JP6957909B2 - Compounds and color filters - Google Patents

Description

The present invention relates to, for example, a compound capable of obtaining excellent contrast when used as a colorant for a color filter, and a color filter containing the compound.

A color filter such as a liquid crystal display device has a red pixel portion (R), a green pixel portion (G), and a blue pixel portion (B). Each of these pixel portions has a structure in which a thin film of synthetic resin in which an organic pigment is dispersed is provided on a substrate, and as the organic pigment, organic pigments of each color of red, green and blue are used.

Of these pixel portions, as the blue organic pigment for forming the blue pixel portion, an ε-type copper phthalocyanine pigment (CI pigment blue 15: 6) is generally used, and toning is required. Therefore, a small amount of dioxazine violet pigment (CI pigment violet 23), which is a purple organic pigment, is used in combination with this.

Organic pigments used in producing color filters are required to have characteristics completely different from those of conventional general-purpose applications. Specifically, there are demands such as making the display screen of a liquid crystal display device or the like brighter (higher brightness) and making it visible more clearly (higher contrast). As one of the means for meeting such a demand, a coloring material other than the ε-type copper phthalocyanine pigment is being studied.

For example, C.I. I. Recently, it has been studied to use a triarylmethane pigment such as Pigment Blue 1 for the blue pixel portion of a color filter (Patent Document 1 and the like).

This C.I. I. As Pigment Blue 1, BASF's fanal color (FANAL BLUE D6340, D6390) having the following chemical structure is prominent, and C.I. I. Pigment Blue 1 is obtained by raked Victoria Pure Blue BO, which is a basic triarylmethane dye, with a heteropolyacid such as phosphomolybdic acid or phosphotungsten molybdic acid. The C.I. I. Pigment Blue 1 is said to have a cation counterion A ^{− which} is a kegin-type PMo _x W _12-x O ₄₀ .

[However, in the general formula (IX), A ^n-is a Keggin type phosphotungstic molybdic acid anion or phosphomolybdate anion. n represents an arbitrary natural number. ]
Further, in recent years, it has been studied to use a triarylmethane dye for the blue pixel portion of a color filter instead of the above-mentioned triarylmethane pigment (Patent Document 2). As anions, these triarylmethane dyes include halide anions, boron anions such as tetraphenylboron, organic carboxylic acid anions, inorganic sulfate anions, inorganic phosphate anions, aliphatic sulfonic acid anions, and aromatic sulfonic acid anions. It is said that sulfonatoanions corresponding to anthraquinone dyes, phthalocyanine dyes, and indigo dyes can be used.
However, when these conventional triarylmethane pigments and triarylmethane dyes are used to prepare the blue pixel portion of the color filter, the pixels may be affected by the light beam for a long time or the thermal history during the production of the color filter. The hue was significantly reduced, and the light resistance and heat resistance were insufficient.
Further, as a dye, it is also being studied to use a dye composed of a salt having the following chemical structure for the blue pixel portion of a color filter (Patent Document 3).

However, when the compound of Patent Document 3 is used for preparing the blue pixel portion of the color filter, the actual situation is that the contrast is insufficient.

Japanese Unexamined Patent Publication No. 2001-81348 Japanese Unexamined Patent Publication No. 2011-68866 Japanese Unexamined Patent Publication No. 2015-28121

An object to be solved by the present invention is to provide a color material capable of obtaining excellent contrast even when subjected to a thermal history of 200 degrees or more required in a manufacturing process at the time of producing a color filter. For example, it is an object of the present invention to provide a compound capable of providing an excellent liquid crystal display capable of displaying an excellent liquid crystal display having high contrast when used for preparing a blue pixel portion of a color filter, and a color filter containing the compound. ..

As a result of diligent studies in view of the above-mentioned actual conditions, the present inventors have found that excellent contrast can be obtained at the time of producing a color filter by using a compound having a structure described later as a coloring material for a color filter, and the present invention has been made. Has been completed.

That is, the present invention provides a compound represented by the following general formula (I) (hereinafter, may be referred to as a compound of the present invention).

(In the general formula (I), B represents an aromatic group which may have a substituent or a heterocyclic group which may have a substituent, n represents an arbitrary natural number, and [A] ^{n. -} represents any anion of n ^valence, in R ^1, R 2, ^{R 3} and ^{R 4} each independently represent a hydrogen atom, an alkyl group or a phenyl group having 1 to 8 carbon atoms).

Further, a compound characterized in that B in the general formula (I) has the following general formula (II) is provided.

(In general formula (II), X represents an oxygen atom, a nitrogen atom or a sulfur atom, R ⁵ represents a phenyl group which may be substituted with a halogen atom, and R ⁶ and R ⁷ are independent hydrogen atoms. , Or an alkyl group having 1 to 8 carbon atoms, or a phenyl group which may be substituted with a halogen atom or an alkyl group having 1 to 8 carbon atoms. * Represents a bond with a carbon atom.)

Further, a compound characterized in that B in the general formula (I) has the following general formula (III) is provided.

(In the general formula (III), R ⁸ and R ⁹ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group. * Represents a bond with a carbon atom.)

^{Provided are compounds in which [A] n−} (anion) in the general formulas (I) to (III) is a polyoxometallate.
Formula (I) ~ (III) in ^{[A] n-} (anion) _provides the ^{_{[P 2 MoW 17 O 62]}} 6- , compound.

A color filter containing at least one selected from the above compounds is provided.

Since the compound of the present invention is a compound represented by the above general formula (I), it exhibits a particularly remarkable technical effect that excellent contrast can be obtained particularly when it is used for preparing a color filter. In addition, the compound of the present invention exhibits a reddish blue color as compared with the triarylmethane compounds known so far, and the expressible color gamut can be expanded.

The x and y chromaticity diagrams are shown. The larger the value of the chromaticity x, the stronger the redness, and the larger the value of the chromaticity y, the stronger the greenness.

The compound of the present invention is a compound represented by the above general formula (I).

As described above, the compound of the general formula (I) of the present invention comprises a triarylmethane cation moiety and an anion.

^{[A] n−} of the general formula (I) is an anion having an arbitrary n-valent value, and details will be described later.
^{The alkyl group having 1 to 8 carbon atoms in R 1} , R ² , R ³ and R ⁴ of the general formula (I) may be linear or branched, and specific examples thereof include methyl, ethyl and normal. Examples include propyl, isopropyl, normal butyl, isobutyl, secondary butyl, tertiary butyl, normal pentyl, isopentyl, neopentyl, tertiary pentyl, normal hexyl, isohexyl, normal heptyl, normal octyl and the like.
The aromatic group or heterocyclic group in B of the general formula (I) is not particularly limited.

