US20220064390A1 - Process for production of film comprising microfibrillated cellulose - Google Patents
Process for production of film comprising microfibrillated cellulose Download PDFInfo
- Publication number
- US20220064390A1 US20220064390A1 US17/454,112 US202117454112A US2022064390A1 US 20220064390 A1 US20220064390 A1 US 20220064390A1 US 202117454112 A US202117454112 A US 202117454112A US 2022064390 A1 US2022064390 A1 US 2022064390A1
- Authority
- US
- United States
- Prior art keywords
- film
- nanoparticles
- coating
- cellulose
- mfc
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 41
- 239000001913 cellulose Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title description 23
- 238000004519 manufacturing process Methods 0.000 title description 19
- 239000002105 nanoparticle Substances 0.000 claims abstract description 35
- 229920000642 polymer Polymers 0.000 claims abstract description 26
- 230000014759 maintenance of location Effects 0.000 claims abstract description 24
- 125000000129 anionic group Chemical group 0.000 claims abstract description 9
- 229920002472 Starch Polymers 0.000 claims abstract description 6
- 239000008107 starch Substances 0.000 claims abstract description 6
- 235000019698 starch Nutrition 0.000 claims abstract description 6
- 230000007935 neutral effect Effects 0.000 claims abstract description 5
- 239000011248 coating agent Substances 0.000 claims description 17
- 238000000576 coating method Methods 0.000 claims description 17
- 125000002091 cationic group Chemical group 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 11
- 229920001577 copolymer Polymers 0.000 claims description 5
- 229920002401 polyacrylamide Polymers 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 230000005540 biological transmission Effects 0.000 claims description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims 2
- 239000000654 additive Substances 0.000 abstract description 5
- 230000000996 additive effect Effects 0.000 abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 26
- 239000000835 fiber Substances 0.000 description 20
- 239000000725 suspension Substances 0.000 description 19
- 239000000123 paper Substances 0.000 description 18
- 239000002245 particle Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- 239000000377 silicon dioxide Substances 0.000 description 11
- -1 polyethylene Polymers 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- 229920003043 Cellulose fiber Polymers 0.000 description 8
- 239000004698 Polyethylene Substances 0.000 description 8
- 229920000573 polyethylene Polymers 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 230000004888 barrier function Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229920001903 high density polyethylene Polymers 0.000 description 5
- 239000004700 high-density polyethylene Substances 0.000 description 5
- 229920001684 low density polyethylene Polymers 0.000 description 5
- 239000004702 low-density polyethylene Substances 0.000 description 5
- 210000001724 microfibril Anatomy 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 229920001169 thermoplastic Polymers 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000004626 polylactic acid Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229920001046 Nanocellulose Polymers 0.000 description 3
- 229920001131 Pulp (paper) Polymers 0.000 description 3
- 229920003020 cross-linked polyethylene Polymers 0.000 description 3
- 239000004703 cross-linked polyethylene Substances 0.000 description 3
- 238000005189 flocculation Methods 0.000 description 3
- 230000016615 flocculation Effects 0.000 description 3
- 150000004676 glycans Chemical class 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920000747 poly(lactic acid) Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920001282 polysaccharide Polymers 0.000 description 3
- 239000005017 polysaccharide Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 239000004709 Chlorinated polyethylene Substances 0.000 description 2
- 229920002488 Hemicellulose Polymers 0.000 description 2
- 239000004706 High-density cross-linked polyethylene Substances 0.000 description 2
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- 239000004704 Ultra-low-molecular-weight polyethylene Substances 0.000 description 2
- 229920002522 Wood fibre Polymers 0.000 description 2
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 2
- 206010061592 cardiac fibrillation Diseases 0.000 description 2
- 229920006317 cationic polymer Polymers 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 230000002600 fibrillogenic effect Effects 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 229920004932 high density cross-linked polyethylene Polymers 0.000 description 2
- 239000002655 kraft paper Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229920001179 medium density polyethylene Polymers 0.000 description 2
- 239000004701 medium-density polyethylene Substances 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- 239000011859 microparticle Substances 0.000 description 2
- 239000002121 nanofiber Substances 0.000 description 2
- 239000011087 paperboard Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000962 poly(amidoamine) Polymers 0.000 description 2
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 239000002025 wood fiber Substances 0.000 description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- ZWAPMFBHEQZLGK-UHFFFAOYSA-N 5-(dimethylamino)-2-methylidenepentanamide Chemical compound CN(C)CCCC(=C)C(N)=O ZWAPMFBHEQZLGK-UHFFFAOYSA-N 0.000 description 1
- FLCAEMBIQVZWIF-UHFFFAOYSA-N 6-(dimethylamino)-2-methylhex-2-enamide Chemical compound CN(C)CCCC=C(C)C(N)=O FLCAEMBIQVZWIF-UHFFFAOYSA-N 0.000 description 1
- 102100031260 Acyl-coenzyme A thioesterase THEM4 Human genes 0.000 description 1
- 241000609240 Ambelania acida Species 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 229920000875 Dissolving pulp Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- 101000638510 Homo sapiens Acyl-coenzyme A thioesterase THEM4 Proteins 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- 229920002201 Oxidized cellulose Polymers 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 229920010741 Ultra High Molecular Weight Polyethylene (UHMWPE) Polymers 0.000 description 1
- 229920010346 Very Low Density Polyethylene (VLDPE) Polymers 0.000 description 1
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000004964 aerogel Substances 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000007774 anilox coating Methods 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000011852 carbon nanoparticle Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 1
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000005021 flexible packaging material Substances 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000003658 microfiber Substances 0.000 description 1
- 108700005457 microfibrillar Proteins 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000000399 optical microscopy Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229940107304 oxidized cellulose Drugs 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000037039 plant physiology Effects 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000004631 polybutylene succinate Substances 0.000 description 1
- 229920002961 polybutylene succinate Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000013615 primer Substances 0.000 description 1
- 239000002987 primer (paints) Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- FZGFBJMPSHGTRQ-UHFFFAOYSA-M trimethyl(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCOC(=O)C=C FZGFBJMPSHGTRQ-UHFFFAOYSA-M 0.000 description 1
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 description 1
- UZNHKBFIBYXPDV-UHFFFAOYSA-N trimethyl-[3-(2-methylprop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)NCCC[N+](C)(C)C UZNHKBFIBYXPDV-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
- B32B23/02—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose in the form of fibres or filaments
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
- D21H11/18—Highly hydrated, swollen or fibrillatable fibres
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
- D21H17/28—Starch
- D21H17/29—Starch cationic
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
- D21H17/375—Poly(meth)acrylamide
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
- D21H17/55—Polyamides; Polyaminoamides; Polyester-amides
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/50—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by form
- D21H21/52—Additives of definite length or shape
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/02—Cellulose; Modified cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/04—Polymer mixtures characterised by other features containing interpenetrating networks
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/38—Coatings with pigments characterised by the pigments
- D21H19/385—Oxides, hydroxides or carbonates
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/38—Coatings with pigments characterised by the pigments
- D21H19/40—Coatings with pigments characterised by the pigments siliceous, e.g. clays
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/52—Cellulose; Derivatives thereof
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/06—Paper forming aids
- D21H21/10—Retention agents or drainage improvers
Definitions
- the present invention relates to a new process for improving runnability and dimensional stability when manufacturing a film comprising high amounts of microfibrillated cellulose (MFC) without negatively impacting the film properties.
