Bio-based polyelectrolyte complex compositions comprising non-water soluble particles

Abstract

The present 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, chitosan has a degree of deacetylation being 66-100%, the pH is less than 7, and wherein said composition further comprises one or more non-water soluble particles. The present invention further relates to a method for preparing the PEC composition, uses of the PEC composition, as well as method of treating materials with the PEC composition.

Claims

1. Method of treating materials comprising fiber based materials, textiles, woven materials or nonwoven materials, comprising: applying a bio-based polyelectrolyte complex (PEC) composition suitable as a binder to the materials, wherein the PEC composition comprises: cationic biopolymer, anionic biopolymer, acid, and a preservative, wherein the net charge of the PEC is cationic, the charge ratio of the anionic biopolymer and the cationic biopolymer is ≤1, the cationic biopolymer is chitosan, wherein the chitosan has a degree of deacetylation being 66-100%, the anionic biopolymer is selected from the group consisting of lignin alkali, lignosulfonic acid, and a polysaccharide, the acid is a Brønsted acid and/or a Lewis acid, wherein the Brønsted acid is selected from any organic and/or inorganic acids, wherein the Lewis acid is selected from any cationic mono- or multivalent atom, the weight ratio between the cationic biopolymer and the anionic biopolymer is 1:0.1 to 1:20, the weight ratio between the cationic biopolymer and the acid is 1:0.01 to 1:30, the pH is less than 7, and wherein said composition in addition comprises non-water soluble particles selected from one or more of plastic particles, bioplastic particles, protein particles, hydrophobic particles, solid wax, and solid resins, and wherein a weight ratio of PEC:non-water soluble particles is 1:0.1 to 1:10.

2. The method of treating according to claim 1, further comprising a step of curing the treated fiber based materials, textiles, woven and nonwoven materials, wherein the curing is performed within the range of 20° C. to 220 ° C.

3. The method of treating according to claim 1, wherein said fiber based material consists of paper and/or paperboard and said treatment is performed either during manufacture of said paper and/or paperboard or on already finished paper and/or paperboard.

4. The method of treating according to claim 1, comprising applying the PEC composition to said fiber based materials, textiles, woven and nonwoven materials by one or more of: spray coating, dip coating, roll coating, impregnation, padding, screen coating, printing, direct coating methods selected from at least one of knife coating, blade coating, wire wound bar coating, round bar coating, crushed foam coating, ink jet coating, slit die coating and slot-die coating; and indirect coating methods selected from at least one of mayer rod coating, direct roll coating, kiss coating, gravure coating and reverse roll coating, inkjet, slit-die and slot-die, and a) optionally performing curing of the treated fiber based materials, textiles, woven and nonwoven materials at a temperature of 20 to 200° C.

5. The method of treating according to claim 1, comprising diluting the PEC composition with water selected from distilled water, tap water, and deionized water and treating the fiber based materials, textiles, woven and nonwoven materials with the diluted PEC composition.

6. The method of treating according to claim 1, comprising increasing hydrophobicity of said materials.

7. The method of treating according to claim 1, comprising increasing hydrophilicity of said materials.

8. The method of treating according to claim 1, comprising increasing dry strength of said materials.

9. The method of treating according to claim 1, comprising increasing wet strength of said materials.

10. The method of treating according to claim 1, comprising increasing tensile stiffness of said materials.

11. The method of treating according to claim 1, comprising increasing tensile softness of said materials.

Description

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

(1) 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 further comprise non-water soluble particles. The PEC compositions are suitable as binders for fiber based materials, textiles, woven and nonwoven materials.

(2) Non-water soluble particles refer herein to solid compounds having a solubility in water not exceeding 15 wt %. The non-water soluble particles of the present invention have a particle size preferably in the range of 100 nm-1 mm, more preferably of 100 nm-500 μm, even more preferably of 100 nm-300 μm.

(3) According to the invention the use of the wording textiles, woven and nonwoven may include cloths or fabrics and may be based on natural or synthetic fibers and mixtures thereof.

