CA1134564A - Modified fibers - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Novel cellulose-containing fibers are provided herin. The fibers are sulphate pulp fibres, sulphite pulp fibres, semi-chemical pulp fibres, chemi-mechanical pulp fibres, thermo-mechanical pulp fibres or mechanical pulp fibres, or waste paper or waste cardboard fibres or fibre bundles, saw dust, wood chip, shavings, wood wool or synthetic cellulose fibres. The fibres are impregnated with an impregnating agent which is silicon oxide acylates, metal oxide acylates (of, e.g.
aluminum, titanium, copper, zinc, antimony, chromium, iron, manganese or zirconium) or a biocidally-active metal compound of a metal e.g.
copper, mercury, chromium, tin and zinc with a salt in a metal organic compound or mixtures of both. These novel cellulose-containing fibers, asbestos fibers, especially in composite materials with cement as a binder.

Description

~13~it~

The present invention relates to cellulose-containing fibres.
Such cellulose-containing fibres have novel properties and novel fields of application.
An object of a main aspect of the present invention is to pro-vide Eibres which can be used as substitution for inorganic fibres in various types of products, and especially, one aspect of the invention is to provide cellulose-containing fibres which can be used as substitute for asbestos in products conventionally conta:ining asbestos, e.g. asbes-tos cement products and brake linings, packings, gaskets seals and washers.
An object of another aspect of this invention is to provide modified cellulose fibres having an increased dimensional stability, i.e.
a minimizing of the tendency of the cellulose-containing fibres to swell under the influence of water. For many purposes where the modified cellulose-containing fibre is to substitute asbestos, it is also desired that it shows a high degree of resistance to deterioration, which means that the modified cellulose-containing fibres should be sufficiently im-pregnated against biodegradation.
By one broad aspect of this invention, cellulose-containing fibres are provided which are selected from the group consisting of sulphate pulp fibres, sulphite pulp fibres, thermo-mechanical pulp fibres and mechanical pulp fibres, or waste paper or waste cardboard fibres or fibre bundles, saw dust, wood chip, shavings, wood wool or synthetic cellulose fibres, the fibres being impregnated with at least one im-pregnating agent selected from the group consisting of silicon oxide acylates, metal oxide ~ -1- ~

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., acylates and a biocidally-active metal compound of a metal selected from the group consisting of copper, mercury, chromium, tin and zinc.
The metal in the mekal oxide acylate includes metals selected from the group consisting of aluminum, titanium, copper, zinc, antimony, cromium, iron, manganese, and zirconium.
The non-metallic portion of the biocidally-active metal com-pound is selected from salts or metal organic compounds or mixtures thereof.
The cellulose containing fibres of one important variant of the present invention are e.g. pulp ibres, sulphate pulp fibers, sul-phite pulp fibres, semi-chemical pulp fibres, chemimechanical pulp fibres, thermomechanical pulp fibers and mechanical pulp fibres, for exam~le prepared - la -, ~' .

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frol~ soft wood or hard wood, straw or bark~ By another variant, the pulp may be bleached or unbleached. By a further variant, the pulp fibers may be in the form of discrete fibers (wet or dry), sheets, rolls~ granu-lates, bales or the like. Important cellulose conta~ning fibers of other variants of the present invention are waste ibers, for example waste paper or waste cardboard. ~owevar, it is also within the scope of other variants of the present invention that the cellulose-containing fibers be fiber bundles, saw dust, wood chip, shavings, wood wool, or synthetic.
cellulose fibers.
By another variant, the impregnating agent is a copper-chromium impregnatlng agent.
By a variation thereof, the impregnating agent is selected from the group consisting of copper naphthenate copper chromium acetate and copper chromium phosphate.
By a further variant~ the metal oxide acylate is a hydrophobizing metal oxide acylate.
By other variants, tha hydrophobi7ing metal oxide acylate is an aluminium oxide acylate or a titanium oxide acylate.
By a still further variant the metal oxide acylate is a biocidal-ly-active metal oxide acylate.
By a still further variant, the biocidally-active metal oxide acylate is a ~inc oxide acylate.
By yet a further variant, the biocidally-active metal oxide acylate and at least one of a hydrophobizing metal ozide acylate and a flame retarding metal oxide acylate.
By a still further variant the fibers also contain a polyelectro-lyte.
The cellulose-contalning fibers of aspects of the invention are thus characteri~ed by the fact that they are impregna~ed with at least