- MFC microfibrillated cellulose
- a high amount of nanoparticles is used as an additive, optionally together with one or more retention polymers.
- MFC microfibrillated cellulose
- MFC films or webs comprising high amounts of MFC are difficult to dewater.
- Various solutions have been tested such as different retention chemicals, polymers, self-healing solutions, long fibers, modifications to wire and mesh size etc.
- the cationic demand or charge of papermaking fiber suspensions in a wet end is close to zero which hence facilitate particle and fiber flocculation.
- charge regulation such as ionic neutralization or polymer bridging assist in traditional fiber flocculation and dewatering and retention.
- retention chemicals based on nanoparticles has been tested to some extent, particularly in conventional papermaking which hence aims towards charge and inter-particle and intra-particle control.
- Silica nanoparticles for example, can be combined with cationic chemicals (polymers) typically in a ratio of 1:2 (polymer:silica) and nanoparticle doses in normal papermaking is about ca 100-400 g/ton.
- An overdose of retention chemicals in papermaking would lead to increased porosity, uneven and stronger flocculation, two-sideness, problem with dimensional stability and subsequently uneven product quality.
- MFC or NFC films such as free standing films by coating NFC on plastic support material like PE, PET, and so on (WO2013060934A2).
- the dewatering is limited to evaporation and/or contact drying which influences both film quality and manufacturing rate.
- WO2012107642A1 addresses the problem with the hygroscopic properties of MFC, which was solved by using organic solvent when preparing the films.
- WO2014154937 A1 relates to a method for production of paper or board comprising providing a stock comprising cellulose fibers, adding a mixture comprising microfibrillated cellulose and a strength additive to the stock, adding a microparticle to the stock after the addition of said mixture, dewatering the stock on a wire to form a web, and drying the web.
- WO2011055017 A1 relates to a process for the preparation of paper or board comprising: adding a retention system to a stream of stock entering a paper machine head box, directing the stream of stock to a wire, dewatering the stream of stock on the wire to form a paper web, and drying the paper web, wherein the retention system comprises a water-soluble cationic polymer, and nanocellulose acting like a micro particle, wherein the nanocellulose is added in an amount of less than 1% as active substance based on dry solids weight of the stock.
- the solution should improve both the rate of dewatering and e.g. barrier properties of the film, which usually are contradicting properties.
- nanoparticle content such as a high silica content as used in the present application leads to improved runnability, improved dimensional stability and less shrinkage on the paper machine.
- high amount of nanoparticles such as silica
- high dosage of nanoparticle particularly particles having a diameter of less than 100 nm in one dimension, has a positive effect on wet strength and dewatering.
- a further benefit of the present invention is that the products obtained are easier to re-disperse in water in view of the fibril spacing effect of the high amount of nanoparticles.
- a suspension comprising microfibrillated cellulose, wherein the content of the microfibrillated cellulose of said suspension is at least 60 weight-% based on the weight of solids of the suspension;
- nanoparticles added to said suspension to provide a mixture of said microfibrillated cellulose and said nanoparticles, wherein the total amount of nanoparticles added is more than 50 kg on dry basis per ton of dry solids of the suspension;
- the process is carried out in a paper making machine.
- the nanoparticles can be e.g. silica or modified silica or silicates, alumina, nanoclays such as montmorillonite or bentonite, nanobentonite, nanokaolinite, nanotalcum, modified silica, nanolatex, nanostarch, aerogel or aerosol, sol-gel silica, modified silica such as doped silica with Al compounds, nanoPCC, swelling clays, zeolites, carbon nanotubes, carbon nanoparticles etc.
- the nanoparticles are silica or nanosilica.
- the particles are anionic.
- said silica or nanosilica or microsilica (also referred to as colloidal silica) is anionic at neutral or alkaline pH.
- the particles are amphoteric at neutral or alkaline pH.
- the particles are non-ionic.
- the nanoparticles used according to the present invention have a diameter of less than 100 nm, such as from 1 nm to 100 nm, in one dimension, but can form clusters which are thus larger aggregates of particles. Thus, when clusters are formed, such aggregates typically have a size corresponding to what may be referred to us colloidal materials.
- the amount of nanoparticles added is more than 50 kg/ton, such as 50-400 kg/ton, 51-400 kg/ton, 50-300 kg/ton, 51-300 kg/ton, 50-250 kg/ton, 51-200 kg/ton or 100-200 kg/ton (on dry basis per ton of dry solids of the suspension).
- the medium used in step c) can be porous or non-porous.
- the porous medium can for example be a wire, a membrane or a substrate such as paper, board or a porous film.
- the non-porous medium can for example be a carrier substrate used in for example cast coating.
- cast forming is used when forming the web.
- a non-porous medium is used.
- the suspension is provided to a substrate such as a plastic film or composite medium.
- the initial dewatering will predominantly occur in the direction away from the non-porous medium.
- the suspension is provided directly to a non-porous medium, such as a metal belt. Different methods for application can be used, such as different types of slots etc. The initial dewatering will therefore also in cast forming predominantly occur in the direction away from the non-porous medium.
- One or more retention polymers may also be used in accordance with the present invention.
- a specific ratio of retention polymer to particle is used.
- the ratio depends on the charge and molecular weight of the retention polymer used, but is typically from about 1:3 to about 1:20, such as from about 1:5 to 1:12 or 1:8 to 1:10.
- Said retention polymer is preferably a cationic polymer such as cationic starch, polyaminoamide-epichlorohydrin (PAE), polyamidoamine (PAMAM), cationic polyacryl amide or copolymer thereof (C-PAM), polyethylene oxide (PEO) or other copolymers thereof or polymers typically used in retention/drainage studies.
