EP0695236B1 - Papier autocopiant sensible a la pression a barriere de retenue d'huile amelioree - Google Patents

Papier autocopiant sensible a la pression a barriere de retenue d'huile amelioree Download PDF

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Publication number
EP0695236B1
EP0695236B1 EP94914390A EP94914390A EP0695236B1 EP 0695236 B1 EP0695236 B1 EP 0695236B1 EP 94914390 A EP94914390 A EP 94914390A EP 94914390 A EP94914390 A EP 94914390A EP 0695236 B1 EP0695236 B1 EP 0695236B1
Authority
EP
European Patent Office
Prior art keywords
oil
paper
carrier paper
pressure
oil barrier
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
EP94914390A
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German (de)
English (en)
Other versions
EP0695236A1 (fr
Inventor
Bodo Hilterhaus
Dieter Baumgarten
Günter GABEL
Wolfram Friesen
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.)
Stora Publication Paper AG
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Stora Publication Paper AG
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Filing date
Publication date
Application filed by Stora Publication Paper AG filed Critical Stora Publication Paper AG
Priority to SI9430072T priority Critical patent/SI0695236T1/xx
Publication of EP0695236A1 publication Critical patent/EP0695236A1/fr
Application granted granted Critical
Publication of EP0695236B1 publication Critical patent/EP0695236B1/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
    • B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components

