WO2010077203A1 - Biopolymer based barrier material and method for making th same - Google Patents
Biopolymer based barrier material and method for making th same Download PDFInfo
- Publication number
- WO2010077203A1 WO2010077203A1 PCT/SE2009/051469 SE2009051469W WO2010077203A1 WO 2010077203 A1 WO2010077203 A1 WO 2010077203A1 SE 2009051469 W SE2009051469 W SE 2009051469W WO 2010077203 A1 WO2010077203 A1 WO 2010077203A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- biopolymer
- plasticizer
- nano
- barrier coating
- coating composition
- Prior art date
Links
- 230000004888 barrier function Effects 0.000 title claims abstract description 119
- 229920001222 biopolymer Polymers 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000000463 material Substances 0.000 title description 13
- 238000000576 coating method Methods 0.000 claims abstract description 100
- 239000004014 plasticizer Substances 0.000 claims abstract description 90
- 239000011248 coating agent Substances 0.000 claims abstract description 73
- 239000004927 clay Substances 0.000 claims abstract description 64
- 229920002472 Starch Polymers 0.000 claims abstract description 57
- 239000008107 starch Substances 0.000 claims abstract description 57
- 235000019698 starch Nutrition 0.000 claims abstract description 57
- 239000002105 nanoparticle Substances 0.000 claims abstract description 47
- 239000008199 coating composition Substances 0.000 claims abstract description 46
- 239000000758 substrate Substances 0.000 claims abstract description 25
- 239000001913 cellulose Substances 0.000 claims abstract description 15
- 229920002678 cellulose Polymers 0.000 claims abstract description 15
- 229920000881 Modified starch Polymers 0.000 claims abstract description 6
- 239000004368 Modified starch Substances 0.000 claims abstract description 6
- 235000019426 modified starch Nutrition 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 73
- 239000006185 dispersion Substances 0.000 claims description 57
- 239000000203 mixture Substances 0.000 claims description 54
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 45
- 239000012802 nanoclay Substances 0.000 claims description 43
- 239000011087 paperboard Substances 0.000 claims description 42
- 239000000123 paper Substances 0.000 claims description 35
- 229920001223 polyethylene glycol Polymers 0.000 claims description 26
- 239000002202 Polyethylene glycol Substances 0.000 claims description 24
- 239000004816 latex Substances 0.000 claims description 23
- 229920000126 latex Polymers 0.000 claims description 23
- 239000010410 layer Substances 0.000 claims description 18
- 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 claims description 12
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 claims description 10
- 229910000278 bentonite Inorganic materials 0.000 claims description 9
- 239000000440 bentonite Substances 0.000 claims description 9
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 9
- 239000000049 pigment Substances 0.000 claims description 8
- 239000011247 coating layer Substances 0.000 claims description 7
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 6
- 239000000600 sorbitol Substances 0.000 claims description 6
- 239000001087 glyceryl triacetate Substances 0.000 claims description 5
- 235000013773 glyceryl triacetate Nutrition 0.000 claims description 5
- 229960002622 triacetin Drugs 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 230000002209 hydrophobic effect Effects 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000004348 Glyceryl diacetate Substances 0.000 claims description 3
- 235000019443 glyceryl diacetate Nutrition 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 229940092782 bentonite Drugs 0.000 claims 8
- ONCZQWJXONKSMM-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4].[Si+4].[Si+4].[Si+4] ONCZQWJXONKSMM-UHFFFAOYSA-N 0.000 claims 6
- 229910000280 sodium bentonite Inorganic materials 0.000 claims 6
- 229940080314 sodium bentonite Drugs 0.000 claims 6
- 229910000281 calcium bentonite Inorganic materials 0.000 claims 5
- 150000001875 compounds Chemical class 0.000 claims 2
- 239000012764 mineral filler Substances 0.000 claims 1
- 239000011734 sodium Substances 0.000 description 26
- 238000009472 formulation Methods 0.000 description 25
- 230000000694 effects Effects 0.000 description 19
- 238000002156 mixing Methods 0.000 description 19
- 238000007792 addition Methods 0.000 description 12
- 239000002245 particle Substances 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 239000000454 talc Substances 0.000 description 11
- 229910052623 talc Inorganic materials 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 238000004806 packaging method and process Methods 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 6
- 235000013305 food Nutrition 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- -1 moisture Substances 0.000 description 6
- 229910052901 montmorillonite Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 5
- 239000004519 grease Substances 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 235000012216 bentonite Nutrition 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- NJVOHKFLBKQLIZ-UHFFFAOYSA-N (2-ethenylphenyl) prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1C=C NJVOHKFLBKQLIZ-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000000670 limiting effect Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229910052618 mica group Inorganic materials 0.000 description 3
- 239000002114 nanocomposite Substances 0.000 description 3
- 229920005615 natural polymer Polymers 0.000 description 3
- 229920001282 polysaccharide Polymers 0.000 description 3
- 230000008092 positive effect Effects 0.000 description 3
- 239000011115 styrene butadiene Substances 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- UYXTWWCETRIEDR-UHFFFAOYSA-N Tributyrin Chemical compound CCCC(=O)OCC(OC(=O)CCC)COC(=O)CCC UYXTWWCETRIEDR-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229920013724 bio-based polymer Polymers 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000002860 competitive effect Effects 0.000 description 2
- 238000010411 cooking Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000001595 flow curve Methods 0.000 description 2
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 2
- 229910000271 hectorite Inorganic materials 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 150000002500 ions Chemical group 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical group [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 description 2
- 150000002892 organic cations Chemical class 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910000275 saponite Inorganic materials 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229910052902 vermiculite Inorganic materials 0.000 description 2
- 239000010455 vermiculite Substances 0.000 description 2
- 235000019354 vermiculite Nutrition 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- 241001057362 Cyra Species 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 240000000359 Triticum dicoccon Species 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 235000019568 aromas Nutrition 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical group OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 238000010227 cup method (microbiological evaluation) Methods 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000007970 homogeneous dispersion Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052900 illite Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000273 nontronite Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001592 potato starch Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 229910000269 smectite group Inorganic materials 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/04—Starch derivatives, e.g. crosslinked derivatives
- C08L3/10—Oxidised starch
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/02—Starch; Degradation products thereof, e.g. dextrin
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
-
- 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
- D21H19/54—Starch
-
- 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
- D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H19/60—Polyalkenylalcohols; Polyalkenylethers; Polyalkenylesters
-
- 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
- D21H19/80—Paper comprising more than one coating
- D21H19/84—Paper comprising more than one coating on both sides of the substrate
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31971—Of carbohydrate
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31971—Of carbohydrate
- Y10T428/31975—Of cellulosic next to another carbohydrate
Definitions
- the present invention relates to biopolymer based barrier coating compositions with improved properties for providing barrier coatings on cellulose based substrates, e.g. paper and paperboard, as well as paper and paperboard provided with such coating.
