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WO2025244088A1 - Matériau d'impression thermique - Google Patents

Matériau d'impression thermique

Info

Publication number
WO2025244088A1
WO2025244088A1 PCT/JP2025/018506 JP2025018506W WO2025244088A1 WO 2025244088 A1 WO2025244088 A1 WO 2025244088A1 JP 2025018506 W JP2025018506 W JP 2025018506W WO 2025244088 A1 WO2025244088 A1 WO 2025244088A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
formula
compound
recording material
methyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2025/018506
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English (en)
Japanese (ja)
Inventor
秀洋 新井
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Kayaku Co Ltd
Original Assignee
Nippon Kayaku Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Kayaku Co Ltd filed Critical Nippon Kayaku Co Ltd
Publication of WO2025244088A1 publication Critical patent/WO2025244088A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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

Definitions

  • the present invention relates to a heat-sensitive recording material that utilizes color development caused by the reaction between a color-forming dye and a color-developing compound, and to a compound that is suitably used in the heat-sensitive recording material.
  • the present invention relates to a heat-sensitive recording material that preferably has excellent heat resistance in the background and excellent water resistance and/or plasticizer resistance and/or oil resistance in the printed portion, and to a compound that is suitably used for the heat-sensitive recording material.
  • Thermal recording materials are generally made by dispersing a leuco dye and a color-developing compound such as a phenolic compound separately into fine particles, mixing the two, and adding additives such as binders, sensitizers, fillers, and lubricants to obtain a coating liquid, which is then applied to paper, film, synthetic paper, etc.
  • the leuco dye and/or the color-developing compound melt when heated and come into contact, resulting in a chemical reaction that produces a colored record.
  • thermal printers with built-in thermal heads are typically used. Compared to other recording methods, this thermal recording method has the following advantages: (1) no noise during recording, (2) no need for development or fixing, (3) no maintenance, and (4) relatively inexpensive equipment. For these reasons, it is widely used in fields such as facsimiles, computer output, printers for calculators, medical measurement recorders, automatic ticket vending machines, and thermal recording labels.
  • thermal recording materials with excellent thermal response that can adequately accommodate high-speed recording.
  • a color-developing compound with a low melting point and low heat of fusion is required.
  • this property can easily cause the unrecorded areas (background) of the thermal recording material to deteriorate during manufacturing, use, or storage, resulting in the drawback of background fogging (unwanted background color development). Therefore, there is a demand for improved stability as well as high whiteness for the background of thermal recording materials.
  • color-developing compounds containing phenolic hydroxyl groups have high color-developing ability.
  • many bisphenol-based color-developing compounds have been reported due to their high color density, including 2,2-bis(4-hydroxyphenylpropane) (bisphenol A) shown in Patent Document 1 and 4,4'-dihydroxydiphenyl sulfone (bisphenol S) shown in Patent Document 2.
  • bisphenol A 2,2-bis(4-hydroxyphenylpropane
  • bisphenol S 4,4'-dihydroxydiphenyl sulfone
  • these color-developing compounds containing phenolic hydroxyl groups have drawbacks, such as poor thermal response due to their high melting points and poor water resistance of printed areas.
  • the use of phenolic compounds such as bisphenol A has been problematic due to endocrine problems, and there is a demand for non-phenolic color-developing compounds that do not contain a phenol structure.
  • Patent Documents 3 to 6 Various non-phenolic color-developing compounds, such as diphenylurea and sulfonylurea compounds, have been proposed (Patent Documents 3 to 6).
  • thermal recording materials using these color-developing compounds have poor thermal stability of the background and low plasticizer resistance in the printed area.
  • These compounds have the drawback of causing the colored recording to fade or disappear when exposed to heat for a relatively short period of time or when used as food labels, placing certain limitations on expanding their applications. Therefore, no color-developing compounds have yet been found that can satisfy the market's demands in a balanced manner.
  • a compound with a specific structure can solve the above-mentioned problems, and that a thermal recording material using this compound as a color-developing compound has excellent heat resistance in the background and excellent water resistance, plasticizer resistance, and/or oil resistance in the printed area, preferably all of these properties, and have thus completed the present invention.
  • a heat-sensitive recording material comprising at least one compound represented by the following general formula (1): (In the formula, R 1 to R 10 , R 21 , and R 22 each independently represent a hydrogen atom, a halogen atom, a nitro group, an amino group, an alkyl group, a hydroxy group, an alkoxy group, an aryloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, an alkylcarbonylamino group, an arylcarbonylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, a monoalkylamino group, a dialkylamino group, or an arylamino group.) [2] The heat-sensitive recording material according to the above [1], wherein in the formula (1), two or more of R 1 to R 5 are hydrogen atoms, and two or more of R 1 to R 5 are hydrogen atoms, and two or more of R 1 to R 5
  • thermosensitive recording material according to the above [1], wherein in the formula (1), R 4 and R 5 are hydrogen atoms, and R 9 and R 10 are hydrogen atoms, and R 1 to R 3 , R 6 to R 8 , R 21 and R 22 are as defined above.
  • R 3 and R 8 are each independently a hydrogen atom or an alkyl group, and R 1 , R 2 , R 4 to R 7 , R 9 , R 10 , R 21 and R 22 are each a hydrogen atom.
