WO2021241484A1 - Instrument d'écriture - Google Patents

Instrument d'écriture Download PDF

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Publication number
WO2021241484A1
WO2021241484A1 PCT/JP2021/019578 JP2021019578W WO2021241484A1 WO 2021241484 A1 WO2021241484 A1 WO 2021241484A1 JP 2021019578 W JP2021019578 W JP 2021019578W WO 2021241484 A1 WO2021241484 A1 WO 2021241484A1
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group
carbon atoms
general formula
preferable
coo
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PCT/JP2021/019578
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English (en)
Japanese (ja)
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久人 羽賀
誠 田村
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三菱鉛筆株式会社
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
    • B43K—IMPLEMENTS FOR WRITING OR DRAWING
    • B43K1/00—Nibs; Writing-points
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
    • B43K—IMPLEMENTS FOR WRITING OR DRAWING
    • B43K8/00—Pens with writing-points other than nibs or balls
    • B43K8/02—Pens with writing-points other than nibs or balls with writing-points comprising fibres, felt, or similar porous or capillary material
    • 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
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0084—Dispersions of dyes
    • 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
    • C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/16—Writing inks
    • C09D11/17—Writing inks characterised by colouring agents

Definitions

  • This specification relates to a writing instrument capable of suppressing discoloration of the ink generated by adhering the coloring material of the ink for writing instruments to the pen tip.
  • Nylon pen nibs have good wear resistance and durability, so they fully exhibit the functions of a brush pen (stopping, splashing, splashing, etc.), but on the other hand, they adsorb specific inks, so they are mixed in different colors. It has the disadvantage of disturbing the condition and losing the original color.
  • the problem of adsorption of these inks is determined by the structure of the coloring material (dye), and red No. 104 and red No. 107 are mentioned as typical dyes.
  • a nylon pen for a brush pen made of a composite structure of a nylon fiber having a single thread of 1 to 10 d and an elastomer resin.
  • a nylon pen tip for a brush pen (see, for example, Patent Document 1), which is characterized in that a dyed seat obstructing element made of a halogenated diphenylurea derivative is adhered to the nylon fiber, and a focused fiber.
  • the present disclosure is intended to solve this problem in view of the above-mentioned problems of the prior art and the current situation, and suppresses discoloration of the ink generated by adhering the coloring material of the writing instrument ink to the pen tip (pen core).
  • the purpose is to provide a writing instrument that can be used.
  • aqueous ink composition containing a colored particle aqueous dispersion composed of a polymer having at least a monomer unit derived from a dye having a specific functional group.
  • the writing instrument of the above purpose can be obtained by mounting an object and constructing the pen tip from a specific material, and have completed the present disclosure.
  • the writing tool of the present disclosure is equipped with an aqueous ink composition containing a colored particle aqueous dispersion composed of a polymer having at least a monomer unit derived from a dye having a polymerizable unsaturated group, and a pen tip (sinter). It is characterized in that (excluding the core) is composed of a polyester-based material.
  • the dye-derived monomer is derived from the compound represented by the following general formula (1).
  • Dye represents a dye residue
  • R 1 represents a hydrogen atom or a methyl group
  • Y 2 represents -O- or -NR 10-
  • R 10 represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.
  • a 1 is -O-, -OCO-, -COO-, -NHCO-, -CONH-, -NHCONH-, an arylene group and the following general formula (2-1).
  • Y 1 is a nitrogen atom or the following formula (2-2). Represents the group represented by, n 1 represents an integer of 0 to 2, and n 2 represents an integer of 2 to 4. However, n 1 + n 2 is 3 or 4.
  • the Dye is a dye residue represented by the following general formulas (I), (III), (IV), (VI) or (VII).
  • each of n 101 R 105s independently has a halogeno group, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, and a substituent.
  • it represents an unsubstituted amino group, a hydroxy group, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms.
  • Y 101 represents an oxygen atom, a sulfur atom, -NR 132- or -Si (R 133 ) 2-
  • R 132 represents an alkyl group having 1 to 6 carbon atoms
  • the two R 133s are independent of each other.
  • Ar 1 has the following general formulas (I-1-1) to (I-1-7).
  • R 101 and R 104 independently represent a hydrogen atom or a methyl group, respectively.
  • R 102 and R 103 each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an aryl group having 6 to 14 carbon atoms or having no substituent.
  • * And ** represent the same positions as * and ** in the general formula (I).
  • R 101 and R 102 may form an alkylene group having 2 to 4 carbon atoms.
  • R 103 and R 104 may form an alkylene group having 2 to 4 carbon atoms.
  • R 131 represents an alkyl group having 1 to 30 carbon atoms. * And ** represent the same positions as * and ** in the general formula (I).
  • Ar 2 represents a benzene ring, a naphthalene ring or an anthracene ring.
  • n 101 represents an integer of 0 to 4
  • Ar 2 is a naphthalene ring
  • n 101 represents an integer of 0 to 6
  • Ar 2 is an anthracene ring
  • n 101 is 0.
  • R 301 and R 306 each independently represent a hydrogen atom or a methyl group.
  • R 302 to R 305 each independently represent an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 14 carbon atoms or having no substituent.
  • n 301 R 308s independently represent an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a naphthyl group, a halogeno group, a hydroxy group, a nitro group or a sulfo group.
  • Ar 3 represents a benzene ring or a naphthalene ring.
  • n 301 represents an integer of 0 to 4
  • n 301 represents an integer of 0 to 6.
  • R 401 to R 404 are independent hydrogen atoms, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkyloxycarbonyl group having 2 to 4 carbon atoms, and an alkyl having 2 to 4 carbon atoms.
  • R 405 and R 406 independently has a hydrogen atom; an alkyl group having 1 to 6 carbon atoms; an alkyl group having 1 to 6 carbon atoms, a nitro group, a halogeno group or a cyano group, or having an unsubstituted carbon number of 7 to 6 to A phenylalkyl group of 9; or a naphthylalkyl group having 11 to 13 carbon atoms.
  • R 407 has a hydrogen atom; an alkoxy group having 1 to 6 carbon atoms, an alkyloxycarbonyl group having 2 to 4 carbon atoms, a hydroxy group, a carboxy group, a halogeno group, a cyano group or an amino group, or an unsubstituted carbon number of 1 Alkyl group of up to 6; alkoxy group of 1 to 6 carbon atoms, halogeno group or phenylalkyl group having or unsubstituted 7 to 9 carbon atoms; or naphthylalkyl group of 11 to 13 carbon atoms.
  • n 401 R 408s are independent of each other, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkyloxycarbonyl group having 2 to 4 carbon atoms, and an alkylcarbonyloxy having 2 to 4 carbon atoms.
  • n 401 represents an integer from 0 to 4.
  • An - is the same as above, R601 represents an alkyl group having 1 to 6 carbon atoms.
  • R 602 and R 603 independently represent an alkyl group having 1 to 30 carbon atoms.
  • R 701 represents an alkyl group having 1 to 30 carbon atoms.
  • the polyester-based material is a polyester-based elastomer.
  • the shape of the pen tip is any of an inclined shape (knife cut shape), a cannonball shape, and a brush shape (brush body).
  • a writing instrument capable of suppressing discoloration of ink generated by adhering a coloring material of ink for writing instruments to a pen tip.
  • FIG. 1 (A) is a front view showing an example of an embodiment of the writing instrument of the present disclosure, and (b) is a vertical sectional view thereof. It is an enlarged vertical sectional view of the illustrated reference numeral X portion of FIG. 1 (b).
  • the writing tool of the present disclosure is equipped with an aqueous ink composition containing a colored particle aqueous dispersion composed of a polymer having at least a monomer unit derived from a dye having a polymerizable unsaturated group, and a pen tip (sintered core). (Excluding) is characterized in that it is composed of a polyester-based material.
  • the monomer derived from the dye having a polymerizable unsaturated group is not particularly limited as long as it is a monomer derived from a dye having a polymerizable unsaturated group, but is derived from a compound represented by the following general formula (1). It is preferable that it is a thing.
  • Dye represents a dye residue
  • R 1 represents a hydrogen atom or a methyl group
  • Y 2 represents -O- or -NR 10-
  • R 10 represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.
  • a 1 is -O-, -OCO-, -COO-, -NHCO-, -CONH-, -NHCONH-, an arylene group and the following general formula (2-1).
  • Y 1 is a nitrogen atom or the following formula (2-2). Represents the group represented by, n 1 represents an integer of 0 to 2, and n 2 represents an integer of 2 to 4. However, n 1 + n 2 is 3 or 4.
  • the dye residue represented by Dye in the general formula (1) is a monovalent residue excluding a group such as hydrogen in a molecule of a conventionally known dye, and may have any dye skeleton.
  • the dye residue include xanthene dyes, triarylmethane dyes, cyanine dyes, coumarin dyes, stilben dyes, naphthalimide dyes, perylene dyes, pyridine dyes, oxadin dyes, and olefin dyes.
  • xanthene dye examples include rhodamine B, rhodamine 6G, rhodamine 3B, rhodamine 101, rhodamine 110, sulfodamine 101, basic violet 11, basic red 2 and other rhodamine dyes; for example, eosin Y, eosin B and the like.
  • Eosin dyes for example, fluorescein dyes such as fluorescein and fluorescein isothiocyanate, and rhodamine dyes are preferable.
  • triarylmethane dye examples include triphenylmethane, basic violet 3, phenol red, phenolphthalein, green S, malachite green, thymol blue and the like.
  • cyanine dye examples include 4-dicyanomethylene-2-methyl-6- (p-dimethylaminostyryl) -4H-pyran (DCM), basic yellow 11, basic yellow 13, basic red 12, and basic red 13. , Basic Red 14, Basic Red 15, Basic Red 37, Basic Violet 15, Basic Violet 16, and other cyanine dyes.
  • coumarin-based dye examples include coumarin-based dyes such as coumarin 6, coumarin 7, coumarin 153, coumarin 314, coumarin 334, coumarin 545, coumarin 545T, coumarin 545P, and 7-hydroxy-4-methylcoumarin. ..
  • stilbene dye examples include stilbene dyes such as 1,4-bis (2-methylstyryl) benzene and trans-4,4'-diphenylstilbenzene.
  • naphthalimide dyes such as Basic Yellow 51, Solvent Yellow 11, Solvent Yellow 98, Solvent Yellow 116, Solvent Yellow 43, and Solvent Yellow 44.
  • perylene dye examples include perylene dyes such as perylene, LUMOGEN (registered trademark) yellow, lumogen green, lumogen orange, lumogen pink, lumogen red, solvent orange 5, and solvent green 5.
  • perylene dyes such as perylene, LUMOGEN (registered trademark) yellow, lumogen green, lumogen orange, lumogen pink, lumogen red, solvent orange 5, and solvent green 5.
  • pyridine dye examples include a pyridine dye such as 1-ethyl-2- [4- (p-dimethylaminophenyl) -1,3-butadienyl] -pyridinium-perchlorate (pyridine 1), and an acridine dye. And so on.
  • a pyridine dye such as 1-ethyl-2- [4- (p-dimethylaminophenyl) -1,3-butadienyl] -pyridinium-perchlorate (pyridine 1), and an acridine dye. And so on.
  • oxazine-based dye examples include oxazine-based dyes such as cresyl violet acetate and dioxazine-based dyes.
  • olefin dye examples include an ethene dye, a butadiene dye, and a hexatriene dye.
  • azole dye examples include oxazole dye, thiazole dye and the like.
  • azo dye examples include Solvent Yellow 14, Solvent Yellow 16, Solvent Yellow 21, Solvent Yellow 61, Solvent Yellow 81, Solvent Red 1, Solvent Red 2, Solvent Red 8, Solvent Red 19, Solvent Red 23, and Solvent. Red 24, Solvent Red 27, Solvent Red 31, Solvent Red 83, Solvent Red 84, Solvent Red 121, Solvent Red 132, Solvent Violet 21, Solvent Black 3, Solvent Black 4, Solvent Black 21, Solvent Black 23, Solvent Black 27 , Solvent Black 28, Solvent Black 31, Solvent Orange 7, Solvent Orange 9, Solvent Orange 37, Solvent Orange 40, Solvent Orange 45 and other monoazo dyes, Disazo, Condensed Azo and other azo dyes. Dyes are preferred.
  • the above-mentioned dyes can be divided into acid dyes, basic dyes and nonionic dyes.
  • the acidic dye means an ionic dye in which the anionic portion becomes a chromogen
  • the basic dye means an ionic dye in which the cation portion becomes a chromogen
  • the nonionic dye Means a dye that does not fall under any of the above-mentioned acidic dyes and basic dyes (however, ionic dyes forming intramolecular salts are also included in the acidic dyes or basic dyes).
  • the dye residue in Dye of the general formula (1) may be derived from any of acid dyes, basic dyes and nonionic dyes, preferably acid dyes or basic dyes, and basic dyes. Derivatives are more preferred. Specifically, among the residues derived from the above-mentioned dyes, xanthene-based basic dyes, triarylmethane-based basic dyes, cyanine-based basic dyes, coumarin-based basic dyes, and azo-based non-ions.
  • Residues derived from sex dyes are preferred, and residues derived from rhodamine-based basic dyes, triarylmethane-based basic dyes, cyanine-based basic dyes, coumarin-based basic dyes, and disazo-based nonionic dyes. Is more preferable.
  • dye residues in Dye of the general formula (1) include dye residues represented by the following general formulas (I), (III), (IV), (VI) and (VII).
  • each of n 101 R 105s independently has a halogeno group, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, and a substituent. Alternatively, it represents an unsubstituted amino group, a hydroxy group, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms.
  • Y 101 represents an oxygen atom, a sulfur atom, -NR 132- or -Si (R 133 ) 2-
  • R 132 represents an alkyl group having 1 to 6 carbon atoms
  • the two R 133s are independent of each other.
  • An - represents an anion
  • Ar 1 has the following general formulas (I-1-1) to (I-1-7).
  • R 101 and R 104 independently represent a hydrogen atom or a methyl group, respectively.
  • R 102 and R 103 each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an aryl group having 6 to 14 carbon atoms or having no substituent. * And ** represent the same positions as * and ** in the general formula (I).
  • R 101 and R 102 may form an alkylene group having 2 to 4 carbon atoms.
  • R 103 and R 104 may form an alkylene group having 2 to 4 carbon atoms.
  • R 131 represents an alkyl group having 1 to 30 carbon atoms.
  • * And ** represent the same positions as * and ** in the general formula (I).
  • Ar 2 represents a benzene ring, a naphthalene ring or an anthracene ring.
  • n 101 represents an integer of 0 to 4
  • Ar 2 is a naphthalene ring
  • n 101 represents an integer of 0 to 6
  • Ar 2 is an anthracene ring
  • n 101 is 0.
  • R 301 and R 306 each independently represent a hydrogen atom or a methyl group.
  • R 302 to R 305 each independently represent an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 14 carbon atoms or having no substituent.
  • n 301 R 308s independently represent an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a naphthyl group, a halogeno group, a hydroxy group, a nitro group or a sulfo group.
  • Ar 3 represents a benzene ring or a naphthalene ring. When Ar 3 is a benzene ring, n 301 represents an integer of 0 to 4, and when Ar 3 is a naphthalene ring, n 301 represents an integer of 0 to 6.
  • R 401 to R 404 are independent hydrogen atoms, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkyloxycarbonyl group having 2 to 4 carbon atoms, and an alkyl having 2 to 4 carbon atoms.
  • Each of R 405 and R 406 independently has a hydrogen atom; an alkyl group having 1 to 6 carbon atoms; an alkyl group having 1 to 6 carbon atoms, a nitro group, a halogeno group or a cyano group, or having an unsubstituted carbon number of 7 to 6 to A phenylalkyl group of 9; or a naphthylalkyl group having 11 to 13 carbon atoms.
  • R 407 has a hydrogen atom; an alkoxy group having 1 to 6 carbon atoms, an alkyloxycarbonyl group having 2 to 4 carbon atoms, a hydroxy group, a carboxy group, a halogeno group, a cyano group or an amino group, or an unsubstituted carbon number of 1 Alkyl group of up to 6; alkoxy group of 1 to 6 carbon atoms, halogeno group or phenylalkyl group having or unsubstituted 7 to 9 carbon atoms; or naphthylalkyl group of 11 to 13 carbon atoms.
  • n 401 R 408s are independent of each other, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkyloxycarbonyl group having 2 to 4 carbon atoms, and an alkylcarbonyloxy having 2 to 4 carbon atoms.
  • n 401 represents an integer from 0 to 4.
  • R601 represents an alkyl group having 1 to 6 carbon atoms.
  • R 602 and R 603 independently represent an alkyl group having 1 to 30 carbon atoms.
  • R 701 represents an alkyl group having 1 to 30 carbon atoms.
  • halide ion examples include fluoride ion (F ⁇ ), chloride ion (Cl ⁇ ), bromide ion (Br ⁇ ), iodide ion (I ⁇ ) and the like. , Chloride ion is preferred.