- It also relates to a method for preparing a biopolymer based barrier coating composition and to a method for preparing cellulose based substrates with barrier properties.
- Barrier coatings are used in paper and paperboard packaging to provide barrier properties to paper and paperboard by reducing or eliminating the permeability of gases through the material and/or the absorption of liquids in the fiber structure.
- Barrier coatings are required to prevent the egress from the package of flavors, aromas and other ingredients of the packaged product as well as to prevent the ingress into the package of oxygen, moisture, grease and other contaminants that might deteriorate the quality of the packaged product.
- Oxygen and water vapour are the gases for which barriers are normally tested but the barriers are useful for other gases as well, including carbon dioxide.
- biopolymer based barrier-coating compositions which are easy and inexpensive to produce, which have good barrier properties with respect to moisture, gas and grease and which have low brittleness.
- barrier coating compositions which can easily be separated from the cellulose fibres in recycling and repulping processes.
- Natural polymers or biopolymers that come from renewable sources show many interesting properties in terms of film forming ability and resistance to oxygen and grease. However, the moisture sensitivity of biopolymers makes them inappropriate as barrier films for food packaging applications.
- barriers based on natural polymers Another disadvantage of barriers based on natural polymers is the brittleness of the coatings, i.e. the sensitivity of barrier properties to mechanical stress applied in converting operations. Cracking of the barrier film causes the barrier properties to be lost.
- the patent document WO 00/40404 describes coated films with improved barrier properties and relates to coating compositions which use a polymeric binder and a nano- scale particle size additive to provide improved moisture barriers.
- the area concerned is thermoplastic films and the coating compositions are suited for application to polypropylene and polyethylene films in order to improve the barrier characteristics of said polypropylene and polyethylene films and thereby making them acceptable for food packaging applications.
- the polymers used are not biopolymers and the intention is not to replace petroleum-based plastic films with more environmentally friendly coatings that provide sufficient barrier protection to paper or paperboard.
- the patent document EP 1 736 504 describes improvement of barrier properties of a water soluble gas barrier material by adding nanoparticles of calcium carbonate.
- the polymers used are synthetic polymers and not biopolymers and the purpose is to improve oxygen barrier properties, not water vapour barrier properties.
- the patent document WO 03/078734 describes a composition for surface treatment of paper by use of nanoparticles of synthetic layered silicates or precipitated calcium carbonate in a carrier fraction comprising plate-like pigment particles (talc and/or kaolin) and a binder such as a polymer latex (styrene-butadiene).
- a carrier fraction comprising plate-like pigment particles (talc and/or kaolin) and a binder such as a polymer latex (styrene-butadiene).
- talc and/or kaolin plate-like pigment particles
- a binder such as a polymer latex (styrene-butadiene).
- Starch is mentioned as a surface sizing agent in order to improve the strength of the paper surface.
- the barrier coatings of the present invention are easily applied as water-borne dispersions on paper and paperboard, are environmentally safe, have excellent film- forming properties and has competitive barrier properties with respect to oxygen, grease and moisture.
- the barrier films formed by the applied dispersion show an intermediate brittleness and therefore some resistance to mechanical stress.
- Starch from potato is an example of a biobased polymer with several interesting features. It is renewable, highly available at low price, approved for food contact and has potential for chemical modification. Starch can be native starch, degraded and/or chemically modified.
- Chemically modified starch can easily be applied as water-borne dispersions on paper and paperboard and shows excellent film- forming properties.
- the film formed has in general good resistance to grease and oxygen but is highly moisture sensitive.
- oxidized, hydroxypropylated potato starch was chosen as the biopolymer.
- Other possible biobased polymer materials could be starch from other plant sources (e.g. wheat or corn); starch with other types of chemical modification, or cellulose derivatives.
- Nanoparticles are very helpful in lowering the moisture sensitivity of the barrier film.
- a particle is defined as a small object that behaves as a whole unit in terms of its transport and properties. It is further classified according to size. Nanoparticles have one dimension in the range between 1 and 100 nanometers and may or may not exhibit size-related properties that differ significantly from those observed in fine particles or bulk materials. Although the size of most molecules would fit into the above outline, individual molecules are usually not referred to as nanoparticles.
- Nanoparticles are, in the present invention, defined as having a size below 100 nm and can be either inorganic (silicates, metal oxides) or organic (polymers, dyes).
- nanoclay nano-sized clay particles, hereinafter called nanoclay, have been investigated.