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one wood preservation agent. In the present context, the term "wood pre-servation agent" is used in its broad sense and comprises all the well~
known types of wood preservation agents, e.g. tar oils, water-borne salts, organic compounds, water repellents, stabilizers, and fire retardants. In other words, quite generally any agent which has been used for or is use-ful for lmproving the propPrties of cellulose-containing fibers or cellu-lose. The term is intended to comprise here not only such agents as have historically been used for wood preservation purposes, but also agents with similar or improved properties which have not been usecl so far, but which are useful ln that they are able to combine wi`th cellulose-containing fibers to yield an impregnated product with properties which are improved in desired regards. Such details concerning the wood preservation agents used according to other variants of the present invention are stated below.
The wood preservation agents used accorcling to various variants of the present invention may be of the same kind or similar to the im-pregnating agents normally used for the impregnation of wood, for example for preservation against biodegradation, for imparting fire resistance, for minimizing moisture content fluctuations9 etc.
The typical classes of wood preservation agents of variants of this invention are:
(a) tar oils, e.g. creosote, carbolineum (anthracene oil~, mix-tures of copper salts in carbolinium, combinations of zinc salts and creosote9 creosote containing ~mall amounts of ar-senic, or different sorts of ~ars, e.g. wood, peat, or shale tars, or petroleum;
~b) water-borne salts of e.g~ mercury, e.g. mercuric shloride, mixtures of mercuric chloride and copper sulphate with either zinc chloride or sodium fluoride, fluorine, e.g. mixed solu-tions of sodium fluoride and zinc chloride, Wolman salts (general~y considered to be formulations containing fluorine,

- 3 -~3'~5~i4 chromium, arsenic and phenol components (FCAP), or fluorille/
chromium/arsenic compounds ~FCA), æinc, e.8 basic ZillC salts, zinc chloride, chromated zinc ch:Loride (CZC), copperized CZC
(CCZC), copperr e. copper compounds e.g~ copper sulphate, copper/chromlum/boron (CCB) mixtllres, copper/chromiumJarsenic (CCA) mixtures, the composition of which is explained ln the examples, the so-called CCP mixtures wherein the arsenic con-tents of CCA has been replaced by phosphorous compounds, e.g~
that known by ~he Trade Mark of BOLIDEN P 50J arsenic, boron, e.g. ammonium borate, ammonium fluoroborates, or trlmethyl-borate, till, eOg. ~riorganotin compounds in emulsified or solubilised form e.g. triphenyltin,and tributyltin compounds, e.g. tributyltin oxide, or tin compounds together with sili-con, germanium or lead, (C) organic compounds, e.g. nltrated co~pounds, e.g. nitrated phenol, cresol, ~ylenol9 naphthol and anthranol, e.g. dini-tro-phenol or dinitro-o-cresol, chlorinated compounds, e.g.
chlorophenols, eOg. pentachloropheDol, chloxonaphthalenes, chlorobenzenes or hexachlorocyclohexane, e.g. that kno~m by the Trade Mark of LINDANE and that known by the Trade Mark of GAMMEXANE) cyclodiene insectle~des, e.g. that known by the Trade Mark of ~EPTACHLOR, that known by the Trade Mark of ALDRIN or that known by the Trade Mark of DIELDRIN~ organo-phosphorus, e.g. that known by the Trade Mark of MALATHION, phosphorous trlchloride, heavy metal salts of acid phosphate esters, carbamate compounds~ or pyrethroids, - 3 a -5~

or metal salts of organ-ic compounds, e.g. copper pentachloro-phenate, copper naphthen.lte, copper-8-hydroxyquinolate, zinc naphthenate or pentachlorophenate, tin naphthenate or mercury compo~mds, e.g. ethyl mercury chloride, sulphate, phosphate or acetate or phenol mercury acetate or preferably oleate, or the above-mentioned organo tin compounds in an organic solvent, d) water-repellent preservatives, e.g. waxes, resins, organosllicon or organoaluminum compounds, e) Eire retardants, e.g. salts or halogenated compounds, e.g.
- organophosphorus amides, phosphoryl ~rianilide (PTA), dimeric phosphoric anilanilide (DIP), tris(haloalkyl)phosphate, nitro--containing polyhydric alkanols, linear tertiary phosphine oxide polymers, ammonium polyphosphate, water soluble organic phosphorus esters and polyesters, ammonium derivatives o~
glyoxylic acid, acid sulphatés of aromatic nitroamino compounds, hexachlorocyclopentadiene c~ndensation pFoducts, phosphorus-and halogen-containing derivatives of diallyl;chlorendate ' ' phosphorus oxychloride, alkyl triatkoxy silanes (+~ceric oxlde i ~- (CeO2)), he~amethylphenyl siloxane (+ prehydrolyzed tetraethyl orthosllicate), lithium-sodium silicate solutlon, silicone sodium bicarbonate, alkalimetal glycol monoborates, magnesium ' oxychloride, tetrabromobisphenol and trixyleny:l phosphate, ~" ~ polyethylene and aluminum trihydrate or antimon compounds~
One particular class of compounds which have been Eound especially interesting as impregnation agents according to a special variant of the present invention'either alone or in combination with other wood preservation agents, are the so-called "metal oxide acylates", which is a class of compounds invented by Dr. Jaco'bus Rinse and disclosed for ~ example in Belgian Patent No. 555,969, Netherlands Patent No. 104,261, 3n U.S. Patent Noa. 3,087,949, 3,243j447~ 3,177,238, 3,518,287, 3,~25,934,

