WO2014181763A1 - Thermosensitive color-developing composition and thermosensitive recording material using same - Google Patents

Thermosensitive color-developing composition and thermosensitive recording material using same Download PDF

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Publication number
WO2014181763A1
WO2014181763A1 PCT/JP2014/062133 JP2014062133W WO2014181763A1 WO 2014181763 A1 WO2014181763 A1 WO 2014181763A1 JP 2014062133 W JP2014062133 W JP 2014062133W WO 2014181763 A1 WO2014181763 A1 WO 2014181763A1
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group
substituted
unsubstituted
ring
groups
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PCT/JP2014/062133
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French (fr)
Japanese (ja)
Inventor
文二 澤野
詫摩　啓輔
長一郎 山本
熊谷　洋二郎
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山本化成株式会社
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Priority to JP2015515864A priority Critical patent/JP6282640B2/en
Publication of WO2014181763A1 publication Critical patent/WO2014181763A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/333—Colour developing components therefor, e.g. acidic compounds
    • B41M5/3333—Non-macromolecular compounds
    • B41M5/3335—Compounds containing phenolic or carboxylic acid groups or metal salts thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/323—Organic colour formers, e.g. leuco dyes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/333—Colour developing components therefor, e.g. acidic compounds
    • B41M5/3333—Non-macromolecular compounds

Definitions

  • the present invention relates to a thermochromic composition that forms a colored body having a clear yellow to blue high density and high fastness. Furthermore, the present invention relates to a heat-sensitive recording material containing the composition.
  • Patent Documents 4 to 5 a method of using an irreversible coloring material by a thermal melting reaction between an aromatic isocyanate and an imino compound as a recording image has been proposed. There was a drawback of being low. In view of the above, there is a need for a heat-sensitive recording material that solves the conventional problems, satisfies practical color development sensitivity and storage stability of a color image at the same time, and has a clear and high density color image. In recent years, transparent thermosensitive recording materials with high transparency, high color density, and excellent image storability have been developed for applications such as medical diagnostic imaging films, image forming films for overhead projectors, and CAD image forming films. It is requested.
  • An object of the present invention is to provide a heat-sensitive color-forming composition that forms a colored body having a high concentration and a high fastness, and a heat-sensitive recording material using the composition.
  • the present invention (I) a thermosensitive coloring composition containing an imino compound represented by the general formula (1), (2) or (3) and a pyrrolinone compound represented by the general formula (4);
  • ring X represents a substituted or unsubstituted aromatic ring or a substituted or unsubstituted heterocyclic ring
  • R 1 represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, substituted or unsubstituted A substituted aryl group, a substituted or unsubstituted aralkyl group is shown.
  • R 2 represents a substituted or unsubstituted alkyl group
  • rings X and R 1 have the same meanings as those shown in formula (1).
  • R 3 and R 4 each independently represent a substituted or unsubstituted alkyl group, and R 3 and R 4 may combine to form a ring.
  • Ring X and R 1 have the same meanings as those shown in formula (1).
  • A represents a substituted or unsubstituted aromatic ring, a substituted or unsubstituted heterocyclic ring
  • R 5 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group.
  • a in formula (4) is substituted or unsubstituted benzene ring, substituted or unsubstituted naphthalene ring, substituted or unsubstituted anthracene ring, substituted or unsubstituted pyridine ring, substituted or unsubstituted quinoline ring , Substituted or unsubstituted pyrrole ring, substituted or unsubstituted indole ring, substituted or unsubstituted thiophene ring, substituted or unsubstituted benzothiophene ring, substituted or unsubstituted furan ring, substituted or unsubstituted benzofuran ring A thermosensitive coloring composition of (i) or (ii),
  • the present invention it has become possible to provide a heat-sensitive recording material that simultaneously satisfies vivid and high-density color development and storage stability of a color image, and a transparent heat-sensitive recording material having high transparency.
  • the present invention relates to an imino compound represented by the general formula (1), (2) or (3) (hereinafter abbreviated as “component I” in the meaning of the color former-forming component I) and the general formula (4).
  • component I an imino compound represented by the general formula (1), (2) or (3)
  • component P the pyrrolinone compound
  • Component I used in the present invention is an imino compound represented by the general formula (1), (2) or (3).
  • ring X represents a substituted or unsubstituted aromatic ring or a substituted or unsubstituted heterocyclic ring
  • R 1 represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, substituted or unsubstituted
  • substituted aryl group a substituted or unsubstituted aralkyl group is shown.
  • R 2 represents a substituted or unsubstituted alkyl group, and rings X and R 1 have the same meanings as those shown in formula (1).
  • R 3 and R 4 each independently represent a substituted or unsubstituted alkyl group, and R 3 and R 4 may combine to form a ring. Ring X and R 1 have the same meanings as those shown in formula (1).
  • X is preferably a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted anthracene ring, a substituted or unsubstituted pyridine ring.
  • X is more preferably a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, or a substituted or unsubstituted anthracene ring.
  • substituents include a halogen atom, a hydroxyl group, a nitro group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted group Aryl group, substituted or unsubstituted aralkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted alkyl A carbonyl group, a substituted or unsubstituted arylcarbonyl group, a substituted or unsubstituted amino group, and the like are preferable.
  • a halogen atom a hydroxyl group, a nitro group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 24 carbon atoms, a substituted or unsubstituted group having 1 to 20 carbon atoms.
  • substituent when X has a substituent are shown below.
  • the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom.
  • the substituted or unsubstituted alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an isopentyl group.
  • Examples of the substituted or unsubstituted alkenyl group include a vinyl group, a propenyl group, a 1-butenyl group, an isobutenyl group, a 1-pentenyl group, a 2-pentenyl group, a 2-methyl-1-butenyl group, and a 2-cyclopentenyl group.
  • Examples of the substituted or unsubstituted alkynyl group include acetylenyl group, propynyl group, 1-butynyl group, 1-pentynyl group, 2-pentynyl group, 2-methyl-1-pentynyl group, and phenylacetylenyl group. It is done.
  • Examples of the substituted or unsubstituted aryl group include a phenyl group, 1-naphthyl group, 2-naphthyl group, 2-anthracenyl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 1-pyrenyl group, Unsubstituted aryl groups such as 2-pyrenyl group, 2-perylenyl group, 3-perylenyl group, 2-fluoranthenyl group, 3-fluoranthenyl group, 7-fluoranthenyl group, 8-fluoranthenyl group; 1-methyl-2-pyrenyl group, 2-methylphenyl group, 4-ethylphenyl group, 4- (4'-tert-butylcyclohexyl) phenyl group, 3-cyclohexylphenyl group, 2-cyclohexylphenyl group, 4-ethyl An aryl group substituted with an alkyl group such as a 1-na
  • Examples of the substituted or unsubstituted aralkyl group include benzyl group, ⁇ -methylbenzyl group, phenethyl group, ⁇ -methylphenethyl group, ⁇ , ⁇ -dimethylbenzyl group, ⁇ , ⁇ -dimethylphenethyl group, 4-methylphenethyl group.
  • An aralkyl group unsubstituted or substituted with an alkyl group such as a group, 4-methylbenzyl group, 4-isopropylbenzyl group
  • An aralkyl group substituted with an aryl group or an aralkyl group such as a 4-benzylbenzyl group, a 4-phenethylbenzyl group, a 4-phenylbenzyl group; 4-methoxybenzyl group, 4-n-tetradecyloxybenzyl group, 4-n-heptadecyloxybenzyl group, 3,4-dimethoxybenzyl group, 4-methoxymethylbenzyl group, 4-vinyloxymethylbenzyl group, 4
  • An aralkyl group substituted with a substituted oxy group such as a benzyloxybenzyl group or 4-phenethyloxybenzyl group
  • An aralkyl group substituted with a hydroxyl group such as a 4-hydroxybenzyl group and
  • Examples of the substituted or unsubstituted alkoxy group include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, tert-butyloxy group, sec-butyloxy group, and n-pentyl.
  • Oxy group isopentyloxy group, n-hexyloxy group, 2-methylpentyloxy group, 1,1-dimethylbutyloxy group, 1,2,2-trimethylpropyloxy group, 2-ethylbutyloxy group, 1, 3-dimethylhexyloxy group, cyclohexyloxy group, methylcyclopentyloxy group, n-heptyloxy group, n-heptyloxy group, n-octyloxy group, 3,5,5-trimethylhexyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, 1-a Manchiruokishi group, a straight-chain, such as n- pentadecyl group, branched or cyclic unsubstituted alkoxy group;
  • An alkoxy group substituted with an alkoxycarbonyl group such as a methoxycarbonylmethoxy group, an ethoxycarbonylmethoxy group, an n-propyloxycarbonylmethoxy group, an isopropyloxycarbonylmethoxy group, or a (4′-ethylcyclohexyloxy) carbonylmethoxy group;
  • An alkoxy group substituted with an alkoxycarbonyl group such as a methoxycarbonylethoxy group, an ethoxycarbonylethoxy group, an n-propyloxycarbonylethoxy group, or an ethoxycarbonylpropyloxy group;
  • Methylaminomethoxy group 2-methylaminoethoxy group, 2- (2-methylaminoethoxy) ethoxy group, 4-methylaminobutyloxy group, 1-methylaminopropan-2-yloxy group, 3-methylaminopropyloxy group 2-methylamino-2-methylpropyloxy group, 2-ethylaminoethoxy group, 2- (2-ethylaminoethoxy) ethoxy group, 3-ethylaminopropyloxy group, 1-ethylaminopropyloxy group, 2- An alkoxy group substituted with an alkylamino group such as an isopropylaminoethoxy group, 2- (n-butylamino) ethoxy group, 3- (n-hexylamino) propyloxy group, 4- (cyclohexylamino) butyloxy group; Dimethylaminomethoxy group, 2-dimethylaminoethoxy group, 2- (2-dimethylaminoe
  • Substituted or unsubstituted aryloxy groups include heteroaryloxy groups such as phenyloxy group, 2-methylphenyloxy group, 4-methylphenyloxy group, 4-ethylphenyloxy group, 4-isopropylphenyl group.
  • Examples of the substituted or unsubstituted alkylthio group include a methylthio group, an ethylthio group, an n-propylthio group, an isopropylthio group, an n-butylthio group, an isobutylthio group, a tert-butylthio group, a sec-butylthio group, and an n-pentylthio group.
  • Methylaminomethylthio group 2-methylaminoethylthio group, 2- (2-methylaminoethoxy) ethylthio group, 4-methylaminobutylthio group, 1-methylaminopropan-2-yloxy group, 3-methylaminopropylthio group Group, 2-ethylaminoethylthio group, 2- (2-ethylaminoethoxy) ethylthio group, 3-ethylaminopropylthio group, 1-ethylaminopropylthio group, 2-isopropylaminoethylthio group, 2- (n An alkylthio group substituted with an alkylamino group such as a butylamino) ethylthio group, a 3- (n-hexylamino) propylthio group, or a 4- (cyclohexylamino) butylthio group; Dimethylaminomethylthio group, 2-
  • the substituted or unsubstituted arylthio group also includes a heteroarylthio group, such as a phenylthio group, a 2-methylphenylthio group, a 4-methylphenylthio group, a 3-ethylphenylthio group, a 4-n-propylphenyl group.
  • a heteroarylthio group such as a phenylthio group, a 2-methylphenylthio group, a 4-methylphenylthio group, a 3-ethylphenylthio group, a 4-n-propylphenyl group.
  • substituted or unsubstituted alkylcarbonyl group examples include formyl group, acetyl group, propionyl group, butyryl group, valeryl group, iso-valeryl group, sec-valeryl group, trimethylacetyl group, hexanoyl group, tert-butylacetyl group , Heptanoyl group, octanoyl group, 2-ethylhexanoyl group, nonanoyl group, decanoyl group, undecanoyl group, lauroyl group, tridecanoyl group, tetraadecanoyl group, pentadecanoyl group, hexadecanoyl group, heptadecanoyl group, octadecanoyl group Group, oleoyl group, cyclopentanecarbonyl group, cyclohexanecarbonyl group, 6-chlorohexano
  • Examples of the substituted or unsubstituted arylcarbonyl group include benzoyl group, 2-methylbenzoyl group, 3-methylbenzoyl group, 4-methylbenzoyl group, 4-ethylbenzoyl group, 4-n-propylbenzoyl group, 4- tert-butylbenzoyl group, 2,4-dimethylbenzoyl group, 2,4,6-trimethylbenzoyl group, 2,4,5-trimethylbenzoyl group, 4-ethylbenzoyl group, 4-isopropylbenzoyl group, 4-n- Butylbenzoyl group, 4-isobutylbenzoyl group, 4-sec-butylbenzoyl group, 4-tert-butylbenzoyl group, 4-n-pentylbenzoyl group, 4-isopentylbenzoyl group, 4-neopentibenzoyl group, 4- Isohexyl benzoyl group, 4-cyclohexyl benzo
  • substituted or unsubstituted amino group examples include amino groups such as methylamino group, ethylamino group, propylamino group, butylamino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, 2-ethylhexyl Monoalkylamino groups such as amino group, cyclohexylamino group, 3,5,5-trimethylhexylamino group, nonylamino group, decylamino group; Dimethylamino group, diethylamino group, methylethylamino group, di-n-propylamino group, di-n-butylamino group, di-n-pentylamino group, N-methyl-N-ethylamino group, N-ethyl- Dialkylamino groups such as N-isopropylamino group, N-ethyl-N-
  • R 1 is preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms.
  • R 1 is a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms or a substituted or unsubstituted aryl group having 6 to 18 carbon atoms.
  • R 1 examples of these R 1 are shown below.
  • the substituted or unsubstituted alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an isopentyl group.
  • a linear, branched or cyclic unsubstituted alkyl group such as 1-methylheptyl group, 2-ethylhexyl group, cyclopentyl group, cyclohexyl group, 4-methylcyclohexyl group;
  • Alkyloxy or alkenyloxy such as methoxymethyl, ethoxymethyl, n-butoxymethyl, n-hexyloxymethyl, (2-ethylbutyloxy) methyl, 2- (4'-pentenyloxy) ethyl
  • Examples of the substituted or unsubstituted alkenyl group include a vinyl group, a propenyl group, a 1-butenyl group, an isobutenyl group, a 1-pentenyl group, a 2-pentenyl group, a 2-methyl-1-butenyl group, and a 2-cyclopentenyl group.
  • Examples of the substituted or unsubstituted aryl group include phenyl group, 1-naphthyl group, 2-naphthyl group, 2-anthracenyl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 1-pyrenyl group, Unsubstituted aryl groups such as 2-pyrenyl group, 2-perylenyl group, 3-perylenyl group, 2-fluoranthenyl group, 3-fluoranthenyl group, 7-fluoranthenyl group, 8-fluoranthenyl group, etc .: 1-methyl-2-pyrenyl group, 2-methylphenyl group, 4-ethylphenyl group, 4- (4′-tert-butylcyclohexyl) phenyl group, 3-cyclohexylphenyl group, 2-cyclohexylphenyl group, 4-ethyl An aryl group substituted with an alkyl group such as a 1-
  • Examples of the substituted or unsubstituted aralkyl group include benzyl group, ⁇ -methylbenzyl group, phenethyl group, ⁇ -methylphenethyl group, ⁇ , ⁇ -dimethylbenzyl group, ⁇ , ⁇ -dimethylphenethyl group, 4-methylphenethyl group.
  • An aralkyl group unsubstituted or substituted with an alkyl group such as a group, 4-methylbenzyl group, 4-isopropylbenzyl group, etc .
  • Aralkyl groups substituted with aryl groups or aralkyl groups such as 4-benzylbenzyl group, 4-phenethylbenzyl group and 4-phenylbenzyl group: 4-methoxybenzyl group, 4-n-tetradecyloxybenzyl group, 4-n-heptadecyloxybenzyl group, 3,4-dimethoxybenzyl group, 4-methoxymethylbenzyl group, 4-vinyloxymethylbenzyl group, 4
  • An aralkyl group substituted by a substituted oxy group such as benzyloxybenzyl group or 4-phenethyloxybenzyl group:
  • Aralkyl groups substituted with hydroxyl groups such as 4-hydroxybenzyl group and 4-hydroxy-3-methoxybenzyl group:
  • R 2 of the imino compound represented by the general formula (2) and R 3 and R 4 of the imino compound represented by the general formula (3) are preferably a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, A substituted or unsubstituted alkyl group having 1 to 8 carbon atoms is more preferable. Specific examples of these R 2 , R 3 and R 4 are shown below.
  • Examples of the substituted or unsubstituted alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an isopentyl group.
  • Alkyloxy or alkenyl such as methoxymethyl, ethoxymethyl, n-butoxymethyl, n-hexyloxymethyl, (2-ethylbutyloxy) methyl, 2- (4'-pentenyloxy) ethyl
  • Alkyl groups substituted with oxy groups Alkyl groups substituted with aralkyloxy groups such as benzyloxymethyl group and 2- (benzyloxymethoxy) ethyl group: Alkyl groups substituted with aryloxy groups such as
  • R 3 and R 4 of the imino compound represented by the general formula (3) are bonded to form a ring.
  • the ring formed by combining R 3 and R 4 includes a substituted or unsubstituted dioxolane ring, substituted or unsubstituted, formed together with the oxygen atom substituted by R 3 and R 4 and their common basic carbon atom.
  • the dioxane ring is preferred.
  • the substituent is the same as the substituent that R 2 , R 3 and R 4 have when they are substituted alkyl groups.
  • ring in which R 3 and R 4 are bonded include, for example, ethane-1,2-diyl ring, propane-1,3-diyl ring, butane-1,4-diyl ring, pentane-1,5-diyl Ring, hexane-1,6-diyl ring, 1-methylethane-1,2-diyl ring, 1-n-butylethane-1,2-diyl ring, 2-ethylpropane-1,3-diyl ring, 1-methyl -Propane-1,3-diyl ring, 1-n-butyl-propane-1,3-diyl ring, 2-n-butyl-butane-1,4-diyl ring, 2,4-dimethyl-butane-1, 4-diyl ring, 3-isopentyl-pentane-1,5-diyl ring, 2,3,4-trimethylpentane
  • component I represented by the general formula (1), (2) or (3) are shown in the following Table 1, but the present invention is not limited thereto.
  • Component I represented by the general formula (1), (2) or (3) is known in JP-A-8-113561, JP-A-8-199081, JP-A-8-225753, etc. It can be produced with reference to the method.
  • the compound of the specific example (3) -1 can be obtained by stirring 1,1-dimethoxy-3-iminoisone indoline and p-toluic acid in acetone for 30 minutes and filtering the precipitate.
  • Component P used in the present invention is a pyrrolinone compound represented by the general formula (4).
  • A represents a substituted or unsubstituted aromatic ring, a substituted or unsubstituted heterocyclic ring
  • R 5 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group.
  • A is preferably a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted anthracene ring, a substituted or unsubstituted pyridine ring, a substituted or unsubstituted quinoline ring.
  • Substituted or unsubstituted pyrrole ring, substituted or unsubstituted indole ring, substituted or unsubstituted thiophene ring, substituted or unsubstituted benzothiophene ring, substituted or unsubstituted furan ring, substituted or unsubstituted benzofuran ring is there.
  • A is more preferably a substituted or unsubstituted benzene ring, a substituted or unsubstituted pyridine ring, a substituted or unsubstituted pyrrole ring, a substituted or unsubstituted thiophene ring, a substituted or unsubstituted benzothiophene ring, substituted or An unsubstituted benzofuran ring.
  • Examples of the substituent when A has a substituent include a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted group
  • An alkoxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted amino group, a substituted or unsubstituted heterocyclic group, a cyano group, a halogen atom and the like are preferable.
  • it is a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted aryl group having 6 to 24 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 25 carbon atoms, or 2 to 2 carbon atoms.
  • it is a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 14 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 15 carbon atoms, or 2 to 2 carbon atoms.
  • Examples of the substituted or unsubstituted alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an isopentyl group.
  • Alkyloxy or alkenyl such as methoxymethyl, ethoxymethyl, n-butoxymethyl, n-hexyloxymethyl, (2-ethylbutyloxy) methyl, 2- (4'-pentenyloxy) ethyl
  • Alkyl groups substituted with oxy groups Alkyl groups substituted with an aralkyloxy group such as benzyloxymethyl group and 2- (benzyloxymethoxy) ethyl group, phenyloxymethyl group, 4-chlorophen
  • Examples of the substituted or unsubstituted aryl group include phenyl group, 1-naphthyl group, 2-naphthyl group, 2-anthracenyl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 1-pyrenyl group, Unsubstituted aryl groups such as 2-pyrenyl group, 2-perylenyl group, 3-perylenyl group, 2-fluoranthenyl group, 3-fluoranthenyl group, 7-fluoranthenyl group, 8-fluoranthenyl group, etc .: 1-methyl-2-pyrenyl group, 2-methylphenyl group, 4-ethylphenyl group, 4- (4′-tert-butylcyclohexyl) phenyl group, 3-cyclohexylphenyl group, 2-cyclohexylphenyl group, 4-ethyl An aryl group substituted with an alkyl group such as a 1-
  • Examples of the substituted or unsubstituted aralkyl group include benzyl group, ⁇ -methylbenzyl group, phenethyl group, ⁇ -methylphenethyl group, ⁇ , ⁇ -dimethylbenzyl group, ⁇ , ⁇ -dimethylphenethyl group, 4-methylphenethyl group.
  • An aralkyl group unsubstituted or substituted with an alkyl group such as a group, 4-methylbenzyl group, 4-isopropylbenzyl group, etc .
  • Aralkyl groups substituted with aryl groups or aralkyl groups such as 4-benzylbenzyl group, 4-phenethylbenzyl group and 4-phenylbenzyl group: 4-methoxybenzyl group, 4-n-tetradecyloxybenzyl group, 4-n-heptadecyloxybenzyl group, 3,4-dimethoxybenzyl group, 4-methoxymethylbenzyl group, 4-vinyloxymethylbenzyl group, 4
  • An aralkyl group substituted by a substituted oxy group such as benzyloxybenzyl group or 4-phenethyloxybenzyl group: Aralkyl groups substituted with hydroxyl groups such as 4-hydroxybenzyl group and 4-hydroxy-3-methoxybenzyl group: Aralky
  • Examples of the substituted or unsubstituted alkenyl group include a vinyl group, a propenyl group, a 1-butenyl group, an isobutenyl group, a 1-pentenyl group, a 2-pentenyl group, a 2-methyl-1-butenyl group, and a 2-cyclopentenyl group.
  • Examples of the substituted or unsubstituted alkoxy group include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, tert-butyloxy group, sec-butyloxy group, and n-pentyl.
  • Oxy group isopentyloxy group, n-hexyloxy group, 2-methylpentyloxy group, 1,1-dimethylbutyloxy group, 1,2,2-trimethylpropyloxy group, 2-ethylbutyloxy group, 1, 3-dimethylhexyloxy group, cyclohexyloxy group, methylcyclopentyloxy group, n-heptyloxy group, n-heptyloxy group, n-octyloxy group, 3,5,5-trimethylhexyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, 1-a Manchiruokishi group, a straight-chain, such as n- pentadecyloxy group, branched or cyclic unsubstituted alkoxy group:
  • Alkoxy groups substituted with alkoxycarbonyl groups such as methoxycarbonylmethoxy group, ethoxycarbonylmethoxy group, n-propyloxycarbonylmethoxy group, isopropyloxycarbonylmethoxy group, (4'-ethylcyclohexyloxy) carbonylmethoxy group, methoxycarbonylethoxy
  • An alkoxy group substituted by an alkoxycarbonyl group such as a group, ethoxycarbonylethoxy group, n-propyloxycarbonylethoxy group, ethoxycarbonylpropyloxy group;
  • Methylaminomethoxy group 2-methylaminoethoxy group, 2- (2-methylaminoethoxy) ethoxy group, 4-methylaminobutyloxy group, 1-methylaminopropan-2-yloxy group, 3-methylaminopropyloxy group 2-methylamino-2-methylpropyloxy group, 2-ethylaminoethoxy group, 2- (2-ethylaminoethoxy) ethoxy group, 3-ethylaminopropyloxy group, 1-ethylaminopropyloxy group, 2- An alkoxy group substituted with an alkylamino group such as an isopropylaminoethoxy group, 2- (n-butylamino) ethoxy group, 3- (n-hexylamino) propyloxy group, 4- (cyclohexylamino) butyloxy group; Dimethylaminomethoxy group, 2-dimethylaminoethoxy group, 2- (2-dimethylaminoe
  • Alkoxy substituted with alkylaminoalkoxy groups such as methylaminomethoxymethoxy group, methylaminoethoxyethoxy group, methylaminoethoxypropyloxy group, ethylaminoethoxypropyloxy group, 4- (2'-isobutylaminopropyloxy) butyloxy group Group; Alkoxy groups substituted with dialkylaminoalkoxy groups such as dimethylaminomethoxymethoxy group, dimethylaminoethoxyethoxy group, dimethylaminoethoxypropyloxy group, diethylaminoethoxypropyloxy group, 4- (2'-diisobutylaminopropyloxy) butyloxy group ; Methylthiomethoxy group, 2-methylthioethoxy group, 2-ethylthioethoxy group, 2-n-propylthioethoxy group, 2-isopropylthioethoxy group, 2-n-buty
  • Examples of the substituted or unsubstituted alkylthio group include a methylthio group, an ethylthio group, an n-propylthio group, an isopropylthio group, an n-butylthio group, an isobutylthio group, a tert-butylthio group, a sec-butylthio group, and an n-pentylthio group.
  • Methylaminomethylthio group 2-methylaminoethylthio group, 2- (2-methylaminoethoxy) ethylthio group, 4-methylaminobutylthio group, 1-methylaminopropan-2-yloxy group, 3-methylaminopropylthio group Group, 2-ethylaminoethylthio group, 2- (2-ethylaminoethoxy) ethylthio group, 3-ethylaminopropylthio group, 1-ethylaminopropylthio group, 2-isopropylaminoethylthio group, 2- (n An alkylthio group substituted with an alkylamino group such as a butylamino) ethylthio group, a 3- (n-hexylamino) propylthio group, or a 4- (cyclohexylamino) butylthio group; Dimethylaminomethylthio group, 2-
  • Methylthiomethylthio group 2-methylthioethylthio group, 2-ethylthioethylthio group, 2-n-propylthioethylthio group, 2-isopropylthioethylthio group, 2-n-butylthioethylthio group, 2-isobutyl
  • An alkylthio group substituted with an alkylthio group such as a thioethylthio group or a (3,5,5-trimethylhexylthio) hexylthio group; 2-N-morpholinylethylthio group, 2-N-pyridylethylthio group, 2-N-pyrrolylethylthio group, 2- (2-furyl) ethylthio group, 2- (1-indolyl) ethylthio group, 2- (3-thienyl) ethylthio group, 3-N-morpholinylpropyl
  • substituted or unsubstituted amino group examples include amino groups such as methylamino group, ethylamino group, propylamino group, butylamino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, 2-ethylhexyl Monoalkylamino groups such as amino group, cyclohexylamino group, 3,5,5-trimethylhexylamino group, nonylamino group, decylamino group;
  • Aryl group such as amino group, N-methyl-N- (3-chlorophenyl) amino group, diphenylamino group, di- (p-tolyl) amino group,
  • R 5 is preferably a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted group having 6 to 24 carbon atoms.
  • R 5 is a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, carbon A substituted or unsubstituted aralkyl group of formulas 7 to 19; More preferably, R 5 is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 8 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, carbon A substituted or unsubstituted aralkyl group of formulas 7 to 13;
  • R 5 examples of the substituted or unsubstituted alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an isopentyl group.
  • Alkyloxy or alkenyloxy such as methoxymethyl, ethoxymethyl, n-butoxymethyl, n-hexyloxymethyl, (2-ethylbutyloxy) methyl, 2- (4'-pentenyloxy) ethyl
  • Examples of the substituted or unsubstituted alkenyl group include a vinyl group, a propenyl group, a 1-butenyl group, an isobutenyl group, a 1-pentenyl group, a 2-pentenyl group, a 2-methyl-1-butenyl group, and a 2-cyclopentenyl group.
  • Examples of the substituted or unsubstituted aryl group include phenyl group, 1-naphthyl group, 2-naphthyl group, 2-anthracenyl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 1-pyrenyl group, Unsubstituted aryl groups such as 2-pyrenyl group, 2-perylenyl group, 3-perylenyl group, 2-fluoranthenyl group, 3-fluoranthenyl group, 7-fluoranthenyl group, 8-fluoranthenyl group, etc .: 1-methyl-2-pyrenyl group, 2-methylphenyl group, 4-ethylphenyl group, 4- (4'-tert-butylcyclohexyl) phenyl group, 3-cyclohexylphenyl group, 2-cyclohexylphenyl group, 4-ethyl An aryl group substituted with an alkyl group such as a 1-
  • Examples of the substituted or unsubstituted aralkyl group include benzyl group, ⁇ -methylbenzyl group, phenethyl group, ⁇ -methylphenethyl group, ⁇ , ⁇ -dimethylbenzyl group, ⁇ , ⁇ -dimethylphenethyl group, 4-methylphenethyl group.
  • An aralkyl group unsubstituted or substituted with an alkyl group such as a group, 4-methylbenzyl group, 4-isopropylbenzyl group, etc .
  • Aralkyl groups substituted with aryl groups or aralkyl groups such as 4-benzylbenzyl group, 4-phenethylbenzyl group and 4-phenylbenzyl group: 4-methoxybenzyl group, 4-n-tetradecyloxybenzyl group, 4-n-heptadecyloxybenzyl group, 3,4-dimethoxybenzyl group, 4-methoxymethylbenzyl group, 4-vinyloxymethylbenzyl group, 4
  • An aralkyl group substituted by a substituted oxy group such as benzyloxybenzyl group or 4-phenethyloxybenzyl group: Aralkyl groups substituted with hydroxyl groups such as 4-hydroxybenzyl group and 4-hydroxy-3-methoxybenzyl group: Aralky
  • the component P represented by the general formula (4) is known in JP-A-61-115056, JP-A-61-115960, JP-A-7-285920, etc., and is prepared by referring to a known method. can do.
  • the compound of the specific example (4) -2 can be produced by heating diethyl 2-benzoylsuccinate and ammonium acetate in acetic acid.
  • thermosensitive coloring composition containing component I and component P of the present invention will be described below.
  • the thermochromic composition of the present invention contains Component I and Component P of the present invention as essential components, but optionally contains other components such as a binder.
  • the type and amount of the other components vary depending on the color developing material to which the thermosensitive coloring composition is applied. It is preferable for application of the thermosensitive coloring composition that component I and component P of the present invention are solid at room temperature. Is not a requirement. Even in the case of a liquid at room temperature, it can be applied by means such as microencapsulation.
  • Component I and Component P can be used alone or in admixture of two or more.
  • the color-forming material include color-forming recording materials such as heat-sensitive recording materials, energized color recording materials, and laser light recording materials, and are used in combination with other recording methods such as magnetic recording, metal thin film recording, and cloudiness recording. It is also possible to do.
  • component I and component P are each ground and dispersed into fine particles, then both are mixed, and if necessary, a binder and other auxiliary agents are added to the thermosensitive color-forming composition of the present invention.
  • a coating liquid containing a product is prepared, and the coating liquid is applied to a support and dried.
  • a color former hereinafter referred to as a component that forms the color former, Component I and Component P are referred to as “color precursors”. Abbreviated
  • the color former can be formed on the entire recording layer, or can be formed only at a desired location. If the heating temperature is lower than 80 ° C., it takes a long time for color development, or if the color density is low and the temperature is higher than 300 ° C., the color precursor tends to be easily decomposed.
  • the thermal energy for forming the color former is not particularly limited, but for example, thermal energy such as a thermal head, hot stamp, and thermal pen may be used, or light energy such as laser light can be obtained by photothermal conversion. Thermal energy may be used. As a result, any energy source that can be converted into thermal energy can be used.
  • the resulting colored body exhibits various hues and exhibits high fastness to light, heat, humidity, plasticizer, oil and the like.
  • a heat-sensitive recording material obtained by selecting paper, film or sheet as a support, and carrying a recording layer containing the heat-sensitive color-forming composition of the present invention on the support, a color image of the heat-sensitive recording material is obtained. Is extremely fast.
  • thermochromic composition of the present invention can also be dissolved or dispersed in a solvent and used as an ink or a paint. If the ink or paint obtained in this way is applied to a part of a food container, such as an aluminum can, a glass bottle, or a rubber packing, the part painted by the heat treatment after filling the food will have a brilliant hue. Since it changes, it can be used to determine whether or not the heat treatment has been completed. Further, by applying heat energy to the heat-sensitive color-forming composition of the present invention, a dark and strong colored body can be obtained, and this colored body can be pulverized to obtain an organic pigment. When a paint is produced using this organic pigment, a strong and robust paint can be obtained.
  • thermosensitive recording material containing the thermosensitive coloring composition of the present invention will be described below.
  • the heat-sensitive recording material is provided with a recording layer containing the heat-sensitive color forming composition of the present invention on a support.
  • the color-forming precursor is uniformly dispersed or dissolved in water or an organic solvent together with a binder resin, or microencapsulated, and this is coated on a support and dried to produce a heat-sensitive coating liquid.
  • the coloring precursor may be dispersed in water or an organic solvent, and a binder may be added.
  • the component I and the component P constituting the color forming precursor may be dispersed together, or may be mixed after being dispersed separately.
  • the recording layer can be formed by applying and drying the heat-sensitive coating liquid thus obtained on a support.
  • the application method is not particularly limited.
  • the heat-sensitive coating liquid may be in a dispersed state in which the color precursor is contained as fine particles, or may be in a completely dissolved solution state.
  • the molar ratio of component I and component P constituting the color precursor is preferably 1: 0.5 to 1: 5, more preferably 1: 1 to 1: 3.
  • the weight ratio of the color former to the binder is preferably 1: 1 to 1: 0.01, more preferably 1: 0.5 to 1: 0.05.
  • the dispersion medium water or an organic solvent (toluene, methanol, ethanol, isopropyl alcohol, n-hexane, cyclohexane, n-octanol, ethylcyclohexane, dioxane, etc.) is used.
  • a binder when the dispersion medium is water polyvinyl alcohol resin, methyl cellulose resin, hydroxyethyl cellulose resin, carboxymethyl cellulose resin, methyl vinyl ether / maleic anhydride copolymer resin, polyacrylic acid resin, polyvinyl pyrrolidone resin, acrylic amide resin, Gelatin, gum arabic, etc. can be used.
  • the binder when the dispersion medium is an organic solvent, alkyd resin, vinyl chloride resin, urethane resin, xylene resin, phenol resin, coumarone resin, vinyl toluene resin, terpene resin, vinyl toluene / butadiene copolymer resin, vinyl toluene / An acrylate copolymer resin, a styrene / acrylate copolymer resin, a vinyl / isobutyl ether copolymer resin, or the like can be used.
  • a light absorber In the recording layer, a light absorber, a melting point depressant, an ultraviolet absorber, an antioxidant, organic and inorganic pigments and the like can be added according to the purpose.
  • the light absorber is not limited as long as it can absorb light in the wavelength region of the laser beam and convert it into thermal energy.
  • Melting point depressants include waxes such as paraffin wax, polyethylene wax, higher fatty acids and esters thereof, acid amides such as stearamide, diphenyls such as 4,4′-dimethylbiphenyl, and methylolamide.
  • Naphthalenes such as 1,3-dinitronaphthalene, ureas, acids such as phthalic anhydride, acetanilide, benzanilide, anilides such as alkylcarboxylic acid anilide, triphenyls, phthalonitriles, bisresorcinol ethylene Ethers such as ether, salicylic acid derivatives such as 4-t-butyl salicylate, ethyl-2-cyano-3,3-diphenyl acrylate, benzotriazoles, fluorene, dimethyl isophthalate, diphenyl sulfone, mandelic acid, Benzoin, Such as ethyl anthraquinone, coumarone compounds, carbazoles such as N-ethylcarbazole, sulfonamides, triphenylmethanes, thiazoles such as dibenzothiazyl disulfide, N-cyclohexyl-2-benzo
  • ultraviolet absorbers examples include benzotriazole and derivatives thereof, benzoin and derivatives thereof, 2-chloroanthraquinone, benzol peroxide, salicylic acid esters such as pt-butylphenyl salicylate, and cyanoacrylates such as ethyl diphenylacrylate. And the like.
  • Antioxidants include 2,6-di-t-butyl-4-methylphenol, di (3-t-butyl-4-hydroxy-5-methylphenyl) thioether, 1,1-bis (2-methyl- Hindered phenols such as 4-hydroxy-5-t-butylphenyl) butane and hindered amines such as di (2,2,6,6-tetramethyl-4-piperidine) sebacate.
  • the pigment include talc, clay, silica, calcined kaolin, zinc oxide, silicon oxide, titanium oxide, aluminum hydroxide, calcium carbonate, magnesium carbonate, and urea-formalin resin.
  • a protective layer can be provided on the recording layer, and an undercoat layer can be provided below the recording layer.
  • urethane resin, polyolefin resin, polyester resin, vinyl resin, epoxy resin, and acrylic resin can be used.
  • the undercoat layer heat-insulating fine hollow particles, calcined kaolin, organic pigments, thermally expandable microcapsules and the like can be used in order to improve color developability.
  • paper, synthetic paper, film, sheet, laminated paper, nonwoven fabric sheet or the like can be used according to the purpose.
  • the film or sheet examples include polyesters such as polyethylene terephthalate and polybutylene terephthalate, cellulose derivatives such as cellulose triacetate, polyolefins such as polypropylene and polyethylene, and plastic films or sheets such as polyethylene naphthalate and polystyrene. Only one of these plastic films or sheets may be used, or a laminate of them may be used. In addition, when a plurality of sheets are stacked and a card is obtained with a punching machine after heat-sealing between the sheets with a vacuum press machine, any one of the sheets serves as a support.
  • polyesters such as polyethylene terephthalate and polybutylene terephthalate
  • cellulose derivatives such as cellulose triacetate
  • polyolefins such as polypropylene and polyethylene
  • plastic films or sheets such as polyethylene naphthalate and polystyrene. Only one of these plastic films or sheets may be used, or a laminate of them may be used.
  • the support may be transparent, opaque, or translucent depending on the application, but the support is substantially used for the production of the transparent heat-sensitive recording material. It is preferably transparent. Specifically, a plastic film or sheet having a Haze value of 10% or less is preferably used, and a polyethylene terephthalate film or sheet is most preferable from the viewpoints of cost, heat resistance of the support, and the like. Moreover, the said plastic film or sheet
  • seat may be colored by arbitrary hues according to the objective. For example, in the case of a medical image diagnostic film used for shaukasten, it may be colored blue.
  • thermosensitive coloring composition of the present invention has a high transparency when dissolved or dispersed in a solvent and has almost no coloration, but has a clear and high color density when colored by heating, and has a very high fastness. Form. Therefore, it is very suitable for a transparent thermosensitive recording material.
  • Synthesis Example 5 Synthesis of Component P (Specific Example Compound (4) -2) 139.1 g of diethyl 2-benzoylsuccinate and 102.1 g of ammonium acetate were added to 300 mL of acetic acid and stirred at 100 to 105 ° C. for 24 hours. After cooling, the reaction mixture was drained into 500 mL of water. The precipitate was collected by filtration, and the filter paste was dispersed and washed with 500 mL of methanol and dried to obtain 52 g of Compound No. (4) -2 of the pyrrolino compound shown in Table 2 as a white powder. Melting point: 180-181 ° C The obtained compound was confirmed to be the target compound from the following analysis results.
  • thermosensitive recording material As component I, 4.2 g of the compound synthesized in Synthesis Example 4 and 5.7 g of the compound synthesized in Synthesis Example 5 as Component P were each mixed with 30 mL of toluene in a sand mill. Time grinding was performed to obtain a dispersion. Next, the dispersion liquid of component I and the dispersion liquid of component P were combined, and 100 g of “Almatex” (trade name: manufactured by Mitsui Chemicals) as a binder was added and mixed well to prepare a thermosensitive coloring composition. This thermosensitive color-developing composition was applied and dried on fine paper so that the dry coating amount was 6 g / m 2 to obtain a thermosensitive recording material.
  • Almatex trade name: manufactured by Mitsui Chemicals
  • the obtained heat-sensitive recording material was brought into contact with an iron at 200 ° C. for 3 seconds to obtain a full color image. This color image was bright blue.
  • the color images of the heat-sensitive recording material obtained above were measured and evaluated for the following items. The evaluation results are shown in Table 4.
  • Example 2 Production of thermosensitive recording material
  • Example 1 5.9 g of the same compound as component I instead of 4.2 g of the compound synthesized in Synthesis Example 4 and Component P as the component P in Example 1 were synthesized.
  • a heat-sensitive recording material and a full color image were obtained in the same manner as in Example 1 except that 4.0 g of the same compound was used instead of 5.8 g of the compound. This color image was bright yellow.
  • the same evaluation test as in Example 1 was performed on this color image. The results are shown in Table 4.
  • Example 3 Production of Thermosensitive Recording Material
  • Component I instead of Compound 4.2 g synthesized in Synthesis Example 4, Compound 4.3 g synthesized in Synthesis Example 1 and Component P as a synthesis example
  • a heat-sensitive recording material and a full-color image were obtained in the same manner as in Example 1 except that 5.6 g of the same compound was used instead of 5.7 g of the compound synthesized in 5.
  • This color image was bright blue-purple.
  • the same evaluation test as in Example 1 was performed on this color image. The results are shown in Table 4.
  • Example 4 to 23 Preparation of heat-sensitive recording material The same operations as in Example 1 were carried out using the compounds listed in Table 3 for component I and component P in Example 1, respectively. I got a statue. The same evaluation test as in Example 1 was performed on the obtained color image. The results are shown in Table 4.
  • Example 24 Preparation of heat-sensitive recording material
  • component I 4.2 g of the compound synthesized in Synthesis Example 4 and 5.7 g of the compound synthesized in Synthesis Example 5 as Component P were each used as a binder in a 5% aqueous polyvinyl alcohol solution.
  • the mixture was ground with a sand mill for 2 hours to obtain a dispersion.
  • the component I dispersion and the component P dispersion were combined, and 5 parts of a 60% light calcium carbonate aqueous dispersion was added and mixed well to prepare a thermosensitive coloring composition.
  • thermosensitive color-developing composition was applied and dried on fine paper so that the dry coating amount was 6 g / m 2 to obtain a thermosensitive recording material.
  • This heat-sensitive recording material was subjected to the same operation as in Example 1 to form a colored body, and the same evaluation test as in Example 1 was performed on this color image. The results are shown in Table 4.
  • thermosensitive coloring composition Production of transparent thermosensitive recording material
  • This thermosensitive coloring composition was applied and dried on a colorless and transparent polyethylene terephthalate film having a thickness of 180 ⁇ m so that the dry coating amount was 6 g / m 2 to obtain a heat-sensitive recording material having high transparency.
  • the transparent thermosensitive recording material was subjected to the same operation as in Example 1 to form a colored body, and the same evaluation test as in Example 1 was performed on this color image. The results are shown in Table 4.
  • thermosensitive recording material in Example 1, instead of the compound synthesized in Synthesis Example 4 as Component I, 5 g of 2-anilino-3-methyl-6-di-n-butylaminofluorane, As component P, the same operation as in Example 1 was carried out except that 5 g of bisphenol A was used instead of the compound synthesized in Synthesis Example 5 to obtain a heat-sensitive recording material and a full color image. This colored image was black. The same evaluation test as in Example 1 was performed on this color image. The results are shown in Table 4.
  • the heat-sensitive recording material using the heat-sensitive color forming composition of the present invention is very useful because it is particularly excellent in fastness of the color image.
  • thermosensitive color-forming composition that forms a colored body having a clear and high color density and extremely high fastness, and a heat-sensitive recording material using the composition. Further, it has become possible to provide a transparent thermosensitive recording material having high transparency, high color density, and excellent image storability.

