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EP0506967B1 - Support d'enregistrement thermique - Google Patents

Support d'enregistrement thermique Download PDF

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Publication number
EP0506967B1
EP0506967B1 EP91916785A EP91916785A EP0506967B1 EP 0506967 B1 EP0506967 B1 EP 0506967B1 EP 91916785 A EP91916785 A EP 91916785A EP 91916785 A EP91916785 A EP 91916785A EP 0506967 B1 EP0506967 B1 EP 0506967B1
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EP
European Patent Office
Prior art keywords
heat
sensitive recording
parts
recording medium
dispersion
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.)
Expired - Lifetime
Application number
EP91916785A
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German (de)
English (en)
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EP0506967A1 (fr
EP0506967A4 (en
Inventor
Nobuo Kanda
Naoto Arai
Tosaku Okamoto
Isamu Nakano
Tetsuo Tsuchida
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New Oji Paper Co Ltd
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New Oji Paper Co Ltd
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Publication date
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Publication of EP0506967A4 publication Critical patent/EP0506967A4/en
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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

Definitions

  • the present invention relates to heat-sensitive recording media and, more particularly, to heat-sensitive recording media excellent in storage stability of record images.
  • Heat-sensitive recording media are well known in the art which make use of the reaction between a colorless or pale-colored basic dye and a color developing material and give images upon application of heat which brings the color developing material into contact with the basic dye.
  • Such heat-sensitive recording media have the drawback that record images generally have insufficient storage stability and become faded with the lapse of time.
  • record images may fade away in a relatively short period of time. Improvement in this respect is earnestly desired.
  • DE-A-3 942 137 discloses a leuco dye/colour developer-containing heat-sensitive recording medium, which also comprises an alkyl or alkylene phosphate or metal salt thereof.
  • EP-A-0 464 502 discloses a leuco dye/colour developer-containing heat-sensitive recording medium, which also comprises a phosphate of present general formula (1) or metal salt thereof, and an alkaline pigment.
  • the present invention thus provides a heat-sensitive recording medium comprising
  • the heat-sensitive recording layer contains at least one of 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate represented by the above general formula (1) and alkali metal and ammonium salts thereof.
  • the above-mentioned heat-sensitive recording layer contains at least one of polyvalent metal salts of 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate.
  • the heat-sensitive recording layer contains at least one phosphate compound selected from among 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate represented by the above general formula (1) and alkali metal and ammonium salts thereof.
  • the heat-sensitive recording layer mentioned above contains at least one of 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate and alkali metal salts thereof.
  • the heat-sensitive recording medium in this embodiment is excellent in storage stability of record images and, in addition, is resistant to fogging , thus generally featuring a high level of whiteness of the heat-sensitive recording layer.
  • the particle size of the above-mentioned compound of general formula (1) or the alkali metal salt or ammonium salt thereof is not specifically limited but it is desirable to subject, as necessary, said compound or salt to wet grinding, for instance, to an average particle size of about 0.1 to 10 ⁇ m, preferably about 0.1 to 3 ⁇ m.
  • the proportions of (A) at least one of the above-mentioned 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate and alkali metal and ammonium salts thereof and (B) the inorganic pigment is adjusted to give an A:B weight ratio within the range of about 80:20 to 20:80, particularly within the range of about 70:30 to 30:70.
  • any of various conventional methods may be used.
  • said adsorption may be effected by dissolving at least one of the compound of general formula (1) and alkali metal and ammonium salts thereof in a small amount of a solvent, such as, methanol, admixing the solution with an inorganic pigment and drying the mixture, followed by pulverizing when necessary.
  • a solvent such as, methanol
  • the particle size of the inorganic pigment mentioned above is not particularly limited but, generally, the mean particle size is preferably about 0.05 to 15 ⁇ m.
  • the phosphate compound is used as absorbed on or blended with an inorganic pigment, it is also preferable that it is pulverized as necessary by wet pulverization for instance, to a mean particle size of about 0.1 to 10 ⁇ m, preferably about 0.1 to 3 ⁇ m.
  • the amount of at least one of the above-mentioned 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate and alkali metal and ammonium salts thereof to be used is not specifically limited. Generally, however, said amount is preferably within the range of 1 to 300 parts by weight, more preferably 1 to 100 parts by weight, per 100 parts by weight of the color developing material.
  • the above-mentioned heat-sensitive recording layer contains at least one of polyvalent metal salts of 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate.
  • the heat-sensitive recording medium in this embodiment is excellent in storage stability of record images and, in addition, has characteristic features that it is resistant to fogging and, in particular, causes less degree of adhesion of residual substances.
  • the polyvalent metal salts mentioned above are not particularly limited in particle size but, generally, the mean particle size thereof is preferably about 0.1 to 10 ⁇ m, more preferably about 0.1 to 3 ⁇ m.
  • metals constituting such polyvalent metal salts there may be mentioned zinc, magnesium, barium, calcium, aluminum, tin, titanium, nickel, cobalt, manganese and iron, among others.
