EP0702737A1 - Traitement de matieres cellulosiques - Google Patents

Traitement de matieres cellulosiques

Info

Publication number
EP0702737A1
EP0702737A1 EP94917857A EP94917857A EP0702737A1 EP 0702737 A1 EP0702737 A1 EP 0702737A1 EP 94917857 A EP94917857 A EP 94917857A EP 94917857 A EP94917857 A EP 94917857A EP 0702737 A1 EP0702737 A1 EP 0702737A1
Authority
EP
European Patent Office
Prior art keywords
coating
process according
weight
coating agent
poly
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.)
Granted
Application number
EP94917857A
Other languages
German (de)
English (en)
Other versions
EP0702737B1 (fr
Inventor
Kilian Kleinhenz
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.)
Klippan AB
Original Assignee
KLIPPANS FINPAPPERSBRUK AB
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 KLIPPANS FINPAPPERSBRUK AB filed Critical KLIPPANS FINPAPPERSBRUK AB
Publication of EP0702737A1 publication Critical patent/EP0702737A1/fr
Application granted granted Critical
Publication of EP0702737B1 publication Critical patent/EP0702737B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/14—Secondary fibres
    • 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
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/60—Polyalkenylalcohols; Polyalkenylethers; Polyalkenylesters
    • 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
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/50—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by form
    • D21H21/52—Additives of definite length or shape

