EP0211263A2 - Matériau sensible à la chaleur pour l'enregistrement - Google Patents

Matériau sensible à la chaleur pour l'enregistrement Download PDF

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Publication number
EP0211263A2
EP0211263A2 EP86109407A EP86109407A EP0211263A2 EP 0211263 A2 EP0211263 A2 EP 0211263A2 EP 86109407 A EP86109407 A EP 86109407A EP 86109407 A EP86109407 A EP 86109407A EP 0211263 A2 EP0211263 A2 EP 0211263A2
Authority
EP
European Patent Office
Prior art keywords
heat
sensitive recording
recording material
carbon atoms
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.)
Granted
Application number
EP86109407A
Other languages
German (de)
English (en)
Other versions
EP0211263B1 (fr
EP0211263A3 (en
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/fr
Publication of EP0211263A3 publication Critical patent/EP0211263A3/de
Application granted granted Critical
Publication of EP0211263B1 publication Critical patent/EP0211263B1/fr
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 slightly colored chromogenic substance and a phenolic substance or an organic acid takes place by the action of heat or heat, u. a. 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 in which an increased recording speed and an 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, 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 method has been proposed to improve stability in which the use of a coating layer on a color developing layer containing the leuco dye and the organic developing agent physically prevents contact with oily materials or solvents such as oils, greases, etc.
  • this method has the disadvantages that it is difficult to produce the coating layer with superior oil resistance and good solvent resistance, and the sensitivity is reduced, etc.
  • 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 and 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.
  • the invention has for its object to provide a heat-sensitive recording sheet which has an improved thermal responsiveness, and whose recording image is very stable against the sticking of hair oils, oily materials and solvents such as alcohol.
  • the recording sheet has a color development layer applied to a support, which comprises a combination of an iron salt of a saturated higher fatty acid with 16-35 carbon atoms as the metal salt of an organic carboxylic acid, and a polyvalent phenol derivative of the following formula (I): in which R represents an alkyl group with 18-35 carbon atoms; n represents an integer of 2-3; "X” here means CH 2 , 0, CONH, CON, SO 2 , S0 3 or SO 2 NH R ', where R' is an alkyl group having 5 to 30 carbon atoms.
  • the coating composition by dispersing this polyhydric phenol in an aqueous or solvent-soluble binder, it is necessary to avoid the reaction of this phenol with an electron donor and to increase the solvent and dispersion stability of this phenol. It is desirable that the non-OH substituent on the color developer has a large number of carbon atoms, namely 18-35, 2-3 OH groups are present, and these OH groups are close to each other.
  • 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 used as an electron donor depending on the intended use and the required function of the heat-sensitive recording material, the combined use of the organic acid and / or the phenol is possible.
  • 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, Novclak phenolic resin, 4-hydruxy -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, for example, the following: anti-mottling agents (for example 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 nitrobenzoe acid).
  • anti-mottling agents for example 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
  • 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, hydroxy ethylcellulose, methylcellulose, carboxymethylcellulose, styrene-maleic anhydride copolymers, styrene-butadiene copolymers, cellulose derivatives such as ethyl cellulose and acetyl cellulose, polyvinyl chloride, polyvinyl acetate, polyacrylamide, polyacrylic acid ester, polyvinylbutyral, polystyrene, copolymers of the above compounds, polyamide resin, silicone resin, petroleum resin, terpene resin, ketone resin and coumarone resin.
  • 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 used by applying the coating composition to a base material such as paper, synthetic paper, film, etc.
  • the heat-sensitive recording material according to the 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 contain an alkyl group having 16 or 18 to 35 carbon atoms, so that the solution diffusion rate against the solvents and the saturation solubility is very small. 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 a non-reversible 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.
  • Solution A electron acceptor dispersion: The solutions of the above compositions were individually milled in a attritor to a particle size of 3 microns.
  • 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.
  • Solution A electron acceptor dispersion: The solutions of the above compositions were individually milled in a attritor to a particle size of 3 microns.
  • 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.
  • Coating mass This coating composition was applied in a coating amount of 6.0 g / m 2 onto a base paper with a weight of 50 g / m 2 applied, 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).
  • 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 Matériau sensible à la chaleur pour l'enregistrement Expired - Lifetime EP0211263B1 (fr)