  • a thermosensitive recording layer comprising the thermosensitive recording material according to any one of the above [1] to [4].
  • thermosensitive recording paper or a thermosensitive film comprising the thermosensitive recording layer according to the above item [5].
  • thermosensitive recording material that has excellent heat resistance in the background and excellent water resistance and/or plasticizer resistance and/or oil resistance in the printed area. Because of the excellent properties described above, such a thermosensitive recording material can be suitably used for a thermosensitive recording layer, and for thermosensitive recording paper or thermosensitive film containing a thermosensitive recording layer.
  • a novel compound represented by general formula (2) which can be used as a color-developing compound.
  • the present invention relates to a heat-sensitive recording material which contains a color-forming compound which is usually colorless or pale in color, and a color-developing compound represented by the above formula (1), and optionally contains other color-developing compounds, sensitizers, storage stability improvers, and further contains the binders shown below, and optionally fillers, other additives, etc.
  • Examples of the halogen atom in R 1 to R 10 , R 21 , and R 22 in formula (1) include a fluorine atom, a chlorine atom, and a bromine atom, with a fluorine atom and a chlorine atom being preferred.
  • the alkyl groups represented by R 1 to R 10 , R 21 , and R 22 in formula (1) include linear, branched, and cyclic alkyl groups. Among these, linear or branched groups are preferred, and linear groups are even more preferred.
  • the carbon number range is usually C1 to C12, preferably C1 to C8, more preferably C1 to C6, and even more preferably C1 to C4.
  • alkyl group examples include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, n-undecyl, and n-dodecyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, t-butyl, isopentyl, isohexyl, and isooctyl; and cyclic alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
  • preferred are methyl, ethyl, and n-propyl, more preferred are methyl and ethyl, and particularly preferred is methyl.
  • the alkoxy groups in R 1 to R 10 , R 21 , and R 22 in formula (1) include linear, branched, and cyclic alkoxy groups. Of these, linear or branched alkoxy groups are preferred, and linear alkoxy groups are more preferred.
  • the carbon number range is usually C1 to C12, preferably C1 to C8, more preferably C1 to C6, and even more preferably C1 to C4.
  • alkoxy group examples include straight-chain alkoxy groups such as methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy, n-hexyloxy, n-heptoxy, n-octyloxy, n-nonyloxy, and n-decyloxy; branched-chain (preferably C3 to C10) alkoxy groups such as isopropoxy, isobutoxy, sec-butoxy, t-butoxy, isoamyloxy, t-amyloxy, isohexyloxy, t-hexyloxy, isoheptoxy, t-heptoxy, isooctyloxy, t-octyloxy, 2-ethylhexyloxy, isononyloxy, and isodecyloxy; and cyclic (preferably C3 to C7) alkoxy groups such as cyclopropoxy, cyclobutoxy, cyclopentoxy,
  • the aryloxy group in R 1 to R 10 , R 21 , and R 22 in formula (1) is not particularly limited as long as it has a structure in which an aromatic hydrocarbon is bonded via an oxygen atom.
  • the aromatic hydrocarbon can be arbitrarily selected from, for example, a monocyclic structure, a polycyclic structure, a fused ring structure, a heterocyclic structure, and the like.
  • Examples of aromatic hydrocarbons constituting the aryloxy group include benzene, pyrrole, thiophene, furan, naphthalene, anthracene, biphenyl, indole, and the like. These aromatic hydrocarbons may further have a substituent.
  • the aryloxy group in R 1 may be, for example, phenoxy, naphthyloxy, anthracenoxy, halogenated phenoxy, alkylphenoxy, biphenoxy, and the like.
  • it may be a C6 to C12 aryloxy group, and specific examples include phenoxy, naphthyloxy, biphenoxy, and the like.
  • the alkylcarbonyloxy group in R 1 to R 10 , R 21 , and R 22 in formula (1) may be a linear, branched, or cyclic alkylcarbonyloxy group, and may be preferably a C1 to C10 alkylcarbonyloxy group.
  • alkylcarbonyloxy group examples include linear ones such as methylcarbonyloxy, ethylcarbonyloxy, n-propylcarbonyloxy, n-butylcarbonyloxy, n-pentylcarbonyloxy, n-hexylcarbonyloxy, n-heptylcarbonyloxy, n-octylcarbonyloxy, n-nonylcarbonyloxy, and n-decylcarbonyloxy; isopropylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, t-butylcarbonyloxy, isoamylcarbonyloxy, t-amylcarbonyloxy, and iso Branched chain (preferably C3 to C10) alkylcarbonyloxy groups such as hexylcarbonyloxy, t-hexylcarbonyloxy, isoheptylcarbonyloxy, t-hepty
  • the arylcarbonyloxy groups represented by R 1 to R 10 , R 21 , and R 22 in formula (1) may preferably be C6 to C12 arylcarbonyloxy groups.
  • Specific examples of the arylcarbonyloxy groups include phenylcarbonyloxy, naphthylcarbonyloxy, and biphenylcarbonyloxy. Of these, the phenylcarbonyloxy group is preferred.
  • the alkylcarbonylamino group in R 1 to R 10 , R 21 , and R 22 in formula (1) includes a linear, branched, or cyclic alkylcarbonylamino group, and is preferably a C1 to C10 alkylcarbonylamino group.
