EP0211263B1 - Wärmeempfindliches Aufzeichnungsmaterial - Google Patents

Wärmeempfindliches Aufzeichnungsmaterial Download PDF

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Publication number
EP0211263B1
EP0211263B1 EP86109407A EP86109407A EP0211263B1 EP 0211263 B1 EP0211263 B1 EP 0211263B1 EP 86109407 A EP86109407 A EP 86109407A EP 86109407 A EP86109407 A EP 86109407A EP 0211263 B1 EP0211263 B1 EP 0211263B1
Authority
EP
European Patent Office
Prior art keywords
sensitive recording
recording material
heat
heat sensitive
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
EP86109407A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0211263A3 (en
EP0211263A2 (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 EP0211263A2 publication Critical patent/EP0211263A2/de
Publication of EP0211263A3 publication Critical patent/EP0211263A3/de
Application granted granted Critical
Publication of EP0211263B1 publication Critical patent/EP0211263B1/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
    • 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 suitable for fast recording and which has a superior storage stability of the image against oils, fats and solvents such as alcohols.
  • Heat-sensitive recording sheets in which a color reaction between a colorless or poorly manufactured chromogenic substance and a phenolic substance or an organic acid takes place due to the action of heat or heat, etc. in Japanese Patent Publications Nos. 4160/1968 and 14039/1970 and in JP-OL No. 27736/1973 and currently widely used in practice.
  • a heat-sensitive recording sheet is generally prepared by applying to the surface of a support such as paper, film, etc. a coating composition which is obtained 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 aids have been obtained.
  • a coating composition which is obtained 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 aids have been obtained.
  • the coating When exposed to heat or heat, the coating immediately undergoes a chemical reaction with color formation. Depending on the selection of the specific, colorless chromogenic substances, various clear colors can be obtained.
  • the heat-sensitive recording system has been further developed and has found a variety of practical uses, with an increased recording speed and improvement in image quality, i.e. the increase in image resolution were aimed for. It is desirable to get by with less thermal energy on the thermal head, therefore 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, 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, acetones, etc. The phenomenon is therefore observed that the image density of the soiled part is reduced or the image is faded, and that the soil is stained or discolored causes color formation.
  • 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 publication 6485/1959 describes the combined use of an electron acceptor such as silver stearate, iron stearate, gold stearate, copper stearate or mercury endonate with an electron endonate such as methyl gallate, ethyl gallate, propyl gallate, butyl gallate or dodecyl gallate.
  • R represents an alkyl group with 18-35 carbon atoms; n is 3; "X" here CH 2 , 0, CONH, SO 2 , S0 3 or S0 2 NH, where R 'is an alkyl group having 5-30 carbon atoms.
  • This polyhydric phenol is used alone or in a mixture as required.
  • Such iron salts of saturated higher fatty acids can be used as an electron acceptor alone or in a mixture. They can be used with a leuco dye, but the solvent resistance is reduced.
  • a special polyhydric phenol is used as the electron donor, the combined use of the organic acid and / or the phenol being possible depending on the intended use and the required function of the heat-sensitive recording material.
  • Suitable color developing agents when using a colorless dye are: bisphenol A, p, p '- (1-methyl-normal-hexylidene) diphenol, p-tert-butylphenyl, p-phenylphenol, p-hydroxybenzoic acid ester, novolak phenolic resin, 4-hydroxy -1-methylsulfonylbenzene, 4-hydroxy-1-butyloxysulfonylbenzene, etc.
  • additives can be added to achieve certain effects.
  • the additives which can be used according to the invention are e.g. the following: anti-mottling agents (e.g. fatty acid amide, ethlenebisamide, montan wax); Sensitizer (e.g. dibenzyl therephthalate, benzyl p-benzyloxybenzoate, di-p-tolyl carbonate, p-benzyl biphenyl); and stabilizer (e.g. 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, ethlenebisamide, montan wax
  • Sensitizer e.g. dibenzyl therephthalate, benzyl p-benzyloxybenzoate, di-p-tolyl carbonate, p-benzyl biphenyl
  • stabilizer e.g. metal
  • Binders according to the invention are, for example, completely 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, styrene-maloxymethylcellulose, methylcellulose acid, carboxylate methylcellulose, carboxylate Cellulose derivatives such as ethyl cellulose and acetyl cellulose, polyvinyl chloride, polyvinyl acetate, polyacrylamide, polyacrylic acid esters, polyvinyl butyral, Polystyrene, copolymers of the above compounds, polyamide resin, silicone resin, petroleum resin, terpene resin, ketone resin and coumarone resin. These high molecular weight binders can be used after being dissolved in a
  • the type and amount of the iron salt of the saturated higher fatty acid, the polyhydric phenol, 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 polyhydric phenol and 2 to 15 parts by weight of filler, based on 1 to 6 parts of the iron salt of the saturated higher fatty acid, and 0.5 to 4 parts by weight To use binders, 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 heat-sensitive recording material of the present invention has a greatly improved resistance to solvents such as alcohol, etc.
  • solvents such as alcohol, etc.
  • both the organic acid iron salt and the polyhydric phenol which can be used in this invention have an alkyl group of 16 or 18 to Contain 35 carbon atoms, so that the solution diffusion rate compared to the solvents and the saturation solubility are very low. Therefore, when the recording material is soiled by the solvent, there is no physical-chemical reaction, so that the stability of the background is not deteriorated.
  • the cause of the superior oil resistance is due to an irreversible hot melt color development reaction between the organic iron salt and the polyhydric phenol. I.e. once this color development reaction occurs, a very stable complex is formed in which the bond of adhering hair oil, oil materials, etc. is not broken. Therefore, the color image is stable.
  • parts As an abbreviation for parts by weight, “parts” is used.
  • This coating mass was applied in a coating amount of 6.0 g / m 2 to a base paper with a weight of 50 g / m 2 , dried and supercalendered to achieve a smoothness of 200-600 seconds.
  • a heat sensitive recording sheet was obtained.
  • This coating composition was applied in a coating amount of 6.0 g / m 2 on a base paper with a weight of 50 g / m 2 , dried and supercalendered to adjust a smoothness of 200-600 seconds. A heat sensitive recording sheet was obtained.
  • a heat-sensitive recording sheet was obtained in the same manner as in Comparative Example 1, except that the lauryl gallate was used individually instead of the propyl gallate.
  • Solution B color developer dispersion
  • This coating composition was applied in a coating amount of 6.0 g / m 2 to a base paper with a weight of 50 g / m 2 , dried and supercalendered to set a smoothness of 200-600 seconds. A heat sensitive recording sheet was obtained.
  • a heat-sensitive recording sheet is imaged under copying conditions with a facsimile machine (KB-4800, manufactured by Toshiba Corporation).
  • the image density is determined using a Macbeth density meter (type RD 514, use of the amber filter, same conditions as below).
  • Oil resistance (after oil treatment): A castor oil is dripped onto the colored part of a record according to note (1). After 10 seconds, the castor oil is wiped off with a filter paper and the paper obtained is left to stand at room temperature for 3 days. The image density is then determined using a Macbeth densimeter.
  • Residual image density The residual image density is calculated from the following formula.
  • Solvent resistance 95% ethyl alcohol solution is dropped on the unstained part of a heat-sensitive recording sheet. The image density is determined after 30 minutes with a Macbeth densimeter.

