[go: up one dir, main page]

WO2025187765A1 - Révélateur et matériau d'impression thermosensible - Google Patents

Révélateur et matériau d'impression thermosensible

Info

Publication number
WO2025187765A1
WO2025187765A1 PCT/JP2025/008151 JP2025008151W WO2025187765A1 WO 2025187765 A1 WO2025187765 A1 WO 2025187765A1 JP 2025008151 W JP2025008151 W JP 2025008151W WO 2025187765 A1 WO2025187765 A1 WO 2025187765A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
carbon atoms
substituent
formula
naphthyl group
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/JP2025/008151
Other languages
English (en)
Japanese (ja)
Other versions
WO2025187765A8 (fr
Inventor
藤原 久美子 亀屋
拓也 玉置
宏樹 西城
拓海 加藤
洋 新納
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.)
Mitsubishi Chemical Corp
Original Assignee
Mitsubishi Chemical Corp
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 Mitsubishi Chemical Corp filed Critical Mitsubishi Chemical Corp
Publication of WO2025187765A1 publication Critical patent/WO2025187765A1/fr
Publication of WO2025187765A8 publication Critical patent/WO2025187765A8/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
    • B41M5/323—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
    • 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
    • B41M5/337—Additives; Binders

Definitions

  • the present invention relates to a color developer that can produce a thermal recording material with excellent color development sensitivity and print storage stability, and to a thermal recording material obtained using the color developer.
  • thermal recording materials with a thermal recording layer primarily composed of a colorless or pale-colored basic (electron-donating) leuco dye (hereinafter sometimes abbreviated as “dye”) and an electron-accepting developer (hereinafter sometimes abbreviated as “developer”) that reacts with the dye to develop color when heated are widely used.
  • Patent Documents 1 to 6 disclose methods using ascorbic acid or an ascorbic acid derivative as a color developer.
  • the object of the present invention is to provide a color developer that can provide a thermal recording material that is even better in terms of color development sensitivity and print area preservation properties, and a thermal recording material obtained using said color developer.
  • the gist of the present invention is as follows:
  • ⁇ 2> The color developer according to ⁇ 1>, wherein in formula (2), m is 1 and A is any one selected from the group consisting of —C( ⁇ O)—, —C( ⁇ O)—NH—, —SO 2 —, and —C( ⁇ O)—NH—SO 2 —.
  • B is an aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 18 carbon atoms which may have a substituent, or an arylalkyl group having 7 to 48 carbon atoms which may have a substituent.
  • ⁇ 5> The color developer according to any one of ⁇ 1> to ⁇ 4>, wherein in formula (2), m is 1, A is —C( ⁇ O)— or —C( ⁇ O)—NH—, and B is an aliphatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, or an aryl group having 6 to 12 carbon atoms which may have a substituent.
  • ⁇ 6> The developer according to any one of ⁇ 1> to ⁇ 5>, wherein R 1 , R 2 and R 3 are the same in formula (1).
  • thermosensitive recording material having a support and a thermosensitive recording layer provided on the support, wherein the thermosensitive recording layer contains the color developer according to any one of ⁇ 1> to ⁇ 7>.
  • the heat-sensitive recording material according to ⁇ 8> further comprising at least one of a compound represented by the following formula (3) and a compound represented by the following formula (5):
  • R 1a , R 2a , and R 3a may be the same or independently different and are a hydrogen atom or a group represented by the following formula (4), and at least one of R 1a , R 2a , and R 3a is a hydrogen atom.
  • m a is 0 or 1
  • a a is any linking group selected from the group consisting of —C( ⁇ O)—, —C( ⁇ S)—, —C( ⁇ O)—NH—, —C( ⁇ S)—NH—, —C( ⁇ O)—NH—SO 2 —, —C( ⁇ S)—NH—SO 2 —, —SO 2 —, —SO 2 —, —SO 2 —NH—, and —C( ⁇ O)—O—;
  • B a is any one selected from the
  • R 31 and R 32 are each independently any one selected from the group consisting of a hydrogen atom, an aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 18 carbon atoms which may have a substituent, and an arylalkyl group having 7 to 48 carbon atoms which may have a substituent.
  • ⁇ 11> The heat-sensitive recording material according to any one of ⁇ 8> to ⁇ 10>, wherein the heat-sensitive recording layer contains a sensitizer.
  • ⁇ 12> The heat-sensitive recording material according to any one of ⁇ 8> to ⁇ 11>, wherein the heat-sensitive recording layer contains a stabilizer.
  • the present invention provides a color developer that can produce a thermal recording material with excellent color development sensitivity and print storage stability, as well as a thermal recording material obtained using the color developer.
  • substituted refers not only to the usual meaning of a substituent but also to the terminal end of a molecule among multiple chemical structural moieties when a single chemical structural moiety cannot be expressed.
  • the structure " -CH2 - CH2 - CH3 " can be expressed as a single chemical structural moiety as a whole, as a propyl group, and is therefore interpreted as having no substituent.
  • the propyl group is not interpreted as "one hydrogen atom from the methyl group is removed, and an ethyl group as a substituent is further bonded to the molecular terminal" or "one hydrogen atom from the ethyl group is removed, and a methyl group as a substituent is further bonded to the molecular terminal.”
  • the structure " -CH2 - CH2 -F" is interpreted as a fluoroethyl group, but since it is expressed as a combination of fluoro and ethyl groups, this is interpreted as a case in which a single chemical structural moiety cannot be expressed, i.e., as a case in which multiple chemical structural moieties exist.
  • the center of the molecule can be interpreted as an "ethyl group” and the terminal side as fluorine, so in this case it can be said that fluorine is the substituent.
  • the option with the largest number of carbon atoms at the center of the molecule is used to interpret the substituent. If the number of carbon atoms at the center of the molecule and the number of carbon atoms at the terminal sides are the same, the option with the largest molecular weight at the center of the molecule is used to interpret the substituent.
  • the "substituent” is not particularly limited, but may be, for example, a group selected from a hydroxy group, a carboxy group, a halogen atom, a nitro group, a cyano group, an amino group, an aliphatic hydrocarbon group, an alkoxy group, an alkenyloxy group, an aryl group, an aryloxy group, and an arylalkyl group, or a combination thereof.
  • halogen atoms include fluorine, chlorine, bromine, iodine, astatine, and tennessine, with fluorine, chlorine, bromine, and iodine being preferred, fluorine, chlorine, and bromine being more preferred, fluorine and chlorine being even more preferred, and fluorine being particularly preferred.
  • aliphatic hydrocarbon groups include alkyl groups, alkenyl groups, and alkynyl groups, with alkyl groups and alkenyl groups being preferred. There is no particular limit to the number of carbon atoms in the aliphatic hydrocarbon group, but it is typically 1 to 8.
  • alkyl group examples include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, an i-butyl group, a t-butyl group, a pentyl group, an i-pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, and a 2-ethylhexyl group, and preferably a methyl group or an ethyl group.
  • the number of carbon atoms in the alkenyl group is not particularly limited, but is usually 2 to 4.