  • alkylcarbonylamino group examples include linear ones such as methylcarbonylamino, ethylcarbonylamino, n-propylcarbonylamino, n-butylcarbonylamino, n-pentylcarbonylamino, n-hexylcarbonylamino, n-heptylcarbonylamino, n-octylcarbonylamino, n-nonylcarbonylamino, and n-decylcarbonylamino; isopropylcarbonylamino, isobutylcarbonylamino, sec-butylcarbonylamino, t-butylcarbonylamino, isoamylcarbonylamino, t-amylcarbonylamino, and iso
  • alkylcarbonylamino group examples include branched (preferably C3 to C10) groups such as hexylcarbonylamino, t-hexy
  • linear or branched alkylcarbonylamino groups are preferably linear alkylcarbonylamino groups.
  • linear alkylcarbonylamino groups preferred are methylcarbonylamino, ethylcarbonylamino, and n-propylcarbonylamino groups, more preferably methylcarbonylamino and ethylcarbonylamino groups, and particularly preferably methylcarbonylamino groups.
  • the arylcarbonylamino groups represented by R 1 to R 10 , R 21 , and R 22 in formula (1) may preferably be C6 to C12 arylcarbonylamino groups.
  • Specific examples of the arylcarbonylamino group include a phenylcarbonylamino group, a naphthylcarbonylamino group, and a biphenylcarbonylamino group. Of these, the phenylcarbonylamino group is preferred.
  • the alkylsulfonylamino groups in R 1 to R 10 , R 21 , and R 22 in formula (1) may be linear, branched, or cyclic alkylsulfonylamino groups, and may preferably be C1 to C10 alkylsulfonylamino groups.
  • alkylsulfonylamino group examples include linear ones such as methylsulfonylamino, ethylsulfonylamino, n-propylsulfonylamino, n-butylsulfonylamino, n-pentylsulfonylamino, n-hexylsulfonylamino, n-heptylsulfonylamino, n-octylsulfonylamino, n-nonylsulfonylamino, and n-decylsulfonylamino; branched-chain (preferably C3 to C10) sulfonylamino groups such as 2-ethylhexylsulfonylamino, t-hexylsulfonylamino, isoheptylsulfonylamino, t-heptyls
  • the arylsulfonylamino groups represented by R 1 to R 10 , R 21 , and R 22 in formula (1) may preferably be C6 to C12 arylsulfonylamino groups.
  • Specific examples of the arylsulfonylamino group include phenylsulfonylamino, toluenesulfonylamino, naphthylsulfonylamino, and biphenylsulfonylamino.
  • the monoalkylamino group in R 1 to R 10 , R 21 , and R 22 in formula (1) may be a linear, branched, or cyclic monoalkylamino group, and is preferably a mono C1 to C10 alkylamino group.
  • monoalkylamino groups include straight-chain ones such as methylamino, ethylamino, n-propylamino, n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-nonylamino, and n-decylamino; branched-chain (preferably C3 to C10) ones such as isopropylamino, isobutylamino, sec-butylamino, t-butylamino, isoamylamino, t-amylamino, isohexylamino, t-hexylamino, isoheptylamino, t-heptylamino, isooctylamino, t-octylamino, 2-ethylhexylamino, isononylamino,
  • dialkylamino groups in R 1 to R 10 , R 21 , and R 22 in formula (1) may be linear, branched, or cyclic dialkylamino groups, and are preferably C1 to C10 dialkylamino groups.
  • Specific examples of dialkylamino groups include linear ones such as dimethylamino, diethylamino, di-n-propylamino, di-n-butylamino, di-n-pentylamino, di-n-hexylamino, di-n-heptylamino, di-n-octylamino, di-n-nonylamino, and di-n-decylamino; diisopropylamino, diisobutylamino, di-sec-butylamino, di-t-butylamino, diisoamylamino, di-t-amylamino, diisohexylamino, and di-t-heptylamino
  • the arylamino groups in R 1 to R 10 , R 21 , and R 22 in formula (1) may be monoarylamino groups or diarylamino groups, and are preferably mono- or di-C6 to C12 arylamino groups.
  • Specific examples of the arylamino group include phenylamino (anilino), naphthylamino, biphenylamino, diphenylamino, dinaphthylamino, and di(biphenyl)amino.
  • the substituents R 1 to R 10 are particularly preferably a hydrogen atom, a methyl group, or a phenyl group.
  • R 3 and R 8 are each independently a hydrogen atom or an alkyl group, and R 1 , R 2 , R 4 to R 7 , R 9 and R 10 are each a hydrogen atom.
  • R 3 and R 8 are hydrogen atoms or methyl groups, and R 1 , R 2 , R 4 to R 7 , R 9 and R 10 are hydrogen atoms.
  • R 1 to R 10 are all hydrogen atoms.
  • the compound represented by formula (1) according to the present invention may be any of the compounds listed as specific examples in Tables 1 to 6 below, but is not limited to these.
  • the compound represented by the above formula (1) can be synthesized by any of the following four methods, although there is no particular limitation. ⁇ Manufacturing method 1> The compound represented by the above formula (1) can be synthesized according to the following reaction route.
  • R 1 to R 10 , R 21 , and R 22 in the above formulas [1-1] to [1-3] have the same meanings as R 1 to R 10 , R 21 , and R 22 in the above formula (1).