Abstract

[Problem] To provide: a thermosensitive color-developing composition for forming a highly robust yellow to blue color-developing body that is sharp and has a high color density; and a thermosensitive recording material containing the thermosensitive color-developing composition. [Solution] A thermosensitive color-developing composition containing an imino compound represented by a specific structural formula and a pyrrolinone compound represented by general formula (4), and a thermosensitive recording material obtained by including said composition in a recording layer. (In the formula, A represents a substituted or unsubstituted aromatic ring or a substituted or unsubstituted heterocyclic ring; and R5 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group.)

Description

感熱発色性組成物及び該組成物を用いてなる感熱記録材料Thermosensitive color-forming composition and thermosensitive recording material using the composition
　本発明は鮮明な黄色～青色の高濃度及び高堅牢度を有する発色体を形成する感熱発色性組成物に関する。さらには、該組成物を含有してなる感熱記録材料に関する。 The present invention relates to a thermochromic composition that forms a colored body having a clear yellow to blue high density and high fastness. Furthermore, the present invention relates to a heat-sensitive recording material containing the composition.
　従来、紙、プラスチック、布、缶、ビン等の物体に着色する場合、色を呈したインキ、墨、塗料等を塗工し、溶媒が蒸発することによって物体に付着し、着色物を得るといった方法が通常とられてきた。ところが、情報化時代の幕開けと共に、どのような文字、図、模様にも即座に対応できるシステムの要求が生じ、予め発色能力を有する層（以下、記録層という）が全面に塗布されている感熱記録材料が登場した。これは電気信号をサーマルヘッドで熱に変換し、さまざまな文字やパターンをたちどころに顕在化させて記録するものであり、簡便な装置で、容易に鮮明な発色像が得られるため、ファクシミリ用紙、ワープロ用紙、各種分析機器のチャート紙、切符、定期券、プリペイドカード、タッグ等として広く実用化されている。
　通常、感熱記録材料の記録層には、電子供与性色素(フタリド系やフルオラン系のロイコ色素)を発色剤とし、電子受容性フェノール化合物を顕色剤として用いた系が良く知られている(特許文献１)。しかしながらこの系では、可逆反応を利用しているため、発色像の自然褪色や可塑剤、油、水、熱、光等による消色が簡単に起こるという欠点を有している。 Conventionally, when coloring an object such as paper, plastic, cloth, can, bottle, etc., apply colored ink, black ink, paint, etc., and the solvent evaporates to adhere to the object to obtain a colored product. The method has usually been taken. However, with the start of the information era, there has been a demand for a system that can respond immediately to any character, figure, or pattern, and a layer that has a color-developing ability (hereinafter referred to as a recording layer) applied to the entire surface. Recording materials have appeared. This is an electrical signal that is converted into heat by a thermal head, and various characters and patterns are instantly revealed and recorded, and a clear color image can be easily obtained with a simple device. Widely used as word processor paper, chart paper for various analytical instruments, tickets, commuter passes, prepaid cards, tags, and the like.
Usually, a system using an electron-donating dye (phthalide-based or fluoran-based leuco dye) as a color former and an electron-accepting phenol compound as a developer is well known for the recording layer of the heat-sensitive recording material ( Patent Document 1). However, since this system uses a reversible reaction, it has the disadvantage that the color fading image is easily faded and the color disappears easily due to plasticizer, oil, water, heat, light and the like.
　この欠点を克服するため、これまでいろいろ検討がなされている。フタロシアニン前駆体から熱による反応でフタロシアニンを形成する試みもその一つで、例えば、１－アミノ－３－イミノイソインドレニンまたはその誘導体と、有機酸金属塩または金属錯塩化合物を記録層に用いる方法が提案されている（特許文献２）。又、１，３－ジイミノイソインドリン等のイミノ化合物を担持させる感熱記録材料が提案されている（特許文献３）。しかしながら、いずれも、発色感度が低く、実際に感熱記録材料として使用するのは困難であった。
　さらに、芳香族イソシアナートとイミノ化合物との熱溶融反応による不可逆発色体を記録像として用いる感熱記録材料に用いる方法も提案されているが（特許文献４～５）、発色像の保存安定性が低いという欠点があった。
　このような点から、従来の問題を解決し、実用的な発色感度と発色像の保存安定性を同時に満足し、鮮明で高濃度の発色画像を有する感熱記録材料が求められている。
　また近年、医療画像診断用フィルム、オーバーヘッドプロジェクター用の画像形成用フィルム、ＣＡＤ用画像形成用フィルムなどの用途に、透明度が高く、高い発色濃度が得られ、画像保存性に優れる透明感熱記録材料が要求されている。 Various studies have been made to overcome this drawback. One of the attempts to form phthalocyanine by a reaction by heat from a phthalocyanine precursor is a method using, for example, 1-amino-3-iminoisoindolenine or a derivative thereof and an organic acid metal salt or metal complex compound in a recording layer. Has been proposed (Patent Document 2). In addition, a heat-sensitive recording material that supports an imino compound such as 1,3-diiminoisoindoline has been proposed (Patent Document 3). However, all of them have low color development sensitivity, and it was difficult to actually use them as heat-sensitive recording materials.
In addition, a method of using an irreversible coloring material by a thermal melting reaction between an aromatic isocyanate and an imino compound as a recording image has been proposed (Patent Documents 4 to 5). There was a drawback of being low.
In view of the above, there is a need for a heat-sensitive recording material that solves the conventional problems, satisfies practical color development sensitivity and storage stability of a color image at the same time, and has a clear and high density color image.
In recent years, transparent thermosensitive recording materials with high transparency, high color density, and excellent image storability have been developed for applications such as medical diagnostic imaging films, image forming films for overhead projectors, and CAD image forming films. It is requested.
特公昭４５－１４０３９号公報Japanese Examined Patent Publication No. 45-14039 特公昭５８－８３５７号公報Japanese Patent Publication No. 58-8357 特公平４－１６３５３号公報Japanese Examined Patent Publication No. 4-16353 特開昭５９－１１５８８７号公報JP 59-115887 A 特開平２－１０３１８０号公報Japanese Patent Laid-Open No. 2-103180
　本発明の課題は高濃度及び高堅牢度を有する発色体を形成する感熱発色性組成物及び該組成物を用いてなる感熱記録材料を提供することである。 An object of the present invention is to provide a heat-sensitive color-forming composition that forms a colored body having a high concentration and a high fastness, and a heat-sensitive recording material using the composition.
　本発明者等は、前記課題について鋭意検討した結果、特定構造のイミノ化合物と、特定構造のピロリノン化合物とを用いることにより課題が解決できることを見出し、本発明を完成するに至った。すなわち、本発明は、
（ｉ）一般式(１)、（２)または(３)で表されるイミノ化合物と、一般式(４)で表されるピロリノン化合物を含有する感熱発色性組成物、
Figure JPOXMLDOC01-appb-I000005
 
〔式中、環Ｘは置換または無置換の芳香環、置換または無置換の複素環を示し、Ｒ１は水素原子、置換または無置換のアルキル基、置換または無置換のアルケニル基、置換または無置換のアリール基、置換または無置換のアラルキル基を示す。〕
Figure JPOXMLDOC01-appb-I000006
〔式中、Ｒ２は置換または無置換のアルキル基を示し、環ＸおよびＲ１は一般式（１）に示したそれらと同義である。〕
Figure JPOXMLDOC01-appb-I000007
 
〔式中、Ｒ３とＲ４はそれぞれ独立して、置換または無置換のアルキル基を示し、Ｒ３とＲ４は結合して環を形成してもよい。環ＸおよびＲ１は一般式（１）に示したそれらと同義である。〕
Figure JPOXMLDOC01-appb-I000008
〔式中、Ａは置換または無置換の芳香環、置換または無置換の複素環を示し、Ｒ５は置換または無置換のアルキル基、置換または無置換のアルケニル基、置換または無置換のアリール基、置換または無置換のアラルキル基を示す〕 As a result of intensive studies on the above problems, the present inventors have found that the problems can be solved by using an imino compound having a specific structure and a pyrrolinone compound having a specific structure, and have completed the present invention. That is, the present invention
(I) a thermosensitive coloring composition containing an imino compound represented by the general formula (1), (2) or (3) and a pyrrolinone compound represented by the general formula (4);
Figure JPOXMLDOC01-appb-I000005

[Wherein, ring X represents a substituted or unsubstituted aromatic ring or a substituted or unsubstituted heterocyclic ring, and R 1 represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, substituted or unsubstituted A substituted aryl group, a substituted or unsubstituted aralkyl group is shown. ]
Figure JPOXMLDOC01-appb-I000006
[Wherein R 2 represents a substituted or unsubstituted alkyl group, and rings X and R 1 have the same meanings as those shown in formula (1). ]
Figure JPOXMLDOC01-appb-I000007

[Wherein, R 3 and R 4 each independently represent a substituted or unsubstituted alkyl group, and R 3 and R 4 may combine to form a ring. Ring X and R 1 have the same meanings as those shown in formula (1). ]
Figure JPOXMLDOC01-appb-I000008
[In the formula, A represents a substituted or unsubstituted aromatic ring, a substituted or unsubstituted heterocyclic ring, and R 5 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group. Represents a substituted or unsubstituted aralkyl group.
（ii）一般式（１）、（２）および（３）におけるＸが置換または無置換のベンゼン環、置換または無置換のナフタレン環、置換または無置換のアントラセン環、置換または無置換のピリジン環、置換または無置換のピラジン環、置換または無置換のキノリン環、置換または無置換のキノキサリン環、置換または無置換のフェノチアジン環である、（ｉ）の感熱発色性組成物、 (Ii) X in the general formulas (1), (2) and (3) is substituted or unsubstituted benzene ring, substituted or unsubstituted naphthalene ring, substituted or unsubstituted anthracene ring, substituted or unsubstituted pyridine ring A thermochromic composition of (i), which is a substituted or unsubstituted pyrazine ring, a substituted or unsubstituted quinoline ring, a substituted or unsubstituted quinoxaline ring, a substituted or unsubstituted phenothiazine ring,
（iii）一般式（４）におけるＡが置換または無置換のベンゼン環、置換または無置換のナフタレン環、置換または無置換のアントラセン環、置換または無置換のピリジン環、置換または無置換のキノリン環、置換または無置換のピロール環、置換または無置換のインドール環、置換または無置換のチオフェン環、置換または無置換のベンゾチオフェン環、置換または無置換のフラン環、置換または無置換のベンゾフラン環である、(ｉ)または(ii)の感熱発色性組成物、 (Iii) A in formula (4) is substituted or unsubstituted benzene ring, substituted or unsubstituted naphthalene ring, substituted or unsubstituted anthracene ring, substituted or unsubstituted pyridine ring, substituted or unsubstituted quinoline ring , Substituted or unsubstituted pyrrole ring, substituted or unsubstituted indole ring, substituted or unsubstituted thiophene ring, substituted or unsubstituted benzothiophene ring, substituted or unsubstituted furan ring, substituted or unsubstituted benzofuran ring A thermosensitive coloring composition of (i) or (ii),
（iv）一般式（１）、（２）または（３）のイミノ化合物と一般式（４）のピロリノン化合物の組成比（モル比）が１：０.５～１：５である(ｉ)～(iii)の感熱発色性組成物、
（ｖ）上記（ｉ）～（iv）のいずれかの感熱発色性組成物を含有する記録層を支持体上に担持させてなる感熱記録材料、
（vi）支持体が紙、合成紙、フィルム、シート、ラミネ－ト紙または不織布である（ｖ）の感熱記録材料。
（vii）支持体のＨａｚｅ値が１０％以下のプラスチック製フィルムもしくはシートである（ｖ）の感熱記録材料
に関するものである。
  (Iv) The composition ratio (molar ratio) of the imino compound of the general formula (1), (2) or (3) and the pyrrolinone compound of the general formula (4) is 1: 0.5 to 1: 5 (i) A thermosensitive coloring composition of (iii),
(V) a heat-sensitive recording material obtained by supporting a recording layer containing any one of the heat-sensitive color forming compositions (i) to (iv) on a support;
(Vi) The heat-sensitive recording material according to (v), wherein the support is paper, synthetic paper, film, sheet, laminated paper or non-woven fabric.
(Vii) The present invention relates to the heat-sensitive recording material (v), which is a plastic film or sheet having a Haze value of 10% or less.
　本発明により、鮮明で高濃度の発色と発色像の保存安定性を同時に満足する感熱記録材料、および透明度の高い透明感熱記録材料を提供することが可能となった。
  According to the present invention, it has become possible to provide a heat-sensitive recording material that simultaneously satisfies vivid and high-density color development and storage stability of a color image, and a transparent heat-sensitive recording material having high transparency.
　以下、本発明に関し詳細に説明する。
　本発明は、一般式（１）、（２）または（３）で表されるイミノ化合物（以下、発色体形成成分Ｉの意で「成分Ｉ」と略す）と、一般式（４）で表されるピロリノン化合物（以下、発色体形成成分Ｐの意で「成分Ｐ」と略す）とを含む組成物が、熱エネルギーを加えることにより高濃度に発色することを基にするものである。 Hereinafter, the present invention will be described in detail.
The present invention relates to an imino compound represented by the general formula (1), (2) or (3) (hereinafter abbreviated as “component I” in the meaning of the color former-forming component I) and the general formula (4). The composition containing the pyrrolinone compound (hereinafter, abbreviated as “component P” in the meaning of the color former-forming component P) develops color based on the application of heat energy.
＜成分Ｉ＞
　本発明で使用される成分Ｉは、一般式（１）、（２）または（３）で表されるイミノ化合物である。
Figure JPOXMLDOC01-appb-I000009
〔式中、環Ｘは置換または無置換の芳香環、置換または無置換の複素環を示し、Ｒ１は水素原子、置換または無置換のアルキル基、置換または無置換のアルケニル基、置換または無置換のアリール基、置換または無置換のアラルキル基を示す。〕
Figure JPOXMLDOC01-appb-I000010
 
〔式中、Ｒ２は置換または無置換のアルキル基を示し、環ＸおよびＲ１は一般式（１）に示したそれらと同義である。〕
Figure JPOXMLDOC01-appb-I000011
〔式中、Ｒ３とＲ４はそれぞれ独立して、置換または無置換のアルキル基を示し、Ｒ３とＲ４は結合して環を形成してもよい。環ＸおよびＲ１は一般式（１）に示したそれらと同義である。〕 <Component I>
Component I used in the present invention is an imino compound represented by the general formula (1), (2) or (3).
Figure JPOXMLDOC01-appb-I000009
[Wherein, ring X represents a substituted or unsubstituted aromatic ring or a substituted or unsubstituted heterocyclic ring, and R 1 represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, substituted or unsubstituted A substituted aryl group, a substituted or unsubstituted aralkyl group is shown. ]
Figure JPOXMLDOC01-appb-I000010