  • alkenyl group examples include a vinyl group, an allyl group, a propenyl group, and a butenyl group, and preferably a vinyl group or an allyl group.
  • the number of carbon atoms in the alkynyl group is not particularly limited, but is usually 2 to 4.
  • Examples of the alkynyl group include an ethynyl group and a prop-2-yn-1-yl group.
  • the number of carbon atoms in the alkoxy group is not particularly limited, but is typically 1 to 8.
  • Examples include methoxy, ethoxy, propoxy, i-propoxy, butoxy, i-butoxy, t-butoxy, pentyloxy, i-pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, and 2-ethylhexyloxy groups, with methoxy and ethoxy being preferred.
  • the number of carbon atoms in the alkenyloxy group is not particularly limited, but is typically 2 to 4. Examples include vinyloxy, allyloxy, 1-propenyloxy, and 2-propenyloxy groups, with vinyloxy and allyloxy being preferred.
  • the number of carbon atoms in the aryl group is not particularly limited, but is typically 6 to 18.
  • aryl groups include phenyl, naphthyl, and anthracenyl groups, with phenyl and naphthyl being preferred.
  • the number of carbon atoms in the aryloxy group is not particularly limited, but is typically 6 to 18.
  • Examples of aryloxy groups include phenyloxy groups, naphthyloxy groups, and anthracenyloxy groups, with phenyloxy groups being preferred.
  • the number of carbon atoms in an arylalkyl group is not particularly limited, but is typically 7 to 20.
  • An arylalkyl group is a group in which one hydrogen atom has been removed from the above alkyl group and the above aryl group is bonded to it.
  • arylalkyl groups include benzyl groups, phenylethyl groups, phenylpropyl groups, naphthylmethyl groups, naphthylethyl groups, naphthylpropyl groups, anthracenylmethyl groups, and anthracenylethyl groups, with benzyl groups, phenylethyl groups, naphthylmethyl groups, and anthracenylmethyl groups being preferred.
  • the color developer of the present invention contains a compound represented by the following formula (1):
  • the compound represented by formula (1) may be referred to as "compound (I).”
  • the color developer of the present invention exhibits remarkable effects, such as excellent color development sensitivity and print preservation properties including heat resistance, plasticizer resistance, moisture resistance, water resistance, alcohol resistance, oil resistance, and grease resistance.
  • the reason why the present invention exhibits such excellent effects is believed to be as follows: By introducing a highly hydrophobic functional group into ascorbic acid, compatibility with the leuco dye is increased, making it more susceptible to reaction with the leuco dye, thereby improving color development sensitivity, and at the same time, stabilizing the color development state and improving storage stability.
  • the compound represented by formula (1) contained in the developer of the present invention has three functional groups introduced into the 2,5,6-O site of ascorbic acid, increasing its molecular weight, which is thought to prevent it from bleeding into plasticizers, oils, greases, etc., thereby improving the storage stability of printed areas.
  • R1 , R2 , and R3 are groups represented by the following formula (2), and R1 , R2 , and R3 may be the same or different from each other independently. However, it is preferable that two of R1 , R2 , and R3 are the same, and it is more preferable that all three are the same. When two or three are the same, it is thought that uniform compatibility with the leuco dye is achieved, improving color development performance.
  • m is 0 or 1. However, from the viewpoint of appropriate compatibility with the leuco dye, m is preferably 1.
  • B is any one selected from the group consisting of an aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 18 carbon atoms which may have a substituent, and an arylalkyl group having 7 to 48 carbon atoms which may have a substituent.
  • B is preferably any one selected from the group consisting of an optionally substituted aliphatic hydrocarbon group having 1 to 30 carbon atoms, an optionally substituted aryl group having 6 to 18 carbon atoms, and an optionally substituted arylalkyl group having 7 to 48 carbon atoms, and more preferably at least one of an optionally substituted aliphatic hydrocarbon group having 1 to 30 carbon atoms or an optionally substituted aryl group having 6 to 18 carbon atoms. It may also be at least one of an optionally substituted aryl group having 6 to 18 carbon atoms or an optionally substituted arylalkyl group having 7 to 48 carbon atoms.
  • Aliphatic hydrocarbon groups having 1 to 30 carbon atoms include alkyl groups, alkenyl groups, and alkynyl groups, with alkyl and alkenyl groups being preferred, and alkyl groups being more preferred.
  • the aliphatic hydrocarbon group may be linear, branched, or cyclic. From the standpoints of suppressing thermal motion of the molecules and improving storage stability, and compatibility with the leuco dye, the carbon number of the aliphatic hydrocarbon group having 1 to 30 carbon atoms, which may have a substituent, is preferably 2 to 18, more preferably 4 to 18, and even more preferably 6 to 18. In the case of alkenyl and alkynyl groups, the carbon number is 2 or more.
  • aliphatic hydrocarbon groups include methyl, ethyl, propyl, i-propyl, butyl, i-butyl, t-butyl, pentyl, i-pentyl, hexyl, cyclohexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, dodecyl, tetradecyl, palmityl, stearyl, behenyl, vinyl, allyl, propenyl, butenyl, ethynyl, and prop-2-yn-1-yl.
  • any of ethyl, propyl, i-propyl, butyl, i-butyl, t-butyl, pentyl, i-pentyl, hexyl, cyclohexyl, heptyl, octyl, 2-ethylhexyl, decyl, dodecyl, tetradecyl, palmityl, stearyl, vinyl, allyl, and propenyl groups are preferred, with butyl, t-butyl, pentyl, hexyl, cyclohexyl, octyl, 2-ethylhexyl, decyl, dodecyl, tetradecyl, palmityl, and stearyl groups being more preferred, and hexyl, cyclohexyl, octyl, 2-ethylhexyl, decyl, dodec
  • alkoxy groups having 1 to 30 carbon atoms include the following. From the standpoint of suppressing thermal motion of the molecules, which tends to improve storage stability, and compatibility with the leuco dye, alkoxy groups having 2 to 18 carbon atoms are preferred, alkoxy groups having 4 to 18 carbon atoms are more preferred, and alkoxy groups having 6 to 18 carbon atoms are even more preferred.
  • alkoxy groups include methoxy, ethoxy, propoxy, i-propoxy, butoxy, i-butoxy, t-butoxy, pentyloxy, i-pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, dodecyloxy, tetradecyloxy, palmityloxy, stearyloxy, and behenyloxy groups.
  • hexyloxy group is any one of a hexyloxy group, a cyclohexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a decyloxy group, a dodecyloxy group, a tetradecyloxy group, a palmityloxy group, or a stearyloxy group
  • it is any one of a hexyloxy group, a cyclohexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a decyloxy group, a dodecyloxy group, a tetradecyloxy group, a palmityloxy group, or a stearyloxy group.
  • aryl groups having 6 to 18 carbon atoms include the following. From the viewpoint of compatibility with the leuco dye, aryl groups having 6 to 12 carbon atoms are preferred, and aryl groups having 6 carbon atoms are more preferred. Specific examples of unsubstituted aryl groups having 6 to 18 carbon atoms include phenyl, 1-naphthyl, 2-naphthyl, and anthracenyl. Of these, phenyl, 1-naphthyl, or 2-naphthyl groups are preferred, and phenyl groups are more preferred.
  • substituted aryl groups having 6 to 18 carbon atoms include o-tolyl, m-tolyl, p-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 3,4-xylyl, 3,5-xylyl, 2,4,6-mesityl, o-ethylphenyl, m-ethylphenyl, p-ethylphenyl, o-propylphenyl, m-propylphenyl, p-propylphenyl, o-i-propylphenyl, m-i-propylphenyl, p-i-propylphenyl, o-butylphenyl, m-butylphenyl, p-butylphenyl, o-i-butylphenyl, m-i-butylphenyl, p-i-butylpheny