Definitions

  • the invention relates to a pressure-sensitive recording paper according to the preamble of claims 1 and 4.
  • CB pressure-sensitive recording papers based on the chemical reaction principle consist of a backing paper and reaction layers applied to it and are referred to as CB, CFB and CF papers according to the common nomenclature.
  • CB means a recording sheet with microcapsules arranged on the back
  • CFB a recording sheet with a color developer layer arranged on the top and a microcapsule layer on the back
  • CF a recording sheet with a color developer layer arranged on the top.
  • the principle of the reaction is that the microcapsules arranged on the reverse side break due to the writing pressure applied to the paper and their contents, leuco dyes dissolved in so-called core oil, are transferred to an underlying receiver layer of the subsequent recording sheet, whereby Due to its chemical composition, the receiver layer develops the leuco dye into a visible color, so that the writing trace is readable by the human eye.
  • Such papers are well known so that they do not have to be described further.
  • Such recording sheets are compiled into so-called copy sets, which in the simplest case consist of a CB and a CF sheet for the purpose of producing an original and a copy or copy.
  • copy sets which in the simplest case consist of a CB and a CF sheet for the purpose of producing an original and a copy or copy.
  • the individual sheet types must be arranged in the following order: CB-CFB ... CFB-CF.
  • Patent application P 36 33 116 which goes back to the applicant, proposes a pressure-sensitive recording paper whose microcapsule contains a vegetative oil such as e.g. Sunflower oil, rapeseed oil, soybean oil, coconut oil or similar as an environmentally friendly core oil as a solvent for the color precursor or known leuco dyes.
  • a vegetative oil such as e.g. Sunflower oil, rapeseed oil, soybean oil, coconut oil or similar as an environmentally friendly core oil as a solvent for the color precursor or known leuco dyes.
  • Non-reactive water repellents such as wax glues, wax emulsions, metal salts of fatty acids, such as. B. stearic acid, ester waxes, oxidized polyethylenes, copolymer dispersions and dispersions from organic prepolymers are known per se and have so far been used in paper technology mainly in combination with gelatinized starch in glue liquors for use in the size press within the paper machine, see. also the literature reference "Handbuch der Textil- und Pappefabrikation", 1971, page 1282 ff. under the heading surface sizing with further references. Such substances are also thought to have a blocking effect against oils and fats.
  • EP-A-0 449 537 relates to the use of a non-film-forming plastic pigment together with a binder and possibly inorganic pigment in an intermediate layer arranged below the microcapsule layer. This is to achieve an improved image intensity, or at constant intensity a reduction in the imaging substances may be possible. According to the examples in this document, a surface-sized paper - 5 g / m 2 application - is used.
  • GB-A-2 022 646 relates to a pressure-sensitive recording paper in which the ballpoint pen writability of the microcapsule layer is said to be improved by an intermediate layer containing inorganic pigment and binder. There is no disclosure regarding any sizing to be carried out.
  • an intermediate layer to be arranged below the microcapsule layer is proposed with the aim of effecting a better transfer of the capsule content to the color developer or of enabling a more effective release of the capsule content in order to have to use fewer microcapsules.
  • the aggregation of the microcapsules is accomplished by adding a flocculant proposed to the intermediate layer, with cationic agents such as. B. cationic starch, cationic polymers and water-soluble cationic compounds are provided.
  • the disadvantage of this proposal is that the cationic compounds have to go into solution in order to be effective as a flocculant. This is done by applying the aqueous microcapsule dispersion to the intermediate layer formed. With the return of the excess microcapsule coating color, however, cationic substance also gets into the coating color container and can lead to flocculation or instability of the coating color. In the same way, an instability of the coating sump cannot be ruled out.
  • GB-A-1 274 667 a preparation of starch and alginate to be applied by means of a size press is provided, the alginate being made insoluble by the addition of aluminum ions. From the mention of alum, acid mass sizing can be concluded.
  • GB-A-1 222 187 provides a latex layer, under which a layer of hydrophilic polymer can optionally be arranged.
  • Ethylene vinyl acetate copolymers, polyvinyl chloride and polyvinylidene chloride are disclosed as suitable latices. There is no information in this document about the type and scope of sizing.
  • the object of the present invention is therefore to provide a pressure-sensitive recording paper which avoids the disadvantages described above and in particular has a better barrier effect against the currently known and proposed core oils of microcapsules.
  • Core oils are understood to mean all currently known solvents and their mixtures with blending agents, in particular organic paraffin derivatives, benzene derivatives, chlorinated hydrocarbons, white oils and vegetative oils, which are known and familiar to the person skilled in the art.
  • the application of the oil barrier according to the invention in the form of a closed surface preparation can be applied in a manner known per se within the paper machine using conventional application devices such as a size press or coating device.
  • An aqueous solution or suspension is produced from the constituents of the impregnating substance and, with the help of roller or nozzle application, a uniform aqueous film is produced on the surface of the backing paper, which results in the desired surface preparation after drying.
  • a device which has become known as "Speedsizer" is particularly suitable for applying the solution or aqueous suspension.
  • the polyisocyanates are described, for example, in DE-A-42 11 480 and DE-A-42 26 110.
  • the oil barrier consists of a mixture of natural or synthetic hydrocolloids or their derivatives and plastics based on copolymers or copolymers of acrylic acid esters, methacrylic acid esters, polycarbonates, butadiene-styrene copolymers, acrylonitrile-styrene-butadiene copolymers and / or polyurethanes, the good film-forming properties of the hydrocolloids are combined with those of the plastics in order to achieve a particularly high barrier action against the core oils.
  • Another advantage is that the surface film formed has a certain elasticity and softness due to the plastic content, which may be important for the later use of the pressure-sensitive recording paper. This is particularly true for the continuous form area, where excessive stiffness is undesirable because of the poorer machinability associated with it.
  • Another preferred composition of the oil barrier consists of a symplex of cationic starch and anionic alginate.
  • Symplex is understood to mean the reaction product from the two constituents if they are combined in aqueous solution in such a way that a complete charge equalization takes place and the original colloids as coacervates or coprecipitates have failed as microflakes.
  • Coacervates of this type are particularly suitable for addition in bulk, but use in the production of a surface film is not excluded.
  • Fluorinated hydrocarbon compounds with excellent properties have been known for a long time for the production of oil and grease repellent finishes in textiles and special papers for food packaging.
  • an oil barrier with outstanding properties can be provided for pressure-sensitive recording papers if it consists of a mixture of polyvinyl alcohol with a degree of saponification of 84-98% and a fluorinated hydrocarbon compound.
  • the mixing ratio of polyvinyl alcohol to fluorinated hydrocarbon compound is selected in the range from 11: 1 to 9: 3.
  • Such a mixture is particularly suitable for producing oil-repellent surface films with the aid of a size press or a coating unit within the paper machine, the surface application per side being chosen between 0.5 to 2 g / m 2 atro.
  • Another solution to the problem is finally to arrange an oil barrier made of oleophobic pigments above the backing paper.
  • an oil barrier made of oleophobic pigments above the backing paper.
  • Such an oil barrier can be obtained in accordance with the applicant's DE-C-30 36 551.
  • a fiber coating is achieved with film-forming clays based on montmorillonite, which has an excellent barrier effect against the core oils.
  • the film-forming clays are activated alkaline and contain up to 40% magnesium ions, the rest being sodium ions.
  • Such clays are produced as follows:
  • Bentonites activated in this way are optionally applied with the aid of an additional binder, such as starch, modified starch, latex binders or other binders known to the person skilled in the art, by means of a size press or a coating device as surface preparation onto a paper which has been pre-sized in an alkaline manner.
  • an additional binder such as starch, modified starch, latex binders or other binders known to the person skilled in the art
  • composition of the backing paper is Composition of the backing paper:
  • the paper is provided with an oil barrier by preparing the surface.
  • the effect of the oil barrier is determined using the Cobb-Unger method in accordance with DIN 53 132 by measuring the absorption of olive oil.