- a cationic polymer such as cationic starch, polyaminoamide-epichlorohydrin (PAE), polyamidoamine (PAMAM), cationic polyacryl amide or copolymer thereof (C-PAM), polyethylene oxide (PEO) or other copolymers thereof or polymers typically used in retention/drainage studies.
- PVAm cationic polyvinyl amine
- PDADMAC cationic polydiallyldimethylammonium chloride
- PEI polyethylene imine
- DCD dicyandiamide formaldehyde
- C-PVA cationic poly
- polymers are any copolymer of acrylamide and/or methacrylamide, prepared using at least as one of the comonomers a cationically charged or cationically chargeable monomer.
- monomers include methacryloyloxyethyltrimethyl ammonium chloride, acryloyloxyethyltrimethyl ammonium chloride, 3-(methacrylamido)propyltrimethyl ammonium chloride, 3-(acryloylamido)propyltrimethyl ammonium chloride, diallyldimethyl ammonium chloride, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, dimethylaminopropylacrylamide, dimethylaminopropylmethacrylamide, or a similar monomer.
- the polymer may also contain monomers other than acrylamide, methacrylamide, or some cationic or cationizable monomer.
- the nanoparticles can be dosed in various ways such as before or after the retention polymers.
- One option is to use an in-line mixing system to make mixing more efficient.
- the nanoparticles are added to the microfibrillated cellulose during or after the manufacturing phase of MFC from pulp.
- One way of carrying out the mixing is to provide one stream of MFC which is essentially free from nanoparticles and mix that stream with another stream which contains a mixture of MFC and nanoparticles. These two streams are thus mixed to provide a suspension comprising both MFC and nanoparticles.
- the microfibrillated cellulose may have a Schopper Riegler value (SR°) of more than 85 SR°, or more than 90 SR°, or more than 92 SR°.
- SR° Schopper Riegler value
- the Schopper-Riegler value can be determined through the standard method defined in EN ISO 5267-1.
- the basis weight of the obtained film is preferably ⁇ 35 g/m 2 , more preferably ⁇ 30 g/m 2 and most preferably ⁇ 25 g/m 2 .
- a laminate comprising a film prepared according to the present invention and a thermoplastic polymer coating, such as any one of a polyethylene, EVOH, starch, styrene/butadiene, styrene/acrylate, polypropylene, a polyethylene terephtalate and a polylactic acid.
- the coating can be provided e.g. by extrusion coating, film coating or dispersion coating. Alternatively the coating can be applied by surface sizing if it comprises polysaccharide, polysaccharide derivative, polyurethane, polyurethane-elastomer, styrene/acrylate, or combinations thereof.
- the MFC film can be present between to coating layers, such as between two layers of polyethylene, with or without a tie layer.
- the polyethylene may be any one of a high density polyethylene and a low density polyethylene or mixtures or modifications thereof that could readily be selected by a skilled person.
- the film or the laminate according to present invention wherein said film or said laminate is applied to the surface of any one of a paper product and a board.
- the film or laminate can also be part of a flexible packaging material, such as a free standing pouch.
- the intermediate thin substrate is an intermediate product which has not yet been processed into the final film having the characteristic OTR values, but may processed into such a film in a later converting process.
- the film is a thin sheet, mouldable film or web. It comprises a high amount of microfibrillated cellulose and can be laminated to form a multilayered structure.
- the film may be opaque, transparent or translucent.
- the OTR (oxygen transmission rate) value (measured at standard conditions) of the film is ⁇ 200 cc/m2*day measured at 50% RH, 23° C., preferably ⁇ 30, more preferably ⁇ 15 and most preferably ⁇ 10 (i.e. before further treatment such as PE lamination) at a grammage of 10-50 gsm.
- the thickness of the film can be selected dependent on the required properties.
- Film thickness may for example be 10-100 ⁇ m, such as 20-50 or 30-40 ⁇ m, having a grammage of for example 10-50 gsm, such as 20-30 gsm.
- the film has good barrier properties (e.g. to gas, aroma, light, etc).
- a further embodiment of the present invention is a product comprising the film produced according to the process of the present invention.
- One embodiment of the present invention is a flexible package produced according to the process of the present invention.
- a further embodiment of the invention is a rigid package comprising a film produced according to the present invention.
- the product may also be used for other purposes, such as in cement, person care or food products, moulded products, composites or as an additive in rubber or plastic.
- a composite product may for example be an extruded laminate or a film comprising MFC which is blended with thermoplastic polymer e.g. in the form of a masterbatch.
- film reject or waste material from the manufacture of a film can be collected and re-used as composite additive.
- a film is formed in a paper making machine or according to a wet laid production method, by providing a suspension onto a wire and dewatering the web to form an intermediate thin substrate or said film According to one embodiment, a suspension comprising microfibrillated cellulose is provided to form said film. In an alternative embodiment of the present invention, a film is formed by casting.
- the microfibrillated cellulose content of the suspension may, according to one embodiment be in the range of from 60 to 99.9 weight-% based on the weight of solids of the suspension. In one embodiment, the microfibrillated cellulose content of the suspension may be in the range of 70 to 99 weight-%, in the range of 70 to 95 weight-%, or in the range of from 75 to 90 weight-%.
- enhanced dewatering effect of MFC suspension in wet laid production method is achieved by dosing the anionic nanoparticles in an early stage of the manufacturing process, not as part of the short circulation retention system in the machine used.
- Microfibrillated cellulose shall in the context of the patent application mean a nano scale cellulose particle fiber or fibril with at least one dimension less than 100 nm. MFC comprises partly or totally fibrillated cellulose or lignocellulose fibers. The liberated fibrils have a diameter less than 100 nm, whereas the actual fibril diameter or particle size distribution and/or aspect ratio (length/width) depends on the source and the manufacturing methods.
- the smallest fibril is called elementary fibril and has a diameter of approximately 2-4 nm (see e.g. Chinga-Carrasco, G., Cellulose fibres, nanofibrils and microfibrils,: The morphological sequence of MFC components from a plant physiology and fibre technology point of view, Nanoscale research letters 2011, 6:417), while it is common that the aggregated form of the elementary fibrils, also defined as microfibril (Fengel, D., Ultrastructural behavior of cell wall polysaccharides, Tappi J ., March 1970, Vol 53, No. 3.), is the main product that is obtained when making MFC e.g. by using an extended refining process or pressure-drop disintegration process.
- the length of the fibrils can vary from around 1 to more than 10 micrometers.
- a coarse MFC grade might contain a substantial fraction of fibrillated fibers, i.e. protruding fibrils from the tracheid (cellulose fiber), and with a certain amount of fibrils liberated from the tracheid (cellulose fiber).
