EP0704317B1 - Matériau d'enregistrement sensible à la chaleur - Google Patents

Matériau d'enregistrement sensible à la chaleur Download PDF

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Publication number
EP0704317B1
EP0704317B1 EP19940115223 EP94115223A EP0704317B1 EP 0704317 B1 EP0704317 B1 EP 0704317B1 EP 19940115223 EP19940115223 EP 19940115223 EP 94115223 A EP94115223 A EP 94115223A EP 0704317 B1 EP0704317 B1 EP 0704317B1
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EP
European Patent Office
Prior art keywords
heat
sensitive recording
sensitive
color
color developing
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
EP19940115223
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German (de)
English (en)
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EP0704317A1 (fr
Inventor
Eriko c/o Kuraray Co. Ltd. Seno
Tetsuya C/O Kuraray Co. Ltd. Katayama
Hirotoshi c/o Kuraray Co. Ltd. Miyazaki
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Kuraray Co Ltd
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Kuraray Co Ltd
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Publication date
Application filed by Kuraray Co Ltd filed Critical Kuraray Co Ltd
Priority to DE1994609522 priority Critical patent/DE69409522T2/de
Priority to EP19940115223 priority patent/EP0704317B1/fr
Publication of EP0704317A1 publication Critical patent/EP0704317A1/fr
Application granted granted Critical
Publication of EP0704317B1 publication Critical patent/EP0704317B1/fr
Anticipated expiration legal-status 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
    • B41M5/3331—Macromolecular compounds