  • Compounds of general formula [1-2] can be produced by reacting compounds of general formula [1-1] with phosgene or triphosgene, urea, or chloroformate, in the presence or absence of a base.
  • the compound of formula [1-1] is available, for example, as sulfanilic acid from Tokyo Chemical Industry Co., Ltd. (see Chemical Communications (Cambridge, United Kingdom) (2020), 56(18), 2735-2738; Communications (2018), 48(3), 247-254).
  • the solvent used in this reaction is not particularly limited, so long as it does not affect the reaction.
  • solvents include amides such as N,N-dimethylformamide, N,N-dimethylacetamide, or N-methylpyrrolidone; halogenated hydrocarbons such as methylene chloride or chloroform; aromatic hydrocarbons such as toluene, xylene, or mesitylene; ethers such as dioxane, tetrahydrofuran, anisole, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, or diethylene glycol diethyl ether; nitriles such as acetonitrile; ketones such as acetone or 2-butanone; esters such as ethyl acetate or butyl acetate; sulfones such as sulfolane; sulfoxides such as dimethyl sulfoxide; and water. Two or more of these solvents may
  • the amount of phosgene or triphosgene, urea, or chloroformate used in this reaction is typically 0.1 to 50 times the molar amount of the compound of general formula [1-1], preferably 0.2 to 20 times the molar amount, and more preferably 0.4 to 1.3 times the molar amount.
  • the base optionally used in this reaction includes, for example, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium carbonate, or cesium carbonate; and organic bases such as triethylamine or diisopropylethylamine.
  • inorganic bases such as sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium carbonate, or cesium carbonate
  • organic bases such as triethylamine or diisopropylethylamine.
  • the amount of these bases used may be 0.01 to 50 times the molar amount of the compound of general formula [1-1], and preferably 0.1 to 2 times the molar amount.
  • the reaction temperature for this reaction may typically be -10 to 250°C, with 0 to 200°C being preferred.
  • the reaction may be carried out for, for example, 10 minutes to 48 hours.
  • the compound of the formula [1-3] can be produced by reacting the compound of the general formula [1-2] with phosphorus oxychloride, thionyl chloride, chlorosulfonic acid, oxalyl chloride, phosphorus pentachloride, or the like in the presence or absence of a base to obtain a sulfonyl chloride, which is then reacted with a phenol, or by a method of reacting the compound of the general formula [1-2] with a phenol by direct dehydration condensation.
  • the solvent used in this reaction is not particularly limited as long as it does not affect the reaction.
  • the solvent examples include amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; halogenated hydrocarbons such as methylene chloride and chloroform; aromatic hydrocarbons such as benzene, toluene, and xylene; ethers such as dioxane, tetrahydrofuran, anisole, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, and diethylene glycol diethyl ether; nitriles such as acetonitrile; ketones such as acetone and 2-butanone, esters such as ethyl acetate and butyl acetate; sulfones such as sulfolane; sulfoxides such as dimethyl sulfoxide; and water. Two or more of these solvents may be used in combination.
  • the amount of the phenol used in this reaction may be 0.1 to 50 times by mole, preferably 0.7 to 3 times by mole, relative to the compound of the general formula [1-2].
  • the reaction temperature for this reaction may usually be ⁇ 78 to 200° C., preferably ⁇ 20 to 120° C.
  • the reaction may be carried out for, for example, 10 minutes to 24 hours.
  • the compound of general formula [2-2] can be produced by reacting the compound of general formula [2-1] with phosgene, triphosgene, urea, a chloroformate, or the like in the presence or absence of a base.
  • the compound of formula [2-1] can be synthesized by a known method using aminobenzenesulfonic acid (obtained from Tokyo Chemical Industry Co., Ltd.) and a phenolic compound as starting materials.
  • the solvent used in this reaction is not particularly limited as long as it does not affect the reaction.
  • the solvent examples include amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; halogenated hydrocarbons such as methylene chloride and chloroform; aromatic hydrocarbons such as toluene, xylene, and mesitylene; ethers such as dioxane, tetrahydrofuran, anisole, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, and diethylene glycol diethyl ether; nitriles such as acetonitrile; ketones such as acetone and 2-butanone; esters such as ethyl acetate and butyl acetate; sulfones such as sulfolane; sulfoxides such as dimethyl sulfoxide; and water. Two or more of these solvents may be mixed and used.
  • the base optionally used in this reaction includes, for example, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium carbonate, or cesium carbonate; and organic bases such as triethylamine or diisopropylethylamine.
  • inorganic bases such as sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium carbonate, or cesium carbonate
  • organic bases such as triethylamine or diisopropylethylamine.
  • the amount of these bases used may be 0.01 to 50 times the molar amount of the compound of general formula [2-1], and preferably 0.1 to 2 times the molar amount.
  • the reaction temperature for this reaction may typically be -10 to 250°C, with 0 to 200°C being preferred.
  • the reaction may be carried out for, for example, 10 minutes to 48 hours.
  • the compound of general formula [3-3] can be produced by reacting the compound of general formula [3-1] with the compound of general formula [3-2] in the presence or absence of a base.
  • the compound of formula [3-1] can be synthesized by a known method using the compound of formula [2-1] as a starting material.
  • the solvent used in this reaction is not particularly limited as long as it does not affect the reaction.