(4) Textiles, woven and nonwoven may consist of a network of natural and/or synthetic fibers often 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 for example be used in textile assembly trades (such as tailoring and dressmaking) as synonyms for 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, or bonding that may be used in the production of further goods (garments, etc.). Cloth may be used synonymously with fabric but often refers to a finished piece of fabric used for a specific purpose (e.g., table cloth). The wording textiles, woven and nonwoven according to the present invention may include all different types of textiles described above. Textiles, woven and nonwoven according to the invention can be made from many different types of materials and fibers for example animal, plant, wood, mineral, synthetic, sugar based, protein based for example 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 and its derivatives, cornfiber, coir, yucca, sisal, bamboo (rayon) fiber, peanut, soybased, chitin based, milk casein based, keratin based and poly lactic acid based etc. Further, nonwoven materials are fabric-like materials made from long fibers, bonded together by chemical, mechanical, heat or solvent treatment. Nonwoven fabrics are also defined as sheet or web structures bonded together by entangling fiber or filaments (and by perforating films) mechanically, thermally or chemically. The term is used in the textile manufacturing industry to denote fabrics, such as felt, which are neither woven nor knitted. They are flat or tufted porous sheets that are made directly from separate fibers, molten plastic or plastic film.

(5) Fiber based materials refer to materials such as paper materials which comprise a high degree of cellulose. As will be understood by those skilled in the present field of art, numerous changes and modifications may be made to the above described and other embodiments of the present invention, without departing from its scope as defined in the appending claims. For example, the pulps for making fiber based materials may be any kind of pulp, i.e. mechanical pulp, thermo-mechanical pulp, chemo-mechanical pulp, sulphate pulp, sulphite pulp, bleached pulp, 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.

(6) The Examples relate to comparative studies and for investigating the ability of PEC to create dispersions of non-water soluble particles such as bioplastics and proteins as well as the ability of PEC to transfer the properties of the dispersed particles to different materials through electrostatic attraction. To the person skilled in the art it will be obvious that the present invention can also be transferred to other types of particles such as pigments, fillers and similar non-water soluble particles.

(7) The PEC composition according to the present invention can be used as a vehicle in the sense that said composition both has space for and fuel to transport other molecules. In more specific terms, the PEC composition can form a micelle around, for example non-water soluble particles comprised in the PEC composition and thanks to its positive charge, it can thereafter arrange itself towards negatively charged fibers and thus transfer the properties of the non-water soluble particles to the fiber based material.

EXPERIMENTAL SECTION

(8) Charge Ratio

(9) Charge density was measured using the Mütek PCD 02 device. Charge (symbol: q, unit: meqv) was calculated using Eq. 1.
q [meqv]=C.sub.counter ion [eqv/l].Math.V.sub.counter ion [l].Math.1000   (1)
where the counter ion is one of sodium polyethylenesulphate (PES-Na, anionic) or poly-diallyl-dimethyl-ammonium-chloride (poly-dadmac, cationic), depending on the charge of the colloid. If the charge at different concentrations are plotted against mass of the current colloid, the charge density (unit: meqv/g) is the slope of the linear curve. The mass of the colloid can be calculated with Eq. 2.
m[g colloid]=wt % colloid [g colloid/g solution].Math.g [g solution for 10 ml].Math.0,0   (2) When the charge densities were known for one polycation and one polyanion, the charge ratio was calculated between the polyelectrolytes so that the overall charge of the complex became positive (i.e. charge ratio <1), see Eq. 3.

(10) $\begin{array}{cc}\mathrm{Charge}\mathrm{ratio}=\frac{{\left[\mathrm{part}\mathrm{of}\mathrm{complex}.Math.\mathrm{charge}\mathrm{density}\right]}_{\mathrm{polyanion}}}{{\left[\mathrm{part}\mathrm{of}\mathrm{complex}.Math.\mathrm{charge}\mathrm{density}\right]}_{\mathrm{polycation}}}& \left(3\right)\end{array}$

(11) The method above is for measuring charge density and then calculate the charge ratio.

Experiment 1-8—Study of Various Hydrophobic Particles Included in the PEC Compositions and Evaluation of Said PEC Compositions on Nonwoven

Background Experiments 1-8

(12) The binder recipe OC-C (see details in abbreviations experiments 1-8) is based on polyelectrolyte complex (PEC). PEC gives good dry and wet mechanical properties to fiber based materials, nonwovens, paper and textiles. PEC can also be seen as a micelle that can emulsify for example non-water soluble particles. To mix PEC and non-water soluble particles can therefore lead to a dispersion that both gives good mechanical properties to materials (the PEC part of the dispersion) and that creates an additional property on the material which is derived from the particle the PEC composition carries (the particle part of the dispersion).

(13) The experiments below demonstrate that PEC can support and stabilize non-water soluble particles in water to form dispersions. These are then further used as binders/additives on different materials and the properties measured. In the following examples the term particle PEC composition refers to polyelectrolyte complex dispersion containing non-water soluble particles while a polyelectrolyte complex formulation without particles is referred to non-particle PEC composition.