[Wherein R 2 represents a substituted or unsubstituted alkyl group, and rings X and R 1 have the same meanings as those shown in formula (1). ]
Figure JPOXMLDOC01-appb-I000011
[Wherein, R 3 and R 4 each independently represent a substituted or unsubstituted alkyl group, and R 3 and R 4 may combine to form a ring. Ring X and R 1 have the same meanings as those shown in formula (1). ]
　一般式（１）、（２）、（３）においてＸは好ましくは、置換または無置換のベンゼン環、置換または無置換のナフタレン環、置換または無置換のアントラセン環、置換または無置換のピリジン環、置換または無置換のピラジン環、置換または無置換のキノリン環、置換または無置換のキノキサリン環、置換または無置換のフェノチアジン環である。Ｘはより好ましくは置換または無置換のベンゼン環、置換または無置換のナフタレン環、置換または無置換のアントラセン環である。 In general formulas (1), (2) and (3), X is preferably a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted anthracene ring, a substituted or unsubstituted pyridine ring. Substituted or unsubstituted pyrazine ring, substituted or unsubstituted quinoline ring, substituted or unsubstituted quinoxaline ring, substituted or unsubstituted phenothiazine ring. X is more preferably a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, or a substituted or unsubstituted anthracene ring.
　Ｘが置換基を有する場合の置換基としては、ハロゲン原子、水酸基、ニトロ基、置換または無置換のアルキル基、置換または無置換のアルケニル基、置換または無置換のアルキニル基、置換または無置換のアリール基、置換または無置換のアラルキル基、置換または無置換のアルコキシ基、置換または無置換のアリールオキシ基、置換または無置換のアルキルチオ基、置換または無置換のアリールチオ基、置換または無置換のアルキルカルボニル基、置換または無置換のアリールカルボニル基、置換または無置換のアミノ基等が好ましい。
　より好ましくは、ハロゲン原子、水酸基、ニトロ基、炭素数１～２０の置換または無置換のアルキル基、炭素数６～２４の置換または無置換のアリール基、炭素数１～２０の置換または無置換のアルコキシ基、炭素数６～２４の置換または無置換のアリールオキシ基、炭素数１～２０の置換または無置換のアルキルチオ基、炭素数６～２４の置換または無置換のアリールチオ基、アミノ基、総炭素数１～２０の置換アミノ基である。
　さらに好ましくは、ハロゲン原子、炭素数１～１２の置換または無置換のアルキル基、炭素数１～１２の置換または無置換のアルコキシ基、総炭素数２～１６の置換アミノ基である。 When X has a substituent, examples of the substituent include a halogen atom, a hydroxyl group, a nitro group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted group Aryl group, substituted or unsubstituted aralkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted alkyl A carbonyl group, a substituted or unsubstituted arylcarbonyl group, a substituted or unsubstituted amino group, and the like are preferable.
More preferably, a halogen atom, a hydroxyl group, a nitro group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 24 carbon atoms, a substituted or unsubstituted group having 1 to 20 carbon atoms. An alkoxy group, a substituted or unsubstituted aryloxy group having 6 to 24 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 20 carbon atoms, a substituted or unsubstituted arylthio group having 6 to 24 carbon atoms, an amino group, A substituted amino group having 1 to 20 carbon atoms in total.
More preferred are a halogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, and a substituted amino group having 2 to 16 carbon atoms in total.
　これらＸが置換基を有する場合の置換基の具体例を下記に示す。
　ハロゲン原子としては、塩素原子、臭素原子、弗素原子、ヨウ素原子が挙げられる。
　置換または無置換のアルキル基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、sec－ブチル基、tert－ブチル基、ｎ－ペンチル基、イソペンチル基、ネオペンチル基、tert－ペンチル基、ｎ－ヘキシル基、１－メチルペンチル基、４－メチル－２－ペンチル基、２－エチルブチル基、ｎ－ヘプチル基、シクロヘキシル基、１－メチルヘキシル基、ｎ－オクチル基、１－メチルヘプチル基、２－エチルヘキシル基などの直鎖、分岐または環状の無置換のアルキル基；
メトキシメチル基、エトキシメチ基、ｎ－ブトキシメチル基、ｎ－ヘキシルオキシメチル基、（２－エチルブチルオキシ）メチル基、２－（４'－ペンテニルオキシ）エチル基などのアルキルオキシ基またはアルケニルオキシ基で置換されたアルキル基；
ベンジルオキシメチル基、２－（ベンジルオキシメトキシ）エチル基などのアラルキルオキシ基で置換されたアルキル基；
フェニルオキシメチル基、４－クロロフェニルオキシメチル基、４－（２'－フェニルオキシエトキシ）ブチル基などのアリ－ルオキシ基で置換されたアルキル基が挙げられる。 Specific examples of the substituent when X has a substituent are shown below.
Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom.
Examples of the substituted or unsubstituted alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an isopentyl group. Group, neopentyl group, tert-pentyl group, n-hexyl group, 1-methylpentyl group, 4-methyl-2-pentyl group, 2-ethylbutyl group, n-heptyl group, cyclohexyl group, 1-methylhexyl group, n -Linear, branched or cyclic unsubstituted alkyl group such as octyl group, 1-methylheptyl group, 2-ethylhexyl group;
Alkyloxy or alkenyloxy groups such as methoxymethyl, ethoxymethyl, n-butoxymethyl, n-hexyloxymethyl, (2-ethylbutyloxy) methyl, 2- (4'-pentenyloxy) ethyl An alkyl group substituted with
An alkyl group substituted with an aralkyloxy group such as a benzyloxymethyl group or 2- (benzyloxymethoxy) ethyl group;
Examples thereof include an alkyl group substituted with an aryloxy group such as a phenyloxymethyl group, a 4-chlorophenyloxymethyl group, and a 4- (2′-phenyloxyethoxy) butyl group.
　置換または無置換のアルケニル基としては、例えば、ビニル基、プロペニル基、１－ブテニル基、イソブテニル基、１－ペンテニル基、２－ペンテニル基、２－メチル－１－ブテニル基、２－シクロペンテニル基、１－ビニルヘキシル基、スチリル基、スチリルメチル基、２－スチリルエチル基などが挙げられる。
　置換または無置換のアルキニル基としては、例えば、アセチレニル基、プロピニル基、１－ブチニル基、１－ペンチニル基、２－ペンチニル基、２－メチル－１－ペンチニル基、フェニルアセチレニル基などが挙げられる。 Examples of the substituted or unsubstituted alkenyl group include a vinyl group, a propenyl group, a 1-butenyl group, an isobutenyl group, a 1-pentenyl group, a 2-pentenyl group, a 2-methyl-1-butenyl group, and a 2-cyclopentenyl group. 1-vinylhexyl group, styryl group, styrylmethyl group, 2-styrylethyl group, and the like.
Examples of the substituted or unsubstituted alkynyl group include acetylenyl group, propynyl group, 1-butynyl group, 1-pentynyl group, 2-pentynyl group, 2-methyl-1-pentynyl group, and phenylacetylenyl group. It is done.
　置換または無置換のアリール基としては、例えば、フェニル基、１－ナフチル基、２－ナフチル基、２－アントラセニル基、１－フェナントリル基、２－フェナントリル基、３－フェナントリル基、１－ピレニル基、２－ピレニル基、２－ペリレニル基、３－ペリレニル基、２－フルオランテニル基、３－フルオランテニル基、７－フルオランテニル基、８－フルオランテニル基などの無置換のアリール基；
１－メチル－２－ピレニル基、２－メチルフェニル基、４－エチルフェニル基、４－（４'－tert－ブチルシクロヘキシル）フェニル基、３－シクロヘキシルフェニル基、２－シクロヘキシルフェニル基、４－エチル－１－ナフチル基、６－ｎ－ブチル－２－ナフチル基、２，４－ジメチルフェニル基などのアルキル基で置換されたアリール基；
４－メトキシフェニル基、３－エトキシフェニル基、２－エトキシフェニル基、４－ｎ－プロポキシフェニル基、３－ｎ－プロポキシフェニル基、４－イソプロポキシフェニル基、３－イソプロポキシフェニル基、２－イソプロポキシフェニル基、２－ｓｅｃ－ブトキシフェニル基、４－ｎ－ペンチルオキシフェニル基、４－イソペンチルオキシフェニル基、２－メチル－５－メトキシフェニル基、２－フェニルオキシフェニル基などのアルコキシ基またはアリ－ルオキシ基で置換されたアリール基；
４－フェニルフェニル基、３－フェニルフェニル基、２－フェニルフェニル基、２，６－ジフェニルフェニル基、４－（２'－ナフチル）フェニル基、２－フェニル－１－ナフチル基、１－フェニル－２－ナフチル基、７－フェニル－１－ピレニル基などのアリ－ル基で置換されたアリール基；
４－フルオロフェニル基、３－フルオロフェニル基、２－フルオロフェニル基、４－クロロフェニル基、４－ブロモフェニル基、２－クロロ－５－メチルフェニル基、２－クロロ－６－メチルフェニル基、２－メチル－３－クロロフェニル基、２－メトキシ－４－フルオロフェニル基、２－フルオロ－４－メトキシフェニル基などのハロゲン原子で置換されたアリール基。
さらには、例えば、２－トリフルオロメチルフェニル基、３－トリフルオロメチルフェニル基、４－トリフルオロメチルフェニル基、３，５－ビストリフルオロメチルフェニル基、４－パ－フルオロエチルフェニル基、４－メチルチオフェニル基、４－エチルチオフェニル基、４－シアノフェニル基、３－シアノフェニル基などが挙げられる。 Examples of the substituted or unsubstituted aryl group include a phenyl group, 1-naphthyl group, 2-naphthyl group, 2-anthracenyl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 1-pyrenyl group, Unsubstituted aryl groups such as 2-pyrenyl group, 2-perylenyl group, 3-perylenyl group, 2-fluoranthenyl group, 3-fluoranthenyl group, 7-fluoranthenyl group, 8-fluoranthenyl group;
1-methyl-2-pyrenyl group, 2-methylphenyl group, 4-ethylphenyl group, 4- (4'-tert-butylcyclohexyl) phenyl group, 3-cyclohexylphenyl group, 2-cyclohexylphenyl group, 4-ethyl An aryl group substituted with an alkyl group such as a 1-naphthyl group, a 6-n-butyl-2-naphthyl group, or a 2,4-dimethylphenyl group;
4-methoxyphenyl group, 3-ethoxyphenyl group, 2-ethoxyphenyl group, 4-n-propoxyphenyl group, 3-n-propoxyphenyl group, 4-isopropoxyphenyl group, 3-isopropoxyphenyl group, 2- Alkoxy groups such as isopropoxyphenyl group, 2-sec-butoxyphenyl group, 4-n-pentyloxyphenyl group, 4-isopentyloxyphenyl group, 2-methyl-5-methoxyphenyl group, 2-phenyloxyphenyl group Or an aryl group substituted with an aryloxy group;
4-phenylphenyl group, 3-phenylphenyl group, 2-phenylphenyl group, 2,6-diphenylphenyl group, 4- (2′-naphthyl) phenyl group, 2-phenyl-1-naphthyl group, 1-phenyl- An aryl group substituted with an aryl group such as a 2-naphthyl group and a 7-phenyl-1-pyrenyl group;
4-fluorophenyl group, 3-fluorophenyl group, 2-fluorophenyl group, 4-chlorophenyl group, 4-bromophenyl group, 2-chloro-5-methylphenyl group, 2-chloro-6-methylphenyl group, 2 An aryl group substituted with a halogen atom such as a methyl-3-chlorophenyl group, a 2-methoxy-4-fluorophenyl group, or a 2-fluoro-4-methoxyphenyl group;
Furthermore, for example, 2-trifluoromethylphenyl group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 3,5-bistrifluoromethylphenyl group, 4-perfluoroethylphenyl group, 4- Examples thereof include a methylthiophenyl group, a 4-ethylthiophenyl group, a 4-cyanophenyl group, and a 3-cyanophenyl group.
　置換または無置換のアラルキル基としては、例えば、ベンジル基、α－メチルベンジル基、フェネチル基、α－メチルフェネチル基、α,α－ジメチルベンジル基、α,α－ジメチルフェネチル基、４－メチルフェネチル基、４－メチルベンジル基、４－イソプロピルベンジル基などの無置換またはアルキル基で置換されたアラルキル基；
４－ベンジルベンジル基、４－フェネチルベンジル基、４－フェニルベンジル基などのアリ－ル基またはアラルキル基で置換されたアラルキル基；
４－メトキシベンジル基、４－ｎ－テトラデシルオキシベンジル基、４－ｎ－ヘプタデシルオキシベンジル基、３,４－ジメトキシベンジル基、４－メトキシメチルベンジル基、４－ビニルオキシメチルベンジル基、４－ベンジルオキシベンジル基、４－フェネチルオキシベンジル基などの置換オキシ基で置換されたアラルキル基；
４－ヒドロキシベンジル基、４－ヒドロキシ－３－メトキシベンジル基などの水酸基で置換されたアラルキル基；
４－フルオロベンジル基、３－クロロベンジル基、３，４－ジクロロベンジル基などのハロゲン原子で置換されたアラルキル基。
さらには、例えば、２－フルフリル基、ジフェニルメチル基、１－ナフチルメチル基、２－ナフチルメチル基などが挙げられる。 Examples of the substituted or unsubstituted aralkyl group include benzyl group, α-methylbenzyl group, phenethyl group, α-methylphenethyl group, α, α-dimethylbenzyl group, α, α-dimethylphenethyl group, 4-methylphenethyl group. An aralkyl group unsubstituted or substituted with an alkyl group, such as a group, 4-methylbenzyl group, 4-isopropylbenzyl group;
An aralkyl group substituted with an aryl group or an aralkyl group such as a 4-benzylbenzyl group, a 4-phenethylbenzyl group, a 4-phenylbenzyl group;
4-methoxybenzyl group, 4-n-tetradecyloxybenzyl group, 4-n-heptadecyloxybenzyl group, 3,4-dimethoxybenzyl group, 4-methoxymethylbenzyl group, 4-vinyloxymethylbenzyl group, 4 An aralkyl group substituted with a substituted oxy group such as a benzyloxybenzyl group or 4-phenethyloxybenzyl group;
An aralkyl group substituted with a hydroxyl group such as a 4-hydroxybenzyl group and a 4-hydroxy-3-methoxybenzyl group;
An aralkyl group substituted with a halogen atom such as a 4-fluorobenzyl group, a 3-chlorobenzyl group, or a 3,4-dichlorobenzyl group;
Further examples include 2-furfuryl group, diphenylmethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group and the like.
　置換または無置換のアルコキシ基としては、例えば、メトキシ基、エトキシ基、ｎ－プロピルオキシ基、イソプロピルオキシ基、ｎ－ブチルオキシ基、イソブチルオキシ基、ｔｅｒｔ－ブチルオキシ基、ｓｅｃ－ブチルオキシ基、ｎ－ペンチルオキシ基、イソペンチルオキシ基、ｎ－ヘキシルオキシ基、２－メチルペンチルオキシ基、１，１－ジメチルブチルオキシ基、１，２，２－トリメチルプロピルオキシ基、２－エチルブチルオキシ基、１，３－ジメチルヘキシルオキシ基、シクロヘキシルオキシ基、メチルシクロペンチルオキシ基、ｎ－へプチルオキシ基、ｎ－へプチルオキシ基、ｎ－オクチルオキシ基、３，５，５－トリメチルヘキシルオキシ基、ｎ－デシルオキシ基、ｎ－ウンデシルオキシ基、ｎ－ドデシルオキシ基、１－アダマンチルオキシ基、ｎ－ペンタデシルオキシ基などの直鎖、分岐又は環状の無置換のアルコキシ基； Examples of the substituted or unsubstituted alkoxy group include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, tert-butyloxy group, sec-butyloxy group, and n-pentyl. Oxy group, isopentyloxy group, n-hexyloxy group, 2-methylpentyloxy group, 1,1-dimethylbutyloxy group, 1,2,2-trimethylpropyloxy group, 2-ethylbutyloxy group, 1, 3-dimethylhexyloxy group, cyclohexyloxy group, methylcyclopentyloxy group, n-heptyloxy group, n-heptyloxy group, n-octyloxy group, 3,5,5-trimethylhexyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, 1-a Manchiruokishi group, a straight-chain, such as n- pentadecyl group, branched or cyclic unsubstituted alkoxy group;
メトキシメトキシ基、エトキシメトキシ基、ｎ－プロピルオキシメトキシ基、ｎ－ブチルオキシメトキシ基、イソブチルオキシメトキシ基、ｔｅｒｔ－ブチルオキシメトキシ基、ｎ－ペンチルオキシメトキシ基、２－メトキシエトキシ基、２－エトキシエトキシ基、２－ｎ－プロピルオキシエトキシ基、２－イソプロピルオキシエトキシ基、２－ｎーブチルオキシエトキシ基、２－イソブチルオキシエトキシ基、２－ｎ－ペンチルオキシエトキシ基、２－イソペンチルオキシエトキシ基、２－シクロペンチルオキシエトキシ基、２－ｎ－ヘキシルオキシエトキシ基、２－（４－エチルシクロヘキシルオキシ）エトキシ基、２－ｎ－ノニルオキシエトキシ基、２－（３，５，５－トリメチルヘキシルオキシ）エトキシ基、２－ｎ－デシルオキシエトキシ基、２－ｎ－ドデシルオキシエトキシ基、３－メトキシプロピルオキシ基、３－エトキシプロピルオキシ基、３－（ｎ－プロピルオキシ）プロピルオキシ基、２－イソペンチルオキシプロピルオキシ基、２－メトキシブチルオキシ基、４－エトキシブチルオキシ基、４－（ｎ－プロピルオキシ）ブチルオキシ基、４－イソプロピルオキシブチルオキシ基、５－メトキシペンチルオキシ基、５－エトキシメトキシ基などのアルコキシ基で置換されたアルコキシ基；
メトキシメトキシメトキシ基、エトキシメトキシメトキシ基、プロピルオキシメトキシメトキシ基、ブチルオキシメトキシメトキシ基、メトキシエトキシメトキシ基、エトキシエトキシメトキシ基、プロピルオキシエトキシメトキシ基、メトキシメトキシエトキシ基、エトキシメトキシエトキシ基、プロピルオキシメトキシエトキシ基、ブチルオキシメトキシエトキシ基、プロピルオキシエトキシエトキシ基、ブチルオキシエトキシエトキシ基、プロピルオキシブチルオキシエトキシ基、メトキシメトキシプロピルオキシ基、エトキシメトキシプロピルオキシ基、ブチルオキシメトキシプロピルオキシ基、メトキシメトキシブチルオキシ基、エトキシメトキシブチルオキシ基、ブチルオキシメトキシブチルオキシ基、エトキシエトキシブチルオキシ基、（４－エチルシクロへキシルオキシ）エトキシエトキシ基、〔４－（３，５，５－トリメチルヘキシルオキシ）ブチルオキシ〕エトキシ基などのアルコキシアルコキシ基で置換されたアルコキシ基； Methoxymethoxy group, ethoxymethoxy group, n-propyloxymethoxy group, n-butyloxymethoxy group, isobutyloxymethoxy group, tert-butyloxymethoxy group, n-pentyloxymethoxy group, 2-methoxyethoxy group, 2-ethoxy Ethoxy group, 2-n-propyloxyethoxy group, 2-isopropyloxyethoxy group, 2-n-butyloxyethoxy group, 2-isobutyloxyethoxy group, 2-n-pentyloxyethoxy group, 2-isopentyloxyethoxy Group, 2-cyclopentyloxyethoxy group, 2-n-hexyloxyethoxy group, 2- (4-ethylcyclohexyloxy) ethoxy group, 2-n-nonyloxyethoxy group, 2- (3,5,5-trimethylhexyl) Oxy) ethoxy group, 2-n-decyloxy Toxi group, 2-n-dodecyloxyethoxy group, 3-methoxypropyloxy group, 3-ethoxypropyloxy group, 3- (n-propyloxy) propyloxy group, 2-isopentyloxypropyloxy group, 2-methoxy Substituted with alkoxy groups such as butyloxy group, 4-ethoxybutyloxy group, 4- (n-propyloxy) butyloxy group, 4-isopropyloxybutyloxy group, 5-methoxypentyloxy group, 5-ethoxymethoxy group An alkoxy group;
Methoxymethoxymethoxy group, ethoxymethoxymethoxy group, propyloxymethoxymethoxy group, butyloxymethoxymethoxy group, methoxyethoxymethoxy group, ethoxyethoxymethoxy group, propyloxyethoxymethoxy group, methoxymethoxyethoxy group, ethoxymethoxyethoxy group, propyloxy Methoxyethoxy group, butyloxymethoxyethoxy group, propyloxyethoxyethoxy group, butyloxyethoxyethoxy group, propyloxybutyloxyethoxy group, methoxymethoxypropyloxy group, ethoxymethoxypropyloxy group, butyloxymethoxypropyloxy group, methoxymethoxy Butyloxy group, ethoxymethoxybutyloxy group, butyloxymethoxybutyloxy group, ethoxyethoxybutyl Alkoxy group, (4 Echirushikuro hexyloxy) ethoxyethoxy group, [4- (3,5,5-trimethyl hexyloxy) butyloxy] alkoxy group substituted with an alkoxyalkoxy group such as ethoxy group;
メトキシカルボニルメトキシ基、エトキシカルボニルメトキシ基、ｎ－プロピルオキシカルボニルメトキシ基、イソプロピルオキシカルボニルメトキシ基、（４'－エチルシクロヘキシルオキシ）カルボニルメトキシ基などのアルコキシカルボニル基で置換されたアルコキシ基；
メトキシカルボニルエトキシ基、エトキシカルボニルエトキシ基、ｎ－プロピルオキシカルボニルエトキシ基、エトキシカルボニルプロピルオキシ基などのアルコキシカルボニル基で置換されたアルコキシ基； An alkoxy group substituted with an alkoxycarbonyl group such as a methoxycarbonylmethoxy group, an ethoxycarbonylmethoxy group, an n-propyloxycarbonylmethoxy group, an isopropyloxycarbonylmethoxy group, or a (4′-ethylcyclohexyloxy) carbonylmethoxy group;
An alkoxy group substituted with an alkoxycarbonyl group such as a methoxycarbonylethoxy group, an ethoxycarbonylethoxy group, an n-propyloxycarbonylethoxy group, or an ethoxycarbonylpropyloxy group;
メチルアミノメトキシ基、２－メチルアミノエトキシ基、２－( ２－メチルアミノエトキシ) エトキシ基、４－メチルアミノブチルオキシ基、１－メチルアミノプロパン－２－イルオキシ基、３－メチルアミノプロピルオキシ基、２－メチルアミノ－２－メチルプロピルオキシ基、２－エチルアミノエトキシ基、２－( ２－エチルアミノエトキシ)エトキシ基、３－エチルアミノプロピルオキシ基、１－エチルアミノプロピルオキシ基、２－イソプロピルアミノエトキシ基、２－（ｎ－ブチルアミノ）エトキシ基、３－（ｎ－ヘキシルアミノ）プロピルオキシ基、４－（シクロヘキシルアミノ）ブチルオキシ基などのアルキルアミノ基で置換されたアルコキシ基；
ジメチルアミノメトキシ基、２－ジメチルアミノエトキシ基、２－( ２－ジメチルアミノエトキシ) エトキシ基、４－ジメチルアミノブチルオキシ基、１－ジメチルアミノプロパン－２－イルオキシ基、３－ジメチルアミノプロピルオキシ基、２－ジメチルアミノ－２－メチルプロピルオキシ基、２－ジエチルアミノエトキシ基、２－(２－ジエチルアミノエトキシ)エトキシ基、３－ジエチルアミノプロピルオキシ基、１－ジエチルアミノプロピルオキシ基、２－ジイソプロピルアミノエトキシ基、２－（ジ－ｎ－ブチルアミノ）エトキシ基、２－ピペリジルエトキシ基、３－（ジ－ｎ－ヘキシルアミノ）プロピルオキシ基などのジアルキルアミノ基で置換されたアルコキシ基；
メチルアミノメトキシメトキシ基、メチルアミノエトキシエトキシ基、メチルアミノエトキシプロピルオキシ基、エチルアミノエトキシプロピルオキシ基、４－（２'－イソブチルアミノプロピルオキシ）ブチルオキシ基などのアルキルアミノアルコキシ基で置換されたアルコキシ基；
ジメチルアミノメトキシメトキシ基、ジメチルアミノエトキシエトキシ基、ジメチルアミノエトキシプロピルオキシ基、ジエチルアミノエトキシプロピルオキシ基、４－（２'－ジイソブチルアミノプロピルオキシ）ブチルオキシ基などのジアルキルアミノアルコキシ基で置換されたアルコキシ基；
メチルチオメトキシ基、２－メチルチオエトキシ基、２－エチルチオエトキシ基、２－ｎ－プロピルチオエトキシ基、２－イソプロピルチオエトキシ基、２－ｎ－ブチルチオエトキシ基、２－イソブチルチオエトキシ基、（３，５，５－トリメチルヘキシルチオ）ヘキシルオキシ基などのアルキルチオ基で置換されたアルコキシ基などが挙げられる。 Methylaminomethoxy group, 2-methylaminoethoxy group, 2- (2-methylaminoethoxy) ethoxy group, 4-methylaminobutyloxy group, 1-methylaminopropan-2-yloxy group, 3-methylaminopropyloxy group 2-methylamino-2-methylpropyloxy group, 2-ethylaminoethoxy group, 2- (2-ethylaminoethoxy) ethoxy group, 3-ethylaminopropyloxy group, 1-ethylaminopropyloxy group, 2- An alkoxy group substituted with an alkylamino group such as an isopropylaminoethoxy group, 2- (n-butylamino) ethoxy group, 3- (n-hexylamino) propyloxy group, 4- (cyclohexylamino) butyloxy group;
Dimethylaminomethoxy group, 2-dimethylaminoethoxy group, 2- (2-dimethylaminoethoxy) ethoxy group, 4-dimethylaminobutyloxy group, 1-dimethylaminopropan-2-yloxy group, 3-dimethylaminopropyloxy group 2-dimethylamino-2-methylpropyloxy group, 2-diethylaminoethoxy group, 2- (2-diethylaminoethoxy) ethoxy group, 3-diethylaminopropyloxy group, 1-diethylaminopropyloxy group, 2-diisopropylaminoethoxy group An alkoxy group substituted with a dialkylamino group such as 2- (di-n-butylamino) ethoxy group, 2-piperidylethoxy group, 3- (di-n-hexylamino) propyloxy group;
Alkoxy substituted with alkylaminoalkoxy groups such as methylaminomethoxymethoxy group, methylaminoethoxyethoxy group, methylaminoethoxypropyloxy group, ethylaminoethoxypropyloxy group, 4- (2'-isobutylaminopropyloxy) butyloxy group Group;
Alkoxy groups substituted with dialkylaminoalkoxy groups such as dimethylaminomethoxymethoxy group, dimethylaminoethoxyethoxy group, dimethylaminoethoxypropyloxy group, diethylaminoethoxypropyloxy group, 4- (2'-diisobutylaminopropyloxy) butyloxy group ;
Methylthiomethoxy group, 2-methylthioethoxy group, 2-ethylthioethoxy group, 2-n-propylthioethoxy group, 2-isopropylthioethoxy group, 2-n-butylthioethoxy group, 2-isobutylthioethoxy group, ( And an alkoxy group substituted with an alkylthio group such as a 3,5,5-trimethylhexylthio) hexyloxy group.
　置換または無置換のアリールオキシ基としては、ヘテロアリールオキシ基も含まれ、例えば、フェニルオキシ基、２－メチルフェニルオキシ基、４－メチルフェニルオキシ基、４－エチルフェニルオキシ基、４－イソプロピルフェニルオキシ基、４－イソブチルフェニルオキシ基、４－ｎ－ペンチルフェニルオキシ基、４－ｔｅｒｔ－ペンチルフェニルオキシ基、４－シクロヘキシルフェニルオキシ基、４－ｎ－オクチルフェニルオキシ基、４－ｎ－デシルフェニルオキシ基、４－ｎ－ドデシルフェニルオキシ基、４－ｎ－ヘキサデシルフェニルオキシ基、２，３－ジメチルフェニルオキシ基、２，５－ジメチルフェニルオキシ基、３，４－ジメチルフェニルオキシ基、３，４，５－トリメチルフェニルオキシ基、５－インダニルオキシ基、１，２，３，４－テトラヒドロ－６－ナフチルオキシ基、３－メトキシフェニルオキシ基、３－エトキシフェニルオキシ基、４－ｎ－プロポキシフェニルオキシ基、４－ｎ－ブトキシフェニルオキシ基、４－ｎ－ペンチルオキシフェニルオキシ基、４－シクロヘキシルオキシフェニルオキシ基、４－ｎ－オクチルオキシフェニルオキシ基、４－ｎ－デシルオキシフェニルオキシ基、４－ｎ－ドデシルオキシフェニルオキシ基、４－ｎ－ヘキサデシルオキシフェニルオキシ基、２，３－ジメトキシフェニルオキシ基、２，５－ジメトキシフェニルオキシ基、３，５－ジメトキシフェニルオキシ基、２－メトキシ－４－メチルフェニルオキシ基、３－メトキシ－４－メチルフェニルオキシ基、３－メチル－４－メトキシフェニルオキシ基、２－フルオロフェニルオキシ基、４－フルオロフェニルオキシ基、３－クロロフェニルオキシ基、４－ブロモフェニルオキシ基、３－トリフルオロメチルフェニルオキシ基、３，５－ジフルオロフェニルオキシ基、３，４－ジクロロフェニルオキシ基、２－メチル－４－クロロフェニルオキシ基、３－クロロ－４－メチルフェニルオキシ基、３－メトキシ－４－フルオロフェニルオキシ基、３－フルオロ－４－メトキシフェニルオキシ基、４－フェニルフェニルオキシ基、３－フェニルフェニルオキシ基、４－(４’－メチルフェニル)フェニルオキシ基、４－(４’－メトキシフェニル)フェニルオキシ基、１－ナフチルオキシ基、４－メチル－１－ナフチルオキシ基、６－ｎ－ブチル－２－ナフチルオキシ基、７－エトキシ－２－ナフチルオキシ基、２－チエニルオキシ基、２－ピリジルオキシ基、４－ピリジルオキシ基などが挙げられる。 Substituted or unsubstituted aryloxy groups include heteroaryloxy groups such as phenyloxy group, 2-methylphenyloxy group, 4-methylphenyloxy group, 4-ethylphenyloxy group, 4-isopropylphenyl group. Oxy group, 4-isobutylphenyloxy group, 4-n-pentylphenyloxy group, 4-tert-pentylphenyloxy group, 4-cyclohexylphenyloxy group, 4-n-octylphenyloxy group, 4-n-decylphenyl Oxy group, 4-n-dodecylphenyloxy group, 4-n-hexadecylphenyloxy group, 2,3-dimethylphenyloxy group, 2,5-dimethylphenyloxy group, 3,4-dimethylphenyloxy group, 3 , 4,5-Trimethylphenyloxy group, 5-indanyloxy group 1,2,3,4-tetrahydro-6-naphthyloxy group, 3-methoxyphenyloxy group, 3-ethoxyphenyloxy group, 4-n-propoxyphenyloxy group, 4-n-butoxyphenyloxy group, 4- n-pentyloxyphenyloxy group, 4-cyclohexyloxyphenyloxy group, 4-n-octyloxyphenyloxy group, 4-n-decyloxyphenyloxy group, 4-n-dodecyloxyphenyloxy group, 4-n- Hexadecyloxyphenyloxy group, 2,3-dimethoxyphenyloxy group, 2,5-dimethoxyphenyloxy group, 3,5-dimethoxyphenyloxy group, 2-methoxy-4-methylphenyloxy group, 3-methoxy-4 -Methylphenyloxy group, 3-methyl-4-methoxyphenyloxy group, 2- Fluorophenyloxy group, 4-fluorophenyloxy group, 3-chlorophenyloxy group, 4-bromophenyloxy group, 3-trifluoromethylphenyloxy group, 3,5-difluorophenyloxy group, 3,4-dichlorophenyloxy group Group, 2-methyl-4-chlorophenyloxy group, 3-chloro-4-methylphenyloxy group, 3-methoxy-4-fluorophenyloxy group, 3-fluoro-4-methoxyphenyloxy group, 4-phenylphenyloxy Group, 3-phenylphenyloxy group, 4- (4'-methylphenyl) phenyloxy group, 4- (4'-methoxyphenyl) phenyloxy group, 1-naphthyloxy group, 4-methyl-1-naphthyloxy group 6-n-butyl-2-naphthyloxy group, 7-ethoxy-2-naphthyloxy group 2-thienyloxy group, 2-pyridyloxy group, 4-pyridyloxy group.
　置換または無置換のアルキルチオ基としては、例えば、メチルチオ基、エチルチオ基、ｎ－プロピルチオ基、イソプロピルチオ基、ｎ－ブチルチオ基、イソブチルチオ基、ｔｅｒｔ－ブチルチオ基、ｓｅｃ－ブチルチオ基、ｎ－ペンチルチオ基、イソペンチルチオ基、ｎ－ヘキシルチオ基、２－メチルペンチルチオ基、１，１－ジメチルブチルチオ基、１，２，２－トリメチルプロピルチオ基、２－エチルブチルチオ基、１，３－ジメチルヘキシルチオ基、シクロヘキシルチオ基、メチルシクロペンチルチオ基、ｎ－へプチルチオ基、ｎ－へプチルチオ基、ｎ－オクチルチオ基、３，５，５－トリメチルヘキシルチオ基、ｎ－デシルチオ基、ｎ－ウンデシルチオ基、ｎ－ドデシルチオ基、１－アダマンチルチオ基、ｎ－ペンタデシルチオ基などの直鎖、分岐又は環状の無置換のアルキルチオ基； Examples of the substituted or unsubstituted alkylthio group include a methylthio group, an ethylthio group, an n-propylthio group, an isopropylthio group, an n-butylthio group, an isobutylthio group, a tert-butylthio group, a sec-butylthio group, and an n-pentylthio group. , Isopentylthio group, n-hexylthio group, 2-methylpentylthio group, 1,1-dimethylbutylthio group, 1,2,2-trimethylpropylthio group, 2-ethylbutylthio group, 1,3-dimethyl Hexylthio group, cyclohexylthio group, methylcyclopentylthio group, n-heptylthio group, n-heptylthio group, n-octylthio group, 3,5,5-trimethylhexylthio group, n-decylthio group, n-undecylthio group N-dodecylthio group, 1-adamantylthio group, n-pentadecylthio group Which linear, branched or cyclic unsubstituted alkylthio group;
メトキシメチルチオ基、エトキシメチルチオ基、ｎ－プロピルオキシメチルチオ基、ｎ－ブチルオキシメチルチオ基、ｔｅｒｔ－ブチルオキシメチルチオ基、ｎ－ペンチルオキシメチルチオ基、２－メトキシエチルチオ基、２－エトキシエチルチオ基、２－ｎ－プロピルオキシエチルチオ基、２－イソプロピルオキシエチルチオ基、２－ｎーブチルオキシエチルチオ基、２－イソペンチルオキシエチルチオ基、２－ｎ－ヘキシルオキシエチルチオ基、２－（４－エチルシクロヘキシルオキシ）エチルチオ基、２－ｎ－ノニルオキシエチルチオ基、２－（３，５，５－トリメチルヘキシルオキシ）エチルチオ基、２－ｎ－デシルオキシエチルチオ基、３－メトキシプロピルチオ基、３－エトキシプロピルチオ基、３－（ｎ－プロピルチオ）プロピルチオ基、２－メトキシブチルチオ基、４－エトキシブチルチオ基、４－（ｎ－プロピルオキシ）ブチルチオ基、５－エトキシペンチルチオ基、６－ｎ－プロピルオキシヘキシルチオ基などのアルコキシ基で置換されたアルキルチオ基； Methoxymethylthio group, ethoxymethylthio group, n-propyloxymethylthio group, n-butyloxymethylthio group, tert-butyloxymethylthio group, n-pentyloxymethylthio group, 2-methoxyethylthio group, 2-ethoxyethylthio group, 2-n-propyloxyethylthio group, 2-isopropyloxyethylthio group, 2-n-butyloxyethylthio group, 2-isopentyloxyethylthio group, 2-n-hexyloxyethylthio group, 2- ( 4-ethylcyclohexyloxy) ethylthio group, 2-n-nonyloxyethylthio group, 2- (3,5,5-trimethylhexyloxy) ethylthio group, 2-n-decyloxyethylthio group, 3-methoxypropylthio Group, 3-ethoxypropylthio group, 3- (n-propylthio) pro Substituted with alkoxy groups such as ruthio, 2-methoxybutylthio, 4-ethoxybutylthio, 4- (n-propyloxy) butylthio, 5-ethoxypentylthio, 6-n-propyloxyhexylthio Alkylthio groups formed;
メトキシメトキシメチルチオ基、エトキシメトキシメチルチオ基、プロピルオキシメトキシメチルチオ基、エトキシエトキシメチルチオ基、プロピルオキシエトキシメチルチオ基、エトキシメトキシエチルチオ基、プロピルオキシメトキシエチルチオ基、プロピルオキシエトキシエチルチオ基、ブチルオキシエトキシエチルチオ基、プロピルオキシブチルオキシエチルチオ基、メトキシメトキシプロピルチオ基、エトキシメトキシプロピルチオ基、ブチルオキシメトキシプロピルチオ基、ブチルオキシメトキシブチルチオ基、エトキシエトキシブチルチオ基、シクロへキシルオキシエトキシエチルチオ基などのアルコキシアルコキシ基で置換されたアルキルチオ基；