  • phenyl group o-pentylphenyl group, m-pentylphenyl group, p-pentylphenyl group, o-i-pentylphenyl group, m-i-pentylphenyl group, p-i-pentylphenyl group, o-hexylphenyl group, m-hexylphenyl group, p-hexylphenyl group, o-cyclohexylphenyl group, m-cyclohexylphenyl group, p-cyclohexylphenyl group, o-heptylphenyl group, m-heptylphenyl group, p-heptylphenyl group, o-octylphenyl group, m-octylphenyl group, p-octylphenyl group, o-2-ethylhexylphenyl group,
  • substituted aryl groups having 6 to 18 carbon atoms include o-tolyl, m-tolyl, p-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 3,4-xylyl, 3,5-xylyl, 2,4,6-mesityl, o-ethylphenyl, m-ethylphenyl, p-ethylphenyl, o-propylphenyl, m-propylphenyl, p-propylphenyl, o-i-propylphenyl, m-i-propylphenyl, p-i-propylphenyl, o-butylphenyl, and m-butylphenyl.
  • p-butylphenyl group o-i-butylphenyl group, m-i-butylphenyl group, p-i-butylphenyl group, o-t-butylphenyl group, m-t-butylphenyl group, p-t-butylphenyl group, o-hexylphenyl group, m-hexylphenyl group, p-hexylphenyl group, o-cyclohexylphenyl group, m-cyclohexylphenyl group, p-cyclohexylphenyl group, o-octylphenyl group, m-octylphenyl group, p-octylphenyl group, o-2-ethylhexylphenyl group, m-2-ethylhexylphenyl group, p-2-ethylhexylphenyl
  • An arylalkyl group having 7 to 48 carbon atoms is a group in which one hydrogen atom has been removed from the alkyl group described above and the aryl group described above is bonded to the alkyl group. From the viewpoint of compatibility with the leuco dye, arylalkyl groups having 7 to 30 carbon atoms are preferred, and arylalkyl groups having 7 to 18 carbon atoms are more preferred.
  • Examples of unsubstituted arylalkyl groups having 7 to 48 carbon atoms include benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylpropyl, 2-phenylpropyl, 3-phenylpropyl, 1-phenylbutyl, 2-phenylbutyl, 3-phenylbutyl, 4-phenylbutyl, cumyl, naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, 1-naphthylpropyl, 2-naphthylpropyl, 3-naphthylpropyl, 1-naphthylbutyl, 2-naphthylbutyl, 3-naphthylbutyl, and 4-naphthylbutyl.
  • substituted arylalkyl groups having 7 to 48 carbon atoms include o-methylbenzyl, m-methylbenzyl, p-methylbenzyl, o-vinylbenzyl, m-vinylbenzyl, p-vinylbenzyl, o-methoxybenzyl, m-methoxybenzyl, p-methoxybenzyl, o-vinyloxybenzyl, m-vinyloxybenzyl, p-vinyloxybenzyl, o-allyloxybenzyl, m-allyloxybenzyl, p-allyloxybenzyl, o-methylcumyl, m-methylcumyl, p-methylcumyl, o-methoxycumyl, m-methoxycumyl, and p-methoxycumyl groups.
  • any of o-methylbenzyl group, m-methylbenzyl group, p-methylbenzyl group, o-vinylbenzyl group, m-vinylbenzyl group, p-vinylbenzyl group, o-methoxybenzyl group, m-methoxybenzyl group, p-methoxybenzyl group, o-vinyloxybenzyl group, m-vinyloxybenzyl group, p-vinyloxybenzyl group, o-allyloxybenzyl group, m-allyloxybenzyl group, and p-allyloxybenzyl group is preferred, and any of o-methylbenzyl group, m-methylbenzyl group, p-methylbenzyl group, o-vinylbenzyl group, m-vinylbenzyl group, p-vinylbenzyl group, o-methoxybenzyl group, m-methoxybenzyl group
  • formula (2) is preferably the following (2A), more preferably the following (2B), even more preferably the following (2C), and even more preferably the following (2D).
  • R 1 , R 2 , and R 3 are the same group represented by formula (2), and formula (2) is preferably (2A) above, more preferably (2B) above, even more preferably (2C) above, and even more preferably (2D) above.
  • the compound represented by formula (1) has isomers, including compounds represented by the following formulas (1-1), (1-2), (1-3), and (1-4). From the perspective of structural stability in light of steric hindrance, at least one of the compounds represented by formula (1-1) or (1-2) is preferred.
  • R 1 to R 3 have the same meanings as R 1 to R 3 in formula (1), respectively.
  • thermosensitive recording material of the present invention is a thermosensitive recording material having a support and a thermosensitive recording layer provided on the support, and the thermosensitive recording layer contains the color developer of the present invention.
  • the "thermosensitive recording material” refers to any material having a thermosensitive recording layer on a support, and may be in the form of paper, film, synthetic paper, card, etc.
  • the thermosensitive recording material of the present invention has a thermosensitive recording layer on a support, but may also have a protective layer, under layer, back layer, intermediate layer, etc., as described below, if necessary.
  • “on the support” refers to at least one side of the support, and typically refers to one side.
  • “on the support” means that the layer is present on at least a portion of the support.
  • thermosensitive recording material of the present invention has a thermosensitive recording layer containing the color developer of the present invention.
  • the thermosensitive recording layer may contain, in addition to the color developer of the present invention, a leuco dye, a color developer other than the compound represented by formula (1), compound (II) described below, a sensitizer, a stabilizer, a binder, a crosslinking agent, a pigment, a lubricant, and other additives.
  • the thermosensitive recording layer preferably contains a leuco dye.
  • Leuco dyes are typically basic, and any leuco dyes known in the art for pressure-sensitive or thermosensitive recording paper can be used. Specific examples of leuco dyes include triphenylmethane-based leuco dyes, fluoran-based leuco dyes, fluorene-based leuco dyes, and divinyl-based leuco dyes. Specific examples of representative colorless or pale-colored dyes (dye precursors) are shown below. These leuco dyes (leuco dye precursors) may be used alone or in combination of two or more. The leuco dye is preferably used in an amount of 10 to 200 parts by weight, more preferably 15 to 150 parts by weight, and even more preferably 20 to 100 parts by weight, per 100 parts by weight of the developer.
  • Triphenylmethane leuco dyes include 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide (also known as crystal violet lactone); 3,3-bis(p-dimethylaminophenyl)phthalide (also known as malachite green lactone); etc.
  • Fluoran leuco dyes include 3-diethylamino-6-methylfluoran; 3-diethylamino-6-methyl-7-anilinofluoran; 3-diethylamino-6-methyl-7-(o,p-dimethylanilino)fluoran; 3-diethylamino-6-methyl-7-chlorofluoran; 3-diethylamino-6-methyl-7-(m-trifluoromethylanilino)fluoran; 3-diethylamino-6-methyl-7-(o-chloroanilino)fluoran; 3-diethylamino-6-methyl-7-(p-chloroanilino)fluoran; 3-diethylamino-6-methyl-7-(o-fluoroanilino)fluoran; 3-diethylamino-6-methyl-7-(m-methylanilino)fluoran; 3 -Diethylamino-6-methyl-7-octylanilinofluoran; 3-die
  • fluorene-based leuco dyes examples include 3,6,6'-tris(dimethylamino)spiro[fluorene-9,3'-phthalide]; 3,6,6'-tris(diethylamino)spiro[fluorene-9,3'-phthalide]; etc.
  • Divinyl leuco dyes include 3,3-bis[2-(p-dimethylaminophenyl)-2-(p-methoxyphenyl)ethenyl]-4,5,6,7-tetrabromophthalide; 3,3-bis[2-(p-dimethylaminophenyl)-2-(p-methoxyphenyl)ethenyl]-4,5,6,7-tetrachlorophthalide; 3,3-bis[1,1-bis(4-pyrrolidinophenyl)ethylene-2-yl]-4,5,6,7-tetrabromophthalide; 3,3-bis[1-(4-methoxyphenyl)-1-(4-pyrrolidinophenyl)ethylene-2-yl]-4,5,6,7-tetrachlorophthalide, etc.
  • leuco dyes include 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide; 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-octyl-2-methylindol-3-yl)-4-azaphthalide; 3-(4-cyclohexylethylamino-2-methoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide; 3,3-bis(1-ethyl-2-methylindol-3-yl)phthalide; 3,6-bis(diethylamino)fluoran- ⁇ -(3'-nitro)anilinolactam; 3, Examples include 6-bis(diethylamino)fluoran- ⁇ -(4'-nitro)anilinolactam; 1,1-bis[2',2',2",