Abbreviations Experiments 1-8

(14) Below, all abbreviations used in experiments 1-8 are listed.

(15) TABLE-US-00001 C Chitosan CHCl.sub.3 Chloroform CMC Carboxymethyl cellulose DBS Dibutyl sebacate EC Ethyl cellulose EC N10 Aqualon EC N10 EC N100 Aqualon EC N100 ID46 Polysorb ID46 LPC Lupine protein concentrate MCC Micro crystalline cellulose MG Maize gluten NW Nonwoven OC-C 2 wt % chitosan 90/100/A1, 2 wt % Finnfix 5, 12 wt % citric acid monohydrate, 0.2 wt % Nipacide BSM, produced according to Method 11 PEC Polyelectrolyte complex PLA Polylactic acid PP Pea protein SPC Soy protein concentrate TBAC tributyl acetyl citrate WG Wheat gluten VWG Vital wheat gluten

Methods Experiments 1-8

(16) Below, all methods used in experiments 1-8 are listed. Method 1: Formulations diluted to 1 wt % and nonwoven treated with padder using 11.6 rpm and pressure 0.1 MPa followed by drying on stenter frame in Termaks oven 150° C. for 3 min. Method 2: Test of hydrophobicity by adding drops of water on the surface. Grades for hydrophobicity: −−=hydrophilic and spreading, −=hydrophilic, +=droplet stays around 1 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: 100 mm/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 was cut 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: 100 mm/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 and two 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 final product. In other words: 1. Homogenize 35.9 g water 1 and 1 g CMC Finnfix 5 using Ultraturrax 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 formulation in aluminum cups in the Termaks oven for 24 h (105° C.). The theoretical dry content was 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. Method 7: 50 g formulation is homogenized using Ultra Turrax T25 with speed 12000 rpm during 1 min after addition of non-water soluble particles. Method 8: General description of production method for PEC composition without non-water soluble particles as additive (100 g formulation): 1. Homogenize 71.8 g water and 2 g CMC Finnfix 5 with Ultraturrax T25 at 9000 rpm for 3 min. 2. Disperse 2 g chitosan in the CMC-solution. 3. Dissolve 12 g citric acid mono hydrate in 12 g water 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 including non-water soluble particles as additive (100 g formulation): 1. Homogenize 69.8 g water and 2 g CMC Finnfix 5 with Ultraturrax T25 at 9000 rpm for 5 min. 2. Disperse 2 g chitosan in the biopolymer solution. 3. Dissolve 12 g citric acid mono hydrate in 12 g water and add to the CMC-solution. Homogenize at 12000 rpm for 5 min. 4. Add 2 g particles to the mixture. Homogenize at 12000 rpm for 5 min. 5. Add 0.2 g Nipacide BMS. Homogenize 1 min. If needed, add 0.2 g Dispelair CF 56 during stirring at the end.

Equipment Experiments 1-8

(17) Below, all equipment used in experiments 1-8 is listed. pH was measured with pHenomenal pH1000H from VWR with Hamilton Polilyte Lab Temp BNC electrode (calibrated with buffers pH 4, 7 and 10). Tensile tests were conducted using Testometric M250-2.5AT (machine capacity 2.5 kN) 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 Viscometer together 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 horizontal padder. Drying of treated paper and nonwoven were done in an oven from Termaks (with stenter frame from Wichelhaus Wi-LD3642 Minidryer/Stenter). Visual evaluation of emulsions and dispersions was done using a Nikon Microphot-FXA with 10× lens.

Chemicals Experiments 1-8

(18) Below, all chemicals used in experiments 1-8 are listed.

