CA3240134A1 - Thermoplastic composition - Google Patents
Thermoplastic composition Download PDFInfo
- Publication number
- CA3240134A1 CA3240134A1 CA3240134A CA3240134A CA3240134A1 CA 3240134 A1 CA3240134 A1 CA 3240134A1 CA 3240134 A CA3240134 A CA 3240134A CA 3240134 A CA3240134 A CA 3240134A CA 3240134 A1 CA3240134 A1 CA 3240134A1
- Authority
- CA
- Canada
- Prior art keywords
- cellulose
- thermoplastic composition
- thermoplastic
- mass
- acid
- 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
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 164
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 129
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 128
- 229920002678 cellulose Polymers 0.000 claims abstract description 108
- 239000001913 cellulose Substances 0.000 claims abstract description 108
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000004519 manufacturing process Methods 0.000 claims abstract description 36
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 150000002772 monosaccharides Chemical class 0.000 claims abstract description 30
- 150000002016 disaccharides Chemical class 0.000 claims abstract description 27
- 239000000374 eutectic mixture Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 239000004310 lactic acid Substances 0.000 claims abstract description 15
- 235000014655 lactic acid Nutrition 0.000 claims abstract description 15
- 239000008103 glucose Substances 0.000 claims abstract description 14
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 12
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 7
- 239000008188 pellet Substances 0.000 claims description 24
- 229920005992 thermoplastic resin Polymers 0.000 claims description 14
- 239000011256 inorganic filler Substances 0.000 claims description 12
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 12
- 238000000465 moulding Methods 0.000 claims description 10
- 229920006167 biodegradable resin Polymers 0.000 claims description 8
- 229920005610 lignin Polymers 0.000 claims description 8
- 229920002488 Hemicellulose Polymers 0.000 claims description 7
- 238000004898 kneading Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 abstract description 25
- 239000000383 hazardous chemical Substances 0.000 abstract description 5
- 150000004820 halides Chemical class 0.000 abstract description 4
- 235000000346 sugar Nutrition 0.000 description 29
- 239000000463 material Substances 0.000 description 23
- 230000005496 eutectics Effects 0.000 description 19
- -1 for example Substances 0.000 description 16
- 229920005989 resin Polymers 0.000 description 15
- 239000011347 resin Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000002699 waste material Substances 0.000 description 12
- 230000000704 physical effect Effects 0.000 description 11
- 241000196324 Embryophyta Species 0.000 description 10
- 239000000654 additive Substances 0.000 description 10
- 238000001746 injection moulding Methods 0.000 description 9
- 239000002023 wood Substances 0.000 description 9
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 239000000454 talc Substances 0.000 description 6
- 229910052623 talc Inorganic materials 0.000 description 6
- 239000012815 thermoplastic material Substances 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- REKYPYSUBKSCAT-UHFFFAOYSA-N 3-hydroxypentanoic acid Chemical compound CCC(O)CC(O)=O REKYPYSUBKSCAT-UHFFFAOYSA-N 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 229920001131 Pulp (paper) Polymers 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 239000010893 paper waste Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- GLDQAMYCGOIJDV-UHFFFAOYSA-N 2,3-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC(O)=C1O GLDQAMYCGOIJDV-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 235000013312 flour Nutrition 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000010348 incorporation Methods 0.000 description 3
- YQUVCSBJEUQKSH-UHFFFAOYSA-N protochatechuic acid Natural products OC(=O)C1=CC=C(O)C(O)=C1 YQUVCSBJEUQKSH-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- WXTMDXOMEHJXQO-UHFFFAOYSA-N 2,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC=C1O WXTMDXOMEHJXQO-UHFFFAOYSA-N 0.000 description 2
