably purple Pigment, as the second The pigment may preferably be CI Pigment Violet 19, 23 or the like, and further preferably CI Pigment Violet 23.

Therefore, in the case where the colored resin composition of the present invention contains a violet pigment, it is preferably 80% by weight or more, particularly 90% by weight or more, and particularly 95 to 100% by weight, based on the total content of the violet pigment, as a CI pigment. Purple 23. These may be used alone or in combination of two or more kinds in any combination and in any ratio.

The (F) pigment used in the colored resin composition of the present invention preferably has a smaller average primary particle diameter in terms of a pixel which can form a higher contrast ratio, and specifically, an average primary particle diameter is preferred. It is 40 nm or less, more preferably 35 nm or less. In particular, the blue phthalocyanine pigment is also preferably an average primary particle diameter of 40 nm or less, more preferably 35 nm or less, still more preferably 20 to 30 nm.

Again, about two The average primary particle diameter of the pigment is preferably 40 nm or less, more preferably 25 to 35 nm. The average primary particle diameter is preferably not too small in terms of the fact that the pigment is less likely to aggregate in the colored resin composition. Here, the average primary particle diameter of the (F) pigment is measured and calculated by the following method.

First, the (F) pigment ultrasonic wave was dispersed in chloroform, dropped onto a mesh to which a colloidion film was adhered, dried, and observed by a transmission electron microscope (TEM). A primary particle image of the pigment is obtained. According to the image, the projected area diameter converted into the diameter of the circle having the same area is calculated from the particle diameter of each of the pigment particles, and the particle diameter is determined for each of a plurality of (generally about 200 to 300) pigment particles.

Using the obtained value of the primary particle diameter, the average value of the number of particles was calculated according to the calculation formula of the following formula. Particle size of each pigment particle: X ₁ , X ₂ , X ₃ , X ₄ ,. . . . , X _i ,. . . . . . X _m (m is the number of particles)

{quantity}

In the present invention, in the case of containing the (F) pigment, the content of the pigment in the colored resin composition is usually 80% by weight or less, preferably 50% by weight or less, based on the total solid content. Further, the content of 100 parts by weight of the dye (A) is usually 2,000 parts by weight or less, preferably 1,000 parts by weight or less. By setting it as the said range, the dye (I) does not have a large influence on the transmittance|permeability, and the heat resistance of the obtained pixel becomes it as it becomes it as it is [

[Dispersant]

In the case where the colored resin composition of the present invention contains (F) a pigment, it is preferred to further contain a dispersing agent. The dispersing agent in the present invention is not particularly limited as long as it can disperse the pigment and remains stable. For example, a cationic, anionic, nonionic or amphoteric dispersing agent can be used, and a polymer dispersing agent is preferred. Specific examples thereof include a block copolymer, a polyurethane, a polyester, an alkylammonium salt or a phosphate salt of a polymer copolymer, a cationic comb-type graft polymer, and the like. Among these dispersants, a block copolymer, a polyurethane, and a cationic comb graft polymer are preferred. More preferably, it is a block copolymer, and among them, a block copolymer comprising a solvophilic A block and a B block having a functional group containing a nitrogen atom is preferred.

Specifically, the B block having a functional group containing a nitrogen atom may have a unit structure having at least one of a quaternary ammonium salt group and an amine group in the side chain, and on the other hand, as a solvophilic substance The A block may have a unit structure which does not have a quaternary ammonium salt group and an amine group. The B block constituting the acrylic block copolymer is a unit structure having a unit structure having at least one of a quaternary ammonium salt group and an amine group, and having a pigment adsorption function.

Further, in the case where the quaternary ammonium salt group is used as the B block, the quaternary ammonium salt group may be directly bonded to the main chain or may be bonded to the main chain via a divalent linking group. As such a block copolymer, for example, those described in JP-A-2009-025813 can be cited.

Further, the colored resin composition of the present invention may contain a dispersing agent other than the above. As another dispersing agent, for example, those described in JP-A-2006-343648 can be cited. In the case where the colored resin composition of the present invention contains (F) a pigment, it is preferred that the content of the dispersant in the total solid content is 2 to 1000% by weight, especially 5%, of the total content of the (F) pigment. It is used in the range of 500% by weight, particularly 10 to 250% by weight. When it is in the above range, it does not affect the heat resistance of the dye (I), and it is preferable in terms of ensuring good pigment dispersibility and further improving the dispersion stability of the pigment.

[Dispersing Aid]

The coloring resin composition of the present invention may also contain a dispersing aid. Here, the dispersing aid may be a pigment derivative, and as a pigment derivative, for example, JP-A-2001-220520, JP-A-2001-271004, JP-A-2002-179976, and JP-A-2002-179976 Various compounds and the like described in JP-A-2007-186681 and the like.

Further, the content of the dispersing aid in the colored resin composition of the present invention is usually 0.1% by weight or more, and usually 30% by weight or less, preferably 20% by weight or less, based on the total solid content of the pigment. It is preferably 10% by weight or less, and more preferably 5% by weight or less. By controlling the amount of addition within the above range, the effect as a dispersing aid can be exhibited, and the dispersibility and dispersion stability are further improved, which is preferable in this respect.

[dispersion resin]

The colored resin composition of the present invention may contain a part or all of a resin selected from the above (C) binder resin or other binder resin as the following dispersion resin. Specifically, in the following [Method for Producing Colored Resin Composition], (C) the binder resin is used together with the component such as the dispersant, and the (C) binder resin utilizes synergy with the dispersant. The effect contributes to (F) the dispersion stability of the pigment. As a result, there is a possibility that the amount of the dispersant added is reduced, which is preferable. In addition, it is preferable to improve the developability and to prevent the undissolved matter from remaining in the non-pixel portion of the substrate, thereby improving the adhesion between the pixel and the substrate. Thus, the (C) binder resin used in the dispersion treatment step is referred to as a dispersion resin. The amount of the dispersion resin relative to the total amount of the pigment in the colored resin composition is preferably from about 0 to 200% by weight, more preferably from about 10 to 100% by weight.