- MFC cellulose microfibrils, fibrillated cellulose, nanofibrillated cellulose, fibril aggregates, nanoscale cellulose fibrils, cellulose nanofibers, cellulose nanofibrils, cellulose microfibers, cellulose fibrils, microfibrillar cellulose, microfibril aggregrates and cellulose microfibril aggregates.
- MFC can also be characterized by various physical or physical-chemical properties such as large surface area or its ability to form a gel-like material at low solids (1-5 wt %) when dispersed in water.
- the cellulose fiber is preferably fibrillated to such an extent that the final specific surface area of the formed MFC is from about 1 to about 300 m 2 /g, such as from 1 to 200 m 2 /g or more preferably 50-200 m 2 /g or 80-200 m 2 /g when determined for a solvent exchanged and freeze-dried material with the BET method.
- MFC multi-pass refining
- pre-hydrolysis followed by refining or high shear disintegration or liberation of fibrils.
- One or several pre-treatment step is usually required in order to make MFC manufacturing both energy efficient and sustainable.
- the cellulose fibers of the pulp to be supplied may thus be pre-treated enzymatically or chemically, for example to reduce the quantity of hemicellulose or lignin.
- the cellulose fibers may be chemically modified before fibrillation, wherein the cellulose molecules contain functional groups other (or more) than found in the original cellulose.
- Such groups include, among others, carboxymethyl (CM), aldehyde and/or carboxyl groups (cellulose obtained by N-oxyl mediated oxydation, for example “TEMPO”), or quaternary ammonium (cationic cellulose).
- CM carboxymethyl
- TEMPO N-oxyl mediated oxydation
- quaternary ammonium cationic cellulose
- the nanofibrillar cellulose may contain some hemicelluloses; the amount is dependent on the plant source.
- Mechanical disintegration of the pre-treated fibers, e.g. hydrolysed, pre-swelled, or oxidized cellulose raw material is carried out with suitable equipment such as a refiner, grinder, homogenizer, colloider, friction grinder, ultrasound sonicator, fluidizer such as microfluidizer, macrofluidizer or fluidizer-type homogenizer.
- suitable equipment such as a refiner, grinder, homogenizer, colloider, friction grinder, ultrasound sonicator, fluidizer such as microfluidizer, macrofluidizer or fluidizer-type homogenizer.
- the product might also contain fines, or nanocrystalline cellulose or e.g. other chemicals present in wood fibers or in papermaking process.
- the product might also contain various amounts of micron size fiber particles that have not been efficiently fibrillated.
- MFC is produced from wood cellulose fibers, both from hardwood or softwood fibers. It can also be made from microbial sources, agricultural fibers such as wheat straw pulp, bamboo, bagasse, or other non-wood fiber sources. It is preferably made from pulp including pulp from virgin fiber, e.g. mechanical, chemical and/or thermomechanical pulps. It can also be made from broke or recycled paper.
- MFC cellulose nanofibril
- the suspension may comprise a mixture of different types of fibers, such as microfibrillated cellulose, and an amount of other types of fiber, such as kraft fibers, fines, reinforcement fibers, synthetic fibers, dissolving pulp, TMP or CTMP, PGW, etc.
- fibers such as microfibrillated cellulose
- other types of fiber such as kraft fibers, fines, reinforcement fibers, synthetic fibers, dissolving pulp, TMP or CTMP, PGW, etc.
- the suspension may also comprise other process or functional additives, such as fillers, pigments, wet strength chemicals, retention chemicals, cross-linkers, softeners or plasticizers, adhesion primers, wetting agents, biocides, optical dyes, fluorescent whitening agents, debonders, de-foaming chemicals, hydrophobizing chemicals such as AKD, ASA, waxes, resins, etc.
- process or functional additives such as fillers, pigments, wet strength chemicals, retention chemicals, cross-linkers, softeners or plasticizers, adhesion primers, wetting agents, biocides, optical dyes, fluorescent whitening agents, debonders, de-foaming chemicals, hydrophobizing chemicals such as AKD, ASA, waxes, resins, etc.
- dewatering encompasses any form of dewatering, including for example evaporation, dewatering under pressure, dewatering using radiation etc.
- the dewatering can be carried out in one or more steps and may involve one form of dewatering or several forms of dewatering in combination.
- the papermaking machine that may be used in the process according to the present invention may be any conventional type of machine known to the skilled person used for the production of paper, paperboard, tissue or similar products.
- the dewatering may be performed by using known techniques with single wire or twin wire system, frictionless dewatering, membrane-assisted dewatering, vacuum- or ultrasound assisted dewatering, etc.
- the wet web is further dewatered and dried by mechanical pressing including shoe press, hot air, radiation drying, convection drying, etc.
- the film might also be dried or smoothened by soft or hard nip (or various combinations) calenders etc.
- the wet web is dewatered by vacuum, i.e. water, and other liquids, is sucked from the furnish when it is placed on the wire.
- vacuum i.e. water, and other liquids
- the suspension may also be provided to a porous medium such as a membrane or substrate such as paper, board or a porous film.
- the film comprising the microfibrillated cellulose and nanoparticles or nanoparticles may be laminated to or with a thermoplastic polymer.
- the thermoplastic polymer may be any one of a polyethylene (PE), a polyethylene terephthalate (PET) and a polylactic acid (PLA).
- the polyethylene may be any one of a high density polyethylene (HDPE) and a low density polyethylene (LDPE), or various combinations thereof.
- polyethyelene examples include ultra-high-molecular-weight polyethylene (UHMWPE), ultra-low-molecular-weight polyethylene (ULMWPE or PE-WAX), high-molecular-weight polyethylene (HMWPE), high-density polyethylene (HDPE), high-density cross-linked polyethylene (HDXLPE), cross-linked polyethylene (PEX or XLPE), medium-density polyethylene (MDPE), linear low-density polyethylene (LLDPE), low-density polyethylene (LDPE), very-low-density polyethylene (VLDPE), chlorinated polyethylene (CPE).
- PLA polyethylene
- suitable polymers are PVDC, Polyethylene furanoate, polymers of lactic acid such as PLA, Polybutylene succinate.
- a polymer coating can also be applied by for example a printing process such as flexogravure roll (anilox).
- the film or the laminate may also be applied to other paper products, such as food containers, paper sheets, paper boards or boards or other structures that need to be protected by a barrier film.
- the pulp used was bleached kraft pulp fibrillated to SR>90.
- the KP1 is the reference furnish comprising mainly of microfibrillated cellulose and small amounts of anionic nanosilica (addition level 5 kg/tn).
