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EP0596224B1 - Matériau d'enregistrement sensible à la chaleur - Google Patents

Matériau d'enregistrement sensible à la chaleur Download PDF

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Publication number
EP0596224B1
EP0596224B1 EP19930114804 EP93114804A EP0596224B1 EP 0596224 B1 EP0596224 B1 EP 0596224B1 EP 19930114804 EP19930114804 EP 19930114804 EP 93114804 A EP93114804 A EP 93114804A EP 0596224 B1 EP0596224 B1 EP 0596224B1
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EP
European Patent Office
Prior art keywords
heat
group
sensitive recording
recording material
formula
Prior art date
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EP19930114804
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German (de)
English (en)
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EP0596224A3 (fr
EP0596224A2 (fr
Inventor
Masakatsu Nakatsuka
Naomasa Mitsubishi Seishi K.K. Nai Koike
Akinori Mitsubishi Seishi K.K. Nai Okada
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Mitsui Chemicals Inc
Mitsubishi Paper Mills Ltd
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Mitsui Chemicals Inc
Mitsubishi Paper Mills Ltd
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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
    • B41M5/337—Additives; Binders
    • B41M5/3375—Non-macromolecular 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
    • B41M5/333—Colour developing components therefor, e.g. acidic compounds
    • B41M5/3333—Non-macromolecular compounds
    • B41M5/3335—Compounds containing phenolic or carboxylic acid groups or metal salts thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/333—Colour developing components therefor, e.g. acidic compounds
    • B41M5/3333—Non-macromolecular compounds
    • B41M5/3335—Compounds containing phenolic or carboxylic acid groups or metal salts thereof
    • B41M5/3336—Sulfur compounds, e.g. sulfones, sulfides, sulfonamides

Definitions

  • the present invention relates to a heat-sensitive recording material and particularly relates to a heat-sensitive recording material which is particularly excellent in thermal response and preservation stability of white portions and images.
  • Heat-sensitive recording materials generally have a heat-sensitive recording layer on a substrate and the recording layer comprises as principal components a usually colorless or pale colored dyestuff precursor which is the electron donor and a developer which is an electron acceptor.
  • the recording materials are heated with a thermal head, hot-pen or laser beam, recording images can be obtained by an instantaneous reaction between the dyestuff precursor and the developer.
  • Heat-sensitive recording materials obtained by using conventional, electron donating colorless dyestuff precursors and electron accepting compounds have characteristics such as high color density.
  • these recording materials have disadvantages in that recorded images fade away when they are kept in contact with plastics such as polyvinyl chloride as plasticizers and additive that are usually contained in them migrate to the recording materials, that preservation characteristic of the recorded images is inferior because the color of these images is deteriorated by contact with chemicals contained in food and cosmetics, or that the color of marks put using a marker on white portions change or marking causes color development. Consequently, these recording materials are restricted in the field of use, and improvement of these recording materials has been strongly desired.
  • heat-sensitive recording materials using as the electron accepting compound salicylic acid derivatives having a substituant such as an alkyl group, aralkyl group, alkyloxy group, and aryl group or using metal salts thereof have been proposed in Japanese Laid-Open Patent SHO 62-169681, 63-22683 and 63-95977.
  • salicylic acid derivatives described in these patents provide unsatisfactory preservation characteristics of developed images, insufficient preservation stability of white portions, and additionally low coloring sensitivity. Thus, these salicylic acid derivatives have been difficult to use as heat-sensitive recording materials in practical high speed recording.
  • EP-A2-0 253 666 discloses heat-sensitive material containing 1.) an electron-donating colorless dye former, 2.) an electron-accepting color developer and 3.) a heat-fusible substance as preferable included component.
  • the electron-accepting compound may be represented by the formula where R 1 may represent a substituted amino group.
  • R 1 may represent a substituted amino group.