- Clay is a generic term which encompasses a well-documented range of minerals; some pertinent examples of which include the kaolinite group, the talc group, the smectite group (which includes montmorillonite, hectorite, saponite and their associated impurities), the vermiculite group, the illite group, the chlorite group and the mica/brittle mica group. It is important to recognize the important group called bentonites. Bentonites are impure smectites, particularly montmorillonite, which contain ancilliary minerals such as quartz, cristabolite, feldspar, mica, illite, calcium carbonate and titania.
- montmorillonite which is a layered clay mineral with an aluminosilicate structure having a hydrophilic character.
- swelling clays can be made organophilic, which makes them more compatible and more easily dispersible in organophilic polymers.
- organic cations e.g. alkylammonium or alkylphosphonium (onium) surfactants.
- the nanoclays used in the present invention have ion exchange capacities and belong to the bentonite type of clays, more precisely sodium montmorillonite and calcium montmorillonite and blends thereof.
- Other possible nanoclays would be multivalent- or organic cation exchanged grades and inorganic cation-exchanged clays, as well as other clays which can be purified and suitably ion exchanged, all of which are available from commercial suppliers and as samples or gifts from deposits from all around the world.
- the relationship between surface diameter and thickness of the nanoclay particles is defined as the aspect ratio.
- commercial nanoclays have aspect ratios between 50 and 1000, which is much larger than for typical clay pigments (10-30) used in conventional paper or paperboard coating.
- the large aspect ratio of nanoclays makes them effective for barrier improvement even at very low ( ⁇ 5% by weight) concentrations. Higher weight additions may be difficult from a processing perspective, because the viscosity of the dispersions increases significantly at increased loads of clay.
- the use of nanoparticles in paper and paperboard coating is thus advantageous, particularly given that less material is required (thinner coating layers) to reach the desired barrier or mechanical properties. Less material use leads to reduced costs and reduced amounts of waste.
- nanoclay exacerbates the brittleness of the film.
- plasticizers to the barrier composition increases the film flexibility and maintains the protective properties.
- the barrier and mechanical properties are however strongly affected by the nature and amount of the plasticizer.
- the plasticizer molecules (often short-chain, low-molecular- weight polymers or oligomers) arrange themselves between the polymer chains such that the intermolecular hydrogen bonding is disrupted, hence giving films with less stiffness.
- plasticizer for starch and proteins is glycerol.
- hydrophilic plasticizers include sorbitol, polyethylene glycol (PEG) and polypropylene glycol (and mixtures thereof), polyvinyl alcohol (PVOH), amino acids, amides, di- and triethanolamine.
- Organophilic (hydrophobic) plasticizers such as diacetin, triacetin and tributyrin, can also be used.
- the plasticizer can also be a mixture including both hydrophilic and organophilic plasticizers. The plasticizer not only affects the properties of the polymer matrix, it also interacts with the clay particles and thereby influences their orientation in the coating layer.
- Multilayer coating is more effective than just increasing the coat weight.
- the coverage of the substrate surface is increased by multilayer coating.
- Calendering of the paper or paperboard improves the barrier properties by elimination of coating defects.
- the biopolymer barrier coating dispersion can be applied on uncoated surfaces as well as on pre-coated surfaces which consist of a pigment coating, a biopolymer based coating, a dispersion barrier coating or laminates thereof.
- the ordering of clay platelets in the coating is affected by plasticizer type, application strategy and post-treatment and will affect the final barrier properties.
- Figure 1 shows XRD patterns for the coated samples presented in Table 3 a.
- the sample designation G refer to glycerol and PEG to polyethylene glycol.
- the values within brackets are the concentration of plasticizer in pph.
- Figure 2 shows various sequences of mixing the three components of the biopolymer based coating composition of the present invention.
- Figure 3 shows flow curves for OHP starch-plasticizer-Na/Ca-Cloisite formulations at 60 0 C and where the figure legends refer to the Na/Ca-Cloisite ratio.
- the present invention describes the performance of water-based coating formulations of oxidized, hydroxypropylated starch, henceforth called OHP starch, plasticized with glycerol or polyethylene glycol or sorbitol or triacetin to which different loads of sodium montmorillonite and/or calcium montmorillonite has been added.
- the plasticizer was added to reduce the brittleness of the coating.
- the goal is to get an aqueous coating suspension which has an appropriate viscosity for use in conventional coating applicators.
- Applying the water-based composition on the paper or paperboard surface comprises the steps of preparing an aqueous based dispersion comprising a biopolymer, a plasticizer and a nanoclay; coating the cellulose based substrate with the dispersion and allowing the dispersion to dry on the substrate.
- the sodium montmorillonite and calcium montmorillonite used in the present invention have the trade names Na-Cloisite and Ca-Cloisite, respectively, and will be the terms henceforth used.
- Example 1 Effects of chemicals on formulation viscosity Na-Cloisite was dispersed in deionized water in a dispergator using a Cowles propeller operated at a speed of 1000 rpm. Two different concentrations of clay were used: 1) low concentration to get a completely delaminated clay, 2) higher concentration to get as high solids content as possible in the formulations. The viscosity was measured by a Brookf ⁇ eld viscometer operated at 100 rpm (Table 1).
- OHP starch was cooked to 20% concentration. Glycerol was used as plasticizer and was added to the cooked starch at a constant level of 30 parts per 100 parts of OHP starch on dry basis. Na-Cloisite dispersion 1 or 2 was added at various amounts and the suspensions were mixed by a propeller rotor operated at 500 rpm for 20 minutes.
- OHP starch, plasticizer and nanoclay were adjusted to reach a viscosity within the range of 500-2000 mPas, which may be an appropriate viscosity for coating runnability with various coating techniques, while keeping the overall solids content at the highest possible level (Table 2).
- row 4 shows the best result resulting in a viscosity within the viscosity range of 500-2000 mPas.
