EP0135901B1 - Matériel pour l'enregistrement thermosensible - Google Patents

Matériel pour l'enregistrement thermosensible Download PDF

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Publication number
EP0135901B1
EP0135901B1 EP84111015A EP84111015A EP0135901B1 EP 0135901 B1 EP0135901 B1 EP 0135901B1 EP 84111015 A EP84111015 A EP 84111015A EP 84111015 A EP84111015 A EP 84111015A EP 0135901 B1 EP0135901 B1 EP 0135901B1
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EP
European Patent Office
Prior art keywords
heat
sensitive recording
developing agent
nitrobenzoic acid
metal salt
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
EP84111015A
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German (de)
English (en)
Other versions
EP0135901A2 (fr
EP0135901A3 (en
Inventor
Toshimi Central Research Laboratory Satake
Toshiaki Central Research Laboratory Minami
Fumio Central Research Laboratory Fujimura
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Jujo Paper Co Ltd
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Jujo Paper Co Ltd
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Publication of EP0135901A2 publication Critical patent/EP0135901A2/fr
Publication of EP0135901A3 publication Critical patent/EP0135901A3/de
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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
    • B41M5/323—Organic colour formers, e.g. leuco dyes
    • B41M5/327—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
    • 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 in which the color image and the whiteness of the background are surprisingly well stabilized against the adverse effects of hair oil, fat, oil, etc.
  • a heat-sensitive recording sheet using a heat color reaction between a basic colorless or lightly colored chromogenic dye and an organic color developing agent such as a phenolic substance or an organic acid is disclosed in Japanese Patent Publication Nos. 4160/1968 and 14039 / 1970, and described in Japanese Patent Laid-Open No. 27736/1973. It has many practical uses.
  • a heat-sensitive recording sheet is generally prepared by applying a coating paint to the surface of the support such as paper, film, etc., which is prepared by grinding and dispersing a colorless chromogenic dye and a color developing material, phenolic substances, into fine particles by mixing the dispersions obtained and by adding a binder, filler, sensitizer, lubricant and other auxiliaries.
  • the oily materials are the color-forming layer consisting of a basic colorless chromogenic dye of fine particles and an organic color developing agent of fine particles, or the color-forming reaction product which is made of a basic colorless chromogenic Dye and an organic color developing agent is formed, partially dissolve or destabilize.
  • the heat-sensitive recording sheets in which 4-hydroxybenzoic acid ester or 4-hydroxyphthalic acid diester are used are superior in the above fundamental qualities, but in terms of the stability to oily materials, they are superior to the previous heat-sensitive recording sheets in which bisphenol compounds as color developing agents used, inferior.
  • the invention has for its object to provide a heat-sensitive recording sheet in which the recording image is very stable against the action of oily materials.
  • the above metal salt of a nitrobenzoic acid brings about both very good color development and superior stability of the recording image, so that it can be used as a color developing agent and / or can improve stability in combination with other color developing agents.
  • color developing agents other than the metal salts of nitrobenzoic acid used in the present invention, but the effects of this invention are significant when monophenolic 4-hydroxyphenyl compounds and / or phthalic acid monoesters are used as the color developing agents.
  • Examples of monophenolic 4-hydroxyphenyl compounds are 4-hydroxybenzoic acid esters, for example propyl 4-hydroxybenzoate, isopropyl 4-hydroxybenzoate, butyl 4-hydroxybenzoate, 4-hydroxybenzoate, 4-hydroxybenzoate, 4-hydroxybenzoate, etc.
