EP0248405B1 - Wärmeempfindliches Aufzeichnungsmaterial - Google Patents

Wärmeempfindliches Aufzeichnungsmaterial Download PDF

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Publication number
EP0248405B1
EP0248405B1 EP87107971A EP87107971A EP0248405B1 EP 0248405 B1 EP0248405 B1 EP 0248405B1 EP 87107971 A EP87107971 A EP 87107971A EP 87107971 A EP87107971 A EP 87107971A EP 0248405 B1 EP0248405 B1 EP 0248405B1
Authority
EP
European Patent Office
Prior art keywords
sensitive recording
recording material
heat sensitive
material according
iron
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
EP87107971A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0248405A2 (de
EP0248405A3 (en
Inventor
Toshimi Central Research Laboratory Satake
Toshiaki Central Research Laboratory Minami
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 EP0248405A2 publication Critical patent/EP0248405A2/de
Publication of EP0248405A3 publication Critical patent/EP0248405A3/de
Application granted granted Critical
Publication of EP0248405B1 publication Critical patent/EP0248405B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
    • G03C1/498—Photothermographic systems, e.g. dry silver
    • G03C1/4989—Photothermographic systems, e.g. dry silver characterised by a thermal imaging step, with or without exposure to light, e.g. with a thermal head, using a laser
    • 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
    • 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 invention relates to a heat-sensitive recording material which is superior in its dispersibility, its image contrast, its resistance to oils and solvents and its optical readability in the near ultra-red range.
  • 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 takes place due to the action of heat or heat include in Japanese Patent Publications No. 4160/1968 and 14039/1970 and in JP-OLS No. 27736/1973. They are used in many different ways in practice.
  • a heat-sensitive recording sheet is generally prepared by applying a coating composition to the surface of a support such as paper, film, etc., which is prepared by finely grinding and dispersing a colorless chromogenic substance and a color developing material, mixing the dispersions obtained with one another and adding a binder, Filler, sensitizer, lubricant and other auxiliary has been obtained. When exposed to heat or heat, the coating immediately undergoes a chemical reaction with color formation.
  • heat-sensitive recording sheets include use in medical and technical recording devices, terminal printers for computers and information systems, printers for facsimile or copying machines and electronic calculating machines, ticket machines and the like.
  • the heat-sensitive recording system has been developed and has found a variety of practical uses, which have been aimed at increasing the recording speed and improving the image quality, that is, increasing the image resolution. It is desirable to get by with less thermal energy on the thermal head, so the heat-sensitive recording sheet should have sufficient color-forming sensitivity for bright chromogenic recordings with little heat input 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, skin secretions, and solvents such as alcohol, acetone, 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, acetones, etc. Therefore, the phenomenon that the image density of the soiled part decreases or the image is faded is observed, and that the stain causes discoloration of the background or Color formation.
  • the heat sensitive recording sheets containing a leuco dye and a coloring agent are used as thermal labels in the field of POS systems.
  • the color development occurs in the visible range, so that the color development cannot be read by the bar code scanner when a semiconducting laser beam is used in the near ultra-red range.
  • Japanese patent publication 8787/1957 describes the combined use of iron stearate as an electron acceptor with tannic acid or gallic acid as an electron donor
  • Japanese Patent publications 6485/1959 describe the combined use of an electron acceptor such as silver stearate, iron 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.
  • JP-OLS No. 89193/1984 describes a combination of a color development system using a leuco dye and a color developing agent and a color development system using a metal compound consisting of an iron salt of a higher fatty acid and a polyhydric phenol.
  • this combination is disadvantageous because it requires a protective layer to cover the color.
  • solvents, such as alcohol penetrate through pinholes in the protective layer, resulting in discoloration due to the reaction between a leuco dye and a color developing agent contained in the color developing layer by the penetrated solvents.
  • the iron salt of a higher fatty acid with 16 to 35 carbon atoms has the disadvantages that fine foams are formed, the viscosity is increased and many, when grinding and dispersing by means of a grinding device such as a ball mill, attritor, sand grinder, etc., down to a particle size of a few micrometers Coagulates arise.
  • the above iron salts of the higher fatty acids as such are also weakly colored, so the background of a heat sensitive material is that Dispersion of the coating composition and the application of this coating composition colored, which leads to an inferior image contrast as a disadvantage.
