WO2017145627A1 - Compound and color filter - Google Patents

Compound and color filter Download PDF

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Publication number
WO2017145627A1
WO2017145627A1 PCT/JP2017/002664 JP2017002664W WO2017145627A1 WO 2017145627 A1 WO2017145627 A1 WO 2017145627A1 JP 2017002664 W JP2017002664 W JP 2017002664W WO 2017145627 A1 WO2017145627 A1 WO 2017145627A1
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group
compound
substituent
ring
parts
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PCT/JP2017/002664
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French (fr)
Japanese (ja)
Inventor
祐貴 野口
育郎 清都
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Dic株式会社
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Priority to JP2017525428A priority Critical patent/JP6255634B1/en
Publication of WO2017145627A1 publication Critical patent/WO2017145627A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C09B11/10—Amino derivatives of triarylmethanes
    • C09B11/12—Amino derivatives of triarylmethanes without any OH group bound to an aryl nucleus
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/02—Diaryl- or thriarylmethane dyes derived from diarylmethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C09B11/10—Amino derivatives of triarylmethanes
    • C09B11/12—Amino derivatives of triarylmethanes without any OH group bound to an aryl nucleus
    • C09B11/16—Preparation from diarylketones or diarylcarbinols, e.g. benzhydrol
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C09B11/26—Triarylmethane dyes in which at least one of the aromatic nuclei is heterocyclic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/02—Dyestuff salts, e.g. salts of acid dyes with basic dyes
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments

Definitions

  • the present invention for example, a triarylmethane compound capable of providing a colored product having a small hue change even when subjected to a thermal history at a high temperature for a long time when used as a colorant, and a color comprising the compound Regarding filters.
  • 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 a synthetic resin in which an organic pigment is dispersed is provided on a substrate, and organic pigments of red, green, and blue are used as the organic pigment.
  • an ⁇ -type copper phthalocyanine pigment (CI Pigment Blue 15: 6) is generally used, and the color is adjusted as necessary. Therefore, a small amount of purple organic pigment dioxazine violet pigment (CI Pigment Violet 23) is used in combination.
  • Organic pigments used in the production of color filters have characteristics that are completely different from those of conventional general-purpose applications, specifically, making display screens of liquid crystal display devices brighter (higher brightness) and the like. .
  • the dioxazine violet pigment is used in combination with the ⁇ -type copper phthalocyanine pigment, high brightness cannot be achieved. Therefore, particularly high brightness is particularly required for the organic pigment used in the blue pixel portion (B).
  • C.I. I. As CI Pigment Blue 1, a final color of BASF (FANAL BLUE D6340, D6390) having the following chemical structure is prominent.
  • I. Pigment Blue 1 is obtained by lake-forming Victoria Pure Blue BO, which is a basic triarylmethane dye, with a heteropoly acid such as phosphomolybdic acid or phosphotungsten molybdic acid.
  • Victoria Pure Blue BO which is a basic triarylmethane dye
  • a heteropoly acid such as phosphomolybdic acid or phosphotungsten molybdic acid.
  • C.I. I. Pigment Blue 1 has a cationic counter ion A ⁇ of Keggin type PMo x W 12-x O 40 .
  • triarylmethane dyes include halide anions, boron anions such as tetraphenylboron, organic carboxylate anions, inorganic sulfate anions, inorganic phosphate anions, aliphatic sulfonate anions, aromatic sulfonate anions, It is said that sulfonate anions corresponding to anthraquinone dyes, phthalocyanine dyes and indigo dyes can be used.
  • Patent Documents 7 and 8 the use of a compound composed of a salt formed of a triarylmethane having a specific structure and a heteropolyoxometalate anion having a specific structure for a blue pixel portion of a color filter has been studied.
  • Patent Document 9 a compound composed of a salt formed by dimerized triarylmethane and an anion is also used in the color filter blue pixel portion.
  • the problem to be solved by the present invention is to provide a colorant with little hue change even when it receives a heat history of 200 ° C. or more required for a manufacturing process at the time of producing a color filter.
  • a triarylmethane compound capable of providing a liquid crystal display device and the like capable of providing an excellent liquid crystal display with little hue change when used for preparing a blue pixel portion of a color filter, and a color filter containing the same are provided. There is to do.
  • the present inventors use a triarylmethane compound composed of a basic multivalent triarylmethane dye cation having a specific structure and a specific counter anion as a colorant for a color filter.
  • a triarylmethane compound composed of a basic multivalent triarylmethane dye cation having a specific structure and a specific counter anion as a colorant for a color filter.
  • the present invention provides a compound represented by the following general formula (I).
  • Z represents an a-valent aliphatic or aromatic hydrocarbon group which may have a substituent.
  • B c- represents a c-valent anion.
  • R 1 to R 3 each independently represent a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group, and R 1 and R 2 combine to form a ring structure May be.
  • A represents an aromatic group which may have a substituent or a heterocyclic group which may have a substituent.
  • a plurality of R 1 to R 3 and A may be the same or different.
  • a represents an integer of 2 or more, and b, c, and d represent an integer of 1 or more.
  • Y each independently represents a hydrogen atom or an arbitrary substituent.
  • R 6 and R 7 are each independently an alkyl group having 1 to 8 carbon atoms which may have a substituent, or 2 to 2 carbon atoms which may have a substituent.
  • 6 represents an alkenyl group having 6 or an optionally substituted cycloalkyl group having 3 to 8 carbon atoms, wherein R 6 and R 7 may be linked to each other to form a ring; The ring may have a substituent.
  • R 8 to R 10 are each independently an alkyl group having 1 to 8 carbon atoms which may have a substituent, and 2 to carbon atoms which may have a substituent.
  • 6 represents an alkenyl group having 6 or an optionally substituted cycloalkyl group having 3 to 8 carbon atoms, wherein R 8 to R 10 may be linked to each other to form a ring; The ring may have a substituent.
  • a color filter containing at least one selected from the compounds described above.
  • the triarylmethane compound of the present invention is a triarylmethane compound as represented by the specific general formula (I), even if it receives a heat history at a high temperature, the hue change of the colored material is small and the heat resistance can be greatly improved. In particular, there is a particularly remarkable technical effect that the heat resistance of a color filter such as a liquid crystal display device can be greatly improved.
  • the color filter of the present invention contains a triarylmethane compound as represented by the specific general formula (I) in the blue pixel portion, the color filter has a long hue change even when subjected to a thermal history at a high temperature. There is a particularly remarkable technical effect that a liquid crystal display device capable of displaying a brighter image over time can be provided.
  • the triarylmethane compound of the present invention is a compound represented by the following general formula (I).
  • Z represents an a-valent aliphatic or aromatic hydrocarbon group which may have a substituent.
  • B c- represents a c-valent anion.
  • R 1 to R 3 each independently represent a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group, and R 1 and R 2 combine to form a ring structure May be.
  • A represents an aromatic group which may have a substituent or a heterocyclic group which may have a substituent.
  • a plurality of R 1 to R 3 and A may be the same or different.
  • a represents an integer of 2 or more, and b, c, and d represent an integer of 1 or more.
  • Y each independently represents a hydrogen atom or an arbitrary substituent.
  • the compound of the general formula (I) of the present invention is a water-insoluble colorant and comprises a triarylmethane cation moiety and an anion.
  • R 1 to R 3 may be the same or different. Accordingly, the —NR 1 R 2 group may be left-right symmetric or left-right asymmetric.
  • R 1 and R 2 When adjacent R 1 and R 2 are combined to form a ring, these may be a ring bridged with a heteroatom. Specific examples of this ring include the following. These rings may have a substituent.
  • R 1 to R 3 are each independently a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent from the viewpoint of chemical stability. It is preferable.
  • each Y is independently a hydrogen atom or an arbitrary substituent.
  • R 1 to R 3 are each independently a hydrogen atom; methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, Alkyl groups such as cyclopentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group and decyl group; any of aryl groups such as phenyl group, naphthyl group, thienyl group, furyl group and thiazolyl group More preferably.
  • R 1 to R 3 and Y represent an alkyl group or an aryl group
  • the alkyl group or aryl group may further have an arbitrary substituent.
  • Examples of the optional substituent that the alkyl group or aryl group may further have include the following [Substituent group R].
  • R 1 to R 3 are more preferably an alkyl group having 1 to 8 carbon atoms which may have a substituent, and more specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group. , Isobutyl group, sec-butyl group, pentyl group, hexyl group, 2-ethylhexyl group and other unsubstituted alkyl groups; 2-methoxyethyl group, 2-ethoxyethyl group and other alkoxyalkyl groups; 2-acetyloxyethyl group, etc. Cyanoalkyl groups such as 2-cyanoethyl group; fluoroalkyl groups such as 2,2,2-trifluoroethyl group, 4,4,4-trifluorobutyl group, and the like.
  • Y may be any group independently as long as the effects of the present invention are not impaired.
  • a hydrogen atom, methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl may be used.
  • alkyl group, alkoxy group and aryl group may further have other optional substituents.
  • substituent group R what was described by the term of the said [substituent group R] is mentioned, for example.
  • adjacent Y may combine to form a ring structure.
  • Y in the present invention is most preferably a hydrogen atom in terms of high color purity.
  • the aromatic group and heterocyclic group in A are not particularly limited.
  • aromatics in the aromatic group in addition to benzene ring, condensed polycyclic aromatic hydrocarbons such as naphthalene ring, tetralin ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring; biphenyl, terphenyl, diphenylmethane, triphenyl
  • chain polycyclic hydrocarbons such as methane and stilbene.
  • the chain polycyclic hydrocarbon may have a heteroatom such as O or S in the chain skeleton such as diphenyl ether.
  • heterocyclic ring in the heterocyclic group examples include 5-membered heterocycles such as furan, thiophene, pyrrole, oxazole, thiazole, imidazole, and pyrazole; 6-membered heterocycles such as pyran, pyrone, pyridine, pyridazine, pyrimidine, and pyrazine; And condensed polycyclic heterocycles such as thionaphthene, indole, carbazole, coumarin, benzo-pyrone, quinoline, isoquinoline, acridine, phthalazine, quinazoline, quinoxaline and the like.
  • aromatic groups and heterocyclic groups may have a substituent. Examples of the substituent include those described in the above section [Substituent group R].
  • the group represented by the following general formula (IV), the following general formula (V), or the following general formula (VI) is preferable as the aromatic group or heterocyclic group in A from the viewpoint of heat resistance.
  • R 11 and R 12 each independently represent a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent, and R 11 and R 12 12 may combine to form a ring structure, each E 1 independently represents a hydrogen atom or an arbitrary substituent, and * represents a bond to a carbon atom.
  • R 13 and R 14 each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and R 13 and R 14 14 may combine to form a ring structure, each E 2 independently represents a hydrogen atom or an arbitrary substituent, and * represents a bond to a carbon atom.
  • R 15 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group which may have a substituent.
  • X represents an oxygen atom, a nitrogen atom or a sulfur atom.
  • R 16 and R 17 each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and R 16 and R 17 are bonded to form a ring; (A structure may be formed. * Represents a bond with a carbon atom.)
  • R 11 and R 12 may be the same or different. Accordingly, the —NR 11 R 12 group may be left-right symmetric or left-right asymmetric.
  • R 11 and R 12 When adjacent R 11 and R 12 are bonded to form a ring, these may be a ring bridged with a heteroatom. These rings may have a substituent.
  • R 11 and R 12 are each independently a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent from the viewpoint of chemical stability. It is preferable. Among them, R 11 and R 12 are each independently a hydrogen atom; methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, Alkyl groups such as cyclopentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group and decyl group; any of aryl groups such as phenyl group, naphthyl group, thienyl group, furyl group and thiazolyl group More preferably.
  • R 11 and R 12 represent an alkyl group or an aryl group
  • the alkyl group or aryl group may further have an optional substituent.
  • the optional substituent that the alkyl group or aryl group may further have include those described in the above-mentioned [Substituent group R] section.
  • R 11 and R 12 are each more preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms which may have a substituent, and more specifically, a methyl group, an ethyl group, or a propyl group.
  • E 1 may be any group independently as long as the effects of the present invention are not impaired.
  • the alkyl group, alkoxy group and aryl group may further have other optional substituents.
  • an arbitrary substituent which the said alkyl group, an alkoxy group, and an aryl group may have further what was described by the term of the said [substituent group R] is mentioned, for example.
  • adjacent E 1 may be bonded to form a ring structure.
  • E 1 in the present invention is most preferably a hydrogen atom in terms of high color purity.
  • R 13 and R 14 each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent.
  • alkyl group in R 13 and R 14 include linear, branched or cyclic alkyl groups, and the number of carbon atoms is usually 1 or more, and usually 8 or less, preferably 5 or less.
  • Specific examples include methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group, isobutyl group, tert-butyl group, cyclohexyl group and the like.
  • Examples of the aryl group in R 13 and R 14 include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
  • the aromatic hydrocarbon ring group may be a single ring or a condensed ring, and is not particularly limited as long as it has 5 to 18 carbon atoms to form the ring.
  • the aromatic heterocyclic group may be a monocyclic ring or a condensed ring, and is not particularly limited as long as the number of carbon atoms forming the ring is 3 to 10.
  • R 13 and R 14 When adjacent R 13 and R 14 are combined to form a ring, these may be a ring bridged with a heteroatom. These rings may have a substituent.
  • R 13 and R 14 are preferably each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or an optionally substituted group. It is a phenyl group.
  • Examples of the substituent that the alkyl group, aryl group, and ring formed by connecting to each other in R 13 and R 14 may have include the following [Substituent group Q].
  • [Substituent group Q] Fluorine atom, chlorine atom, alkyl group having 1 to 8 carbon atoms, alkenyl group having 2 to 8 carbon atoms, alkoxyl group having 1 to 8 carbon atoms, phenyl group, mesityl group, tolyl group, naphthyl group, cyano group, acetyloxy Groups, alkylcarbonyloxy groups having 2 to 9 carbon atoms, sulfonic acid amide groups, sulfonealkylamide groups having 2 to 9 carbon atoms, alkylcarbonyl groups having 2 to 9 carbon atoms, Phenethyl group, hydroxyethyl group, acetylamide group, dialkylaminoethyl group formed by bonding an alkyl group having 1 to 4 carbon atoms, trifluoromethyl group, trialkylsilyl group having 1 to 8 carbon atoms, nitro group, carbon number 1 to 8 alkylthio groups.
  • the alkyl group, aryl group, and ring formed by connecting to each other in R 13 and R 14 may have, preferably an alkyl group having 1 to 8 carbon atoms, or 2 to 8 carbon atoms.
  • E 2 may be any group independently as long as the effects of the present invention are not impaired.
  • the alkyl group, alkoxy group and aryl group may further have other optional substituents.
  • an arbitrary substituent which the said alkyl group, an alkoxy group, and an aryl group may have further what was described by the term of the said [substituent group R] is mentioned, for example.
  • adjacent E 2 may be bonded to form a ring structure.
  • E 2 in the present invention is most preferably a hydrogen atom in terms of high color purity.
  • Examples of the alkyl group having 1 to 20 carbon atoms represented by R 15 in the general formula (VI) include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, linear alkyl groups such as n-heptyl group and n-octyl group; isopropyl group, sec-butyl group, tert-butyl group, isopentyl group, 1-methylpentyl group, 2-methylpentyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1-methylhexyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 1-ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group, 1-propyl A branched al
  • Examples of the aryl group represented by R 15 in the general formula (VI) include aryl groups having 6 to 14 carbon atoms such as a phenyl group, a naphthyl group, and a benzyl group.
  • examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; methyl group, ethyl
  • An alkyl group having 1 to 6 carbon atoms such as a group; a haloalkyl group having 1 to 6 carbon atoms such as a chloromethyl group and a trifluoromethyl group; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group; a hydroxy group;
  • X represents an oxygen atom, a nitrogen atom or a sulfur atom. From the viewpoint of ease of synthesis, a sulfur atom is preferred.
  • R 16 and R 17 may be the same or different. Accordingly, the —NR 16 R 17 group may be left-right symmetric or left-right asymmetric.
  • R 16 and R 17 When adjacent R 16 and R 17 are combined to form a ring, these may be a ring bridged with a heteroatom. These rings may have a substituent.
  • R 16 and R 17 are each independently a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent from the viewpoint of chemical stability. It is preferable. Among them, R 16 and R 17 are each independently a hydrogen atom; methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, Alkyl groups such as cyclopentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group and decyl group; any of aryl groups such as phenyl group, naphthyl group, thienyl group, furyl group and thiazolyl group More preferably.
  • R 16 and R 17 represent an alkyl group or an aryl group
  • the alkyl group or aryl group may further have an optional substituent.
  • the optional substituent that the alkyl group or aryl group may further have include those described in the above-mentioned [Substituent group R] section.
  • the group represented by the general formula (VI) is preferably a group represented by the following formula. * Represents a bond with a carbon atom.
  • Z in the general formula (I) is an a-valent aliphatic or aromatic hydrocarbon group which may have a substituent.
  • the aliphatic hydrocarbon group may be linear, branched or cyclic, may have an unsaturated bond, may have a substituent, and has an O in the carbon chain. , S, N may be included.
  • a carbonyl group, a carboxy group, an oxycarbonyl group, an amide group or the like may be contained, and a hydrogen atom may be further substituted with a halogen atom or the like.
  • the aromatic hydrocarbon group includes a monocyclic or polycyclic aromatic group, may have a substituent, and may be a heterocyclic ring containing O, S, and N.
  • condensed polycyclic aromatic hydrocarbons such as naphthalene ring, tetralin ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring; chain polycyclic aromatic hydrocarbons such as biphenyl and terphenyl; 5-membered heterocycles such as furan, thiophene, pyrrole, oxazole, thiazole, imidazole, pyrazole; 6-membered heterocycles such as pyran, pyrone, pyridine, pyrone, pyridazine, pyrimidine, pyrazine; benzofuran, thionaphthene, indole, carbazole, coumarin, And groups containing a condensed polycyclic heterocycle such as benzo-pyrone, quinoline, isoquinoline, acridine, phthalazine, quin
  • Z in the general formula (I) is an a-valent organic group in which a carbon atom directly bonded to N (nitrogen atom) does not have a ⁇ bond, and the organic group is at least a terminal directly bonded to N.
  • the aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the terminal directly bonded to N is linear, branched or cyclic unless the terminal carbon atom directly bonded to N has a ⁇ bond.
  • the carbon atom other than the terminal may have an unsaturated bond, may have a substituent, and the carbon chain contains O, S, and N. Also good.
  • a carbonyl group, a carboxy group, an oxycarbonyl group, an amide group or the like may be contained, and a hydrogen atom may be further substituted with a halogen atom or the like.
  • the aromatic group having an aliphatic hydrocarbon group in Z is a monocyclic or polycyclic aromatic group having an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the terminal directly bonded to N. And may have a substituent, and may be a heterocyclic ring containing O, S, and N.
  • Z contains a cyclic
  • a bridged alicyclic hydrocarbon group is preferable from the viewpoint of skeleton fastness.
  • the bridged alicyclic hydrocarbon group means a polycyclic aliphatic hydrocarbon group having a bridged structure in the aliphatic ring and having a polycyclic structure, for example, norbornane, bicyclo [2,2,2]. Examples include octane and adamantane.
  • norbornane is preferable.
  • the group containing a benzene ring and a naphthalene ring is mentioned, for example, Among these, the group containing a benzene ring is preferable.
  • Z is preferably divalent from the viewpoint of easy availability of raw materials.
  • Z is a divalent organic group, an aromatic group in which two linear, branched, or cyclic alkylene groups having 1 to 20 carbon atoms or two alkylene groups having 1 to 20 carbon atoms such as xylylene groups are substituted.
  • Z include the following, but are not limited thereto. * Represents a bond with a nitrogen atom.
  • a plurality of R 1 to R 3 and A present in one molecule may be the same or different.
  • the color development site exhibits the same color development, so that the same color as the single color development site can be reproduced, which is preferable from the viewpoint of color purity.
  • at least one of R 1 to R 3 and A is a different substituent, a color obtained by mixing plural types of monomers can be reproduced and adjusted to a desired color. .
  • [B c- ] is a monovalent or higher anion.
  • [B c- ] is not particularly limited as long as it is a monovalent or higher anion, but preferred anions from the viewpoint of heat resistance are heteropolyoxometalate anions, anions represented by the following general formula (II), and the following general formula (III) And an anion represented by the formula (I) and a sulfonate anion.
  • R 6 and R 7 are each independently an alkyl group having 1 to 8 carbon atoms which may have a substituent, or 2 to 2 carbon atoms which may have a substituent.
  • 6 represents an alkenyl group having 6 or an optionally substituted cycloalkyl group having 3 to 8 carbon atoms, wherein R 6 and R 7 may be linked to each other to form a ring; The ring may have a substituent.
  • R 8 to R 10 are each independently an alkyl group having 1 to 8 carbon atoms which may have a substituent, and 2 to carbon atoms which may have a substituent.
  • 6 represents an alkenyl group having 6 or an optionally substituted cycloalkyl group having 3 to 8 carbon atoms, wherein R 8 to R 10 may be linked to each other to form a ring; The ring may have a substituent.
  • the heteropolyacid anion is referred to as a heteropolyoxometalate anion.
  • a heteropoly acid is an inorganic acid having a relatively large molecular weight that does not contain an organic structure, and can exhibit unique properties not found in low-molecular inorganic acids or organic acids such as hydrochloric acid and sulfuric acid.
  • the first is to form a water-insoluble triarylmethane compound by rake formation with a cationic heteropolyacid.
  • Heteropolyacids do not contain organic structures or can contain relatively large molecular weights, including metals, so by selecting them appropriately, they can be derived from anionic structures even when exposed to high temperatures or light. It becomes possible to greatly suppress the alteration of the triarylmethane compound.
  • [B c- ] when it is desired to obtain a triarylmethane compound having higher heat resistance, for example, [B c- ] contains P (phosphorus) and Si (with W (tungsten) and O (oxygen) as essential elements.
  • a heteropolyoxometalate anion containing at least one kind of silicon) is preferred.
  • W (tungsten), Mo (molybdenum), O (oxygen) are essential elements, and a heteropolyoxometalate anion containing at least one of P (phosphorus) and Si (silicon) is improved in light resistance. This is more preferable.
  • Keggin type phosphotungstate ion ⁇ - (PW 12 O 40 ) 3 ⁇ Dawson type phosphotungstate ion ⁇ - (P 2 W 18 O 62 ) 6 ⁇ , ⁇ - (P 2 W 18 O 62 ) 6- , Keggin-type silicotungstate ion ⁇ - (SiW 12 O 40 ) 4- , ⁇ - (SiW 12 O 40 ) 4- , ⁇ - (SiW 12 O 40 ) 4- , and other examples ( 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 ⁇ , ⁇ - (SiW 9 O 34 ) 10 ⁇ , ⁇ - (SiW 10 O 36 ) 8 ⁇ , ⁇ - (SiW 11 O 39 ) 8 ⁇ , ⁇ - (SiW 11 O 39 ) 8 ⁇ and the like
  • the deficient Dawson-type phosphotungstic acid heteropolyoxometalate anion is (P 2 W 17 O 61 ) 10- .
  • heteropolyacids or alkali metal salts thereof examples 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 ), Na 10 (P 2 W 17 O 61 ), and the like can be used.
  • a heteropolyacid such as H 6 can be easily obtained, for example, according to the method described in Inorganic Chemistry, vol 47, p3679. Specifically, it can be obtained by dissolving an alkali metal tungstate and an alkali metal molybdate in water, adding phosphoric acid thereto, and heating to reflux for 5 to 10 hours while stirring with heating. The heteropolyacid thus obtained is reacted with an alkali metal chloride to form Na 6 (P 2 Mo y W 18-y O 62 ), which is a Dawson type heteropolyoxometalate alkali metal salt, in the same manner as described above. I can do it.
  • the number of molybdenum y in the heteropolyoxometalate anion is changed. It can be prepared in the range of 0-3.
  • an alkali metal molybdate salt is dissolved in water, hydrochloric acid is added thereto, and then an ⁇ 2-type deficient doson-type phosphotungstic alkali such as K 10 ( ⁇ 2-type P 2 W 17 O 61 ) is used. 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 converted to a Dawson type heteropolyoxometalate alkali metal salt in the same manner as described above by reacting with an alkali metal chloride.
  • P 2 MoW 17 O 62 can be obtained by preparing ⁇ 2 type P 2 W 17 O 61 by hydrolysis from P 2 W 18 O 62 and reacting it with Mo. By doing so, it is possible to obtain the above-described heteropolyacid and its alkali metal salt having no distribution in the numerical value of y.
  • a heteropolyacid such as H 4 (SiMoW 11 O 40 ) or a heteropolyoxometalate alkali metal salt can be easily obtained according to the method described in, for example, Journal of American Chemical Society, 104 (1982), p3194. Specifically, it can be obtained by mixing and stirring a nitric acid aqueous solution and an alkali metal molybdate aqueous solution, adding K 8 ( ⁇ -type SiW 11 O 39 ) thereto, and stirring for 2 to 6 hours.
  • the heteropolyacid thus obtained can be converted to a Keggin heteropolyoxometalate alkali metal salt in the same manner as described above by reacting with an alkali metal chloride.
  • Heteropolyacids such as H 6 (P 2 W 18 O 62 ) and H 10 (P 2 W 17 O 61 ) can be easily obtained according to the method described in, for example, Inorganic Chemistry, vol 47, p3679. Specifically, it can be obtained by dissolving an alkali metal tungstate in water, adding hydrochloric acid and phosphoric acid thereto, and heating to reflux for 10 to 50 hours with heating and stirring.
  • the heteropolyacid can be converted to a Dawson type heteropolyoxometalate alkali metal salt by reacting with an alkali metal chloride.
  • the deficient Dawson-type heteropolyoxometalate alkali metal salt can be easily obtained using the former Dawson-type phosphotungstic acid heteropolyoxometalate alkali metal salt as a raw material, for example, according to the method described in Inorganic Synthesis, vol 27, p104. I can do it. Specifically, it can be obtained by dissolving an alkali metal salt of Dawson type phosphotungstic acid heteropolyoxometalate in water, adding an alkali metal hydrogencarbonate to this, and stirring while heating if necessary. .
  • R 6 and R 7 in the general formula (II) are optionally substituted alkyl groups having 1 to 8 carbon atoms, optionally substituted alkenyl groups having 2 to 6 carbon atoms, Represents a C3-C8 cycloalkyl group which may have a substituent.
