CN104204105B - Triarylmethane compound, colored resin composition, color filter, liquid crystal display device, and organic EL display device - Google Patents

Abstract

The invention provides a colored resin composition which can obtain a pixel having both brightness and a voltage holding ratio. It is another object of the present invention to provide a color filter including a pixel having high luminance and high voltage holding ratio, and a high-quality liquid crystal display device and an organic EL display device. The colored resin composition according to the present invention contains a dye (A), a solvent (B) and a binder resin (C), and is characterized in that the dye (A) contains a compound represented by the following formula (I) (wherein R is R)¹～R⁸、M⁺And n represents the meaning described in claim 1).

Description

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

technical field

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

Background technique

Flat panel displays represented by liquid crystal display devices and organic EL (Electroluminescence) display devices are widely used, and color filters are used in these displays.

With the trend of the times such as energy saving, higher brightness and higher contrast are required as color filters.

Colored resin compositions are mainly used in color filters, and pigments are used in the colored resin compositions. However, in order to obtain high brightness and high contrast, for example, non-patent document 1 discloses that the particle diameter of pigment particles is finely dispersed to the The method is less than 1/2 of the color wavelength.

On the other hand, dyes are also being developed as coloring agents.

For example, Patent Document 1 discloses the use of triarylmethane derivatives as dyes. In addition, Patent Documents 2 and 3 disclose techniques for further making anions into specific structures in triarylmethane salts.

prior art literature

patent documents

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

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

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

non-patent literature

Non-Patent Document 1: Kiyoshi Hashizuo, "Color Material Association Journal" ("Color Material Association Journal"), December 1967, p608

Contents of the invention

The problem to be solved by the invention

However, with regard to the method disclosed in Non-Patent Document 1, especially blue pigments have a shorter color-emitting wavelength than other red and green pigments, in this case, further microdispersion is required, which leads to increased cost and dispersion. Later stability becomes an issue.

In addition, in Patent Documents 1 to 3 in which triarylmethane salts were improved, it was found that it was difficult to achieve both luminance and voltage retention in the pixel to be obtained.

Therefore, an object of the present invention is to provide a novel triarylmethane compound capable of obtaining a pixel having both luminance and voltage retention.

Another object of the present invention is to provide a novel colored resin composition containing a triarylmethane compound capable of forming a pixel with high luminance and high voltage retention.

Another object of the present invention is to provide a color filter including pixels having high luminance and a high voltage retention rate, and a high-quality liquid crystal display device and an organic EL display device.

way of solving the problem

As a result of intensive studies, the inventors of the present invention found that the above-mentioned problems can be solved by using a novel triarylmethane compound having a specific structure, and completed the present invention.

That is, the present invention relates to a triarylmethane compound (hereinafter, sometimes simply referred to as "compound (I)"), a colored resin composition containing compound (I), a color filter, a liquid crystal display device, and an organic EL display device. The triarylmethane compound is characterized by being represented by the following formula (I).

[1] A triarylmethane 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 with 1 to 10 carbon atoms optionally having a substituent, or an aromatic ring group optionally having a substituent, adjacent R ¹ to R ⁶ in may be connected 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 any substituent,

Wherein, at least one of ^R7 and ^R8 is a halogen atom, or an alkyl group with 1 to 10 carbon atoms optionally having a substituent,

M ⁺ means a cation,

n represents an integer of 0-4. )

[2] The triarylmethane compound according to the above [1], wherein, in the above formula (I), R ⁷ is a hydrogen atom, and R ⁸ is a halogen atom or a carbon atom having 1 to 10 carbon atoms optionally having a substituent of alkyl.

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

[chemical formula 2]

(In the above formula (II), n, M ⁺ , R ¹ to R ⁵ , R ⁷ and R ⁸ have the same meaning as defined in the above formula (I),

R ¹¹ and R ¹² each independently represent a hydrogen atom or any substituent,

m represents the integer of 1-8. )

[4] A colored resin composition comprising (A) a dye, (B) a solvent, and (C) a binder resin, wherein,

(A) The dye is the triarylmethane compound described in any one of the above [1] to [3].

[5] The colored resin composition as described in [4] above, further comprising (D) a polymerizable monomer.

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

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

[8] A liquid crystal display device comprising the color filter described in the above [7].

[9] An organic EL display device comprising the color filter described in the above [7]. The effect of the invention

According to the present invention, it is possible to provide a novel triarylmethane-based compound capable of obtaining a pixel having both luminance and voltage retention.

Furthermore, according to the present invention, it is possible to provide a novel colored resin composition containing a triarylmethane compound capable of forming a pixel with high luminance and high voltage retention.

In addition, the present invention can provide a color filter including pixels having high luminance and a high voltage retention rate, and a high-quality liquid crystal display device and an organic EL display device.

Description of drawings

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

[ Fig. 2] Fig. 2 is a diagram of direct peaks appearing due to liquid crystal orientation in Examples.

Symbol Description

100 organic EL elements

10 Transparent support substrate

20 pixels

30 organic protective layer

40 inorganic oxide film

50 transparent anode

500 organic emitters

51 Hole injection layer

52 hole transport layer

53 luminous layer

54 electron injection layer

55 Cathode

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 (select the largest peak among the impurity peaks)

f Direct peak of liquid crystal

detailed description

Hereinafter, the embodiment of the present invention will be described in detail, but the following description is only an example of the embodiment of the present invention, and the present invention is not limited to these contents.

It should be noted that, in the present invention, "(meth)acryloyl", "(meth)acrylate" and the like refer to "at least one of acryloyl and methacryloyl", "acrylate and methacryl". At least one of acrylic acid esters", etc., for example, "(meth)acrylic acid" means "at least one of acrylic acid and methacrylic acid".

In addition, "total solid content" means the total components of the colored resin composition of this invention other than the solvent component mentioned later.

In addition, "aromatic ring" refers to both "aromatic hydrocarbon ring" and "aromatic heterocyclic ring".

In addition, terms such as "C.I. Pigment Green" refer to the color index number (C.I.).

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

[About compound (I)]

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

[chemical formula 3]

(In the above formula (I), R ¹ to R ⁶ each independently represent a hydrogen atom, an alkyl group with 1 to 10 carbon atoms optionally having a substituent, or an aromatic ring group optionally having a substituent, adjacent R ¹ to R ⁶ in may be connected 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 any substituent,

Wherein, at least one of ^R7 and ^R8 is a halogen atom, or an alkyl group with 1 to 10 carbon atoms optionally having a substituent,

M ⁺ means a cation,

n represents an integer of 0-4. )

It should be noted that in the above formula (I), the -SO ₃ ^- group and the -(SO ₃ ^- M ⁺ ) _n group outside [] represent the aromatic ring, R ¹ to R ⁸ , Or the substituents of R ¹ to R ⁸ are each substituted with -SO ₃ ^- or -(SO ₃ ^- M ⁺ ) _n .

(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.

Examples of the alkyl group in R ¹ to R ⁶ include straight-chain, branched-chain or cyclic alkyl groups having usually 1 to 10 carbon atoms. Specific examples include methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, tert-butyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl, phenethyl, etc. .

Examples of the aromatic ring groups in R ¹ to R ⁶ include aromatic hydrocarbon ring groups and aromatic heterocyclic groups.

The aromatic hydrocarbon ring group may be a single ring or a condensed ring, and there are no particular limitations as long as the number of carbon atoms forming the ring is 5 to 18. Examples include benzene rings and naphthalene rings having one free valence. ring, anthracene ring, phenanthrene ring, perylene ring, naphthacene ring, pyrene ring, benzopyrene ring, ring, triphenylene ring, acenaphthylene ring, benzoacenaphthylene ring, fluorene ring, etc.

In addition, the aromatic heterocyclic group may be a monocyclic ring or a condensed ring, and there are no particular limitations as long as the number of carbon atoms forming the ring is 3 to 10. For example, a furan ring having one free valence, Benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, Oxadiazole ring, indole ring, carbazole ring, pyrrolopyrrole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thieno Furan ring, benzoiso Azole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline (cinnoline) ring, quinoxa Phenylline ring, phenanthridine ring, benzimidazole ring, A group such as a pyrene ring, a quinazoline ring, a quinazolinone ring, an azulene ring, or the like.

Adjacent R ¹ to R ⁶ (specifically, R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ ) may be connected to each other to form a ring, and the ring may have a substituent.

In addition, the ring may be a ring formed by bridging heteroatoms, and specific examples thereof include, for example, the following structures.

[chemical formula 4]

From the viewpoint of chemical stability, R ¹ to R ⁶ are each independently preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms optionally having a substituent, or a phenyl group optionally having a substituent, or adjacent The case where R ¹ to R ⁶ are connected to each other to form a ring. These substituents are also preferable in terms of brightness. From the standpoint of improving the heat resistance of the compound (I) and excellent light resistance of the obtained color filter, it is more preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms optionally having a substituent, or an alkyl group optionally having a substituent. phenyl.

When R ¹ to R ⁶ are alkyl groups having 1 to 10 carbon atoms which may have substituents, it is presumed that the charge in the cation is dispersed and the cation is stabilized by the effect of hyperconjugation.

More specifically, for the number of carbon atoms of the alkyl groups in R ¹ to R ⁴ , it is difficult to affect the structure of the triarylmethane skeleton (the impact on brightness is small) and the substituent on the N is difficult to leave (compound (I ) and stability) are preferably 8 or less, more preferably 4 or less, and preferably 2 or more.

^In addition, R ⁵ and R ⁶ are preferably a hydrogen atom and R ⁶ is an alkyl group from the standpoints that the compound (I) is not easily decomposed and has a color tone (high brightness). The number of carbon atoms of the alkyl group in R ⁶ is more preferably 8 or less, still more preferably 5 or less.

In addition, when adjacent R ¹ to R ⁶ are connected to each other to form a ring, the substituent on N is not easily detached, and thus stable.

When R ¹ to R ⁶ are phenyl groups which may have substituents, since the conjugated system is extended, charges in the cation are dispersed and the cation is stabilized. In this way, it is considered that as a result of cation stabilization, the heat resistance of the obtained color filter can be further improved.

Examples of the substituents that the alkyl groups in R ¹ to R ⁶ , the aromatic ring groups, and the rings that are connected to each other may have are those in the following (substituent group W).

(substituent group W)

Fluorine atom, chlorine atom, alkyl group having 1 to 8 carbon atoms, alkenyl group having 2 to 8 carbon atoms, alkoxy group having 1 to 8 carbon atoms, phenyl group, group, tolyl group, naphthyl group, cyano group, acetoxy group, alkylcarbonyloxy group with 2 to 9 carbon atoms, sulfamoyl group, alkylsulfamoyl group with 2 to 9 carbon atoms, and alkylsulfamoyl group with 2 to 9 carbon atoms 9 alkylcarbonyl group, phenethyl group, hydroxyethyl group, acetamido group, dialkylaminoethyl group bonded with an alkyl group having 1 to 4 carbon atoms, trifluoromethyl group, 1 to 4 carbon atoms 8 trialkylsilyl group, nitro group, and alkylthio group having 1 to 8 carbon atoms.

Among them, as substituents which may be optionally possessed by the alkyl groups, aromatic ring groups, and rings formed by R ¹ to R ⁶ are preferably alkyl groups having 1 to 10 carbon atoms, and alkyl groups having 2 to 8 carbon atoms. alkoxy group, cyano group, acetoxy group, alkyl carboxyl group with 2 to 8 carbon atoms, sulfamoyl group, alkylsulfamoyl group with 2 to 9 carbon atoms, and fluorine atom.

(about R ⁷ and R ⁸ )

R ⁷ and R ⁸ represent a hydrogen atom or an arbitrary substituent.

Examples of the optional 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.

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 substituents.

That is, in the benzene ring in the formula (I), with respect to the bond with the carbon atom located in the center of the triarylmethane structure, if a bulky group is bonded at the ortho position, the center of the triarylmethane structure will be sterically viewed. Protected, thereby improving the heat resistance of compound (I).