[Preparation method of colored resin composition]

In the present invention, the colored resin composition can be produced by a suitable method, for example, by using the (A) dye containing the compound (I) and (C) the binder resin and (B) the solvent and optionally using any of them. The ingredients are prepared by mixing together. Further, as a preparation method of the (F) pigment, in a solvent containing the (F) pigment, in the presence of a dispersant and optionally a dispersing aid, optionally, part of the (C) binder resin Further, a pigment shaker is prepared by mixing and dispersing while pulverizing, using, for example, a paint shaker, a sand mill, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like. A method of adding (A) a dye containing the compound (I), (C) a binder resin, optionally (D) a polymerizable monomer, and (E) photopolymerization from the pigment dispersion liquid At least one of the initial component and the thermal polymerization starting component is prepared by mixing.

[Application of colored resin composition]

The colored resin composition of the present invention is usually in a state in which all constituent components are dissolved or dispersed in a solvent. Supplying such a colored resin composition onto a substrate to form a color filter or A constituent member such as a liquid crystal display device or an organic EL display device. In the following, as an application example of the colored resin composition of the present invention, a liquid crystal display device (panel) and an organic EL display device using the same as a pixel of a color filter will be described.

<Color Filter>

The color filter of the present invention has pixels formed of the colored resin composition of the present invention. Hereinafter, a method of forming the color filter of the present invention will be described. The pixels of the color filter can be formed by various methods. Here, a case where the photopolymerizable coloring resin composition is formed by photolithography will be described as an example, but the production method is not limited thereto.

First, a black matrix is formed on the surface of the substrate as needed to form a portion of the pixel, and after coating the colored resin composition of the present invention on the substrate, prebaking is performed to evaporate the solvent to form a coating film. Then, the coating film is exposed through a photomask, and then developed using an alkali developing solution to dissolve and remove the unexposed portion of the coating film, followed by post-baking, thereby forming red, green, and blue colors. A pixel pattern is used to make a color filter. In the present invention, it is particularly preferred that the pixel formed using the colored resin composition of the present invention is a blue pixel.

The substrate to be used for forming the pixel is not particularly limited as long as it is transparent and has moderate strength. Examples thereof include a polyester resin, a polyolefin resin, a polycarbonate resin, and an acrylic resin. A thermoplastic resin sheet, an epoxy resin, a thermosetting resin, various glasses, and the like. In addition, appropriate pretreatment such as a film formation treatment such as a decane coupling agent or an urethane resin, a surface treatment such as a corona discharge treatment or an ozone treatment may be carried out on the substrate as required.

When the colored resin composition is applied to a substrate, a spin coating method, a wire bar coating method, a flow coating method, a squeeze and spin coating method, and a die coating method are mentioned. Method, roll coating method, spraying method, and the like. Among them, extrusion and spin coating methods and die coating methods are preferred. The thickness of the coating film is usually 0.2 to 20 μm, preferably 0.5 to 10 μm, and more preferably 0.8 to 5.0 μm, in terms of film thickness after drying.

If it is in the above range, the gap adjustment in the pattern development or liquid crystal unitization step is easy, and the desired color is easily formed, which is preferable in this respect. As the radiation used for 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.

The light source used for the exposure of the image to use radiation having a wavelength of 190 to 450 nm is not particularly limited, and examples thereof include a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, and a metal halide lamp. Pressure light source such as mercury lamp, low pressure mercury lamp, carbon arc lamp, fluorescent lamp; argon ion laser, YAG, Yttrium Aluminum Garnet laser, excimer laser, nitrogen laser, cesium-cadmium Laser light sources such as lasers and semiconductor lasers. An optical filter can also be used when it is used to illuminate light of a specific wavelength.

The exposure amount of the radiation is preferably from 10 to 10,000 J/m ² . Further, as the alkaline developing solution, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium citrate, potassium citrate or metasilicate is preferred. Inorganic basic compounds such as sodium, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide; monoethanolamine, diethanolamine, triethanolamine, monomethylamine, Methylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, n-butylamine, monoisopropanolamine, diisopropyl An aqueous solution of an alcoholic amine, triisopropanolamine, ethyl iminoamine, ethyldiimide, tetramethylammonium hydroxide (TMAH), an organic basic compound such as choline or the like.

An appropriate amount of, for example, isopropanol or benzyl may be added to the above alkaline developing solution. A water-soluble organic solvent such as an alcohol, ethyl celecoxib, butyl sarbuta, phenyl racerus, propylene glycol or diacetone alcohol or a surfactant. Further, after alkaline development, water washing is usually carried out. As the development processing method, any one of a dipping development method, a jet development method, a brush development method, and an ultrasonic development method can be used. The developing conditions are preferably carried out at room temperature (23 ° C) for 5 to 300 seconds.

The conditions of the development treatment are not particularly limited, and the development temperature is usually 10 ° C or higher, and preferably 15 ° C or higher, more preferably 20 ° C or higher, and usually 50 ° C or lower, and preferably 45 ° C or lower. Further, it is preferably in the range of 40 ° C or lower. The developing method may be any one of a dipping development method, a jet development method, a brush development method, and an ultrasonic development method.