- the KP2 and KP3 are the same MFC grades but with higher level of silica (140 and 50 kg/tn respectively and with different point of addition (added before/during fibrillation (KP2), and added during furnish preparation of the furnish (KP3)).
- the film was made on a fourdrinier type of pilot paper machine to a grammage of ca 25-30 g/m 2 .
- Process and performance chemicals were used e.g. cationic starch and hydrophobic internal sizing chemical (AKD). Targeted moisture content was 6.5%.
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Abstract
A film comprising microfibrillated cellulose, nanoparticles, and a retention polymer. The nanoparticles are nanosilica nanoparticles that are anionic at neutral or alkaline pH and have at least one dimension less than 100 nm; and the retention polymer is starch. According to the present invention a high amount of nanoparticles is used as an additive, optionally together with a retention polymer.
Description
- This application is a divisional of U.S. patent application Ser. No. 16/489,801 having a filing/§ 371(c) date of Aug. 29, 2019, which is a § 371 National Phase of International Application No. PCT/IB2018/051216, filed on Feb. 27, 2018, which claims priority to Swedish Patent Application No. 1750219-6 filed on Mar. 1, 2017, the entirety of which is incorporated herein by reference.
- The present invention relates to a new process for improving runnability and dimensional stability when manufacturing a film comprising high amounts of microfibrillated cellulose (MFC) without negatively impacting the film properties. According to the present invention a high amount of nanoparticles is used as an additive, optionally together with one or more retention polymers.
- The manufacturing of a film from a web comprising microfibrillated cellulose (MFC) on a paper machine or similar wet laid technique at high speeds is very demanding. Due to a low dewatering speed, which is related to MFC fineness, charge and quantity, there are problems when releasing the material from the wire of the paper machine. MFC is also capable of forming a gel at relatively low solids concentration. One solution would be to reduce machine speeds, but then the production of the film is not economically attractive. Thus, at higher speeds stronger dewatering is required which hence results in the above problem. There is also a risk that a too strong dewatering may cause pin-holes in the web, which deteriorates the quality of the film Another critical variable is the formation of the web, which in turn affects the web properties.
- It is known that MFC films or webs comprising high amounts of MFC are difficult to dewater. Various solutions have been tested such as different retention chemicals, polymers, self-healing solutions, long fibers, modifications to wire and mesh size etc. Typically, the cationic demand or charge of papermaking fiber suspensions in a wet end is close to zero which hence facilitate particle and fiber flocculation. Thus, charge regulation such as ionic neutralization or polymer bridging assist in traditional fiber flocculation and dewatering and retention.
- The use of retention chemicals based on nanoparticles, sometimes referred to as colloidal particles, has been tested to some extent, particularly in conventional papermaking which hence aims towards charge and inter-particle and intra-particle control. Silica nanoparticles, for example, can be combined with cationic chemicals (polymers) typically in a ratio of 1:2 (polymer:silica) and nanoparticle doses in normal papermaking is about ca 100-400 g/ton. An overdose of retention chemicals in papermaking would lead to increased porosity, uneven and stronger flocculation, two-sideness, problem with dimensional stability and subsequently uneven product quality.
- Various manufacturing methods have been proposed to make MFC or NFC films such as free standing films by coating NFC on plastic support material like PE, PET, and so on (WO2013060934A2). In many cases, the dewatering is limited to evaporation and/or contact drying which influences both film quality and manufacturing rate.
- WO2012107642A1 addresses the problem with the hygroscopic properties of MFC, which was solved by using organic solvent when preparing the films.
- WO2014154937 A1 relates to a method for production of paper or board comprising providing a stock comprising cellulose fibers, adding a mixture comprising microfibrillated cellulose and a strength additive to the stock, adding a microparticle to the stock after the addition of said mixture, dewatering the stock on a wire to form a web, and drying the web.
- WO2011055017 A1 relates to a process for the preparation of paper or board comprising: adding a retention system to a stream of stock entering a paper machine head box, directing the stream of stock to a wire, dewatering the stream of stock on the wire to form a paper web, and drying the paper web, wherein the retention system comprises a water-soluble cationic polymer, and nanocellulose acting like a micro particle, wherein the nanocellulose is added in an amount of less than 1% as active substance based on dry solids weight of the stock.
- There is a need for a method and a composition where the dewatering rate can be significantly improved when forming a film from a wet web comprising high amounts of microfibrillated cellulose. More preferably, the solution should improve both the rate of dewatering and e.g. barrier properties of the film, which usually are contradicting properties.
- It is an object of the present disclosure to provide an improved method of manufacturing a film comprising microfibrillated cellulose, which eliminates or alleviates at least some of the disadvantages of the prior art methods.
- It has been surprisingly found that high nanoparticle content, such as a high silica content as used in the present application leads to improved runnability, improved dimensional stability and less shrinkage on the paper machine. Surprisingly, high amount of nanoparticles, such as silica, did not negatively affect the oxygen barrier properties of the MFC film, although based on opacity/light transmittance of the film fibril-to-fibril bonding was substantially decreased. It has also been seen that high dosage of nanoparticle, particularly particles having a diameter of less than 100 nm in one dimension, has a positive effect on wet strength and dewatering. A further benefit of the present invention is that the products obtained are easier to re-disperse in water in view of the fibril spacing effect of the high amount of nanoparticles.
- According to a first aspect, there is provided a process for the production of an intermediate thin substrate or film comprising the steps of:
- providing a suspension comprising microfibrillated cellulose, wherein the content of the microfibrillated cellulose of said suspension is at least 60 weight-% based on the weight of solids of the suspension;
- adding nanoparticles to said suspension to provide a mixture of said microfibrillated cellulose and said nanoparticles, wherein the total amount of nanoparticles added is more than 50 kg on dry basis per ton of dry solids of the suspension;
- providing said mixture to a medium to form a web; and
- dewatering said web to form an intermediate thin substrate or film.
- In one embodiment, the process is carried out in a paper making machine.
- The nanoparticles can be e.g. silica or modified silica or silicates, alumina, nanoclays such as montmorillonite or bentonite, nanobentonite, nanokaolinite, nanotalcum, modified silica, nanolatex, nanostarch, aerogel or aerosol, sol-gel silica, modified silica such as doped silica with Al compounds, nanoPCC, swelling clays, zeolites, carbon nanotubes, carbon nanoparticles etc. In one embodiment of the present invention, the nanoparticles are silica or nanosilica. In one embodiment of the invention, the particles are anionic. In one embodiment of the invention, said silica or nanosilica or microsilica (also referred to as colloidal silica) is anionic at neutral or alkaline pH. In one embodiment of the present invention, the particles are amphoteric at neutral or alkaline pH. In one embodiment of the present invention, the particles are non-ionic. The nanoparticles used according to the present invention have a diameter of less than 100 nm, such as from 1 nm to 100 nm, in one dimension, but can form clusters which are thus larger aggregates of particles. Thus, when clusters are formed, such aggregates typically have a size corresponding to what may be referred to us colloidal materials.