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5~4 3,5~6,262, 3,~34,~)74. ancl 3,673,229 and Belginn Patent ~o. 735,5~
and U.K. Patellt Nos. 1,230,4l2 an(l 1,274,71~. The metal oxide acylates are believed to be able to react chernlcally with the hydroxy groups of cellulose~conta-[nLng ~ibres, resulting Ln the attachment of a metal acylate grnup v:La an oxygen briclge. ~letal oxide acylates may be prepared Erom a variety of metals, and it is also possible to prepare metal oxide acylates containing more than one metal ln the molecule.
Hence, metal ox:Lde acylates may be tailored for the p-resent purpose as hydrofobizing agents (aluminum oxide acylates~ e.g. aluminum oxide tallate or aluminum oxlde stearate or tltanium oxide acylates, e.g.
titanium oxide versate and silicon oxide acylates), blocidal metal oxide acylates, e.g. copper oxide acylates and zinc oxide acylates, and fire-retardant metal oxide acylates, e.g. antimony oxide acylates. Further F
interesting metal oxlde acylates for the present purpose according to other variants are oxide acylates of chromium, iron, manganese, and zirconium.
By another variant, the fibers are impregnated with a bioci~ally active heavy metal compound and at least one oE a hydrophobizing and a t flame retarding metal oxide acylate.
The metal oxide acylates are generally soluble in organic solvents and may be formulated for impregnation as will be described hereinafter.
The impregnation agents used according to various aspects and variants of the invention are preferably so chosen that they are sub-stantially water-insolubly fixed in the fiber structure, if necessary by combination with a sepcarate agent improving the Eixation. For example, a water-borne salt impregnation may be combined with a hydrofobization with an effective hydrofobizing agent e.g. aluminum or titanium oxide acylate.

. . . ~

~ le present invention teaches a process for preparing the im-pregnated cellulose-conta~ning Elbers. The process disclosed hcrein com-prises impregnating cellulos&-conta:Lning fibels with at least one wood preservation agent by a vacuum and/or pressure impregnation technique.
This process may be performed ln a manner which is known per se in con~
nection with the wood preservation~ The cellulose-containing fibers to be impregnated may be in any desired form, e.g. granulates, sheets, rolls, bales or - when the fibers to be impregnated are waste fibers - simply in the form of paper waste or cardboard waste.
If the impregnation is performed in the same factory where the impregnated fibers are to be used in a wet process, the defibration can be performed immediately subsequent to the impregnation and without any in-termediary drying stages. The impregnated cellulose-containing fiber materials of aspects of the present inven~ion may be defibrated by conven-tional methods, for example wet defibration in a pulper, or dry defibra-tion.
The impregnation technique may also be combined with the prepara-tion of paper pulp of any kind, in which case, for axample, impregnation with water-borne salts may take place at a stage subsequent to taking up the pulp on the wire but prior to the drying. In this case, the equiva-lent of a vacuum/pressure treatment may be obtained by pressing the web to a low water content before it is passed through the impregnating bath.
Alternatively, impregnation in connection with paper production may of course be performed by impregnating a roll of dried pulp in one of the manners described above.
A further process taught herein for impregnating cellulose fi-bers especially in connection with the wet preparation of composite mater-ial is to carry out the impregnation in situ by means of an oil emulsion which has affinity for the cellulose fibers and in which the wood pre-~~~ - 6 -~3~
servation agent is dissolved in the oil. Thus, for instance, ln the pro-duct:Lon of cemen~-bound composite m~terlals wherein cellulose fibers as substitute for asbestos or other fibers are used dlspersed in water9 an oil emulsion of the above-mentloned type may be added to the fiber sus-pension prior to the addltion of the cement.
The impregnation may involve an initial evaporation stage followed by application of the impre&nation agent at normal pressure or at super atmospheric pressure. Alternatively the wood preservation agent may be ~
applied dissolved in a low-boiling organlc solvent at a temperature immedi-ately below the boiling point of the solvent.
The impregnation for the preparation of the fibers of aspects of the present invention may be carried out according to known procedures~
e.g. by spraying, rolling, dipping, squeezing, etc., but the preferred impregnation procedure is one or both of vacuum and pressure impregnation e.g. impregnation by pressure, in which the impregnating agent is intro-duced into the materlal by applying an external pressure, or vacuum im-pregnation, in which the fibers to be impregnated are first subjected to a vacuum, whereafter tbe impregnating agent is introduced into the material by releasing the vacuum and optionally applying superatmospheric pressure.
It is also possible to apply alternating pressure-vacuum steps so as to "pump" the impregnating agent through the material.
Depending upon the solubility characteristics of the impregnation agent, the i~pregnation may be performed by using an impregnating agent dissolved in a volatile solvent at a temperature just below the boiling point of the solven~. The solvent may, for example by methylene chloride, ethylene trichloride, lSl~l-trichloroethane, fluoro-trichloromethane, or the like. Impregnation by this procedure offers the advantage that the sol-vent is easily and quickly removed from the impregnated cellulose-con-taining fibers, thus substantially avoiding the fire hazard cf the use of - 7 ~
~ ,~

