EP0173232B1 - Wärmeempfindliches Aufzeichnungsblatt - Google Patents

Wärmeempfindliches Aufzeichnungsblatt Download PDF

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Publication number
EP0173232B1
EP0173232B1 EP85110455A EP85110455A EP0173232B1 EP 0173232 B1 EP0173232 B1 EP 0173232B1 EP 85110455 A EP85110455 A EP 85110455A EP 85110455 A EP85110455 A EP 85110455A EP 0173232 B1 EP0173232 B1 EP 0173232B1
Authority
EP
European Patent Office
Prior art keywords
parts
heat
weight
isopropoxy
developing agent
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
Application number
EP85110455A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0173232A2 (de
EP0173232A3 (en
Inventor
Toshimi Central Research Laboratory Satake
Toshiaki Central Research Laboratory Minami
Kazuo Central Research Laboratory Maruyama
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 EP0173232A2 publication Critical patent/EP0173232A2/de
Publication of EP0173232A3 publication Critical patent/EP0173232A3/de
Application granted granted Critical
Publication of EP0173232B1 publication Critical patent/EP0173232B1/de
Expired legal-status Critical Current

Links

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
    • 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 sheet which is suitable for clear, intensive recordings at high speed and has a superior shelf life.
  • a heat sensitive recording sheet is generally made 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, e.g. such as a phenolic substance, mixing the dispersions obtained together and adding a binder, filler, sensitizer, lubricant and other auxiliaries.
  • a coating composition which is obtained by finely grinding and dispersing a colorless chromogenic substance and a color developing material, e.g. such as a phenolic substance, mixing the dispersions obtained together and adding a binder, filler, sensitizer, lubricant and other auxiliaries.
  • the coating Due to the effect of heat or heat, the coating is instantly chemically converted to form a color. Depending on the choice of specific, colorless, chromogenic substances, various clear colors can be obtained.
  • Bisphenol A 4,4'-isopropylidenediphenol
  • the heat-sensitive recording sheets using p-hydroxybenzoic acid benzyl ester as a color developing agent have the disadvantages in terms of the stability of the image that the density of the image formed when the heat is applied decreases with the lapse of time, and that the p-hydroxybenzoic acid benzyl ester melted when the heat is applied decreases with that Recrystallized over time, forming white crystals.
  • the invention has for its object to provide a heat-sensitive recording sheet which has a superior stability of the image (ie a stable recording image when stored for a long time), in particular in which neither discoloration of the image takes place under high atmospheric humidity, high temperature etc. nor discoloration of the background .
  • the heat-sensitive recording paper according to the invention contains both 4-isopropyl-4'-hydroxydiphenylsulfone of the following formula (I) as an organic color developing agent in the color formation layer and also at least one compound from the group of substances of the following general formulas (11 ) or (III) contains as a sensitizer.
  • the present invention thus relates to a heat-sensitive recording sheet with a color-forming layer which contains a basic colorless or pale-colored chromogenic dye and an organic color developing agent which is characterized in that the color forming layer is an organic color developing agent 4-isopropoxy-4'-hydroxy-diphenyl sulfone of the following Contains formula (I) and as a sensitizer at least one substance which is selected from the group of substances of the general formulas (11) and (III) below: wherein A represents an H or halogen atom, an NO 2 , lower alkyl, lower alkoxy or hydroxyl group; I represents an integer from 1 to 5; and m represents an integer from 0 to 3.
  • the lower alkyl or lower alkoxy group (A) usually has 1 to 5 carbon atoms.
  • lower alkyl groups are the methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tert-butyl group.
  • lower alkoxy groups are the methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy and tert-butoxy groups.
  • the 4-isopropoxy-4'-hydroxydiphenylsulfone as an organic color developing agent according to the invention has a melting point of 129-130 ° C.
  • a known sensitizer such as stearic acid amide, benzyl p-benzyloxybenzoate, dibenzyl terephthalate, di-p-tolyl carbonate, etc.
  • the reason for this can be attributed to the fact that the 4-isopropoxy-4'-hydroxydiphenylsulfone as a color developing agent has a high rate of solution diffusion and very high solubility in the sensitizer according to the invention, namely that the sensitizer of the general formulas (II) or (III) has great solvency for 4-isopropoxy-4'-hydroxydiphenyl sulfone.
  • the sensitizer according to the invention also has a high solubility for a basic colorless dye.
  • sensitizers according to the invention of the general formulas (II) and (III) are:
  • the addition amount for the sensitizer according to the invention of the general formulas (11) or (III) is preferably 10-100 percent by weight, based on the 4-isopropoxy-4'-hydroxydiphenyl sulfone as organic color developing agent. With an addition of sensitizer of less than 10 percent by weight, the effect is small, but with an addition of more than 100 percent by weight, the image density is reduced because the organic color developing agent is diluted because of the large amount of sensitizer.
  • the above-mentioned organic color developing agent, the above-mentioned basic colorless dye and the sensitizer are mixed by means of a grinder, e.g. a ball mill, grinder, sand grinder, etc. or ground to a particle size of several microns or smaller using a suitable emulsifying machine.
  • a grinder e.g. a ball mill, grinder, sand grinder, etc. or ground to a particle size of several microns or smaller using a suitable emulsifying machine.
  • additives are added, depending on the intended use, in order to produce the coating composition.
  • the additives that can be used according to the invention are e.g. B.
  • binders such as polyvinyl alcohol, modified polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose, starch, styrene-maleic anhydride copolymers, vinyl acetate-maleic anhydride copolymers, styrene-butadiene copolymers, etc .
  • inorganic or organic fillers such as kaolin, baked kaolin, diatomaceous earth, talc, titanium dioxide, aluminum hydroxide, etc .
  • Release agents such as metal salts of fatty acids
  • Lubricants such as waxes
  • waterproofing agents such as glyoxal, etc .
  • Dispersing agents, anti-foaming agents, mottoling-preventing agents for example fatty acid amide, e
  • the kind and the amount of the organic color developing agent, the basic colorless dye, the sensitizer and the other components, which are determined depending on the desired effect and suitability for recording purposes, are not particularly limited. It is generally advantageous to use 3 to 12 parts by weight of 4-isopropoxy-4'-hydroxydiphenyl sulfone as a color developing agent, 3 to 12 parts by weight of sensitizer and 1 to 20 parts by weight of filler based on 1 part by weight of the basic colorless dye, and 10 to 25 parts by weight of binder, based on the total substance content, to be used.
  • Parts is used as an abbreviation for parts by weight.
  • the heat-sensitive recording sheet was produced according to Example 1, but without using solution C. The result is summarized in Table 1.
  • Solution D (dispersion of the sensitizer)
  • Each sensitizer in Table 1 4 parts of 10% solution of polyvinyl alcohol 5 parts of water 3 parts
  • the heat-sensitive recording sheets were produced according to Example 1, but with solution D instead of solution C.
  • the heat-sensitive recording sheet was produced according to Example 3, but without using solution C.
  • the result is summarized in Table 1.
  • the heat-sensitive recording sheet of the present invention in which both 4-isopropoxy-4'-hydroxydiphenylsulfone as a color developing agent and p-benzylbiphenyl are added to the color formation layer gives higher dynamic image density, superior durability of the undyed part and an improved durability of the recording image.