  • substituents include those described in the above section [Substituent group R].
  • the anion charge is more delocalized, and the heat resistance of the coloring material is improved. It preferably has a fluorine atom as a substituent. That is, R 6 and R 7 are preferably perfluoroalkyl groups having 1 to 8 carbon atoms in that the anion charge is dispersed and the anion is stabilized. On the other hand, R 6 and R 7 may be connected to each other to form a ring. When forming a ring, the group formed by linking R 6 and R 7 is particularly preferably a fluoroalkylene group having 2 to 12 carbon atoms.
  • R 8 to R 10 in the general formula (III) are each an optionally substituted alkyl group having 1 to 8 carbon atoms, an optionally substituted alkenyl group having 2 to 6 carbon atoms, Represents a C3-C8 cycloalkyl group which may have a substituent.
  • substituents include those described in the above section [Substituent group R].
  • R 8 to R 10 are preferably perfluoroalkyl groups having 1 to 8 carbon atoms in that the anion charge is dispersed and the anion is stabilized.
  • R 8 to R 10 may be connected to each other to form a ring.
  • the group formed by linking R 8 to R 10 is particularly preferably a fluoroalkylene group having 2 to 12 carbon atoms.
  • sulfonate anion examples include aliphatic sulfonate anions which may have a substituent such as trifluoromethanesulfonic acid, methanesulfonic acid, pentanesulfonic acid, hexanesulfonic acid, heptanesulfonic acid, dodecanesulfonic acid, and camphorsulfonic acid. ; Benzenesulfonic acid, p-toluenesulfonic acid, 1-naphthalenesulfonic acid, 2-naphthalenesulfonic acid, 2,6-naphthalenesulfonic acid, 1,3,6-naphthalenetrisulfonic acid, etc.
  • a is the number of chromogenic cation sites constituting the cation.
  • a is an integer of 2 or more.
  • the upper limit of a is not particularly limited, but a is preferably 4 or less, and more preferably 3 or less, from the viewpoint of ease of production.
  • b represents the number of cations in the molecular aggregate
  • d represents the number of anions in the molecular aggregate
  • b and d represent an integer of 1 or more.
  • the color material of the present invention is not limited to the case where each of b and d is 1 in the crystal or aggregate, and can take any natural number of 2, 3, 4,. From the viewpoint of heat resistance, it is preferable that at least a part of the coloring material of the present invention forms a molecular aggregate of b ⁇ 2. Moreover, it is preferable that at least a part of the coloring material of the present invention forms a molecular aggregate having d ⁇ 2 from the viewpoint of heat resistance.
  • a plurality of cations in the molecular aggregate may be one kind alone, or two or more kinds may be combined.
  • the anions present in the molecular aggregate may be one kind or a combination of two or more kinds.
  • the triarylmethane compound of the present invention can be easily produced, for example, by reacting the corresponding cation moiety chloride with the corresponding heteropolyacid or heteropolyoxometalate alkali metal salt.
  • the corresponding cation moiety chloride is used and a heteropolyacid is used
  • the corresponding cation moiety chloride is used by dehydrochlorination
  • the heteropolyoxometalate alkali metal salt is When used, it can be produced by salt substitution by dealkalizing metal chloride reaction.
  • the heteropolyacid is first converted to a heteropolyoxometalate alkali metal salt and then subjected to the dealkali metal chloride reaction, so that the salt substitution can be carried out more reliably, and the yield is improved.
  • This is preferable because not only the triarylmethane compound of the present invention can be obtained at a high level, but also the triarylmethane compound of the present invention can be obtained with less by-products and high purity.
  • the heteropolyoxometalate alkali metal salt can be used after being purified by recrystallization or the like.
  • the corresponding heteropolyoxometalate alkali metal salt can be obtained in a higher yield by reducing the solubility by cooling the reaction solution.
  • the amount of the anion source used for the heteropolyacid or heteropolyoxometalate alkali metal salt is charged so as to be an equimolar number depending on the ionic value. It is preferable to carry out the above reaction.
  • the triarylmethane compound of the present invention includes a step of rake (water insolubilization) with a heteropolyacid (or since it is raked (water insolubilization) with a heteropolyacid), it may be performed during or after the production process.
  • rake water insolubilization
  • a heteropolyacid or since it is raked (water insolubilization) with a heteropolyacid
  • it may be performed during or after the production process.
  • water in order to perform a more reliable reaction or to prevent the rake structure of the obtained compound from being destroyed, for example, metal ions or halogens such as purified water, ion-exchanged water, pure water, etc. It is preferable to use water with as little ion content as possible.
  • the triarylmethane compound of the present invention is a water-insoluble colorant.
  • the triarylmethane compound of the present invention thus obtained can be used as it is as a colorant for a synthetic resin or the like, but if necessary, the particle diameter can be adjusted by known and conventional pulverization or granulation.
  • the colorant can be optimal for various applications.
  • the colorant preferably has an average primary particle diameter of 100 nm or less because a clearer blue colored product can be easily obtained.
  • the average particle diameter of primary particles is measured as follows. First, the particle
  • the triarylmethane compound of the present invention is used for the production of a color filter pixel part because it has a small hue change and excellent heat resistance even after a thermal history at a high temperature in various known and commonly used applications.
  • the color filter of the liquid crystal display device capable of excellent image display with little hue change can be obtained.
  • the conventional cold cathode tube CCFL light source
  • white LED LED; Light Emitting Diode
  • three-color independent LED light source white organic EL (EL; Electro Luminescence)
  • EL Electro Luminescence
  • the triarylmethane compound of the present invention includes ⁇ -type copper phthalocyanine pigment, dioxazine pigment (CI Pigment Violet 23, CI Pigment Violet 37, CI Pigment Blue 80, etc.) and the like.
  • a synthetic resin that is liquid and water-insoluble at room temperature, such as a derivative, can be contained. Addition of these dispersants and resins also contributes to reduction of flocculation, improvement of dispersion stability, and improvement of viscosity characteristics of the dispersion.
  • the triarylmethane compound of the present invention itself has a hue suitable for the preparation of a color filter blue pixel part. If necessary, the ⁇ -type copper phthalocyanine pigment (C.I. By using 0.1 to 30 parts of Pigment Blue 15: 6) together, the hue can be optimized.
  • the triarylmethane compound of the present invention itself has heat resistance and light resistance suitable for the preparation of the color filter blue pixel portion, but if necessary, the antioxidant non-volatile per 100 parts of the triarylmethane compound. 0.1 to 10 parts per minute, and in particular 0.5 to 8 parts can be used.
  • the term “antioxidant” is a general term for additives that prevent oxidative degradation. Those that prevent oxidative degradation due to heat (antioxidants in a narrow sense) and those that prevent oxidative degradation due to light (mainly ultraviolet rays). (Referred to in the narrow sense as light stabilizers). *
  • antioxidants have the ability to trap radicals and prevent auto-oxidation (radical chain prevention) and the action to decompose hydroperoxide (peroxide) into harmless ones (peroxide decomposition action)
  • the former is called a primary antioxidant and the latter is called a secondary antioxidant.
  • primary antioxidants include phenolic (including hindered phenols) and amine (including hindered amines) antioxidants
  • secondary antioxidants include, for example, sulfur and phosphorus. Each of these antioxidants is typical.
  • the triarylmethane compound of the present invention itself has heat resistance suitable for the preparation of a color filter blue pixel portion, but if necessary, heat resistance and light resistance can be improved by using a cationic resin together. It can be raised one step further.
  • a cationic resin for example, an acrylic resin, a polyurethane resin, an epoxy resin, a polyamide resin, or the like is preferably used because the hue change is small even under a thermal history and the heat resistance of the color filter can be greatly improved.
  • the ratio of the triarylmethane compound and the cationic resin on the basis of mass of the non-volatile content is not particularly limited, but the non-volatile content of the latter resin is 0.1 to 10 parts per 100 parts of the former compound.
  • the content is preferably 0.5 to 5 parts, particularly 1 to 3 parts.
  • the triarylmethane 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 triarylmethane compound of the present invention is a photolithography method, which includes a photocurable composition described later on the side where a black matrix of a transparent substrate for a color filter is provided. After applying to the surface, heating and drying (pre-baking), pattern exposure is performed by irradiating ultraviolet rays through a photomask to cure the photocurable compound at the location corresponding to the pixel portion, and then the unexposed portion This is a method of developing with a developer, 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 to be described later is prepared, and the above-described operation is repeated to manufacture a color filter having red, green, and blue colored pixel portions at predetermined positions. be able to.
  • a blue pixel portion can be formed from the triarylmethane compound of the present invention.
  • a well-known and usual red pigment and green pigment can be used.
  • pigments for forming the red pixel portion for example, C.I. I. Pigment Red 177, 209, 242 and 254 are pigments for forming the green pixel portion, for example, C.I. I. Pigment Green 7, 10, 36, 47, 58 and the like.
  • a yellow pigment can be used in combination for forming the red pixel portion and the green pixel portion.
  • the entire color filter can be heat-treated (post-baked) in order to thermally cure the unreacted photocurable compound.
  • Examples of a method for applying a photocurable composition described later on a transparent substrate such as glass include a spin coating method, a roll coating method, and an ink jet method.
  • 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 blending ratio, and the like, but are usually about 50 to 150 ° C. for about 1 to 15 minutes.
  • light used for photocuring the photocurable composition it is preferable to use light in the 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, and a spray method.
  • the transparent substrate on which the necessary color pixel portion is formed is washed with water and dried.
  • the color filter thus obtained is subjected to a heat treatment (post-baking) at 90 to 280 ° C. for a predetermined time by a heating device such as a hot plate or an oven, thereby removing volatile components in the colored coating film and simultaneously applying light.
  • the unreacted photocurable compound remaining in the cured colored film of the curable composition is thermally cured to complete the color filter.
  • the photocurable composition for forming the blue pixel portion of the color filter comprises the triarylmethane compound of the present invention, a dispersant, a photocurable compound, and an organic solvent as essential components, and if necessary, heat It can prepare by mixing these using a plastic resin.
  • a photocurable compound is used in preparing the photocurable composition.
  • a thermoplastic resin is used in combination, it is preferable to use an organic solvent that dissolves it.
  • the triarylmethane compound of the present invention As a method for producing the photocurable composition, the triarylmethane compound of the present invention, an organic solvent and a dispersant are used as essential components, and these are mixed and stirred and dispersed so as to be uniform. After preparing a dispersion for forming the pixel portion of the color filter, a photocurable compound and, if necessary, a thermoplastic resin or a photopolymerization initiator are added to the photocurable composition. The method to do is common.
  • dispersant and the organic solvent those described above can be used.
  • thermoplastic resin used for the preparation of the photocurable composition examples include urethane resins, acrylic resins, polyamide resins, polyimide resins, styrene maleic acid resins, styrene maleic anhydride resins, and the like. .
  • photocurable compound examples include 1,6-hexanediol diacrylate, ethylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, bis (acryloxyethoxy) bisphenol A, and 3-methylpentanediol diacrylate.
  • Bifunctional monomers such as acrylate, trimethylol propaton triacrylate, pentaerythritol triacrylate, tris [2- (meth) acryloyloxyethyl) isocyanurate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, etc.
  • High molecular weight such as low molecular weight polyfunctional monomer, polyester acrylate, polyurethane acrylate, polyether acrylate, etc. Polyfunctional monomers.
  • photopolymerization initiator examples include acetophenone, benzophenone, benzyldimethyl ketal, benzoyl peroxide, 2-chlorothioxanthone, 1,3-bis (4′-azidobenzal) -2-propane, 1,3-bis (4′- Azidobenzal) -2-propane-2′-sulfonic acid, 4,4′-diazidostilbene-2,2′-disulfonic acid, and the like.
  • photopolymerization initiators examples include “Irgacure (trade name) -184”, “Irgacure (trade name) -369”, “Darocur (trade name) -1173” manufactured by Ciba Specialty Chemicals, and BASF Corporation. “Lucirin-TPO”, Nippon Kayaku Co., Ltd. “Kayacure (trade name) DETX”, “Kayacure (tradename) OA”, Stoffer “Bicure 10”, “Bicure 55”, Akzo Corporation “Trigonal PI” “Sandray 1000” manufactured by Sand, “Deep” manufactured by Upjohn, and “Biimidazole” manufactured by Kurokin Kasei.
  • a known and commonly used photosensitizer can be used in combination with the photopolymerization initiator.
  • the photosensitizer include amines, ureas, compounds having a sulfur atom, compounds having a phosphorus atom, compounds having a chlorine atom, nitriles or 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 less than 0.1%, the photosensitivity at the time of photocuring tends to decrease, and if it exceeds 30%, when the resist coating film is dried, crystals of the photopolymerization initiator are precipitated, and the coating film properties. May cause deterioration.
  • a photocurable composition for forming a color filter pixel portion can be obtained by adding an agent and, if necessary, further an organic solvent, and stirring and dispersing so as to be uniform.
  • the developer a known and commonly used organic solvent or alkaline aqueous solution can be used.
  • the photocurable composition contains a thermoplastic resin or a photocurable compound, and at least one of them has an acid value and exhibits alkali solubility
  • the color filter can be washed with an alkaline aqueous solution. It is effective for forming the pixel portion.
  • the method for producing the color filter pixel portion by photolithography was described in detail.
  • the color filter pixel portion prepared using the triarylmethane compound of the present invention is the other
  • a color filter may be manufactured by forming a blue pixel portion by a method such as an electrodeposition method, a transfer method, a micellar electrolysis method, a PVED (Photovoltaic Electrodeposition) method, an ink jet method, a reverse printing method, or a thermosetting method.
  • the color filter uses a photocurable composition of each color obtained by using a red pigment, a green pigment, and the triarylmethane compound of the present invention as an organic pigment, and encloses a liquid crystal material between a pair of parallel transparent electrodes.
  • the transparent electrode is divided into discontinuous fine sections, and a color selected from any one of red, green, and blue is provided for each of the fine sections divided into a grid by the black matrix on the transparent electrode. It can be obtained by providing filter colored pixel portions alternately in a pattern or by providing a transparent electrode after forming color filter colored pixel portions on a substrate.
  • the triarylmethane compound of the present invention can provide a dispersion having excellent sharpness and lightness, and for color filter applications, paints, plastics (resin molded products), printing inks, rubber, leather, textile printing, electrostatic image development
  • the present invention can also be applied to coloring toner, ink jet recording ink, thermal transfer ink, and the like.
  • reaction solution was poured into ice water, adjusted to pH 10 or higher with 15% aqueous sodium hydroxide solution, and extracted with chloroform.
  • the chloroform layer was washed with 5% aqueous sodium hydroxide solution and saturated brine, and dried over anhydrous sodium sulfate.
  • reaction solution was poured into ice water, adjusted to pH 10 or higher with 15% aqueous sodium hydroxide solution, and extracted with chloroform.
  • the chloroform layer was washed with 5% aqueous sodium hydroxide solution and saturated brine, and dried over anhydrous sodium sulfate.
  • An evaluation glass substrate was obtained in the same manner as in Example 1 except that Compound 7 was used instead of Compound 6.
  • An evaluation glass substrate was obtained in the same manner as in Example 1 except that Compound 8 was used instead of Compound 6.
  • An evaluation glass substrate was obtained in the same manner as in Example 1 except that Compound 9 was used instead of Compound 6.
  • An evaluation glass substrate was obtained in the same manner as in Example 1 except that Compound 10 was used instead of Compound 6.
  • An evaluation glass substrate was obtained in the same manner as in Example 1 except that Compound 11 was used instead of Compound 6.
  • An evaluation glass substrate was obtained in the same manner as in Example 1 except that Compound 12 was used instead of Compound 6.
  • An evaluation glass substrate was obtained in the same manner as in Example 1 except that Compound 13 was used instead of Compound 6.
  • An evaluation glass substrate was obtained in the same manner as in Example 1 except that Compound 16 was used instead of Compound 6.
  • An evaluation glass substrate was obtained in the same manner as in Example 1 except that Compound 17 was used instead of Compound 6.
  • the present invention can be synthesized by freely changing the A part effective in heat resistance by linking the linking group Z at a specific site. It is excellent in that the property can be further improved. For example, if the intermediate 1 or the intermediate 2 is synthesized, the part A can be easily changed. Furthermore, since the color is changed by changing the A portion, it can be adjusted to a desired color.

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Abstract

It becomes possible to provide a coloring material which undergoes little change in hue even under temperature history of 200ºC or higher which is required for color filter production processes. Provided are, for example: a triarylmethane compound which, when used in the preparation of blue color pixel parts in a color filter, can make it possible to provide a liquid crystal display device capable of excellent liquid crystal display with little change in hue and others; and a color filter containing the triarylmethane compound. It is found that, when a triarylmethane compound composed of a basic polymerized triarylmethane dye cation having a specific structure and a specific counter anion is used as a coloring material for a color filter, little change in hue is observed even under temperature history in the production of a color filter. This finding leads to the accomplishment of the present invention.

Description

化合物及びカラーフィルタCompound and color filter
　本発明は、例えば、着色剤として用いた際に、高温での熱履歴を長時間に亘って受けても色相変化の小さい着色物を提供できるトリアリ－ルメタン化合物及び該化合物を含有してなるカラーフィルタに関する。 The present invention, for example, a triarylmethane compound capable of providing a colored product having a small hue change even when subjected to a thermal history at a high temperature for a long time when used as a colorant, and a color comprising the compound Regarding filters.
　液晶表示装置等のカラーフィルタは、赤色画素部（Ｒ）、緑色画素部（Ｇ）及び青色画素部（Ｂ）を有する。これらの各画素部は、いずれも有機顔料が分散した合成樹脂の薄膜が基板上に設けられた構造であり、有機顔料としては、赤、緑及び青の各色の有機顔料が用いられている。 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 a synthetic resin in which an organic pigment is dispersed is provided on a substrate, and organic pigments of red, green, and blue are used as the organic pigment.
　これら画素部のうち、青色画素部を形成するための青色有機顔料としては、一般に、ε型銅フタロシアニン顔料（Ｃ．Ｉ．ピグメントブルー１５：６）が用いられており、必要に応じて調色のために、これに紫色有機顔料のジオキサジンバイオレット顔料（Ｃ．Ｉ．ピグメントバイオレット２３）が少量併用されている。 Among these pixel portions, as a blue organic pigment for forming a blue pixel portion, an ε-type copper phthalocyanine pigment (CI Pigment Blue 15: 6) is generally used, and the color is adjusted as necessary. Therefore, a small amount of purple organic pigment dioxazine violet pigment (CI Pigment Violet 23) is used in combination.
　カラーフィルタを作成する際の有機顔料は、従来の汎用用途とは全く異なる特性、具体的には、液晶表示装置等の表示画面がより明るくなる様にする（高輝度化）等の要求がある。しかしながら、ε型銅フタロシアニン顔料にジオキサジンバイオレット顔料を併用したのでは、高輝度が達成できないことから、特に青色画素部（Ｂ）に用いる有機顔料には、高輝度化がとりわけ要求されている。 Organic pigments used in the production of color filters have characteristics that are completely different from those of conventional general-purpose applications, specifically, making display screens of liquid crystal display devices brighter (higher brightness) and the like. . However, when the dioxazine violet pigment is used in combination with the ε-type copper phthalocyanine pigment, high brightness cannot be achieved. Therefore, particularly high brightness is particularly required for the organic pigment used in the blue pixel portion (B).
　この様な高輝度化に対応するために、輝度の点においてはε型銅フタロシアニン顔料より優れた、Ｃ．Ｉ．ピグメントブルー１の様なトリアリールメタン顔料をカラーフィルタの青色画素部に用いることが最近検討されてきている（特許文献１～３）。 In order to cope with such high brightness, C.I. is superior to ε-type copper phthalocyanine pigment in terms of brightness. I. Recently, the use of a triarylmethane pigment such as CI Pigment Blue 1 in the blue pixel portion of a color filter has been studied (Patent Documents 1 to 3).
　このＣ．Ｉ．ピグメントブルー１としては、以下の化学構造のＢＡＳＦ社のファナルカラー（ＦＡＮＡＬ　ＢＬＵＥ　Ｄ６３４０、同Ｄ６３９０）が著名であり、Ｃ．Ｉ．ピグメントブルー１は、塩基性トリアリールメタン染料であるビクトリアピュアブルーＢＯを、リンモリブデン酸やリンタングステンモリブデン酸の様なヘテロポリ酸でレーキ化して得られる。こうして得られたＣ．Ｉ．ピグメントブルー１は、カチオンの対イオンＡ－がケギン型ＰＭｏｘＷ１２－ｘＯ４０であるとされている。 This C.I. I. As CI Pigment Blue 1, a final color of BASF (FANAL BLUE D6340, D6390) having the following chemical structure is prominent. I. Pigment Blue 1 is obtained by lake-forming Victoria Pure Blue BO, which is a basic triarylmethane dye, with a heteropoly acid such as phosphomolybdic acid or phosphotungsten molybdic acid. Thus obtained C.I. I. Pigment Blue 1 has a cationic counter ion A − of Keggin type PMo x W 12-x O 40 .
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
〔但し、一般式（ＩＸ）中、Ａｎ－は、ケギン型リンタングステンモリブデン酸アニオンまたはリンモリブデン酸アニオンである。ｎは任意の自然数を表す。〕 [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. ]
　また、上記したトリアリールメタン顔料ではなく、トリアリールメタン染料をカラーフィルタの青色画素部に用いることも最近検討されてきている（特許文献４～５）。これらトリアリールメタン染料は、アニオンとしては、ハロゲン化物アニオン、テトラフェニルホウ素の様なホウ素アニオン、有機カルボン酸アニオン、無機硫酸アニオン、無機リン酸アニオン、脂肪族スルホン酸アニオン、芳香族スルホン酸アニオン、アントラキノン色素やフタロシアニン色素やインジゴ色素の対応するスルホナトアニオン等を用いることが出来るとされている。 Further, it has recently been studied to use a triarylmethane dye in the blue pixel portion of a color filter instead of the triarylmethane pigment described above (Patent Documents 4 to 5). These triarylmethane dyes include halide anions, boron anions such as tetraphenylboron, organic carboxylate anions, inorganic sulfate anions, inorganic phosphate anions, aliphatic sulfonate anions, aromatic sulfonate anions, It is said that sulfonate anions corresponding to anthraquinone dyes, phthalocyanine dyes and indigo dyes can be used.
　更に、トリアリールメタン染料として、金属フタロシアニンスルホン酸とトリアリールメタンカチオンとの塩からなる染料をカラーフィルタの青色画素部に用いることも検討されている（特許文献６）。 Furthermore, the use of a dye comprising a salt of a metal phthalocyanine sulfonic acid and a triarylmethane cation as a triarylmethane dye for the blue pixel portion of a color filter has been studied (Patent Document 6).
　また、特定構造のトリアリールメタンと特定構造のヘテロポリオキソメタレートアニオンにより形成されている塩からなる化合物をカラーフィルタの青色画素部に用いることも検討されている（特許文献７、８）。 Also, the use of a compound composed of a salt formed of a triarylmethane having a specific structure and a heteropolyoxometalate anion having a specific structure for a blue pixel portion of a color filter has been studied (Patent Documents 7 and 8).
　さらに、２量化されたトリアリールメタンとアニオンにより形成されている塩からなる化合物も同様にカラーフィルタ青色画素部に用いることも検討されている（特許文献９）。 Furthermore, it has been studied that a compound composed of a salt formed by dimerized triarylmethane and an anion is also used in the color filter blue pixel portion (Patent Document 9).
　しかしながら、これら従来のトリアリールメタン顔料やトリアリールメタン染料をカラーフィルタの青色画素部の調製に用いた場合、光線を長時間に亘って受けた場合やカラーフィルタ作製時の熱履歴によって、画素の色相は著しく低下してしまい、依然として長時間に亘って満足のいく輝度を維持できず、耐光性、耐熱性の点では不充分であるというのが実態である。 However, when these conventional triarylmethane pigments or triarylmethane dyes are used for the preparation of the blue pixel portion of the color filter, the pixels of the pixel are affected by the heat history when receiving light for a long time or when producing the color filter. The actual condition is that the hue is remarkably lowered, and a satisfactory luminance cannot be maintained for a long time, which is insufficient in terms of light resistance and heat resistance.
特開２００１－８１３４８号公報JP 2001-81348 A 特開２０１０－８３９１２号公報JP 2010-83912 A 特開２０１０－８５４４４号公報JP 2010-85444 A 特開２０１１－６８８６６号公報JP 2011-68866 A 特開２０１１－７０１７１号公報JP 2011-70171 A 特開２０１１－７０１７２号公報JP 2011-70172 A ＷＯ／２０１２／０３９４１６号WO / 2012/039416 ＷＯ／２０１２／０３９４１７号WO / 2012/039417 特開２０１３－０５７０５４号公報JP 2013-057054 A
　本発明が解決しようとする課題は、カラーフィルタ作製時の製造工程に要求される２００度以上の熱履歴を受けても、色相変化の少ない着色材を提供できることにある。例えば、カラーフィルタの青色画素部の調製に用いた際に、色相変化の少ない優れた液晶表示が可能となる液晶表示装置等を提供できるトリアリールメタン化合物及びそれを含有してなるカラーフィルタを提供することにある。 The problem to be solved by the present invention is to provide a colorant with little hue change even when it receives a heat history of 200 ° C. or more required for a manufacturing process at the time of producing a color filter. For example, a triarylmethane compound capable of providing a liquid crystal display device and the like capable of providing an excellent liquid crystal display with little hue change when used for preparing a blue pixel portion of a color filter, and a color filter containing the same are provided. There is to do.
　本発明者らは、前記実状に鑑みて鋭意検討した結果、特定の構造を有する塩基性多量化トリアリールメタン染料カチオンと特定の対アニオンからなるトリアリールメタン化合物をカラーフィルタの着色材として使用することで、カラーフィルタ作製時の熱履歴を受けても色相変化が少ないことを見出し、本発明を完成するに至った。 As a result of intensive studies in view of the above-mentioned circumstances, the present inventors use a triarylmethane compound composed of a basic multivalent triarylmethane dye cation having a specific structure and a specific counter anion as a colorant for a color filter. Thus, the present inventors have found that there is little change in hue even when receiving a thermal history during the production of a color filter, and have completed the present invention.