- CJBDUOMQLFKVQC-UHFFFAOYSA-N 3-(2-hydroxyphenyl)propanoic acid Chemical compound OC(=O)CCC1=CC=CC=C1O CJBDUOMQLFKVQC-UHFFFAOYSA-N 0.000 description 2
- WHBMMWSBFZVSSR-UHFFFAOYSA-N 3-hydroxybutyric acid Chemical compound CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 description 2
- SJZRECIVHVDYJC-UHFFFAOYSA-N 4-hydroxybutyric acid Chemical compound OCCCC(O)=O SJZRECIVHVDYJC-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- WQZGKKKJIJFFOK-IVMDWMLBSA-N D-allopyranose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@H](O)[C@@H]1O WQZGKKKJIJFFOK-IVMDWMLBSA-N 0.000 description 2
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 2
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 229920001046 Nanocellulose Polymers 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229920001893 acrylonitrile styrene Polymers 0.000 description 2
- 150000001323 aldoses Chemical class 0.000 description 2
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000306 component Substances 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920001038 ethylene copolymer Polymers 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229930182830 galactose Natural products 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- ROBFUDYVXSDBQM-UHFFFAOYSA-N hydroxymalonic acid Chemical compound OC(=O)C(O)C(O)=O ROBFUDYVXSDBQM-UHFFFAOYSA-N 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
- 239000002655 kraft paper Substances 0.000 description 2
- 210000001724 microfibril Anatomy 0.000 description 2
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 2
- 229930014626 natural product Natural products 0.000 description 2
- AMKYESDOVDKZKV-UHFFFAOYSA-N o-orsellinic acid Chemical compound CC1=CC(O)=CC(O)=C1C(O)=O AMKYESDOVDKZKV-UHFFFAOYSA-N 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 2
- 229920000747 poly(lactic acid) Polymers 0.000 description 2
- 229920000070 poly-3-hydroxybutyrate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 239000004626 polylactic acid Substances 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- PCMORTLOPMLEFB-ONEGZZNKSA-N sinapic acid Chemical compound COC1=CC(\C=C\C(O)=O)=CC(OC)=C1O PCMORTLOPMLEFB-ONEGZZNKSA-N 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
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- JMSVCTWVEWCHDZ-UHFFFAOYSA-N syringic acid Chemical compound COC1=CC(C(O)=O)=CC(OC)=C1O JMSVCTWVEWCHDZ-UHFFFAOYSA-N 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- QAIPRVGONGVQAS-DUXPYHPUSA-N trans-caffeic acid Chemical compound OC(=O)\C=C\C1=CC=C(O)C(O)=C1 QAIPRVGONGVQAS-DUXPYHPUSA-N 0.000 description 2
- HDTRYLNUVZCQOY-UHFFFAOYSA-N α-D-glucopyranosyl-α-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OC1C(O)C(O)C(O)C(CO)O1 HDTRYLNUVZCQOY-UHFFFAOYSA-N 0.000 description 1
- QBYIENPQHBMVBV-HFEGYEGKSA-N (2R)-2-hydroxy-2-phenylacetic acid Chemical compound O[C@@H](C(O)=O)c1ccccc1.O[C@@H](C(O)=O)c1ccccc1 QBYIENPQHBMVBV-HFEGYEGKSA-N 0.000 description 1
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- AAWZDTNXLSGCEK-LNVDRNJUSA-N (3r,5r)-1,3,4,5-tetrahydroxycyclohexane-1-carboxylic acid Chemical compound O[C@@H]1CC(O)(C(O)=O)C[C@@H](O)C1O AAWZDTNXLSGCEK-LNVDRNJUSA-N 0.000 description 1
- ACEAELOMUCBPJP-UHFFFAOYSA-N (E)-3,4,5-trihydroxycinnamic acid Natural products OC(=O)C=CC1=CC(O)=C(O)C(O)=C1 ACEAELOMUCBPJP-UHFFFAOYSA-N 0.000 description 1
- KSEBMYQBYZTDHS-HWKANZROSA-M (E)-Ferulic acid Natural products COC1=CC(\C=C\C([O-])=O)=CC=C1O KSEBMYQBYZTDHS-HWKANZROSA-M 0.000 description 1
- KJTLQQUUPVSXIM-ZCFIWIBFSA-N (R)-mevalonic acid Chemical compound OCC[C@](O)(C)CC(O)=O KJTLQQUUPVSXIM-ZCFIWIBFSA-N 0.000 description 1
- OTOIIPJYVQJATP-BYPYZUCNSA-N (R)-pantoic acid Chemical compound OCC(C)(C)[C@@H](O)C(O)=O OTOIIPJYVQJATP-BYPYZUCNSA-N 0.000 description 1
- AFENDNXGAFYKQO-VKHMYHEASA-N (S)-2-hydroxybutyric acid Chemical compound CC[C@H](O)C(O)=O AFENDNXGAFYKQO-VKHMYHEASA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- KPAPHODVWOVUJL-UHFFFAOYSA-N 1-benzofuran;1h-indene Chemical compound C1=CC=C2CC=CC2=C1.C1=CC=C2OC=CC2=C1 KPAPHODVWOVUJL-UHFFFAOYSA-N 0.000 description 1