  • the invention has for its object to provide a heat-sensitive recording material which is superior in dispersion, image contrast, oil resistance, solvent resistance and optical readability in the near ultraviolet range.
  • the recording sheet has a color development layer applied to a support which contains a metal double salt of a higher fatty acid having 16 to 35 carbon atoms as an electron acceptor and a suitable electron donor.
  • the type of electron donor is not particularly limited, but the preferred electron donor is selected from at least one of the following connecting groups or compounds: Polyvalent aromatic hydroxyl compounds diphenylcarbazide, diphenylcarbazone, hexamethylenetetramine, spirobenzopyran and 1-formyl-4-phenylsemicarbazide.
  • the heat-sensitive recording material according to the invention is produced by applying the coating composition, which contains the combination of a previous electron donor and an above electron acceptor, to a base support.
  • the metal double salts of higher fatty acids according to the invention are double salts which have at least two types of metal atoms per molecule. They therefore differ significantly in their physicochemical properties from the previous metal salts of higher fatty acids, which only contain one type of metal atom in their molecule.
  • These metal double salts of the higher fatty acids are prepared by reacting at least two inorganic metal salts with an alkali metal salt or ammonium salt of the selected higher fatty acid.
  • the type and the mixing ratio of the metal atoms of the at least two inorganic metal salts can be easily adjusted and controlled in this way.
  • the zinc-iron double salt of behenic acid with iron and zinc in a ratio of 2: 1 can be prepared by mixing sodium behenate with an aqueous solution of ferrichloride and zinc chloride in one Molar ratio of 2: 1 is implemented.
  • Suitable metals for the double salt formation of the higher fatty acids are polyvalent metals, for example iron, zinc, calcium, magnesium, aluminum, barium, lead, manganese, tin, nickel, cobalt, copper, silver, mercury, etc .; preferably iron, zinc, calcium, aluminum, magnesium and silver.
  • Suitable fatty acids for the double salt formation are saturated and / or unsaturated aliphatic fatty acids with 16 to 35 carbon atoms.
  • the electron donors of the invention which are used with the metal double salt of a higher fatty acid, are preferably polyvalent aromatic hydroxyl compounds, dipenyl carbazide, diphenyl carbazone, hexamethylenetetramine, spirobenzopyran and 1-formyl-4-phenylsemicarbazide; most preferred are the polyvalent aromatic hydroxyl compounds of the general formula (I): in which R is an alkyl group with 18 to 35 carbon atoms, means (wherein R1 represents an alkyl group having 18 to 35 carbon atoms); n represents an integer from 2 to 3; and "-X-" for -CH2-, -CO2-, -CO-, -O-, -CONH-, (wherein R ⁇ is an alkyl group having 5 to 30 carbon atoms), -SO2 -, -SO3 - or - SO2NH - is.
  • R is an alkyl group with 18 to 35 carbon atoms, means (wherein R1 represents an al
  • Such metal double salts of higher fatty acids can be used as an electron acceptor alone or in a mixture.
  • polyvalent aromatic hydroxyl compounds according to the invention as an electron donor is not subject to any particular restrictions, for example a compound of the following formulas can be used, wherein R is an alkyl group with 18 to 35 carbon atoms and R ⁇ is an alkyl group with 5 to 30 carbon atoms,
  • the coating composition When preparing the coating composition by dispersing this polyvalent phenol derivative in an aqueous or solvent-free binder, it is necessary to avoid a reaction of this phenol derivative with an electron donor and to increase the solvent and dispersion stability of this phenol. It is desirable that the substituent other than the color developing group has a large number of carbon atoms, namely 18 to 35, 2 to 3 OH groups are present, and these OH groups are close to each other.
  • This polyhydric phenol, etc. is used alone or in a mixture as needed.
  • Suitable color developing agents when using a colorless dye are: bisphenol A, p, p ⁇ - (1-methyl-normal-hexylidene) diphenol, p-tertiary-butylphenol, p-phenylphenol, p-hydroxybenzoic acid ester, novolak phenolic resin, 4-hydroxy 1-methylsulfonylbenzene, 4-hydroxy-1-butyloxysulfonylbenzene, etc.
  • the electron donor of the invention is particularly superior.
  • the additives which can be used according to the invention are, for example, the following: Anti-mottling agents (e.g. fatty acid amide, ethylene bisamide, montan wax); Sensitizer (e.g. dibenzyl therephthalate, benzyl p-benzyloxybenzoate, di-p-tolyl carbonate, p-benzyl biphenyl); and stabilizer (for example, metal salt of a phthalic acid monoester, metal salt of p-tert, butylbenzoic acid, metal salt of nitrobenzoic acid).
  • Anti-mottling agents e.g. fatty acid amide, ethylene bisamide, montan wax
  • Sensitizer e.g. dibenzyl therephthalate, benzyl p-benzyloxybenzoate, di-p-tolyl carbonate, p-benzyl biphenyl
  • stabilizer for example, metal salt of a phthalic acid monoester, metal salt of p-tert
