EP0439612B1 - Papier d'enregistrement thermosensible - Google Patents

Papier d'enregistrement thermosensible Download PDF

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Publication number
EP0439612B1
EP0439612B1 EP89911885A EP89911885A EP0439612B1 EP 0439612 B1 EP0439612 B1 EP 0439612B1 EP 89911885 A EP89911885 A EP 89911885A EP 89911885 A EP89911885 A EP 89911885A EP 0439612 B1 EP0439612 B1 EP 0439612B1
Authority
EP
European Patent Office
Prior art keywords
heat
sensitive recording
recording paper
substrate
paper
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
EP89911885A
Other languages
German (de)
English (en)
Other versions
EP0439612A4 (en
EP0439612A1 (fr
Inventor
Yoshimi Ishibashi
Katsumi Moronuki
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.)
Honshu Paper Co Ltd
Original Assignee
Honshu 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 Honshu Paper Co Ltd filed Critical Honshu Paper Co Ltd
Publication of EP0439612A1 publication Critical patent/EP0439612A1/fr
Publication of EP0439612A4 publication Critical patent/EP0439612A4/en
Application granted granted Critical
Publication of EP0439612B1 publication Critical patent/EP0439612B1/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
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/41—Base layers supports or substrates

Definitions

  • the present invention relates to heat-sensitive recording paper and more specifically to heat-sensitive recording paper which is cheap and excellent in storage stability and which has high reliability to the thermal head.
  • the heat-sensitive recording system which makes use of a basic colorless dye and an acidic substance capable of causing the color-development of the basic colorless dye upon heating shows various characteristic properties. For instance, the system does not require the use of any developing process and the maintenance of the hard thereof is very easy. For this reason, such a heat-sensitive recording system has widely been used in a variety of fields such as facsimiles, printers and recorders for measuring machinery and tools.
  • the resulting recording paper suffers from a variety of problems. For instance, the color-printing density thereof is reduced (discoloration) during storage under a high humidity condition, fogging of the white ground thereof is caused during storage under a high temperature condition and further when a long term running test is performed, there is observed the dot-missing of a thermal head (partial breakage of the thermal head).
  • the object of the present invention is to provide heat-sensitive recording paper which is cheap, makes it possible to save resources, is excellent in storage stability and exhibits high reliability to the thermal head.
  • the inventors of this invention have conducted various studies to achieve the foregoing object and as a result have found out that the aforementioned object of the present invention can effectively be achieved if the amount of the surfactants remaining in a substrate for heat-sensitive recording paper can be reduced to a level of not more than 1,000 ppm in the case where the substrates for the heat-sensitive recording paper comprise waste paper. Moreover, the inventors have also found out that a more excellent effect can be attained by disposing a barrier layer between the foregoing substrate and a heat-sensitive recording layer.
  • waste paper is prepared according to any combination of the following three processes:
  • the waste paper thus obtained is simply incorporated into a substrate for the heat-sensitive recording paper, the resulting recording paper is greatly affected by surfactants as deinking agents which are used in the foregoing deinking process (3).
  • the recording paper causes discoloration during storage under a high humidity condition, fogging of the white ground thereof during storage under a high temperature condition and the dot-missing of the thermal head.
  • the present invention relates to heat-sensitive recording paper which comprises a substrate provided thereon with a heat-sensitive recording layer, which comprises a basic colorless dye and an acidic substance capable of color-developing the basic colorless dye upon heating, wherein the substrate comprises waste paper and the amount of surfactants remaining in the substrate is controlled to not more than 1,000 ppm.
