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    • 专利摘要:
    The invention relates to a bio-based polyelectrolyte complex (PEC) composition suitable as a binder for fiber based materials, textiles, woven and nonwoven materials, said PEC composition comprising cationic biopolymer, anionic biopolymer, acid and preservative, and wherein the net charge of the PEC is cationic, the charge ratio of the anionic polymer and the cationic polymer is ≤1, the cationic biopolymer is chitosan, the anionic biopolymer is a polyanion derived from nature, the acid is a Brønsted acid and/or a Lewis acid, wherein the Brønsted acid is selected from any organic and/or inorganic acids, and wherein the Lewis acid is selected from any cationic mono- or multivalent atom, the weight ratio between cation and anion is 1:0.1 to 1:20, the weight ratio between the cation and acid is 1:0.01 to 1:30, the pH is less than 7, and wherein said composition further comprises one or more non-water soluble particles.
    公开号:SE1651138A1
    申请号:SE1651138
    申请日:2016-08-24
    公开日:2018-02-25
    发明作者:Aydin Juhanes；WENNMAN Maria
    申请人:Organoclick Ab；
    IPC主号:
    专利说明:

    BIO-BASED POLYELECTROLYTE COMPLEX COMPOSITIONS COMPRISING NON-WATER SOLUBLE PARTICLES FIELD OF THE INVENTION The present invention relates to bio-based polyelectrolyte complex (PEC) compositions Whichare environmentally benign, renewable and biodegradable. The PEC compositions comprisechitosan as a cationic polymer, an anionic polymer being represented by polyanions derived from nature, especially polysaccharides, and one or more additives.
    The PEC compositions according to the present inVention are suitable as binders for fiberbased materials, textiles, Woven and nonWoVen materials. The treatment of fiber basedmaterials, textiles, Woven and nonWoVen materials With the PEC composition of the presentinVention provides materials Which have higher dry and/or Wet strengths, i.e. higher dryand/or Wet tensile indexes. Thanks to the one or more additiVes they contain, the PEC compositions can transfer specific properties of the additiVes to the treated materials.
    BACKGROUND INFORMATION PECs are the association complexes formed between oppositely charged particles such aspolymer-polymer, polymer-drug and polymer-drug-polymer. These complexes are formeddue to electrostatic interaction between oppositely charged polyions and thereby avoids theuse of chemical cross linking agents (S. Lankalapalli, 2009). Based on origin PECs areclassif1ed as natural polyelectrolytes, synthetic polyelectrolytes and chemically modifiedbiopolymers.
    The PEC composition according to the present invention comprises organic mo lecules ofbiological origin (i.e. biopolymers) represented by polyanions derived from nature Which areeither natural polyelectrolytes or chemically modified biopolymers. Hence, the PECs do notcomprise synthetic polymers and synthetic polyelectrolytes and therefore the PEC compositions according to the present invention are bio-based PEC compositions.
    EP0723047 relates to PEC suspensions for papermaking. However, the PEC suspensions donot comprise chitosan as a cation. Instead the cation is a synthetic polymer such as a copolymer of acrylamide With diallyldimethylammonium chloride. Hence, the PECs in EP0723047 are not bio-based PECs. More importantly, there is no data or reference to (i) anyincrease in wet strength of treated materials, (ii) effect on tensile stiffness of treated materials, and/or (iii) stability of the PECs over a period of several months.
    EP19l8455 relates to producing fibrous webs by using PECs having a negative net charge.Furthermore, the PECs do not comprise chitosan as a cation. Instead the cation is a syntheticpolymer such as acrylic polymers, polyacrylamides and amido-amine polymers.
    Consequently, the PECs according to EPl9l 8455 are not bio-based.
    US8993505, US90l23 89 and US9273220 relate to PECs for reduced soiling tendency,reduced cleaning effort and reducing microbial challenge. However, the PECs are not whollyof biological origin since they in addition to biopolymers also comprise synthetic polymersuch as (i) homopolymer of diallyl dimethyl ammonium chloride "DADMAC" disclosed inclaim 1 of US8993505, (ii) homopolymer of acrylic acid or a random copolymer of acrylicacid disclosed in claim 1 of US90l23 89, (iii) homo- or copolymers of the following anionicmonomers: acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, styrene sulfonic acid and acrylamide propane sulfonic acid disclosed in US9273220.
    Consequently, the PECs according to US8993505, US90l23 89 and US9273220 are not bio-based. More importantly, there are no data or reference to (i) any increase in dry strength andwet strength of treated materials, (ii) effect on tensile stiffness of treated materials, and/or (iii) stability of the PECs over a period of several months.
    US20l32l6592 relates to PECs consisting of biopolymers. However, the PECs are in theform of particles and not in solution. Moreover, the charge ratio between the cationic polymerand the anionic polymer is 1.05 to 5. More importantly, there are no data or reference to (i) any increase in dry strength and wet strength of treated materials, (ii) effect on tensile stiffness of treated materials, and/or (iii) stability of the PECs over a period of several months.
    US6936746 relates to PEC solid material systems. Hence, the PECs are in the form of solidmaterials and not as solutions. Moreover, US693 6746 is silent about the net charge of thePECs. Furthermore, US6936746 is also silent about the charge ratio between the cationicpolymer and the anionic polymer. More importantly, there is no data or reference to (i) anyincrease in dry strength and wet strength of treated materials, (ii) effect on tensile stiffness of treated materials, and/or (iii) stability of the PECs over a period of several months.
    Furthermore, specific embodiments of PEC composition described in the prior art have aconcentration of 0.04 % PEC due to stability issues. Hence there is also a need for PEC compositions having a higher concentration of PEC.
    OBJECT OF THE INVENTION It is an object of the present invention to overcome the drawbacks and disadvantages of theabove described compositions and to provide a bio-based PEC composition that is environmentally benign, renewable and biodegradable.
    A further object of the invention is to provide a bio -based PEC composition Which is stable for at least 1.5 months.
    A further object of the invention is to provide a bio -based PEC composition comprising atleast 0.04 Wt%, preferably at least l.5 Wt% PEC, more preferably at least 4 Wt% PEC, mostpreferably 4-l0 Wt% PEC.
    A further object of the invention is to provide a bio -based PEC composition Which does not mo ld.
    A further object of the invention is to provide a bio -based PEC composition Which comprises an anionic biopolymer Which has a low cost.
    A further object of the invention is to provide a bio -based PEC composition Which is suitableas a binder for fiber based materials, textile, Woven and nonWoven materials, and for pulp, paper and paperboard.
    A further object of the invention is to provide a bio -based PEC composition Which is stable in tap Water. According to prior art minerals in Water destabilizes the PEC.
    A further object of the invention is to provide a bio -based PEC composition having the abilityto transport and transfer specific properties from additives, such as wet tensile strength, hydrophobicity, etc. to fiber based materials, textiles, Woven and nonWoven materials.
    A further object according to the invention is to provide a biopolymer PEC composition, Wherein the nonWoven materials are mineral fibres such as glass or rock f1bres.
    A further object of the invention is to provide a method for achieving the above bio-based PEC compositions.
    A further object of the invention is to provide fiber based, textile, Woven and nonwovenmaterials Which have (i) high Wet tensile strength, and/or (ii) high dry tensile strength and/or(iii) softness and/or (iv) stiffness and/or (v) hydrophobicity.
    Any combination of the above objects is also possible.
    SUMMARY OF THE INVENTION The olijects of the iriveiitioii are attainetí by a bio-based PEC composition comprising cationicbiopolymer, anionic biopolymer, acid and preservative. The expression bio-based indicates that the PEC composition is of biological origin.
    The PEC composition of the present invention further comprises non-Water soluble particles.By non-Water soluble particles are herein understood any solid compound having a solubilityin Water not exceeding 15 Wt%. Further non-Water soluble particles are one or more plastic particles and/or bioplastic particles and/or protein particles and/or hydrophobic particles.
    While the PEC composition is of biological origin, the non-Water soluble particles and the additives can be, independently of each other, of natural or synthetic origin.
    The net charge of the PEC composition is cationic and the charge ratio bfetwftäen tlitæ ßiiionitïpolynier :irid the cationic polyniei” is íš-l. hfíoreover. the Weight ratio betvveeii cationic polynier and anionic iioljvfrner is 126.1 to l IZÜ. 'Üflie ÉïEC composition according to the present iriveritioii comprises ehitosari *which inipaitsiiigiiei” tensiltf iiidex Wh en tvoinpzireti to other eatioiis such as tfatiriiiit: stareii zind eatioriieceilulose. E-íence, tiie preferred ernhodirnents of the iiiveiitirön eonipirise cationic cliitrösari ascationic hiopolyiner. The conceritratioii of chitosan in the composition is ÜÜÛS-åfi Xvttšß.ivítoreovfelr, ehitosaii preferalily' lias a degree of deaeetyiatiori ttvhicii ranges from 66 % -100 %.The of diearïet§flation is important for the tiliysical properties, of chittisan in tlie PEC coinposititin.
    The anionic "tiiopolyrneiff being a poiyaiiirin derived from iiature tfan be selected frotri ligriin. alliali, lignosulfoiiic acid, or a polysaccharide, stieh as carlïioxyfrnetiiyl cellulose (Ctvííf), algiiiic acid (preffsrahhf the scidiuiii salt), xantliaii guin, tifzctiii, carrageenzin aiidnanocrystailirie tfeihiitise (NCC) and giini arahirt. Lighiri alkali and iigiitisiiitonifc ttciti iriaypreferatily' he in the fonn of their sodinrn salt. The concentratioii of anionic ihiopoiïvfniei" in tiie tfirnriptisitiori is (3,005~3 % hy weight.