  • 4-hydroxyphthalic diesters for example dimethyl 4-hydroxyphthalate, diisopropyl 4-hydroxyphthalate, dibenzyl 4-hydroxyphthalate, di-4-hydroxyphthalate, etc.; 4-hydroxyacetophenone; p-phenylphenol; Benzyl-4-hydroxyphenylacetate; p-benzylphenol; 4-hydroxyphenyl-4'-n-sulfone, 4-hydroxyphenyl-4'-n-butyloxyphenylsulfone, 4-hydroxyphenyl-4'-n-hexyloxyphenylsulfone, 4-hydroxyphenyl-4'-n-octyloxyphenylsulfone, 4-hydroxyphenyl-4 ' -n-decyloxyphene sulfone, 4-hydroxyphenyl-4'-n-dodecyloxyphenyl sulfone, 4-hydroxyphenyl-4'-benzyloxyphenyl sulfone, 4-hydroxyphenyl-4'-p-isopropylbenzy
  • phthalic acid monoesters are phthalic acid monophenyl ester, phthalic acid monobenzyl ester, phthalic acid monocyclohexyl ester, phthalic acid monomethylphenyl ester, phthalic acid monoethylphenyl ester, phthalic acid monoalkylbenzyl ester, phthalic acid monohalobenzyl ester, and phthalic acid mono-ester, phthalic acid mononate.
  • Such color developing agents are superior in terms of the quality required in principle, but have a disadvantage that they are inferior to the bisphenol compounds which have hitherto been used in terms of stability to oily materials.
  • bisphenol compounds examples include 4,4'-isopropylidenediphenol (bisphenol A); 4,4 '- (1-methyl-n-hexylidene) diphenol; 4,4'-cyclohexylidenediphenol; 4,4'-thiobis (4-tertiary-butyl-3-methylphenol) and the like.
  • bisphenol A 4,4'-isopropylidenediphenol
  • 4,4'-cyclohexylidenediphenol 4,4'-thiobis (4-tertiary-butyl-3-methylphenol) and the like.
  • Colorless or slightly colored chromogenic dyes useful in the present invention are many, and they are not particularly limited.
  • colorless chromogenic fluoran dyes are: 3-diethylamino-6-methyl-7-anilinofluoran (black), 3- (N-ethyl-para-toluidino) -6-methyl-7-anilinofluoran (black), 3-diethylamino- 6-methyl-7- (ortho, paradimethylanilino) -fluorane (black), 3-pyrolidino-6-rhethyl-7-anilinofluoran (black), 3-piperidino-6-methyl-7-anilinofluoran (black), 3- ( n-cyclohexyl-n-methylamino) -6-methyl-7-anilinefluorane (black), 3-diethylamino-7- (metha-trifluoromethylanilino) -fluorane (black), 3-diethylamino-6-methylchlorofluorane (red), 3-diethylamino-6-methylfluorane (red), 3-cyclo
  • the following dyes from the black color developing fluoran dyes yield a heat sensitive recording sheet with a little low image density: 3-diethylamino-6-methyl- (para-chloroanilino) fluorane, 3-diethylamino-7- (ortho-chloroanilino) fluorane, 3- (N-ethyl-P-toluidino) -6-methyl-7-anilinofluorane, 3-dibutylamino-6-methyl- (ortho-chloroanilino) fluorane, 3- (N-ethyl-isoamyl) -6-methyl-anilinofluorane, etc.
  • thermochromic phenomenon occurs in which the color image is extinguished immediately or slowly. Therefore, these dyes cannot be used in heat-sensitive recording sheets.
  • this thermochromic phenomenon is eliminated by using the metal salt derivatives according to the invention of nitrobenzoic acid, which means that the above basic colorless dyes can be used.
  • metal salt derivatives of nitrobenzoic acid according to the invention are used as an organic color developing agent together with at least one substance from the group consisting of crystal violet lactone, fluorene leuco dye and azaphthalide leuco dye, superior stability towards oily materials is obtained.
  • Fluorene-leuco dyes of the general formulas (111) or (IV) are particularly superior among the above basic colorless or slightly colored chromogenic dyes.
  • the metal salts of nitrobenzoic acid according to the invention are very advantageous as organic color developing agents. They are characterized by the fact that they absorb the ultraviolet rays more strongly than other organic color developing agents and have a superior stability towards oily materials.
  • Typical examples of metal salt derivatives according to the invention of nitrobenzoic acid of the general formulas (I) or (11) are metal salts of 4-nitrobenzoic acid, 3-nitrobenzoic acid, 3,4-dinitrobenzoic acid acid, 4-nitro-3-methylbenzoic acid, 4-nitro-5-methylbenzoic acid, 3,5-dinitrobenzoic acid, 2-benzoyl-4-nitrobenzoic acid, 2-benzoyl-3-nitrobenzoic acid, 4-t-butyl-3-nitrobenzoic acid, 4-t-butyl-3,5-dinitrobenzoic acid, 3-nitro-4-methylbenzoic acid, 3-nitro-5-methylbenzoic acid, 3-nitro-2-methylbenzoic acid, 4-nitro-5-chlorobenzoic acid, 4-nitro-2- chlorobenzoic acid, 4-nitro-5-chlorobenzoic acid, 3-nitro-4-chlorobenzoic acid, 3-nitro-5-chlorobenzoic acid, etc., the metal salts of 3-nitrobenzoic acid and 4-nitrobenzo