メトキシカルボニルメチルチオ基、エトキシカルボニルメチルチオ基、ｎ－プロピルオキシカルボニルメチルチオ基、メトキシカルボニルエチルチオ基、エトキシカルボニルエチルチオ基、ｎ－プロピルオキシカルボニルエチルチオ基、エトキシカルボニルプロピルチオなどのアルコキシカルボニル基で置換されたアキルチオ基； Methoxymethoxymethylthio group, ethoxymethoxymethylthio group, propyloxymethoxymethylthio group, ethoxyethoxymethylthio group, propyloxyethoxymethylthio group, ethoxymethoxyethylthio group, propyloxymethoxyethylthio group, propyloxyethoxyethylthio group, butyloxyethoxy Ethylthio group, propyloxybutyloxyethylthio group, methoxymethoxypropylthio group, ethoxymethoxypropylthio group, butyloxymethoxypropylthio group, butyloxymethoxybutylthio group, ethoxyethoxybutylthio group, cyclohexyloxyethoxyethyl An alkylthio group substituted with an alkoxyalkoxy group such as a thio group;
Substituted with alkoxycarbonyl groups such as methoxycarbonylmethylthio, ethoxycarbonylmethylthio, n-propyloxycarbonylmethylthio, methoxycarbonylethylthio, ethoxycarbonylethylthio, n-propyloxycarbonylethylthio, ethoxycarbonylpropylthio, etc. An acetylthio group;
メチルアミノメチルチオ基、２－メチルアミノエチルチオ基、２－( ２－メチルアミノエトキシ) エチルチオ基、４－メチルアミノブチルチオ基、１－メチルアミノプロパン－２－イルオキシ基、３－メチルアミノプロピルチオ基、２－エチルアミノエチルチオ基、２－( ２－エチルアミノエトキシ)エチルチオ基、３－エチルアミノプロピルチオ基、１－エチルアミノプロピルチオ基、２－イソプロピルアミノエチルチオ基、２－（ｎ－ブチルアミノ）エチルチオ基、３－（ｎ－ヘキシルアミノ）プロピルチオ基、４－（シクロヘキシルアミノ）ブチルチオ基などのアルキルアミノ基で置換されたアルキルチオ基；
ジメチルアミノメチルチオ基、２－ジメチルアミノエチルチオ基、４－ジメチルアミノブチルチオ基、１－ジメチルアミノプロパン－２－イルチオ基、３－ジメチルアミノプロピルチオ基、２－ジエチルアミノエチルチオ基、３－ジエチルアミノプロピルチオ基、２－ジイソプロピルアミノエチルチオ基、２－（ジ－ｎ－ブチルアミノ）エチルチオ基、２－ピペリジルエチルチオ基、３－（ジ－ｎ－ヘキシルアミノ）プロピルチオ基などのジアルキルアミノ基で置換されたアルキルチオ基；
メチルチオメチルチオ基、２－メチルチオエチルチオ基、２－エチルチオエチルチオ基、２－ｎ－プロピルチオエチルチオ基、２－イソプロピルチオエチルチオ基、２－ｎ－ブチルチオエチルチオ基、２－イソブチルチオエチルチオ基、（３，５，５－トリメチルヘキシルチオ）ヘキシルチオ基などのアルキルチオ基で置換されたアルキルチオ基などが挙げられる。 Methylaminomethylthio group, 2-methylaminoethylthio group, 2- (2-methylaminoethoxy) ethylthio group, 4-methylaminobutylthio group, 1-methylaminopropan-2-yloxy group, 3-methylaminopropylthio group Group, 2-ethylaminoethylthio group, 2- (2-ethylaminoethoxy) ethylthio group, 3-ethylaminopropylthio group, 1-ethylaminopropylthio group, 2-isopropylaminoethylthio group, 2- (n An alkylthio group substituted with an alkylamino group such as a butylamino) ethylthio group, a 3- (n-hexylamino) propylthio group, or a 4- (cyclohexylamino) butylthio group;
Dimethylaminomethylthio group, 2-dimethylaminoethylthio group, 4-dimethylaminobutylthio group, 1-dimethylaminopropan-2-ylthio group, 3-dimethylaminopropylthio group, 2-diethylaminoethylthio group, 3-diethylamino Dialkylamino groups such as propylthio, 2-diisopropylaminoethylthio, 2- (di-n-butylamino) ethylthio, 2-piperidylethylthio, 3- (di-n-hexylamino) propylthio; A substituted alkylthio group;
Methylthiomethylthio group, 2-methylthioethylthio group, 2-ethylthioethylthio group, 2-n-propylthioethylthio group, 2-isopropylthioethylthio group, 2-n-butylthioethylthio group, 2-isobutyl Examples thereof include an alkylthio group substituted with an alkylthio group such as a thioethylthio group and a (3,5,5-trimethylhexylthio) hexylthio group.
　置換または無置換のアリールチオ基としては、ヘテロアリールチオ基も含まれ、例えば、フェニルチオ基、２－メチルフェニルチオ基、４－メチルフェニルチオ基、３－エチルフェニルチオ基、４－ｎ－プロピルフェニルチオ基、４－ｎ－ブチルフェニルチオ基、４－イソブチルフェニルチオ基、４－ｔｅｒｔ-ブチルフェニルチオ基、４－ｎ－ペンチルフェニルチオ基、４－ｎ－ヘキシルフェニルチオ基、４－シクロヘキシルフェニルチオ基、４－ｎ－オクチルフェニルチオ基、４－ｎ－ドデシルフェニルチオ基、４－ｎ－オクタデシルフェニルチオ基、２，５－ジメチルフェニルチオ基、３，４－ジメチルフェニルチオ基、５－インダニルチオ基、１，２，３，４－テトラヒドロ－６－ナフチルチオ基、２－メトキシフェニルチオ基、３－メトキシフェニルチオ基、４－エトキシフェニルチオ基、４－ｎ－プロポキシフェニルチオ基、２，４－ジメトキシフェニルチオ基、３，５－ジエトキシフェニルチオ基、２－メトキシ－４－メチルフェニルチオ基、２－メチル－４－メトキシフェニルチオ基、２－フルオロフェニルチオ基、４－フルオロフェニルチオ基、２－クロロフェニルチオ基、４－ブロモフェニルチオ基、４－トリフルオロメチルフェニルチオ基、３－トリフルオロメチルフェニルチオ基、２，４－ジフルオロフェニルチオ基、２，４－ジクロロフェニルチオ基、２－クロロ－４－メトキシフェニルチオ基、２－ナフチルチオ基、４－メチル－１－ナフチルチオ基、４－エトキシ－１－ナフチルチオ基、２－ピリジルチオ基、４－アミノフェニルチオ基、４－（Ｎ，Ｎ－ジメチルアミノ）フェニルチオ基、４－（Ｎ，Ｎ－ジエチルアミノ）－１－ナフチルチオ基、４－〔Ｎ，Ｎ－ジ（４’－メチルフェニル）アミノ〕フェニルチオ基、４－（Ｎ－フェノキサジイル）フェニルチオ基などが挙げられる。 The substituted or unsubstituted arylthio group also includes a heteroarylthio group, such as a phenylthio group, a 2-methylphenylthio group, a 4-methylphenylthio group, a 3-ethylphenylthio group, a 4-n-propylphenyl group. Thio group, 4-n-butylphenylthio group, 4-isobutylphenylthio group, 4-tert-butylphenylthio group, 4-n-pentylphenylthio group, 4-n-hexylphenylthio group, 4-cyclohexylphenyl Thio group, 4-n-octylphenylthio group, 4-n-dodecylphenylthio group, 4-n-octadecylphenylthio group, 2,5-dimethylphenylthio group, 3,4-dimethylphenylthio group, 5- Indanylthio group, 1,2,3,4-tetrahydro-6-naphthylthio group, 2-methoxyphenylthio group, 3 -Methoxyphenylthio group, 4-ethoxyphenylthio group, 4-n-propoxyphenylthio group, 2,4-dimethoxyphenylthio group, 3,5-diethoxyphenylthio group, 2-methoxy-4-methylphenylthio group Group, 2-methyl-4-methoxyphenylthio group, 2-fluorophenylthio group, 4-fluorophenylthio group, 2-chlorophenylthio group, 4-bromophenylthio group, 4-trifluoromethylphenylthio group, 3 -Trifluoromethylphenylthio group, 2,4-difluorophenylthio group, 2,4-dichlorophenylthio group, 2-chloro-4-methoxyphenylthio group, 2-naphthylthio group, 4-methyl-1-naphthylthio group, 4-ethoxy-1-naphthylthio group, 2-pyridylthio group, 4-aminophenylthio group, 4- (N N-dimethylamino) phenylthio group, 4- (N, N-diethylamino) -1-naphthylthio group, 4- [N, N-di (4′-methylphenyl) amino] phenylthio group, 4- (N-phenoxadi Yl) phenylthio group and the like.
　置換または無置換のアルキルカルボニル基としては、例えば、ホルミル基、アセチル基、プロピオニル基、ブチリル基、バレリル基、ｉｓｏ－バレリル基、ｓｅｃ－バレリル基、トリメチルアセチル基、ヘキサノイル基、ｔｅｒｔ－ブチルアセチル基、ヘプタノイル基、オクタノイル基、２－エチルヘキサノイル基、ノナノイル基、デカノイル基、ウンデカノイル基、ラウロイル基、トリデカノイル基、テトラアデカノイル基、ペンタデカノイル基、ヘキサデカノイル基、ヘプタデカノイル基、オクタデカノイル基、オレオイル基、シクロペンタンカルボニル基、シクロヘキサンカルボニル基、６－クロロヘキサノイル基、６－ブロモヘキサノイル基、トリフルオロアセチル基、ペンタフルオロプロピオニル基、パ－フルオロオクタノイル基、２，２，４，４，５，５，７，７，７－ノナフルオロ－３，６－ジオキサヘプタノイル基、メトキシアセチル基、３，６－ジオキサヘプタノイル基、シンナモイル基などが挙げられる。 Examples of the substituted or unsubstituted alkylcarbonyl group include formyl group, acetyl group, propionyl group, butyryl group, valeryl group, iso-valeryl group, sec-valeryl group, trimethylacetyl group, hexanoyl group, tert-butylacetyl group , Heptanoyl group, octanoyl group, 2-ethylhexanoyl group, nonanoyl group, decanoyl group, undecanoyl group, lauroyl group, tridecanoyl group, tetraadecanoyl group, pentadecanoyl group, hexadecanoyl group, heptadecanoyl group, octadecanoyl group Group, oleoyl group, cyclopentanecarbonyl group, cyclohexanecarbonyl group, 6-chlorohexanoyl group, 6-bromohexanoyl group, trifluoroacetyl group, pentafluoropropionyl group, perfluorooctanoyl 2,2,4,4,5,5,7,7,7-nonafluoro-3,6-dioxaheptanoyl group, methoxyacetyl group, 3,6-dioxaheptanoyl group, cinnamoyl group, etc. It is done.
　置換または無置換のアリールカルボニル基としては、例えば、ベンゾイル基、２－メチルベンゾイル基、３－メチルベンゾイル基、４－メチルベンゾイル基、４－エチルベンゾイル基、４－ｎ－プロピルベンゾイル基、４－ｔｅｒｔ－ブチルベンゾイル基、２，４－ジメチルベンゾイル基、２，４，６－トリメチルベンゾイル基、２，４，５－トリメチルベンゾイル基、４－エチルベンゾイル基、４－イソプロピルベンゾイル基、４－ｎ－ブチルベンゾイル基、４－イソブチルベンゾイル基、４－ｓｅｃ－ブチルベンゾイル基、４－ｔｅｒｔ-ブチルベンゾイル基、４－ｎ－ペンチルベンゾイル基、４－イソペンチルベンゾイル基、４－ネオペンチベンゾイル基、４－イソヘキシルベンゾイル基、４－シキロヘキシルベンゾイル基、４－オクチルベンゾイル基、４－シアノベンゾイル基、４－ニトロベンゾイル基、４－トリフルオロメチルベンゾイル基、３－ブロモベンゾイル基、２－フロロベンゾイル基、４－クロロベンゾイル基、２，６－ジクロロベンゾイル基、２，４－ジフロロベンゾイル基、ナフチルカルボニル－１－イル基、ナフチルカルボニル－２－イル基などが挙げられる。 Examples of the substituted or unsubstituted arylcarbonyl group include benzoyl group, 2-methylbenzoyl group, 3-methylbenzoyl group, 4-methylbenzoyl group, 4-ethylbenzoyl group, 4-n-propylbenzoyl group, 4- tert-butylbenzoyl group, 2,4-dimethylbenzoyl group, 2,4,6-trimethylbenzoyl group, 2,4,5-trimethylbenzoyl group, 4-ethylbenzoyl group, 4-isopropylbenzoyl group, 4-n- Butylbenzoyl group, 4-isobutylbenzoyl group, 4-sec-butylbenzoyl group, 4-tert-butylbenzoyl group, 4-n-pentylbenzoyl group, 4-isopentylbenzoyl group, 4-neopentibenzoyl group, 4- Isohexyl benzoyl group, 4-cyclohexyl benzoyl group, 4-octyl Tylbenzoyl group, 4-cyanobenzoyl group, 4-nitrobenzoyl group, 4-trifluoromethylbenzoyl group, 3-bromobenzoyl group, 2-fluorobenzoyl group, 4-chlorobenzoyl group, 2,6-dichlorobenzoyl group, Examples include 2,4-difluorobenzoyl group, naphthylcarbonyl-1-yl group, and naphthylcarbonyl-2-yl group.
　置換または無置換のアミノ基としては、アミノ基、例えば、メチルアミノ基、エチルアミノ基、プロピルアミノ基、ブチルアミノ基、ペンチルアミノ基、ヘキシルアミノ基、ヘプチルアミノ基、オクチルアミノ基、２－エチルヘキシルアミノ基、シクロヘキシルアミノ基、３，５，５－トリメチルヘキシルアミノ基、ノニルアミノ基、デシルアミノ基などのモノアルキルアミノ基；
ジメチルアミノ基、ジエチルアミノ基、メチルエチルアミノ基、ジ－ｎ－プロピルアミノ基、ジ－ｎ－ブチルアミノ基、ジ－ｎ－ペンチルアミノ基、Ｎ－メチル－Ｎ－エチルアミノ基、Ｎ－エチル－Ｎ－イソプロピルアミノ基、Ｎ－エチル－Ｎ－シクロヘキシルアミノ基、Ｎ－メチル－Ｎ－ｎ－オクチルアミノ基などのジアルキルアミノ基；
Ｎ－メチル－Ｎ－フェニルアミノ基、Ｎ－エチル－Ｎ－フェニルアミノ基、Ｎ－エチル－Ｎ－（２，４－ジメチルフェニル）アミノ基、Ｎ－ｎ－プロピル－Ｎ－（２－エトキシフェニル）アミノ基、Ｎ－メチル－Ｎ－（３－クロロフェニル）アミノ基、ジフェニルアミノ基、ジ－（ｐ－トリル）アミノ基、Ｎ－メチル－Ｎ－（２－ナフチル）アミノ基などのアリール基で置換されたアミノ基；
ベンジルアミノ基、フェネチルアミノ基、３－フェニルプロピルアミノ基、４－エチルベンジルアミノ基、４－イソプロピルベンジルアミノ基、ジベンジルアミノ基、ジフェネチルアミノ基、ビス（４－エチルベンジル）アミノ基、ビス（４－イソプロピルベンジル）アミノ基、Ｎ－エチル－Ｎ－ベンジルアミノ基、Ｎ－メチル－Ｎ－フェネチルアミノ基などのアラルキル基で置換されたアミノ基などが挙げられる。 Examples of the substituted or unsubstituted amino group include amino groups such as methylamino group, ethylamino group, propylamino group, butylamino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, 2-ethylhexyl Monoalkylamino groups such as amino group, cyclohexylamino group, 3,5,5-trimethylhexylamino group, nonylamino group, decylamino group;
Dimethylamino group, diethylamino group, methylethylamino group, di-n-propylamino group, di-n-butylamino group, di-n-pentylamino group, N-methyl-N-ethylamino group, N-ethyl- Dialkylamino groups such as N-isopropylamino group, N-ethyl-N-cyclohexylamino group, N-methyl-Nn-octylamino group;
N-methyl-N-phenylamino group, N-ethyl-N-phenylamino group, N-ethyl-N- (2,4-dimethylphenyl) amino group, Nn-propyl-N- (2-ethoxyphenyl) ) Aryl group such as amino group, N-methyl-N- (3-chlorophenyl) amino group, diphenylamino group, di- (p-tolyl) amino group, N-methyl-N- (2-naphthyl) amino group A substituted amino group;
Benzylamino group, phenethylamino group, 3-phenylpropylamino group, 4-ethylbenzylamino group, 4-isopropylbenzylamino group, dibenzylamino group, diphenethylamino group, bis (4-ethylbenzyl) amino group, bis And an amino group substituted with an aralkyl group such as (4-isopropylbenzyl) amino group, N-ethyl-N-benzylamino group, N-methyl-N-phenethylamino group, and the like.
　一般式（１）、（２）、（３）において、Ｒ１は好ましくは水素原子、炭素数１～２０の置換または無置換のアルキル基、炭素数２～２０の置換または無置換のアルケニル基、炭素数６～２４の置換または無置換のアリール基、炭素数７～２５の置換または無置換のアラルキル基である。
より好ましくは、Ｒ１は炭素数１～１２の置換または無置換のアルキル基、炭素数６～１８の置換または無置換のアリール基である。 In the general formulas (1), (2) and (3), R 1 is preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms. A substituted or unsubstituted aryl group having 6 to 24 carbon atoms and a substituted or unsubstituted aralkyl group having 7 to 25 carbon atoms.
More preferably, R 1 is a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms or a substituted or unsubstituted aryl group having 6 to 18 carbon atoms.
　これらＲ１の具体例を以下に示す。
置換または無置換のアルキル基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、イソペンチル基、ネオペンチル基、ｔｅｒｔ－ペンチル基、ｎ－ヘキシル基、１－メチルペンチル基、４－メチル－２－ペンチル基、２－エチルブチル基、ｎ－ヘプチル基、１－メチルヘキシル基、ｎ－オクチル基、１－メチルヘプチル基、２－エチルヘキシル基、シクロペンチル基、シクロヘキシル基、４－メチルシクロヘキシル基などの直鎖、分岐または環状の無置換のアルキル基：
メトキシメチル基、エトキシメチル基、ｎ－ブトキシメチル基、ｎ－ヘキシルオキシメチル基、（２－エチルブチルオキシ）メチル基、２－（４'－ペンテニルオキシ）エチル基などのアルキルオキシ基またはアルケニルオキシ基で置換されたアルキル基；
ベンジルオキシメチル基、２－（ベンジルオキシメトキシ）エチル基などのアラルキルオキシ基で置換されたアルキル基：
フェニルオキシメチル基、４－クロロフェニルオキシメチル基、４－（２'－フェニルオキシエトキシ）ブチル基などのアリ－ルオキシ基で置換されたアルキル基：
ｎ－ブチルチオメチル基、２－ｎ－オクチルチオエチル基などのチオアルキル基で置換されたアルキル基：
フルオロメチル基、トリフルオロメチル基、パ－フルオロエチル基、４－フルオロシクロヘキシル基、クロロメチル基、ジクロロメチル基、４－クロロシクロヘキシル基、７－クロロヘプチル基などのハロゲン原子で置換されたアルキル基：
メチルオキシカルボニルメチル基、エチルオキシカルボニルエチル基などのアルキルオキシカルボニルアルキル基で置換されたアルキル基：
ｐ－トリルオキシカルボニルメチル基、フェニルオキシカルボニルエチル基などのアリールオキシカルボニルアルキル基で置換されたアルキル基などが挙げられる。 Specific examples of these R 1 are shown below.
Examples of the substituted or unsubstituted alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an isopentyl group. Group, neopentyl group, tert-pentyl group, n-hexyl group, 1-methylpentyl group, 4-methyl-2-pentyl group, 2-ethylbutyl group, n-heptyl group, 1-methylhexyl group, n-octyl group A linear, branched or cyclic unsubstituted alkyl group such as 1-methylheptyl group, 2-ethylhexyl group, cyclopentyl group, cyclohexyl group, 4-methylcyclohexyl group;
Alkyloxy or alkenyloxy such as methoxymethyl, ethoxymethyl, n-butoxymethyl, n-hexyloxymethyl, (2-ethylbutyloxy) methyl, 2- (4'-pentenyloxy) ethyl An alkyl group substituted with a group;
Alkyl groups substituted with aralkyloxy groups such as benzyloxymethyl group and 2- (benzyloxymethoxy) ethyl group:
Alkyl groups substituted with aryloxy groups such as phenyloxymethyl group, 4-chlorophenyloxymethyl group, 4- (2′-phenyloxyethoxy) butyl group:
an alkyl group substituted with a thioalkyl group such as an n-butylthiomethyl group or 2-n-octylthioethyl group:
Alkyl groups substituted with halogen atoms such as fluoromethyl group, trifluoromethyl group, perfluoroethyl group, 4-fluorocyclohexyl group, chloromethyl group, dichloromethyl group, 4-chlorocyclohexyl group, 7-chloroheptyl group :
Alkyl groups substituted with alkyloxycarbonylalkyl groups such as methyloxycarbonylmethyl group and ethyloxycarbonylethyl group:
Examples thereof include an alkyl group substituted with an aryloxycarbonylalkyl group such as a p-tolyloxycarbonylmethyl group and a phenyloxycarbonylethyl group.
　置換または無置換のアルケニル基としては、例えば、ビニル基、プロペニル基、１－ブテニル基、イソブテニル基、１－ペンテニル基、２－ペンテニル基、２－メチル－１－ブテニル基、２－シクロペンテニル基、１－ビニルヘキシル基、スチリル基、スチリルメチル基、２－スチリルエチル基などが挙げられる。 Examples of the substituted or unsubstituted alkenyl group include a vinyl group, a propenyl group, a 1-butenyl group, an isobutenyl group, a 1-pentenyl group, a 2-pentenyl group, a 2-methyl-1-butenyl group, and a 2-cyclopentenyl group. 1-vinylhexyl group, styryl group, styrylmethyl group, 2-styrylethyl group, and the like.
　置換または無置換のアリール基としては、例えば、フェニル基、１－ナフチル基、２－ナフチル基、２－アントラセニル基、１－フェナントリル基、２－フェナントリル基、３－フェナントリル基、１－ピレニル基、２－ピレニル基、２－ペリレニル基、３－ペリレニル基、２－フルオランテニル基、３－フルオランテニル基、７－フルオランテニル基、８－フルオランテニル基などの無置換のアリール基：
１－メチル－２－ピレニル基、２－メチルフェニル基、４－エチルフェニル基、４－（４'－ｔｅｒｔ－ブチルシクロヘキシル）フェニル基、３－シクロヘキシルフェニル基、２－シクロヘキシルフェニル基、４－エチル－１－ナフチル基、６－ｎ－ブチル－２－ナフチル基、２，４－ジメチルフェニル基などのアルキル基で置換されたアリール基：
４－メトキシフェニル基、３－エトキシフェニル基、２－エトキシフェニル基、４－ｎ－プロポキシフェニル基、３－ｎ－プロポキシフェニル基、４－イソプロポキシフェニル基、３－イソプロポキシフェニル基、２－イソプロポキシフェニル基、２－ｓｅｃ－ブトキシフェニル基、４－ｎ－ペンチルオキシフェニル基、４－イソペンチルオキシフェニル基、２－メチル－５－メトキシフェニル基、２－フェニルオキシフェニル基などのアルコキシ基またはアリ－ルオキシ基で置換されたアリール基：
４－フェニルフェニル基、３－フェニルフェニル基、２－フェニルフェニル基、２，６－ジフェニルフェニル基、４－（２'－ナフチル）フェニル基、２－フェニル－１－ナフチル基、１－フェニル－２－ナフチル基、７－フェニル－１－ピレニル基などのアリ－ル基で置換されたアリール基：
４－フルオロフェニル基、３－フルオロフェニル基、２－フルオロフェニル基、２－クロロフェニル基、４－クロロフェニル基、４－ブロモフェニル基、２－クロロ－５－メチルフェニル基、２－クロロ－６－メチルフェニル基、２－メチル－３－クロロフェニル基、２－メトキシ－４－フルオロフェニル基、２－フルオロ－４－メトキシフェニル基などのハロゲン原子で置換されたアリール基：
２－ヒドロキシフェニル基、２－ヒドロキシフェニル基などの水酸基で置換されたアリール基：
３－カルボキシフェニル基などのカルボキシル基で置換されたアリール基：
２－ベンゾイルフェニル基などのアリールカルボニル基で置換されたアリール基。
　さらには、例えば、２－トリフルオロメチルフェニル基、３－トリフルオロメチルフェニル基、４－トリフルオロメチルフェニル基、３，５－ビストリフルオロメチルフェニル基、４－パ－フルオロエチルフェニル基、４－メチルチオフェニル基、４－エチルチオフェニル基、４－シアノフェニル基、３－シアノフェニル基などが挙げられる。 Examples of the substituted or unsubstituted aryl group include phenyl group, 1-naphthyl group, 2-naphthyl group, 2-anthracenyl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 1-pyrenyl group, Unsubstituted aryl groups such as 2-pyrenyl group, 2-perylenyl group, 3-perylenyl group, 2-fluoranthenyl group, 3-fluoranthenyl group, 7-fluoranthenyl group, 8-fluoranthenyl group, etc .:
1-methyl-2-pyrenyl group, 2-methylphenyl group, 4-ethylphenyl group, 4- (4′-tert-butylcyclohexyl) phenyl group, 3-cyclohexylphenyl group, 2-cyclohexylphenyl group, 4-ethyl An aryl group substituted with an alkyl group such as a 1-naphthyl group, a 6-n-butyl-2-naphthyl group, or a 2,4-dimethylphenyl group:
4-methoxyphenyl group, 3-ethoxyphenyl group, 2-ethoxyphenyl group, 4-n-propoxyphenyl group, 3-n-propoxyphenyl group, 4-isopropoxyphenyl group, 3-isopropoxyphenyl group, 2- Alkoxy groups such as isopropoxyphenyl group, 2-sec-butoxyphenyl group, 4-n-pentyloxyphenyl group, 4-isopentyloxyphenyl group, 2-methyl-5-methoxyphenyl group, 2-phenyloxyphenyl group Or an aryl group substituted with an aryloxy group:
4-phenylphenyl group, 3-phenylphenyl group, 2-phenylphenyl group, 2,6-diphenylphenyl group, 4- (2′-naphthyl) phenyl group, 2-phenyl-1-naphthyl group, 1-phenyl- An aryl group substituted with an aryl group such as 2-naphthyl group and 7-phenyl-1-pyrenyl group:
4-fluorophenyl group, 3-fluorophenyl group, 2-fluorophenyl group, 2-chlorophenyl group, 4-chlorophenyl group, 4-bromophenyl group, 2-chloro-5-methylphenyl group, 2-chloro-6- An aryl group substituted with a halogen atom such as a methylphenyl group, 2-methyl-3-chlorophenyl group, 2-methoxy-4-fluorophenyl group, 2-fluoro-4-methoxyphenyl group:
An aryl group substituted with a hydroxyl group such as a 2-hydroxyphenyl group or a 2-hydroxyphenyl group:
An aryl group substituted with a carboxyl group such as a 3-carboxyphenyl group:
An aryl group substituted with an arylcarbonyl group such as 2-benzoylphenyl group.
Furthermore, for example, 2-trifluoromethylphenyl group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 3,5-bistrifluoromethylphenyl group, 4-perfluoroethylphenyl group, 4- Examples thereof include a methylthiophenyl group, a 4-ethylthiophenyl group, a 4-cyanophenyl group, and a 3-cyanophenyl group.
　置換または無置換のアラルキル基としては、例えば、ベンジル基、α－メチルベンジル基、フェネチル基、α－メチルフェネチル基、α,α－ジメチルベンジル基、α,α－ジメチルフェネチル基、４－メチルフェネチル基、４－メチルベンジル基、４－イソプロピルベンジル基などの無置換またはアルキル基で置換されたアラルキル基：
４－ベンジルベンジル基、４－フェネチルベンジル基、４－フェニルベンジル基などのアリ－ル基またはアラルキル基で置換されたアラルキル基：
４－メトキシベンジル基、４－ｎ－テトラデシルオキシベンジル基、４－ｎ－ヘプタデシルオキシベンジル基、３,４－ジメトキシベンジル基、４－メトキシメチルベンジル基、４－ビニルオキシメチルベンジル基、４－ベンジルオキシベンジル基、４－フェネチルオキシベンジル基などの置換オキシ基で置換されたアラルキル基：
４－ヒドロキシベンジル基、４－ヒドロキシ－３－メトキシベンジル基などの水酸基で置換されたアラルキル基：
４－フルオロベンジル基、３－クロロベンジル基、３，４－ジクロロベンジル基などのハロゲン原子で置換されたアラルキル基。
さらには、例えば、２－フルフリル基、ジフェニルメチル基、１－ナフチルメチル基、２－ナフチルメチル基などが挙げられる。 Examples of the substituted or unsubstituted aralkyl group include benzyl group, α-methylbenzyl group, phenethyl group, α-methylphenethyl group, α, α-dimethylbenzyl group, α, α-dimethylphenethyl group, 4-methylphenethyl group. An aralkyl group unsubstituted or substituted with an alkyl group, such as a group, 4-methylbenzyl group, 4-isopropylbenzyl group, etc .:
Aralkyl groups substituted with aryl groups or aralkyl groups such as 4-benzylbenzyl group, 4-phenethylbenzyl group and 4-phenylbenzyl group:
4-methoxybenzyl group, 4-n-tetradecyloxybenzyl group, 4-n-heptadecyloxybenzyl group, 3,4-dimethoxybenzyl group, 4-methoxymethylbenzyl group, 4-vinyloxymethylbenzyl group, 4 An aralkyl group substituted by a substituted oxy group such as benzyloxybenzyl group or 4-phenethyloxybenzyl group:
Aralkyl groups substituted with hydroxyl groups such as 4-hydroxybenzyl group and 4-hydroxy-3-methoxybenzyl group:
An aralkyl group substituted with a halogen atom such as a 4-fluorobenzyl group, a 3-chlorobenzyl group, or a 3,4-dichlorobenzyl group;
Further examples include 2-furfuryl group, diphenylmethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group and the like.
　一般式（２）で表されるイミノ化合物のＲ２及び一般式（３）で表されるイミノ化合物のＲ３及びＲ４は、炭素数１～１２の置換または無置換のアルキル基が好ましく、炭素数１～８の置換または無置換のアルキル基がより好ましい。
これらＲ２、Ｒ３及びＲ４の具体例を以下に示す R 2 of the imino compound represented by the general formula (2) and R 3 and R 4 of the imino compound represented by the general formula (3) are preferably a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, A substituted or unsubstituted alkyl group having 1 to 8 carbon atoms is more preferable.
Specific examples of these R 2 , R 3 and R 4 are shown below.
　置換または無置換のアルキル基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、イソペンチル基、ネオペンチル基、ｔｅｒｔ－ペンチル基、ｎ－ヘキシル基、１－メチルペンチル基、４－メチル－２－ペンチル基、２－エチルブチル基、ｎ－ヘプチル基、１－メチルヘキシル基、ｎ－オクチル基、１－メチルヘプチル基、２－エチルヘキシル基などの直鎖または分岐の無置換のアルキル基：
メトキシメチル基、エトキシメチル基、ｎ－ブトキシメチル基、ｎ－ヘキシルオキシメチル基、（２－エチルブチルオキシ）メチル基、２－（４'－ペンテニルオキシ）エチル基などの、アルキルオキシ基またはアルケニルオキシ基で置換されたアルキル基：
ベンジルオキシメチル基、２－（ベンジルオキシメトキシ）エチル基などのアラルキルオキシ基で置換されたアルキル基：
フェニルオキシメチル基、４－クロロフェニルオキシメチル基、４－（２'－フェニルオキシエトキシ）ブチル基などのアリ－ルオキシ基で置換されたアルキル基：
ｎ－ブチルチオメチル基、２－ｎ－オクチルチオエチル基などのチオアルキル基で置換されたアルキル基：
フルオロメチル基、トリフルオロメチル基、パ－フルオロエチル基、４－フルオロシクロヘキシル基、ジクロロメチル基、４－クロロシクロヘキシル基、７－クロロヘプチル基などのハロゲン原子で置換されたアルキル基が挙げられる。 Examples of the substituted or unsubstituted alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an isopentyl group. Group, neopentyl group, tert-pentyl group, n-hexyl group, 1-methylpentyl group, 4-methyl-2-pentyl group, 2-ethylbutyl group, n-heptyl group, 1-methylhexyl group, n-octyl group A linear or branched unsubstituted alkyl group such as 1-methylheptyl group and 2-ethylhexyl group;
Alkyloxy or alkenyl such as methoxymethyl, ethoxymethyl, n-butoxymethyl, n-hexyloxymethyl, (2-ethylbutyloxy) methyl, 2- (4'-pentenyloxy) ethyl Alkyl groups substituted with oxy groups:
Alkyl groups substituted with aralkyloxy groups such as benzyloxymethyl group and 2- (benzyloxymethoxy) ethyl group:
Alkyl groups substituted with aryloxy groups such as phenyloxymethyl group, 4-chlorophenyloxymethyl group, 4- (2′-phenyloxyethoxy) butyl group:
an alkyl group substituted with a thioalkyl group such as an n-butylthiomethyl group or 2-n-octylthioethyl group:
Examples thereof include alkyl groups substituted with halogen atoms such as fluoromethyl group, trifluoromethyl group, perfluoroethyl group, 4-fluorocyclohexyl group, dichloromethyl group, 4-chlorocyclohexyl group and 7-chloroheptyl group.
　また一般式（３）で表されるイミノ化合物のＲ３とＲ４は、結合して環を形成することも好ましい。Ｒ３とＲ４が結合して形成した環としては、Ｒ３，Ｒ４が置換する酸素原子、およびこれらの共通基礎炭素原子とともに形成される、置換または無置換のジオキソラン環、置換または無置換のジオキサン環が好ましい。環が置換基を有する場合の置換基は、上記したＲ２、Ｒ３及びＲ４が置換のアルキル基である場合に有する置換基と同様である。特に、それぞれ炭素数１～８のアルキル基を１個以上有しても良いジオキソラン環またはジオキサン環が好ましい。 Moreover, it is also preferable that R 3 and R 4 of the imino compound represented by the general formula (3) are bonded to form a ring. The ring formed by combining R 3 and R 4 includes a substituted or unsubstituted dioxolane ring, substituted or unsubstituted, formed together with the oxygen atom substituted by R 3 and R 4 and their common basic carbon atom. The dioxane ring is preferred. When the ring has a substituent, the substituent is the same as the substituent that R 2 , R 3 and R 4 have when they are substituted alkyl groups. In particular, a dioxolane ring or a dioxane ring, each of which may have one or more alkyl groups having 1 to 8 carbon atoms, is preferable.
　Ｒ３とＲ４が結合した環の具体例としては、例えばエタン－１,２－ジイル環、プロパン－１,３－ジイル環、ブタン－１,４－ジイル環、ペンタン－１,５－ジイル環、ヘキサン－１,６－ジイル環、１－メチルエタン－１,２－ジイル環、１－ｎ－ブチルエタン－１,２－ジイル環、２－エチルプロパン－１，３－ジイル環、１－メチル－プロパン－１,３－ジイル環、１－ｎ－ブチル－プロパン－１,３－ジイル環、２－ｎ－ブチル－ブタン－１,４－ジイル環、２,４－ジメチル－ブタン－１,４－ジイル環、３－イソペンチル－ペンタン－１,５－ジイル環、２,３,４－トリメチルペンタン－１,５－ジイル環、２,３,４,５－テトラメチルヘキサン－１,６－ジイル環などが挙げられる。 Specific examples of the ring in which R 3 and R 4 are bonded include, for example, ethane-1,2-diyl ring, propane-1,3-diyl ring, butane-1,4-diyl ring, pentane-1,5-diyl Ring, hexane-1,6-diyl ring, 1-methylethane-1,2-diyl ring, 1-n-butylethane-1,2-diyl ring, 2-ethylpropane-1,3-diyl ring, 1-methyl -Propane-1,3-diyl ring, 1-n-butyl-propane-1,3-diyl ring, 2-n-butyl-butane-1,4-diyl ring, 2,4-dimethyl-butane-1, 4-diyl ring, 3-isopentyl-pentane-1,5-diyl ring, 2,3,4-trimethylpentane-1,5-diyl ring, 2,3,4,5-tetramethylhexane-1,6- And diyl ring.
　一般式（１）、（２）または（３）で表わされる成分Ｉの具体例を下記表１に示すが本発明はこれらに限定されるものではない。
Figure JPOXMLDOC01-appb-I000012
Specific examples of component I represented by the general formula (1), (2) or (3) are shown in the following Table 1, but the present invention is not limited thereto.
Figure JPOXMLDOC01-appb-I000012
Figure JPOXMLDOC01-appb-I000013
Figure JPOXMLDOC01-appb-I000013
Figure JPOXMLDOC01-appb-I000014
Figure JPOXMLDOC01-appb-I000014
Figure JPOXMLDOC01-appb-I000015
Figure JPOXMLDOC01-appb-I000015
Figure JPOXMLDOC01-appb-I000016
Figure JPOXMLDOC01-appb-I000016
Figure JPOXMLDOC01-appb-I000017
Figure JPOXMLDOC01-appb-I000017
 