    The pH of tlie PEC etiniposititin is heiow pH 7 aint this tnay he attliieveti hy Biføiisteti. ttcitiand/or a Letvis acid. Brønsted acids are selected trorn ariy organic or inorgahic acids, Whereirithe concentration of the acid is 0531-30 (ffs. Lewis acids are se ected from any catioiiic inono-or ninltivalerit atom, Whenifin the conceritratitin of the E..evvis acid is 0.01 »S0 (Ai. The PECconiptisitioii preferahlja has a. pH *xaiue of2-4. The Weigiit ratio hetvifeeii the catioiiit: polgfriierand the acid is litšíil to 11:30 in the PEC coniposition. The ttciti ofithe Piïíf tfortipositifon isselected from one or more of acetic acid, acetyflsaiicylic acid, adipic acid, ihenzeiiestiifonicacid, eaniphorstiifiiniat acid, ttitritt afcid, tiihytiroxy fiirnaiie acid, tfoririic ttcid, giyetiiit: aei d,giyoxjfiic acid, iiydrochloric acid, iactic acid, rnaiic acid, rnaloiiic acid, inaieic acid, niaiideiicarsiti, oxalirï acid, tiara-tolnenesultonic acid, phtalic acid, iffyruvic acid, salicylic acid, suifiiricacid, tartaric acid and succiiiic acid, rnore preferahly' citric acid, tixalic acid atid. tartaric acid, even inore. preterahijy' citric acid, and iiiost iiiefereihly rsitritï acid monohydrate.
    The conceritration of the FBC in the PEC rfoinpositioii is at least 0.04 Wt% PEC, preferably atleast 1.5 Wt % PEC, more preferably at least 4 Wt % PEC, most preferably 4-10 Wt % PEC.lïnrthermore, the PEC coniposition according to the preseiit inventioii is dilutahle.h/ianiiiatttuiirig of highiy ttoiitteritrattfd PEC coniposititins is advantageoiis in view' of iovueringsliippiiig cost, i.e. tiie PEC coniposition can he prepared *with a liigli concentration and then dilntfed attan* sliiiipiiig by the user or customer.
    The solvent of the. PEC conipositirin is water selrficteti ironi distilled vxfatei", tap vvater, andfieioiiizefi wifatei”. PEC coinpositioiis coinpiisiiig chitosan are in the prior' art irriowfn for lieitigtinstahle. in tap ærfatei* and are tlieiefoie prepared in tiistiiled wvateii Hovvesniàir, the PEC cotnposititin according to the present invention is stahie in tap Water.
    The PEC coniiaositiriii ofitiie present irweiitiori tnay aiso he tiiepared in neat forni, i.e. the PEC cornposition does not comprise added 'water The PEC composition comprises one or more additives selected from, Water solubleplasticizer, defoamer, foaming agent, Wetting agent, coalescent agent, Catalyst, surfactant, emulsifier, conservative, cross-linker, rheology modifier, filler, nonionic polymer, dye, pigment. Said one or more additives are selected depending on the application method and theexpected properties of the final material, wherein the concentration of the additive(s) is 0-99 wt%, preferably 0-50 wt%, most preferably 0-30 wt%.
    The preservative may be selected from the group consisting of a fiangicide, bactericide,pharrnaceutical preservative, cosmetic preservative and/or food preservative. Theconcentration of the preservative is 0.005-10wt%, preferably 0.005 - 1.5wt%, more preferably0.005-0.5wt %. Moreover, the preservative is preferably biodegradable and/or renewable.Food preservatives, pharrnaceutical preservatives and cosmetic preservatives are preferredsince they are non-toxic. The inclusion of a preservative helps to inhibit the growth of mo ld inthe PEC composition. Moreover, we have discovered that PEC compositions withoutpreservative becomes more yellow/brown than a composition comprising preservative. Evenif performance is the same between the more yellow and less yellow PEC composition, theyellow color is transferred to material and causes yellowing which is unwanted especially for nonwovens and fiber based materials such as textiles.
    The PEC composition of the present invention further comprises one or more non-watersoluble particles. The composition”s ability to incorporate and transport the non-water solubleparticles gives the opportunity of transferring the properties of named non-water solubleparticles to different materials treated with the PEC composition. This ability is explored by the present invention.
    The non-water soluble particles of the present invention may be present in the PECcomposition at a weight ratio of PEC:non-water soluble particles of 1:0.01 to 1:50, preferably1:0.05 to 1:20, more preferably 1:0.1 to 1:10, most preferably 1:0.5 to 1:1. Moreover, the non-water soluble particles of the present invention have a particle size preferably in the range of 100 nm-1mm, more preferably of 100nm-500 um, even more preferably of 100nm-300 um.
    The non-water soluble particles may be of the following types, namely plastics, bioplastics,hydrophobic particles, proteins, solid waxes, solid resins, fillers, pigments, fiamed silica, and mixtures thereof The plastics employed in the PEC composition of the present invention may be selected fromthe group consisting of Polyester , Polyethylene terephthalate, Polyethylene, High-densitypolyethylene, Polyvinyl chloride, Polyvinylidene chloride, Low-density polyethylene,Polypropylene, Polystyrene, High impact polystyrene, Polyamides, Acrylonitrile butadiene styrene, Polyethylene/Acrylonitrile Butadiene Styrene, Polycarbonate, PolycarbonateButadiene Styrene, Acrylonitrile Butadiene Styrene, Polyurethanes, Maleimide,Bismaleimide, Melamine forrnaldehyde, Phenolics, Polyepoxide, Polyetheretherketone,Polyetherimide, Polyimide, Polymethyl methacrylate, Polytetrafluoroethylene, Urea-formaldehyde, Furan resin, Silicone, Polysulfone, Polyoxymethylene, preferably selectedfrom Polycaprolactone, Polyethylene terephthalate, Polyethylene, Polypropylene and mixturesthereof Where the plastics are of biological nature, they can preferably be selected from the groupconsisting of polylactic acid (PLA), PLA co-coplymers such as L-PLA, D-PLA, DL-PLA,PLGA, PDLA, polyhydroxy alkanoates (PHA) and Variations of thereof such as PHB, PHBV,P3HB, P4HB, PHbHHx, P(3HB-co 20%mol-3HV, P(3HB-co 4HB), P(3HB-co 6% mol-3HA), P(3HB-co 4HP), P(3HB-co 3HHX), PHBHHx), ethylcellulose, cellulose acetate,therrnoplastic starch, polybutylene succinate, preferably selected from PLA, PHA and therrnoplastic starch, and mixtures thereof PEC composition according to the present invention may contain proteins as non-Watersoluble particles, preferably selected from one or more of pea protein, vital Wheat gluten,Wheat gluten, lupine protein, soy protein, soybean protein, maize protein, zein protein, peanutprotein, caseine, and similar plant-based or yeast based proteins as iso lates and/or flours.Other useful proteins are hydrophobins (small proteins of from about 100 to 150 amino acidsand are characteristic of filamentous fungi, for example Schízophyllum commune. Theygenerally have 8 cysteine units.), keratin, animal protein such as fish protein, albumin, milkprotein, and Non-limiting examples of other sources of vegetable protein include, forexample, proteins extracted from nuts, seeds, grains, and legumes. These sources include, butare not limited to, almonds, brazil nuts, casheWs, Walnuts, pecans, hazel nuts, macadamianuts, sunflower seeds, pumpkin seeds, com, and the like. Other sources include protein-containing biomasses, such as Waste sludge, manure, and composted manure. More preferredproteins are pea protein, vital Wheat gluten, Wheat gluten, lupine protein, soybean protein, maize protein, zein protein, caseine and keratin.
    The non-Water soluble particles may originate from solid Waxes, as vegetable and/or animalWaxes, having a melting point of 27 °C-220 °C. They may preferably be selected from the group consisting of Bayberry Wax, candelilla Wax, camauba Wax, castor Wax, esparto Wax, japan Wax, ouricury Wax, rice bran Wax, soy Wax, talloW tree Wax, beesWax, Chinese Wax, lano lin Wax (Wool Wax), shellac Wax, sperrnaceti Wax, and mixtures thereof The solid Waxes may as Well be mineral, synthetic Waxes and/or petroleum derived Waxes,and may have a melting point of 27 °C-220 °C. They may preferably be selected from thegroup consisting of paraff1n Wax, microcrystalline Wax, ceresin Wax, montan Wax, ozocerite Wax, polyethylene Wax, peat Wax, and mixtures thereof The non-Water soluble particles may be solid resins. The solid resin may be plant and/oranimal and/or petroleum derived resins and/or synthetic resin preferably selected from thegroup consisting of petroleum resin such as asphaltite and Utah resin, insect resins such asshellac, plant resins such as copals, dammars, mastic, and sandarac, oleo-resins (frankincense,elemi, turpentine, copaiba), gum resins and Aleppo pine resin, synthetic resins such asbisphenol A diglycidyl ether and silicone resins. More preferred solid resins are selected from plant based resins such as furan, rosin and gum resins.
    Thenon-Water soluble particles of the present inVention may be inorganic and/or organic pigments.
    The f1llers and pigments used as non-Water soluble particles may preferably be selected fromthe group consisting of clay, calcium carbonate, titanium dioxide, talc, iron oxides, bariumsulfate, barium carbonate, aluminium sulfate, kaolinite, calcium magnesium carbonate,magnesium carbonate, satin pigment, zinc oxide and zinc sulfide, more preferably selected from clay, titanium dioxide, and aluminum sulfate and mixtures thereof The composition can additionally comprise an acid or basic catalyst Which has in particular therole of adjusting the temperature at Which crosslinking begins. The catalyst can be chosen fromLeWis bases and acids, such as clays, colloidal or noncolloidal silica, organic amines, quaternaryamines, metal oxides, metal sulphates, metal chlorides, urea sulphates, urea chlorides and catalysts based on silicates.
    The catalyst can also be a phosphorus-comprising compound, for example an alkali metalhypophosphite salt, an alkali metal phosphite, an alkali metal polyphosphate, an alkali metalhydrogenphosphate, a phosphoric acid or an alkylphosphonic acid. Preferably, the alkali metal is sodium or potassium.