Aromatic groups include condensed polycyclic aromatic hydrocarbons such as benzene ring, naphthalene ring, tetraline ring, inden ring, fluorene ring, anthracene ring, and phenanthrene ring; biphenyl, terphenyl, diphenylmethane, and triphenylmethane. Examples thereof include chain polycyclic hydrocarbons such as stilben. The chain polycyclic hydrocarbon may have heteroatoms such as O and S in the chain skeleton such as diphenyl ether and the like. On the other hand, the heterocycles in the heterocyclic group include 5-membered heterocycles such as furan, thiophene, pyrrole, oxazole, thiazole, imidazole and pyrazole; and 6-membered heterocycles such as pyran, pyrone, pyridine, pyridazine, pyrimidine and pyrazine; benzofuran. , Thionaphten, indol, carbazole, coumarin, benzo-pyrone, quinoline, isoquinoline, aclysine, phthalazine, quinazoline, quinoxalin and the like. These aromatic groups and heterocyclic groups may have a substituent. Examples of the substituent include those described in the section [Substituent Group P] described later.

[Substituent group P]
Substituent groups P include methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, cyclopentyl group, hexyl group and cyclohexyl group. , Heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group and other alkyl groups; phenyl group, naphthyl group, thienyl group, furyl group, thiazolyl group and other aryl groups; fluorine atom, chlorine atom, bromine atom, Halogen atoms such as iodine atoms; cyano groups; hydroxyl groups; alkoxy groups with 1 to 8 carbon atoms such as methoxy groups, ethoxy groups, propoxy groups and butoxy groups; haloalkyl groups such as chloromethyl groups and trifluoromethyl groups; amino groups, Examples thereof include an amino group which may have a substituent such as a diethylamino group, a dibutylamino group and an acetylamino group; an acyl group such as an acetyl group and a benzoyl group; an acyloxy group such as an acetyloxy group and a benzoyloxy group; and the like.

Among them, the group represented by the general formula (II) or the general formula (III) is preferable as the aromatic group or the heterocyclic group in B from the viewpoint of exhibiting a more reddish blue color.

Examples of the halogen as a substituent in the general formula (II) include atoms of fluorine, chlorine, bromine and iodine.
^{The alkyl group having 1 to 8 carbon atoms in R 6} and R ⁷ of the general formula (II) may be linear or branched, and specific examples thereof include methyl, ethyl, normal propyl, isopropyl and normal butyl. , Isobutyl, secondary butyl, tertiary butyl, normal pentyl, isopentyl, neopentyl, tertiary pentyl, normal hexyl, isohexyl, normal heptyl, normal octyl and the like.

In the general formula (III), ^{the alkyl group having 1 to 8 carbon atoms in R 8} and R ⁹ may be linear or branched, and specific examples thereof include methyl, ethyl, normal propyl, isopropyl and normal. Examples include butyl, isobutyl, secondary butyl, tertiary butyl, normal pentyl, isopentyl, neopentyl, tertiary pentyl, normal hexyl, isohexyl, normal heptyl, normal octyl.

The group represented by the general formula (II) is preferably a group represented by the following formula. Note that * represents a bond with a carbon atom.

Such a method for producing the compound of the present invention is not particularly limited, and can be produced by appropriately using a conventionally known method. Hereinafter, one aspect of the method for producing the compound of the present invention will be described. However, the present invention is not limited thereto.

The compound of the present invention may have a compound containing a thiazole ring substituted with a dialkylamine (hereinafter, may be referred to as compound T) and an aromatic group or a substituent which may have a substituent. It can be produced by reacting a compound having a heterocycle (hereinafter, may be referred to as compound U).

Compound T is a compound containing a thiazole ring substituted with a dialkylamine, and a compound represented by the formula (t-II) is exemplified. In order to obtain the compound of the present invention, it is necessary to link two compounds containing the thiazole ring, but a compound in which two thiazole ring compounds are linked in advance may be used, or the compound of the present invention is reacted. It may be linked at the time (during the reaction with compound U). The formula (t-I) is exemplified as a compound in which two thiazole rings are linked in advance. When a compound in which two thiazole ring compounds are linked in advance is used, the compound T must have a reaction site with compound U, and from the viewpoint of the reactivity of compound U, the linking site of the two thiazole rings It is preferable that the compound has a ketone group.

^R 1 to R ⁴ in the formula (t-I) and Formula (t-II) is as previously described.

Compound U is a compound having an aromatic group which may have at least a substituent or a heterocycle which may have a substituent. When reacting with the compound T represented by the formula (t-I), the reaction site with the compound T may be a hydrogen group or Y (linking group) described later. Specific examples thereof include the formula (v-I), the formula (w-I), and the formula (w-II). Further, when reacting with the compound T represented by the formula (t-II), a site capable of reacting with the compound T is required, and it is preferable to have an aldehyde group. Specific examples thereof include the formula (v-II) and the formula (w-III).

In the case of producing a compound in which B in the formula (I) is the formula (II), which is one form of the compound of the present invention, the compound U has X (described later) and N substituted with dialkylamine. A member ring compound is used. Specifically, the compound represented by the formula (v-I) is exemplified. A compound of formula (II) can be obtained by reacting a combination of formula (t-I) and formula (v-I). Further, as another form, a compound represented by the formula (v-II) is exemplified. A compound of formula (II) can be obtained by reacting a combination of formula (t-II) and formula (v-II).

In formulas (v-I) and (v-II), X represents an oxygen atom, a nitrogen atom or a sulfur atom, and R ⁵ , R ⁶ and R ⁷ are as described above.

When producing a compound in which B in the formula (I) is the formula (III), which is another form of the compound of the present invention, a naphthyl compound substituted with a dialkylamine is used as the compound U. Specifically, the compound represented by the formula (w-I) or the formula (w-II) is exemplified. Compound (III) can be obtained by reacting the formula (t-I) with the formula (w-I) or the formula (w-II) in combination. Further, as another form, a compound represented by the formula (w-III) is exemplified. The formula (III) can be obtained by reacting the formula (t-II) and the formula (w-III) in combination.

In formulas (w-I), formula (w-II) and formula (w-III), R ⁸ and R ⁹ are as described above, and Y is a chlorine atom, a bromine atom or an iodine atom.

The amount of compound T used is preferably 0.5 mol or more and 8 mol or less, and more preferably 1 mol or more and 3 mol or less, based on 1.0 mol of compound U.

The reaction temperature is preferably −100 ° C. to 180 ° C., more preferably −78 ° C. to 130 ° C. The reaction time is preferably 1 hour to 48 hours, more preferably 4 hours to 24 hours.

The reaction of compound T and compound U may be carried out without a solvent, but it is preferably carried out in an organic solvent from the viewpoint of yield. Examples of the organic solvent include hydrocarbon solvents such as toluene, xylene and hexane; ether solvents such as tetrahydrofuran and 1,4-dioxane; halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene and chloroform; methanol, ethanol, isopropanol and butanol and the like. Alcohol solvent; etc. The amount of the organic solvent used is 1 part by mass of the compound represented by the formula (v-I), the formula (v-II), the formula (w-I), the formula (w-II) or the formula (w-III). On the other hand, it is preferably 1 part by mass or more and 20 parts by mass or less, and more preferably 2 parts by mass or more and 10 parts by mass or less.

The reaction of compound T and compound U may be carried out in the presence of a condensing agent or a lithiolytic agent, or may be carried out without adding anything. From the viewpoint of yield, it is preferable to carry out in the presence of Grignard method, lithiolytic agent or condensing agent. More preferably, it is carried out in the presence of a lithiolytic agent.

Examples of the lithiating agent include n-butyllithium, sec-butyllithium, tert-butyllithium and the like.