(19) TABLE-US-00002 Producer/ Chemical name Commercial name Distributor 1,2-Benzisothiazol- Nipacide BSM Clariant 3(2H)-one, 2-methyl- 2H-isothiazol-3-one Carboxymethyl cellulose FinnFix 5 CP Kelco (CMC) Chitosan Chitosan 90/100/A1 Kraeber Chloroform (CHCl.sub.3) Sigma Aldrich Citric acid mono hydrate Citronsyra Mono Univar AB E33 8-80M LT Defatted toasted soy flour Frasoy-D IP <0.9% L.I. frank, Frank (soy protein concentrate) Food 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 biopolymer Ethyl cellulose water Aquacoat ECD FMC Biopolymer dispersion, 30 wt % Isosorbid ester Polysorb ID46 Roquette Maize gluten Concentra P 13882 Cargill Micro crystalline cellulese Hightcel 90M MCC Sigachi cellulose (MCC) PVT LTD/Brenntag Nordic Pea protein Lysamine GPS Roquette PLA powder Tianjin Glory Tang Technology (through Per Sundblad, SPCC) Polylactic acid (PLA) Ingeo 10361D Nature works Polyoxyethylenesorbitan Tween 40 Sigma Aldrich monopalmitate Polyvinyl alcohol PVOH Mowiol 28-99 Clariant Sodium dodecyl sulfate Sigma Aldrich (SDS) Sorbitol Neosorb 70 Roquette Toasted lupine concentrate Fralu-con L.I. frank, Frank (lupine protein concentrate) Food Products Tributyl acetyl citrate Tecnosintesi (TBAC) Wheat gluten Viten CWS Roquette Vital wheat gluten Gluvital 21040 Cargill

Experiment 1—Study of the Dispersing Properties of PEC

(20) To produce bioplastic particles of suitable size, solvent exchange method was used. The polymer and/or plasticizers were dissolved in an organic solvent. 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 1 for the composition of the PLA- and EC-dispersions used.

(21) TABLE-US-00003 TABLE 1 Composition of PLA- and EC-dispersion prepared with organic solvent. Particle size Dry d(0.5) content Name Polymer Plasticizer Organic solvent Surfactant Stabilizer Water (μm) (%).sup.1 Dispersion 5 PLA (2 g) TBAC CHCl.sub.3 (20 ml) SDS (0.16 g) PVOH 160 g 4.4 1.28 (PLA + 22.5% (450 mg) (0.32 g) TBAC) Dispersion 6 EC DBS Ethyl acetate (50 ml) SDS (0.16 g) PVOH 160 g 0.9 1.66 (EC + 25% DBS) N100 (625 mg) (0.32 g) (2.5 g) Dispersion 7 PLA 10 g — CHCl.sub.3 (100 ml) SDS 1 g — 989 g 21 1.25 (PLA) .sup.1)According to Method 8.

(22) To disperse bioplastic particles using PEC, OC-C was produced with a bioplastic dispersion (Dispersion 5, 6 or 7) as the “Water 1” in the recipe according to Method 7.

(23) 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 forming properties when making 400 μm films with film applicator (drying overnight in 23° C.). Also, the dispersions have an even and homogenous 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 the Treated Material

(24) 100% viscose NW was treated according to Method 1 with the particle PEC compositions from experiment 1. Hydrophobicity of the particle PEC compositions was studied according to Method 2, see Table 2.

(25) TABLE-US-00004 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 5 Dispersion 5 −− −− Particle PEC composition 5 − − to ++ Dispersion 6 −− −− Particle PEC composition 6 − to + − to +  Dispersion 7 −− −− Particle PEC composition 7  ++ to +++ ++ to +++

(26) Table 2 shows that the bioplastic dispersions themselves give hydrophilic NW (probably because of the surfactants) but together with the particle PEC composition of the invention the treated NW becomes hydrophobic. Particle PEC composition comprising PLA without softener 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 PLA Particles

(27) Coating of 100% viscose NW with particle PEC compositions comprising bioplastic particles was done according to Method 1. Tensile tests were conducted according to Method 3. See results in Table 3. Dry tests were performed on 100% viscose NW.

(28) TABLE-US-00005 TABLE 3 Mechanical properties for NW treated with non- particle PEC composition and particle PEC compositions and cured in two different temperatures. DRY Tensile stiffness Sample index (Nm/g) stadv Reference, untreated 170.3 11.9 OC-C, 150° C. 891.7 196.5 OC-C, 180° C. 936.4 348.4 Particle PEC composition 5, 150° C. 1358.7 396.2 Particle PEC composition 6, 150° C. 968.4 157.7 Particle PEC composition 6, 180° C. 981.1 203.08 Particle PEC composition 7, 150° C. 897.9 272.9 Particle PEC composition 7, 180° C. 1324.4 118.1

(29) Dry tensile stiffness increases significantly when PLA particles are used in PEC composition compared to PEC composition without. The required curing temperature, when using pure PLA particles in the PEC composition, is higher (180° C.) than when using PLA plasticized particles (150° C.) in the PEC composition, to reach similar dry tensile stiffness. This is due to the lowering of the melting point of the PLA particles imparted by the plasticizer. This gives the end user of the particle PEC composition an option to choose PLA particle PEC composition with and without a PLA plasticizer depending on the curing temperature used in the process. EC particles have no or small effect on the tensile stiffness index of the treated material.