Definitions

  • the present invention relates to a heat-sensitive recording material.
  • the present invention further relates to the use of a dispersing agent having excellent dispersing capability for heat-sensitive dyes and color developing agents which is suited for producing heat-sensitive recording materials.
  • the present invention still further relates to a process for producing aqueous dispersions having a dispersoid of a particulate heat-sensitive dye or color developing agent.
  • Heat-sensitive recording materials comprise a paper, plastic film or metal-deposited paper and, provided thereon, a heat-sensitive recording layer that will undergo, by heat energy, chemical or physical change to form color and give recorded images.
  • the heat-sensitive recording materials have advantages of giving recorded images by simple heating, requiring no complex treatments such as developing and fixing, causing no noise upon recording and providing relatively inexpensive recording system.
  • the materials therefore have been widely used as recording materials for electronic calculators, word processors, telex machines, facsimiles and various calculators.
  • These heat-sensitive recording materials generally have a heat-sensitive recording layer comprising a colorless or light-color leuco dye and an acid such as an organic acid or a phenol, that reacts upon heating with the leuco dye, thereby causing it to form color.
  • a heat-sensitive recording layer comprising a colorless or light-color leuco dye and an acid such as an organic acid or a phenol, that reacts upon heating with the leuco dye, thereby causing it to form color.
  • a heat-sensitive recording material having heat-sensitive recording layer in which a heat-sensitive dye and a color developing agent (developer) having a particle diameter of not more than 1 ⁇ m are dispersed uniformly and present in high density and in a thin layer, so that the color or the texture of the substrate used is not observable.
  • a heat-sensitive dye and a color developing agent (developer) having a particle diameter of not more than 1 ⁇ m are dispersed uniformly and present in high density and in a thin layer, so that the color or the texture of the substrate used is not observable.
  • Known dispersing agents for heat-sensitive dyes and color developing agents include a partially saponified polyvinyl alcohol having a low molecular weight (JP-A-62-105687 (1987)), a sulfonic acid group-modified polyvinyl alcohol having a low molecular weight (JP-B-2-52637 (1990)), and alkali metal salts or ester of an ⁇ -olefin-maleic anhydride copolymer (JP-A-63-214479 (1998)).
  • these agents have been incapable of exhibiting sufficient performance.
  • the partially saponified polyvinyl alcohol having a low molecular weight has insufficient dispersing capability for heat-sensitive dyes and color developing agents and cannot stably disperse them in a particle size of not more than 1 ⁇ m.
  • the sulfonic acid-modified polyvinyl alcohol having a low molecular weight has a dispersing capability of some level but makes considerably visible the texture color of the substrate.
  • the maleic anhydride-based copolymer is, when used in a coating liquid, only insufficiently compatible with the binder contained in the liquid, thereby often causing agglomeration of dispersed particles or viscosity increase of the liquid and, further, has the problem of making considerably visible the texture color of the substrate.
  • an object of the present invention is to provide a heat-sensitive recording material capable of making invisible the texture color of the substrate and giving clear images even upon high-speed printing.
  • Another object of the present invention is to provide the use of a dispersing agent having excellent dispersing capability for particulate heat-sensitive dyes and color developing agents and suited for producing heat-sensitive recording materials.
  • Still another object of the present invention is to provide a process for producing aqueous dispersions having a dispersoid of a particulate heat-sensitive dye or color developing agent.
  • the modified polyvinyl alcohol (hereinafter the term “polyvinyl alcohol” is sometimes referred to as "PVA”) used in the present invention should contain 2.5 to 8 mole % of units from a carboxyl group-containing monomer and have a degree of saponification of 40 to 65 mole % and a viscosity average degree of polymerization of 50 to 500.
  • the content of the carboxyl group-containing monomer units be 2.5 to 8 mole %, preferably 3 to 6 mole %.
  • the degree of modification by carboxyl group being less than 2.5 mole %, the printed parts on the heat-sensitive recording material have a low color density and the PVA has low dispersing capability for heat-sensitive dyes and color developing agents so that the dispersoid agglomerates after an aqueous dispersion has been prepared.
  • the degree of modification exceeding 8 mole %, the non-printed part on the heat-sensitive recording material has a low whiteness and aqueous dispersions prepared with the PVA also have a very low whiteness.
  • carboxyl group-containing monomer unit there is no specific limitation to the type of the carboxyl group-containing monomer unit and its examples include units from fumaric acid, maleic acid, itaconic acid, maleic anhydride, phthalic anhydride, trimellitic anhydride and itaconic anhydride.
  • monomer units dibasic acids are preferred and itaconic acid is particularly preferred.
  • the modified PVA has a degree of saponification of 40 to 65 mole %, preferably 45 to 60 mole % and more preferably 50 to 60 mole %. If the degree of saponification is less than 40 mole %, the dispersing capability for heat-sensitive dyes and color developing agents will decrease and aqueous dispersions prepared with the PVA will, after preparation thereof, cause the dispersoid to agglomerate, so that a usable heat-sensitive recording material cannot be obtained.
  • the resulting heat-sensitive recording material will give printed parts having a low color density and, besides, aqueous dispersions prepared with the PVA will have too high a viscosity to be handled with ease so that the concentration of the dispersions cannot be elevated.