- The amount of nanoparticles added is more than 50 kg/ton, such as 50-400 kg/ton, 51-400 kg/ton, 50-300 kg/ton, 51-300 kg/ton, 50-250 kg/ton, 51-200 kg/ton or 100-200 kg/ton (on dry basis per ton of dry solids of the suspension).
- The medium used in step c) can be porous or non-porous. The porous medium can for example be a wire, a membrane or a substrate such as paper, board or a porous film. The non-porous medium can for example be a carrier substrate used in for example cast coating. In one embodiment, cast forming is used when forming the web. In cast coating and cast forming, a non-porous medium is used. Thus, in cast coating, the suspension is provided to a substrate such as a plastic film or composite medium. Thus, the initial dewatering will predominantly occur in the direction away from the non-porous medium. In cast forming, the suspension is provided directly to a non-porous medium, such as a metal belt. Different methods for application can be used, such as different types of slots etc. The initial dewatering will therefore also in cast forming predominantly occur in the direction away from the non-porous medium.
- One or more retention polymers may also be used in accordance with the present invention. In one embodiment of the present invention, a specific ratio of retention polymer to particle is used. The ratio (by weight) depends on the charge and molecular weight of the retention polymer used, but is typically from about 1:3 to about 1:20, such as from about 1:5 to 1:12 or 1:8 to 1:10.
- Said retention polymer is preferably a cationic polymer such as cationic starch, polyaminoamide-epichlorohydrin (PAE), polyamidoamine (PAMAM), cationic polyacryl amide or copolymer thereof (C-PAM), polyethylene oxide (PEO) or other copolymers thereof or polymers typically used in retention/drainage studies. Examples of such polymers are cationic polyvinyl amine (PVAm), cationic polydiallyldimethylammonium chloride (PDADMAC), polyethylene imine (PEI), dicyandiamide formaldehyde (DCD), cationic polyvinylalcohol (C-PVA), cationic protein, etc. Further examples of polymers are any copolymer of acrylamide and/or methacrylamide, prepared using at least as one of the comonomers a cationically charged or cationically chargeable monomer. Such monomers include methacryloyloxyethyltrimethyl ammonium chloride, acryloyloxyethyltrimethyl ammonium chloride, 3-(methacrylamido)propyltrimethyl ammonium chloride, 3-(acryloylamido)propyltrimethyl ammonium chloride, diallyldimethyl ammonium chloride, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, dimethylaminopropylacrylamide, dimethylaminopropylmethacrylamide, or a similar monomer. The polymer may also contain monomers other than acrylamide, methacrylamide, or some cationic or cationizable monomer.
- The nanoparticles can be dosed in various ways such as before or after the retention polymers. One option is to use an in-line mixing system to make mixing more efficient. In one embodiment of the present invention, the nanoparticles are added to the microfibrillated cellulose during or after the manufacturing phase of MFC from pulp. One way of carrying out the mixing is to provide one stream of MFC which is essentially free from nanoparticles and mix that stream with another stream which contains a mixture of MFC and nanoparticles. These two streams are thus mixed to provide a suspension comprising both MFC and nanoparticles.
- In one embodiment of the present invention, the microfibrillated cellulose may have a Schopper Riegler value (SR°) of more than 85 SR°, or more than 90 SR°, or more than 92 SR°. The Schopper-Riegler value can be determined through the standard method defined in EN ISO 5267-1.
- The basis weight of the obtained film is preferably <35 g/m2, more preferably <30 g/m2 and most preferably <25 g/m2.
- According to a further embodiment of the present invention, there is provided a laminate comprising a film prepared according to the present invention and a thermoplastic polymer coating, such as any one of a polyethylene, EVOH, starch, styrene/butadiene, styrene/acrylate, polypropylene, a polyethylene terephtalate and a polylactic acid. The coating can be provided e.g. by extrusion coating, film coating or dispersion coating. Alternatively the coating can be applied by surface sizing if it comprises polysaccharide, polysaccharide derivative, polyurethane, polyurethane-elastomer, styrene/acrylate, or combinations thereof. This laminate structure may provide for even more superior barrier properties. In one embodiment, the MFC film can be present between to coating layers, such as between two layers of polyethylene, with or without a tie layer. According to one embodiment of the present invention, the polyethylene may be any one of a high density polyethylene and a low density polyethylene or mixtures or modifications thereof that could readily be selected by a skilled person. According to further embodiment there is provided the film or the laminate according to present invention, wherein said film or said laminate is applied to the surface of any one of a paper product and a board. The film or laminate can also be part of a flexible packaging material, such as a free standing pouch.
- The intermediate thin substrate is an intermediate product which has not yet been processed into the final film having the characteristic OTR values, but may processed into such a film in a later converting process.
- One embodiment of the present invention is a film produced according to the process of the present invention. The film is a thin sheet, mouldable film or web. It comprises a high amount of microfibrillated cellulose and can be laminated to form a multilayered structure. The film may be opaque, transparent or translucent. The OTR (oxygen transmission rate) value (measured at standard conditions) of the film is <200 cc/m2*day measured at 50% RH, 23° C., preferably <30, more preferably <15 and most preferably <10 (i.e. before further treatment such as PE lamination) at a grammage of 10-50 gsm. The thickness of the film can be selected dependent on the required properties. Film thickness may for example be 10-100 μm, such as 20-50 or 30-40 μm, having a grammage of for example 10-50 gsm, such as 20-30 gsm. The film has good barrier properties (e.g. to gas, aroma, light, etc).
- A further embodiment of the present invention is a product comprising the film produced according to the process of the present invention.
- One embodiment of the present invention is a flexible package produced according to the process of the present invention. A further embodiment of the invention is a rigid package comprising a film produced according to the present invention. The product may also be used for other purposes, such as in cement, person care or food products, moulded products, composites or as an additive in rubber or plastic. A composite product may for example be an extruded laminate or a film comprising MFC which is blended with thermoplastic polymer e.g. in the form of a masterbatch. For example, film reject or waste material from the manufacture of a film can be collected and re-used as composite additive.
- In one embodiment of the present invention, a film is formed in a paper making machine or according to a wet laid production method, by providing a suspension onto a wire and dewatering the web to form an intermediate thin substrate or said film According to one embodiment, a suspension comprising microfibrillated cellulose is provided to form said film. In an alternative embodiment of the present invention, a film is formed by casting.