When a color filter produced in this manner is used in a liquid crystal display device, a transparent electrode such as indium tin oxide (ITO) is formed on the image in a state of being used as a color display. A part of a component such as a liquid crystal display device, but in order to improve surface smoothness or durability, it is also possible to provide a top coat such as polyimide or polyimide on the image. Further, in some applications such as a planar alignment type driving method (in the case of an IPS (In-Plane Switching) mode), a transparent electrode may not be formed. Further, in the vertical alignment type drive mode (Multi-Domain Vertical Alignment (MVA) mode), ribs may be formed. Further, there is also a case where a pillar structure (light spacer) is formed by photolithography instead of a bead-scattering spacer.

<Liquid crystal display device>

The liquid crystal display device of the present invention uses the above-described color filter of the present invention. The type or configuration of the liquid crystal display device of the present invention is not particularly limited, and can be assembled according to a conventional method using the color filter of the present invention. For example, you can use the "Liquid Crystal Equipment Handbook" (Nikkei Industrial News Agency, issued on September 29, 1989, the 142th Committee of the Japan Society for the Promotion of Science) The method described in the above forms the liquid crystal display device of the present invention.

<Organic EL display device>

In the case of producing an organic EL display device having the color filter of the present invention, for example, as shown in FIG. 1, a pixel 20 is formed on the transparent support substrate 10 by the colored resin composition of the present invention. On the blue color filter, the organic light-emitting body 500 is laminated via the organic protective layer 30 and the inorganic oxide film 40 to produce a multi-color organic EL device.

As a method of laminating the organic light-emitting body 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 are sequentially formed on the upper surface of the color filter. The method of 55, or the method of bonding the organic light-emitting body 500 formed on another substrate to the inorganic oxide film 40, or the like. The organic EL element 100 fabricated in this manner can be applied to an organic EL display device of a passive driving method, and can also be applied to an organic EL display device of an active driving method.

[Examples]

Hereinafter, the present invention will be specifically described by way of Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to the following examples as long as the scope of the present invention is not exceeded.

<Dye synthesis>

(Synthesis Example 1: Synthesis of Dye A)

(Synthesis of Compound 2)

1-Aminonaphthalene (14.3 g) was dissolved in 1-propanol (300 ml), and a solution of 1,3-propane sultone (12.2 g) in methanol (20 ml) was added, and the mixture was refluxed for 2 hr. The resulting precipitate was collected by filtration and washed with 1-propanol to give Compound 2 (12.3 g).

(Synthesis of Dye A)

Sodium borohydride (1.0 g) was added to a mixture of Compound 1 (synthesized by the method described in JP-A-2011-70171) (8.05 g) and 2-propanol (100 ml), and the mixture was heated under reflux for 18.5 hours. Sodium borohydride (1.0 g) was added, and the mixture was further heated under reflux for 1.5 hours. The mixture was concentrated under reduced pressure, and tetrahydrofurane (50 ml) was then evaporated and evaporated. The mixture was concentrated under reduced pressure, and a 1N aqueous sodium hydroxide solution was added, and the mixture was extracted with toluene, washed with saturated brine, and dried over anhydrous sodium sulfate. To the obtained oily substance (total amount), Compound 2 (3.71 g) and 2N hydrochloric acid (40 ml) were added, and the mixture was heated under reflux for 2 hours. After adding an aqueous sodium hydroxide solution to become alkaline, a tar-like insoluble matter is produced. After the supernatant liquid was removed by decantation, it was concentrated under reduced pressure, and water was added thereto and stirred, and then water was removed by decantation, and the obtained solid was dried. Methanol (100 ml) and chloro-p-benzoquinone (3.44 g) were added to the obtained solid (total amount), and the mixture was stirred at 50 ° C for 2 hours. The organic layer was concentrated under reduced pressure, and chloroform and water were added, and the chloroform layer was separated, and purified by silica gel column chromatography (developing solvent: chloroform-chloroform/methanol = 10/1) to obtain dye A (1.30 g).

Compound Identification: Mass Spectrometry

Ionization mode: Laser Desorption Ionization (LDI)

Posi m/z=586[M+H] ⁺

Neg m/z=585[M] ^-

The compound had a maximum absorption wavelength (λmax) of 639 nm and a gram extinction coefficient of 125 in a solution of 10 ppm propylene glycol monomethyl ether acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 4/6.

(Synthesis Example 2: Synthesis of Dye B)

(Synthesis of Compound 11)

1,7-kelev acid (2.23 g, manufactured by Tokyo Chemical Industry Co., Ltd.), 1,1,1-trifluoro-4-iodobutane (2.98 g, manufactured by Tokyo Chemical Industry Co., Ltd.), potassium carbonate (2.76 g, and The product was mixed with N-methylpyrrolidone (22 mL), and stirred at 80 ° C for 10 hours under a nitrogen atmosphere. After cooling the reaction mixture to room temperature, it was mixed with water (150 mL), adjusted to pH 5.3 with concentrated hydrochloric acid, and then extracted with ethyl acetate. After drying the organic layer with anhydrous sodium sulfate, the desiccant was separated by filtration, and the solvent was distilled off. The obtained crystals were suspended and washed with diisopropyl ether, and separated with a solvent by filtration under reduced pressure, and the obtained solid was removed at 50 ° C under reduced pressure to give Compound 11 (2.79 g) as a white solid. The results of liquid chromatography mass spectrometry of the compound are shown below. LCMS (Liquid Chromatography Mass Spectrometry) (ESI (Electrospray Ionization, posi) m/z 334 (M+H ⁺ , C ₁₄ H ₁₅ F ₃ NO ₃ S)

(Synthesis of Dye B)

