EP0224075B1 - Wärmeempfindliches Aufzeichnungsmaterial - Google Patents

Wärmeempfindliches Aufzeichnungsmaterial Download PDF

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Publication number
EP0224075B1
EP0224075B1 EP86115166A EP86115166A EP0224075B1 EP 0224075 B1 EP0224075 B1 EP 0224075B1 EP 86115166 A EP86115166 A EP 86115166A EP 86115166 A EP86115166 A EP 86115166A EP 0224075 B1 EP0224075 B1 EP 0224075B1
Authority
EP
European Patent Office
Prior art keywords
sensitive recording
recording material
heat sensitive
heat
material according
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
EP86115166A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0224075A1 (de
Inventor
Toshimi Central Research Laboratory Satake
Tomoaki Central Research Laboratory Nagai
Fumio Central Research Laboratory Fujimura
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jujo Paper Co Ltd
Original Assignee
Jujo Paper Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jujo Paper Co Ltd filed Critical Jujo Paper Co Ltd
Publication of EP0224075A1 publication Critical patent/EP0224075A1/de
Application granted granted Critical
Publication of EP0224075B1 publication Critical patent/EP0224075B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • B41M5/32—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers one component being a heavy metal compound, e.g. lead or iron
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/913—Material designed to be responsive to temperature, light, moisture
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/914—Transfer or decalcomania