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- GZCGUPFRVQAUEE-UHFFFAOYSA-N 2,3,4,5,6-pentahydroxyhexanal Chemical compound OCC(O)C(O)C(O)C(O)C=O GZCGUPFRVQAUEE-UHFFFAOYSA-N 0.000 description 1
- HGEFWFBFQKWVMY-DUXPYHPUSA-N 2,4-dihydroxy-trans cinnamic acid Chemical compound OC(=O)\C=C\C1=CC=C(O)C=C1O HGEFWFBFQKWVMY-DUXPYHPUSA-N 0.000 description 1
- UBDZFAGVPPMTIT-UHFFFAOYSA-N 2-aminoguanidine;hydron;chloride Chemical compound [Cl-].NC(N)=N[NH3+] UBDZFAGVPPMTIT-UHFFFAOYSA-N 0.000 description 1
- LVRFTAZAXQPQHI-UHFFFAOYSA-N 2-hydroxy-4-methylvaleric acid Chemical compound CC(C)CC(O)C(O)=O LVRFTAZAXQPQHI-UHFFFAOYSA-N 0.000 description 1
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
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- 239000004925 Acrylic resin Substances 0.000 description 1
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 235000018185 Betula X alpestris Nutrition 0.000 description 1
- 235000018212 Betula X uliginosa Nutrition 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 241000218645 Cedrus Species 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000019743 Choline chloride Nutrition 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- XFTRTWQBIOMVPK-YFKPBYRVSA-N Citramalic acid Natural products OC(=O)[C@](O)(C)CC(O)=O XFTRTWQBIOMVPK-YFKPBYRVSA-N 0.000 description 1
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- BJHIKXHVCXFQLS-PQLUHFTBSA-N keto-D-tagatose Chemical compound OC[C@@H](O)[C@H](O)[C@H](O)C(=O)CO BJHIKXHVCXFQLS-PQLUHFTBSA-N 0.000 description 1
- 150000002584 ketoses Chemical class 0.000 description 1
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- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
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- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
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- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
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- 239000002184 metal Substances 0.000 description 1
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- 229920000609 methyl cellulose Polymers 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
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- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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- 239000003208 petroleum Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000013502 plastic waste Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001652 poly(etherketoneketone) Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 239000004631 polybutylene succinate Substances 0.000 description 1
- 229920002961 polybutylene succinate Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
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- 229920000570 polyether Polymers 0.000 description 1
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- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
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- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
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- 229960004889 salicylic acid Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 230000001932 seasonal effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- UQDJGEHQDNVPGU-UHFFFAOYSA-N serine phosphoethanolamine Chemical compound [NH3+]CCOP([O-])(=O)OCC([NH3+])C([O-])=O UQDJGEHQDNVPGU-UHFFFAOYSA-N 0.000 description 1
- JXOHGGNKMLTUBP-HSUXUTPPSA-N shikimic acid Chemical compound O[C@@H]1CC(C(O)=O)=C[C@@H](O)[C@H]1O JXOHGGNKMLTUBP-HSUXUTPPSA-N 0.000 description 1
- JXOHGGNKMLTUBP-JKUQZMGJSA-N shikimic acid Natural products O[C@@H]1CC(C(O)=O)=C[C@H](O)[C@@H]1O JXOHGGNKMLTUBP-JKUQZMGJSA-N 0.000 description 1
- PCMORTLOPMLEFB-UHFFFAOYSA-N sinapinic acid Natural products COC1=CC(C=CC(O)=O)=CC(OC)=C1O PCMORTLOPMLEFB-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- YIBXWXOYFGZLRU-UHFFFAOYSA-N syringic aldehyde Natural products CC12CCC(C3(CCC(=O)C(C)(C)C3CC=3)C)C=3C1(C)CCC2C1COC(C)(C)C(O)C(O)C1 YIBXWXOYFGZLRU-UHFFFAOYSA-N 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 229920006230 thermoplastic polyester resin Polymers 0.000 description 1
