WO1994023952A1 - 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
WO1994023952A1
WO1994023952A1 PCT/EP1994/001186 EP9401186W WO9423952A1 WO 1994023952 A1 WO1994023952 A1 WO 1994023952A1 EP 9401186 W EP9401186 W EP 9401186W WO 9423952 A1 WO9423952 A1 WO 9423952A1
Authority
WO
WIPO (PCT)
Prior art keywords
oil
pressure
oil barrier
paper
sensitive carbonless
Prior art date
Application number
PCT/EP1994/001186
Other languages
German (de)
English (en)
Inventor
Bodo Hilterhaus
Dieter Baumgarten
Günter GABEL
Wolfram Friesen
Original Assignee
Stora Feldmühle Ag
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 Stora Feldmühle Ag filed Critical Stora Feldmühle Ag
Priority to SI9430072T priority Critical patent/SI0695236T1/xx
Priority to DE59403256T priority patent/DE59403256D1/de
Priority to EP94914390A priority patent/EP0695236B1/fr
Publication of WO1994023952A1 publication Critical patent/WO1994023952A1/fr

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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 carbonless paper according to the preamble of claim 1.
  • CB pressure-sensitive carbonless 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 current nomenclature.
  • CB means a copy sheet with microcapsules arranged on the back
  • CFB a copy sheet with color developer layer arranged on the top and a microcapsule layer on the back
  • CF a copy sheet with color developer layer arranged on the top.
  • the principle of the reaction is that the microcapsules arranged on the back break up as a result of 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 following copy sheet, whereby Due to its chemical composition, the receiving 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.
  • carbonless sheets of this type are compiled into so-called carbonless records, 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.
  • CB-CFB a sheet for the purpose of producing an original and a copy or copy.
  • CFB-CF a sheet for the purpose of producing an original and a copy or copy.
  • Carbonless papers must be printed, although it cannot always be avoided that individual capsules are destroyed during the printing process and their contents are released onto the carrier paper. If its resistance to core oil penetration is too low, the leuco dyes contained in the core oil react with the color developer located on the top of the carrier sheet, so that the carbonless paper or the set of forms made from it shows a discolouring discoloration even before it is actually used. In the past, it has been shown in particular that yellow and red color precursors tend to migrate through the carrier paper in the event of premature capsule destruction. As a result, copies of important documents that were kept in the file turned strongly yellow or red over time, so that their document character is ultimately endangered.
  • patent application P 36 33 116 which goes back to the applicant, a pressure-sensitive carbonless paper is proposed, the microcapsule of which contains a vegetative oil such as e.g. Sunflower oil, rapeseed oil, soybean oil, coconut oil etc. 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 etc.
  • 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.
  • the object of the present invention is therefore to provide a pressure-sensitive carbonless 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 the organic paraffin derivatives, benzene derivatives, Chlorinated hydrocarbons, white oils and vegetative oils are meant, which are known and familiar to the person skilled in the art.
  • the oil barrier according to the invention preferably consists of an impregnation incorporated into the mass of the backing paper. This is obtained in a manner known per se in the production of the backing paper by adding the impregnation substances to the aqueous fiber suspension before the sheet is formed on the paper machine screen. After intensive mixing with the fiber suspension, possibly with the aid of retention agents known per se, such as cationic polyethyleneimines or cationic polyacrylamides, the sheet is formed on the paper machine screen, which contains the impregnating substance which forms the oil barrier according to the invention evenly distributed over its cross section. If the impregnating substance or the mixture of such substances has a charge or an ionic character, this can be used for the retention of the substance in the fiber structure Increasing the oil barrier effect can be used.
  • the anionic charge of the cellulose fiber is sufficient to obtain sufficient retention.
  • the impregnation substance is anionically charged, it is advisable to precipitate onto the fiber by adding cationic substances such as the retention agents mentioned above.
  • cationization reagents to increase their affinity for the pulp fiber.
  • Such cationization reagents are known under the generic term quaternary ammonium compounds.
  • Another representative is the now well-known polydadmac (polydimethyldiallylammonium chloride), dimethyldistearylammonium chloride and benzidimethylstearyl monium chloride.
  • the impregnation substance it may be advisable not to add the impregnation substance to the fiber suspension when producing the base paper. This is especially the case if the paper machine has a limited drainage capacity or if the fiber suspension used is already a bad one Has drainage behavior. The addition of the impregnating substance would then further deteriorate the drainage, so that the
