EP0122468B1 - Feuille pour l'enregistrement sensible à la chaleur - Google Patents

Feuille pour l'enregistrement sensible à la chaleur Download PDF

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Publication number
EP0122468B1
EP0122468B1 EP84102807A EP84102807A EP0122468B1 EP 0122468 B1 EP0122468 B1 EP 0122468B1 EP 84102807 A EP84102807 A EP 84102807A EP 84102807 A EP84102807 A EP 84102807A EP 0122468 B1 EP0122468 B1 EP 0122468B1
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EP
European Patent Office
Prior art keywords
phthalic acid
sensitive recording
heat
recording sheet
heat sensitive
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
EP84102807A
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German (de)
English (en)
Other versions
EP0122468A3 (en
EP0122468A2 (fr
Inventor
Noboru Central Research Laboratory Yamato
Toshimi Central Research Laboratory Satake
Toshiaki Central Research Laboratory Minami
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 EP0122468A2 publication Critical patent/EP0122468A2/fr
Publication of EP0122468A3 publication Critical patent/EP0122468A3/de
Application granted granted Critical
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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
    • B41M5/333—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

Definitions

  • the invention relates to a heat-sensitive recording sheet which has a high degree of whiteness, which is retained better than before even over a long period of time.
  • a heat-sensitive recording sheet is generally obtained by placing it on the surface of a support, e.g. B. a paper or film, etc., a coating composition which is obtained by finely grinding and dispersing a colorless chromogenic substance and a color developing material, e.g. B. a phenolic substance, mixing the dispersions obtained and adding a binder, filler, sensitizer, lubricant and other auxiliaries has been obtained.
  • a support e.g. B. a paper or film, etc.
  • a coating composition which is obtained by finely grinding and dispersing a colorless chromogenic substance and a color developing material, e.g. B. a phenolic substance, mixing the dispersions obtained and adding a binder, filler, sensitizer, lubricant and other auxiliaries has been obtained.
  • the coating When exposed to heat or heat, the coating immediately undergoes a chemical reaction in which a color is formed. Depending on the choice of special, colorless chromogenic substances, various clear colors can be created.
  • the heat-sensitive recording sheet should still have sufficient color-forming sensitivity for bright recordings with little heat input from the thermal head.
  • a particularly effective and preferred phenol is 4,4'-isopropylidenediphenol (bisphenol A) which is now commonly used, inter alia because of its stability, low cost, availability in trade, etc.
  • 4,4'-isopropylidenediphenol has the disadvantage that it requires a higher color formation temperature. It is therefore not well suited for recordings in which the amount of heat supplied is small and difficulties such as sticking to the thermal head, etc. can easily arise.
  • the color formation temperature of a heat-sensitive sheet must be such that the colorless chromogenic dye or an organic acid such as a phenol is melted or liquid due to the application of heat. If both color forming materials have higher melting points, a substance with a lower melting point is added. The color formation reaction can occur at a lower temperature if one of the farting materials is dissolved due to the melting of this substance.
  • heat-fusible substances with a low melting point e.g. B. various waxes, fatty acid amides, alkylated bisphenols, substituted biphenylalkanes, coumarin compounds or diphenylamines, as sensitizers or melting point depressants.
  • the color formation reaction can only take place when the sensitizer has melted, so that a thermal response sufficient for rapid dynamic recording to the small amount of heat delivered in short time pulses cannot be achieved.
  • the invention is therefore based on the object of providing a heat-sensitive recording sheet which, because of its advantageous thermal responsiveness, enables intensive, clear, high-density recording with rapid recording.
  • the heat-sensitive recording sheet is said to have a high degree of whiteness, which is retained better over a longer period than before.
