WO2002068206A1 - Materiau d'enregistrement thermosensible - Google Patents

Materiau d'enregistrement thermosensible Download PDF

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Publication number
WO2002068206A1
WO2002068206A1 PCT/EP2002/001539 EP0201539W WO02068206A1 WO 2002068206 A1 WO2002068206 A1 WO 2002068206A1 EP 0201539 W EP0201539 W EP 0201539W WO 02068206 A1 WO02068206 A1 WO 02068206A1
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WO
WIPO (PCT)
Prior art keywords
methyl
heat sensitive
diethylamino
image
bis
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PCT/EP2002/001539
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English (en)
Inventor
James Philip Taylor
John Barry Henshall
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Ciba Specialty Chemicals Holding Inc.
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Publication of WO2002068206A1 publication Critical patent/WO2002068206A1/fr

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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

Definitions

  • the present invention relates to heat sensitive composition and heat sensitive recording materials. It more particularly relates to such recording material in the form of a supporting substrate, for example, a paper sheet, synthetic paper sheet or plastic resin film coated with colour-forming systems comprising a colourless or pale coloured electron donative compound (colour forming compound), an organic electron acceptor (developer) and a compound that improves image stability (stabiliser).
  • a colourless or pale coloured electron donative compound colour forming compound
  • developer organic electron acceptor
  • stabiliser a compound that improves image stability
  • Heat sensitive recording has conventionally been used as a system for recording transferred information through the mediation of heat, by utilising a colour reaction between a colour forming compound and a developer.
  • the properties which are most desirable in a colour forming material, in addition to the effective development of colour, are thermal response, background whiteness and image stability, especially light fastness of the developed colour, heat and moisture fastness of the developed colour, oil fastness of the developed colour, plasticiser resistance of the developed colour and water fastness of the developed colour.
  • a disadvantage of heat sensitive recording materials is the stability of the image, particularly towards light over a prolonged period of time.
  • the stability of the image is lowered when it is stored under severe conditions, for example at elevated temperatures and / or humidity, or when the recording material is brought into contact with water, oils or plasticisers.
  • JP 03053982 A describes the use of 2,2'-thiobis derivatives as sensitizers not as stabilizers.
  • a sensitizer is a compound with a relatively low melting point that melts with the application of heat and assists in the interaction of the color former and the developer to produce the image, it is clearly different from a stabilizer which stabilizes the produced image against outside influences such as humidity, oil, fat, light, water etc.
  • EP 0,993,965 A discloses the use of benzoxadinone compounds as UV absorbing agents in thermal systems.
  • 2,2'-thiobis derivatives are described which, however, are substituted twice at the phenyl rings.
  • the present invention is directed to a heat sensitive composition, comprising a) at least one colour forming compound, b) at least one developer, c) at least one stabiliser of the formula (II)
  • Ri and R 2 are independently from each other hydrogen, C ⁇ - C 20 alkyl, C 3 - C ⁇ 0 cycloalkyl, unsubstituted or substituted aralkyl of from 7 to 10 carbon atoms or unsubstituted or substituted phenyl,
  • R 3 and R are indepedently from each other hydrogen or d - C o alkyl or C -C 10 cycloalkyl, wherein R 3 and R 4 are not in ortho-position to the hydroxyl group, and n is 0, 1 or 2, preferably 0.
  • stabilisers of formula (II) in the much smaller quantities described and without the addition of a known developer produce little or no image upon the application of heat.
  • the compounds of formula (II) can thus be described as acting in such a manner as to produce a stabilising effect upon the developed image on the thermal recording material and can thus be described as a stabiliser for applications described herein.