  • the heat-sensitive recording paper there is used a substrate comprising waste paper.
  • waste paper is a generic name which embraces used paper, paper board or cutting scraps thereof.
  • the substrate used in the present invention may be completely composed of waste paper, but it preferably comprises waste paper in an amount of not more than 60%. If the waste paper is incorporated into the substrate in an amount of greater than 60%, the strength of the substrate is liable to be impaired and it is apt to cause a decrease in whiteness.
  • the content of the surfactants remaining in the substrate must be in general controlled to not more than 1,000 ppm and preferably not more than 800 ppm.
  • the storage stability of the substrate is impaired and the dot-missing of the thermal head is apt to cause as the content of the remaining surfactants increases.
  • triarylmethane type dyes such as 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3,3-bis(p-dimethylaminophenyl)phthalide, 3-(p-dimethylaminophenyl)-3-(1,2-dimethylindol-3-yl)phthalide, 3-(p-dimethylaminophenyl)-3-(2-methylindol-3-yl)phthalide, 3,3-bis(1,2-dimethylindol-3-yl)-5-dimethylaminophthalide, 3,3-bis(1,2-dimethylindol-3-yl)-6-dimethylaminophthalide, 3,3-bis(9-ethylcarbazol-3-yl)-6-dimethylaminophthalide, 3,3-bis(9-ethylcarbazol-3-yl)-6-dimethylaminophthalide, 3,3-bis (2-phenylindo
  • inorganic or organic acidic substance capable of color-developing the basic colorless dyes by heating examples thereof include inorganic acidic substances such as active china clay, acidic china clay, attapulgite, bentonite, colloidal silica and aluminum silicate; and organic acidic compounds, for instance, phenolic compounds such as 4-tert-butylphenol, 4-hydroxydiphenoxide, ⁇ -naphthol, ⁇ -naphthol, 4-hydroxyacetophenol, 4-tert-octylcatechol, 2,2'-dihydroxydiphenol, 2, 2'-methylenebis (4-methyl-6-tert-isobutylphenol), 4,4'-isopropylidenebis (2- tert-butylphenol), 4,4'-sec-butylidenephenol, 4-phenylphenol, 4,4'-isopropylidenediphenol (bisphenol A), 2,2'-methylenebis(4-chlorophenol), hydroquinone
  • inorganic acidic substances such as active
  • the ratio of the amount of the basic colorless dye to that of the acidic substance in the heat-sensitive recording layer is appropriately selected depending on the kinds of these basic colorless dyes and the acidic substances employed, but in general the acidic substance is used in an amount ranging from 1 to 50 parts by weight and preferably in the order of 1 to 10 parts by weight per 1 part by weight of the basic colorless dye.
  • a coating solution containing these substances is prepared by simultaneously or separately dispersing the basic colorless dye and the acidic substance in a dispersion medium which is usually water utilizing an apparatus for agitation ⁇ pulverization such as a ball mill, an attritor and a sand grinder to thus give a coating solution.
  • a dispersion medium which is usually water utilizing an apparatus for agitation ⁇ pulverization such as a ball mill, an attritor and a sand grinder to thus give a coating solution.
  • the particle size of the dispersed particles are desirably as small as possible and more specifically this dispersion process is desirably continued till the size of the dispersed particles reaches not more than 2 ⁇ m.
  • Such a coating solution may comprise, as an adhesive, starches, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, gum arabic, polyvinyl alcohol, salts of diisobutylene ⁇ maleic anhydride copolymers, salts of styrene ⁇ maleic anhydride copolymers, salts of ethylene ⁇ acrylic acid copolymers, salts of styrene ⁇ acrylic acid copolymers and styrene ⁇ butadiene copolymer emulsion in an amount ranging from 10 to 40% by weight and preferably 15 to 30% by weight on the basis of the total weight of the solid content of the solution.
  • the coating solution may further comprise a variety of auxiliary agents, for instance, dispersants such as sodium dioctylsulfosuccinate, sodium dodecylbenzenesulfonate, lauryl alcohol sulfuric acid ester ⁇ lsodium salts, alginic acid salts and metal salts of fatty acids; and ultraviolet light absorbers such as benzophenol type and triazole type ultraviolet light absorbers; as well as other additives such as antifoaming agents, fluorescent dyes and coloring dyes.