Definitions

  • the invention relates to a heat-sensitive recording material which has both an improved image contrast and a superior resistance of the image to oils, fats and solvents such as alcohols.
  • Heat-sensitive recording sheets in which a color reaction between a colorless or slightly colored chromogenic substance and a phenolic substance or an organic acid arises as a result of the action of heat or heat, include in Japanese Patent Publications Nos. 4160/1968 and 14039/1970 and in JP-OL No. 27736/1973 and are currently widely used in practice.
  • a heat-sensitive recording sheet is generally prepared by placing it on the surface of a support, e.g. paper, film, etc. applies a coating composition obtained by grinding into fine particles and dispersing a colorless chromogenic substance and a color developing material, mixing the dispersions obtained together and adding a binder, filler, sensitizer, lubricant and other auxiliaries.
  • a coating composition obtained by grinding into fine particles and dispersing a colorless chromogenic substance and a color developing material, mixing the dispersions obtained together and adding a binder, filler, sensitizer, lubricant and other auxiliaries.
  • the thermal energy of the thermal head is lower, so that the heat-sensitive recording sheet should have sufficient sensitivity for color formation and for bright chromogenic recordings with less heat from the thermal head.
  • a heat sensitive recording sheet Because of its function as an information recording paper, it is inevitable that a heat sensitive recording sheet comes into contact with human hands. Since oily materials such as hair oil, sweat and solvents such as alcohol, etc. often stick to the hands and fingers of workers, a heat-sensitive recording sheet is often soiled by such substances. In general, a heat-sensitive recording sheet is not sufficiently stable against such oily materials and solvents as alcohols, ketones, etc. Therefore, the phenomenon that the image density of the soiled part is reduced or the image is faded, and that the soiling of the background becomes discolored or causes color to form.
  • heat-sensitive color development system using a colorless dye there is also known a heat-sensitive color development system using a metal compound.
  • a heat-sensitive color development system using a metal compound for example, in Japanese patent publication 8787/1957 the combined use of iron stearate as an electron acceptor with tannic acid or gallic acid (electron donor) and in Japanese patent publication 6485/1959 the combined use of an electron acceptor such as silver stearate, gold stearate, copper stearate or mercury behenate with an electron donor. such as methyl gallate, ethyl gallate, propyl gallate, butyl gallate or dodecyl gallate.
  • JL-OL No. 89193/1984 describes a combination of a color development system using a leuco dye and a color developing agent with a color development system using a metal compound consisting of an iron salt of a saturated higher fatty acid and a polyhydric phenol.
  • the invention has for its object to provide a heat-sensitive recording material which gives an improved contrast without deteriorating the solvent resistance and the oil resistance.
  • a heat-sensitive recording material in that it has a color development layer applied to a support, which has a colorless leuco dye and, as the metal salt of an organic carboxylic acid, at least one iron salt of a saturated higher fatty acid having 16 to 35 carbon atoms and at least one polyvalent phenol derivative of the following formula (I) contains in which R represents an alkyl group with 18 to 35 carbon atoms and n represents 3.
  • Such iron salts of saturated higher fatty acids can be used as an electron acceptor alone or in a mixture.
  • additives can be added to these polyvalent phenol derivatives in order to achieve certain effects.
  • the additives which can be used according to the invention are e.g. the following: anti-mottling agents (preventing agents for printing, e.g. fatty acid amides, ethylene bisamide, montan wax); Sensitizers (e.g. dibenzyl terephthalate, benzyl p-benzyloxybenzoate, di-p-tolyl carbonate, p-benzyl biphenyl); and stabilizers (for example metal salts of phthalic acid monoester, metal salts of p-tert-butylbenzoic acid, metal salts of nitrobenzoic acid).
  • anti-mottling agents preventing agents for printing, e.g. fatty acid amides, ethylene bisamide, montan wax
  • Sensitizers e.g. dibenzyl terephthalate, benzyl p-benzyloxybenzoate, di-p-
  • a colorless leuco dye is added to the color development system using the previous metal compound.
  • colorless leuco dyes leuco dyes of the triphenylmethane series, the fluoran series, the azophthalide series and the fluorene series are preferred.
  • the leuco dye can be used alone or in a mixture. If a leuco dye is used in a large amount, there is a fear that the resistance to solvents such as alcohols will decrease. Therefore, the leuco dye is used in an amount of at most 50% by weight, preferably at most 25% by weight, based on the polyvalent phenol derivative.
  • the leuco dyes 3-diethylamino-7- (o-chloroanilino) fluorane and 3- (N-ethyl-p-toluidino-6-methyl-7-anilinofluorane) are preferred because of their greater resistance to solvents.
  • water-soluble binders can also be used in the color development layer, e.g. fully saponified polyvinyl alcohol with a degree of polymerization of 200-1900, partly saponified polyvinyl alcohol, carboxylated polyvinyl alcohol, amide-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, butyral-modified polyvinyl alcohol, other modified polyvinyl alcohols, cellulose derivatives, such as hydroxyethyl carboxy styrene and methyl malcellulose methyl methyl cellulose Copolymers.
  • These water-soluble binders can be used alone or in a mixture, depending on the intended use and their suitability for recording purposes.
  • the iron salt of the saturated higher fatty acid, the polyvalent phenol derivative and the basic, colorless chromogenic dye are ground to a particle size of several microns or smaller by means of a grinding device, such as a ball mill, attritor, sanding machine, etc., or by means of a suitable emulsifying machine.
  • a grinding device such as a ball mill, attritor, sanding machine, etc.
  • a suitable emulsifying machine emulsifying machine.
  • additives are added, depending on the purpose of the recording.
  • the additives which can be used according to the invention are e.g. the following:
  • Inorganic or organic fillers such as silicon dioxide, calcium carbonate, kaolin, baked kaolin, diatomaceous earth, talc, titanium dioxide, aluminum hydroxide, etc .; Release agents, such as metal salts of fatty acids; Lubricants such as waxes; UV absorbers of the benzophenone and triazole series; waterproofing agents such as glyoxal, etc .; Dispersants; Antifoam, etc.
  • the type and the amount of the salt of the saturated higher fatty acid, the polyhydric phenol derivative, the water-soluble binder, the leuco dye, the other additives, which are selected depending on the desired effect and suitability for recording purposes, are not particularly limited. In general, it is advantageous to use 1 to 6 parts by weight of the polyhydric phenol derivative, 2 to 15 parts by weight of filler and 0.2 to 1.2 parts by weight of the iron salt of the saturated higher fatty acid, and 0.5 to 4 Parts by weight of binder, based on the total solids content, to be used.
  • the heat-sensitive material of the present invention is produced by applying the coating composition forming the color development layer on a base material such as paper, synthetic paper, film, etc.
  • the heat-sensitive recording material of the present invention is stable against solvents such as alcohol, etc. in the background.
  • Both the iron salt of the organic acid and the polyvalent phenol derivative which can be used according to the invention contain an alkyl group with at least 16 or 18 carbon atoms, so that their rate of diffusion and solubility in the solvents are very low.
  • the reason for the superior oil resistance is based on an irreversible color development reaction between the organic iron salt and the polyvalent phenol derivative. This means that once this color development reaction takes place, a very stable complex is formed, the binding of which is not released when the hair oil, oil materials, etc. adhere. Therefore, the color image is stable.
  • parts As an abbreviation for parts by weight, “parts” is used.
  • This coating composition was applied in an amount of 6.0 g / m 2 to a base paper with a weight of 50 g / m 2 , dried and calendered to set a smoothness of 200-600 seconds. A heat-sensitive recording material was obtained.
  • This coating composition was applied, dried and calendered in the same manner as in Example 1. A heat sensitive recording material was obtained.
  • This coating composition was applied, dried and calendered in the same manner as in Example 1. A heat sensitive recording material was obtained.
  • This coating composition was applied, dried and calendered in the same manner as in Example 1. A heat sensitive recording material was obtained.
  • This coating composition was applied, dried and calendered in the same manner as in Example 1. A heat sensitive recording material was obtained.
  • This coating composition was applied in the same manner as in Comparative Example 4, dried and calendered.
  • a heat-sensitive recording sheet is recorded at a pulse width of 3.2 milliseconds and an applied voltage of 18.03 V using a thermal facsimile machine (manufactured by TOSHIBA CORPORATION), the optical density of which is determined using a Macbeth density meter.
  • the optical density of the non-recorded part is determined using a Macbeth density meter.
  • the part on which a 95% alcohol solution is dropped is determined with a Macbeth density meter.
  • a heat-sensitive recording sheet is recorded at a pulse width of 3.2 milliseconds and an applied voltage of 18.03 V using a thermal facsimile machine (manufactured by TOSHIBA CORPORATION), the optical density of which is determined with a Macbeth density meter, and as the optical density is defined before the oil treatment. Castor oil is dripped onto the recorded part, wiped with filter paper, left for 3 days. The optical density is then determined using a Macbeth density meter and defined as the optical density after oil treatment.
  • the residual image density is calculated from the following formula:
  • the heat-sensitive recording material according to the invention has a high solvent resistance of the background and a high oil resistance of the image despite the addition of the leuco dye, and a superior image density due to the Add the leuco dye.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
EP86115166A 1985-11-01 1986-10-31 Wärmeempfindliches Aufzeichnungsmaterial Expired - Lifetime EP0224075B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP60246063A JPS62105688A (ja) 1985-11-01 1985-11-01 感熱記録体
JP246063/85 1985-11-01