  • the solvent examples include amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; halogenated hydrocarbons such as methylene chloride and chloroform; aromatic hydrocarbons such as toluene, xylene, and mesitylene; ethers such as dioxane, tetrahydrofuran, anisole, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, and diethylene glycol diethyl ether; nitriles such as acetonitrile; ketones such as acetone and 2-butanone; esters such as ethyl acetate and butyl acetate; sulfones such as sulfolane; sulfoxides such as dimethyl sulfoxide; and water. Two or more of these solvents may be mixed and used.
  • the base optionally used in this reaction includes, for example, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium carbonate, or cesium carbonate; and organic bases such as triethylamine or diisopropylethylamine.
  • inorganic bases such as sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium carbonate, or cesium carbonate
  • organic bases such as triethylamine or diisopropylethylamine.
  • the amount of these bases used may be 0.01 to 50 times the molar amount of the compound of general formula [3-1], and preferably 0.1 to 2 times the molar amount.
  • the reaction temperature for this reaction may typically be between -10 and 200°C, with 0 to 120°C being preferred.
  • the reaction may be carried out for, for example, 10 minutes to 24 hours.
  • R 1 to R 10 , R 21 , and R 22 in the above formulas [4-1] to [4-3] have the same meanings as R 1 to R 10 , R 21 , and R 22 in the above formula (1).
  • R 11 represents an alkyl group or an aryl group. Specifically, R 11 may be, for example, a methyl group, an ethyl group, a phenyl group, a chlorophenyl group, a nitrophenyl group, or the like. R 11 is not particularly limited as long as it is a group that does not interfere with the synthesis of the compound [4-3].
  • the compound of general formula [4-3] can be produced by reacting the compound of general formula [4-1] with the compound of general formula [4-2] in the presence or absence of a base.
  • the compound of formula [4-1] can be synthesized by a known method using the compound of formula [2-1] or [3-1] as a starting material.
  • the solvent used in this reaction is not particularly limited as long as it does not affect the reaction.
  • the solvent examples include amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; halogenated hydrocarbons such as methylene chloride and chloroform; aromatic hydrocarbons such as toluene, xylene, and mesitylene; ethers such as dioxane, tetrahydrofuran, anisole, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, and diethylene glycol diethyl ether; nitriles such as acetonitrile; ketones such as acetone and 2-butanone; esters such as ethyl acetate and butyl acetate; sulfones such as sulfolane; sulfoxides such as dimethyl sulfoxide; and water. Two or more of these solvents may be used in combination.
  • the base optionally used in this reaction includes, for example, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium carbonate, and cesium carbonate; and organic bases such as triethylamine and diisopropylethylamine.
  • inorganic bases such as sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium carbonate, and cesium carbonate
  • organic bases such as triethylamine and diisopropylethylamine.
  • the amount of these bases used may be 0.01 to 50 times the molar amount of the compound of general formula [4-1], and preferably 0.1 to 2 times the molar amount.
  • the reaction temperature for this reaction may typically be between -10 and 200°C, with 0 to 120°C being preferred.
  • the reaction may be carried out for, for example, 10 minutes to 24 hours.
  • the heat-sensitive recording material of the present invention usually contains a color-developing compound including the compound shown in (1) above, and a color-forming compound, and may further optionally contain known color-developing compounds other than those mentioned above, sensitizers, binders, storage stability improvers, fillers, and other additives.
  • the color-forming compound is typically used in an amount of 1 to 50% by weight, preferably 5 to 30% by weight
  • the compound represented by formula (1) is typically used in an amount of 1 to 70% by weight, preferably 10 to 50% by weight
  • the sensitizer is typically used in an amount of 0 to 80% by weight, preferably 1 to 80% by weight
  • the storage stability improver is typically used in an amount of 0 to 30% by weight
  • the binder is typically used in an amount of 0 to 90% by weight, preferably 1 to 90% by weight
  • the filler is typically used in an amount of 0 to 80% by weight
  • other lubricants, surfactants, antifoaming agents, and ultraviolet absorbers are each used in an optional proportion, for example, 0 to 30% by weight (here, "% by weight” refers to the weight proportion of each component in the thermosensitive color-forming layer).
  • the total content of the color-forming compound, the compound represented by formula (1), and other optional components constituting the thermosensitive recording material is 100% by
  • the compound represented by formula (1) can be used in a mass ratio of typically 0.5 to 20 times, more preferably 1 to 5 times, the mass of the color-forming compound.
  • the color-forming compound used in the present invention is not particularly limited, as long as it is generally used in pressure-sensitive recording paper or heat-sensitive recording paper.
  • the color-forming compound used include fluoran-based compounds, triarylmethane-based compounds, spiro-based compounds, diphenylmethane-based compounds, thiazine-based compounds, lactam-based compounds, and fluorene-based compounds.
  • fluoran-based compounds are preferred.