  • dispersants such as sodium dioctylsulfosuccinate, sodium dodecylbenzenesulfonate, lauryl alcohol sulfuric acid ester ⁇ lsodium salts, alginic acid salts and metal salts of fatty acids
  • ultraviolet light absorbers such as benzophenol type and triazole type ultraviolet light absorbers
  • other additives such as antifoaming agents, fluorescent dyes and coloring dyes.
  • lubricants such as zinc stearate, calcium stearate, polyethylene wax, carnauba wax, paraffin wax and ester wax; inorganic pigments such as kaolin, clay, talc, calcium carbonate, calcined clay, titanium oxide, diatomaceous earth, finely pulverized anhydrous silica and active china clay; sensitizing agents such as stearic acid amide, stearic acid methylenebisamide, oleic acid amide, palmitic acid amide, sperm oil oleic acid amide, coconut oil fatty acid amide, meta-terphenyl, p-benzylbiphenyl, ester derivatives of hydroxynaphthoic acid, dibenzyl terephthalate and tribenzylamine.
  • lubricants such as zinc stearate, calcium stearate, polyethylene wax, carnauba wax, paraffin wax and ester wax
  • inorganic pigments such as kaolin, clay, tal
  • a barrier layer between the substrate and the heat-sensitive recording layer.
  • the presence of such a barrier layer makes it possible to reduce the influence of the surfactants included in the substrate and to provide an improved heat-sensitive recording paper which does not show any discoloration and fogging of the white ground during storage and whose reliability to the thermal head is further enhanced.
  • the barrier layer can be formed from, for instance, film-forming polymeric compounds and examples thereof include casein, polyvinyl alcohol, ammonium alginate, methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, maleic anhydride copolymers, styrene ⁇ maleic anhydride copolymers and styrene ⁇ butadiene copolymers. These polymeric compounds are in general used in the form of an emulsion.
  • the amount thereof to be coated in general ranges from 0.3 g/m2 to 5.0 g/m2 and preferably 0.5 g/m2 to 2.0 g/m2. This is because, if the coated amount of the polymer is less than 0.3 g/m2, the effect of lowering the influence of the surfactants is impaired, while if it exceeds5.0 g/m2, the resulting images are apt to have insufficient quality.
  • a protective layer may optionally be applied onto the heat-sensitive recording layer.
  • an intermediate layer containing a pigment may also be applied onto the foregoing barrier layer.
  • Each of the solutions A and B was dispersed using a sand grinder so that the average particle size of the dispersed particles therein reached not more than 2 ⁇ m.
  • the solution C was dispersed with a homomixer for 10 minutes.
  • a coating solution for heat-sensitive recording layer was prepared by mixing 54.7 parts by weight of the solution A, 155.3 parts by weight of the solution B and 50 parts by weight of the solution C and then adding, to the resulting mixture, 33.3 parts by weight of a 30% dispersion of zinc stearate, 100 parts by weight of a 12% aqueous solution of polyvinyl alcohol and 130 parts by weight of water.
  • the foregoing coating solution for heat-sensitive recording layer was applied onto base paper having a waste paper content of 40%, an amount of a remaining surfactant (sodium alkylbenzenesulfonate) of 240 ppm and a basis weight of 50 g/m2 so that the coated amount thereof (weighed after drying) was equal to 5 g/m2, dried and further subjected to calendering to thus give heat-sensitive recording paper whose recording surface has a Bekk smoothness of 600 seconds.
  • a remaining surfactant sodium alkylbenzenesulfonate
  • Heat-sensitive recording paper was prepared in the same manner used in Example 1 except that base paper having a waste paper content of 50%, an amount of a remaining nonionic surfactant (polyoxyethylene-alkylphenyl ether) of 430 ppm and a basis weight of 50 g/m2 was used as a substrate.
  • base paper having a waste paper content of 50%
  • Heat-sensitive recording paper was prepared in the same manner used in Example 1 except that base paper having a waste paper content of 60%, an amount of a remaining nonionic surfactant (polyoxyethylene-alkylphenyl ether) of 510 ppm and a basis weight of 50 g/m2 was used as a substrate.