Definitions

  • the present invention is within the field of paper or board or similar cellulosic materials used as wrapping and packaging materials. More specifically the invention relates to a novel process for the treatment of such a cellulosic material to impart thereto water vapour barrier characteristics to make said material useful as a wrapping and packaging material for moisture sensitive articles, e.g. copying or printing quality papers, certain food ⁇ stuffs or similar. At the same time, however, the treated material shows repulpability properties of such a nature that it can be recycled as a waste material to a paper or board production line without prior screening or sorting being necessary.
  • the invention also relates to the material treated by said process as well as to the coating agent utilized in said treatment process.
  • Fine paper qualities have to be wrapped in a wrapping material having such a moisture or water vapour imperme ⁇ ability that the wrapped papers remain more or less at a constant relative humidity for lengthy periods of time.
  • the dominating wrapping material for this purpose is a composite material where polyethylene has been extruded onto paper.
  • polyethylene-extruded paper is said to be far from an ideal material.
  • polyethylene-extruded paper can be rendered recyclable only after difficult, time and money consuming screening processes.
  • a direct recycling of said wrapping material is, thus, impossible as the use thereof in a paper manufacturing process will indispensably give a paper quality that is deficient or said use may even cause a production failure.
  • the present invention is based on the use of a poly(vinyl alcohol)-based material as a coating on paper inspite pf the fact that poly(vinyl alcohol) is known to be a water sensitive material.
  • a new process for the treat ⁇ ment of a cellulosic material such as selected from the group consisting of paper, board, paperboard and similar materials, to impart thereto water vapour and aroma barri ⁇ er characteristics while retaining the repulpability pro- perties thereof so as to enable a direct recycling to a pulper of a paper, board or paperboard production plant or line, said process being characterized by:
  • a coating agent preferably in the form of an aqueous slurry, comprising a) 30-70% by weight of poly(vinyl alcohol), and b) 70-30% by weight of a non-spherical particulate filler, preferably having an aspect ratio, i.e. a ratio of average particle diameter to thickness, of at least 2:1, said percentages being calculated as solids contents based on the combined weights of a) + b),
  • a coated material is obtained where said coating agent is the sole or major water vapour barrier-forming agent and outstanding water vapour barrier properties are still accomplished.
  • the new barrier-pro ⁇ vided material is directly repulpable without any other equipment than those conventional pulpers which are indi ⁇ genous to the paper or board industry.
  • the cellulosic base material to be barrier coated in accordance with the present invention can be any type of material suitable as a wrapping or packaging material.
  • it can be any type of bleached or unbleached kraft or sulphite paper which has been refined in such a way that it achieves high tensile, tearing and bursting strengths.
  • ingredients a) and b) As concerns the major ingredients of the coating agent, i.e. ingredients a) and b), the following details can be given.
  • the poly(vinyl alcohol) can generally be selected among such qualities which are suitable for coating pur ⁇ poses. Furthermore, it should be highly hydrolyzed and have a low to medium molecular weight. Preferably this means a degree of hydrolysis within the range of 95-100%, more preferably 97-100%, for instance 98% or around 98%, expressed as mole %.
  • the molecular weight or mass is pre ⁇ ferably within the range of 16 000-200000, more prefer ⁇ ably 16 000-75 000, most preferably 16 000-47 000, g/mole, the molecular weights being determined according to the GPC (Gel Permeation Chromatography) method.
  • a molecular weight of at most 47 000 is preferable for instance for the reason that it enables low viscosi- ties of the coating agent to be attained (e.g. below 5 000 cps/Brookfield, 100 rpm), which in turn makes it possible to carry out the coating process with a great precision.
  • a preferable embo- diment in this respect is one with a molecular weight of about 16 000 and a degree of hydrolysis of about 98%, and the other with a molecular weight of about 145 000 and a degree of hydrolysis of about 99%.
  • the invention does not exclude the possibi ⁇ lity of copolymerizing said vinyl alcohol with a minor amount of any monomer that is copolymerizable therewith without substantially altering the favourable barrier pro ⁇ perties aimed at.
  • major water vapour and aroma barrier-for ⁇ ming agent in connection with the coating agent means that said poly(vinyl alcohol) based coating agent repre ⁇ sents more than 50% by weight, preferably more than 75% by weight and more preferably more than 85% by weight of the total weight of the coating materials used to cover the cellulosic material.
  • the particulate filler for the poly(vinyl alcohol) can be of any type or nature that is generally used in connection with poly(vinyl alcohol) or any other particu- late filler normally used for pigment coating.