  • Such polyvalent metal salts of 2,2'-methylenebis-(4,6-di-tert-butylphenyl) phosphate can be prepared by various methods. Mention may be made of, for instance, (i) the method comprising reacting an alkali metal salt of 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate with a water-soluble salt containing a polyvalent metal as mentioned above in water to thereby effect salt exchange and (ii) the method comprising subjecting at least one of 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate and alkali metal salts thereof together with a polyvalent metal compound to dry or wet pulverization to thereby effect salt exchange.
  • polyvalent metal compound that can be used in the above-mentioned method (ii) there may be mentioned an oxide, hydroxide, sulfide, halide, carbonate, phosphate, silicate, sulfate, nitrate or aluminate of a polyvalent metal selected from the group consisting of zinc, magnesium, barium, calcium, aluminum, tin, titanium, nickel, cobalt, manganese and iron, silica surface-treated with a substance containing said polyvalent metal, higher fatty acid salts of said polyvalent metal, and mixtures of two or more of these compounds.
  • a polyvalent metal selected from the group consisting of zinc, magnesium, barium, calcium, aluminum, tin, titanium, nickel, cobalt, manganese and iron, silica surface-treated with a substance containing said polyvalent metal, higher fatty acid salts of said polyvalent metal, and mixtures of two or more of these compounds.
  • the following examples may be given: (a) zinc oxide, zinc hydroxide, zinc sulfide, zinc chloride, zinc carbonate, zinc phosphate, zinc silicate, zinc sulfate, zinc nitrate, zinc aluminate, magnesium oxide, magnesium hydroxide, magnesium sulfide, magnesium chloride, magnesium carbonate, magnesium phosphate, magnesium silicate, magnesium sulfate, magnesium nitrate, magnesium aluminate, barium chloride, barium carbonate, barium sulfate, calcium oxide, calcium hydroxide, calcium chloride, calcium carbonate, calcium silicate, aluminum oxide, aluminum hydroxide, aluminum phosphate, aluminum silicate, titanium oxide, etc., (b) silica surface-treated with a substance containing a polyvalent metal such as zinc, magnesium, barium, calcium or aluminum, for example calcium carbonate or aluminum oxide, and (c) polyvalent metal salts of higher fatty acids, in particular C 10 - C 20 higher fatty acids, for example zinc stearate
  • the above-mentioned method (ii) is preferred since the polyvalent metal salt of 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate as prepared can efficiently be pulverized simultaneously.
  • the method (ii) in which wet pulverization is employed is more preferred since the salt exchange progresses smoothly and more uniform pulverization can be achieved.
  • Such wet pulverization may be carried out in the presence of water in a conventional grinding apparatus, for example a sand mill, using 100 parts by weight of at least one of the above-mentioned 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate and alkali metal salts (sodium salt etc.) thereof together with 1 to 500 parts by weight of a polyvalent metal compound, to a particle size of about 0.1 to 10 ⁇ m, preferably about 0.1 to 3 ⁇ m.
  • a conventional grinding apparatus for example a sand mill
  • sulfone group-modified polyvinyl alcohol is preferably used as a dispersion aid since the use thereof makes it possible to conduct the pulverization treatment efficiently and, as a result, produce heat-sensitive recording media excellent in storage stability of record images and causing lesser degree of adhesion of residual substances.
  • Such sulfone group-modified polyvinyl alcohol is a per se known compound. It is prepared, for instance, by saponifying a copolymer of vinyl acetate and an olefinsulfonic acid, such as ethylenesulfonic acid, allylsulfonic acid or methallylsulfonic acid, or a salt (e.g. sodium salt) thereof or by treating polyvinyl alcohol with bromine or the like, followed by heating in an aqueous solution of sodium hydrogen sulfite. It contains, within the molecule thereof, the sulfonic acid group and/or a salt (e.g. alkali metal salt such as sodium salt) thereof.
  • a salt e.g. alkali metal salt such as sodium salt
  • a sulfone group-modified polyvinyl alcohol species having a degree of modification (proportion of monomer units containing the sulfonic acid group or a salt thereof to all monomer units) of about 1 to 10 mole percent, a degree of saponification of about 60 to 100 mole percent and a degree of polymerization of about 100 to 1,000 is preferred.
  • Such sulfone group-modified polyvinyl alcohol is used preferably in an amount within the range of about 0.05 to 50 parts by weight, more preferably about 0.5 to 25 parts by weight, per 100 parts by weight of at least one of 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate and alkali metal salts thereof.
  • the use of a polyvalent metal salt mixture comprising two or more different metal species is particularly preferred since said use leads to production of particularly good results in achieving the desired performance characteristics to be attained according to the invention.
  • polyvalent metal salts mentioned above those polyvalent metal salts in which the polyvalent metal is magnesium, calcium, barium, zinc or aluminum are particularly preferred.
  • the amount of at least one of the polyvalent metal salts of the compound of general formula (1) which is to be used is not limited but, generally, it is preferably within the range of about 1 to 300 parts by weight, more preferably about 1 to 100 parts by weight, per 100 parts by weight of the color developing material.