  • base paper having a waste paper content of 60%
  • Heat-sensitive recording paper was prepared in the same manner used in Example 1 except that base paper having a waste paper content of 50%, an amount of a remaining cationic surfactant (alkyltrimethyl ammonium chloride) of 700 ppm and a basis weight of 50 g/m2 was used as a substrate.
  • Heat-sensitive recording paper was prepared in the same manner used in Example 1 except that base paper having a waste paper content of 50%, an amount of a remaining anionic surfactant (sodium alkylbenzenesulfonate) of 950 ppm and a basis weight of 50 g/m2 was used as a substrate.
  • base paper having a waste paper content of 50%
  • Heat-sensitive recording paper was prepared in the same manner used in Example 1 except that base paper having a waste paper content of 50%, an amount of a remaining anionic surfactant (sodium alkylbenzenesulfonate) of 1200 ppm and a basis weight of 50 g/m2 was used as a substrate.
  • Heat-sensitive recording paper was prepared in the same manner used in Example 1 except that base paper having a waste paper content of 50%, an amount of a remaining nonionic surfactant (polyoxyethylene-alkylphenyl ether) of 1400 ppm and a basis weight of 50 g/m2 was used as a substrate.
  • base paper having a waste paper content of 50%
  • Heat-sensitive recording paper was prepared in the same manner used in Example 1 except that base paper having a waste paper content of 50%, an amount of a remaining cationic surfactant (alkyltrimethyl ammonium chloride) of 1500 ppm and a basis weight of 50 g/m2 was used as a substrate.
  • Heat-sensitive recording paper was prepared in the same manner used in Example 1 except that base paper having a waste paper content of 40%, an amount of a remaining nonionic surfactant (polyoxyethylene-alkylphenyl ether) of 1500 ppm and a basis weight of 50 g/m2 was used as a substrate.
  • base paper having a waste paper content of 40% an amount of a remaining nonionic surfactant (polyoxyethylene-alkylphenyl ether) of 1500 ppm and a basis weight of 50 g/m2 was used as a substrate.
  • Heat-sensitive recording paper was prepared in the same manner used in Example 4 except that polyvinyl alcohol was applied onto the base paper in an amount of 1 g/m2.
  • Heat-sensitive recording paper was prepared in the same manner used in Example 5 except that polyvinyl alcohol was applied onto the base paper in an amount of 1 g/m2.
  • Heat-sensitive recording paper was prepared in the same manner used in Example 7 except that the amount of polyvinyl alcohol coated was changed to 2 g/m2.
  • a test pattern was printed and recorded on each heat-sensitive recording paper with a heat-sensitive facsimile FF 621C (available from Fujitsu Limited) and the density of the white ground and the printed portion thereof were determined by a Macbeth densitometer RD-514. Further, the samples which had been printed with the facsimile FF 621C were used in the following storability test.
  • a heat-sensitive facsimile FF 621C available from Fujitsu Limited
  • Each sample was stored under a high humidity condition of 40°C-90% RH for 24 hours and after the storage, the density of the white ground and the printed portion of the sample were determined by a Macbeth densitometer RD-514.
  • Each heat-sensitive recording paper was wound around a platen roll, the platen roll and a thermal head (KJT-216-8MGF1) commercially available from Kyocera Corp. were fixed (0.15 kgf/cm), stored in an environment of 80 °C-85% RH for 20 hours while applying a voltage to the thermal head and then subjected to a solid printing operation to determine the rate of the dot-missing of the thermal head.
  • KJT-216-8MGF1 commercially available from Kyocera Corp.
  • improved heat-sensitive recording paper can be obtained by controlling the amount of the remaining surfactants to not more than 1,000 ppm, the resulting recording paper being cheap, making it possible to save resources, being excellent in storage stability and exhibiting high reliability to the thermal head, though waste paper is incorporated into the substrate of the recording paper.
  • the quality of the recording paper can further be improved by disposing a barrier layer between the substrate and the heat-sensitive recording layer.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)