  • examples of the anion moiety in the anion containing an aryl group having an electron-withdrawing substituent, a sulfonyl group having an electron-withdrawing substituent or a haloalkyl group include a sulfonic acid anion and a nitrogen anion ( N ⁇ ), quaternary boron anion, nitrate ion, phosphate ion and the like can be mentioned, with sulfonic acid anion, nitrogen anion, quaternary boron anion being preferable, and quaternary boron anion being more preferable.
  • examples of the anion portion in the anion containing a halogeno group include quaternary boron anion, phosphorus anion, antimony anion and the like, and phosphorus anion and antimony anion are preferable, and phosphorus anion is more preferable.
  • examples of the electron-withdrawing substituent in the aryl group having an electron-withdrawing substituent or the electron-withdrawing substituent include a haloalkyl group having 1 to 3 carbon atoms and a halogeno. Examples thereof include a group and a nitro group. Among them, a haloalkyl group having 1 to 3 carbon atoms and a halogeno group are preferable, and a halogeno group is particularly preferable.
  • haloalkyl group having 1 to 3 carbon atoms as the electron-withdrawing substituent examples include a chloromethyl group, a trichloromethyl group, a 2-chloroethyl group, a 2,2,2-trichloroethyl group, and a pentachloroethyl group.
  • Chloroalkyl groups such as 2-chloropropyl group, 3-chloropropyl group, 2-chloro-2-propyl group, heptachloropropyl group; bromomethyl group, tribromomethyl group, 2-bromoethyl group, 2,2,2- Bromoalkyl groups such as tribromoethyl group, pentabromoethyl group, 2-bromopropyl group, 3-bromopropyl group, 2-bromo-2-propyl group, heptabromopropyl group; iodomethyl group, triiodomethyl group, 2 -Iodoalkyl groups such as iodoethyl group, 2,2,2-triiodoethyl group, pentaiodoethyl group, 2-iodopropyl group, 3-iodopropyl group, 2-iodo-2-propyl group and heptaiodopropyl
  • Fluoromethyl group trifluoromethyl group, 2-fluoroethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, pentafluoroethyl group, 3-fluoropropyl group , 3,3,3-Trifluoropropyl group, 2,2,3,3-tetrafluoropropyl group, heptafluoropropyl group and other fluoroalkyl groups.
  • trichloromethyl group pentachloroethyl group, heptachloropropyl group, tribromomethyl group, pentabromoethyl group, heptabromopropyl group, triiodomethyl group, pentaiodoethyl group, heptaiodopropyl group and trifluoromethyl group.
  • Pentafluoroethyl group, heptafluoropropyl group and other perhalogenoalkyl groups are preferred, trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group and other perfluoroalkyl groups are more preferred, and trifluoromethyl group is particularly preferred. ..
  • the electron-withdrawing substituent in the aryl group having an electron-withdrawing substituent among the above specific examples, those having a strong electron-withdrawing power are preferable, and a trifluoromethyl group and a fluoro group are preferable.
  • the nitro group is preferable, and the fluoro group is more preferable.
  • the electron-withdrawing substituent includes a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, and a fluoro group among the above specific examples. Groups are preferred.
  • Examples of the aryl group among the aryl groups having an electron-withdrawing substituent in the anion according to the present disclosure include a phenyl group, a naphthyl group and the like, and a phenyl group is preferable.
  • aryl group having an electron-withdrawing substituent in the anion include those represented by the following general formulas (20-1) and (20-2).
  • m represents an integer of 1 to 5
  • m R 41s independently represent a haloalkyl group, a halogeno group, or a nitro group having 1 to 3 carbon atoms.
  • m is usually an integer of 1 to 5, and when R 41 is a halogeno group, 2 to 5 is preferable, 3 to 5 is more preferable, and 5 is even more preferable.
  • R 41 is a nitro group, 1 to 3 is preferable, and 1 is more preferable.
  • R 41 is a haloalkyl group, 1 to 5 is preferable, and 1 to 3 is more preferable.
  • K in the general formula (20-2) is usually an integer of 1 to 7, and when R 41 is a halogeno group, 2 to 7 is preferable.
  • R 41 is a nitro group, 1 to 3 is preferable, and 1 is more preferable.
  • R 41 is a haloalkyl group, 1 to 7 is preferable, and 1 to 3 is more preferable.
  • the haloalkyl group having 1 to 3 carbon atoms of R 41 in the general formulas (20-1) and (20-2) is a haloalkyl group having 1 to 3 carbon atoms as an electron-withdrawing substituent in the anion according to the present disclosure.
  • the same as the group is mentioned, and the preferable one is also the same.
  • Examples of the halogeno group of R 41 in the general formulas (20-1) and (20-2) include a fluoro group, a chloro group, a bromo group and an iodine group, and a fluoro group is preferable.
  • R 41 in the general formulas (20-1) and (20-2) are the same as those of the electron-withdrawing substituent in the aryl group having the above-mentioned electron-withdrawing substituent.
  • Specific examples of the group represented by the general formula (20-1) include a trifluoromethylphenyl group, a di (trifluoromethyl) phenyl group, a tri (trifluoromethyl) phenyl group, and a pentafluoroethylphenyl group.
  • Specific examples of the group represented by the general formula (20-2) include a trifluoromethylnaphthyl group, a di (trifluoromethyl) naphthyl group, a tri (trifluoromethyl) naphthyl group, and a pentafluoroethylnaphthyl group.
  • Examples thereof include a group, a diiodonaftyl group, a triiodonaftyl group, a peryodnaphthyl group, a nitronaphthyl group, a dinitronaphthyl group, a trinitronaphthyl group and the like.
  • the group represented by the general formula (20-1) is preferable among the above specific examples, and specifically, a trifluoromethylphenyl group and a penta.
  • Fluoroethylphenyl group, heptafluoropropylphenyl group, nitrophenyl group, dinitrophenyl group, trinitrophenyl group, monofluorophenyl group, difluorophenyl group, trifluorophenyl group, perfluorophenyl group are preferable, difluorophenyl group, tri Fluorophenyl group and perfluorophenyl group are more preferable, and perfluorophenyl group is particularly preferable.
  • Examples of the sulfonyl group having an electron-withdrawing substituent in the anion according to the present disclosure include -SO 2 -CF 3 , -SO 2 -C 2 F 5 , -SO 2 -C 3 F 7 , and -SO 2 -F. , -SO 2 -Cl, -SO 2 -Br, -SO 2 -I and the like.
  • haloalkyl group in the anion according to the present disclosure examples include the same group as the haloalkyl group having 1 to 3 carbon atoms as the electron-withdrawing substituent in the anion according to the present disclosure, and the preferred one is also the same.
  • halogeno group in the anion according to the present disclosure examples include a fluoro group, a chloro group, a bromo group and an iodine group, and a fluoro group is preferable.
  • anion comprising an aryl group having an electron-withdrawing substituent, a sulfonyl group having an electron-withdrawing substituent, a haloalkyl group or a halogeno group in the anion according to the present disclosure
  • general formula ( 13) to (19) are mentioned.
  • R 41 and m are the same as above, and m R 41 may be the same or different.
  • R 41 and k are the same as above, and k R 41 may be the same or different.
  • R 41 and k are the same as above, and k R 41 may be the same or different.
  • R 42 to R 45 independently represent a haloalkyl group, a halogeno group or a nitro group having 1 to 3 carbon atoms
  • m 2 to m 5 independently represent an integer of 1 to 5 respectively.
  • M 2 R 42s , m 3 R 43s , m 4 R 44s and m 5 R 45s may be the same or different, respectively).
  • each of the four R 46s independently represents a haloalkyl group or a halogeno group having 1 to 3 carbon atoms.
  • R 47 and R 48 each independently represents a haloalkyl group or a halogeno group having 1 to 3 carbon atoms, with the R 47 and R 48, to form a haloalkylene group having 2 to 3 carbon atoms May be good.
  • R 49 represents a phosphorus atom or an antimony atom, and 6 Xs represent the same halogeno group.
  • haloalkyl groups having 1 to 3 carbon atoms in R 42 to R 45 of the general formula (16), R 46 of the general formula (17), and R 47 and R 48 of the general formula (18) are anions according to the present disclosure.
  • the electron-withdrawing substituent in the above the same group as the haloalkyl group having 1 to 3 carbon atoms can be mentioned, and the preferred group is also the same.
  • R 42 to R 45 of the general formula (16), R 46 of the general formula (17), R 47 and R 48 of the general formula (18), and the halogen group in X of the general formula (19) are fluoro groups. Examples thereof include a chloro group, a bromo group and an iodine group, and a fluoro group is preferable.
  • Examples of the haloalkylene group having 2 to 3 carbon atoms formed by R 47 and R 48 of the general formula (18) include a tetrafluoroethylene group and a hexafluorotrimethylene group, and a hexafluorotrimethylene group is used. preferable.
  • R 49 of the general formula (19) a phosphorus atom is preferable.
  • Examples of the combination of R 41 and m in the general formula (13) include those described in the following table. It is preferable that the m R 41s are all the same group.
  • Preferred specific examples of the anion represented by the general formula (13) include, for example, the following.
  • Examples of the combinations of R 41 and k in the general formulas (14) and (15) include those described in the following table. It is preferable that the k R 41s are all the same group.
  • Preferred specific examples of the anions represented by the general formulas (14) and (15) include, for example, the following.
  • m 2 R 42 , m 3 R 43 , m 4 R 44, and m 5 R 45 in the general formula (16) are each the same group.
  • Examples of the combinations of R 42 to R 45 and m 2 to m 5 in the general formula (16) include those described in the following table.
  • Preferred specific examples of the anion represented by the general formula (16) include, for example, the following.
  • anion represented by the general formula (17) for example, BF 4 -, CF 3 BF 3 -, C 2 F 5 BF 3 -, C 3 F 7 BF 3 -, (CF 3) 4 B - , (C 2 F 5) 4 B -, (C 3 F 7) 4 B - , and the like.
  • Preferred specific examples of the anion represented by the general formula (18) include, for example, the following.
  • Preferred specific examples of the anion represented by the general formula (19) include, for example, PF 6 ⁇ , SbF 6 ⁇ and the like, and PF 6 ⁇ is preferable.
  • halogen oxo acid anion in the anions according to the present disclosure include hypochlorate anion, chlorate anion, chlorate anion, perchlorate anion and the like, and perchlorate anion is preferable.
  • sulfonic acid anion in the anions according to the present disclosure include alkyl sulfonic acid anions having 1 to 20 carbon atoms such as methane sulfonic acid anions; and haloalkyl sulfonic acids having 1 to 20 carbon atoms such as trifluoromethane sulfonic acid anions.
  • General formula (I), An of the general formula (III), general formula (IV) and the general formula (VI) - as has anion are preferred according to the present disclosure, halide ions, and an electron-withdrawing group More preferably, an anion containing an aryl group, a sulfonyl group having an electron-withdrawing substituent, a haloalkyl group or a halideno group.
  • chloride ions and anions represented by the general formulas (16) to (19) are preferable, and chloride ions and anions represented by the general formulas (16), (18) or (19) are more preferable.
  • Chloride ions and anions represented by the general formula (16) or (19) are more preferred.
  • Examples of the halogeno group in R 105 of the general formula (I) include a fluoro group, a chloro group, a bromo group and an iodine group, and a fluoro group is preferable.
  • the alkyl group having 1 to 30 carbon atoms in R 105 of the general formula (I) may be any of linear, branched and cyclic, and among them, linear and branched are preferable. Further, among the alkyl groups having 1 to 30 carbon atoms, those having 1 to 12 carbon atoms are preferable, those having 1 to 6 carbon atoms are more preferable, those having 1 to 4 carbon atoms are further preferable, and those having 1 to 2 carbon atoms are more preferable. Is particularly preferable.
  • n-butyl group isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, neopentyl group, 2-methylbutyl group, 1,2- Dimethylpropyl group, 1-ethylpropyl group, n-hexyl group, isohexyl group, sec-hexyl , 3-Dimethylbutyl group, 1-ethylbutyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group are preferable, and methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group,
  • the alkoxy group having 1 to 20 carbon atoms in R 105 of the general formula (I) may be any of linear, branched and cyclic, and among them, linear and branched are preferable. Further, among the alkoxy groups having 1 to 20 carbon atoms, those having 1 to 12 carbon atoms are preferable, those having 1 to 6 carbon atoms are more preferable, and those having 1 to 4 carbon atoms are particularly preferable.
  • the alkylthio group having 1 to 20 carbon atoms in R 105 of the general formula (I) may be any of linear, branched and cyclic, and among them, linear and branched are preferable. Further, among the alkylthio groups having 1 to 20 carbon atoms, those having 1 to 12 carbon atoms are preferable, those having 1 to 6 carbon atoms are more preferable, and those having 1 to 4 carbon atoms are particularly preferable.
  • Tert-octylthio group neooctylthio group, 2-ethylhexylthio group, cyclooctylthio group, n-nonylthio group, isononylthio group, sec-nonylthio group, tert-nonylthio group, neononylthio group, cyclononylthio group, n- Decylthio group, isodecylthio group, sec-decylthio group, tert-decylthio group, neodecylthio group, cyclodecylthio group, n-undecylthio group, cycloundecylthio group, n-dodecylthio group, cyclododecylthio group, n-tridecylthio group, Isotridecylthio group, n-t-t
  • n-butylthio group isobutylthio group, sec-butylthio group, tert-butylthio group, n-pentylthio group, isopentylthio group, sec-pentylthio group, tert-pentylthio group, neopentylthio group, 2-methyl Butylthio group, 1,2-dimethylpropylthio group, 1-ethylpropylthio group, n-hexylthio Group, isohexylthio group, sec-hexylthio group, tert-hexylthio group, neohexylthio group, 2-methylpentylthio group, 1,2-dimethylbutylthio group, 2,3-dimethylbutylthio group, 1-ethyl A butylthio group is preferable, a methylthio group, an ethylthio group, an ethyl
  • the amino group having a substituent in R 105 of the general formula (I) has one or two substituents.
  • substituents include an alkyl group having 1 to 30 carbon atoms, a haloalkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an arylalkyl group having 7 to 13 carbon atoms and the like.
  • the alkyl group having 1 to 30 carbon atoms in the substituent of the amino group having the substituent in R 105 of the general formula (I) is the same as the alkyl group having 1 to 30 carbon atoms in R 105 of the general formula (I). And the preferred ones are the same.
  • the haloalkyl group having 1 to 20 carbon atoms in the substituent of the amino group having the substituent in R 105 of the general formula (I) may be any of linear, branched and cyclic, and among them, direct. Chain-shaped and branched-shaped are preferable. Further, among the haloalkyl groups having 1 to 20 carbon atoms, those having 1 to 12 carbon atoms are preferable, those having 1 to 6 carbon atoms are more preferable, and those having 1 to 3 carbon atoms are particularly preferable.
  • chloromethyl group trichloromethyl group, 2-chloroethyl group, 2,2,2-trichloroethyl group, pentachloroethyl group, 2-chloropropyl group, 3-chloropropyl group, 2-chloro- Chloroalkyl groups such as 2-propyl group and heptachloropropyl group; bromomethyl group, tribromomethyl group, 2-bromoethyl group, 2,2,2-tribromoethyl group, pentabromoethyl group, 2-bromopropyl group, Bromoalkyl groups such as 3-bromopropyl group, 2-bromo-2-propyl group, heptabromopropyl group; iodomethyl group, triiodomethyl group, 2-iodoethyl group, 2,2,2-triiodoethyl group, penta Iodoalkyl groups such as iod
  • trichloromethyl group pentachloroethyl group, heptachloropropyl group, tribromomethyl group, pentabromoethyl group, heptabromopropyl group, triiodomethyl group, pentaiodoethyl group, heptaiodopropyl group and trifluoromethyl group.
  • Pentafluoroethyl group, heptafluoropropyl group and other perhalogenoalkyl groups are preferred, trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group and other perfluoroalkyl groups are more preferred, and trifluoromethyl group is particularly preferred. ..
  • Examples of the aryl group having 6 to 10 carbon atoms in the substituent of the amino group having the substituent in R 105 of the general formula (I) include a phenyl group and a naphthyl group, and a phenyl group is preferable.
  • Examples of the arylalkyl group having 7 to 13 carbon atoms in the substituent of the amino group having the substituent in R 105 of the general formula (I) include a phenylalkyl group having 7 to 9 carbon atoms and a naphthylalkyl group having 11 to 13 carbon atoms. Etc., and a phenylalkyl group having 7 to 9 carbon atoms is preferable.
  • a benzyl group a phenethyl group (2-phenylethyl group), a 1-phenylethyl group, a hydrocinnamyl group (3-phenylpropyl group), a 2-phenylpropyl group, a 1-phenylpropyl group, a cumyl group ( 2-Phenylpropan-2-yl group), naphthylmethyl group, 2-naphthylethyl group, 3-naphthylpropyl group and the like, including benzyl group, phenethyl group, 1-phenylethyl group, hydrocinnamyl group and 2-phenylpropyl group.