  • Binders according to the invention are e.g. B. fully saponified polyvinyl alcohol, degree of polymerization: 200-1900, partially saponified polyvinyl alcohol, carboxylated polyvinyl alcohol, amide-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, butyral-modified polyvinyl alcohol, other modified polyvinyl alcohols, hydroxyethyl cellulose, Methyl cellulose, carboxymethyl cellulose, styrene-maleic anhydride copolymers, styrene-butadiene copolymers, cellulose derivatives such as ethyl cellulose and acetyl cellulose, polyvinyl chloride, polyvinyl acetate, polyacrylamide, polyacrylic acid ester, polyvinyl butyral, polystyrene, copolymers of the above compounds, polyamide resin, cylon resin, silicone resin, polyamide resin, silicone resin . These high molecular
  • the type and amount of the metal double salt of the higher fatty acid, the polyhydric phenol derivative, the binder, the other additives, which are determined 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 electron donor and 2 to 15 parts by weight of filler, based on 1 to 9 parts of the metal double salt of the higher fatty acid, and 0.5 to 4 parts by weight of binder , based on the total solids content.
  • the heat-sensitive material according to the invention is produced by applying the coating composition to a base material such as paper, synthetic paper, film, etc.
  • the above-mentioned metal double salt of a higher fatty acid, the above electron donor, optionally the organic color developing agent and the basic, colorless chromogenic dye are by means of a grinding device such as a ball mill, attritor, sanding machine, etc., or by means of a suitable emulsifying machine to a particle size of several microns or grind smaller. Various additives are added to this.
  • the additives which can be used according to the invention are, for example, 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 and so on.
  • the metal salt of a higher fatty acid has both hydrophilic groups and hydrophobic groups, and therefore has the properties of a surfactant. Therefore, when grinding and dispersing by means of a grinding device such as a ball mill, attritor, sand grinder, etc. down to a particle size of a few microns and less, it has the disadvantages that foams are formed, the viscosity is increased and many coagulates are formed. Surprisingly, this is not the case when using the double salts according to the invention. Perhaps the different metals cause subtle differences in the surface-active properties, so that the dispersibility is increased.
  • the superior optical readability of the heat-sensitive recording sheet of the present invention in the near-red range may have the following cause.
  • the color is formed by the heat-melt reaction
  • the color development area results in a recordable image in the visible range and in the near ultra-red range (wavelength range from 700 to 1000 nm).
  • the cause of the superior resistance of the recording image to oil and solvent is an irreversible color-forming reaction which occurs when it is melted and which occurs between a metal double salt of the higher fatty acid as an electron acceptor and a polyvalent phenol derivative, etc. as an electron donor.
  • the heat-melt color formation reaction forms a very stable complex which is not dissolved by adhering hair oil, oil materials and solvents such as alcohol.
  • the metal double salt of higher fatty acids according to the invention has 16-35 carbon atoms per. Molecule has, and therefore that Solubility in the hair oil, the oil materials and the organic solvent such as alcohol, etc. is very small, so that when it comes into contact with the contaminant, there is no chemical reaction between the metal double salt of higher fatty acids and the electron donor, such as a polyhydric phenol, etc. The better image contrast is also surprising.
  • the metal salts of higher fatty acids have different colors, from colorless to clearly colored, depending on the properties of the metals.
  • the iron salt of higher fatty acids is pale yellow, whereas the zinc salt of higher fatty acids is colorless.
  • the iron-zinc double salt of a fatty acid, in which iron and zinc are present in one molecule, is only very weakly colored, which leads to only a very slight coloration of the heat-sensitive recording material after application of the coating material obtained by dispersing the double salt. In this way, a suitable combination of the metals can be used to produce a heat-sensitive recording material with a very lightly colored background.
  • This coating composition was applied in a coating amount of 6.0 g / m2 on a base paper with a weight of 50 g / m2, dried and supercalendered to achieve a smoothness of 200-600 seconds.
  • a heat sensitive recording sheet was obtained.
  • the solutions of the above compositions were individually milled in a attritor to a particle size of 3 microns. The solutions were then mixed together in the same ratio as in the examples, a heat-sensitive coating composition being obtained.
  • This coating composition was applied in a coating amount of 6.0 g / m2 on a base paper with a weight of 50 g / m2, dried and supercalendered to achieve a smoothness of 200-600 seconds.
  • a heat sensitive recording sheet was obtained.
  • the recording sheets obtained in the examples and comparative examples were tested for the qualities given in Tables 1 and 2, where the results are also summarized.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
EP87107971A 1986-06-03 1987-06-02 Wärmeempfindliches Aufzeichnungsmaterial Expired - Lifetime EP0248405B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP61128691A JPS62284782A (ja) 1986-06-03 1986-06-03 感熱記録体
JP128691/86 1986-06-03