Compound 1 (8.46 g) was dissolved in tetrahydrofuran (THF, Tetrahydrofuran) (68 mL), and lithium borohydride (3 mol/L, THF solution, 9.2 mL) was added, and the mixture was stirred at 50 ° C for 3 hours under a nitrogen atmosphere. After cooling to room temperature, an aqueous sodium hydroxide solution (1 mol/L, 10 mL) was added and stirred, and the mixture was mixed with water (300 mL), and extracted with ethyl acetate. The organic layer was washed with water and saturated brine, and dried over anhydrous sodium sulfate. The desiccant was separated by filtration, and the solvent was distilled away, whereby an oil (7.96 g) was obtained. The oily substance (2.04 g) obtained in the above reaction and Compound 11 (2.06 g) were dissolved in acetic acid (26 mL), and stirred at room temperature for 5 hours. The reaction liquid was mixed with water (150 mL), and the pH was adjusted to 6.5 with an aqueous sodium hydroxide solution (20% by weight) to precipitate a solid. The obtained solid was separated by filtration and dried under reduced pressure at 50 ° C to give a pale blue solid (3.16 g). 2.5 g of this was purified by silica gel chromatography (developing solvent: chloroform/methanol=93/7-78/22) to give a pale blue solid (1.66 g). The results of liquid chromatography mass spectrometry of the compound are shown below. LCMS (ESI, posi) m/z 656 (M+H ⁺ , C ₃₆ H ₄₅ F ₃ N ₃ O ₃ S) as a light blue solid (1.64 g) obtained in the above reaction, chloro-p-benzoquinone (0.61) g) mixed with methanol (33 mL), stirred at room temperature for 4 hours and at 45 ° C for 8 hours. After cooling the reaction solution to room temperature, the solvent was distilled off. This crude product was purified by silica gel chromatography (developing solvent: chloroform/methanol = 95/5 to 82/18) to obtain a dark blue solid dye B (0.82 g). The compound had a maximum absorption wavelength (λmax) of 633 nm and a gram extinction coefficient of 126 in a solution of 10 ppm propylene glycol monomethyl ether acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65. The results of liquid chromatography mass spectrometry of the compound are shown below. LCMS (ESI, Posi) m/z 654 (M+H ⁺ , C ₃₆ H ₄₃ F ₃ N ₃ O ₃ S)

(Synthesis Example 3: Synthesis of Dye C)

(Synthesis of Compound 12)

[Chemistry 20]

1,6-kelev acid (3.35 g, manufactured by Tokyo Chemical Industry Co., Ltd.), 1,1,1-trifluoro-4-iodobutane (3.57 g, manufactured by Tokyo Chemical Industry Co., Ltd.), potassium carbonate (2.07 g, and The product was mixed with N-methylpyrrolidone (27 mL), and stirred at 80 ° C for 8 hours under a nitrogen atmosphere. Thereafter, 1,1,1-trifluoro-4-iodobutane (0.71 g) was added and further heated at 80 ° C for 2 hours. After cooling the reaction solution to room temperature, it was mixed with water (150 ml), adjusted to pH = 4 with concentrated hydrochloric acid, and then extracted with ethyl acetate. The extraction layer is obtained by distilling off the solvent by means of an evaporator, and the precipitated crystal is suspended and washed with diisopropyl ether, separated from the solvent by filtration under reduced pressure, and the obtained solid is removed at 50 ° C under reduced pressure. Compound 12 (2.43 g) was obtained as a white solid. The results of liquid chromatography mass spectrometry of the compound are shown below. LCMS (ESI, Posi) m/z 334 (M+H ⁺ , C ₁₄ H ₁₅ F ₃ NO ₃ S)

(Synthesis of Dye C)

The compound 1 (2.71 g) was dissolved in THF (22 mL), and lithium borohydride (3 mol/L, THF solution, 2.9 mL) was added, and the mixture was stirred at 50 ° C for 2 hours under a nitrogen atmosphere. After cooling to room temperature, an aqueous sodium hydroxide solution (1 mol/L, 6 mL) was added and stirred, and the mixture was mixed with water (150 mL), and extracted with ethyl acetate. The organic layer was washed with water and saturated brine, and dried over anhydrous sodium sulfate. The desiccant was separated by filtration, and the solvent was distilled away, whereby an oil (2.74 g) was obtained. The oily substance (2.38 g) obtained in the above reaction and the compound 12 (2.31 g) were dissolved in acetic acid (19 mL), and stirred at room temperature for 1 hour, and left overnight. On the next day, the reaction liquid was mixed with water (200 mL), and the pH was adjusted to 4.1 with an aqueous sodium hydroxide solution (20% by weight) to precipitate a solid. The obtained solid was separated by filtration and dried under reduced pressure at 50 ° C to afford a pale blue solid (3.77 g). The results of liquid chromatography mass spectrometry of the compound are shown below. LCMS (ESI, posi) m/z 356 (M+H ⁺ , C ₃₆ H ₄₅ F ₃ N ₃ O ₃ S) as a light blue solid (1.44 g) obtained in the above reaction, chloro-p-benzoquinone (0.54) g) mixed with methanol (29 mL), stirred at room temperature for 4 hours and at 55 ° C for 4.5 hours. Thereafter, chloro-p-benzoquinone (0.27 g) was added and further heated for 10.75 hours. After cooling the reaction liquid to room temperature, the reaction liquid was filtered to remove insoluble matter, and then the solvent was distilled off. This crude product was purified by silica gel chromatography (developing solvent: chloroform/methanol = 95/5 to 85/15) to obtain a dark blue solid dye C (0.31 g). The compound had a maximum absorption wavelength (λmax) of 639 nm and a gram extinction coefficient of 111 in a solution of 10 ppm propylene glycol monomethyl ether acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65. The results of liquid chromatography mass spectrometry of the compound are shown below. LCMS (ESI, Posi) m/z 654 (M+H ⁺ , C ₃₆ H ₄₃ F ₃ N ₃ O ₃ S)