即ち本発明は、下記一般式（Ｉ）で表される化合物を提供する。 That is, the present invention provides a compound represented by the following general formula (I).
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
（一般式（Ｉ）中、Ｚは、置換基を有していてもよいａ価の、脂肪族系又は芳香族系の炭化水素基を表す。Ｂｃ－はｃ価のアニオンを表す。Ｒ１～Ｒ３は各々独立に水素原子、置換基を有していてもよいアルキル基又は置換基を有していてもよいアリール基を表し、Ｒ１とＲ２が結合して環構造を形成してもよい。　
Ａは置換基を有していてもよい芳香族基又は置換基を有していてもよい複素環基を表す。
複数あるＲ１～Ｒ３及びＡはそれぞれ同一であっても異なっていてもよい。ａは２以上の整数、ｂ、ｃ、ｄは１以上の整数を表す。Ｙは各々独立に、水素原子、または任意の置換基を示す。） (In the general formula (I), Z represents an a-valent aliphatic or aromatic hydrocarbon group which may have a substituent. B c- represents a c-valent anion. R 1 to R 3 each independently represent a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group, and R 1 and R 2 combine to form a ring structure May be.
A represents an aromatic group which may have a substituent or a heterocyclic group which may have a substituent.
A plurality of R 1 to R 3 and A may be the same or different. a represents an integer of 2 or more, and b, c, and d represent an integer of 1 or more. Y each independently represents a hydrogen atom or an arbitrary substituent. )
前記一般式（Ｉ）におけるアニオン（Ｂｃ－）が、ヘテロポリオキソメタレートアニオンである、化合物。 A compound in which the anion (B c− ) in the general formula (I) is a heteropolyoxometalate anion.
前記一般式（Ｉ）におけるアニオン（Ｂｃ－）が、下記一般式（ＩＩ）で表される、化合物。 A compound in which the anion (B c− ) in the general formula (I) is represented by the following general formula (II).
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
（一般式（ＩＩ）中、Ｒ６及びＲ７は、各々独立に、置換基を有していてもよい炭素数１～８のアルキル基、置換基を有していてもよい炭素数２～６のアルケニル基、又は置換基を有していてもよい炭素数３～８のシクロアルキル基を表す。尚、Ｒ６及びＲ７は、互いに連結して環を形成していてもよく、該環は置換基を有していてもよい。） (In the general formula (II), R 6 and R 7 are each independently an alkyl group having 1 to 8 carbon atoms which may have a substituent, or 2 to 2 carbon atoms which may have a substituent. 6 represents an alkenyl group having 6 or an optionally substituted cycloalkyl group having 3 to 8 carbon atoms, wherein R 6 and R 7 may be linked to each other to form a ring; The ring may have a substituent.)
前記一般式（Ｉ）におけるアニオン（Ｂｃ－）が、下記一般式（ＩＩＩ）で表される、化合物。 A compound in which the anion (B c− ) in the general formula (I) is represented by the following general formula (III).
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
（一般式（ＩＩＩ）中、Ｒ８～Ｒ１０は、各々独立に、置換基を有していてもよい炭素数１～８のアルキル基、置換基を有していてもよい炭素数２～６のアルケニル基、又は置換基を有していてもよい炭素数３～８のシクロアルキル基を表す。尚、Ｒ８～Ｒ１０は、互いに連結して環を形成していてもよく、該環は置換基を有していてもよい。） (In the general formula (III), R 8 to R 10 are each independently an alkyl group having 1 to 8 carbon atoms which may have a substituent, and 2 to carbon atoms which may have a substituent. 6 represents an alkenyl group having 6 or an optionally substituted cycloalkyl group having 3 to 8 carbon atoms, wherein R 8 to R 10 may be linked to each other to form a ring; The ring may have a substituent.)
前記一般式（Ｉ）におけるアニオン（Ｂc－）が、スルホン酸アニオンである、化合物。 A compound in which the anion (B c− ) in the general formula (I) is a sulfonate anion.
上記記載の化合物から選択される少なくとも一種を含有するカラーフィルタを提供する。 Provided is a color filter containing at least one selected from the compounds described above.
　本発明のトリアリールメタン化合物は、特定一般式（Ｉ）で表される様な、トリアリールメタン化合物なので、高温での熱履歴を受けても着色物の色相変化が小さく耐熱性を大きく改善でき、特に、液晶表示装置等のカラーフィルタの耐熱性を大きく改善できるという格別顕著な技術的効果を奏する。 Since the triarylmethane compound of the present invention is a triarylmethane compound as represented by the specific general formula (I), even if it receives a heat history at a high temperature, the hue change of the colored material is small and the heat resistance can be greatly improved. In particular, there is a particularly remarkable technical effect that the heat resistance of a color filter such as a liquid crystal display device can be greatly improved.
　さらに、本発明のカラーフィルタは、青色画素部に、特定一般式（Ｉ）で表される様な、トリアリールメタン化合物を含有するので、高温での熱履歴を受けても色相変化の少ない長時間に亘りより明るい画像表示が可能な液晶表示装置等を提供できるという格別顕著な技術的効果を奏する。 Furthermore, since the color filter of the present invention contains a triarylmethane compound as represented by the specific general formula (I) in the blue pixel portion, the color filter has a long hue change even when subjected to a thermal history at a high temperature. There is a particularly remarkable technical effect that a liquid crystal display device capable of displaying a brighter image over time can be provided.
　本発明のトリアリールメタン化合物は、下記一般式（Ｉ）で表される化合物である。 The triarylmethane compound of the present invention is a compound represented by the following general formula (I).
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
（一般式（Ｉ）中、Ｚは、置換基を有していてもよいａ価の、脂肪族系又は芳香族系の炭化水素基を表す。Ｂｃ－はｃ価のアニオンを表す。Ｒ１～Ｒ３は各々独立に水素原子、置換基を有していてもよいアルキル基又は置換基を有していてもよいアリール基を表し、Ｒ１とＲ２が結合して環構造を形成してもよい。　
Ａは置換基を有していてもよい芳香族基又は置換基を有していてもよい複素環基を表す。
複数あるＲ１～Ｒ３及びＡはそれぞれ同一であっても異なっていてもよい。ａは２以上の整数、ｂ、ｃ、ｄは１以上の整数を表す。Ｙは各々独立に、水素原子、または任意の置換基を示す。） (In the general formula (I), Z represents an a-valent aliphatic or aromatic hydrocarbon group which may have a substituent. B c- represents a c-valent anion. R 1 to R 3 each independently represent a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group, and R 1 and R 2 combine to form a ring structure May be.
A represents an aromatic group which may have a substituent or a heterocyclic group which may have a substituent.
A plurality of R 1 to R 3 and A may be the same or different. a represents an integer of 2 or more, and b, c, and d represent an integer of 1 or more. Y each independently represents a hydrogen atom or an arbitrary substituent. )
　本発明の一般式（Ｉ）の化合物は、水不溶性の色材でありトリアリールメタンカチオン部分とアニオンからなる。 The compound of the general formula (I) of the present invention is a water-insoluble colorant and comprises a triarylmethane cation moiety and an anion.
　一般式（Ｉ）において、Ｒ１～Ｒ３は同一であっても異なるものであってもよい。従って、－ＮＲ１Ｒ２基は左右対称であっても、左右非対称であってもよい。　 In the general formula (I), R 1 to R 3 may be the same or different. Accordingly, the —NR 1 R 2 group may be left-right symmetric or left-right asymmetric.
　隣接するＲ１とＲ２が結合して環を形成する場合、これらはヘテロ原子で架橋された環であってもよい。この環の具体例として、例えば以下のものが挙げられる。これらの環は置換基を有していてもよい。 When adjacent R 1 and R 2 are combined to form a ring, these may be a ring bridged with a heteroatom. Specific examples of this ring include the following. These rings may have a substituent.
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
　また、Ｒ１～Ｒ３は、化学的安定性の点から、各々独立に、水素原子、置換基を有していてもよいアルキル基、又は置換基を有していてもよいアリール基であることが好ましい。　 R 1 to R 3 are each independently a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent from the viewpoint of chemical stability. It is preferable.
　Ｙは、各々独立に、水素原子、または任意の置換基であることが好ましい。 It is preferable that each Y is independently a hydrogen atom or an arbitrary substituent.
　中でも、Ｒ１～Ｒ３は、各々独立に水素原子；メチル基、エチル基、プロピル基、イソプロピル基、シクロプロピル基、ブチル基、イソブチル基、ｓｅｃ‐ブチル基、ｔｅｒｔ‐ブチル基、ペンチル基、シクロペンチル基、ヘキシル基、シクロヘキシル基、ヘプチル基、オクチル基、２‐エチルヘキシル基、ノニル基、デシル基等のアルキル基；フェニル基、ナフチル基、チエニル基、フリル基、チアゾリル基等のアリール基のいずれかであることがより好ましい。　 Among them, R 1 to R 3 are each independently a hydrogen atom; methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, Alkyl groups such as cyclopentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group and decyl group; any of aryl groups such as phenyl group, naphthyl group, thienyl group, furyl group and thiazolyl group More preferably.
　Ｒ１～Ｒ３およびＹは、アルキル基又はアリール基を示す場合、該アルキル基又はアリール基は更に任意の置換基を有していてもよい。そのアルキル基又はアリール基が更に有していてもよい任意の置換基としては、例えば、下記［置換基群Ｒ］が挙げられる。 When R 1 to R 3 and Y represent an alkyl group or an aryl group, the alkyl group or aryl group may further have an arbitrary substituent. Examples of the optional substituent that the alkyl group or aryl group may further have include the following [Substituent group R].
　［置換基群Ｒ］
メチル基、エチル基、プロピル基、イソプロピル基、シクロプロピル基、ブチル基、イソブチル基、ｓｅｃ‐ブチル基、ｔｅｒｔ‐ブチル基、ペンチル基、シクロペンチル基、ヘキシル基、シクロヘキシル基、ヘプチル基、オクチル基、２‐エチルヘキシル基、ノニル基、デシル基等のアルキル基；フェニル基、ナフチル基、チエニル基、フリル基、チアゾリル基等のアリール基；フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子；シアノ基；水酸基；メトキシ基、エトキシ基、プロポキシ基、ブトキシ基など炭素原子数１～８のアルコキシ基；クロロメチル基、トリフルオロメチル基等のハロアルキル基；アミノ基、ジエチルアミノ基、ジブチルアミノ基、アセチルアミノ基など置換基を有していてもよいアミノ基；アセチル基、ベンゾイル基等のアシル基；アセチルオキシ基、ベンゾイルオキシ基等のアシルオキシ基；等が挙げられる。 [Substituent group R]
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, cyclohexyl group, heptyl group, octyl group, Alkyl groups such as 2-ethylhexyl group, nonyl group, decyl group; aryl groups such as phenyl group, naphthyl group, thienyl group, furyl group, thiazolyl group; halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; Cyano group; hydroxyl group; alkoxy group having 1 to 8 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group; haloalkyl group such as chloromethyl group and trifluoromethyl group; amino group, diethylamino group, dibutylamino group, An amino group which may have a substituent such as an acetylamino group; Acetyloxy group, an acyloxy group such as a benzoyloxy group; group, an acyl group such as benzoyl group and the like.
　Ｒ１～Ｒ３としては、置換基を有していてもよい炭素原子数１～８のアルキル基が更に好ましく、より具体的には、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｓｅｃ‐ブチル基、ペンチル基、ヘキシル基、２‐エチルヘキシル基など無置換のアルキル基；２‐メトキシエチル基、２‐エトキシエチル基等のアルコキシアルキル基；２‐アセチルオキシエチル基等のアシルオキシ基；２‐シアノエチル基等のシアノアルキル基；２，２，２‐トリフルオロエチル基、４，４，４‐トリフルオロブチル基等のフルオロアルキル基、などが挙げられる。 R 1 to R 3 are more preferably an alkyl group having 1 to 8 carbon atoms which may have a substituent, and more specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group. , Isobutyl group, sec-butyl group, pentyl group, hexyl group, 2-ethylhexyl group and other unsubstituted alkyl groups; 2-methoxyethyl group, 2-ethoxyethyl group and other alkoxyalkyl groups; 2-acetyloxyethyl group, etc. Cyanoalkyl groups such as 2-cyanoethyl group; fluoroalkyl groups such as 2,2,2-trifluoroethyl group, 4,4,4-trifluorobutyl group, and the like.
　又、Ｙとしては、本発明の効果を損なわない限り、各々独立に任意の基であってもよいが、例えば、水素原子、メチル基、エチル基、プロピル基、イソプロピル基、シクロプロピル基、ブチル基、イソブチル基、ｓｅｃ‐ブチル基、ｔｅｒｔ‐ブチル基、ペンチル基、シクロペンチル基、ヘキシル基、シクロヘキシル基、ヘプチル基、オクチル基、２‐エチルヘキシル基など炭素原子数１～８のアルキル基；メトキシ基、エトキシ基、プロポキシ基、ブトキシ基など炭素原子数１～８のアルコキシ基；フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子；フェニル基、ナフチル基、チエニル基、フリル基、チアゾリル基等のアリール基；シアノ基等が挙げられる。 Y may be any group independently as long as the effects of the present invention are not impaired. For example, a hydrogen atom, methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl may be used. Group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group and other alkyl groups having 1 to 8 carbon atoms; methoxy group Alkoxy group having 1 to 8 carbon atoms such as ethoxy group, propoxy group, butoxy group; halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom; phenyl group, naphthyl group, thienyl group, furyl group, thiazolyl group An aryl group such as cyano group;
　又、上記アルキル基、アルコキシ基及びアリール基には、更に他の任意置換基を有していてもよい。上記アルキル基、アルコキシ基及びアリール基が更に有していてもよい任意の置換基としては、例えば、前記［置換基群Ｒ］の項で記載したものが挙げられる。尚、隣接するＹが結合して更に環構造を形成していてもよい。本発明におけるＹは、色純度が高い点で、水素原子であることが最も好ましい。 In addition, the alkyl group, alkoxy group and aryl group may further have other optional substituents. As an arbitrary substituent which the said alkyl group, an alkoxy group, and an aryl group may have further, what was described by the term of the said [substituent group R] is mentioned, for example. In addition, adjacent Y may combine to form a ring structure. Y in the present invention is most preferably a hydrogen atom in terms of high color purity.
Ａにおける芳香族基や複素環基は特に限定されない。芳香族基における芳香族としては、ベンゼン環の他、ナフタレン環、テトラリン環、インデン環、フルオレン環、アントラセン環、フェナントレン環等の縮合多環芳香族炭化水素；ビフェニル、ターフェニル、ジフェニルメタン、トリフェニルメタン、スチルベン等の鎖状多環式炭化水素が挙げられる。当該鎖状多環式炭化水素においては、ジフェニルエーテル等のように鎖状骨格中にＯ、Ｓ等のヘテロ原子を有していてもよい。一方、複素環基における複素環としては、フラン、チオフェン、ピロール、オキサゾール、チアゾール、イミダゾール、ピラゾール等の５員複素環；ピラン、ピロン、ピリジン、ピリダジン、ピリミジン、ピラジン等の６員複素環；ベンゾフラン、チオナフテン、インドール、カルバゾール、クマリン、ベンゾ－ピロン、キノリン、イソキノリン、アクリジン、フタラジン、キナゾリン、キノキサリン等の縮合多環式複素環が挙げられる。これらの芳香族基や複素環基は置換基を有していてもよい。該置換基としては、例えば、前記［置換基群Ｒ］の項に記載のものが挙げられる。 The aromatic group and heterocyclic group in A are not particularly limited. As aromatics in the aromatic group, in addition to benzene ring, condensed polycyclic aromatic hydrocarbons such as naphthalene ring, tetralin ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring; biphenyl, terphenyl, diphenylmethane, triphenyl Examples thereof include chain polycyclic hydrocarbons such as methane and stilbene. The chain polycyclic hydrocarbon may have a heteroatom such as O or S in the chain skeleton such as diphenyl ether. On the other hand, examples of the heterocyclic ring in the heterocyclic group include 5-membered heterocycles such as furan, thiophene, pyrrole, oxazole, thiazole, imidazole, and pyrazole; 6-membered heterocycles such as pyran, pyrone, pyridine, pyridazine, pyrimidine, and pyrazine; And condensed polycyclic heterocycles such as thionaphthene, indole, carbazole, coumarin, benzo-pyrone, quinoline, isoquinoline, acridine, phthalazine, quinazoline, quinoxaline and the like. These aromatic groups and heterocyclic groups may have a substituent. Examples of the substituent include those described in the above section [Substituent group R].
中でも、耐熱性の点から、Ａにおける芳香族基や複素環基としては、下記一般式（ＩＶ）、下記一般式（Ｖ）又は下記一般式（ＶＩ）で表される基が好ましい。 Especially, the group represented by the following general formula (IV), the following general formula (V), or the following general formula (VI) is preferable as the aromatic group or heterocyclic group in A from the viewpoint of heat resistance.
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
（一般式（ＩＶ）中、Ｒ１１とＲ１２は各々独立に水素原子、置換基を有していてもよいアルキル基又は置換基を有していてもよいアリール基を表し、Ｒ１１とＲ１２が結合して環構造を形成してもよい。Ｅ１は各々独立に、水素原子、または任意の置換基を示す。＊は炭素原子との結合手を表す。） (In the general formula (IV), R 11 and R 12 each independently represent a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent, and R 11 and R 12 12 may combine to form a ring structure, each E 1 independently represents a hydrogen atom or an arbitrary substituent, and * represents a bond to a carbon atom.)
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
（一般式（Ｖ）中、Ｒ１３とＲ１４は各々独立に水素原子、置換基を有していてもよいアルキル基又は置換基を有していてもよいアリール基を表し、Ｒ１３とＲ１４が結合して環構造を形成してもよい。Ｅ２は各々独立に、水素原子、または任意の置換基を示す。＊は炭素原子との結合手を表す。） (In the general formula (V), R 13 and R 14 each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and R 13 and R 14 14 may combine to form a ring structure, each E 2 independently represents a hydrogen atom or an arbitrary substituent, and * represents a bond to a carbon atom.)
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
（一般式（ＶＩ）中、Ｒ１５は水素原子、炭素数１～２０のアルキル基、または置換基を有していてもよいアリール基を表す。Ｘは、酸素原子、窒素原子または硫黄原子を示す。Ｒ１６とＲ１７は各々独立に水素原子、置換基を有していてもよいアルキル基又は置換基を有していてもよいアリール基を表し、Ｒ１６とＲ１７が結合して環構造を形成してもよい。＊は炭素原子との結合手を表す。） (In the general formula (VI), R 15 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group which may have a substituent. X represents an oxygen atom, a nitrogen atom or a sulfur atom. R 16 and R 17 each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and R 16 and R 17 are bonded to form a ring; (A structure may be formed. * Represents a bond with a carbon atom.)
＜一般式（ＩＶ）について＞
一般式（ＩＶ）において、Ｒ１１とＲ１２は同一であっても異なるものであってもよい。従って、－ＮＲ１１Ｒ１２基は左右対称であっても、左右非対称であってもよい。　 <About general formula (IV)>
In the general formula (IV), R 11 and R 12 may be the same or different. Accordingly, the —NR 11 R 12 group may be left-right symmetric or left-right asymmetric.
隣接するＲ１１とＲ１２が結合して環を形成する場合、これらはヘテロ原子で架橋された環であってもよい。これらの環は置換基を有していてもよい。 When adjacent R 11 and R 12 are bonded to form a ring, these may be a ring bridged with a heteroatom. These rings may have a substituent.
また、Ｒ１１とＲ１２は、化学的安定性の点から、各々独立に、水素原子、置換基を有していてもよいアルキル基、又は置換基を有していてもよいアリール基であることが好ましい。　中でも、Ｒ１１とＲ１２は、各々独立に水素原子；メチル基、エチル基、プロピル基、イソプロピル基、シクロプロピル基、ブチル基、イソブチル基、ｓｅｃ‐ブチル基、ｔｅｒｔ‐ブチル基、ペンチル基、シクロペンチル基、ヘキシル基、シクロヘキシル基、ヘプチル基、オクチル基、２‐エチルヘキシル基、ノニル基、デシル基等のアルキル基；フェニル基、ナフチル基、チエニル基、フリル基、チアゾリル基等のアリール基のいずれかであることがより好ましい。 R 11 and R 12 are each independently a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent from the viewpoint of chemical stability. It is preferable. Among them, R 11 and R 12 are each independently a hydrogen atom; methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, Alkyl groups such as cyclopentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group and decyl group; any of aryl groups such as phenyl group, naphthyl group, thienyl group, furyl group and thiazolyl group More preferably.
Ｒ１１とＲ１２は、アルキル基又はアリール基を示す場合、該アルキル基又はアリール基は更に任意の置換基を有していてもよい。そのアルキル基又はアリール基が更に有していてもよい任意の置換基としては、例えば、前記［置換基群Ｒ］の項で記載したものが挙げられる。 When R 11 and R 12 represent an alkyl group or an aryl group, the alkyl group or aryl group may further have an optional substituent. Examples of the optional substituent that the alkyl group or aryl group may further have include those described in the above-mentioned [Substituent group R] section.
Ｒ１１とＲ１２としては、各々独立に水素原子や置換基を有していてもよい炭素原子数１～８のアルキル基が更に好ましく、より具体的には、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｓｅｃ‐ブチル基、ペンチル基、ヘキシル基、２‐エチルヘキシル基など無置換のアルキル基；２‐メトキシエチル基、２‐エトキシエチル基等のアルコキシアルキル基；２‐アセチルオキシエチル基等のアシルオキシ基；２‐シアノエチル基等のシアノアルキル基；２，２，２‐トリフルオロエチル基、４，４，４‐トリフルオロブチル基等のフルオロアルキル基、などが挙げられる。 R 11 and R 12 are each more preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms which may have a substituent, and more specifically, a methyl group, an ethyl group, or a propyl group. , An isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a pentyl group, a hexyl group, a 2-ethylhexyl group, an unsubstituted alkyl group; a 2-methoxyethyl group, a 2-ethoxyethyl group, and the like; 2 Acyloxy groups such as -acetyloxyethyl group; cyanoalkyl groups such as 2-cyanoethyl group; fluoroalkyl groups such as 2,2,2-trifluoroethyl group, 4,4,4-trifluorobutyl group, etc. It is done.
又、Ｅ１としては、本発明の効果を損なわない限り、各々独立に任意の基であってもよいが、例えば、水素原子、メチル基、エチル基、プロピル基、イソプロピル基、シクロプロピル基、ブチル基、イソブチル基、ｓｅｃ‐ブチル基、ｔｅｒｔ‐ブチル基、ペンチル基、シクロペンチル基、ヘキシル基、シクロヘキシル基、ヘプチル基、オクチル基、２‐エチルヘキシル基など炭素原子数１～８のアルキル基；メトキシ基、エトキシ基、プロポキシ基、ブトキシ基など炭素原子数１～８のアルコキシ基；フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子；フェニル基、ナフチル基、チエニル基、フリル基、チアゾリル基等のアリール基；シアノ基等が挙げられる。 E 1 may be any group independently as long as the effects of the present invention are not impaired. For example, a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, Alkyl groups having 1 to 8 carbon atoms such as butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group and 2-ethylhexyl group; Group, ethoxy group, propoxy group, butoxy group, etc., alkoxy group having 1 to 8 carbon atoms; halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom; phenyl group, naphthyl group, thienyl group, furyl group, thiazolyl An aryl group such as a group; and a cyano group.
又、上記アルキル基、アルコキシ基及びアリール基には、更に他の任意置換基を有していてもよい。上記アルキル基、アルコキシ基及びアリール基が更に有していてもよい任意の置換基としては、例えば、前記［置換基群Ｒ］の項で記載したものが挙げられる。尚、隣接するＥ１が結合して更に環構造を形成していてもよい。本発明におけるＥ１は、色純度が高い点で、水素原子であることが最も好ましい。 The alkyl group, alkoxy group and aryl group may further have other optional substituents. As an arbitrary substituent which the said alkyl group, an alkoxy group, and an aryl group may have further, what was described by the term of the said [substituent group R] is mentioned, for example. In addition, adjacent E 1 may be bonded to form a ring structure. E 1 in the present invention is most preferably a hydrogen atom in terms of high color purity.
＜一般式（Ｖ）について＞
一般式（Ｖ）においてＲ１３とＲ１４は、各々独立に、水素原子、置換基を有していてもよいアルキル基、又は置換基を有していてもよいアリール基を示す。Ｒ１３とＲ１４におけるアルキル基としては、直鎖状、分岐鎖状又は環状のアルキル基であって、その炭素数が通常１以上、また、通常８以下、好ましくは５以下のものが挙げられる。具体例としては、メチル基、エチル基、ｎ－プロピル基、２－プロピル基、ｎ－ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、シクロヘキシル基等が挙げられる。 <About general formula (V)>
In the general formula (V), R 13 and R 14 each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. Examples of the alkyl group in R 13 and R 14 include linear, branched or cyclic alkyl groups, and the number of carbon atoms is usually 1 or more, and usually 8 or less, preferably 5 or less. . Specific examples include methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group, isobutyl group, tert-butyl group, cyclohexyl group and the like.
Ｒ１３とＲ１４におけるアリール基としては、芳香族炭化水素環基及び芳香族複素環基が挙げられる。 Examples of the aryl group in R 13 and R 14 include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
　芳香族炭化水素環基としては、単環であっても縮合環であってもよく、環を形成する炭素数が５～１８であれば特に制限はないが、例えば、１個の遊離原子価を有する、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、ペリレン環、テトラセン環、ピレン環、ベンズピレン環、クリセン環、トリフェニレン環、アセナフテン環、フルオランテン環、フルオレン環などの基が挙げられる。 The aromatic hydrocarbon ring group may be a single ring or a condensed ring, and is not particularly limited as long as it has 5 to 18 carbon atoms to form the ring. Benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring and the like.