  • the substituted amino group of EP-A2-0 253 666 may be acylamino, aryl-sulfonylamino, alkyl(aryl)aminocarbonyl and dialkyl(diaryl)amino group
  • the substituted aminogroups of the invention are carbamate groups, i.e. oxycarbonylamino, thiocarbonylamino, thiolthiocarbonylamino and oxythiocarbonyl amino groups, thus completely different substituted groups.
  • the heat-fusible compound disclosed in EP-A2-0 253 666 is different, the effect improving the wet heat resistance as obtained by the invention is not reached according to EP-A2-0 253 666.
  • EP-A1-0 534 257 discloses a heat sensitive recording material containing the same salicylic and derivatives as the present invention but a different fusible compound; i.e. aliphatic amide compounds having 19 to 60 carbon atoms. are not disclosed in EP-A1-0 534 257
  • the object of the invention is to provide a heat-sensitive recording material having excellent thermal response and preservation stability of white portions and images.
  • the aspect of the invention is a heat-sensitive recording material having a usually colorless or pale colored dyestuff precursor and an electron accepting compound which develops color of said dyestuff precursor by heat-reaction, comprising one or more compounds selected from a salicylic acid derivative represented by the formula (1) : wherein X 1 and X 2 are a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aralkyl group, or an aryl group, Y 1 and Y 2 are an oxygen atom or a sulfur atom, R 1 is a hydrogen atom, an alkyl group, an aralkyl group or an aryl group, and R 2 is an alkyl group, an alkenyl group, an aralkyl group or an aryl group, or a divalent, trivalent or tetravalent metal salt of said salicylic acid derivative, further comprising an aliphatic amide compound having 19 ⁇ 60 carbon atoms in molecular structure and being excellent in thermal
  • the heat-sensitive recording material of the invention is prepared by using the salicylic acid derivative of the formula (1) or the metal salt of the derivative in combination with the aliphatic amide compound having 19 ⁇ 60 carbon atoms in the molecular structure, and has further improved thermal response in addition to thermal response and preservation stability of developed images which are essential properties of the salicylic acid derivative of the formula (1) or the metal salt of the derivative as the electron accepting compound for use in the heat-sensitive recording material.
  • the invention provides the heat-sensitive recording material which is particularly excellent in thermal response, also excellent in preservation stability of white portions and images, and can be compatible with practical high speed recording.
  • the principal electron accepting compound used in the invention is a salicylic acid derivative represented by the formula(1) and/or a metal salt of the salicylic acid derivative.
  • X 1 and X 2 are a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aralkyl group or an aryl group
  • Y 1 and Y 2 are an oxygen or a sulfur atom
  • R 1 is a hydrogen atom, an alkyl group, an aralkyl group or an aryl group
  • R 2 is an alkyl group, an alkenyl group, an aralkyl group or an aryl group.
  • the salicylic acid derivative and the metal salt of the derivative which can be used in the invention have following atoms and groups in the formula(1).
  • X 1 and X 2 are a hydrogen, an alkyl, alkoxy, aralkyl or aryl group or halogen atom, preferably hydrogen, C 1 ⁇ C 20 alkyl, C 5 ⁇ C 14 alicyclic, C 1 ⁇ C 20 alkoxy, C 7 ⁇ C 20 aralkyl, phenyl, fluorine, chlorine or bromine, more preferably hydrogen, C 1 ⁇ C 4 alkyl, cyclohexyl, C 1 ⁇ C 4 alkoxy, benzyl, ⁇ -methylbenzyl, cumyl, phenyl or chlorine, and most preferably hydrogen.
  • Y 1 and Y 2 are a oxygen or sulfur atom, and preferably Y 1 is oxygen.
  • R 1 is a hydrogen atom, an alkyl, aralkyl or aryl group, preferably hydrogen, C 1 ⁇ C 20 alkyl, C 5 ⁇ C 14 alicyclic, C 7 ⁇ C 20 aralkyl, phenyl or substituted phenyl, more preferably hydrogen, C 1 ⁇ C 8 alkyl, cyclopentyl, cyclohexyl, cycloheptyl, benzyl or phenyl, further preferably hydrogen, C 1 ⁇ C 4 alkyl or phenyl, and most preferably hydrogen.