Experiment 4—Study of the Influence of the Mechanical Properties of 100% Viscose Nonwoven by Particle PEC Compositions

(30) 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.

(31) Grinded PLA-powder with mixed particle size was filtered through 150 mesh wire, equal to <100 μm holes, and tested together with PEC in a particle PEC composition. The PEC-particles used had a melting point of 170° C. The filtered particles were dispersed in OC-C according to Method 7 to reach the ratio PEC:PLA-powder 1:1 and 1:2.

(32) Treatment of NW was done according to Method 1 (curing in 140° C. and 170° C.). Dry properties were tested to investigate the dependence of ratio PEC:PLA, curing temperature and time. Tensile tests were done according to Method 3. The results are presented in Table 4

(33) TABLE-US-00006 TABLE 4 Dry mechanical properties for NW treated with the particle PEC compositions comprising PEC:PLA- particles (150 mesh) with ratio 1:1 and 1:2. DRY Ratio PEC:PLA- Tensile stiffness particles Curing conditions index (Nm/g) stadv 1:1 140° C. 2 min 697.3 154.0 140° C. 4 min 896.6 164.0 170° C. 2 min 1015.1 228.7 170° C. 4 min 1253.1 65.6 1:2 140° C. 2 min 643.3 164.7 140° C. 4 min 782.1 59.2 170° C. 2 min 788.0 107.6 170° C. 4 min 909.9 66.3

(34) The difference in stiffness is dependent on both temperature and time. Curing at 140° C., did not melt all the PLA particles which could be observed on the material (dusty material). The stiffness did not increase when the ratio was changed from 1:1 to 1:2 PEC:PLA.

(35) Based on the above conclusions NW was treated according to Method 1 (curing at 190° C. for 2, 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% viscose NW.

(36) TABLE-US-00007 TABLE 5 Dry mechanical properties for NW treated with non-particle PEC composition and particle PEC composition comprising PEC:PLA-particles (150 mesh) with ratio 1:1. DRY PROPERTIES Tensile Strain Tensile stiffness @ peak index index Treatment (%) stadv (Nm/g) stadv (Nm/g) stadv Untreated reference 16.4 2.5 24.4 1.1 170.3 11.9 OC-C 7.0 0.9 21.0 0.9 1600.9 141.6 190° C. 2 min OC-C 7.73 1.9 20.6 0.7 1411.53 530.84 190° C. 4 min OC-C 6.57 1.1 18.99 0.7 1799.32 236.03 190° C. 6 min PEC + PLA-particles 1:1 190° C. 2 min 10.5 1.4 22.8 1.2 1673.5 51.5 PEC + PLA-particles 1:1 190° C. 4 min 10.2 1.0 22.3 1.3 1447.1 261.3 PEC + PLA-particles 1:1 190° C. 6 min 8.0 0.7 22.9 1.0 1939.3 141.4

(37) The percentage increase in the different mechanical properties were calculated from Table 5 and are presented in Table 6. The comparison is performed between non-particle PEC composition and particle PEC composition for each curing temperature and time.

(38) TABLE-US-00008 TABLE 6 Increase in percentage of dry mechanical properties for particle PEC composition comprising PEC:PLA-particles (150 mesh) with ratio 1:1 in comparison to non-particle PEC composition OC-C. DRY PROPERTIES Increase Increase in tensile Increase in tensile stiffness Minutes of in strain @ index index curing peak (Nm/g) (Nm/g) Curing at 190° C. 2 49.00 8.59 4.54 4 32.08 8.40 2.52 6 21.77 20.48 7.78

(39) It is obvious that PLA-powder (melting point 170° C.) needs to melt properly to have an effect on the mechanical properties. Curing at 190° C. for 2 min results in 49% increase in strain/elongation for PEC compositions with addition of PLA-particles. Curing at 190° C. for 6 min 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 Through Performance Test

(40) To evaluate the stability of the particle PEC composition comprising PEC:PLA-particle (150 mesh) 1:1, a test to treat NW with 6 weeks old formulation was performed. The NW was treated according to Method 1 (curing at 190° C. for 2 min). Tensile tests were conducted according to Method 3 and Method 4. Results are shown in Table 7. Dry tests were performed on 100% viscose NW and wet tests on 100% bio-based NW.