~3'~L56~

conventional hi~h-boiling flamm~ble solvents.
The amount of lmpregnating agent in the impregnated flbers of ~spects of the present invention is usally at least 1 percent by weight, calculated on dry fiber weight, and usually at l~ast 5 percen~
by weight and often 7 - 10 percent by weight.
By another aspect of this invention, a composite material is provided comprising the above described impregnated cell~lose~containing fibres and a binder material.
By variants thereof, the blnder i8 an organic polymer, or an inorganic binder, or a combination of inorganlc and organic binder.
By another variant, the composite material lncludes a poly-electrolyte.
Thus, it has been found, that the impregnation with suitable wood preservation agents imparts, to the cellalose-containin~ fibers9 imr proved properties with respect to their incorporation in a matrix con-taining an inorganic binder, e.g. cement~ This is believed to be the case especially for impregnation agents which are capable of reducing the inherent capability of the cellulose fibers to attach to each other via hydrogen bonds, which means that an effective test for assessing the suitability of a wood preservation agen~ for treatment of cellulose-con-taining fibers for the present purpose is to form a sheet of the impreg-nated cellulose fibers, dry the sheet and determine the strength of the sheet. The less bonding between the impregnated cellulose fibers in the~
resulting sheet~ the more inert is the impregnated fiber and, it is be-lieved, the more suitable for incorporation in inorganic blnder matrices and other purposes where the ~iber is to substitute inorganic fibers, e.g. asbestos.

_ ~ _ ~' .
~ .

~L3~5~fl~
One advantage of the impregnsted fiber of aspects of the present invention is that it can be used as a subgtitution for asbestos in exist-ing asbestos cement-producing machinery, e.g. the so called ~atschek and Magnani machinesl but the impregnated fibers of aspects ~ 8 a -., .
: .

~ 3 ~

of the present invention i.n the form of pulp fibers may also e.g. be incorporated in webs formed on a papermaking machine. Thus, one utility o.E the cellulose-containing fibers oE aspects of the present invention is their appliration as partially or completely inert fibers in the process described in Canaclian Patent Application No. 2~2,361. The ~iber according to various aspects of the prevent invention may be used to suhstitute, fully or in part~ the mineral fihers used in some of the compositions described in the said prior Canad:Lan application. For . example, the fibers according to the present invention impregnated with wood-preserving heavy metal compounds may 6e used for partial or complete replacement of the mineral fibers in the carpet or flooring backing compositions disclosed in the above-mentioned prior p~tent applications. Other composite materials in which mineral fibers can be wholly or partially replaced with the fibers of the present invention are roofing felt, wall paper, laminated boards, brake linings and other composite materials of the types disclosed in the above-mentioned prior applications, as well as similar composite materials prepared by other methods, including dry methods.

Tfie impregnated fihers of aspects of the present invention may also be used as replacement ior~glass fibers as reiDforcing fibers in composite materials with an organic binder matrix, e.g. polyester and epoxypolyester, In this case, a web or pli.es of the impregnated fibers made by either a dry or a wet method, may be formed usi.ng a sui~able ~. .

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binder, analogllously to tlle prep.~ t-lon o~ webs or plie9 products oE glass f:ibers.
When the fibers are incorporated in a composite material containing cement as binder, the cement content of the compo~site material will usually be in the range of 25 - ~ percent by weight, e.g. SQ - 90 percent by weight and often 80 - 90 percent by weight, and the amount of the impregnated cellulose fibers may typically be :L - 75 percent by weight, i more typically 5 - 50 percent by weight, and often lO - 20 percent by r weight of the composite material. The composite material may, in addition to a cement-binder, contain other lnorganic material e.g.
po~olana, for example in an amount of 2 - 20 percent by weight, ca]culated on the weight of the cement, fly ash, etc~
Other composite materials with an inorganic binder w1iich may be made using the impregnated Eibers of aspects of the present invention are materials in which the binder is a calcium silicate or plaster, and the relative amounts of these inorganic binders and the impregnated fibers may be the same as stated above in connection with cement-bound r composite materials.
Composite materials incorporating the impregnated fibers of aspects of the present invention may also contain both an inorganic binder and an organic binder. Especially su:itabIe organic binders for this purpose - are polymer materials constituted by so:Lid discrete particles or fibers having polymer at least at their surfaces, the polymer being a water-insoluble solid synthetlc polymer which is film-forming on heating, especlally such polymer materials which are disclosed in detail in the prior pending patent applications mentioned hereinabove. The amount of '~
such polymer in composite materials also containing an inorganic binder is usually l - 30 percent by~weight, calculated on the total weight of the composite material ~ccorclingly, a process Eor preparing a composite maeerial using the impregrlated fibers oE aspects oE the present LnventLon rllay comprise incorporating the impregnated cellulose fiber material dispersed in ~ater. When this process is used Eor preparing a composite material containing an inorganic binder, e.g. cement, the effective retention and flocculation of the system is, accord-Lng to aspects of the present invention, obtained by using a polyelectrolyte, in accordance with the principles disclosed in the prior pending patent applications mentioned hereinabove.
Tlle polyeLectrolyte is preferably of the neutral or cationic type.

Accordingly, one aspect of the present invention provides a composite material comprising the novel impregnated cellulose-containing fibers and additionally comprising a polyelectrolyte. A polyelectrolyte may also be a useful flocculation agent in composite materials of aspects , of the invention which use an organic binder, as taught in the disclosure of the prior pending applications mentioned hereinabove.
I~hen a polymer whicH is film-forming on heating is incorporated 1.
in the composite material also incorporating an inorganic binder, a suitable method of preparing such composite material comprises subjecting the resulting material, after the shaping in the desired configuration, E

to a treatment eliciting the film-forming properties of the polymer.
The treatment eliciting the film-forming properties of the polymer may be performed after the curing of the inorganic binder, or the treatment eliciting the film-forming properties of the polymer may be performed prior to curing of the lnorganic bînder, and, subsequently~to the eliciting oE the film-Eorming properties of the polymer, the amount of water necessary for curing the inorganic binder may be added, whereaEter the final curing may be perEormed. Another possibility is to combine curing of the inorganic binder and eliciting oE the film-Eorming properties of the polymer in one treatment, fo~ example in an autoclave, depending , ................................................................. .. ..

