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WO1997013922A1 - Procede de fixation de fibres de cellulose - Google Patents

Procede de fixation de fibres de cellulose Download PDF

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Publication number
WO1997013922A1
WO1997013922A1 PCT/SE1996/001095 SE9601095W WO9713922A1 WO 1997013922 A1 WO1997013922 A1 WO 1997013922A1 SE 9601095 W SE9601095 W SE 9601095W WO 9713922 A1 WO9713922 A1 WO 9713922A1
Authority
WO
WIPO (PCT)
Prior art keywords
cellulose fibres
acid
polyethylene glycol
carboxylic acid
treated
Prior art date
Application number
PCT/SE1996/001095
Other languages
English (en)
Inventor
Ingegerd Hjorth
Original Assignee
Ab Klippans Finpappersbruk
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 Ab Klippans Finpappersbruk filed Critical Ab Klippans Finpappersbruk
Priority to AU72327/96A priority Critical patent/AU7232796A/en
Publication of WO1997013922A1 publication Critical patent/WO1997013922A1/fr

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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
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/001—Modification of pulp properties
    • D21C9/002—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives

Definitions

  • the present invention relates to a method of fixing cellulose fibres, primarily cellulose fibres in paper and board.
  • cellulose fibres is intended fibres in materials that contain cellulose fibres, such as solid wood, veneer, paper, paperboard, board, corru ⁇ gated fibreboard, and the like.
  • cellulose fibres in paper materials the expression paper materials being intended to comprise all types of mate ⁇ rials produced by depositing a starting material contain- ing cellulose fibres onto a support, such as deposition of stock on a wire or air-deposition of cellulose fibres on a wire.
  • the expression "cellulose material” thus com ⁇ prises paper as well as paperboard, board, corrugated fibreboard and similar two-dimensional products contain- ing cellulose fibres.
  • NO 149,415 describes treatment with heat and pres- sure to render wood dimensionally stable.
  • the treatment 4 HO ( CH 2 CH 2 0 ) n H ( I ) wherein n ⁇ 20 , and c) an agent crosslinking the polyethylene glycol.
  • the carboxylic acid has 1-8 carbon atoms and more preferably it is chosen from the group consist ⁇ ing of formic acid, acetic acid, propionic acid, oxalic acid, maleic acid, citric acid, thioglycol acid, acetic acid being the most preferable carboxylic acid.
  • cellulose fibres It is preferable to treat the cellulose fibres with about 3-15% by weight of carboxylic acid, calculated on dry cellulose fibres.
  • the cellulose fibres are treated with approximately 3-15% by weight, more preferably about 3-7% by weight polyethylene glycol, calculated on dry cellu ⁇ lose fibres.
  • the relative proportions of the carboxylic acid to the polyethylene glycol are not critical in accordance with the method of the invention, provided that the con- tents are within the ranges defined above, but preferably the weight ratio of carboxylic acid to polyethylene gly ⁇ col is from approximately 2:1 to approximately 1:2 and most preferably approximately 1:1.
  • the method in accordance with the invention is gene- rally carried out by first bringing the material contain ⁇ ing the cellulose fibre material into contact with the amine/silane complex rendering the cellulose material water-repellent.
  • CH 614,882 which relates to treatment of wood flour with an acid solution, such as oxalic acid, acetic acid, or salicylic acid, whereupon the wood flour is dried to dryness.
  • the treated wood flour is used as an insert between glass sheets for protection against oxidation.
  • the composi ⁇ tion may be used e.g. for treatment of paper.
  • the present invention has for its object to eli i- nate the disadvantages inherent in the prior-art techno ⁇ logy and to provide a treatment producing improved fixa ⁇ tion, i.e. dimensional stability, of materials containing cellulose fibres, primarily paper materials.
  • the object of the invention is achieved by treating the cellulose fibres with a carboxylic acid and a poly ⁇ ethylene glycol that is crosslinked.
  • the invention thus provides a method of fixing cel ⁇ lulose fibres, which is characterised by treating the cellulose fibres, in sequence, with a) a carboxylic acid, optionally in combination with an inorganic acid, b) a polyethylene glycol having the general formula ( I ) 6 ethylene glycol to be immobilised and fixed in the mate ⁇ rial containing the cellulose fibres.
  • a carboxylic acid optionally in combination with an inorganic acid
  • a polyethylene glycol having the general formula ( I ) 6 ethylene glycol to be immobilised and fixed in the mate ⁇ rial containing the cellulose fibres Various crosslink ⁇ ing agents that may be used with polyethylene glycols are known to the expert in the field and there is no need for an extensive enumeration of the crosslinking agents of this kind.