(41) TABLE-US-00009 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 formulation. Curing was done in 190° C. for 2 min. DRY PROPERTIES WET PROPERTIES Tensile Tensile Strain @ Tensile stiffness Strain @ Tensile stiffness peak index index peak index index Treatment (%) stadv (Nm/g) stadv (Nm/g) stadv (%) stadv (Nm/g) stadv (Nm/g) stadv Freshly 10.5 1.4 22.8 1.2 1673.5 51.5 12.6 2.2 5.6 0.6 162.1 19.4 produced Stored 6 9.6 1.6 20.9 1.5 1358.7 255.8 12.8 2.4 5.9 0.4 191.3 38.3 weeks at 23° C.

(42) There is no significant change between the two series which shows that the particle PEC composition is stable.

(43) The same stability study was performed 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 performed on 100% viscose NW and wet tests on 100% bio-based NW.

(44) TABLE-US-00010 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 PROPERTIES Tensile Tensile Tensile stiffness Tensile stiffness index index index index Treatment (Nm/g) stadv (Nm/g) stadv (Nm/g) stadv (Nm/g) stadv Particle PEC 17.5 6.9 1058.2 165.7 5.7 0.2 229.9 12.1 composition 5, freshly produced Particle PEC 21.0 1.7 1006.4 296.0 5.9 0.7 182.3 47.0 composition 5, Stored for 7 weeks at 23° C. Particle PEC 17.1 1.6 981.1 203.08 5.1 0.5 161.6 35.4 composition 6, freshly produced Particle PEC 21.9 0.5 990.2 290.6 5.4 0.4 219.2 24.6 composition 6, Stored for 7 weeks at 23° C.

(45) 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 time is dry tensile index which seems to slightly increase as the formulation is aged yielding a stronger material.

Experiment 6—Production of Particle PEC Composition Comprising Protein Powders and their Stability

(46) 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 1:0.5 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% Viscose Nonwoven by Particle PEC Compositions Comprising Protein Powders

(47) NW was treated with particle PEC composition comprising proteins with the ratio 1:0.5 (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.

(48) TABLE-US-00011 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 PROPERTIES Tensile Tensile Strain @ Tensile stiffness Strain @ Tensile stiffness peak index index peak index index Treatment (%) stdv (Nm/g) stdv (Nm/g) stdv (%) stdv (Nm/g) stdv (Nm/g) stdv Ref untreated 16.4 2.5 24.4 1.1 170.3 11.9 17.7 2.7 1.4 0.1 22.5 3.3 OC-C 12.9 1.0 25.3 1.0 891.7 196.5 18.9 3.0 3.4 0.2 102.5 6.4 PEC:VWG 13.5 0.7 22.3 1.6 1060.4 163.7 15.6 2.0 3.3 0.3 105.6 33.8 1:0.5 PEC:PP 11.6 1.8 21.5 1.1 1356.3 229.8 18.0 1.9 4.2 0.3 116.4 29.1 1:0.5 PEC:LPC 9.5 1.8 15.3 0.9 1240.4 214.4 18.2 2.3 2.7 0.3 77.1 16.1 1:0.5 PEC:SPC 13.7 1.4 22.8 1.0 929.4 283.1 19.4 3.0 3.0 0.3 94.5 38.8 1:0.5

(49) Same treated materials were tested for hydrophobicity according to method 2 presented in table 10.

(50) TABLE-US-00012 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 5 PEC:VWG + to +++ ++ to +++ PEC:PP − − PEC:LPC + ++ to +++ PEC:SPC −− −

(51) Besides the fact that the tested proteins result in good dispersions, it is seen that by adding VWG to PEC, the wet strength can be increased. Almost all of the tested protein powders did not affect the dry tensile index negatively, showing that the powders did not interfere with the binding properties of PEC. Hydrophobic properties could be achieved by incorporating VWG and 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

(52) PEC creates stable dispersions of bioplastic particles. The PEC compositions comprising bioplastic particles show good dry mechanical properties on NW. The dry mechanical properties are increasing with temperature and time. While the melting point of bioplastic particles 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.

(53) PEC also creates good dispersions of many non-water soluble protein powders. NW treated with PEC composition comprising protein powders increase: wet strength (PP) with maintained hydrophilicity, hydrophobicity without losing dry mechanical properties (VWG),

(54) PLA is known to degrade in water and especially in acidic conditions which is a requirement for forming the PEC. This is however not observed in PLA PEC compositions of the present invention shown by the fact that mechanical properties change very little over time when comparing treated materials using freshly prepared particle PEC composition vs. aged composition.