Figure JPOXMLDOC01-appb-I000018
 
Figure JPOXMLDOC01-appb-I000018
Figure JPOXMLDOC01-appb-I000019
　一般式（１）、（２）または（３）で表される成分Ｉは、特開平８－１１３５６１号報、特開平８－１９９０８１号報、特開平８－２２５７５３等で公知であり、公知の方法を参考にして製造することができる。
例えば、具体例（３）－１の化合物は、アセトン中、１，１－ジメトキシ－３－イミノイソンインドリンとｐ－トルイル酸を３０分間撹拌し、析出物を濾過して得ることが出来る。
 
Figure JPOXMLDOC01-appb-I000019
Component I represented by the general formula (1), (2) or (3) is known in JP-A-8-113561, JP-A-8-199081, JP-A-8-225753, etc. It can be produced with reference to the method.
For example, the compound of the specific example (3) -1 can be obtained by stirring 1,1-dimethoxy-3-iminoisone indoline and p-toluic acid in acetone for 30 minutes and filtering the precipitate.
＜成分Ｐ＞
　本発明で使用される成分Ｐは、一般式（４）で表されるピロリノン化合物である。
Figure JPOXMLDOC01-appb-I000020
〔式中、Ａは置換または無置換の芳香環、置換または無置換の複素環を示し、Ｒ５は置換または無置換のアルキル基、置換または無置換のアルケニル基、置換または無置換のアリール基、置換または無置換のアラルキル基を示す〕
一般式（４）においてＡは好ましくは、置換または無置換のベンゼン環、置換または無置換のナフタレン環、置換または無置換のアントラセン環、置換または無置換のピリジン環、置換または無置換のキノリン環、置換または無置換のピロール環、置換または無置換のインドール環、置換または無置換のチオフェン環、置換または無置換のベンゾチオフェン環、置換または無置換のフラン環、置換または無置換のベンゾフラン環である。
Ａは、より好ましくは、置換または無置換のベンゼン環、置換または無置換のピリジン環、置換または無置換のピロール環、置換または無置換のチオフェン環、置換または無置換のベンゾチオフェン環、置換または無置換のベンゾフラン環である。
Ａが置換基を有する場合の置換基としては、置換または無置換のアルキル基、置換または無置換のアリール基、置換または無置換のアラルキル基、置換または無置換のアルケニル基、置換または無置換のアルコキシ基、置換または無置換のアルキルチオ基、置換または無置換のアミノ基、置換または無置換の複素環基、シアノ基、ハロゲン原子等が好ましい。 <Component P>
Component P used in the present invention is a pyrrolinone compound represented by the general formula (4).
Figure JPOXMLDOC01-appb-I000020
[In the formula, A represents a substituted or unsubstituted aromatic ring, a substituted or unsubstituted heterocyclic ring, and R 5 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group. Represents a substituted or unsubstituted aralkyl group.
In general formula (4), A is preferably a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted anthracene ring, a substituted or unsubstituted pyridine ring, a substituted or unsubstituted quinoline ring. , Substituted or unsubstituted pyrrole ring, substituted or unsubstituted indole ring, substituted or unsubstituted thiophene ring, substituted or unsubstituted benzothiophene ring, substituted or unsubstituted furan ring, substituted or unsubstituted benzofuran ring is there.
A is more preferably a substituted or unsubstituted benzene ring, a substituted or unsubstituted pyridine ring, a substituted or unsubstituted pyrrole ring, a substituted or unsubstituted thiophene ring, a substituted or unsubstituted benzothiophene ring, substituted or An unsubstituted benzofuran ring.
Examples of the substituent when A has a substituent include a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted group An alkoxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted amino group, a substituted or unsubstituted heterocyclic group, a cyano group, a halogen atom and the like are preferable.
　より好ましくは、炭素数１～１８の置換または無置換のアルキル基、炭素数６～２４の置換または無置換のアリール基、炭素数７～２５の置換または無置換のアラルキル基、炭素数２～２０の置換または無置換のアルケニル基、炭素数１～３０の置換または無置換のアルコキシ基、炭素数１～３０の置換または無置換のアルキルチオ基、アミノ基、総炭素数１～２４の置換アミノ基、置換基としてアルキル基、アルコキシ基、アルキルチオ基、アミノ基、ハロゲン原子を有してもよいモルホリノ基、ピリジル基、ピペリジニル基、インドリル基、フリル基、フルフリル基、チオフェニル基等の複素環基、シアノ基、塩素原子、フッ素原子である。
　さらに好ましくは、炭素数１～１２の置換または無置換のアルキル基、炭素数６～１４の置換または無置換のアリール基、炭素数７～１５の置換または無置換のアラルキル基、炭素数２～１０の置換または無置換のアルケニル基、炭素数１～２４の置換または無置換のアルコキシ基、炭素数１～２４の置換または無置換のアルキルチオ基、アミノ基、総炭素数１～１２の置換アミノ基、置換基としてアルキル基、アルコキシ基、アルキルチオ基、アミノ基、ハロゲン原子を有してもよいモルホリノ基、ピリジル基、ピペリジニル基、インドリル基、フリル基、フルフリル基、チオフェニル基等の複素環基、シアノ基、塩素原子、フッ素原子である。 More preferably, it is a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted aryl group having 6 to 24 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 25 carbon atoms, or 2 to 2 carbon atoms. 20 substituted or unsubstituted alkenyl groups, substituted or unsubstituted alkoxy groups having 1 to 30 carbon atoms, substituted or unsubstituted alkylthio groups having 1 to 30 carbon atoms, amino groups, substituted amino groups having 1 to 24 carbon atoms in total Groups, substituents such as alkyl groups, alkoxy groups, alkylthio groups, amino groups, morpholino groups optionally having a halogen atom, pyridyl groups, piperidinyl groups, indolyl groups, furyl groups, furfuryl groups, thiophenyl groups and the like , A cyano group, a chlorine atom, and a fluorine atom.
More preferably, it is a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 14 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 15 carbon atoms, or 2 to 2 carbon atoms. 10 substituted or unsubstituted alkenyl groups, substituted or unsubstituted alkoxy groups having 1 to 24 carbon atoms, substituted or unsubstituted alkylthio groups having 1 to 24 carbon atoms, amino groups, substituted amino groups having 1 to 12 carbon atoms in total Groups, substituents such as alkyl groups, alkoxy groups, alkylthio groups, amino groups, morpholino groups optionally having a halogen atom, pyridyl groups, piperidinyl groups, indolyl groups, furyl groups, furfuryl groups, thiophenyl groups and the like , A cyano group, a chlorine atom, and a fluorine atom.
　これらＡが置換基を有する場合の置換基の具体例を下記に示す。
置換または無置換のアルキル基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、イソペンチル基、ネオペンチル基、ｔｅｒｔ－ペンチル基、ｎ－ヘキシル基、１－メチルペンチル基、４－メチル－２－ペンチル基、２－エチルブチル基、ｎ－ヘプチル基、１－メチルヘキシル基、ｎ－オクチル基、１－メチルヘプチル基、２－エチルヘキシル基などの直鎖または分岐の無置換アルキル基：
メトキシメチル基、エトキシメチル基、ｎ－ブトキシメチル基、ｎ－ヘキシルオキシメチル基、（２－エチルブチルオキシ）メチル基、２－（４'－ペンテニルオキシ）エチル基などの、アルキルオキシ基またはアルケニルオキシ基で置換されたアルキル基：
ベンジルオキシメチル基、２－（ベンジルオキシメトキシ）エチル基などの、アラルキルオキシ基で置換されたアルキル基、フェニルオキシメチル基、４－クロロフェニルオキシメチル基、４－（２'－フェニルオキシエトキシ）ブチル基などのアリ－ルオキシ基で置換されたアルキル基：
ｎ－ブチルチオメチル基、２－ｎ－オクチルチオエチル基などのチオアルキル基で置換されたアルキル基：
フルオロメチル基、トリフルオロメチル基、パ－フルオロエチル基、４－フルオロシクロヘキシル基、ジクロロメチル基、４－クロロシクロヘキシル基、７－クロロヘプチル基などのハロゲン原子で置換されたアルキル基が挙げられる。 Specific examples of the substituent when A has a substituent are shown below.
Examples of the substituted or unsubstituted alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an isopentyl group. Group, neopentyl group, tert-pentyl group, n-hexyl group, 1-methylpentyl group, 4-methyl-2-pentyl group, 2-ethylbutyl group, n-heptyl group, 1-methylhexyl group, n-octyl group A linear or branched unsubstituted alkyl group such as 1-methylheptyl group and 2-ethylhexyl group;
Alkyloxy or alkenyl such as methoxymethyl, ethoxymethyl, n-butoxymethyl, n-hexyloxymethyl, (2-ethylbutyloxy) methyl, 2- (4'-pentenyloxy) ethyl Alkyl groups substituted with oxy groups:
Alkyl groups substituted with an aralkyloxy group such as benzyloxymethyl group and 2- (benzyloxymethoxy) ethyl group, phenyloxymethyl group, 4-chlorophenyloxymethyl group, 4- (2′-phenyloxyethoxy) butyl An alkyl group substituted with an aryloxy group such as a group:
an alkyl group substituted with a thioalkyl group such as an n-butylthiomethyl group or 2-n-octylthioethyl group:
Examples thereof include alkyl groups substituted with halogen atoms such as fluoromethyl group, trifluoromethyl group, perfluoroethyl group, 4-fluorocyclohexyl group, dichloromethyl group, 4-chlorocyclohexyl group and 7-chloroheptyl group.
　置換または無置換のアリール基としては、例えば、フェニル基、１－ナフチル基、２－ナフチル基、２－アントラセニル基、１－フェナントリル基、２－フェナントリル基、３－フェナントリル基、１－ピレニル基、２－ピレニル基、２－ペリレニル基、３－ペリレニル基、２－フルオランテニル基、３－フルオランテニル基、７－フルオランテニル基、８－フルオランテニル基などの無置換のアリール基：
１－メチル－２－ピレニル基、２－メチルフェニル基、４－エチルフェニル基、４－(４'－ｔｅｒｔ－ブチルシクロヘキシル)フェニル基、３－シクロヘキシルフェニル基、２－シクロヘキシルフェニル基、４－エチル－１－ナフチル基、６－ｎ－ブチル－２－ナフチル基、２，４－ジメチルフェニル基などのアルキル基で置換されたアリール基：
４－メトキシフェニル基、３－エトキシフェニル基、２－エトキシフェニル基、４－ｎ－プロポキシフェニル基、３－ｎ－プロポキシフェニル基、４－イソプロポキシフェニル基、３－イソプロポキシフェニル基、２－イソプロポキシフェニル基、２－ｓｅｃ－ブトキシフェニル基、４－ｎ－ペンチルオキシフェニル基、４－イソペンチルオキシフェニル基、２－メチル－５－メトキシフェニル基、２－フェニルオキシフェニル基などのアルコキシ基またはアリ－ルオキシ基で置換されたアリール基：
４－フェニルフェニル基、３－フェニルフェニル基、２－フェニルフェニル基、２，６－ジフェニルフェニル基、４－（２'－ナフチル）フェニル基、２－フェニル－１－ナフチル基、１－フェニル－２－ナフチル基、７－フェニル－１－ピレニル基などのアリ－ル基で置換されたアリール基：
４－フルオロフェニル基、３－フルオロフェニル基、２－フルオロフェニル基、４－クロロフェニル基、４－ブロモフェニル基、２－クロロ－５－メチルフェニル基、２－クロロ－６－メチルフェニル基、２－メチル－３－クロロフェニル基、２－メトキシ－４－フルオロフェニル基、２－フルオロ－４－メトキシフェニル基などのハロゲン原子を有するアリール基。
さらには、例えば、２－トリフルオロメチルフェニル基、３－トリフルオロメチルフェニル基、４－トリフルオロメチルフェニル基、３，５－ビストリフルオロメチルフェニル基、４－パ－フルオロエチルフェニル基、４－メチルチオフェニル基、４－エチルチオフェニル基、４－シアノフェニル基、３－シアノフェニル基などが挙げられる。 Examples of the substituted or unsubstituted aryl group include phenyl group, 1-naphthyl group, 2-naphthyl group, 2-anthracenyl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 1-pyrenyl group, Unsubstituted aryl groups such as 2-pyrenyl group, 2-perylenyl group, 3-perylenyl group, 2-fluoranthenyl group, 3-fluoranthenyl group, 7-fluoranthenyl group, 8-fluoranthenyl group, etc .:
1-methyl-2-pyrenyl group, 2-methylphenyl group, 4-ethylphenyl group, 4- (4′-tert-butylcyclohexyl) phenyl group, 3-cyclohexylphenyl group, 2-cyclohexylphenyl group, 4-ethyl An aryl group substituted with an alkyl group such as a 1-naphthyl group, a 6-n-butyl-2-naphthyl group, or a 2,4-dimethylphenyl group:
4-methoxyphenyl group, 3-ethoxyphenyl group, 2-ethoxyphenyl group, 4-n-propoxyphenyl group, 3-n-propoxyphenyl group, 4-isopropoxyphenyl group, 3-isopropoxyphenyl group, 2- Alkoxy groups such as isopropoxyphenyl group, 2-sec-butoxyphenyl group, 4-n-pentyloxyphenyl group, 4-isopentyloxyphenyl group, 2-methyl-5-methoxyphenyl group, 2-phenyloxyphenyl group Or an aryl group substituted with an aryloxy group:
4-phenylphenyl group, 3-phenylphenyl group, 2-phenylphenyl group, 2,6-diphenylphenyl group, 4- (2′-naphthyl) phenyl group, 2-phenyl-1-naphthyl group, 1-phenyl- An aryl group substituted with an aryl group such as 2-naphthyl group and 7-phenyl-1-pyrenyl group:
4-fluorophenyl group, 3-fluorophenyl group, 2-fluorophenyl group, 4-chlorophenyl group, 4-bromophenyl group, 2-chloro-5-methylphenyl group, 2-chloro-6-methylphenyl group, 2 An aryl group having a halogen atom such as a methyl-3-chlorophenyl group, a 2-methoxy-4-fluorophenyl group, or a 2-fluoro-4-methoxyphenyl group;
Furthermore, for example, 2-trifluoromethylphenyl group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 3,5-bistrifluoromethylphenyl group, 4-perfluoroethylphenyl group, 4- Examples thereof include a methylthiophenyl group, a 4-ethylthiophenyl group, a 4-cyanophenyl group, and a 3-cyanophenyl group.
　置換または無置換のアラルキル基としては、例えば、ベンジル基、α－メチルベンジル基、フェネチル基、α－メチルフェネチル基、α,α－ジメチルベンジル基、α,α－ジメチルフェネチル基、４－メチルフェネチル基、４－メチルベンジル基、４－イソプロピルベンジル基などの無置換またはアルキル基で置換されたアラルキル基：
４－ベンジルベンジル基、４－フェネチルベンジル基、４－フェニルベンジル基などのアリ－ル基またはアラルキル基で置換されたアラルキル基：
４－メトキシベンジル基、４－ｎ－テトラデシルオキシベンジル基、４－ｎ－ヘプタデシルオキシベンジル基、３,４－ジメトキシベンジル基、４－メトキシメチルベンジル基、４－ビニルオキシメチルベンジル基、４－ベンジルオキシベンジル基、４－フェネチルオキシベンジル基などの置換オキシ基で置換されたアラルキル基：
４－ヒドロキシベンジル基、４－ヒドロキシ－３－メトキシベンジル基などの水酸基で置換されたアラルキル基：
４－フルオロベンジル基、３－クロロベンジル基、３，４－ジクロロベンジル基などのハロゲン原子で置換されたアラルキル基：
　さらには、例えば、２－フルフリル基、ジフェニルメチル基、１－ナフチルメチル基、２－ナフチルメチル基などが挙げられる。 Examples of the substituted or unsubstituted aralkyl group include benzyl group, α-methylbenzyl group, phenethyl group, α-methylphenethyl group, α, α-dimethylbenzyl group, α, α-dimethylphenethyl group, 4-methylphenethyl group. An aralkyl group unsubstituted or substituted with an alkyl group, such as a group, 4-methylbenzyl group, 4-isopropylbenzyl group, etc .:
Aralkyl groups substituted with aryl groups or aralkyl groups such as 4-benzylbenzyl group, 4-phenethylbenzyl group and 4-phenylbenzyl group:
4-methoxybenzyl group, 4-n-tetradecyloxybenzyl group, 4-n-heptadecyloxybenzyl group, 3,4-dimethoxybenzyl group, 4-methoxymethylbenzyl group, 4-vinyloxymethylbenzyl group, 4 An aralkyl group substituted by a substituted oxy group such as benzyloxybenzyl group or 4-phenethyloxybenzyl group:
Aralkyl groups substituted with hydroxyl groups such as 4-hydroxybenzyl group and 4-hydroxy-3-methoxybenzyl group:
Aralkyl groups substituted with halogen atoms such as 4-fluorobenzyl group, 3-chlorobenzyl group, 3,4-dichlorobenzyl group:
Further examples include 2-furfuryl group, diphenylmethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group and the like.
　置換または無置換のアルケニル基としては、例えば、ビニル基、プロペニル基、１－ブテニル基、イソブテニル基、１－ペンテニル基、２－ペンテニル基、２－メチル－１－ブテニル基、２－シクロペンテニル基、１－ビニルヘキシル基、スチリル基、スチリルメチル基、２－スチリルエチル基などが挙げられる。 Examples of the substituted or unsubstituted alkenyl group include a vinyl group, a propenyl group, a 1-butenyl group, an isobutenyl group, a 1-pentenyl group, a 2-pentenyl group, a 2-methyl-1-butenyl group, and a 2-cyclopentenyl group. 1-vinylhexyl group, styryl group, styrylmethyl group, 2-styrylethyl group, and the like.
　置換または無置換のアルコキシ基としては、例えば、メトキシ基、エトキシ基、ｎ－プロピルオキシ基、イソプロピルオキシ基、ｎ－ブチルオキシ基、イソブチルオキシ基、ｔｅｒｔ－ブチルオキシ基、ｓｅｃ－ブチルオキシ基、ｎ－ペンチルオキシ基、イソペンチルオキシ基、ｎ－ヘキシルオキシ基、２－メチルペンチルオキシ基、１，１－ジメチルブチルオキシ基、１，２，２－トリメチルプロピルオキシ基、２－エチルブチルオキシ基、１，３－ジメチルヘキシルオキシ基、シクロヘキシルオキシ基、メチルシクロペンチルオキシ基、ｎ－へプチルオキシ基、ｎ－へプチルオキシ基、ｎ－オクチルオキシ基、３，５，５－トリメチルヘキシルオキシ基、ｎ－デシルオキシ基、ｎ－ウンデシルオキシ基、ｎ－ドデシルオキシ基、１－アダマンチルオキシ基、ｎ－ペンタデシルオキシ基などの直鎖、分岐又は環状の無置換のアルコキシ基： Examples of the substituted or unsubstituted alkoxy group include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, tert-butyloxy group, sec-butyloxy group, and n-pentyl. Oxy group, isopentyloxy group, n-hexyloxy group, 2-methylpentyloxy group, 1,1-dimethylbutyloxy group, 1,2,2-trimethylpropyloxy group, 2-ethylbutyloxy group, 1, 3-dimethylhexyloxy group, cyclohexyloxy group, methylcyclopentyloxy group, n-heptyloxy group, n-heptyloxy group, n-octyloxy group, 3,5,5-trimethylhexyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, 1-a Manchiruokishi group, a straight-chain, such as n- pentadecyloxy group, branched or cyclic unsubstituted alkoxy group:
メトキシメトキシ基、エトキシメトキシ基、ｎ－プロピルオキシメトキシ基、ｎーブチルオキシメトキシ基、イソブチルオキシメトキシ基、ｔｅｒｔ－ブチルオキシメトキシ基、ｎ－ペンチルオキシメトキシ基、２－メトキシエトキシ基、２－エトキシエトキシ基、２－ｎ－プロピルオキシエトキシ基、２－イソプロピルオキシエトキシ基、２－ｎーブチルオキシエトキシ基、２－イソブチルオキシエトキシ基、２－ｔｅｒｔ－ブチルオキシエトキシ基、２－ｓｅｃ－ブチルオキシエトキシ基、２－ｎ－ペンチルオキシエトキシ基、２－イソペンチルオキシエトキシ基、２－ｔｅｒｔ－ペンチルオキシエトキシ基、２－ｓｅｃ－ペンチルオキシエトキシ基、２－シクロペンチルオキシエトキシ基、２－ｎ－ヘキシルオキシエトキシ基、２－（４－エチルシクロヘキシルオキシ）エトキシ基、２－ｎ－ノニルオキシエトキシ基、２－（３，５，５－トリメチルヘキシルオキシ）エトキシ基、２－ｎ－デシルオキシエトキシ基、２－ｎ－ドデシルオキシエトキシ基、３－メトキシプロピルオキシ基、３－エトキシプロピルオキシ基、３－（ｎ－プロピルオキシ）プロピルオキシ基、２－イソペンチルオキシプロピルオキシ基、２－メトキシブチルオキシ基、４－エトキシブチルオキシ基、４－（ｎ－プロピルオキシ）ブチルオキシ基、４－イソプロピルオキシブチルオキシ基、５－メトキシペンチルオキシ基、５－エトキシメトキシ基、６－ｎ－プロピルヘキシルオキシ基などのアルコキシ基で置換されたアルコキシ基； Methoxymethoxy group, ethoxymethoxy group, n-propyloxymethoxy group, n-butyloxymethoxy group, isobutyloxymethoxy group, tert-butyloxymethoxy group, n-pentyloxymethoxy group, 2-methoxyethoxy group, 2-ethoxy Ethoxy group, 2-n-propyloxyethoxy group, 2-isopropyloxyethoxy group, 2-n-butyloxyethoxy group, 2-isobutyloxyethoxy group, 2-tert-butyloxyethoxy group, 2-sec-butyloxy Ethoxy group, 2-n-pentyloxyethoxy group, 2-isopentyloxyethoxy group, 2-tert-pentyloxyethoxy group, 2-sec-pentyloxyethoxy group, 2-cyclopentyloxyethoxy group, 2-n-hexyl Oxyethoxy group, 2- ( -Ethylcyclohexyloxy) ethoxy group, 2-n-nonyloxyethoxy group, 2- (3,5,5-trimethylhexyloxy) ethoxy group, 2-n-decyloxyethoxy group, 2-n-dodecyloxyethoxy group 3-methoxypropyloxy group, 3-ethoxypropyloxy group, 3- (n-propyloxy) propyloxy group, 2-isopentyloxypropyloxy group, 2-methoxybutyloxy group, 4-ethoxybutyloxy group, Alkoxy groups substituted with alkoxy groups such as 4- (n-propyloxy) butyloxy group, 4-isopropyloxybutyloxy group, 5-methoxypentyloxy group, 5-ethoxymethoxy group, 6-n-propylhexyloxy group ;
　メトキシメトキシメトキシ基、エトキシメトキシメトキシ基、プロピルオキシメトキシメトキシ基、ブチルオキシメトキシメトキシ基、メトキシエトキシメトキシ基、エトキシエトキシメトキシ基、プロピルオキシエトキシメトキシ基、メトキシメトキシエトキシ基、エトキシメトキシエトキシ基、プロピルオキシメトキシエトキシ基、ブチルオキシメトキシエトキシ基、プロピルオキシエトキシエトキシ基、ブチルオキシエトキシエトキシ基、プロピルオキシブチルオキシエトキシ基、メトキシメトキシプロピルオキシ基、エトキシメトキシプロピルオキシ基、ブチルオキシメトキシプロピルオキシ基、メトキシメトキシブチルオキシ基、エトキシメトキシブチルオキシ基、ブチルオキシメトキシブチルオキシ基、エトキシエトキシブチルオキシ基、（４－エチルシクロへキシルオキシ）エトキシエトキシ基、〔４－（３，５，５－トリメチルヘキシルオキシ）ブチルオキシ〕エトキシ基などのアルコキシアルコキシ基で置換されたアルコキシ基； Methoxymethoxymethoxy group, ethoxymethoxymethoxy group, propyloxymethoxymethoxy group, butyloxymethoxymethoxy group, methoxyethoxymethoxy group, ethoxyethoxymethoxy group, propyloxyethoxymethoxy group, methoxymethoxyethoxy group, ethoxymethoxyethoxy group, propyloxy Methoxyethoxy group, butyloxymethoxyethoxy group, propyloxyethoxyethoxy group, butyloxyethoxyethoxy group, propyloxybutyloxyethoxy group, methoxymethoxypropyloxy group, ethoxymethoxypropyloxy group, butyloxymethoxypropyloxy group, methoxymethoxy Butyloxy, ethoxymethoxybutyloxy, butyloxymethoxybutyloxy, ethoxyethoxybuty Oxy group, (4 Echirushikuro hexyloxy) ethoxyethoxy group, [4- (3,5,5-trimethyl hexyloxy) butyloxy] alkoxy group substituted with an alkoxyalkoxy group such as ethoxy group;
　メトキシカルボニルメトキシ基、エトキシカルボニルメトキシ基、ｎ－プロピルオキシカルボニルメトキシ基、イソプロピルオキシカルボニルメトキシ基、（４'－エチルシクロヘキシルオキシ）カルボニルメトキシ基等のアルコキシカルボニル基で置換されたアルコキシ基、メトキシカルボニルエトキシ基、エトキシカルボニルエトキシ基、ｎ－プロピルオキシカルボニルエトキシ基、エトキシカルボニルプロピルオキシ基などのアルコキシカルボニル基で置換されたアルコキシ基； Alkoxy groups substituted with alkoxycarbonyl groups such as methoxycarbonylmethoxy group, ethoxycarbonylmethoxy group, n-propyloxycarbonylmethoxy group, isopropyloxycarbonylmethoxy group, (4'-ethylcyclohexyloxy) carbonylmethoxy group, methoxycarbonylethoxy An alkoxy group substituted by an alkoxycarbonyl group such as a group, ethoxycarbonylethoxy group, n-propyloxycarbonylethoxy group, ethoxycarbonylpropyloxy group;
　メチルアミノメトキシ基、２－メチルアミノエトキシ基、２－( ２－メチルアミノエトキシ) エトキシ基、４－メチルアミノブチルオキシ基、１－メチルアミノプロパン－２－イルオキシ基、３－メチルアミノプロピルオキシ基、２－メチルアミノ－２－メチルプロピルオキシ基、２－エチルアミノエトキシ基、２－( ２－エチルアミノエトキシ)エトキシ基、３－エチルアミノプロピルオキシ基、１－エチルアミノプロピルオキシ基、２－イソプロピルアミノエトキシ基、２－（ｎ－ブチルアミノ）エトキシ基、３－（ｎ－ヘキシルアミノ）プロピルオキシ基、４－（シクロヘキシルアミノ）ブチルオキシ基などのアルキルアミノ基で置換されたアルコキシ基；
　ジメチルアミノメトキシ基、２－ジメチルアミノエトキシ基、２－( ２－ジメチルアミノエトキシ) エトキシ基、４－ジメチルアミノブチルオキシ基、１－ジメチルアミノプロパン－２－イルオキシ基、３－ジメチルアミノプロピルオキシ基、２－ジメチルアミノ－２－メチルプロピルオキシ基、２－ジエチルアミノエトキシ基、２－(２－ジエチルアミノエトキシ)エトキシ基、３－ジエチルアミノプロピルオキシ基、１－ジエチルアミノプロピルオキシ基、２－ジイソプロピルアミノエトキシ基、２－（ジ－ｎ－ブチルアミノ）エトキシ基、２－ピペリジルエトキシ基、３－（ジ－ｎ－ヘキシルアミノ）プロピルオキシ基などのジアルキルアミノ基で置換されたアルコキシ基； Methylaminomethoxy group, 2-methylaminoethoxy group, 2- (2-methylaminoethoxy) ethoxy group, 4-methylaminobutyloxy group, 1-methylaminopropan-2-yloxy group, 3-methylaminopropyloxy group 2-methylamino-2-methylpropyloxy group, 2-ethylaminoethoxy group, 2- (2-ethylaminoethoxy) ethoxy group, 3-ethylaminopropyloxy group, 1-ethylaminopropyloxy group, 2- An alkoxy group substituted with an alkylamino group such as an isopropylaminoethoxy group, 2- (n-butylamino) ethoxy group, 3- (n-hexylamino) propyloxy group, 4- (cyclohexylamino) butyloxy group;
Dimethylaminomethoxy group, 2-dimethylaminoethoxy group, 2- (2-dimethylaminoethoxy) ethoxy group, 4-dimethylaminobutyloxy group, 1-dimethylaminopropan-2-yloxy group, 3-dimethylaminopropyloxy group 2-dimethylamino-2-methylpropyloxy group, 2-diethylaminoethoxy group, 2- (2-diethylaminoethoxy) ethoxy group, 3-diethylaminopropyloxy group, 1-diethylaminopropyloxy group, 2-diisopropylaminoethoxy group An alkoxy group substituted with a dialkylamino group such as 2- (di-n-butylamino) ethoxy group, 2-piperidylethoxy group, 3- (di-n-hexylamino) propyloxy group;
メチルアミノメトキシメトキシ基、メチルアミノエトキシエトキシ基、メチルアミノエトキシプロピルオキシ基、エチルアミノエトキシプロピルオキシ基、４－（２'－イソブチルアミノプロピルオキシ）ブチルオキシ基などのアルキルアミノアルコキシ基で置換されたアルコキシ基；
　ジメチルアミノメトキシメトキシ基、ジメチルアミノエトキシエトキシ基、ジメチルアミノエトキシプロピルオキシ基、ジエチルアミノエトキシプロピルオキシ基、４－（２'－ジイソブチルアミノプロピルオキシ）ブチルオキシ基などのジアルキルアミノアルコキシ基で置換されたアルコキシ基；
　メチルチオメトキシ基、２－メチルチオエトキシ基、２－エチルチオエトキシ基、２－ｎ－プロピルチオエトキシ基、２－イソプロピルチオエトキシ基、２－ｎ－ブチルチオエトキシ基、２－イソブチルチオエトキシ基、（３,５,５－トリメチルヘキシルチオ）ヘキシルオキシ基などのアルキルチオ基で置換されたアルコキシ基；
２－Ｎ－モルホリニルエトキシ基、２－Ｎ－ピリジルエトキシ基、２－Ｎ－ピロリルエトキシ基、２－（２－フリル）エトキシ基、２－（１－インドリル）エトキシ基、２－（３－チエニル）エトキシ基、３－Ｎ－モルホリニルプロピルオキシ基、３－Ｎ－ピリジルプロピルオキシ基、３－Ｎ－ピロリルプロピルオキシ基、３－（１－インドリル）プロピルオキシ基などの複素環基で置換されたアルコキシ基などが挙げられる。 Alkoxy substituted with alkylaminoalkoxy groups such as methylaminomethoxymethoxy group, methylaminoethoxyethoxy group, methylaminoethoxypropyloxy group, ethylaminoethoxypropyloxy group, 4- (2'-isobutylaminopropyloxy) butyloxy group Group;
Alkoxy groups substituted with dialkylaminoalkoxy groups such as dimethylaminomethoxymethoxy group, dimethylaminoethoxyethoxy group, dimethylaminoethoxypropyloxy group, diethylaminoethoxypropyloxy group, 4- (2'-diisobutylaminopropyloxy) butyloxy group ;
Methylthiomethoxy group, 2-methylthioethoxy group, 2-ethylthioethoxy group, 2-n-propylthioethoxy group, 2-isopropylthioethoxy group, 2-n-butylthioethoxy group, 2-isobutylthioethoxy group, ( An alkoxy group substituted with an alkylthio group such as a 3,5,5-trimethylhexylthio) hexyloxy group;
2-N-morpholinylethoxy group, 2-N-pyridylethoxy group, 2-N-pyrrolylethoxy group, 2- (2-furyl) ethoxy group, 2- (1-indolyl) ethoxy group, 2- ( 3-thienyl) ethoxy group, 3-N-morpholinylpropyloxy group, 3-N-pyridylpropyloxy group, 3-N-pyrrolylpropyloxy group, 3- (1-indolyl) propyloxy group and the like Examples thereof include an alkoxy group substituted with a ring group.
　置換または無置換のアルキルチオ基としては、例えば、メチルチオ基、エチルチオ基、ｎ－プロピルチオ基、イソプロピルチオ基、ｎ－ブチルチオ基、イソブチルチオ基、ｔｅｒｔ－ブチルチオ基、ｓｅｃ－ブチルチオ基、ｎ－ペンチルチオ基、イソペンチルチオ基、ｎ－ヘキシルチオ基、２－メチルペンチルチオ基、１，１－ジメチルブチルチオ基、１，２，２－トリメチルプロピルチオ基、２－エチルブチルチオ基、１，３－ジメチルヘキシルチオ基、シクロヘキシルチオ基、メチルシクロペンチルチオ基、ｎ－へプチルチオ基、ｎ－へプチルチオ基、ｎ－オクチルチオ基、３，５，５－トリメチルヘキシルチオ基、ｎ－デシルチオ基、ｎ－ウンデシルチオ基、ｎ－ドデシルチオ基、１－アダマンチルチオ基、ｎ－ペンタデシルチオ基などの直鎖、分岐又は環状の無置換のアルキルチオ基： Examples of the substituted or unsubstituted alkylthio group include a methylthio group, an ethylthio group, an n-propylthio group, an isopropylthio group, an n-butylthio group, an isobutylthio group, a tert-butylthio group, a sec-butylthio group, and an n-pentylthio group. , Isopentylthio group, n-hexylthio group, 2-methylpentylthio group, 1,1-dimethylbutylthio group, 1,2,2-trimethylpropylthio group, 2-ethylbutylthio group, 1,3-dimethyl Hexylthio group, cyclohexylthio group, methylcyclopentylthio group, n-heptylthio group, n-heptylthio group, n-octylthio group, 3,5,5-trimethylhexylthio group, n-decylthio group, n-undecylthio group N-dodecylthio group, 1-adamantylthio group, n-pentadecylthio group Which linear, branched or cyclic unsubstituted alkylthio group:
メトキシメチルチオ基、エトキシメチルチオ基、ｎ－プロピルオキシメチルチオ基、ｎーブチルオキシメチルチオ基、イソブチルオキシメチルチオ基、ｔｅｒｔ－ブチルオキシメチルチオ基、ｎ－ペンチルオキシメチルチオ基、２－メトキシエチルチオ基、２－エトキシエチルチオ基、２－ｎ－プロピルオキシエチルチオ基、２－イソプロピルオキシエチルチオ基、２－ｎーブチルオキシエチルチオ基、２－イソブチルオキシエチルチオ基、２－ｔｅｒｔ－ブチルオキシエチルチオ基、２－ｓｅｃ－ブチルオキシエチルチオ基、２－ｎ－ペンチルオキシエチルチオ基、２－イソペンチルオキシエチルチオ基、２－ｓｅｃ－ペンチルオキシエチルチオ基、２－ｎ－ヘキシルオキシエチルチオ基、２－（４－エチルシクロヘキシルオキシ）エチルチオ基、２－ｎ－ノニルオキシエチルチオ基、２－（３，５，５－トリメチルヘキシルオキシ）エチルチオ基、２－ｎ－デシルオキシエチルチオ基、２－ｎ－ドデシルオキシエチルチオ基、３－メトキシプロピルチオ基、３－エトキシプロピルチオ基、３－（ｎ－プロピルチオ）プロピルチオ基、２－イソペンチルオキシプロピルチオ基、２－メトキシブチルチオ基、４－エトキシブチルチオ基、４－（ｎ－プロピルオキシ）ブチルチオ基、５－メトキシペンチルチオ基、５－エトキシペンチルチオ基、６－ｎ－プロピルオキシヘキシルチオ基などのアルコキシ基で置換されたアルキルチオ基； Methoxymethylthio group, ethoxymethylthio group, n-propyloxymethylthio group, n-butyloxymethylthio group, isobutyloxymethylthio group, tert-butyloxymethylthio group, n-pentyloxymethylthio group, 2-methoxyethylthio group, 2- Ethoxyethylthio group, 2-n-propyloxyethylthio group, 2-isopropyloxyethylthio group, 2-n-butyloxyethylthio group, 2-isobutyloxyethylthio group, 2-tert-butyloxyethylthio group 2-sec-butyloxyethylthio group, 2-n-pentyloxyethylthio group, 2-isopentyloxyethylthio group, 2-sec-pentyloxyethylthio group, 2-n-hexyloxyethylthio group, 2- (4-Ethylcyclohexyloxy) ethyl O group, 2-n-nonyloxyethylthio group, 2- (3,5,5-trimethylhexyloxy) ethylthio group, 2-n-decyloxyethylthio group, 2-n-dodecyloxyethylthio group, 3 -Methoxypropylthio group, 3-ethoxypropylthio group, 3- (n-propylthio) propylthio group, 2-isopentyloxypropylthio group, 2-methoxybutylthio group, 4-ethoxybutylthio group, 4- (n -Propyloxy) butylthio group, 5-methoxypentylthio group, 5-ethoxypentylthio group, alkylthio group substituted by alkoxy group such as 6-n-propyloxyhexylthio group;