  • a preferred group of crosslinking agents to be used in connection with the present invention is a group consisting of ammonium-zirconium carbonate, glyoxal, and epichlorohydrine-modified polyamides. Especially good results have been achieved with ammonium-zirconium car ⁇ bonate.
  • the amount of crosslinking agent to be used is the one that suffices to crosslink the polyethylene gly ⁇ col. Usually an amount of at most approximately 0.5% by weight, calculated on the polyethylene glycol, is suffi- cient and preferably the amount of crosslinking agent is in the range of approximately 0.1-0.5% by weight.
  • the polyethy ⁇ lene glycol any suitable method may be used that will bring the cellulose fibres into intimate contact with the reagent.
  • the contact is preferably established in con ⁇ nection with the very production of the paper material by adding the carboxylic acid and the polyethylene glycol to the stock, or at an earlier stage of the process. How ⁇ ever, it is likewise possible, although less preferable, to treat the finished paper material by coating or spray ⁇ ing it with the carboxylic acid and the polyethylene gly ⁇ col. The treatment may be carried out batchwise but a continuous treatment is preferred.
  • the con ⁇ tact preferably is effected by way of impregnation, the material being immersed in the carboxylic acid and the polyethylene glycol, respectively.
  • the carboxylic acid and the polyethylene glycol are applied carboxylic acid, preferably in the form of an aqueous solution, and the polyethylene glycol is added when the acid has been allowed to work for a sufficient length of time, preferably about 1-30 min, more preferably about 10-15 min. It has then been found according to the inven ⁇ tion that the order in which the material is treated with carboxylic acid and polyethylene glycol is critical.
  • the material containing the cellulose fibre material is first treated with carboxylic acid and only thereafter with polyethylene glycol. If the order is changed, for instance such that the material containing the cellulose fibre is first treated with polyethylene glycol and then with carboxylic acid or simultaneously with carboxylic acid and polyethylene gly- col, the desired fixation and dimension stability of the cellulose fibres are not achieved.
  • the treatment with carboxylic acid preferably is carried out in combination with an inorganic acid. It seems that the inorganic acid acts as a catalyst, accelerating the effects of the carboxylic acid. If an inorganic acid is used, it is preferably add ⁇ ed at the same time as the carboxylic acid. However, the inorganic acid could also be added prior to or after the carboxylic acid, although in the latter case the inorga- nic acid must be added prior to the treatment with poly ⁇ ethylene glycol.
  • the inorganic acid may be chosen from a variety of different inorganic acids, such as sulphuric acid, hydrochloric acid, nitric acid. Sulphuric acid is particularly preferred.
  • the amounts of inorganic acid to be added preferably are approximately 0.3% by weight at the most, preferably about 0.1-0.3% by weight and more preferably about 0.2% by weight, calculated on the amount of carboxylic acid.
  • the latter is crosslinked in accordance with the invention with a polyethylene gly ⁇ col crosslinking agent.
  • the crosslinking causes the poly- 8 means of the carboxylic groups of the carboxylic acid.
  • an inorganic acid such as sulphuric acid, is added in addi ⁇ tion to the carboxylic acid this inorganic acid acts as a catalyst accelerating the opening-up of the cellular structure of the cellulose-containing material.
  • the treatment of the fibre with poly ⁇ ethylene glycol becomes an efficient one and is not restricted to being a treatment affecting the surface of the cellulose fibre but one that also penetrates into the interior of the cellulose fibre. It is assumed that the polyethylene glycol is attached by being bonded to the free hydroxyl groups of the cellulose fibres. Because the polyethylene glycol penetrates into the fibres and is bonded to them via hydroxyl groups, the polyethylene gly ⁇ col is fixed in a stable manner to the cellulose fibres. In addition, the polyethylene glycol is fixed through crosslinking with the aid of a crosslinking agent, as described in the foregoing.
  • a cellulose fibre is created which is essentially unaffected by changes in the ambient moisture conditions, i.e. the cel ⁇ lulose fibre becomes fixed or dimensionally stable.
  • the strong fixation of the polyethylene glycol in accordance with the invention differs from prior-art treatments of material containing cellulose fibres with polyethylene glycol, in accordance with which the polyethylene glycol was applied to the surface of the fibre from whence it could easily be removed.
  • the second component is a polyethylene glycol.