In addition, from the aspect that it is not easy to cause the change of absorption spectrum due to the change of molecular structure of compound (I), and the brightness of the resulting pixel is reduced, the number of carbon atoms of the alkyl group in ^R7 and R8 is preferably ⁸ or less, more preferably 6 or less, particularly preferably 4 or less, and usually 1 or more.

As a preferred form among ^R7 and ^R8 , ^R7 is preferably a hydrogen atom, ^R8 is an alkyl group, and particularly preferably ^R7 is a hydrogen atom, and ^R8 is a methyl group.

In addition, R ⁷ and R ⁸ may be connected to each other to form a ring, and this ring may have a substituent. Examples of such substituents include groups described in the above-mentioned (substituent group W) section.

When the alkyl group in R ⁷ and R ⁸ has a substituent, it is preferably a halogen atom. That is, preferable examples include fluoromethyl groups such as trifluoromethyl groups.

(About M ⁺ and n)

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

Lithium, sodium, potassium, etc. are mentioned as an alkali metal of an alkali metal cation. Moreover, magnesium, calcium, barium etc. are mentioned as an alkaline earth metal of an alkaline earth metal cation.

N ⁺ HR ₃ for tertiary ammonium cations (R represents a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aromatic ring group. It should be noted that multiple Rs may be the same or different) To represent.

The preferred number of carbon atoms of the alkyl group in the above R and examples of substituents that the alkyl group may have are the same as the number of carbon atoms and substituents listed in the case of the alkyl groups of R ¹ to R ⁶ above. Examples of the preferred number of carbon atoms of the aromatic ring group and the substituents that the aromatic ring group may have are the number of carbon atoms and substituents listed in the case of the above-mentioned R ¹ to R ⁶ aromatic ring groups same. Specific examples include: lower alkylammonium cations with 1 to 6 carbon atoms (such as methylammonium cations, ethylammonium cations, diethylammonium cations, triethylammonium cations, etc.), carbon atoms substituted with hydroxyl groups Alkyl ammonium cations of 1 to 6 (such as ethanol ammonium cations, diethanol ammonium cations, triethanolammonium cations, etc.), carboxy-substituted alkyl ammonium cations with 1 to 6 carbon atoms (such as carboxymethyl ammonium cations, carboxyethyl ammonium cations, etc.) Ammonium cations, carboxypropylammonium cations, dicarboxymethylammonium cations, etc.), ammonium cations substituted with aromatic ring groups and alkyl groups (such as N,N-diethylphenylammonium cations, etc.) and the like.

The quaternary ammonium cation is represented by N ⁺ R ₄ , and R represents an alkyl group optionally having a substituent or an aromatic ring group optionally having a substituent. It should be noted that the plurality of R contained may be the same or different. The preferred number of carbon atoms of the alkyl group and examples of substituents that the alkyl group may have are the same as the number of carbon atoms and substituents mentioned above for the alkyl groups of R ¹ to R ⁶ . Examples of the preferred number of carbon atoms of the aromatic ring group and the substituents that the aromatic ring group may have are the number of carbon atoms and substituents listed in the case of the above-mentioned R ¹ to R ⁶ aromatic ring groups same.

Specifically, quaternary alkylammonium cations having 1 to 6 carbon atoms (for example, tetramethylammonium cation, tetraethylammonium cation, tetrabutylammonium cation, etc.) etc. are mentioned.

It should be noted that the type of M ⁺ cations is not limited to one type, and multiple types may be mixed. In addition, multiple types of M ⁺ cations may be mixed in one molecule of the compound, or multiple types may be mixed in the colored resin composition. Preferred examples of M ⁺ are hydrogen ions, alkali metal cations, tertiary ammonium cations, and quaternary ammonium cations, more preferably lithium cations, sodium cations, Unsubstituted ammonium cation, tetrabutylammonium cation.

n represents an integer of 0-4.

The larger n is, the more the compound (I) is substituted by the sulfo group of the hydrophilic group, the heat resistance and light resistance are improved, and the solubility of the compound (I) in the hydrophobic liquid crystal is also reduced, so the voltage Although retention improves, it is preferable that it is 0-2 from a viewpoint of the solubility in the organic solvent used for a colored resin composition being high.

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

In the compound (I), the -SO ₃ ^- group outside [] represents substitution on an aromatic ring, R ¹ to R ⁸ , or a substituent of R ¹ to R ⁸ in []. A preferable substitution position of the -SO ₃ ^- group is a hydrogen atom on a naphthalene ring forming a triarylmethane skeleton or a hydrogen atom of a substituent on R ⁶ .

The reason why the -SO ₃ ^- group is preferably substituted on the naphthalene ring forming the triarylmethane skeleton is as follows. In the case of intermolecular salt formation, the compound (I) substituted by -SO ₃ ^- on the naphthalene ring forms an ionic bond with the nitrogen atom or central carbon atom of another molecule. At this time, due to the -SO of the compound (I) The ₃ ^- group is located on the naphthalene ring, and the distance between the naphthalene ring of compound (I) and the aromatic ring possessed by another molecule becomes closer. Therefore, in addition to the ionic bond, π-π interaction occurs between the two molecules, so the intermolecular force is strengthened, and the heat resistance and electrical reliability become high. In addition, since the -SO ₃ ^- group is located on the naphthalene ring, the position of the central carbon of the same molecule and the -SO ₃ ^- group becomes closer, and a strong salt-forming effect in the molecule can also be expected. In addition, especially when the -SO ₃ ^- group is substituted on the ring where the nitrogen atom of the naphthalene ring is not substituted, the contribution of the triarylmethane skeleton to the conjugated system is small, and the influence on the color development is small, and it is excellent in terms of brightness. preferred.

Next, the reason why the -SO ₃ ^- group is preferably substituted on the substituent on R ⁶ is as follows. Compared with the case of introducing the -SO ₃ ^- group to the substituent of R ¹ to R ⁴ , the introduction of the -SO ₃ ^- group into the substituent of R ⁶ has less constraints on the synthesis and is relatively easy. At the same time, R When the -SO ₃ ^- group on the substituent of ⁶ forms an ionic bond within or between molecules, it can take a relatively free position and is easily arranged at a position where a strong ionic bond can be formed. In particular, when R ⁶ is an alkyl group, since the degree of freedom of the substituent is high, the -SO ₃ ^- group is easily located at an ideal position for forming intramolecular and intermolecular ionic bonds, thereby forming a strong ionic bond. Therefore, It is preferable from the viewpoint of heat resistance and electrical reliability. In addition, it is also preferable from the viewpoints that the contribution of the triarylmethane skeleton to the conjugated system is small, the influence on color development is small, and the luminance of the obtained pixel is small.

It should be noted that, in formula (I) ^, the covalent bond of -SO ₃ ^- group and -SO ₃ -M ⁺ group is marked as being connected with [], which means that there are multiple substitution positions, and the result obtained in the synthesis is A mixture of compounds having different substitution positions, etc.

[compound represented by formula (II)]

Compound (I) is preferably a compound represented by the following formula (II) (hereinafter referred to as "compound (II)") from the viewpoint of excellent luminance and voltage retention of the resulting pixel.

[chemical formula 5]

(In the above formula (II), n, M ⁺ , R ¹ to R ⁵ , R ⁷ and R ⁸ are synonymous with n, M ⁺ , R ¹ to R ⁵ , R ⁷ and R ⁸ in the above formula (I) .

R ¹¹ and R ¹² each independently represent a hydrogen atom or an arbitrary substituent.

m represents the integer of 1-8. )

(about R ¹¹ and R ¹² )

Optional substituents in R ¹¹ and R ¹² include the groups described in the above (substituent group W) section, and are preferably hydrogen atoms from the viewpoint of ease of synthesis.

In addition, a plurality of R ¹¹ and R ¹² contained in one molecule may be the same or different from each other, but are preferably the same from the viewpoint of ease of synthesis.

In addition, R ¹¹ and R ¹² may be the same or different, but are preferably the same from the viewpoint of ease of synthesis.

(about m)

m is usually 1 or more, preferably 2 or more, and 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 it is easy to form an ionic bond between molecules and a central carbon atom in the molecule. , It is preferable from the point of view that heat resistance and voltage retention become good.

[molecular weight]

The molecular weight of the compound (I) in the present invention is usually 450 or more, preferably 500 or more, and usually 5000 or less, preferably 2000 or less.

If it is within the above range, it is preferable from the viewpoint of easy synthesis.

[specific example]

[chemical formula 6]

[chemical formula 7]

[chemical formula 8]

[chemical formula 9]

＜About the synthesis method of compound (I)＞

Compound (I) can be based, for example, on the basis of "A Review of Synthetic Dyes (Synthetic Dyes)" (Horiguchi Hiroshi, Sankyo Publishing, 1968), "Theoretical Manufacturing Dye Chemistry" (Hosoda Toyo, Gihodo, 1957) method to synthesize, but not limited to this method.

Specifically, there are methods of (i) constructing a triarylmethane skeleton from a compound having a sulfo group, and (ii) introducing a sulfo group after constructing the triarylmethane skeleton.

In the case of (i), there is a method in which a sulfo group is directly substituted on a benzene ring or a naphthalene ring forming a triarylmethane skeleton by a usual method, or a sulfo group is directly substituted on a benzene ring or a naphthalene ring forming a triarylmethane skeleton. The substituent has a raw material substituted with a sulfo group to construct a triarylmethane skeleton.

In the case of (ii), there are the following methods: a method of constructing a triarylmethane skeleton by a usual method, and using sulfuric acid, chlorosulfonic acid, fuming sulfuric acid, etc. to carry out sulfonation to introduce a sulfo group; A method in which a compound having a methane skeleton is reacted with sodium hydroxymethanesulfonate, 1,3-propane sultone, 1,4-butane sultone, etc. to introduce a substituent having a sulfo group.

＜Applications of compound (I)＞

The use of the compound (I) of the present invention is not particularly limited, and it can be used for various purposes. Among them, the compound (I) of the present invention is preferably used in a color filter because the luminance and voltage retention of the obtained pixel are high, and the heat resistance of the compound (I) is high.

That is, the compound (I) of the present invention is preferably used as a dye for color filters.

Hereinafter, the colored resin composition containing compound (I) when used as a dye for color filters is demonstrated.

＜Colored resin composition＞

The colored resin composition of the present invention contains (A) dye, (B) solvent and (C) binder resin, wherein, (A) dye contains compound (1), and the colored resin composition of the present invention more preferably further contains ( At least one of D) a polymerizable monomer, (E) a photopolymerization initiation component, and a thermal polymerization initiation component, and other components are contained as needed.

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

[about (A) dye]

In the colored resin composition of the present invention, the dye (A) includes the compound (I), but may contain other dyes other than the compound (I) as long as the effect of the present invention is not impaired.

As other dyes, for example, azo-based dyes, anthraquinone-based dyes, phthalocyanine-based dyes, quinoneimine-based dyes, quinoline-based dyes, nitro-based dyes, carbonyl-based dyes, methine-based dyes, Cyan dyes, triarylmethane dyes, methine dipyrrole dyes, xanthene dyes, etc.

Examples of azo dyes include: C.I. Acid Yellow 11, C.I. Acid Orange 7, C.I. Acid Red 37, C.I. Acid Red 180, C.I. Acid Blue 29, C.I. Direct Red 28, C.I. Direct Red 83, C.I. Direct Yellow 12 , C.I. Direct Orange 26, C.I. Direct Green 28, C.I. Direct Green 59, C.I. Reactive Yellow 2, C.I. Reactive Red 17, C.I. Reactive Red 120, C.I. Reactive Black 5, C.I. Disperse Orange 5, C.I. Disperse Red 58, C.I. Disperse Blue 165 , C.I. Basic Blue 41, C.I. Basic Red 18, C.I. Media Red 7, C.I. Media Yellow 5, C.I. Media Black 7, etc.

Examples of anthraquinone dyes include: C.I. Vat Blue 4, C.I. Acid Blue 25, C.I. Acid Blue 40, C.I. Acid Blue 80, C.I. Acid Green 25, C.I. Reactive Blue 19, C.I. Reactive Blue 49, C.I. Disperse Red 60 , C.I. Disperse Blue 56, C.I. Disperse Blue 60, etc.