- the amount of total solids decreases with increasing addition of dispersion of Na- Cloisite as a result of the addition of more water to the composition.
- Table 2 shows that even small variations in total solids results in large variations in viscosity, e.g. a comparison of the results in rows 1 and 2 shows a difference in total solids of 0.6% resulting in a difference in viscosity of 3610 mPas. It is understood from Table 2 that the proportions of the Na-CIo isite-OHP starch- plasticizer and the amount of total solids have a very big influence on the viscosity. It is of great importance to find out the optimal proportions in order to get a viscosity within the range of optimal viscosity for coating runnability.
- Glycerol and polyethylene glycol (PEG) were used as plasticizers and were added at levels of 10, 20 and 30 parts per 100 parts of OHP starch on dry basis.
- a water dispersion of Na-Cloisite (with 9.5 wt% clay) was used.
- the nanoclay dispersion was mixed into the starch-plasticizer solutions while keeping the temperature at 60 0 C using a hotplate.
- Table 3a shows the total solids content, the relative concentrations of Na-Cloisite, OHP starch and plasticizer (as percentages of dry matter) and the resulting Brookfield viscosities (confer Table 2).
- Table 3a Viscosity and water vapour transmission rate (WVTR) for formulations of OHP starch-Na-Cloisite as a function of plasticizer type and concentration. Brookfield viscosities at 100 rpm were recorded at a temperature of 60 0 C. Data for pure OHP starch is shown or com arison.
- a OHP starch-plasticizer-nanoclay composition should preferably consist of 20-40 wt% nanoclay, 50-70 wt% OHP starch and 5-30 wt% plasticizer.
- the of content of nanoclay in the coating composition may be as high as 70 wt%.
- the water vapour transmission rate, WVTR is defined as the amount of water vapour that is transmitted through a unit area in a unit time under specified conditions of temperature and humidity.
- WVTR water vapour transmission rate
- Common standards for measurement of WVTR by the gravimetric method are ASTM E 96, DIN 53122-1, ISO 2528, TAPPI T 448 and T 464.
- the WVTR of coated paperboard materials generally decreases exponentially with increased coating layer or film thickness. Permeation will mainly take place through coating defects such as cracks, voids and pinholes or through the amorphous regions of polymer films. Packaging of foodstuff with intermediate requirements on moisture protection typically have a critical level of WVTR below 10 g/m 2 -d.
- WVTR data is presented in Table 3a. All formulations containing Na-Cloisite showed a significant decrease in WVTR compared to the reference OHP starch coating. At all plasticizer levels, the formulations containing polyethylene glycol showed lower WVTR values than those containing glycerol. This may partly be due to the hygroscopic character of the latter. A minimum in WVTR was observed at 20 pph PEG.
- WVTR Water vapour transmission rate
- FIG. 1 presents the x-ray traces for the six samples in Table 3 a. These samples all displayed relatively sharp, intense x-ray peaks when using the peak intensities from the paper, at 2 ⁇ values near 16 and 22.5°, as a comparative standard (2 ⁇ refers to the angle between the incident and diffracted x-ray beam). Note that some of the peaks near 5 °2 ⁇ exhibited two poorly resolved peaks. The position of these peaks was used to calculate the d- spacings presented in the two right hand columns in Table 3a.
- the XRD traces in Figure 1 illustrate the considerable differences in clay particle ordering and gallery spacing in the presence of PEG compared with glycerol.
- the broad, weak peaks displayed by the coatings prepared using glycerol suggest that the platelets are poorly ordered with respect to each other, whereas the narrow, intense peaks displayed by the samples containing PEG indicate that the clay platelets are well- aligned with respect to each other and oriented with their basal surface parallel to the paper surface.
- the d- spacings of the clay in different coatings are shown in the last two columns in Table 3a.
- the OHP starch is dispersed in water and cooked, thus forming a biopolymer solution with a starch concentration of 10-30 percent by weight on dry basis.
- the plasticizer is then added to said biopolymer solution forming a biopolymer- plasticizer solution with a concentration of 10-30 parts plasticizer per 100 parts of biopolymer on dry basis.
- a water dispersion of nanoclay is added to the biopolymer-plasticizer solution.
- Sequence 2 involves the dispersion of nanoclay as a dry substance (and not as a water dispersion of nanoclay as in Seq. 1), henceforth called dry nanoclay, in the OHP starch- plasticizer solution.
- Sequence 3 implies dispersion of dry nanoclay in a water solution containing a predetermined amount of plasticizer, followed by mixing the nanoclay-plasticizer- water dispersion with cooked starch to reach identical proportions of the three components as in Example 2 corresponding to 20 parts plasticizer per 100 parts of OHP starch (Table 3 a, row 6). This composition was selected for investigation of mixing sequences because it showed the lowest WVTR when following Sequence 1.
- Sequence 4 implies blending dry nanoclay with OHP starch in powder form, followed by addition of water and plasticizer, prior to cooking, to reach identical proportions of the three components as in Example 2 corresponding to 20 parts plasticizer per 100 parts of OHP starch (Table 3 a, row 6). Coating of paperboard and measurement of WVTR was carried out as in Example 2.
- Sequence 1 is thus preferred from a viscosity perspective.
- Sequence 4 gives WVTR values of coated paperboard comparable to Sequence 1.
- Sequence 3 and 4 the complete delamination of clay platelets could be obstructed by the presence of plasticizer (or starch) in the water mixture.
- plasticizer or starch
- nanoclay particles is suspected to impair the swelling and gelatinization of OHP starch granules during the initial cooking step according to Sequence 4.
- Sequence 2 resulted in a high increase in the viscosity (>6000 mPas) even at low (14 weight percent on dry basis) additions of nanoclay and hence the composition fell outside the range for making application on paper possible.