  • 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide also known as crystal violet lactone
  • 3-diethylamino-6-methyl-7-anilinofluoran 3-diethylamino-6-methyl-7-octylaminofluoran
  • 3-dibutylamino-6-methyl-7-anilinofluoran 3-(N-ethyl-N-isoamylamino)-6-methyl-7-anilinofluoran
  • 3-(N-ethyl-N-isoamylamino)-6-methyl-7-anilinofluoran are preferred.
  • the thermosensitive recording layer may contain a color developer other than Compound (I) of the present invention (hereinafter referred to as "other color developers") to the extent that the effects of the present invention are not impaired.
  • a color developer other than Compound (I) of the present invention hereinafter referred to as "other color developers"
  • Any other color developer known in the field of conventional pressure-sensitive or thermosensitive recording paper can be used as the other color developer, and there are no particular limitations on the other color developers.
  • An electron-accepting color developer is preferred.
  • One type of other color developer may be used alone, or two or more types may be used in combination.
  • color developers include bisphenol compounds, urea compounds, novolac-type phenolic compounds, and amino acid derivative compounds.
  • Compound (II), described below, may also be used as the other color developer.
  • Bisphenol compounds include 4,4'-isopropylidenediphenol, 2,2'-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 4,4'-dihydroxydiphenyl sulfide, di(4-hydroxy-3-methylphenyl) sulfide, 2,2'-thiobis(3-tert-octylphenol), 2,2'-thiobis(4-tert-octylphenol), 4,4'-dihydroxydiphenyl sulfone, and 2,4'-dihydroxydiphenyl Examples include sulfone, 4-hydroxy-4'-propoxydiphenyl sulfone, 4-hydroxy-4'-isopropoxydiphenyl sulfone, 4-hydroxy-4'-allyloxydiphenyl sulfone, bis(3-allyl-4-hydroxyphenyl)
  • Urea compounds include 4,4'-bis(3-(phenoxycarbonylamino)methylphenylureido)diphenyl sulfone, N-(p-toluenesulfonyl)-N'-(3-p-toluenesulfonyloxyphenyl)urea described in Japanese Patent No. 4601174, 4,4'-bis(3-tosylureido)diphenylmethane described in Japanese Patent Publication No. 2011-105638, N-[2-(3-phenylureido)phenyl]benzenesulfonamide described in Japanese Patent Publication No.
  • Examples include N'-phenylurea, [3-(3-phenylureido)phenyl] 4-methylbenzenesulfonate described in Japanese Patent Application No.
  • Novolak-type phenolic compounds include the phenol-formalin condensates described in WO 02/098674.
  • Amino acid derivative compounds include N-(m-tolylaminocarbonyl)-phenylalanine, N-(p-toluenesulfonyl)-phenylalanine, N-(benzyloxycarbonyl)-valine, N-(m-tolylaminocarbonyl)-methionine, N-(m-tolylaminocarbonyl)-tyrosine, N-(m-tolylaminocarbonyl)-phenylglycine, N-(m-tolylaminocarbonyl)-valine, and N- Examples include amino acid derivatives such as (m-tolylaminocarbonyl)-cysteine-S-benzyl, N-(m-tolylaminocarbonyl)- ⁇ -alanine, N-phenylaminothiocarbonyl-glycylglycine, N-(p-toluenesulfonylaminocarbonyl)-phenylalanine-
  • inorganic acidic substances such as activated clay, attapulgite, colloidal silica, and aluminum silicate, hydroquinone monobenzyl ether, benzyl 4-hydroxybenzoate, aminobenzenesulfonamide derivatives described in JP-A-8-59603, bis(4-hydroxyphenylthioethoxy)methane, 1,5-di(4-hydroxyphenylthio)-3-oxapentane, butyl bis(p-hydroxyphenyl)acetate, methyl bis(p-hydroxyphenyl)acetate, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,4-bis[ ⁇ -methyl- ⁇ -(4'-hydroxyphenyl)ethyl]benzene, 1,3-bis[ ⁇ -methyl- ⁇ -(4'-hydroxyphenyl)ethyl]benzene, and WO 02/081229 and JP-A-2002-301873, thiourea compounds such as N
  • WO 2022/045 More preferred are 4-methylphenyl [3-[[(phenylamino)carbonyl]amino]benzenesulfonate] described in Japanese Patent Application No. 2021-131277, N,N'-bis(3-[ ⁇ 4-methylphenyl ⁇ sulfonylamino]phenyl)urea described in Japanese Patent Application No. 2021-131277, N,N'-di-[3-(p-toluenesulfonyloxy)phenyl]urea described in Japanese Patent Application No. 2019-539154, 3-[(phenylcarbamoyl)amino]phenyl-4-methylbenzenesulfonate described in Japanese Patent Application No.
  • the thermosensitive recording layer may contain compound (II), which is at least one of a compound represented by the following formula (3) and a compound represented by the following formula (5), within a range that does not impair the effects of the present invention.
  • Compound (II) may be used alone or in combination of two or more types. That is, compound (II) may be only a compound represented by formula (3), only a compound represented by formula (5), or a compound represented by formula (3) and a compound represented by formula (5). In each case, the compound represented by formula (3) may be one or two or more types, and the compound represented by formula (5) may be one or two or more types.
  • R 1a , R 2a , and R 3a may be the same or independently different from each other and are a hydrogen atom or a group represented by the following formula (4), and at least one of R 1a , R 2a , and R 3a is a hydrogen atom.
  • m a is 0 or 1;
  • a a is a linking group selected from the group consisting of —C( ⁇ O)—, —C( ⁇ S)—, —C( ⁇ O)-NH—, —C( ⁇ S)-NH—, —C( ⁇ O)-NH—SO 2 —, —C( ⁇ S)-NH—SO 2 —, —SO 2 —, —SO 2 —NH—, and —C( ⁇ O)-O—; and
  • B a is any group selected from the group consisting of an aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 18 carbon atoms which may have a substituent, and an arylalkyl group having 7 to 48 carbon atoms which may have a substituent.
  • the compound represented by formula (3) has the same meaning as the compound represented by formula (1), except that at least one of R 1a , R 2a , or R 3a is a hydrogen atom.
  • R 1a in formula (3) is a group represented by formula (4)
  • R 1a has the same meaning as R 1 in formula (1)
  • R 2a in formula (3) is a group represented by formula (4)
  • R 2a has the same meaning as R 2 in formula (1)
  • R 3a in formula (3) is a group represented by formula (4)
  • R 3a has the same meaning as R 3 in formula (1).
  • one, two, or three of R 1a , R 2a , or R 3a may be a hydrogen atom.
  • R 1a , R 2a , or R 3a it is preferable that one or two of R 1a , R 2a , or R 3a be hydrogen atoms, and it is more preferable that two of them be hydrogen atoms.
  • R 1a may be a hydrogen atom
  • R 2a and R 3a may be a group represented by formula (4)
  • R 2a may be a hydrogen atom
  • R 1a and R 3a may be a group represented by formula (4)
  • R 3a may be a hydrogen atom
  • R 1a and R 2a may be a group represented by formula (4)
  • R 1a and R 2a may be a hydrogen atom
  • R 3a may be a group represented by formula (4)
  • R 1a and R 3a may be a hydrogen atom
  • R 2a may be a group represented by formula (4)
  • R 2a and R 3a may be a hydrogen atom
  • R 1a may be a group represented by formula (4)
  • R 1a , R 2a , and R 3a may be a hydrogen atom
  • R 1a may be
  • R 1a is a hydrogen atom
  • R 2a and R 3a are groups represented by formula (4)
  • R 1a and R 3a are hydrogen atoms
  • R 2a is a group represented by formula (4).
  • formula (3) is preferably the following (3A), more preferably the following (3B), and even more preferably the following (3C).
  • the compound represented by formula (3) exists in four isomers depending on the positions of the hydrogen atom bonded to the carbon atom corresponding to the 4th position of ascorbic acid and the oxygen atom bonded to the carbon atom corresponding to the 5th position of ascorbic acid, and at least one of the compounds represented by formula (3-1) or formula (3-2) is preferred.
  • R 31 and R 32 are each independently any one selected from the group consisting of a hydrogen atom, an aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 18 carbon atoms which may have a substituent, and an arylalkyl group having 7 to 48 carbon atoms which may have a substituent.
  • aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent the alkoxy group having 1 to 30 carbon atoms which may have a substituent, the aryl group having 6 to 18 carbon atoms which may have a substituent, and the arylalkyl group having 7 to 48 carbon atoms which may have a substituent are the same as those for B in formula (2).
  • R 31 and R 32 are each independently any one selected from the group consisting of a hydrogen atom, an aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 18 carbon atoms which may have a substituent, and an arylalkyl group having 7 to 48 carbon atoms which may have a substituent, and it is more preferred that R 31 and R 32 are each independently any one selected from the group consisting of a hydrogen atom, an aliphatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, and an arylalkyl group having 7 to 18 carbon atoms which may have a substituent.
  • R 31 and R 32 are other than a hydrogen atom.
  • the compound represented by formula (5) exists in four isomers depending on the positions of the hydrogen atom bonded to the carbon atom corresponding to the 4th position of ascorbic acid and the oxygen atom bonded to the carbon atom corresponding to the 5th position of ascorbic acid, and at least one of the compounds represented by formula (5-1) or formula (5-2) is preferred.
  • thermosensitive recording material of the present invention a known sensitizer may be used in the thermosensitive recording layer. From the viewpoint of enabling color development with lower energy, it is preferable that the thermosensitive recording layer contains a sensitizer.
  • sensitizer examples thereof include 1,2-di-(3-methylphenoxy)ethane, 2-benzyloxynaphthalene, fatty acid amides having 10 to 21 carbon atoms (e.g., stearic acid amide, palmitic acid amide, etc.), ethylene bisamide, montanic acid wax, polyethylene wax, p-benzylbiphenyl, diphenyl sulfone, 4-biphenyl-p-tolyl ether, m-terphenyl, 1,2-diphenoxyethane, dibenzyl oxalate, di(p-chlorobenzyl oxalate), di(p-methylbenzyl oxalate), dibenzyl terephthalate, and p-benzyloxybenzoate.
  • 1,2-di-(3-methylphenoxy)ethane examples thereof include 1,2-di-(3-methylphenoxy)ethane, 2-benzyloxynaphthalene, fatty acid amide
  • benzoates examples include benzyl benzoate, di-p-tolyl carbonate, phenyl- ⁇ -naphthyl carbonate, 1,4-diethoxynaphthalene, 1-hydroxy-2-naphthoic acid phenyl ester, o-xylene-bis-(phenyl ether), 4-(m-methylphenoxymethyl)biphenyl, 4,4′-ethylenedioxy-bis-benzoic acid dibenzyl ester, dibenzoyloxymethane, 1,2-di(3-methylphenoxy)ethylene, bis[2-(4-methoxy-phenoxy)ethyl]ether, methyl p-nitrobenzoate, and phenyl p-toluenesulfonate.
  • 1,2-di-(3-methylphenoxy)ethane, 1,2-diphenoxyethane, fatty acid amides having 10 to 21 carbon atoms e.g., stearic acid amide, palmitic acid amide, etc.
  • 2-benzyloxynaphthalene, diphenyl sulfone, p-toluenesulfonamide, and oxalic acid-di-p-methylbenzyl ester are preferred, and 1,2-di-(3-methylphenoxy)ethane, 1,2-diphenoxyethane, and 2-benzyloxynaphthalene, which exhibit high color-developing sensitivity even at low energy, are particularly preferred.
  • These sensitizers may be used alone or in combination of two or more. When a sensitizer is used, the amount used is preferably 25 to 250 parts by mass, more preferably 50 to 150 parts by mass, per 100 parts by mass of Compound (I).
  • a stabilizer may be used in the thermosensitive recording layer to improve the image storage stability of the thermosensitive recording material.
  • a stabilizer is a substance that has the effect of improving the image storage stability.
  • stabilizers include hindered phenol compounds, ultraviolet absorbers (e.g., benzophenone compounds, triazole compounds), and antioxidants. Among these, hindered phenol compounds are preferred in terms of improving the image storage stability (heat resistance, moisture resistance, water resistance, plasticizer resistance, etc.) of the recorded area.
  • Hindered phenol compounds are compounds that typically have 1 to 15, and preferably 2 to 6, hydroxyphenyl groups per molecule.
  • the molecular weight of hindered phenol compounds is typically 200 to 2,000, preferably 250 to 1,800, and more preferably 300 to 1,500.
  • the melting point of hindered phenol compounds is preferably 100°C to 300°C.
  • the carbon atom at either the 2nd or 6th position is bonded to a hydrogen atom (i.e., there is no substituent at the 2nd or 6th position).
  • hindered phenol compounds include tris(hydroxyphenyl)alkanes and 1,1,3-tris-substituted butane compounds, as described in Japanese Patent Publication No. 39-4469 or Japanese Patent Application Laid-Open No. 56-40629. These may be used in combination of two or more types.
  • One type of hindered phenol compound may be used alone, or two or more types may be used in combination.
  • the content thereof is preferably 1 to 100 parts by mass, more preferably 1 to 70 parts by mass, and even more preferably 1 to 50 parts by mass, per 100 parts by mass of compound (I). If the content of the hindered phenol compound is less than this range, the moisture resistance, water resistance, and heat resistance of the recorded area may be reduced, and color development in blank areas due to heating may not be suppressed. Furthermore, if the content is greater than this range, the color development sensitivity may be reduced, and the plasticizer resistance of the recorded area may be reduced.
  • a binder it is preferable to use a binder to form the heat-sensitive recording layer.
  • the binder include fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, acetoacetylated polyvinyl alcohol, carboxy-modified polyvinyl alcohol, amide-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, butyral-modified polyvinyl alcohol, olefin-modified polyvinyl alcohol, nitrile-modified polyvinyl alcohol, pyrrolidone-modified polyvinyl alcohol, silicone-modified polyvinyl alcohol, other modified polyvinyl alcohols, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, polystyrene, styrene copolymers such as styrene-maleic anhydride copolymer and styrene-butadiene copolymer,
  • Binders are generally used as solutions, emulsions, dispersions, pastes, or combinations thereof.
  • solvents for solutions, emulsions, or dispersions, or media for pastes include water, alcohols, ketones, esters, and hydrocarbons.
  • a crosslinking agent may be used in the heat-sensitive recording layer.
  • crosslinking agents include glyoxal, methylol melamine, melamine formaldehyde resin, melamine urea resin, polyamine epichlorohydrin resin, polyamide epichlorohydrin resin, potassium persulfate, ammonium persulfate, sodium persulfate, ferric chloride, magnesium chloride, borax, boric acid, alum, and ammonium chloride.
  • the amount thereof is preferably 0.5 to 500 parts by mass per 100 parts by mass of compound (I).
  • a pigment may be used in the heat-sensitive recording layer.
  • the pigment include inorganic or organic pigments such as silica (excluding colloidal silica), calcium carbonate, kaolin, calcined kaolin, diatomaceous earth, talc, titanium oxide, and aluminum hydroxide.
  • silica excluding colloidal silica
  • calcium carbonate calcium carbonate
  • kaolin calcined kaolin
  • diatomaceous earth talc
  • titanium oxide titanium oxide
  • aluminum hydroxide aluminum hydroxide.
  • the amount thereof is preferably 25 to 1,000 parts by mass per 100 parts by mass of compound (I).
  • a lubricant may be used in the thermosensitive recording layer.
  • lubricants include fatty acid metal salts such as zinc stearate and calcium stearate, waxes, silicone resins, etc.
  • the amount thereof is preferably 0.5 to 500 parts by mass per 100 parts by mass of compound (I).
  • additives may be used in the heat-sensitive recording layer.