In addition, examples of phthalocyanine dyes include C.I. Direct Blue 86, C.I. Direct Blue 199, C.I. Vat Blue 5, JP-A-2002-14222, JP-A-2005-134759, JP-A-2010 -Phthalocyanine dyes etc. described in Publication No. 191358 and Japanese Patent Application Laid-Open No. 2011-148950; as quinone imine dyes, for example: C.I. Basic Blue 3, C.I. Basic Blue 9, etc., as quinoline Examples of dyes include: C.I. Solvent Yellow 33, C.I. Acid Yellow 3, C.I. Disperse Yellow 64, etc. Nitro-based dyes include, for example: C.I. Acid Yellow 1, C.I. Acid Orange 3, C.I. Disperse Yellow 42, etc. .

In addition, examples of triarylmethane dyes include triaryl dyes described in C.I. Acid Blue 86, C.I. Acid Blue 88, C.I. Acid Blue 108, International Publication No. 2009/107734, International Publication No. 2011/162217, etc. Methane dyes.

In addition, examples of cyanine dyes include cyanine dyes described in International Publication No. 2011/162217, and preferred embodiments are also the same.

Examples of methine dipyrrole dyes include JP-A-2008-292970, JP-A 2010-84009, JP-A 2010-84141, JP-A 2010-85454, JP 2011-158654, JP 2012-158739, JP 2012-224852, JP 2012-224849, JP 2012-224847, JP 2012- A methine dipyrrole dye described in Publication No. 224846 or the like.

Examples of xanthene-based dyes include C.I. Acid Red 50, C.I. Acid Red 52, C.I. Acid Red 289, Japanese Patent No. 3387541, Japanese Patent Laid-Open No. 2010-32999, and Japanese Patent No. 4492760. , "Summary of Synthetic Dyes (Synthetic Dyes)" (Horiguchi Hiroshi, Sankyo Publishing, 1968) The xanthene dyes described in pages 326 to 348.

Especially when forming blue pixels, xanthene-based dyes, triarylmethane-based dyes, anthraquinone-based dyes, azo-based dyes, methine dipyrrole-based dyes, cyanine-based dyes, and phthalocyanine-based dyes are preferable.

In the colored resin composition of this invention, as (A) dye, only 1 type of compound (I) may be contained, and 2 or more types may be contained.

In addition, one or two or more other dyes other than 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, or preferably 50% by weight or less in the total solid content.

In addition, the content of compound (I) in the colored resin composition 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 in the total solid content. % by weight or less, preferably 40% by weight or less, more preferably 30% by weight or less.

Since the curability of a coating film is hard to fall and film strength is sufficient as it is below the said upper limit, it is preferable. Moreover, if it is more than the said minimum, since tinting power is sufficient, it becomes easy to obtain the chroma of desired density|concentration, and since film thickness becomes hard to become thick, it is preferable.

In addition, in the colored resin composition of this invention, it is preferable that content of compound (I) is 30 weight% or more in solid content of all (A) dyes.

[(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 and adjusting the viscosity.

As (B) solvent, what is necessary is just to be a solvent which can dissolve or disperse each component which comprises a colored resin composition, and it is preferable to select the solvent whose boiling point is in the range of 100-200 degreeC. More preferred are solvents having a boiling point of 120 to 170°C.

As such a solvent, the following solvents 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 mono-tert-butyl ether, diethylene glycol monomethyl ether, diethylene glycol Glycol monoalkanes such as monoethyl ether, methoxymethylpentanol, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, and tripropylene glycol monomethyl ether base ethers;

Glycol dialkyl groups such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether 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, methoxybutyl acetate, acetic acid 3-methoxybutyl ester, methoxypentyl acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methyl acetate - diol alkyl ether acetates such as 3-methoxybutyl ester;

Ethers such as diethyl ether, dipropyl ether, diisopropyl ether, dipentyl ether, ethyl isobutyl ether, and dihexyl ether;

Acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethylpentyl ketone Ketones such as methyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone;

Monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin;

Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutene, n-hexane, hexene, isoprene, dipentene and dodecane;

Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and dicyclohexyl;

Aromatic hydrocarbons such as benzene, toluene, xylene, and cumene;

Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, cyclohexyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate ester, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl octanoate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, 3-ethoxypropionate Ethyl 3-methoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, γ-butyrolactone, etc. chain or cyclic esters;

Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;

Halogenated hydrocarbons such as chlorobutane and chloropentane;

ether ketones such as methoxymethylpentanone;

Nitriles such as acetonitrile and benzonitrile.

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

Among the above-mentioned solvents, glycol monoalkyl ethers are preferable from the viewpoint of the solubility of the (A) dye of the present invention. Among them, propylene glycol monomethyl ether is particularly preferable from the viewpoint of the solubility of various components in the colored resin composition.

In addition, for example, when the (F) pigment described later is included as an optional component, when a glycol alkyl ether acetate is further mixed and used as a solvent, a good balance of coatability, surface tension, etc. can be obtained, and the coloring Since the solubility of the constituent components in a resin composition is high, it is more preferable. It should be noted that, in the colored resin composition containing the pigment, since the polarity of the diol monoalkyl ethers is high, there is a tendency to aggregate the pigment, and thus the viscosity of the colored resin composition may increase and the storage stability may be reduced. reduced situation. Therefore, it is preferable not to use too much glycol monoalkyl ethers, and the proportion of glycol monoalkyl ethers in (B) solvent is preferably 5 to 50% by weight, more preferably 5 to 30% by weight.

In addition, it is also preferable to use a solvent having a boiling point of 150° C. or higher in combination in consideration of adaptability to the recent slit coat method corresponding to large substrates and the like. In this case, the content of the high boiling point solvent is preferably 3 to 50% by weight, more preferably 5 to 40% by weight, and particularly preferably 5 to 30% by weight based on the total amount of the solvent (B). If the amount of high-boiling-point solvent is too small, for example, precipitation and solidification of dye components may occur at the front end of the slit nozzle, which may cause foreign matter defects; The drying speed becomes slow, which in turn may cause problems such as poor production tact and pre-bake pinhole marks in the reduced-pressure drying process in the color filter manufacturing process described later.

It should be noted that the solvent having a boiling point of 150°C or higher may be glycol alkyl ether acetates or glycol alkyl ethers, and in this case, the solvent having a boiling point of 150°C or higher may not be contained separately. .

The colored resin composition of the present invention can be supplied to the manufacture of color filters by the inkjet method. In the manufacture of color filters by the inkjet method, the ink ejected from the nozzle is very small, ranging from several pL to several tens of pL. , before spraying to the periphery of the nozzle or into the pixel storage tank, the solvent evaporates, and the ink tends to concentrate and dry. In order to avoid this, the boiling point of the solvent is preferably high, and specifically, the (B) solvent preferably includes a solvent having a boiling point of 180° C. or higher. It is particularly preferable to contain a solvent having a boiling point of 200°C or higher, especially a boiling point of 220°C or higher. Moreover, it is preferable that the high boiling point solvent with a boiling point of 180 degreeC or more is 50 weight% or more in (B) solvent. When the proportion of such a high boiling point solvent is less than 50% by weight, there is a possibility that the effect of preventing solvent from evaporating from ink droplets cannot be sufficiently exhibited.

In the colored resin composition of the present invention, the content of the (B) solvent is not particularly limited, and the upper limit thereof is usually 99% by weight. When the content of the (B) solvent in the composition exceeds 99% by weight, the concentration of each component other than the (B) solvent becomes too small, and it may be difficult to form a coating film. On the other hand, the lower limit of the content of the (B) solvent is usually 75% by weight, preferably 80% by weight, and more preferably 82% by weight, considering the viscosity suitable for coating and the like.

[(C) binder resin]

As for (C) binder resin, preferable resin differs with the hardening method of a colored resin composition.

When the colored resin composition of the present invention is a photopolymerizable resin composition, as (C) binder resin, for example, JP-A-7-207211, JP-A-8-259876, JP-A, Kokai No. 10-300922, Japanese Patent Laid-Open No. 11-140144, Japanese Patent Laid-Open No. 11-174224, Japanese Patent Laid-Open No. 2000-56118, Japanese Patent Laid-Open No. 2003-233179, etc. Among the molecular compounds, resins of the following (C-1) to (C-5) and the like are preferably exemplified.

(C-1): For a copolymer of an epoxy group-containing (meth)acrylate and other radically polymerizable monomers, at least a part of the epoxy groups contained in the copolymer is added to an unsaturated monobasic acid The resulting resin, or an alkali-soluble resin obtained by adding at least a part of the hydroxyl groups generated by the addition reaction to a polybasic acid anhydride (hereinafter, sometimes referred to as "resin (C-1)")

(C-2): Linear alkali-soluble resin (C-2) containing a carboxyl group (hereinafter, sometimes referred to as "resin (C-2)")

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

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

(C-5): Epoxy acrylate resin having a carboxyl group (hereinafter sometimes referred to as "resin (C-5))

Among them, resin (C-1) is particularly preferably used, and the resin will be described below.

It should be noted that the resins (C-2) to (C-5) only need to be dissolved by an alkaline developer and have a solubility that enables the target development process to be completed. The resins described as the same items in JP-A-2009-025813 are the same. Preferred embodiments are also the same.

(C-1): For a copolymer of an epoxy group-containing (meth)acrylate and other radically polymerizable monomers, at least a part of the epoxy groups contained in the copolymer is added to an unsaturated monobasic acid The resulting resin, or an alkali-soluble resin obtained by adding at least a part of the hydroxyl groups generated by the addition reaction to a polybasic acid anhydride

As one of the particularly preferable resins of the resin (C-1), it is possible to enumerate: A copolymer formed from a body, a resin obtained by adding 10 to 100 mol% of epoxy groups in the copolymer to an unsaturated monobasic acid, or 10 to 100 mol of hydroxyl groups generated by the addition reaction % Alkali-soluble resin obtained by addition of polybasic acid anhydride.

Examples of (meth)acrylates containing epoxy groups include glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, (meth)acrylic acid (3 , 4-epoxycyclohexyl) methyl ester, 4-hydroxybutyl (meth)acrylate glycidyl ether, etc. Among them, glycidyl (meth)acrylate is preferable. The said epoxy group containing (meth)acrylate may be used individually by 1 type, and may use it in combination of 2 or more types.

The other radically polymerizable monomers to be copolymerized with the above-mentioned epoxy group-containing (meth)acrylate are not particularly limited as long as the effect of the present invention is not impaired, and examples thereof include vinyl aromatics, di Alkenes, (meth)acrylic esters, (meth)acrylamides, vinyl compounds, unsaturated dicarboxylic acid diesters, monomaleimides, etc., particularly preferably have the following formula (7 ) mono(meth)acrylate of the structure shown.

Among the repeating units derived from "other radically polymerizable monomers", the content ratio of repeating units derived from mono(meth)acrylate having a structure represented by the following formula (7) is preferably 5 to 90 mol%, and further Preferably it is 10-70 mol%, Especially preferably, it is 15-50 mol%.

[chemical formula 10]

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).

[chemical formula 11]

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. It should be noted that R ⁹⁶ and R ⁹⁸ are optionally connected to each other to form a ring.

The ring formed by linking R ⁹⁶ and R ⁹⁸ is preferably an aliphatic ring, which may be either a saturated ring or an unsaturated ring, and the number of carbon atoms is preferably 5-6.

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

[chemical formula 12]

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

As "other radically polymerizable monomers" other than the mono(meth)acrylate having the structure represented by the above formula (8), it is possible to improve the excellent heat resistance and strength of the colored resin composition. Examples: styrene, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, Benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, N-phenylmaleimide, N-cyclohexylmaleimide.

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

In addition, a well-known solution polymerization method can be employ|adopted for the copolymerization reaction of the said epoxy group containing (meth)acrylate, and the said other radically polymerizable monomer.