  • the colorless or pale-colored basic dye which is a constituent of the recording layer, may be any of various known dyes conventionally used in this field of art, inclusive of the following examples: triarylmethane dyes such as 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3,3-bis(p-dimethylaminophenyl)phthalide, 3-(p-dimethylaminophenyl)-3-(1,2-dimethylindol-3-yl)phthalide, 3-(p-dimethylaminophenyl)-3-(2-methylindol-3-yl)phthalide, 3,3-bis(1,2-dimethylindol-3-yl)-5-dimethylaminophthalide, 3,3-bis(1,2-dimethylindol-3-yl)-6-dimethylaminophthalide, 3,3-bis(9-ethylcarbazol-3-yl)-6-dimethyla
  • 3-di-n-butylamino-6-methyl-7-phenylaminofluoran and 3-di-n-butylamino-7-(o-chlorophenylamino)fluoran are preferred since they give heat-sensitive recording media featuring particularly high whiteness in white portions.
  • phenolic compounds such as 4-tert-butylphenol, ⁇ -naphthol, ⁇ -naphthol, 4-acetylphenol, 4-tert-octylphenol, 4,4'-secbutylidenediphenol, 4-phenylphenol, 4,4'-dihydroxydiphenylmethane, 4,4'-isopropylidenediphenol, hydroquinone, 4,4'-cyclohexylidenediphenol, 4,4'-(1,3-dimethylbutylidene)bisphenol, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 4,4'-dihydroxydiphenyl sulfide, 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-dihydroxydiphenyl sulfone, 2,
  • the proportions of the basic dye and color developing material are not particularly limited but should suitably be selected depending on the basic dye and/or color developing material employed.
  • the color developing material is used in an amount of about 100 to 700 parts by weight, preferably about 150 to 400 parts by weight, per 100 parts by weight of the basic dye.
  • the heat-sensitive recording layer of the heat-sensitive recording medium of the present invention is formed by preparing a coating composition containing at least one of the compound of the above general formula (1) and alkali metal, ammonium and polyvalent metal salts thereof (hereinafter referred to as storage stability improving agent), a basic dye and a color developing material, applying the coating composition to a support, and drying the same.
  • a coating composition containing at least one of the compound of the above general formula (1) and alkali metal, ammonium and polyvalent metal salts thereof (hereinafter referred to as storage stability improving agent), a basic dye and a color developing material
  • the coating composition mentioned above is prepared in the conventional manner, in a stirring and pulverizing means such as a ball mill, attritor or sand mill, generally using water as a dispersion medium.
  • a stirring and pulverizing means such as a ball mill, attritor or sand mill, generally using water as a dispersion medium.
  • the storage stability improving agent, basic dye and color developing material may be dispersed either simultaneously or separately.
  • a binder is generally incorporated in such coating composition.
  • the binder those conventional in this field of art may be used, for example starches, hydroxyethylcellulose, methylcellulose, carboxymethylcellulose, gelatin, casein, gum arabic, polyvinyl alcohol, carboxyl group-modified polyvinyl alcohol, sulfone group-modified polyvinyl alcohol, silicon-modified polyvinyl alcohol, acetoacetyl group-modified polyvinyl alcohol, graft copolymers derived from a vinyl alcohol-vinyl acetate copolymer and acrylamide-acrylic acid-allyl acetoacetate, styrene-maleic anhydride copolymer salts, styrene-acrylic acid copolymer salts, and styrene-butadiene copolymer emulsions.
  • these binders are incorporated generally in an amount of about 2 to 40% by weight, preferably about 5 to 25% by weight,
  • auxiliaries may be added to the coating composition.
  • dispersants such as sodium dioctyl sulfosuccinate, sodium dodecylbenzenesulfonate, sodium salt of lauryl alcohol sulfate and fatty acid metal salts, antifoaming agents, fluorescent dyes, coloring dyes, etc.
  • pigments conventionally used in the field of heat-sensitive recording media may be added, for example inorganic pigments such as silicon oxide pigments, kaolin, clay, talc, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcined clay, titanium oxide, diatomaceous earth and activated clay, and organic pigments such as polystyrene microballs, nylon powders, polyethylene powders, urea-formalin resin fillers, and starch particles.
  • inorganic pigments such as silicon oxide pigments, kaolin, clay, talc, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcined clay, titanium oxide, diatomaceous earth and activated clay
  • organic pigments such as polystyrene microballs, nylon powders, polyethylene powders, urea-formalin resin fillers, and starch particles.
  • These pigments are not specifically limited in particle size but, generally, they should preferably have a mean particle size of about 0.1 to 15 ⁇ m.
  • alkaline pigments such as calcium carbonate, magnesium carbonate, calcium silicate and magnesium silicate are preferred since, when they are used in combination with the storage stability improving agent such as the compound of general formula (1), heat-sensitive recording media showing a particularly reduced degree of fogging can be obtained.
  • the alkaline pigments calcium carbonate and magnesium carbonate are superior in that effect and, in particular, calcium carbonate is the most preferred because of its low cost.