(Synthesis Example 4: Synthesis of Dye D)

(Synthesis of Compound 13)

1,8-kelev acid (3.35 g, manufactured by Tokyo Chemical Industry Co., Ltd.), 1,1,1-trifluoro-4-iodobutane (3.57 g, manufactured by Tokyo Chemical Industry Co., Ltd.), potassium carbonate (2.07 g, and The product was mixed with N-methylpyrrolidone (27 mL), and stirred at 80 ° C for 7.5 hours under a nitrogen atmosphere. Thereafter, 1,1,1-trifluoro-4-iodobutane (0.89 g) was added and further heated for 3.75 hours. After cooling the reaction mixture to room temperature, it was mixed with water (150 mL), and the solid was precipitated by the concentration of hydrochloric acid to pH = 1.3, and the precipitated solid was separated by filtration and dried under reduced pressure at 50 ° C to obtain a white solid. Compound 13 (4.23 g). The results of liquid chromatography mass spectrometry of the compound are shown below. LCMS (ESI, Posi) m/z 334 (M+H ⁺ , C ₁₄ H ₁₅ F ₃ NO ₃ S)

(synthesis of dye D)

Compound 1 (1.69 g) was dissolved in THF (14 mL), and lithium borohydride (3 mol/L, THF solution, 1.8 mL) was added, and the mixture was stirred at 50 ° C for 2 hours under a nitrogen atmosphere. After cooling to room temperature, a sodium hydroxide aqueous solution (1 mol/L, 6 mL) was added and stirred, and the mixture was mixed with water (100 mL), and extracted with ethyl acetate. The organic layer was washed with water and saturated brine, and dried over anhydrous sodium sulfate. The desiccant was separated by filtration, and the solvent was distilled away, whereby an oil (1.76 g) was obtained. The oily substance (1.57 g) obtained in the above reaction and the compound 13 (1.53 g) were dissolved in acetic acid (23 mL), and stirred at room temperature for 1.5 hours, and left overnight. On the next day, the reaction liquid was mixed with water (150 mL), and the pH was adjusted to 3.83 with an aqueous sodium hydroxide solution (20% by weight) to precipitate a solid. The obtained solid was separated by filtration and dried under reduced pressure at 50 ° C to give a pale blue solid (2.5 g). The crude product (2.5 g) and the crude product (0.8 g) which were synthesized by the same synthesis method were purified by silica gel chromatography (developing solvent: chloroform/methanol = 98/2 to 90/10) to obtain a pale blue solid. (1.89g). The results of liquid chromatography mass spectrometry of the compound are shown below. LCMS (ESI, Posi) m/z 656 (M+H ⁺ , C ₃₆ H ₄₅ F ₃ N ₃ O ₃ S) as a light blue solid (1.89 g) obtained in the above reaction, chloro-p-benzoquinone (0.71) g) Mix with methanol (30 mL) and stir at 45 °C for 4 hours. After cooling the reaction liquid to room temperature, insoluble matter was removed by filtration, and the solvent was distilled off. This crude product was purified by silica gel chromatography (developing solvent: chloroform/methanol = 98/2 to 92/8) to obtain a dark blue solid dye D (0.75 g). The compound had a maximum absorption wavelength (λmax) of 648 nm and a gram extinction coefficient of 104 in a solution of 10 ppm propylene glycol monomethyl ether acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65. The results of liquid chromatography mass spectrometry of the compound are shown below. LCMS (ESI, Posi) m/z 654 (M+H ⁺ , C ₃₆ H ₄₃ F ₃ N ₃ O ₃ S)

(Refer to Synthesis Example 1: Comparative Dye 1)

Compound 21 (6.0 g, 25 mmol, synthesized by the method described in International Publication No. 2008/003604), Compound 22 (6.4 ml, 50 mmol, purchased from Tokyo Chemical Co., Ltd.), potassium carbonate (6.9 g, 50 mmol), N- A mixture of methyl-2-pyrrolidone (25 ml) was stirred with heating at 110 to 125 ° C for 4 hours. After cooling to room temperature, water was added, and extraction was carried out with toluene, and the toluene layer was washed with dilute hydrochloric acid and saturated brine, and dried. Dry with sodium sulfate. Concentration under reduced pressure gave a pale brown oil (9.2 g). This light brown oil was dissolved in ethanol (40 ml), and a solution of sodium hydroxide (2 g, 52.3 mmol) in water (25 ml) was added, and the mixture was stirred at 85 ° C for 1 hour. The mixture was cooled, extracted with toluene, and the toluene layer was washed with saturated brine and dried over anhydrous sodium sulfate. The organic layer was concentrated under reduced pressure and purified by silica gel column chromatography (hexane/ethyl acetate=3/1) to afford compound 23 (5.95 g, yield 94%).

A mixture of Compound 1 (1.47 g, 4.34 mmol, synthesized by the method described in International Publication No. 2009/107734), Compound 23 (1.1 g, 4.34 mmol), toluene (30 ml), and phosphonium chloride (0.6 ml) After heating under reflux for 4 hours, it was cooled to room temperature, water was added, and extraction was performed with chloroform. The chloroform layer was concentrated under reduced pressure, and purified by silica gel column chromatography (developing solvent: chloroform/methanol = 15/1 to 10/1), and the obtained solid was washed with hexane to obtain compound 25 (1.32). g, yield 50%).