  • R 2 is an alkyl, alkenyl, aralkyl or aryl group, preferably alkyl or substituted alkyl, alicyclic or substituted alicyclic, alkenyl or substituted alkenyl, cyclic alkenyl or substituted cyclic alkenyl, aralkyl or substituted aralkyl, phenyl or substituted phenyl, naphthyl or substituted naphthyl, or heteroaromatic or substituted heteroaromatic.
  • the alkyl or alkenyl represented by R 2 can be monosubstituted or polysubstituted.
  • the substituents include, for example, C 1 ⁇ C 20 alkoxy, C 2 ⁇ C 20 alkoxyalkyloxy, C 2 ⁇ C 20 alkenyloxy, C 7 ⁇ C 20 aralkyloxy, C 8 ⁇ C 20 aralkyloxyalkoxy, C 6 ⁇ C 20 aryloxy, C 7 ⁇ C 20 aryloxyalkoxy, C 8 ⁇ C 20 arylalkenyl, C 9 ⁇ C 20 aralkylalkenyl, C 1 ⁇ C 20 alkylthio, C 2 ⁇ C 20 alkoxyalkylthio, C 2 ⁇ C 20 alkylthioalkylthio, C 2 ⁇ C 20 alkenylthio, C 7 ⁇ C 20 aralkylthio, C 8 ⁇ C 20 aralkyloxyalkylthio, C 8 ⁇ C 20 aralkylthioalkylthio, C 6 ⁇ C 20 arylthio, C 7 ⁇ C
  • aryl which is included in these substituents can be substituted with C 1 ⁇ C 6 alkyl, C 1 ⁇ C 6 alkoxy, C 1 ⁇ C 6 alkylthio, C 7 ⁇ C 10 aralkyl, C 7 ⁇ C 10 aralkyloxy, hydroxyl or halogen.
  • the aralkyl or aryl represented by R 2 can be monosubstituted or polysubstituted.
  • substituents include, C 1 ⁇ C 20 alkyl, C 2 ⁇ C 20 alkenyl, C 7 ⁇ C 20 aralkyl, C 6 ⁇ C 20 aryl, C 1 ⁇ C 20 alkoxy, C 2 ⁇ C 20 alkoxyalkyl, C 2 ⁇ C 20 alkoxyalkyloxy, C 2 ⁇ C 20 alkenyloxy, C 3 ⁇ C 20 alkenyloxyalkyl, C 3 ⁇ C 20 alkenyloxyalkyloxy, C 7 ⁇ C 20 aralkyloxy, C 8 ⁇ C 20 aralkyloxyalkyl, C 8 ⁇ C 20 aralkyloxyalkyloxy, C 6 ⁇ C 20 aryloxy, C 7 ⁇ C 20 aryloxyalkyl, C 7 ⁇ C 20 aryloxyalkyloxy, C 2 ⁇ C 20 alkylcarbonyl, C 3 ⁇ C 20 alkenylcarbonyl, C 8 ⁇ C 20 aralkylcarbon
  • Aryl which is present in these substituents can be further substituted with C 1 ⁇ C 6 alkyl, C 1 ⁇ C 6 alkoxy, C 1 ⁇ C 6 alkylthio, C 7 ⁇ C 10 aralkyl, C 7 ⁇ C 10 aralkyloxy, hydroxy or halogen.
  • R 2 is nonsubstituted or substituted alkyl having from 1 to 24 total carbon atoms, nonsubstituted or substituted alkenyl having from 2 to 24 total carbon atoms, nonsubstituted or substituted aralkyl having from 7 to 24 total carbon atoms, or nonsubstituted or substituted aryl having from 6 to 24 total carbon atoms.
  • the compound represented by the formula(1) in the invention has a carbamate group on a salicylic acid skeleton.