　メトキシメトキシメチルチオ基、エトキシメトキシメチルチオ基、プロピルオキシメトキシメチルチオ基、ブチルオキシメトキシメチルチオ基、エトキシエトキシメチルチオ基、プロピルオキシエトキシメチルチオ基、メトキシメトキシエチルチオ基、エトキシメトキシエチルチオ基、プロピルオキシメトキシエチルチオ基、ブチルオキシメトキシエチルチオ基、プロピルオキシエトキシエチルチオ基、ブチルオキシエトキシエチルチオ基、プロピルオキシブチルオキシエチルチオ基、メトキシメトキシプロピルチオ基、エトキシメトキシプロピルチオ基、ブチルオキシメトキシプロピルチオ基、ブチルオキシメトキシブチルチオ基、エトキシエトキシブチルチオ基、シクロへキシルオキシエトキシエチルチオ基、〔４－（３，５，５－トリメチルヘキシルオキシ）ブチルオキシ〕エチルチオ基などのアルコキシアルコキシ基で置換されたアルキルチオ基；
　メトキシカルボニルメチルチオ基、エトキシカルボニルメチルチオ基、ｎ－プロピルオキシカルボニルメチルチオ基、メトキシカルボニルエチルチオ基、エトキシカルボニルエチルチオ基、ｎ－プロピルオキシカルボニルエチルチオ基、エトキシカルボニルプロピルチオ基などのアルコキシカルボニル基で置換されたアキルチオ基； Methoxymethoxymethylthio group, ethoxymethoxymethylthio group, propyloxymethoxymethylthio group, butyloxymethoxymethylthio group, ethoxyethoxymethylthio group, propyloxyethoxymethylthio group, methoxymethoxyethylthio group, ethoxymethoxyethylthio group, propyloxymethoxyethylthio Group, butyloxymethoxyethylthio group, propyloxyethoxyethylthio group, butyloxyethoxyethylthio group, propyloxybutyloxyethylthio group, methoxymethoxypropylthio group, ethoxymethoxypropylthio group, butyloxymethoxypropylthio group, Butyloxymethoxybutylthio group, ethoxyethoxybutylthio group, cyclohexyloxyethoxyethylthio group, [4- (3,5,5-tri Ethylhexyl oxy) butyloxy] alkylthio group substituted with an alkoxyalkoxy group such as an ethylthio group;
In alkoxycarbonyl groups such as methoxycarbonylmethylthio group, ethoxycarbonylmethylthio group, n-propyloxycarbonylmethylthio group, methoxycarbonylethylthio group, ethoxycarbonylethylthio group, n-propyloxycarbonylethylthio group, ethoxycarbonylpropylthio group, etc. A substituted alkylthio group;
　メチルアミノメチルチオ基、２－メチルアミノエチルチオ基、２－( ２－メチルアミノエトキシ) エチルチオ基、４－メチルアミノブチルチオ基、１－メチルアミノプロパン－２－イルオキシ基、３－メチルアミノプロピルチオ基、２－エチルアミノエチルチオ基、２－( ２－エチルアミノエトキシ)エチルチオ基、３－エチルアミノプロピルチオ基、１－エチルアミノプロピルチオ基、２－イソプロピルアミノエチルチオ基、２－（ｎ－ブチルアミノ）エチルチオ基、３－（ｎ－ヘキシルアミノ）プロピルチオ基、４－（シクロヘキシルアミノ）ブチルチオ基などのアルキルアミノ基で置換されたアルキルチオ基；
　ジメチルアミノメチルチオ基、２－ジメチルアミノエチルチオ基、４－ジメチルアミノブチルチオ基、１－ジメチルアミノプロパン－２－イルチオ基、３－ジメチルアミノプロピルチオ基、２－ジエチルアミノエチルチオ基、３－ジエチルアミノプロピルチオ基、２－ジイソプロピルアミノエチルチオ基、２－（ジ－ｎ－ブチルアミノ）エチルチオ基、２－ピペリジルエチルチオ基、３－（ジ－ｎ－ヘキシルアミノ）プロピルチオ基などのジアルキルアミノ基で置換されたアルキルチオ基； Methylaminomethylthio group, 2-methylaminoethylthio group, 2- (2-methylaminoethoxy) ethylthio group, 4-methylaminobutylthio group, 1-methylaminopropan-2-yloxy group, 3-methylaminopropylthio group Group, 2-ethylaminoethylthio group, 2- (2-ethylaminoethoxy) ethylthio group, 3-ethylaminopropylthio group, 1-ethylaminopropylthio group, 2-isopropylaminoethylthio group, 2- (n An alkylthio group substituted with an alkylamino group such as a butylamino) ethylthio group, a 3- (n-hexylamino) propylthio group, or a 4- (cyclohexylamino) butylthio group;
Dimethylaminomethylthio group, 2-dimethylaminoethylthio group, 4-dimethylaminobutylthio group, 1-dimethylaminopropan-2-ylthio group, 3-dimethylaminopropylthio group, 2-diethylaminoethylthio group, 3-diethylamino Dialkylamino groups such as propylthio, 2-diisopropylaminoethylthio, 2- (di-n-butylamino) ethylthio, 2-piperidylethylthio, 3- (di-n-hexylamino) propylthio; A substituted alkylthio group;
　メチルチオメチルチオ基、２－メチルチオエチルチオ基、２－エチルチオエチルチオ基、２－ｎ－プロピルチオエチルチオ基、２－イソプロピルチオエチルチオ基、２－ｎ－ブチルチオエチルチオ基、２－イソブチルチオエチルチオ基、（３,５,５－トリメチルヘキシルチオ)ヘキシルチオ基などのアルキルチオ基で置換されたアルキルチオ基；
２－Ｎ－モルホリニルエチルチオ基、２－Ｎ－ピリジルエチルチオ基、２－Ｎ－ピロリルエチルチオ基、２－（２－フリル）エチルチオ基、２－（１－インドリル）エチルチオ基、２－（３－チエニル）エチルチオ基、３－Ｎ－モルホリニルプロピルチオ基、３－Ｎ－ピリジルプロピルチオ基、３－Ｎ－ピロリルプロピルチオ基、３－（１－インドリル）プロピルチオ基などの複素環基で置換されたアルキルチオ基などが挙げられる。 Methylthiomethylthio group, 2-methylthioethylthio group, 2-ethylthioethylthio group, 2-n-propylthioethylthio group, 2-isopropylthioethylthio group, 2-n-butylthioethylthio group, 2-isobutyl An alkylthio group substituted with an alkylthio group such as a thioethylthio group or a (3,5,5-trimethylhexylthio) hexylthio group;
2-N-morpholinylethylthio group, 2-N-pyridylethylthio group, 2-N-pyrrolylethylthio group, 2- (2-furyl) ethylthio group, 2- (1-indolyl) ethylthio group, 2- (3-thienyl) ethylthio group, 3-N-morpholinylpropylthio group, 3-N-pyridylpropylthio group, 3-N-pyrrolylpropylthio group, 3- (1-indolyl) propylthio group, etc. And an alkylthio group substituted with a heterocyclic group.
　置換または無置換のアミノ基としては、アミノ基、例えば、メチルアミノ基、エチルアミノ基、プロピルアミノ基、ブチルアミノ基、ペンチルアミノ基、ヘキシルアミノ基、ヘプチルアミノ基、オクチルアミノ基、２－エチルヘキシルアミノ基、シクロヘキシルアミノ基、３，５，５－トリメチルヘキシルアミノ基、ノニルアミノ基、デシルアミノ基などのモノアルキルアミノ基； Examples of the substituted or unsubstituted amino group include amino groups such as methylamino group, ethylamino group, propylamino group, butylamino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, 2-ethylhexyl Monoalkylamino groups such as amino group, cyclohexylamino group, 3,5,5-trimethylhexylamino group, nonylamino group, decylamino group;
ジメチルアミノ基、ジエチルアミノ基、メチルエチルアミノ基、ジ－ｎ－プロピルアミノ基、ジ－ｎ－ブチルアミノ基、ジ－ｎ－ペンチルアミノ基、Ｎ－メチル－Ｎ－エチルアミノ基、Ｎ－エチル－Ｎ－イソプロピルアミノ基、Ｎ－エチル－Ｎ－シクロヘキシルアミノ基、Ｎ－メチル－Ｎ－ｎ－オクチルアミノ基などのジアルキルアミノ基；
Ｎ－メチル－Ｎ－フェニルアミノ基、Ｎ－エチル－Ｎ－フェニルアミノ基、Ｎ－エチル－Ｎ－（２，４－ジメチルフェニル）アミノ基、Ｎ－ｎ－プロピル－Ｎ－（２－エトキシフェニル）アミノ基、Ｎ－メチル－Ｎ－（３－クロロフェニル）アミノ基、ジフェニルアミノ基、ジ－(ｐ－トリル)アミノ基、Ｎ－メチル－Ｎ－(２－ナフチル)アミノ基などのアリール基で置換されたアミノ基； Dimethylamino group, diethylamino group, methylethylamino group, di-n-propylamino group, di-n-butylamino group, di-n-pentylamino group, N-methyl-N-ethylamino group, N-ethyl- Dialkylamino groups such as N-isopropylamino group, N-ethyl-N-cyclohexylamino group, N-methyl-Nn-octylamino group;
N-methyl-N-phenylamino group, N-ethyl-N-phenylamino group, N-ethyl-N- (2,4-dimethylphenyl) amino group, Nn-propyl-N- (2-ethoxyphenyl) ) Aryl group such as amino group, N-methyl-N- (3-chlorophenyl) amino group, diphenylamino group, di- (p-tolyl) amino group, N-methyl-N- (2-naphthyl) amino group A substituted amino group;
ベンジルアミノ基、フェネチルアミノ基、３－フェニルプロピルアミノ基、４－エチルベンジルアミノ基、４－イソプロピルベンジルアミノ基、ジベンジルアミノ基、ジフェネチルアミノ基、ビス（４－エチルベンジル）アミノ基、ビス（４－イソプロピルベンジル）アミノ基、Ｎ－エチル－Ｎ－ベンジルアミノ基、Ｎ－メチル－Ｎ－フェネチルアミノ基などのアラルキル基で置換されたアミノ基などが挙げられる。 Benzylamino group, phenethylamino group, 3-phenylpropylamino group, 4-ethylbenzylamino group, 4-isopropylbenzylamino group, dibenzylamino group, diphenethylamino group, bis (4-ethylbenzyl) amino group, bis And an amino group substituted with an aralkyl group such as (4-isopropylbenzyl) amino group, N-ethyl-N-benzylamino group, N-methyl-N-phenethylamino group, and the like.
　一般式（４）において、Ｒ５は好ましくは、炭素数１～２０の置換または無置換のアルキル基、炭素数２～２０の置換または無置換のアルケニル基、炭素数６～２４の置換または無置換のアリール基、炭素数７～２５の置換または無置換のアラルキル基である。
　より好ましくは、Ｒ５は炭素数１～１２の置換または無置換のアルキル基、炭素数２～１０の置換または無置換のアルケニル基、炭素数６～１８の置換または無置換のアリール基、炭素数７～１９の置換または無置換のアラルキル基である。
　さらに好ましくは、Ｒ５は炭素数１～８の置換または無置換のアルキル基、炭素数２～８の置換または無置換のアルケニル基、炭素数６～１２の置換または無置換のアリール基、炭素数７～１３の置換または無置換のアラルキル基である。 In the general formula (4), R 5 is preferably a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted group having 6 to 24 carbon atoms. A substituted aryl group, a substituted or unsubstituted aralkyl group having 7 to 25 carbon atoms.
More preferably, R 5 is a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, carbon A substituted or unsubstituted aralkyl group of formulas 7 to 19;
More preferably, R 5 is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 8 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, carbon A substituted or unsubstituted aralkyl group of formulas 7 to 13;
　Ｒ５の具体例を以下に示す。
　置換または無置換のアルキル基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、イソペンチル基、ネオペンチル基、ｔｅｒｔ－ペンチル基、ｎ－ヘキシル基、１－メチルペンチル基、４－メチル－２－ペンチル基、２－エチルブチル基、ｎ－ヘプチル基、１－メチルヘキシル基、ｎ－オクチル基、１－メチルヘプチル基、２－エチルヘキシル基、シクロペンチル基、シクロヘキシル基、4－メチルシクロヘキシル基などの直鎖、分岐または環状の無置換のアルキル基： Specific examples of R 5 are shown below.
Examples of the substituted or unsubstituted alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an isopentyl group. Group, neopentyl group, tert-pentyl group, n-hexyl group, 1-methylpentyl group, 4-methyl-2-pentyl group, 2-ethylbutyl group, n-heptyl group, 1-methylhexyl group, n-octyl group Linear, branched or cyclic unsubstituted alkyl groups such as 1-methylheptyl group, 2-ethylhexyl group, cyclopentyl group, cyclohexyl group and 4-methylcyclohexyl group:
メトキシメチル基、エトキシメチル基、ｎ－ブトキシメチル基、ｎ－ヘキシルオキシメチル基、（２－エチルブチルオキシ）メチル基、２－（４'－ペンテニルオキシ）エチル基などのアルキルオキシ基またはアルケニルオキシ基で置換されたアルキル基：
ベンジルオキシメチル基、２－（ベンジルオキシメトキシ）エチル基などのアラルキルオキシ基で置換されたアルキル基：
フェニルオキシメチル基、４－クロロフェニルオキシメチル基、４－（２'－フェニルオキシエトキシ）ブチル基などのアリ－ルオキシ基で置換されたアルキル基：
ｎ－ブチルチオメチル基、２－ｎ－オクチルチオエチル基などのチオアルキル基で置換されたアルキル基：
フルオロメチル基、トリフルオロメチル基、パ－フルオロエチル基、４－フルオロシクロヘキシル基、ジクロロメチル基、４－クロロシクロヘキシル基、７－クロロヘプチル基などのハロゲン原子で置換されたアルキル基が挙げられる。 Alkyloxy or alkenyloxy such as methoxymethyl, ethoxymethyl, n-butoxymethyl, n-hexyloxymethyl, (2-ethylbutyloxy) methyl, 2- (4'-pentenyloxy) ethyl Alkyl groups substituted with groups:
Alkyl groups substituted with aralkyloxy groups such as benzyloxymethyl group and 2- (benzyloxymethoxy) ethyl group:
Alkyl groups substituted with aryloxy groups such as phenyloxymethyl group, 4-chlorophenyloxymethyl group, 4- (2′-phenyloxyethoxy) butyl group:
an alkyl group substituted with a thioalkyl group such as an n-butylthiomethyl group or 2-n-octylthioethyl group:
Examples thereof include alkyl groups substituted with halogen atoms such as fluoromethyl group, trifluoromethyl group, perfluoroethyl group, 4-fluorocyclohexyl group, dichloromethyl group, 4-chlorocyclohexyl group and 7-chloroheptyl group.
　置換または無置換のアルケニル基としては、例えば、ビニル基、プロペニル基、１－ブテニル基、イソブテニル基、１－ペンテニル基、２－ペンテニル基、２－メチル－１－ブテニル基、２－シクロペンテニル基、１－ビニルヘキシル基、スチリル基、スチリルメチル基、２－スチリルエチル基などが挙げられる。 Examples of the substituted or unsubstituted alkenyl group include a vinyl group, a propenyl group, a 1-butenyl group, an isobutenyl group, a 1-pentenyl group, a 2-pentenyl group, a 2-methyl-1-butenyl group, and a 2-cyclopentenyl group. 1-vinylhexyl group, styryl group, styrylmethyl group, 2-styrylethyl group, and the like.
　置換または無置換のアリール基としては、例えば、フェニル基、１－ナフチル基、２－ナフチル基、２－アントラセニル基、１－フェナントリル基、２－フェナントリル基、３－フェナントリル基、１－ピレニル基、２－ピレニル基、２－ペリレニル基、３－ペリレニル基、２－フルオランテニル基、３－フルオランテニル基、７－フルオランテニル基、８－フルオランテニル基などの無置換のアリール基：
１－メチル－２－ピレニル基、２－メチルフェニル基、４－エチルフェニル基、４－(４'－tert－ブチルシクロヘキシル）フェニル基、３－シクロヘキシルフェニル基、２－シクロヘキシルフェニル基、４－エチル－１－ナフチル基、６－ｎ－ブチル－２－ナフチル基、２,４－ジメチルフェニル基などのアルキル基で置換されたアリール基：
４－メトキシフェニル基、３－エトキシフェニル基、２－エトキシフェニル基、４－ｎ－プロポキシフェニル基、３－ｎ－プロポキシフェニル基、４－イソプロポキシフェニル基、３－イソプロポキシフェニル基、２－イソプロポキシフェニル基、２－ｓｅｃ－ブトキシフェニル基、４－ｎ－ペンチルオキシフェニル基、４－イソペンチルオキシフェニル基、２－メチル－５－メトキシフェニル基、２－フェニルオキシフェニル基などのアルコキシ基またはアリ－ルオキシ基で置換されたアリール基：
４－フェニルフェニル基、３－フェニルフェニル基、２－フェニルフェニル基、２，６－ジフェニルフェニル基、４－（２'－ナフチル）フェニル基、２－フェニル－１－ナフチル基、１－フェニル－２－ナフチル基、７－フェニル－１－ピレニル基などのアリ－ル基で置換されたアリール基：
４－フルオロフェニル基、３－フルオロフェニル基、２－フルオロフェニル基、４－クロロフェニル基、４－ブロモフェニル基、２－クロロ－５－メチルフェニル基、２－クロロ－６－メチルフェニル基、２－メチル－３－クロロフェニル基、２－メトキシ－４－フルオロフェニル基、２－フルオロ－４－メトキシフェニル基などのハロゲン原子で置換されたアリール基：
２－トリフルオロメチルフェニル基、３－トリフルオロメチルフェニル基、４－トリフルオロメチルフェニル基、３，５－ビストリフルオロメチルフェニル基、４－パ－フルオロエチルフェニル基、４－メチルチオフェニル基、４－エチルチオフェニル基、４－シアノフェニル基、３－シアノフェニル基などが挙げられる。 Examples of the substituted or unsubstituted aryl group include phenyl group, 1-naphthyl group, 2-naphthyl group, 2-anthracenyl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 1-pyrenyl group, Unsubstituted aryl groups such as 2-pyrenyl group, 2-perylenyl group, 3-perylenyl group, 2-fluoranthenyl group, 3-fluoranthenyl group, 7-fluoranthenyl group, 8-fluoranthenyl group, etc .:
1-methyl-2-pyrenyl group, 2-methylphenyl group, 4-ethylphenyl group, 4- (4'-tert-butylcyclohexyl) phenyl group, 3-cyclohexylphenyl group, 2-cyclohexylphenyl group, 4-ethyl An aryl group substituted with an alkyl group such as a 1-naphthyl group, a 6-n-butyl-2-naphthyl group, or a 2,4-dimethylphenyl group:
4-methoxyphenyl group, 3-ethoxyphenyl group, 2-ethoxyphenyl group, 4-n-propoxyphenyl group, 3-n-propoxyphenyl group, 4-isopropoxyphenyl group, 3-isopropoxyphenyl group, 2- Alkoxy groups such as isopropoxyphenyl group, 2-sec-butoxyphenyl group, 4-n-pentyloxyphenyl group, 4-isopentyloxyphenyl group, 2-methyl-5-methoxyphenyl group, 2-phenyloxyphenyl group Or an aryl group substituted with an aryloxy group:
4-phenylphenyl group, 3-phenylphenyl group, 2-phenylphenyl group, 2,6-diphenylphenyl group, 4- (2′-naphthyl) phenyl group, 2-phenyl-1-naphthyl group, 1-phenyl- An aryl group substituted with an aryl group such as 2-naphthyl group and 7-phenyl-1-pyrenyl group:
4-fluorophenyl group, 3-fluorophenyl group, 2-fluorophenyl group, 4-chlorophenyl group, 4-bromophenyl group, 2-chloro-5-methylphenyl group, 2-chloro-6-methylphenyl group, 2 An aryl group substituted with a halogen atom such as a methyl-3-chlorophenyl group, a 2-methoxy-4-fluorophenyl group, or a 2-fluoro-4-methoxyphenyl group:
2-trifluoromethylphenyl group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 3,5-bistrifluoromethylphenyl group, 4-perfluoroethylphenyl group, 4-methylthiophenyl group, 4 -Ethylthiophenyl group, 4-cyanophenyl group, 3-cyanophenyl group and the like.
　置換または無置換のアラルキル基としては、例えば、ベンジル基、α－メチルベンジル基、フェネチル基、α－メチルフェネチル基、α,α－ジメチルベンジル基、α,α－ジメチルフェネチル基、４－メチルフェネチル基、４－メチルベンジル基、４－イソプロピルベンジル基などの無置換またはアルキル基で置換されたアラルキル基：
４－ベンジルベンジル基、４－フェネチルベンジル基、４－フェニルベンジル基などのアリ－ル基またはアラルキル基で置換されたアラルキル基：
４－メトキシベンジル基、４－ｎ－テトラデシルオキシベンジル基、４－ｎ－ヘプタデシルオキシベンジル基、３,４－ジメトキシベンジル基、４－メトキシメチルベンジル基、４－ビニルオキシメチルベンジル基、４－ベンジルオキシベンジル基、４－フェネチルオキシベンジル基などの置換オキシ基で置換されたアラルキル基：
４－ヒドロキシベンジル基、４－ヒドロキシ－３－メトキシベンジル基などの水酸基で置換されたアラルキル基：
４－フルオロベンジル基、３－クロロベンジル基、３，４－ジクロロベンジル基などのハロゲン原子で置換されたアラルキル基：
さらには、例えば、２－フルフリル基、ジフェニルメチル基、１－ナフチルメチル基、２－ナフチルメチル基などが挙げられる。
（４）で表わされる成分Ｐの具体例を下記表２に示すが、本発明はこれらに限定されるものではない。 Examples of the substituted or unsubstituted aralkyl group include benzyl group, α-methylbenzyl group, phenethyl group, α-methylphenethyl group, α, α-dimethylbenzyl group, α, α-dimethylphenethyl group, 4-methylphenethyl group. An aralkyl group unsubstituted or substituted with an alkyl group, such as a group, 4-methylbenzyl group, 4-isopropylbenzyl group, etc .:
Aralkyl groups substituted with aryl groups or aralkyl groups such as 4-benzylbenzyl group, 4-phenethylbenzyl group and 4-phenylbenzyl group:
4-methoxybenzyl group, 4-n-tetradecyloxybenzyl group, 4-n-heptadecyloxybenzyl group, 3,4-dimethoxybenzyl group, 4-methoxymethylbenzyl group, 4-vinyloxymethylbenzyl group, 4 An aralkyl group substituted by a substituted oxy group such as benzyloxybenzyl group or 4-phenethyloxybenzyl group:
Aralkyl groups substituted with hydroxyl groups such as 4-hydroxybenzyl group and 4-hydroxy-3-methoxybenzyl group:
Aralkyl groups substituted with halogen atoms such as 4-fluorobenzyl group, 3-chlorobenzyl group, 3,4-dichlorobenzyl group:
Further examples include 2-furfuryl group, diphenylmethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group and the like.
Although the specific example of the component P represented by (4) is shown in following Table 2, this invention is not limited to these.
Figure JPOXMLDOC01-appb-I000021
Figure JPOXMLDOC01-appb-I000021
Figure JPOXMLDOC01-appb-I000022
Figure JPOXMLDOC01-appb-I000022
Figure JPOXMLDOC01-appb-I000023
Figure JPOXMLDOC01-appb-I000023
Figure JPOXMLDOC01-appb-I000024
Figure JPOXMLDOC01-appb-I000024
　一般式（４）で表される成分Ｐは、特開昭６１－１１５０５６号報、特開昭６１－１１５９６０号報、特開平７－２８５９２０等で公知であり、公知の方法を参考にして製造することができる。例えば具体例（４）－２の化合物は、２－ベンゾイルコハク酸ジエチルと酢酸アンモニウムを酢酸中加熱することにより製造することができる。 The component P represented by the general formula (4) is known in JP-A-61-115056, JP-A-61-115960, JP-A-7-285920, etc., and is prepared by referring to a known method. can do. For example, the compound of the specific example (4) -2 can be produced by heating diethyl 2-benzoylsuccinate and ammonium acetate in acetic acid.
＜感熱発色性組成物＞
本発明の成分Ｉと成分Ｐを含有する感熱発色性組成物について以下に説明する。
　本発明の感熱発色性組成物は、本発明の成分Ｉと成分Ｐとを必須成分として含有するが、必要に応じバインダー等の他成分を含有する。他成分の種類や量は、感熱発色性組成物が適用される発色性材料の態様により異なる
　本発明の成分Ｉと成分Ｐは、常温で固体であることが感熱発色性組成物の適用において好ましいが必須の条件ではない。常温で液体の場合にもマイクロカプセル化等の手段により適用可能である。又、成分Ｉと成分Ｐは単独で、あるいは２種以上混合して使用することもできる。 <Thermosensitive coloring composition>
The thermosensitive coloring composition containing component I and component P of the present invention will be described below.
The thermochromic composition of the present invention contains Component I and Component P of the present invention as essential components, but optionally contains other components such as a binder. The type and amount of the other components vary depending on the color developing material to which the thermosensitive coloring composition is applied. It is preferable for application of the thermosensitive coloring composition that component I and component P of the present invention are solid at room temperature. Is not a requirement. Even in the case of a liquid at room temperature, it can be applied by means such as microencapsulation. In addition, Component I and Component P can be used alone or in admixture of two or more.
　成分Ｉと成分Ｐの組成比は、適用される発色性材料の態様により異なるが、通常、モル比で成分Ｉ：成分Ｐ＝１：０．５～１：５が好ましく、１：１～１～３がより好ましい。
　発色性材料としては、例えば感熱記録材料、通電発色記録材料、レーザー光記録材料等の発色性記録材料が挙げられ、他の記録方法、例えば磁気記録、金属薄膜記録、白濁記録等と組み合わせて使用することも可能である。 The composition ratio of component I and component P varies depending on the mode of the color forming material to be applied, but usually, the molar ratio of component I: component P = 1: 0.5 to 1: 5 is preferable, and 1: 1 to 1 ~ 3 are more preferred.
Examples of the color-forming material include color-forming recording materials such as heat-sensitive recording materials, energized color recording materials, and laser light recording materials, and are used in combination with other recording methods such as magnetic recording, metal thin film recording, and cloudiness recording. It is also possible to do.
　発色性記録材料の場合、成分Ｉ及び成分Ｐをそれぞれ微細な粒子に磨砕分散した後、両者を混合し、必要に応じ、バインダー及びその他の助剤を添加して本発明の感熱発色性組成物を含む塗液を調製し、該塗液を支持体に塗工し、乾燥する。得られた発色性記録材料に、８０～３００℃の温度範囲において熱エネルギーを与えることにより、発色体（以下、発色体を形成する成分の意で成分Ｉと成分Ｐを「発色前駆体」と略す）を形成することができる。発色体を記録層全体に形成することも可能であるし、所望の箇所のみに形成することも可能である。加熱温度が８０℃より低温であると発色に長時間を要するか、あるいは発色濃度が低く、３００℃より高温であると発色前駆体の分解を伴い易くなる傾向がある。 In the case of a color-forming recording material, component I and component P are each ground and dispersed into fine particles, then both are mixed, and if necessary, a binder and other auxiliary agents are added to the thermosensitive color-forming composition of the present invention. A coating liquid containing a product is prepared, and the coating liquid is applied to a support and dried. By applying thermal energy to the obtained color-forming recording material in the temperature range of 80 to 300 ° C., a color former (hereinafter referred to as a component that forms the color former, Component I and Component P are referred to as “color precursors”. Abbreviated) can be formed. The color former can be formed on the entire recording layer, or can be formed only at a desired location. If the heating temperature is lower than 80 ° C., it takes a long time for color development, or if the color density is low and the temperature is higher than 300 ° C., the color precursor tends to be easily decomposed.
　発色体を形成する熱エネルギーについては特に限定されていないが、例えば、サーマルヘッド、ホットスタンプ、熱ペンのような熱エネルギーでも良いし、レーザー光のような光エネルギーを光熱変換する事で得られる熱エネルギーでも良い。結果として熱エネルギーに変換され得るエネルギー源であればなんでも用いることができる。 The thermal energy for forming the color former is not particularly limited, but for example, thermal energy such as a thermal head, hot stamp, and thermal pen may be used, or light energy such as laser light can be obtained by photothermal conversion. Thermal energy may be used. As a result, any energy source that can be converted into thermal energy can be used.
　得られた発色体は、さまざまな色相を呈し、光、熱、湿度、可塑剤、油等に対して高堅牢性を示す。例えば、支持体として紙、フィルムもしくはシート等を選び、該支持体上に本発明の感熱発色性組成物を含有する記録層を担持させて得られる感熱記録材料では、該感熱記録材料の発色像は、堅牢度に極めて優れている。 The resulting colored body exhibits various hues and exhibits high fastness to light, heat, humidity, plasticizer, oil and the like. For example, in a heat-sensitive recording material obtained by selecting paper, film or sheet as a support, and carrying a recording layer containing the heat-sensitive color-forming composition of the present invention on the support, a color image of the heat-sensitive recording material is obtained. Is extremely fast.
　本発明の感熱発色性組成物はまた、溶剤に溶解あるいは分散させ、インクあるいは塗料としても用いることができる。このようにして得られたインクあるいは塗料を食品容器、例えば、アルミ缶、ガラスビン、ゴムパッキンの一部に塗っておけば、食品を詰めた後の加熱処理によって塗られた箇所があざやかな色相に変化するので、加熱処理を済ませたか、否かの判定に用いることができる。また、本発明の感熱発色性組成物に熱エネルギーを与えて、濃色で堅牢な発色体を得、この発色体を粉砕して有機顔料とすることもできる。この有機顔料を用いてペイントを製造すると、強く堅牢なペイントを得ることができる。 The thermochromic composition of the present invention can also be dissolved or dispersed in a solvent and used as an ink or a paint. If the ink or paint obtained in this way is applied to a part of a food container, such as an aluminum can, a glass bottle, or a rubber packing, the part painted by the heat treatment after filling the food will have a brilliant hue. Since it changes, it can be used to determine whether or not the heat treatment has been completed. Further, by applying heat energy to the heat-sensitive color-forming composition of the present invention, a dark and strong colored body can be obtained, and this colored body can be pulverized to obtain an organic pigment. When a paint is produced using this organic pigment, a strong and robust paint can be obtained.
　＜感熱記録材料＞
本発明の感熱発色性組成物を含有する感熱記録材料について以下に説明する。
感熱記録材料は、支持体上に本発明の感熱発色性組成物を含有する記録層を設けてなる。
　記録層の製造方法としては、発色前駆体をバインダー樹脂とともに水もしくは有機溶剤中で均一に分散もしくは溶解するか、またはマイクロカプセル化し、これを支持体上に塗布、乾燥して感熱塗液を作製する。また、発色前駆体を水もしくは有機溶剤中で分散し、バインダーを加えて作製しても良い。この時、発色前駆体を構成する成分Ｉと成分Ｐは、併せて分散してもよいし、別々に分散した後、混合しても良い。
　この様にして得られた感熱塗液を支持体上に塗布・乾燥することにより記録層が形成できる。塗布方式は特に限定されない。 <Thermal recording material>
The thermosensitive recording material containing the thermosensitive coloring composition of the present invention will be described below.
The heat-sensitive recording material is provided with a recording layer containing the heat-sensitive color forming composition of the present invention on a support.
As a method for producing the recording layer, the color-forming precursor is uniformly dispersed or dissolved in water or an organic solvent together with a binder resin, or microencapsulated, and this is coated on a support and dried to produce a heat-sensitive coating liquid. To do. Alternatively, the coloring precursor may be dispersed in water or an organic solvent, and a binder may be added. At this time, the component I and the component P constituting the color forming precursor may be dispersed together, or may be mixed after being dispersed separately.
The recording layer can be formed by applying and drying the heat-sensitive coating liquid thus obtained on a support. The application method is not particularly limited.
　なお、感熱塗液は、発色前駆体が微粒子として含有した分散状態であってもよいし、完全に溶解した溶液状態であってもよい。
　発色前駆体を構成する成分Ｉと成分Ｐとのモル比は１：０．５～１：５が好ましく、１：１～１：３がさらに好ましい。また、発色前駆体とバインダーの重量比は１：１～１：０．０１が好ましく、１：０．５～１：０．０５がさらに好ましい。
　分散媒としては、水や有機溶媒（トルエン、メタノール、エタノール、イソプロピルアルコール、ｎ－ヘキサン、シクロヘキサン、ｎ－オクタノール、エチルシクロヘキサン、ジオキサン等）が用いられる。
　分散媒が水の時のバインダーとしては、ポリビニルアルコール樹脂、メチルセルロース樹脂、ヒドロキシエチルセルロース樹脂、カルボキシメチルセルロース樹脂、メチルビニルエーテル／無水マレイン酸共重合体樹脂、ポリアクリル酸樹脂、ポリビニルピロリドン樹脂、アクリルアマイド樹脂、ゼラチン、アラビアゴム等が使用できる。
　分散媒が有機溶媒の時のバインダーとしては、アルキッド樹脂、塩化ビニル樹脂、ウレタン樹脂、キシレン樹脂、フェノール樹脂、クマロン樹脂、ビニルトルエン樹脂、テルペン樹脂、ビニルトルエン／ブタジエン共重合体樹脂、ビニルトルエン／アクリレート共重合体樹脂、スチレン／アクリレ－ト共重合体樹脂、ビニル／イソブチルエーテル共重合体樹脂等が使用できる。 The heat-sensitive coating liquid may be in a dispersed state in which the color precursor is contained as fine particles, or may be in a completely dissolved solution state.
The molar ratio of component I and component P constituting the color precursor is preferably 1: 0.5 to 1: 5, more preferably 1: 1 to 1: 3. The weight ratio of the color former to the binder is preferably 1: 1 to 1: 0.01, more preferably 1: 0.5 to 1: 0.05.
As the dispersion medium, water or an organic solvent (toluene, methanol, ethanol, isopropyl alcohol, n-hexane, cyclohexane, n-octanol, ethylcyclohexane, dioxane, etc.) is used.