  • other additives include dispersants, antifoaming agents, fluorescent dyes, etc.
  • the amount thereof is preferably 0.5 to 500 parts by mass per 100 parts by mass of Compound (I).
  • the thermal recording layer preferably contains a color developer, a leuco dye, a binder, a pigment, and a lubricant, and more preferably contains 25 to 75 parts by mass of the leuco dye, 5 to 40 parts by mass of the binder, 100 to 500 parts by mass of the pigment, and 5 to 30 parts by mass of the lubricant, per 100 parts by mass of the color developer.
  • the thermal recording layer preferably contains a color developer, a leuco dye, a binder, a pigment, a lubricant, a sensitizer, and a stabilizer, and the amounts of the leuco dye, binder, pigment, lubricant, sensitizer, lubricant, sensitizer, sensitizer, and stabilizer are 25 to 75 parts by weight, 5 to 30 parts by weight, 100 to 500 parts by weight, 5 to 40 parts by weight, 25 to 200 parts by weight, and 5 to 100 parts by weight, per 100 parts by weight of the color developer.
  • the shape, structure, size, material, etc. of the support used in the thermal recording material of the present invention are not particularly limited and can be appropriately selected depending on the purpose.
  • Examples of the shape of the support include sheet, roll, and flat plate.
  • the support may have a single-layer structure or a laminated structure.
  • the size of the support can be appropriately selected depending on the intended use of the thermal recording material.
  • Examples of support materials include plastic film, synthetic paper, wood-free paper, waste paper pulp, recycled paper, one-side glossy paper, greaseproof paper, coated paper, art paper, cast-coated paper, lightly coated paper, resin-laminated paper, and release paper. A composite sheet combining these materials may also be used as the support.
  • the thickness of the support there are no particular restrictions on the thickness of the support, and it can be selected appropriately depending on the purpose. It is preferably 30 to 2,000 ⁇ m, and more preferably 50 to 1,000 ⁇ m.
  • thermosensitive recording material of the present invention a protective layer may be provided on the thermosensitive recording layer.
  • a protective layer on the thermosensitive recording layer to improve the image storage stability of the thermosensitive recording material reduces the color development sensitivity.
  • the highly sensitive compound (I) is used as a color developer, the sensitivity required for thermal paper can be maintained even when a protective layer is provided on the thermosensitive recording layer.
  • the types and amounts of various components used in the protective layer are determined according to the required performance and recording suitability and are not particularly limited.
  • thermosensitive recording material of the present invention an underlayer mainly composed of a pigment and a binder may be provided between the support and the thermosensitive recording layer in order to further enhance color development sensitivity. Furthermore, in order to correct curling of the thermosensitive recording material of the present invention, a back layer may be provided on the surface of the support opposite to the surface on which the thermosensitive recording layer is located.
  • One embodiment of the layers in the thermosensitive recording material of the present invention includes, but is not limited to, a layered structure in the order of protective layer/thermosensitive recording layer/under layer/support/back layer.
  • an intermediate layer may be formed between the support and the under layer, between the under layer and the thermosensitive recording layer, between the thermosensitive recording layer and the protective layer, and/or between the support and the back layer.
  • thermosensitive recording material of the present invention can be produced by, for example, applying a coating liquid containing a basic leuco dye and a developer, and optionally a hindered phenol compound, a sensitizer, etc., to at least a portion of at least one surface of a support, followed by drying to form a thermosensitive recording layer.
  • This coating liquid can be applied according to well-known conventional techniques.
  • an off-machine or on-machine coater equipped with various coaters such as an air knife coater, a rod blade coater, a bent blade coater, a bevel blade coater, a roll coater, or a curtain coater can be used.
  • the coating liquid for forming the thermosensitive recording layer can be prepared by blending, for example, a color developer and, if necessary, a leuco dye, a hindered phenol compound, a sensitizer, etc., and then atomizing the mixture to a particle size of several microns or less using a grinder such as a ball mill, an attritor, or a sand grinder, or an appropriate emulsifying device, and then adding a binder, etc. to the mixture.
  • a grinder such as a ball mill, an attritor, or a sand grinder, or an appropriate emulsifying device, and then adding a binder, etc. to the mixture.
  • solvents that can be used in this coating liquid include water and alcohol.
  • the solid content of the coating liquid is usually 20 to 40% by mass.
  • the coating amount of the heat-sensitive recording layer can be appropriately selected depending on the composition and the use of the heat-sensitive recording material, but is usually in the range of 1 to 20 g/m 2
  • the coating liquid preferably contains a color developer, a leuco dye, a binder, a pigment, a lubricant, and water, and more preferably contains 25 to 75 parts by mass of the leuco dye, 5 to 40 parts by mass of the binder, 100 to 500 parts by mass of the pigment, and 5 to 30 parts by mass of the lubricant, relative to 100 parts by mass of the color developer, and the solids content is 14 to 25% by mass.
  • the coating liquid contains a color developer, a leuco dye, a binder, a pigment, a lubricant, a sensitizer, a stabilizer, and water, and that the amounts of the leuco dye, binder, pigment, lubricant, sensitizer, stabilizer, and water are 25 to 75 parts by mass, 5 to 30 parts by mass, 100 to 500 parts by mass, lubricant, 5 to 40 parts by mass, sensitizer, 25 to 200 parts by mass, and stabilizer, relative to 100 parts by mass of the color developer, and that the solids content is 14 to 25% by mass.
  • the protective layer, under layer, back layer, and intermediate layer can also be formed by applying and drying a coating liquid containing the constituent components, just like the above-mentioned thermosensitive recording layer.
  • the thermosensitive recording material of the present invention, on which each layer has been formed may be subjected to treatments known in the art (for example, smoothing treatment using a supercalender, etc.).
  • the heat-sensitive recording material of the present invention can be suitably used for applications such as paper, film, IC cards, and friction ballpoint pens.
  • thermosensitive recording layer thermosensitive coloring layer
  • the resulting sticky substance was dissolved in ethyl acetate and subjected to silica gel chromatography with heptane/ethyl acetate/formic acid. The solvent was evaporated to obtain 5.1 g of the desired product, a white crystal.
  • the resulting crystals were dissolved in a small amount of ethyl acetate, and the resulting solution was subjected to silica gel chromatography with heptane/ethyl acetate/formic acid to elute and isolate each component of the composition.
  • the solvent was removed from the eluate containing the target product, and the concentrated solution was added dropwise to toluene to obtain crude crystals.
  • the resulting crude crystals were repeatedly recrystallized using heptane/ethyl acetate to obtain 7.6 g of the target white crystals.