Examples of the condensing agent include phosphoric acid, polyphosphoric acid, phosphorus oxychloride, sulfuric acid, thionyl chloride and the like.

The amount of the lithiating agent used is preferably 0.5 parts by mass or more and 5 parts by mass or less, and more preferably 1 part by mass or more and 3 parts by mass or less with respect to 1.0 mol of the compound U.

The amount of the condensing agent used is preferably 0.1 part by mass or more and 20 parts by mass or less, and more preferably 0.2 parts by mass or more and 5 parts by mass or less with respect to 1.0 mol of the compound U.

Next, a method for producing the compound T and the compound U, which are raw materials for producing the compound of the present invention, will be described.

Examples of the method for producing the formula (t-I) include various known methods, for example, the methods described in Tetrahedron, Vol58, p2137.

As a method for producing the formula (v-I), the formula (v-II) or the formula (t-II), various known methods can be mentioned. For example, the method described in US Pat. No. 5,101,035 can be mentioned.

As the compound represented by the formula (w-II), a commercially available product can be used.

Examples of the method for producing the formula (v-II) include various known methods. For example, the method described in Tetrahedron Letters, Vol47, p3889 can be mentioned.

As the production method of the formula (w-III), various known methods are adopted, and examples thereof include the methods described in Tetrahedron Letters, Vol48, p1955.

Next, the anion portion will be described in detail. The anion is not particularly limited, and examples thereof include various known polyoxometallate anions and sulfonyl anions. Examples of the sulfonyl anion include sulfonyl anions of formula IV or formula V. A particularly preferable anion from the viewpoint of heat resistance is a polyoxometallate anion.

In the present invention, the heteropolyacid anion is referred to as a heteropolyoxometallate anion.

Heteropolyacids are inorganic acids with a relatively large molecular weight that do not contain an organic structure, and can exhibit unique properties not found in low-molecular-weight inorganic acids such as hydrochloric acid and sulfuric acid and organic acids. The first is to produce a water-insoluble triarylmethane compound by rake with a heteropolyacid of a cation. Second, there is room for improving the heat resistance and light resistance of the obtained triarylmethane compound by selecting the heteropolyacid used for rake formation. Heteropolyacids do not contain organic structures or can contain metals and have a relatively large molecular weight. Therefore, by selecting them appropriately, they are derived from anionic structures even when exposed to high temperatures or light. It is possible to greatly suppress the alteration of the triarylmethane compound.

In the present invention, when it is desired to obtain a triarylmethane compound having higher heat resistance, for example, the anion [A] ⁿ⁻ contains W (tungsten) and O (oxygen) as essential elements, and P (phosphorus) and Si. It is preferable to use a heteropolyoxometallate anion containing at least one of (silicon). Examples are Kegin-type phosphotungstate ion α- (PW ₁₂ O ₄₀ ) ^3- , Dawson-type phosphotungstate ion α- (P ₂ W ₁₈ O ₆₂ ) ^6- , β- (P ₂ W ₁₈ O _62). ) ^6- , Kegin-type silicotungstate ion α- (SiW ₁₂ O ₄₀ ) ^4- , β- (SiW ₁₂ O ₄₀ ) ^4- , γ- (SiW ₁₂ O ₄₀ ) ^4- , and as another example (P) ₂ W ₁₇ O ₆₁ ) ^10- , (P ₂ W ₁₅ O ₅₆ ) ^12- , (H ₂ P ₂ W ₁₂ O ₄₈ ) ^12- , (NaP ₅ W ₃₀ O ₁₁₀ ) ^14- , α- (SiW ₉ O) ₃₄ ) ^10- , γ- (SiW ₁₀ O ₃₆ ) ^8- , α- (SiW ₁₁ O ₃₉ ) ^8- , β- (SiW ₁₁ O ₃₉ ) ^{8- and the} like can be mentioned.

In the present invention, triarylmethane compounds having a higher heat resistance, for example, anionic ^{[A] _n-is} represented by ^{_{6- (P 2 Mo y W 18}} -y O 62), y = 0,1, is an integer of 2 or 3 heteropolyoxometalate anion _{or, (SiMo z W 12-z} O 40) is represented by ^4, heteropolyoxometalate anion or an integer of z = 0, 1, 2 or 3, It is a triarylmethane compound of at least one anion selected from deficient Dawson-type phosphotungstate heteropolyoxometalate anions.

Note that the defective Dawson type phosphotungstic acid heteropolyoxometalate anion _is a ^{_{10- (P 2 W 17 O 61}} ).

Examples of the heteropolyacid or its alkali metal salt include H ₆ (P ₂ Mo _y W _18-y O ₆₂ ), Na ₆ (P ₂ Mo _y W _18-y O ₆₂ ), and H ₄ (SiMo _Z W _{12-). Z O 40), Na 4 (} SiMo Z W 12-Z O 40), H 10 (P 2 W 17 O 61) and _{Na 10 (P 2 W 17 O} 61) or the like can be used.

Heteropolyacids such _{H 6 (P 2 Mo y W} 18-y O 62) , for example, Inorganic Chemistry, vol47, according to the method described in P3679, it can be obtained easily. Specifically, it can be obtained by dissolving an alkali metal tungate and an alkali metal molybdicate in water, adding phosphoric acid to the alkali metal salt, and heating and refluxing the mixture for 5 to 10 hours with heating and stirring.
Heteropolyacids thus obtained, is reacted with an alkali metal chloride, in the same manner as described above, _Na 6 is a Dawson type hetero polyoxometalate alkali metal salt and _{(P 2 Mo y W 18-} y O 62) Can be done.

By changing the charged molar ratio of molybdenum (Mo) and tungsten (W), that is, by adjusting the molar ratio of the alkali metal tunganoic acid salt and the alkali metal molybdenum salt, the number y of molybdenum in the heteropolyoxometallate anion can be increased. It can be prepared in the range of 0 to 3.

Alternatively, molybdenum alkali metal salts are dissolved in water, to which hydrochloric acid was added, followed, K _{10 ([alpha]} 2 type P _{2 W} 17 _{O 61),} such as, [alpha] 2 type defect Dawson type phosphotungstic acid alkali It can be obtained by adding a metal salt and stirring at 10 to 30 ° C. for 30 minutes to 2 hours. The heteropolyacid thus obtained can be reacted with an alkali metal chloride to obtain a Dawson-type heteropolyoxometallate alkali metal salt in the same manner as described above.

For example, _{by preparing α2 type P 2} W ₁₇ O _{61 from P 2} W ₁₈ O ₆₂ by a hydrolysis reaction and reacting it with Mo, _{only P 2 Mo W 17} O ₆₂ can be obtained. By doing so, the above-mentioned heteropolyacid and its alkali metal salt having no distribution in the numerical value of y can be obtained.

H _{4 (SiMoW} 11 _{O 40)} such heteropolyacids, hetero polyoxometallate alkali metal salt, for example, Journal of American Chemical Society, 104 ( 1982), according to the method described in P3194, it can be obtained easily. Specifically, it stirred and mixed nitrate solution and molybdenum alkali metal salt solution, to which _{K 8} (alpha type _SiW 11 _{O 39)} was added, can be obtained by stirring for 2 to 6 hours. The heteropolyacid thus obtained can be reacted with an alkali metal chloride to obtain a kegin-type heteropolyoxometalate alkali metal salt in the same manner as described above.