    The Catalyst can also be a compound comprising fluorine and boron, for example tetrafluoroboricacid or a salt of this acid, in particular an alkali metal tetrafluoroborate, such as sodiumtetrafluoroborate or potassium tetrafluoroborate, an alkaline earth metal tetrafluoroborate, such ascalcium tetrafluoroborate or magnesium tetrafluoroborate, a zinc tetrafluoroborate and anammonium tetrafluoroborate. Preferably, the catalyst is sodium hypophosphite, sodium phosphite and the mixtures of these compounds.
    The amount of catalyst introduced into the composition can represent up to 20 wt%, preferably up to 10%, and advantageously is at least equal to 1%.
    The objects of the irweritiori are ttlsri attainerli lny ai rnetliori tiífprfeparitrrg the ahove diseloserlernhodirnerits of lšlhltf cornpositions. 'Üflie method cornprises the steps of rnixing chitosan,arlionitt polyrner, artid, preseirvaetive, water and non-Water soluble particles and optionally one or more aclditives. "fhe method may cornprise one or more hornogenization steps. ln a preferred ernhodirnent, the method comprises the steps of: a) ßidding the anionio polymer to vvaterf., b) Aflding eliitosaii to the resultiiig rnixture in step a, c) hflixing the alcid vvith tvater, and adding the resulting arsidic solution to the restilting niixture in step h,d) Adding one or more particle types to the resulting mixture in step c,e) Adding a preservative to the resulting rrrixtrlre in du, arid ifvlierein the resultirig rnixttires in steps a-e are iriixed and optionally hornogeriizecl.
    The olrlects of the iriverition are also attairied hy using the above diselosed emhodiments of PEC cornpositions a binder for fihtfir based, textile, Woven and nonwowfen rnaterialls.
    The ribjects of the invention are also attanltfd hy' tlhfezr based, textile, Woven and nonwoven niaterials coinprisirig the above riiseioseri ernhodirnents of Pfitlï cornpositiraris as a liinder.
    The olijeets of the inveention are also attained hy an apparatus comprising the ahove tliseiosetiernlfiotiirnehts of PEC eornriositioris as a 'hiiicleii The apparatus is any kind of lahoratory orirldastrial eoaiprrrerrt using lovv or liigh sliear torees for ptrrirlueirig the PEC rtorrrprisitioris. Thismight lie a magnet stirrer., oiferhead stirrer With propeller or tiisperser or like, homogehizei' vvith or wvitho nt lligh pressure, iii-line or external lrornogerrizers, extruders, shallririg equipnierit, niortar arid iifzstle, blender type ofinstruriient, any kind of mixer (static mixer,rnirrfri rnixerï, vortex iriixer, industrial rnixer, ribbori blender; V blender; rforitiriurius rprocessrirfi,eone screw' blender, sereiv blender, doulïfle eone blender, double planetarjf, higli vriseositgvfrriixer, counter-rotatioii, tiouble and triple shatt, vafeuiini rnixeir, high shear rotor stater,dispersion mixer, paddle, jet niixer, inobile mixer, drum mixer, intermix rnixer, planetaqfmixer, Banbum niixtëi” or like), Freneli press, disintegratrir, niill (grindiiig by bead inill, rsolloidniill, harnniei' rnill, ball rniil, rod rnill, autogenous inili, senii-afutogenous giindiiiiig, peltbleniill, high pressure. grinding rolls, buhrstorie mill, vertical shait impactoi* mill, toifvffsi* mill orlike), riltrasonie treatment, rottinstattir inechanieal equipment, any lrind or propeller' or niixer; high temperature and/or high riressure bituiiien eninlsifiers or conibiiiations of the above.
    The olqiects of the iiiveiition are also attained by a method of treating fiber based, textile,Woven and nonwoven rnateriizrls vvith. tiie above diselosafd enibodinieiits of PEC conipositiiirisas a binder, eoniprising the steps of:a. Treating the fiber based, textile, Woven and nonwoveri inaterials vvith a PECconiivositioii byi. addition to fiber based arid iionvvforafeii suspensions, ii. spray coating, iii. dip coating, iv. roll coating, V. impregnation, vi. padding, vii. screen coating,Viii. printing,ix. direct coating methods including knife coating, blade coating, WireWound bar coating, round bar coating and foam coating (e.g. crushedfoam coating),x. indirect coating methods including mayer rod coating, direct rollcoating, kiss coating, gravure coating and reverse roll coating,xi. ink jet and/or slit-die/slot-die, andb. optionally curing the treated 'fiber liaseri, textile, Woven arid iiorivx/oxraf .rnateiials. ln a preferred embodimerit, the rnethod of treating comprises the step of curing the treated fiber based and nonwoven materials. In a further preferred embodiment, the curing is perforined. at 20 °C to 200 CE", preferably at 80 °C to 190 CC, inore preferably' at 120 °C to 180”C DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention relates to bio-based PEC compositions that are environmentally benign,reneWable and biodegradable mixtures of a cationic biopolymer and an anionic biopolymer.The cationic and anionic polymers are balanced so that the net charge of the PEC is cationic.The PEC compositions are preferably prepared in the presence of an acid and furthercomprise non-Water soluble particles. The PEC compositions are suitable as binders for fiber based materials, textiles, Woven and nonWoven materials.
    Non-Water soluble particles refer herein to solid compounds having a solubility in Water notexceeding 15 Wt%. The non-Water soluble particles of the present invention have a particlesize preferably in the range of 100 nm-lmm, more preferably of l00nm-500 um, even more preferably of l00nm-300 um.
    According to the invention the use of the Wording textiles, Woven and nonWoven may includecloths or fabrics and may be based on natural or synthetic fibers and mixtures thereofTextiles, Woven and nonWoven may consist of a network of natural and/ or synthetic fibersoften referred to as thread or yarn. Yarn is produced by spinning raW fibers of Wool, flax,cotton, or other material to produce long strands. Textiles are formed by Weaving, knitting,crocheting, knotting, or pressing fibers together (felt). The Words fabric and cloth may forexample be used in textile assembly trades (such as tailoring and dressmaking) as synonymsfor textile. Textile may refer to any material made of interlacing fibers or nonWoven textiles.Fabric refers to any material made through Weaving, knitting, spreading, crocheting, orbonding that may be used in the production of further goods (garrnents, etc.). Cloth may beused synonymously With fabric but often refers to a finished piece of fabric used for a specificpurpose (e. g., table cloth). The Wording textiles, Woven and nonWoven according to thepresent invention may include all different types of textiles described above. Textiles, Wovenand nonWoven according to the invention can be made from many different types of materialsand fibers for example animal, plant, Wood, mineral, synthetic, sugar based, protein based forexample Wool, silk, mohair, cashmere, pygora, cameldoWn, alpaca, ilama, vicuna, guanaco,angora, qiviut, ramie, nettle, milkweed, cotton, linen, flax, jute, hemp, viscose, asbestos, glass fiber, rock fiber, nylon, elastan, polyester, acrylic, polyamide, polypropylene, polyurethane 11 and its derivatives, comfiber, coir, yucca, sisal, bamboo (rayon) fiber, peanut, soybased, chitinbased, milk casein based, keratin based and poly lactic acid based etc. Further, nonwovenmaterials are fabric-like materials made from long f1bers, bonded together by chemical,mechanical, heat or solvent treatment. Nonwoven fabrics are also defined as sheet or Webstructures bonded together by entangling fiber or f1laments (and by perforating f1lms)mechanically, therrnally or chemically. The term is used in the textile manufacturing industryto denote fabrics, such as felt, Which are neither Woven nor knitted. They are flat or tufted porous sheets that are made directly from separate f1bers, molten plastic or plastic film.
    Fiber based materials refer to materials such as paper materials Which comprise a high degreeof cellulose. As Will be understood by those skilled in the present field of art, numerouschanges and modifications may be made to the above described and other embodiments of thepresent invention, Without departing from its scope as defined in the appending claims. Forexample, the pulps for making fiber based materials may be any kind of pulp, i.e. mechanicalpulp, therrno-mechanical pulp, chemo-mechanical pulp, sulphate pulp, sulphite pulp, bleachedpulp, unbleached pulp, short-fiber pulp, long-fiber pulp, recycled fibers, mixtures of different pulp grades etc. The invention Works irrespective of the kind of pulp chosen.
    The Examples relate to comparative studies and for investigating the ability of PEC to createdispersions of non-Water soluble particles such as bioplastics and proteins as Well as theability of PEC to transfer the properties of the dispersed particles to different materialsthrough electrostatic attraction. To the person skilled in the art it Will be obvious that thepresent invention can also be transferred to other types of particles such as pigments, f1llers and similar non-Water soluble particles.
    The PEC composition according to the present invention can be used as a vehicle in the sensethat said composition both has space for and fuel to transport other mo lecules. In morespecific terms, the PEC composition can form a micelle around, for example non-Watersoluble particles comprised in the PEC composition and thanks to its positive charge, it canthereafter arrange itself towards negatively charged f1bers and thus transfer the properties of the non-Water soluble particles to the fiber based material. 12 Experiment 1-8 - Study of various hydrophobic particles included in the PEC compositions and evaluation of said PEC compositions on nonwoven Background experiments 1-8The binder recipe OC-C (see details in abbreviations experiments l-8) is based on polyelectrolyte complex (PEC). PEC gives good dry and wet mechanical properties to fiberbased materials, nonwovens, paper and textiles. PEC can also be seen as a micelle that canemulsify for example non-water soluble particles. To mix PEC and non-water solubleparticles can therefore lead to a dispersion that both gives good mechanical properties tomaterials (the PEC part of the dispersion) and that creates an additional property on thematerial which is derived from the particle the PEC composition carries (the particle part of the dispersion).
    The experiments below demonstrate that PEC can support and stabilize non-water solubleparticles in water to form dispersions. These are then further used as binders/additives ondifferent materials and the properties measured. In the following examples the term particlePEC composition refers to polyelectrolyte complex dispersion containing non-water solubleparticles while a polyelectrolyte complex forrnulation without particles is refferd to non- particle PEC composition.
    Abbreviations experiments 1-8 Below, all abbreviations used in experiments l-8 are listed.