In the present invention, as the copolymer formed of the above-mentioned epoxy group-containing (meth)acrylate and the above-mentioned other radically polymerizable monomers, it is preferable that the repeating unit derived from the epoxy group-containing (meth)acrylate A copolymer formed of ~90 mol% and 10-95 mol% of repeating units derived from other radically polymerizable monomers, more preferably a copolymer formed by the former 20-80 mol% and the latter 80-20 mol%, especially preferably A copolymer formed from 30 to 70 mol% of the former and 70 to 30 mol% of the latter.

When it is within the above-mentioned range, the added amount of the polymerizable component and the alkali-soluble component described later is sufficient, and heat resistance and strength of the film are sufficient, so it is preferable.

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

Here, well-known compounds can be used as an unsaturated monobasic acid added to an epoxy group, For example, the unsaturated carboxylic acid which has an ethylenic unsaturated double bond is mentioned.

Specific examples include: (meth)acrylic acid, crotonic acid, o-vinyl benzoic acid, m-vinyl benzoic acid, p-vinyl benzoic acid, α-position substituted by haloalkyl, alkoxy, halogen, nitro , or monocarboxylic acids such as (meth)acrylic acid substituted with cyano group, etc. Among them, (meth)acrylic acid is preferable. These unsaturated carboxylic acids may be used alone or in combination of two or more.

By adding the above components, polymerizability can be imparted to the binder resin used in the present invention.

Usually, these unsaturated monobasic acids are added to 10 to 100 mol% of the epoxy groups which the said copolymer has, Preferably they add 30 to 100 mol%, More preferably, they add 50 to 100 mol%. When it is in the said range, since the temporal stability of a colored resin composition is excellent, it is preferable. Among them, a known method can be employed as a method of adding an unsaturated monobasic acid to the epoxy group of the copolymer.

In addition, a known polybasic acid anhydride can be used as the polybasic acid anhydride added to the hydroxyl group generated when the unsaturated monobasic acid is added to the epoxy group of the copolymer.

For example, dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, hexachloronorbornene diacid anhydride; trimellitic anhydride , Pyromellitic dianhydride, benzophenone tetracarboxylic anhydride, biphenyl tetracarboxylic anhydride and other acid anhydrides of trivalent or higher acids. Among them, succinic anhydride and tetrahydrophthalic anhydride are preferable. These polybasic acid anhydrides may be used individually by 1 type, and may use it in combination of 2 or more types.

Alkali solubility can be imparted to the binder resin used for this invention by adding the said component.

Usually, 10 to 100 mol% of the hydroxyl group formed by adding an unsaturated monobasic acid to the epoxy group of the above copolymer is added to the above polybasic acid anhydride, preferably 20 to 90 mol%, more preferably 20 to 90 mol%. 30-80 mol% addition.

When it is in the said range, since the remaining film rate and solubility at the time of image development are sufficient, it is preferable.

In addition, a well-known method can be employ|adopted as the method of adding this hydroxyl group and polybasic acid anhydride.

Moreover, in order to improve photosensitivity, after adding the said polybasic acid anhydride, you may add some carboxyl groups produced|generated to glycidyl (meth)acrylate or the glycidyl ether compound which has a polymerizable unsaturated group. The structures of such resins are described in, for example, JP-A-8-297366 and JP-A-2001-89533.

The polystyrene-equivalent weight average molecular weight (Mw) of the binder resin (C-1) measured by GPC (gel permeation chromatography) is preferably 3,000 to 100,000, particularly preferably 5,000 to 50,000. If it is in the said range, heat resistance, film strength, and the solubility to a developing solution will become favorable, and it is preferable at this point.

In addition, the ratio of weight average molecular weight (Mw)/number average molecular weight (Mn) is preferably 2.0 to 5.0 as an approximate standard of molecular weight distribution.

In addition, the acid value of binder resin (C-1) is 10-200 mg-KOH/g normally, Preferably it is 15-150 mg-KOH/g, More preferably, it is 25-100 mg-KOH/g. If the acid value is too low, the solubility in the developer may decrease. On the contrary, if the acid value is too high, film cracking may sometimes occur.

Content of (C) binder resin in a colored resin composition is 0.1-80 weight% normally in total solid content, Preferably it is 1-60 weight%.

If it is within the above-mentioned range, the adhesion to the substrate is good, and the permeability of the developing solution to the exposed part is suitable, and the surface smoothness and sensitivity of the pixel are good, which is preferable.

[(D) Polymerizable monomer]

The colored resin composition of the present invention preferably contains (D) a polymerizable monomer.

(D) The polymerizable monomer is not particularly limited as long as it is a polymerizable low-molecular compound, but an addition-polymerizable compound (hereinafter, sometimes referred to as "olefinic compound") having at least one ethylenic double bond is preferable.

The ethylenic compound is a compound having an ethylenic double bond that is cured by addition polymerization under the action of a photopolymerization initiating component described later when the colored resin composition of the present invention is irradiated with active light. It should be noted that (D) polymerizable monomer in the present invention is a concept opposite to so-called high molecular substance, and includes dimers, trimers, and oligomers in addition to monomers in a narrow sense.

Examples of the ethylenic compound in the (D) polymerizable monomer include unsaturated carboxylic acids such as (meth)acrylic acid; esters of monohydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds and unsaturated carboxylic acids; Esters formed by acids; esters formed by aromatic polyhydroxy compounds and unsaturated carboxylic acids; polyhydroxy compounds such as unsaturated carboxylic acids and polycarboxylic acids and the above-mentioned aliphatic polyhydroxy compounds, aromatic polyhydroxy compounds, etc. The obtained ester; the olefinic compound having a urethane skeleton obtained by reacting a polyisocyanate compound with a (meth)acryloyl group-containing hydroxyl compound; and the like.

Examples of esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, trimethylolpropane tri(methyl) ) acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate base) acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, glycerol (meth)acrylate and other (meth)acrylates. In addition, itaconate esters in which the (meth)acrylic acid moieties of these (meth)acrylates are replaced by itaconic acid moieties, and those in which the (meth)acrylic acid moieties of these (meth)acrylate esters are replaced by crotonic acid Some crotonic acid esters, or maleic acid esters obtained by substituting the (meth)acrylic acid moieties of these (meth)acrylates for maleic acid moieties, etc.

Examples of esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include: hydroquinone di(meth)acrylate, resorcinol di(meth)acrylate, pyrogallol tri(methyl) ) acrylate, etc.

The ester obtained by the esterification reaction of an unsaturated carboxylic acid, a polyvalent carboxylic acid, and a polyhydric hydroxy compound may be a single substance or a mixture. As a representative example, a condensate of (meth)acrylic acid, phthalic acid and ethylene glycol; a condensate of (meth)acrylic acid, maleic acid and diethylene glycol; a condensate of (meth)acrylic acid, p- Condensates of phthalic acid and pentaerythritol; condensates of (meth)acrylic acid, adipic acid, butanediol and glycerol, etc.

Examples of olefinic compounds having a urethane skeleton obtained by reacting a polyisocyanate compound with a hydroxyl compound containing a (meth)acryloyl group include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and the like. Aliphatic diisocyanate; cyclohexane diisocyanate, isophorone diisocyanate and other alicyclic diisocyanates; toluene diisocyanate, diphenylmethane diisocyanate and other aromatic diisocyanates and 2-hydroxyethyl (meth)acrylate , 3-Hydroxy[1,1,1-tri(meth)acryloyloxymethyl]propane and other reaction products of hydroxyl compounds containing (meth)acryloyl groups.

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

Among the above, 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 particularly preferable.

In addition, the olefinic compound may also be a monomer having an acid value. The monomer having an acid value is, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, preferably one having an acid group obtained by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride. The polyfunctional monomer, particularly preferably, the aliphatic polyhydroxy compound in the ester is at least one of pentaerythritol and dipentaerythritol.

The above-mentioned monomers may be used alone, but since it is difficult to obtain a single compound in terms of production, a mixture of two or more may be used.

Moreover, the polyfunctional monomer which does not have an acidic group, and the polyfunctional monomer which has an acidic group can also be used in combination as needed as (D) polymerizable monomer.

The preferable acid value of the polyfunctional monomer which has an acid group is 0.1-40 mg-KOH/g, Especially preferably, it is 5-30 mg-KOH/g.

If it is in the said range, the image development dissolution characteristic will not fall easily, and manufacture and handling will become easy. Moreover, photopolymerization performance is hard to fall, and curability, such as the surface smoothness of a pixel, is favorable, and it is preferable.

In the present invention, a more preferable polyfunctional monomer having an acid group is, for example, a mixture mainly composed of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, or succinate of dipentaerythritol pentaacrylate. It is also possible to use this polyfunctional monomer 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, more preferably 10% by weight or more in the total solid content, and Usually, it is 80 weight% or less, Preferably it is 70 weight% or less, More preferably, it is 50 weight% or less, Especially preferably, it is 40 weight% or less.

In addition, the ratio of the (D) polymerizable monomer to the above (A) dye is usually at least 1% by weight, preferably at least 5% by weight, more preferably at least 10% by weight, especially It is preferably 20% by weight or more, and usually 200% by weight or less, preferably 100% by weight or less, more preferably 80% by weight or less.

When it is within the above range, the photocuring is moderate, and it is difficult to cause poor adhesion during development, and the cross-section after development is difficult to become an inverted conical shape, and it is difficult to cause peeling phenomenon and poor mold release caused by the decrease in solubility, so it is preferred. .

[(E) Photopolymerization Initiating Component, Thermal Polymerization Initiating Component]

For the purpose of curing the coating film, the colored resin composition of the present invention preferably contains at least one of (E) a photopolymerization initiating component and a thermal polymerization initiating component. However, the curing method may not use these initiators.

In particular, when the colored resin composition of the present invention contains a resin having an ethylenic double bond as the component (C) or an ethylenic compound as the component (D), it is preferable to contain At least one of a photopolymerization initiating component capable of generating a polymerization active free radical by light or photosensitization to cause a decomposition reaction or a dehydrogenation reaction, and a thermal polymerization initiating component that generates a polymerization active free radical under the action of heat. It should be noted that in the present invention, the (E) component as a photopolymerization initiating component means that a polymerization accelerator (hereinafter arbitrarily referred to as (E2) component), a mixture of additives such as a sensitizing dye (hereinafter arbitrarily referred to as (E3) component).

[(E) Photopolymerization Initiating Component]

The (E) photopolymerization initiating component in the present invention is usually used in the form of a mixture of (E1) photopolymerization initiator, (E2) polymerization accelerator and (E3) additives such as sensitizing dyes added as needed, and has A component that absorbs light directly, or undergoes photosensitization to initiate a decomposition reaction or a dehydrogenation reaction, thereby generating active free radicals for polymerization.

As the (E1) photopolymerization initiator constituting the photopolymerization initiating component, for example: titanocene derivatives described in JP-A-59-152396 A, JP-A-61-151197, etc.; Hexaaryldiimidazole derivatives described in JP 10-300922, JP 11-174224, JP 2000-56118, etc.; JP 10-39503, etc. Halomethylation of Oxadiazole derivatives, halomethyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α- Radical activators such as amino acid esters, α-aminoalkylphenone derivatives, oxime ester derivatives described in JP-A-2000-80068 and the like.

Specific examples include photopolymerization initiators described in International Publication No. 2009/107734 and the like.

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

In addition, examples of oxime ester derivatives include 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyl oxime), 1-[9 -Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ketene-1-(O-acetyl oxime), and compounds represented by the following formula (XI), etc. .

[chemical formula 13]

(In formula (XI), R ¹⁰¹ represents a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an alkenyl group with 2 to 25 carbon atoms, a heteroaryl group with 3 to 20 carbon atoms, or a heteroaryl group with 4 to 25 carbon atoms Heteroarylalkyl groups, all of which optionally have substituents. Alternatively, R ¹⁰¹ can also be bonded to X or Z to form a ring.