  • a group, a 1-phenylpropyl group and a cumyl group are preferable, a benzyl group, a phenethyl group and a hydrocinnamyl group are more preferable, and a benzyl group is further preferable.
  • an amino group having a substituent is preferable, an alkyl group having 1 to 30 carbon atoms, a haloalkyl group having 1 to 20 carbon atoms, and carbon.
  • An amino group having an aryl group having 6 to 10 or an arylalkyl group having 7 to 13 carbon atoms is more preferable, and an alkyl group having 1 to 12 carbon atoms, a phenyl group or an amino group having a phenylalkyl group having 7 to 9 carbon atoms is more preferable.
  • an amino group having an alkyl group having 1 to 6 carbon atoms is particularly preferable.
  • Diethylamino group, diphenylamino group, dibenzylamino group are more preferable, and methylamino group, ethylamino group, dimethylamino group and diethylamino group are further preferable.
  • aryl group having 6 to 14 carbon atoms in R 105 of the general formula (I) include a phenyl group, a naphthyl group, an anthrasenyl group and the like, and a phenyl group is preferable.
  • aryloxy group having 6 to 14 carbon atoms in R 105 of the general formula (I) include a phenoxy group, a naphthyloxy group, an anthracenyloxy group and the like, and a phenoxy group is preferable.
  • Examples of the arylalkyl group having 7 to 20 carbon atoms in R 105 of the general formula (I) include a phenylalkyl group having 7 to 12 carbon atoms, a naphthylalkyl group having 11 to 16 carbon atoms, and anthracenyl having 15 to 20 carbon atoms.
  • Examples thereof include an alkyl group, and a phenylalkyl group having 7 to 12 carbon atoms is preferable, and a phenylalkyl group having 7 to 9 carbon atoms is more preferable.
  • a benzyl group, a phenethyl group (2-phenylethyl group), a 1-phenylethyl group, a hydrocinnamyl group (3-phenylpropyl group), a 2-phenylpropyl group, a 1-phenylpropyl group, and a cumyl group 2-Phenylpropan-2-yl group
  • R 105 of the general formula (I) includes a halideno group; an alkyl group having 1 to 12 carbon atoms; an alkoxy group having 1 to 12 carbon atoms; an alkylthio group having 1 to 12 carbon atoms; an alkyl group having 1 to 30 carbon atoms, and the like.
  • a group; a hydroxy group; a phenyl group; a phenoxy group; and a phenylalkyl group having 7 to 9 carbon atoms are more preferable, and an alkyl group having 1 to 4 carbon atoms; and an amino group having an alkyl group having 1 to 6 carbon atoms are particularly preferable. ..
  • fluorine atom methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, n- Hexyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, methylthio group, ethylthio group, n-propylthio group, isopropylthio group , N-butylthio group, isobutylthio group, sec-butylthio group, tert-butylthio group, methylamino group, ethylamino group, n-propylamino group, isopropylamino group, n-butyl group,
  • the alkyl group having 1 to 6 carbon atoms in R 132 and R 133 in Y 101 of the general formula (I) may be any of linear, branched and cyclic, particularly linear and cyclic. Branched is preferable. Further, among the alkyl groups having 1 to 6 carbon atoms, those having 1 to 4 carbon atoms are preferable. Specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, n-pentyl group, isopentyl group, sec.
  • An isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group are preferable, and a methyl group and an ethyl group are more preferable.
  • Examples of the aryl group having 6 to 14 carbon atoms in R 133 in Y 101 of the general formula (I) include a phenyl group, a naphthyl group, an anthrasenyl group and the like, and a phenyl group is preferable.
  • R 133 in Y 101 of the general formula (I) it is preferable that the two R 133s are the same, a methyl group, an ethyl group and a phenyl group are preferable, and a methyl group and a phenyl group are more preferable. Methyl groups are particularly preferred.
  • an oxygen atom, -NR 132- and -Si (R 133 ) 2- are preferable, an oxygen atom and -NR 132- are more preferable, and an oxygen atom is particularly preferable.
  • oxygen atom, sulfur Atoms, -NCH 3- , -Si (CH 3 ) 2- , -Si (C 6 H 5 ) 2- are preferred, oxygen atoms, -NCH 3- , -Si (CH 3 ) 2- are more preferred, oxygen.
  • Atoms, -NCH 3- are more preferred, and oxygen atoms are particularly preferred.
  • Examples of the alkyl group having 1 to 30 carbon atoms in R 102 and R 103 of the general formula (I-1-1) include the same alkyl group having 1 to 30 carbon atoms in R 105 of the general formula (I). , The preferred ones are the same.
  • the aryl group having 6 to 14 carbon atoms in the "aryl group having or not substituted with a substituent and having 6 to 14 carbon atoms" in R 102 and R 103 of the general formula (I-1-1) includes a phenyl group and a naphthyl. Examples thereof include a group, an anthracenyl group and the like, and a phenyl group is preferable.
  • the aryl group having 6 to 14 carbon atoms having a substituent in R 102 and R 103 of the general formula (I-1-1) is usually substituted with 1 to 5, preferably 1 to 3, and more preferably 1.
  • the substituent include an alkyl group having 1 to 30 carbon atoms.
  • Examples of the alkyl group having 1 to 30 carbon atoms include the same alkyl groups having 1 to 30 carbon atoms in R 105 of the general formula (I), and preferred ones are also the same.
  • Examples of the aryl group having 6 to 14 carbon atoms having a substituent in R 102 and R 103 of the general formula (I-1-1) include an aryl group having 6 to 14 carbon atoms having an alkyl group having 1 to 30 carbon atoms.
  • a phenyl group having an alkyl group having 1 to 30 carbon atoms, a naphthyl group and an anthrasenyl group are preferable, a phenyl group having an alkyl group having 1 to 12 carbon atoms is more preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable.
  • a phenyl group having a phenyl group is more preferable, and a phenyl group having an alkyl group having 1 to 3 carbon atoms is particularly preferable.
  • o-tolyl group methylphenyl group
  • m-tolyl group m-tolyl group
  • p-tolyl group o-ethylphenyl group
  • m-ethylphenyl group m-ethylphenyl group
  • p-ethylphenyl group o-propylphenyl group, m-propylphenyl group, p-propylphenyl group, o-butylphenyl group, m-butylphenyl group, p-butylphenyl group, o-pentylphenyl group, m-pentylphenyl group, p-pentylphenyl group, o- Hexylphenyl group, m-hexy
  • alkyl group in the above specific example is not limited to the normal-form, and all of the branched ones such as sec-form, tert-form, iso-form (iso-form) and neo-form (neo-form) are also included. include.
  • R 101 and R 102 of the general formula (I-1-1) form an alkylene group having 2 to 4 carbon atoms
  • R 103 and R 104 form an alkylene group having 2 to 4 carbon atoms
  • the alkylene group having 2 to 4 carbon atoms may be linear or branched, and linear is preferable.
  • an ethylene group, a trimethylene group, a propylene group, a 1,1-dimethylmethylene group, a tetramethylene group, a 1-methyltrimethylene group, a 2-methyltrimethylene group, a 1,2-dimethylethylene group, 1 , 1-Dimethylethylene group, ethylethylene group and the like are mentioned, and an ethylene group, a trimethylene group and a tetramethylene group are preferable, and a trimethylene group is more preferable.
  • R 101 of the general formula (I-1-1) a hydrogen atom, a methyl group, and a linear alkylene group having 2 to 4 carbon atoms formed by R 101 and R 102 are preferable.
  • R 102 of the general formula (I-1-1) includes an alkyl group having 1 to 12 carbon atoms, a phenyl group having or not substituted with an alkyl group having 1 to 6 carbon atoms, and carbons of R 101 and R 102.
  • Those forming an alkylene group having a number of 2 to 4 are preferable, and an alkyl group having 1 to 6 carbon atoms, a phenyl group having an alkyl group having 1 to 3 carbon atoms or an unsubstituted phenyl group, and R 101 and R 102 are used.
  • Those forming a linear alkylene group having 2 to 4 carbon atoms are more preferable, and an alkyl group having 1 to 6 carbon atoms is further preferable.
  • ethylene group which form a trimethylene group and R 101 and R 102, or the like which forms a tetramethylene group in the R 101 and R 102, and a methyl group , Ethyl group, propyl group, butyl group, pentyl group, hexyl group, phenyl group, p-tolyl group, those forming a trimethylene group with R 101 and R 102 are preferable, and methyl group and ethyl group are more preferable. ..
  • the alkyl group in the above specific example is not limited to the normal-form, and all of the branched ones such as sec-form, tert-form, iso-form (iso-form) and neo-form (neo-form) are also included. include.
  • R 103 of the general formula (I-1-1) includes a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group having or not substituted with an alkyl group having 1 to 6 carbon atoms, and R 103 and R 104. Those forming an alkylene group having 2 to 4 carbon atoms are preferable, and a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 3 carbon atoms or an unsubstituted phenyl group, and R.
  • 103 and R 104 form a linear alkylene group having 2 to 4 carbon atoms, and further preferably a hydrogen atom and an alkyl group having 1 to 6 carbon atoms.
  • a hydrogen atom and an alkyl group having 1 to 6 carbon atoms for example, hydrogen atom, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, phenyl group, p-tolyl group, p-ethylphenyl group, p-propylphenyl group, R 103.
  • R 104 form an ethylene group
  • R 103 and R 104 form a trimethylene group
  • R 103 and R 104 form a tetramethylene group.
  • Hydrogen atom, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, phenyl group, p-tolyl group, those forming a trimethylene group with R 103 and R 104 are preferable.
  • Methyl group, ethyl group is more preferable.
  • the alkyl group in the above specific example is not limited to the normal-form, and all of the branched ones such as sec-form, tert-form, iso-form (iso-form) and neo-form (neo-form) are also included. include.
  • R 104 of the general formula (I-1-1) a hydrogen atom, a methyl group, and a linear alkylene group having 2 to 4 carbon atoms formed by R 103 and R 104 are preferable.
  • R 101 to R 104 in the general formula (I-1-1) include, for example, those described in the following table.
  • the alkyl group having 1 to 30 carbon atoms in R 131 of the general formulas (I-1-2) to (I-1-7) includes the alkyl group having 1 to 30 carbon atoms in R 105 of the general formula (I). The same is mentioned, and the preferred ones are the same.
  • * And ** in the general formula (I) correspond to * and ** in the general formulas (I-1-1) to (I-1-7), and the general formulas (I-1-1) to ** It represents that the ring structure represented by (I-1-7) is bound to the positions represented by * and ** of the dye residue represented by the general formula (I). Specifically, it is shown by the following structure. (Wherein, R 101 ⁇ R 105, R 131, Y 101, An -, Ar 2 and n 101 have the same as above.)
  • a benzene ring and a naphthalene ring are preferable, and a benzene ring is more preferable.
  • n 101 of the general formula (1) when Ar 2 is a benzene ring, an integer of 0 to 3 is preferable, 1 or 2 is more preferable, and when Ar 2 is a naphthalene ring and an anthracene ring, 0 or 1 is preferable. , 0 is more preferable.
  • the general formula (I) when Ar 2 is a benzene ring, the general formula (I) is represented by the following general formula (I-2-1), and when Ar 2 is a naphthalene ring, the general formula (I) is as follows. It is represented by the general formulas (I-2-2) to (I-2-4), and when Ar 2 is an anthracene ring, the general formula (I) is the following general formulas (I-2-5) to (I-2). It is represented by -7). Among these, the general formulas (I-2-1), (I-2-2) and (I-2-5) are preferable, and the general formula (I-2-1) is more preferable.
  • n 101 R 105s in the general formula (I-2-1) may be any of the I to IV positions of the benzene ring, and when n 101 is 1, it is located at the II position or the III position. Is preferable, and it is more preferable that it is located at the II position.
  • n 101 is 2, it is preferably located at the II and III positions, or the II and IV positions, and more preferably located at the II and III positions.
  • n 101 is 3, it is preferably located at the I, II and III positions or the II, III and IV positions, and more preferably located at the I, II and III positions. ..
  • n 101 R 105s in the general formula (I-2-2) may be any of the I to VI positions of the naphthalene ring, and is preferably located at the IV position or the VI position.
  • n 101 R 105s in the general formula (I-2-3) may be any of the I to VI positions of the naphthalene ring, and is preferably located at the III position.
  • n 101 R 105s in the general formula (I-2-4) may be any of the I to VI positions of the naphthalene ring, and is preferably located at the II position or the IV position.
  • n 101 R 105s in the general formula (I-2-5) may be any of the I to VIII positions of the anthracene ring, and is preferably located at the I position, the V position or the VI position.
  • n 101 R 105s in the general formula (I-2-6) may be any of the I to VIII positions of the anthracene ring, and is preferably located at the II position, the V position or the VII position.
  • n 101 R 105s in the general formula (I-2-7) may be any of the I to VIII positions of the anthracene ring, and is preferably located at the IV position or the V position.
  • Dye of the general formula (1) is a dye residue represented by formula (I)
  • the site of the general formula (I) ortho position of the phenyl group in which A 1 is bonded in the dye residue, meta It may be located at either the position or the para position, and the ortho position or the para position is preferable, and the ortho position is more preferable.
  • a 1 is bound as shown by the following general formula (I'-1).
  • * and ** represent the bonding positions with the ring structure represented by the general formulas (I-1-1) to (I-1-7), and represent R 1 , R 105 , Y 2 , Y 101. , a 1, Ar 1, Ar 2, an - and n 101 have the same as above).
  • Preferred specific examples of the general formula (I) include dye residues represented by the following general formula (I-3).
  • An '- represents a halide ion, or an aryl group having an electron withdrawing group, a sulfonyl group having an electron withdrawing group, an anion containing a haloalkyl group or a halogeno group, R 101 ⁇ R 105 , Ar 2 and n 101 are the same as above.
  • the anions comprising the halide ions, and aryl groups having an electron-withdrawing group, a sulfonyl group having an electron withdrawing group, a haloalkyl group or a halogeno group, - the general formula (I-3)
  • An in ' The same ones as those of the anions according to the present disclosure are mentioned, and the preferred ones are also the same.
  • Preferred specific examples of the general formula (I-3) include dye residues represented by the following general formula (I-4). (Wherein, R 101 ⁇ R 105, An '- and n 101 have the same as above.)
  • Preferred specific examples of the general formula (I-4) include dye residues represented by the following general formula (I-5).
  • R 201 and R 204 independently represent a hydrogen atom or a methyl group, respectively.
  • R 202 represents an alkyl group having 1 to 12 carbon atoms, or a phenyl group having or not substituted with an alkyl group having 1 to 6 carbon atoms.
  • R 203 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a phenyl group having or not substituted with an alkyl group having 1 to 6 carbon atoms.
  • n 201 R 205s are halideno groups; alkyl groups with 1 to 12 carbon atoms; alkoxy groups with 1 to 12 carbon atoms; alkylthio groups with 1 to 12 carbon atoms; alkyl groups with 1 to 30 carbon atoms, 1 carbon atoms.
  • n 201 represents an integer from 0 to 4.
  • R 201 and R 202 may form an alkylene group having 2 to 4 carbon atoms.
  • R 203 and R 204 may form an alkylene group having 2 to 4 carbon atoms.
  • An '- is the same as
  • the alkyl group having 1 to 12 carbon atoms in R 202 and R 203 of the general formula (I-5) may be any of linear, branched and cyclic, and among them, linear and branched.
  • the shape is preferable.
  • those having 1 to 6 carbon atoms are more preferable, those having 1 to 4 carbon atoms are further preferable, and those having 1 to 2 carbon atoms are particularly preferable.
  • a decyl group and an n-dodecyl group are preferable, and a methyl group, an ethyl group, an n-propyl group, an isoprop
  • the phenyl group having an alkyl group having 1 to 6 carbon atoms in R 202 and R 203 of the general formula (I-5) usually has 1 to 5, preferably 1 to 3, and more preferably 1 alkyl group.
  • Examples of the alkyl group include the same alkyl groups having 1 to 6 carbon atoms in R 132 and R 133 in Y 101 of the general formula (I), and preferred ones are also the same.
  • a phenyl group having an alkyl group having 1 to 6 carbon atoms in R 202 and R 203 of the general formula (I-5) a phenyl group having an alkyl group having 1 to 3 carbon atoms is particularly preferable, and specifically, for example.
  • the alkyl group in the above specific example is not limited to the normal-form, and all of the branched ones such as sec-form, tert-form, iso-form (iso-form) and neo-form (neo-form) are also included. include.
  • R 201 and R 202 of the general formula (I-5) form an alkylene group having 2 to 4 carbon atoms
  • R 203 and R 204 form an alkylene group having 2 to 4 carbon atoms
  • the alkylene group having 2 to 4 carbon atoms is the case where the alkylene group having 2 to 4 carbon atoms is formed by R 101 and R 102 of the general formula (I-1-1), and R 103 and R.