  • the viscosity average degree of polymerization (hereinafter simply referred to as "degree of polymerization") of the modified PVA should be in a range of 50 to 500 and is preferably in a range of 100 to 300. If the degree of polymerization is less than 50, the PVA will become incapable of dispersing fine particles and, after preparation of an aqueous dispersion, the dispersoid will agglomerate, whereby a usable heat-sensitive recording material cannot be obtained.
  • the resulting heat-sensitive recording material will give printed parts having a low color density and, besides, aqueous dispersions prepared with the PVA will have too high a viscosity to be handled with ease so that the concentration of the dispersions cannot be elevated.
  • the carboxyl group-modified PVA can be prepared by any process with no specific restrictions.
  • one of the above mentioned carboxylic acids is reacted with polyvinyl alcohol by post-reaction, or a copolymer of vinyl acetate and an ethylenically unsaturated carboxylic acid is saponified.
  • Concrete examples of such processes are disclosed in Japanese Patent Publication No. 21312/1970 and Japanese Patent Application Laid-open Nos. 91995/1978, 28389/1979 and 28390/1979.
  • the carboxyl groups in the PVA of the invention may either be present in the form of an alkali metal salt such as COONa or in the form of COOH. Where the carboxyl group-containing monomer is a dibasic acid, one of the two carboxylic acids present in the monomer may form a lactone ring.
  • the carboxyl group-modified polyvinyl alcohol used in the present invention may be copolymerized with other monomers or its ends may be modified by using a chain transfer agent.
  • Any ethylenically unsaturated monomer may be copolymerized with a vinyl ester as long as it is copolymerizable therewith.
  • Examples of such monomers are ⁇ -olefins, e.g. ethylene, propylene, n-butene, isobutene and 1-hexadecene; carboxylic acid-containing monomers, e.g.
  • (meth)acrylic acid fumaric acid, crotonic acid, maleic acid and maleic anhydride, and salts of the foregoing;
  • (meth)acrylic acid esters e.g. methyl (meth)acrylate, n-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate and stearyl (meth)acrylate; other esters, e.g. dimethyl fumarate, dimethyl itaconate, dimethyl maleate, monomethyl maleate and methyl crotonate; vinyl ethers, e.g.
  • sulfonic acid group-containing monomers e.g. vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid and 2-acrylamide-2-methylpropanesulfonic acid, and salts of the foregoing; amido group-containing monomers, e.g.
  • (meth) acrylamide N,N-dimethyl(meth)acrylamide, N-methylol(meth)acrylamide, N-t-butoxy(meth)acrylamide, N-t-octyl(meth)acrylamide and N-vinylpyrrolidone; quaternary ammonium salt-containing monomers, e.g. dimethylaminoethyl(meth)acrylamide; silyl group-containing monomers, e.g. vinylhydroxysilane and 3-trimethoxysilylpropyl (meth)acrylate; and acetyl group-containing monomers, e.g. allyl acetate, dimethylallyl acetate and isopropenyl acetate.
  • quaternary ammonium salt-containing monomers e.g. dimethylaminoethyl(meth)acrylamide
  • silyl group-containing monomers e.g. vinylhydroxysilane and 3-trimethoxysilylpropyl (
  • the modified PVA can be contained in a heat-sensitive recording layer of the heat-sensitive recording material in any amount with no particular limitation. However, it is preferred that the modified PVA be contained in an amount of 3 to 30 parts by weight based on 100 parts by weight of the sum of the amounts of a heat-sensitive dye and a color developing agent, more preferably 5 to 20 parts by weight and most preferably 7 to 16 parts by weight on the same basis.
  • the dye or agent is dispersed by using a dispersing agent of the above modified PVA.
  • the dispersing agent can be used in any amount, but preferably in an amount of 3 to 30 parts by weight based on 100 parts by weight of the heat-sensitive dye or the color developing agent, more preferably 5 to 20 parts by weight and most preferably 7 to 16 parts by weight on the same basis.
  • the finished aqueous dispersion preferably has a dispersoid concentration of 20 to 70% by weight, more preferably 40 to 60% by weight.
  • Dispersing operation for the heat-sensitive dye or the color developing agent is carried out in a sand mill containing a multiplicity of glass beads having an average particle diameter of 0.2 to 3 mm (preferably 0.3 to 0.8 mm)
  • the dispersing operation is completed in 1 hour to 1 week (preferably 3 hours to 4 days, in particular 1 to 4 days where it is desired to obtain fine dispersoid particles having an average particle diameter of not more than 0.45 ⁇ m).
  • the use of the dispersing agent of the present invention can give aqueous dispersions having a dispersoid of a heat-sensitive dye or a color developing agent having a particle diameter ranging from 0.1 to 1 ⁇ m (preferably 0.3 to 0.8 ⁇ m, more preferably 0.2 to 0.6 ⁇ m and most preferably 0.2 to 0.45 ⁇ m).
  • Any heat-sensitive dye being used for conventional pressure- or heat-sensitive papers can be used in the present invention and its concrete examples include triarylmethane-based compounds, e.g. 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide (Crystal Violet Lactone), 3-(p-dimethylaminophenyl)-3-(1,2-dimethylindole-3-yl)phthalide, 3-(p-dimethylaminophenyl)-3-(2-phenylindole-3-yl)phthalide and 3,3-bis(9-ethylcarbazole-3-yl)-5-dimethylaminophthalide; diphenylmethane-based compounds, e.g.
  • the color developing agent used in the present invention be selected from phenol derivatives and aromatic carboxylic acid derivatives, in particular from bisphenols.
  • phenols e.g. p-octylphenol, p-tert-butylphenol, p-phenylphenol, 1,1-bis(p-hydroxyphenyl)propane, 1,1-bis(p-hydroxyphenyl)pentane, 2,2-bis(p-hydroxyphenyl)propane, 1,1-bis(p-hydroxyphenyl)hexane, 2,2-bis(p-hydroxyphenyl)hexane, 1,1-bis(p-hydroxyphenyl)-2-ethyl-hexane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane and dihydroxydiphenyl ether; and aromatic carboxylic acid derivatives, e.g.
  • binders usable for this purpose are cellulose derivatives, e.g. starch, starch derivatives, hydroxymethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, methylcellulose and ethylcellulose; water-soluble polymers, e.g.
  • polyvinyl alcohol poly(sodium acrylate), polyvinylpyrrolidone, acrylamide/acrylic acid ester copolymers, acrylamide/acrylic acid ester/methacrylic acid ternary copolymers, alkali metal salts of styrene/maleic anhydride copolymer, alkali metal salts of isobutylene/maleic anhydride copolymer; polyacrylamide, sodium alginate, gelatin and casein; emulsions of polyvinyl acetate, polyurethanes, polyacrylic acid, polyacrylic acid esters, vinyl chloride/vinyl acetate copolymer, polybutyl methacrylate, ethylene/vinyl acetate copolymer and the like; and latices of styrene/butadiene copolymer, styrene/butadiene/acrylic acid ester and the like.