  • Suitable metals are polyvalent metals, such as zinc, calcium, magnesium, aluminum, barium and lead, preferably zinc, calcium and magnesium.
  • radicals R 1 , R 2 , R 3 , R 4 in the general formulas I and II represent a halogen atom, it is preferably a chlorine or bromine atom. If the above radicals R 1-4 represent an alkyl radical, then this is preferably an H 3 C, H 5 C 2 -, H 7 C 3 -, iso-H 7 C 3 , tert.-H 9 C 4 - or H 11 C 5 group.
  • the metal salts of nitrobenzoic acids can be used individually or in a mixture.
  • the above-mentioned organic color developing agent, the above-mentioned organic colorless chromogenic dye and the metal salt derivative of the nitrobenzoic acid are ground to a particle size of several microns or smaller by means of a grinding device such as a ball mill, grinder, sand grinder, etc. or by means of 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. the following: 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, calcium carbonate, magnesium carbonate, 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.; Dispersing agents, anti-foaming agents, etc.
  • the desired heat-sensitive sheet is obtained by applying this coating
  • the amount of the metal salt derivatives of nitrobenzoic acid according to the invention and the type and the amount of the other constituents which are determined depending on the desired effect and suitability for recording purposes are not particularly limited.
  • a metal salt derivative of nitrobenzoic acid and another color developing agent are used in combination, it is generally advantageous to use 1 to 8 parts by weight of the metal salt derivative of nitrobenzoic acid, 3 to 10 parts by weight of the other organic color developing agent and 1 to 20 parts by weight Filler, based on 1 part by weight of the basic colorless or slightly colored chromogenic dye, and 10 to 25 parts by weight of binder, based on the total solids content.
  • the metal salt derivative of nitrobenzoic acid when using the metal salt derivative of nitrobenzoic acid as an organic color developing agent, it is generally advantageous to use 1 to 8 parts by weight of the metal salt derivative of nitrobenzoic acid and 1 to 20 parts by weight of filler, based on 1 part by weight of the basic colorless or slightly colored to use chromogenic dye, and to use 10 to 25 parts by weight of binder, based on the total solids content.
  • a non-recorded material is left to stand at 60 ° C and 45% relative humidity for 24 hours and then measured with a Macbeth sealing knife.
  • the recording image was very stable even when left standing for 7 days after being contaminated with castor oil.
  • the residual image density was more than 80%.
  • the examples according to the invention in which the zinc salt derivative of a nitrobenzoic acid is used, have a high residual image density even when contaminated with oil.
  • Another solution B using the same amount of 4-hydroxyphthalic acid monobenzyl ester instead of the 4-hydroxybenzoic acid benzyl ester in solution B (color developing agent dispersion) of Example 1, was prepared and with calcium carbonate dispersion and solutions A and C in the weight ratio of the table 3 mixed.
  • the metal salt derivatives of nitrobenzoic acid according to the invention have superior effects even when using phthalic acid monobenzyl ester as color developing agent.
  • the inventive examples using the zinc salt of a nitrobenzoic acid in the coating composition give a recording image of superior stability, particularly when using 4-hydroxybenzoic acid ester or phthalic acid monoester as color developing agent.
  • a recording image is obtained with a metal salt derivative of nitrobenzoic acid as a color developing agent in combination with crystal violet lactone, fluorene leuco dye or azaphthalide leuco dye, which is very stable to the action of oily materials.
  • the heat-sensitive recording sheets were printed with a bar-cord printer at a pulse width of 4.0 milliseconds and an applied voltage of 30 volts.
  • the reflectance of the recorded image was measured with a spectrophotometer (at a wavelength of 800 nm).