  • the same as the alkylene group having 2 to 4 carbon atoms in the case where the alkylene group having 2 to 4 carbon atoms is formed with 104 can be mentioned, and the preferable one is also the same.
  • R 201 and R 202 form an alkylene group having 2 to 4 carbon atoms and / or, R 203 and R 204 form an alkylene group having 2 to 4 carbon atoms.
  • Specific examples of the above include the following general formulas (I-5-1) to (I-5-9), and the general formulas (I-5-2) and (I-5-5).
  • Or (I-5-8) is preferable, and the general formula (I-5-8) is more preferable.
  • R 201 ⁇ R 205, An '- and n 201 are the same as above.
  • R 201 of the general formula (I-5) a hydrogen atom, a methyl group, and a linear alkylene group having 2 to 4 carbon atoms formed by R 201 and R 202 are preferable.
  • the R 202 of the general formula (I-5) includes an alkyl group having 1 to 6 carbon atoms, a phenyl group having or not substituted with an alkyl group having 1 to 3 carbon atoms, and R 201 and R 202 having 2 carbon atoms. Those forming a linear alkylene group of to 4 are preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable.
  • ethylene group which form a trimethylene group and R 201 and R 202, or the like which forms a tetramethylene group in the R 201 and R 202, and a methyl group , Ethyl group, propyl group, butyl group, pentyl group, hexyl group, phenyl group, p-tolyl group, R 201 and R 202 forming a trimethylene group are preferable, and methyl group and ethyl group are more preferable. ..
  • the alkyl group in the above specific example is not limited to the normal-form, and all of the branched ones such as sec-form, tert-form, iso-form (iso-form) and neo-form (neo-form) are also included. include.
  • R 203 of the general formula (I-5) includes a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group having or not substituted with an alkyl group having 1 to 3 carbon atoms, and R 203 and R 204 .
  • Those forming a linear alkylene group having 2 to 4 carbon atoms are preferable, and a hydrogen atom and an alkyl group having 1 to 6 carbon atoms are more preferable.
  • R 203 hydrogen atom, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, phenyl group, p-tolyl group, p-ethylphenyl group, p-propylphenyl group, R 203.
  • R 204 form an ethylene group
  • R 203 and R 204 form a trimethylene group
  • R 203 and R 204 form a tetramethylene group.
  • Hydrogen atom, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, phenyl group, p-tolyl group, those forming a trimethylene group with R 203 and R 204 are preferable.
  • Methyl group, ethyl group is more preferable.
  • the alkyl group in the above specific example is not limited to the normal-form, and all of the branched ones such as sec-form, tert-form, iso-form (iso-form) and neo-form (neo-form) are also included. include.
  • R 204 of the general formula (I-5) a hydrogen atom, a methyl group, and a linear alkylene group having 2 to 4 carbon atoms formed by R 203 and R 204 are preferable.
  • Examples of the halogeno group in R 205 of the general formula (I-5) include a fluoro group, a chloro group, a bromo group and an iodine group, and a fluoro group is preferable.
  • Examples of the alkyl group having 1 to 12 carbon atoms in R 205 of the general formula (I-5) include the same alkyl groups having 1 to 12 carbon atoms in R 202 and R 203 of the general formula (I-5). , The preferred ones are the same.
  • the alkoxy group having 1 to 12 carbon atoms in R 205 of the general formula (I-5) may be any of linear, branched and cyclic, and among them, linear and branched are preferable. .. Further, among the alkoxy groups having 1 to 12 carbon atoms, those having 1 to 6 carbon atoms are preferable, and those having 1 to 4 carbon atoms are more preferable.
  • the alkylthio group having 1 to 12 carbon atoms in R 205 of the general formula (I-5) may be any of linear, branched and cyclic, and among them, linear and branched are preferable. .. Further, among the alkylthio groups having 1 to 12 carbon atoms, those having 1 to 6 carbon atoms are preferable, and those having 1 to 4 carbon atoms are more preferable.
  • Tert-octylthio group neooctylthio group, 2-ethylhexylthio group, cyclooctylthio group, n-nonylthio group, isononylthio group, sec-nonylthio group, tert-nonylthio group, neononylthio group, cyclononylthio group, n- Examples include decylthio group, isodecylthio group, sec-decylthio group, tert-decylthio group, neodecylthio group, cyclodecylthio group, n-undecylthio group, cycloundecylthio group, n-dodecylthio group, cyclododecylthio group, and methylthio.
  • R 205 of the general formula (I-5) has an "alkyl group having 1 to 30 carbon atoms, a haloalkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms or an arylalkyl group having 7 to 13 carbon atoms.
  • Specific examples of the alkyl group having 1 to 30 carbon atoms, the haloalkyl group having 1 to 20 carbon atoms, the aryl group having 6 to 10 carbon atoms and the arylalkyl group having 7 to 13 carbon atoms in the "amino group” are given by the general formula (I).
  • the same as those of the "amino group having a substituent" in R 105 of the above can be mentioned, and the preferred one is also the same.
  • R 205 of the general formula (I-5) "having an alkyl group having 1 to 30 carbon atoms, a haloalkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms or an arylalkyl group having 7 to 13 carbon atoms".
  • an alkyl group having 1 to 12 carbon atoms, a phenyl group or an amino group having a phenylalkyl group having 7 to 9 carbon atoms is preferable, and an amino group having an alkyl group having 1 to 6 carbon atoms is more preferable.
  • Diethylamino group, diphenylamino group, dibenzylamino group are more preferable, and methylamino group, ethylamino group, dimethylamino group and diethylamino group are further preferable.
  • arylalkyl group general formula (I-5) an aryl group having 6 to 14 carbon atoms R 205, an aryloxy group and having 7 to 20 carbon atoms having 6 to 14 carbon atoms of general formula (I)
  • R 105 the same ones as those in R 105 are mentioned, and so are the preferred ones.
  • R 205 of the general formula (I-5) includes a halogeno group; an alkyl group having 1 to 12 carbon atoms; an alkoxy group having 1 to 12 carbon atoms; an alkylthio group having 1 to 12 carbon atoms; an alkyl group having 1 to 12 carbon atoms.
  • a group, a phenyl group or an amino group having a phenylalkyl group having 7 to 9 carbon atoms; a hydroxy group; a phenyl group; a phenoxy group; and a phenylalkyl group having 7 to 12 carbon atoms are preferable, and a halogeno group; Alkyl group; alkoxy group with 1 to 6 carbon atoms; alkylthio group with 1 to 6 carbon atoms; alkyl group with 1 to 12 carbon atoms, phenyl group or amino group having phenylalkyl group with 7 to 9 carbon atoms; hydroxy group; A phenyl group; a phenoxy group; and a phenylalkyl group having 7 to 9 carbon atoms are more preferable, and an alkyl group having 1 to 4 carbon atoms; and an amino group having an alkyl group having 1 to 6 carbon atoms are further preferable.
  • fluorine atom methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, n- Hexyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, methylthio group, ethylthio group, n-propylthio group, isopropylthio group , N-butylthio group, isobutylthio group, sec-butylthio group, tert-butylthio group, methylamino group, ethylamino group, n-propylamino group, isopropylamino group, n-butyl group,
  • n 201 of the general formula (I-5) an integer of 0 to 3 is preferable, and 1 or 2 is more preferable.
  • n 201 R 205s in the general formula (I-5) may be any of the I to IV positions of the benzene ring in the following general formula (I-6), and when n 201 is 1, the II position or III It is preferably located at the position, and more preferably located at the II position. When n 201 is 2, it is preferably located at the II and III positions, or the II and IV positions, and more preferably located at the II and III positions. When n 201 is 3, it is preferably located at the I, II and III positions, or the II, III and IV positions, and more preferably at the I, II and III positions. preferable. (Wherein, I ⁇ IV represent substitutable positions R 205, R 201 ⁇ R 205 , An '- and n 201 is the same as above.)
  • Preferred specific examples of the general formula (I-5) include dye residues represented by the following general formula (II).
  • R 206 represents an alkyl group having 1 to 12 carbon atoms, a phenyl group or a phenyl alkyl group having 7 to 9 carbon atoms
  • R 207 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a phenyl group. or a phenyl group having a carbon number of 7 ⁇ 9,
  • n 202 represents an integer of 0 ⁇ 3, R 201 ⁇ R 205 and an '- are the same as above).
  • Examples of the alkyl group having 1 to 12 carbon atoms in R 206 and R 207 of the general formula (II) include the same alkyl groups having 1 to 12 carbon atoms in R 202 and R 203 of the general formula (I-5). And the preferred ones are the same.
  • Examples of the phenylalkyl group having 7 to 9 carbon atoms of R 206 and R 207 of the general formula (II) include a benzyl group, a phenethyl group, a 1-phenylethyl group, a hydrocinnamyl group, a 2-phenylpropyl group and a 1-phenylpropyl group. , Cumyl group, preferably benzyl group, phenethyl group, hydrocinnamyl group, cumyl group.
  • Specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a phenyl group, a benzyl group, a phenethyl group, a hydrocinnamyl group, a cumyl group and the like, and examples thereof include a methyl group, an ethyl group and the like.
  • a propyl group, a butyl group, a pentyl group and a hexyl group are preferable, a methyl group, an ethyl group, a propyl group and a butyl group are more preferable, and a methyl group and an ethyl group are particularly preferable.
  • the alkyl group in the above specific example is not limited to the normal-form, and all of the branched ones such as sec-form, tert-form, iso-form (iso-form) and neo-form (neo-form) are also included. include.
  • R 207 of the general formula (II) a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group and a phenylalkyl group having 7 to 9 carbon atoms are preferable, and a hydrogen atom and an alkyl group having 1 to 6 carbon atoms are preferable. More preferred. Specific examples thereof include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a phenyl group, a benzyl group, a phenethyl group, a hydrocinnamyl group, a cumyl group and the like.
  • Methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group are preferable, hydrogen atom, methyl group, ethyl group, propyl group and butyl group are more preferable, and hydrogen atom, methyl group and ethyl group are particularly preferable.
  • the alkyl group in the above specific example is not limited to the normal-form, and all of the branched ones such as sec-form, tert-form, iso-form (iso-form) and neo-form (neo-form) are also included. include.
  • R 203 and R 206 of the general formula (II) are the same, and it is preferable that R 202 and R 207 of the general formula (II) are the same.
  • n 202 of the general formula (II) 0 or 1 is preferable.
  • n 202 R 205s in the general formula (II) may be any of the I-position, III-position or IV-position of the benzene ring in the following general formula (II-1), and when n 202 is 1, the position III. Or, it is preferably located at the IV position, more preferably at the III position, and when n202 is 2, it is preferably located at the I and III positions, or the III and IV positions. It is preferably located at positions I and III, more preferably. (Wherein, I, III and IV represent substitutable positions R 205, R 201 ⁇ R 207 , An '- and n 202 is the same as above.)
  • R 201 to R 207 and n 202 in the general formula (II) include, for example, those described in the following table.
  • An used in conjunction with the combinations described in Table '- include include those described below, chloride ions, tetrakis (pentafluorophenyl) boron (IV) anions, PF 6 - are preferable.
  • R 301 and R 306 in the general formula (III) a hydrogen atom is preferable, and it is preferable that R 301 and R 306 are the same.
  • Examples of the alkyl group having 1 to 30 carbon atoms in R 302 to R 305 and R 308 of the general formula (III) include the same alkyl group having 1 to 30 carbon atoms in R 105 of the general formula (I). The preferred ones are the same.
  • Examples of the unsubstituted aryl group having 6 to 14 carbon atoms in R 302 to R 305 of the general formula (III) include a phenyl group, a naphthyl group, an anthrasenyl group and the like, and a phenyl group is preferable.
  • the aryl group having 6 to 14 carbon atoms having a substituent in R 302 to R 305 of the general formula (III) has 6 carbon atoms.
  • the same are the same as the aryl groups of ⁇ 14, and the preferred ones are also the same.
  • R 302 to R 305 in the general formula (III) a hydrogen atom and an alkyl group having 1 to 30 carbon atoms are preferable, a hydrogen atom and an alkyl group having 1 to 12 carbon atoms are more preferable, and an alkyl having 1 to 6 carbon atoms is more preferable. Groups are particularly preferred.
  • Examples of the alkoxy group having 1 to 6 carbon atoms in R 308 of the general formula (III) include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group and a tert-.
  • Examples thereof include a butoxy group, an n-pentyloxy group, an n-hexyloxy group, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group and a tert-butoxy group.
  • a group is preferable, and a methoxy group, an ethoxy group, an n-propoxy group, and an n-butoxy group are more preferable.
  • Examples of the halogeno group in R 308 of the general formula (III) include a fluoro group, a chloro group, a bromo group and an iodine group.
  • an alkoxy group having 1 to 6 carbon atoms, a halogeno group, a hydroxy group, a nitro group and a sulfo group are preferable, and an alkoxy group having 1 to 4 carbon atoms, a halogeno group, a hydroxy group and a nitro group are preferable.
  • Groups and sulfo groups are more preferred.
  • a hydroxy group, a nitro group and a sulfo group are preferable, and a methoxy group, an ethoxy group, a fluoro group, a hydroxy group, a nitro group and a sulfo group are more preferable.
  • n 301 of the general formula (III) 0 to 1 is preferable, and 0 is more preferable.
  • Dye of the general formula (1) is a dye residue represented by the general formula (III)
  • Ar 3 of the general formula (III) is a benzene ring at the site to which A 1 binds at the dye residue. In this case, it may be located at any of the ortho position, the meta position, and the para position, and the para position is preferable. Further, when Ar 3 of the general formula (III) is a naphthalene ring, the site to which A 1 binds may be located at any of the 2nd to 8th positions, and the 4th position is preferable. Specifically, when Ar 3 of the general formula (III) is a benzene ring, it is preferable that A 1 is bonded as shown by the following general formula (III'-1-1). Further, when Ar 3 of the general formula (III) is a naphthalene ring, it is preferable that A 1 is bonded as shown by the following general formula (III'-2-1).
  • R 301 to R 306 , R 308 , Ar 3 and n 301 in the general formula (III) include, for example, those described in the following table.
  • the alkyl groups having 1 to 6 carbon atoms in R 401 to R 406 and R 408 of the general formula (IV) include the alkyl groups having 1 to 6 carbon atoms in R 132 and R 133 in Y 101 of the general formula (I). The same is mentioned, and the preferred one is also the same.
  • Examples of the alkoxy group having 1 to 6 carbon atoms in R 401 to R 404 and R 408 of the general formula (IV) include the same alkoxy group having 1 to 6 carbon atoms in R 308 of the general formula (III). The preferred ones are the same.
  • Examples of the alkyloxycarbonyl group having 2 to 4 carbon atoms in R 401 to R 404 and R 408 of the general formula (IV) include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, and an isopropoxycarbonyl group. Can be mentioned.
  • Examples of the alkylcarbonyloxy group having 2 to 4 carbon atoms in R 401 to R 404 and R 408 of the general formula (IV) include a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group and an isopropylcarbonyloxy group. The group etc. can be mentioned.
  • Examples of the halogeno group in R 401 to R 404 and R 408 of the general formula (IV) include a fluoro group, a chloro group, a bromo group and an iodine group.
  • R 401 to R 404 of the general formula (IV) a hydrogen atom and an alkyl group having 1 to 6 carbon atoms are preferable, and a hydrogen atom is more preferable.
  • an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms are preferable, an alkoxy group having 1 to 6 carbon atoms is more preferable, and an alkoxy group having 1 to 4 carbon atoms is more preferable.
  • Groups are particularly preferred. Specifically, for example, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group and a tert-butoxy group are preferable, and a methoxy group and an ethoxy group are more preferable.
  • phenylalkyl group having 1 to 6 carbon atoms, a nitro group, a halogeno group or an unsubstituted phenylalkyl group having 7 to 9 carbon atoms in R 405 and R 406 of the general formula (IV).
  • the phenylalkyl group to 9 include a benzyl group, a phenethyl group, a 3-phenylpropyl group and the like.
  • Alkyl group having 1 to 6 carbon atoms, nitro group, halogeno group or cyano group or unsubstituted phenylalkyl group having 7 to 9 carbon atoms in R 405 and R 406 of the general formula (IV) has 1 carbon number.
  • Examples of the alkyl group to 6 include the same as the alkyl group having 1 to 6 carbon atoms in R 132 and R 133 in Y 101 of the general formula (I), and the preferred one is also the same.
  • examples include a fluoro group, a chloro group, a bromo group, and an iodo group.
  • phenylalkyl group having 7 to 9 carbon atoms having an alkyl group having 1 to 6 carbon atoms, a nitro group, a halogeno group or a cyano group in R 405 and R 406 of the general formula (IV) are, for example, methyl.