  • the heat-sensitive recording sheet is said to provide an excellent copy paper for a thermal copying machine of the infrared or strobe type when coated on a thin base paper or a film.
  • the coating amount should be reduced and the productivity should be increased in the production thereof.
  • a heat-sensitive recording sheet which contains a phthalic acid monoester of the general formula as a color developing agent in the color formation layer in the R for -C 6 H 5 , -CH 2 is where X is alkyl, halogen or alkoxy.
  • Color developing agents used to date are phenolic substances such as bisphenol A, p-hydroxybenzoic acid ester, etc.
  • organic carboxylic acids are also described in Japanese Patent Publication 4160/1968, Japanese Patent Laid-Open 39139/1978, etc., but they are described because of the insufficient color developing ability and unstable background whiteness not used in practice.
  • FR-A-2 243 830 describes heat-sensitive recording sheets which contain, in addition to conventional additives, a colorless or slightly colored chromogenic dye in the color formation layer and a phthalic acid monoester as color developing agent.
  • phthalic acid monoesters can include cycloalkyl esters or alkyl esters with at least 4 carbon atoms, the alkyl esters in the alkyl part being unsubstituted or substituted with oxygen functions, such as a hydroxyl, etherified hydroxy or acyloxy group.
  • the phthalic acid monoesters according to the invention have a much better color development capacity and a considerably more stable degree of whiteness of the background than the known organic carboxylic acids.
  • Typical examples of the phthalic acid monoesters according to the invention are phthalic acid monophenyl ester, phthalic acid monobenzyl ester, phthalic acid monomethylphenyl ester, phthalic acid monoethylphenyl ester, phthalic acid monoalkylbenzyl ester, phthalic acid monohalobenzyl ester, phthalic acid monoalkoxybenzyl ester, etc.
  • the phthalic acid monoesters used in the invention can be used alone or in a mixture with organic acids or phenols, such as bisphenol A (4,4'-isopropylidenediphenol), p, p '- (1-methyl-n-hexylidene) diphenol, p-tertiary butylphenol, p-phenylphenol, p-hydroxylbenzoic acid ester, novolactypphenol resin, 4-hydroxy-1-methylsulfonylbenzene, 4-hydroxy-1-butyloxysulfonylbenzene, etc. can be used.
  • organic acids or phenols such as bisphenol A (4,4'-isopropylidenediphenol), p, p '- (1-methyl-n-hexylidene) diphenol, p-tertiary butylphenol, p-phenylphenol, p-hydroxylbenzoic acid ester, novolactypphenol resin, 4-hydroxy-1-methylsulfonylbenzene
  • the amount of the phthalic acid monoesters according to the invention and the type and amount of the other constituents which are chosen depending on the desired effect and the suitability for recording purposes are not particularly limited.
  • phthalic acid monoester 1-20 parts by weight of a filler per 1 part by weight of the chromogenic dye and 10-20% by weight, based on the total solids content, of a binder.
  • Dispersions A and B were separately ground to a particle size of 3 ⁇ m by a ball mill, and then mixed together in the following ratio to produce the heat-sensitive coating colors.
  • working examples 1-a to 1-d according to the invention give a recording sheet with a good whiteness and a less reduction in time compared to the sheet according to comparative experiment 1-e in which bisphenol A was used.
  • the exemplary embodiments according to the invention result in a highly dynamic image density during rapid recording with a facsimile machine.
  • phthalic acid monobenzyl ester has exceptional effects.
  • the dispersions were ground separately into a dispersion by means of an attritor until the particle size was 3 1 1 m. The dispersions were then mixed together in the ratio described below to produce heat sensitive coating colors.
  • Heat-sensitive recording sheets were produced as in Example 1.
  • the heat-sensitive recording sheet of the present invention gives a high whiteness of the background and good durability at high humidity compared to the sheet of Comparative Experiment 2 in which bisphenol A was used together with a sensitizer.
  • the heat-sensitive recording sheet according to the invention has an astonishingly high image density when recorded quickly with a facsimile machine in comparison with the sheet of comparative experiment 2.