Claims (11)

1. Feuille thermosensible pour enregistrement, comportant une couche de formation de couleur qui i contient un colorant chromogène basique incolore ou faiblement coloré et un produit organique de développement de la couleur, caractérisée en ce que le produit de développement de la couleur contient au moins un sel métallique d'un acide nitrobenzoïque des formules générales (I) ou (II).
Figure imgb0031
Figure imgb0032
dans lesquelles R1 R2, R3 et R4 sont identiques ou différents et désignent respectivement un atome H ou un atome d'halogène, un groupe N02 ou alcoxy contenant de 1 à 6 atomes C, un radical alcoyle à chaîne droite ou ramifiée contenant de 1 à 6 atomes C ou un groupe
Figure imgb0033
M désigne un métal polyvalent ; et
n désigne un nombre entier 2 ou 3.
2. Feuille thermosensible pour enregistrement selon la revendication 1, caractérisée en ce que, comme produit organique de développement de la couleur, on emploie le sel métallique de l'acide nitrobenzoïque.
3. Feuille thermosensible pour enregistrement selon l'une des revendications 1 et 2, caractérisée en ce que, dans les formules générales (I) ou (II), M est au moins un métal du groupe zinc, calcium et magnésium.
4. Feuille thermosensible pour enregistrement selon la revendication 1-3, caractérisée en ce que le sel métallique de l'acide nitrobenzoïque est un sel métallique de l'acide nitro-4 benzoïque.
5. Feuille thermosensible pour enregistrement selon l'une des revendications 1-3, caractérisée en ce que, comme produit organique de développement de la couleur, on emploie le sel métallique de l'acide nitrobenzoïque et que, comme colorant chromogène basique incolore ou faiblement coloré, on emploie au moins une substance du groupe constitué par lactone violette cristalline, leucocolorant à base d'azaphtalide et leucocolorant fluoren des formules générales (III) ou (IV) :
Figure imgb0034
Figure imgb0035
6. Feuille thermosensible pour enregistrement selon l'une des revendications 1-3, caractérisée en ce que la couche de formation de la couleur contient de 1 à 8 parties en poids de sels métalliques de l'acide nitrobenzoïque, de 1 à 20 parties en poids de charge, rapporté à une partie en poids du colorant chromogène basique, incolore ou faiblement coloré, et de 10 à 20 parties en poids de liant, rapporté à la teneur totale en produit.
7. Feuille thermosensible pour enregistrement selon l'une des revendications 1-3, caractérisée en ce que, comme produit organique de développement de la couleur, on emploie encore au moins une autre substance que le sel métallique de l'acide nitrobenzoïque.
8. Feuille thermosensible pour enregistrement selon la revendication 7, caractérisée en ce que comme produit organique de développement de la couleur, on emploie au moins une substance du groupe des composés hydroxy-4 phényl monophénoliques et des monoesters de l'acide phtalique.
9. Feuille thermosensible pour enregistrement selon la revendication 7 ou 8, caractérisée en ce que la couche de formation de la couleur contient de 1 à 8 parties en poids de sel métallique de l'acide nitrobenzoïque, de 3 à 10 parties en poids de l'autre produit organique de développement de la couleur et de 1 à 20 parties en poids de charge, rapporté à 1 partie en poids du colorant chromogène basique incolore ou faiblement coloré et de 10 à 25 parties en poids de liant, rapporté à la teneur totale en produit solide.
10. Procédé de fabrication d'une feuille thermosensible pour enregistrement selon l'une des revendications 1-9, dans lequel on applique sur la surface d'un support un revêtement que l'on obtient par broyage fin individuel et dispersion fine d'un colorant chromogène incolore et d'un produit de développement de la couleur, puis mélange des dispersions obtenues et addition de liants, charges, produits de sensibilisation, lubrifiants et autres auxiliaires, caractérisé en ce que l'on emploie dans la masse de revêtement un-sel métallique d'un acide nitrobenzoïque des formules générales (I) ou (II), comme produit organique de développement de la couleur, seul ou en combinaison avec un autre produit de développement de la couleur.
11. Emploi d'au moins un sel métallique d'un acide nitrobenzoïque des formules générales (I) ou (II) selon une des revendications 1-4 comme additif aux masses de revêtement pour des produits thermosensibles pour enregistrement.
EP84111015A 1983-09-16 1984-09-14 Matériel pour l'enregistrement thermosensible Expired EP0135901B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP58169269A JPS6061289A (ja) 1983-09-16 1983-09-16 感熱記録紙
JP169269/83 1983-09-16

Publications (3)

Publication Number Publication Date
EP0135901A2 EP0135901A2 (fr) 1985-04-03
EP0135901A3 EP0135901A3 (en) 1986-05-14
EP0135901B1 true EP0135901B1 (fr) 1988-11-30

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP84111015A Expired EP0135901B1 (fr) 1983-09-16 1984-09-14 Matériel pour l'enregistrement thermosensible

Country Status (4)

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US (1) US4591888A (fr)
EP (1) EP0135901B1 (fr)
JP (1) JPS6061289A (fr)
DE (1) DE3475387D1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6147292A (ja) * 1984-08-15 1986-03-07 Jujo Paper Co Ltd 感熱記録紙
US4658276A (en) * 1985-06-22 1987-04-14 Kanzaki Paper Manufacturing Co., Ltd. Phthalide derivatives and recording system utilizing the same
JPH0773950B2 (ja) * 1986-06-17 1995-08-09 新王子製紙株式会社 感熱記録体
JPS634990A (ja) * 1986-06-25 1988-01-09 Jujo Paper Co Ltd 感熱記録材料
US4820683A (en) * 1987-12-04 1989-04-11 Appleton Papers Inc. Thermally-responsive record material

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1330984A (en) * 1970-09-28 1973-09-19 Fuji Photo Film Co Ltd Colour-developer compositions
CA1009841A (en) * 1971-06-16 1977-05-10 Shinichi Oda Sensitized record sheet material and process for making the same
JPS5318921B2 (fr) * 1972-07-28 1978-06-17
US4147830A (en) * 1976-01-28 1979-04-03 Fuji Photo Film Co., Ltd. Recording sheet
JPS5538826A (en) * 1978-09-11 1980-03-18 Fuji Photo Film Co Ltd Color-developing ink

Also Published As

Publication number Publication date
JPH0239994B2 (fr) 1990-09-07
US4591888A (en) 1986-05-27
EP0135901A2 (fr) 1985-04-03
JPS6061289A (ja) 1985-04-09
DE3475387D1 (en) 1989-01-05
EP0135901A3 (en) 1986-05-14

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