また、芳香族複素環基としては、単環であっても縮合環であってもよく、環を形成する炭素数が３～１０であれば特に制限はないが、例えば、１個の遊離原子価を有する、フラン環、ベンゾフラン環、チオフェン環、ベンゾチオフェン環、ピロール環、ピラゾール環、イミダゾール環、オキサジアゾール環、インドール環、カルバゾール環、ピロロイミダゾール環、ピロロピラゾール環、ピロロピロール環、チエノピロール環、チエノチオフェン環、フロピロール環、フロフラン環、チエノフラン環、ベンゾイソオキサゾール環、ベンゾイソチアゾール環、ベンゾイミダゾール環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、イソキノリン環、シノリン環、キノキサリン環、フェナントリジン環、ベンゾイミダゾール環、ペリミジン環、キナゾリン環、キナゾリノン環、アズレン環などの基が挙げられる。 The aromatic heterocyclic group may be a monocyclic ring or a condensed ring, and is not particularly limited as long as the number of carbon atoms forming the ring is 3 to 10. For example, one free atom Having a valence, furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole Ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, Synoline ring, quinoxaline ring, phenanthridine ring, Zone imidazole ring, perimidine ring, a quinazoline ring, a quinazolinone ring, groups such as azulene ring.
隣接するＲ１３とＲ１４が結合して環を形成する場合、これらはヘテロ原子で架橋された環であってもよい。これらの環は置換基を有していてもよい。 When adjacent R 13 and R 14 are combined to form a ring, these may be a ring bridged with a heteroatom. These rings may have a substituent.
化学的安定性の点からＲ１３及びＲ１４として好ましくは、各々独立に、水素原子、置換基を有していてもよい炭素数１～８のアルキル基又は置換基を有していてもよいフェニル基である。 From the viewpoint of chemical stability, R 13 and R 14 are preferably each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or an optionally substituted group. It is a phenyl group.
Ｒ１３及びＲ１４におけるアルキル基、アリール基及び互いに連結して形成される環が有していてもよい置換基としては、例えば、下記[置換基群Ｑ]のものが挙げられる。 Examples of the substituent that the alkyl group, aryl group, and ring formed by connecting to each other in R 13 and R 14 may have include the following [Substituent group Q].
[置換基群Ｑ]
フッ素原子、塩素原子、炭素数１～８のアルキル基、炭素数２～８のアルケニル基、炭素数１～８のアルコキシル基、フェニル基、メシチル基、トリル基、ナフチル基、シアノ基、アセチルオキシ基、炭素数２～９のアルキルカルボニルオキシ基、スルホン酸アミド基、炭素数２～９のスルホンアルキルアミド基、炭素数２～９のアルキルカルボニル基、
フェネチル基、ヒドロキシエチル基、アセチルアミド基、炭素数１～４のアルキル基が結
合してなるジアルキルアミノエチル基、トリフルオロメチル基、炭素数１～８のトリアル
キルシリル基、ニトロ基、炭素数１～８のアルキルチオ基。 [Substituent group Q]
Fluorine atom, chlorine atom, alkyl group having 1 to 8 carbon atoms, alkenyl group having 2 to 8 carbon atoms, alkoxyl group having 1 to 8 carbon atoms, phenyl group, mesityl group, tolyl group, naphthyl group, cyano group, acetyloxy Groups, alkylcarbonyloxy groups having 2 to 9 carbon atoms, sulfonic acid amide groups, sulfonealkylamide groups having 2 to 9 carbon atoms, alkylcarbonyl groups having 2 to 9 carbon atoms,
Phenethyl group, hydroxyethyl group, acetylamide group, dialkylaminoethyl group formed by bonding an alkyl group having 1 to 4 carbon atoms, trifluoromethyl group, trialkylsilyl group having 1 to 8 carbon atoms, nitro group, carbon number 1 to 8 alkylthio groups.
中でも、Ｒ１３及びＲ１４におけるアルキル基、アリール基及び互いに連結して形成される環が有していてもよい置換基として、好ましくは炭素数１～８のアルキル基、炭素数２～８のアルコキシル基、シアノ基、アセチルオキシ基、炭素数２～８のアルキルカルボキシル基、スルホン酸アミド基、炭素数２～８のスルホンアルキルアミド基及びフッ素原子である。 Among them, as the substituent that the alkyl group, aryl group, and ring formed by connecting to each other in R 13 and R 14 may have, preferably an alkyl group having 1 to 8 carbon atoms, or 2 to 8 carbon atoms. An alkoxyl group, a cyano group, an acetyloxy group, an alkyl carboxyl group having 2 to 8 carbon atoms, a sulfonic acid amide group, a sulfone alkylamide group having 2 to 8 carbon atoms, and a fluorine atom.
又、Ｅ２としては、本発明の効果を損なわない限り、各々独立に任意の基であってもよいが、例えば、水素原子、メチル基、エチル基、プロピル基、イソプロピル基、シクロプロピル基、ブチル基、イソブチル基、ｓｅｃ‐ブチル基、ｔｅｒｔ‐ブチル基、ペンチル基、シクロペンチル基、ヘキシル基、シクロヘキシル基、ヘプチル基、オクチル基、２‐エチルヘキシル基など炭素原子数１～８のアルキル基；メトキシ基、エトキシ基、プロポキシ基、ブトキシ基など炭素原子数１～８のアルコキシ基；フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子；フェニル基、ナフチル基、チエニル基、フリル基、チアゾリル基等のアリール基；シアノ基等が挙げられる。 E 2 may be any group independently as long as the effects of the present invention are not impaired. For example, a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, Alkyl groups having 1 to 8 carbon atoms such as butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group and 2-ethylhexyl group; Group, ethoxy group, propoxy group, butoxy group, etc., alkoxy group having 1 to 8 carbon atoms; halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom; phenyl group, naphthyl group, thienyl group, furyl group, thiazolyl An aryl group such as a group; and a cyano group.
又、上記アルキル基、アルコキシ基及びアリール基には、更に他の任意置換基を有していてもよい。上記アルキル基、アルコキシ基及びアリール基が更に有していてもよい任意の置換基としては、例えば、前記［置換基群Ｒ］の項で記載したものが挙げられる。尚、隣接するＥ２が結合して更に環構造を形成していてもよい。本発明におけるＥ２は、色純度が高い点で、水素原子であることが最も好ましい。 The alkyl group, alkoxy group and aryl group may further have other optional substituents. As an arbitrary substituent which the said alkyl group, an alkoxy group, and an aryl group may have further, what was described by the term of the said [substituent group R] is mentioned, for example. Further, adjacent E 2 may be bonded to form a ring structure. E 2 in the present invention is most preferably a hydrogen atom in terms of high color purity.
＜一般式（ＶＩ）について＞
一般式（ＶＩ）におけるＲ１５で表される、炭素数１～２０のアルキル基としては、メチル基、エチル基、ｎ－プロピル基、ｎ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基等の直鎖状アルキル基；イソプロピル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、イソペンチル基、１－メチルペンチル基、２－メチルペンチル基、１－エチルブチル基、２－エチルブチル基、１－メチルヘキシル基、２－メチルヘキシル基、３－メチルヘキシル基、４－メチルヘキシル基、１－エチルペンチル基、２－エチルペンチル基、３－エチルペンチル基、１－プロピルブチル基、１－（１－メチルエチル）ブチル基等の分枝鎖状のアルキル基；シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、アダマンチル基等の環状アルキル基が挙げられ、なかでも、炭素数１～８のアルキル基が好ましく、炭素数１～６のアルキル基がより好ましく、炭素数１～４のアルキル基がさらに好ましい。 <About general formula (VI)>
Examples of the alkyl group having 1 to 20 carbon atoms represented by R 15 in the general formula (VI) include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, linear alkyl groups such as n-heptyl group and n-octyl group; isopropyl group, sec-butyl group, tert-butyl group, isopentyl group, 1-methylpentyl group, 2-methylpentyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1-methylhexyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 1-ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group, 1-propyl A branched alkyl group such as butyl group and 1- (1-methylethyl) butyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group And a cyclic alkyl group such as an adamantyl group. Among them, an alkyl group having 1 to 8 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable.
一般式（ＶＩ）におけるＲ１５で表されるアリール基としては、フェニル基、ナフチル基、ベンジル基等の炭素数６～１４のアリール基が挙げられる。
一般式（ＶＩ）におけるＲ１５で表される置換基を有していてもよいアリール基における、置換基としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子；メチル基、エチル基等の炭素数１～６のアルキル基；クロロメチル基、トリフルオロメチル基等の炭素数１～６のハロアルキル基；メトキシ基、エトキシ基等の炭素数１～６のアルコキシ基；ヒドロキシ基；スルファモイル基；メチルスルホニル基等の炭素数１～６のアルキルスルホニル基等；－ＳＯ３－が挙げられる。 Examples of the aryl group represented by R 15 in the general formula (VI) include aryl groups having 6 to 14 carbon atoms such as a phenyl group, a naphthyl group, and a benzyl group.
In the aryl group which may have a substituent represented by R 15 in the general formula (VI), examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; methyl group, ethyl An alkyl group having 1 to 6 carbon atoms such as a group; a haloalkyl group having 1 to 6 carbon atoms such as a chloromethyl group and a trifluoromethyl group; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group; a hydroxy group; A sulfamoyl group; an alkylsulfonyl group having 1 to 6 carbon atoms such as a methylsulfonyl group; and —SO 3- .
一般式（ＶＩ）において、Ｘは、酸素原子、窒素原子または硫黄原子を示す。合成の容易さの観点から、好ましくは硫黄原子である。 In general formula (VI), X represents an oxygen atom, a nitrogen atom or a sulfur atom. From the viewpoint of ease of synthesis, a sulfur atom is preferred.
一般式（ＶＩ）において、Ｒ１６とＲ１７は同一であっても異なるものであってもよい。従って、－ＮＲ１６Ｒ１７基は左右対称であっても、左右非対称であってもよい。　 In the general formula (VI), R 16 and R 17 may be the same or different. Accordingly, the —NR 16 R 17 group may be left-right symmetric or left-right asymmetric.
隣接するＲ１６とＲ１７が結合して環を形成する場合、これらはヘテロ原子で架橋された環であってもよい。これらの環は置換基を有していてもよい。 When adjacent R 16 and R 17 are combined to form a ring, these may be a ring bridged with a heteroatom. These rings may have a substituent.
また、Ｒ１６とＲ１７は、化学的安定性の点から、各々独立に、水素原子、置換基を有していてもよいアルキル基、又は置換基を有していてもよいアリール基であることが好ましい。中でも、Ｒ１６とＲ１７は、各々独立に水素原子；メチル基、エチル基、プロピル基、イソプロピル基、シクロプロピル基、ブチル基、イソブチル基、ｓｅｃ‐ブチル基、ｔｅｒｔ‐ブチル基、ペンチル基、シクロペンチル基、ヘキシル基、シクロヘキシル基、ヘプチル基、オクチル基、２‐エチルヘキシル基、ノニル基、デシル基等のアルキル基；フェニル基、ナフチル基、チエニル基、フリル基、チアゾリル基等のアリール基のいずれかであることがより好ましい。 R 16 and R 17 are each independently a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent from the viewpoint of chemical stability. It is preferable. Among them, R 16 and R 17 are each independently a hydrogen atom; methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, Alkyl groups such as cyclopentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group and decyl group; any of aryl groups such as phenyl group, naphthyl group, thienyl group, furyl group and thiazolyl group More preferably.
Ｒ１６とＲ１７は、アルキル基又はアリール基を示す場合、該アルキル基又はアリール基は更に任意の置換基を有していてもよい。そのアルキル基又はアリール基が更に有していてもよい任意の置換基としては、例えば、前記［置換基群Ｒ］の項で記載したものが挙げられる。 When R 16 and R 17 represent an alkyl group or an aryl group, the alkyl group or aryl group may further have an optional substituent. Examples of the optional substituent that the alkyl group or aryl group may further have include those described in the above-mentioned [Substituent group R] section.
一般式（ＶＩ）で表される基としては、下記式で表される基であることが好ましい。＊は炭素原子との結合手を表す。 The group represented by the general formula (VI) is preferably a group represented by the following formula. * Represents a bond with a carbon atom.
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
前記一般式（Ｉ）におけるＺは、置換基を有していてもよいａ価の、脂肪族系又は芳香族系の炭化水素基である。脂肪族系の炭化水素基は、直鎖、分岐又は環状のいずれであってもよく、不飽和結合を有していてもよく、置換基を有していてもよく、炭素鎖中に、Ｏ、Ｓ、Ｎが含まれていてもよい。例えば、カルボニル基、カルボキシ基、オキシカルボニル基、アミド基等が含まれていてもよく、水素原子が更にハロゲン原子等に置換されていてもよい。芳香族系の炭化水素基は、単環又は多環芳香族基が挙げられ、置換基を有していてもよく、Ｏ、Ｓ、Ｎが含まれる複素環であってもよい。例えば、ベンゼン環の他、ナフタレン環、テトラリン環、インデン環、フルオレン環、アントラセン環、フェナントレン環等の縮合多環芳香族炭化水素；ビフェニル、ターフェニル等の鎖状多環式芳香族炭化水素；フラン、チオフェン、ピロール、オキサゾール、チアゾール、イミダゾール、ピラゾール等の５員複素環；ピラン、ピロン、ピリジン、ピロン、ピリダジン、ピリミジン、ピラジン等の６員複素環；ベンゾフラン、チオナフテン、インドール、カルバゾール、クマリン、ベンゾ－ピロン、キノリン、イソキノリン、アクリジン、フタラジン、キナゾリン、キノキサリン等の縮合多環式複素環を含む基が挙げられる。 Z in the general formula (I) is an a-valent aliphatic or aromatic hydrocarbon group which may have a substituent. The aliphatic hydrocarbon group may be linear, branched or cyclic, may have an unsaturated bond, may have a substituent, and has an O in the carbon chain. , S, N may be included. For example, a carbonyl group, a carboxy group, an oxycarbonyl group, an amide group or the like may be contained, and a hydrogen atom may be further substituted with a halogen atom or the like. The aromatic hydrocarbon group includes a monocyclic or polycyclic aromatic group, may have a substituent, and may be a heterocyclic ring containing O, S, and N. For example, in addition to a benzene ring, condensed polycyclic aromatic hydrocarbons such as naphthalene ring, tetralin ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring; chain polycyclic aromatic hydrocarbons such as biphenyl and terphenyl; 5-membered heterocycles such as furan, thiophene, pyrrole, oxazole, thiazole, imidazole, pyrazole; 6-membered heterocycles such as pyran, pyrone, pyridine, pyrone, pyridazine, pyrimidine, pyrazine; benzofuran, thionaphthene, indole, carbazole, coumarin, And groups containing a condensed polycyclic heterocycle such as benzo-pyrone, quinoline, isoquinoline, acridine, phthalazine, quinazoline, quinoxaline and the like.
中でも、前記一般式（Ｉ）におけるＺは、Ｎ（窒素原子）と直接結合する炭素原子がπ結合を有しないａ価の有機基であって、当該有機基は、少なくともＮと直接結合する末端に飽和脂肪族炭化水素基を有する脂肪族炭化水素基、又は当該脂肪族炭化水素基を有する芳香族基を表し、炭素鎖中にＯ（酸素原子）、Ｓ（硫黄原子）、Ｎ（窒素原子）が含まれていてもよい基であることが好ましい。Ｎと直接結合する炭素原子がπ結合を有しないため、カチオン性の発色部位が有する色調や透過率等の色特性は、連結基Ｚや他の発色部位の影響を受けず、単量体と同様の色を保持することができる。 Among them, Z in the general formula (I) is an a-valent organic group in which a carbon atom directly bonded to N (nitrogen atom) does not have a π bond, and the organic group is at least a terminal directly bonded to N. Represents an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group or an aromatic group having the aliphatic hydrocarbon group, and O (oxygen atom), S (sulfur atom), N (nitrogen atom) in the carbon chain ) Is preferable. Since the carbon atom directly bonded to N does not have a π bond, the color characteristics such as color tone and transmittance of the cationic coloring site are not affected by the linking group Z and other coloring sites, Similar colors can be retained.
Ｚにおいて、少なくともＮと直接結合する末端に飽和脂肪族炭化水素基を有する脂肪族炭化水素基は、Ｎと直接結合する末端の炭素原子がπ結合を有しなければ、直鎖、分岐又は環状のいずれであってもよく、末端以外の炭素原子が不飽和結合を有していてもよく、置換基を有していてもよく、炭素鎖中に、Ｏ、Ｓ、Ｎが含まれていてもよい。例えば、カルボニル基、カルボキシ基、オキシカルボニル基、アミド基等が含まれていてもよく、水素原子が更にハロゲン原子等に置換されていてもよい。 In Z, the aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the terminal directly bonded to N is linear, branched or cyclic unless the terminal carbon atom directly bonded to N has a π bond. The carbon atom other than the terminal may have an unsaturated bond, may have a substituent, and the carbon chain contains O, S, and N. Also good. For example, a carbonyl group, a carboxy group, an oxycarbonyl group, an amide group or the like may be contained, and a hydrogen atom may be further substituted with a halogen atom or the like.
また、Ｚにおいて上記脂肪族炭化水素基を有する芳香族基は、少なくともＮと直接結合する末端に飽和脂肪族炭化水素基を有する脂肪族炭化水素基を有する、単環又は多環芳香族基が挙げられ、置換基を有していてもよく、Ｏ、Ｓ、Ｎが含まれる複素環であってもよい。 The aromatic group having an aliphatic hydrocarbon group in Z is a monocyclic or polycyclic aromatic group having an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the terminal directly bonded to N. And may have a substituent, and may be a heterocyclic ring containing O, S, and N.
中でも、骨格の堅牢性の点から、Ｚは、環状の脂肪族炭化水素基又は芳香族基を含むことが好ましい。 Especially, it is preferable that Z contains a cyclic | annular aliphatic hydrocarbon group or an aromatic group from the point of the robustness of frame | skeleton.
環状の脂肪族炭化水素基としては、中でも、有橋脂環式炭化水素基が、骨格の堅牢性の点から好ましい。有橋脂環式炭化水素基とは、脂肪族環内に橋かけ構造を有し、多環構造を有する多環状脂肪族炭化水素基をいい、例えば、ノルボルナン、ビシクロ［２，２，２］オクタン、アダマンタン等が挙げられる。有橋脂環式炭化水素基の中でも、ノルボルナンが好ましい。また、芳香族基としては、例えば、ベンゼン環、ナフタレン環を含む基が挙げられ、中でも、ベンゼン環を含む基が好ましい。　 Among the cyclic aliphatic hydrocarbon groups, a bridged alicyclic hydrocarbon group is preferable from the viewpoint of skeleton fastness. The bridged alicyclic hydrocarbon group means a polycyclic aliphatic hydrocarbon group having a bridged structure in the aliphatic ring and having a polycyclic structure, for example, norbornane, bicyclo [2,2,2]. Examples include octane and adamantane. Among the bridged alicyclic hydrocarbon groups, norbornane is preferable. Moreover, as an aromatic group, the group containing a benzene ring and a naphthalene ring is mentioned, for example, Among these, the group containing a benzene ring is preferable. *
原料入手の容易さの観点からＺは２価が好ましい。例えば、Ｚが２価の有機基の場合、炭素数１～２０の直鎖、分岐、又は環状のアルキレン基や、キシリレン基等の炭素数１～２０のアルキレン基を２個置換した芳香族基等が挙げられる。 Z is preferably divalent from the viewpoint of easy availability of raw materials. For example, when Z is a divalent organic group, an aromatic group in which two linear, branched, or cyclic alkylene groups having 1 to 20 carbon atoms or two alkylene groups having 1 to 20 carbon atoms such as xylylene groups are substituted. Etc.
Ｚの具体例としては、以下のようなものを挙げることができるが、これらに限定されるものではない。＊は窒素原子との結合手を表す。 Specific examples of Z include the following, but are not limited thereto. * Represents a bond with a nitrogen atom.
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
１分子内に複数あるＲ１～Ｒ３及びＡは、同一であっても異なっていてもよい。複数あるＲ１～Ｒ３及びＡがそれぞれ同一である場合には、発色部位が同一の発色を示すため、発色部位の単体と同様の色が再現でき、色純度の点から好ましい。一方、Ｒ１～Ｒ３及びＡのうち少なくとも１つを異なる置換基とした場合には、複数種の単量体を混合した色を再現することができ、所望の色に調整することができる。 A plurality of R 1 to R 3 and A present in one molecule may be the same or different. In the case where a plurality of R 1 to R 3 and A are the same, the color development site exhibits the same color development, so that the same color as the single color development site can be reproduced, which is preferable from the viewpoint of color purity. On the other hand, when at least one of R 1 to R 3 and A is a different substituent, a color obtained by mixing plural types of monomers can be reproduced and adjusted to a desired color. .
次に、アニオン部分について詳細に説明をする。[Ｂｃ－]は、１価以上のアニオンである。[Ｂｃ－]は１価以上のアニオンであれば特に制限されないが、耐熱性の点から好ましいアニオンは、ヘテロポリオキソメタレートアニオン、下記一般式（ＩＩ）で表せるアニオン、下記一般式（ＩＩＩ）で表せるアニオン、及びスルホン酸アニオンが挙げられる。 Next, the anion portion will be described in detail. [B c- ] is a monovalent or higher anion. [B c- ] is not particularly limited as long as it is a monovalent or higher anion, but preferred anions from the viewpoint of heat resistance are heteropolyoxometalate anions, anions represented by the following general formula (II), and the following general formula (III) And an anion represented by the formula (I) and a sulfonate anion.
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
（一般式（ＩＩ）中、Ｒ６及びＲ７は、各々独立に、置換基を有していてもよい炭素数１～８のアルキル基、置換基を有していてもよい炭素数２～６のアルケニル基、又は置換基を有していてもよい炭素数３～８のシクロアルキル基を表す。尚、Ｒ６及びＲ７は、互いに連結して環を形成していてもよく、該環は置換基を有していてもよい。） (In the general formula (II), R 6 and R 7 are each independently an alkyl group having 1 to 8 carbon atoms which may have a substituent, or 2 to 2 carbon atoms which may have a substituent. 6 represents an alkenyl group having 6 or an optionally substituted cycloalkyl group having 3 to 8 carbon atoms, wherein R 6 and R 7 may be linked to each other to form a ring; The ring may have a substituent.)
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
（一般式（ＩＩＩ）中、Ｒ８～Ｒ１０は、各々独立に、置換基を有していてもよい炭素数１～８のアルキル基、置換基を有していてもよい炭素数２～６のアルケニル基、又は置換基を有していてもよい炭素数３～８のシクロアルキル基を表す。尚、Ｒ８～Ｒ１０は、互いに連結して環を形成していてもよく、該環は置換基を有していてもよい。） (In the general formula (III), R 8 to R 10 are each independently an alkyl group having 1 to 8 carbon atoms which may have a substituent, and 2 to carbon atoms which may have a substituent. 6 represents an alkenyl group having 6 or an optionally substituted cycloalkyl group having 3 to 8 carbon atoms, wherein R 8 to R 10 may be linked to each other to form a ring; The ring may have a substituent.)
本発明では、ヘテロポリ酸アニオンを、ヘテロポリオキソメタレートアニオンという。 In the present invention, the heteropolyacid anion is referred to as a heteropolyoxometalate anion.
ヘテロポリ酸は、有機構造を含まない比較的大きな分子量の無機酸であり、塩酸や硫酸の様な低分子の無機酸や有機酸に無い、特異な性質を発現させることが出来る。その第一は、カチオンのヘテロポリ酸によるレーキ化で水不溶のトリアリールメタン化合物を生成することである。第二は、レーキ化に用いるヘテロポリ酸を選択することで、得られるトリアリールメタン化合物の耐熱性や耐光性を向上させうる余地があることである。ヘテロポリ酸は、有機構造を含ませない或いは金属を含めた上で分子量も比較的大きく出来るが故に、それを適切に選択することで、高温や光線に曝された場合でも、アニオン構造に由来するトリアリールメタン化合物の変質を大きく抑制することが可能となる。 A heteropoly acid is an inorganic acid having a relatively large molecular weight that does not contain an organic structure, and can exhibit unique properties not found in low-molecular inorganic acids or organic acids such as hydrochloric acid and sulfuric acid. The first is to form a water-insoluble triarylmethane compound by rake formation with a cationic heteropolyacid. Second, there is room for improving the heat resistance and light resistance of the resulting triarylmethane compound by selecting a heteropolyacid used for rake formation. Heteropolyacids do not contain organic structures or can contain relatively large molecular weights, including metals, so by selecting them appropriately, they can be derived from anionic structures even when exposed to high temperatures or light. It becomes possible to greatly suppress the alteration of the triarylmethane compound.
　本発明で、より高い耐熱性を有するトリアリールメタン化合物を得たい場合は、例えば、[Ｂｃ－]が、Ｗ（タングステン）、Ｏ（酸素）を必須元素として、Ｐ（リン）とＳｉ（珪素）の少なくとも一種を含有するヘテロポリオキソメタレートアニオンとすることが好ましい。更には、Ｗ（タングステン）、Ｍｏ（モリブデン）、Ｏ（酸素）を必須元素として、Ｐ（リン）とＳｉ（珪素）の少なくとも一種を含有するヘテロポリオキソメタレートアニオンとすることが耐光性を向上させる点でより好ましい。これらの例としては、ケギン型リンタングステン酸イオンα－（ＰＷ１２Ｏ４０）３－、ドーソン型リンタングステン酸イオンα－（Ｐ２Ｗ１８Ｏ６２）６－、β－（Ｐ２Ｗ１８Ｏ６２）６－、ケギン型ケイタングステン酸イオンα－（ＳｉＷ１２Ｏ４０）４－、β－（ＳｉＷ１２Ｏ４０）４－、γ－（ＳｉＷ１２Ｏ４０）４－、さらにその他の例として（Ｐ２Ｗ１７Ｏ６１）１０－、（Ｐ２Ｗ１５Ｏ５６）１２－、（Ｈ２Ｐ２Ｗ１２Ｏ４８）１２－、（ＮａＰ５Ｗ３０Ｏ１１０）１４－、α－（ＳｉＷ９Ｏ３４）１０－、γ－（ＳｉＷ１０Ｏ３６）８－、α－（ＳｉＷ１１Ｏ３９）８－、β－（ＳｉＷ１１Ｏ３９）８－等が挙げられる。 In the present invention, when it is desired to obtain a triarylmethane compound having higher heat resistance, for example, [B c- ] contains P (phosphorus) and Si (with W (tungsten) and O (oxygen) as essential elements. A heteropolyoxometalate anion containing at least one kind of silicon) is preferred. Furthermore, W (tungsten), Mo (molybdenum), O (oxygen) are essential elements, and a heteropolyoxometalate anion containing at least one of P (phosphorus) and Si (silicon) is improved in light resistance. This is more preferable. Examples of these include Keggin 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- , Keggin-type silicotungstate ion α- (SiW 12 O 40 ) 4- , β- (SiW 12 O 40 ) 4- , γ- (SiW 12 O 40 ) 4- , and other examples ( 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.