- the advantage with this mixing procedure is however that the total solids content of the OHP starch-plasticizer-nanoclay formulation can be raised to higher levels than with any of the other methods.
- Sequence 1 was selected as the most successful one.
- An alternative mixing procedure would be to disperse nano-sized clay in water forming a water dispersion of nano-sized clay at a concentration of 5-10 percent by weight on dry basis and to dissolve the biopolymer in water forming a biopolymer solution at a concentration of 10-30 percent by weight on dry basis and then to add the biopolymer solution to the water dispersion of nano-sized clay followed by addition of the plasticizer.
- Another alternative mixing procedure would be to disperse nano-sized clay at a concentration of 5-10 percent by weight on dry basis, the plasticizer is added to said water dispersion forming a water dispersion of nano sized clay-plasticizer, dissolve the biopolymer in water forming a water solution of biopolymer at a concentration of 10-30 percent by weight on dry basis followed by mixing the water solution of biopolymer with the nano sized clay-plasticizer dispersion.
- the different mixing sequences result in the same final composition of the biopolymer based barrier coating composition but the viscosity of the final coating composition may differ from mixing sequence to mixing sequence as a result of in which order the components have been added.
- mixing Sequence 1 is preferred from a viscosity perspective for mixing the components in the desired proportion. If another mixing proportion of the ingredients is preferred, one of the other mixing sequences may be more advantageous in order to reach a viscosity within the preferred viscosity range of 500-2000 mPas.
- Example 4 Effect of gallery cation on starch-plasticizer-nanoclay dispersion and coating properties
- Dry blends of Na-Cloisite and Ca-Cloisite with the following Na/Ca percentage ratios were mixed: 100/0; 80/20; 60/40; 50/50; 40/60; 20/80 and 0/100.
- the Na/Ca-Cloisite blends were dispersed in deionized water in a dispergator.
- the resulting solids content was about 8% in all dispersions.
- OHP starch was cooked to 20% concentration.
- Polyethylene glycol was added to the cooked starch solution corresponding to 20 parts polyethylene glycol per 100 parts starch on dry basis.
- the Na/Ca-Cloisite dispersions were added to the starch-plasticizer solution as in Example 2.
- the resulting compositions were 27 wt% clay, 61 wt% OHP starch and 12 wt% PEG on dry basis.
- the viscosity of the OHP starch-plasticizer-nanoclay dispersions were measured by a controlled shear stress rheometer (Physica MCR 300, Physica Messtechnik GmbH, Ostfildern, Germany) with shear rates from 1 to 4000 s "1 in concentric cylinder geometry at 60 0 C. Flow curves are shown in Figure 3. All types of dispersions showed shear thinning behavior. It was anticipated that mixtures of Na- and Ca-exchanged nanoclay would exhibit a reduced viscosity which would allow higher nanoclay contents to be used. The results showed that the overall viscosity of the OHP starch-plasticizer-Na/Ca-Cloisite dispersions decreased with increasing amount of Ca-Cloisite. A remarkably large decrease in the viscosity was observed when going from 60 to 80% Ca-Cloisite and similarly when going from 80 to 100%.
- Example 2 Laboratory coating and WVTR Coating of paperboard and measurement of WVTR were carried out as in Example 2. The dry coating thickness was measured to about 15-20 ⁇ m and the coat weights were determined to about 6-8 g/m 2 . The effect of Na/Ca-Cloisite ratio on WVTR is shown in Table 5.
- the WVTR was found to increase with increasing content of Ca-Cloisite.
- 100% Ca-Cloisite there is only a slight improvement of the barrier compared to the pure OHP starch coating (ca 295 g/m 2 -d).
- introduction of a small amount of Ca-Cloisite may favor the water vapor barrier properties over a coating with pure Na-Cloisite.
- the effect of Ca-Cloisite was further studied in the region between 0 and 20 wt% to validate the positive effect of a small amount of a divalent cation in the clay gallery, and to find out the optimum mixture of monovalent and divalent cations with respect to barrier properties.
- the proportions between nanoclay, starch and PEG was kept constant at 27:61 :12 on dry basis.
- OHP starch-PEG-Na/Ca-Cloisite formulations were applied on paperboard by bench coater in a single layer of about 8-10 g/m 2 as described in previous examples.
- the formulations were applied in a single layer on top of the following substrates:
- WVTR values for the pre-coated substrates and the same substrates top-coated with the different Na/Ca-Cloisite formulations are shown in Table 6.
- the talc-filled barrier latex shows low WVTR values and should represent one of the most efficient dispersion barriers, using non-sustainable polymer matrices, commercially available on the market today.
- Substrate pre-coating Substrate 100/0 95/5 90/10 85/15 80/20
- a single layer (ca 8-10 g/m 2 ) of OHP starch-PEG-Na/Ca-Cloisite resulted in a WVTR around 50-57 g/m 2 -d, irrespective of the Na/Ca-Cloisite ratio (Table 6, row 1). It is notable that these values are lower than for a double layer coating of the SA-latex (WVTR 65 g/m 2 -d; Table 6, row 5) despite that the coat weight of the SA-latex coating (29 g/m 2 ) was three times higher.
- OHP starch-PEG-Na/Ca-Cloisite formulations on top of a conventional pigment pre-coating has a favorable effect on the WVTR, with a 15-25% reduction. This should be due to a more surface- located barrier layer, i.e. reduced porosity of the substrate prevents too severe absorption of the barrier coating into the fiber structure.
- the WVTR of the talc-filled styrene-butadiene latex coated paperboard was further reduced by application of the OHP starch-PEG-Na/Ca-Cloisite on top and these combined pre- and top coatings together give WVTR values approaching the target level of ⁇ 10 g/m 2 -d set for food packaging with intermediate demand for water vapor barriers.