- ODBLHEXUDAPZAU-UHFFFAOYSA-N threo-D-isocitric acid Natural products OC(=O)C(O)C(C(O)=O)CC(O)=O ODBLHEXUDAPZAU-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- QURCVMIEKCOAJU-UHFFFAOYSA-N trans-isoferulic acid Natural products COC1=CC=C(C=CC(O)=O)C=C1O QURCVMIEKCOAJU-UHFFFAOYSA-N 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- WKOLLVMJNQIZCI-UHFFFAOYSA-N vanillic acid Chemical compound COC1=CC(C(O)=O)=CC=C1O WKOLLVMJNQIZCI-UHFFFAOYSA-N 0.000 description 1
- TUUBOHWZSQXCSW-UHFFFAOYSA-N vanillic acid Natural products COC1=CC(O)=CC(C(O)=O)=C1 TUUBOHWZSQXCSW-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010887 waste solvent Substances 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000002916 wood waste Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
-
- 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
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1545—Six-membered rings
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/16—Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention intrends to provide a composition that is cellulose-based but thermoplastic and can be manufactured withtout disposing a solvent or using environmentally hazardous substances such as halide-containing substances; and a method for producing the same. The thermoplastic composition contains cellulose and a eutectic mixture of monosaccharide and/or disaccharide and hydroxycarboxylic acid. The method for manufacturing a thermoplastic composition comprises: a first step of mixing hydroxycarboxylic acid and monosaccharide and/or disaccharide at a temperature of 150-240 °C; and a second step of mixing the mixture obtained in the first step and cellulose at a temperature of 150-240 °C. In addition, the method for manufacturing a thermoplastic composition comprises a step of mixing cellulose, hydroxycarboxylic acid and monosaccharide and/or disaccharide in an extruder at a temperature of 150-240 °C. The eutectic mixture is preferably a mixture of lactic acid and glucose. In addition, the cellulose content is preferably 0.05-60.0 mass%.
Description
DESCRIPTION
Title of the Invention: THERMOPLASTIC COMPOSITION
TECHNICAL FIELD
[0001]
The present invention relates to a cellulose-based thermoplastic composition, specifically, a thermoplastic composition containing cellulose and an eutectic mixture of a hydroxycarboxylic acid and a sugar.
BACKGROUND ART
Title of the Invention: THERMOPLASTIC COMPOSITION
TECHNICAL FIELD
[0001]
The present invention relates to a cellulose-based thermoplastic composition, specifically, a thermoplastic composition containing cellulose and an eutectic mixture of a hydroxycarboxylic acid and a sugar.
BACKGROUND ART
[0002]
In recent years, biomass-derived materials have been attracting attention against a backdrop of issues such as global environmental protection or oil depletion, etc. From an environmental standpoint, plastic waste has also been perceived as a problem, increasing importance of biodegradable thermoplastic materials. Cellulose is one of representative biomass-derived materials and conventionally has been heavily used. In particular, since plant-derived cellulose is also biodegradable, it is attracting attention again from an environmental standpoint. Recently, several studies have begun to examine new use of such cellulose as a resin-like material.
In recent years, biomass-derived materials have been attracting attention against a backdrop of issues such as global environmental protection or oil depletion, etc. From an environmental standpoint, plastic waste has also been perceived as a problem, increasing importance of biodegradable thermoplastic materials. Cellulose is one of representative biomass-derived materials and conventionally has been heavily used. In particular, since plant-derived cellulose is also biodegradable, it is attracting attention again from an environmental standpoint. Recently, several studies have begun to examine new use of such cellulose as a resin-like material.