As a binder when the dispersion medium is water, polyvinyl alcohol resin, methyl cellulose resin, hydroxyethyl cellulose resin, carboxymethyl cellulose resin, methyl vinyl ether / maleic anhydride copolymer resin, polyacrylic acid resin, polyvinyl pyrrolidone resin, acrylic amide resin, Gelatin, gum arabic, etc. can be used.
As the binder when the dispersion medium is an organic solvent, alkyd resin, vinyl chloride resin, urethane resin, xylene resin, phenol resin, coumarone resin, vinyl toluene resin, terpene resin, vinyl toluene / butadiene copolymer resin, vinyl toluene / An acrylate copolymer resin, a styrene / acrylate copolymer resin, a vinyl / isobutyl ether copolymer resin, or the like can be used.
　この記録層中には、目的に応じて光吸収剤、融点降下剤、紫外線吸収剤、酸化防止剤、有機及び無機顔料等を添加することができる。
　光吸収剤としては、レーザービームの波長領域の光を吸収し熱エネルギーに変換できるものであれば、限定されるものではないが、例えばカーボンブラック、シアニン系色素、ポリメチン系色素、アントラキノン系色素、フタロシアニン系色素、ナフタロシアニン系色素等が挙げられる。これらの光吸収剤は１種のみ使用しても良く、２種以上を混合して使用しても構わない。
　融点降下剤としては、パラフィンワックス、ポリエチレンワックス、高級脂肪酸及びそのエステル類等のワックス、ステアリン酸アミドのような酸アミド類、４，４’－ジメチルビフェニ－ルのようなジフェニル類、メチロ－ルアミド類、１，３－ジニトロナフタリンのようなナフタリン類、尿素類、無水フタル酸のような酸類、アセトアニリド、ベンズアニリド、アルキルカルボン酸アニリドのようなアニリド類、トリフェニル類、フタロニトリル類、ビスレゾルシノールエチレンエーテルのようなエ－テル類、４－ｔ－ブチルサリシレートのようなサリチル酸誘導体、エチル－２－シアノ－３，３－ジフェニルアクリレート、ベンゾトリアゾール類、フルオレン、ジメチルイソフタレート、ジフェニルスルホン、マンデル酸、ベンゾイン、エチルアントラキノン、クマロン化合物、Ｎ－エチルカルバゾ－ルのようなカルバゾール類、スルホンアミド類、トリフェニルメタン類、ジベンゾチアジルジスルフィドのようなチアゾール類、Ｎ－シクロヘキシル－２－ベンゾチアゾリルスルフェンアミドのようなスルフェンアミド類、テトラメチルチウラムジスルフィドのようなチウラム類、ジブチルジチオカルバミン酸亜鉛のようなジチオ酸塩類、ジフェニルグアニジンのようなグアニジン類、Ｎ，Ｎ－ジフェニルチオ尿素のようなチオ尿素類、カルボン酸のフェニルヒドラジド誘導体、ｐ－ヒドロキシ安息香酸エステル類、Ｎ，Ｎ－ジフェニルホルムアミドのようなアミド類等が挙げられる。 In the recording layer, a light absorber, a melting point depressant, an ultraviolet absorber, an antioxidant, organic and inorganic pigments and the like can be added according to the purpose.
The light absorber is not limited as long as it can absorb light in the wavelength region of the laser beam and convert it into thermal energy. For example, carbon black, cyanine dye, polymethine dye, anthraquinone dye, Examples include phthalocyanine dyes and naphthalocyanine dyes. These light absorbers may be used alone or in combination of two or more.
Melting point depressants include waxes such as paraffin wax, polyethylene wax, higher fatty acids and esters thereof, acid amides such as stearamide, diphenyls such as 4,4′-dimethylbiphenyl, and methylolamide. , Naphthalenes such as 1,3-dinitronaphthalene, ureas, acids such as phthalic anhydride, acetanilide, benzanilide, anilides such as alkylcarboxylic acid anilide, triphenyls, phthalonitriles, bisresorcinol ethylene Ethers such as ether, salicylic acid derivatives such as 4-t-butyl salicylate, ethyl-2-cyano-3,3-diphenyl acrylate, benzotriazoles, fluorene, dimethyl isophthalate, diphenyl sulfone, mandelic acid, Benzoin, Such as ethyl anthraquinone, coumarone compounds, carbazoles such as N-ethylcarbazole, sulfonamides, triphenylmethanes, thiazoles such as dibenzothiazyl disulfide, N-cyclohexyl-2-benzothiazolylsulfenamide Sulfenamides, thiurams such as tetramethylthiuram disulfide, dithioacid salts such as zinc dibutyldithiocarbamate, guanidines such as diphenylguanidine, thioureas such as N, N-diphenylthiourea, carvone And phenylhydrazide derivatives of acids, p-hydroxybenzoic acid esters, amides such as N, N-diphenylformamide, and the like.
　紫外線吸収剤としては、ベンゾトリアゾ－ル及びその誘導体、ベンゾイン及びその誘導体、２－クロロアントラキノン、ベンゾールパーオキサイド、サリチル酸ｐ－ｔ－ブチルフェニルのようなサリチル酸エステル類、ジフェニルアクリル酸エチルのようなシアノアクリレ－ト類が挙げられる。
　酸化防止剤としては、２,６－ジ－ｔ－ブチル－４－メチルフェノール、ジ(３－ｔ－ブチル－４－ヒドロキシ－５－メチルフェニル)チオエーテル、１,１－ビス(２－メチル－４－ヒドロキシ－５－ｔ－ブチルフェニル)ブタンのようなヒンダードフェノール類、セバシン酸ジ(２,２,６,６－テトラメチル－４－ピペリジン)のようなヒンダードアミン類が挙げられる。
　顔料としては、タルク、クレ－、シリカ、焼成カオリン、酸化亜鉛、酸化ケイ素、酸化チタン、水酸化アルミニウム、炭酸カルシウム、炭酸マグネシウム、尿素－ホルマリン樹脂が挙げられる。 Examples of ultraviolet absorbers include benzotriazole and derivatives thereof, benzoin and derivatives thereof, 2-chloroanthraquinone, benzol peroxide, salicylic acid esters such as pt-butylphenyl salicylate, and cyanoacrylates such as ethyl diphenylacrylate. And the like.
Antioxidants include 2,6-di-t-butyl-4-methylphenol, di (3-t-butyl-4-hydroxy-5-methylphenyl) thioether, 1,1-bis (2-methyl- Hindered phenols such as 4-hydroxy-5-t-butylphenyl) butane and hindered amines such as di (2,2,6,6-tetramethyl-4-piperidine) sebacate.
Examples of the pigment include talc, clay, silica, calcined kaolin, zinc oxide, silicon oxide, titanium oxide, aluminum hydroxide, calcium carbonate, magnesium carbonate, and urea-formalin resin.
また、記録層の上に保護層、記録層の下に下塗り層を設けることもできる。
保護層には、ウレタン系樹脂、ポリオレフィン系樹脂、ポリエステル系樹脂、ビニル系樹脂、エポキシ系樹脂、アクリル系樹脂が使用できる。
　下塗り層は、発色性を向上させるために断熱性の微小中空粒子、焼成カオリン、有機顔料、熱膨張性マイクロカプセル等を使用することができる。
　支持体としては、紙、合成紙、フィルム、シート、ラミネ－ト紙、不織布シ－ト等が目的に応じて使用できる。例えば、フィルムもしくはシートとしては、ポリエチレンテレフタレート、ポリブチレンテレフタレートなどのポリエステル、三酢酸セルロース等のセルロース誘導体、ポリプロピレン、ポリエチレン等のポリオレフィン、ポリエチレンナフタレート、ポリスチレンなどのプラスチック製フィルムもしくはシートが挙げられる。
　これらのプラスチック製フィルムもしくはシートは一枚のみ使用しても良く、あるいは、これらをそれぞれ貼り合わせたものを使用しても構わない。
なお、複数枚のシートを重ね、真空プレス機により各シート間を加熱融着した後、打ち抜き機にてカードを得る場合には、その内のいずれか一枚のシートが支持体となる。 A protective layer can be provided on the recording layer, and an undercoat layer can be provided below the recording layer.
For the protective layer, urethane resin, polyolefin resin, polyester resin, vinyl resin, epoxy resin, and acrylic resin can be used.
For the undercoat layer, heat-insulating fine hollow particles, calcined kaolin, organic pigments, thermally expandable microcapsules and the like can be used in order to improve color developability.
As the support, paper, synthetic paper, film, sheet, laminated paper, nonwoven fabric sheet or the like can be used according to the purpose. Examples of the film or sheet include polyesters such as polyethylene terephthalate and polybutylene terephthalate, cellulose derivatives such as cellulose triacetate, polyolefins such as polypropylene and polyethylene, and plastic films or sheets such as polyethylene naphthalate and polystyrene.
Only one of these plastic films or sheets may be used, or a laminate of them may be used.
In addition, when a plurality of sheets are stacked and a card is obtained with a punching machine after heat-sealing between the sheets with a vacuum press machine, any one of the sheets serves as a support.
　本発明の感熱記録材料において、支持体は用途に応じ透明であっても不透明であっても、また半透明であっても良いが、透明感熱記録材料の製造には、支持体が実質的に透明であるのが好ましい。
具体的には、Ｈａｚｅ値が１０％以下のプラスチックフィルムもしくはシートを使用することが好ましく、コスト、支持体の耐熱性等の観点からポリエチレンテレフタレートフイルムもしくはシートが最も好ましい。また、上記プラスチックフィルムもしくはシートは目的に応じ、任意の色相に着色されていてもよい。例えばシャウカステンに用いる医療画像診断用フィルムの場合、青色に着色されていても良い。
　本願発明の感熱発色性組成物は、溶剤に溶解または分散した際の透明度が高く、かつ着色がほとんど無いが、加熱により発色すると鮮明で高い色濃度を有し、堅牢性が非常に高い発色体を形成する。そのため透明感熱記録材料にも非常に好適である。
  In the heat-sensitive recording material of the present invention, the support may be transparent, opaque, or translucent depending on the application, but the support is substantially used for the production of the transparent heat-sensitive recording material. It is preferably transparent.
Specifically, a plastic film or sheet having a Haze value of 10% or less is preferably used, and a polyethylene terephthalate film or sheet is most preferable from the viewpoints of cost, heat resistance of the support, and the like. Moreover, the said plastic film or sheet | seat may be colored by arbitrary hues according to the objective. For example, in the case of a medical image diagnostic film used for shaukasten, it may be colored blue.
The thermosensitive coloring composition of the present invention has a high transparency when dissolved or dispersed in a solvent and has almost no coloration, but has a clear and high color density when colored by heating, and has a very high fastness. Form. Therefore, it is very suitable for a transparent thermosensitive recording material.
　以下、合成例、実施例により本発明をさらに詳細に説明するが、本発明はこれらに限定されるものではない。
（合成例１）成分Ｉ（具体例化合物（１）－２２）の合成
　メタノール１００ｍＬに４－ｎ－ブトキシ－１，３－ジイミノイソインドリン２１．７ｇ及び２－メチル安息香酸１３．６ｇを加え、６０～６５℃にて３０分間撹拌した。冷却後、濾過した。濾過ペーストをメタノールにて洗浄、乾燥して前記表１に示したイミノ化合物の化合物番号（１）－２２を白色粉末として３２．５ｇを得た。
　　融点：１６２－１６３℃（分解を伴う）
得られた化合物は下記の分析結果より目的の化合物であることを確認した。
・元素分析値：実測値（Ｃ：６８．００％、Ｈ：６．５９％、Ｎ：１１．８６％）；理論値（Ｃ：６７．９７％、Ｈ：６．５６％、Ｎ：１１．８９％） EXAMPLES Hereinafter, although a synthesis example and an Example demonstrate this invention further in detail, this invention is not limited to these.
(Synthesis Example 1) Synthesis of Component I (Specific Example Compound (1) -22) To 100 mL of methanol was added 21.7 g of 4-n-butoxy-1,3-diiminoisoindoline and 13.6 g of 2-methylbenzoic acid. The mixture was stirred at 60 to 65 ° C. for 30 minutes. After cooling, it was filtered. The filter paste was washed with methanol and dried to obtain 32.5 g of the imino compound compound number (1) -22 shown in Table 1 as a white powder.
Melting point: 162-163 ° C (with decomposition)
The obtained compound was confirmed to be the target compound from the following analysis results.
Elemental analysis values: measured values (C: 68.00%, H: 6.59%, N: 11.86%); theoretical values (C: 67.97%, H: 6.56%, N: 11) .89%)
（合成例２）成分Ｉ（具体例化合物（２）－７）の合成
　１－イソプロポキシ－３－イミノイソインドリン２０．２ｇ及び４－クロロ安息香酸１５．７ｇをトルエン３００ｍＬに加え、１５～２０℃で４時間撹拌した。　冷却後、晶析物をろ取、トルエン洗浄乾燥して、前記表１に示したイミノ化合物の化合物番号（２）－７を白色粉末として３２．２ｇを得た。
　　融点：１２６－１２７℃（分解を伴う）
得られた化合物は下記の分析結果より目的の化合物であることを確認した。
・元素分析値：実測値（Ｃ：６３．６４％、Ｈ：５．３６％、Ｎ：７．７９％）；理論値（Ｃ：６３．６０％、Ｈ：５．３４％、Ｎ：７．８１％） (Synthesis Example 2) Synthesis of Component I (Specific Example Compound (2) -7) 20.2 g of 1-isopropoxy-3-iminoisoindoline and 15.7 g of 4-chlorobenzoic acid were added to 300 mL of toluene, and 15-20 Stir at 4 ° C. for 4 hours. After cooling, the crystallized product was collected by filtration, washed with toluene and dried to obtain 32.2 g of Compound No. (2) -7 of the imino compound shown in Table 1 as a white powder.
Melting point: 126-127 ° C (with decomposition)
The obtained compound was confirmed to be the target compound from the following analysis results.
Elemental analysis values: measured values (C: 63.64%, H: 5.36%, N: 7.79%); theoretical values (C: 63.60%, H: 5.34%, N: 7 .81%)
（合成例３）成分Ｉ（具体例化合物（３）－２）の合成
合成例２における１－イソプロポキシ－３－イミノイソインドリン２０．２ｇの代わりに１，１－ジエトキシ－３－イミノイソインドリン２２ｇ、４－クロロ安息香酸１５.７ｇの代わりに４－メチル安息香酸１３.６ｇを用いた以外は合成例２と同様にして操作を行い、前記表１に示したイミノ化合物の化合物番号（３）－２を白色粉末として３１.０ｇを得た。
　　融点：７５－７６℃（分解を伴う）
得られた化合物は下記の分析結果より目的の化合物であることを確認した。
・元素分析値：実測値（Ｃ：６７．４４％、Ｈ：６．８１％、Ｎ：７．８３％）；理論値（Ｃ：６７．４０％、Ｈ：６．７９％、Ｎ：７．８６％） (Synthesis Example 3) Synthesis of Component I (Specific Example Compound (3) -2) 1,1-diethoxy-3-iminoisoindoline in place of 20.2 g of 1-isopropoxy-3-iminoisoindoline in Synthesis Example 2 22 g, except that 13.6 g of 4-methylbenzoic acid was used instead of 15.7 g of 4-chlorobenzoic acid. The same procedure as in Synthesis Example 2 was followed, and the compound numbers (3 ) -2 was obtained as a white powder to obtain 31.0 g.
Melting point: 75-76 ° C (with decomposition)
The obtained compound was confirmed to be the target compound from the following analysis results.
Elemental analysis values: measured values (C: 67.44%, H: 6.81%, N: 7.83%); theoretical values (C: 67.40%, H: 6.79%, N: 7 .86%)
（合成例４）成分Ｉ（具体例化合物（３）－１３）の合成
　合成例２における１－イソプロポキシ－３－イミノイソインドリン２０．２ｇの代わりに１，１－（１‘－メチルエチレンジオキシ）－３－イミノイソインドリン２０．４ｇ、４－クロロ安息香酸１５．７ｇの代わりに２－メチル安息香酸１３．６ｇを用いた以外は合成例２と同様にして操作を行い、前記表１に示したイミノ化合物の化合物番号（３）－１３を白色粉末として３０．９ｇを得た。
　　融点：１１６℃（分解を伴う）
得られた化合物は下記の分析結果より目的の化合物であることを確認した。
・元素分析値：実測値（Ｃ：６７．０７％、Ｈ：５．９５％、Ｎ：８．２１％）；理論値（Ｃ：６７．０５％、Ｈ：５．９２％、Ｎ：８．２３％） Synthesis Example 4 Synthesis of Component I (Specific Example Compound (3) -13) 1,2- (1′-methylethylenedi) instead of 20.2 g of 1-isopropoxy-3-iminoisoindoline in Synthesis Example 2 Oxy) -3-iminoisoindoline 20.4 g, instead of 15.7 g of 4-chlorobenzoic acid, 13.6 g of 2-methylbenzoic acid was used. As a white powder, 30.9 g of the compound number (3) -13 of the imino compound shown in the above was obtained.
Melting point: 116 ° C. (with decomposition)
The obtained compound was confirmed to be the target compound from the following analysis results.
Elemental analysis values: measured values (C: 67.07%, H: 5.95%, N: 8.21%); theoretical values (C: 67.05%, H: 5.92%, N: 8 .23%)
（合成例５）成分Ｐ（具体例化合物（４）－２）の合成
２－ベンゾイルコハク酸ジエチル１３９．１ｇ及び酢酸アンモニウム１０２．１ｇを酢酸３００ｍＬに加え、１００～１０５℃で２４時間撹拌した。
冷却後、反応混合物を水５００ｍＬに排出した。析出物をろ取、濾過ペーストをメタノール５００ｍＬにて分散洗浄、乾燥して前記表２に示したピロリノ化合物の化合物番号（４）－２を白色粉末として５２ｇを得た。
　　融点：１８０－１８１℃
得られた化合物は下記の分析結果より目的の化合物であることを確認した。
・ＭＳ：（ＥＩ）ｍ／ｚ　２３１Ｍ＋）　
・元素分析値：実測値（Ｃ：６７．５６％、Ｈ：５．６９％、Ｎ：６．０４％）；理論値（Ｃ：６７．５２％、Ｈ：５．６７％、Ｎ：６．０６％） Synthesis Example 5 Synthesis of Component P (Specific Example Compound (4) -2) 139.1 g of diethyl 2-benzoylsuccinate and 102.1 g of ammonium acetate were added to 300 mL of acetic acid and stirred at 100 to 105 ° C. for 24 hours.
After cooling, the reaction mixture was drained into 500 mL of water. The precipitate was collected by filtration, and the filter paste was dispersed and washed with 500 mL of methanol and dried to obtain 52 g of Compound No. (4) -2 of the pyrrolino compound shown in Table 2 as a white powder.
Melting point: 180-181 ° C
The obtained compound was confirmed to be the target compound from the following analysis results.
MS: (EI) m / z 231M +)
Elemental analysis values: measured values (C: 67.56%, H: 5.69%, N: 6.04%); theoretical values (C: 67.52%, H: 5.67%, N: 6 .06%)
（合成例６）成分Ｐ（具体例化合物（４）－３）の合成
合成例５における２－ベンゾイルコハク酸ジエチル１３９．１ｇの代わりに２－ベンゾイルコハク酸ジイソプロピル１５３．２ｇを用いた以外は合成例５と同様にして操作を行い、前記表２に示したピロリノ化合物の化合物番号（４）－３を白色粉末として４９．１ｇを得た。
　　融点：１４８－１５０℃
得られた化合物は、下記の分析結果より目的の化合物であることを確認した。
・ＭＳ：（ＥＩ）ｍ／ｚ　２４５Ｍ＋）　
・元素分析値：実測値（Ｃ：６８．５９％、Ｈ：６．２０％、Ｎ：５．６９％）；理論値（Ｃ：６８．５６％、Ｈ：６．１６％、Ｎ：５．７１％） (Synthesis Example 6) Synthesis of Component P (Specific Example Compound (4) -3) Synthesis except that 153.2 g of diisopropyl 2-benzoylsuccinate was used in place of 139.1 g of diethyl 2-benzoylsuccinate in Synthesis Example 5 The same operation as in Example 5 was performed to obtain 49.1 g of Compound No. (4) -3 of the pyrrolino compound shown in Table 2 as a white powder.
Melting point: 148-150 ° C
The obtained compound was confirmed to be the target compound from the following analysis results.
MS: (EI) m / z 245M +)
Elemental analysis values: measured values (C: 68.59%, H: 6.20%, N: 5.69%); theoretical values (C: 68.56%, H: 6.16%, N: 5 .71%)
（合成例７）成分Ｐ（具体例化合物（４）－１５の合成
　合成例５における２－ベンゾイルコハク酸ジエチル１３９．１ｇの代わりに２－（４－クロロ－ベンゾイル）コハク酸ジエチル１５６．４ｇを用いた以外は合成例５と同様にして操作を行い、前記表２に示したピロリノ化合物の化合物番号（４）－１５を白色粉末として７０．４ｇを得た。
　　融点：１９５－１９６℃
得られた化合物は下記の分析結果より目的の化合物であることを確認した。
・ＭＳ：（ＥＩ）ｍ／ｚ　２６５Ｍ＋）　
・元素分析値：実測値（Ｃ：５８．８１％、Ｈ：４．５８％、Ｎ：５．２６％）；理論値（Ｃ：５８．７７％、Ｈ：４．５５％、Ｎ：５．２７％） (Synthesis Example 7) Component P (Synthesis of Specific Example Compound (4) -15) In place of 139.1 g of diethyl 2-benzoylsuccinate in Synthesis Example 5, 156.4 g of diethyl 2- (4-chloro-benzoyl) succinate was used. The procedure was the same as in Synthesis Example 5 except that it was used, and 70.4 g of the pyrrolino compound No. (4) -15 shown in Table 2 was obtained as a white powder.
Melting point: 195-196 ° C
The obtained compound was confirmed to be the target compound from the following analysis results.
MS: (EI) m / z 265M +)
Elemental analysis values: measured values (C: 58.81%, H: 4.58%, N: 5.26%); theoretical values (C: 58.77%, H: 4.55%, N: 5 .27%)
（実施例１）感熱記録材料の作製
　成分Ｉとして、合成例４で合成した化合物４.２ｇと、成分Ｐとして、合成例５で合成した化合物５.７ｇを、それぞれトルエン３０ｍＬとともに、サンドミルで２時間磨砕し、分散液を得た。次いで、成分Ｉの分散液と成分Ｐの分散液を合わせ、これにバインダーとして「アルマテックス」(商品名：三井化学製)１００ｇを加えよく混合し感熱発色性組成物を作製した。この感熱発色性組成物を上質紙上に乾燥塗布量が６ｇ／ｍ２ となるように塗布・乾燥し、感熱記録材料を得た。
　得られた感熱記録材料に２００℃のアイロンを３秒間接触させ、全面発色像を得た。この発色像は鮮やかな青であった。
　なお、上記で得た感熱記録材料の発色像を以下の項目に付いて測定、評価した。評価結果を表４に示した。 (Example 1) Production of thermosensitive recording material As component I, 4.2 g of the compound synthesized in Synthesis Example 4 and 5.7 g of the compound synthesized in Synthesis Example 5 as Component P were each mixed with 30 mL of toluene in a sand mill. Time grinding was performed to obtain a dispersion. Next, the dispersion liquid of component I and the dispersion liquid of component P were combined, and 100 g of “Almatex” (trade name: manufactured by Mitsui Chemicals) as a binder was added and mixed well to prepare a thermosensitive coloring composition. This thermosensitive color-developing composition was applied and dried on fine paper so that the dry coating amount was 6 g / m 2 to obtain a thermosensitive recording material.
The obtained heat-sensitive recording material was brought into contact with an iron at 200 ° C. for 3 seconds to obtain a full color image. This color image was bright blue.
The color images of the heat-sensitive recording material obtained above were measured and evaluated for the following items. The evaluation results are shown in Table 4.
（ａ）濃度
　マクベス濃度計（ＴＲ－２５４型）により測定し、アンバーフィルターを用いた時のＯＤ値を表す。
（ｂ）発色像堅牢度
　次式に示す残存率で評価した。
　残存率（％）＝（試験後の発色像濃度／試験前の発色像濃度）×１００
（ｂ－１）耐光性試験
発色像に、紫外線カーボンアーク（スガ試験機製）を２４時間照射後の残存率で表した。
（ｂ－２）耐湿性試験
　発色像を、６０℃、相対湿度９０％で２４時間保った後の濃度を測定し、残存率を求めた。
（ｂ－３）可塑剤安定性試験
　発色像に、ジオクチルフタレートを含有したカプセル塗工液を塗布した紙を重ね合わせ、加圧ロールを通過させた後、２５℃で１週間保った後の濃度を測定し、残存率を求めた。
（ｂ－４）ラップ安定性試験
　発色像に、ハイラップ（三井化学製）を接触させ、１００ｇ／ｃｍ２の荷をかけて４０℃で２４時間保った後の濃度を測定し、残存率を求めた。 (A) Concentration Measured with a Macbeth densitometer (TR-254 type) and represents an OD value when an amber filter is used.
(B) Colored image fastness The evaluation was based on the residual ratio shown in the following formula.
Residual rate (%) = (color image density after test / color image density before test) × 100
(B-1) Light resistance test The color development image was represented by the residual ratio after 24 hours of irradiation with ultraviolet carbon arc (manufactured by Suga Test Instruments).
(B-2) Humidity resistance test The density after the color image was kept at 60 ° C. and 90% relative humidity for 24 hours was measured to determine the residual ratio.
(B-3) Plasticizer stability test The density of the color image after overlaying paper coated with a capsule coating solution containing dioctyl phthalate, passing through a pressure roll, and maintaining at 25 ° C. for 1 week Was measured to determine the residual rate.
(B-4) Lap Stability Test A high wrap (made by Mitsui Chemicals) is brought into contact with the color image, the concentration after being kept at 40 ° C. for 24 hours with a load of 100 g / cm 2 is obtained, and the residual rate is obtained. It was.
（実施例２） 感熱記録材料の作製
　実施例１において、成分Ｉとして、合成例４で合成した化合物４.２ｇの代わりに同化合物を５.９ｇと、成分Ｐとして、合成例５で合成した化合物５.８ｇの代わりに同化合物を４.０ｇ用いた以外は実施例１と同様の操作を行って、感熱記録材料及び全面発色像を得た。この発色像は鮮やかな黄色であった。この発色像に対して実施例１と同様の評価試験を行った。結果を表４に示す。 (Example 2) Production of thermosensitive recording material In Example 1, 5.9 g of the same compound as component I instead of 4.2 g of the compound synthesized in Synthesis Example 4 and Component P as the component P in Example 1 were synthesized. A heat-sensitive recording material and a full color image were obtained in the same manner as in Example 1 except that 4.0 g of the same compound was used instead of 5.8 g of the compound. This color image was bright yellow. The same evaluation test as in Example 1 was performed on this color image. The results are shown in Table 4.
（実施例３） 感熱記録材料の作製
　実施例１において、成分Ｉとして、合成例４で合成した化合物４．２ｇの代わりに合成例１で合成した化合物４．３ｇと、成分Ｐとして、合成例５で合成した化合物５．７ｇの代わりに同化合物を５．６ｇ用いた以外は実施例１と同様の操作を行って、感熱記録材料及び全面発色像を得た。この発色像は鮮やかな青紫色であった。この発色像に対して実施例１と同様の評価試験を行った。結果を表４に示す。 Example 3 Production of Thermosensitive Recording Material In Example 1, as Component I, instead of Compound 4.2 g synthesized in Synthesis Example 4, Compound 4.3 g synthesized in Synthesis Example 1 and Component P as a synthesis example A heat-sensitive recording material and a full-color image were obtained in the same manner as in Example 1 except that 5.6 g of the same compound was used instead of 5.7 g of the compound synthesized in 5. This color image was bright blue-purple. The same evaluation test as in Example 1 was performed on this color image. The results are shown in Table 4.
（実施例４～２３）感熱記録材料の作製
　実施例１における成分Ｉと成分Ｐにおいて、表３に記載した化合物を用いて、実施例１と同様の操作を行い、それぞれ感熱記録材料及び全面発色像を得た。それぞれ、得られた発色像に対して実施例１と同様の評価試験を行った。結果を表４に示す。 (Examples 4 to 23) Preparation of heat-sensitive recording material The same operations as in Example 1 were carried out using the compounds listed in Table 3 for component I and component P in Example 1, respectively. I got a statue. The same evaluation test as in Example 1 was performed on the obtained color image. The results are shown in Table 4.
（実施例２４）感熱記録材料の作製
成分Ｉとして、合成例４で合成した化合物４．２ｇと、成分Ｐとして、合成例５で合成した化合物５．７ｇを、それぞれバインダーとして５％ポリビニルアルコール水溶液５０ｍＬとともに、サンドミルで２時間磨砕し、分散液を得た。次いで、成分Ｉの分散液と成分Ｐの分散液を合わせ、これに６０％軽質炭酸カルシウムの水分散液５部を加えよく混合し、感熱発色性組成物を作製した。この感熱発色性組成物を上質紙上に乾燥塗布量が６ｇ／ｍ２ となるように塗布・乾燥し、感熱記録材料を得た。
　この感熱記録材料に実施例１と同様の操作を行って、発色体を形成し、この発色像に対して実施例１と同様の評価試験を行った。結果を表４に示す。 (Example 24) Preparation of heat-sensitive recording material As component I, 4.2 g of the compound synthesized in Synthesis Example 4 and 5.7 g of the compound synthesized in Synthesis Example 5 as Component P were each used as a binder in a 5% aqueous polyvinyl alcohol solution. Along with 50 mL, the mixture was ground with a sand mill for 2 hours to obtain a dispersion. Next, the component I dispersion and the component P dispersion were combined, and 5 parts of a 60% light calcium carbonate aqueous dispersion was added and mixed well to prepare a thermosensitive coloring composition. This thermosensitive color-developing composition was applied and dried on fine paper so that the dry coating amount was 6 g / m 2 to obtain a thermosensitive recording material.
This heat-sensitive recording material was subjected to the same operation as in Example 1 to form a colored body, and the same evaluation test as in Example 1 was performed on this color image. The results are shown in Table 4.
（実施例２５）透明感熱記録材料の作製
実施例１と同じ操作を行って、感熱発色性組成物を作製した。この感熱発色性組成物を厚さ１８０μｍの無色透明なポリエチレンテレフタレートフイルムに、乾燥塗布量が６ｇ／ｍ２となるように塗布・乾燥し、透明度の高い感熱記録材料を得た。この透明感熱記録材料に実施例１と同様の操作を行って、発色体を形成し、この発色像に対して実施例１と同様の評価試験を行った。結果を表４に示す。 (Example 25) Production of transparent thermosensitive recording material The same operation as in Example 1 was carried out to produce a thermosensitive coloring composition. This thermosensitive coloring composition was applied and dried on a colorless and transparent polyethylene terephthalate film having a thickness of 180 μm so that the dry coating amount was 6 g / m 2 to obtain a heat-sensitive recording material having high transparency. The transparent thermosensitive recording material was subjected to the same operation as in Example 1 to form a colored body, and the same evaluation test as in Example 1 was performed on this color image. The results are shown in Table 4.
（比較例１） 感熱記録材料の作製
　実施例１において、成分Ｉとして合成例４で合成した化合物の代わりに、２－アニリノ－３－メチル－６－ジ－ｎ－ブチルアミノフルオラン ５ｇと、成分Ｐとして、合成例５で合成した化合物の代わりに、ビスフェノールＡ ５ｇを用いた以外は実施例１と同様の操作を行って、感熱記録材料及び全面発色像を得た。この発色像は黒色であった。この発色像に対して実施例１と同様の評価試験を行った。結果を表４に示す。 (Comparative Example 1) Preparation of thermosensitive recording material In Example 1, instead of the compound synthesized in Synthesis Example 4 as Component I, 5 g of 2-anilino-3-methyl-6-di-n-butylaminofluorane, As component P, the same operation as in Example 1 was carried out except that 5 g of bisphenol A was used instead of the compound synthesized in Synthesis Example 5 to obtain a heat-sensitive recording material and a full color image. This colored image was black. The same evaluation test as in Example 1 was performed on this color image. The results are shown in Table 4.
Figure JPOXMLDOC01-appb-I000025
Figure JPOXMLDOC01-appb-I000025
Figure JPOXMLDOC01-appb-I000026
　表４から判るように、本発明の感熱発色性組成物を用いた感熱記録材料は、特に発色像の堅牢性に優れるため非常に有用である。
 