  • the amount of such an alkaline pigment is not specifically limited but preferably 1 to 30% by weight and more preferably 3 to 15% by weight based on the total solids contained in the coating composition for the formation of the heat-sensitive recording layer. It is of course possible to use any of these alkaline pigments in combination with other pigments mentioned hereinabove.
  • the total amount of the pigments should preferably be controlled within the range of about 5 to 50% by weight based on the total solids content of the coating composition for heat-sensitive recording layer formation.
  • any of stearic acid, polyethylene, carnauba wax, paraffin wax, zinc stearate, calcium stearate, ester wax and the like may be added in the form of a dispersion or emulsion.
  • fatty acid amides such as stearamide, methylenebisstearamide, oleamide, palmitamide and coco fatty acid amide
  • hindered phenols such as 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 4,4'-butylidenebis(6-tert-butyl-3-methylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane and 1,1,3-tris(2-methyl-4-hydroxy-5-cyclohexylphenyl)butane
  • biphenyls such as p-benzylbiphenyl and p-(4-tolyloxy)biphenyl
  • ethers such as 1,5-bis(4-methoxyphenoxy)-3-oxa-pentane, 1,2-bis(phenoxy)e
  • the amount of the heat-fusible substance, when such is used, is not critical but, generally, it is preferably within the range of 50 to 1,000 parts by weight, more preferably 100 to 500 parts by weight, per 100 parts by weight of the basic dye.
  • the support may include paper, plastic films, synthetic paper and the like, among which paper is preferred from the price and coating performance viewpoints.
  • the method of forming the recording layer is not limited to any particular one but may include those techniques conventional and well-known in the art.
  • the coating composition for heat-sensitive recording layer formation is applied to the support using an appropriate application device such as an air knife coater, blade coater, bar coater, gravure coater, curtain coater or short dwell coater, and the coated support is then dried.
  • the amount of the coating composition to be applied is not critical, either, but, generally, it is adjusted within the range of 2 to 12 g/m 2 , preferably 2 to 8 g/m 2 , on the dry weight basis.
  • Various additional techniques known in the field of heat-sensitive recording medium manufacture can be applied as required.
  • an overcoat layer may be provided on the recording layer. It is of course possible to provide a protective layer on the reverse side of the support and/or a undercoat layer between the support and heat-sensitive recording layer. It is further possible to provide the recording media with an adhesive layer.
  • the mixture of the above components was pulverized in a sand mill to a mean particle size of 1.0 ⁇ m.
  • the mixture of the above components was pulverized in a sand mill to a mean particle size of 1.5 ⁇ m.
  • the mixture of the above components was pulverized in a sand mill to a mean particle size of 1.5 ⁇ m.
  • Dispersion A Fifty-five parts of Dispersion A, 80 parts of Dispersion B, 31 parts of Dispersion C, 15 parts of silicon dioxide pigment (oil absorption 180 ml/100g), 50 parts of 20% aqueous solution of polyvinyl alcohol and 10 parts of water were mixed with stirring.
  • the coating composition thus obtained was applied to a base paper weighing 50 g/m 2 in an amount of 6 g/m 2 (on dry basis), followed by drying to give a heat-sensitive recording paper.
  • a heat-sensitive recording paper was produced in the same manner as in Example I-1 except that, in preparing Dispersion C, 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate was used in lieu of the sodium salt of 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate.
  • a heat-sensitive recording paper was produced in the same manner as in Example I-1 except that, in preparing Dispersion C, potassium salt of 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate was used in lieu of the sodium salt of 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate.
  • the mixture of the above components was pulverized in a sand mill to a mean particle size of 1.0 ⁇ m.
  • the mixture of the above components was pulverized in a sand mill to a mean particle size of 1.5 ⁇ m.
  • the mixture of the above components was pulverized in a sand mill to a mean particle size of 1.5 ⁇ m.
  • Dispersion D Ninety parts of Dispersion D, 80 parts of Dispersion E, 34 parts of Dispersion F, 15 parts of silicon dioxide pigment (oil absorption 180 ml/100 g), 50 parts of 20% aqueous solution of polyvinyl alcohol and 10 parts of water were mixed with stirring.
  • the coating composition thus obtained was applied to a base paper weighing 50 g/m 2 in an amount of 6 g/m 2 (on dry basis), followed by drying to give a heat-sensitive recording paper.
  • a heat-sensitive recording paper was produced in the same manner as in Example I-4 except that, in preparing Dispersion E, 4-hydroxy-4'-isopropoxydiphenyl sulfone was used in lieu of 4,4'-isopropylidenediphenol.
  • a heat-sensitive recording paper was produced in the same manner as in Example I-1 except that, in preparing Dispersion A, 3-di-n-butylamino-6-methyl-7-phenylaminofluoran was used in lieu of 3-(N-ethyl-N-isoamyl)amino-6-methyl-7-phenylaminofluoran.
  • the mixture of the above components was pulverized in a sand mill to a mean particle size of 1.0 ⁇ m.
  • Dispersion G Ninety parts of Dispersion G, 80 parts of Dispersion E, 31 parts of Dispersion C, 15 parts of silicon dioxide pigment (oil absorption 180 ml/100 g), 50 parts of 20% aqueous solution of polyvinyl alcohol and 10 parts of water were mixed with stirring.