- the combination of two layers of OHP starch-PEG-Na/Ca-Cloisite (Table 6, row 3) and one layer of OHP starch-PEG-Na/Ca-Cloisite on top of a SA- latex pre- coating (Table 6, row 5) also results in acceptable WVTR values, around 30 g/m 2 -d.
- Another alternative coating approach may be to first apply a single or double layer of biopolymer based barrier coating followed by application of a layer of a barrier latex coating, i.e. a first, single or double, layer of OHP starch-PEG-Na/Ca-Cloisite is applied to the paper or paperboard followed by application of a top coating comprising a dispersion barrier latex.
- a layer of a barrier latex coating i.e. a first, single or double, layer of OHP starch-PEG-Na/Ca-Cloisite is applied to the paper or paperboard followed by application of a top coating comprising a dispersion barrier latex.
- the water vapor transmission rate of the most promising coatings i.e. the OHP starch- plasticizer-nanoclay formulations applied in two layers (row 3 in Table 6) and the OHP starch-plasticizer-nanoclay formulations applied on top of the talc-filled SB-latex (row 6 in Table 6) was also measured at elevated relative humidity (23°C and 85% RH) and at tropical conditions (38°C and 90% RH). Both testing conditions are standard climates according to DIN 53122 and ISO 2528. In the packaging industry, the test conditions are often set to 23°C and 85% RH to match realistic packaging environments. The tests were carried out in a climate chamber. All samples were conditioned for > 12 hours in each climate before starting the test.
- a commercial nanocomposite coating consisting of a nanosilicate dispersed in a polyester resin (Nanolok PT 3575, InMat Inc.) was applied on top of the talc-filled SB-latex.
- the obtained WVTR was 9 ⁇ 1 g/m 2 -d.
- some of the starch-based nanoclay coatings are tangent to these values.
- Double layer application seem to be more efficient for reduction of WVTR than the application of an increased thickness of an applied single layer.
- Starch-based nanoclay coatings were proven to offer competitive WVTR values when compared with commercial unfilled styrene-acrylate dispersion coatings.
- the surface energy of the pre-coating and the surface tension of the top coating is beneficially controlled to get optimum wetting and spreading properties of the top coating layer.
- a conventional, inexpensive pigment pre-coating strongly facilitates the barrier properties of a starch-based nanoclay coating.
- the nanoclay acts as a compatibiliser between starch and PEG. It is understood that the objects of the present invention set forth above, among those made apparent by the detailed description, shall be interpreted as illustrative and not in a limiting sense.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paper (AREA)
- Paints Or Removers (AREA)
- Laminated Bodies (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP09836462.3A EP2370533B1 (en) | 2008-12-30 | 2009-12-21 | Biopolymer based barrier material and method for making the same |
US13/139,814 US8734959B2 (en) | 2008-12-30 | 2009-12-21 | Barrier material and method for making the same |
BRPI0923880-8A BRPI0923880A2 (en) | 2008-12-30 | 2009-12-21 | Biopolymer barrier material and method for obtaining the same |
CA2748801A CA2748801C (en) | 2008-12-30 | 2009-12-21 | Biopolymer based barrier material and method for making the same |
CN200980157532.3A CN102333829B (en) | 2008-12-30 | 2009-12-21 | Biopolymer based barrier material and method for making the same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
SE0802677 | 2008-12-30 | ||
SE0802677-5 | 2008-12-30 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2010077203A1 true WO2010077203A1 (en) | 2010-07-08 |
Family
ID=42310010
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/SE2009/051469 WO2010077203A1 (en) | 2008-12-30 | 2009-12-21 | Biopolymer based barrier material and method for making th same |
Country Status (6)
Country | Link |
---|---|
US (1) | US8734959B2 (en) |
EP (1) | EP2370533B1 (en) |
CN (1) | CN102333829B (en) |
BR (1) | BRPI0923880A2 (en) |
CA (1) | CA2748801C (en) |
WO (1) | WO2010077203A1 (en) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012150904A1 (en) * | 2011-05-04 | 2012-11-08 | Kth Holding Ab | Oxygen barrier for packaging applications |
WO2013182757A1 (en) | 2012-06-08 | 2013-12-12 | Upm-Kymmene Corporation | A method and a system for manufacturing packaging material, as well as packaging material and a package |
EP3156540A1 (en) * | 2015-10-12 | 2017-04-19 | Omya International AG | Process for the deinking of coated paper or paperboard |
EP3286378B1 (en) | 2015-04-20 | 2019-04-10 | Kotkamills Group Oyj | Method and system for manufacturing a coated paperboard and a coated paperboard |
EP3186441B1 (en) | 2014-07-30 | 2019-12-25 | Ahlstrom-Munksjö OYJ | Method for the production of heat-sealing barrier paper |
US10894392B2 (en) | 2011-12-22 | 2021-01-19 | Plantic Technologies Limited | Multilayer films |
WO2023067602A1 (en) * | 2021-10-21 | 2023-04-27 | Melodea Ltd. | Improvement in water-vapor barrier properties in foldable materials |
WO2023192912A1 (en) * | 2022-04-01 | 2023-10-05 | Ecolab Usa Inc. | Compositions and methods for coating a substrate |
Families Citing this family (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103850152B (en) * | 2014-03-18 | 2017-01-18 | 中国工程物理研究院核物理与化学研究所 | Nanometer paper material and preparation method thereof |