本発明において、更に高い耐熱性を有するトリアリールメタン化合物は、例えば、[Ｂｃ－]が、（Ｐ２ＭｏｙＷ１８－ｙＯ６２）６－で表され、ｙ＝０，１，２または３の整数であるヘテロポリオキソメタレートアニオンか、（ＳｉＭｏｚＷ１２－ｚＯ４０）４－で表され、ｚ＝０，１，２または３の整数であるヘテロポリオキソメタレートアニオンか、欠損ドーソン型リンタングステン酸ヘテロポリオキソメタレートアニオンから選ばれる少なくとも一種のアニオンのトリアリールメタン化合物である。 In the present invention, a triarylmethane compound having higher heat resistance includes, for example, [B c- ] represented by (P 2 Mo y W 18-y O 62 ) 6- , and y = 0, 1, 2, Or a heteropolyoxometalate anion which is an integer of 3, or a heteropolyoxometalate anion represented by (SiMo z W 12-z O 40 ) 4− and an integer of z = 0, 1, 2 or 3, or a deficiency It is a triarylmethane compound of at least one anion selected from Dawson type phosphotungstic acid heteropolyoxometalate anions.
　尚、欠損ドーソン型リンタングステン酸ヘテロポリオキソメタレートアニオンとは、（Ｐ２Ｗ１７Ｏ６１）１０－である。 The deficient Dawson-type phosphotungstic acid heteropolyoxometalate anion is (P 2 W 17 O 61 ) 10- .
ヘテロポリ酸またはそのアルカリ金属塩としては、例えば、Ｈ６（Ｐ２ＭｏｙＷ１８－ｙＯ６２）、Ｎａ６（Ｐ２ＭｏｙＷ１８－ｙＯ６２）、Ｈ４（ＳｉＭｏＺＷ１２－ＺＯ４０）、Ｎａ４（ＳｉＭｏＺＷ１２－ＺＯ４０）、Ｈ１０（Ｐ２Ｗ１７Ｏ６１）及びＮａ１０（Ｐ２Ｗ１７Ｏ６１）等を用いることが出来る。 Examples of heteropolyacids or alkali metal salts thereof 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 ), Na 10 (P 2 W 17 O 61 ), and the like can be used.
Ｈ６（Ｐ２ＭｏｙＷ１８－ｙＯ６２）といったヘテロポリ酸は、例えば、Ｉｎｏｒｇａｎｉｃ　Ｃｈｅｍｉｓｔｒｙ，　ｖｏｌ４７，　ｐ３６７９に記載された方法に従って、容易に得ることが出来る。具体的には、タングステン酸アルカリ金属塩とモリブデン酸アルカリ金属塩とを水に溶解させ、これに燐酸を加え、加熱攪拌しながら５～１０時間加熱還流することで得ることが出来る。
こうして得られたヘテロポリ酸は、アルカリ金属塩化物と反応させることで、上記と同様にして、ドーソン型ヘテロポリオキソメタレートアルカリ金属塩であるＮａ６（Ｐ２ＭｏｙＷ１８－ｙＯ６２）とすることが出来る。 A heteropolyacid such as H 6 (P 2 Mo y W 18-y O 62 ) can be easily obtained, for example, according to the method described in Inorganic Chemistry, vol 47, p3679. Specifically, it can be obtained by dissolving an alkali metal tungstate and an alkali metal molybdate in water, adding phosphoric acid thereto, and heating to reflux for 5 to 10 hours while stirring with heating.
The heteropolyacid thus obtained is reacted with an alkali metal chloride to form Na 6 (P 2 Mo y W 18-y O 62 ), which is a Dawson type heteropolyoxometalate alkali metal salt, in the same manner as described above. I can do it.
モリブデン（Ｍｏ）とタングステン（Ｗ）の仕込みモル比を変えること、すなわちタングステン酸アルカリ金属塩とモリブデン酸アルカリ金属塩のモル比を調整することで、上記ヘテロポリオキソメタレートアニオンにおけるモリブデン数ｙを、０～３の範囲に調製することが出来る。 By changing the charged molar ratio of molybdenum (Mo) and tungsten (W), that is, by adjusting the molar ratio of alkali metal tungstate and alkali metal molybdate, the number of molybdenum y in the heteropolyoxometalate anion is changed. It can be prepared in the range of 0-3.
別法としては、モリブデン酸アルカリ金属塩を水に溶解させ、これに塩酸を加え、次いで、Ｋ１０（α２型Ｐ２Ｗ１７Ｏ６１）の様な、α２型の欠損ドーソン型リンタングステン酸アルカリ金属塩を加えて、１０～３０℃にて、３０分～２時間攪拌することで得ることが出来る。こうして得られたヘテロポリ酸は、アルカリ金属塩化物と反応させることで、上記と同様にして、ドーソン型ヘテロポリオキソメタレートアルカリ金属塩とすることが出来る。 Alternatively, an alkali metal molybdate salt is dissolved in water, hydrochloric acid is added thereto, and then an α2-type deficient doson-type phosphotungstic alkali such as K 10 (α2-type P 2 W 17 O 61 ) is used. 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 converted to a Dawson type heteropolyoxometalate alkali metal salt in the same manner as described above by reacting with an alkali metal chloride.
例えば、Ｐ２Ｗ１８Ｏ６２より加水分解反応でα２型Ｐ２Ｗ１７Ｏ６１を調製して、これにＭｏを反応させることで、Ｐ２ＭｏＷ１７Ｏ６２のみを得ることも出来る。こうすることで、ｙの数値に分布の無い上記したヘテロポリ酸やそのアルカリ金属塩を得ることが出来る。 For example, only P 2 MoW 17 O 62 can be obtained by preparing α2 type P 2 W 17 O 61 by hydrolysis from P 2 W 18 O 62 and reacting it with Mo. By doing so, it is possible to obtain the above-described heteropolyacid and its alkali metal salt having no distribution in the numerical value of y.
Ｈ４（ＳｉＭｏＷ１１Ｏ４０）といったヘテロポリ酸、ヘテロポリオキソメタレートアルカリ金属塩は、例えばＪｏｕｒｎａｌ　ｏｆ　Ａｍｅｒｉｃａｎ　Ｃｈｅｍｉｃａｌ　Ｓｏｃｉｅｔｙ，　１０４（１９８２），　ｐ３１９４に記載された方法に従って、容易に得ることが出来る。具体的には、硝酸水溶液とモリブデン酸アルカリ金属塩水溶液を混合攪拌し、これにＫ８（α型ＳｉＷ１１Ｏ３９）を加え、２～６時間攪拌することで得ることが出来る。こうして得られたヘテロポリ酸は、アルカリ金属塩化物と反応させることで、上記と同様にして、ケギン型ヘテロポリオキソメタレートアルカリ金属塩とすることが出来る。 A heteropolyacid such as H 4 (SiMoW 11 O 40 ) or a heteropolyoxometalate alkali metal salt can be easily obtained according to the method described in, for example, Journal of American Chemical Society, 104 (1982), p3194. Specifically, it can be obtained by mixing and stirring a nitric acid aqueous solution and an alkali metal molybdate aqueous solution, adding K 8 (α-type SiW 11 O 39 ) thereto, and stirring for 2 to 6 hours. The heteropolyacid thus obtained can be converted to a Keggin heteropolyoxometalate alkali metal salt in the same manner as described above by reacting with an alkali metal chloride.
Ｈ６（Ｐ２Ｗ１８Ｏ６２）やＨ１０（Ｐ２Ｗ１７Ｏ６１）といったヘテロポリ酸は、例えば、Ｉｎｏｒｇａｎｉｃ　Ｃｈｅｍｉｓｔｒｙ，　ｖｏｌ４７，　ｐ３６７９に記載された方法に従って、容易に得ることが出来る。具体的には、タングステン酸アルカリ金属塩を水に溶解させ、これに塩酸及び燐酸を加えて、加熱攪拌しながら１０～５０時間加熱還流することで得ることが出来る。
ヘテロポリ酸は、アルカリ金属塩化物と反応させることで、ドーソン型ヘテロポリオキソメタレートアルカリ金属塩とすることが出来る。 Heteropolyacids such as H 6 (P 2 W 18 O 62 ) and H 10 (P 2 W 17 O 61 ) can be easily obtained according to the method described in, for example, Inorganic Chemistry, vol 47, p3679. Specifically, it can be obtained by dissolving an alkali metal tungstate in water, adding hydrochloric acid and phosphoric acid thereto, and heating to reflux for 10 to 50 hours with heating and stirring.
The heteropolyacid can be converted to a Dawson type heteropolyoxometalate alkali metal salt by reacting with an alkali metal chloride.
欠損ドーソン型ヘテロポリオキソメタレートアルカリ金属塩は、前者のドーソン型リンタングステン酸ヘテロポリオキソメタレートアルカリ金属塩を原料として、例えば、Ｉｎｏｒｇａｎｉｃ　Ｓｙｎｔｈｅｓｉｓ，　ｖｏｌ２７，　ｐ１０４に記載された方法に従って、容易に得ることが出来る。具体的には、ドーソン型リンタングステン酸ヘテロポリオキソメタレートアルカリ金属塩を水に溶解させ、これにアルカリ金属炭酸水素化物を加えて、必要に応じて加熱しながら、攪拌することで得ることが出来る。 The deficient Dawson-type heteropolyoxometalate alkali metal salt can be easily obtained using the former Dawson-type phosphotungstic acid heteropolyoxometalate alkali metal salt as a raw material, for example, according to the method described in Inorganic Synthesis, vol 27, p104. I can do it. Specifically, it can be obtained by dissolving an alkali metal salt of Dawson type phosphotungstic acid heteropolyoxometalate in water, adding an alkali metal hydrogencarbonate to this, and stirring while heating if necessary. .
　前記一般式（ＩＩ）におけるＲ６及びＲ７は、置換基を有していてもよい炭素数１～８のアルキル基、置換基を有していてもよい炭素数２～６のアルケニル基、置換基を有していてもよい炭素数３～８のシクロアルキル基を表す。
該置換基としては、前記［置換基群Ｒ］の項で記載したものが挙げられる。 R 6 and R 7 in the general formula (II) are optionally substituted alkyl groups having 1 to 8 carbon atoms, optionally substituted alkenyl groups having 2 to 6 carbon atoms, Represents a C3-C8 cycloalkyl group which may have a substituent.
Examples of the substituent include those described in the above section [Substituent group R].
　これらの内、特に、Ｒ６及びＲ７におけるアルキル基、アルケニル基又はシクロアルキル基が有する置換基としては、アニオンの電荷がより非局在化して、色材の耐熱性が向上する点で、フッ素原子を置換基として有することが好ましい。　
　つまり、Ｒ６及びＲ７は、アニオンの電荷が分散されて、アニオンが安定化する点で、炭素数１～８のパーフルオロアルキル基が好ましい。
一方、Ｒ６及びＲ７は、互いに連結して環を形成していてもよい。環を形成している場合、Ｒ６及びＲ７が連結して形成される基は、特に炭素数２～１２のフルオロアルキレン基であることが好ましい。 Among these, in particular, as the substituent of the alkyl group, alkenyl group or cycloalkyl group in R 6 and R 7 , the anion charge is more delocalized, and the heat resistance of the coloring material is improved. It preferably has a fluorine atom as a substituent.
That is, R 6 and R 7 are preferably perfluoroalkyl groups having 1 to 8 carbon atoms in that the anion charge is dispersed and the anion is stabilized.
On the other hand, R 6 and R 7 may be connected to each other to form a ring. When forming a ring, the group formed by linking R 6 and R 7 is particularly preferably a fluoroalkylene group having 2 to 12 carbon atoms.
　前記一般式（ＩＩＩ）におけるＲ８～Ｒ１０は、置換基を有していてもよい炭素数１～８のアルキル基、置換基を有していてもよい炭素数２～６のアルケニル基、置換基を有していてもよい炭素数３～８のシクロアルキル基を表す。
該置換基としては、前記［置換基群Ｒ］の項で記載したものが挙げられる。 R 8 to R 10 in the general formula (III) are each an optionally substituted alkyl group having 1 to 8 carbon atoms, an optionally substituted alkenyl group having 2 to 6 carbon atoms, Represents a C3-C8 cycloalkyl group which may have a substituent.
Examples of the substituent include those described in the above section [Substituent group R].
　これらの内、特に、Ｒ８～Ｒ１０におけるアルキル基、アルケニル基又はシクロアルキル基が有する置換基としては、アニオンの電荷がより非局在化して、色材の耐熱性が向上する点で、フッ素原子を置換基として有することが好ましい。　
　つまり、Ｒ８～Ｒ１０は、アニオンの電荷が分散されて、アニオンが安定化する点で、炭素数１～８のパーフルオロアルキル基が好ましい。
一方、Ｒ８～Ｒ１０は、互いに連結して環を形成していてもよい。環を形成している場合、Ｒ８～Ｒ１０が連結して形成される基は、特に炭素数２～１２のフルオロアルキレン基であることが好ましい。 Among these, in particular, as the substituent of the alkyl group, alkenyl group or cycloalkyl group in R 8 to R 10 , the anion charge is more delocalized, and the heat resistance of the coloring material is improved. It preferably has a fluorine atom as a substituent.
That is, R 8 to R 10 are preferably perfluoroalkyl groups having 1 to 8 carbon atoms in that the anion charge is dispersed and the anion is stabilized.
On the other hand, R 8 to R 10 may be connected to each other to form a ring. In the case of forming a ring, the group formed by linking R 8 to R 10 is particularly preferably a fluoroalkylene group having 2 to 12 carbon atoms.
スルホン酸アニオンとしては、例えばトリフルオロメタンスルホン酸、メタンスルホン酸、ペンタンスルホン酸、ヘキサンスルホン酸、ヘプタンスルホン酸、ドデカンスルホン酸、カンファースルホン酸など置換基を有していてもよい脂肪族スルホン酸アニオン；　ベンゼンスルホン酸、ｐ‐トルエンスルホン酸、１‐ナフタレンスルホン酸、２‐ナフタレンスルホン酸、２，６－ナフタレンジスルホン酸、１，３，６－ナフタレントリスルホン酸など置換基を有していてもよい芳香族スルホン酸アニオン；　ａｃｉｄ　ｂｌｕｅ ８０（Ｃ．Ｉ．６１５８５）、ａｃｉｄ　ｇｒｅｅｎ ２５（Ｃ．Ｉ．６１５７０）、ａｃｉｄ　ｂｌｕｅ ４５（Ｃ．Ｉ．６３０１０）、ａｃｉｄ　ｂｌｕｅ ４３（Ｃ．Ｉ．６３０００）、ａｃｉｄ　ｂｌｕｅ ２５（Ｃ．Ｉ．６２０５５）、ａｃｉｄ　ｂｌｕｅ ４０（Ｃ．Ｉ．６５１２５）等のスルホナト基を有するアントラキノン系色素のアニオン；　ｄｉｒｅｃｔ　ｂｌｕｅ ８６（Ｃ．Ｉ．７４８１０）、ｄｉｒｅｃｔ　ｂｌｕｅ １９９ （Ｃ．Ｉ．１４１９０）等のスルホナト基を有するフタロシアニン系色素のアニオン；　ａｃｉｄ ｂｌｕｅ ７４（Ｃ．Ｉ．７３０１５）等のスルホナト基を有するインジゴ系色素のアニオン等が挙げられる。 Examples of the sulfonate anion include aliphatic sulfonate anions which may have a substituent such as trifluoromethanesulfonic acid, methanesulfonic acid, pentanesulfonic acid, hexanesulfonic acid, heptanesulfonic acid, dodecanesulfonic acid, and camphorsulfonic acid. ; Benzenesulfonic acid, p-toluenesulfonic acid, 1-naphthalenesulfonic acid, 2-naphthalenesulfonic acid, 2,6-naphthalenesulfonic acid, 1,3,6-naphthalenetrisulfonic acid, etc. Good aromatic sulfonate anion; acid blueｂ80 (C.I. 61585), acid green 25 (C.I.61570), acid blue 、 45 (C.I.63010), acid blue 43 (C.I.63000) , Acid blue 25 (C.I.62055), anion of anthraquinone dyes having a sulfonate group such as acid blue 40 (C.I. 65125); direct blue 86 (CI.74810), direct blue 199 (C.I. Anions of phthalocyanine dyes having a sulfonate group such as 14190); anions of indigo dyes having a sulfonate group such as acid blue 74 (C.I.73015).
前記一般式（Ｉ）におけるａは、カチオンを構成する発色性カチオン部位の数である。ａは２以上の整数である。ａの上限は特に限定されないが、製造の容易性の点からは、ａが４以下であることが好ましく、３以下であることがより好ましい。 In the general formula (I), a is the number of chromogenic cation sites constituting the cation. a is an integer of 2 or more. The upper limit of a is not particularly limited, but a is preferably 4 or less, and more preferably 3 or less, from the viewpoint of ease of production.
また、前記一般式（Ｉ）におけるｂは分子会合体中のカチオンの分子数を、ｄは分子会合体中のアニオンの分子数を示し、ｂ及びｄは１以上の整数を表す。本発明の色材はその結晶乃至凝集体において、ｂ及びｄがそれぞれ１の場合に限られず、それぞれ２、３、４…と２以上のいかなる自然数をもとり得る。本発明の色材は、耐熱性の点から、少なくとも一部がｂ≧２の分子会合体を形成していることが好ましい。また、本発明の色材は、耐熱性の点から、少なくとも一部がｄ≧２の分子会合体を形成していることが好ましい。 In the general formula (I), b represents the number of cations in the molecular aggregate, d represents the number of anions in the molecular aggregate, and b and d represent an integer of 1 or more. The color material of the present invention is not limited to the case where each of b and d is 1 in the crystal or aggregate, and can take any natural number of 2, 3, 4,. From the viewpoint of heat resistance, it is preferable that at least a part of the coloring material of the present invention forms a molecular aggregate of b ≧ 2. Moreover, it is preferable that at least a part of the coloring material of the present invention forms a molecular aggregate having d ≧ 2 from the viewpoint of heat resistance.
ｂが２以上の場合、分子会合体中に複数あるカチオンは、１種単独であっても、２種以上が組み合わされていてもよい。また、ｄが２以上の場合、分子会合体中に複数あるアニオンは、１種単独であっても、２種以上が組み合わされていてもよい。 When b is 2 or more, a plurality of cations in the molecular aggregate may be one kind alone, or two or more kinds may be combined. Moreover, when d is 2 or more, the anions present in the molecular aggregate may be one kind or a combination of two or more kinds.
　本発明のトリアリールメタン化合物は、例えば、前記した対応するカチオン部の塩化物と、前記した対応するヘテロポリ酸またはヘテロポリオキソメタレートアルカリ金属塩とを反応させることで容易に製造することが出来る。前記した対応するカチオン部の塩化物を用い、かつヘテロポリ酸を用いる場合には、脱塩化水素反応により、また、前記した対応するカチオン部の塩化物を用い、かつヘテロポリオキソメタレートアルカリ金属塩を用いる場合には、脱アルカリ金属塩化物反応により、塩置換することで製造することが出来る。　　 The triarylmethane compound of the present invention can be easily produced, for example, by reacting the corresponding cation moiety chloride with the corresponding heteropolyacid or heteropolyoxometalate alkali metal salt. When the corresponding cation moiety chloride is used and a heteropolyacid is used, the corresponding cation moiety chloride is used by dehydrochlorination, and the heteropolyoxometalate alkali metal salt is When used, it can be produced by salt substitution by dealkalizing metal chloride reaction. *
　前記ヘテロポリ酸を用いる脱塩化水素反応に比べて、ヘテロポリ酸をいったんヘテロポリオキソメタレートアルカリ金属塩としてから脱アルカリ金属塩化物反応を行う方が、塩置換を確実に行うことが出来、より収率高く本発明のトリアリールメタン化合物が得られるばかりでなく、副生成物がより少ない純度の高い本発明のトリアリールメタン化合物が得られるので好ましい。勿論、ヘテロポリオキソメタレートアルカリ金属塩は、再結晶等により精製してから用いることも出来る。　 Compared to the dehydrochlorination reaction using the heteropolyacid, the heteropolyacid is first converted to a heteropolyoxometalate alkali metal salt and then subjected to the dealkali metal chloride reaction, so that the salt substitution can be carried out more reliably, and the yield is improved. This is preferable because not only the triarylmethane compound of the present invention can be obtained at a high level, but also the triarylmethane compound of the present invention can be obtained with less by-products and high purity. Of course, the heteropolyoxometalate alkali metal salt can be used after being purified by recrystallization or the like. *
　反応液からの沈殿が得られ難い場合には、当該反応液を冷却するなどして溶解度を低下させることにより、対応するヘテロポリオキソメタレートアルカリ金属塩をより収率高く得ることが出来る。 If precipitation from the reaction solution is difficult to obtain, the corresponding heteropolyoxometalate alkali metal salt can be obtained in a higher yield by reducing the solubility by cooling the reaction solution.
　本発明のカチオンは、２価以上であることから、アニオン源である、ヘテロポリ酸またはヘテロポリオキソメタレートアルカリ金属塩の使用量は、それらのイオン価に応じて、等モル数となる様に仕込んで上記反応を行うことが好ましい。 Since the cation of the present invention is divalent or more, the amount of the anion source used for the heteropolyacid or heteropolyoxometalate alkali metal salt is charged so as to be an equimolar number depending on the ionic value. It is preferable to carry out the above reaction.
　本発明のトリアリールメタン化合物は、ヘテロポリ酸でレーキ化（水不溶化）する工程を含むので（或いはヘテロポリ酸でレーキ化（水不溶化）されているので）、製造工程中または製造後の何らかの工程で水を用いる場合や、より確実な反応を行ったり、得られた化合物のレーキ構造が破壊されないようにするには、例えば、精製水、イオン交換水、純水等のような、金属イオンやハロゲンイオンの含有率が極力少ない水を用いることが好ましい。 Since the triarylmethane compound of the present invention includes a step of rake (water insolubilization) with a heteropolyacid (or since it is raked (water insolubilization) with a heteropolyacid), it may be performed during or after the production process. In the case of using water, in order to perform a more reliable reaction or to prevent the rake structure of the obtained compound from being destroyed, for example, metal ions or halogens such as purified water, ion-exchanged water, pure water, etc. It is preferable to use water with as little ion content as possible.
　本発明のトリアリールメタン化合物は、水不溶性の色材である。こうして得られた本発明のトリアリールメタン化合物は、そのままで、合成樹脂等の着色剤として用いることが出来るが、必要であれば、公知慣用の粉砕や造粒により、粒子径を調整することで、各種の用途に最適な着色剤とすることが出来る。着色剤は、乾燥粉体において、一次粒子の平均粒子径１００ｎｍ以下であると、より鮮明な青色の着色物を得られやすいので好ましい。 The triarylmethane compound of the present invention is a water-insoluble colorant. The triarylmethane compound of the present invention thus obtained can be used as it is as a colorant for a synthetic resin or the like, but if necessary, the particle diameter can be adjusted by known and conventional pulverization or granulation. The colorant can be optimal for various applications. In the dry powder, the colorant preferably has an average primary particle diameter of 100 nm or less because a clearer blue colored product can be easily obtained.
　本発明において一次粒子の平均粒子径とは、次の様に測定される。まず、透過型電子顕微鏡または走査型電子顕微鏡で視野内の粒子を撮影する。そして、二次元画像上の、凝集体を構成する一次粒子の５０個につき、個々の粒子の内径の最長の長さ（最大長）を求める。個々の粒子の最大長の平均値を一次粒子の平均粒子径とする。 In the present invention, the average particle diameter of primary particles is measured as follows. First, the particle | grains in a visual field are image | photographed with a transmission electron microscope or a scanning electron microscope. And the longest length (maximum length) of the internal diameter of each particle | grain is calculated | required about 50 of the primary particles which comprise the aggregate on a two-dimensional image. The average value of the maximum length of each particle is defined as the average particle size of the primary particles.
　本発明のトリアリールメタン化合物は、公知慣用の各種の用途において、高温での熱履歴を経ても色相変化が小さく、優れた耐熱性を有していることから、カラーフィルタ画素部の製造に用いた場合に、色相変化の少ない優れた画像表示が可能な液晶表示装置のカラーフィルタを得ることができる。 The triarylmethane compound of the present invention is used for the production of a color filter pixel part because it has a small hue change and excellent heat resistance even after a thermal history at a high temperature in various known and commonly used applications. The color filter of the liquid crystal display device capable of excellent image display with little hue change can be obtained.
　本発明のカラーフィルタにおいては、バックライト光源としては、従来の冷陰極管（ＣＣＦＬ光源）、白色ＬＥＤ（ＬＥＤ；Ｌｉｇｈｔ　Ｅｍｉｔｔｉｎｇ　Ｄｉｏｄｅ）光源、３色独立ＬＥＤ光源、白色有機ＥＬ（ＥＬ；Ｅｌｅｃｔｒｏ　Ｌｕｍｉｎｅｓｃｅｎｃｅ）光源等をいずれも用いることが出来る。 In the color filter of the present invention, the conventional cold cathode tube (CCFL light source), white LED (LED; Light Emitting Diode) light source, three-color independent LED light source, white organic EL (EL; Electro Luminescence) are used as the backlight light source. Any light source or the like can be used.