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)

Claims (6)

1. Feuille pour l'enregistrement sensible à la chaleur, qui comprend dans la couche de formation de couleurs, en plus de différents additifs, un pigment chromogène incolore ou faiblementcoloré et un monoester d'acide phtalique en tant qu'agent révélateur de couleurs caractérisée en ce que le monoester d'acide phtalique est un composé de formule générale
Figure imgb0033
dans laquelle R est
-C6H5, -CH2
Figure imgb0034
Figure imgb0035
Figure imgb0036
Figure imgb0037
Figure imgb0038
Figure imgb0039
Figure imgb0040
dans laquelle X représente un alkyle, un halogène ou un alcoxy.
2. Feuille pour l'enregistrement sensible à la chaleur selon la revendication 1, caractérisée en ce que le monoester d'acide phtalique est le monobenzyl ester d'acide phtalique.
3. Feuille pour l'enregistrement sensible à la chaleur selon la revendication 1, caractérisée en ce que le monoester d'acide phlalique est au moins un composé du groupe: monophényl ester d'acide phtalique, monométhylphényl ester d'acide phtalique, monoéthyl phényl ester d'acide phtalique, monoalkylbenzyl ester d'acide phtalique, monohalogénobenzyl ester d'acide phtalique et monoalcoxybenzyl ester d'acide phtalique.
4. Feuille pour l'enregistrement sensible à la chaleur selon l'une des revendications 1 à 3, caractérisée en'ce que la couche de révélateur de couleurs contient, comme agent révélateur de coleurs en outre au moins un composé du groupe: phénols et acides carboxyliques organiques.
5. Feuille pour l'enregistrement sensible à la chaleur selon l'une des revendications 1 à 4, caractérisée en ce que la couche de révélateur de couleurs contient 3-10 parties en poids de monoester d'acide phtalique, 1-20 parties en poids d'une charge pour une partie en poids du pigment chromogène et 10-20 % en poids, par rapport à la quantité de solides totale, d'un liant.
6. Utilisation des monoesters d'acide phtalique selon la revendication 1 comme agents révélateurs de couleurs pour un produit pour l'enregistrement sensible à la chaleur.
EP84102807A 1983-03-15 1984-03-14 Feuille pour l'enregistrement sensible à la chaleur Expired EP0122468B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP41436/83 1983-03-15
JP58041436A JPS59167294A (ja) 1983-03-15 1983-03-15 感熱記録シ−ト

Publications (3)

Publication Number Publication Date
EP0122468A2 EP0122468A2 (fr) 1984-10-24
EP0122468A3 EP0122468A3 (en) 1984-12-27
EP0122468B1 true EP0122468B1 (fr) 1987-07-01

Family

ID=12608317

Family Applications (1)

Application Number Title Priority Date Filing Date
EP84102807A Expired EP0122468B1 (fr) 1983-03-15 1984-03-14 Feuille pour l'enregistrement sensible à la chaleur

Country Status (4)

Country Link
US (1) US4498091A (fr)
EP (1) EP0122468B1 (fr)
JP (1) JPS59167294A (fr)
DE (1) DE3464474D1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6046293A (ja) * 1983-08-24 1985-03-13 Jujo Paper Co Ltd 感熱記録紙
JPS60122191A (ja) * 1983-12-06 1985-06-29 Ricoh Co Ltd 感熱記録材料
JPS62148288A (ja) * 1985-12-24 1987-07-02 Kanzaki Paper Mfg Co Ltd 感熱記録体
JPS6317081A (ja) * 1986-07-10 1988-01-25 Kanzaki Paper Mfg Co Ltd 感熱記録体
DE69309886T2 (de) * 1993-01-29 1997-11-20 Agfa Gevaert Nv Wärme- und lichtempfindliches Aufzeichnungselement

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3965282A (en) * 1973-09-14 1976-06-22 Agfa-Gevaert N.V. Thermographic recording material
US3911171A (en) * 1973-09-14 1975-10-07 Agfa Gevaert A Naamloze Vennoo Thermographic recording process

Also Published As

Publication number Publication date
EP0122468A3 (en) 1984-12-27
EP0122468A2 (fr) 1984-10-24
DE3464474D1 (en) 1987-08-06
US4498091A (en) 1985-02-05
JPH0211439B2 (fr) 1990-03-14
JPS59167294A (ja) 1984-09-20

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