  • the oil barrier consists of an oil-repellent, closed surface preparation applied to one or both sides of the carrier paper.
  • a 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 known under the name "Speed ⁇ izer” is particularly suitable for applying the solution or aqueous suspension.
  • the oil barrier preferably consists of natural or synthetic hydrocolloids or their derivatives with a high film-forming property.
  • Pretreatment of these hydrocolloids with quaternary ammonium compounds such as polydimethyldially, dimethyldistearyl or benzyldimethylstearyl ammonium chloride, where appropriate, will result in an increase in the oil barrier.
  • Further preferred substances with a high film-forming property for the oil barrier are copolymers, mixed or terpolymers of acrylates, methacrylates, styrene, butadiene, styrene-butadiene, acrylonitrile, polyisocyanate or polyurethane compounds. These substances are available as aqueous plastic dispersions and are e.g. sold under the trade names Basopla ⁇ t, Baysynthol, Isovin or Cyclopal KE.
  • the polyisocyanates are described, for example, in DE-A-42 11 480 and DE-A-42 26 110.
  • the oil barrier very particularly preferably consists of a mixture of natural or synthetic hydrocolloids or their derivatives and plastics based on acrylic acid, methacrylic acid, polycarbonates, butadiene-styrene copolymers, butadiene-styrene-acrylonitrile terpolymers and / or polyurethanes or polyisocyanates.
  • a combination combines the good film-forming properties of the hydrocolloids with those of the plastics in order to achieve a particularly high barrier action against the core oils.
  • Another advantage is that the - lo ⁇
  • the surface film formed has a certain elasticity and softness due to the proportion of plastic, which can be important for the later use of the pressure-sensitive carbonless paper, this applies in particular to the endless 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.
  • the reaction product from the two constituents is understood to be symplex if they are combined in an 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.
  • Such coacervates are particularly suitable for addition in bulk, but use for producing 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 equipment in textiles and special papers for food packaging. Such compounds are available, for example, under the trade name "Scotchban". However, their use has so far been limited to a few special products because of the high cost price. It has now surprisingly been found that an oil barrier with outstanding properties can be made available for pressure-sensitive carbonless papers if this 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 glue press or a coating unit within the paper machine, the surface application per side being selected between 0.5 to 2 g / m 2 atro.
  • an oil barrier made of olephobic pigments in or above the backing paper.
  • these pigments are added in an amount of 10 to 15%, based on dry fiber, as filler of the fiber suspension before the sheet is formed.
  • the oil barrier is to be arranged as a surface coating, it is sufficient to mix the glue liquor with these pigments in an existing size press and to apply it in an amount of 3 to 5 g / m 2 , the liquor being 5-20% atro pigment in addition to the usual surface sizing - and binders.
  • Such an oil barrier can be obtained in accordance with DE-C-30 36 551, which goes back to the applicant. It uses film-forming clays based on montmorillonite achieved a fiber coating that 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:
  • Calcium bentonite suspension 1.5 wt.% NaOH and 7 wt.% MgS0 4 are added. There is a high viscosity, which is a sign of good activation.
  • a polyethylene glycol with a molecular weight of 20,000 is added from a 6% solution, and the amount added is 18% by weight, based on atro-activated bentonite.
  • a fiber suspension at pH 7 1 to 3% by weight of the mixture is activated bentonite and
  • Polyethylene glycol added and with the addition of a known alkali sizing agent such as. B. AKD glue, processed on the paper machine to a carrier paper for pressure-sensitive carbonless papers.
  • a known alkali sizing agent such as. B. AKD glue
  • coacervates made from organic pigment and a high molecular weight polymer according to DE-A-40 15 252 or organophilic layered silicates according to DE-A-41 37 091 have also proven their worth, with the purpose of maintaining the oil barrier both in the bulk of the carrier paper incorporated as well as can be applied as a surface preparation.
  • the following examples serve to further clarify:
  • composition of the backing paper is Composition of the backing paper:
  • the paper has a degree of sizing according to DIN 53 132 from 12 to 18.
  • the paper is provided with an oil barrier by adding it to the mass or by preparing the surface.
  • the effect of the oil barrier is determined according to the Cobb-Unger method analogous to DIN 53 132 by measuring the absorption of olive oil.
  • An additional evaluation is carried out by the climate aging test on the test sample, a CFB paper being produced therefrom, this aging at 70 ° C. F. is subjected to for 6 days and then through the dye migration caused discoloration of the surface (F side) of the CFB sheet is assessed.
  • Procote 5000 chemically modified 1.5 g / m '16.1 soy protein according to EP-A-0 491 487