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upon the particular binder and polymer used.
I~hen composite materials using the impregnated fibers of aspects of the present invention and wit:h an inorganic binder hy ~ wet tnethod, another possibility Eor obtaining improved dispersion of the impregnated fibers is to use an oil as dispersing aid, possibly combined with the use of a polyelectroLyte. The oil may suitably be a non-drying oil which may be added to the Eibers in the Eorm of an emulsion.
In the present context, the term l'hydrophobizing agentl' is intended to designate not only agents wh:ich impart true hydrophobi-city to the treated fibers, but also agents which change the properties of the fibers in direction from hydlophi:licity towards hydrophobicity.
In the present context, the term llcementl' is intended to designateboth portland cement types and the other inorganic cement types."

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~3~5~4 The following examples teach varlous aspects and ~ariants of this inventlon.
Example 1.
U~bleached sulphate cellulose fibers in shset form were impregnated with a CCA agent that known by the Trade Mark BOLIDEN K-35 (composition: arsenic, chromium and copper compounds in quantitative ratios corresponding to As~05:
34.0% ~ 2%, CrO3: 26.6% - 1.5%, CuO: 14.8 - 1%, H20: 26.6~ - 4X) in two different ways:
I. The specimen was evacuated to about 60 mm Hg with a water let air pump and was left for 20 minutes ln the impregnating liquid~ whereafter the pressure was raised to atmospheric pressure and the specimen was left for a further 20 minutes.
II. The specimen was evacuated to approximately 60 mm Hg, and the pres-sure was again raised to atmospheric pressure. This cyclus was repeated 20 times within 20 minutes, whereafter the specimen was left for a further 20 minutes at atmospheric pressure in the impregnating liquid.
The water content of the fibers impregnated according to method I or II
was de~ermined by weighing during drying until constant weight at 105C~
The copper, chromium and arsenic contents were determined in the dried specimens. A known quantity of impregnated fibers of speciments I and II
were beaten, that is dispersed in water, by means of a blender. Specimens were taken out for washing out experiments. Washing out experiments were performed;on the beaten fibers impregnated according to method I or II by the following two methods:
A. Washing with hot water (30C) for 2 hours under simple stirrlng with a propeller, the fiber concen~ration being approximately 2 g/liter water.

JL~--J-~ ~J-~;

B. Washing at 20C for 24 hours with a calc.ium hydroxide solution at pH 12.0 under simp:Le stirring with a propeller, the fiber concen-tration being approxi.mately 10 g/liter sollltion.

After the washlng experiments, copper, chromium and arsenic contents were determined in both the washing liquids and the washed f ibers.

The water concents in specimens I and II and the resul-ts o:E
weighing of fibers are listed in the below Table I.

The.results of the determinations of the copper, chromium and arsenic contents are listed in the below Table II. The figures are in mg metal per g dry fiber used.

Table I. .

Fibers impregnated according -to Method I Method II
Water content in fibers 57.1% 58.9 Beating of specimens (moist) 100 g 50 g in water in 200 ml in 500 ml r In diluting the beaten specimens for the washings, there was cor-rected for the initial water content of the specimens, and hence, the below-listed concentratlons of fibers in washing liquid represent dry fibers.

Fiber concentration in the washing experiment.
.
Washing A 2.21 g/1000 ml 2.12 g/1000 ml Washing B 5.36 g/S00 ml 5~14 g/500 ml , ~ ",~ .. ., . ... , .. , . . . .. _ ,~ ~
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.. _.,,__ . _.. ............. , ..... . .___.

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The determination of the copper, chromiurn and arsenic contents in the fibers shows that the fibers were impre~nated equally according to -the two methods, and that there were the same proportions hetween copper, chromium and arsenic in -the fibers as in -the impregnating liquid. The total impreqnation corresponds to an uptake of salts of 8 ~ 9~ o the weight o the fibers.

In the washing experiments with wa~er according to method ~, part of the copper, chromium and arsenic contents :Ln the fibers was washed out, mostly from the fibers impregnated according to method I.

In the washing experiments with calcium hydroxide solution according to method B, practically no copper and little arsenic were washed out, whereas approximat~ely as much chromium was washed out as in the washing experimen-t A. ~s regards chromium, again most was washed out from the fibers which were impregnated according to me~
thod I. As regards copper and arsenic, the difference in washing out from the fibers impregnated according to method I or II was so little that it was within the uncertainty of the experiment.

Sheets of sulphate celluIose fibers impregnated with Boliden K 33 in the manner described above were defibrated ln water to yield 1/2~ suspension. The defibration required about 50~ more beating time than the defibration of corresponding untreated sheets. ~fter the defibration, the suspension was converted into sheets on a laboratory sheet former and dried in an oven at 100C. After the drying, the resulting sheets showed much less strength than cor-responding sheets made -From untreated starting fibers: the fibers of the sheets made from the impregnated material could easily be drawn from each other and showed virtually no coherency except that resulting from the entangling.