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)
  • Credit Cards Or The Like (AREA)
  • Color Printing (AREA)
EP86109407A 1985-07-10 1986-07-09 Wärmeempfindliches Aufzeichnungsmaterial Expired - Lifetime EP0211263B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP150090/85 1985-07-10
JP60150090A JPS6211681A (ja) 1985-07-10 1985-07-10 感熱記録体

Publications (3)

Publication Number Publication Date
EP0211263A2 EP0211263A2 (de) 1987-02-25
EP0211263A3 EP0211263A3 (en) 1987-07-01
EP0211263B1 true EP0211263B1 (de) 1990-05-16

Family

ID=15489291

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86109407A Expired - Lifetime EP0211263B1 (de) 1985-07-10 1986-07-09 Wärmeempfindliches Aufzeichnungsmaterial

Country Status (5)

Country Link
US (1) US4729983A (enrdf_load_stackoverflow)
EP (1) EP0211263B1 (enrdf_load_stackoverflow)
JP (1) JPS6211681A (enrdf_load_stackoverflow)
CA (1) CA1249720A (enrdf_load_stackoverflow)
DE (1) DE3671194D1 (enrdf_load_stackoverflow)

Families Citing this family (16)

* 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
US4999333A (en) * 1987-10-02 1991-03-12 Fuji Photo Film Co., Ltd. Heat sensitive recording material
WO1990011898A1 (en) * 1989-04-07 1990-10-18 Toppan Printing Co., Ltd. Composition for reversible thermal recording medium
GB8911419D0 (en) * 1989-05-18 1989-07-05 Smith & Mclaurin Limited Heat-sensitive record material
EP0867881A3 (en) * 1997-03-26 2002-10-23 Sony Corporation Recording medium recording apparatus and method and recording medium.
AU2005322998B2 (en) * 2005-01-07 2012-05-31 Bay Materials, Llc Thermally-responsive materials and devices comprising such materials
MX2012011843A (es) 2010-04-16 2012-11-12 Valspar Sourcing Inc Composiciones de revestimiento para envasar articulos y metodos de revestimiento.
BR122015001646B1 (pt) 2011-02-07 2021-06-15 Swimc Llc Composição de revestimento, artigo, e, método
CN104541210A (zh) 2012-08-09 2015-04-22 威士伯采购公司 用于热响应记录材料的显影剂
KR102093405B1 (ko) 2012-08-09 2020-03-25 에스더블유아이엠씨 엘엘씨 용기 코팅 시스템
EP2882401A4 (en) 2012-08-09 2016-03-30 Valspar Sourcing Inc DENTAL MATERIALS AND MANUFACTURING METHOD
EP2882818B1 (en) 2012-08-09 2020-05-06 Swimc Llc Stabilizer and coating compositions thereof
WO2014025407A1 (en) 2012-08-09 2014-02-13 Valspar Sourcing, Inc. Polycarbonates
CA2879424C (en) 2012-08-09 2020-06-30 Valspar Sourcing, Inc. Compositions for containers and other articles and methods of using same
CA2942399C (en) 2014-04-14 2022-08-30 Valspar Sourcing, Inc. Methods of preparing compositions for containers and other articles and methods of using same
TWI614275B (zh) 2015-11-03 2018-02-11 Valspar Sourcing Inc 用於製備聚合物的液體環氧樹脂組合物

Family Cites Families (5)

* 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.
US4232083A (en) * 1975-07-22 1980-11-04 Minnesota Mining And Manufacturing Company Imaging compositions and methods
JPS5989193A (ja) * 1982-11-15 1984-05-23 Ricoh Co Ltd 感熱記録材料
JPS5993386A (ja) * 1982-11-19 1984-05-29 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

Also Published As

Publication number Publication date
DE3671194D1 (de) 1990-06-21
EP0211263A3 (en) 1987-07-01
EP0211263A2 (de) 1987-02-25
JPH0422155B2 (enrdf_load_stackoverflow) 1992-04-15
CA1249720A (en) 1989-02-07
JPS6211681A (ja) 1987-01-20
US4729983A (en) 1988-03-08

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