  • the method in accordance with the invention thus cannot be carried out by using other polyalkylene glycols, such as polypropy- lene glycol, as the second component. The reason therefor is not clear.
  • the treatment reagent is present in liquid or gaseous form, preferably in liquid form.
  • the temperature and the pressure of the treatment of the cellulose fibres with carboxylic acid and polyethy ⁇ lene glycol are not critical but for economical reasons the treatment preferably is carried out at ambient tempe- rature and ambient pressure. Some increase of the tempe ⁇ rature, for instance to approximately 40-80°C, may in ⁇ crease the reactivity and make the treatment more effi ⁇ cient, but in order to avoid evaporation of the reagent the temperature should not exceed approximately 100°C.
  • the pressure may be increased to above the atmospheric pressure, for instance up to approximately 20 bar, e.g. to approximately 5-10 bar, in order to render the treat ⁇ ment more efficient, for instance in the impregnation of wood.
  • both the carboxylic acid and the polyethylene gly ⁇ col are essential components.
  • the carboxylic acid component acts as a reagent that attacks the cellulose fibre, "opening" it up and thus making it accessible to treatment with the polyethylene glycol.
  • the carboxylic acid is then assumed to produce holes in the cell wall of the cellulose fibre and to be bonded to hydroxylic groups of the cellulose fibre.
  • the bonds to the hydroxylic groups are in the form of ester bonds by 10 all specifications related to percentage and proportions are by weight unless otherwise specified.
  • a slurry of cellulose fibres consisting of approximately 1800 kg sulphate pulp of softwood and water having a cellulose fibre concentration of approximately 10% by weight were added, with stirring, in a pulper of brand Grubbens, 5% by weight of acetic acid and, as a catalyst, 0.2% by weight, calculated on the acetic acid, of sulphuric acid.
  • the mixture was stirred thereafter at 225 rpm for about 15 min, whereupon the pH value was increased to 7.0 by means of NaOH, whereafter 3% by weight of polyethylene glycol having a molecular weight of approximately 200, (i.e. n is approximately 4 in For- mula I) was added.
  • To the mixture was also added 0.2% by weight, calculated on the amount of polyethylene glycol, of ammonium zirconium carbonate as a crosslinking agent.
  • the sheets were placed in a water bath having a temperature of 20 ⁇ 2°C and were left in the bath for 10 min. The sheets were thereafter removed from the water bath and a rubber roller was manually rolled backwards and forwards across the A4 sheets.
  • the swelling in percentage was measured in the cross direction and considered as a measurement of the any type of polyethylene glycol but, as already mention ⁇ ed, the polyethylene glycol should have a degree of poly ⁇ merisation below approximately 20. When a polyethylene glycol having a degree of polymerisation above 20 is used, the fixation of the cellulose fibre will be unsa ⁇ tisfactory.
  • poly ⁇ ethylene glycol having a degree of polymerisation above 20 has a molecular size that is too large to allow the molecules to efficiently penetrate into the cellulose fibre.
  • Optimum function is, as already mentioned, obtained with polyethylene glycol having a degree of polymerisation of approximately 3-20, most preferably about 4-9.
  • the present invention is useful generally for fixing cellulose fibres of all types of materials containing cellulose fibres
  • the invention is particu ⁇ larly useful for fixing the cellulose fibres of paper material.
  • Materials of this kind conventionally are pro ⁇ **d from paper pulp that is prepared into stock which is dewatered on a wire on which the desired paper product is formed.
  • the paper pulp could for instance be of sulphite type, sulphate type, recycled pulp or mixtures thereof.
  • the method in accordance with the invention is applicable to all types of paper pulp. In the manufacture of paper the method in accordance with the invention typically is carried out by adding the carboxylic acid in the pulper to which the polyethylene glycol is likewise added.
  • Example 1 The procedure of Example 1 was repeated, with the exception that the acetic acid was replaced by 5% by weight of formic acid. The following results were obtain- ed when determining the dimensional stability of the sheet.
  • Example 2 The procedure of Example 1 was repeated, with the exception that the fibre slurry consisted of sulphate pulp of hardwood and that the acetic acid was replaced by 5% by weight of formic acid. The following results were obtained when determining the dimensional stability of the sheet.
  • Example 7 The procedure of Example 1 was repeated, with the exception that the fibre slurry consisted of recycled pulp and that the acetic acid was replaced by 5% by weight of formic acid. The following results were obtained when determining the dimensional stability of the sheet.