- ~
Example 2.

Scannin Electron Microsco (SEM) on Im regnated Fibers.
g ~ P

L3~
Various sorts o~ ~i.bers were imprc~gnated with various impregna-tion agents accorclin(J to various Illettlods, as stated in the below scheme, whereafter SEM was performecl on the fihers and t.he contents of S, Ca, Cr, Cu and As were determined by X-ray analysis.

The determinati.ons show that -there is no sicJniEicant difference between the degree of impregnation a-t the middle of the fibers, at -the surEace or in between,which indica-tes that the im~re~nating agent penetrates into ancl is evenly distributed in the cell and no-t only impregnates the surface.

o Experiments 6 and 7 show the effec-t of pressure impregnation.
Experiments 4 and 6 show that the impregnation is improved if the specimen is evacuated before the pressure influence, and the .
experimen-ts 1 and 4 indicate that the impregnation is improved to a higher extent by application of longer acting evacuation than by ap-plication of a higher pressure after the evacuation. r ~, 3~i6 o n ,~
~1 LD t~ r`J t~) O ~J' O O O O O ~ t~) t~ t~ ' t`J O O (~1 ~D O O O
tn r~ tl~ ) L~ r ~D ~1 0 ~ ~
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rl r-l N ~ ~r Ln ID ~D 1-- }C ~; _ Example 3.
Strips of filter material made of bleached sulphate cellulose were dipped for one second in a solution of 7 parts by weight of FRIGEN Sll (the trade mark for a brand of fluorotrichloromethane) and 1 part by weight of metal oxide acylate containing 30% of white spirltO The strips were dr1ed in an oven at 100C for one hour. The metal oxide acylates used were titanlum oxidc stearate (D-14-00), zinc oxide versate (E-12-80~ containing only 20~ of white spirit) 9 aluminum oxide phthalate (C-10-70), alu~inum oxide stearate (C-14-70) and aluminum oxide stearate/phthalate (C-10/14-70), all supplied by MOACO S.A., Echallens, Switzerland. The impregnated paper strips, with the exception of the strlps treated with zinc oxide versate, showed hydrophobicity, especially the specimen impregnated with titanium oxide stearate, and all the impregnated paper strips, lncluding the zinc oxide versate-treated strip, showed less elongation upon dipping in water than the controls.
The strips were defibrated by beating in water in a blender. The zlnc oxide versate-treated strip was defibrated as easily as the untreated strips, whereas about 50% longer treating time was required for the defi- `
bration of the other metal oxide acylate-treated strips~ After the de-fibration, the pulp of aluminum oxide phthalate-treated fibers was con-verted into a sheet in a laboratory sheet former~ and the sheet was dreid in an oven at 100C for one hour. The resulting dried sheet showed con-siderably less str~ngth than a corresponding sheet made of untreated fi-bers, indicating little or no chemical bonding between the fibers.

Example 4.
The sheet of BOLIDEN K-35 impregnated fibers made in a laboratory sheet former and thereafter dried ~vide Example 1) was dipped into a soll1tion of 1 part of titanium oxlde stearate (D-14-00 from ~OACO S.A.) in 7 parts of FRIGEN Sll for one second. Thereafter, the fibrous ~ass was dried in - lg -W ,~ .

~L3~ 6~

an oven at 100C for one hour. After the drying, the ~aterial showed ex-cellent hydrophobic properties, in contrast to the BOLIDEN K-33-impregna-ted fibers which had not been treated with titanium oxide stearate.

Example 5.
Sulphate cellulose pulp was lmpregnated with BOLIDEN K 33 as described in Example 1~ method I. The impregnated fibers had a salt content of 5% by weight. The resulting impregnated sheet of fiber pulp was defibrated in a blender and, to the defibrated suspension in a quantlty corresponding to 40 g of dry material conslsting of impregnated fibers was added 160 g of cement (super rapid). The quantity of water present was such that the total content of dry matter, cement ~ fibers, was approximately 1/2% by weight.
The suspension was poured into the chest of a sheet former, and immediate-ly before the water was suctioned off, a polyelectrolyte was added in a quantity of 0.04%, calculated on the dry matter. The polyelectrolyte was, one run,the polyelectrolyte known by the Trade Mark PRODEFLOC CL and, in another run,the polyelectrolyte known by the Trade Mark PRODEFLOC NZM.
By suction of the water, a sheet was produced having a thickness of approximately 3 mm. The sheet was le~t for curing in a plastic bag which was closed so that no water could evaporate from the specimen. After curing, the board was judged to have a tensile strength about equal to that of conventional asbestos cement.

Example 6 Using the same process as described in Example 5, but using 80 g of im-pregnated fibers, calculated as dry matter, in~tead of 40 g of impregnated fibers, a board having a thickness of 12 mm was produced.

-~ ~ - 20 -.. . . . .