Publications (2)

Publication Number Publication Date
EP0224075A1 EP0224075A1 (de) 1987-06-03
EP0224075B1 true EP0224075B1 (de) 1990-06-20

Family

ID=17142917

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86115166A Expired - Lifetime EP0224075B1 (de) 1985-11-01 1986-10-31 Wärmeempfindliches Aufzeichnungsmaterial

Country Status (5)

Country Link
US (1) US4861749A (enrdf_load_stackoverflow)
EP (1) EP0224075B1 (enrdf_load_stackoverflow)
JP (1) JPS62105688A (enrdf_load_stackoverflow)
CA (1) CA1263019A (enrdf_load_stackoverflow)
DE (1) DE3672112D1 (enrdf_load_stackoverflow)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62284782A (ja) * 1986-06-03 1987-12-10 Jujo Paper Co Ltd 感熱記録体
JP2681907B2 (ja) * 1992-11-20 1997-11-26 日本製紙株式会社 感熱記録体
US5618063A (en) * 1992-12-09 1997-04-08 Wallace Computer Services, Inc. Multicolor heat-sensitive verification and highlighting system
US5424182A (en) * 1993-01-15 1995-06-13 Labelon Corporation Aqueous coating composition for thermal imaging film
US5984363A (en) * 1993-05-03 1999-11-16 The Standard Register Company Business record having a thermally imagable surface
US5810397A (en) * 1993-05-03 1998-09-22 The Standard Register Company Thermally imagable business record and method of desensitizing a thermally imagable surface
EP1382459A1 (en) * 2002-07-17 2004-01-21 Sihl GmbH Thermosensitive recording sheet for labeling foodstuff having direct contact with said foodstuff
EP2325018A1 (de) 2009-11-24 2011-05-25 Mondi Uncoated Fine & Kraft Paper GmbH Thermisch sensibles Aufzeichnungsmaterial

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DK113443B (da) * 1965-04-02 1969-03-24 Laforest A Thiard Kopimateriale bestående af en bærefolie med et varmefølsomt overtræk.
JPS57176196A (en) * 1981-04-23 1982-10-29 Kanzaki Paper Mfg Co Ltd Heat-sensitive recording medium
JPS6032697A (ja) * 1983-08-04 1985-02-19 Mitsubishi Paper Mills Ltd 感熱記録材料
JPS6063192A (ja) * 1983-09-17 1985-04-11 Mitsubishi Paper Mills Ltd 熱転写記録材
JPS6083886A (ja) * 1983-10-17 1985-05-13 Mitsubishi Paper Mills Ltd 感熱熱転写記録材
JPS6083885A (ja) * 1983-10-17 1985-05-13 Mitsubishi Paper Mills Ltd 熱転写記録材

Also Published As

Publication number Publication date
CA1263019A (en) 1989-11-21
JPS62105688A (ja) 1987-05-16
EP0224075A1 (de) 1987-06-03
US4861749A (en) 1989-08-29
DE3672112D1 (de) 1990-07-26
JPH0416072B2 (enrdf_load_stackoverflow) 1992-03-19

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