  • the thus-obtained coating composition was applied to a base paper weighing 50 g/m 2 in an amount of 6 g/m 2 (on dry basis), followed by drying to give a heat-sensitive recording paper.
  • a heat-sensitive recording paper was produced in the same manner as in Example I-8 except that 34 parts of Dispersion F was used in lieu of 31 parts of Dispersion C.
  • the mixture of the above components was pulverized in a sand mill to a mean particle size of 1.0 ⁇ m.
  • Dispersion H Ninety parts of Dispersion H, 80 parts of Dispersion E, 31 parts of Dispersion C, 15 parts of silicon dioxide pigment (oil absorption 180 ml/100 g), 50 parts of 20% aqueous solution of polyvinyl alcohol and 10 parts of water were mixed with stirring.
  • the coating composition thus obtained was applied to a base paper weighing 50 g/m 2 in an amount of 6 g/m 2 (on dry basis), followed by drying to give a heat-sensitive recording paper.
  • a heat-sensitive recording paper was produced in the same manner as in Example I-10 except that 34 parts of Dispersion F was used in lieu of 31 parts of Dispersion C.
  • the mixture of the above components was pulverized in a sand mill to a mean particle size of 1.0 ⁇ m.
  • Dispersion I Ninety parts of Dispersion I, 80 parts of Dispersion E, 31 parts of Dispersion C, 15 parts of silicon dioxide pigment (oil absorption 180 ml/100 g), 50 parts of 20% aqueous solution of polyvinyl alcohol and 10 parts of water were mixed with stirring.
  • the coating composition thus obtained was applied to a base paper weighing 50 g/m 2 in an amount of 6 g/m 2 (on dry basis), followed by drying to give a heat-sensitive recording paper.
  • a heat-sensitive recording paper was produced in the same manner as in Example I-12 except that 34 parts of Dispersion F was used in lieu of 31 parts of Dispersion C.
  • the mixture of the above components was pulverized in a sand mill to a mean particle size of 1.0 ⁇ m.
  • Dispersion J Ninety parts of Dispersion J, 80 parts of Dispersion E, 31 parts of Dispersion C, 15 parts of silicon dioxide pigment (oil absorption 180 ml/100 g), 50 parts of 20% aqueous solution of polyvinyl alcohol and 10 parts of water were mixed with stirring.
  • the coating composition thus obtained was applied to a base paper weighing 50 g/m 2 in an amount of 6 g/m 2 (on dry basis), followed by drying to give a heat-sensitive recording paper.
  • a heat-sensitive recording paper was produced in the same manner as in Example I-14 except that 34 parts of Dispersion F was used in lieu of 31 parts of Dispersion C.
  • the mixture of the above components was pulverized in a sand mill to a mean particle size of 1.0 ⁇ m.
  • Dispersion K Ninety parts of Dispersion K, 80 parts of Dispersion E, 31 parts of Dispersion C, 15 parts of silicon dioxide pigment (oil absorption 180 ml/100 g), 50 parts of 20% aqueous solution of polyvinyl alcohol and 10 parts of water were mixed with stirring.
  • the coating composition thus obtained was applied to a base paper weighing 50 g/m 2 in an amount of 6 g/m 2 (on dry basis), followed by drying to give a heat-sensitive recording paper.
  • a heat-sensitive recording paper was produced in the same manner as in Example I-16 except that 34 parts of Dispersion F was used in lieu of 31 parts of Dispersion C.
  • the mixture of the above components was pulverized in a sand mill to a mean particle size of 1.0 ⁇ m.
  • Dispersion L Ninety parts of Dispersion L, 80 parts of Dispersion E, 31 parts of Dispersion C, 15 parts of silicon dioxide pigment (oil absorption 180 ml/100 g), 50 parts of 20% aqueous solution of polyvinyl alcohol and 10 parts of water were mixed with stirring.
  • the thus-obtained coating composition was applied to a base paper weighing 50 g/m 2 in an amount of 6 g/m 2 (on dry basis), followed by drying to give a heat-sensitive recording paper.
  • a heat-sensitive recording paper was produced in the same manner as in Example I-18 except that 34 parts of Dispersion F was used in lieu of 31 parts of Dispersion C.
  • the mixture of the above components was pulverized in a sand mill to a mean particle size of 1.0 ⁇ m.
  • Dispersion M Ninety parts of Dispersion M, 80 parts of Dispersion E, 31 parts of Dispersion C, 15 parts of silicon dioxide pigment (oil absorption 180 ml/100 g), 50 parts of 20% aqueous solution of polyvinyl alcohol and 10 parts of water were mixed with stirring.
  • the thus-obtained coating composition was applied to a base paper weighing 50 g/m 2 in an amount of 6 g/m 2 (on dry basis), followed by drying to give a heat-sensitive recording paper.
  • a heat-sensitive recording paper was produced in the same manner as in Example I-20 except that 34 parts of Dispersion F was used in lieu of 31 parts of Dispersion C.
  • a heat-sensitive recording paper was produced in the same manner as in Example I-8 except that Dispersion C was used in an amount of 10 parts.