    C Chitosan CHCls Chloroforrn CMC Carboxymethyl cellulose DBS Dibutyl sebacate EC Ethyl cellulose EC N10 Aqualon EC N10 EC Nl00 Aqualon EC Nl00 ID46 Polysorb ID46 LPC Lupine protein concentrate MCC Micro crystalline cellulose MG Maize gluten NW Nonwoven OC-C 2 wt% chitosan 90/100/Al, 2 wt% Finnfix 5, l2 wt% citric acid monohydrate, 0.2 wt% Nipacide BSM, produced according to Method ll PEC Polyelectrolyte complex 13 PLA Polylactic acid PP Pea protein SPC Soy protein concentrateTBAC tributyl acetyl citrateWG Wheat gluten VWG Vital wheat gluten Methods experiments 1-8 Below, all methods used in experiments 1-8 are listed.
    Method 1: Forrnulations diluted to 1 wt% and nonwoven treated with padder using11,6 rpm and pressure 0,1 MPa followed by drying on stenter frame in Termaks oven150 °C for 3 min.
    Method 2: Test of hydrophobicity by adding drops of water on the surface. Grades forhydrophobicity: --=hydrophilic and spreading, -= hydrophilic, += droplet stays around1 s, ++=droplet stays 10-30 s, +++= droplet stays >60 s and is defined as hydrophobic.Method 3: Tensile test for dry nonwoven were performed by using Testometric M250-2.5AT (pretension: 0,01 N, sample length: 200 mm, width: 50 mm, speed: 100mm/min, Load cell 1: 50 kgf) after acclimatization at 23 °C and 50 % RH for 1 day.Three nonwoven sheets were treated and two test specimen for each treated piece wascut out and tested.
    Method 4: Tensile test for wet nonwoven were performed by using Testometric M250-2.5AT (pretension: 0,01 N, sample length: 200 mm, width: 50 mm, speed: 100mm/min, Load cell 1: 50 kgf) after having test specimens at least 20 h in 23 °C and 50% RH and then soaked in water for 15 min. Three nonwoven sheets were treated andtwo test specimen for each treated piece were tested.
    Method 5: Use a bioplastic dispersion (see experiment 1) as the whole amount of“Water 1” in OC-C recipe. The amounts were multiplied with 0.5 to receive 50 g finalproduct. In other words: 1. Homogenize 35,9 g water 1 and 1 g CMC Finnfix 5 usingUltraturrax T25 at 9000 rpm for 3 min. 2. Disperse 1 g chitosan in the CMC-solution.3. Dissolve 6 g citric acid mono hydrate in 6 g water 2 and add to the CMC-solution.Homogenize at 12000 rpm for 3 min. 4. Add 0,1 g Nipacide. Homogenize 1 min.Method 6: Dry content was measured by adding three times 10 g of the forrnulation inaluminum cups in the Termaks oven for 24 h (105 °C). The theoretical dry contentwas then calculated by the equation (W2-W0)/W1 where W2= weight of the cup,W1=weight of the original sample, W2= weight of the cup and the final sample. 14 Method 7: 50 g forrnulation is homogenized using Ultra Turrax T25 With speed 12000rpm during 1 min after addition of non-Water soluble particles.
    Method 8: General description of production method for PEC composition Withoutnon-Water soluble particles as additive (100 g forrnulation): 1. Homogenize 71.8 gWater and 2 g CMC Finnfix 5 With Ultraturrax T25 at 9000 rpm for 3 min. 2. Disperse2 g chitosan in the CMC-solution. 3. Dissolve 12 g citric acid mono hydrate in 12 gWater and add to the biopolymer solution. Homogenize at 12000 rpm for 3 min. 4.Add 0,2 g Nipacide BSM. Homogenize 1 min.
    Method 9: General description of production method for PEC composition includingnon-Water soluble particles as additive (100 g forrnulation): 1. Homogenize 69.8 gWater and 2 g CMC Finnfix 5 With Ultraturrax T25 at 9000 rpm for 5 min. 2. Disperse2 g chitosan in the biopolymer solution. 3. Dissolve 12 g citric acid mono hydrate in12 g Water and add to the CMC-solution. Homogenize at 12000 rpm for 5 min. 4. Add2 g particles to the mixture. Homogenize at 12000 rpm for 5 min. 5. Add 0,2 gNipacide BMS. Homogenize 1 min. If needed, add 0.2 g Dispelair CF 56 during stirring at the end.
    Equipment experiments 1-8Below, all equipment used in experiments 1-8 is listed. pH Was measured With pHenomenal pH1000H from VWR With Hamilton Polilyte LabTemp BNC electrode (calibrated With buffers pH 4, 7 and 10).
    Tensile tests Were conducted using Testometric M250-2.5AT (machine capacity 2,5kN) together With Wintest Analysis software.
    Homogenization of formulations in lab scale Was done using IKA T25 digital Ultra-Turrax.
    Viscosity of formulations Were measured With Brookfield DV-II+ Pro LV Viscometertogether With Rheocal software using spindle LV4 at 200, 150, 100, 50, 10 and 6 rpm.Coating of nonwoven Was performed With Wichelhaus WI-MU 505 A horizontalpadder.
    Drying of treated paper and nonwoven Were done in an oVen from Termaks (Withstenter frame from Wichelhaus Wi-LD3 642 Minidryer/Stenter).
    Visual evaluation of emulsions and dispersions Was done using a Nikon Microphot - FXA With 10x lens.
    Chemicals experiments 1-8Below, all chemicals used in experiments l-8 are listed. l,2-Benz1soth1azol-3(2H)-one, N1pac1de BSM Clariant2-methyl-2H-isothiazol-3-one Carboxymethyl cellulose FinnFix 5 CP Kelco (CMC) Chitosan Chitosan 90/1 00/A1 Kraeber Chloroforrn (CHClg) Sigma Aldrich Citric acid mono hydrate Citronsyra Mono E33 8- Univar AB 80M LT Defatted toasted soy flour (soy Frasoy-D IP<0,9% L.I. frank, Frank Foodprotein concentrate) Products Dibutyl sebacate (DBS) Arkema Defoamer Dispelair CF56 Chemec Ethyl acetate Sigma Aldrich Ethyl cellulose (EC) N100 Aqualon EC N100 Ashland Ethyl cellulose dispersion Aquacoat ECD FMC biopolymerEthyl cellulose Water Aquacoat ECD FMC Biopolymerdispersion, 30 Wt% Isosorbid ester Polysorb ID46 Roquette Maize gluten Concentra P 13882 Cargill Micro crystalline cellulese Hightcel 90M MCC Sigachi cellulose PVT LTD /(MCC) Brenntag Nordic Pea protein Lysamine GPS Roquette PLA powder Tianjin Glory Tang Technology (through PerSundblad, SPCC) Polylactic acid (PLA) Ingeo 1036lD Nature WorksPolyoxyethylenesorbitan TWeen 40 Sigma Aldrichmonopalmitate PolyVinyl alcohol PVOH MoWiol 28-99 Clariant Sodium dodecyl sulfate (SDS) Sigma AldrichSorbitol Neosorb 70 Roquette Toasted lupine concentrate Fralu-con L.I. frank, Frank Food(lupine protein concentrate) Products Tributyl acetyl citrate (TBAC) Tecnosintesi Wheat gluten Viten CWS Roquette Vital Wheat gluten Gluvital 21040 Cargill Experiment 1 - Study of the dispersing properties of PEC To produce bioplastic particles of suitable size, solvent exchange method Was used. The polymer and/or plasticizers Were dissolved in an organic so lvent. The surfactant and stabilizer Were dissolved in Water. The organic phase Was slowly added to the aqueous phase during mixing using UltraTurrax. The organic solvent Was then evaporated. See Table l for the composition of the PLA- and EC-dispersions used.
    Table 1. Composition of PLA- and EC-dispersion prepared With organic solvent.
    Particle DryName Polymer Plasticizer Organic solvent Surfactant Stabilizer Water slze content d(0.5) (%)1 (um)Dispersion 5(PLA+22,5% P)LA (2 ä-:âfn ) CHC13 (20 m1) Sågs (M6 ä] 30214) 160 g 4.4 1,28TBAC) g g g ' gDispersion 6 Ilšïoo DBS Ethyl acetate (50 SDS (0.l6 PVOH 160 0 9 1 66(Ec+25% DBS) (2 5 g) (625mg) m1) g) (032 g) g ' =Dispersion 7 PLA 10(PLA) g - CHClg (100 ml) SDS 1 g - 989 g 21 1,251) According to Method 8.
    To disperse bioplastic particles using PEC, OC-C Was produced With a bioplastic dispersion (Dispersion 5, 6 or 7) as the “Water l” in the recipe according to Method 7.
    The particle PEC compositions PEC/Dispersion 5 (called particle PEC composition 5), PEC/Dispersion 6 (called particle PEC composition 6) and PEC/Dispersion 7 (called particle PEC composition 7) show good film forrning properties When making 400 um films With film applicator (drying overnight in 23 °C). Also, the dispersions have an even and homo genous texture shoWing that it is possible to use PEC as an emulsifier of bioplastic particles. The dispersions also look homogenous and non-flocculating When studied in microscope.
    Experiment 2 - Study of the hydrophobicity contributed by the particle PEC compositions comprising PEC and bioplastic particles by adding Water droplets on thetreated material 100% viscose NW Was treated according to Method l With the particle PEC compositions from experiment l. Hydrophobicity of the particle PEC compositions Was studied accordingto Method 2, see Table 2. 17 Table 2. The hydrophobicity of NW treated With PEC/bioplastic dispersions. Drop test(Method 2) Was done day two and day five.
    Dispersion Day 2 Day 5Dispersion 5 -- -- Particle PEC composition 5 - -to ++Dispersion 6 -- -- Particle PEC composition 6 -to + -to +Dispersion 7 -- -- Particle PEC composition 7 ++ to +++ ++ to +++ Table 2 shows that the bioplastic dispersions themselves give hydrophilic NW (probablybecause of the surfactants) but together With the particle PEC composition of the invention thetreated NW becomes hydrophobic. Particle PEC composition comprising PLA Withoutsoftener gives the most hydrophobic NW.