  • Example 1 The procedure of Example 1 was repeated, with the exception that the fibre slurry consisted to 20% by weight of sulphate pulp of softwood and to 80% of sul- phate pulp of hardwood and that the acetic acid was replaced by 5% by weight of formic acid.
  • the following results were obtained when determining the dimensional stability of the sheet. dimensional stability. It is easily understood that the lower the percentage of swelling of the sheet, the higher the dimensional stability of the sheet. The results which are the mean value from measurements on three sheets, are indicated below.
  • Example 1 The procedure of Example 1 was repeated, with the exception that the slurry of cellulose fibre consisted of sulphate pulp of hardwood instead of sulphate pulp of softwood. The following results were obtained when measuring the dimensional stability.
  • Treated sheet Untreated sheet Change, in % 0.14 0.58
  • Example 1 The procedure of Example 1 was repeated, with the exception that the slurry of cellulose fibre consisted of recycled pulp. The following results were obtained when determining the dimensional stability of the sheet.
  • Example 4 The procedure of Example 1 was repeated, with the exception that the fibre slurry consisted to 20% of sul ⁇ phate pulp of softwood and to 80% of sulphate pulp of hardwood. The following results were obtained when deter ⁇ mining the dimensional stability of the sheet.
  • Treated sheet Untreated sheet Change, in % 0.18 0.62 14
  • Example 2 The procedure of Example 1 was repeated, with the exception that the fibre slurry consisted to 20% of sul ⁇ phate pulp of softwood and to 80% of sulphate pulp of hardwood, that the polyethylene glycol had a molecular weight of approximately 400, and that no sulphuric acid catalyst was added. The following results were obtained when determining the dimensional stability of the sheet.
  • Example 1 The procedure of Example 1 was repeated, with the exception that the polyethylene glycol having a molecular weight of approximately 200 was replaced by a polyethy ⁇ lene glycol having a molecular weight of approximately 1000 (i.e. n is approximately 22 in Formula I).
  • n is approximately 22 in Formula I.
  • the fol ⁇ lowing results were obtained when determining the dimen ⁇ sional stability of the sheet.
  • Example 1 The procedure of Example 1 was repeated, with the exception that no polyethylene glycol was used.
  • Example 1 The procedure of Example 1 was repeated, with the exception that the polyethylene glycol having a molecular weight of approximately 200 was replaced by a polyethy ⁇ lene glycol having a molecular weight of approximately 400 (i.e. n equals approximately 9 in Formula I). The following results were obtained when determining the dimensional stability of the sheet.
  • Example 2 The procedure of Example 1 was repeated, with the exception that the fibre slurry consisted to 20% of sul ⁇ phate pulp of softwood and to 80% of sulphate mass of hardwood, and that the polyethylene glycol having a mole- cular weight of approximately 200 was replaced by a poly ⁇ ethylene glycol having a molecular weight of approximate ⁇ ly 400.
  • the following results were obtained when deter ⁇ mining the dimensional stability of the sheet.
  • Example 2 The procedure of Example 1 was repeated, with the exception that the fibre slurry consisted to 20% of sul ⁇ phate pulp of softwood and to 80% of sulphate pulp of hardwood, that the polyethylene glycol had a molecular weight of approximately 400 and that as a crosslinking agent was used 0.2% by weight of glyoxal, calculated on the amount of polyethylene glycol, instead of ammonium zirconium carbonate. The following results were obtained when determining the dimensional stability of the sheet. 16
  • Treated sheet Untreated sheet Change in % 0.68 0.68 As appears from these values no improvement of the dimensional stability was obtained when the polyethylene glycol was replaced by spent liquor.
  • Example 1 The procedure of Example 1 was repeated, with the exception that no acetic acid or sulphuric acid were used. The following results were obtained when determin ⁇ ing the dimensional stability of the sheet.
  • Treated sheet Untreated sheet Change in % 0.68 0.68 As appears from these values the dimensional stability was not improved in the absence of carboxylic acid.
  • Example 1 The procedure of Example 1 was repeated, with the exception that the polyethylene glycol was replaced by a polypropylene glycol having a molecular weight of approximately 400. The following results were obtained when determining the dimensional stability of the sheet.
  • Example 1 The procedure of Example 1 was repeated, with the exception that the polyethylene glycol having a molecular weight of approximately 200 was replaced by spent liquor. 18 fibres are treated with about 3-15% by weight of poly ⁇ ethylene glycol, calculated on dry cellulose fibres.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Paper (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)