[0003]
For example, Patent Document 1 discloses a method for producing a nanocellulose material in which a cellulosic fibrous material such as pulp is swollen and suspended in the presence of a deep eutectic solvent and water, treated with sodium hydroxide, etc., filtered and washed, and then homogenized at high pressure. The deep eutectic solvent is a solvent that is liquid at room temperature and that is obtained by mixing a hydrogen bond donor compound with a hydrogen bond acceptor compound in a certain ratio. A solvent with any physical property can be created by combining the donor compound and the acceptor compound, and various combinations have been reported (e.g., Non-Patent Document 1).
Since the deep eutectic solvent generally has excellent solubility, cellulose, etc. can be microdispersed therein.
Furthermore, a colloidal solution of a nanocellulose fiber can be made depending on a combination of raw materials. In Patent Document 1, a urea/choline chloride-based deep eutectic solvent is used.
For example, Patent Document 1 discloses a method for producing a nanocellulose material in which a cellulosic fibrous material such as pulp is swollen and suspended in the presence of a deep eutectic solvent and water, treated with sodium hydroxide, etc., filtered and washed, and then homogenized at high pressure. The deep eutectic solvent is a solvent that is liquid at room temperature and that is obtained by mixing a hydrogen bond donor compound with a hydrogen bond acceptor compound in a certain ratio. A solvent with any physical property can be created by combining the donor compound and the acceptor compound, and various combinations have been reported (e.g., Non-Patent Document 1).
Since the deep eutectic solvent generally has excellent solubility, cellulose, etc. can be microdispersed therein.
Furthermore, a colloidal solution of a nanocellulose fiber can be made depending on a combination of raw materials. In Patent Document 1, a urea/choline chloride-based deep eutectic solvent is used.
[0004]
Non-patent Document 2 discloses a technique for producing a wood-based fiber by dispersing bleached birch pulp in a reactive or non-reactive deep eutectic solvent such as urea/ammonium thiocyanate, urea/sulfamic acid, or glycerol/aminoguanidine hydrochloride deep eutectic solvent, followed by filtering and washing. Non-patent Document 3 discloses a technique for producing a film with various mechanical properties by dispersing sawdust in an imidazole/triethylammonium chloride deep eutectic solvent, treating the resulting dispersion with anhydrous succinic acid, and then filtering and drying the resulting suspension.
Such technology makes it possible to produce a resin-like material from a cellulosic material, such as discarded paper and thus can contribute to waste reduction.
Citation List Patent Document
Non-patent Document 2 discloses a technique for producing a wood-based fiber by dispersing bleached birch pulp in a reactive or non-reactive deep eutectic solvent such as urea/ammonium thiocyanate, urea/sulfamic acid, or glycerol/aminoguanidine hydrochloride deep eutectic solvent, followed by filtering and washing. Non-patent Document 3 discloses a technique for producing a film with various mechanical properties by dispersing sawdust in an imidazole/triethylammonium chloride deep eutectic solvent, treating the resulting dispersion with anhydrous succinic acid, and then filtering and drying the resulting suspension.
Such technology makes it possible to produce a resin-like material from a cellulosic material, such as discarded paper and thus can contribute to waste reduction.