  • fluoran compounds include 3-diethylamino-6-methyl-7-anilinofluoran, 3-dibutylamino-6-methyl-7-anilinofluoran, 3-(N-methyl-N-cyclohexylamino)-6-methyl-7-anilinofluoran, 3-(N-ethyl-N-isopentylamino)-6-methyl-7-anilinofluoran, 3-(N-ethyl-N-isobutylamino)-6-methyl-7-anilinofluoran, 3-[N-ethyl-N-(3-ethoxypropyl)amino ]-6-methyl-7-anilinofluoran, 3-(N-ethyl-N-hexylamino)-6-methyl-7-anilinofluoran, 3-dipentylamino-6-methyl-7-anilinofluoran, 3-(N-methyl-N-propylamino)-6-methyl-7-anilinoflu
  • triarylmethane compounds include 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide (also known as crystal violet lactone or CVL), 3,3-bis(p-dimethylaminophenyl)phthalide, 3-(p-dimethylaminophenyl)-3-(1,2-dimethylaminoindol-3-yl)phthalide, 3-(p-dimethylaminophenyl)-3-(2-methylindol-3-yl)phthalide, and 3-(p-dimethylaminophenyl)-3-(2-phenylindol-3-yl).
  • Examples include 3,3-bis(1,2-dimethylindol-3-yl)phthalide, 3,3-bis(1,2-dimethylindol-3-yl)-5-dimethylaminophthalide, 3,3-bis(1,2-dimethylindol-3-yl)-6-dimethylaminophthalide, 3,3-bis(9-ethylcarbazol-3-yl)-5-dimethylaminophthalide, 3,3-(2-phenylindol-3-yl)-5-dimethylaminophthalide, and 3-p-dimethylaminophenyl-3-(1-methylpyrrol-2-yl)-6-dimethylaminophthalide.
  • spiro compounds include 3-methylspirodinaphthopyran, 3-ethylspirodinaphthopyran, 3,3'-dichlorospirodinaphthopyran, 3-benzylspirodinaphthopyran, 3-propylspirobenzopyran, 3-methylnaphtho-(3-methoxybenzo)spiropyran, 1,3,3-trimethyl-6-nitro-8'-methoxyspiro(indoline-2,2'-benzopyran), and the like.
  • diphenylmethane compounds include N-halophenyl-leucoauramine, 4,4-bis-dimethylaminophenyl benzhydryl benzyl ether, and N-2,4,5-trichlorophenyl leucoauramine.
  • thiazine compounds include benzoyl leucomethylene blue, p-nitrobenzoyl leucomethylene blue, and the like.
  • lactam compounds include rhodamine B anilinolactam and rhodamine B p-chloroanilinolactam.
  • fluorene compounds include 3,6-bis(dimethylamino)fluorene spiro(9,3')-6'-dimethylaminophthalide, 3,6-bis(dimethylamino)fluorene spiro(9,3')-6'-pyrrolidinophthalide, and 3-dimethylamino-6-diethylaminofluorene spiro(9,3')-6'-pyrrolidinophthalide. These color-forming compounds may be used alone or in combination of two or more.
  • thermosensitive recording material of the present invention contains the compound represented by formula (1) as a color-developing compound, but may also use one or a mixture of two or more other color-developing compounds in combination.
  • the color-developing compounds that can be used in combination with the compound represented by formula (1) are not particularly limited, and may be any compounds commonly used in pressure-sensitive recording paper or thermosensitive recording paper.
  • color-developing compounds examples include ⁇ -naphthol, ⁇ -naphthol, p-octylphenol, 4-t-octylphenol, p-t-butylphenol, p-phenylphenol, 1,1-bis(p-hydroxyphenyl)propane, 2,2-bis(p-hydroxyphenyl)propane (also known as bisphenol A or BPA), 2,2-bis(p-hydroxyphenyl)butane, 1,1-bis(p-hydroxyphenyl)cyclohexane, 4,4'-thiobisphenol, 4,4'- Cyclohexylidene diphenol, 2,2'-bis(2,5-dibromo-4-hydroxyphenyl)propane, 4,4'-isopropylidenebis(2-t-butylphenol), 2,2'-methylenebis(4-chlorophenol), 4,4'-dihydroxydiphenyl sulfone, 4-hydroxy-4'-methoxydiphenyl
  • sensitizers heat-fusible compounds
  • waxes such as animal and vegetable waxes and synthetic waxes
  • higher fatty acids such as animal and vegetable waxes and synthetic waxes
  • higher fatty acid such as animal and vegetable waxes and synthetic waxes
  • higher fatty acid such as animal and vegetable waxes and synthetic waxes
  • higher fatty acid such as animal and vegetable waxes and synthetic waxes
  • higher fatty acid such as animal and vegetable waxes and synthetic waxes
  • higher fatty acids such as animal and vegetable waxes and synthetic waxes
  • higher fatty acid amides such as higher fatty acid anilides
  • naphthalene derivatives such as aromatic ethers
  • aromatic carboxylic acid derivatives such as aromatic sulfonic acid ester derivatives
  • carbonic acid or oxalic acid diester derivatives such as biphenyl derivatives, terphenyl derivatives, sulfonic acid derivatives, aromatic ketone derivatives, aromatic hydrocarbon compounds, etc.
  • naphthalene derivatives include, for example, 1-benzyloxynaphthalene, 2-benzyloxynaphthalene, 1-hydroxynaphthoic acid phenyl ester, 2,6-diisopropylnaphthalene, etc.