    Experiment 3 - Study of the curing temperature on the mechanical properties of 100%viscose nonwoven by particle PEC compositions With and Without plasticized PLAparticles Coating of 100% Viscose NW With particle PEC compositions comprising bioplastic particlesWas done according to Method 1. Tensile tests Were conducted according to Method 3. Seeresults in Table 3. Dry tests Were performed on 100% Viscose NW.
    Table 3. Mechanical properties for NW treated With non-particle PEC composition and particle PEC compositions and cured in tWo different temperatures.
    DRYSample Tensile stiffness stadvindex (Nm/g) Reference, untreated 170,3 11,9OC-C, 150 °C 891,7 196,5OC-C, 180 °C 936,4 348,4Particle PEC composition 5, 150 °C 1358,7 396,2Particle PEC composition 6, 150 °C 968,4 157,7Particle PEC composition 6, 180 °C 981,1 203,08Particle PEC composition 7, 150 °C 897,9 272,9Particle PEC composition 7, 180 °C 1324,4 118,1 18 Dry tensile stiffness increases signif1cantly When PLA particles are used in PEC compositioncompared to PEC composition Without. The required curing temperature, When using purePLA particles in the PEC composition, is higher (180 °C) than When using PLA plasticizedparticles (150 °C) in the PEC composition, to reach similar dry tensile stiffr1ess. This is due tothe lowering of the melting point of the PLA particles imparted by the plasticizer. This givesthe end user of the particle PEC composition an option to choose PLA particle PECcomposition With and Without a PLA plasticizer depending on the curing temperature used inthe process. EC particles have no or small effect on the tensile stiffness index of the treatedmaterial.
    Experiment 4 - Study of the influence of the mechanical properties of 100% viscosenonwoven by particle PEC compositions In experiment 3 PLA particles used in the particle PEC composition had smaller particle size(see table 1) compared to the size of PLA particles used in particle PEC compositions in experiment 4.
    Grinded PLA-powder With mixed particle size Was f1ltered through 150 mesh Wire, equal to <100 um holes, and tested together With PEC in a particle PEC composition. The PEC-particlesused had a melting point of 170 °C. The f1ltered particles Were dispersed in OC-C accordingto Method 7 to reach the ratio PEC:PLA-powder 1:1 and 1:2.
    Treatment of NW Was done according to Method 1 (curing in 140°C and 170 °C). Dryproperties Were tested to investigate the dependence of ratio PEC:PLA, curing temperatureand time. Tensile tests Were done according to Method3. The results are presented in Table 4 Table 4. Dry mechanical properties for NW treated With the particle PEC compositionscomprising PEC:PLA-particles (150 mesh) With ratio 1:1 and 1:2.
    DRYRatio PEC:PLA- . . . Tensile stiffness particles Curlng conditions index (Nm/g) stadv140 °C 2 min 697,3 154,01:1 140 °C 4 min 896,6 164,0170 °C2min 1015,1 228,7 170 °C4min 1253,1 65,6140 °C 2 min 643,3 164,7 1:2 140 °C 4 min 782,1 59,2170 °C 2 min 788,0 107,6 170 °C 4 min 909,9 66,3 The difference in stiffness is dependent on both temperature and time. Curing at 140 °C, didnot melt all the PLA particles Which could be observed on the material (dusty material). Thestiffness did not increase When the ratio Was changed from 1:1 to 1:2 PEC:PLA.
    Based on the above conclusions NW Was treated according to Method 1 (curing at 190°C for2, 4 and 6 min) to investigate the effect of curing time. Tensile tests Were conducted according to Method 3. See results in Table 5. Dry tests Were performed on 100% ViscoseNW.
    Table 5. Dry mechanical properties for NW treated With non-particle PEC composition andparticle PEC composition comprising PEC:PLA-particles (150 mesh) With ratio 1:1.
    DRY PROPERTIESTreatment Strain stadv Tensile stadv Tensile stadv@ peak index stiffness(%) (Nm/g) index(Nm/g)Untreated reference 16,4 2,5 24,4 1,1 170,3 11,9OC-C 7,0 0,9 21,0 0,9 1600,9 141,6190 °C 2 minOC-C 7,73 1,9 20,6 0,7 1411,53 530,84190 °C 4 minOC-C 6,57 1,1 18,99 0,7 1799,32 236,03190 °C 6 minPEC+PLA-particles 1:1 190 °C 2 min 10,5 1,4 22,8 1,2 1673,5 51,5PEC+PLA-particles 1:1 190 °C 4 min 10,2 1,0 22,3 1,3 l447,1 261,3PEC+PLA-particles 1:1 190 °C 6 min 8,0 0,7 22,9 1,0 1939,3 141,4 The percentage increase in the different mechanical properties were calculated from Table 5and are presented in Table 6. The comparison is performed between non-particle PEC composition and particle PEC composition for each curing temperature and time.
    Table 6. Increase in percentage of dry mechanical properties for particle PEC compositioncomprising PEC:PLA-particles (150 mesh) with ratio 1:1 in comparison to non-particle PECcomposition OC-C.
    DRY PROPERTIESIncrease in. Increase in Increase in tensileMinutes of . . . .curin stram @ tensile mdex stlffnessg peak (Nm/g) index(Nm/g)Curing at 190 °C 2 49,00 8,59 4,544 32,08 8,40 2,526 21,77 20,48 7,78 It is obVious that PLA-powder (melting point 170 °C) needs to melt properly to have an effecton the mechanical properties. Curing at 190 °C for 2 min results in 49 % increase instrain/elongation for PEC compositions with addition of PLA-particles. Curing at 190 °C for 6min results in 20% increase in dry tensile index for PEC compositions with addition of PLA- particles.
    Experiment 5 - Evaluation of the stability of particle PEC compositions throughperformance test To evaluate the stability of the particle PEC composition comprising PEC:PLA-particle (150mesh) 1:1, a test to treat NW with 6 weeks old forrnulation was performed. The NW wastreated according to Method 1 (curing at 190 °C for 2 min). Tensile tests were conductedaccording to Method 3 and Method 4. Results are shown in Table 7. Dry tests were performedon 100% Viscose NW and wet tests on 100% bio-based NW. 21 Table 7. Test of stability of the particle PEC composition comprising PEC:PLA-powder (150 mesh) 1:1 by treating NW With 6 weeks old forrnulation. Curing was done in 190 °C for 2 min.DRY PROPERTIES WET PROPERTIESTreatment Strain stadv Tensile stadv Tensile stadv Strain stadv Tensile stadv Tensile stadv@ index stiffness @ index stiffnesspeak (Nm/g) index peak (Nm/g) index(%) (Nm/g) (%) (Nm/g)Freshly 10,5 1,4 22,8 1,2 1673,5 51,5 12,6 2,2 5,6 0,6 162,1 19,4producedStored 6 9,6 1,6 20,9 1,5 l358,7 255,8 12,8 2,4 5,9 0,4 191,3 38,3weeks at23 °C There is no significant change between the two series which shows that the particle PEC composition is stable.
    The same stability study was perforrned for particle PEC composition 5 and particle PEC composition 6. The NW was treated according to Method 1 (curing at 180 °C for 3 min).
    Tensile tests were conducted according to Method 3 and Method 4. The results are shown in Table 8. Dry tests were perforrned on 100% Viscose NW and wet tests on 100% bio-based NW.
    Table 8. Test of stability of the particle PEC composition by treating NW with 7 weeks old formulation. Curing was done in 180 °C for 3 min.
    DRY PROPERTIES WET PROPERTIESTreatment Tensile stadv Tensile stadv Tensile stadv Tensile stadvindex stiffness index stiffness(Nm/g) index (Nm/g) index(Nm/g) (Nm/g)Particle PECcomposition 5, 17,5 6,9 1058,2 165,7 5,7 0,2 229,9 12,1freshly producedParticle PECcom osition 5,Storedpfor 7 Weeks 21,0 1,7 1006,4 296,0 5,9 0,7 182,3 47,0at 23 °CParticle PECcomposition 6, 17,1 1,6 981,1 203,08 5,1 0,5 161,6 35,4freshly producedParticle PEC 21,9 0,5 990,2 290,6 5,4 0,4 219,2 24,6composition 6,Stored for 7 weeksat 23 °C As can be seen in Table 8, both the dry tensile stiffness and the wet tensile index are more or less unchanged for 7 weeks old particle PEC composition. One property that changes over 22 time is dry tensile index Which seems to slightly increase as the forrnulation is aged yielding a stronger material.
    Experiment 6 -Production of particle PEC composition comprising protein powders and their stability Since PEC disperses bioplastic particles Well, it Was tested to disperse other types of hydrophobic particles such as proteins (soy protein concentrate (SPC), lupine protein concentrate (LPC), pea protein (PP), Wheat gluten (WG), Vital Wheat gluten (VWG)). Particle PEC composition With the ratio PEC:protein powder 130.5 Was produced according to Method 7. A defoamer Was added in 0.2 Wt% concentration to reduce foam, resulting in smooth formulations Which did not separate during storing for at least 1.5 months.
    Experiment 7 - Influence of the mechanical and surface properties of 100% viscosenonwoven by particle PEC compositions comprising protein powders NW Was treated With particle PEC composition comprising proteins With the ratio 130.5 (produced according to Method 7) according to Method 1. Tensile tests Were conducted according to Method 3 and Method 4. See Table 9 for results. Dry tests Were performed on 100% viscose NW and Wet tests on 100% bio-based NW.
    Table 9. Dry and Wet mechanical properties for nonWoVen treated With particle PEC composition comprising proteins With ratio PEC:protein 1:0.5.
