EP0406039B1 - Verfahren zur Herstellung von mit elastomerischen Harzen angereicherten Faserbahnen aus Zellstoff nach Papiermacherart - Google Patents

Verfahren zur Herstellung von mit elastomerischen Harzen angereicherten Faserbahnen aus Zellstoff nach Papiermacherart Download PDF

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Publication number
EP0406039B1
EP0406039B1 EP19900401474 EP90401474A EP0406039B1 EP 0406039 B1 EP0406039 B1 EP 0406039B1 EP 19900401474 EP19900401474 EP 19900401474 EP 90401474 A EP90401474 A EP 90401474A EP 0406039 B1 EP0406039 B1 EP 0406039B1
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EP
European Patent Office
Prior art keywords
impregnation
elastomer
resin
constituted
process according
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Expired - Lifetime
Application number
EP19900401474
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English (en)
French (fr)
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EP0406039A1 (de
Inventor
Joseph Lecomte
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PAPETERIES DALLE ET LECOMTE SA
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PAPETERIES DALLE ET LECOMTE SA
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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/76—Processes or apparatus for adding material to the pulp or to the paper characterised by choice of auxiliary compounds which are added separately from at least one other compound, e.g. to improve the incorporation of the latter or to obtain an enhanced combined effect
    • D21H23/765—Addition of all compounds to the pulp
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/76—Processes or apparatus for adding material to the pulp or to the paper characterised by choice of auxiliary compounds which are added separately from at least one other compound, e.g. to improve the incorporation of the latter or to obtain an enhanced combined effect