  • aromatic ethers include, for example, 1,2-diphenoxyethane, 1,4-diphenoxybutane, 1,2-bis(3-methylphenoxy)ethane, 1,2-bis(4-methoxyphenoxy)ethane, 1,2-bis(3,4-dimethylphenyl)ethane, 1-phenoxy-2-(4-chlorophenoxy)ethane, 1-phenoxy-2-(4-methoxyphenoxy)ethane, 1,2-diphenoxymethyl ethylbenzene, diphenyl glycol, etc.; aromatic carboxylic acid derivatives, for example, p-hydroxybenzoic acid benzyl ester, p-benzyloxybenzoic acid benzyl ester,
  • ⁇ Storability improver> Specific examples of the storage stability improver that may be used in the heat-sensitive recording material of the present invention include 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2,2'-ethylidenebis(4,6-di-tert-butylphenol), 4,4'-thiobis(2-methyl-6-tert-butylphenol), 4,4'-butylidenebis(6-tert-butyl-m-cresol), 1-[ ⁇ -methyl- ⁇ -(4'-hydroxyphenyl)ethyl]-4-[ ⁇ ', ⁇ '-bis(4'-hydroxyphenyl)ethyl]benzene, 1,1,3-tris(2-methyl-4-hydroxy-5-cyclohexylphenyl)butane, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butan
  • a is an integer of 0 to 6.
  • binders include acrylic acid ester copolymers, styrene/(meth)acrylic acid ester copolymers, poly
  • fillers that may be used in the present invention include calcium carbonate, magnesium carbonate, magnesium oxide, silica, white carbon, talc, clay, alumina, magnesium hydroxide, aluminum hydroxide, aluminum oxide, barium sulfate, polystyrene resin, urea-formalin resin, etc. These fillers may be used alone or as a mixture of two or more.
  • additives other than those mentioned above can also be used in the present invention.
  • additives include higher fatty acid metal salts such as zinc stearate and calcium stearate for purposes such as preventing thermal head wear and sticking, ultraviolet absorbers such as phenol derivatives, benzophenone compounds, and benzotriazole compounds for providing antioxidant or anti-aging effects, various surfactants, and antifoaming agents. These additives may be used alone or in combination.
  • thermosensitive recording material A typical example of a method for preparing the thermosensitive recording material of the present invention will now be described.
  • the color-forming compound and the compound represented by formula (1) used in the present invention are separately pulverized and dispersed in a disperser such as a ball mill, attritor, or sand mill together with a binder and, if necessary, other additives to prepare dispersions (usually, water is used as the medium when pulverization or dispersion is carried out wet), and these dispersions are then mixed to prepare a thermosensitive recording material coating solution, which is then coated onto a support such as paper (plain paper, wood-free paper, coated paper, etc.), a plastic sheet, or synthetic paper using a bar coater, blade coater, or the like to a dry weight of 0.1 to 20 g/ m2 , and then dried to produce a thermosensitive recording layer containing the thermosensitive recording material of the present invention, and thermosensitive recording paper or thermosensitive recording film having the thermosensitive recording
  • thermosensitive recording paper or thermosensitive recording film of the present invention can be produced by a process including, for example, pulverizing and dispersing the above-mentioned binder and/or other additives as needed in the same manner as in the preparation of the thermosensitive recording material coating solution to prepare an intermediate layer coating solution or an overcoat layer (protective layer) coating solution, and then coating the resulting coating solution to a dry weight of usually about 0.1 to 10 g/m2, and drying it.
  • Example 1 Synthesis of Compound No. 1 in Table 1 [Step 1] To 100 parts of DMF, 100.0 parts of 3-aminobenzenesulfonic acid (the above-mentioned compound [1-1]: obtained from Tokyo Chemical Industry Co., Ltd.) and 40 parts of urea were added, and the mixture was stirred at 160°C for 12 hours. Then, the reaction solution was added dropwise to 250 parts of water to precipitate crystals. The crystals were washed successively with methanol and water, and dried, to obtain 70 parts of the above-mentioned compound [1-2] as a pale yellowish white solid. MS (ESI): [MH] - : cal. :371.4, found:371.4.
  • Step 2 30.0 parts of compound [1-2] was added to 100 parts of DMF and stirred, and then 22 parts of thionyl chloride was added dropwise and reacted at room temperature for 2 hours. Next, a DMF solution of 35 parts of phenol was added, and the mixture was stirred at 65°C for 2 hours. The reaction solution was then added dropwise to 250 parts of water to precipitate crystals. The precipitate was separated by filtration, washed with methanol and water, and dried to obtain the compound [1-3] (32 parts) as a pale yellowish white solid.
  • Example 2 Preparation of thermal recording material Compound No. 1 shown in Table 1, obtained in Example 1, was pulverized and dispersed for 1 hour using a Multi-Beads Shocker (model: PV1001(S)) manufactured by Yasui Kikai Co., Ltd. in the following composition to prepare the following solution [A].
  • a Multi-Beads Shocker model: PV1001(S) manufactured by Yasui Kikai Co., Ltd. in the following composition to prepare the following solution [A].
  • a mixture of the following composition was pulverized and dispersed using a sand grinder so that the median particle size measured with a laser diffraction/scattering particle size distribution analyzer LA-950 (manufactured by Horiba, Ltd.) was 1 ⁇ m, thereby preparing a dispersion liquid [B] of a color-forming compound.
  • thermosensitive recording layer (Formation of protective layer) Next, a protective layer coating solution having the following composition was applied onto the thermosensitive recording layer so that the dry weight was 2 g/m 2 , and then dried to prepare a thermosensitive recording layer with a protective layer.