Abstract

La présente invention concerne un procédé servant à fixer les fibres de cellulose et à leur conférer la stabilité dimensionnelle. Elles sont incluses dans une autre matière, de préférence du papier. Le procédé selon l'invention comprend tout d'abord un traitement des fibres de cellulose avec un acide carboxylique, de préférence combiné à un acide minéral tel que l'acide sulfurique, après quoi elles sont traitées avec un polyéthylèneglycol qui est ensuite réticulé au moyen d'un agent de réticulation approprié. La proportion d'acide carboxylique est de préférence d'environ 3 à 15 % en poids par rapport aux fibres de cellulose sèches, et la proportion de polyéthylèneglycol est de préférence d'environ 3 à 15 % en poids sur la même base. L'acide carboxylique est de préférence l'acide acétique et le polyéthylèneglycol a de préférence un poids moléculaire d'environ 200 à 400. Dans le traitement de papier, on peut ajouter l'acide carboxylique et le polyéthylèneglycol à la pâte en commençant par l'acide carboxylique, le polyéthylèneglycol suivant environ 1 à 30 minutes plus tard.
PCT/SE1996/001095 1995-10-09 1996-09-04 Procede de fixation de fibres de cellulose WO1997013922A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU72327/96A AU7232796A (en) 1995-10-09 1996-09-04 Method of fixing cellulose fibres

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE9503483-1 1995-10-09
SE9503483A SE9503483L (sv) 1995-10-09 1995-10-09 Sätt att fixera cellulosafibrer

Publications (1)

Publication Number Publication Date
WO1997013922A1 true WO1997013922A1 (fr) 1997-04-17

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Application Number Title Priority Date Filing Date
PCT/SE1996/001095 WO1997013922A1 (fr) 1995-10-09 1996-09-04 Procede de fixation de fibres de cellulose

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AU (1) AU7232796A (fr)
SE (1) SE9503483L (fr)
WO (1) WO1997013922A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6994770B2 (en) 2002-12-20 2006-02-07 Kimberly-Clark Worldwide, Inc. Strength additives for tissue products
US7147751B2 (en) 2002-12-20 2006-12-12 Kimberly-Clark Worldwide, Inc. Wiping products having a low coefficient of friction in the wet state and process for producing same
US20100096096A1 (en) * 2007-04-30 2010-04-22 Jose Luis Egiburu Use of an additive for the production of decorative paper

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3674632A (en) * 1968-09-10 1972-07-04 Johan Jakob Wennergren Process for moisture stabilizing cellulosic sheet material using a polyoxyalkylene glycol and a polyoxyethylene-oxypropylene glycol block polymer
US4291101A (en) * 1978-08-11 1981-09-22 Nippon Oil And Fats Co., Ltd. Wood fibrous material and a method for improving the qualities thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3674632A (en) * 1968-09-10 1972-07-04 Johan Jakob Wennergren Process for moisture stabilizing cellulosic sheet material using a polyoxyalkylene glycol and a polyoxyethylene-oxypropylene glycol block polymer
US4291101A (en) * 1978-08-11 1981-09-22 Nippon Oil And Fats Co., Ltd. Wood fibrous material and a method for improving the qualities thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6994770B2 (en) 2002-12-20 2006-02-07 Kimberly-Clark Worldwide, Inc. Strength additives for tissue products
US7147751B2 (en) 2002-12-20 2006-12-12 Kimberly-Clark Worldwide, Inc. Wiping products having a low coefficient of friction in the wet state and process for producing same
US20100096096A1 (en) * 2007-04-30 2010-04-22 Jose Luis Egiburu Use of an additive for the production of decorative paper

Also Published As

Publication number Publication date
SE9503483D0 (sv) 1995-10-09
SE503887C2 (sv) 1996-09-23
AU7232796A (en) 1997-04-30
SE9503483L (sv) 1996-09-23

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