Heteropolyacids such as H ₆ (P ₂ W ₁₈ O ₆₂ ) and H ₁₀ (P ₂ W ₁₇ O ₆₁ ) can be readily obtained according to, for example, the methods described in Inorganic Chemistry, vol47, p3679. Specifically, it can be obtained by dissolving an alkali metal tungstic acid salt in water, adding hydrochloric acid and phosphoric acid to the salt, and heating and refluxing the mixture for 10 to 50 hours with heating and stirring.
The heteropolyacid can be made into a Dawson-type heteropolyoxometallate alkali metal salt by reacting with an alkali metal chloride.

The defective Dawson-type heteropolyoxometalate alkali metal salt can be easily obtained by using the former Dawson-type phosphotungstate heteropolyoxometalate alkali metal salt as a raw material, for example, according to the method described in Organic Synthesis, vol27, p104. You can. Specifically, it can be obtained by dissolving a Dawson-type phosphotungstate heteropolyoxometallate alkali metal salt in water, adding an alkali metal hydride to the alkali metal salt, and stirring the mixture while heating as necessary. ..

The mixing temperature of the formula (II) or the formula (III) and the anion [A] ^{n- with} the alkali metal salt is preferably 0 ° C. to 150 ° C., more preferably 10 ° C. to 120 ° C., still more preferably 20 ° C. to 100. ℃. The mixing time is preferably 1 hour to 72 hours, more preferably 2 hours to 24 hours, still more preferably 3 hours to 12 hours.

The compound of the present invention can be easily produced, for example, by reacting the chloride of the corresponding cation part described above with the corresponding heteropolyacid or heteropolyoxometallate alkali metal salt described above. When the above-mentioned chloride of the corresponding cation part is used and a heteropolyacid is used, a dechlorination reaction is performed, and the above-mentioned chloride of the corresponding cation part is used and a heteropolyoxometallate alkali metal salt is used. When used, it can be produced by salt substitution by a dealkali metal chloride reaction.

Compared with the hydrogen dechloride reaction using the heteropolyacid, it is possible to more reliably perform salt substitution and obtain a higher yield by first converting the heteropolyacid into a heteropolyoxometallate alkali metal salt and then performing the dealkali metal chloride reaction. Not only is the triarylmethane compound of the present invention obtained at a high price, but also the triarylmethane compound of the present invention having a higher purity with less by-products can be obtained, which is preferable. Of course, the heteropolyoxometallate alkali metal salt can also be used after being purified by recrystallization or the like.

When it is difficult to obtain a precipitate from the reaction solution, the corresponding heteropolyoxometallate alkali metal salt can be obtained in a higher yield by lowering the solubility by cooling the reaction solution or the like.

Since the compound of the present invention includes a step of rake (water insolubilization) with heteropolyacid (or because it is raked (water insolubilized) with heteropolyacid), when water is used in some step during or after production. In order to carry out a more reliable reaction and prevent the rake structure of the obtained compound from being destroyed, for example, the content of metal ions or halogen ions such as purified water, ion-exchanged water, pure water, etc. It is preferable to use as little water as possible.

The compound of the present invention is a water-insoluble coloring material. The compound of the present invention thus obtained can be used as it is as a colorant for synthetic resins and the like, but if necessary, it can be used for various purposes by adjusting the particle size by known and commonly used pulverization and granulation. It can be the most suitable colorant. As the colorant, when the average particle size of the primary particles is 100 nm or less in the dry powder, a clearer blue colorant can be easily obtained, which is preferable.

In the present invention, the average particle size of the primary particles is measured as follows. First, the particles in the field of view are photographed with a transmission electron microscope or a scanning electron microscope. Then, the maximum length (maximum length) of the inner diameter of each particle is obtained for each of the 50 primary particles constituting the aggregate on the two-dimensional image. The average value of the maximum lengths of individual particles is taken as the average particle size of the primary particles.

The compound of the present invention can be used for various known and commonly used applications, and when used for manufacturing a color filter pixel portion, it is possible to obtain a color filter of a liquid crystal display device capable of displaying an excellent image with high contrast. ..

In the color filter of the present invention, the backlight light source includes a conventional cold cathode tube (CCFL light source), a white LED (LED; Light Emitting Diode) light source, a three-color independent LED light source, and a white organic EL (EL; Electro Luminescence). Any light source or the like can be used.

The compounds of the present invention include, if necessary, epsilon-type phthalocyanine pigments, dioxazine pigments (CI Pigment Violet 23, CI Pigment Violet 37, CI Pigment Blue 80, etc.), and xanthene dyes (C). I. Basic Violet 10 etc.), Triarylmethane dyes (CI Acid Blue 1, CI Acid Blue 90, CI Acid Blue 83 etc.), Phthalocyanine dyes (CI Direct) Blue 86, etc.), sulfonic acid derivatives of metal-free or metallic phthalocyanines, N- (dialkylamino) methyl derivatives of metal-free or metal phthalocyanines, N- (dialkylaminoalkyl) sulfonic acid amide derivatives of metal-free or metal phthalocyanines, Dioxazine violet sulfonic acid derivative, indanslen blue sulfonic acid derivative, organic pigment derivative such as phthalocyanine sulfonic acid, etc., and Big Chemie's Disparbic 130, Disparbic 161, Disparbic 162, Disparbic 163, Disperbic 170. , Disperbic 171 Big 2096, Disperbic 2150, Disperbic LPN21116, Disperbic LPN6919, Lubrizol Solspurce 3000, Solsperse 9000, Solsperse 13240, Solsperse 13650, Solsperse 13940, Solsperse 17000, Solsperse 18000, Solsperse 20000, Solsperse 21000, Solsperse 21000. 26000, Solspurs 27000, Solsperse 28000, Solsperse 32000, Solsperse 36000, Solsperse 37000, Solsperse 38000, Solsperse 41000, Solsperse 42000, Solsperse 43000, Solsperse 46000, Solsperse 54000, Solsperse 71000, Ajinomoto Co., Ltd. , Ajispar PB814, Ajisper PN411, Ajis Dispersants such as par PA111, natural rosins such as acrylic resin, urethane resin, alkyd resin, wood rosin, gum rosin, and tall oil rosin, polymerized rosin, disproportionated rosin, hydrogenated rosin, oxide rosin, and maleated rosin. Such modified rosin, rosinamine, lime rosin, rosin alkylene oxide adduct, rosin alkyd adduct, rosin derivative such as rosin-modified phenol, and other rosin derivatives that are liquid and water-insoluble at room temperature can be contained. The addition of these dispersants and resins also contributes to the reduction of flocculation, the improvement of dispersion stability, and the improvement of the viscosity characteristics of the dispersion.

The compound of the present invention itself has a hue suitable for preparing a blue pixel portion of a color filter, but if necessary, an epsilon-type copper phthalocyanine pigment (CI pigment blue 15:) per 100 parts by mass conversion thereof. Hue can be optimized by using 0.1 to 30 parts in combination with 6).