  • the aqueous binder is added preferably in an amount of 1 to 20 parts by weight based on 100 parts by weight of the sum of the amounts of the dye and the color developing agent.
  • the heat-sensitive recording layer may incorporate, besides a heat-sensitive dye and a color developing agent, auxiliary additives used for conventional heat-sensitive recording materials, such as a filler, surfactant, heat-fusible substance (or lubricant) and agent for preventing color development under pressure.
  • auxiliary additives used for conventional heat-sensitive recording materials, such as a filler, surfactant, heat-fusible substance (or lubricant) and agent for preventing color development under pressure.
  • the heat-sensitive recording layer can be formed by any of known processes, e.g. air-knife coating, plate coating, embossing, roll coating, spraying, dipping, bar coating and extrusion coating.
  • any substrate can be used for the heat-sensitive recording material.
  • Appropriate selection is made for example from various papers, synthetic papers and synthetic resin films. It is, however, generally desirable to use a paper.
  • the heat-sensitive recording materials of the present invention give printed parts having good color development and non-printed part that hardly fogs (coloration of substrate).
  • the heat-sensitive recording materials of the present invention having excellent high-speed printability and excellent resolution of images, are suitably usable in the field requiring high-speed printing, such as facsimile.
  • the dispersing agent used in the present invention having excellent dispersing capability for heat-sensitive dyes and color developing agents, can give aqueous dispersion having a dispersoid of a particulate heat-sensitive dye or color developing agent in a high concentration and having a low viscosity.
  • the aqueous dispersion obtained having excellent applicability to the surface of the base paper upon preparation of heat-sensitive recording papers and containing dispersoids of a heat-sensitive dye and a color developing agent dispersed in fine particles, can produce heat-sensitive recording materials having markedly high resolution.
  • Leuco dye S-205, made by Yamada Kagaku K.K. 20% Ten % aqueous solution of a carboxyl group-modified PVA (modified by copolymerization of 4 mole % of itaconic acid; degree of polymerization: 500; degree of saponification: 46 mole %) 20% Water 59.9% Antifoam (SURFYNOL® 440, made by Nisshin Chemical Co., Ltd.) 0.1%
  • aqueous mixtures A and B were each transferred into a sand mill (batch type, desk-top sand mill made by Kansai Paint Co.), and 300 cc of glass beads (soda quartz glass having a diameter of 0.5 mm) was added. Dispersion was effected at a high rotation (2,170 rpm) for 6 hours.
  • the aqueous mixture C was dispersed in a homogenizer (10,000 rpm) for 2 minutes.
  • the aqueous dispersion A of the heat-sensitive dye was evaluated according to the following methods.
  • the particle diameter was measured with a laser diffraction particle size analyzer (SALD-1000, made by Shimadzu Corp.).
  • the aqueous dispersion was allowed to stand for about 1 hour after completion of 6-hour dispersion and then tested for viscosity at 30°C.
  • the aqueous dispersion was allowed to stand for about 1 hour after completion of 6-hour dispersion and then tested for whiteness with a color and color and color difference meter (Z-1001DP, made by Nippon Denshoku Kogyo Co., Ltd.).
  • the whiteness value of "0" means completely white, and the degree of discoloration increases with the absolute value of the negative values.
  • a coating liquid for heat-sensitive recording layer was prepared by mixing with stirring 1 part of the aqueous dispersion A, 4 parts of the aqueous dispersion B, 2 parts of the aqueous dispersion C and 2 parts of a 10% aqueous solution of polyvinyl alcohol (degree of polymerization: 1,750, degree of saponification: 98.5 mole %).
  • the coating liquid was applied with a wire bar coater on a base paper (woodfree paper having a weight of 52 g/m 2 ) in an amount of 6 g/m 2 (solid base), dried at 50° C for 10 minutes and then surface-treated with a super calender (linear pressure: 30 kg/cm; roll diameter: top (metal): 20 cm, bottom (rubber): 30 cm), to obtain a heat-sensitive recording paper.
  • a base paper woodfree paper having a weight of 52 g/m 2
  • 6 g/m 2 solid base
  • the heat-sensitive recording paper thus obtained was evaluated in the following manner.
  • Printing was made on the paper with a printer for heat-sensitive facsimile (RIFAX 300, made by Ricoh Co.) and the color density of the printed parts were measured with a Macbeth color density tester (RD-514, made by Macbeth Co.).
  • RIFAX 300 made by Ricoh Co.
  • RD-514 made by Macbeth Co.
  • the non-printed part was measured for color density with the same Macbeth tester as above.
  • a Macbeth density of 0 and 1.82 means completely white and completely black, respectively.
  • Example 1 was repeated except that itaconic acid-modified polyvinyl alcohols as shown in Table 1 were used, instead of the itaconic acid-modified polyvinyl alcohol used in Example 1, to prepare coating liquids (dispersions of the heat-sensitive dye and the color developing agent). The obtained coating liquids were then used to prepare heat-sensitive recording materials in the same manner. The results are shown in table 1.
  • Example 1 was repeated except that various polyvinyl alcohols as shown in Table 1 were used, instead of the itaconic acid-modified polyvinyl alcohol used in Example 1, to prepare coating liquids (dispersions of the heat-sensitive dye and the color developing agent). The obtained coating liquids were then used to prepare heat-sensitive recording materials in the same manner. The results are also shown in table 1.
  • Dispersing agent Aqueous dispersion of heat-sensitive dye Properties of heat-sensitive recording paper(color density) Comonomer D.M. (mole %) D.S. (mole %) D.P. Dia. ( ⁇ m) Viscosity (cs) Whiteness Printed part Non-printed part Ex. 1 IA 4.0 46 500 0.44 38.0 -8.0 1.34 0.08 Ex. 2 " 4.0 42 300 0.35 17.1 -7.4 1.36 0.07 Ex. 3 " 4.0 52 200 0.28 15.4 -7.6 1.38 0.07 Ex.