13~

Example 7 Using the same process as described in Example 5, but using 160 g of dry matter consisting of impregnated fibers instead of 40 g of dry matter con-sisting of lmpregnated fibers, a board having a thickness of 20 mm was produced, which board had the character of a fiber board. The dewatering was in this example somewhat slower than in Examples 5 and 6.

Example 8 The process described in Example 5 was followed, but additionally, 5% by ;
weight of epoxypolyester powder, calculated on the total dry matter, was added together with the cement. After one day of curing in a plastic bag, the board was removed and placed for drying at 100C in an oven, and when the board had dried to constant weight, the temperature was raised to 200~C, and the board was kept for 2 minutes at 200C. After cooling, the board was moistened again so that the cement could continue curing. After cur-ing, the board had an excellent tensi]e strength and a tight, smooth and beautiful surface. A similar experiment was performed using a smaller amount of water, YiZ. a water/cement rati~ of approximately 50. A similar excellent result was obtained.

Example 9 Dry sulphate cellulose pulp (approximately 5 g) was soaked with colourless SOLIGNUM ULTRA (the trade mark for a wood preservation agent based on oil binders and fungic~des) by dipping, exce6s impregnating liquid ~as squeezed out manually, and the pulp was immediately thereafter beaten in water in a blender. The defibrated pulp was dewatered by manual pressing and was mixed with approximately 20 g of cement (super rapid) to which was added about 10 g of water. The fibers were easily dispersed homogeneously in the cement and the resulting pulp W8S soft and plastic without lumps.

~L3~S~i~

E~ample lO.
Dry sulphate ce]lulose pulp (about 5 g) was soaked wlth silicon oil by dipping, e~cess oil was squeezad out manually and the pulp was immediately thereafter beaten in water in a blender. The pulp was easily deibrated, and the fibers were dewatered by manual pressin~ and were blended with approximately 20 g of cement (super rapid), to which was added approximately lO g of water. The fibers were easily dispersecl homogenously in the ce-ment matrix, and the resulting pulp was soft ancl plastic without lumps.

Example 11.
A piece of cardboard (approximately S g) was soaked with colourless "BON-DEX" (the trade mark for a wood preservation agent based on oil binders and fungicides) by dipping, excess impregnation liquid was squeazed out manually, and the pulp was immediately thereafter beaten in water in a blender. The pulp was easily defibrated, the fibers were dewatered by manual pressing and were mixed with approximately 20 g of cement (super rapid), to which was added approximately lO g of water. The fibers were easily dispersed homogenously in the cement matrlx, and the resulting pulp was poured into a mould and left for drying. After 5 days of curing, t~e reinforced cement board had a thickness of approximately 1 cm, had high strength, and in the microscope, fractured surfaces showed homogenous dis-tribution of the fibers.

Example 12.
Sulphate cellulose pulp was impregnated with BOLIDEN K 33 as described in Example 1, method I. The impregnated fibers had a salt content vf 5~ by weight. The resulting impregnated sheets of fiber pulp were defibrated in a blender and the defibrated suspension in a quantity corresponding tc 8.5 g of dry material ~ - 22 consisting of impregnated fibers was admixed with 66.5 g of cement (rapi.d), 30 g of amorphous silica (fly ash from the production of ferrosilicon) and 5 g of a powder of epoxypolyester (55% by weight) applied on 43~ by weight of TiO2/2~ by weight of BaSO4, particle size 30 - 80/u. Water was added so that the concentration of dry matter in the resulting suspension was 4~. The suspension was poured into the chest of a laboratory sheet former, and imme-diately prior to suctioning off the water, 0.5~ of Prodefloc N2M
(a polyelectrolyte) was added. By suctioning off the water, a sheet was formed which was allowed to cure for about 12 hours. Thereafter, the sheet was kept for 1 hour in an oven at 100C and sub-sequently for about 15 minutes at 220C. The resulting board had a smooth surface and showed uni~orm fiber distributi.on.

The i~pregnated ce1lulose-containing fi~ers of aspects of tbe present inYention ~ay thus be used for a wide range of applications in which their modified and improved propert~es are desired.

Claims (31)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. Cellulose-containing fibres selected from the group con-sisting of sulphate pulp fibres, sulphite fibres, semi-chemical fibres, chemi-mechanical pulp fibres, theremo-mechanical pulp fibres and mechani-cal pulp fibres, or waste paper or waste cardboard fibres or fibre bun-dles, saw dust, wood chip, shavings, wood wool or synthetic cellulose fibres, said fibres being impregnated with at least one impregnating agent selected from the group consisting of silicon oxide acylates, metal oxide acylates and a biocidally-active metal compound of a metal selected from the group consisting of copper, mercury, chromium, tin and zinc.

2. The cellulose-containing fibres of claim 1 wherein said metal oxide acylates include metals selected from the group consisting of copper, zinc, antimony, chromium, iron, manganese, and zirconium.

3. The cellulose-containing fibres of claim 1 wherein the non-metallic portion of the biocidally-active metal compound is selected from salts or metal organic compounds or mixtures thereof.

4. The cellulose-containing fibres of claims 1, 2 or 3 wherein said fibres are in one of the following forms:
(a) dry discrete fibres (b) wet discrete fibres (c) sheets (d) rolls (e) bales or (f) granulates

5. The cellulose-containing fibres of claims 1, 2 or 3 wherein said fibres are in one of the following forms:
(a) dry discrete fibres (b) wet discrete fibres (c) sheets (d) rolls (e) bales or (f) granulates and wherein said fibres are in the form of fibre bundles.