  • Ri or R 2 are preferably Ci . - C 12 alkyl, cyclohexyl, unsubstituted phenylalkyl of from 7 to 10 carbon atoms or unsubstituted phenyl. Of these Ri or R 2 are Ci - C 12 alkyl, cyclohexyl, benzyl, phenethyl or phenyl are most preferable. In a preferred embodiment, R 3 and R are preferably C r C 4 alkyl and especially hydrogen.
  • the stabilisers of formula (II) preferably Ri and R 2 are identical, and/or R 3 and R 4 are also preferably identical.
  • C C 2 o alkyl stands for methyl, ethyl, n-, i-propyl, n-, i-, sec- or tert.-butyl, n-, i-, tert.-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethyl-hexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n- tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, preferably CrC 12 alkyl such as methyl, ethyl, n-, i-propyl,
  • C 3 -C 10 cycloalkyl stands for cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclodecyl, preferably cyclohexyl,
  • unsubstituted or substituted aralkyl of from 7 to 10 carbon atoms stands for benzyl, 2- phenylethyl, 3-phenylpropyl, 4-phenylbutyl,
  • substituted phenyl stands for phenyl, which is substituted one to three times by d-C 4 alkyl such as methylphenyl, ethylphenyl, propylphenyl, isopropylphenyl, or n-butylphenyl.
  • the ratio of the compound of formula (II) : colour former can be in the range of from 0.05:1 to 1.0:1 , although preferably the ratio of the compound of formula (II) : colour former is in the range of 0.1 :1 to 0.7:1. Most preferably the ratio is about 0.5:1.
  • Stabilisers of formula (II) are exemplified by but are not limited to; 2,2'-thiobis[4- methylphenol], 2,2'-thiobis[4-ethylphenol], 2,2'-thiobis[4-isopropylphenol], 2,2'-thiobis[4-tert- butylphenol], 2,2'-thiobis[4-t-octylphenol], 2,2'-thiobis[4-dodecylphenol], 2,2'-thiobis[4- cyclohexylphenol], 2,2'-thiobis[4-benzylphenol], 2,2'-thiobis[4-cumylphenol], 2,2'-thiobis[4- phenylphenol].
  • the most preferred stabiliser is 2,2'-thiobis[4-t-octylphenol].
  • the compounds of formula (II) can be prepared by known methods, most common being the condensation of a 4-substituted phenol with sulphur dichloride in a suitable solvent and in the presence or absence of a Lewis Acid.
  • the colour forming compounds are, for example, triphenylmethanes, lactones, benzoxazines, spiropyrans or preferably fluorans.
  • Preferred colour formers include but are not limited to; 3-diethylamino-6-methylfluoran, 3- dimethylamino-6-methyl-7-anilinofluoran, 3-diethylamino-6-methyl-7-anilinofluoran, 3- diethylamino-6-methyl-7-(2,4-dimethylanilino) fluoran, 3-diethylamino-6-methyl-7- chlorofluoran, 3-diethylamino-6-methyl-7-(3-trifluoromethylanilino) fluoran, 3-diethylamino-6- methyl-7-(2-chloroanilino) fluoran, 3-diethylamino-6-methyl-7-(4-chloroanilino) fluoran, 3- diethylamino-6-methyl-7-(2-fIuoroanilino) fluoran, 3-diethylamino-6-methyl-7-(4-n-octylanilino) fluoran, 3-die
  • the monophase solid solutions can be used singly or as a mixture with other colour forming compounds such as triphenylmethanes, lactones, fluorans, benzoxazines and spiropyrans; or they may also be used together with further black colour forming compounds. Examples of such other colour forming compounds are given hereinbefore.
  • the heat sensitive recording material contains a developer.
  • developers are exemplified by but not limited to; 4,4'-isopropylidene bisphenol, 4,4'-sec-butylidene bisphenol, 4,4'-cyclohexylidene bisphenol, 2,2-bis-(4-hydroxyphenyl)-4-methylpentane, 2,2- dimethyl-3,3-di(4-hydroxyphenyl)butane, 2,2'-dihydroxydiphenyl, 1-phenyl-1 ,1-bis(4- hydroxyphenyl)butane, 4-phenyl-2,2-bis(4-hydroxyphenyl)butane, 1 -phenyl-2,2-bis(4- hydroxyphenyl)butane, 2,2-bis(4'-hydroxy-3'-methylphenyl)-4-methylpentane, 2,2-bis(4'- hydroxy-3'-tert-butylphenyl)-4-methylpentane, 4,4'-sec-butylidene
  • the heat sensitive composition of the invention can contain a sensitiser.
  • sensitiser are stearamide, methylol stearamide, p- benzylbiphenyl, m-terphenyl, 2-benzyloxynaphthalene, 4-methoxybiphenyl, dibenzyl oxalate, di(4-methylbenzyl) oxalate, di(4-chlorobenzyl) oxalate, dimethyl phthalate, dibenzyl terephthalate, dibenzyl isophthalate, 1 ,2-diphenoxyethane, 1 ,2-bis(4-methylphenoxy) ethane, 1 ,2-bis(3-methylphenoxy) ethane, 4,4'-dimethylbiphenyl, phenyl-l-hydroxy-2-naphthoate, 4- methylphenyl biphenyl ether, 1 ,2-bis(3,4-dimethylphenyl) ethane, 2,3,5, 6,4'-methyldiphenyl methane
  • Another preferred embodiment of this invention relates to a heat sensitive recording material comprising a substrate sheet and a heat sensitive coloured image-forming layer formed on the surface of the substrate sheet and comprising the inventive heat sensitive composition.