Compound 25 (8.9 g, 14.6 mmol), Compound 26 (4.2 g, 14.6) After stirring at 50 ° C for 1.5 hours, a mixture of methanol (50 ml) was concentrated under reduced pressure, and the obtained solid was washed with methanol/water = 1/2 to obtain a comparative dye 1 (11.5). g, yield 92.3%).

(Refer to Synthesis Example 2: Comparative Dye 2)

A mixture of Compound 25 (1.95 g), CI Acid Blue 80 (manufactured by Aldrich Co., Ltd.: 1.36 g), and methanol (25 mL) was stirred at 50 ° C for 30 minutes, and then concentrated under reduced pressure using water / methanol = 2 / 1 The obtained solid was washed with a mixed solvent to obtain Comparative Dye 2 (2.22 g).

<Resin Synthesis>

(Refer to Synthesis Example 3: Synthesis of Resin A)

One of the 145 parts by weight of propylene glycol monomethyl ether acetate was stirred while being purged with nitrogen, and the temperature was raised to 120 °C. 10 parts by weight of styrene, 85.2 parts by weight of glycidyl methacrylate, and a monoacrylate FA-513M (manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton, 66 parts by weight and 2.2'- were added dropwise thereto over 3 hours. A mixture of azobis(2-methylbutyronitrile) of 8.47 parts by weight was further stirred at 90 ° C for 2 hours. Then, the inside of the reaction vessel was replaced with air, and 0.7 parts by weight of tris(dimethylaminomethyl)phenol and 0.12 parts by weight of hydroquinone were placed in 43.2 parts by weight of acrylic acid, and the reaction was continued at 100 ° C for 12 hours. Thereafter, 56.2 parts by weight of tetrahydrophthalic anhydride (THPA) and 0.7 parts by weight of triethylamine were added. The reaction was carried out at 100 ° C for 3.5 hours. The resin solution thus obtained had a weight average molecular weight Mw of about 8400 and an acid value of 80 mg-KOH/g as measured by GPC. Propylene glycol monomethyl ether acetate was added to the resin solution so that the solid content became 44% by weight, and it was used as the resin A.

(Refer to Synthesis Example 4: Synthesis of Resin B)

One of the 145 parts by weight of propylene glycol monomethyl ether acetate was stirred while being purged with nitrogen, and the temperature was raised to 120 °C. 5.2 parts by weight of styrene, 132 parts by weight of glycidyl methacrylate, and a monoacrylate FA-513M (manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton, 4.4 parts by weight and 2.2'- were added dropwise thereto over 3 hours. A mixture of azobis(2-methylbutyronitrile) of 8.47 parts by weight was further stirred at 90 ° C for 2 hours. Then, the inside of the reaction vessel was replaced with air, and 1.1 parts by weight of tris(dimethylaminomethyl)phenol and 0.19 parts by weight of hydroquinone were placed in 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 the mixture was reacted at 100 ° C for 3.5 hours. The resin solution thus obtained had a weight average molecular weight Mw of about 9000 in terms of polystyrene measured by GPC, and an acid value of 25 mg-KOH/g. Propylene glycol monomethyl ether acetate was added to the resin solution so that the solid content became 40% by weight, and it was used as the resin B.

(Refer to Synthesis Example 5: Synthesis of Resin C)

400 parts by weight of "NC3000H" (manufactured by Nippon Kayaku Co., Ltd.) (epoxy equivalent 288, softening point 69 ° C), 102 parts by weight of acrylic acid, 0.3 parts by weight of p-methoxyphenol, 5 parts by weight of triphenylphosphine, and propylene glycol 264 parts by weight of monomethyl ether acetate was added to the reaction container, and the mixture was stirred at 95 ° C until the acid value became 3 mg-KOH/g or less. It takes 9 hours (acid value 2.2 mg-KOH/g) until the acid value reaches the target. Then, 151 parts by weight of tetrahydrophthalic anhydride was further added, and the mixture was reacted at 95 ° C for 4 hours to obtain an acid value of 102 mg-KOH/g, and the weight average molecular weight (Mw) in terms of polystyrene measured by GPC was 3,900. Solvent dissolution liquid. Propylene glycol monomethyl ether acetate was added to the resin solution so that the solid content became 44% by weight, and it was used as the resin C.

<Preparation of Colored Resin Composition>

The dyes A, B, C and D obtained in the above Synthesis Examples 1 to 4, the comparative dyes 1 and 2 obtained in Reference Synthesis Examples 1 and 2, and the resin A obtained in Reference Synthesis Example 3, and the like The components were mixed, and a colored resin composition was prepared in such a manner as to have the composition described in the following Table 1. The values in Table 1 all indicate the parts by weight of the ingredients added. At the time of mixing, the mixture was stirred for 1 hour or more until the components were sufficiently mixed, and finally filtered by a 5 μm wedge type filter to remove foreign matter.

The dyes A, B, C and D obtained in the above Synthesis Examples 1 to 4, the comparative dyes 1 and 2 obtained in Reference Synthesis Examples 1 and 2, and the resin B obtained in Reference Synthesis Examples 4 and 5 and C. Further, the other components were mixed, and a colored resin composition was prepared so as to have the composition described in the following Table 2. The values in Table 2 all indicate the parts by weight of the ingredients added. At the time of mixing, the mixture was stirred for 1 hour or more until the components were sufficiently mixed, and finally filtered by a 5 μm wedge type filter to remove foreign matter.

Each of the compounds in Table 1 is as follows.