US10837143B2 (en) | 2014-05-14 | 2020-11-17 | Bioastra Technologies, Inc. | Thermoregulatory coatings for paper |
GB201408675D0 (en) * | 2014-05-15 | 2014-07-02 | Imerys Minerals Ltd | Coating composition |
CZ305000B6 (en) * | 2014-05-27 | 2015-03-18 | Jaromír Kelárek | Paper with enhanced strength and enhanced resistance to fats |
US10674738B2 (en) * | 2014-12-31 | 2020-06-09 | Toray Plastics (America), Inc. | Starch coated polyester film for release of canned meat products |
US11027523B2 (en) * | 2015-11-30 | 2021-06-08 | Toray Plastics (America), Inc. | Polyester film incorporating silicone for release of canned meat products |
DE102016118587A1 (en) * | 2016-09-30 | 2018-04-05 | Drewsen Spezialpapiere Gmbh & Co Kg | Packaging paper and process for its production |
CA3038208A1 (en) | 2016-09-30 | 2018-04-05 | Maria Izabel Magalhaes Viana Fittipaldi | Waterproofing composition of cellulosic substrates, process of preparation of waterproofing composition, process of application of waterproofing composition, use of waterproofing composition and product |
CN110073056B (en) | 2016-10-31 | 2022-05-17 | 太阳化学公司 | Grease-resistant, oil-resistant and water-resistant coating composition |
WO2018195625A1 (en) * | 2017-04-27 | 2018-11-01 | Fittipaldi Maria Izabel Magalhaes Viana | Composition for acting on a moisture barrier for a thermoplastic polymer, method for preparing the composition, method for preparing a polymer substrate, product and substrate |
CN110740647A (en) * | 2017-06-15 | 2020-01-31 | 荷兰联合利华有限公司 | Frozen confectionery product packaging |
EP3943293A4 (en) * | 2019-03-18 | 2022-12-21 | Nippon Paper Industries Co., Ltd. | Paper barrier material |
SE544664C2 (en) * | 2019-10-31 | 2022-10-11 | Organoclick Ab | Flourocarbon free and biobased oil and water barrier materials |
US20230235166A1 (en) * | 2020-07-02 | 2023-07-27 | Aquaspersions Limited | Aqueous biopolymer dispersions |
US11913174B2 (en) | 2020-07-30 | 2024-02-27 | The Procter & Gamble Company | Recyclable paper barrier laminate |
US20220033158A1 (en) * | 2020-07-30 | 2022-02-03 | The Procter & Gamble Company | Biodegradable paper barrier laminate |
WO2022077009A1 (en) | 2020-10-09 | 2022-04-14 | The Procter & Gamble Company | Methods of producing biodegradable and recyclable barrier paper laminate |
WO2022077008A1 (en) | 2020-10-09 | 2022-04-14 | The Procter & Gamble Company | Biodegradable and recyclable barrier paper laminate |
CN114379162B (en) * | 2021-12-29 | 2023-08-18 | 和盛包装科技(海宁)股份有限公司 | Waterproof breathable composite membrane with microporous structure and preparation method thereof |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5288318A (en) * | 1993-07-01 | 1994-02-22 | The United States Of America As Represented By The Secretary Of The Army | Cellulose acetate and starch based biodegradable injection molded plastics compositions and methods of manufacture |
WO2000040404A1 (en) | 1998-12-30 | 2000-07-13 | Mobil Oil Corporation | Coated films with improved barrier properties |
WO2003078734A1 (en) | 2002-03-19 | 2003-09-25 | Raisio Chemicals Ltd | Composition for surface treatment of paper |
WO2006055504A2 (en) * | 2004-11-19 | 2006-05-26 | Michigan State University | Chemically modified plasticized starch compositions by extrusion processing |
EP1736504A1 (en) | 2005-06-21 | 2006-12-27 | Weyerhaeuser Company | Barrier material and method of making the same |
EP1860138A1 (en) * | 2006-05-25 | 2007-11-28 | Sabanci Universitesi | Biodegradable thermoplastic nanocomposite polymers |
-
2009
- 2009-12-21 WO PCT/SE2009/051469 patent/WO2010077203A1/en active Application Filing
- 2009-12-21 EP EP09836462.3A patent/EP2370533B1/en not_active Not-in-force
- 2009-12-21 BR BRPI0923880-8A patent/BRPI0923880A2/en not_active Application Discontinuation
- 2009-12-21 US US13/139,814 patent/US8734959B2/en not_active Expired - Fee Related
- 2009-12-21 CN CN200980157532.3A patent/CN102333829B/en not_active Expired - Fee Related
- 2009-12-21 CA CA2748801A patent/CA2748801C/en not_active Expired - Fee Related
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5288318A (en) * | 1993-07-01 | 1994-02-22 | The United States Of America As Represented By The Secretary Of The Army | Cellulose acetate and starch based biodegradable injection molded plastics compositions and methods of manufacture |
WO2000040404A1 (en) | 1998-12-30 | 2000-07-13 | Mobil Oil Corporation | Coated films with improved barrier properties |
WO2003078734A1 (en) | 2002-03-19 | 2003-09-25 | Raisio Chemicals Ltd | Composition for surface treatment of paper |
WO2006055504A2 (en) * | 2004-11-19 | 2006-05-26 | Michigan State University | Chemically modified plasticized starch compositions by extrusion processing |
EP1736504A1 (en) | 2005-06-21 | 2006-12-27 | Weyerhaeuser Company | Barrier material and method of making the same |
EP1860138A1 (en) * | 2006-05-25 | 2007-11-28 | Sabanci Universitesi | Biodegradable thermoplastic nanocomposite polymers |
Non-Patent Citations (3)
Title |
---|
HWAN-MAN PARK: "Environmentally friendly polymer hybrids. Part 1. Mechanical, thermal, and barrier properties of thermoplastic starch/clay nanocomposites", JOURNAL OF MATERIALS SCIENCE, vol. 38, no. 5, 2003, pages 909 - 915, XP003026461 * |
SORRENTINO A. ET AL: "Potential perspectives of bio-nanocomposites for food packaging applications", TRENDS IN FOOD SCIENCE AND TECHNOLOGY, vol. 18, 2007, pages 84 - 95, XP005888559 * |