- The microfibrillated cellulose content of the suspension may, according to one embodiment be in the range of from 60 to 99.9 weight-% based on the weight of solids of the suspension. In one embodiment, the microfibrillated cellulose content of the suspension may be in the range of 70 to 99 weight-%, in the range of 70 to 95 weight-%, or in the range of from 75 to 90 weight-%.
- In one embodiment of the present invention, enhanced dewatering effect of MFC suspension in wet laid production method is achieved by dosing the anionic nanoparticles in an early stage of the manufacturing process, not as part of the short circulation retention system in the machine used.
- Microfibrillated cellulose (MFC) shall in the context of the patent application mean a nano scale cellulose particle fiber or fibril with at least one dimension less than 100 nm. MFC comprises partly or totally fibrillated cellulose or lignocellulose fibers. The liberated fibrils have a diameter less than 100 nm, whereas the actual fibril diameter or particle size distribution and/or aspect ratio (length/width) depends on the source and the manufacturing methods.
- The smallest fibril is called elementary fibril and has a diameter of approximately 2-4 nm (see e.g. Chinga-Carrasco, G., Cellulose fibres, nanofibrils and microfibrils,: The morphological sequence of MFC components from a plant physiology and fibre technology point of view, Nanoscale research letters 2011, 6:417), while it is common that the aggregated form of the elementary fibrils, also defined as microfibril (Fengel, D., Ultrastructural behavior of cell wall polysaccharides, Tappi J., March 1970, Vol 53, No. 3.), is the main product that is obtained when making MFC e.g. by using an extended refining process or pressure-drop disintegration process. Depending on the source and the manufacturing process, the length of the fibrils can vary from around 1 to more than 10 micrometers. A coarse MFC grade might contain a substantial fraction of fibrillated fibers, i.e. protruding fibrils from the tracheid (cellulose fiber), and with a certain amount of fibrils liberated from the tracheid (cellulose fiber).
- There are different acronyms for MFC such as cellulose microfibrils, fibrillated cellulose, nanofibrillated cellulose, fibril aggregates, nanoscale cellulose fibrils, cellulose nanofibers, cellulose nanofibrils, cellulose microfibers, cellulose fibrils, microfibrillar cellulose, microfibril aggregrates and cellulose microfibril aggregates. MFC can also be characterized by various physical or physical-chemical properties such as large surface area or its ability to form a gel-like material at low solids (1-5 wt %) when dispersed in water. The cellulose fiber is preferably fibrillated to such an extent that the final specific surface area of the formed MFC is from about 1 to about 300 m2/g, such as from 1 to 200 m2/g or more preferably 50-200 m2/g or 80-200 m2/g when determined for a solvent exchanged and freeze-dried material with the BET method.
- Various methods exist to make MFC, such as single or multiple pass refining, pre-hydrolysis followed by refining or high shear disintegration or liberation of fibrils. One or several pre-treatment step is usually required in order to make MFC manufacturing both energy efficient and sustainable. The cellulose fibers of the pulp to be supplied may thus be pre-treated enzymatically or chemically, for example to reduce the quantity of hemicellulose or lignin. The cellulose fibers may be chemically modified before fibrillation, wherein the cellulose molecules contain functional groups other (or more) than found in the original cellulose. Such groups include, among others, carboxymethyl (CM), aldehyde and/or carboxyl groups (cellulose obtained by N-oxyl mediated oxydation, for example “TEMPO”), or quaternary ammonium (cationic cellulose). After being modified or oxidized in one of the above-described methods, it is easier to disintegrate the fibers into MFC or nanofibrillar size fibrils. Preferably, the MFC used according to the present invention is substantially free from unrefined fibers, which can be visually determined using optical microscopy.
- The nanofibrillar cellulose may contain some hemicelluloses; the amount is dependent on the plant source. Mechanical disintegration of the pre-treated fibers, e.g. hydrolysed, pre-swelled, or oxidized cellulose raw material is carried out with suitable equipment such as a refiner, grinder, homogenizer, colloider, friction grinder, ultrasound sonicator, fluidizer such as microfluidizer, macrofluidizer or fluidizer-type homogenizer. Depending on the MFC manufacturing method, the product might also contain fines, or nanocrystalline cellulose or e.g. other chemicals present in wood fibers or in papermaking process. The product might also contain various amounts of micron size fiber particles that have not been efficiently fibrillated.
- MFC is produced from wood cellulose fibers, both from hardwood or softwood fibers. It can also be made from microbial sources, agricultural fibers such as wheat straw pulp, bamboo, bagasse, or other non-wood fiber sources. It is preferably made from pulp including pulp from virgin fiber, e.g. mechanical, chemical and/or thermomechanical pulps. It can also be made from broke or recycled paper.
- The above described definition of MFC includes, but is not limited to, the new proposed TAPPI standard W13021 on cellulose nanofibril (CMF) defining a cellulose nanofiber material containing multiple elementary fibrils with both crystalline and amorphous regions.
- According to another embodiment, the suspension may comprise a mixture of different types of fibers, such as microfibrillated cellulose, and an amount of other types of fiber, such as kraft fibers, fines, reinforcement fibers, synthetic fibers, dissolving pulp, TMP or CTMP, PGW, etc.
- The suspension may also comprise other process or functional additives, such as fillers, pigments, wet strength chemicals, retention chemicals, cross-linkers, softeners or plasticizers, adhesion primers, wetting agents, biocides, optical dyes, fluorescent whitening agents, debonders, de-foaming chemicals, hydrophobizing chemicals such as AKD, ASA, waxes, resins, etc.
- The term “dewatering” as used herein encompasses any form of dewatering, including for example evaporation, dewatering under pressure, dewatering using radiation etc. The dewatering can be carried out in one or more steps and may involve one form of dewatering or several forms of dewatering in combination.
- The papermaking machine that may be used in the process according to the present invention may be any conventional type of machine known to the skilled person used for the production of paper, paperboard, tissue or similar products.
- Subsequent to the wet web being placed onto medium, it is dewatered to form an intermediate thin substrate or film.
- The dewatering may be performed by using known techniques with single wire or twin wire system, frictionless dewatering, membrane-assisted dewatering, vacuum- or ultrasound assisted dewatering, etc. After the wire section, the wet web is further dewatered and dried by mechanical pressing including shoe press, hot air, radiation drying, convection drying, etc. The film might also be dried or smoothened by soft or hard nip (or various combinations) calenders etc.
- According to one embodiment the wet web is dewatered by vacuum, i.e. water, and other liquids, is sucked from the furnish when it is placed on the wire.