Definitions

  • the present invention relates to a process for the preparation of sheet materials, of fibrous structure and of cellulose base, in particular by wet papermaking and constituting paper, nonwoven or cardboard, ennobled by impregnation of elastomeric resins.
  • the present invention thus makes it possible to obtain, from a process using a papermaking production line, fibrous sheets based on cellulose, in particular smooth or creped and ennobled by various synthetic materials of elastomeric or plastomeric nature.
  • the process thus makes it possible to obtain cartons having specific properties originating from the impregnation of products made up of said resins and allowing the use of the material thus obtained in numerous applications such as artificial leathers and the production of shoes and leather goods, high value printing sheets, gummed papers or labels as well as abrasive layer supports; the invention also makes it possible to obtain pressure-sensitive adhesive tapes, substrates usable in tapestry (floor or wall coverings); the invention also makes it possible to produce materials for technical uses, in particular for winding and protecting filiform elements such as cables or electrical cables, as well as envelopes of various shapes, in particular sterilization envelopes.
  • drying cylinder tends to retain on its surface the sheet during drying therefore having only weak mechanical properties which comes to tear with rupture in the continuity of the course.
  • the cylinders are regularly fouled by the deposits of resins, which leads to the need for regular stops for cleaning operations, resulting in a lowering of the general production yield.
  • a first solution consisted in coating the drying cylinders and rollers with a non-stick resin with a low coefficient of friction such as fluorocarbon resins.
  • the invention makes it possible to manufacture paper products containing a large proportion of finishing composition in the form of polymers and elastomers or plastomers and without any risk of deposition of elements originating from the finishing resin along the machinery and in particular at level of drying rollers.
  • the invention relates to a process for wet preparation of cellulose-based fibrous structure sheet materials, such as paper, cardboard or nonwovens in which the fibrous web structure is enriched with finishing materials made of synthetic polymers of elastomeric or plastomeric resins, and in which the wet sheet formed on the endless fabric passes through an impregnation press, to receive there in its mass, before drying on heating rollers, the impregnation of the finishing material constituted by the elastomeric or plastomeric resin, in the form of an aqueous dispersion, characterized in that said aqueous dispersion contains an additive capable of causing spontaneous coagulation of said resin above a given temperature with the release of a quantity of water, thus capable of constituting an interface opposing adhesion of the aqueous dispersion.
  • a long fiber paste is used which allows sufficient absorption and resistance adapted to the use for which the product is intended; the long-fiber, bleached, semi-bleached or unbleached pulp is not very refined (16 to 30 ° SR); the medium is maintained at a substantially neutral pH, between 6.5 and 7.5; it will be noted however that all the pastes, including the recycled pastes can be used within the framework of the finishing process according to the invention.
  • the fibers in a conventional and conventional manner are disintegrated in the pulper and possibly refined and in the paste thus produced is then introduced a first bonding composition or a first finish constituting a retention product and chosen from the products designated under the registered trademarks Retaminol (Bayer), Cartaretine (Sandoz), Percol (Allied Colloid); this first primer is introduced in a proportion of between 0.1 and 3% of the total.
  • a second primer is introduced into this dough consisting of a relatively hard and polar polymer, giving off a fairly large surface energy; preferably this polymer is an elastomer and it is dispersed in the fibrous mass in very fine particles in the form of an aqueous dispersion; a great aptitude for adhesion between the elastomers is thus obtained, or dispersion of elastomers or plastomers with the fibers of the pulp.
  • polychloroprene, polybutadiene acrylonitrile, polyacrylate and polyvinyl acetate have been noted.
  • This second elastomeric primer is introduced in a proportion of 0.1 to 3% of the total.
  • the retention product introduced into the paste lowers the zeta potential and at the same time reduces the degree of refining by fixing the fines and by crosslinking between the long-chain polyelectrolyte molecules and the cellulose fibers of the sheet. .
  • the successive additions - at predetermined intervals - of auxiliary products to the dough distribute very finely over the surface of the fiber where they present - in the form of a veil - an adhesive base excellent for "soft" latex subsequent and constituting the main finishing product.
  • the prepared and surface-modified dough will be brought to the top of the machine at a concentration of 0.4% in water.
  • the necessary quantity of crosslinking resin (4 to 8%) is added thereto continuously.
  • the sheet is then formed on the endless canvas to be finally dried.
  • the formation of the sheet is done without obstacle to the felting of the fiber, that is to say without hindrance to the formation of water bridges which naturally bind the fibers together.
  • the fibrous material leaving the endless fabric is dried to a humidity level of 8 to 15% and it then has an adequate absorption power which can be adjusted initially by refining the dough.
  • the sheet is then introduced into the impregnation press, at the aforementioned degree of humidity (8 to 15%) to be introduced into the impregnation bath comprising between 15 and 45% of elastomeric resin or plastomer in the form of an aqueous dispersion.