Experiments 9-11—Addition of PEC Compositions to Pulp Suspensions

(55) To evaluate the ability of the particle PEC composition to transfer particle properties to fibers in a fiber suspension, paper sheets were produced where PEC composition without particles and particle PEC compositions were added in the wet end of the paper process respectively and compared. The formed paper sheets were evaluated with tensile tests, contact angle measurements and Gurley.

Abbreviations Experiments 9-11

(56) Below, all abbreviations used in experiments 13-14 are listed.

(57) TABLE-US-00013 C Chitosan CMC Carboxymethyl cellulose OC-C (2 wt % chitosan 90/100/A1, 2 wt % Finnfix 5, 12 wt % citric acid mono hydrate, 0.2 wt % 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

(58) Method 10: Pulp suspension consisting of sodium hydrogen sulfate bleached CTMP fibres (mean fibre length 1.2-1.5 mm) from Rottneros was prepared in 18-22° C. tap water and diluted to 0.5 wt %. The total amount (40 l) was divided to 2.5 l and the pH was 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 then added to the pulp suspension in different amounts and stirred vigorously with a propeller 10 min before the sheet forming was started. The pH was controlled 1-2 times during this 10 min and adjusted to <6.5 if it had risen. Method 11: Paper sheets were produced using Rapid Köthen sheet former and then dried for 8 min at 92° C. under vacuum (about 100 kPa). The resulting sheets got a paper density of around 60 g/m.sup.2. Five sheets at each test point were made. In some cases, additional drying was performed at 190° C. for 3 min in a Termaks oven. Method 12: Tensile tests for dry paper sheets were performed by using Testometric M250-2.5AT (pretension: 0.1 N, sample length: 100 mm, sample width: 15 mm, speed: 20 mm/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

(59) Below, the equipment used in examples 9-11 is listed. pH in formulations and paper suspension was measured with pHenomenal pH1000H from VWR with Hamilton Polilyte Lab Temp BNC electrode (calibrated with buffers pH 4, 7 and 10). Homogenization of formulations in lab scale was performed using IKA T25 digital Ultra-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 formulations and pulp suspensions was done with an overhead stirrer from IKA (either Eurostar digital IKA-Werke or IKA RW28 basic) together with a propeller. 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 2.5 kN) together with Wintest Analysis software. Contact angles were measured with PGX Serial 50585 from FIBRO Systems AB together with the software The PocketGonimeter Program version 3.3 Gurley was measured with L&W Densometer (Type: 6_4, No.: 2241) from Lorentzen&Wettre

Chemicals Used in Experiments 9-11

(60) Below, all chemicals used in experiments 9-11 are listed.

(61) TABLE-US-00014 Producer/ Chemical name Commercial name Distributor 1,2-Benzisothiazol-3(2H)-one, Nipacide BSM Clariant 2-methyl-2H-isothiazol-3-one Carboxymethyl cellulose FinnFix 5 CP Kelco Chitosan Chitosan 90/100/A1 Kraeber Citric acid monohydrate Citronsyra Mono E33 8- Univar AB 80M LT Sodium dodecyl sulfate (SDS) Sigma Aldrich Sunflower oil Sunflower oil 745100 AAK PLA Ingeo 10361D Natureworks

Experiment 9—Influence of Particle PEC Compositions on the Mechanical Properties of Paper Sheets

(62) Paper suspension was made according to Method 10 and paper sheets with and without additives were produced according to Method 11. Since the amount of PEC in relation to fibers is important, it was decided to add the two formulations (OC-C and PEC+PLA) to the paper suspension so that amount of solid content in the formulations in relation to fibers became 1% respectively.

(63) The formulations were diluted to 1 wt % based on total solid content (i.e. 10 g formulation and 130 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.

(64) TABLE-US-00015 TABLE 11 Additions of OC-C and PEC + PLA. Addition to fiber is calculated on the total solid content in the formulations. Increase Mean Stdav in Addition Mean Stdav Mean Stdav Increase tensile tensile tensile Drying to fiber tensile tensile Increase final final in final stiffness stiffness stiffness temp (dry/dry) index index in tensile strain strain strain index index index Formulation [° C.] [%] [Nm/g] [Nm/g] index [%] [%] [%] [%] [Nm/g] [Nm/g] [%] ref 95 0 18.84 2.11 1.03 0.16 2800.54 221.34 OC-C 95 1 19.65 1.74 4.31 1.09 0.12 5.50 2726.42 153.53 −2.65 PEC + PLA 95 1 22.80 1.22 21.00 1.16 0.11 12.97 3128.06 154.98 11.70

(65) Since PLA melts above 95° C. (which is the drying temperature in Rapid Köthen) it was tested to 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.