　本発明のトリアリールメタン化合物には、必要に応じて、ε型銅フタロシアニン顔料、ジオキサジン顔料（Ｃ．Ｉ．ピグメントバイオレット２３、Ｃ．Ｉ．ピグメントバイオレット３７、Ｃ．Ｉ．ピグメントブルー８０等）等や、無金属または金属フタロシアニンのスルホン酸誘導体、無金属または金属フタロシアニンのＮ－（ジアルキルアミノ）メチル誘導体、無金属または金属フタロシアニンのＮ－（ジアルキルアミノアルキル）スルホン酸アミド誘導体、ジオキサジンバイオレットのスルホン酸誘導体、インダンスレンブルーのスルホン酸誘導体、フタロシアニンスルホン酸等の有機顔料誘導体等や、ビックケミー社のディスパービック１３０、ディスパービック１６１、ディスパービック１６２、ディスパービック１６３、ディスパービック１７０、ディスパービック１７１、ディスパービック１７４、ディスパービック１８０、ディスパービック１８２、ディスパービック１８３、ディスパービック１８４、ディスパービック１８５、ディスパービック２０００、ディスパービック２００１、ディスパービック２０２０、ディスパービック２０５０、ディスパービック２０７０、ディスパービック２０９６、ディスパービック２１５０、ディスパービックＬＰＮ２１１１６、ディスパービックＬＰＮ６９１９エフカ社のエフカ４６、エフカ４７、エフカ４５２、エフカＬＰ４００８、エフカ４００９、エフカＬＰ４０１０、エフカＬＰ４０５０、エフカＬＰ４０５５、エフカ４００、エフカ４０１、エフカ４０２、エフカ４０３、エフカ４５０、エフカ４５１、エフカ４５３、エフカ４５４０、エフカ４５５０、エフカＬＰ４５６０、エフカ１２０、エフカ１５０、エフカ１５０１、エフカ１５０２、エフカ１５０３、ルーブリゾール社のソルスパース３０００、ソルスパース９０００、ソルスパース１３２４０、ソルスパース１３６５０、ソルスパース１３９４０、ソルスパース１７０００、ソルスパース１８０００、ソルスパース２００００、ソルスパース２１０００、ソルスパース２４０００、ソルスパース２６０００、ソルスパース２７０００、ソルスパース２８０００、ソルスパース３２０００、ソルスパース３６０００、ソルスパース３７０００、ソルスパース３８０００、ソルスパース４１０００、ソルスパース４２０００、ソルスパース４３０００、ソルスパース４６０００、ソルスパース５４０００、ソルスパース７１０００、味の素株式会社のアジスパーＰＢ７１１、アジスパーＰＢ８２１、アジスパーＰＢ８２２、アジスパーＰＢ８１４、アジスパーＰＮ４１１、アジスパーＰＡ１１１等の分散剤や、アクリル系樹脂、ウレタン系樹脂、アルキッド系樹脂、ウッドロジン、ガムロジン、トール油ロジン等の天然ロジン、重合ロジン、不均化ロジン、水添ロジン、酸化ロジン、マレイン化ロジン等の変性ロジン、ロジンアミン、ライムロジン、ロジンアルキレンオキシド付加物、ロジンアルキド付加物、ロジン変性フェノール等のロジン誘導体等の、室温で液状かつ水不溶性の合成樹脂を含有させることが出来る。これら分散剤や、樹脂の添加は、フロッキュレーションの低減、分散安定性の向上、分散体の粘度特性を向上にも寄与する。 If necessary, the triarylmethane compound of the present invention includes ε-type copper phthalocyanine pigment, dioxazine pigment (CI Pigment Violet 23, CI Pigment Violet 37, CI Pigment Blue 80, etc.) and the like. Metal-free or metal phthalocyanine sulfonic acid derivatives, metal-free or metal phthalocyanine N- (dialkylamino) methyl derivatives, metal-free or metal phthalocyanine N- (dialkylaminoalkyl) sulfonic acid amide derivatives, dioxazine violet sulfone Acid derivatives, indanthrene blue sulfonic acid derivatives, organic pigment derivatives such as phthalocyanine sulfonic acid, etc., Big Chemie Dispersic 130, Dispersic 161, Dispersic 162, Dispersic 163, Dispersic -Big 170, Dispersic 171, Dispersic 174, Dispersic 180, Dispersic 182, Dispersic 183, Dispersic 184, Dispersic 185, Dispersic 2000, Dispersic 2001, Dispersic 2020, Dispersic 2050, Dispersic 2070 Dispersic 2096, Dispersic 2150, Dispersic LPN21116, Dispersic LPN6919 Fuka 46, Fuka 47, Fuka 452, Fuka LP4008, Fuka 4009, Fuka LP4010, Fuka LP4050, Fuka LP4055, Fuka 400, Fuka 401 402, Fuka 403, Fuka 450, Fuka 451, Fuka 4 53, EFKA 4540, EFKA 4550, EFKA LP4560, EFKA120, EFKA150, EFKA1501, EFKA1502, EFKA1503, Lubrizol SolSparse 3000, Solsparse 9000, Solsparse 13240, Solsparse 13650, Solsparse 137000, Solsparse 17000, Solsparse 18000 Solsparse 20000, Solsparse 21000, Solsparse 24000, Solsparse 26000, Solsparse 27000, Solsparse 28000, Solsparse 32000, Solsparse 36000, Solspers 37000, Solsparse 38000, Solsparse 41000, Solsparse 42000, Solsparse 43000, Solsparse 46000, Solsparse 5 000, Solsperse 71000, Ajinomoto Co., Inc. Ajisper PB711, Ajisper PB821, Ajisper PB822, Ajisper PB814, Ajisper PN411, Ajisper PA111, dispersants, acrylic resins, urethane resins, alkyd resins, wood rosin, gum rosin, tall oil Natural rosin such as rosin, polymerized rosin, disproportionated rosin, hydrogenated rosin, modified rosin such as rosin oxide, maleated rosin, rosin amine, lime rosin, rosin alkylene oxide adduct, rosin alkyd adduct, rosin modified phenolic rosin A synthetic resin that is liquid and water-insoluble at room temperature, such as a derivative, can be contained. Addition of these dispersants and resins also contributes to reduction of flocculation, improvement of dispersion stability, and improvement of viscosity characteristics of the dispersion.
　本発明のトリアリールメタン化合物は、それ自体でカラーフィルタ青色画素部の調製に適した色相を有しているが、必要ならば、その質量換算１００部当たりε型銅フタロシアニン顔料（Ｃ．Ｉ．ピグメントブルー１５：６）を０．１～３０部併用することで、色相の最適化を行うことが出来る。 The triarylmethane compound of the present invention itself has a hue suitable for the preparation of a color filter blue pixel part. If necessary, the ε-type copper phthalocyanine pigment (C.I. By using 0.1 to 30 parts of Pigment Blue 15: 6) together, the hue can be optimized.
　本発明のトリアリールメタン化合物は、それ自体でカラーフィルタ青色画素部の調製に適した耐熱性や耐光性を有しているが、必要ならば、トリアリールメタン化合物１００部当たり、酸化防止剤不揮発分０．１～１０部、中でも、０．５～８部用いることが出来る。ここで酸化防止剤とは、酸化劣化を防止する添加剤の総称であり、熱による酸化劣化を防止するもの（狭義の酸化防止剤）と、光（主に紫外線）による酸化劣化を防止するもの（狭義には、光安定剤と呼ばれる）とが包含される。　 The triarylmethane compound of the present invention itself has heat resistance and light resistance suitable for the preparation of the color filter blue pixel portion, but if necessary, the antioxidant non-volatile per 100 parts of the triarylmethane compound. 0.1 to 10 parts per minute, and in particular 0.5 to 8 parts can be used. Here, the term “antioxidant” is a general term for additives that prevent oxidative degradation. Those that prevent oxidative degradation due to heat (antioxidants in a narrow sense) and those that prevent oxidative degradation due to light (mainly ultraviolet rays). (Referred to in the narrow sense as light stabilizers). *
　この様な酸化防止剤は、ラジカルを捕捉し自動酸化の防止作用（ラジカル連鎖防止作用）を有するものと、ハイドロパーオキサイド（過酸化物）を無害なものに分解する作用（過酸化物分解作用）を有するものとがあり、前者は一次酸化防止剤、後者は二次酸化防止剤と呼ばれる。これら両方の作用を兼備した、一次二次両用酸化防止剤も知られている。一次酸化防止剤としては、例えば、フェノール系（ヒンダードフェノール系を含む）やアミン系（ヒンダードアミン系を含む）の各酸化防止剤が、二次酸化防止剤としては、例えば、硫黄系やリン系の各酸化防止剤が典型的なものである。 Such antioxidants have the ability to trap radicals and prevent auto-oxidation (radical chain prevention) and the action to decompose hydroperoxide (peroxide) into harmless ones (peroxide decomposition action) The former is called a primary antioxidant and the latter is called a secondary antioxidant. There are also known primary and secondary antioxidants having both of these functions. Examples of primary antioxidants include phenolic (including hindered phenols) and amine (including hindered amines) antioxidants, and secondary antioxidants include, for example, sulfur and phosphorus. Each of these antioxidants is typical.
　本発明のトリアリールメタン化合物は、それ自体でカラーフィルタ青色画素部の調製に適した耐熱性を有しているが、必要ならば、カチオン性樹脂を併用することで、耐熱性や耐光性をもう一段高めることが出来る。　 The triarylmethane compound of the present invention itself has heat resistance suitable for the preparation of a color filter blue pixel portion, but if necessary, heat resistance and light resistance can be improved by using a cationic resin together. It can be raised one step further. *
　この様なカチオン性樹脂としては、例えば、アクリル樹脂、ポリウレタン樹脂、エポキシ樹脂、ポリアミド樹脂等を用いることが、熱履歴の下でも色相変化が小さく、カラーフィルタの耐熱性を大きく改善できるので好ましい。 As such a cationic resin, for example, an acrylic resin, a polyurethane resin, an epoxy resin, a polyamide resin, or the like is preferably used because the hue change is small even under a thermal history and the heat resistance of the color filter can be greatly improved.
　本発明では、トリアリールメタン化合物とカチオン性樹脂の不揮発分の質量基準での割合は、特に制限されるものではないが、前者化合物１００部当たり、後者樹脂の不揮発分０．１部以上１０部未満、中でも、０．５～５部、特に１～３部とすることが好ましい。 In the present invention, the ratio of the triarylmethane compound and the cationic resin on the basis of mass of the non-volatile content is not particularly limited, but the non-volatile content of the latter resin is 0.1 to 10 parts per 100 parts of the former compound. The content is preferably 0.5 to 5 parts, particularly 1 to 3 parts.
　トリアリールメタン化合物とカチオン性樹脂とを含有する着色組成物を調製する際に、前記化合物と樹脂とを加熱する場合には、両者を混合した後、密閉系にて、化合物自体に不具合が生じない温度での攪拌下、３０分～５時間の範囲にて行なうことができる。こうして加圧状態が形成されることで、前記した様に、化合物粒子の空隙にまで、カチオン性樹脂が浸透することになり、単に粒子表面だけを被覆するのに比べて、より優れた効果が発現される。 When preparing a colored composition containing a triarylmethane compound and a cationic resin, when the compound and the resin are heated, after the two are mixed, the compound itself becomes defective in a closed system. The reaction can be performed in the range of 30 minutes to 5 hours with stirring at a low temperature. By forming a pressurized state in this way, as described above, the cationic resin penetrates into the voids of the compound particles, and a superior effect is obtained as compared to simply covering only the particle surface. Expressed.
　本発明のトリアリールメタン化合物は、従来公知の方法でカラーフィルタ画素部の形成に使用することができる。本発明のトリアリールメタン化合物の分散方法で代表的な方法としては、フォトリソグラフィー法であり、これは、後記する光硬化性組成物を、カラーフィルタ用の透明基板のブラックマトリックスを設けた側の面に塗布、加熱乾燥（プリベーク）した後、フォトマスクを介して紫外線を照射することでパターン露光を行って、画素部に対応する箇所の光硬化性化合物を硬化させた後、未露光部分を現像液で現像し、非画素部を除去して画素部を透明基板に固着させる方法である。この方法では、光硬化性組成物の硬化着色皮膜からなる画素部が透明基板上に形成される。 The triarylmethane 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 triarylmethane compound of the present invention is a photolithography method, which includes a photocurable composition described later on the side where a black matrix of a transparent substrate for a color filter is provided. After applying to the surface, heating and drying (pre-baking), pattern exposure is performed by irradiating ultraviolet rays through a photomask to cure the photocurable compound at the location corresponding to the pixel portion, and then the unexposed portion This is a method of developing with a developer, 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.
　赤色、緑色、青色の色ごとに、後記する光硬化性組成物を調製して、前記した操作を繰り返すことにより、所定の位置に赤色、緑色、青色の着色画素部を有するカラーフィルタを製造することができる。本発明のトリアリールメタン化合物からは、青色画素部を形成することができる。尚、赤色画素部および緑色画素部を形成するための光硬化性組成物を調製するには、公知慣用の赤色顔料と緑色顔料を使用することができる。 For each color of red, green, and blue, a photocurable composition to be described later is prepared, and the above-described operation is repeated to manufacture a color filter having red, green, and blue colored pixel portions at predetermined positions. be able to. A blue pixel portion can be formed from the triarylmethane compound of the present invention. In addition, in order to prepare the photocurable composition for forming a red pixel part and a green pixel part, a well-known and usual red pigment and green pigment can be used.
　赤色画素部を形成するための顔料としては、例えば、Ｃ．Ｉ．ピグメントレッド１７７、同２０９、同２４２、同２５４等が、緑色画素部を形成するための顔料としては、例えば、Ｃ．Ｉ．ピグメントグリーン７、同１０、同３６、同４７、同５８等が挙げられる。これら赤色画素部と緑色画素部の形成には、黄色顔料を併用することもできる。その後、必要に応じて、未反応の光硬化性化合物を熱硬化させるために、カラーフィルタ全体を加熱処理（ポストベーク）することもできる。 As a pigment for forming the red pixel portion, for example, C.I. I. Pigment Red 177, 209, 242 and 254 are pigments for forming the green pixel portion, for example, C.I. I. Pigment Green 7, 10, 36, 47, 58 and the like. A yellow pigment can be used in combination for forming the red pixel portion and the green pixel portion. Thereafter, if necessary, the entire color filter can be heat-treated (post-baked) in order to thermally cure the unreacted photocurable compound.
　後記する光硬化性組成物をガラス等の透明基板上に塗布する方法としては、例えば、スピンコート法、ロールコート法、インクジェット法等が挙げられる。 Examples of a method for applying a photocurable composition described later on a transparent substrate such as glass include a spin coating method, a roll coating method, and an ink jet method.
　透明基板に塗布した光硬化性組成物の塗膜の乾燥条件は、各成分の種類、配合割合等によっても異なるが、通常、５０～１５０℃で、１～１５分間程度である。また、光硬化性組成物の光硬化に用いる光としては、２００～５００ｎｍの波長領域の光線を使用するのが好ましい。この波長範囲の光を発する各種光源が使用できる。 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 blending ratio, and the like, but are usually about 50 to 150 ° C. for about 1 to 15 minutes. In addition, as light used for photocuring the photocurable composition, it is preferable to use light in the wavelength region of 200 to 500 nm. Various light sources that emit light in this wavelength range can be used.
　現像方法としては、例えば、液盛り法、ディッピング法、スプレー法等が挙げられる。光硬化性組成物の露光、現像の後に、必要な色の画素部が形成された透明基板は水洗いし乾燥させる。こうして得られたカラーフィルタは、ホットプレート、オーブン等の加熱装置により、９０～２８０℃で、所定時間加熱処理（ポストベーク）することによって、着色塗膜中の揮発性成分を除去すると同時に、光硬化性組成物の硬化着色皮膜中に残存する未反応の光硬化性化合物が熱硬化し、カラーフィルタが完成する。 Examples of the developing method include a liquid filling method, a dipping method, and a spray method. After exposure and development of the photocurable composition, the transparent substrate on which the necessary color pixel portion is formed is washed with water and dried. The color filter thus obtained is subjected to a heat treatment (post-baking) at 90 to 280 ° C. for a predetermined time by a heating device such as a hot plate or an oven, thereby removing volatile components in the colored coating film and simultaneously applying light. The unreacted photocurable compound remaining in the cured colored film of the curable composition is thermally cured to complete the color filter.
　カラーフィルタの青色画素部を形成するための光硬化性組成物は、本発明のトリアリールメタン化合物と、分散剤と、光硬化性化合物と、有機溶剤とを必須成分とし、必要に応じて熱可塑性樹脂を用いて、これらを混合することで調製することができる。青色画素部を形成する着色樹脂皮膜に、カラーフィルタの実生産で行われるベーキング等に耐え得る強靱性等が要求される場合には、前記光硬化性組成物を調製するに当たって、光硬化性化合物だけでなく、この熱可塑性樹脂を併用することが不可欠である。熱可塑性樹脂を併用する場合には、有機溶剤としては、それを溶解するものを使用するのが好ましい。 The photocurable composition for forming the blue pixel portion of the color filter comprises the triarylmethane compound of the present invention, a dispersant, a photocurable compound, and an organic solvent as essential components, and if necessary, heat It can prepare by mixing these using a plastic resin. When the colored resin film that forms the blue pixel portion requires toughness that can withstand baking, etc. performed in the actual production of a color filter, a photocurable compound is used in preparing the photocurable composition. In addition, it is essential to use this thermoplastic resin in combination. When a thermoplastic resin is used in combination, it is preferable to use an organic solvent that dissolves it.
　前記光硬化性組成物の製造方法としては、本発明のトリアリールメタン化合物と、有機溶剤と分散剤とを必須成分として使用し、これらを混合し均一となる様に攪拌分散を行って、まずカラーフィルタの画素部を形成するための分散液を調製してから、そこに、光硬化性化合物と、必要に応じて熱可塑性樹脂や光重合開始剤等を加えて前記光硬化性組成物とする方法が一般的である。 As a method for producing the photocurable composition, the triarylmethane compound of the present invention, an organic solvent and a dispersant are used as essential components, and these are mixed and stirred and dispersed so as to be uniform. After preparing a dispersion for forming the pixel portion of the color filter, a photocurable compound and, if necessary, a thermoplastic resin or a photopolymerization initiator are added to the photocurable composition. The method to do is common.
　ここで分散剤、有機溶剤は、前記のものが使用可能である。 Here, as the dispersant and the organic solvent, those described above can be used.
　光硬化性組成物の調製に使用する熱可塑性樹脂としては、例えば、ウレタン系樹脂、アクリル系樹脂、ポリアミド系樹脂、ポリイミド系樹脂、スチレンマレイン酸系樹脂、スチレン無水マレイン酸系樹脂等が挙げられる。 Examples of the thermoplastic resin used for the preparation of the photocurable composition include urethane resins, acrylic resins, polyamide resins, polyimide resins, styrene maleic acid resins, styrene maleic anhydride resins, and the like. .
　光硬化性化合物としては、例えば、１，６－ヘキサンジオールジアクリレート、エチレングリコールジアクリレート、ネオペンチルグリコールジアクリレート、トリエチレングリコールジアクリレート、ビス（アクリロキシエトキシ）ビスフェノールＡ、３－メチルペンタンジオールジアクリレート等のような２官能モノマー、トリメチルロールプロパトントリアクリレート、ペンタエリスリトールトリアクリレート、トリス〔２－（メタ）アクリロイルオキシエチル）イソシアヌレート、ジペンタエリスリトールヘキサアクリレート、ジペンタエリスリトールペンタアクリレート等の比較的分子量の小さな多官能モノマー、ポリエステルアクリレート、ポリウレタンアクリレート、ポリエーテルアクリレート等の様な比較的分子量の大きな多官能モノマーが挙げられる。 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 diacrylate. Bifunctional monomers such as acrylate, trimethylol propaton triacrylate, pentaerythritol triacrylate, tris [2- (meth) acryloyloxyethyl) isocyanurate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, etc. High molecular weight such as low molecular weight polyfunctional monomer, polyester acrylate, polyurethane acrylate, polyether acrylate, etc. Polyfunctional monomers.
　光重合開始剤としては、例えばアセトフェノン、ベンゾフェノン、ベンジルジメチルケタール、ベンゾイルパーオキサイド、２－クロロチオキサントン、１，３－ビス（４’－アジドベンザル）－２－プロパン、１，３－ビス（４’－アジドベンザル）－２－プロパン－２’－スルホン酸、４，４’－ジアジドスチルベン－２，２’－ジスルホン酸等が挙げられる。市販の光重合開始剤としては、たとえば、チバスペシャルティーケミカルズ社製「イルガキュア（商標名）－１８４」、「イルガキュア（商標名）－３６９」、「ダロキュア（商標名）－１１７３」、ＢＡＳＦ社製「ルシリン－ＴＰＯ」、日本化薬社製「カヤキュアー（商標名）ＤＥＴＸ」、「カヤキュアー（商標名）ＯＡ」、ストーファー社製「バイキュアー１０」、「バイキュアー５５」、アクゾー社製「トリゴナールＰＩ」、サンド社製「サンドレー１０００」、アップジョン社製「デープ」、黒金化成社製「ビイミダゾール」などがある。 Examples of the photopolymerization initiator include acetophenone, benzophenone, benzyldimethyl ketal, benzoyl peroxide, 2-chlorothioxanthone, 1,3-bis (4′-azidobenzal) -2-propane, 1,3-bis (4′- Azidobenzal) -2-propane-2′-sulfonic acid, 4,4′-diazidostilbene-2,2′-disulfonic acid, and the like. Examples of commercially available photopolymerization initiators include “Irgacure (trade name) -184”, “Irgacure (trade name) -369”, “Darocur (trade name) -1173” manufactured by Ciba Specialty Chemicals, and BASF Corporation. “Lucirin-TPO”, Nippon Kayaku Co., Ltd. “Kayacure (trade name) DETX”, “Kayacure (tradename) OA”, Stoffer “Bicure 10”, “Bicure 55”, Akzo Corporation “Trigonal PI” “Sandray 1000” manufactured by Sand, “Deep” manufactured by Upjohn, and “Biimidazole” manufactured by Kurokin Kasei.
　また上記光重合開始剤に公知慣用の光増感剤を併用することもできる。光増感剤としては、たとえば、アミン類、尿素類、硫黄原子を有する化合物、燐原子を有する化合物、塩素原子を有する化合物またはニトリル類もしくはその他の窒素原子を有する化合物等が挙げられる。これらは、単独で用いることも、２種以上を組み合わせて用いることもできる。 Also, 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 or other compounds having a nitrogen atom. These can be used alone or in combination of two or more.
　光重合開始剤の配合率は、特に限定されるものではないが、質量基準で、光重合性あるいは光硬化性官能基を有する化合物に対して０．１～３０％の範囲が好ましい。０．１％未満では、光硬化時の感光度が低下する傾向にあり、３０％を超えると、レジストの塗膜を乾燥させたときに、光重合開始剤の結晶が析出して塗膜物性の劣化を引き起こすことがある。 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 less than 0.1%, the photosensitivity at the time of photocuring tends to decrease, and if it exceeds 30%, when the resist coating film is dried, crystals of the photopolymerization initiator are precipitated, and the coating film properties. May cause deterioration.
　前記した様な各材料を使用して、質量基準で、本発明のトリアリールメタン化合物１００部当たり、３００～１０００部の有機溶剤と、１～１００部の分散剤とを、均一となる様に攪拌分散して前記分散液を得ることができる。次いでこの分散液に、本発明のトリアリールメタン化合物１部当たり、熱可塑性樹脂と光硬化性化合物の合計が３～２０部、光硬化性化合物１部当たり０．０５～３部の光重合開始剤と、必要に応じてさらに有機溶剤を添加し、均一となる様に攪拌分散してカラーフィルタ画素部を形成するための光硬化性組成物を得ることができる。 Using each of the materials as described above, 300 to 1000 parts of the organic solvent and 1 to 100 parts of the dispersant are made uniform on a mass basis per 100 parts of the triarylmethane compound of the present invention. The dispersion can be obtained by stirring and dispersing. Next, in this dispersion liquid, 3 to 20 parts of the total of the thermoplastic resin and the photocurable compound per 1 part of the triarylmethane compound of the present invention and 0.05 to 3 parts per 1 part of the photocurable compound are started. A photocurable composition for forming a color filter pixel portion can be obtained by adding an agent and, if necessary, further an organic solvent, and stirring and dispersing so as to be uniform.
　現像液としては、公知慣用の有機溶剤やアルカリ水溶液を使用することができる。特に前記光硬化性組成物に、熱可塑性樹脂または光硬化性化合物が含まれており、これらの少なくとも一方が酸価を有し、アルカリ可溶性を呈する場合には、アルカリ水溶液での洗浄がカラーフィルタ画素部の形成に効果的である。 As the developer, 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 exhibits alkali solubility, the color filter can be washed with an alkaline aqueous solution. It is effective for forming the pixel portion.
　本発明のトリアリールメタン化合物の分散方法のうち、フォトリソグラフィー法によるカラーフィルタ画素部の製造方法について詳記したが、本発明のトリアリールメタン化合物を使用して調製されたカラーフィタ画素部は、その他の電着法、転写法、ミセル電解法、ＰＶＥＤ（ＰｈｏｔｏｖｏｌｔａｉｃＥｌｅｃｔｒｏｄｅｐｏｓｉｔｉｏｎ）法、インクジェット法、反転印刷法、熱硬化法等の方法で青色画素部を形成して、カラーフィルタを製造してもよい。 Of the methods for dispersing the triarylmethane compound of the present invention, the method for producing the color filter pixel portion by photolithography was described in detail. However, the color filter pixel portion prepared using the triarylmethane compound of the present invention is the other A color filter may be manufactured by forming a blue pixel portion by a method such as an electrodeposition method, a transfer method, a micellar electrolysis method, a PVED (Photovoltaic Electrodeposition) method, an ink jet method, a reverse printing method, or a thermosetting method.
　カラーフィルタは、有機顔料として、赤色顔料、緑色顔料、本発明のトリアリールメタン化合物を使用して得た各色の光硬化性組成物を使用し、平行な一対の透明電極間に液晶材料を封入し、透明電極を不連続な微細区間に分割すると共に、この透明電極上のブラックマトリクスにより格子状に区分けされた微細区間のそれぞれに、赤、緑および青のいずれか１色から選ばれたカラーフィルタ着色画素部を交互にパターン状に設ける方法、あるいは基板上にカラーフィルタ着色画素部を形成した後、透明電極を設ける様にすることで得ることができる。 The color filter uses a photocurable composition of each color obtained by using a red pigment, a green pigment, and the triarylmethane compound of the present invention as an organic pigment, and encloses a liquid crystal material between a pair of parallel transparent electrodes. The transparent electrode is divided into discontinuous fine sections, and a color selected from any one of red, green, and blue is provided for each of the fine sections divided into a grid by the black matrix on the transparent electrode. It can be obtained by providing filter colored pixel portions alternately in a pattern or by providing a transparent electrode after forming color filter colored pixel portions on a substrate.