Abstract

L'invention se rapporte à du papier d'enregistrement thermosensible et plus particulièrement à du papier d'enregistrement thermosensible composé d'une couche d'enregistrement thermosensible contenant une teinture de base incolore et une substance acide entraînant la coloration de la teinture de base incolore lors de l'application de chaleur sur un substrat. Dans le papier d'enregistrement thermosensible de la présente invention, le support contient du papier usagé et la quantité d'agent tensio-actif résiduelle contenue dans le support est inférieure à 1,000 ppm. La présente invention permet d'obtenir un papier thermosensible qui est économique et qui se caractérise par une stabilité en stockage élevée et par une fiabilité élevée dans des conditions de chute du potentiel thermique.

Claims (7)

  1. Papier de reproduction thermosensible qui comprend un support et une couche de reproduction thermosensible qui est appliquée sur le support et qui comprend un colorant incolore basique et une substance acide capable de développer en couleur le colorant incolore basique par chauffage, dans lequel le support comprend du papier de rebut et la quantité de tensioactifs restants dans le support est réglée à pas plus de 1000 ppm.
  2. Papier de reproduction thermosensible selon la revendication 1, dans lequel la teneur en papier de rebut est de pas plus de 60 %.
  3. Papier de reproduction thermosensible selon la revendication 1, dans lequel la teneur en tensioactifs est de pas plus de 800 ppm.
  4. Papier de reproduction thermosensible selon la revendication 1, dans lequel il comprend une couche écran entre le support et la couche de reproduction thermosensible.
  5. Papier de reproduction thermosensible selon la revendication 4, dans lequel la couche écran comprend un composé polymère choisi parmi la caséine, l'alcool polyvinylique, l'alginate d'ammonium, la méthylcellulose, l'hydroxyéthylcellulose, la carboxyméthylcellulose, les copolymères d'anhydride maléique, les copolymères styrène-anhydride maléique et les copolymères styrène-butadiène.
  6. Papier de reproduction thermosensible selon la revendication 5, dans lequel le pouvoir couvrant de la couche écran varie de 0,3 à 5,0 g/m².
  7. Papier de reproduction thermosensible selon la revendication 6, dans lequel le pouvoir couvrant de la couche écran varie de 0,5 à 2,0 g/m².
EP89911885A 1989-08-23 1989-10-31 Papier d'enregistrement thermosensible Expired - Lifetime EP0439612B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP217143/89 1989-08-23
JP21714389 1989-08-23
PCT/JP1989/001121 WO1991002653A1 (fr) 1989-08-23 1989-10-31 Papier d'enregistrement thermosensible

Publications (3)

Publication Number Publication Date
EP0439612A1 EP0439612A1 (fr) 1991-08-07
EP0439612A4 EP0439612A4 (en) 1991-12-11
EP0439612B1 true EP0439612B1 (fr) 1994-09-14

Family

ID=16699530

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89911885A Expired - Lifetime EP0439612B1 (fr) 1989-08-23 1989-10-31 Papier d'enregistrement thermosensible

Country Status (3)

Country Link
EP (1) EP0439612B1 (fr)
DE (1) DE68918287T2 (fr)
WO (1) WO1991002653A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05162443A (ja) * 1991-12-16 1993-06-29 Kanzaki Paper Mfg Co Ltd 感熱記録紙
FR2789040B1 (fr) 1999-02-02 2001-03-09 Armtop Chariot porte-charge et son vehicule d'embarquement

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57128346A (en) * 1981-02-02 1982-08-09 Honshu Paper Co Ltd Paper for electrophotography and form
JPS5825986A (ja) * 1981-08-07 1983-02-16 Ricoh Co Ltd 感熱記録材料
JPS5840556A (ja) * 1981-09-04 1983-03-09 Ricoh Co Ltd 電子写真圧力定着転写紙及びその転写紙用原紙の製造法
SE439787B (sv) * 1984-03-19 1985-07-01 Berol Kemi Ab Sett att reducera missfergning och/eller klibbighet vid upparbetning av avfallspapper

Also Published As

Publication number Publication date
DE68918287T2 (de) 1995-03-16
EP0439612A4 (en) 1991-12-11
DE68918287D1 (de) 1994-10-20
WO1991002653A1 (fr) 1991-03-07
EP0439612A1 (fr) 1991-08-07

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