  • the target product was obtained by the same procedure as in Synthesis Example 1, except that 28 g of p-toluoyl chloride was used instead of benzoyl chloride.
  • a pale yellow oily substance was obtained by distilling off the solvent. This substance was subjected to silica gel chromatography using hexane/ethyl acetate, and each component of the composition was eluted and isolated. The eluate containing the target product was then distilled off, and the resulting white solid was repeatedly recrystallized using hexane/ethyl acetate to obtain 3.6 g of the target white crystal.
  • the target product was obtained by the same procedure as in Synthesis Example 1, except that the same amount of D-isoascorbic acid was used instead of ascorbic acid.
  • thermosensitive recording layer ⁇ Coating liquid for the thermosensitive recording layer>
  • Solutions A to E were prepared. Solutions A and B were wet-milled using a ready mill (RMB-02) manufactured by Imex Co., Ltd. until the average particle size of each component reached 0.5 ⁇ m.
  • the average particle size here is the average size in a volume-based distribution, and was measured using a laser diffraction/scattering particle size distribution analyzer (Microtrac MT3000II) manufactured by Nikkiso Co., Ltd.
  • the coating liquid for the heat-sensitive recording layer was prepared by mixing the respective liquids in the following ratios. Liquid A: 85.00 parts Liquid B: 10.00 parts Liquid C: 17.87 parts Liquid D: 6.00 parts Liquid E: 19.62 parts Next, the coating liquid for the thermosensitive recording layer was applied to one side (smooth side) of the paper support so that the dry mass of the thermosensitive recording layer would be 4 to 6 g/ m2 , and then dried (air dryer, 60°C, 2 minutes) to form a thermosensitive recording layer. The support on which the thermosensitive recording layer had been formed was then treated with a supercalender to achieve a smoothness of 500 to 1000 seconds, yielding a thermosensitive recording material. This was then smoothed with a pressure of 1 kgf/ cm2 using the supercalender to obtain a thermosensitive recording material.
  • Example 2 A thermal recording material was produced in the same manner as in Example 1, except that the compound in Synthesis Example 1 in Solution A was changed to the compound in Synthesis Example 2, and the components of Solution A were prepared by stirring, mixing, and dissolving them.
  • Example 3 A thermal recording material was produced in the same manner as in Example 1, except that the compound in Synthesis Example 1 in Solution A was changed to the compound in Synthesis Example 3, and the components of Solution A were prepared by stirring, mixing, and dissolving them.
  • Example 4 A thermal recording material was produced in the same manner as in Example 1, except that the compound of Synthesis Example 1 in Solution A was changed to the compound of Synthesis Example 4, and the components of Solution A were prepared by stirring, mixing, and dissolving them.
  • Example 5 A thermal recording material was produced in the same manner as in Example 1, except that the amount of the compound in Synthesis Example 1 in Solution A was changed to 7.2 parts, 1.8 parts of 6-O-palmitoyl-L-ascorbic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the components of Solution A were mixed and dissolved by stirring to prepare Solution A.
  • Example 6 A thermal recording material was produced in the same manner as in Example 1, except that the amount of the compound in Synthesis Example 1 in Solution A was changed to 5.4 parts, 3.6 parts of 6-O-palmitoyl-L-ascorbic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the components of Solution A were mixed and dissolved by stirring to prepare Solution A.
  • Example 7 A thermal recording material was produced in the same manner as in Example 1, except that the amount of the compound in Synthesis Example 1 in Solution A was changed to 5.4 parts, 3.6 parts of 6-O-stearoyl-L-ascorbic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the components of Solution A were mixed and dissolved by stirring to prepare Solution A.
  • Example 8 A thermal recording material was produced in the same manner as in Example 1, except that the compound of Synthesis Example 1 in Solution A was changed to the compound of Synthesis Example 5, and the components of Solution A were prepared by stirring, mixing, and dissolving them.
  • ⁇ Plasticizer resistance> A checkerboard pattern was printed on both sides of a thermal recording material using a thermal printer (TH-M2/PX) manufactured by Okura Electric Co., Ltd. with an applied energy of 0.396 mJ/dot. DiaWrap (registered trademark) i-GSW manufactured by Mitsubishi Chemical Corporation was then brought into contact with the front and back of the thermal recording material, and the material was left at 20°C for 2 hours, after which the image density was measured with an eXact densitometer manufactured by X-Rite Corporation. Table 1 shows the image densities after the test. Note that a higher image density value in this test indicates better plasticizer resistance.
  • ⁇ Moisture resistance> A checkerboard pattern was printed on a thermal recording material using an Okura Electric thermal printer (TH-M2/PS) at an applied energy of 0.396 mJ/dot. The material was then left for 24 hours in an environment of 40°C and 90% humidity, after which the image density was measured using an X-Rite eXact densitometer. Table 1 shows the image densities after the test. Note that a higher image density value in this test indicates better moisture resistance.
  • ⁇ Alcohol resistance> A thermal recording material was printed in a checkerboard pattern using an Okura Electric thermal printer (TH-M2/PS) with an applied energy of 0.396 mJ/dot, and then immersed in 25% ethanol water for 20 minutes, removed, and left at room temperature for 24 hours. The image density was then measured using an X-Rite eXact densitometer. Table 1 shows the image densities after the test. Note that a higher image density value in this test indicates better alcohol resistance.
  • ⁇ Oil resistance> A checkerboard pattern was printed on a thermal recording material using an Okura Electric thermal printer (TH-M2/PS) with an applied energy of 0.396 mJ/dot.
  • a drop of Nissin salad oil (manufactured by The Nissin Oillio Group, Inc.) was dropped onto the printed area of the material, lightly wiped off, and the material was left at 20°C for 24 hours, after which the print density of the printed area was measured using an X-Rite eXact densitometer. Table 1 shows the image density after the test. Note that a higher image density value in this test indicates better oil resistance.
  • ⁇ Grease resistance> A checkerboard pattern was printed on a thermal recording material using a thermal printer (TH-M2/PS) manufactured by Okura Electric Co., Ltd. at an applied energy of 0.396 mJ/dot.
  • a drop of Skin Milk (manufactured by Nivea-Kao Corporation) was dropped onto the printed area of the material, lightly wiped off, and the material was left at 20°C for 24 hours, after which the print density of the printed area was measured using an eXact densitometer manufactured by X-Rite. Table 1 shows the image density after the test. Note that a higher image density value in this test indicates better grease resistance.
  • Examples 1 to 8 which used the compound of the present invention as a color developer, showed improved color development sensitivity as well as improved print preservation properties, such as heat resistance, plasticizer resistance, moisture resistance, water resistance, alcohol resistance, oil resistance, and grease resistance, compared to Comparative Examples 1 to 3, which used conventional color developers.