  • the carbamate group locates on the position 3, 4, 5 or 6, preferably on the position 3, 4 or 5, most preferably on the position 4 or 5 in the salicylic acid skeleton.
  • more preferred salicylic acid derivative is represented by the formula(1-a): wherein X 1 , X 2 , Y 1 , Y 2 , R 1 and R 2 are the same as above, or by the formula(1-b): wherein X 1 , X 2 , Y 1 , Y 2 , R 1 and R 2 are the same as above.
  • Most preferred salicylic acid derivative is represented by the formula(1-c): wherein X 1 and X 2 are the same as above, R is an alkyl group, an alkenyl group, an aralkyl group or an aryl group.
  • R in the formula (1-c) is an alkyl group such as methyl, ethyl, n-butyl, n-octyl, n-decyl, n-octadecyl, iso-butyl, isopentyl or cyclohexyl; an alkenyl group such as allyl; an aralkyl group such as benzyl or substituted benzyl; or a phenyl group such as phenyl or substituted phenyl.
  • the metal salt of salicylic acid derivative represented by the formula(1) which is used for the electron accepting compound in the heat-sensitive recording material of the invention includes salts of monovalent metals such as sodium, potassium and lithium and polyvalent metals having 2, 3 and 4 valence.
  • the salt is preferably a metal salt which is difficultly soluble or insoluble in water and composed of a polyvalent metal of 2, 3 and 4 valence, more preferably a salt of the polyvalent metal having 2 or 3 valence.
  • Exemplary metal salts are salts of sodium, potassium, lithium, zinc, cadmium, mercury, magnesium, calcium, barium, nickel, tin, gallium, chromium, copper, molybdenum, wolfram, zirconium, strontium, manganese, cobalt, titanium, aluminum and iron, preferably salts of zinc, calcium, barium, nickel, manganese, cobalt and aluminum, more preferably salts of zinc, magnesium, nickel and manganese, most preferably a zinc salt.
  • the metal salt of the salicylic acid derivative can be used for the heat-sensitive recording material of the invention.
  • the salicylic acid derivative represented by the formula(1) and the metal salt of the derivative can be used singly or as a mixture for the electron accepting compound in the heat-sensitive recording material of the invention.
  • a combination of one or more salicylic acid derivative and a metal salt of salicylic acid derivative can also be used.
  • the salicylic acid derivative represented by the formula (1) or the metal salt of the derivative which is used in the invention can be prepared by known processes described, for example, in J.Pharm.Sci., 52,927(1963) and Bull.de.Socie. Chim. France, 1189(1955). That is, the derivative and its metal salt can be suitably prepared, for example, by reacting an aminosalicylic acid derivative with an almost equivalent amount of a chloroformate compound.
  • the heat-sensitive recording material of the invention is characterized in that preferred preservation characteristic of developed images, good preservation stability of white portions and very excellent thermal response can be obtained by using the aliphatic amide compound described below in combination with the above salicylic acid derivative or the metal salt of the derivative.
  • the aliphatic amide compound that can be used in the invention and has 19 to 60 carbon atoms in the molecular structure is represented by the formula (3) : R 3 CONH 2 wherein R 3 is an alkyl group or an alkenyl group and has 18 to59 carbon, the formula (4) : R 4 CONHR 5 wherein R 4 is an alkyl group or an alkenyl group, R 5 is an alkyl group, an alkenyl group or a hydroxymethyl group, and the sum of carbon atoms in R 4 and R 5 is 18 to 59, the formula (5) : R 6 CONHR 7 NHOCR 6 wherein R 6 is an alkyl group or an alkenyl group, R 7 is a divalent aliphatic radical and the sum of carbon in R 6 and R 7 is 17 to 58 or the formula (6) : R 8 NHOCR 9 CONHR 8 wherein R 8 is an alkyl group or an alkenyl group, R 9 is a divalent aliphatic group, and the sum of carbon atom
  • Exemplary compounds represented by the formula (3) include, behenic acid amide, erucic acid amide, tricosanoic acid amide, lignoceric acid amide, pentacosanoic acid amide, cerotic acid amide and melissic acid amide.