  • a heat-sensitive recording paper was produced in the same manner as in Example I-8 except that Dispersion C was used in an amount of 60 parts.
  • a heat-sensitive recording paper was produced in the same manner as in Example I-8 except that Dispersion C was used in an amount of 100 parts.
  • a heat-sensitive recording paper was produced in the same manner as in Example I-4 except that, in recording layer formation, 55 parts of Dispersion A was used in lieu of 90 parts of Dispersion D.
  • a heat-sensitive recording paper was produced in the same manner as in Example I-14 except that, in recording layer formation, precipitated calcium carbonate (oil absorption 90 ml/100 g) was used in lieu of the silicon dioxide pigment.
  • a heat-sensitive recording paper was produced in the same manner as in Example I-14 except that ammonium salt of 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate was used in lieu of the sodium salt of 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate.
  • a heat-sensitive recording paper was produced in the same manner as in Example I-1 except that Dispersion C was not used.
  • a heat-sensitive recording paper was produced in the same manner as in Example I-4 except that Dispersion F was not used.
  • a heat-sensitive recording paper was produced in the same manner as in Example I-6 except that Dispersion F was not used.
  • a heat-sensitive recording paper was produced in the same manner as in Example I-7 except that Dispersion C was not used.
  • a heat-sensitive recording paper was produced in the same manner as in Example I-8 except that Dispersion C was not used.
  • a heat-sensitive recording paper was produced in the same manner as in Example I-10 except that Dispersion C was not used.
  • a heat-sensitive recording paper was produced in the same manner as in Example I-12 except that Dispersion C was not used.
  • a heat-sensitive recording paper was produced in the same manner as in Example I-8 except that, in preparing Dispersion C, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane was used in lieu of the sodium salt of 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate.
  • a heat-sensitive recording paper was produced in the same manner as in Example I-8 except that, in preparing Dispersion C, 4,4'-butylidenebis(6-tert-butyl-m-cresol) was used in lieu of the sodium salt of 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate.
  • each heat-sensitive recording paper was allowed to stand in an atmosphere maintained at 40°C and 90% RH for 24 hours and then the color density (D 2 ) of the record images was measured using the Macbeth densitometer.
  • the whiteness of each heat-sensitive recording paper before recording was measured using a Hunter whiteness meter.
  • Each heat-sensitive recording paper was allowed to stand in an atmosphere maintained at 40°C and 90% RH or in an atmosphere maintained at 60°C and 10% RH for 24 hours and then the fog color density of the white portion was measured using the Macbeth densitometer.
  • Table 1 the fog color density data obtained after treatment in the 40°C and 90% RH atmosphere are shown in the column headed F 1 , and those obtained after treatment in the 60°C and 10% RH atmosphere in the column headed F 2 .
  • the heat-sensitive recording media of the present invention were excellent in storage stability of record images and were almost free from fogging which tends to accompany the improvements in storage stability.
  • the mixture of the above components was pulverized in a sand mill to a mean particle size of 1.0 ⁇ m.
  • the mixture of the above components was pulverized in a sand mill to a mean particle size of 1.5 ⁇ m.
  • the mixture of the above components was pulverized in a sand mill to a mean particle size of 1.5 ⁇ m. It was confirmed that the mixture after pulverization contained magnesium salt of 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate as resulting from salt exchange.
  • Dispersion A Ninety parts of Dispersion A, 80 parts of Dispersion B, 34 parts of Dispersion C, 7 parts of silicon dioxide pigment (oil absorption 180 ml/100 g), 8 parts of precipitated calcium carbonate (oil absorption 90 ml/100 g), 50 parts of 20% aqueous solution of polyvinyl alcohol, 15 parts of 30% aqueous dispersion of zinc stearate and 10 parts of water were mixed with stirring.
  • the thus-obtained coating composition was applied to a base paper weighing 50 g/m 2 in an amount of 6 g/m 2 (on dry basis), followed by drying to give a heat-sensitive recording paper.
  • a heat-sensitive recording paper was produced in the same manner as in Example II-1 except that, in preparing Dispersion C, calcium silicate was used in lieu of magnesium silicate.
  • a heat-sensitive recording paper was produced in the same manner as in Example II-1 except that, in preparing Dispersion A, 3-di-n-butylamino-7-(o-chlorophenylamino)fluoran was used in lieu of 3-di-n-butylamino-6-methyl-7-phenylaminofluoran, and that di(4-methylbenzyl) oxalate was used in lieu of 1,2-bis(3-methylphenoxy)ethane and that, in preparing Dispersion C, a 1:1 mixture of magnesium silicate and calcium carbonate was used in lieu of magnesium silicate.
  • a heat-sensitive recording paper was produced in the same manner as in Example II-3 except that, in preparing Dispersion A, dibenzyl oxalate was used in lieu of di(4-methylbenzyl) oxalate, and that, in preparing Dispersion B, 4-hydroxy-4'-isopropoxydiphenyl sulfone was used in lieu of 4,4'-isopropylidenediphenol and that, in preparing Dispersion C, a 1:1 mixture of zinc chloride and calcium carbonate was used in lieu of the 1:1 mixture of magnesium silicate and calcium carbonate.