    DRY PROPERTIES WET PROPERTIESStëlin Tensile Sïšlíišâls: Ståhl Tensile Sïšlíišåls:Treatment stdv index stdv . stdv stdv index stdv . stdvpeak (Nm/g) index peak (Nm/g) index(%) (Nm/g) (%) (Nm/g)Refunrreared 16,4 2,5 24,4 1,1 170,3 11,9 17,7 2,7 1,4 0,1 22,5 3,3oc-c 12,9 1,0 25,3 1,0 891,7 196,5 18,9 3,0 3,4 0,2 102,5 6,4PEffà/:VG 13,5 0,7 22,3 1,6 1060,4 163,7 15,6 2,0 3,3 0,3 105,6 33,8pågå 11,6 1,8 21,5 1,1 1356,3 229,8 18,0 1,9 4,2 0,3 116,4 29,1pEföLgc 9,5 1,8 15,3 0,9 1240,4 214,4 18,2 2,3 2,7 0,3 77,1 16,1PEIçöSÉC 13,7 1,4 22,8 1,0 929,4 283,1 19,4 3,0 3,0 0,3 94,5 38,8 Same treated materials Were tested for hydrophobicity according to method 2 presented in table 10. 23 Table 10. Hydrophobicity according to method 2 for material treated with particle PEC composition comprising proteins with ratio PEC:protein 1:0.5.
    Particle PEC composition Day 1 Day 5PEC:VWG + to +++ ++ to +++PEC:PP - -PEC:LPC + ++ to +++PEC:SPC -- - Besides the fact that the tested proteins result in good dispersions, it is seen that by addingVWG to PEC, the wet strength can be increased. Almost all of the tested protein powders didnot affect the dry tensile index negatively, showing that the powders did not interfere with thebinding properties of PEC. Hydrophobic properties could be achieved by incorporating VWGand LPC. On the other hand, the inherent hydrophilicity of the PEC composition could be maintained when incorporating PP and at the same time boosting up wet strength.
    Summary of experiment 1-8 PEC creates stable dispersions of bioplastic particles. The PEC compositions comprisingbioplastic particles show good dry mechanical properties on NW. The dry mechanicalproperties are increasing with temperature and time. While the melting point of bioplasticparticles is individual for each type of plastic, the treatment temperature and time need to be optimized for each case. The treated NW are showing low to excellent hydrophobicity.
    PEC also creates good dispersions of many non-water soluble protein powders. NW treatedwith PEC composition comprising protein powders increase:0 wet strength (PP) with maintained hydrophilicity,0 hydrophobicity without losing dry mechanical properties (VWG), PLA is known to degrade in water and especially in acidic conditions which is a requirementfor forming the PEC. This is however not observed in PLA PEC compositions of the presentinvention shown by the fact that mechanical properties change very little over time whencomparing treated materials using freshly prepared particle PEC composition vs. aged composition. 24 Experiments 9-11 - addition of PEC compositions to pulp suspensions To evaluate the ability of the particle PEC composition to transfer particle properties to fibersin a fiber suspension, paper sheets Were produced Where PEC composition Without particlesand particle PEC compositions Were added in the wet end of the paper process respectivelyand compared. The forrned paper sheets Were evaluated With tensile tests, contact angle measurements and Gurley.
    Abbreviations experiments 9-11 Below, all abbreviations used in experiments 13-14 are listed.
    C Chitosan CMC Carboxymethyl cellulose OC-C (2 Wt% chitosan 90/100/A1, 2 Wt% Finnfix 5, 12 Wt% citric acid mono hydrate, 0,2Wt% Nipacide BSM) produced according to Method 11 PEC+PLA OC-C but With 71,8 Wt% Water in the recipe exchanged With Dispersion 7 (1 %PLA With 0,1% SDS as only additional compound) produced according to Method 12 PEC Polyelectrolyte complex PLA Polylactic acid Methods experiments 9-11 0 Method 10: Pulp suspension consisting of sodium hydrogen sulfate bleached CTMPfibres (mean fibre length 1,2-1,5 mm) from Rottneros Was prepared in 18-22 °C tapWater and diluted to 0.5 Wt%. The total amount (40 1) Was divided to 2.5 l and the pHWas adjusted to 5.5-6.5 With citric acid solution (citric acid mono hydrate:tap Water,1:2) in every batch, prior to use. The strength system (i.e. PEC composition) Was thenadded to the pulp suspension in different amounts and stirred vigorously With apropeller 10 min before the sheet forrning Was started. The pH Was controlled 1-2times during this 10 min and adjusted to <6.5 if it had risen. 0 Method 11: Paper sheets Were produced using Rapid Köthen sheet former and thendried for 8 min at 92 °C under vacuum (about 100 kPa). The resulting sheets got apaper density of around 60 g/mz. Five sheets at each test point Were made. In somecases, additional drying Was performed at 190 °C for 3 min in a Termaks oven. 0 Method 12: Tensile tests for dry paper sheets Were performed by using TestometricM250-2.5AT (pretension: 0,1 N, sample length: 100 mm, sample Width: 15 mm,speed: 20 mn1/min, Loadcell 0: 50 kgf) after having test specimens at least 1 day at 23°C and 50 % RH. Three test specimen for each paper sheet Were cut out and tested.
    Equipment experiments 9-11 Below, the equipment used in examples 9-11 is listed. pH in forrnulations and paper suspension was measured with pHenomenal pH1000Hfrom VWR with Hamilton Polilyte Lab Temp BNC electrode (calibrated with bufferspH 4, 7 and 10).
    Homogenization of forrnulations in lab scale was performed using IKA T25 digitalUltra-Turrax.
    Pulp suspension was created using a pulper Tico 732 Hengstler from PTI Austria.Paper sheets were produced on lab scale using Rapid-Köthen sheet former type RK-2A.
    Stirring of forrnulations and pulp suspensions was done with an overhead stirrer fromIKA (either Eurostar digital IKA-Werke or IKA RW28 basic) together with apropeller.
    Additional drying of papers from Rapid Köthen was done in an oVen from Termaks(suspended with clamps).
    Tensile tests were conducted using Testometric M250-2.5AT (machine capacity 2,5kN) together with Wintest Analysis software.
    Contact angles were measured with PGX Serial 50585 from FIBRO Systems ABtogether with the software The PocketGonimeter Program Verison 3.3 Gurley was measured with L&W Densometer (Type: 6_4, No.: 2241) fromLorentzen&Wettre Chemicals used in experiments 9-11 Below, all chemicals used in experiments 9-11 are listed. 1,2-Benzisothiazol-3(2H)-one, Nipacide BSM Clariant2-methyl-2H-isothiazol-3-one Carboxymethyl cellulose FinnFix 5 CP KelcoChitosan Chitosan 90/100/A1 Kraeber Citric acid monohydrate Citronsyra Mono E33 8- Univar AB SOM LT Sodium dodecyl sulfate (SDS) Sigma AldrichSunflower oil Sunflower oil 745100 AAK PLA Ingeo 103 61D Natureworks 26 Experiment 9 - Influence of particle PEC compositions on the mechanical properties ofpaper sheets Paper suspension was made according to Method 10 and paper sheets with and withoutadditives were produced according to Method 11. Since the amount of PEC in relation tofibers is important, it was decided to add the two forrnulations (OC-C and PEC+PLA) to thepaper suspension so that amount of solid content in the forrnulations in relation to fibersbecame 1 % respectively.
    The forrnulations were diluted to 1 wt% based on total solid content (i.e. 10 g forrnulation and130 g and 150 g water for OC-C and PEC+PLA, respectively), to receive a lower Viscosity.
    Dry tensile tests were conducted using Method 15. The results are shown in Table 11.
    Table 11. Additions of OC-C and PEC+PLA. Addition to fiber is calculated on the total solid content in the forrnulations.
    Mean Stdav Increase. Addition Mean Stdav Mean Stdav Increase . . inDrymg to fiber tensile tensile Increase final final in final tenslle tenslle tensileFormulation temp . . in tensile . . . stifïness stifïness .if [oc] (dry/dry) index mdex index [%] stram stram stram index index stl ness 1%] 1Nn1/g] 1Nn1/g] 1%] 1%] 1%] [Nm/g] [Nm/g] ilfïlx rêf 95 0 18,84 2,11 1,03 0,16 2800,54 221,34OC-C 95 1 19,65 1,74 4,31 1,09 0,12 5,50 2726,42 153,53 -2,65PECJPPLA 95 1 22,80 1,22 21,00 1,16 0,11 12,97 3128,06 154,98 11,70 Since PLA melts above 95 °C (which is the drying temperature in Rapid Köthen) it was testedto dry half the numbers of the paper sheet for the OC-C and PEC+PLA series at 190 °C for 3 min, see Table 12.
    Table 12. Additions of OC-C and PEC+PLA. Addition to fiber is calculated on the total solidcontent in the forrnulations. The increases in different properties are based on the reference series that only has been dried in 95 °C in the Rapid Köthen dryer.
    IncreaseDr .n Addition Mean Stdav Increase Mean Stdav Increase àïâ: ëåisâilš inFormulation yl g to fiber tensile tensile in tensile final final in final . . tensiletemp . . . . . . stlfïness stlfïness . if[oc] (dry/dry) mdex mdex mdex stram stram stram index index st] ness1%] 1Nn1/g] 1Nn1/g] 1%] 1%] 1%] 1%] [Nm/g] [Nm/g] index1%]ref 190 0 21,52 1,02 14,21 1,31 0,08 26,92 2480,12 183,92 -11,44OC-C 190 1 22,65 1,45 20,22 1,42 0,09 38,04 2403,85 140,94 -14,16PEC+PLA 190 1 26,13 1,13 38,71 1,45 0,14 40,46 2841,61 193,35 1,47 27 The inclusion of PLA to the PEC composition clearly shows that the PLA properties aretransferred to the fibers in a pulp suspension. This yields a 21% increase in tensile index and a11.7% increase in tensile stiffness index if the paper sheets are dried at 95 °C (see table 11).The differences in paper sheet properties are also obvious When comparing PLA PEC compositions (PEC+PLA) With only PEC composition (OC-C).