　本発明のトリアリールメタン化合物は、鮮明性と明度に優れる分散体を提供でき、カラーフィルタ用途の他、塗料、プラスチック（樹脂成型品）、印刷インク、ゴム、レザー、捺染、静電荷像現像用トナー、インクジェット記録用インク、熱転写インキ等の着色にも適用することができる。 The triarylmethane compound of the present invention can provide a dispersion having excellent sharpness and lightness, and for color filter applications, paints, plastics (resin molded products), printing inks, rubber, leather, textile printing, electrostatic image development The present invention can also be applied to coloring toner, ink jet recording ink, thermal transfer ink, and the like.
　以下、実施例により本発明を詳細に説明するが、もとより本発明はこれら実施例の範囲に限定されるものではない。尚、特に断りのない限り、「部」、「％」及び「ｐｐｍ」はいずれも質量基準である。 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, “part”, “%”, and “ppm” are based on mass.
＜中間体１の合成＞
以下の反応は窒素雰囲気下で行った。Ｎ－エチルアニリン（東京化成工業株式会社製試薬）１５．５部をＮ，Ｎ－ジメチルホルムアミド（和光純薬工業株式会社製試薬）３００ｍｌに溶解させて、α，α’－ジブロモ－ｐ－キシレン（東京化成工業株式会社製試薬）１６部を加え、室温で３０分攪拌した。次いで、炭酸カリウム（和光純薬工業株式会社製試薬）１８．５部を加えて５０℃で３時間攪拌した。反応液を室温まで冷却し、酢酸エチル２５０ｍｌで希釈した。水及び飽和食塩水で洗浄後、無水硫酸ナトリウムを加えて乾燥した。減圧下で溶媒を留去して、残渣に酢酸エチルを加えて加熱溶解し、冷蔵庫中で冷却した。生じた結晶をろ過して、ヘキサン／酢酸エチル＝４／１で洗浄した。得られた結晶を減圧下で加熱乾燥して中間物（１）（１６．１部、収率７７％）を得た。
４－ジエチルアミノ安息香酸（東京化成工業株式会社製試薬）２０．２部とトルエン１００ｍｌの混合物に塩化チオニル（和光純薬工業株式会社製試薬）１８．７部を加え、８０℃で３時間攪拌後、減圧濃縮し、４－ジエチルアミノ安息香酸クロライドを得た。
無水塩化アルミニウム（和光純薬工業株式会社製試薬）２３．４部と１，２－ジクロロエタン（和光純薬工業株式会社製試薬）１２０ｍｌの混合物を氷浴で冷却し、前記４－ジエチルアミノ安息香酸クロライドを１，２－ジクロロエタン５０ｍｌに溶かした溶液を５０分かけて滴下した。氷浴で冷却しながら１時間攪拌した後、中間物（１）、１５部を１，２－ジクロロエタン６０ｍｌに溶かした溶液を５０分かけて滴下した。氷浴で冷却しながら１時間攪拌した後、室温で一晩攪拌した。反応液を氷水に注ぎ、１５％水酸化ナトリウム水溶液でｐＨ１０以上にして、クロロホルムで抽出した。クロロホルム層を５％水酸化ナトリウム水溶液及び飽和食塩水で洗浄し、無水硫酸ナトリウムで乾燥した。減圧濃縮し、シリカゲルカラムクロマトグラフィー（クロロホルム／酢酸エチル＝２０／１から５／１）で精製して、中間体１（６．５部、収率２０％）を得た。 <Synthesis of Intermediate 1>
The following reaction was performed in a nitrogen atmosphere. 15.5 parts of N-ethylaniline (reagent manufactured by Tokyo Chemical Industry Co., Ltd.) is dissolved in 300 ml of N, N-dimethylformamide (reagent manufactured by Wako Pure Chemical Industries, Ltd.), and α, α′-dibromo-p-xylene is dissolved. (Reagent manufactured by Tokyo Chemical Industry Co., Ltd.) 16 parts were added and stirred at room temperature for 30 minutes. Subsequently, 18.5 parts of potassium carbonate (a reagent manufactured by Wako Pure Chemical Industries, Ltd.) was added and stirred at 50 ° C. for 3 hours. The reaction solution was cooled to room temperature and diluted with 250 ml of ethyl acetate. After washing with water and saturated saline, anhydrous sodium sulfate was added and dried. The solvent was distilled off under reduced pressure, and ethyl acetate was added to the residue to dissolve it with heating, followed by cooling in a refrigerator. The resulting crystals were filtered and washed with hexane / ethyl acetate = 4/1. The obtained crystals were dried by heating under reduced pressure to obtain Intermediate (1) (16.1 parts, yield 77%).
18.7 parts of thionyl chloride (a reagent manufactured by Wako Pure Chemical Industries, Ltd.) was added to a mixture of 20.2 parts of 4-diethylaminobenzoic acid (a reagent manufactured by Tokyo Chemical Industry Co., Ltd.) and 100 ml of toluene, and the mixture was stirred at 80 ° C. for 3 hours. The solution was concentrated under reduced pressure to give 4-diethylaminobenzoic acid chloride.
A mixture of 23.4 parts of anhydrous aluminum chloride (reagent manufactured by Wako Pure Chemical Industries, Ltd.) and 120 ml of 1,2-dichloroethane (reagent manufactured by Wako Pure Chemical Industries, Ltd.) was cooled in an ice bath, and the 4-diethylaminobenzoic acid chloride was cooled. Was added dropwise over 50 minutes in 50 ml of 1,2-dichloroethane. After stirring for 1 hour while cooling in an ice bath, a solution of 15 parts of Intermediate (1) in 60 ml of 1,2-dichloroethane was added dropwise over 50 minutes. The mixture was stirred for 1 hour while being cooled in an ice bath, and then stirred overnight at room temperature. The reaction solution was poured into ice water, adjusted to pH 10 or higher with 15% aqueous sodium hydroxide solution, and extracted with chloroform. The chloroform layer was washed with 5% aqueous sodium hydroxide solution and saturated brine, and dried over anhydrous sodium sulfate. The mixture was concentrated under reduced pressure and purified by silica gel column chromatography (chloroform / ethyl acetate = 20/1 to 5/1) to obtain Intermediate 1 (6.5 parts, yield 20%).
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
＜中間体２の合成＞
以下の反応は窒素雰囲気下で行った。Ｎ－エチルアニリン（東京化成工業株式会社製試薬）２８．３部をＮ，Ｎ－ジメチルホルムアミド（和光純薬工業株式会社製試薬）５００ｍｌに溶解させて、１，４－ビス（ブロモメチル）シクロヘキサン（cis-trans混合物、Journal of Organic Chemistry, vol60, p7865 (1995)記載の方法で合成）３０部を加え、室温で３０分攪拌した。次いで、炭酸カリウム（和光純薬工業株式会社製試薬）３３．８部を加えて５０℃で４時間攪拌した。反応液を室温まで冷却し、酢酸エチル５００ｍｌで希釈した。水及び飽和食塩水で洗浄後、無水硫酸ナトリウムを加えて乾燥した。減圧下で溶媒を留去して、残渣に酢酸エチルを加えて加熱溶解し、冷蔵庫中で冷却した。生じた結晶をろ過して、ヘキサン／酢酸エチル＝４／１で洗浄した。得られた結晶を減圧下で加熱乾燥して中間物（２）（２０部、収率５１％）を得た。
４－ジエチルアミノ安息香酸（東京化成工業株式会社製試薬）２６．４部とトルエン１５０ｍｌの混合物に塩化チオニル（和光純薬工業株式会社製試薬）２４．４部を加え、８０℃で３時間攪拌後、減圧濃縮し、４－ジエチルアミノ安息香酸クロライドを得た。
無水塩化アルミニウム（和光純薬工業株式会社製試薬）３０．５部と１，２－ジクロロエタン（和光純薬工業株式会社製試薬）１５０ｍｌの混合物を氷浴で冷却し、前記４－ジエチルアミノ安息香酸クロライドを１，２－ジクロロエタン７０ｍｌに溶かした溶液を５０分かけて滴下した。氷浴で冷却しながら１時間攪拌した後、中間物（２）、２０部を１，２－ジクロロエタン８０ｍｌに溶かした溶液を５０分かけて滴下した。氷浴で冷却しながら１時間攪拌した後、室温で一晩攪拌した。反応液を氷水に注ぎ、１５％水酸化ナトリウム水溶液でｐＨ１０以上にして、クロロホルムで抽出した。クロロホルム層を５％水酸化ナトリウム水溶液及び飽和食塩水で洗浄し、無水硫酸ナトリウムで乾燥した。減圧濃縮し、シリカゲルカラムクロマトグラフィー（クロロホルム／酢酸エチル＝２０／１から５／１）で精製して、中間体２（６．０部、収率１５％）を得た。 <Synthesis of Intermediate 2>
The following reaction was performed in a nitrogen atmosphere. 28.3 parts of N-ethylaniline (reagent manufactured by Tokyo Chemical Industry Co., Ltd.) is dissolved in 500 ml of N, N-dimethylformamide (reagent manufactured by Wako Pure Chemical Industries, Ltd.), and 1,4-bis (bromomethyl) cyclohexane ( 30 parts of a cis-trans mixture, synthesized by the method described in Journal of Organic Chemistry, vol 60, p7865 (1995) was added, and the mixture was stirred at room temperature for 30 minutes. Subsequently, 33.8 parts of potassium carbonate (a reagent manufactured by Wako Pure Chemical Industries, Ltd.) was added and stirred at 50 ° C. for 4 hours. The reaction solution was cooled to room temperature and diluted with 500 ml of ethyl acetate. After washing with water and saturated saline, anhydrous sodium sulfate was added and dried. The solvent was distilled off under reduced pressure, and ethyl acetate was added to the residue to dissolve it with heating, followed by cooling in a refrigerator. The resulting crystals were filtered and washed with hexane / ethyl acetate = 4/1. The obtained crystal was heat-dried under reduced pressure to obtain an intermediate (2) (20 parts, yield 51%).
To a mixture of 26.4 parts of 4-diethylaminobenzoic acid (reagent made by Tokyo Chemical Industry Co., Ltd.) and 150 ml of toluene, 24.4 parts of thionyl chloride (reagent made by Wako Pure Chemical Industries, Ltd.) was added and stirred at 80 ° C. for 3 hours. The solution was concentrated under reduced pressure to give 4-diethylaminobenzoic acid chloride.
A mixture of 30.5 parts of anhydrous aluminum chloride (reagent manufactured by Wako Pure Chemical Industries, Ltd.) and 150 ml of 1,2-dichloroethane (reagent manufactured by Wako Pure Chemical Industries, Ltd.) was cooled in an ice bath, and the 4-diethylaminobenzoic acid chloride was cooled. Was added dropwise over 50 minutes in a solution of 70 ml of 1,2-dichloroethane. After stirring for 1 hour while cooling in an ice bath, a solution of 20 parts of intermediate (2) in 80 ml of 1,2-dichloroethane was added dropwise over 50 minutes. The mixture was stirred for 1 hour while being cooled in an ice bath, and then stirred overnight at room temperature. The reaction solution was poured into ice water, adjusted to pH 10 or higher with 15% aqueous sodium hydroxide solution, and extracted with chloroform. The chloroform layer was washed with 5% aqueous sodium hydroxide solution and saturated brine, and dried over anhydrous sodium sulfate. Concentration under reduced pressure and purification by silica gel column chromatography (chloroform / ethyl acetate = 20/1 to 5/1) gave Intermediate 2 (6.0 parts, 15% yield).
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
＜中間体３の合成＞
以下の反応は窒素雰囲気下で行った。チオシアン酸カリウム（和光純薬工業株式会社製試薬）１８．２部をアセトン１１０ｍｌに投入した後、室温下で３０分攪拌した。次いで、塩化ベンゾイル（和光純薬工業株式会社製試薬）２５部を１０分かけて滴下した。滴下終了後、さらに室温下で２時間攪拌した。氷浴で冷却しながらＮ－エチル－ｏ－トルイジン（東京化成工業株式会社製試薬）２２．９部を１５分かけて滴下した。滴下終了後、さらに室温下で３０分攪拌した。氷浴で冷却しながら３０％水酸化ナトリウム水溶液１７．１部を１５分かけて滴下した。室温下で３０分攪拌後、クロロ酢酸（和光純薬工業株式会社製試薬）１７．７部を少量ずつ添加して、７時間加熱還流した。室温まで冷却した後、反応液を水の中に注いでトルエンで抽出した。有機層を１Ｎ塩酸、水、飽和食塩水の順で洗浄して無水硫酸ナトリウムで乾燥した。減圧下で溶媒を留去して、残渣に１２％水酸化ナトリウム水溶液１３５部とクロロ酢酸２０．７部を加えた。一晩加熱還流した後、室温まで冷却してトルエンで抽出した。有機層を１Ｎ塩酸、水、飽和食塩水の順で洗浄して無水硫酸ナトリウムで乾燥した。減圧濃縮し、シリカゲルカラムクロマトグラフィー（ヘキサン／アセトン＝６／１）で精製して、中間体３（１８．２部、収率３５％）を得た。 <Synthesis of Intermediate 3>
The following reaction was performed in a nitrogen atmosphere. After putting 18.2 parts of potassium thiocyanate (a reagent manufactured by Wako Pure Chemical Industries, Ltd.) into 110 ml of acetone, the mixture was stirred at room temperature for 30 minutes. Subsequently, 25 parts of benzoyl chloride (Wako Pure Chemical Industries, Ltd. reagent) 25 parts was dripped over 10 minutes. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours. While cooling in an ice bath, 22.9 parts of N-ethyl-o-toluidine (a reagent manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 15 minutes. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. While cooling in an ice bath, 17.1 parts of a 30% aqueous sodium hydroxide solution was added dropwise over 15 minutes. After stirring at room temperature for 30 minutes, 17.7 parts of chloroacetic acid (a reagent manufactured by Wako Pure Chemical Industries, Ltd.) was added little by little, and the mixture was heated to reflux for 7 hours. After cooling to room temperature, the reaction solution was poured into water and extracted with toluene. The organic layer was washed with 1N hydrochloric acid, water and saturated brine in that order, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and 135 parts of a 12% aqueous sodium hydroxide solution and 20.7 parts of chloroacetic acid were added to the residue. After heating to reflux overnight, the mixture was cooled to room temperature and extracted with toluene. The organic layer was washed with 1N hydrochloric acid, water and saturated brine in that order, and dried over anhydrous sodium sulfate. The mixture was concentrated under reduced pressure and purified by silica gel column chromatography (hexane / acetone = 6/1) to obtain Intermediate 3 (18.2 parts, yield 35%).
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
＜化合物１の合成＞
中間体１、６．０部とＮ－エチル－１－ナフチルアミン（東京化成工業株式会社製試薬）３．０部をトルエン４０ｍｌに混合した後、オキシ塩化リン（関東化学株式会社製試薬）３．３部を加え、５時間還流した。室温に冷却後、１Ｎ塩酸を加えて１５分攪拌し、クロロホルムで抽出した。クロロホルム層を飽和食塩水で洗浄し、無水硫酸ナトリウムで乾燥した。減圧濃縮し、シリカゲルカラムクロマトグラフィー（クロロホルム／メタノール＝１５／１から５／１）で精製して、化合物１（５．１部、収率５５％）を得た。 <Synthesis of Compound 1>
After mixing 6.0 parts of Intermediate 1 and 3.0 parts of N-ethyl-1-naphthylamine (reagent manufactured by Tokyo Chemical Industry Co., Ltd.) in 40 ml of toluene, phosphorus oxychloride (reagent manufactured by Kanto Chemical Co., Inc.) 3 parts were added and refluxed for 5 hours. After cooling to room temperature, 1N hydrochloric acid was added, stirred for 15 minutes, and extracted with chloroform. The chloroform layer was washed with saturated brine and dried over anhydrous sodium sulfate. Concentration under reduced pressure and purification by silica gel column chromatography (chloroform / methanol = 15/1 to 5/1) gave compound 1 (5.1 parts, yield 55%).
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
＜化合物２の合成＞
中間体１、６．３部と１－メチル－２－フェニルインドール（東京化成工業株式会社製試薬）３．８部をトルエン４０ｍｌに混合した後、オキシ塩化リン（関東化学株式会社製試薬）３．５部を加え、５時間還流した。室温に冷却後、１Ｎ塩酸を加えて１５分攪拌し、クロロホルムで抽出した。クロロホルム層を飽和食塩水で洗浄し、無水硫酸ナトリウムで乾燥した。減圧濃縮し、シリカゲルカラムクロマトグラフィー（クロロホルム／メタノール＝１５／１から５／１）で精製して、化合物２（４．８部、収率４６％）を得た。 <Synthesis of Compound 2>
After mixing 6.3 parts of intermediate 1 and 3.8 parts of 1-methyl-2-phenylindole (reagent manufactured by Tokyo Chemical Industry Co., Ltd.) in 40 ml of toluene, phosphorus oxychloride (reagent manufactured by Kanto Chemical Co., Ltd.) 3 .5 parts was added and refluxed for 5 hours. After cooling to room temperature, 1N hydrochloric acid was added, stirred for 15 minutes, and extracted with chloroform. The chloroform layer was washed with saturated brine and dried over anhydrous sodium sulfate. The mixture was concentrated under reduced pressure and purified by silica gel column chromatography (chloroform / methanol = 15/1 to 5/1) to obtain Compound 2 (4.8 parts, yield 46%).
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
＜化合物３の合成＞
中間体１、５．８部と中間体３、４．９部をトルエン４０ｍｌに混合した後、オキシ塩化リン（関東化学株式会社製試薬）３．２部を加え、５時間還流した。室温に冷却後、１Ｎ塩酸を加えて１５分攪拌し、クロロホルムで抽出した。クロロホルム層を飽和食塩水で洗浄し、無水硫酸ナトリウムで乾燥した。減圧濃縮し、シリカゲルカラムクロマトグラフィー（クロロホルム／メタノール＝１５／１から５／１）で精製して、化合物３（６．４部、収率５８％）を得た。 <Synthesis of Compound 3>
After mixing 5.8 parts of Intermediate 1 and 4.9 parts of Intermediate 3 with 40 ml of toluene, 3.2 parts of phosphorus oxychloride (a reagent manufactured by Kanto Chemical Co., Inc.) was added and refluxed for 5 hours. After cooling to room temperature, 1N hydrochloric acid was added, stirred for 15 minutes, and extracted with chloroform. The chloroform layer was washed with saturated brine and dried over anhydrous sodium sulfate. Concentration under reduced pressure and purification by silica gel column chromatography (chloroform / methanol = 15/1 to 5/1) gave compound 3 (6.4 parts, yield 58%).
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
＜化合物４の合成＞
中間体２、６．０部とＮ－エチル－１－ナフチルアミン（東京化成工業株式会社製試薬）２．９部をトルエン４０ｍｌに混合した後、オキシ塩化リン（関東化学株式会社製試薬）３．３部を加え、５時間還流した。室温に冷却後、１Ｎ塩酸を加えて１５分攪拌し、クロロホルムで抽出した。クロロホルム層を飽和食塩水で洗浄し、無水硫酸ナトリウムで乾燥した。減圧濃縮し、シリカゲルカラムクロマトグラフィー（クロロホルム／メタノール＝１５／１から５／１）で精製して、化合物４（４．５部、収率４８％）を得た。 <Synthesis of Compound 4>
2. After mixing 6.0 parts of intermediate 2 and 2.9 parts of N-ethyl-1-naphthylamine (reagent manufactured by Tokyo Chemical Industry Co., Ltd.) with 40 ml of toluene, phosphorus oxychloride (reagent manufactured by Kanto Chemical Co., Inc.) 3 parts were added and refluxed for 5 hours. After cooling to room temperature, 1N hydrochloric acid was added, stirred for 15 minutes, and extracted with chloroform. The chloroform layer was washed with saturated brine and dried over anhydrous sodium sulfate. Concentration under reduced pressure and purification by silica gel column chromatography (chloroform / methanol = 15/1 to 5/1) gave compound 4 (4.5 parts, yield 48%).
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
＜化合物５の合成＞
特開２０１３－０５７０５４号公報の段落番号［００８７］を参考にして化合物５（７．５部、収率６０％）を得た。 <Synthesis of Compound 5>
With reference to paragraph number [0087] of JP2013-057054A, Compound 5 (7.5 parts, yield 60%) was obtained.
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
＜アニオンＫ６（Ｐ２ＭｏＷ１７Ｏ６２）の合成＞
Ｎａ２ＷＯ４・２Ｈ２Ｏ（和光純薬工業株式会社製試薬）、４４．０部、Ｎａ２ＭｏＯ４・２Ｈ２Ｏ（関東化学株式会社製試薬）、１．９０部を精製水２３０部に溶解した。この溶液に攪拌しながら８５％リン酸６４．９部を滴下ロートを用いて添加した。得られた溶液を８時間、加熱還流した。反応液を室温に冷却し、臭素水１滴を加え、攪拌しながら塩化カリウム４５．０部を添加することで、Ｋ６（Ｐ２ＭｏＷ１７Ｏ６２）を得た。更に１時間攪拌後、生じた黄色の沈殿Ｋ６（Ｐ２ＭｏＷ１７Ｏ６２）をろ別し、９０℃で乾燥し、収量２９．４部の乾燥物を得た。 <Synthesis of Anion K 6 (P 2 MoW 17 O 62 )>
Na 2 WO 4 · 2H 2 O ( Wako Pure Chemical Industries Co., Ltd .: reagent), 44.0 parts, Na 2 MoO 4 · 2H 2 O ( Kanto Chemical Co., Ltd .: reagent), 230 parts of purified water 1.90 parts Dissolved in. While stirring, 64.9 parts of 85% phosphoric acid was added using a dropping funnel. The resulting solution was heated to reflux for 8 hours. The reaction solution 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 further stirring for 1 hour, the resulting yellow precipitate K 6 (P 2 MoW 17 O 62 ) was filtered off and dried at 90 ° C. to obtain a dried product with a yield of 29.4 parts.
＜アニオンＫ４（ＳｉＭｏＷ１１Ｏ４０）の合成＞
１３ｍｏｌ／ＬのＨＮＯ３水溶液９．８部に１ｍｏｌ／ＬのＮａ２ＭｏＯ４水溶液１６．４部を加えて攪拌した。この溶液に下記文献１に記載の方法で調整したＫ８（ＳｉＷ１１Ｏ３９）・１３Ｈ２Ｏを少量ずつ１６．４部添加した。室温で４時間攪拌後、飽和ＫＣｌ水溶液２６部を添加することで、Ｋ４（ＳｉＭｏＷ１１Ｏ４０）の沈殿物を得た。この沈殿物をろ別し、飽和ＫＣｌ水溶液で洗浄した。得られた固体を室温で減圧下乾燥した。収量１２．２部の乾燥物を得た。（文献１：Ｉｎｏｒｇａｎｉｃ　Ｓｙｎｔｈｅｓｉｓ　ｖｏｌ．２７　ｐ８５　を参照。） <Synthesis of Anion K 4 (SiMoW 11 O 40 )>
16.4 parts of 1 mol / L Na 2 MoO 4 aqueous solution was added to 9.8 parts of 13 mol / L HNO 3 aqueous solution and stirred. To this solution, 16.4 parts of K 8 (SiW 11 O 39 ) · 13H 2 O prepared by the method described in Reference 1 below was added little by little. After stirring at room temperature for 4 hours, a precipitate of K 4 (SiMoW 11 O 40 ) was obtained by adding 26 parts of a saturated aqueous KCl solution. The precipitate was filtered off and washed with saturated aqueous KCl solution. The obtained solid was dried under reduced pressure at room temperature. A dry product with a yield of 12.2 parts was obtained. (Ref. Reference 1: Inorganic Synthesis vol. 27 p85.)
＜化合物６の合成＞
化合物１、２．０部を水／メタノール＝１／１混合液５００ｍｌに投入し、５０℃で３０分攪拌させて溶解した。次にＫ６（Ｐ２ＭｏＷ１７Ｏ６２）２．９部を温水２０ｍｌに溶解した後、化合物１の溶液にゆっくりと加え、４０℃～４５℃で１．５時間攪拌した。冷却後ろ過し、水／メタノール＝２／１混合液１００ｍｌと水１５０ｍｌで洗浄した。得られた固体を乾燥して、化合物６（３．４部、収率７５％）を得た。
また、化合物６は次の方法でも同様に得ることができた。化合物１、２．０部に酢酸１００部を加えて５０℃で加熱撹拌して溶解した。この溶液を１０％ＫＯＨ水溶液でｐＨ２．０に調整した後、酢酸濃度が３０％となるように水を追加した。次にＫ６（Ｐ２ＭｏＷ１７Ｏ６２）３．１部を温水２０ｍｌに溶解した後、化合物１の溶液にゆっくりと加え、５０℃で１時間撹拌した。その後内温を８０℃に上げ、さらに１時間撹拌した。冷却後ろ過し、１００ｍｌの水で２回洗浄した。得られた固体に水２００ｍｌを加え、室温で１時間撹拌して再度ろ過をした。１００ｍｌの水で３回洗浄した後、得られた固体を乾燥して化合物６（４．０、収率８９％）を得た。
<Synthesis of Compound 6>
Compound 1, 2.0 parts was put into 500 ml of a water / methanol = 1/1 mixed solution and dissolved by stirring at 50 ° C. for 30 minutes. Next, after 2.9 parts of K 6 (P 2 MoW 17 O 62 ) was dissolved in 20 ml of warm water, it was slowly added to the solution of Compound 1 and stirred at 40 ° C. to 45 ° C. for 1.5 hours. After cooling, the mixture was filtered and washed with 100 ml of a water / methanol = 2/1 mixture and 150 ml of water. The obtained solid was dried to obtain Compound 6 (3.4 parts, yield 75%).
Compound 6 could also be obtained by the following method. 100 parts of acetic acid was added to 2.0 parts of Compound 1 and dissolved by heating and stirring at 50 ° C. This solution was adjusted to pH 2.0 with a 10% aqueous KOH solution, and water was added so that the acetic acid concentration was 30%. Next, 3.1 parts of K 6 (P 2 MoW 17 O 62 ) was dissolved in 20 ml of hot water, and then slowly added to the solution of Compound 1 and stirred at 50 ° C. for 1 hour. Thereafter, the internal temperature was raised to 80 ° C., and the mixture was further stirred for 1 hour. After cooling, it was filtered and washed twice with 100 ml of water. 200 ml of water was added to the obtained solid, stirred at room temperature for 1 hour, and filtered again. After washing three times with 100 ml of water, the obtained solid was dried to obtain Compound 6 (4.0, yield 89%).