  • the impregnation bath based on elastomeric resin comprises, according to a characteristic element of the invention, the incorporation of a component constituting a gelling agent capable of causing coagulation of the elastomeric resin from a certain thermal level.
  • the impregnation bath is maintained at a temperature below said pre-adjusted coagulation temperature so that the dispersion is stable at the level of the impregnation bath.
  • the elastomeric polymer or plastomer of the impregnation bath can be chosen from the same family as the elastomers used as a second finish (in the dough preparation phase); however the polymer of the impregnation bath will be different in each case from that already used for the preparation of the surface of the fibers as a second bonding primer.
  • the choice of the elastomeric impregnation resin will be determined with a view to good adhesion, that is to say good compatibility from the chemical and physical point of view between the two formulas, that is to say between the elastomer used as a second attachment primer and the elastomer for impregnation in the sheet.
  • the pH of the impregnation bath is maintained at an acid value corresponding to a pH between 4 and 5 and preferably between 4 and 4.5, by adding in particular maleic acid or paratoluenesulfonic acid; adjusting the pH to obtain coagulation at the programmed temperature.
  • the sheet After passing through the impregnation press and absorption of the quantity of dispersion provided, the sheet is led to the drying devices, in particular by infrared radiation and passage over heating rollers.
  • the thermal rise to which the impregnated sheet is subjected then causes coagulation of the dispersion of elastomeric resin within the fibrous structure; this coagulation is accompanied by a release on the two surfaces of the sheet of a certain amount of water; it thus occurs when passing over the heating rollers a wet interface which opposes "dry” contact between the elastomeric resin and the surface of the roller and consequently prevents any parasitic deposition of this resin on the roller.
  • the sheet thus formed can then receive surface coatings on one or on two sides.
  • These coatings can be a simple protective varnish, but more commonly and more usefully, it will cause the establishment of layers giving antinomic properties from one side to the other, namely on one side a varnish of non-stick and hydrophobic character, while on the other side a layer facilitating the subsequent attachment of an adhesive mass or any other element to obtain a self-adhesive assembly.
  • Film forming temperature greater than 10 ° C.
  • BASF Polysar products with higher proportions of butyl and octyl esters
  • the styrene content is between 50 and 65%.
  • the film formation temperature is above 10 ° C.
  • products with a styrene content of approximately 30% were chosen, the film formation temperatures of which are less than 5 ° C.
  • the surface preparation can be carried out with polychloroprene dispersions having a low tendency to crystallize, the impregnation with an impregnation press compensating for this effect. Very good results are obtained with a subsequent impregnation based on polybutadiene-acrylonitrile latex and polyvinyl acetate latex or blends of these with types of polychloroprene latex (Dupont, Bayer) which do not crystallize.
  • Polyvinyl acetate is suitable for surface preparation, not only as a homopolymer but also as a copolymer with acrylates maleinates and other derivatives of polyvinyl alcohol, especially since these are highly polymerized types with film forming temperatures above 10 ° C.
  • an impregnating product - with regard to the uses mentioned at the beginning - it is used only as a cutting partner for the latexes of nitril, butadienestyrene or acrylic esters.
  • the polyethers of propylene-ethylene, the methylether of polyvinyl alcohol, the polyoxyethylenes are coagulating agents, called “gelling agents” like other products of polycondensation of different aliphatic diols with long chains. They have the property of becoming insoluble in water during a rise in temperature after which, there is spontaneously a general coagulation of the dispersion. At the same time, the whole quantity of water is released. We work at pH values below 5.
  • Polyvinyl alcohol polyacrylamide, polyacrylic acid + NH3. They are viscosity regulators and used for the purpose of increasing viscosity. Polyvinyl alcohol also gives hydrophilicity. Polyglycol, triethanolamine, glyoxal have softening, plasticizing and hydrophilic functions.
  • Some resins can be used for the physical reinforcement of the fiber to fiber bond (rosin resin, rosin ester) or for the chemical crosslinking of fibers (melamine formaldehyde resins, phenolformaldehyde resins). Under very specific conditions (high temperature, energy-rich rays), the combinations of urea-formaldehyde, melamine-formaldehyde and phenol-formaldehyde also crosslink the impregnation product.
  • an integral impregnation of the paper is carried out in order to constitute a pre-anchoring capable of improving the efficiency and the resistance of the adhesive layer deposited subsequently.
  • the following basic formulas were used:
  • the invention also covers various variants which allow, by the use of elastomeric resins, in particular natural or synthetic latexes, to obtain an impregnation of the sheet while adopting a pH lying in a wider range than previously mentioned and likely to be between 3 and 33.
  • the primers generally deposited by the transformers in the form of a coating layer have a tendency over time, because of the migration of the charges, to deplete the adhesive capacity of the adhesive mass. This results in a gain in efficiency of the adhesive mass anchored to the paper having undergone the pre-anchoring impregnation according to the invention.
  • the method according to the invention is therefore a factor in improving the quality and efficiency as well as a source of substantial savings; the transformer can indeed obtain identical efficiency while benefiting from a weight saving in the use of the adhesive mass of between 15 and 30%.