Landscapes

  • Color Printing (AREA)
  • Paper (AREA)

Abstract

Une couche contenant des microcapsules avec des leucocolorants dissous dans de l'huile de noyaux est située sur la face inférieure d'un papier autocopiant sensible à la pression. Afin d'empêcher l'huile de noyaux de traverser le papier de support, celui-ci contient une barrière de retenue d'huile avec une valeur d'adsorption d'huile inférieure à 10 g/m2, mesurée selon Cobb-Unger, l'extrait à l'eau chaude ayant une valeur de pH comprise entre 7,5 et 9,5. La barrière de retenue d'huile est constituée d'une imprégnation incorporée à la masse du papier de support ou une préparation de surface oléorésistante en hydrocolloïdes filmogènes, en dispersions de matières plastiques, en pigments ou en mélanges de ceux-ci appliquée sur une ou les deux faces du papier.

Claims (4)

  1. Papier d'enregistrement sensible à la pression, dans lequel est disposée, sur le côté inférieur, une couche contenant des micro-capsules avec des leuco-colorants dissous dans une huile, le papier support ayant été encollé dans la masse en milieu neutre ou alcalin, caractérisé par la combinaison des caractéristiques suivantes : le pH d'un extrait à l'eau chaude du papier support vaut de 7,5 à 9,5, et le papier support comporte une couche-barrière de rétention d'huile dont l'indice d'adsorption d'huile, mesuré d'après Cobb-Unger selon la norme DIN 53 132, est inférieur à 10 g/m2 et qui est formée par un film étanche oléofuge, déposé au moyen d'une préparation de surface sur un côté ou sur les deux côtés du papier support et constitué de composants filmogènes, obtenu à partir de :
    a) alginates de sodium ou leurs dérivés, amidon, éthers d'ami-don, esters d'amidon, éthers de cellulose comme la carboxyméthylcellulose, dérivés de guar, gomme arabique, chitosane, dérivés de xanthane, poly(alcool vinylique) partiellement ou hautement saponifié, hémicellulose purifiée, ou leurs dérivés, ou un mélange de ces composants, ou
    b) copolymères, terpolymères ou mélange de polymères de composés de type ester acrylate, ester méthacrylate, styrène, butadiène styrène-butadiène, acrylonitrile, polyisocyanate et polyuréthane, ou
    c) un mélange d'hydrocolloïdes ou de dérivés d'hydrocolloïdes et de matières synthétiques à base de copolymères ou de mélanges de polymères d'esters acrylates ou d'esters méthacrylates, de polycarbonates, de copolymères sryrène-butadiène, de copolymères acrylonitrile-styrène-butadiène et/ou de polyuréthanes.
  2. Papier d'enregistrement sensible à la pression, conforme à la revendication 1, caractérisé en ce que la couche-barrière de rétention d'huile est constituée d'un simplex d'amidon cationique et d'alginate anionique et/ou d'éther de cellulose.
  3. Papier d'enregistrement sensible à la pression, dans lequel est disposée, sur le côté inférieur, une couche contenant des micro-capsules avec des leuco-colorants dissous dans une huile, le papier support ayant été encollé dans la masse en milieu neutre ou alcalin, caractérisé par la combinaison des caractéristiques suivantes : le pH d'un extrait à l'eau chaude du papier support vaut de 7,5 à 9,5, et le papier support comporte une couche-barrière de rétention d'huile dont l'indice d'adsorption d'huile, mesuré d'après Cobb-Unger selon la norme DIN 53 132, est inférieur à 10 g/m2 et qui est formée par une préparation de surface oléofuge, déposée sur un côté ou sur les deux côtés du papier support et constituée d'un poly(alcool vinylique) saponifié à un degré de 84 à 98 % et mélangé, en des proportions de 11/1 à 9/3, avec un composé de type hydrocarbure fluoré.
  4. Papier d'enregistrement sensible à la pression, dans lequel est disposée, sur le côté inférieur, une couche contenant des micro-capsules avec des leuco-colorants dissous dans une huile, le papier support ayant été encollé dans la masse en milieu neutre ou alcalin, caractérisé par la combinaison des caractéristiques suivantes : le pH d'un extrait à l'eau chaude du papier support vaut de 7,5 à 9,5, et le papier support comporte une couche-barrière de rétention d'huile dont l'indice d'adsorption d'huile, mesuré d'après Cobb-Unger selon la norme DIN 53 132, est inférieur à 10 g/m2 et qui est formée par un film étanche oléofuge, déposé au moyen d'une préparation de surface sur un côté ou sur les deux côtés du papier support et constitué
    a) d'une argile filmogène à base de montmorillonite, éventuellement mélangée avec un liant ou
    b) d'un coacervat de pigment minéral et de haut polymère, ou
    c) d'un silicate feuilleté organophile.
EP94914390A 1993-04-21 1994-04-16 Papier autocopiant sensible a la pression a barriere de retenue d'huile amelioree Expired - Lifetime EP0695236B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
SI9430072T SI0695236T1 (en) 1993-04-21 1994-04-16 Pressure-sensitive self-copying paper with improved oil barrier