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  • 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 (3)

  1. Matériau d'enregistrement thermosensible comportant une couche d'enregistrement thermosensible, constitué par un alcool de polyvinyle modifié, un colorant thermosensible et un agent développant la couleur, cet alcool de polyvinyle contenant 2,5 à 8 % en mole de motifs d'un monomère contenant un groupe carboxyle et ayant un degré de saponification de 40 à 65 % en mole et un degré moyen de viscosité de polymérisation de 50 à 500.
  2. Utilisation de l'alcool de polyvinyle modifié tel que défini dans la revendication 1, pour la mise en dispersion d'un colorant thermosensible ou d'un agent développant la couleur pouvant faire en sorte que le colorant thermosensible développe une couleur lors du chauffage.
  3. Procédé pour la production de dispersions aqueuses qui comprend la mise en dispersion d'un colorant thermosensible ou d'un agent développant la couleur pouvant faire former une couleur par le colorant thermosensible lors du chauffage, dans un milieu aqueux avec un agent de dispersion de l'alcool de polyvinyle modifié selon la revendication 1.
EP19940115223 1994-09-27 1994-09-27 Matériau d'enregistrement sensible à la chaleur Expired - Lifetime EP0704317B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE1994609522 DE69409522T2 (de) 1994-09-27 1994-09-27 Wärmeempfindliches Aufzeichnungsmaterial
EP19940115223 EP0704317B1 (fr) 1994-09-27 1994-09-27 Matériau d'enregistrement sensible à la chaleur

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP19940115223 EP0704317B1 (fr) 1994-09-27 1994-09-27 Matériau d'enregistrement sensible à la chaleur

Publications (2)

Publication Number Publication Date
EP0704317A1 EP0704317A1 (fr) 1996-04-03
EP0704317B1 true EP0704317B1 (fr) 1998-04-08

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EP19940115223 Expired - Lifetime EP0704317B1 (fr) 1994-09-27 1994-09-27 Matériau d'enregistrement sensible à la chaleur

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EP (1) EP0704317B1 (fr)
DE (1) DE69409522T2 (fr)

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59159394A (ja) * 1983-03-03 1984-09-08 Ricoh Co Ltd 感熱記録材料
JPS62105687A (ja) * 1985-11-01 1987-05-16 Fuji Photo Film Co Ltd 感熱記録材料
JP2604367B2 (ja) * 1987-01-16 1997-04-30 株式会社クラレ 耐水性に優れたインクジエツト記録用シート
JPH01111439A (ja) * 1987-10-26 1989-04-28 Nippon Shokubai Kagaku Kogyo Co Ltd 水酸化アルミニウム水分散液の製造方法
JP3194644B2 (ja) * 1993-04-05 2001-07-30 株式会社クラレ 感熱記録材料

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EP0704317A1 (fr) 1996-04-03
DE69409522D1 (de) 1998-05-14
DE69409522T2 (de) 1998-10-15

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