  • a major feature of the filler to be used in the present invention is, however, that it is non-spherical, i.e. it has to be elongated, flat, flaky or similar, as it seems that some kind of mutual over-lapping arrangement of the filler is needed for obtaining the required moisture vapour trans ⁇ mission rate.
  • the aspect ratio which is defined as the ratio of average particle diameter to thickness of the filler, should preferably be at least 2:1.
  • the upper limit of said aspect ratio should not be critical to the invention, but generally said ratio is within the range of 2:1-300:1. According to a preferable embodiment thereof said ratio is 3:1-300:1, more prefer ⁇ ably 5:1-300:1, and most preferably 5:1-200:1.
  • the filler is a mineral pigment, especially preferred pigments being kaolin, talcum, chalk and marble (CaC0«), the two latter in a chemically precipitated form (such as precipitated CaC0 3 ).
  • cross-linking agent c As to the cross-linking agent c), it should be noted that the term cross-linking agent is used in a broad sense in connection with the present invention. Thus, it include- des an agent that can create covalent bonds between the linear chains of the poly(vinyl alcohol) to form a network structure as well as an agent that can create such a net ⁇ work by means of ionic bonds. Thus, said network formation can also be referred to as gelling or similar.
  • the first group of cross-linking agent creating cova ⁇ lent bonds is generally selected among agents which are previously known per se as cross-linking agents for poly- (vinyl alcohol), especially as thermal cross-linking agents which do not react to any appreciable extent until the temperature is raised above room-temperature.
  • a preferable group of cross-linking agents of this type for use in connection with the present invention is the group consisting of ammonium-zirconium carbonate, glyoxal, melamine-formaldehyde resins, urea-formaldehyde resins, dimers of alkylketone, epichlorohydrin-modified polyamides, and chromium compounds.
  • cross-linking agent is, thus, an agent selected from the group consisting of salt or ionic bond-forming substances which immobilize or gel the poly- (vinyl alcohol) coating agent. Depending on their reacti ⁇ vities they can be added together or admixed with the coa ⁇ ting agent (i.e. without any separate step B)) or in a se- parate step B).
  • borax e.g. in the form of a diluted aqueous so ⁇ lution (typically a 4% solution), which is generally used as a pre-coating, i.e. where step B) is performed before step A).
  • borax used as a pre-coating and as the only or major cross-linking agent imparts outstanding properties to the cellulosic material referred to.
  • Another agent of said second type is boric acid (a typical acid being a 1% aqueous solution thereof) which can be added together with a) and b), as well as in pre- and post-coating steps, but for said agent it will gene ⁇ rally be necessary to adjust the pH of the coating agent to an alkaline or basic one, e.g. at least pH 8, before the curing step C) is performed, to initiate the curing or gelling reaction.
  • a pH adjustment can e.g. be made by the addition of a base, such as Na 2 HP0 4 , or by using a buffer or acid-base system with a volatile acid, such as acetic acid, which is evaporated before step C) is fina- lized.
  • the mutual composition of the coating agent concerning poly(vinyl alcohol) to filler is essential to the invention, which means that said in ⁇ gredients a) and b) are present in a weight ratio of from 3:7 to 7:3.
  • a more preferred composition as to said two ingredients is when a) is present at 40-60, especially 42- 58, % by weight and b) is present at 60-40, especially 58- 42, % by weight, calculated as defined above, i.e. as so ⁇ lids contents based on the combined weights of a) + b).
  • the cross-linking agent c) is, as was mentioned above, present in an amount of not more than 7% by weight, also based on the solids contents and calculated on the combined weights of a) + b). On the same basis the per ⁇ centage of c) is generally within the range of 0.2-7% by weight, preferably 0,5-6% by weight and most preferably 1- 5% by weight.
  • Step C) of the process according to the present in ⁇ vention is preferably of a short duration, depending on the temperature, and often the duration or contact time is not more than 10 sees, very often at most 5 sees, prefer ⁇ ably at most 2 sees and most preferably at most 1 sec.
  • the above-mentioned duration or contact times are re ⁇ lated to a drying or curing temperature that is rather mo ⁇ derate, preferably at most 120°C, more preferably at most 105°C.
  • temperature is hereby meant the temperature which the coated material reaches during said drying and curing step.
  • Preferably said temperature is within the range of about 70-120°C, more preferably 70-105°C, such as 75-100°C.
  • the coating agent to be used in step A) is generally prepared in the form of an aqueous slurry in a conventio ⁇ nal manner, e.g.
  • the coating operation per se can be performed in a simple way and with a non-complex equipment.
  • step A) the coating or combined coatings of step A) are preferably performed to a dry surface weight of 2-30 g/m 2, especially 3-15 g/m2, per side of said coating agent. Generally this means that a coated end product is manufactured, which has a water vapour transmission rate
  • a product is manufactured having a water vapour transmission rate of at most 20,