The compound of the present invention itself has heat resistance and light resistance suitable for preparing a blue pixel portion of a color filter, but if necessary, per 100 parts of the compound of the present invention, an antioxidant non-volatile content of 0.1 to 1. 10 copies, especially 0.5 to 8 copies, can be used. Here, antioxidant is a general term for additives that prevent oxidative deterioration, and those that prevent oxidative deterioration due to heat (antioxidant in a narrow sense) and those that prevent oxidative deterioration due to light (mainly ultraviolet rays). (In a narrow sense, it is called a light stabilizer).

Such antioxidants have an action of capturing radicals and preventing autoxidation (radical chain prevention action) and an action of decomposing hydroperoxide (peroxide) into harmless substances (peroxide decomposition action). ), The former is called a primary antioxidant and the latter is called a secondary antioxidant. Also known are primary and secondary antioxidants that have both of these effects. As the primary antioxidant, for example, phenol-based (including hindered phenol-based) and amine-based (including hindered amine-based) antioxidants are used, and as the secondary antioxidant, for example, sulfur-based and phosphorus-based. Each of the antioxidants in is typical.

The compound of the present invention itself has heat resistance suitable for preparing the blue pixel portion of the color filter, but if necessary, the heat resistance and light resistance can be further improved by using a cationic resin in combination. Can be done.

As such a cationic resin, for example, it is preferable to use an acrylic resin, a polyurethane resin, an epoxy resin, a polyamide resin or the like because the hue change is small even under the thermal history and the heat resistance of the color filter can be greatly improved.

In the present invention, the ratio of the compound of the present invention to the cationic resin on a mass basis is not particularly limited, but the non-volatile content of the latter resin is 0.1 part or more and less than 10 parts per 100 parts of the former compound. Above all, it is preferably 0.5 to 5 parts, particularly 1 to 3 parts.

When preparing a coloring composition containing the compound of the present invention and a cationic resin, when the compound and the resin are heated, after mixing the two, no problem occurs in the compound itself in a closed system. It can be carried out in the range of 30 minutes to 5 hours under stirring at temperature. By forming the pressurized state in this way, as described above, the cationic resin permeates into the voids of the compound particles, which has a better effect than simply covering the particle surface alone. It is expressed.

The compound of the present invention can be used for forming a color filter pixel portion by a conventionally known method. A typical method for dispersing the compound of the present invention is a photolithography method, in which a photocurable composition described later is applied to a surface of a transparent substrate for a color filter on the side provided with a black matrix. After heat-drying (pre-baking), pattern exposure is performed by irradiating ultraviolet rays through a photo mask to cure the photocurable compound at the portion corresponding to the pixel portion, and then the unexposed portion is developed with a developing solution. This is a method of removing the non-pixel portion and fixing the pixel portion to the transparent substrate. In this method, a pixel portion made of a cured colored film of a photocurable composition is formed on a transparent substrate.

A photocurable composition described later is prepared for each of the red, green, and blue colors, and by repeating the above operation, a color filter having red, green, and blue colored pixel portions at predetermined positions is manufactured. be able to. A blue pixel portion can be formed from the compound of the present invention. In order to prepare the photocurable composition for forming the red pixel portion and the green pixel portion, known and commonly used red pigments and green pigments can be used.

Examples of the pigment for forming the red pixel portion include C.I. I. Pigment Red 177, 209, 242, 254 and the like can be used as pigments for forming the green pixel portion, for example, C.I. I. Pigment Green 7, 10, 36, 47, 58, 59, 62, 63 and the like. A yellow pigment can also be used in combination for forming the red pixel portion and the green pixel portion. Then, if necessary, the entire color filter can be heat-treated (post-baked) in order to thermoset the unreacted photocurable compound.

Examples of the method of applying the photocurable composition described later on a transparent substrate such as glass include a spin coating method, a roll coating method, an inkjet method and the like.

The drying conditions of the coating film of the photocurable composition applied to the transparent substrate vary depending on the type of each component, the mixing ratio, etc., but are usually about 1 to 15 minutes at 50 to 150 ° C. Further, as the light used for photocuring the photocurable composition, it is preferable to use light rays in a wavelength region of 200 to 500 nm. Various light sources that emit light in this wavelength range can be used.

Examples of the developing method include a liquid filling method, a dipping method, a spray method and the like. After the exposure and development of the photocurable composition, the transparent substrate on which the pixel portions of the required colors are formed is washed with water and dried. The color filter thus obtained is heat-treated (post-baked) at 90 to 280 ° C. for a predetermined time by a heating device such as a hot plate or an oven to remove volatile components in the colored coating film, and at the same time, light is applied. The unreacted photocurable compound remaining in the cured colored film of the curable composition is thermoset to complete the color filter.

The photocurable composition for forming the blue pixel portion of the color filter contains the compound of the present invention, a dispersant, a photocurable compound, and an organic solvent as essential components, and a thermoplastic resin is used as necessary. It can be prepared by mixing these. When the colored resin film forming the blue pixel portion is required to have toughness or the like that can withstand baking or the like performed in actual production of a color filter, a photocurable compound is used in preparing the photocurable composition. Not only that, it is indispensable to use this thermoplastic resin together. When a thermoplastic resin is used in combination, it is preferable to use a solvent that dissolves the organic solvent.

As a method for producing the photocurable composition, the compound of the present invention, an organic solvent and, if necessary, a dispersant are used, and these are mixed and dispersed by stirring so as to be uniform. A method of preparing a dispersion liquid for forming a pixel portion and then adding a photocurable compound, a thermoplastic resin, a photopolymerization initiator, etc., if necessary, to obtain the photocurable composition. It is common.

Here, as the dispersant and the organic solvent, the above-mentioned ones can be used.

Examples of the thermoplastic resin used for preparing the photocurable composition include urethane-based resin, acrylic-based resin, polyamide-based resin, polyimide-based resin, styrene-maleic acid-based resin, and styrene-maleic anhydride-based resin. ..

Examples of the photocurable compound include 1,6-hexanediol diacrylate, ethylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, bis (acryloxyethoxy) bisphenol A, and 3-methylpentanediol di. Bifunctional monomers such as acrylates, trimethylroll propaton triacrylates, pentaerythritol triacrylates, tris [2- (meth) acryloyloxyethyl) isocyanurates, dipentaerythritol hexaacrylates, dipentaerythritol pentaacrylates and the like. Examples thereof include polyfunctional monomers having a small molecular weight, and polyfunctional monomers having a relatively large molecular weight such as polyester acrylate, polyurethane acrylate, and polyether acrylate.

Examples of the photopolymerization initiator include acetophenone, benzophenone, benzyl dimethyl ketal, benzoyl peroxide, 2-chlorothioxanthone, 1,3-bis (4'-azidobenzal) -2-propane, and 1,3-bis (4'-). Azidobenzal) -2-propane-2'-sulfonic acid, 4,4'-diazidostilbene-2,2'-disulfonic acid and the like can be mentioned. Examples of commercially available photopolymerization initiators include "Irgacure (trade name) -184", "Irgacure (trade name) -369", "DaroCure (trade name) -1173" manufactured by Ciba Specialty Chemicals, and BASF. "Lucillin-TPO", "Kayacure (trade name) DETX" manufactured by Nippon Kayaku Co., Ltd., "Kayacure (trade name) OA", "BiCure 10", "BiCure 55" manufactured by Stoffer, "Trigonal PI" manufactured by Akzo , Sandley 1000, Upjon's "Dap", Kurogane Kasei's "Biimidazole", etc.