6. The cellulose containing fibres of claims 1, 2 or 3 wherein said fibres are in one of the following forms:
(a) dry discrete fibres (b) wet discrete fibres (e) sheets (d) rolls (e) bales or (f) granulates and wherein said fibres are of saw dust, wood chips, wood wool or synthetic cellulose.

7. The cellulose-containing fibres of claims 1, 2 or 3 wherein said impregnating agent is a copper-chromium impregnating agent.

8. The cellulose-containing fibres of claims 1, 2 or 3 wherein said impregnating agent is selected from the group consisting of copper naphthenate, copper chromium acetate, and copper chromium phosphate.

9. The cellulose-containing fibres as claimed in claims 2, 2 or 3 wherein said metal oxide acylate is a hydrophobizing metal oxide acylate.

10. The cellulose-containing fibres as claimed in claims 1, 2 or 3 wherein said metal oxide acylate is an aluminium oxide acylate.

11. The cellulose-containing fibres as claimed in claims 1, 2 or 3 wherein said metal oxide acylate is a titanium oxide acylate.

12. The cellulose-containing fibres as claimed in claims 1, 2 or 3 wherein said metal oxide acylate is a biocidally-active metal oxide acylate.

13. The cellulose-containing fibres as claimed in claims 1, 2 or 3 wherein said metal oxide acylate is a zinc oxide acylate.

14. The cellulose-containing fibres as claimed in claims 1, 2 or 3 wherein said fibres are impregnated with a biocidally-active metal oxide acylate and at least one of a hydrophobizing metal oxide acylate and a flame retarding metal oxide acylate.

15. The cellulose-containing-fibres as claimed in claims 1, 2 or 3 also containing a polyelectrolyte.

16. A composite material comprising (A) the cellulose-contain-ing fibers of claims 1, 2 or 3 and (B) a binder.

17. A composite material comprising (A) the cellulose-contain-ing fibers of claims 1, 2 or 3 and (B) an organic polymer binder.

18. A composite material comprising (A) the cellulose-containing fibers of claims 1, 2 or 3 and (B) an inorganic binder.

19. A composite material comprising (A) the cellulose-contain-ing fibres of claims 1, 2 or 3 and (B) a combination of an inorganic and an organic binder.

20. A composite material comprising (A) the cellulose-containing fibres of claims 1, 2 or 3 and (B) a binder, wherein said fibres are in one of the following forms:
(a) dry discrete fibres (b) wet discrete fibres (e) sheets (d) rolls (e) bales or (f) granulates.

21. A composite material comprising (A) the cellulose-contain-ing fibres of claims 1, 2 or 3 and (B) a binder wherein said fibres are in one of the following forms:

(a) dry discrete fibres (b) wet discrete fibres (c) sheets (d) rolls (e) bales or (f) granulates and further wherein are in the form of fibre bundles.

22. A composite material comprising (A) the cellulose-contain-ing fibres of claims 1, 2 or 3 and (B) a binder, and wherein said fibres are in one of the following forms:

(a) dry discrete fibres (b) wet discrete fibres (c) sheets (d) rolls (e) bales or (f) granulates and further wherein are of saw dust, wood chips, wood wool or synthetic cellulose.

23. A composite material comprising (A) the cellulose-contain-ing fibres of claims 1, 2 or 3 and (B) a binder and wherein said impregna-ting agent is a copper chromium impregnating agent.

24. A composite material comprising (A) the cellulose-contain-ing fibres of claims 1, 2 or 3 and (B) a binder and wherein said impreg-nating agent is selected from the group consisting of copper naphthenate copper chromium acetate and copper chromium phosphate.

25. A composite material comprising (A) the cellulose-contain-ing fibres of claims 1, 2 or 3 and (B) a binder and wherein said metal oxide acylate is a hydrophobizing metal oxide acylate.

26. A composite material comprising (A) the cellulose-contain-ing fibres of claims 1, 2 or 3 and (B) a binder and wherein said metal oxide acylate is an alumium oxide acylate.

27, A composite material comprising (A) the cellulose-contain-ing fibres of claims 1, 2 or 3 and (B) a binder and wherein said metal oxide acylate is a titanium oxide acylate.

28. A composite material comprising (A) the cellulose-contain-ing fibres of claims 1, 2 or 3 and (B) a binder and wherein said metal oxide acylate is a biocidally-active metal oxide acylate.

29. A composite material comprising (A) the cellulose-contain-ing fibres of claims 1, 2 or 3 and (B) a binder and wherein said metal oxide acylate is a zinc oxide acylate.

30. A composite material comprising (A) the cellulose-contain-ing fibres of claims 1, 2 or 3 and (B) a binder and wherein said fibres are impregnated with a biocidally-active metal oxide acylate and at least one of a hydrophobizing metal oxide acylate and a flame retarding metal oxide acylate.

31. A composite material comprising (A) the cellulose-contain-ing fibres of claims 1, 2 or 3 and (B) a binder and also containing a polyelectrolyte.