  • Benzyl group methylphenethyl group, 3- (methylphenyl) propyl group, ethylbenzyl group, ethylphenethyl group, 3- (ethylphenyl) propyl group, n-propylbenzyl group, n-propylphenethyl group, 3- (n-) Propylphenyl) propyl group, isopropylbenzyl group, isopropylphenethyl group, 3- (isopropylphenyl) propyl group, n-butylbenzyl group, n-butylphenetyl group, 3- (n-butylphenyl) propyl group, isobutylbenzyl group, Isobutylphenetyl group, 3- (isobutylphenyl) propyl group, sec-butylbenzyl group, sec-butylphenetyl group, 3- (sec-butylphenyl)
  • the phenylalkyl group having 1 to 6 carbon atoms a nitro group, a halogeno group or a cyano group in R 405 and R 406 of the general formula (IV) or having an unsubstituted phenylalkyl group having 7 to 9 carbon atoms
  • the phenylalkyl group is unsubstituted.
  • a phenylalkyl group having 7 to 9 carbon atoms is preferable.
  • the naphthylalkyl groups having 11 to 13 carbon atoms in R405 and R406 of the general formula (IV) include 1-naphthylmethyl group, 2-naphthylmethyl group, 2- (1-naphthyl) ethyl group and 2- (2).
  • -Examples include a naphthyl) ethyl group, a 3- (1-naphthyl) propyl group, a 3- (2-naphthyl) ethyl group and the like.
  • a hydrogen atom and an alkyl group having 1 to 6 carbon atoms are preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable.
  • a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group are preferable, and a methyl group and an ethyl group are more preferable.
  • R 407 of the general formula (IV) "an alkoxy group having 1 to 6 carbon atoms, an alkyloxycarbonyl group having 2 to 4 carbon atoms, a hydroxy group, a carboxy group, a halogeno group, a cyano group or an amino group having or not substituted
  • alkyl group having 1 to 6 carbon atoms in the "alkyl group having 1 to 6 carbon atoms” include the same alkyl groups having 1 to 6 carbon atoms in R 132 and R 133 in Y 101 of the general formula (I). And the preferred ones are the same.
  • an alkoxy group having 1 to 6 carbon atoms an alkyloxycarbonyl group having 2 to 4 carbon atoms, a hydroxy group, a carboxy group, a halogeno group, a cyano group or an amino group having 1 to 6 carbon atoms.
  • the alkyl group is preferably one having one or more substituents of any one or more types on the alkyl group, and preferably one having one substituent of any one type.
  • Examples thereof include a benzyl group, a phenethyl group, a 3-phenylpropyl group and the like.
  • the phenylalkyl group having 1 to 6 carbon atoms, the halogeno group or the phenylalkyl group having 7 to 9 carbon atoms in R 407 of the general formula (IV) has at least one kind on the benzene ring of the phenylalkyl group. It has 1 to 5 substituents, preferably 1 to 3 of any one type of substituent, and more preferably one of any one type of substituent. Further, the position of the substituent may be any of the ortho position, the meta position and the para position, and the para position is preferable.
  • alkoxy group having 1 to 6 carbon atoms alkyloxycarbonyl group having 2 to 4 carbon atoms, hydroxy group, carboxy group, halogeno group, cyano group or amino group having or not substituted.
  • an alkoxy group having 1 to 6 carbon atoms an alkyloxycarbonyl group having 2 to 4 carbon atoms, a hydroxy group, a carboxy group, a halogeno group, a cyano group or an amino group having or not substituted.
  • alkyloxycarbonyl group having 2 to 4 carbon atoms of the "alkyl group having 1 to 6 carbon atoms” include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group and the like.
  • the halogeno group of "an alkyl group having 1 to 6 carbon atoms” or "a phenylalkyl group having 1 to 6 carbon atoms, a halogeno group or an unsubstituted or unsubstituted phenylalkyl group having 7 to 9 carbon atoms” are fluoro. Examples thereof include a group, a chloro group, a bromo group and an iodo group.
  • an alkoxy group having 1 to 6 carbon atoms, an alkyloxycarbonyl group having 2 to 4 carbon atoms, a hydroxy group, a carboxy group, a halogeno group, a cyano group or an amino group having 1 to 6 carbon atoms has 1 to 6 carbon atoms.
  • Specific examples of the alkyl group include methoxymethyl group, methoxyethyl group, 3-methoxy-n-propyl group, 4-methoxy-n-butyl group, ethoxymethyl group, ethoxyethyl group and 3-ethoxy-.
  • n-propyl group 4-ethoxy-n-butyl group, n-propoxymethyl group, n-propoxyethyl group, 3-n-propoxy-n-propyl group, 4-n-propoxy-n-butyl group, n-butoxymethyl group, n-butoxyethyl group, 3-n-butoxy-n-propyl group, 4-n-butoxy-n-butyl group, methoxycarbonylmethyl group, methoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl Group, 4-methoxycarbonyl-n-butyl group, ethoxycarbonylmethyl group, ethoxycarbonylethyl group, 3-ethoxycarbonyl-n-propyl group, 4-ethoxycarbonyl-n-butyl group, n-propoxycarbonylmethyl group, n -Propoxycarbonylethyl group, 3-n-propoxycarbonyl-n-propyl group, 4-
  • an alkyl group having the number 1 to 6 an unsubstituted alkyl group having 1 to 6 carbon atoms is preferable.
  • the phenylalkyl group having an alkoxy group having 1 to 6 carbon atoms, a halogeno group or an amino group or having an unsubstituted 7 to 9 carbon atoms in R 407 of the general formula (IV) has an unsubstituted carbon number of 7 to 9 carbon atoms.
  • a phenylalkyl group is preferred.
  • Examples of the naphthylalkyl group having 11 to 13 carbon atoms in R 407 of the general formula (IV) include the same naphthylalkyl groups having 11 to 13 carbon atoms in R 405 and R 406 of the general formula (IV), which are preferable. The same is true for things.
  • the R 407 of the general formula (IV) has or does not have an alkoxy group having 1 to 6 carbon atoms, an alkyloxycarbonyl group having 2 to 4 carbon atoms, a hydroxy group, a carboxy group, a halogeno group, a cyano group or an amino group.
  • Alkyl groups having 1 to 6 carbon atoms are preferable, unsubstituted alkyl groups having 1 to 6 carbon atoms are more preferable, and unsubstituted alkyl groups having 1 to 4 carbon atoms are particularly preferable.
  • a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group are preferable, and a methyl group and an ethyl group are more preferable.
  • n 401 of the general formula (IV) is preferably 0 to 2, and more preferably 0.
  • Dye of the general formula (1) is a dye residue represented by formula (IV), site ortho position of the phenyl group in the general formula (IV) in which A 1 is bonded in the dye residue, meta It may be located at either the position or the para position, and the ortho position and the para position are preferable, and the para position is more preferable.
  • a 1 is bonded as represented by the following general formula (IV'-1) or (IV'-2) is represented by preferably the general formula (IV'-1) It is more preferable that A 1 is bound. (Wherein, R 1, R 401 ⁇ R 408, Y 2, A 1, An - and n 401 are the same as above.)
  • Preferred specific examples of the general formula (IV) include dye residues represented by the following general formula (V).
  • R 501 to R 506 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • R 507 has an alkoxy group having 1 to 6 carbon atoms, an alkyloxycarbonyl group having 2 to 4 carbon atoms, a hydroxy group, a carboxy group, a halogeno group, a cyano group or an amino group, or has 1 to 6 carbon atoms substituted.
  • n 501 represents an integer of 0 to 2.
  • a carboxy group, a halogeno group, a cyano group, an alkyl group having 1 to 6 carbon atoms or unsubstituted, and an alkoxy group having 1 to 6 carbon atoms in R 508 are R of the general formula (IV).
  • the same ones as those in 401 to R408 are mentioned, and the preferred ones are also the same.
  • R 501 to R 504 of the general formula (V) a hydrogen atom is preferable.
  • an alkyl group having 1 to 6 carbon atoms is preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable.
  • a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group are preferable, and a methyl group and an ethyl group are more preferable.
  • R 505 and R 506 of the general formula (V) are the same.
  • an unsubstituted alkyl group having 1 to 6 carbon atoms is preferable, and an unsubstituted alkyl group having 1 to 4 carbon atoms is more preferable.
  • a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group are preferable, and a methyl group and an ethyl group are more preferable.
  • an alkoxy group having 1 to 6 carbon atoms is preferable, and an alkoxy group having 1 to 4 carbon atoms is more preferable.
  • a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group and a tert-butoxy group are preferable, and a methoxy group and an ethoxy group are more preferable.
  • R 501 to R 508 and n 501 in the general formula (V) include, for example, those described in the following table.
  • Examples of the alkyl group having 1 to 6 carbon atoms in R 601 of the general formula (VI) include the same alkyl groups having 1 to 6 carbon atoms in R 132 and R 133 in Y 101 of the general formula (I). , The preferred ones are the same.
  • Examples of the alkyl group having 1 to 30 carbon atoms in R 602 and R 603 of the general formula (VI) include the same alkyl groups having 1 to 30 carbon atoms in R 105 of the general formula (I), and preferred ones are also used. It is the same.
  • R 601 to R 603 in the general formula (VI) include, for example, those described in the following table.
  • Examples of the alkyl group having 1 to 30 carbon atoms in R 701 of the general formula (VII) include the same alkyl groups having 1 to 30 carbon atoms in R 105 of the general formula (I), and preferred ones are also the same. ..
  • the position where the azo group is bonded may be any of the 4th to 9th positions of the 2,3-dihydroperimidine ring, and the 4th and 6th positions are preferable. Specifically, those to which an azo group is bonded as represented by the following general formula (VII-1) or (VII-2) are preferable. (In the formula, R 701 is the same as above.)
  • the dye residue represented by the general formula (I), (III), (IV), (VI) or (VII) is preferable, and the general formula (II),
  • the dye residue represented by (III), (V), (VI) or (VII) is more preferable, and the dye residue represented by the general formula (VI) or (VII) is further preferable.
  • a 1 is -O-, -OCO-, -COO-, -NHCO-, -CONH-, -NHCONH-, an arylene group and the following general formula (2-1).
  • Y 1 is a nitrogen atom or the following formula (2-2). Represents the group represented by, n 1 represents an integer of 0 to 2, and n 2 represents an integer of 2 to 4.
  • n 1 + n 2 is 3 or 4.
  • An alkylene group having 1 to 21 carbon atoms having at least one group selected from the groups represented by the above in the chain and / or at the end; -O-, -OCO-, -COO-, -NHCO-, -CONH-,- It has at least one group selected from NHCONH-, an arylene group and a group represented by the general formula (2-1) in the chain and / or at the end, and has a hydroxy group as a substituent and has 1 to 21 carbon atoms.
  • R 1 of the general formula (1) a methyl group is preferable.
  • the alkyl group having 1 to 12 carbon atoms in R 10 in Y 2 of the general formula (1) is the same as the alkyl group having 1 to 12 carbon atoms in R 202 and R 203 of the general formula (I-5). The same is true for those mentioned and preferred.
  • Y 2 of the general formula (1) —O— and —NH— are preferable, and —O— is more preferable.
  • the alkylene group having 1 to 21 carbon atoms having a hydroxy group as a substituent and "The alkylene group having 1 to 21 carbon atoms", the alkylene group having 1 to 21 carbon atoms is linear or branched. It may be either cyclic or cyclic, and a linear one is preferable. Further, among the alkylene groups having 1 to 21 carbon atoms, 1 to 12 carbon atoms are preferable, and 1 to 6 carbon atoms are more preferable.
  • n 2 of the general formula (2-1) is preferable.
  • group represented by the general formula (2-1) include groups represented by the following formulas (2-1-1) to (2-1-10), among which the groups are represented by the formula (2-1-1).
  • the group represented by 9) and the group represented by the formula (2-1-10) are preferable, and the group represented by the formula (2-1-10) is more preferable.
  • a 2-1 represents -OCO-, -COO-, -NHCO-, -CONH-, -NHCONH- or a group represented by the general formula (2-1), and h 1 represents 1 to 1. Represents an integer of 21.
  • a 2-2 represents -O-, -OCO-, -COO-, -NHCO-, -CONH-, -NHCONH- or -O-CONH-, and h 2 and h 3 are independent of each other. And represents an integer from 1 to 10.
  • a 2-3 represents -OCO-, -COO-, -NHCO-, -CONH-, -NHCONH- or a group represented by the general formula (2-1)
  • a 2-4 is -O-, -OCO-, -COO-, -NHCO-, -CONH-, -NHCONH- or -O-CONH-, each of h 4 and h 5 independently represents an integer of 1 to 10. .
  • R 51 represents an alkylene group having 1 to 7 carbon atoms or an arylene group having 6 to 10 carbon atoms
  • a 2-5 represents -OCO- or -NHCO-
  • a 2-6 represents.
  • -COO- or -CONH-, h 6 and h 7 each independently represent an integer of 1 to 7).
  • R 52 represents an alkylene group having 1 to 7 carbon atoms or an arylene group having 6 to 10 carbon atoms
  • a 2-7 is -OCO-, -COO-, -NHCO-, -CONH-, -NHCONH- or a group represented by the general formula (2-1)
  • a 2-8 represents -OCO- or -NHCO-
  • a 2-9 represents -COO- or -CONH-.
  • h 8 and h 9 each independently represent an integer of 1 to 7).
  • Examples of the alkylene group having 1 to 7 carbon atoms in R 52 of R 51 and of the general formula (21-4) (21-5) may be any of linear, branched and cyclic Of these, linear is preferable. Further, among the alkyl groups having 1 to 7 carbon atoms, those having 1 to 3 carbon atoms are preferable.
  • methylene group ethylene group, trimethylene group, propylene group, tetramethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 1,2-dimethylethylene group, 1,1-dimethylethylene Group, ethylethylene group, pentamethylene group, hexamethylene group, n-heptylene group, cyclobutylene group, cyclopentylene group, cyclohexylene group, cycloheptylene group, etc., among which methylene group, ethylene group, etc.
  • a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, and an n-heptylene group are preferable, a methylene group, an ethylene group, and a trimethylene group are more preferable, and an ethylene group is particularly preferable.
  • an integer of 1 to 12 is preferable, an integer of 1 to 6 is more preferable, an integer of 1 to 4 is further preferable, and 2 is particularly preferable.
  • a 2-2 of the general formula (21-2) -O-, -COO- and -CONH- are preferable, and -COO- is more preferable.
  • h 2 of the general formula (21-2) an integer of 1 to 3 is preferable, and 1 is more preferable.
  • h 3 in the general formula (21-2) an integer of 1 to 3 is preferable, and 2 is more preferable.
  • the group represented by 10) is preferable, and -COO-, -NHCO- and -CONH- are more preferable.
  • a 2-4 of the general formula (21-3) -O-, -COO-, -NHCONH- and -O-CONH- are preferable, and -COO- and -NHCONH- are more preferable.
  • h 4 and h 5 of the general formula (21-3) it is preferable that h 4 and h 5 are the same, an integer of 1 to 6 is preferable, an integer of 1 to 3 is more preferable, and 2 is further preferable. ..
  • a linear alkylene group having 1 to 7 carbon atoms and a phenylene group are preferable, and a linear alkylene group having 1 to 3 carbon atoms is more preferable.
  • a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an n-heptylene group and a phenylene group are preferable, and a methylene group, an ethylene group and a trimethylene group are more preferable.
  • Methylene groups are more preferred.
  • a 2-5 and A 2-6 of the general formula (21-4) a combination of -OCO- and -COO- and a combination of -NHCO- and -CONH- are preferable, and -OCO- and -COO- The combination of is more preferable.
  • an integer of 1 to 3 is preferable, 1 or 2 is more preferable, and 2 is particularly preferable.
  • h 7 in the general formula (21-4) an integer of 1 to 3 is preferable, and 2 is more preferable.
  • a linear alkylene group having 1 to 7 carbon atoms and a phenylene group are preferable, and a linear alkylene group having 1 to 3 carbon atoms is more preferable.
  • a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an n-heptylene group and a phenylene group are preferable, and a methylene group, an ethylene group and a trimethylene group are more preferable.
  • Methylene groups are more preferred.
  • a 2-8 and A 2-9 of the general formula (21-5) a combination of -OCO- and -COO- and a combination of -NHCO- and -CONH- are preferable, and -OCO- and -COO- The combination of is more preferable.
  • h 8 and h 9 of the general formula (21-5) it is preferable that h 8 and h 9 are the same, an integer of 1 to 3 is preferable, and 2 is more preferable.