Landscapes

  • 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

L'invention concerne un révélateur susceptible de produire un matériau d'impression thermosensible qui présente une excellente sensibilité de révélation des couleurs et une excellente aptitude à la conservation des parties imprimées. Le révélateur contient un composé représenté par la formule (1). (R1, R2, R3 sont des groupes représentés par la formule (2), qui peuvent être identiques ou indépendamment différents les uns des autres.) (Dans la formule (2), m est 0 ou 1, A est un groupe de liaison choisi dans le groupe constitué par -C(=O)-, -C(=S)-, -C(=O)-NH-, -C(=S)-NH-, -C(=O)-NH-SO2-, -C(=S)-NH-SO2-, -SO2-, -SO2-NH- et -C(=O)-O-, et B est l'un quelconque choisi dans le groupe constitué par un groupe hydrocarboné aliphatique ayant 1 à 30 atomes de carbone qui peut avoir un substituant, un groupe alcoxy ayant 1 à 30 atomes de carbone qui peut avoir un substituant, un groupe aryle ayant 6 à 18 atomes de carbone qui peut avoir un substituant, ou un groupe arylalkyle ayant 7 à 48 atomes de carbone qui peut avoir un substituant.)
PCT/JP2025/008151 2024-03-06 2025-03-06 Révélateur et matériau d'impression thermosensible Pending WO2025187765A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2024034155 2024-03-06
JP2024-034155 2024-03-06

Publications (2)

Publication Number Publication Date
WO2025187765A1 true WO2025187765A1 (fr) 2025-09-12
WO2025187765A8 WO2025187765A8 (fr) 2025-10-02

Family

ID=96991150

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2025/008151 Pending WO2025187765A1 (fr) 2024-03-06 2025-03-06 Révélateur et matériau d'impression thermosensible

Country Status (1)

Country Link
WO (1) WO2025187765A1 (fr)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02117890A (ja) * 1988-10-28 1990-05-02 Ricoh Co Ltd 感熱記録材料

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02117890A (ja) * 1988-10-28 1990-05-02 Ricoh Co Ltd 感熱記録材料

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
TANAKA, HIROYOSHI ET AL.: "Pharmaceutucal Studies on Ascorbic Acid Derivatives. I. : Syntheses of Esters of Ascorbic Acid and Their Physicochemical Properties", YAKUGAKU ZASSHI, vol. 86, no. 5, 1966, pages 376 - 383, DOI: 10.1248/yakushil947.86.5_376 *

Also Published As

Publication number Publication date
WO2025187765A8 (fr) 2025-10-02

Similar Documents

Publication Publication Date Title
JP6184325B2 (ja) フェノールスルホン酸アリールエステル、顕色剤および感熱記録材料
KR101548182B1 (ko) 신규 페놀술폰산 아릴 에스테르 유도체 및 그것을 사용한 감열 기록 재료
JP7552614B2 (ja) 顕色剤及び感熱記録材料
JP2010053128A (ja) フェノールスルホン酸エステル、顕色剤及び感熱記録材料
JP7643188B2 (ja) 顕色剤及び感熱記録材料
WO2025187765A1 (fr) Révélateur et matériau d'impression thermosensible
JP2025056808A (ja) 顕色剤及び感熱記録材料
JP5808279B2 (ja) 感熱記録材料
JP7067559B2 (ja) 感熱記録材料及び積層体
WO2025187766A1 (fr) Révélateur de couleur et matériau d'impression thermosensible
JP7632157B2 (ja) 感熱記録材料
JP2025136009A (ja) 顕色剤及び感熱記録材料
JP2019142056A (ja) 顕色剤及び感熱記録材料
JP2022183803A (ja) 顕色剤及び感熱記録材料
JP3336609B2 (ja) 感熱記録体
JP3336610B2 (ja) 感熱記録体
JP3334127B2 (ja) 感熱記録体
JPWO2019031526A1 (ja) 感熱記録材料及び積層体

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 25768260

Country of ref document: EP

Kind code of ref document: A1