  • Comparative Example 1 A mixture of the following composition was ground and dispersed using a sand grinder to a median particle size of 1 ⁇ m as measured with a laser diffraction/scattering particle size distribution analyzer LA-950 (manufactured by Horiba, Ltd.) to prepare solution [C].
  • a comparative thermosensitive recording paper was obtained in the same manner as in Example 1, except that solution [C] was used in place of solution [A] of the thermosensitive recording layer coating solution described in Example 2 above, and mixed in the following composition ratio to prepare a thermosensitive recording material coating solution.
  • Example 2 and Comparative Example 1 were printed using a thermal printer (TH-M2/PP) manufactured by Okura Engineering Co., Ltd. with a pulse width of 1.2 msec, and the samples were immersed in water at 25°C for 24 hours.
  • the Macbeth reflection density of the printed area (colored area) of the samples before and after the test was measured using a colorimeter manufactured by Gretag-Macbeth Co., Ltd., trade name "SpectroEye.” Color measurements were performed using Illuminant C as the light source, ANSI A as the density standard, and a viewing angle of 2 degrees. The results are shown in Table 7 below. It can be seen that the higher the retention rate in this test, the better the water resistance.
  • Residual rate (%) [(Macbeth reflection density of the printed portion of the sample after the test) / (Macbeth reflection density of the printed portion of the sample before the test)] ⁇ 100 (I)
  • Example 2 which used the compound represented by formula (1) above as the color-developing compound, had a higher survival rate in the above test than Comparative Example 1, which used bisphenol S, a color-developing compound described in Patent Document 2.
  • This means that the present invention can be said to provide superior water resistance in printed areas compared to conventional technology.
  • Example 2 in which the compound of the present invention was used as the color-developing compound, showed a smaller change in ISO whiteness in the above test than Comparative Example 1, in which bisphenol S, a color-developing compound described in Patent Document 2, was used. This means that the present invention can be said to have superior heat resistance in the background area compared to conventional technology.
  • the Macbeth reflection density of the printed area of the sample before and after the test was measured using a colorimeter manufactured by GRETAG-MACBETH, trade name "SpectroEye.” All color measurements were performed using Illuminant C as the light source, ANSI A as the density standard, and a viewing angle of 2 degrees.
  • Example 2 in which the compound of the present invention was used as the developer, had a higher retention rate in the above test than Comparative Example 1, in which bisphenol S, a developer compound described in Patent Document 2, was used. It can be said that the present invention provides superior plasticizer resistance in printed areas compared to conventional technology.
  • Residual rate (%) [(reflection density of printed area after test) / (reflection density of printed area before test)] x 100 The results are shown in Table 10 below.
  • Example 2 in which the compound of the present invention was used as the color-developing compound, had a higher retention rate in the above test than Comparative Example 1, in which bisphenol S, a color-developing compound described in Patent Document 2, was used.
  • This means that the present invention can be said to provide superior oil resistance in printed areas compared to conventional technology.
  • the present invention provides a thermal recording material that has excellent heat resistance in the background, as well as water resistance, plasticizer resistance, and oil resistance in the printed area, and overcomes the drawback of color recording fading and disappearance under various conditions. This opens up the possibility of developing a wide range of applications for non-phenolic thermal recording materials, including food labels.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)

Abstract

Est divulgué ici un matériau d'impression thermique caractérisé en ce qu'il comprend au moins un composé représenté par la formule générale (1). (Dans la formule (1), les R1 à R10, ainsi que R21 et R22 représentent chacun indépendamment un atome d'hydrogène, un atome d'halogène, un groupe nitro, un groupe amino, un groupe alkyle, un groupe hydroxy, un groupe alcoxy, un groupe aryloxy, un groupe alkylcarbonyloxy, un groupe arylcarbonyloxy, un groupe alkylcarbonylamino, un groupe arylcarbonylamino, un groupe alkylsulfonylamino, un groupe arylsulfonylamino, un groupe monoalkylamino, un groupe dialkylamino ou un groupe arylamino). Dans la formule (1), deux groupes ou plus parmi les R1 à R5 peuvent être des atomes d'hydrogène et deux groupes ou plus parmi les R6 à R10 peuvent être des atomes d'hydrogène. Dans la formule (1), R4 et R5 peuvent être des atomes d'hydrogène et R9 et R10 peuvent être des atomes d'hydrogène.
PCT/JP2025/018506 2024-05-22 2025-05-22 Matériau d'impression thermique Pending WO2025244088A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019044462A1 (fr) * 2017-08-31 2019-03-07 三光株式会社 Dérivé de n,n'-diarylurée, son procédé de fabrication, et matériau d'enregistrement thermosensible l'utilisant
WO2022045287A1 (fr) * 2020-08-27 2022-03-03 日本化薬株式会社 Matériau d'enregistrement thermosensible

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019044462A1 (fr) * 2017-08-31 2019-03-07 三光株式会社 Dérivé de n,n'-diarylurée, son procédé de fabrication, et matériau d'enregistrement thermosensible l'utilisant
WO2022045287A1 (fr) * 2020-08-27 2022-03-03 日本化薬株式会社 Matériau d'enregistrement thermosensible

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