Further, a known and commonly used photosensitizer can be used in combination with the photopolymerization initiator. Examples of the photosensitizer include amines, ureas, compounds having a sulfur atom, compounds having a phosphorus atom, compounds having a chlorine atom, nitriles, and other compounds having a nitrogen atom. These can be used alone or in combination of two or more.

The blending ratio of the photopolymerization initiator is not particularly limited, but is preferably in the range of 0.1 to 30% with respect to the compound having a photopolymerizable or photocurable functional group on a mass basis. If it is 0.1% or more, it is possible to suppress a decrease in photosensitivity during photocuring. Further, if it is 30% or less, it is possible to prevent the crystals of the photopolymerization initiator from precipitating and deteriorating the physical characteristics of the coating film when the coating film of the resist is dried.

Using each of the above-mentioned materials, 300 to 1000 parts of the organic solvent and 1 to 100 parts of the dispersant are uniformly stirred and dispersed per 100 parts of the compound of the present invention on a mass basis. The dispersion can be obtained. Next, in this dispersion, the total amount of the thermoplastic resin and the photocurable compound was 0.1 to 5.0 parts per part of the compound of the present invention, and 0.05 to 3 parts of photopolymerization was started per part of the photocurable compound. An agent and, if necessary, an organic solvent are further added, and the mixture is stirred and dispersed so as to be uniform, and a photocurable composition for forming a color filter pixel portion can be obtained.

As the developing solution, a known and commonly used organic solvent or alkaline aqueous solution can be used. In particular, when the photocurable composition contains a thermoplastic resin or a photocurable compound, and at least one of them has an acid value and is alkali-soluble, washing with an alkaline aqueous solution is a color filter. It is effective in forming the pixel portion.

Among the methods for dispersing the compound of the present invention, the method for producing the color filter pixel portion by the photolithography method has been described in detail. A color filter may be manufactured by forming a blue pixel portion by a method such as a micelle electrolysis method, a PVED (Photolithography) method, an inkjet method, a reverse printing method, or a heat curing method.

The color filter uses a red pigment, a green pigment, and a photocurable composition of each color obtained by using the compound of the present invention as an organic pigment, and a liquid crystal material is sealed between a pair of parallel transparent electrodes to form a transparent electrode. Is divided into discontinuous fine sections, and each of the fine sections divided in a grid pattern by the black matrix on the transparent electrode is a color filter colored pixel portion selected from any one color of red, green, and blue. Can be obtained by alternately providing a pattern, or by forming a color filter colored pixel portion on a substrate and then providing a transparent electrode.

The compound of the present invention can provide a dispersion having excellent sharpness and brightness, and can be used for color filters, paints, plastics (resin molded products), printing inks, rubber, leather, printing, toners for static charge image development, inkjet recording. It can also be applied to coloring of ink for ink, thermal transfer ink, and the like.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to the scope of these Examples. Unless otherwise specified, "parts", "%" and "ppm" are all based on mass.

Synthesis Example 1 (Synthesis of Intermediate 1)
10.3 parts of trifluoroacetic acid (manufactured by Wako Pure Chemical Industries, Ltd.) was added to a round-bottom flask containing 150 parts of toluene (equipped with a magnetic stirrer and in a state where it can be stirred). To this, 13.0 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and then 35.0 parts of potassium thiocyanate (manufactured by Wako Pure Chemical Industries, Ltd.) was added.
The reaction solution was stirred under reflux for 2 hours. After cooling to room temperature, toluene was distilled off with an evaporator. The resulting solid was dissolved in dichloromethane and the organic layer was washed with saturated sodium hydrogen carbonate and then with saturated brine. Then, it was dried over sodium sulfate, filtered, and concentrated. The obtained solid was washed with hexane / dichloromethane = 3/2 to obtain Intermediate 1 (15.0 parts, yield 86%) having the following structure.

Synthesis Example 2 (Synthesis of Intermediate 2)
Intermediate 1 (14.9 parts) obtained in Synthesis Example 1 was added to a round-bottom flask containing 100 parts of ethanol (equipped with a magnetic stirrer and in a state where it can be stirred). To this, 15.3 parts of 2-bromoacetophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and then 11.2 parts of triethylamine (manufactured by Kanto Chemical Co., Inc.) was added.
The reaction solution was stirred at room temperature for 4 hours, and then half of the solvent was distilled off with an evaporator. The reaction solution was then washed with saturated sodium hydrogen carbonate and then with saturated saline. It was then dried over sodium sulfate. Then, it was filtered, concentrated, and purified by silica gel column chromatography (developing solvent: n-hexane / ethyl acetate) to obtain Intermediate 2 (22.7 parts, yield 100%) having the following structure.

Synthesis Example 3 (Synthesis of Intermediate 3)
2-Bromo-2-fluoroacetophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) 25.0 parts and 1- (manufactured by Tokyo Chemical Industry Co., Ltd.) in a round-bottom flask containing 120 parts of ethanol (equipped with a magnetic stirrer and in a state where it can be stirred) o-trill) Thiourea (manufactured by Tokyo Chemical Industry Co., Ltd.) 19.5 parts was added. To this, 17.8 parts of triethylamine (manufactured by Kanto Chemical Co., Inc.) was added dropwise.
The mixed solution was stirred at room temperature for 24 hours. After completion of the reaction, the mixture was filtered and the residue was washed with water to obtain Intermediate 3 (32.0 parts, yield 98%) having the following structure.

Synthesis Example 4 (Synthesis of Intermediate 4)
Intermediate 3 (13.2 parts) obtained in Synthesis Example 3 and carbonic acid in a round-bottom flask (equipped with a magnetic stirrer and in a state where it can be stirred) containing 100 parts of N, N-dimethylacetamide. 10.6 parts of potassium (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. To this, 25.5 parts of 1-bromoethane (manufactured by Tokyo Chemical Industry Co., Ltd.) was gradually added.
The reaction solution was refluxed for 16 hours. After cooling to room temperature, the mixed solution was poured into ice water and extracted with ethyl acetate. Next, the organic layer was dried with sodium sulfate, filtered, concentrated, and purified by silica gel column chromatography (developing solvent: heptane) to obtain intermediate 4 (10.0 parts, yield 71%) having the following structure. rice field.

Synthesis Example 5 (Synthesis of Intermediate 5)
89.9 parts of benzoyl isothiocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to a round-bottom flask containing 200 parts of 1,2-dichloroethane (equipped with a magnetic stirrer and in a state where it can be stirred). Then, 59.0 parts of diethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After completion of the reaction, the solvent was distilled off. Next, 84.8 parts of hydrazine monohydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the residue, and the mixture was stirred at room temperature for 6 hours.
The reaction solution was then poured into water and extracted with 1,2-dichloroethane. The organic layer is dried over sodium sulfate, filtered, concentrated, and purified by silica gel column chromatography (developing solvent: dichloromethane / methanol) to obtain Intermediate 5 (39.0 parts, yield 54%) having the following structure. rice field.