WILHELM H.-M. ET AL: "The influence of layered compounds on the properties of starch/layered compound composites", POLYMER INTERNATIONAL, vol. 52, 2003, pages 1035 - 1044, XP003026462 * |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20140065406A1 (en) * | 2011-05-04 | 2014-03-06 | Kth Holding Ab | Oxygen barrier for packaging applications |
WO2012150904A1 (en) * | 2011-05-04 | 2012-11-08 | Kth Holding Ab | Oxygen barrier for packaging applications |
US10894392B2 (en) | 2011-12-22 | 2021-01-19 | Plantic Technologies Limited | Multilayer films |
US11590738B2 (en) | 2011-12-22 | 2023-02-28 | Plantic Technologies Limited | Multilayer films |
EP2858823A4 (en) * | 2012-06-08 | 2016-02-24 | Upm Kymmene Corp | A method and a system for manufacturing packaging material, as well as packaging material and a package |
WO2013182757A1 (en) | 2012-06-08 | 2013-12-12 | Upm-Kymmene Corporation | A method and a system for manufacturing packaging material, as well as packaging material and a package |
EP3186441B1 (en) | 2014-07-30 | 2019-12-25 | Ahlstrom-Munksjö OYJ | Method for the production of heat-sealing barrier paper |
EP3286378B1 (en) | 2015-04-20 | 2019-04-10 | Kotkamills Group Oyj | Method and system for manufacturing a coated paperboard and a coated paperboard |
US11220788B2 (en) | 2015-04-20 | 2022-01-11 | Kotkamills Group Oyj | Method and system for manufacturing a coated paperboard and a coated paperboard |
WO2017063971A1 (en) * | 2015-10-12 | 2017-04-20 | Omya International Ag | Process for the deinking of coated paper or paperboard |
US10544544B2 (en) | 2015-10-12 | 2020-01-28 | Omya International Ag | Process for the deinking of coated paper or paperboard |
EP3156540A1 (en) * | 2015-10-12 | 2017-04-19 | Omya International AG | Process for the deinking of coated paper or paperboard |
WO2023067602A1 (en) * | 2021-10-21 | 2023-04-27 | Melodea Ltd. | Improvement in water-vapor barrier properties in foldable materials |
WO2023192912A1 (en) * | 2022-04-01 | 2023-10-05 | Ecolab Usa Inc. | Compositions and methods for coating a substrate |
Also Published As
Publication number | Publication date |
---|---|
CN102333829A (en) | 2012-01-25 |
CA2748801A1 (en) | 2010-07-08 |
US20110293957A1 (en) | 2011-12-01 |
CN102333829B (en) | 2014-07-16 |
EP2370533B1 (en) | 2016-04-20 |
EP2370533A4 (en) | 2012-09-19 |
BRPI0923880A2 (en) | 2015-07-28 |
EP2370533A1 (en) | 2011-10-05 |
CA2748801C (en) | 2017-07-04 |
US8734959B2 (en) | 2014-05-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA2748801C (en) | Biopolymer based barrier material and method for making the same | |
CA2467284C (en) | Barrier coatings for oil and grease resistance | |
US20140065406A1 (en) | Oxygen barrier for packaging applications | |
BR112012029601B1 (en) | composition, method for producing a self-supporting film, self-supporting film, multilayered object, method for producing a multilayered object and use of a composition | |
JP2010527384A (en) | Polymer film or coating containing hemicellulose | |
AU2011257349A1 (en) | Cellulosic barrier composition comprising anionic polymer | |
WO2011147823A1 (en) | Cellulosic barrier composition comprising anionic polymer | |
CN107090213A (en) | Matrix, method, packaging and the dispersion coating of the matrix of manufacture coating of coating | |
Adibi et al. | Recent progress in sustainable barrier paper coating for food packaging applications | |
Gaikwad et al. | Overview on in polymer-nano clay composite paper coating for packaging application | |
Breen et al. | Exploring the interactions between starches, bentonites and plasticizers in sustainable barrier coatings for paper and board | |
Andersson et al. | Preparation and incorporation of microcapsules in functional coatings for self‐healing of packaging board | |
Saroha et al. | Preparation and characterization of PVOH/kaolin and PVOH/talc coating dispersion by one-step process | |
Ibrahim et al. | Superhydrophobic coating polymer/silica nanocomposites: enhancing water vapor barrier properties of packaging paper with ultra-thin PS/silica nanocomposite polymer coating | |
Setajit et al. | Development of grease resistant packaging paper using cellulose nanocrystals and sodium alginate | |
WO2018211440A1 (en) | Moisture barrier compositions | |
PT104702A (en) | AQUEOUS COATING FORMULATIONS FOR APPLICATION IN THE SURFACE TREATMENT OF CELLULOSIC SUBSTRATES | |
Raynaud | Development of new barrier materials using microfibrillated cellulose | |
WO2022003472A1 (en) | Barrier coating for paper and paperboard | |
WO2022259134A1 (en) | Barrier coating for paper and paperboard | |
JP2004338798A (en) | Packaging container for powdery detergent | |
LAGARON et al. | Développement de nouveaux matériaux barrières utilisant des microfibrilles de cellulose | |
JP2024523213A (en) | Barrier Coatings for Paper and Board |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200980157532.3 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 09836462 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2009836462 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2748801 Country of ref document: CA |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13139814 Country of ref document: US |
|
REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: PI0923880 Country of ref document: BR |
|
ENP | Entry into the national phase |
Ref document number: PI0923880 Country of ref document: BR Kind code of ref document: A2 Effective date: 20110630 |