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4312854 1993-04-21
DE4312854A DE4312854A1 (de) 1993-04-21 1993-04-21 Druckempfindliches Durchschreibepapier mit verbesserter Ölsperre
PCT/EP1994/001186 WO1994023952A1 (fr) 1993-04-21 1994-04-16 Papier autocopiant sensible a la pression a barriere de retenue d'huile amelioree

Publications (2)

Publication Number Publication Date
EP0695236A1 EP0695236A1 (fr) 1996-02-07
EP0695236B1 true EP0695236B1 (fr) 1997-07-02

Family

ID=6485900

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94914390A Expired - Lifetime EP0695236B1 (fr) 1993-04-21 1994-04-16 Papier autocopiant sensible a la pression a barriere de retenue d'huile amelioree

Country Status (5)

Country Link
EP (1) EP0695236B1 (fr)
CZ (1) CZ274795A3 (fr)
DE (2) DE4312854A1 (fr)
ES (1) ES2105702T3 (fr)
WO (1) WO1994023952A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9817042D0 (en) * 1998-08-06 1998-09-30 Carrs Paper Ltd Carbonless copy paper
ITMI20011424A1 (it) * 2001-07-05 2003-01-05 Ausimont Spa Dispersioni di polimeri fluorurati
US8034847B2 (en) 2005-03-11 2011-10-11 International Paper Company Compositions containing expandable microspheres and an ionic compound, as well as methods of making and using the same
CN102137878B (zh) 2008-08-28 2014-06-18 国际纸业公司 可膨胀微球及其制造和使用方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4015252A1 (de) * 1990-05-12 1991-11-21 Hoechst Ag Verfahren zur einbindung eines binders in ein in der masse gefuelltes papier

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3565666A (en) * 1968-04-01 1971-02-23 Ncr Co Capsule-coated record sheet (with subcoat of latex)
GB1274667A (en) * 1968-06-07 1972-05-17 Wiggins Teape Res Dev Coated fibrous sheet material
US4111461A (en) * 1976-12-16 1978-09-05 Great Northern Nekoosa Corporation Barrier coat for groundwood carbonless coated paper
JPS54150210A (en) * 1978-05-15 1979-11-26 Kanzaki Paper Mfg Co Ltd Microcapsuleecoated paper for pressureesensitive copying
JPS61206689A (ja) * 1985-03-12 1986-09-12 Fuji Photo Film Co Ltd 感圧複写紙用マイクロカプセル塗布紙
ES2084100T3 (es) * 1990-03-27 1996-05-01 Wiggins Teape Group Ltd Papel copia sensible a la presion.

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4015252A1 (de) * 1990-05-12 1991-11-21 Hoechst Ag Verfahren zur einbindung eines binders in ein in der masse gefuelltes papier

Also Published As

Publication number Publication date
EP0695236A1 (fr) 1996-02-07
WO1994023952A1 (fr) 1994-10-27
DE59403256D1 (de) 1997-08-07
CZ274795A3 (en) 1996-02-14
DE4312854A1 (de) 1994-10-27
ES2105702T3 (es) 1997-10-16

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