Synthesis Example 6 (Synthesis of Intermediate 6)
Intermediate 5 (39.0 parts) obtained in Synthesis Example 5 was added to a round bottom flask containing 150 parts of dichloromethane (equipped with a magnetic stirrer and in a state where it could be stirred). To this solution, 49.1 parts of 1,1-dimethoxy-N, N-dimethylmethaneamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise.
After reacting as it was for 2 hours, the solvent was distilled off to obtain Intermediate 6 (59.0 parts, yield 77%) having the following structure.

Synthesis Example 7 (Synthesis of Intermediate 7)
Synthesized with 15.4 parts of 1,3-dichloropropane-2-one (manufactured by Tokyo Chemical Industry Co., Ltd.) in a round-bottom flask containing 150 parts of acetonitrile (equipped with a magnetic stirrer and in a state where it can be stirred). Intermediate 6 (59.0 parts) obtained in Example 6 was added.
The mixed solution was refluxed for 4 hours, then 50.0 parts of triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. The reaction solution was then poured into water to give a precipitate. This precipitate was filtered, washed with water, and dried to obtain Intermediate 7 (50.0 parts, yield 62%) having the following structure.

Synthesis Example 8 (Synthesis of Intermediate 8)
20 parts of tetrahydrofuran was added to a round-bottom flask (equipped with a magnetic stirrer and in a state where it could be stirred) containing 3 parts of N, N-diethyl-1-naphthylamine (manufactured by Tokyo Chemical Industry Co., Ltd.). The reaction solution was cooled in an ice bath. Then, 10 parts of a tetrahydrofuran solution of 2.8 parts of N-bromosuccinimide was added dropwise to this reaction solution.
After stirring the reaction solution at room temperature for 1 hour, water was added to stop the reaction, and the solution was extracted twice with ethyl acetate. The organic layer was dried over sodium sulfate, filtered, and concentrated to obtain Intermediate 8 (4.2 parts, yield 100%) having the following structure.

Synthesis Example 9 (Synthesis of anion _{K 6 (P 2 MoW 17 O} 62))
NaWO 4 · _2H 2 _O (Wako Pure Chemical Industries, Ltd.) 44.0 _parts of the _{Na 2 MoO 4 · 2H 2 O} ( manufactured by Kanto Chemical Co., Inc.) 1.90 parts, was dissolved in 230 parts of purified water. While stirring, 64.9 parts of 85% phosphoric acid was added to this solution using a dropping funnel. The resulting solution was heated to reflux for 8 hours. The reaction mixture was cooled to room temperature, 1 drop of bromine water was added, and 45.0 parts of potassium chloride was added with stirring to obtain _{K 6} (P ₂ MoW ₁₇ O _62). After a further 1 hour stirring, the precipitated _K resulting yellow _{6 (P 2 MoW 17 O 62} ) was filtered off and dried at 90 ° C., to obtain a dried product yield 29.4 parts.

Synthesis Example 10 (Synthesis of Compound 1)
Under a nitrogen atmosphere, 25.0 parts of anhydrous dioxane was placed in a round-bottom flask (equipped with a magnetic stirrer and in a state where it can be stirred) containing the intermediate 2 (0.61 part) obtained in Synthesis Example 2. Was added. After adjusting this reaction solution to 0 ° C. in an ice bath, a hexane solution of n-butyllithium (1.6M) (manufactured by Sigma-Aldrich) was added dropwise using a syringe under a nitrogen atmosphere. The reaction solution was reacted between 0 ° C. and room temperature for 2 hours. Then, in this reaction solution, the intermediate 7 (2.0 parts) obtained in Synthesis Example 7 dissolved in dioxane (20 parts) was added dropwise over 45 minutes.
After reacting this reaction solution at room temperature for 21 hours, water was added to stop the reaction, and extraction with dichloromethane was performed twice. The organic layer was dried over sodium sulfate, filtered, and concentrated under reduced pressure. The obtained oily substance was dissolved in methanol, and 0.19 parts of concentrated hydrochloric acid was added dropwise while stirring the solution. The reaction solution was reacted at room temperature for 19 hours and then purified by silica gel column chromatography (developing solvent: dichloromethane / methanol) to obtain Compound 1 (0.35 part, yield 26%) having the following structure.
^{1 1} H NMR (CDCl ₃ ): 8.28-7.08 (m, 11H), 3.65-3.57 (m, 10H), 2.39 (s, 3H), 1.32-1.27 (m, 15H)
m / z (FD-MS): 615.24 (M ⁺ )

Synthesis Example 11 (Synthesis of Compound 2)
Under a nitrogen atmosphere, 10.0 parts anhydrous tetrahydrofuran is placed in a round-bottom flask (equipped with a magnetic stirrer and in a state where it can be stirred) containing the intermediate 4 (0.88 parts) obtained in Synthesis Example 4. Was added. After adjusting this reaction solution to −80 ° C., a hexane solution of n-butyllithium (2.7M) (manufactured by Sigma-Aldrich) was added dropwise using a syringe under a nitrogen atmosphere. The reaction solution was stirred at −80 ° C. for 1 hour, then warmed to −10 ° C., held for 10 minutes, and brought to −80 ° C. again. Then, a solution prepared by dissolving the intermediate 7 (2.0 eq.) Obtained in Synthesis Example 7 in tetrahydrofuran (30 parts) was gradually added dropwise to this reaction solution. The reaction solution was gradually heated to room temperature and refluxed for 3 hours, then water was added to stop the reaction, and extraction with dichloromethane was performed. The organic layer was dried over sodium sulfate, filtered, and concentrated under reduced pressure. The obtained oily substance was dissolved in methanol, and 0.2 part of concentrated hydrochloric acid was added dropwise while stirring the solution. The reaction solution was reacted overnight at room temperature and then purified by silica gel column chromatography (developing solvent: ethyl acetate / dichloromethane / methanol) to obtain Compound 2 (0.18 part, yield 10%) having the following structure. rice field.
^{1 1} H NMR (CDCl ₃ ): 8.25-6.98 (m, 10H), 3.71-3.52 (m, 10H), 2.39 (s, 3H), 1.32-1.27 (m, 15H)
m / z (FD-MS): 633.23 (M ⁺ )

Synthesis Example 12 (Synthesis of Compound 3)
Under a nitrogen atmosphere, 20.0 parts of anhydrous tetrahydrofuran is placed in a round-bottom flask (equipped with a magnetic stirrer and in a state where it can be stirred) containing the intermediate 8 (4.2 parts) obtained in Synthesis Example 8. Was added. After adjusting this reaction solution to −78 ° C., a hexane solution of n-butyllithium (1.6M) (manufactured by Sigma-Aldrich) was added dropwise using a syringe under a nitrogen atmosphere. The reaction solution was reacted at −78 ° C. for 1 hour. Then, a solution prepared by dissolving the intermediate 7 (2.0 eq.) Obtained in Synthesis Example 7 in tetrahydrofuran (10 parts) was added dropwise to this reaction solution over 45 minutes. After reacting this reaction solution at room temperature for 21 hours, water was added to stop the reaction, and extraction with dichloromethane was performed twice. The organic layer was dried over sodium sulfate, filtered, and concentrated under reduced pressure. The obtained oily substance was dissolved in methanol, and 1.38 parts of concentrated hydrochloric acid was added dropwise while stirring the solution. The reaction solution was reacted at room temperature for 19 hours and then purified by silica gel column chromatography (developing solvent: dichloromethane / methanol) to obtain Compound 3 (0.84 part, yield 10%) having the following structure.
^{1 1} H NMR (CDCl ₃ ): 9.35-6.78 (m, 8H), 4.14-3.38 (m, 12H), 1.45-1.07 (m, 18H)