Applications Claiming Priority (2)

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

Publications (3)

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

Family

ID=15489291

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86109407A Expired - Lifetime EP0211263B1 (fr) 1985-07-10 1986-07-09 Matériau sensible à la chaleur pour l'enregistrement

Country Status (5)

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

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0248405A2 (fr) * 1986-06-03 1987-12-09 Jujo Paper Co., Ltd. Matériel pour l'enregistrement, sensible à la chaleur
WO1990014235A1 (fr) * 1989-05-18 1990-11-29 Smith & Mclaurin Limited Materiau d'enregistrement d'inscriptions thermosensible

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2210702B (en) * 1987-10-02 1991-11-06 Fuji Photo Film Co Ltd Heat sensitive recording material
CA2030799A1 (fr) * 1989-04-07 1990-10-08 Watanabe Niro Composition pour milieux de thermogravure reversibles
EP0867881A3 (fr) * 1997-03-26 2002-10-23 Sony Corporation Appareil d'enregistrement pour milieu d'enregistrement et méthode et milieu d'enregistrement
US7875207B2 (en) * 2005-01-07 2011-01-25 Bay Materials, Llc Thermally-responsive materials and devices comprising such materials
KR20130061132A (ko) 2010-04-16 2013-06-10 발스파 소싱 인코포레이티드 패키징 용품을 위한 코팅 조성물 및 코팅 방법
BR112013020026B1 (pt) 2011-02-07 2021-03-02 Swimc Llc artigo, composição de revestimento, e, método
EP2883113A4 (fr) * 2012-08-09 2016-03-30 Valspar Sourcing Inc Développeur pour des matières d'enregistrement thermosensibles
US9944749B2 (en) 2012-08-09 2018-04-17 Swimc, Llc Polycarbonates
ES2849526T3 (es) 2012-08-09 2021-08-19 Swimc Llc Composiciones para contenedores y otros artículos y métodos de utilización de los mismos
WO2014025411A1 (fr) 2012-08-09 2014-02-13 Valspar Sourcing, Inc. Système de revêtement de récipient
EP2882401A4 (fr) 2012-08-09 2016-03-30 Valspar Sourcing Inc Matériaux dentaires et procédé de fabrication associé
CN104583347B (zh) 2012-08-09 2016-11-16 威士伯采购公司 稳定剂和其涂料组合物
EP3131965B1 (fr) 2014-04-14 2024-06-12 Swimc Llc Procédés de préparation de compositions pour contenants et autres articles et procédés d'utilisation desdites compositions
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

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1145567A (en) * 1965-04-02 1969-03-19 Alexander Thiard Laforest Heat-sensitive copying material and process for its manufacture
JPS57176196A (en) * 1981-04-23 1982-10-29 Kanzaki Paper Mfg Co Ltd Heat-sensitive recording medium

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1145567A (en) * 1965-04-02 1969-03-19 Alexander Thiard Laforest Heat-sensitive copying material and process for its manufacture
JPS57176196A (en) * 1981-04-23 1982-10-29 Kanzaki Paper Mfg Co Ltd Heat-sensitive recording medium

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN, Band 7, Nr. 24 (M-189)[1169], 29. Januar 1983; & JP-A-57 176 196 (KANZAKI SEISHI K.K.) 29.10.1982 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0248405A2 (fr) * 1986-06-03 1987-12-09 Jujo Paper Co., Ltd. Matériel pour l'enregistrement, sensible à la chaleur
EP0248405A3 (en) * 1986-06-03 1989-04-26 Jujo Paper Co., Ltd. Heat-sensitive registration material
WO1990014235A1 (fr) * 1989-05-18 1990-11-29 Smith & Mclaurin Limited Materiau d'enregistrement d'inscriptions thermosensible

Also Published As

Publication number Publication date
DE3671194D1 (de) 1990-06-21
JPH0422155B2 (fr) 1992-04-15
CA1249720A (fr) 1989-02-07
US4729983A (en) 1988-03-08
JPS6211681A (ja) 1987-01-20
EP0211263B1 (fr) 1990-05-16
EP0211263A3 (en) 1987-07-01

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