R ¹⁰² represents an alkanoyl group with 2 to 20 carbon atoms, an alkenoyl group with 3 to 25 carbon atoms, a cycloalkanoyl group with 4 to 8 carbon atoms, an aroyl group with 7 to 20 carbon atoms, an aroyl group with 2 to 10 carbon atoms alkoxycarbonyl, aryloxycarbonyl with 7 to 20 carbon atoms, heteroaryl with 2 to 20 carbon atoms, heteroaroyl with 3 to 20 carbon atoms or alkylaminocarbonyl with 2 to 20 carbon atoms, Each of these groups may have a substituent.

X represents at least one of a divalent aromatic hydrocarbon ring group and an aromatic heterocyclic group which may have substituents and which are condensed from two or more rings.

Z represents an aromatic ring group which may have a substituent. )

It should be noted that, among the compounds represented by the above-mentioned formula (XI), preferred is a compound in which X is a carbazole ring optionally having a substituent, and specific examples include compounds represented by the following formula (XII), among which, the following is particularly preferred: The compound represented by the formula (XIII).

[chemical formula 14]

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

[chemical formula 15]

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

[chemical formula 16]

(In the formula, R ¹⁰³ and R ¹⁰⁴ each independently represent a hydrogen atom, a phenyl group or an N-acetyl-N-acetyloxyamino group.

*Indicates the bonding site. )

R ^102a represents an alkanoyl group having 2 to 4 carbon atoms, and X ^a represents a 3,6-carbazolyl group whose nitrogen atom is optionally substituted by an alkyl group having 1 to 4 carbon atoms. Z ^a represents phenyl optionally substituted with alkyl or naphthyl optionally substituted with morpholinyl. )

A commercial item can be used as an oxime initiator. Examples of commercially available products include OXE-01, OXE-02 (manufactured by BASF), TRONLYTR-PBG-304, TRONLYTR-PBG-309, TRONLYTR-PBG-305 (Changzhou Qiangli Electronic New Material Co., Ltd. (CHANGZHOU) TRONLY NEW ELECTRONIC MATERIALS CO., LTD) production).

As photopolymerization initiators, in addition: benzoin alkyl ethers, anthraquinone derivatives; 2-methyl-(4'-methylthiophenyl)-2-morpholinyl-1- Acetophenone derivatives such as acetone, thioxanthone derivatives such as 2-ethylthioxanthone and 2,4-diethylthioxanthone, benzoate derivatives, acridine derivatives, phen Oxazine derivatives, anthrone derivatives, etc. These initiators can also use commercially available items.

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

Among the above-mentioned photopolymerization initiators, α-aminoalkylphenone derivatives, thioxanthone derivatives, and oxime ester derivatives are more preferable. Particularly preferred are oxime ester derivatives.

Examples of (E2) polymerization accelerators used as needed include N,N-dialkylaminobenzoic acid alkyl esters such as N,N-dimethylaminobenzoic acid ethyl esters; Thiazole, 2-Mercaptobenzo Heterocyclic mercapto compounds such as azoles and 2-mercaptobenzimidazoles; mercapto compounds such as aliphatic polyfunctional mercapto compounds, etc.

The said (E1) photoinitiator and (E2) polymerization accelerator may be used individually by 1 type, respectively, and may use it in combination of 2 or more types.

In addition, in order to improve the sensitivity, (E3) sensitizing dye can be used as needed. As the sensitizing dye, an appropriate sensitizing dye can be adopted according to the wavelength of the image exposure light source, for example: xanthene dyes described in Japanese Patent Application Laid-Open No. 4-221958, Japanese Patent Laid-Open No. 4-219756, etc.; The coumarin pigments with heterocycles described in JP-P3-239703, JP-5-289335, etc.; JP-P3-239703, JP-5-289335, etc. 3-oxocoumarin-based pigments described in Japanese Patent Application Laid-Open No. 6-19240, etc., methylene pyrrole-based pigments described in Japanese Patent Application Publication No. 47-2528 and Japanese Patent Application Publication No. 54-155292 , Japanese Patent Publication No. 45-37377, Japanese Patent Application Publication No. 48-84183, Japanese Patent Application Publication No. 52-112681, Japanese Patent Application Publication No. 58-15503, Japanese Patent Application Publication No. 60-88005, JP-A-59-56403, JP-A-2-69, JP-A-57-168088, JP-A-5-107761, JP-A-5-210240, JP-A A dye having a dialkylaminobenzene skeleton described in Publication No. 4-288818 and the like.

(E3) The sensitizing dye may be used alone or in combination of two or more.

In the colored resin composition of the present invention, the content of the above-mentioned (E) photopolymerization initiating component is usually 0.1% by weight or more, preferably 0.2% by weight or more, and more preferably 0.5% by weight or more, based on the total solid content. , and usually 40% by weight or less, preferably 30% by weight or less, more preferably 20% by weight or less.

When it is within the above range, the sensitivity to exposure light is good, and the solubility of the unexposed part in the developing solution is good, and poor development and the like are less likely to occur, which is preferable.

[(E) Thermal polymerization initiating component]

Specific examples of the (E) thermal polymerization initiation component contained in the colored resin composition of the present invention include azo compounds, organic peroxides, hydrogen peroxide, and the like. Among these, azo compounds are preferably used. More specifically, thermal polymerization initiating components described in, for example, International Publication No. 2009/107734 and the like can be used.

The said thermal polymerization initiation component may be used individually by 1 type, and may use it in combination of 2 or more types.

[other optional ingredients]

In addition to the above-mentioned components, the colored resin composition of the present invention may further contain: a surfactant, at least one of an organic carboxylic acid and an organic carboxylic acid anhydride, a thermosetting compound, a plasticizer, a thermal polymerization inhibitor, and a storage stabilizer. , surface protection agent, adhesion improver, development improver, etc. Various compounds described in JP 2007-113000 A, for example, can be used as the above-mentioned arbitrary components. Moreover, when containing the (F) pigment mentioned later, you may contain a dispersing agent and a dispersing aid further.

[(F) pigment]

In order to improve the heat resistance of the obtained color filter, etc., the colored resin composition of this invention may contain (F) pigment within the range which does not impair the effect of this invention.

As (F) pigment, when forming the pixel of a color filter etc., the pigment of various colors, such as blue and purple, can be used, for example. In addition, as the chemical structure thereof, for example, phthalocyanines, quinacridones, benzimidazolones, bismuth Organic pigments such as azines, indanthrene, perylenes, etc. In addition, various inorganic pigments and the like can also be used. Hereinafter, specific examples of pigments that can be used are shown by pigment index numbers.

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

Among these, a blue copper phthalocyanine pigment is preferable, and examples of the copper phthalocyanine pigment include C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, etc., and more preferable For C.I. Pigment Blue 15:6.

Therefore, when the colored resin composition of the present invention contains a blue pigment, it is preferable that C.I. Pigment Blue 15:6 is 80% by weight or more, particularly preferably 90% by weight or more, particularly preferably 95 to 100% by weight.

Examples of purple pigments include: C.I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50, etc.

Of these, the purple two oxazine pigments, as the two As an oxazine pigment, CI Pigment Violet 19, 23 etc. are mentioned preferably, CI Pigment Violet 23 is more preferable.

Therefore, when the colored resin composition of the present invention contains a purple pigment, the C.I. Pigment Violet 23 is preferably 80% by weight or more, particularly preferably 90% by weight or more, particularly preferably 95 to 100% by weight, based on the total content of the purple pigment. %.

These may be used individually by 1 type, and may mix and use 2 or more types by arbitrary combinations and ratios.

The pigment (F) used in the colored resin composition of the present invention preferably has a small average primary particle diameter from the viewpoint of being able to form a high-contrast pixel. Specifically, the average primary particle diameter is preferably 40 nm or less, more preferably 35 nm or less. .

In particular, for blue copper phthalocyanine pigments, the average primary particle diameter is also preferably 40 nm or less, more preferably 35 nm or less, and still more preferably 20 to 30 nm.

Additionally, for two For the oxazine pigment, the average primary particle diameter is preferably 40 nm or less, more preferably 25 to 35 nm. It is preferable that the average primary particle diameter is not too small from the viewpoint that the pigment is not easily aggregated in the colored resin composition.

In addition, here, the average primary particle diameter of (F) pigment is the value measured and calculated by the following method.

First, the (F) pigment was ultrasonically dispersed in chloroform, dropped onto a mesh bonded with a collodion film, dried, and observed with a transmission electron microscope (TEM) to obtain an image of the primary particle of the pigment. From this image, the particle diameter of each pigment particle is converted into the diameter of a circle with the same area as the area-equivalent circle diameter, and the particle diameter is obtained for a plurality of (usually about 200 to 300) pigment particles.

Using the obtained value of the primary particle diameter, the number average value was calculated according to the following calculation formula, and the average particle diameter was obtained.

The particle size of each pigment particle: X ₁ , X ₂ , X ₃ , X ₄ ,...,X _i ,...X _m (m is the number of particles)

[mathematical formula 1]

{Compounding amount}

In the present invention, when the pigment (F) is contained, the content of the pigment in the colored resin composition is usually 80% by weight or less, preferably 50% by weight or less, in the total solid content.

Moreover, content with respect to 100 weight part of said (A) dyes is 2000 weight part or less normally, Preferably it is 1000 weight part or less.

By being within the above range, the dye (I) does not have a large influence on the transmittance, and the heat resistance of the obtained pixel tends to become better, which is preferable.

[Dispersant]

When the colored resin composition of the present invention contains the (F) pigment, it is preferable to further contain a dispersant.

The type of the dispersant of the present invention is not limited as long as it can disperse and stabilize the pigment.

Dispersants such as cationic, anionic, nonionic, or amphoteric can be used, but polymeric dispersants are preferred. Specific examples thereof include block copolymers, polyurethanes, polyesters, alkylammonium salts or phosphate ester salts of polymer copolymers, cationic comb graft polymers, and the like. Among these dispersants, block copolymers, polyurethanes, and cationic comb graft polymers are preferable. Block copolymers are particularly preferable, and among them, block copolymers composed of a solvophilic A block and a B block having a functional group containing a nitrogen atom are preferable.

Specifically, as the B block having a functional group containing a nitrogen atom, a unit structure having a side chain having at least one of a quaternary ammonium base and an amino group can be cited; on the other hand, as a solvophilic A block , A unit structure that does not have a quaternary ammonium salt group or an amino group can be mentioned.

The B block constituting the acrylic block copolymer has a unit structure including at least one of a quaternary ammonium salt group and an amino group, and is a site having a pigment adsorption function.

In addition, when the B block has a quaternary ammonium group, the quaternary ammonium 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, the copolymer described in Unexamined-Japanese-Patent No. 2009-025813 is mentioned, for example.

Moreover, the colored resin composition of this invention may contain the dispersing agent other than the above. Examples of other dispersants include those described in JP-A-2006-343648.

When the colored resin composition of the present invention contains the (F) pigment, the content of the dispersant used in the total solid content is preferably 2 to 1000% by weight, particularly preferably 5 to 500% by weight, of the total content of the (F) pigment. % by weight, especially preferably in the range of 10 to 250% by weight.

When it is within the above-mentioned range, the heat resistance of the dye (I) is not affected, good pigment dispersibility can be ensured, and better pigment dispersion stability can be obtained, so it is preferable.

[Dispersion Auxiliary]

The colored resin composition of the present invention may further contain a dispersion aid. The dispersing aid herein may be a pigment derivative, and as a pigment derivative, for example, JP-A-2001-220520, JP-A-2001-271004, JP-A-2002-179976, JP-A Various compounds described in KOKAI Publication No. 2007-113000 and JP-A No. 2007-186681 and the like.

The content of the dispersing aid in the colored resin composition of the present invention is usually at least 0.1% by weight, and usually at most 30% by weight, preferably at most 20% by weight, based on the total solid content of the pigment. , more preferably 10% by weight or less, still more preferably 5% by weight or less. By controlling the addition amount within the above-mentioned range, the effect as a dispersion aid can be exhibited, and further favorable dispersibility and dispersion stability can be obtained, which is preferable.

[Dispersion resin]

The colored resin composition of the present invention may contain part or all of resins selected from the aforementioned (C) binder resin or other binder resins as the dispersion resin described below.