  • Exemplary compounds represented by the formula (4) include : N-octylpalmitic acid amide, N-methylstearic acid amide, N-ethylstearic acid amide, N-butylstearic acid amide, N-cyclohexylstearic acid amide, N-decylstearic acid amide, N-stearylstearic acid amide, N-oleylstearic acid amide, N-hydroxyymethylstearic acid amide and N-hydroxymethylbehenic acid amide.
  • Exemplary compounds represented by the formula (5) include : ethylenebisstearic acid amide, butylenebisstearic acid amide, pentamethylenebisstearic acid amide, hexamethylenebisoleic acid amide, hexamethylenebisstearic acid amide, hexamethylenebislauric acid amide, hexamethylenebispalmitic acid amide, and octamethylenebispalmitic acid amide.
  • Exemplary compounds represented by the formula (6) include
  • aliphatic amide compounds can be used singly or as a mixture.
  • thermal response of the heat-sensitive recording material can be improved without giving adverse effect on the preservation stability of white portions and images.
  • the aliphatic amide compound When an aliphatic amide compound having 19 or more carbon atoms is used, wet heat resistance (i.e. resistance to heat under a moist environment), which is an attribute of the image preservation stability, is improved as compared with when an aliphatic amide having 18 carbon atoms is used. That is, the aliphatic amide compound has 19 ⁇ 60 carbon atoms, preferably 19 ⁇ 50 carbon atoms in the molecular structure. Use of such aliphatic amide compound in combination provides a heat-sensitive recording material which is excellent in preservation stability of white portions and images, and particularly excellent in thermal response.
  • the aliphatic amide compound When the aliphatic amide compound has less than 19 carbon atoms in the molecular structure, the resulting heat-sensitive recording material is inferior in preservation stability of white portions, particularly in heat resistance, and additionally sensitivity for color development is insufficiently improved. On the other hand, the aliphatic amide compound having more than 60 carbon atoms in the molecular structure renders inferior preservation stability for the heat-sensitive recording material and is unfavorably difficult to obtain in some cases.
  • the amount of the aliphatic amide compound is preferably 10 ⁇ 300 % by weight, more preferably 20 ⁇ 200 % by weight based on the salicylic acid derivative of the formula (1) or the metal salt of the derivative.
  • a usually colorless or pale colored dyestuff precursor having electron donating ability and an electron accepting compound are generally used as principal components, these components are dispersed in a binder and coated on a substrate to form a heat-sensitive recording layer, and the layer is heated by a thermal head, hot pen or laser beam to develop recording images by an instantaneous reaction between the dyestuff precursor and the electron accepting compound.
  • the process has been disclosed in Japanese Patent Publication SHO 43-4160 and 45-14039.
  • Fillers, sensitizers, antioxidants and antisticking agents are added to the heat-sensitive recording layer, when desired.
  • These color forming, electron donating compounds can be used singly, or as a mixture in order to control color tone of developed image or to obtain multi-colored heat-sensitive recording materials.
  • the heat-sensitive recording material of the invention is characterized by comprising as the electron accepting compound one or more salicylic acid derivatives of the formula(1) and/or the metal salts of said derivatives.
  • Other electron accepting compounds can be simultaneously used in the range giving no adverse effect on the desired properties of the heat-sensitive recording material of the invention.
  • the electron accepting compound to be used in combination with the salicylic acid derivative of the invention is an acidic substance and is generally used for heat-sensitive recording materials.
  • the compound is an acidic substance and is generally used for heat-sensitive recording materials.
  • phenol derivatives, aromatic carboxylic acid derivatives, N,N'-diarylthiourea derivatives, and zinc salt and other multivalent metal salts of organic compounds can be used.