  • Specific examples of the group represented by the general formula (21-1) include, for example. -COO-CH 2 -, - COO- (CH 2) 2 -, - COO- (CH 2) 3 -, - COO- (CH 2) 4 -, -COO- (CH 2 ) 5- , -COO- (CH 2 ) 6- , -CONH-CH 2- , -CONH- (CH 2 ) 2- , -CONH- (CH 2) 3 -, - CONH- (CH 2) 4 -, - CONH- (CH 2) 5 -, - CONH- (CH 2) 6 -, -NHCONH-CH 2 -, - NHCONH- (CH 2) 2 -, - NHCONH- (CH 2) 3 -, - NHCONH- (CH 2) 4 -, -NHCONH- (CH 2 ) 5- , -NHCONH- (CH 2 ) 6- , Etc., among others -COO-CH
  • Specific examples of the group represented by the general formula (21-2) include, for example. -CH 2 -O-CH 2- , -CH 2 -O- (CH 2 ) 2- , -CH 2 -O- (CH 2 ) 3- , -(CH 2 ) 2 -O-CH 2 -,-(CH 2 ) 2 -O- (CH 2 ) 2 -,-(CH 2 ) 2 -O- (CH 2 ) 3- , -(CH 2 ) 3 -O-CH 2 -,-(CH 2 ) 3 -O- (CH 2 ) 2 -,-(CH 2 ) 3 -O- (CH 2 ) 3- , -CH 2 -COO-CH 2- , -CH 2 -COO- (CH 2 ) 2- , -CH 2 -COO- (CH 2 ) 3- , -(CH 2 ) 2 -COO-CH 2 -,-(CH 2 -COO- (CH 2 ) 2-
  • Specific examples of the group represented by the general formula (21-3) include, for example. -COO-CH 2 -O-CH 2- , -COO- (CH 2 ) 2 -O- (CH 2 ) 2- , -COO- (CH 2 ) 3 -O- (CH 2 ) 3- , -COO-CH 2 -COO-CH 2- , -COO- (CH 2 ) 2 -COO- (CH 2 ) 2- , -COO- (CH 2 ) 3 -COO- (CH 2 ) 3- , -COO-CH 2 -NHCONH-CH 2- , -COO- (CH 2 ) 2 -NHCONH- (CH 2 ) 2- , -COO- (CH 2 ) 3 -NHCONH- (CH 2 ) 3- , -COO-CH 2 -O-CONH-CH 2- , -COO- (CH 2 ) 2 -O-CONH- (CH 2 ) 2- ,
  • combinations 1 to 32 described in the table below are preferable, combinations 1 to 16 are more preferable, combinations 1 to 3 and 9 to 11 are further preferable, and combination 2 is particularly preferable.
  • Examples of the combinations of R 52 , A 2-7 , A 2-8 , A 2-9 , h 8 and h 9 in the general formula (21-5) include those described in the following table.
  • the combinations 1 to 32 shown in the table below are preferable, the combinations 1 to 16 are more preferable, and the combinations 1 to 3 and 9 to 11 are further preferable.
  • R 53 represents an arylene group having 6 to 10 carbon atoms having a hydroxy group as a substituent
  • a 3-1 is -OCO-, -COO-, -NHCO-, -CONH- or -NHCONH.
  • h 8 represents an integer of 1 to 21.
  • R 54 represents an alkylene group having 1 to 7 carbon atoms having a hydroxy group as a substituent or an arylene group having 6 to 10 carbon atoms as a substituent
  • a 3-2 is ⁇ OCO. -, -COO-, -NHCO-, -CONH- or -NHCONH-, where A 3-3 represents -O-, -OCO-, -COO-, -NHCO-, -CONH-, -NHCONH- or.
  • -O-CONH- is represented, and h 11 represents an integer from 1 to 14.
  • alkylene group having 1 to 7 carbon atoms having a hydroxy group at R 54 of general formula (22-2) as a substituent specifically, for example, hydroxymethylene group, hydroxyethylene group, hydroxy trimethylene group, hydroxy tetra
  • substituents specifically, for example, hydroxymethylene group, hydroxyethylene group, hydroxy trimethylene group, hydroxy tetra
  • examples thereof include a methylene group, a hydroxypentamethylene group, a hydroxyhexamethylene group, a hydroxy-n-heptylene group, a hydroxycyclobutylene group, a hydroxycyclopentylene group, a hydroxycyclohexylene group, a hydroxycycloheptylene group, and the like.
  • a group, a hydroxyethylene group, a hydroxytrimethylene group, a hydroxytetramethylene group, a hydroxypentamethylene group, a hydroxyhexamethylene group, a hydroxy-n-heptylene group is preferable, and a hydroxyethylene group is more preferable.
  • h 10 of the general formula (22-1) an integer of 1 to 4 is preferable.
  • an alkylene group having a hydroxy group as a substituent and having 1 to 7 carbon atoms is preferable, and more specifically, a hydroxyethylene group is more preferable.
  • a 3-2 of the general formula (22-2) -COO-, -CONH- and -NHCONH- are preferable.
  • Specific examples of the group represented by the general formula (22-1) include, for example. -COO-C 6 H 3 (OH) -CH 2- , -COO-C 6 H 3 (OH)-(CH 2 ) 2- , -COO-C 6 H 3 (OH)-(CH 2 ) 3- , -COO-C 6 H 3 (OH ) - (CH 2) 4 -, - CONH-C 6 H 2 (OH) 2 -CH 2 -, - CONH-C 6 H 2 (OH) 2 - (CH 2) 2- , -CONH-C 6 H 2 (OH ) 2 - (CH 2) 3 -, - CONH-C 6 H 2 (OH) 2 - (CH 2) 4 -, - NHCONH-C 6 H 3 (OH) -CH 2- , -NHCONH-C 6 H 3 (OH)-(CH 2 ) 2- , -NHCONH-C 6 H 3 (OH)-(CH 2 ) 2- , -NHCON
  • Specific examples of the group represented by the general formula (22-2) include, for example. -COO-CH (OH) CH 2 -O- (CH 2 ) 2- , -COO-CH (OH) CH 2 -O- (CH 2 ) 3- , -COO-CH (OH) CH 2 -O- (CH 2) 4 -, - CONH-CH (OH) CH 2 -O- (CH 2) 2 -, -CONH-CH (OH) CH 2 -O- (CH 2) 3 -, - CONH-CH (OH) CH 2 -O- (CH 2) 4 -, -NHCONH-CH (OH) CH 2 -O- (CH 2 ) 2- , -NHCONH-CH (OH) CH 2 -O- (CH 2 ) 3- , -NHCONH-CH (OH) CH 2 -O- (CH 2) 4 -, -COO-CH (OH) CH 2 -O-CONH- (CH 2 ) 2- , -COO-
  • alkylene group having 1 to 21 carbon atoms having a hydroxy group as a substituent an alkylene group having 2 to 11 carbon atoms having a hydroxy group as a substituent is preferable, and specifically.
  • a 1 in the general formula (1) is represented by "-O-, -OCO-, -COO-, -NHCO-, -CONH-, -NHCONH-, an arylene group and the following general formula (2-1).
  • "The alkylene group having 1 to 21 carbon atoms” and “the alkylene group having 1 to 21 carbon atoms” having at least one group selected from the groups in the chain and / or at the end are preferable, and among these, the alkylene group having 1 to 12 carbon atoms is preferable.
  • An alkylene group and a group represented by the general formulas (21-1) to (21-5) are more preferable.
  • the Dye in formula (1) is a dye residue represented by the general formula (I), as A 1 in the general formula (1), among the more preferred ones of said A 1, the general formula (21 The group represented by 1), (21-3) or (21-5) is more preferable, and the group represented by the general formula (21-1) is particularly preferable.
  • Dye in formula (1) is a dye residue represented by general formula (II)
  • a 1 in the general formula (1) Dye in the above “general formula (1) is general formula (II) same as a 1 of in time is a dye residue represented "are mentioned as preferred.
  • Dye in the general formula (1) is a dye residue represented by the general formula (III) and Ar 3 in the general formula (III) is a benzene ring
  • the A 1 in the general formula (1) is described above.
  • the group represented by the general formula (21-1), (21-3) or (21-5) is more preferable, and the group represented by the general formula (21-1) is particularly preferable.
  • Dye in the general formula (1) is a dye residue represented by the general formula (III) and Ar 3 in the general formula (III) is a naphthalene ring
  • the A 1 in the general formula (1) is described above.
  • the group represented by the general formula (21-1) or (21-3) is more preferable, and the group represented by the general formula (21-1) is particularly preferable.
  • Dye in formula (1) is a dye residue represented by formula (IV), as the A 1 in the general formula (1), even more preferred among those described above A 1, several linear carbon 1
  • the alkylene group of to 6 and the group represented by the general formula (21-1), (21-2) or (21-4) are more preferable, and the group represented by the general formula (21-1) is particularly preferable.
  • Dye in formula (1) is a dye residue represented by formula (V), as the A 1 in the general formula (1), Dye in the above “general formula (1) is general formula (IV) same as a 1 of in time is a dye residue represented "are mentioned as preferred.
  • Dye in formula (1) is a dye residue represented by the general formula (VI), as the A 1 in the general formula (1), among the more preferred ones of the A 1, an alkylene having 1 to 12 carbon atoms The group is more preferable, and a linear alkylene group having 1 to 6 carbon atoms is particularly preferable. More specifically, a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group are preferable, a methylene group, an ethylene group, a trimethylene group, and a tetramethylene group are more preferable, and an ethylene group is particularly preferable. ..
  • the A 1 in the general formula (1) is the general formula (21-2) among the more preferable ones in the above A 1.
  • the group represented by (21-4) is more preferable, and the group represented by the general formula (21-4) is particularly preferable.
  • a method for producing the compound represented by the above general formula (1) of the present disclosure a method known per se may be used.
  • Dye in the general formula (1) is a dye residue represented by the general formula (I) or (II), WO2014-126167, WO2015-147285, WO2016-98889.
  • the production method described in JP-A may be used; when Dye in the general formula (1) is a dye residue represented by the general formula (III), WO2015-98999A, WO2015-182680.
  • the production method described in the publications may be used; when Dye in the general formula (1) is a dye residue represented by the general formula (IV) or (V), it is described in the International Publication No. WO2015-133578.
  • the manufacturing method may be used.
  • R 1 represents a hydrogen atom or a methyl group.
  • R601 represents an alkyl group having 1 to 6 carbon atoms.
  • R 602 and R 603 each independently represent an alkyl group having 1 to 30 carbon atoms.
  • Y 2 represents -O- or -NR 10- , and
  • R 10 represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.
  • An - represents an anion
  • a 1 is -O-, -OCO-, -COO-, -NHCO-, -CONH-, -NHCONH-, an arylene group and the following general formula (2-1).
  • Y 1 is a nitrogen atom or the following formula (2-2). Represents the group represented by, n 1 represents an integer of 0 to 2, and n 2 represents an integer of 2 to 4. However, n 1 + n 2 is 3 or 4.
  • the compound represented by the general formula (2) of the present disclosure is a Basic Yellow 40-based compound in which the Dye (dye residue) in the general formula (1) is the general formula (VI), and the hue is yellowish. It can be suitably used as a polymerizable dye having excellent water resistance, light resistance and the like as well as heat resistance.
  • the compound represented by the above general formula (2) of the present disclosure for example, it can be produced by a series of methods represented by the following reactions [I] to [III]. That is, first, the compound represented by the following general formula (101) is mesylated or tosylated to obtain the compound represented by the following general formula (102) (reaction [I]). Then, the obtained compound represented by the general formula (102) is reacted with the compound represented by the following general formula (103) to obtain a compound represented by the following general formula (104) (reaction [II]). Then, the obtained compound represented by the general formula (104) may be reacted with the compound represented by the following general formula (105), and then subjected to a salt formation reaction (reaction [III]).
  • R 1 , R 601 to R 603 , Y 2 , An - and A 1 are the same as above, and R 604 is a methyl sulfonyl group (mesyl group) or a p-toluene sulfonyl group (tosyl group). Represents. ⁇
  • mesylation or tosylation of the compound represented by the general formula (101) is carried out in a solvent in the presence of a base, usually at -10 to 80 ° C, preferably 0 to 50 ° C, usually 1 to 1.
  • the reaction may be carried out for 24 hours, preferably 3 to 10 hours.
  • the compound represented by the general formula (101) When mesylation is carried out in the reaction [I], for example, the compound represented by the general formula (101) may be reacted with methanesulfonyl chloride. At this time, the amount of the methanesulfonyl chloride used is usually 1 to 2 equivalents, preferably 1 to 1.5 equivalents, relative to the mol number of the compound represented by the general formula (101).
  • the compound represented by the general formula (101) may be reacted with p-toluenesulfonyl chloride. At this time, the amount of the p-toluenesulfonyl chloride used is usually 1 to 2 equivalents, preferably 1 to 1.5 equivalents, relative to the mol number of the compound represented by the general formula (101).
  • Examples of the base include amines and the like, among which triethylamine and the like are used for mesylation and pyridine and the like are used for tosylation.
  • the amount of the base used is usually 1 to 2 equivalents, preferably 1 to 1.5 equivalents, relative to the mol number of the compound represented by the general formula (101).
  • the solvent examples include organic solvents such as methanol, ethanol, isopropyl alcohol, tetrahydrofuran, dioxane, N, N-dimethylformamide, dichloromethane, dichloroethane, ethyl acetate and the like, and dichloromethane is preferable. These may be used alone or in combination of two or more.
  • the amount of the solvent used is usually 0.1 to 100 ml, preferably 1 to 50 ml with respect to 1 mmol of the compound represented by the general formula (101).
  • Specific examples of the compound represented by the general formula (101) include hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, and 5-hydroxypentyl methacrylate. , 6-Hydroxyhexyl methacrylate and the like, among which hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate and 4-hydroxybutyl methacrylate are preferred, and 2-hydroxyethyl methacrylate is more preferred. .
  • As the compound represented by the general formula (101) a commercially available compound or a compound appropriately synthesized by a method known per se may be used.
  • the compound represented by the general formula (102) and the compound represented by the general formula (103) are usually mixed at 0 to 80 ° C., preferably 10 to 50 ° C. in a solvent in the presence of a catalyst. , Usually 1 to 24 hours, preferably 2 to 10 hours.
  • Specific examples of the compound represented by the general formula (103) include 3- (2-benzimidazolyl) -7- (dimethylamino) coumarin and 3- (2-benzimidazolyl) -7- (diethylamino) coumarin. , 3- (2-benzimidazolyl) -7- (di-n-propylamino) coumarin, 3- (2-benzimidazolyl) -7- (diisopropylamino) coumarin, 3- (2-benzimidazolyl) -7- (Di-n-butylamino) coumarin, 3- (2-benzimidazolyl) -7- (diisobutylamino) coumarin, 3- (2-benzimidazolyl) -7- (di-sec-butylamino) coumarin, 3- (2-benzimidazolyl) -7- (di-tert-butylamino) coumarin, 3- (2-benzimidazolyl) -7- (di
  • the amount of the compound represented by the general formula (102) to be used is usually 1 to 5 equivalents, preferably 2 to 3 equivalents, relative to the mol number of the compound represented by the general formula (103).
  • the catalyst examples include carbonates of alkali metals such as sodium carbonate, potassium carbonate and cesium carbonate.
  • the amount of the catalyst used is usually 1 to 5 equivalents, preferably 2 to 3 equivalents, relative to the mol number of the compound represented by the general formula (103).
  • the solvent examples include organic solvents such as methanol, ethanol, isopropyl alcohol, tetrahydrofuran, dioxane, N, N-dimethylformamide, dichloromethane, dichloroethane and ethyl acetate, and N, N-dimethylformamide is preferable. These may be used alone or in combination of two or more.
  • the amount of the solvent used is usually 0.1 to 100 ml, preferably 1 to 50 ml with respect to 1 mmol of the compound represented by the general formula (103).
  • the compound represented by the general formula (104) and the compound represented by the general formula (105) are mixed in a solvent at a temperature of usually 0 to 80 ° C, preferably 10 to 50 ° C, and usually 1 to 24.
  • the reaction is carried out for a period of time, preferably 6 to 18 hours, and then the salt of the anion represented by An ⁇ and water are added, and the temperature is usually 0 to 80 ° C., preferably 10 to 50 ° C., usually 10 minutes to 12 hours, preferably 10 minutes to 12 hours.
  • the reaction may be carried out for 20 minutes to 6 hours.
  • Specific examples of the compound represented by the general formula (105) include dimethyl sulfate, diethyl sulfate, di-n-propyl sulfate, diisopropyl sulfate, di-n-butyl sulfate, diisobutyl sulfate, and di-sec-butyl sulfate. , Di-tert-butyl sulfate and the like, among which dimethyl sulfate and diethyl sulfate are preferable, and dimethyl sulfate is more preferable.
  • the compound represented by the general formula (105) a commercially available compound or a compound appropriately synthesized by a method known per se may be used.
  • the amount of the compound represented by the general formula (105) to be used is usually 1 to 5 equivalents, preferably 2 to 3 equivalents, relative to the mol number of the compound represented by the general formula (104).
  • the solvent examples include organic solvents such as methanol, ethanol, isopropyl alcohol, tetrahydrofuran, dioxane, N, N-dimethylformamide, dichloromethane, dichloroethane and ethyl acetate, and dichloromethane is preferable. These may be used alone or in combination of two or more.
  • the amount of the solvent used is usually 0.1 to 100 ml, preferably 1 to 50 ml with respect to 1 mmol of the compound represented by the general formula (104).
  • the alkali metal salt of the anion represented by, An - - the An and anions represented by, sodium, potassium, salts consisting of alkali metal such as lithium, An - consists anion potassium or lithium represented by Salt is preferred.