Specifically, in [Method for producing colored resin composition] described later, by including (C) binder resin together with the above-mentioned dispersant and other components, the (C) binder resin and the dispersed The synergistic effect of the additive is beneficial to the dispersion stability of (F) pigment. This makes it possible to reduce the amount of dispersant added, which is preferable. In addition, it is preferable to improve the developability and improve the adhesiveness between the pixel and the substrate without leaving undissolved matter in the non-pixel portion of the substrate.

In this way, the (C) binder resin used in the dispersion treatment step is also referred to as a dispersion resin. The amount of the dispersion resin used is preferably about 0 to 200% by weight, more preferably about 10 to 100% by weight, based on the total amount of pigment in the colored resin composition.

[Manufacturing method of colored resin composition]

In the present invention, the colored resin composition can be prepared by an appropriate method, for example, by mixing (A) dye and (C) binder resin containing compound (I) with (B) solvent and optionally any The ingredients are mixed together to prepare.

In addition, as the preparation method in the case of including the (F) pigment, the following method is exemplified: in the presence of a dispersant and, if necessary, a dispersing aid added in a solvent containing the (F) pigment, in some cases (C) A part of the binder resin is mixed and dispersed while pulverizing using, for example, a paint shaker, a sand mill, a ball mill, a roller mill, a stone mill, a jet mill, a homogenizer, etc., thereby A pigment dispersion liquid is prepared, and (A) dye containing compound (I), (C) binder resin, (D) polymerizable monomer, (E) photopolymerization initiator and At least one of thermal polymerization initiators and the like are mixed to prepare a colored resin composition.

[Application of Colored Resin Composition]

The colored resin composition of the present invention is usually in a state where all constituent components are dissolved or dispersed in a solvent. Such a colored resin composition is supplied onto a substrate to form components such as color filters, liquid crystal display devices, and organic EL display devices.

Hereinafter, as an application example of the colored resin composition of the present invention, its application as a pixel of a color filter, and a liquid crystal display device (panel) and an organic EL display device using them will be described.

＜Color filter＞

The color filter of the present invention has pixels formed from the colored resin composition of the present invention.

The method for forming the color filter of the present invention will be described below.

The pixels of the color filter can be formed by various methods. Here, a case where a photopolymerizable colored resin composition is used and a pixel is formed by photolithography will be described as an example, but the production method is not limited to this method.

First, on the surface of the substrate, a black matrix is formed as necessary to define a portion where pixels are to be formed, and the colored resin composition of the present invention is coated on the substrate, and then prebaked to evaporate the solvent, thereby Form a coating film. Next, the coating film is exposed through a mask, and then developed using an alkaline developer to dissolve and remove the unexposed portion of the coating film, and then perform post-baking to form each pixel pattern of red, green, and blue. Can be made into color filters.

In the present invention, a pixel formed using the colored resin composition of the present invention is particularly preferably a blue pixel.

The substrate used for forming pixels is not particularly limited as long as it is transparent and has appropriate strength, and examples thereof include polyester resins, polyolefin resins, polycarbonate resins, acrylic resins, thermoplastic Resin sheets, epoxy resins, thermosetting resins, various glasses, etc.

In addition, these substrates may be subjected to appropriate pretreatments such as thin film formation treatment with a silane coupling agent, polyurethane resin, etc., corona discharge treatment, ozone treatment, and other surface treatments as necessary.

When coating the colored resin composition on the substrate, spin coating, wire bar (Wire bar) method, flow coating method, slit spin coating method (Slit and Spin Coating) method, die coating method, roll coating method are mentioned. , spraying method, etc. Among them, the slit spin coating method and the die coating method are preferable.

The thickness of the coating film is usually 0.2 to 20 μm, preferably 0.5 to 10 μm, particularly preferably 0.8 to 5.0 μm, as the film thickness after drying.

When it exists in the said range, it becomes easy to perform gap adjustment in a pattern development and a liquid crystal cell formation process, and it becomes easy to express a desired color, and it is preferable.

As the radiation used for exposure, for example, visible light, ultraviolet rays, extreme ultraviolet rays, electron beams, X-rays, etc. can be used, and radiation having a wavelength in the range of 190 to 450 nm is preferable.

There are no particular limitations on the light source used for image exposure to obtain radiation with a wavelength of 190 to 450 nm, and examples thereof include xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, and medium-pressure mercury lamps. , Low-pressure mercury lamp, carbon arc, fluorescent lamp and other light sources; Argon ion laser, YAG laser, excimer laser, nitrogen laser, helium-cadmium laser, semiconductor laser and other laser light sources. When irradiating with light of a specific wavelength, an optical filter can also be used.

The amount of radiation exposure is preferably 10 to 10000 J/m ² .

In addition, as the above-mentioned alkaline developing solution, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, Sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide and other inorganic alkaline compounds; monoethanolamine, diethanolamine, triethanolamine, monomethylamine, dimethylamine Amine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, n-butylamine, monoisopropanolamine, diisopropanolamine , triisopropanolamine, ethyleneimine, ethylenediimine (ethylenediimine), tetramethylammonium hydroxide (TMAH), choline and other organic basic compounds.

It is also possible to add an appropriate amount of water-soluble organic solvents such as isopropanol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol, and surfactants to the above-mentioned alkaline developer. . In addition, washing with water is usually performed after alkali image development.

As the development treatment method, any of dip development, spray development, brush development, ultrasonic development, and the like can be employed. The image development conditions are preferably at room temperature (23° C.) for 5 to 300 seconds.

The conditions of the developing treatment are not particularly limited, and the developing temperature is usually 10°C or higher, preferably 15°C or higher, more preferably 20°C or higher, and usually 50°C or lower, preferably 45°C or lower, more preferably 40°C or lower. scope.

As the image development method, any method of dip image development, spray image development, brush image development, ultrasonic image image development, etc. can be used.

When the color filter thus produced is used in a liquid crystal display device, transparent electrodes such as ITO can be directly formed on the image in the state after manufacture, and it can be used as a part of components such as a color display and a liquid crystal display device, but in order to improve Surface smoothness and durability, and surface coatings such as polyamide and polyimide can also be provided on the image as needed. In addition, in applications such as a partial planar alignment type driving method (IPS mode), transparent electrodes may not be formed either. In addition, in the vertical alignment driving method (MVA mode), ribs may also be formed. In addition, column structures (photosensitive spacers) are sometimes formed by photolithography instead of bead-dispersed spacers.

＜Liquid crystal display device＞

The liquid crystal display device of the present invention is a liquid crystal display device using the above-mentioned color filter of the present invention. The type and structure of the liquid crystal display device of the present invention are not particularly limited, and the color filter of the present invention can be used to assemble by conventional methods.

For example, the method described in "Liquid Crystal Device Handbook" (Nikkan Kogyo Shimbun (Nikkan Kogyo Shimbunsha), published on September 29, 1989, by the 142nd Committee of the Japan Society for the Promotion of Science) can be used to form the liquid crystal display device of the present invention .

＜Organic EL display device＞

When producing the organic EL display device comprising the color filter of the present invention, the following method can be adopted: For example, as shown in FIG. A blue color filter, and an organic light-emitting body 500 is laminated on the blue color filter with an organic protective layer 30 and an inorganic oxide film 40 interposed therebetween, thereby producing a multi-color organic EL element.

As a lamination method of the organic luminescent body 500, a method of sequentially forming a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 on the upper surface of a color filter can be mentioned. ; a method of attaching the organic luminescent body 500 formed on another substrate to the inorganic oxide film 40 ; and the like. The organic EL element 100 produced in this way can be applied to an organic EL display device of a passive drive type, and can also be applied to an organic EL display device of an active drive type.

Example

Next, the present invention will be described more specifically with reference to synthesis examples, examples, and comparative examples, but the present invention is not limited to the following examples within the scope not exceeding the gist of the present invention.

＜Synthesis of Dye＞

(Synthesis Example 1: Synthesis of Dye A)

[chemical formula 17]

(Synthesis of compound 2)

1-Aminonaphthalene (14.3 g) was dissolved in 1-propanol (300 ml), a methanol (20 ml) solution of 1,3-propane sultone (12.2 g) was added, and the mixture was heated to reflux for 2 hours. The generated precipitate was filtered off and washed with 1-propanol to obtain compound 2 (12.3 g).

(Synthesis of Dye A)

Sodium borohydride (1.0 g) was added to a mixture of compound 1 (synthesized according to the method described in JP-A-2011-70171) (8.05 g) and 2-propanol (100 ml), and heated to reflux for 18.5 hours. Sodium borohydride (1.0 g) was added, and it heated and refluxed for 1.5 hours further. Concentration under reduced pressure was carried out, tetrahydrofuran (50 ml) was added, and the mixture was heated under reflux for 2 hours. It was concentrated under reduced pressure, 1N aqueous sodium hydroxide solution was added, extracted with toluene, washed with saturated brine, and dried over anhydrous sodium sulfate to obtain an oily substance.

Compound 2 (3.71 g) and 2N hydrochloric acid (40 ml) were added to the obtained oily substance (total amount), followed by heating under reflux for 2 hours. After adding an aqueous solution of sodium hydroxide to make it alkaline, a tar-like insoluble product was formed. After removing the supernatant by decantation, it was concentrated under reduced pressure, water was added and stirred, water was removed by decantation, and the obtained solid was dried.

Methanol (100 ml) and chloranil (3.44 g) were added to the obtained solid (total amount), and it stirred at 50 degreeC for 2 hours. After concentration under reduced pressure, chloroform and water were added, and the chloroform layer was separated and purified by silica gel chromatography (elution solvent: chloroform to chloroform/methanol=10/1) to obtain dye A (1.30 g).

Compound Identification: Mass Spectrometry

Ionization mode: LDI

Posi m/z＝586[M+H] ⁺

Neg m/z＝585[M] ^-

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

(Synthesis Example 2: Synthesis of Dye B)

(Synthesis of Compound 11)

[chemical formula 18]

1,7-Clevivic acid (2.23 g, manufactured by Tokyo Chemical Industry), 1,1,1-trifluoro-4-iodobutane (2.98 g, manufactured by Tokyo Chemical Industry), potassium carbonate (2.76 g, manufactured by Wako Junyaku Kogyo) and N-methylpyrrolidone (22 mL) were mixed, and stirred at 80° C. for 10 hours under a nitrogen atmosphere. The reaction solution was cooled to room temperature, mixed with water (150 mL), adjusted to pH=5.3 with concentrated hydrochloric acid, and extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, the desiccant was filtered off, and the solvent was distilled off. The obtained crystals were suspended and washed with diisopropyl ether, separated from the solvent by filtration under reduced pressure, and the residual solvent was removed from the obtained solid at 50° C. under reduced pressure to obtain Compound 11 (2.79 g) as a white solid.

The results of liquid chromatography-mass spectrometry analysis of this compound are shown below.

LCMS (ESI, posi) m/z 334 (M+H ⁺ , C ₁₄ H ₁₅ F ₃ NO ₃ S)

(Synthesis of Dye B)

[chemical formula 19]

Compound 1 (8.46 g) was dissolved in THF (68 mL), lithium borohydride (3 mol/L, THF solution, 9.2 mL) was added, and 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, 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 filtered off, and the solvent was distilled off to obtain an oily substance (7.96 g).

The oily substance (2.04 g) obtained by 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 filtered off, and dried at 50° C. under reduced pressure to obtain a light blue solid (3.16 g). 2.5 g of them were purified by silica gel chromatography (elution solvent: chloroform/methanol=93/7 to 78/22) to obtain a light blue solid (1.66 g). The results of liquid chromatography-mass spectrometry analysis of this compound are shown below.

LCMS (ESI, posi) m/z 656 (M+H ⁺ , C ₃₆ H ₄₅ F ₃ N ₃ O ₃ S)

The light blue solid (1.64 g) obtained by the above reaction, chloro-p-benzoquinone (0.61 g) and methanol (33 mL) were mixed and stirred at room temperature for 4 hours and at 45° C. for 8 hours. After cooling the reaction liquid to room temperature, the solvent was distilled off. This crude product was purified by silica gel chromatography (elution solvent: chloroform/methanol=95/5 to 82/18) to obtain dye B (0.82 g) as a dark blue solid.