Publications (3)

Publication Number Publication Date
EP0248405A2 EP0248405A2 (de) 1987-12-09
EP0248405A3 EP0248405A3 (en) 1989-04-26
EP0248405B1 true EP0248405B1 (de) 1991-12-11

Family

ID=14991036

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87107971A Expired - Lifetime EP0248405B1 (de) 1986-06-03 1987-06-02 Wärmeempfindliches Aufzeichnungsmaterial

Country Status (5)

Country Link
US (1) US4849396A (ja)
EP (1) EP0248405B1 (ja)
JP (1) JPS62284782A (ja)
CA (1) CA1263020A (ja)
DE (1) DE3775117D1 (ja)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0669755B2 (ja) * 1987-02-25 1994-09-07 日本製紙株式会社 感熱記録体
GB8911419D0 (en) * 1989-05-18 1989-07-05 Smith & Mclaurin Limited Heat-sensitive record material
JP2681907B2 (ja) * 1992-11-20 1997-11-26 日本製紙株式会社 感熱記録体
US5498772A (en) * 1993-10-14 1996-03-12 Mitsubishi Paper Mills Limited Reversible heat-sensitive recording material
US6093528A (en) * 1997-09-17 2000-07-25 Agfa-Gevaert Reducing agents for use in thermographic recording materials
EP0903625B1 (en) * 1997-09-17 2003-05-14 Agfa-Gevaert Thermographic recording materials
US6287755B1 (en) * 1998-04-20 2001-09-11 Konica Corporation Thermally developable photosensitive material
US6211115B1 (en) 1998-08-07 2001-04-03 Agfa-Gevaert Reducing agents for use in thermographic recording materials
EP0978760B1 (en) * 1998-08-07 2003-07-02 Agfa-Gevaert Thermographic recording materials
FI110677B (fi) * 2001-10-12 2003-03-14 Jujo Thermal Oy Lämpöherkkä tallennusmateriaali
GB0400813D0 (en) * 2004-01-14 2004-02-18 Sherwood Technology Ltd Laser imaging
EP2325018A1 (de) 2009-11-24 2011-05-25 Mondi Uncoated Fine & Kraft Paper GmbH Thermisch sensibles Aufzeichnungsmaterial

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3795532A (en) * 1971-03-10 1974-04-05 Minnesota Mining & Mfg Wide latitude copy sheet
US4461496A (en) * 1982-08-17 1984-07-24 Minnesota Mining And Manufacturing Company Soap having improved carbonless imaging properties
JPS5989193A (ja) * 1982-11-15 1984-05-23 Ricoh Co Ltd 感熱記録材料
US4531141A (en) * 1983-01-17 1985-07-23 Minnesota Mining And Manufacturing Company Heat-sensitive composition and imaging sheet incorporating same
JPS6211681A (ja) * 1985-07-10 1987-01-20 Jujo Paper Co Ltd 感熱記録体
JPS62105688A (ja) * 1985-11-01 1987-05-16 Jujo Paper Co Ltd 感熱記録体
JPH01163890A (ja) * 1987-12-21 1989-06-28 Toshiba Corp 入室管理システム

Also Published As

Publication number Publication date
US4849396A (en) 1989-07-18
CA1263020A (en) 1989-11-21
JPH0478115B2 (ja) 1992-12-10
JPS62284782A (ja) 1987-12-10
DE3775117D1 (de) 1992-01-23
EP0248405A2 (de) 1987-12-09
EP0248405A3 (en) 1989-04-26

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