  • phenol derivatives include phenol compounds such as p-phenyphenol, p-hydroxyacetophenone, 4-hydroxy-4'-methyldiphenyl sulfone, 4-hydroxy-4'-isopropoxydiphenyl sulfone, 4-hydroxy-4'-benzenesulfonyloxydiphenyl sulfone, 1,1-bis(p-hydroxyphenyl)propane, 1,1-bis(p-hydroxyphenyl)pentane, 1,1-bis(p-hydroxyphenyl)hexane, 1,1-bis(p-hydroxyphenyl)cyclohexane, 2,2-bis(p-hydroxyphenyl)propane, 2,2-bis(p-hydroxyphenyl)hexane, 1,1-bis(p-hydroxyphenyl)-2-ethylhexane, 2,2-bis(3-chloro-4-hydroxyphenyl)propane, 1,1-bis(p-hydroxyphenyl)-1-phenylethane, 1,
  • Exemplary binders which can be used for the heat-sensitive recording material of the invention include water soluble adhesives such as starches, hydroxyethylcellulose, methylcellulose, gelatin, casein, polyvinyl alcohol, modified polyvinyl alcohol, sodium polyacrylate, and alkali metal salt of acrylic amide/acrylic ester copolymer, acrylic amide/acrylic ester/methacrylic acid ternary copolymer, styrene/maleic anhydride copolymer and ethylene/maleic anhydride copolymer ; and latexes such as polyvinyl acetate, polyurethane, polyacrylic ester, styrene/butadiene copolymer, acrylonitrile/butadiene copolymer, methyl acrylate/butadiene copolymer and ethylene/vinyl acetate copolymer.
  • water soluble adhesives such as starches, hydroxyethylcellulose, methylcellulose, gelatin, casein
  • Fillers which can be used include, for example, diatomaceous earth, tale, kaolin, calcined kaolin, calcium carbonate, magnesium carbonate, titanium oxide, zinc oxide, silicon oxide, aluminum hydroxide and urea-formaldehyde resin.
  • Metal salts of higher fatty acids such as zinc stearate and calcium stearate, and waxes such as paraffin, oxidized paraffin, polyethylene, oxidized polyethylene, stearic acid amide and castor wax can be added in order to prevent head abrasion and sticking.
  • Dispersants such as sodium dioctylsulfosuccinate, benzophenone base and benzotriazol base ultraviolet absorbers, surface active agents and fluorescent dyes can also be added, if desired.
  • Substrate used for the invention is primarily paper. Non woven fabrics, plastic films, synthetic paper, metal foil or composite sheets obtained by combination of these matters can also be arbitrarily used. Further, application of an overcoat layer for protecting the heat-sensitive recording layer, application of single or more undercoat layers comprising fillers or resin between the heat-sensitive recording layer and the substrate, and a variety other known techniques in the preparation of heat-sensitive recording materials can also be used in the invention.
  • Coating amount of the heat-sensitive recording layer depends upon the amounts of the dyestuff precursor and the electron accepting compound which are color developing components. Preferred amount of the dyestuff precursor is usually 0.1 ⁇ 1.0 g/m 2 . The amount of the electron accepting compound is 5 ⁇ 700% by weight, preferably 20 ⁇ 500% by weight based on the dyestuff precursor.
  • a coating liquid having the formulation described below was applied on a base paper having a basis weight of 40 g/m 2 so as to obtain a solid coating weight of 9 g/m 2 , and dried to obtain the paper to be used for heat-sensitive coating.
  • Calcined Kaolin 100 parts 50% Aqueous styrene/butadiene latex 24 parts Water 200 parts
  • the heat-sensitive coating liquid prepared in (A) was coated on the paper prepared in (B) so as to obtain a solid coating weight of 4 g/m 2 , and dried to obtain a heat-sensitive recording material.
  • the heat-sensitive recording material thus prepared was calendered so as to obtain 400 ⁇ 500 seconds in Beck smoothness of the heat-sensitive surface, and successively following evaluation tests were carried out. Results are summarized in Table 1.