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
＜化合物７の合成＞
化合物１、２．０部を水／メタノール＝１／１混合液５００ｍｌに投入し、５０℃で３０分攪拌させて溶解した。次にＫ４（ＳｉＭｏＷ１１Ｏ４０）２．８部を温水２０ｍｌに溶解した後、化合物１の溶液にゆっくりと加え、４０℃～４５℃で１．５時間攪拌した。冷却後ろ過し、水／メタノール＝２／１混合液１００ｍｌと水１５０ｍｌで洗浄した。得られた固体を乾燥して、化合物７（３．６部、収率８０％）を得た。
また、化合物７は次の方法でも同様に得ることができた。化合物１、２．０部に酢酸１００部を加えて５０℃で加熱撹拌して溶解した。この溶液を１０％ＫＯＨ水溶液でｐＨ２．０に調整した後、酢酸濃度が３０％となるように水を追加した。次にＫ４（ＳｉＭｏＷ１１Ｏ４０）３．０部を温水２０ｍｌに溶解した後、化合物１の溶液にゆっくりと加え、５０℃で１時間撹拌した。その後内温を８０℃に上げ、さらに１時間撹拌した。冷却後ろ過し、１００ｍｌの水で３回洗浄した。得られた固体に水２００ｍｌを加え、室温で１時間撹拌して再度ろ過をした。１００ｍｌの水で５回洗浄した後、得られた固体を乾燥して化合物７（３．７、収率８２％）を得た。 <Synthesis of Compound 7>
Compound 1, 2.0 parts was put into 500 ml of a water / methanol = 1/1 mixed solution and dissolved by stirring at 50 ° C. for 30 minutes. Next, 2.8 parts of K 4 (SiMoW 11 O 40 ) was dissolved in 20 ml of hot water, and then slowly added to the solution of Compound 1 and stirred at 40 ° C. to 45 ° C. for 1.5 hours. After cooling, the mixture was filtered and washed with 100 ml of a water / methanol = 2/1 mixture and 150 ml of water. The obtained solid was dried to obtain Compound 7 (3.6 parts, yield 80%).
Compound 7 could also be obtained by the following method. 100 parts of acetic acid was added to 2.0 parts of Compound 1 and dissolved by heating and stirring at 50 ° C. This solution was adjusted to pH 2.0 with a 10% aqueous KOH solution, and water was added so that the acetic acid concentration was 30%. Next, after dissolving 3.0 parts of K 4 (SiMoW 11 O 40 ) in 20 ml of warm water, it was slowly added to the solution of Compound 1 and stirred at 50 ° C. for 1 hour. Thereafter, the internal temperature was raised to 80 ° C., and the mixture was further stirred for 1 hour. After cooling, it was filtered and washed 3 times with 100 ml of water. 200 ml of water was added to the obtained solid, stirred at room temperature for 1 hour, and filtered again. After washing 5 times with 100 ml of water, the obtained solid was dried to obtain compound 7 (3.7, yield 82%).
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
＜化合物８の合成＞
化合物１、３．０部にメタノール９０ｍｌを加えて５０℃で加熱攪拌して溶解した。この溶液にメタノール３０ｍｌに溶解したpotassium bis(trifluoromethanesulfonyl) imide（和光純薬工業株式会社製試薬）１．８部を滴下した。５０℃で１時間攪拌後、反応液をろ過してエバポレーターで濃縮した。得られた残渣に水／メタノール＝２／１混合液９０ｍｌを加えて３０分攪拌した。固形分をろ過して乾燥し、化合物８（３．０部、収率６８％）を得た。 <Synthesis of Compound 8>
90 ml of methanol was added to 3.0 parts of Compound 1 and dissolved by heating and stirring at 50 ° C. To this solution, 1.8 parts of potassium bis (trifluoromethanesulfonyl) imide (reagent manufactured by Wako Pure Chemical Industries, Ltd.) dissolved in 30 ml of methanol was added dropwise. After stirring at 50 ° C. for 1 hour, the reaction solution was filtered and concentrated by an evaporator. To the obtained residue, 90 ml of a water / methanol = 2/1 mixed solution was added and stirred for 30 minutes. The solid content was filtered and dried to obtain Compound 8 (3.0 parts, yield 68%).
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
＜化合物９の合成＞
化合物１、３．０部にメタノール９０ｍｌを加えて５０℃で加熱攪拌して溶解した。この溶液にメタノール３０ｍｌに溶解したcesium tris(trifluoromethanesulfonyl) methide（セントラル硝子株式会社製試薬）３．１部を滴下した。５０℃で１時間攪拌後、反応液をろ過してエバポレーターで濃縮した。得られた残渣に水／メタノール＝２／１混合液９０ｍｌを加えて３０分攪拌した。固形分をろ過して乾燥し、化合物９（３．６部、収率７１％）を得た。 <Synthesis of Compound 9>
90 ml of methanol was added to 3.0 parts of Compound 1 and dissolved by heating and stirring at 50 ° C. To this solution, 3.1 parts of cesium tris (trifluoromethanesulfonyl) methide (reagent manufactured by Central Glass Co., Ltd.) dissolved in 30 ml of methanol was added dropwise. After stirring at 50 ° C. for 1 hour, the reaction solution was filtered and concentrated by an evaporator. To the obtained residue, 90 ml of a water / methanol = 2/1 mixed solution was added and stirred for 30 minutes. The solid content was filtered and dried to obtain Compound 9 (3.6 parts, yield 71%).
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
＜化合物１０の合成＞
２，６－ナフタレンジスルホン酸二ナトリウム（東京化成工業株式会社製試薬）１．０部を水／メタノール＝１／２混合液６０ｍｌに投入し、５０℃で攪拌した。ここに化合物１を３．２部加えて、５０℃で１時間攪拌後、エバポレーターで濃縮した。得られた残渣に水１００ｍｌを加えてろ過し、水で洗浄した。得られた固体を乾燥して、化合物１０（３．１部、収率８０％）を得た。 <Synthesis of Compound 10>
1.0 part of disodium 2,6-naphthalenedisulfonate (reagent manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 60 ml of a water / methanol = 1/2 mixture, and stirred at 50 ° C. To this, 3.2 parts of Compound 1 was added, stirred at 50 ° C. for 1 hour, and concentrated with an evaporator. 100 ml of water was added to the obtained residue, filtered, and washed with water. The obtained solid was dried to obtain Compound 10 (3.1 parts, yield 80%).
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
＜化合物１１の合成＞
化合物２、２．５部を水／メタノール＝１／１混合液５００ｍｌに投入し、５０℃で３０分攪拌させて溶解した。次にＫ６（Ｐ２ＭｏＷ１７Ｏ６２）３．４部を温水２０ｍｌに溶解した後、化合物２の溶液にゆっくりと加え、４０℃～４５℃で１．５時間攪拌した。冷却後ろ過し、水／メタノール＝２／１混合液１００ｍｌと水１５０ｍｌで洗浄した。得られた固体を乾燥して、化合物１１（４．２部、収率７７％）を得た。 <Synthesis of Compound 11>
Compound 2, 2.5 parts was put into 500 ml of a water / methanol = 1/1 mixed solution and dissolved by stirring at 50 ° C. for 30 minutes. Next, 3.4 parts of K 6 (P 2 MoW 17 O 62 ) was dissolved in 20 ml of warm water, and then slowly added to the solution of Compound 2, followed by stirring at 40 ° C. to 45 ° C. for 1.5 hours. After cooling, the mixture was filtered and washed with 100 ml of a water / methanol = 2/1 mixture and 150 ml of water. The obtained solid was dried to obtain Compound 11 (4.2 parts, yield 77%).
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
＜化合物１２の合成＞
化合物３、２．５部を水／メタノール＝１／１混合液５００ｍｌに投入し、５０℃で３０分攪拌させて溶解した。次にＫ６（Ｐ２ＭｏＷ１７Ｏ６２）３．０部を温水２０ｍｌに溶解した後、化合物３の溶液にゆっくりと加え、４０℃～４５℃で１．５時間攪拌した。冷却後ろ過し、水／メタノール＝２／１混合液１００ｍｌと水１５０ｍｌで洗浄した。得られた固体を乾燥して、化合物１２（４．４部、収率８６％）を得た。 <Synthesis of Compound 12>
Compound 3 (2.5 parts) was added to 500 ml of a water / methanol = 1/1 mixed solution and dissolved by stirring at 50 ° C. for 30 minutes. Next, 3.0 parts of K 6 (P 2 MoW 17 O 62 ) was dissolved in 20 ml of warm water, and then slowly added to the solution of Compound 3, followed by stirring at 40 ° C. to 45 ° C. for 1.5 hours. After cooling, the mixture was filtered and washed with 100 ml of a water / methanol = 2/1 mixture and 150 ml of water. The obtained solid was dried to obtain Compound 12 (4.4 parts, yield 86%).
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
＜化合物１３の合成＞
化合物４、２．５部を水／メタノール＝１／１混合液５００ｍｌに投入し、５０℃で３０分攪拌させて溶解した。次にＫ６（Ｐ２ＭｏＷ１７Ｏ６２）３．６部を温水２０ｍｌに溶解した後、化合物４の溶液にゆっくりと加え、４０℃～４５℃で１．５時間攪拌した。冷却後ろ過し、水／メタノール＝２／１混合液１００ｍｌと水１５０ｍｌで洗浄した。得られた固体を乾燥して、化合物１３（４．０部、収率７１％）を得た。 <Synthesis of Compound 13>
Compound 4, 2.5 parts was added to 500 ml of a water / methanol = 1/1 mixed solution, and dissolved by stirring at 50 ° C. for 30 minutes. Next, 3.6 parts of K 6 (P 2 MoW 17 O 62 ) was dissolved in 20 ml of warm water, and then slowly added to the solution of Compound 4, followed by stirring at 40 ° C. to 45 ° C. for 1.5 hours. After cooling, the mixture was filtered and washed with 100 ml of a water / methanol = 2/1 mixture and 150 ml of water. The obtained solid was dried to obtain Compound 13 (4.0 parts, yield 71%).
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000032
＜化合物１４の合成＞
化合物５、２．０部を水／メタノール＝１／１混合液５００ｍｌに投入し、５０℃で３０分攪拌させて溶解した。次にＫ６（Ｐ２ＭｏＷ１７Ｏ６２）２．９部を温水２０ｍｌに溶解した後、化合物５の溶液にゆっくりと加え、４０℃～４５℃で１．５時間攪拌した。冷却後ろ過し、水／メタノール＝２／１混合液１００ｍｌと水１５０ｍｌで洗浄した。得られた固体を乾燥して、化合物１４（３．６部、収率７９％）を得た。 <Synthesis of Compound 14>
Compound 5 (2.0 parts) was added to 500 ml of a water / methanol = 1/1 mixed solution, and dissolved by stirring at 50 ° C. for 30 minutes. Next, after 2.9 parts of K 6 (P 2 MoW 17 O 62 ) was dissolved in 20 ml of warm water, it was slowly added to the solution of Compound 5 and stirred at 40 ° C. to 45 ° C. for 1.5 hours. After cooling, the mixture was filtered and washed with 100 ml of a water / methanol = 2/1 mixture and 150 ml of water. The obtained solid was dried to obtain Compound 14 (3.6 parts, yield 79%).
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000033
＜化合物１５の合成＞
ベーシックブルー７（東京化成工業株式会社製試薬）５．０部を水３５０ｍｌに投入し、４０℃で３０分攪拌させて溶解した。次にＫ６（Ｐ２ＭｏＷ１７Ｏ６２）７．６部を温水５０ｍｌに溶解した後、ベーシックブルー７の溶液にゆっくりと加え、４０℃で１時間攪拌した。ついで内温を８０℃に上げ、さらに該温度で１時間攪拌した。冷却後ろ過し、３００ｍｌの水で３回洗浄した。得られた固体を乾燥して、化合物１５（１０．１部、収率８７％）を得た。 <Synthesis of Compound 15>
5.0 parts of Basic Blue 7 (reagent manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 350 ml of water and dissolved by stirring at 40 ° C. for 30 minutes. Next, 7.6 parts of K 6 (P 2 MoW 17 O 62 ) was dissolved in 50 ml of warm water, and then slowly added to the solution of Basic Blue 7, followed by stirring at 40 ° C. for 1 hour. Next, the internal temperature was raised to 80 ° C., and the mixture was further stirred at the temperature for 1 hour. After cooling, it was filtered and washed 3 times with 300 ml of water. The obtained solid was dried to obtain Compound 15 (10.1 parts, yield 87%).
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000034
＜化合物１６の合成＞
化合物２、２．５部を水／メタノール＝１／１混合液５００ｍｌに投入し、５０℃で３０分攪拌させて溶解した。次にＫ４（ＳｉＭｏＷ１１Ｏ４０）３．３部を温水２０ｍｌに溶解した後、化合物２の溶液にゆっくりと加え、４０℃～４５℃で１．５時間攪拌した。冷却後ろ過し、水／メタノール＝２／１混合液１００ｍｌと水１５０ｍｌで洗浄した。得られた固体を乾燥して、化合物１６（４．３部、収率８０％）を得た。 <Synthesis of Compound 16>
Compound 2, 2.5 parts was put into 500 ml of a water / methanol = 1/1 mixed solution and dissolved by stirring at 50 ° C. for 30 minutes. Next, 3.3 parts of K 4 (SiMoW 11 O 40 ) was dissolved in 20 ml of warm water, and then slowly added to the solution of Compound 2 and stirred at 40 ° C. to 45 ° C. for 1.5 hours. After cooling, the mixture was filtered and washed with 100 ml of a water / methanol = 2/1 mixture and 150 ml of water. The obtained solid was dried to obtain Compound 16 (4.3 parts, yield 80%).
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000035
＜化合物１７の合成＞
化合物３、２．５部を水／メタノール＝１／１混合液５００ｍｌに投入し、５０℃で３０分攪拌させて溶解した。次にＫ４（ＳｉＭｏＷ１１Ｏ４０）２．９部を温水２０ｍｌに溶解した後、化合物３の溶液にゆっくりと加え、４０℃～４５℃で１．５時間攪拌した。冷却後ろ過し、水／メタノール＝２／１混合液１００ｍｌと水１５０ｍｌで洗浄した。得られた固体を乾燥して、化合物１７（３．９部、収率７８％）を得た。 <Synthesis of Compound 17>
Compound 3 (2.5 parts) was added to 500 ml of a water / methanol = 1/1 mixed solution and dissolved by stirring at 50 ° C. for 30 minutes. Next, after 2.9 parts of K 4 (SiMoW 11 O 40 ) was dissolved in 20 ml of warm water, it was slowly added to the solution of Compound 3 and stirred at 40 ° C. to 45 ° C. for 1.5 hours. After cooling, the mixture was filtered and washed with 100 ml of a water / methanol = 2/1 mixture and 150 ml of water. The obtained solid was dried to obtain Compound 17 (3.9 parts, yield 78%).
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000036
市販のジューサーにて粉砕した化合物６、１．８０部、ＢＹＫ―２１６４（ビックケミー社製分散剤）２．１０部、プロピレングリコールモノメチルエーテルアセテート１１．１０部、０．３－０．４ｍｍφのセプルビーズをポリビンに入れ、ペイントコンディショナー（東洋精機株式会社製）で２時間分散し、色材分散液を得た。
この色材分散液３．００部に、ユニディックＺＬ－２９５（ＤＩＣ株式会社製アクリル樹脂）１．８５部、プロピレングリコールモノメチルエーテルアセテート０．８０部を加えて、ペイントコンディショナーで混合することで、カラーフィルタ用青色画素部を形成するための評価用組成物を得た。
この評価用組成物をソーダガラスに色度ｙ＝０．１１０が内挿するように回転数を変えて４種類スピンコートした。こうして得られた回転数の異なるガラス板を９０℃で３分乾燥して評価用ガラス基板を得た。 Compound 6, pulverized with a commercially available juicer, 1.80 parts, 2.10 parts of BYK-2164 (dispersant manufactured by Big Chemie), 11.10 parts of propylene glycol monomethyl ether acetate, and 0.3-0.4 mmφ sepul beads. It was put in a polybin and dispersed for 2 hours with a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) to obtain a color material dispersion.
By adding 1.85 parts Unidic ZL-295 (acrylic resin manufactured by DIC Corporation) and 0.80 parts propylene glycol monomethyl ether acetate to 3.00 parts of this colorant dispersion, and mixing with a paint conditioner, An evaluation composition for forming a blue pixel portion for a color filter was obtained.
This evaluation composition was spin-coated on soda glass at various rotational speeds so that the chromaticity y = 0.110 was interpolated. The glass plates having different rotational speeds thus obtained were dried at 90 ° C. for 3 minutes to obtain glass substrates for evaluation.
化合物６に代えて、化合物７を用いる以外は、上記実施例１と同様な操作を行い、評価用ガラス基板を得た。 An evaluation glass substrate was obtained in the same manner as in Example 1 except that Compound 7 was used instead of Compound 6.
化合物６に代えて、化合物８を用いる以外は、上記実施例１と同様な操作を行い、評価用ガラス基板を得た。 An evaluation glass substrate was obtained in the same manner as in Example 1 except that Compound 8 was used instead of Compound 6.
化合物６に代えて、化合物９を用いる以外は、上記実施例１と同様な操作を行い、評価用ガラス基板を得た。 An evaluation glass substrate was obtained in the same manner as in Example 1 except that Compound 9 was used instead of Compound 6.
化合物６に代えて、化合物１０を用いる以外は、上記実施例１と同様な操作を行い、評価用ガラス基板を得た。 An evaluation glass substrate was obtained in the same manner as in Example 1 except that Compound 10 was used instead of Compound 6.
化合物６に代えて、化合物１１を用いる以外は、上記実施例１と同様な操作を行い、評価用ガラス基板を得た。 An evaluation glass substrate was obtained in the same manner as in Example 1 except that Compound 11 was used instead of Compound 6.
化合物６に代えて、化合物１２を用いる以外は、上記実施例１と同様な操作を行い、評価用ガラス基板を得た。 An evaluation glass substrate was obtained in the same manner as in Example 1 except that Compound 12 was used instead of Compound 6.
化合物６に代えて、化合物１３を用いる以外は、上記実施例１と同様な操作を行い、評価用ガラス基板を得た。 An evaluation glass substrate was obtained in the same manner as in Example 1 except that Compound 13 was used instead of Compound 6.
化合物６に代えて、化合物１６を用いる以外は、上記実施例１と同様な操作を行い、評価用ガラス基板を得た。 An evaluation glass substrate was obtained in the same manner as in Example 1 except that Compound 16 was used instead of Compound 6.
化合物６に代えて、化合物１７を用いる以外は、上記実施例１と同様な操作を行い、評価用ガラス基板を得た。 An evaluation glass substrate was obtained in the same manner as in Example 1 except that Compound 17 was used instead of Compound 6.
＜比較例１＞
化合物６に代えて、化合物１４を用いる以外は、上記実施例１と同様な操作を行い、評価用ガラス基板を得た。 <Comparative Example 1>
An evaluation glass substrate was obtained in the same manner as in Example 1 except that Compound 14 was used instead of Compound 6.
＜比較例２＞
化合物６に代えて、化合物１５を用いる以外は、上記実施例１と同様な操作を行い、評価用ガラス基板を得た。 <Comparative example 2>
An evaluation glass substrate was obtained in the same manner as in Example 1 except that Compound 15 was used instead of Compound 6.
＜耐熱性試験評価方法＞
上記実施例１～１０及び比較例１、２で得られた評価用ガラス基板を２３０℃で１時間加熱し、加熱前後の色差△Ｅ＊ａｂを分光光度計Ｕ－３９００（株式会社日立ハイテクサイエンス製）を用いて測定した。色差△Ｅ＊ａｂは、その値が小さいほど高い耐熱性を有する材料であることを示す。なお、色差△Ｅ＊ａｂは各回転数のガラス板の色差△Ｅ＊ａｂの平均値とする。この結果を表１に示した。 <Evaluation method for heat resistance test>
The glass substrates for evaluation obtained in Examples 1 to 10 and Comparative Examples 1 and 2 were heated at 230 ° C. for 1 hour, and the color difference ΔE * ab before and after heating was measured with a spectrophotometer U-3900 (Hitachi High-Tech Science Co., Ltd.). ). The color difference ΔE * ab indicates that the smaller the value, the higher the heat resistance. The color difference ΔE * ab is the average value of the color difference ΔE * ab of the glass plate at each rotation speed. The results are shown in Table 1.






Figure JPOXMLDOC01-appb-T000037
Figure JPOXMLDOC01-appb-T000037
表１からわかるように、本発明の実施例１～１０と比較例１～２を比較すると色差△Ｅ＊ａｂが小さく、２３０℃の高温の熱履歴を受けても色差が小さく、本発明の化合物の熱安定性が非常に高いことが判明した。
また、本発明は、前記一般式（Ｉ）のように、連結基Ｚを特定の部位で連結させることで、耐熱性に効果のあるＡ部を自由に変更して合成することができ、耐熱性をより向上することができる点で優れている。例えば、前記中間体１や前記中間体２を合成すれば、Ａ部は容易に変更することが可能である。更に、Ａ部を変更することで色が変わるため、所望の色に調整することができる。 As can be seen from Table 1, when Examples 1 to 10 of the present invention are compared with Comparative Examples 1 and 2, the color difference ΔE * ab is small, and the color difference is small even when subjected to a high-temperature heat history of 230 ° C. It was found that the thermal stability of the compound was very high.
In addition, as in the general formula (I), the present invention can be synthesized by freely changing the A part effective in heat resistance by linking the linking group Z at a specific site. It is excellent in that the property can be further improved. For example, if the intermediate 1 or the intermediate 2 is synthesized, the part A can be easily changed. Furthermore, since the color is changed by changing the A portion, it can be adjusted to a desired color.

Claims (6)

  1. 下記一般式（Ｉ）で表される化合物。 
    Figure JPOXMLDOC01-appb-C000001
     （一般式（Ｉ）中、Ｚは、置換基を有していてもよいａ価の、脂肪族系又は芳香族系の炭化水素基を表す。Ｂｃ－はｃ価のアニオンを表す。Ｒ１～Ｒ３は各々独立に水素原子、置換基を有していてもよいアルキル基又は置換基を有していてもよいアリール基を表し、Ｒ１とＲ２が結合して環構造を形成してもよい。　
    Ａは置換基を有していてもよい芳香族基又は置換基を有していてもよい複素環基を表す。
    複数あるＲ１～Ｒ３及びＡはそれぞれ同一であっても異なっていてもよい。ａは２以上の整数、ｂ、ｃ、ｄは１以上の整数を表す。Ｙは各々独立に、水素原子、または任意の置換基を示す。）     The compound represented by the following general formula (I).
    Figure JPOXMLDOC01-appb-C000001
     (In the general formula (I), Z represents an a-valent aliphatic or aromatic hydrocarbon group which may have a substituent. B c- represents a c-valent anion. R 1 to R 3 each independently represent a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group, and R 1 and R 2 combine to form a ring structure May be.
    A represents an aromatic group which may have a substituent or a heterocyclic group which may have a substituent.
    A plurality of R 1 to R 3 and A may be the same or different. a represents an integer of 2 or more, and b, c, and d represent an integer of 1 or more. Y each independently represents a hydrogen atom or an arbitrary substituent. )
  2. 前記一般式（Ｉ）におけるアニオン（Ｂｃ－）が、ヘテロポリオキソメタレートアニオンである、請求項１記載の化合物。 The compound according to claim 1, wherein the anion (B c- ) in the general formula (I) is a heteropolyoxometalate anion.
  3. 前記一般式（Ｉ）におけるアニオン（Ｂｃ－）が、下記一般式（ＩＩ）で表される、請求項１記載の化合物。　
    Figure JPOXMLDOC01-appb-C000002
     （一般式（ＩＩ）中、Ｒ６及びＲ７は、各々独立に、置換基を有していてもよい炭素数１～８のアルキル基、置換基を有していてもよい炭素数２～６のアルケニル基、又は置換基を有していてもよい炭素数３～８のシクロアルキル基を表す。尚、Ｒ６及びＲ７は、互いに連結して環を形成していてもよく、該環は置換基を有していてもよい。）     The compound according to claim 1, wherein the anion (B c- ) in the general formula (I) is represented by the following general formula (II).
    Figure JPOXMLDOC01-appb-C000002
     (In the general formula (II), R 6 and R 7 are each independently an alkyl group having 1 to 8 carbon atoms which may have a substituent, or 2 to 2 carbon atoms which may have a substituent. 6 represents an alkenyl group having 6 or an optionally substituted cycloalkyl group having 3 to 8 carbon atoms, wherein R 6 and R 7 may be linked to each other to form a ring; The ring may have a substituent.)
  4. 前記一般式（Ｉ）におけるアニオン（Ｂｃ－）が、下記一般式（ＩＩＩ）で表される、請求項１記載の化合物。
    Figure JPOXMLDOC01-appb-C000003
     （一般式（ＩＩＩ）中、Ｒ８～Ｒ１０は、各々独立に、置換基を有していてもよい炭素数１～８のアルキル基、置換基を有していてもよい炭素数２～６のアルケニル基、又は置換基を有していてもよい炭素数３～８のシクロアルキル基を表す。尚、Ｒ８～Ｒ１０は、互いに連結して環を形成していてもよく、該環は置換基を有していてもよい。）     The compound according to claim 1, wherein the anion (B c- ) in the general formula (I) is represented by the following general formula (III).
    Figure JPOXMLDOC01-appb-C000003
     (In the general formula (III), R 8 to R 10 are each independently an alkyl group having 1 to 8 carbon atoms which may have a substituent, and 2 to carbon atoms which may have a substituent. 6 represents an alkenyl group having 6 or an optionally substituted cycloalkyl group having 3 to 8 carbon atoms, wherein R 8 to R 10 may be linked to each other to form a ring; The ring may have a substituent.)
  5. 前記一般式（Ｉ）におけるアニオン（Ｂc－）が、スルホン酸アニオンである、請求項１記載の化合物。 The compound according to claim 1, wherein the anion (B c- ) in the general formula (I) is a sulfonate anion.
  6. 請求項１～５記載の化合物から選択される少なくとも一種を含有するカラーフィルタ。 A color filter comprising at least one selected from the compounds according to claims 1 to 5.
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