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)
EP85110455A 1984-08-23 1985-08-20 Wärmeempfindliches Aufzeichnungsblatt Expired EP0173232B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP175374/84 1984-08-23
JP59175374A JPS6153084A (ja) 1984-08-23 1984-08-23 感熱記録紙

Publications (3)

Publication Number Publication Date
EP0173232A2 EP0173232A2 (de) 1986-03-05
EP0173232A3 EP0173232A3 (en) 1986-10-29
EP0173232B1 true EP0173232B1 (de) 1989-11-08

Family

ID=15994981

Family Applications (1)

Application Number Title Priority Date Filing Date
EP85110455A Expired EP0173232B1 (de) 1984-08-23 1985-08-20 Wärmeempfindliches Aufzeichnungsblatt

Country Status (4)

Country Link
US (1) US4644375A (enrdf_load_stackoverflow)
EP (1) EP0173232B1 (enrdf_load_stackoverflow)
JP (1) JPS6153084A (enrdf_load_stackoverflow)
DE (1) DE3574117D1 (enrdf_load_stackoverflow)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH068073B2 (ja) * 1985-04-09 1994-02-02 三菱製紙株式会社 感熱記録材料
US4688058A (en) * 1985-11-20 1987-08-18 Mitsubishi Paper Mills, Ltd. Thermal recording materials
JPS63272582A (ja) * 1987-04-30 1988-11-10 Jujo Paper Co Ltd 感熱記録紙
JPH0777829B2 (ja) * 1987-11-09 1995-08-23 三菱製紙株式会社 感熱記録材料
US4981835A (en) * 1988-07-27 1991-01-01 Fuji Photo Film Co., Ltd. Recording material
US5019548A (en) * 1988-09-07 1991-05-28 Kanzaki Paper Manufacturing Co., Ltd. Heat sensitive recording material
EP0367384B1 (en) * 1988-11-02 1994-09-21 Oji Paper Co. Ltd. Heat-sensitive recording material
JPH0745266B2 (ja) * 1989-10-13 1995-05-17 日本製紙株式会社 感熱記録シート
JP2520335B2 (ja) * 1991-07-05 1996-07-31 北越製紙株式会社 耐薬品性、耐文具性に優れた感熱記録体
JP2734502B2 (ja) * 1992-02-28 1998-03-30 日本製紙株式会社 感熱記録シート
JP2671285B2 (ja) * 1992-03-18 1997-10-29 日本製紙株式会社 感熱記録シート
AU4144500A (en) * 1999-04-28 2000-11-17 Nippon Steel Chemical Co. Ltd., Thermal recording material

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5857989A (ja) * 1981-10-02 1983-04-06 Fuji Photo Film Co Ltd 感熱記録材料
JPS5882788A (ja) * 1981-11-11 1983-05-18 Fuji Photo Film Co Ltd 感熱記録材料
JPS59197463A (ja) * 1983-04-26 1984-11-09 Shin Nisso Kako Co Ltd フルオラン化合物
JPS6013852A (ja) * 1983-07-04 1985-01-24 Shin Nisso Kako Co Ltd ジフエニルスルホン誘導体およびそれを含有する発色性記録材料
JPS6079996A (ja) * 1983-10-11 1985-05-07 Ueno Seiyaku Oyo Kenkyusho:Kk 感熱記録紙
EP0164417B1 (en) * 1983-10-14 1989-03-15 Nippon Steel Chemical Co., Ltd. Thermal recording material

Also Published As

Publication number Publication date
JPH04477B2 (enrdf_load_stackoverflow) 1992-01-07
US4644375A (en) 1987-02-17
EP0173232A2 (de) 1986-03-05
JPS6153084A (ja) 1986-03-15
EP0173232A3 (en) 1986-10-29
DE3574117D1 (en) 1989-12-14

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