  • a further preferred embodiment of this invention concerns the use of the inventive composition as heat sensitive coloured image-forming layer for the manufacture of a heat- sensitive recording material.
  • the heat sensitive recording material of the invention can be prepared according to conventional methods.
  • at least one colour forming compound, at least one developer, optionally at least one sensitiser are pulverised separately in water or a suitable dispersing medium, such as aqueous polyvinyl alcohol, to form an aqueous or other dispersion.
  • a suitable dispersing medium such as aqueous polyvinyl alcohol
  • a compound of formula (II) is treated in the same manner.
  • the fine particle dispersions thus obtained are combined and then usually mixed with conventional amounts of binder, filler and lubricant.
  • binders used for the heat sensitive recording material include polyvinyl alcohol (fully and partially hydrolysed), carboxy, amide, sulfonic and butyral modified polyvinyl alcohols, derivatives of cellulose such as hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, carboxymethyl cellulose and acetyl cellulose, copolymer of styrene-maleic anhydride, copolymer of styrene-butadiene, polyvinyl chloride, polyvinyl acetate, polyacrylamide, polyamide resin and mixtures thereof.
  • Exemplary fillers which can be used, include calcium carbonate, kaolin, calcined kaolin, aluminium hydroxide, talc, titanium dioxide, zinc oxide, silica, polystyrene resin, urea- formaldehyde resin, hollow plastic pigment and mixtures thereof.
  • Representative lubricants for use in heat sensitive recording materials include stearamide, methylene bisstearamide, polyethylene, carnauba wax, paraffin wax, zinc stearate or calcium stearate and mixtures thereof.
  • additives can also be employed, if necessary.
  • additives are for example fluorescent whitening agents and ultraviolet absorbers.
  • the coating liquid so obtained can be applied to a suitable substrate such as paper, plastic sheet and resin coated paper, and used as the heat sensitive recording material.
  • the system of the invention can be employed for other end use applications using colour forming materials, for example, a temperature indicating material.
  • the quantity of the coating is usually in the range of 2 to 10 g/m 2 , most often in the range 4 to 8 g/m 2 .
  • thermosensitive colouring layer can in addition contain a protective layer and, if desired, an undercoat layer.
  • the undercoat layer may be interposed between the substrate and the thermosensitive colouring layer.
  • the protective layer usually comprises a water-soluble resin in order to protect the thermosensitive colouring layer. If desired, the protective layer may contain water-soluble resins in combination with water-insoluble resins.
  • resins conventional resins can be employed.
  • polyvinyl alcohol starch and starch derivatives
  • cellulose derivatives such as methoxycellulose, hydroxyethylcellulose, carboxymethylcellulose, methylcellulose and ethylcellulose
  • sodium polyacrylate polyvinyl pyrrolidone
  • polyacrylamide/acrylic acid ester copolymers acrylamide/acrylie acid ester/methacrylic acid copolymers
  • alkali metal salts of styrene/maleic anhydride copolymers alkali metal salts of isobutylene/maleic anhydride copolymers
  • polyacrylamide sodium alginate; gelatin; casein; water-soluble polyesters and carboxyl-group-modified polyvinyl alcohols.
  • the protective layer may also contain a water-resisting agent such as a polyamide resin, melamine-formaldehyde resin, formaldehyde, glyoxal or chromium alum.
  • a water-resisting agent such as a polyamide resin, melamine-formaldehyde resin, formaldehyde, glyoxal or chromium alum.
  • the protective layer may contain fillers, such as finely-divided inorganic powders, e.g. of calcium carbonate, silica, zinc oxide, titanium oxide, aluminium hydroxide, zinc hydroxide, barium sulphate, clay, talc, surface-treated calcium or silica, or a finely- divided organic powder of, e.g., a urea-formaldehyde resin, a styrene/methacrylic acid copolymer or polystyrene.
  • the undercoat layer usually contains as its main components a binder resin and a filler.