    When paper sheets are subjected to an additional drying step (190 °C/3 min) tensile indexincrease is further elevated to about 39 % and increase on final strain to about 40% (see table 12). This further demonstrates the effect PLA PEC composition has on the paper sheets.
    Experiment 10 - Influence of particle PEC compositions on the surface properties ofpaper sheets measured by contact angle Contact angles for sheets produced according to Method 10 and Method 11 Were measured.Table 13 shows the dynamic contact angle over a period of 60 s for paper With OC-C and PEC+PLA as additive When the 0.5 % and 1 % (d/d) additions to fiber Was calculated on the total solid content.
    In table 13 it can be seen that When using OC-C or PEC composition of the invention(PEC+PLA) as additive to pulp suspension a relatively elevated initial contact angle can beachieved Which diminishes quickly. HoWever, increasing drying time and temperature to 190°C for 3 minutes yields a contact angle of 71 .3° over 60 second for the PEC+PLA composition.
    Table 13. Contact angle for papers With additions of OC-C and PEC+PLA. Addition to fiber is calculated on the total solid content in the forrnulations.
    Dynamic contact angle [°] Formulation Drying temp [°C] Addition to fiber (dry/dry) [%] Dynaïllllèlceontact1 s 30 s 60 s Ref 95 0 <45 0 0 95 0.5 <45 0 0 OOC 95 i 79.4 0 0 95 0.5 47.2 0 0 PEC+PLA 95 1 <45 0 0 PEC+PLA 190 °C 0.5 91.2 0 0190 °C 190 °C 1 92.4 83.2 71.3 28 Experiment 11 - Influence of particle PEC compositions on the air permeabilityproperties of paper sheets measured using the Gurley method To investigate if the air perrneability of the paper sheets (i.e. the internal structure and thesurface finish of the paper) is affected when the PEC compositions were used as additives inthe wet end of the paper making process, the Gurley method was used and Gurley seconds for 100 cc were deterrnined.
    Two paper sheets for each test point were measured at three different spots. The results are shown in table 14.
    Table 14. Gurley (100 CC) for paper sheets with additions of OC-C and PEC+PLA. Addition to fiber is calculated on the PEC solid content in the forrnulations. Two sheets were tested at three spots.Gurley for 100 CC [Gurley seconds]Formulation Drying temp [°C] Addition to fiber (dry/dry) [%] Mesïlëšfdllslliley stdavRef 95 0 3.6 0.795 0.5 3.5 0.5OOC 95 1 2.9 0.295 0.5 2.4 0.2PEC+PLA 95 1 2.3 0.2PEC+PLA 190 °C 0.5 2.4 0.2190 °C 190 °C 1 2.3 0.2 Table 14 shows that the Gurley is lower (air perrneability is higher) for the sheets includingPEC+PLA (both when compared to reference sheets and sheets containing OC-C). From thisit can be concluded that the PLA particles from PEC+PLA composition make the paper sheets more porous, nevertheless both stiffer and stronger.
    Summary of experiments 9-11 In the above examples it is shown that PEC can transfer the hydrophobic, mechanical and surface properties of PLA, in the particle PEC composition, to the forrned paper sheets.
    Materials treated with the PEC composition of the present invention need curing to developthe mechanical and hydrophobic properties meant through treatment. The curing can be done at temperatures between 20 °C and 200 °C, preferably between 80 °C and 190 °C, more 29 preferably between 120 °C and 180 °C. For reaching the best results, the curing temperature and time need to be optimized for each material and process.
    As will be understood by those skilled in the present field of art, numerous changes andmodifications may be made to the above described and other embodiments of the presentinVention, without departing from its scope as defined in the appending claims. For example,the pulps may be any kind of pulp, i.e. mechanical pulp, therrno-mechanical pulp, chemo-mechanical pulp, sulphate pulp, sulphite pulp, bleached pulp, unbleached pulp, short-fibrepulp, long-fibre pulp, mixtures of different pulp grades etc. The invention works irrespective of the kind of pulp chosen.
    The term paperboard is here used as wide term including all kinds of different cellulose-basedboard grades, e. g. paper board, cardboard, corrugated board, single or multiply board, foldingboxboard, chipboard etc.
    While for the clarity reasons, the PEC compositions are described in the following claimsonly as binders for fiber based materials, textiles, woven and nonwoven materials (i.e. appliedin the dry end of the process), it is equally understood that they can act as strength additiVes in the wet end of the process.
    A Various number of plasticizers may be used together with plastics known in the art without departing from the scope of the inVention.
    Other type of particles may be used instead of plastics such as proteins, inorganic fillers, resins, pigments.
    Various aspects and embodiments of the present invention are defined by the following numbered claims.
    权利要求:
    Claims (37)
    [1] 1. Bio-based polyelectrolyte complex (PEC) composition suitable as a binder for fiber basedmaterials, textiles, woven and nonwoven materials, said PEC composition comprisingcationic biopolymer, anionic biopolymer, acid, and a preserVatiVe wherein - net charge of the PEC is cationic, - the charge ratio of the anionic polymer and the cationic polymer is S1, - the cationic biopolymer is chitosan, - the anionic biopolymer is a polyanion deriVed from nature, - the acid is a Brønsted acid and/or a Lewis acid, wherein the Brønsted acid isselected from any organic and/or inorganic acids, wherein the Lewis acid isselected from any cationic mono- or multivalent atom, - the weight ratio between cation and anion is l:0.l to 1:20, - the weight ratio between the cation and acid is l:0.0l to 1:30, - the pH is less than 7, and wherein said composition further comprises non-water soluble particles.
    [2] 2. PEC composition according to claim 1, wherein the non-water soluble particles are one ormore of plastic particles and/or bioplastic particles and/or protein particles and/or hydrophobic particles.
    [3] 3. PEC composition according to any one of the preceding claims, wherein a weight ratio ofPEC:non-water soluble particles is l:0.0l to 1:50, preferably l:0.05 to 1:20, more preferably1:0.1to 1:10, most preferably l:0.5 to 1:1.
    [4] 4. PEC composition according to claim 1, wherein chitosan has a degree of deacetylation being 66-100 %.
    [5] 5. PEC composition according to any one of the preceding claims, wherein the anionicpolymer is selected from the group consisting of lignin alkali, lignosulfonic acid, and apolysaccharide, preferably chosen from the group consisting of carboxymethyl cellulose(CMC), alginic acid, pectin, carrageenan, gum arabic and nanocrystalline cellulose(N CC),more preferably from the group consisting of carboxymethyl cellulose, alginic acid sodiumsalt, lignin alkali, NCC and gum arabic, most preferably carboxymethyl cellulose;,and *wherein the concentratiori of the ariicm is 0005-30 31
    [6] 6. PEC composition according to any one of the preceding claims, Wherein the concentrationof the acid is 001-30 xxftïê, and the acid is selected from the group consisting of acetic acid,acetylsalicylic acid, adipic acid, benzenesulfonic acid, camphorsulfonic acid, citric acid,dihydroxy fumaric acid, forrnic acid, glycolic acid, glyoxylic acid, hydrochloric acid, lacticacid, malic acid, malonic acid, maleic acid, mandelic acid, oxalic acid, para-toluenesulfonicacid, phtalic acid, pyruvic acid, salicylic acid, sulfuric acid, tartaric acid and succinic acid,preferably citric acid, oxalic acid and tartaric acid, more preferably citric acid, most preferably citric acid monohydrate.
    [7] 7. PEC composition according to any one of the preceding claims, Wherein the PECcomposition further comprises Water, and said Water being selected from tap water, distiiled xvater, and/or deioriized vvater.
    [8] 8. PEC composition according to any of the preceding claims, Wherein said pH preferably is in the interVal of 1 .8-4.
    [9] 9. PEC composition according to any one of the preceding claims, comprising at least 0.04Wt% PEC, preferably at least 1.5 Wt % PEC, more preferably at least 4 Wt % PEC, mostpreferably 4-10 Wt% PEC.
    [10] 10. PEC composition according to any of the preceding claims, Wherein the concentration of the anion is 0.005-30 Wt%, preferably 0.05-10 Wt%, and more preferred 0.75-2 Wt%.
    [11] 11. PEC composition according to any of the preceding claims, Wherein concentration of chitosan is 0.005-30Wt%, preferably 0.05-10 Wt%, and more preferred 0.75-2 Wt%.
    [12] 12. PEC composition according to any of the preceding claims, Wherein the concentration of the acid is 0.01-30 Wt%, preferably 1-20 Wt%, and more preferably 9-12 Wt%.
    [13] 13. PEC composition according to any one of the preceding claims, Wherein the compositionoptionally comprises one or more additives selected from the group consisting of non-Watersoluble plasticizer, Water soluble plasticizer, defoamer, foaming agent, Wetting agent,coalescent agent, catalyst, surfactant, emulsif1er, conserVatiVe, cross-linker, rheologymodif1ers, , nonionic polymers, dye, pigment, Wherein the concentration of the additive is 0- 99 Wt%, preferably 0-50 Wt%, more preferably 0-30 Wt%. 32
    [14] 14. PEC composition according to any one of the previous claims, Wherein the preservative isselected from fiangicide, bactericide, pharrnaceutical preservative, cosmetic preservativeand/or food preservatives, and Wherein the food preservative is selected from benzoic acid,sodium benzoate, hydroxybenzoate and deriVatiVes thereof, lactic acid, propionic acid andsodium propionate, sulfur dioxide and sulfites, sorbic acid and sodium sorbate, ascorbic acid,sodium ascorbate, butylated hydroxytoluene, butylated hydroxyanisole, gallic acid andsodium gallate and tocopherols , and Wherein the fungicide or bactericide is selected from 1,2-benzisothiazolin-3-one, and Wherein the cosmetic preservative is selected from 2-methyl-4-isothiazolin-3-one, and Wherein the pharrnaceutical preserVatiVe is selected from 2-bromo-2- nitro- 1 ,3-propanediol
    [15] 15. PEC composition according to claim 14, Wherein the PEC composition comprises 0.005-10 Wt% preservative, preferably 0.005-1.5 Wt% preservative, more preferably 0.005-0.5 Wt% preservative.