  • test method used for determining the water vapour transmission rate is TAPPI Standard T 448 m-49, "Water
  • the process according to the present invention is preferably performed as a continuous operation where a running web of said material is surface coated in step A), optionally also with a separate step B), and then immedia ⁇ tely dried and cured in step C).
  • This operation can be performed in a step separate from the manufacture of the paper web or in direct connection therewith.
  • a novel coated material obtainable by the above-defined process is provided.
  • the coated material according to the present invention comprises a cellulosic based sub ⁇ strate, such as selected from the group consisting of paper, board, paperboard and similar materials, said ma ⁇ terial having water vapour and aroma barrier characteris ⁇ tics as well as repulpability properties, which coated material is characterized in that the coating layer(s) thereof has (have) been obtained essentially from a coa ⁇ ting agent comprising: a) poly(vinyl alcohol) b) a non-spherical particulate filler, preferably having an aspect ratio, i.e.
  • a ratio of average particle diameter to thickness, of at least 2:1 and c) a cross-linking agent for said poly(vinyl alcohol), a) and b) being present in a weight percentage of 30- 70% and 70-30%, respectively, and c) being present in a weight percentage of at most 7%, all percentages being calculated as solids contents based on the combined weights of a) + b), said coating agent forming a cross- linked layer having water vapour and aroma barrier cha ⁇ racteristics as well as repulpability properties.
  • a third aspect of the invention relates to the coa ⁇ ting agent per se, i.e. a coating agent for a cellulosic based material, such as selected from the group consisting of paper, board, paperboard and similar materials to im ⁇ part thereto water vapour and aroma barrier characteris ⁇ tics while retaining the repulpability properties thereof, the characterizing features of said coating agent being the same as have been defined above in connection with the process aspect of the invention.
  • a coating agent for a cellulosic based material such as selected from the group consisting of paper, board, paperboard and similar materials to im ⁇ part thereto water vapour and aroma barrier characteris ⁇ tics while retaining the repulpability properties thereof, the characterizing features of said coating agent being the same as have been defined above in connection with the process aspect of the invention.
  • a novel use is provided, viz. the use of a coated material whenever prepared as defined in connection with the process aspect of the invention or as defined in con ⁇ nection with the coated material aspect of the invention, as a waste paper to be recycled directly to a pulper of a paper, board or paperboard production line.
  • directly generally means that there is no separation or other pretreatment step needed before the coated material can be utilized in a pulper of such a line.
  • Said figure shows a supply roll 1 for a paper sub ⁇ strate from which a web 2 of said paper substrate is un ⁇ wound.
  • Said runnig web 2 then passes via guide rolls 3 through a coating station 4, which is a common flexography coater with three coating rolls 5 and a backing roll 6 and over three separate heated drying cylinders 7 and via fur ⁇ ther guide rolls 3 onto a rewind roll 8. Close to the first one of the three heated cylinders 7 there is also an IR drier 9.
  • the coating process comprises applying the coa ⁇ ting agent from the coating station 4 onto the running web 2 and curing the coated substrate by means of the IR drier 9 and post-drying the same by means of the drying cylin ⁇ ders 7, the coated and cured product then being wound onto the rewind roll 8.
  • the production speed was 75 m/min; the IR-drier in ⁇ creased the web-temperature from 22°C to 75°C; the web temperature after the third contact drier was 103°C; the temperature of the coating agent was 35°C; the solids con ⁇ tent of the coating agent was 33%; and the water vapour transmission rates were determined according to TAPPI T 448-m-49 (6 hours at 23°C, 50% humidity). All percentages are % by weight.
  • the coating agent was the following mixture: 44% of poly(vinyl alcohol) (PVA)
  • the coating weight was 5.0 g/m on one side of a sul-
  • Example 2 Same as Example 1 except a PVA with a molecular weight of 16 000.
  • the coating weight was 5.2 g/m .
  • Coating agent 30% of PVA (98%, 27 000 Mw) 70% of kaolin, delaminated 4.5% of AZC
  • Coating agent same as in Example 1 except that AZC was replaced by glyoxal.
  • Example 1 Paper: same as in Example 1 but after the application of the coating agent and before the curing operation the coated paper was treated with a 4% solution of borax in a separate operation.
  • Coating agent same as in Example 1
  • Coating agent same as in Example 1 but also with 1% of boric acid added. After the coating operation the coa ⁇ ted paper was treated with a 20% solution of Na ⁇ HPO ⁇ to increase the pH value of the coated paper to approximately
  • Coated papers as produced in Examples 1-10 were tes ⁇ ted for their repulpability in a laboratory desintegrator. After 30 000 revolutions hand sheets were formed and the fiber uniformity was evaluated visually. All papers proved to be fully repulpable.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Paints Or Removers (AREA)