  • binder resins for use in the undercoat layer are: polyvinyl alcohol; starch and starch derivatives; cellulose derivatives such as methoxycellulose, hydroxyethylcellulose, carboxymethylcellulose, methylcellulose and ethylcellulose; sodium polyacrylate; polyvinyl pyrrolidone; polyacrylamide/acrylic acid ester copolymers; acrylamide/acrylic acid ester/methacrylic acid copolymers; alkali metal salts of styrene/maleic anhydride copolymers; alkali metal salts of isobutylene/maleic anhydride copolymers; polyacrylamide; sodium alginate; gelatin; casein; water-soluble polymers such as water-soluble polyesters and carboxyl-group-modified polyvinyl alcohols; polyvinyl acetate; polyurethanes; styrene/butadiene copolymers; polyacrylic acid; polyacrylic acid esters; vinyl chloride/vinyl
  • fillers for use in the undercoat layer are: finely-divided inorganic powders, e.g. of calcium carbonate, silica, zinc oxide, titanium oxide, aluminium hydroxide, zinc hydroxide, barium sulphate, clay, talc, surface-treated calcium, silica or calcined clay (e.g. Ansilex, Engelhard Corp.), and finely-divided organic powders of, e.g., urea-formaldehyde resins, styrene/methacrylic acid copolymers and polystyrene.
  • finely-divided inorganic powders e.g. of calcium carbonate, silica, zinc oxide, titanium oxide, aluminium hydroxide, zinc hydroxide, barium sulphate, clay, talc, surface-treated calcium, silica or calcined clay (e.g. Ansilex, Engelhard Corp.)
  • finely-divided organic powders e.g.,
  • the undercoat layer may contain a water-resisting agent. Examples of such agents are given above.
  • the recording material comprises a colour forming compound that will generate a blue image and which is selected from the group consisting of 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide,3-(4-diethylamino-2- ethoxyphenyl)-3-(1 -ethyl-2-methylindole-3-yl)-4-azaphthalide, and 3-(4-diethylamino-2- ethoxyphenyl)-3-(1-octyl-2-methylindole-3-yl)-4-azaphthalide.
  • a colour forming compound that will generate a blue image and which is selected from the group consisting of 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide,3-(4-diethylamino-2- ethoxyphenyl)-3-(1 -ethyl-2-methylindole-3-yl)-4-azaphthalide
  • the recording material comprises a colour forming compound that will generate a green image and which is 3-diethylamino-7-(dibenzylamino) fluoran.
  • the recording material comprises a colour forming compound that will generate an orange image and which is selected from the group consisting of 3-diethylamino-7-t-butylfluoran, and 3-diethylamino-7-carboxyethylfluoran.
  • the recording material comprises a colour forming compound that will generate a red image and which is selected from the group consisting of 3,3-bis(1 -ethyl-2methylindole-3-yl)phthalide, 3,3-bis(1 -octyl-2-methylindole-3-yl)phthalide, 9- (diethylamino)-spiro[12H-benzo[a]xanthene-12,1'(3'H)-isobenzofuran]-3'-one, and 6-(N-ethyl- N-4-methylphenyl)amino-2-methylfluoran.
  • a colour forming compound that will generate a red image and which is selected from the group consisting of 3,3-bis(1 -ethyl-2methylindole-3-yl)phthalide, 3,3-bis(1 -octyl-2-methylindole-3-yl)phthalide, 9- (diethylamino)-spiro[12H
  • the invention provides exceptional resistance to plasticiser, oil and heat ageing whilst showing improved background whiteness.
  • Stabilisers of the formula (II) may be used in much smaller quantities in conjunction with a known developer, to give a thermal recording material whose developed image has improved properties over systems using the same developer without the inclusion of a compound of formula (II).
  • Dispersions A to D are prepared by grinding the compositions shown below in an attritor until an average particle size of 1-1.5 ⁇ is attained.
  • a thermal coating mixture is then prepared by combining together the following components: parts by weight
  • Zinc stearate (33% aqueous dispersion) 1.5
  • Tinopal® ABP-X fluorescent whitening agent 0.12
  • This coating mixture is applied on one side of a base paper weighing 50 g/m 2 in a coating weight of about 5.0 g/m 2 and then dried.
  • the resulting sheet is calendered by means of a laboratory calender to produce a recording sheet with excellent background whiteness.
  • Li ⁇ htfastness Tests 120 Hours Exposure: This test assesses the stability of the imaged and un-imaged thermal paper to sunlight.
  • An image is produced using an Atlantek thermal response tester model 200.
  • the image including background is placed at a distance of 8cm below 40W fluorescent tubes emitting artificial sunlight (approximately 1200 Lux) for 120 hours.