PBG-305: TRONLYTR-PBG-305 manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS GO., LTD

DPHA: dipentaerythritol hexaacrylate

PGMEA: propylene glycol monomethyl ether acetate

PGME: propylene glycol monomethyl ether

F475 DIC company: oligomers containing perfluoroalkyl groups

Irganox1010 manufactured by BASF: pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]

JPP-100 manufactured by Chengbei Chemical Industry Co., Ltd.: tetraphenyldipropylene glycol diphosphite

Further, each of the compounds in Table 2 was as follows.

DPHA: dipentaerythritol hexaacrylate

PET-P: pentaerythritol tetrakis(3-mercaptopropionate)

IRGACURE 907: 2-methyl-1-[4-(methylthio)phenyl]-2- Phenylpropen-1-one

EABF: 4,4'-bis(diethylamino)diphenyl ketone

Compound X: 3-(2-Ethyloxyimino-1,5-di-oxy-5-methoxypentyl)-9-ethyl-6-(o-tolyl)-9H- Carbazole

F475 DIC company: oligomers containing perfluoroalkyl groups

Irganox1010 manufactured by BASF: pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]

JPP-100 manufactured by Chengbei Chemical Industry Co., Ltd.: tetraphenyldipropylene glycol diphosphite

PGMEA: propylene glycol monomethyl ether acetate

PGME: propylene glycol monomethyl ether

<evaluation>

[1] Evaluation of brightness and heat resistance of a film made of a colored resin composition (Examples 1 to 4 and Comparative Examples 1 and 2)

The colored resin composition prepared according to the above Table 1 was applied onto a glass substrate cut into 5 cm squares by a spin coating method to have a sy value of 0.120 after drying, dried under reduced pressure, and then dried on a hot plate at 80°. Pre-bake for 3 minutes at °C. Thereafter, the entire surface exposure was performed at an exposure amount of 60 mJ/cm ² . Then, it was calcined at 200 ° C for 30 minutes in a clean oven, and the spectrophotometer U-3310 (manufactured by Hitachi, Ltd.) was used to measure the spectral transmittance, and the chromaticity (C light source) in the XYZ color system was calculated. The results are summarized in Table 3.

[2] Measurement of voltage holding ratio and ion density by liquid crystal (Examples 5 to 16 and Comparative Examples 3 to 6)

The coloring resin composition containing the dyes of the examples and the comparative examples in the above ratio and composition was set so that the thickness of the coating film was 2 to 3 μm (the film thickness after heat curing was about 2 μm) (300 rpm to 700 rpm). It was applied to a glass substrate on which an ITO (indium-tin oxide alloy) electrode was vapor-deposited on the entire surface (MN-1392 of pure glass ITO for evaluation by EHC) using a spin coater, and preheated on a hot plate at 80 °C. After baking for 3 minutes, it was dried in a vacuum chamber for 1 minute. Then, using a high-pressure mercury lamp, a mask is applied to the outer periphery of the electrode, and the coating film is exposed to an exposure amount of 30 mW and 62 mJ/cm ² of radiation of respective wavelengths of 303 nm, 313 nm, 334 nm, 365 nm, 405 nm, and 436 nm, and further, After baking for 60 minutes at 200 ° C (hereinafter also referred to as "hardening temperature"), the coating film was cured to obtain a blue pixel substrate for liquid crystal evaluation (hereinafter also referred to as "resist film"). The substrate on which the blue pixel is formed and the electrode substrate (the evaluation glass SZ-B11MIN (B) MN11396 manufactured by EHC) which is formed by evaporating the ITO electrode into a predetermined shape are washed with water and warm water of 45° C., and then The film was dried in an oven at 105 ° C, and after bonding with a sealing agent mixed with glass beads of 5 μm (with a gap of 5 μm), it was annealed in an oven at 180 ° C for 2 hours to obtain a unit, and liquid crystal MLC- was injected into the obtained unit. 7021-000 (manufactured by Merck Co., Ltd.), a liquid crystal cell having an electrode area of 1 cm ^{2 was} produced. Next, the voltage holding ratio of the liquid crystal cell was measured at 25 ° C by a liquid crystal physical property evaluation system 6254 type manufactured by Toyo Corporation. At this time, the applied voltage was a square wave of 5.0 V, and the measurement frequencies were 60 Hz, 2 Hz, and 0.6 Hz. Here, the voltage holding ratio is generally known as an area ratio and a voltage ratio. In this case, the area ratio (the trajectory of the voltage from 0 milliseconds to 16.7 milliseconds (60 Hz) is used. The area surrounded by the voltage zero level maintains the observation time of 16.7 milliseconds (measurement of 60 Hz), or maintains the observation time of 0.5 second (measurement of 2 Hz), or maintains 1.67 seconds (0.6 Hz). Situation) The ratio of the area obtained). The ion density was measured using a device having the same voltage holding ratio. A triangular wave having a frequency of 0.1 Hz and ±10 V is applied to calculate a waveform output of a time change of the current. The direct peak of the liquid crystal in the waveform is measured in advance by the above-described unit corresponding to the liquid crystal, and then the liquid crystal cell of each example is measured. The calculation method of the direct peak, the impurity ion peak, and the impurity ion density of the liquid crystal visible in the ion waveform is shown in FIG. The voltage holding ratio is preferably 85% or more at 60 Hz, preferably 25% or more, more preferably 30% or more, further preferably 60% or more, and particularly preferably 80% or more at 2 Hz, ideally It is more than 90%. Further, the voltage holding ratio of 2 Hz or less is extremely sensitive to ionic impurities. The voltage holding ratio of 2 Hz or less is such that the ionic interaction or the like is combined with the ion density measurement result (ion density, liquid crystal direct peak current/impurity ion peak current) or voltage holding ratio at 60 Hz or behavioral observation of liquid crystal. Its preferred range. Further, the voltage holding ratio at 0.6 Hz reflects the influence of ionic impurities more. For the reason, in the case of 0.6 Hz, the time for measuring the voltage change of the impurity ions on the surface of the resist film to a sufficient extent in the liquid crystal is extremely long. The influence of the ionic impurities derived from the resist film can be known by measuring the ion density. That is, when a voltage is applied to the positive side and the negative side, the higher the ion density is, the more ionic impurities are contained in the liquid crystal, and the more the factors that impede the voltage application to the liquid crystal cell and the voltage holding of the liquid crystal cell are contained. . That is, the smaller the ion density, the better the electrical characteristics. Furthermore, in the case of only liquid crystal, it is 0 nC. The liquid crystal evaluation results are summarized in Table 4 (the colored resin composition of Table 1) and Table 5 (the colored composition of Table 2).