  • a printing test was carried out using a facsimile tester TH-PMD (Trade Mark of Ohkura Electric Co.).
  • a thermal head having a dot density of 8 dots/mm head resistance of 185 ⁇ was used.
  • Printing was carried out at a head voltage of 12V and pulse duration of 0.7 and 1.0 millisecond.
  • Developed color density was measured by a Macbeth Model RD-918 reflection densitometer.
  • each sample specimen of the heat-sensitive recording material was allowed to stand 60 °C for 24 hours, thereafter whiteness of each sample specimen was measured by a Macbeth Model RD-918 reflection densitometer. The higher the value, the higher cooling - i.e. poorer heat resistance.
  • the heat resistance is determined good; when the value exceeds 0.20, the property determined poor reflecting degraded image quality that likely to occur on use depending on printing condotions or smudging of white background during storing.
  • Preservation stability is determined to be good when the residual rate is 70 % or higher; preservation stability is determined to be excellent when the rate is 80 % or higher.
  • a heat-sensitive recording material was prepared by carrying out the same procedures as described in Example 1 except that behenic acid amide was replaced by N-hydroxymethylstearic acid amide.
  • the heat-sensitive recording material obtained was evaluated by the same procedures as Example 1.
  • a heat-sensitive recording material was prepared by carrying out the same procedures as described in Example 1 except that behenic acid amide was replaced by N-hydroxymethylbehenic acid amide.
  • the heat-sensitive recording material obtained was evaluated by the same procedures as Example 1.
  • a heat-sensitive recording material was prepared by carrying out the same procedures as described in Example 1 except that behenic acid amide was replaced by ethylenebisstearic acid amide.
  • the heat-sensitive recording material obtained was evaluated by the same procedures as Example 1.
  • a heat-sensitive recording material was prepared by carrying out the same procedures as described in Example 1 except that behenic acid amide was replaced by N-stearylstearic acid amide.
  • the heat-sensitive recording material obtained was evaluated by the same procedures as Example 1.
  • a heat-sensitive recording material was prepared by carrying out the same procedures as described in Example 1 except that behenic acid amide was replaced by N,N'-dioleylsebacic acid amide.
  • the heat-sensitive recording material obtained was evaluated by the same procedures as Example 1.
  • a heat-sensitive recording material was prepared by carrying out the same procedures as described in Example 1 except that behenic acid amide was not used.
  • the heat-sensitive recording material obtained was evaluated by the same procedures as Example 1.
  • a heat-sensitive recording material was prepared by carrying out the same procedures as described in Example 1 except that behenic acid amide was replaced by 2-benzyloxynaphthalene.
  • the heat-sensitive recording material obtained was evaluated by the same procedures as Example 1.
  • a heat-sensitive recording material was prepared by carrying out the same procedures as described in Example 1 except that behenic acid amide was replaced by palmitic acid amide.
  • the heat-sensitive recording material obtained was evaluated by the same procedures as Example 1.
  • a heat-sensitive recording material was prepared by carrying out the same procedures as described in Example 1 except that behenic acid amide was replaced by lauric acid amide.
  • the heat-sensitive recording material obtained was evaluated by the same procedures as Example 1.
  • a heat-sensitive recording material was prepared by carrying out the same procedures as described in Example 1 except that zinc 4-n-octyloxycarbonylaminosalicylate was replaced by 2,2-bis(4-hydroxyphenyl)propane.
  • the heat-sensitive recording material obtained was evaluated by the same procedures as Example 1.
  • a heat-sensitive recording material was prepared by carrying out the same procedures as described in Example 1 except that zinc 4-n-octyloxycarbonylaminosalicylate was replaced by zinc 3,5-bis( ⁇ -methylbenzyl)salicylate.
  • the heat-sensitive recording material obtained was evaluated by the same procedures as Example 1.