Figure JPOXMLDOC01-appb-I000026
As can be seen from Table 4, the heat-sensitive recording material using the heat-sensitive color forming composition of the present invention is very useful because it is particularly excellent in fastness of the color image.
　本発明により、鮮明で高い色濃度を有し、堅牢性が非常に高い発色体を形成する感熱発色性組成物及び該組成物を用いてなる感熱記録材料を提供することが可能になった。また、透明度が高く、高い発色濃度が得られ、画像保存性に優れる透明感熱記録材料を提供することが可能になった。
  According to the present invention, it has become possible to provide a heat-sensitive color-forming composition that forms a colored body having a clear and high color density and extremely high fastness, and a heat-sensitive recording material using the composition. Further, it has become possible to provide a transparent thermosensitive recording material having high transparency, high color density, and excellent image storability.

Claims (7)

  1. 一般式(１)、(２)または(３)で表されるイミノ化合物と、一般式(４)で表されるピロリノン化合物とを含有する感熱発色性組成物。
    Figure JPOXMLDOC01-appb-I000001
    〔式中、環Ｘは置換または無置換の芳香環、置換または無置換の複素環を示し、Ｒ１は水素原子、置換または無置換のアルキル基、置換または無置換のアルケニル基、置換または無置換のアリール基、置換または無置換のアラルキル基を示す。〕
    Figure JPOXMLDOC01-appb-I000002
    〔式中、Ｒ２は置換または無置換のアルキル基を示し、環ＸおよびＲ１は一般式（１）に示したそれらと同義である。〕
    Figure JPOXMLDOC01-appb-I000003
    〔式中、Ｒ３とＲ４はそれぞれ独立して、置換または無置換のアルキル基を示し、Ｒ３とＲ４は結合して環を形成してもよい。環ＸおよびＲ１は一般式（１）に示したそれらと同義である。〕
    Figure JPOXMLDOC01-appb-I000004
    〔式中、Ａは置換または無置換の芳香、置換または無置換の複素環を示し、Ｒ５は置換または無置換のアルキル基、置換または無置換のアルケニル基、置換または無置換のアリール基、置換または無置換のアラルキル基を示す〕     A thermosensitive coloring composition comprising an imino compound represented by general formula (1), (2) or (3) and a pyrrolinone compound represented by general formula (4).
    Figure JPOXMLDOC01-appb-I000001
    [Wherein, ring X represents a substituted or unsubstituted aromatic ring or a substituted or unsubstituted heterocyclic ring, and R 1 represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, substituted or unsubstituted A substituted aryl group, a substituted or unsubstituted aralkyl group is shown. ]
    Figure JPOXMLDOC01-appb-I000002
    [Wherein R 2 represents a substituted or unsubstituted alkyl group, and rings X and R 1 have the same meanings as those shown in formula (1). ]
    Figure JPOXMLDOC01-appb-I000003
    [Wherein, R 3 and R 4 each independently represent a substituted or unsubstituted alkyl group, and R 3 and R 4 may combine to form a ring. Ring X and R 1 have the same meanings as those shown in formula (1). ]
    Figure JPOXMLDOC01-appb-I000004
    [In the formula, A represents a substituted or unsubstituted aromatic group, a substituted or unsubstituted heterocyclic ring, R 5 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, (Represents a substituted or unsubstituted aralkyl group)
  2. 　一般式（１）、（２）および（３）におけるＸが置換または無置換のベンゼン環、置換または無置換のナフタレン環、置換または無置換のアントラセン環、置換または無置換のピリジン環、置換または無置換のピラジン環、置換または無置換のキノリン環、置換または無置換のキノキサリン環、置換または無置換のフェノチアジン環である、請求項１の感熱発色性組成物。 X in the general formulas (1), (2) and (3) is substituted or unsubstituted benzene ring, substituted or unsubstituted naphthalene ring, substituted or unsubstituted anthracene ring, substituted or unsubstituted pyridine ring, substituted or The thermosensitive coloring composition according to claim 1, which is an unsubstituted pyrazine ring, a substituted or unsubstituted quinoline ring, a substituted or unsubstituted quinoxaline ring, or a substituted or unsubstituted phenothiazine ring.
  3. 　一般式（４）におけるＡが置換または無置換のベンゼン環、置換または無置換のナフタレン環、置換または無置換のアントラセン環、置換または無置換のピリジン環、置換または無置換のキノリン環、置換または無置換のピロール環、置換または無置換のインドール環、置換または無置換のチオフェン環、置換または無置換のベンゾチオフェン環、置換または無置換のフラン環、置換または無置換のベンゾフラン環である、請求項１または２の感熱発色性組成物。 In the general formula (4), A is a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted anthracene ring, a substituted or unsubstituted pyridine ring, a substituted or unsubstituted quinoline ring, substituted or An unsubstituted pyrrole ring, a substituted or unsubstituted indole ring, a substituted or unsubstituted thiophene ring, a substituted or unsubstituted benzothiophene ring, a substituted or unsubstituted furan ring, a substituted or unsubstituted benzofuran ring, Item 3. The thermosensitive coloring composition according to item 1 or 2.
  4. 　一般式(１)、(２)または(３)のイミノ化合物と一般式(４)のピロリノン化合物の組成比（モル比）が１：０.５～１：５である、請求項１～３いずれかの感熱発色性組成物。 The composition ratio (molar ratio) of the imino compound of the general formula (1), (2) or (3) and the pyrrolinone compound of the general formula (4) is 1: 0.5 to 1: 5. Any thermosensitive coloring composition.
  5. 　請求項１～４いずれかの感熱発色性組成物を含有する記録層を支持体上に担持させてなる感熱記録材料。 A heat-sensitive recording material comprising a recording layer containing the heat-sensitive color-developing composition according to any one of claims 1 to 4 supported on a support.
  6. 　支持体が紙、合成紙、フィルム、シート、ラミネ－ト紙または不織布である、請求項５の感熱記録材料。 The heat-sensitive recording material according to claim 5, wherein the support is paper, synthetic paper, film, sheet, laminated paper or non-woven fabric.
  7. 　支持体のＨａｚｅ値が１０％以下のプラスチック製フィルムもしくはシートである、請求項５の感熱記録材料。
          The heat-sensitive recording material according to claim 5, wherein the support is a plastic film or sheet having a Haze value of 10% or less.
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US11097951B2 (en) 2016-06-24 2021-08-24 The Regents Of The University Of California Production of carbon-based oxide and reduced carbon-based oxide on a large scale
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