The maximum absorption wavelength (λmax) of the compound in 10 ppm propylene glycol monomethyl ether acetate (PGMEA)/propylene glycol monomethyl ether (PGME)=35/65 solution is 633 nm, and the gram absorption coefficient is 126. The results of liquid chromatography-mass spectrometry analysis of this 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)

[chemical formula 20]

1,6-Clevivic acid (3.35 g, manufactured by Tokyo Chemical Industry), 1,1,1-trifluoro-4-iodobutane (3.57 g, manufactured by Tokyo Chemical Industry), potassium carbonate (2.07 g, manufactured by Wako Junyaku Kogyo) and N-methylpyrrolidone (27 mL) were mixed and stirred at 80° C. for 8 hours under a nitrogen atmosphere. Then, 1,1,1-trifluoro-4-iodobutane (0.71 g) was added, and it heated at 80 degreeC for 2 hours.

The reaction liquid was cooled to room temperature, mixed with water (150 ml), adjusted to pH=4 with concentrated hydrochloric acid, and extracted with ethyl acetate. Use a rotary evaporator to distill off the solvent in the extraction layer, suspend and wash the precipitated crystals with diisopropyl ether, separate from the solvent by filtration under reduced pressure, and then remove the residual solvent from the obtained solid at 50°C under reduced pressure , Compound 12 (2.43 g) was obtained as a white solid.

The results of liquid chromatography-mass spectrometry analysis of this 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)

[chemical formula 21]

Compound 1 (2.71 g) was dissolved in THF (22 mL), lithium borohydride (3 mol/L, THF solution, 2.9 mL) was added, and 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, 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 filtered off, and the solvent was distilled off to obtain an oily substance (2.74 g).

The oil (2.38 g) obtained by the above reaction and compound 12 (2.31 g) were dissolved in acetic acid (19 mL), stirred at room temperature for 1 hour, and then 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 filtered off, and dried at 50° C. under reduced pressure to obtain a light blue solid (3.77 g). The results of liquid chromatography-mass spectrometry analysis of this compound are shown below.

LCMS (ESI, posi) m/z 656 (M+H ⁺ , C ₃₆ H ₄₅ F ₃ N ₃ O ₃ S)

The light blue solid (1.44 g) obtained by the above reaction, chloro-p-benzoquinone (0.54 g) and methanol (29 mL) were mixed and stirred at room temperature for 4 hours and at 55°C for 4.5 hours. Then, tetrachloro-p-benzoquinone (0.27 g) was added, and it heated further for 10.75 hours. After cooling the reaction solution to room temperature, the reaction solution was filtered to remove insoluble matter, and the solvent was distilled off. This crude product was purified by silica gel chromatography (elution solvent: chloroform/methanol = 95/5 to 85/15) to obtain Dye C (0.31 g) as a dark blue solid.

The maximum absorption wavelength (λmax) of the compound in 10 ppm propylene glycol monomethyl ether acetate (PGMEA)/propylene glycol monomethyl ether (PGME)=35/65 solution is 639 nm, and the gram absorption coefficient is 111. The results of liquid chromatography-mass spectrometry analysis of this 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)

[chemical formula 22]

1,8-Clevic acid (3.35 g, manufactured by Tokyo Chemical Industry), 1,1,1-trifluoro-4-iodobutane (3.57 g, manufactured by Tokyo Chemical Industry), potassium carbonate (2.07 g, manufactured by Wako Junyaku Kogyo) and N-methylpyrrolidone (27 mL) were mixed and stirred at 80° C. for 7.5 hours under a nitrogen atmosphere. Then, 1,1,1-trifluoro-4-iodobutane (0.89 g) was added, and it heated further for 3.75 hours. After cooling the reaction solution to room temperature, it was mixed with water (150 mL), adjusted to pH = 1.3 with concentrated hydrochloric acid, and the precipitated solid was filtered and dried at 50°C under reduced pressure to obtain compound 13 (4.23 g) as a white solid .

The results of liquid chromatography-mass spectrometry analysis of this 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)

[chemical formula 23]

Compound 1 (1.69 g) was dissolved in THF (14 mL), lithium borohydride (3 mol/L, THF solution, 1.8 mL) was added, and 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, 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 filtered off, and the solvent was distilled off to obtain an oily substance (1.76 g).

The oil (1.57 g) obtained by the above reaction and Compound 13 (1.53 g) were dissolved in acetic acid (23 mL), stirred at room temperature for 1.5 hours, and left overnight. The next day, the reaction solution 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 resulting solid was filtered off and dried at 50°C under reduced pressure to obtain a light blue solid (2.5 g).

This crude product (2.5 g) was combined with a crude product (0.8 g) synthesized by the same synthesis method, and purified by silica gel chromatography (elution solvent: chloroform/methanol=98/2 to 90/10) to obtain Light blue solid (1.89g). The results of liquid chromatography-mass spectrometry analysis of this compound are shown below.

LCMS (ESI, posi) m/z 656 (M+H ⁺ , C ₃₆ H ₄₅ F ₃ N ₃ O ₃ S)

The light blue solid (1.89 g) obtained by the above reaction, chloro-p-benzoquinone (0.71 g) and methanol (30 mL) were mixed and stirred at 45° C. for 4 hours. After cooling the reaction liquid to room temperature, the insoluble matter was filtered off, and the solvent was distilled off. This crude product was purified by silica gel chromatography (elution solvent: chloroform/methanol = 98/2 to 92/8) to obtain dye D (0.75 g) as a dark blue solid.

The maximum absorption wavelength (λmax) of the compound in 10 ppm propylene glycol monomethyl ether acetate (PGMEA)/propylene glycol monomethyl ether (PGME)=35/65 solution is 648 nm, and the gram absorption coefficient is 104. The results of liquid chromatography-mass spectrometry analysis of this 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)

[chemical formula 24]

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

[chemical formula 25]

A mixture of Compound 1 (1.47g, 4.34mmol, synthesized according to the method described in International Publication No. 2009/107734), Compound 23 (1.1g, 4.34mmol), toluene (30ml), and phosphorus oxychloride (0.6ml) was heated to reflux After 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 chromatography (elution solvent: chloroform/methanol=15/1 to 10/1). The obtained solid was washed with alkane to obtain compound 25 (1.32 g, yield 50%).

[chemical formula 26]

A mixture of Compound 25 (8.9 g, 14.6 mmol), Compound 26 (4.2 g, 14.6 mmol, purchased from Tokyo Chemical Industry), methanol (50 ml) was stirred at 50° C. for 1.5 hours, concentrated under reduced pressure, and the obtained solid Washing with methanol/water = 1/2 gave comparative dye 1 (11.5 g, yield 92.3%).

(Refer to Synthesis Example 2: Comparative Dye 2)

[chemical formula 27]

A mixture of Compound 25 (1.95 g), C.I. Acid Blue 80 (manufactured by Aldrich: 1.36 g), and methanol (25 mL) was stirred at 50° C. for 30 minutes, then concentrated under reduced pressure, and the obtained solid was diluted with water/methanol= Washing with a mixed solvent of 2/1 gave Comparative Dye 2 (2.22 g).

＜Synthesis of resin＞

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

It stirred while nitrogen-substituting 145 parts by weight of propylene glycol monomethyl ether acetate, and heated up to 120 degreeC. 10 parts by weight of styrene, 85.2 parts by weight of glycidyl methacrylate, 66 parts by weight of monoacrylate FA-513M (manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton, and 2,2 The mixed solution of 8.47 parts by weight of '-azobis-2-methylbutyronitrile was further stirred at 90° C. for 2 hours. Next, the inside of the reaction container was replaced with air, 0.7 parts by weight of tris(dimethylaminomethyl)phenol and 0.12 parts by weight of hydroquinone were added to 43.2 parts by weight of acrylic acid, and the reaction was continued at 100° C. for 12 hours. Then, 56.2 parts by weight of tetrahydrophthalic anhydride (THPA) and 0.7 parts by weight of triethylamine were added, and reacted at 100° C. for 3.5 hours. The weight average molecular weight Mw of the above-obtained resin solution measured by GPC was about 8400, and the acid value was 80 mg-KOH/g. Propylene glycol monomethyl ether acetate was added to this resin solution so that the solid content would be 44% by weight, and it was used as resin A.

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

It stirred while nitrogen-substituting 145 parts by weight of propylene glycol monomethyl ether acetate, and heated up to 120 degreeC. 5.2 parts by weight of styrene, 132 parts by weight of glycidyl methacrylate, 4.4 parts by weight of monoacrylate FA-513M (manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton, and 2,2 The mixed solution of 8.47 parts by weight of '-azobis-2-methylbutyronitrile was further stirred at 90° C. for 2 hours. Next, the inside of the reaction container was replaced with air, 1.1 parts by weight of tris(dimethylaminomethyl)phenol and 0.19 parts by weight of hydroquinone were added to 67.0 parts by weight of acrylic acid, and the reaction was continued at 100° C. for 12 hours. Then, 15.2 parts by weight of tetrahydrophthalic anhydride (THPA) and 0.2 parts by weight of triethylamine were added, and reacted at 100° C. for 3.5 hours. The resin solution obtained above had a polystyrene-equivalent weight average molecular weight Mw of about 9000 and an acid value of 25 mg-KOH/g measured by GPC. Propylene glycol monomethyl ether acetate was added to this resin solution so that the solid content would be 40% by weight, and it was used as 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, triphenylphosphine 5 parts by weight and 264 parts by weight of propylene glycol monomethyl ether acetate were stirred at 95° C. until the acid value became 3 mg-KOH/g or less. It took 9 hours for the acid value to reach the target value (acid value 2.2 mg-KOH/g). Next, 151 parts by weight of tetrahydrophthalic anhydride was further added and reacted at 95° C. for 4 hours to obtain an acid value of 102 mg-KOH/g and a polystyrene-equivalent weight average molecular weight (Mw) measured by GPC. For 3900 resin solution. Propylene glycol monomethyl ether acetate was added to this resin solution so that the solid content would be 44% by weight, and it was used as 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 the reference synthesis examples 1 and 2, the resin A obtained in the reference synthesis example 3, and other components were mixed to make These were the composition described in following Table 1, and the colored resin composition was prepared.

The numerical values in Table 1 all represent parts by weight of each component added.

When mixing, stir for more than 1 hour until the components are fully mixed, and finally filter with a 5 µm cover plate filter (Komata 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 the reference synthesis examples 1 and 2, the resins B and C obtained in the reference synthesis examples 4 and 5, and other The components were mixed so that they had the composition described in Table 1 below, and a colored resin composition was prepared.

The numerical values in Table 2 all represent parts by weight of each component added.

When mixing, the mixture was stirred for at least 1 hour until the components were fully mixed, and finally filtered through a 5 μm cover plate filter to remove foreign matter.

Each compound in Table 1 is shown below, respectively.

PBG-305: TRONLYTR-PBG-305 Manufactured by Changzhou Qiangli New Electronic Materials Co., Ltd.

DPHA: dipentaerythritol hexaacrylate

PGMEA: Propylene Glycol Monomethyl Ether Acetate

PGME: Propylene Glycol Monomethyl Ether

F475 Manufactured by DIC Corporation: Perfluoroalkyl-containing oligomers

Irganox 1010 Manufactured by BASF Corporation: Pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate]

JPP-100 manufactured by Johoku Chemical Industry Co., Ltd.: Tetraphenyldipropylene glycol diphosphite [Table 2]

In addition, each compound in Table 2 is as follows, respectively.