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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (6)

  1. Matière d'enregistrement thermosensible possédant un précurseur de matière colorante incolore ou de couleur pâle et un composé accepteur d'électrons qui développe la couleur dudit précuseur de matière colorante par réaction thermique, comprenant un ou plusieurs composés choisis parmi un dérivé de l'acide salicylique représenté par la formule (1):
    Figure 00470001
    dans laquelle X1 et X2 représentent un atome d'hydrogène, un atome d'halogène, un groupe alkyle, un groupe alcoxy, un groupe aralkyle ou un groupe aryle, Y1 et Y2 représentent un atome d'oxygène ou un atome de soufre, R1 représente un atome d'hydrogène, un groupe alkyle, un groupe aralkyle ou un groupe aryle, et R2 représente un groupe alkyle, un groupe alcényle, un groupe aralkyle ou un groupe aryle, ou un sel métallique dudit dérivé de l'acide salicylique, caractérisé en ce qu'elle comprend de plus un composé amide aliphatique ayant 19 à 60 atomes de carbone dans sa structure moléculaire.
  2. Matière d'enregistrement thermosensible selon la revendication 1, dans laquelle le composé amide aliphatique est représenté par la formule (3): R3CONH2 dans laquelle R3 représente un groupe alkyle ou un groupe alcényle et possède 18 à 59 atomes de carbone.
  3. Matière d'enregistrement thermosensible selon la revendication 1, dans laquelle le composé amide aliphatique est représenté par la formule (4): R4CONHR5 dans laquelle R4 représente un groupe alkyle ou un groupe alcényle, R5 représente un groupe alkyle, un groupe alcényle ou un groupe hydroxyméthyle, et la somme des atomes de carbone dans R4 et R5 vaut 18 à 59.
  4. Matière d'enregistrement thermosensible selon la revendication 1, dans laquelle le composé amide aliphatique est représenté par la formule (5): R6CONHR7NHOCR6 dans laquelle R6 représente un groupe alkyle ou un groupe alcényle, R7 représente un radical aliphatique divalent et la somme des atomes de carbone dans R6 et R7 vaut 17 à 58.
  5. Matière d'enregistrement thermosensible selon la revendication 1, dans laquelle le composé amide aliphatique est représenté par la formule (6): R8NHOCR9CONHR8 dans laquelle R8 représente un groupe alkyle ou un groupe alcényle, R9 représente un groupe aliphatique divalent, et la somme des atomes de carbone dans R8 et R9 vaut 17 à 58.
  6. Matière d'enregistrement thermosensible selon la revendication 1, dans laquelle la quantité du composé amide aliphatique est de 10 à 300% en poids par rapport au poids du dérivé d'acide salicylique ou du sel métallique dudit dérivé.
EP19930114804 1992-11-06 1993-09-15 Matériau d'enregistrement sensible à la chaleur Expired - Lifetime EP0596224B1 (fr)

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JP297027/92 1992-11-06
JP29702792A JP3156107B2 (ja) 1992-11-06 1992-11-06 感熱記録材料

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EP0596224A2 EP0596224A2 (fr) 1994-05-11
EP0596224A3 EP0596224A3 (fr) 1996-07-03
EP0596224B1 true EP0596224B1 (fr) 1999-01-13

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Publication number Priority date Publication date Assignee Title
EP0253666A3 (fr) * 1986-07-16 1988-04-27 Fuji Photo Film Co., Ltd. Matériel d'enregistrement thermosensible contenant un composé producteur de colorant
DE69218091T2 (de) * 1991-09-24 1997-10-09 Mitsubishi Paper Mills Ltd Salicylsäurederivate, Verfahren zu ihrer Herstellung, und diese enthaltende wärmeempfindliche Aufzeichnungsmaterialien

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DE69323035D1 (de) 1999-02-25
JPH06143824A (ja) 1994-05-24
DE69323035T2 (de) 1999-06-10
EP0596224A3 (fr) 1996-07-03
EP0596224A2 (fr) 1994-05-11
JP3156107B2 (ja) 2001-04-16

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