(66) TABLE-US-00016 TABLE 12 Additions of OC-C and PEC + PLA. Addition to fiber is calculated on the total solid content in the formulations. The increases in different properties are based on the reference series that only has been dried in 95° C. in the Rapid Köthen dryer. Increase Mean Stdav in Addition Mean Stdav Increase Mean Stdav Increase tensile tensile tensile Drying to fiber tensile tensile in tensile final final in final stiffness stiffness stiffness temp (dry/dry) index index index strain strain strain index index index Formulation [° C.] [%] [Nm/g] [Nm/g] [%] [%] [%] [%] [Nm/g] [Nm/g] [%] ref 190 0 21.52 1.02 14.21 1.31 0.08 26.92 2480.12 183.92 −11.44 OC-C 190 1 22.65 1.45 20.22 1.42 0.09 38.04 2403.85 140.94 −14.16 PEC + PLA 190 1 26.13 1.13 38.71 1.45 0.14 40.46 2841.61 193.35 1.47

(67) The inclusion of PLA to the PEC composition clearly shows that the PLA properties are transferred to the fibers in a pulp suspension. This yields a 21% increase in tensile index and a 11.7% 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).

(68) When paper sheets are subjected to an additional drying step (190° C./3 min) tensile index increase 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 of Paper Sheets Measured by Contact Angle

(69) 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.

(70) 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 be achieved 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.

(71) TABLE-US-00017 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 formulations. Dynamic contact angle [°] Addition to Drying temp fiber (dry/dry) Dynamic contact angle Formulation [° C.] [%] 1 s 30 s 60 s Ref 95 0 <45 0 0 OC-C 95 0.5 <45 0 0 95 1 79.4 0 0 PEC + PLA 95 0.5 47.2 0 0 95 1 <45 0 0 PEC + PLA 190° C. 0.5 91.2 0 0 190° C. 190° C. 1 92.4 83.2 71.3

Experiment 11—Influence of Particle PEC Compositions on the Air Permeability Properties of Paper Sheets Measured Using the Gurley Method

(72) To investigate if the air permeability of the paper sheets (i.e. the internal structure and the surface finish of the paper) is affected when the PEC compositions were used as additives in the wet end of the paper making process, the Gurley method was used and Gurley seconds for 100 cc were determined.

(73) Two paper sheets for each test point were measured at three different spots. The results are shown in table 14.

(74) TABLE-US-00018 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 formulations. Two sheets were tested at three spots. Gurley for 100 CC [Gurley seconds] Addition to Mean Drying temp fiber (dry/dry) [Gurley Formulation [° C.] [%] seconds] stdav Ref 95 0 3.6 0.7 OC-C 95 0.5 3.5 0.5 95 1 2.9 0.2 PEC + PLA 95 0.5 2.4 0.2 95 1 2.3 0.2 PEC + PLA 190° C. 0.5 2.4 0.2 190° C. 190° C. 1 2.3 0.2

(75) Table 14 shows that the Gurley is lower (air permeability is higher) for the sheets including PEC+PLA (both when compared to reference sheets and sheets containing OC-C). From this it 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

(76) 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 formed paper sheets.

(77) Materials treated with the PEC composition of the present invention need curing to develop the 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 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.

(78) As will be understood by those skilled in the present field of art, numerous changes and modifications may be made to the above described and other embodiments of the present invention, 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, thermo-mechanical pulp, chemo-mechanical pulp, sulphate pulp, sulphite pulp, bleached pulp, unbleached pulp, short-fibre pulp, long-fibre pulp, mixtures of different pulp grades etc. The invention works irrespective of the kind of pulp chosen.

(79) The term paperboard is here used as wide term including all kinds of different cellulose-based board grades, e.g. paper board, cardboard, corrugated board, single or multiply board, folding boxboard, chipboard etc.

(80) While for the clarity reasons, the PEC compositions are described in the following claims only as binders for fiber based materials, textiles, woven and nonwoven materials (i.e. applied in the dry end of the process), it is equally understood that they can act as strength additives in the wet end of the process.

(81) A various number of plasticizers may be used together with plastics known in the art without departing from the scope of the invention.

(82) Other type of particles may be used instead of plastics such as proteins, inorganic fillers, resins, pigments.

(83) Various aspects and embodiments of the present invention are defined by the following numbered claims.