  • a heat-sensitive recording paper was produced in the same manner as in Example II-1 except that, in preparing Dispersion C, 3 parts of 5% aqueous solution of methylcellulose was used in lieu of 3 parts of 5% aqueous solution of sulfone group-modified polyvinyl alcohol.
  • a heat-sensitive recording paper was produced in the same manner as in Example II-1 except that, in recording layer formation, 15 parts of silicone dioxide pigment (oil absorption 180 ml/100 g) was used in lieu of the combination of 7 parts of silicon dioxide pigment and 8 parts of precipitated calcium carbonate.
  • a heat-sensitive recording paper was produced in the same manner as in Example II-1 except that, in recording layer formation, 8 parts of magnesium carbonate was used in lieu of 8 parts of precipitated calcium carbonate.
  • a heat-sensitive recording paper was produced in the same manner as in Example II-1 except that, in preparing Dispersion C, 6 parts of 1,1,3-tris(5-cyclohexyl-4-hydroxy-2-methylphenyl)butane was used in lieu of the combination of sodium salt of 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate and magnesium silicate.
  • Each heat-sensitive recording paper was subjected to recording on a heat-sensitive recording paper color development tester (a product of Okura Electric Co., Ltd.; model TH-PMD; applied voltage: 16 V; pulse cycle: 0.51 ms) at a pulse width of 0.30 ms, and the color density (D 1 ) was measured using a Macbeth densitometer (model RD-914, a product of Macbeth Corp.).
  • a heat-sensitive recording paper color development tester a product of Okura Electric Co., Ltd.; model TH-PMD; applied voltage: 16 V; pulse cycle: 0.51 ms
  • D 1 was measured using a Macbeth densitometer (model RD-914, a product of Macbeth Corp.).
  • the whiteness of each heat-sensitive recording paper before recording was measured using a Hunter whiteness meter.
  • Each heat-sensitive recording paper was allowed to stand in an atmosphere maintained at 40°C and 90% RH, or 60°C and 10% RH, for 48 hours, and the resultant fog color density of the white portion was measured using the Macbeth densitometer.
  • Table 2 the fog color density data after treatment in the 40°C and 90% RH atmosphere are shown in the column headed F 1 and those after treatment in the 60°C and 10% RH atmosphere are shown in the column headed F 2 .
  • Example II-1 1.33 1.10 1.06 83 80 85 0.10 0.11 A
  • Example II-2 1.33 1.12 1.08 84 81 84 0.10 0.12 A
  • Example II-3 1.30 1.13 1.11 87 85 85 0.10 0.12 A
  • Example II-4 1.28 1.14 1.10 89 86 83 0.13 0.14 A
  • Example II-5 1.32 1.07 1.03 81 78 84 0.11 0.12 B
  • Example II-6 1.34 1.10 1.06 82 79 80 0.13 0.14
  • Example II-7 1.32 1.10 1.06 83 80 86 0.09 0.10 A Comparative Example II-1 1.27 0.80 0.68 63 54 84 0.08 0.10 C
  • the heat-sensitive recording media according to the invention were superior in storage stability of record images and were substantially free from adhesion of residual substances which tends to accompany the improvements in storage stability.

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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

L'invention se rapporte à un support d'enregistrement thermique, qui se compose d'un substrat sur lequel est placée une couche d'enregistrement thermique contenant un colorant basique incolore ou clair et un agent de développement qui développe une couleur au contact du colorant lorsqu'il est chauffé. La couche d'enregistrement thermique contient au moins un phosphate choisi parmi du phosphate de 2,2'-méthylènebis(4,6-di-tert-butylphenyle) représenté par la formule (1) et des sels de ce phosphate, avec un métal alcalin, un ammonium et un métal polyvalent. Dans la formule (1), R représente tert-butyle.

Claims (15)

  1. Milieu d'enregistrement sensible à la chaleur comprenant : (a) un support et (b) une couche d'enregistrement sensible à la chaleur formée sur le support et comprenant un colorant basique incolore ou de couleur pâle et une matière développatrice de couleur capable de provoquer un développement de couleur lorsqu'elle entre en contact avec le colorant sous l'effet d'un chauffage, lequel milieu est caractérisé en ce que la couche d'enregistrement sensible à la chaleur contient au moins un phosphate choisi dans le groupe consistant en phospbate de 2,2'-méthylène-bis-(4,6-di-t-butylphényle) de formule générale (1) indiquée ci-après et sels de métal alcalin, d'ammonium et de métal polyvalent de celui-ci :
    Figure imgb0014
     dans laquelle R représente un groupe t-butyle.
  2. Milieu d'enregistrement sensible à la chaleur suivant la revendication 1, dans lequel ce phosphate est le phosphate de 2,2'-méthylène-bis-(4,6-di-t-butylphényle) ou un sel de métal alcalin de celui-ci.
  3. Milieu d'enregistrement sensible à la chaleur suivant la revendication 2, dans lequel ce sel de métal alcalin est le sel de sodium ou de potassium.