    [16] 16. PEC composition according to claim 13, Wherein said non-Water soluble plasticizer isnaturally based, preferably selected from one or more of the group consisting of polyethyleneglycol, triacetin, dibutyl sebacate, epoxidized soy bean oil, isosorbide ester, isosorbide diester,triethyl citrate, tributyl citrate, diethyl succinate, dimethyl glutarate, dimethyl adipate,dimethyl succinate, glyceryl oleate, glyceryl linoleate, glyceryl palmitate, diethyl adipate,sorbitan distearate, glyceryl stearate, sucrose distearate, rapseed methyl ester, diethylhexyladipate, sorbitan tristearate, diisopropyl adipate, diethylhexylsuccinate, glycerylmonostearate, sucrose distearate, dimethyl succinate, tributyl-2-acetylcitrate, tributyl acetylcitrate, oligomeric ester amide, more preferably selected from epoxidized soy bean oil, sorbitan laurate and sorbitan oleate.
    [17] 17. PEC composition according to any one of the preceding claims, Wherein said bioplasticsparticles are selected from one or more of polylactic acid (PLA), (and co-coplymers such asL-PLA, D-PLA, DL-PLA, PLGA, PDLA), polyhydroxy alkanoates (PHA) (and Variations ofthereof such as PHB, PHBV, P3HB, P4HB, PHbHHx, P(3HB-co 20%mol-3HV, P(3HB-co4HB), P(3HB-co 6% mol-3HA), P(3HB-co 4HP), P(3HB-co SHHX), PHBHHX),ethylcellulose, cellulose acetate, polycaprolactone, therrnoplastic starch, polybutylenesuccinate, preferably selected from PLA, PHA and therrnoplastic starch 33
    [18] 18. PEC composition according to any of the preceding claims, Wherein said protein particlesis selected from one or more of pea protein, vital Wheat gluten, Wheat gluten, lupine protein,soy protein, soybean protein, maize protein, zein protein, peanut protein, caseine, andsimilarplant-based or yeast based proteins as isolates and/or fluors, or hydrophobins(small proteinsof from 100 to 150 amino acids and are characteristic of filamentous fungi e. g.Schízophyllum commune generally having 8 cysteine units) keratin, animal protein such asfish protein, albumin, milk protein and non-limiting examples of other sources of vegetableprotein including e g nuts, seeds, grains and legumes especially almonds, brazil nuts, casheWs,Walnuts, pecans, hazel nuts, macadamia nuts, sunfloWer seeds, pumpkin seeds, com and thelike, or protein-containing biomasses, such as Waste sludge manure and composed manure,preferably selected from pea protein, vital Wheat gluten, Wheat gluten, lupine protein, soybean protein, maize protein, zein protein, caseine and keratin.
    [19] 19. PEC composition according to any one of the preceding claims, Wherein said plastics areselected from one or more of Polyester , Polyethylene terephthalate, Polyethylene, High-density polyethylene, Polyvinyl chloride, Polyvinylidene chloride, LoW-density polyethylene,Polypropylene, Polystyrene, High impact polystyrene, Polyamides, Acrylonitrile butadienestyrene, Polyethylene/Acrylonitrile Butadiene Styrene, Polycarbonate,Polycarbonate/Acrylonitrile Butadiene Styrene, Polycarbonate, Polycarbonate/AcrylonitrileButadiene Styrene,, Polyurethanes, Maleimide/ Bismaleimide, Melamine forrnaldehyde,Phenolics, Polyepoxide, Polyetheretherketone, Polyetherimide, Polyimide, Polymethylmethacrylate, Polytetrafluoroethylene, Urea-forrnaldehyde, Furan resin, Silicone, Polysulfone,and Polyoxymethylene, preferably selected from Polycaprolactone, Polyethyleneterephthalate, Polyethylene, Polypropylene.
    [20] 20. PEC composition according to any one of the preceding claims, Wherein the non-Watersoluble particles are selected from the group consisting of plastics, proteins, solid Waxes, solid resins, f1llers, pigments, fiamed silica, and mixtures thereof
    [21] 21. Bio-based polyelectrolyte complex (PEC) composition according to claim 1 or2, Whereinsaid non-Water soluble particles have a particle size in the range of >0-1 mm, more preferably of >0-500 um, most preferably of >0-300 um.
    [22] 22. PEC composition according to claim 20, Wherein said solid Wax is a vegetable Wax or ananimal Wax having a melting point of 27 °C-220 °C, and being preferably selected from the group consisting of Bayberry Wax, candelilla Wax, camauba Wax, castor Wax, esparto Wax, 34 japan Wax, ouricury Wax, rice bran Wax, soy Wax, talloW tree Wax, beesWax, Chinese Wax, lano lin Wax (Wool Wax), shellac Wax, sperrnaceti Wax, and mixtures thereof
    [23] 23. PEC composition according to claim 20, Wherein said solid Wax is a mineral, syntheticWax and/or petroleum derived Wax having a melting point of 27 °C-220 °C, and beingpreferably selected from the group consisting of paraff1n Wax, microcrystalline Wax, ceresin Wax, montan Wax, ozocerite Wax, polyethylene Wax, and peat Wax.
    [24] 24. PEC composition according to claim 20, Wherein said resin is solid at temperature 0 °C-35°C and is a plant and/or animal and/or petroleum derived resin and/or a synthetic resinpreferably selected from the group consisting of asphaltite and Utah resin, shellac, copals,dammars, mastic, and sandarac, frankincense, elemi, turpentine, copaiba, gum resins, Aleppopine resin, bisphenol A diglycidyl ether and silicone resins, more preferably selected from plant based resins such as furan, rosin and gum resins.
    [25] 25. PEC composition according to claim 20, Wherein said particle is a pigment selected from inorganic and/or organic pigments.
    [26] 26.. PEC composition according to claim l8, Wherein said f1llers and pigments are preferablyselected from the group consisting of clay, calcium carbonate, titanium dioxide, talc, ironoxides, barium sulfate, barium carbonate, aluminum sulfate, kaolinite, calcium magnesiumcarbonate, magnesium carbonate, satin pigment, zinc oxide and zinc sulf1de, more preferably selected from clay, titanium dioxide, and aluminum sulfate.
    [27] 27. PEC composition according to claim l8, Wherein said particle is hydrophobic or hydrophilic fumed silica.
    [28] 28. Method of preparing a PEC cornpositioii according to any one ofthe precerliiig claims,conigviisiiig the steps of:rriixing Ltliitosêtri, anionic polyrïmfr, and acid, - and including one or more particle types.
    [29] 29. Method of preparing according to claim 28, Wherein said method optionally comprises at least one homo genization step.
    [30] 30. Method of preparing according to claim 28, comprising the steps of: a) Adding the anionic polymer to Water, b) Adding chitosan to the resulting mixture in step a,c) Adding acid to the resulting mixture in step b,d) Adding one or more particle types to the resulting mixture in step c, *Nhereiii the rafsultirig niixtures in steps a-d are iriixed and olfrtionally liorriogeriizeti
    [31] 31. Method of preparing according to claim 28 comprising the steps of a) .Addin g the anionic polyiner to water, b) Adding chitosan to the resulting niixture in step a, e) ivlixiiig the acid ayitii Water, and adding the Jresidting acidic solution to the resulthig mixtuirein step b, d) Adding one or more particle types to the resulting mixture in step c, Wherein the resulting mixtures in steps a-d are mixed and optionally homogenized.
    [32] 32. Method of preparing according to claim 28, comprising the steps of a) Adding the anionic polymer to Water, b) Adding chitosan to the resulting mixture in step a, c) Mixing the acid With Water, and adding the resulting acidic solution to the resulting mixture in step b,d) Adding one or more particle types to the resulting mixture in step c,e) Adding the preserVatiVe to the resulting mixture in step d, and Wherein the resulting mixtures in steps a-e are mixed and optionally homogenized.
    [33] 33. Use of a particle PEC composition according to any one of claims 1-27 as binder for fiber based materials, textiles, Woven and nonWoVen materials.
    [34] 34. Fiber based materials, textiles, Woven and nonWoVen materials comprising a particle PEC composition according to any one of claims 1-27 as a binder.
    [35] 35. Method of treating fiber based materials, textiles, Woven and nonWoVen materials With aparticle PEC composition according to any one of claims 1-27, comprising the following stepsof a. Treating the fiber based materials, textiles, Woven and nonWoVen materials With a PEC composition byi. addition to suspensions of fiber based materials, textiles, Woven andnonwoven materials ii. spray coating, 36 iii. iv. Vi.5 Vii.Viii. iX. Xi. dip coating, roll coating, impregnation, padding, screen coating, printing, direct coating methods including knife coating, blade coating, WireWound bar coating, round bar coating and crushed foam coating,indirect coating methods including Mayer rod coating, direct rollcoating, kiss coating, graVure coating and reverse roll coating, ink jet and/or slit-die/slot-die, b. Optionally curing the treated fiber based materials, textiles, Woven and nonWoVen materials.
    [36] 36. lwíaäthod of treating according to claim 35, further rsoinprrising the step of curing the treated 15 fiber laaseol inaterials, textiles, Woven arxd iionwoven materials, Wherein the curing is performed at 20 °C to 220 °C, more preferred at 100 °C to 200 °C, most preferred at 140°C to 195 °C.
    [37] 37. Method of treating according to any one of claims 35-36, Wherein said fiber based material consists of paper and/or paperboard and said treatment is performed either during 20 manufacture of said paper and/or paperboard or on already finished paper and/or paperboard. 37
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    SE1651138A|SE540758C2|2016-08-24|2016-08-24|Bio-based polyelectrolyte complex compositions comprising non-water soluble particles|SE1651138A| SE540758C2|2016-08-24|2016-08-24|Bio-based polyelectrolyte complex compositions comprising non-water soluble particles|
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