- As an alternative to a wire, the suspension may also be provided to a porous medium such as a membrane or substrate such as paper, board or a porous film.
- According to one embodiment, the film comprising the microfibrillated cellulose and nanoparticles or nanoparticles may be laminated to or with a thermoplastic polymer. The thermoplastic polymer may be any one of a polyethylene (PE), a polyethylene terephthalate (PET) and a polylactic acid (PLA). The polyethylene may be any one of a high density polyethylene (HDPE) and a low density polyethylene (LDPE), or various combinations thereof. Further examples of polyethyelene are ultra-high-molecular-weight polyethylene (UHMWPE), ultra-low-molecular-weight polyethylene (ULMWPE or PE-WAX), high-molecular-weight polyethylene (HMWPE), high-density polyethylene (HDPE), high-density cross-linked polyethylene (HDXLPE), cross-linked polyethylene (PEX or XLPE), medium-density polyethylene (MDPE), linear low-density polyethylene (LLDPE), low-density polyethylene (LDPE), very-low-density polyethylene (VLDPE), chlorinated polyethylene (CPE). By using for instance PLA as the thermoplastic polymer the product may be formed completely from biodegradable materials. Further examples of suitable polymers are PVDC, Polyethylene furanoate, polymers of lactic acid such as PLA, Polybutylene succinate. A polymer coating can also be applied by for example a printing process such as flexogravure roll (anilox).
- The film or the laminate may also be applied to other paper products, such as food containers, paper sheets, paper boards or boards or other structures that need to be protected by a barrier film.
- The pulp used was bleached kraft pulp fibrillated to SR>90. The KP1 is the reference furnish comprising mainly of microfibrillated cellulose and small amounts of anionic nanosilica (addition level 5 kg/tn). The KP2 and KP3 are the same MFC grades but with higher level of silica (140 and 50 kg/tn respectively and with different point of addition (added before/during fibrillation (KP2), and added during furnish preparation of the furnish (KP3)).
- The results show that high amount of silica can be used.
- The film was made on a fourdrinier type of pilot paper machine to a grammage of ca 25-30 g/m2. Process and performance chemicals were used e.g. cationic starch and hydrophobic internal sizing chemical (AKD). Targeted moisture content was 6.5%.
-
Unit KP1 KP2 KP3 Property Microfibrillated % 100 100 100 fiber Added nanosilica kg/tn 5 140 50 (anionic) Amount of kg/tn 2.1 59.5 21.3 nanosilica (anionic) in film produced Ash content wt-% 0.45 2.13 2.38 determined at [ISO 1762] 525° C. Property (dry sheets) Grammage g/m2 31.4 25.5 25.5 Thickness, single μm 48 40 41 sheet Tear index, md mNm2/g 4 4.4 4 Tear index, cd mNm2/g 4.3 4.2 4 E-modulus, cd Mpa 1705 2077 2044 E-modulus, md Mpa 4226 3003 3631 OTR value cc/m2/d 23 C, 644 / 17/48 measure- 50 RH 1130 ment failed Dimensional % 0.44 0.37 0.42 stability, 33-84% RH, total CD/MD geom. mean - CD: cross direction
- MD: machine direction
- In view of the above detailed description of the present invention, other modifications and variations will become apparent to those skilled in the art. However, it should be apparent that such other modifications and variations may be effected without departing from the spirit and scope of the invention.
Claims (14)
1. A film comprising:
microfibrillated cellulose;
nanoparticles, wherein said nanoparticles are nanosilica nanoparticles that are anionic at neutral or alkaline pH and have at least one dimension less than 100 nm; and
a retention polymer, wherein said retention polymer comprises starch,
wherein the film has an oxygen transmission rate <200 cc/m2*day measured at 50% RH, 23° C., and a grammage of 10-50 gsm.
2. The film according to claim 1 , wherein the amount of nanoparticles in the film is at least 5 kg/ton dry film.
3. The film according to claim 2 , further comprising:
a coating, provided on at least one side of the film,
4. The film according to claim 3 , further comprising: a tie layer between the film and the coating.
5. The film according to claim 1 , further comprising:
a coating, provided on at least one side of the film,
6. The film according to claim 5 , further comprising: a tie layer between the film and the coating.
7. The film according to claim 1 , wherein said retention polymer further comprises polyaminoamide, epichlorohydrin, cationic polyacryl amide, copolymers of cationic polyacryl amide, and mixtures thereof.
8. A product comprising:
a surface having a film, wherein the film comprises
microfibrillated cellulose;
nanoparticles, wherein said nanoparticles are nanosilica nanoparticles that are anionic at neutral or alkaline pH and have at least one dimension less than 100 nm; and
a retention polymer, wherein said retention polymer comprises starch,
wherein the film has an oxygen transmission rate <200 cc/m2*day measured at 50% RH, 23° C., and a grammage of 10-50 gsm
9. The product according to claim 8 , wherein the amount of nanoparticles in the film is at least 5 kg/ton dry film
10. The product according to claim 9 , further comprising:
a coating, provided on at least one side of the film,
11. The product according to claim 10 , further comprising: a tie layer between the film and the coating.
12. The product according to claim 8 , further comprising:
a coating, provided on at least one side of the film,
13. The product according to claim 12 , further comprising: a tie layer between the film and the coating.
14. The product according to claim 8 , wherein said retention polymer further comprises polyaminoamide, epichlorohydrin, cationic polyacryl amide, copolymers of cationic polyacryl amide, and mixtures thereof.
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SE542388C2 (en) * | 2018-02-02 | 2020-04-21 | Stora Enso Oyj | Process for production of film comprising microfibrillated cellulose |
SE543616C2 (en) * | 2019-06-17 | 2021-04-20 | Stora Enso Oyj | A method to produce a fibrous product comprising microfibrillated cellulose |
WO2021224776A1 (en) * | 2020-05-04 | 2021-11-11 | Chen George Dah Ren | Method and system of a fibrillated cellulose material |
CN114402104B (en) * | 2020-05-29 | 2024-04-05 | 株式会社Lg化学 | Fibrillated fibers and methods for making the same |
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WO2022219377A1 (en) * | 2021-04-16 | 2022-10-20 | Stora Enso Oyj | Method for manufacturing a barrier film, and a barrier film |
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JP2020509255A (en) | 2020-03-26 |
US11192987B2 (en) | 2021-12-07 |
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BR112019018018A2 (en) | 2020-04-28 |
EP3589685A4 (en) | 2020-11-25 |
JP7149282B2 (en) | 2022-10-06 |
CA3054147A1 (en) | 2018-09-07 |
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