  4. Milieu d'enregistrement sensible à la chaleur suivant la revendication 1, dans lequel ce phosphate est un sel de métal polyvalent du phosphate de 2,2'-méthylène-bis-(4,6-di-t-butylphényle).
  5. Milieu d'enregistrement sensible à la chaleur suivant la revendication 4, dans lequel ce sel de métal polyvalent est le sel de magnésium, de calcium, de baryum, de zinc ou d'aluminium.
  6. Milieu d'enregistrement sensible à la chaleur suivant la revendication 4, dans lequel ce sel de métal polyvalent est utilisé sous la forme d'un mélange d'au moins deux sels de métal polyvalent.
  7. Milieu d'enregistrement sensible à la chaleur suivant la revendication 1, dans lequel ce phosphate est utilisé en une quantité de 1 à 300 parties en poids pour 100 parties en poids de la matière développatrice de couleur.
  8. Milieu d'enregistrement sensible à la chaleur suivant la revendication 1, dans lequel la couche d'enregistrement sensible à la chaleur contient de plus au moins une substance fusible à chaud.
  9. Milieu d'enregistrement sensible à la chaleur suivant la revendication 8, dans lequel cette substance fusible à chaud est au moins une substance choisie dans le groupe consistant en 1,2-bis-(3-méthylphénoxy)-éthane, 1,2-bis-(phénoxy)-éthane, 1-(2-méthylphénoxy)-2-(4-méthoxyphénoxy)-éthane, oxalate de dibenzyle, oxalate de di-(4-méthylbenzyle), oxalate de di-(4-chlorobenzyle), p-benzylbiphényle, p-(4-tolyloxy)-biphényle et 1,5-bis-(4-méthoxyphénoxy)-3-oxapentane.
  10. Milieu d'enregistrement sensible à la chaleur suivant la revendication 8, dans lequel cette substance fusible à chaud est utilisée en une quantité de 50 à 1.000 parties en poids pour 100 parties du colorant basique.
  11. Milieu d'enregistrement sensible à la chaleur suivant la revendication 1, dans lequel cette couche d'enregistrement sensible à la chaleur contient de plus au moins un pigment alcalin.
  12. Milieu d'enregistrement sensible à la chaleur suivant la revendication 11, dans lequel ce pigment alcalin est du carbonate de calcium, du carbonate de magnésium, du silicate de calcium ou du silicate de magnésium.
  13. Milieu d'enregistrement sensible à la chaleur suivant la revendication 12, dans lequel ce pigment alcalin est du carbonate de calcium ou du carbonate de magnésium.
  14. Milieu d'enregistrement sensible à la chaleur suivant la revendication 13, dans lequel ce pigment alcalin est du carbonate de calcium.
  15. Milieu d'enregistrement sensible à la chaleur suivant la revendication 11, dans lequel ce pigment alcalin est utilisé en une quantité de 1 à 30% en poids par rapport à la teneur totale en solides de la couche d'enregistrement sensible à la chaleur.
EP91916785A 1990-09-29 1991-09-27 Support d'enregistrement thermique Expired - Lifetime EP0506967B1 (fr)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
JP261236/90 1990-09-29
JP26123690 1990-09-29
JP408460/90 1990-12-27
JP40846090 1990-12-27
JP12176/91 1991-02-01
JP1217691 1991-02-01
PCT/JP1991/001291 WO1992005963A1 (fr) 1990-09-29 1991-09-27 Support d'enregistrement thermique

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EP0506967A1 EP0506967A1 (fr) 1992-10-07
EP0506967A4 EP0506967A4 (en) 1992-11-04
EP0506967B1 true EP0506967B1 (fr) 1996-11-13

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KR (1) KR0160268B1 (fr)
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8652464B2 (en) 2002-02-04 2014-02-18 Alkermes Pharma Ireland Limited Method of treatment using nanoparticulate compositions having lysozyme as a surface stabilizer

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Publication number Priority date Publication date Assignee Title
JPS57167380A (en) * 1981-04-08 1982-10-15 Pilot Ink Co Ltd Thermochromic material
JPS58138690A (ja) * 1982-02-10 1983-08-17 Ricoh Co Ltd 感熱記録材料
JPH074967B2 (ja) * 1985-10-16 1995-01-25 株式会社リコー 感熱記録材料
JPH02258289A (ja) * 1988-12-20 1990-10-19 Ricoh Co Ltd 感熱記録材料
JP2903250B2 (ja) * 1990-06-22 1999-06-07 旭電化工業株式会社 感熱記録材料

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8652464B2 (en) 2002-02-04 2014-02-18 Alkermes Pharma Ireland Limited Method of treatment using nanoparticulate compositions having lysozyme as a surface stabilizer

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DE69123139T2 (de) 1997-06-12
EP0506967A1 (fr) 1992-10-07
EP0506967A4 (en) 1992-11-04
DE69123139D1 (de) 1996-12-19
KR920703341A (ko) 1992-12-17
WO1992005963A1 (fr) 1992-04-16
KR0160268B1 (ko) 1999-02-18

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