DPHA: dipentaerythritol hexaacrylate

PET-P: Pentaerythritol tetrakis (3-mercaptopropionate)

IRGACURE 907: 2-Methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-1-propanone

EABF: 4,4'-bis(diethylamino)benzophenone

Compound X: 3-(2-Acetoxyimino-1,5-dioxo-5-methoxypentyl)-9-ethyl-6-(o-toluoyl)-9H-carbazole

F475 Manufactured by DIC Corporation: Perfluoroalkyl-containing oligomers

Irganox 1010 Manufactured by BASF Corporation: Pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate]

JPP-100 made by Johoku 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 Films Produced from Colored Resin Compositions (Examples 1 to 4, and Comparative Examples 1 and 2)

The colored resin composition prepared in the above table 1 was coated on a glass substrate cut into 5 cm squares by a spin coating method so that the sy value after drying was 0.120. minute pre-bake. Then, the entire surface was exposed at an exposure amount of 60 mJ/cm ² , then fired in a dust-free oven at 200° C. for 30 minutes, and the spectral transmittance was measured using a spectrophotometer U-3310 (manufactured by Hitachi, Ltd.). Calculate its chromaticity (C light source) in the XYZ color system.

The results are summarized in Table 3.

[table 3]

Colored resin composition sx sy brightness Example 1 A-1 0.139 0.120 17.0 Example 2 B-1 0.138 0.120 16.9 Example 3 C-1 0.139 0.120 16.5 Example 4 D-1 0.141 0.120 16.5 Comparative example 1 Compare 1 0.138 0.120 17.0 Comparative example 2 Compare 2 0.139 0.120 16.4

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

Use a spin coater at a set speed (300rpm to 700rpm) to coat a glass substrate (EHC evaluation glass ITO solid (beta) MN-1392) on which an ITO (indium-doped tin oxide alloy) electrode is deposited on the entire surface. Cloth the colored resin composition so that the thickness of the coating film is 2 to 3 μm (the film thickness after heat curing is about 2 μm), and the colored resin composition includes the dyes of the examples and the comparative examples and is prepared in the above ratio and composition , pre-baked on a hot plate at 80°C for 3 minutes, and then dried in a vacuum chamber for 1 minute.

Then, using a high-pressure mercury lamp, a photomask is implemented on the periphery as an electrode, and the coating film is exposed to 30 mW of radiation of each wavelength including 303 nm, 313 nm, 334 nm, 365 nm, 405 nm and 436 nm with an exposure amount of 62 mJ/cm ² , and then Post-curing was performed at °C for 60 minutes (hereinafter also referred to as "curing temperature") to cure the coating film to obtain a blue pixel substrate for liquid crystal evaluation (hereinafter also referred to as "resist film").

After washing with water and warm water at 45°C, the substrate on which the blue pixels were formed and the electrode substrate on which only the ITO electrode was vapor-deposited into a predetermined shape (EHC evaluation glass SZ-B11MIN(B)MN11396) were cleaned, and then heated at 105°C After drying in an oven, bonding with a sealant mixed with 5 μm glass beads (with a gap of 5 μm), annealing in an oven at 180° C. for 2 hours, and injecting liquid crystal MLC-7021-000 (manufactured by Merck) into the resulting cell ), a liquid crystal cell with an electrode area of 1 cm ² was fabricated.

Next, the voltage holding ratio of the liquid crystal cell was measured at 25° C. using a liquid crystal physical property evaluation system Model 6254 (manufactured by TOYO Corporation). The applied voltage at this time was a square wave of 5.0 V, and the measurement frequencies were 60 Hz, 2 Hz, and 0.6 Hz. The voltage retention mentioned here is generally known to have two expression methods of area ratio and voltage ratio. In this application, the value of area ratio (the voltage trace from 0 milliseconds to 16.7 milliseconds (60Hz example) and the voltage zero level The enclosed area is obtained by holding a voltage of 0 milliseconds for an observation time of 16.7 milliseconds (in the case of 60 Hz), an observation time of 0.5 seconds (in the case of 2 Hz), or 1.67 seconds (in the case of 0.6 Hz) area ratio).

The ion density was measured using the same device as the voltage holding ratio. A triangular wave with a frequency of 0.1 Hz and ±10 V is applied, and the waveform in which the hourly change of the current is calculated is output. The direct peak of the liquid crystal in the waveform was measured in advance with the above-mentioned cell of only the liquid crystal, and then, the measurement was performed for the liquid crystal cell of each example. FIG. 2 shows the liquid crystal direct peaks and impurity ion peaks appearing in the ion waveform and how to obtain the impurity ion density.

For the voltage retention rate, it is preferably 85% or more at 60 Hz, preferably 25% or more at 2 Hz, more preferably 30% or more, further preferably 60% or more, and particularly preferably 80% or more. The ideal voltage retention rate is more than 90 percent.

In addition, the voltage retention rate below 2 Hz is a characteristic that is extremely sensitive to ionic impurities. The voltage retention rate below 2 Hz should be considered in combination with ionic intervention and ion density measurement results (ion density, liquid crystal direct peak current/impurity ion peak current), voltage retention rate at 60 Hz, and liquid crystal performance observation. range.

In addition, the voltage holding ratio at 0.6 Hz is more significantly affected by ionic impurities. This is because, in the case of 0.6 Hz, the more fully the impurity ions on the surface of the resist film move in the liquid crystal, the longer the time for measuring the voltage change is.

The influence of ionic impurities originating in the resist film can be known by measuring the ion density. That is, when a voltage is applied to the positive ion side and the negative ion side, it means that the higher the ion density on either side, the more ionic impurities are contained in the liquid crystal, and the more the liquid crystal cell is hindered from applying voltage to the liquid crystal cell and hindering the liquid crystal cell. The voltage maintenance factor. That is, the smaller the ion density, the better the electrical characteristics. In addition, in the case of only liquid crystals, the ion density is 0 nC.

The liquid crystal evaluation results are summarized in Table 4 (colored resin composition of Table 1) and Table 5 (colored composition of Table 2).

It should be noted that in the table, the voltage retention rate "cannot be quantified due to current leakage" means that the voltage drops to It is lower than 2V, therefore, the voltage when the liquid crystal cell is working is not applied to the liquid crystal cell, and the electrical characteristics are obviously lower.

In addition, the ion density being "not measurable due to current leakage" means that in a cell whose voltage holding rate is "unmeasurable due to current leakage", the electrical characteristics are remarkably low, and thus the ion density cannot be accurately measured.

"The ion density is too high to be measured" means that the liquid crystal does not respond due to current leakage, so the direct peak of the liquid crystal is not reflected in the ion density, and because the generated current is too large, the ion peak is covered and cannot be discerned, Exceeding the ion density measurement limit of the device indicates low electrical characteristics.

As shown in Table 3, the pixels formed using the colored resin composition of the present invention had high brightness and were good blue pixels. In addition, as shown in Table 4 and Table 5, the voltage retention rate of the liquid crystal cell formed by the blue pixel substrate (resist film) using the colored resin composition of the present invention is also high, the ion density is small, and it has good performance. electrical characteristics. In particular, a temperature of 200° C. is slightly low as the curing temperature of the resin composition, and ionic components are eluted in the liquid crystal or at the interface between the liquid crystal and the resist film, which tends to be unfavorable for evaluation characteristics of the liquid crystal. Even at a slightly lower curing temperature of 200° C., the ion density of the liquid crystal cell formed from the resist film containing the compound of the example was low, and the elution of ionic impurities tended to be suppressed compared with the comparative example. As a result, the voltage retention rate is high and favorable. In particular, for the colored resin compositions (Examples 6, 8, 10, and 14) containing the dye B compound, the ion density was lower than 1 nC at the highest, and the voltage retention at 0.2 Hz exceeded 85%. That is, it can be seen that the electrical characteristics are good and the voltage retention rate is also high.

As described above, a color filter having pixels formed using the colored resin composition of the present invention, and a liquid crystal display device and an organic EL display device including the color filter are of high quality.

Although the present invention has been described in detail with reference to specific embodiments, it will be understood by those skilled in the art that various changes and corrections can be made without departing from the spirit and scope of the present invention. This application is based on the JP Patent application (Japanese Patent Application No. 2012-077457) of an application on March 29, 2012, The content is taken in here as a reference.

Industrial Applicability

According to the present invention, it is possible to provide a novel triarylmethane compound from which a pixel achieving both luminance and voltage retention can be obtained. Furthermore, according to the present invention, it is possible to provide a novel colored resin composition from which a pixel having high luminance and high voltage retention can be obtained. In addition, the present invention can provide a color filter including pixels having high luminance and a high voltage retention rate, and a high-quality liquid crystal display device and an organic EL display device. Therefore, the present invention is useful in application to color filters, liquid crystal display devices, organic EL display devices, and the like.

Claims (21)

1. Triarylmethane compounds 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 optionally having a fluorine substituent, or an aromatic ring group having 5 to 18 carbon atoms, R ⁷ and R ⁸ each independently represent a hydrogen atom, a halogen atom or an alkyl group with 1 to 10 carbon atoms, Wherein, at least one of ^R7 and ^R8 is a halogen atom or an alkyl group with 1 to 10 carbon atoms, M ⁺ means a cation, n represents an integer from 0 to 4, The substitution position of the -SO ₃ ^- group outside [] is a hydrogen atom on a naphthalene ring forming a triarylmethane skeleton or a hydrogen atom of a substituent on R ⁶ . 2. The triarylmethane compound according to claim 1, wherein, in the 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. 3. The triarylmethane compound according to claim 2, wherein, in the formula (I), R ⁷ is a hydrogen atom, and R ⁸ is a halogen atom or an alkyl group having 1 to 4 carbon atoms. 4. The triarylmethane compound according to claim 2, wherein, in the above-mentioned formula (I), R ⁷ is a hydrogen atom, and R ⁸ is a methyl group. The triarylmethane compound according to claim 1 or 2, wherein, in the above formula (I), R ¹ to R ⁴ are alkyl groups having 1 to 8 carbon atoms optionally having a fluorine substituent. The triarylmethane compound according to claim 1 or 2, wherein, in the formula (I), R ¹ to R ⁴ are C 1 to C 4 alkyl groups optionally having a fluorine substituent. 7. The triarylmethane compound according to claim 1 or 2, wherein, in the formula (I), R ¹ to R ⁴ are ethyl groups. 8. The triarylmethane compound according to claim 1 or 2, wherein, in the above-mentioned formula (I), the substitution position of the -SO ₃ ^- group outside [] is on the naphthalene ring forming the triarylmethane skeleton A hydrogen atom. 9. The triarylmethane compound according to claim 1 or 2, 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 have the same definitions as in the above formula (I), R ¹¹ and R ¹² each independently represent a hydrogen atom, a fluorine atom or an alkyl group with 1 to 8 carbon atoms, m represents the integer of 1-8. 10. The triarylmethane compound according to claim 9, wherein, in the formula (II), R ⁷ is a hydrogen atom, and R ⁸ is a halogen atom or an alkyl group having 1 to 4 carbon atoms. 11. The triarylmethane compound according to claim 9, wherein, in the above-mentioned formula (II), R ⁷ is a hydrogen atom, and R ⁸ is a methyl group. 12 . The triarylmethane compound according to claim 9 , wherein, in the formula (II), R ¹ to R ⁴ are an alkyl group having 1 to 8 carbon atoms optionally having a fluorine substituent. 13. The triarylmethane compound according to claim 9, wherein, in the formula (II), R ¹ to R ⁴ are an alkyl group having 1 to 4 carbon atoms optionally having a fluorine substituent. 14. The triarylmethane compound according to claim 9, wherein, in the above formula (II), R ¹ to R ⁴ are ethyl groups. 15 . The triarylmethane compound according to claim 9 , wherein, in the formula (II), m is an integer of 2 to 5. 16 . 16. A colored resin composition comprising (A) a dye, (B) a solvent, and (C) a binder resin, wherein, (A) The dye is the triarylmethane compound according to any one of claims 1 to 15. 17. The colored resin composition according to claim 16, further comprising (D) a polymerizable monomer. 18. The colored resin composition according to claim 16 or 17, further comprising at least one of (E) a photopolymerization initiating component and a thermal polymerization initiating component. The color filter which has the pixel formed using the colored resin composition in any one of Claims 16-18. 20. A liquid crystal display device comprising the color filter according to claim 19. 21. An organic EL display device comprising the color filter according to claim 19.