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.
PCT/EP1994/001186 1993-04-21 1994-04-16 Papier autocopiant sensible a la pression a barriere de retenue d'huile amelioree WO1994023952A1 (fr)

Priority Applications (3)

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
DE59403256T DE59403256D1 (de) 1993-04-21 1994-04-16 Druckempfindliches durchschreibepapier mit verbesserter ölsperre
EP94914390A EP0695236B1 (fr) 1993-04-21 1994-04-16 Papier autocopiant sensible a la pression a barriere de retenue d'huile amelioree

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4312854A DE4312854A1 (de) 1993-04-21 1993-04-21 Druckempfindliches Durchschreibepapier mit verbesserter Ölsperre
DEP4312854.8 1993-04-21

Publications (1)

Publication Number Publication Date
WO1994023952A1 true WO1994023952A1 (fr) 1994-10-27

Family

ID=6485900

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1994/001186 WO1994023952A1 (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)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8030365B2 (en) 2005-03-11 2011-10-04 International Paper Company Compositions containing expandable microspheres and an ionic compound as well as methods of making and using the same

Families Citing this family (3)

* 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
US8382945B2 (en) 2008-08-28 2013-02-26 International Paper Company Expandable microspheres and methods of making and using the same

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2005271A1 (fr) * 1968-04-01 1969-12-12 Ncr Co
FR2010349A1 (fr) * 1968-06-07 1970-02-13 Wiggins Teape Res Dev
US4111461A (en) * 1976-12-16 1978-09-05 Great Northern Nekoosa Corporation Barrier coat for groundwood carbonless coated paper
GB2022646A (en) * 1978-05-15 1979-12-19 Kanzaki Paper Mfg Co Ltd Recording material for use un a pressure sensitive copyingsystem
GB2173225A (en) * 1985-03-12 1986-10-08 Fuji Photo Film Co Ltd Microcapsule-coated sheet for pressure-sensitive copying paper
EP0449537A1 (fr) * 1990-03-27 1991-10-02 The Wiggins Teape Group Limited Papier d'enregistrement sensible à la pression

Family Cites Families (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

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2005271A1 (fr) * 1968-04-01 1969-12-12 Ncr Co
FR2010349A1 (fr) * 1968-06-07 1970-02-13 Wiggins Teape Res Dev
US4111461A (en) * 1976-12-16 1978-09-05 Great Northern Nekoosa Corporation Barrier coat for groundwood carbonless coated paper
GB2022646A (en) * 1978-05-15 1979-12-19 Kanzaki Paper Mfg Co Ltd Recording material for use un a pressure sensitive copyingsystem
GB2173225A (en) * 1985-03-12 1986-10-08 Fuji Photo Film Co Ltd Microcapsule-coated sheet for pressure-sensitive copying paper
EP0449537A1 (fr) * 1990-03-27 1991-10-02 The Wiggins Teape Group Limited Papier d'enregistrement sensible à la pression

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8030365B2 (en) 2005-03-11 2011-10-04 International Paper Company Compositions containing expandable microspheres and an ionic compound as well as methods of making and using the same

Also Published As

Publication number Publication date
EP0695236A1 (fr) 1996-02-07
EP0695236B1 (fr) 1997-07-02
DE59403256D1 (de) 1997-08-07
ES2105702T3 (es) 1997-10-16
DE4312854A1 (de) 1994-10-27
CZ274795A3 (en) 1996-02-14

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