  • the amount of the alkali metal salt of the anion represented by An ⁇ is usually 1 to 5 equivalents, preferably 1.5 to 2 equivalents, relative to the mol number of the compound represented by the general formula (104).
  • the inorganic acid examples include inorganic acids such as hydrochloric acid, hydrogen bromide, hydrogen iodide, hypochlorous acid, chloric acid, chloric acid, perchloric acid, hexafluorophosphate and hexafluoroantimonic acid, and hydrochloric acid. , Perchloric acid, hexafluorophosphate, hexafluoroantimonic acid are preferable.
  • the amount of the inorganic acid used is usually 1 to 50 equivalents, preferably 1 to 10 equivalents, relative to the mol number of the compound represented by the general formula (104).
  • the amount of water used is usually 0.1 to 100 ml, preferably 1 to 50 ml with respect to 1 mmol of the compound represented by the general formula (104).
  • the pressure at the time of reaction in the reactions [I] to [III] is not particularly limited as long as the series of reactions is carried out without delay, and may be carried out at normal pressure, for example.
  • the reactants and products obtained after the reactions in Reactions [I] to [III] may be isolated by general post-treatment operations and purification operations usually performed in this field. Specifically, for example, the reactants and products obtained by performing filtration, washing, extraction, concentration under reduced pressure, recrystallization, distillation, column chromatography and the like may be isolated.
  • R 1 represents a hydrogen atom or a methyl group.
  • R701 represents an alkyl group having 1 to 30 carbon atoms.
  • Y 2 represents -O- or -NR 10- , and R 10 represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.
  • a 1 is -O-, -OCO-, -COO-, -NHCO-, -CONH-, -NHCONH-, an arylene group and the following general formula (2-1).
  • Y 1 is a nitrogen atom or the following formula (2-2).
  • n 1 represents an integer of 0 to 2
  • n 2 represents an integer of 2 to 4.
  • n 1 + n 2 is 3 or 4.
  • An alkylene group having 1 to 21 carbon atoms having at least one group selected from the groups represented by the above in the chain and / or at the end; -O-, -OCO-, -COO-, -NHCO-, -CONH-,- It has at least one group selected from NHCONH-, an arylene group and a group represented by the general formula (2-1) in the chain and / or at the end, and has a hydroxy group as a substituent and has 1 to 21 carbon atoms.
  • the compound represented by the general formula (3) of the present disclosure is a Solvent Black 3 compound in which the Dye (dye residue) in the general formula (1) is the general formula (VII), and the hue is black. Therefore, it can be suitably used as a polymerizable dye having excellent water resistance, light resistance and the like as well as heat resistance.
  • a diazo coupling reaction may be carried out between the compound represented by the following general formula (111) and 4-phenylazo-1-naphthylamine.
  • reaction [IV] In the formula, R 1 , R 701 , Y 2 and A 1 are the same as above.
  • the reaction [IV] may be carried out according to a diazo coupling reaction method known per se. Specifically, 4-phenylazo-1-naphthylamine, hydrochloric acid and sodium nitrite are reacted in water at 5 ° C. or lower (cooled with ice water) for usually 10 minutes to 12 hours, preferably 30 minutes to 6 hours. A diazo solution is obtained, and then the compound represented by the general formula (111) and the diazo solution are reacted in a solvent at 5 ° C. or lower (under ice-water cooling) for usually 1 to 24 hours, preferably 2 to 10 hours. Just do it.
  • the amount of 4-phenylazo-1-naphthylamine used is usually 1 to 2 equivalents, preferably 1 to 1.5 equivalents, relative to the mol number of the compound represented by the general formula (111).
  • the amount of hydrochloric acid used is usually 2 to 5 equivalents, preferably 2.5 to 4 equivalents, relative to the number of mols of 4-phenylazo-1-naphthylamine.
  • the amount of sodium nitrite used is usually 1 to 2 equivalents, preferably 1 to 1.5 equivalents, relative to the mol number of 4-phenylazo-1-naphthylamine.
  • the amount of water used is usually 0.1 to 100 ml, preferably 1 to 50 ml with respect to 1 mmol of 4-phenylazo-1-naphthylamine.
  • the solvent examples include organic solvents such as methanol, ethanol, isopropyl alcohol, tetrahydrofuran, dioxane, N, N-dimethylformamide, dichloromethane, dichloroethane and ethyl acetate, and tetrahydrofuran is preferable. These may be used alone or in combination of two or more.
  • the amount of the solvent used is usually 0.1 to 100 ml, preferably 1 to 50 ml with respect to 1 mmol of the compound represented by the general formula (111).
  • a 1 is the general formula (21-4) (represented by the following general formula (115)).
  • the compound can be produced by a series of methods shown in the following reactions [V] and [VI]. That is, first, 1,8-naphthalenediamine is reacted with the compound represented by the following general formula (112) to obtain the compound represented by the following general formula (113) (reaction [V]). Then, the obtained compound represented by the general formula (113) may be reacted with the compound represented by the following general formula (114) (reaction [VI]).
  • R 1 , R 51 , R 701 , Y 2 , A 2-5 , A 2-6 , h 6 and h 7 are the same as above, and R 702 represents a hydroxy group or an amino group. .
  • R 702 of the general formula (112) is a hydroxy group
  • a 2-5 represents -OCO-
  • R 702 is an amino group
  • a 2-5 represents -NHCO-.
  • a hydroxy group is preferable.
  • 1,8-naphthalenediamine and the compound represented by the following general formula (112) are usually mixed at 10 to 100 ° C., preferably 60 to 100 ° C., usually 1 to 24 hours, preferably 3 The reaction may be carried out for about 10 hours.
  • Specific examples of the compound represented by the general formula (112) include, for example, CH 3 -CO-CH 2 -OH, CH 3 -CO- (CH 2 ) 2 -OH, CH 3 -CO- (CH 2 ) 3 -OH, CH 3 -CH 2 -CO-CH 2 -OH, CH 3 -CH 2 -CO- (CH 2 ) 2 -OH, CH 3 -CH 2 -CO- (CH 2 ) 3 -OH, CH 3- (CH 2 ) 2 -CO-CH 2 -OH, CH 3- (CH 2 ) 2 -CO- (CH 2 ) 2 -OH, CH 3- (CH 2 ) 2 -CO- (CH 2 ) 3 -OH, CH (CH 3 ) 2 -CO-CH 2 -OH, CH (CH 3 ) 2 -CO- (CH 2 ) 2 -OH, CH (CH 3 ) 2 -CO- (CH 2 ) 2 -OH, CH (CH 3 ) 2 -CO- (CH 2
  • CH 3 -CO-CH 2 -OH, CH 3 -CO- (CH 2 ) 2 -OH, CH 3 -CH 2 -CO-CH 2 -OH, CH 3 -CH 2 -CO- (CH 2 ) 2 -OH are more preferable.
  • CH 3- CO-CH 2- OH (hydroxyacetone) is particularly preferred.
  • a commercially available compound or a compound appropriately synthesized by a method known per se may be used as the compound represented by the general formula (112).
  • the amount of the compound represented by the general formula (112) to be used is usually 1 to 2 equivalents, preferably 1 to 1.5 equivalents, relative to the mol number of 1,8-naphthalenediamine.
  • the compound represented by the general formula (113) and the compound represented by the general formula (114) are usually mixed at 0 to 80 ° C., preferably 10 to 50 ° C. in a solvent in the presence of a dehydration condensing agent.
  • the reaction may be carried out at ° C. for usually 1 to 48 hours, preferably 6 to 24 hours.
  • the combinations 1 to 32 shown in the table below are preferable, the combinations 1 to 16 are more preferable, the combinations 1 to 3 and 9 to 11 are further preferable, and the combination 10 is particularly preferable.
  • the amount of the compound represented by the general formula (114) to be used is usually 1 to 2 equivalents, preferably 1 to 1.5 equivalents, relative to the mol number of the compound represented by the general formula (113).
  • the dehydration condensing agent may be any one generally used as a dehydration condensing agent, for example, inorganic dehydrating agents such as diphosphorus pentoxide and anhydrous zinc chloride; for example, dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethyl-.
  • Carbodiimides such as 3- (3-dimethylaminopropyl) carbodiimide hydrochloride; for example, polyphosphate, anhydrous acetic acid, sulfuric acid, carbonyldiimidazole, p-toluenesulfonic acid and the like, with carbodiimides being preferred.
  • Ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride is more preferred.
  • the amount of the dehydration condensing agent used is usually 1 to 20 equivalents, preferably 1 to 10 equivalents, relative to the mol number of the compound represented by the general formula (113).
  • a catalyst such as dimethylaminopyridine may be used in order to improve the efficiency of the dehydration condensing agent.
  • the amount of the catalyst used is usually 0.1 to 10 equivalents with respect to the mol number of the compound represented by the general formula (113).
  • the solvent examples include ethers such as diethyl ether, diisopropyl ether, ethylmethyl ether, tetrahydrofuran, 1,4-dioxane and dimethoxyethane; for example, acetone, dimethyl ketone, methyl ethyl ketone, diethyl ketone, 2-hexanone and tert-butyl methyl.
  • ethers such as diethyl ether, diisopropyl ether, ethylmethyl ether, tetrahydrofuran, 1,4-dioxane and dimethoxyethane
  • acetone dimethyl ketone
  • methyl ethyl ketone diethyl ketone
  • 2-hexanone 2-hexanone
  • tert-butyl methyl 2-hexanone
  • Ketones such as ketones, cyclopentanone, cyclohexanone; halogenated hydrocarbons such as chloromethane, chloroform, dichloromethane, dichloroethane, trichloroethane, carbon tetrachloride, chlorobenzene; eg carbonization of n-hexane, benzene, toluene, xylene, etc.
  • Hydrogens for example, esters such as ethyl acetate, butyl acetate, methyl propionate; nitriles such as acetonitrile; for example, amides such as N, N-dimethylformamide, etc., among which esters are preferable, and ethyl acetate is preferable. More preferred. These may be used alone or in combination of two or more.
  • the amount of the solvent used is usually 0.1 to 100 ml, preferably 1 to 50 ml with respect to 1 mmol of the compound represented by the general formula (113).
  • the pressure at the time of reaction in the reactions [IV] to [VI] is not particularly limited as long as the series of reactions is carried out without delay, and may be carried out at normal pressure, for example.
  • Reactants and products obtained after the reactions in Reactions [IV]-[VI] may, if necessary, be isolated by common post-treatment and purification operations usually performed in the art. Specifically, for example, the reactants and products obtained by performing filtration, washing, extraction, concentration under reduced pressure, recrystallization, distillation, column chromatography and the like may be isolated.
  • the colored particle aqueous dispersion of the present disclosure is composed of a polymer having at least a monomer unit derived from a dye having a polymerizable unsaturated group, and is derived from, for example, the compound represented by the above general formula (1).
  • Examples thereof include those in which colored particles (polymers) composed of a monomer unit (polymerizable dye) and a polymerizable monomer are dispersed in water.
  • the Dye in the general formula (1) described in detail above is the general formula (I), (III), It is preferable that the dye residue is represented by (IV), (VI) or (VII), and R 1 , Y 2 and A 1 in the general formula (1) are the functionalities described in detail above. Group etc. can be mentioned. More preferably, the monomer unit (polymerizable dye) derived from the compound represented by the general formula (1) is the Dye in the general formula (1) described in detail above, and the general formula (II), ( It is desirable that it is a dye residue represented by III), (V), (VI) or (VII). Particularly preferably, the monomer unit (polymerizable dye) derived from the compound represented by the general formula (1) is a compound represented by the general formula (2) or (3) described in detail above.
  • the polymerizable monomer used may have a function of causing a polymerization or cross-linking reaction by a starting species such as a radical generated from a polymerization initiator and the like, and curing a composition containing these.
  • the polymerizable monomer that can be used is not particularly limited as long as it is a compound that causes a polymerization reaction and cures, and any type of monomer, oligomer, or polymer can be used.
  • various known polymerizable monomers known as radically polymerizable monomers, which cause a polymerization reaction by an initiator generated from a polymerization initiator or the like added as desired, are preferable.
  • a polymerizable compound having at least one ethylenically unsaturated double bond is preferable.
  • the polymerizable monomer include (meth) acrylate compounds, vinyl ether compounds, compounds having (meth) acrylate groups and vinyl ether groups, allyl compounds, N-vinyl compounds, unsaturated carboxylic acids and the like.
  • the polymerizable monomer may be used alone or in combination for the purpose of adjusting the reaction rate, the physical characteristics of particles, the physical characteristics of use for ink, and the like. Further, the polymerizable monomer may be a monofunctional monomer or a bifunctional or higher polyfunctional monomer.
  • Preferred colored particle aqueous dispersions include a monomer (polymerizable dye) derived from the compound represented by the above general formula (1), a carboxyl group-containing vinyl monomer, and acrylic acid from the viewpoint of improving water resistance and light resistance.
  • a monomer (polymerizable dye) derived from the compound represented by the above general formula (1) a carboxyl group-containing vinyl monomer, and acrylic acid from the viewpoint of improving water resistance and light resistance.
  • colored particles (polymer) composed of an ester monomer of methacrylic acid and a linear or cyclic alcohol having 2 to 18 carbon atoms are dispersed in water.
  • the carboxyl group-containing vinyl monomer that can be used is not particularly limited as long as it is a carboxyl group-containing vinyl monomer.
  • At least one of acid-2-methacryloyloxyethyl, hexahydrophthalic acid-2-methacryloyloxyethyl and the like can be mentioned, and more preferably, phthalate-2-methacryloyloxyethyl is used.
  • the ester monomer of acrylic acid or methacrylic acid and a linear or cyclic alcohol having 2 to 18 carbon atoms which can be used is an ester of acrylic acid or methacrylic acid and a linear or cyclic alcohol having 2 to 18 carbon atoms.
  • At least one such as stearyl and behenyl (meth) acrylate can be preferably shown.
  • the above notation of "(meth) acrylic acid” represents "acrylic acid and / or methacrylic acid”.
  • a monomer (polymerizable dye) derived from a compound represented by the general formula (1) or the like is dissolved in the polymerizable monomer and polymerized using a polymerization initiator or the like.
  • a polymerization initiator or the like By doing so, an aqueous dispersion of colored particles can be produced.
  • a monomer (polymerizable dye) derived from the compound represented by the above general formula (1) or the like is dissolved in the monomer, and ammonium persulfate, potassium persulfate, hydrogen peroxide, etc. are used as a polymerization initiator, and a reducing agent is further used in combination.
  • An aqueous dispersion of colored particles can be produced by using the above-mentioned polymerization initiator and, if necessary, emulsion polymerization using a polymerizable surfactant.
  • the polymerizable surfactant that can be used as needed is not particularly limited as long as it is a polymerizable surfactant usually used in a polymerization reaction such as emulsification polymerization, but as a polymerizable surfactant, for example.
  • At least one of Latemul S-180, S-180A, S-120A manufactured by Sanyo Kasei Kogyo Co., Ltd., Eleminor JS-20 manufactured by Sanyo Kasei Kogyo Co., Ltd., and the like can be mentioned.
  • the amount of these polymerizable surfactants used is preferably 0 to 50% by mass, preferably 0.1 to 50% by mass, based on the total amount of the above-mentioned monomers.
  • a monomer (polymerizable dye) derived from the compound represented by the above general formula (1) or the like is dissolved in the above-mentioned polymerizable monomer and emulsion-polymerized, or at least containing the above-mentioned carboxyl group.
  • the monomer (polymerizable dye) derived from the compound represented by the above general formula (1) or the like is dissolved and dyed to color the resin solid content in an amount of 20 to 50% by mass. A dispersion of colored particles in which the particles are dispersed in water can be obtained.
  • the polymerizable monomer and the monomer unit (polymerizable dye) derived from the compound represented by the above general formula (1) are polymerized [covalent bond (polymer C-of the polymer). And the polymerizable dye -C-polymerizable dye)] to form an integral (polymer C- "-C-" -polymerizable dye), so there is little fading due to heating and it has excellent heat resistance, as well as water resistance and light resistance.
  • An aqueous dispersion of colored particles having even better properties can be obtained.
  • each color such as the monomer unit (polymerizable dye) derived from the compound represented by the above-mentioned general formula (1) to be used, almost infinite color alignment can be performed, and there is an advantage that pinpoint toning can be performed. .. Therefore, the colored particle aqueous dispersion can be suitably used as a coloring material for writing tool ink.
  • the average particle size of the colored particles varies depending on the intended use, but from the viewpoints of storage stability, clogging of the pen core for writing instruments, clogging of the nozzle for inkjet ink, etc., 30 to 30 to The one with 200 nm is desirable.
  • the average particle size of the colored particles is adjusted by the polymerizable monomer species such as the above-mentioned carboxyl group-containing vinyl monomer, acrylic acid or methacrylic acid and an ester monomer of a linear or cyclic alcohol having 2 to 18 carbon atoms, the amount thereof, and polymerization. It is adjusted by appropriately combining conditions (temperature, pressure, etc.).