  • the optical density of the image and background whiteness of the paper are measured before and after exposure with a Macbeth 1200 series Densitometer.
  • An image is produced using an Atlantek thermal response tester model 200. Cottonseed oil is then gravure printed onto the image which is then stored at 40°C for 24 hours. The optical density of the image is measured using a Macbeth 1200 series Densitometer before and after exposure.
  • An image is produced using an Atlantek thermal response tester model 200.
  • the image is put into contact with the PVC under 107g cm "2 pressure for 24 hours at 50°C.
  • the optical density of the image and background are measured using a Macbeth 1200 series Densitometer before and after exposure. Waterfastness of Image:
  • An image is produced using an Atlantek thermal response tester model 200.
  • the image is immersed in de-ionised water at room temperature for 3 hours.
  • the optical density of the image is measured using a Macbeth 1200 series Densitometer before and after immersion.
  • Heat and Moisture Resistance of Image :
  • An image is produced using an Atlantek thermal response tester model 200.
  • the image is aged at 60°C at 70% R.H. for 24 hours.
  • the optical density of the image is measured using a Macbeth 1200 series Densitometer before and after exposure.
  • Example 1 Three coating mixtures are prepared using 2,2'-thiobis(4-t-octylphenol) as stabiliser (Dispersion D): a] Bisphenol A as developer (Dispersion B) p-Benzylbiphenol as sensitiser (Dispersion C)
  • the heat sensitive recording paper obtained demonstrates excellent background whiteness of the paper after application of the coating liquid and also after carrying out storage stability i.e. resistance to light, heat and moisture, of the uncoloured portion of the coated paper. Image stability is also excellent and the performance against thermal paper coated without a stabiliser is summarised in Table 1.
  • Example 2 Three coating mixtures are prepared as described in example 1 except that 2,2'- thiobis(4-methylphenol) is used as stabiliser. The performance obtained using this change in formulation shows similar good results to the performance obtained as described in example
  • Example 3 Three coating mixtures are prepared as described in example 1 except that 2,2'- thiobis(4-ethylphenol) is used as stabiliser. The performance obtained using this change in formulation shows similar good results to the performance obtained as described in example 1.
  • Example 4 Three coating mixtures are prepared as described in example 1 except that 2,2'- thiobis(4-isopropylphenol) is used as stabiliser. The performance obtained using this change in formulation shows similar good results to the performance obtained as described in example 1.
  • Example 5 Three coating mixtures are prepared as described in example 1 except that 2,2'- thiobis(4-t-butylphenol) is used as stabiliser. The performance obtained using this change in formulation shows similar good results to the performance obtained as described in example 1.
  • Example 6 Three coating mixtures are prepared as described in example 1 except that 2,2'- thiobis(4-cumylphenol) is used as stabiliser. The performance obtained using this change in formulation shows similar good results to the performance obtained as described in example 1.
  • Example 7 Three coating mixtures are prepared as described in example 1 except that 2,2'- thiobis(4-dodecylphenol) is used as stabiliser. The performance obtained using this change in formulation shows similar good results to the performance obtained as described in example 1.
  • Example 8 Three coating mixtures are prepared as described in example 1 except that 2,2'- thiobis(4-benzylphenol) is used as stabiliser. The performance obtained using this change in formulation shows similar good results to the performance obtained as described in example 1.
  • Example 9 Three coating mixtures are prepared as described in example 1 except that 2,2'- thiobis(4-phenylphenol) is used as stabiliser. The performance obtained using this change in formulation shows similar good results to the performance obtained as described in example 1.
  • Example 10 Three coating mixtures are prepared as described in example 1 except that 2,2'-thiobis(4-cyclohexylphenol) is used as stabiliser. The performance obtained using this change in formulation shows similar good results to the performance obtained as described in example 1.