Abstract

Traitement de matières cellulosiques, ces matières étant recouvertes d'un agent de revêtement comprenant: a) un alcool polyvinylique; b) une charge de particules non sphériques; et c) un agent de réticulation, les pourcentages en poids étant compris entre 30 et 70 % dans le cas de a), entre 70 et 30 % dans le cas de b), et ne dépassant pas 7 % dans le cas de c). Le traitement consiste ensuite à soumettre la matière recouverte à une opération de polymérisation, afin de former une couche barrière réticulée sur ladite matière cellulosique. L'invention se rapporte également à une matière recouverte, que l'on obtient à l'aide de l'agent de revêtement, ainsi qu'à l'agent de revêtement en soi et à l'utilisation de la matière recouverte comme papier de rebut destiné au recyclage direct dans un désintégrateur.
EP94917857A 1993-05-28 1994-05-26 Traitement de matieres cellulosiques Expired - Lifetime EP0702737B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
SE9301833 1993-05-28
SE9301833A SE502675C2 (sv) 1993-05-28 1993-05-28 Förfarande för behandling av cellulosamaterial för användning som omslags- och förpackningsmaterial, belagt cellulosamaterial samt användning av materialet
PCT/SE1994/000498 WO1994028243A1 (fr) 1993-05-28 1994-05-26 Traitement de matieres cellulosiques

Publications (2)

Publication Number Publication Date
EP0702737A1 true EP0702737A1 (fr) 1996-03-27
EP0702737B1 EP0702737B1 (fr) 1998-09-23

Family

ID=20390090

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94917857A Expired - Lifetime EP0702737B1 (fr) 1993-05-28 1994-05-26 Traitement de matieres cellulosiques

Country Status (8)

Country Link
EP (1) EP0702737B1 (fr)
AT (1) ATE171493T1 (fr)
AU (1) AU6939994A (fr)
DE (1) DE69413536T2 (fr)
FI (1) FI955719L (fr)
NO (1) NO954821L (fr)
SE (1) SE502675C2 (fr)
WO (1) WO1994028243A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4447348C5 (de) * 1994-12-31 2006-11-30 Remco-Chemie Rentzsch Gmbh Siebfüllmittel für Textil-, Film- und Siebdruckschablonen
DE69611645T2 (de) * 1995-09-22 2001-09-06 Oji Paper Co., Ltd. Feuchtigkeitsdichtes Papierblatt
FI124104B (fi) * 2011-05-11 2014-03-14 Upm Kymmene Corp Materiaali elintarvikkeen pakkaamiseksi sekä elintarvikepakkaus
FI125255B (fi) 2012-06-08 2015-08-14 Upm Kymmene Corp Menetelmä ja järjestelmä pakkausmateriaalin valmistamiseksi sekä pakkausmateriaali ja pakkaus

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA961714A (en) * 1965-04-05 1975-01-28 Saburo Imoto Method of improving the water resistance of paper
US3532534A (en) * 1967-02-09 1970-10-06 Us Plywood Champ Papers Inc Method of making a waterproof polyvinyl alcohol coated paper
US3711321A (en) * 1970-02-24 1973-01-16 Du Pont Rapid drying polyvinyl alcohol color coating process
AT395617B (de) * 1990-06-11 1993-02-25 Patria Papier & Zellstoff Verfahren zur verringerung der wasserdampfdurchlaessigkeit von papier oder pappe

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9428243A1 *

Also Published As

Publication number Publication date
EP0702737B1 (fr) 1998-09-23
SE9301833D0 (sv) 1993-05-28
FI955719A7 (fi) 1996-01-12
SE9301833L (sv) 1994-11-29
DE69413536D1 (de) 1998-10-29
NO954821D0 (no) 1995-11-27
FI955719L (fi) 1996-01-12
DE69413536T2 (de) 1999-04-08
AU6939994A (en) 1994-12-20
ATE171493T1 (de) 1998-10-15
FI955719A0 (fi) 1995-11-27
WO1994028243A1 (fr) 1994-12-08
SE502675C2 (sv) 1995-12-04
NO954821L (no) 1996-01-24

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