In addition, in the table, the voltage holding ratio is "not quantifiable due to current leakage", which means that the voltage is shorter than the response speed of the liquid crystal, that is, the voltage below 1 millisecond after the application of the voltage drops to less than 2V. The phenomenon that a voltage sufficient for the liquid crystal cell to operate is not applied to the liquid crystal cell means that the electrical characteristics are extremely low. In addition, the "impossible measurement by current leakage" means that the voltage retention rate is "the measurement cannot be measured by current leakage", and the electrical characteristics are extremely low, so that the ion density cannot be accurately measured. The phrase "the ion density is too high to be measured" means that the liquid crystal cannot respond due to the current leakage. Therefore, the ion density does not show a direct peak of the liquid crystal, and the ion peak is buried because the generated current is too large to be discriminated, that is, By using the limits of the ion density measurement of the device, it is indicated that the electrical characteristics are low.

As shown in Table 3, the pixel formed using the colored resin composition of the present invention has a high luminance and is a good blue pixel. Further, as shown in Tables 4 and 5, the liquid crystal cell including the blue pixel substrate (resist film) using the colored resin composition of the present invention has a high voltage holding ratio and a small ion density, which is good. Electrical characteristics. In particular, the temperature at 200 ° C is slightly lower as the curing temperature of the resin composition, and the ionic component is eluted in the liquid crystal or at the interface between the liquid crystal and the resist film, which tends to be detrimental to the liquid crystal evaluation property. Even with such a slightly lower curing temperature of 200 ° C, the liquid crystal cell including the resist film containing the compound of the example has a low ion density, and the elution of the ionic impurities tends to be suppressed as compared with the comparative example. As a result, the voltage holding ratio is high and good. Particularly, in the colored resin composition (Examples 6, 8, 10, 14) of the compound containing the dye B, the ion density was at most 1 nC. The voltage holding ratio at 0.2 Hz exceeds 85%. That is, it is judged that the electrical characteristics are good and the voltage holding ratio is also high. As described above, it has a coloring resin composition using the present invention. The color filter of the pixel and the liquid crystal display device and the organic EL display device including the color filter are of high quality.

The present invention has been described in detail above with reference to the specific embodiments thereof, and it is understood that various changes and modifications may be made without departing from the spirit and scope of the invention. The present application is based on Japanese Patent Application No. 2012-077457, filed on Mar.

(industrial availability)

According to the present invention, it is possible to provide a novel triarylmethane-based compound which can obtain pixels which simultaneously achieve luminance and voltage retention. Further, according to the present invention, it is possible to provide a novel colored resin composition which can form a pixel having a high luminance and a high voltage holding ratio. Moreover, the present invention can provide a color filter including a pixel having a high luminance and a high voltage holding ratio, and a high-quality liquid crystal display device and an organic EL display device. Therefore, the present invention is useful for applications such as color filters, liquid crystal display devices, and organic EL display devices.

10‧‧‧Transparent support substrate

20‧‧ ‧ pixels

30‧‧‧Organic protective layer

40‧‧‧Inorganic oxide film

50‧‧‧Transparent anode

51‧‧‧ hole injection layer

52‧‧‧ hole transport layer

53‧‧‧Lighting layer

54‧‧‧Electronic injection layer

55‧‧‧ cathode

100‧‧‧Organic EL components

500‧‧‧Organic emitters

Claims (8)

A triarylmethane-based compound represented by the following formula (I), (In the above formula (I), R ¹ to R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or an aromatic ring group which may have a substituent; adjacent R ¹ ~ R ⁶ may be bonded to each other to form a ring, and the ring may have a substituent; R ⁷ is a hydrogen atom, R ⁸ is a halogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent; M ⁺ represents a cation; An integer from 0 to 4.) The arylmethane-based compound according to the first aspect of the invention, wherein the compound represented by the above formula (I) is a compound represented by the following formula (II). (In the above formula (II), n, M ⁺ , R ¹ to R ⁵ , R ⁷ and R ⁸ are the same as defined in the above formula (I); and R ¹¹ and R ¹² each independently represent a hydrogen atom or an arbitrary substitution. Base; m represents an integer from 1 to 8.) A colored resin composition comprising (A) a dye, (B) a solvent, and (C) a binder resin, and (A) a dye containing a triarylmethane-based compound according to claim 1 or 2. The colored resin composition of claim 3, which further contains (D) a polymerizable monomer. The colored resin composition of claim 3 or 4, which further comprises at least one of (E) a photopolymerization starting component and a thermal polymerization starting component. A color filter having a pixel formed using the colored resin composition of any one of claims 3 to 5. A liquid crystal display device having the color filter of claim 6 of the patent application. An organic EL display device having the color filter of claim 6 of the patent application.