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Claims (8)

  1. Verfahren zur nassen Vorbereitung von blattförmigen Materialien mit Faserstruktur auf Zellulosebasis wie Papier, Karton oder ungewobener Stoff, bei denen die schichtförmige Faserstruktur durch Veredelungsmaterialien aus synthetischen Polymeren, Elastomer- oder Plastomerharzen bestehen, wobei das nasse, auf einem Endlosband beformte Blatt in eine Imprägnierpresse gelangt, wo seine Masse vor dem Trocknen durch Heiztrommeln mit dem Veredelungsmaterial aus Elastomer- oder Plastomerharz in Form einer wäßrigen Lösung imprägniert wird,
    dadurch gekennzeichnet, daß die o.a. wäßrige Lösung ein Zusatzmittel enthält, durch das die spontane Koagulation des o.a. Kunstharzes oberhalb einer bestimmten Temperatur unter Abgabe einer bestimmten Wassermenge bewirkt wird, die somit eine Zwischenschicht bilden kann, durch die ein Anhaften der Elastomer- bzw. Plastomerschicht an den bei der Weiterbehandlung verwendeten Heiztrommeln verhindert wird, und das o.a. Zusatzmittel zur Koagulation des Elastomer- bzw. Plastomerharzes aus Geliermitteln wie z.B. Polycondensationsmitteln für langkettigen aliphatische Polyole und insbesondere Propylenethylenpolyester, Methylester von Polyvinylalkohol oder Polyoxethylen besteht.
  2. Verfahren nach Patentanspruch 1, dadurch gekennzeichnet, daß vor der Formung des Blattes der Vorbereitung der Papiermasse eine erste Appretur zur Verhinderung eines späteren Anhaftens des Elastomerharzes beigegeben wird, und daß diese erste Appretur aus einem Rückhaltemittel besteht, durch das das Zeta-Potential der Masse gesenkt werden kann, das aus einem Polymer mitlangen Polyelektrolytketten aus der Familie mit Polychloropren-, Polybutadienstyrol-, Polymethacrylat-, Vinylpolyacetatdispersionen besteht, und daß der Papiermasse mehr als 15 Minuten, vorzugsweise 20 Minuten nach der Beigabe der ersten Appretur eine zweite Appretur beigegeben wird, die aus einem synthetischen Elastomertharz besteht, der mit dem später in Form einer wäßrigen Lösung beigefügten Veredelungs- bzw. Imprägniermittel verträglich ist, wobei die zweite Appretur aus der Familie mit Chloropren, Polybutadienacrylnitril, Polyacrylat, Vinylpolyacetat, Polybutadienstyrol und deren Mischungen bzw. Copolymeren stammt.
  3. Verfahren nach einem der Patentansprüche 1 oder 2, dadurch gekennzeichnet, daß das Imprägnierbad für die Imprägnierpresse mit den Elastomer- bzw. Plastomerdispersionen aus einer wäßrigen Kunstharzlösung aus natürlichem Latex, Polybutadienacrylnitril, Styrol-Vinylpolyacetat, den Copolymeren Acrylnitril-Butadien und Styrol oder den Copolymeren Acrylester und Vinylacetat sowie deren Mischungen und Copolymeren besteht.
  4. Verfahren nach einem der Patentansprüche 1 bis 3, dadurch gekennzeichnet, daß die Abgabe von Wasser zur Isolation durch einen Wärmeschock aufgrund einer Wärmestrahlung mit geeigneter Wellenlänge erfolgt.
  5. Verfahren nach einem der Patentansprüche 1 bis 4, dadurch gekennzeichnet, daß das Imprägnierbad für die Imprägnierpresse Zusatzmittel aus Viskositätsreglern wie Polyvinylalkohol, Polyacrylamid, Polyacrylsäure mit einer Beigabe von Salzsäure besitzt.
  6. Verfahren nach einem der Patentansprüche 1 bis 5, dadurch gekennzeichnet, daß das Imprägnierbad weiterhin Zusatzmittel zur Herstellung mit weichmachenden, plastifizierenden und wasseranziehenden Eigenschaften wie Polyglykol, Triethanolamin oder Glyoxal, Emulgierungsmittel zur Einstellung der Kagulationstemperatur des Elastomerharzes, Schwermetallkollektoren wie Ethylenediamin-IV-Essigsäure sowie Farb- und Füllstoffe besitzt.
  7. Verfahren nach einem der Patentansprüche 1 bis 6, dadurch gekennzeichnet, daß es nach der Trockenphase eine Phase der Benetzung auf mindestens einer Seite mit einer wäßrigen Lösung eines Schutzlacks aus der Familie der Polyvinylchlorid-, Polyvinylacetat-, Polyacrylester- Polystyroldispersion beinhaltet.
  8. Verfahren nach einem der Patentansprüche 1 bis 7, dadurch gekennzeichnet, daß eine Seite des derart hergestellten Materials wasserabweisend und nichthaftend gemacht wird, indem die entsprechende Seite des Blattes mit einem Stoff aus der Familie der wasserlöslichen und vernetzbaren Stearinsäure- und dreiwertigen Chromkomplexe, Melaminharze, langkettigen Fettsäuren, Melaminformole oder Ureaformole beschichtet wird.
EP19900401474 1989-05-31 1990-05-31 Verfahren zur Herstellung von mit elastomerischen Harzen angereicherten Faserbahnen aus Zellstoff nach Papiermacherart Expired - Lifetime EP0406039B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8907198 1989-05-31
FR8907198A FR2647819B1 (fr) 1989-05-31 1989-05-31 Procede de preparation de produits fibreux en forme de feuilles et a base de cellulose par voie papetiere et enrichis de resines elastomeres

Publications (2)

Publication Number Publication Date
EP0406039A1 EP0406039A1 (de) 1991-01-02
EP0406039B1 true EP0406039B1 (de) 1993-11-10

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EP19900401474 Expired - Lifetime EP0406039B1 (de) 1989-05-31 1990-05-31 Verfahren zur Herstellung von mit elastomerischen Harzen angereicherten Faserbahnen aus Zellstoff nach Papiermacherart

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EP (1) EP0406039B1 (de)
DE (1) DE69004499T2 (de)
FR (1) FR2647819B1 (de)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3035082B1 (fr) * 2015-04-16 2017-11-24 Cie Des Gaz De Petrole Primagaz Structure de conditionnement

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2887431A (en) * 1957-01-11 1959-05-19 Armstrong Cork Co Method of forming a slurry of different filler particles uniformly coated with a binder
FR2519663B2 (fr) * 1981-05-12 1985-08-16 Jeandheurs Papeteries Perfectionnements apportes au procede de fabrication en milieu aqueux de feuilles en matieres fibreuses contenant du latex ou analogue et/ou des phenoplastes ou aminoplastes, nouvelles feuilles ainsi obtenues et leur eventuelle reutilisation
FI77707C (fi) * 1987-06-04 1989-04-10 Valmet Paper Machinery Inc Foerfarande foer kontaktloes torkning av en pappers- eller kartongbana.

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Publication number Publication date
EP0406039A1 (de) 1991-01-02
DE69004499D1 (de) 1993-12-16
DE69004499T2 (de) 1994-06-09
FR2647819B1 (fr) 1991-09-20
FR2647819A1 (fr) 1990-12-07

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