Synthesis Example 13 (Synthesis of Compound 4)
350.0 parts of pure water was added to a round-bottom flask (equipped with a magnetic stirrer and in a state where it can be stirred) containing compound 2 (5.0 parts) obtained in Synthesis Example 11. The reaction mixture was dissolved by stirring at 40 ° C. for 30 minutes. Next, _{a solution prepared by dissolving 7.6 parts of K 6} (P ₂ MoW ₁₇ O ₆₂ ) in warm pure water (50 parts) was slowly added, and the mixture was stirred at 40 ° C. for 1 hour. The reaction solution was then raised to 80 ° C., stirred for 1 hour, cooled and filtered. The obtained solid was washed 3 times with 300 parts of water and dried under reduced pressure to give compound 4 (yield 84%).

Synthesis Example 14 (Synthesis of Comparative Compound 1)
Comparative compound 1 (C1) having the following structure was obtained (yield 71%) by the method described on pages 49 to 50 of Japanese Patent Application Laid-Open No. 2015-28212.

Synthesis Example 15 (Synthesis of Comparative Compound 2)
Following the method described in Synthesis Example 13, Comparative Compound 2 (C2) having the following structure was obtained (yield 91%).

Synthesis Example 16 (Synthesis of Comparative Compound 3)
For a compound having the following structure (cation moiety) synthesized by the method described on pages 115 to 116 of International Publication No. 2012/128318, the anion was replaced by the method described in Synthesis Example 13. Comparative compound 3 (C3) having the following structure was obtained (yield 94%).

<Evaluation test>
[Spectroscopic measurement]
A stock solution of 1000 ppm was prepared by dissolving 10 mg of a sample in 10 mL of isopropyl alcohol, and further diluted with isopropyl alcohol to 125 ppm, 100 ppm, 75 ppm, 50 ppm, and 25 ppm. Measure the transmission spectrum of the isopropyl alcohol solution of each sample (evaluation sample is as shown in the table below) with a spectrophotometer U-3900 (manufactured by Hitachi High-Tech Science Co., Ltd.) in a quartz cell with a path length of 1 cm, and use a C light source. The chromaticity x value in Table 1 is shown in Table 1. The larger the value of chromaticity x, the stronger the redness.
[X value]
The CIE color system mathematically displays colors in coordinates. As shown in FIG. 1, the colors represented in the so-called "horseshoe-shaped" region of the Cartesian coordinate plane represented by the horizontal axis x and the vertical axis y are represented by the coordinates of x and y (x, It is called a y chromaticity diagram). The curved part of the outer circumference where the hues are sequentially changed and arranged in the circumferential direction around the achromatic area is called the spectral locus (or monochromatic light locus), which is the arrangement order of the rainbow colors, that is, the right end. It changes from red to yellow-red, yellow, yellow-green, green, blue-green, blue, blue-purple, purple, and red-purple, and returns to the original red position.

[Evaluation of contrast]
1.36 parts of the compound 4 obtained in Synthesis Example 13 was placed in a polybin, and 10.97 parts of propylene glycol monomethyl ether acetate (Dycel Chemical Industry Co., Ltd.), 1.93 parts of DISPERBYK LPN21116 (manufactured by Big Chemie Co., Ltd.), Add 0.83 parts of UNIDIC ZL-295 (manufactured by DIC Co., Ltd.) and 34.2 parts of 0.3-0.4 mmφ Sepul beads (manufactured by Coral Van Co., Ltd.) and disperse with a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) for 4 hours. Then, a pigment dispersion was obtained.
2.78 parts of the obtained pigment dispersion liquid and 0.72 parts of UNIDIC ZL-295 (manufactured by DIC Corporation) were mixed with a paint conditioner to obtain a color resist. The obtained color resist was spin-coated on 50 mm × 50 mm, 1 mm thick glass with a C light source to change the film thickness so that the chromaticity y = 0.1380, and then pre-dried at 90 ° C. for 3 minutes to form a coating film. Was further formed and fired at 230 ° C. for 1 hour to obtain a color filter for evaluation including a blue pixel portion.
A color filter was prepared in the same manner using Comparative Compound 2 instead of Compound 4.
Further, a color filter was prepared in the same manner using Comparative Compound 3 instead of Compound 4.

The contrast of each of the obtained color filters was measured using a contrast tester (manufactured by Tsubosaka Electric Co., Ltd., device name: CT-1). The larger the contrast value, the less the degree of light scattering, the less the leaked light when used as a color filter of a liquid crystal display device, and the clearer the brightness of the liquid crystal panel. In order to increase the contrast, the coating film is required to be uniform. The contrast value becomes small in a non-uniform coating film in which crystal precipitation or phase separation occurs. Then, the color filter was measured using a spectrophotometer U-3900 (manufactured by Hitachi High-Tech Science Co., Ltd.), and the chromaticity x value of chromaticity y = 0.110 was measured. Table 2 shows the contrast and the chromaticity x value. The higher the contrast, the better.

From Table 1 above, it can be seen that the triarylmethane compound of the present invention has a significantly reddish blue color as compared with the triarylmethane compound of Comparative Example 1.
Further, from Table 2 above, it can be seen that the triarylmethane lake compound of Example 4 has a significantly higher contrast than Comparative Examples 2 and 3 and is excellent as a color filter.

Claims (4)

The following general formula (I):

(I)
(In the general formula (I), B is the following general formula (II) or general formula (III) , n represents an arbitrary natural number, [A] ⁿ⁻ represents an arbitrary n-valent anion, and R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a phenyl group)

(II)
(In general formula (II), X represents an oxygen atom, a nitrogen atom or a sulfur atom, R ⁵ represents a phenyl group which may be substituted with a halogen atom, and R ⁶ and R ⁷ are independent hydrogen atoms. , Or an alkyl group having 1 to 8 carbon atoms, or a phenyl group which may be substituted with a halogen atom or an alkyl group having 1 to 8 carbon atoms. * Represents a bond with a carbon atom.)

(III)
(In the general formula (III), R ⁸ and R ⁹ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group. * Represents a bond with a carbon atom.)
The compound represented by. The compound according to claim 1 ^{, wherein [A] n−} in the general formulas (I) to (III) is a polyoxometallate. Wherein in the general formula (I) ~ (III) [ A] n- _{is, [P 2 MoW 17 O 62} ] A compound according to claim 1 or 2, characterized in that a ^6-. A color filter containing the compound according to any one of claims 1 to 3.

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