  • the “average particle size” defined in the present disclosure means the histogram average particle size (D50) based on the scattered light intensity distribution measured by the particle size distribution measuring device [FPAR1000 (manufactured by Otsuka Electronics Co., Ltd.)].
  • the weight average molecular weight of the colored particles is preferably 300,000 to 3 million, more preferably 500,000 to 2 million. Within this range, heat resistance, light resistance, and storage stability are realized.
  • the weight average molecular weight is measured by GPC, and the value is a polystyrene-equivalent value.
  • the water-based ink composition mounted on the writing instrument of the present disclosure contains the colored particle aqueous dispersion having the above-mentioned constitution.
  • a water-soluble organic solvent As a preferable water-based ink composition to be mounted on the writing tool of the present disclosure, it is desirable that the colored particle water dispersion having the above-mentioned constitution, a water-soluble organic solvent, and water are contained.
  • the water-soluble organic solvent that can be used include ethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, 1,2-propanediol, 1,3-propanediol, and 1,2-butane.
  • Glycol 2,3-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentanediol, 2,5-hexanediol, 3-methyl 1,3 -Alkylene glycols such as butanediol, 2methylpentane-2,4-diol, 3-methylpentane-1,3,5 triol, 1,2,3-hexanetriol, polyalkylene glycol such as polyethylene glycol and polypropylene glycol.
  • Glycols such as glycerol, diglycerols and triglycerols, lower alkyl ethers of glycols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol mono-n-butyl ether, N- At least one such as methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and the like can be mentioned.
  • alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, hexyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, benzyl alcohol, dimethylformamide
  • Water-soluble solvents such as amides such as diethylacetamide and ketones such as acetone can also be mixed.
  • the content of these water-soluble organic solvents varies depending on the type of writing instrument such as felt-tip pens, marking pens, and ballpoint pens, and is preferably 1 to 40% by mass with respect to the total amount of the ink composition.
  • the content of water is preferably 30 to 90% by mass, more preferably 40 to 60% by mass, based on the total amount of the ink composition.
  • the content of the colored particles varies depending on the writing instrument type, the outflow mechanism (pen core, ballpoint pen), etc., but the solid content is preferably 1 to 30% by mass with respect to the total amount of the writing instrument ink composition.
  • an antiseptic, an antifungal agent, a pH adjuster, an antifoaming agent and the like can be appropriately selected and used as long as the effects of the present disclosure are not impaired.
  • a pH adjuster alkali metal salts of carbonic acid or phosphoric acid such as ammonia, urea, monoethanolamine, diethanolamine, triethanolamine, aminomethylpropanol, sodium tripolynate, sodium carbonate, and alkali metal water such as sodium hydroxide. At least one such as an oxide can be mentioned.
  • phenol sodium omadin, sodium pentachlorophenol, 1,2-benzisothiazolin 3-one, 2,3,5,6-tetrachloro-4 (methylphonyl) pyridine, benzoic acid and sorbin
  • an alkali metal salt of an acid or dehydroacetic acid, a benzimidazole compound and the like can be mentioned.
  • Phosphores as lubricants polyalkylene glycol derivatives such as polyoxyethylene lauryl ether, fatty acid alkali salts, nonionic surfactants, fluorosurfactants such as perfluoroalkyl phosphates, polyethylene glycol of dimethylpolysiloxane At least one such as a polyether-modified silicone such as an adduct may be mentioned.
  • the writing tool of the present disclosure is equipped with an aqueous ink composition containing a colored particle aqueous dispersion composed of a polymer having at least a monomer unit derived from a dye having a polymerizable unsaturated group having the above composition, and a pen tip (baking). It is characterized in that (excluding the core) is composed of a polyester-based material.
  • the other structures are particularly limited.
  • the structure of the writing instrument, the ink loading structure (ink occlusion impregnation, direct liquid method), the ink supply method, and the like are not particularly limited.
  • 1 and 2 are a front view showing an example of an embodiment of the writing instrument of the present disclosure, a vertical sectional view thereof, and a partially enlarged vertical sectional view of a pen tip portion. As shown in FIGS.
  • the writing instrument A of this embodiment includes a shaft body 10, an ink occlusion body 20, a pen tip (pen core) 30, and a cap 40, which are the main body of the writing instrument.
  • the shaft body 10 is formed of, for example, a thermoplastic resin, a thermosetting resin, or the like, and as shown in FIG. 1 (b), a polymer having at least a monomer unit derived from a dye having a polymerizable unsaturated group.
  • the ink storage body 20 impregnated with the water-based ink composition containing the colored particle aqueous dispersion composed of the above is accommodated, and the tip portion 11 having a tapered tip portion into which the pen tip 30 is fitted is accommodated.
  • a tail plug 15 that holds and closes the rear end side of the ink storage body 20 to be accommodated is fixed to the rear end side while being integrally held. Further, a cylindrical mounting member 16 is fixed to the step portion 12 on the outer periphery of the front side of the shaft body 10 by fitting.
  • the cross-sectional shape of the shaft body 10 is a round square shape, which has no corners and is easy to grip.
  • the ink reservoir 20 is impregnated with an aqueous ink composition containing a colored particle aqueous dispersion composed of a polymer having at least a monomer unit derived from a dye having a polymerizable unsaturated group as described above, and is, for example, natural.
  • it is a fiber bundle composed of a combination of two or more kinds, a processed fiber bundle such as felt, or a porous body such as a sponge or resin particles.
  • the ink storage body 20 is housed and held in the shaft body 10.
  • the pen tip 30 is made of a porous body, and examples thereof include those formed of a porous body having pores, and specific examples thereof include a molded body such as a foam, which is disclosed in the present disclosure. Excludes the pen tip made of a sintered body. The reason for this is not clear, but since the surface condition of the sintered pen tip and the pen tip composed of a molded body other than the sintered body are different, the pen tip composed of the sintered body is used for ink. It is presumed that discoloration does not occur.
  • the material forming the pen tip 30 (excluding the sintered body) is made of a polyester-based material.
  • the pen is compatible with an aqueous ink composition containing a colored particle aqueous dispersion composed of a polymer having at least a monomer unit derived from a dye having a polymerizable unsaturated group having the above characteristics, and from the viewpoint of exhibiting the effects of the present disclosure.
  • the tip 30 is made of a polyester-based material.
  • polyester-based material to be used examples include polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene terephthalate (PET) and the like.
  • PBT polybutylene terephthalate
  • PET polytrimethylene terephthalate
  • PET polyethylene terephthalate
  • the pen tip 30 made of a polyester-based elastomer is desirable from the viewpoint of further exerting the effects of the present disclosure.
  • polyester-based elastomer used examples include a block copolymer of an aromatic polyester and an aliphatic polyester, and a block copolymer of an aromatic polyester and an aliphatic polyether.
  • polyester-based thermoplastic elastomers for example, at least polyester forms a hard segment which is crystalline and has a high melting point, and other polymers (for example, polyester or polyether) are amorphous and have a glass transition temperature. Examples include materials forming low soft segments.
  • aromatic polyester can be used as the polyester forming the hard segment.
  • the aromatic polyester can be formed from, for example, an aromatic dicarboxylic acid or an ester-forming derivative thereof and an aliphatic diol.
  • the aromatic polyester is preferably polybutylene terephthalate derived from at least one of terephthalic acid and dimethyl terephthalate and 1,4-butanediol.
  • the aromatic polyester is, for example, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenoxyetanedicarboxylic acid, 5 -A dicarboxylic acid component such as sulfoisophthalic acid or an ester-forming derivative thereof, and a diol having a molecular weight of 300 or less (for example, ethylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, decamethylene glycol, etc.) Alibo diols; 1,4-cyclohexanedimethanol, alicyclic diols such as tricyclodecanedimethylol; xylylene glycol, bis (p-hydroxy) diphenyl, bis (p-hydroxyphenyl) propane, 2,
  • polyester forming the hard segment examples include polyethylene terephthalate, polybutylene terephthalate, polymethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate and the like, and polybutylene terephthalate is preferable.
  • Examples of the polymer forming the soft segment include aliphatic polyesters and aliphatic polyethers.
  • the aliphatic polyether include poly (ethylene oxide) glycol, poly (propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, a copolymer of ethylene oxide and propylene oxide, and poly (propylene oxide).
  • Glycol ethylene oxide addition polymer, copolymer of ethylene oxide and tetrahydrofuran, and the like can be mentioned.
  • Examples of the aliphatic polyester include poly ( ⁇ -caprolactone), polyenant lactone, polycaprilolactone, polybutylene adipate, polyethylene adipate and the like.
  • poly (tetramethylene oxide) glycol and poly (propylene oxide) glycol are examples of polymers that form soft segments from the viewpoint of the elastic properties of the obtained polyester block copolymer.
  • Ethylene oxide adduct, poly ( ⁇ -caprolactone), polybutylene adipate, polyethylene adipate and the like are preferable.
  • the number average molecular weight of the polymer forming the soft segment is preferably 300 to 6000 from the viewpoint of toughness and low temperature flexibility.
  • the mass ratio (x: y) of the hard segment (x) and the soft segment (y) is preferably 99: 1 to 20:80, more preferably 98: 2 to 30:70 from the viewpoint of moldability. ..
  • each combination of the above-mentioned hard segment and the soft segment for example, each combination of the above-mentioned hard segment and the soft segment can be mentioned.
  • a combination in which the hard segment is polybutylene terephthalate and the soft segment is an aliphatic polyether is preferable, and the hard segment is polybutylene terephthalate and the soft segment. More preferably, the combination is poly (ethylene oxide) glycol.
  • These polyester-based thermoplastic elastomers can be synthesized by copolymerizing a polymer forming a hard segment and a polymer forming a soft segment by a known method.
  • polyester-based thermoplastic elastomers include, for example, the "Hitrel” series manufactured by Toray DuPont Co., Ltd. (for example, 3046, 5557, 6347, 4047N, 4767N, etc.) and the "Perprene” series manufactured by Toyobo Co., Ltd. (For example, P30B, P40B, P40H, P55B, P70B, P150B, P280B, E450B, P150M, S1001, S2001, S5001, S6001, S9001, etc.) can be used.
  • Hitrel manufactured by Toray DuPont Co., Ltd.
  • Perprene manufactured by Toyobo Co., Ltd.
  • the pen tip 30 of the present embodiment is made of a molded polyester-based thermoplastic elastomer.
  • the shape, size, hardness, etc. of the pen tip 30 vary depending on the use of the writing instrument, the ink supply method, the drawing line width, etc., and are not particularly limited. , Inclined shape (knife cut shape), bullet shape, brush shape (brush body), etc., and the size, hardness, etc. can be within predetermined ranges.
  • the ink storage body 20 containing the water-based ink composition having the above characteristics is inserted and held in the shaft body 10 which is the main body of the writing tool, and the pen tip 30 and the tail plug are held.
  • the writing tool A can be easily produced by sequentially fixing the mounting members 16 to the pen tip 30 by means of capillary force. It will be efficiently supplied and used for writing.
  • the structure of the marking pen is not particularly limited, and is, for example, a direct liquid type having a collector structure (ink holding mechanism) in which the shaft body itself is used as an ink container and the shaft body is filled with the water-based ink composition having the above characteristics.
  • the marking pen may be a valve valve type writing instrument.
  • the writing tools of the present disclosure are equipped with an aqueous ink composition containing a colored particle aqueous dispersion composed of a polymer having at least a monomer unit derived from a dye having a polymerizable unsaturated group, and the writing tool thereof. Due to the specific combination of the characteristic water-based ink composition and the pen tip (excluding the sintered core) composed of the polyester-based material, the free dye does not move to the polyester-based material and may be adsorbed on the pen tip. This eliminates the problem and provides a writing tool that suppresses discoloration of the ink.
  • 2-methacryloyloxyethyl succinate (Compound 8: manufactured by Shin-Nakamura Chemical Industries, Ltd., trade name: NK ester SA) 43.7 g (190 mmol), 4-dimethylaminopyridine (manufactured by Wako Pure Chemical Industries, Ltd.) Add 1.9 g (15.8 mmol), 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (WSC) (manufactured by Wako Pure Chemical Industries, Ltd.) 51.5 g (269 mmol), and add 18 at room temperature. Stirred for hours.
  • ⁇ Dye 9 Commercial product 1> A commercially available water-soluble dye (manufactured by Hodogaya Chemical Industry Co., Ltd., AIZEN CATHILON RED BLH 200%, CIbasic Red39) was used.
  • ⁇ Dye 10 Commercial product 2> A commercially available water-soluble dye (manufactured by Hodogaya Chemical Industry Co., Ltd., AIZEN CATHILON YELLOW GLH, CIBasic Yellow14) was used.
  • the average particle size of each of the obtained resin particles (particles 1 to 16) was measured by the above-mentioned measuring device [particle size distribution measuring device], and the weight average molecular weight was measured by the following method. These measured values are shown in Table 1 below.
  • the weight average molecular weight is measured by GPC, and the value is a polystyrene-equivalent value.
  • Examples 1 to 14 and Comparative Examples 1 to 2 Preparation of ink composition for writing instruments and preparation of writing instruments] Using the aqueous dispersions (particles 1 to 16) of each colored particle produced in Production Examples 1 to 16, each ink composition for writing utensils is prepared by a conventional method according to the compounding composition (total amount 100% by mass) shown in Table 2 below. Prepared. The obtained ink composition for each writing instrument was mounted on the writing instrument produced below.
  • Pen tip A Material: Polyethylene terephthalate elastomer, Shape: Inclined shape (knife cut shape): ⁇ 3.2 x 32 mm
  • Pen tip B Material: Polybutylene terephthalate elastomer, Shape: Bullet shape: ⁇ 2.0 x 30 mm
  • Pen tip C Material: Polyethylene terephthalate elastomer, Shape: Brush shape (brush body) Shaft 10, tail plug 15, mounting member 16, cap 40: All polypropylene (PP) resin
  • Ink storage 20 Polyethylene terephthalate resin, Porosity: 80%
  • Evaluation method of discoloration of drawn lines Using a marking pen (PEM-SY: manufactured by Mitsubishi Pencil Co., Ltd.) having the above configuration filled with each of the obtained ink compositions, a circle having a diameter of about 5 cm was written on PPC paper, and this was set as the initial state. These marking pens were capped and allowed to stand sideways at 60 ° C. for 3 days, and then lines were drawn on PPC paper in the same manner as in the initial stage, and comparison with the initial state was performed according to the following evaluation criteria. Evaluation criteria: A: No discoloration of the drawn lines is observed. B: Slight discoloration of the drawn lines is observed. C: The discoloration of the drawn lines is obvious.
  • Examples 1 to 14 which are within the scope of the present disclosure can exhibit the effect of the present disclosure without discoloration of drawn lines as compared with Comparative Examples 1 and 2 which are outside the scope of the present disclosure. confirmed.
  • the writing tool of the present disclosure can be suitably used for writing tools such as felt-tip pens and marking pens.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Pens And Brushes (AREA)

Abstract

L'invention concerne un instrument d'écriture capable de supprimer la décoloration de l'encre provoquée par l'adsorption d'une encre d'instrument d'écriture sur une pointe de stylo.　Cet instrument d'écriture utilise, par exemple, un instrument d'écriture caractérisé en ce que : une composition d'encre aqueuse est incluse qui contient une dispersion aqueuse de particules colorées composée d'un polymère qui a au moins une unité monomère dérivée d'un colorant ayant un groupe insaturé polymérisable; et une pointe de stylo (à l'exclusion d'un noyau fritté) est composé d'un matériau à base de polyester.
PCT/JP2021/019578 2020-05-25 2021-05-24 Instrument d'écriture WO2021241484A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0939465A (ja) * 1995-07-31 1997-02-10 Teiboo Kk 高弾性ポリエステル製筆ペン
US5672021A (en) * 1995-02-10 1997-09-30 Avery Dennison Corporation Fibrous nib for use in a capillary feed marker
JP3144589U (ja) * 2008-06-24 2008-09-04 ヤマハチケミカル株式会社 多孔質ペン先
JP2013144379A (ja) * 2012-01-13 2013-07-25 Taisei:Kk バルブ機構を備えた筆記具
WO2019117134A1 (fr) * 2017-12-14 2019-06-20 三菱鉛筆株式会社 Dispersion aqueuse de particules colorées

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5672021A (en) * 1995-02-10 1997-09-30 Avery Dennison Corporation Fibrous nib for use in a capillary feed marker
JPH0939465A (ja) * 1995-07-31 1997-02-10 Teiboo Kk 高弾性ポリエステル製筆ペン
JP3144589U (ja) * 2008-06-24 2008-09-04 ヤマハチケミカル株式会社 多孔質ペン先
JP2013144379A (ja) * 2012-01-13 2013-07-25 Taisei:Kk バルブ機構を備えた筆記具
WO2019117134A1 (fr) * 2017-12-14 2019-06-20 三菱鉛筆株式会社 Dispersion aqueuse de particules colorées

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