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

Abstract

La présente invention concerne une composition thermosensible, qui comprend: a) au moins un composé chromogène; b) au moins un développateur; et c) au moins un stabilisateur correspondant à la formule (II), dans laquelle R1 et R2 représentent, indépendamment l'un de l'autre, alkyle C1-C20, cycloalkyle C3-C10, aralkyle non substitué ou substitué possédant 7 à 10 atomes de carbone, ou bien phényle non substitué ou substitué, R3 et R4 représentent, indépendamment l'un de l'autre, hydrogène ou alkyle C1-C20 ou bien cycloalkyle C3-C10, R3 et R4 n'étant pas en position ortho par rapport au groupe hydroxyle, et n vaut 0, 1 ou 2.
PCT/EP2002/001539 2001-02-23 2002-02-14 Materiau d'enregistrement thermosensible WO2002068206A1 (fr)

Applications Claiming Priority (2)

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EP01810189.9 2001-02-23
EP01810189 2001-02-23

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4312522A (en) 1979-08-24 1982-01-26 Mitsui Toatsu Chemicals, Inc. Heat sensitive recording sheet
US4540999A (en) 1983-07-13 1985-09-10 Kanzaki Paper Manufacturing Co., Ltd. Heat-sensitive record material
JPH0353982A (ja) 1989-07-24 1991-03-07 Kemipuro Kasei Kk 感熱記録材料
US5281570A (en) 1991-07-22 1994-01-25 Mitsui Toatsu Chemicals, Incorporated Thermochromic materials
EP0993965A2 (fr) 1998-10-16 2000-04-19 Nippon Paper Industries Co., Ltd. Milieu d'enregistrement sensible à la chaleur

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4312522A (en) 1979-08-24 1982-01-26 Mitsui Toatsu Chemicals, Inc. Heat sensitive recording sheet
US4540999A (en) 1983-07-13 1985-09-10 Kanzaki Paper Manufacturing Co., Ltd. Heat-sensitive record material
JPH0353982A (ja) 1989-07-24 1991-03-07 Kemipuro Kasei Kk 感熱記録材料
US5281570A (en) 1991-07-22 1994-01-25 Mitsui Toatsu Chemicals, Incorporated Thermochromic materials
EP0993965A2 (fr) 1998-10-16 2000-04-19 Nippon Paper Industries Co., Ltd. Milieu d'enregistrement sensible à la chaleur

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 015, no. 199 (M - 1115) 22 May 1991 (1991-05-22) *

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