Citation List Patent Document
[0005]
Patent Document 1: Japanese Unexamined Patent Application (Translation of PCT Application), Publication No. 2020-518715 Non-Patent Document
Patent Document 1: Japanese Unexamined Patent Application (Translation of PCT Application), Publication No. 2020-518715 Non-Patent Document
[0006]
Non-Patent Document 1: L. Wils, et al., Molecules, 26, 6556-6575 (2021) Non-Patent Document 2: P. Li, ACTA UNIVERSITATIS OULUENSIS, C
Technica 739(2020) Non-Patent Document 3: J. Antti Sirvio, et al., Cellulose, 28, 6881-6898 (2021) DISCLOSURE OF THE INVENTION
Problems to be Solved by the Invention
Non-Patent Document 1: L. Wils, et al., Molecules, 26, 6556-6575 (2021) Non-Patent Document 2: P. Li, ACTA UNIVERSITATIS OULUENSIS, C
Technica 739(2020) Non-Patent Document 3: J. Antti Sirvio, et al., Cellulose, 28, 6881-6898 (2021) DISCLOSURE OF THE INVENTION
Problems to be Solved by the Invention
[0007]
As described above, a resin-like material can be obtained from cellulose using a deep eutectic solvent, but the thus-obtained conventional materials are not thermoplastic and their applications tend to be limited. Also, in the techniques described in Patent Document 1 and Non-Patent Documents 2 and 3, the thus-prepared cellulose materials are all formed as films on filters by filtration. This not only requires time-consuming preparation, but also causes a problem of disposal of the deep eutectic solvent. These technologies also use a sulfur-containing strong acid compound such as sulfamic acid or a chloride as the deep eutectic solvent, and there is room for improvement from an environmental standpoint.
As described above, a resin-like material can be obtained from cellulose using a deep eutectic solvent, but the thus-obtained conventional materials are not thermoplastic and their applications tend to be limited. Also, in the techniques described in Patent Document 1 and Non-Patent Documents 2 and 3, the thus-prepared cellulose materials are all formed as films on filters by filtration. This not only requires time-consuming preparation, but also causes a problem of disposal of the deep eutectic solvent. These technologies also use a sulfur-containing strong acid compound such as sulfamic acid or a chloride as the deep eutectic solvent, and there is room for improvement from an environmental standpoint.
[0008]
In order to solve the above problems, an object of the present invention is to provide a material that is thermoplastic while being a cellulose-based composition, and that does not require disposal of a solvent or use of an environmentally hazardous substance such as a halide-containing substance in a manufacturing process; and a method for manufacturing the material.
Means for Solving the Problems
In order to solve the above problems, an object of the present invention is to provide a material that is thermoplastic while being a cellulose-based composition, and that does not require disposal of a solvent or use of an environmentally hazardous substance such as a halide-containing substance in a manufacturing process; and a method for manufacturing the material.
Means for Solving the Problems
[0009]
The present inventors conducted extensive studies to achieve the above object and have found that a composition containing cellulose and an eutectic mixture of a monosaccharide and/or a disaccharide and a hydroxycarboxylic acid has a resin-like property, exhibits thermoplasticity, and can be produced without disposal of a solvent or use of an environmentally hazardous substance. Thus, the present invention has been completed.
The present inventors conducted extensive studies to achieve the above object and have found that a composition containing cellulose and an eutectic mixture of a monosaccharide and/or a disaccharide and a hydroxycarboxylic acid has a resin-like property, exhibits thermoplasticity, and can be produced without disposal of a solvent or use of an environmentally hazardous substance. Thus, the present invention has been completed.
[0010]
That is, the present invention provides the following aspects (1) to (11).
(1) A thermoplastic composition including: cellulose; and an eutectic mixture of a monosaccharide and/or a disaccharide and a hydroxycarboxylic acid.
(2) The thermoplastic composition according to (1), in which the eutectic mixture is a mixture of lactic acid and glucose.
(3) The thermoplastic composition according to (1) or (2), further comprising hemicellulose and/or lignin, wherein the cellulose is plant-derived cellulose.
(4) The thermoplastic composition according to any one of (1) to (3), in which the composition includes 0.05 to 60.0% by mass of the cellulose.
(5) The thermoplastic composition according to any one of (1) to (4), in which the composition has a mass ratio of the hydroxycarboxylic acid : the monosaccharide and/or the disaccharide in a range of 1:2 to 6:1.
(6) The thermoplastic composition according to any one of (1) to (5), further including one or more substances selected from the group consisting of an inorganic filler, a natural thermoplastic resin, a synthetic thermoplastic resin, and a biodegradable resin.
(7) A method for producing a thermoplastic composition, the method including:
mixing a hydroxycarboxylic acid and a monosaccharide and/or a disaccharide at a temperature of 150 to 240 C (first step); and mixing the mixture obtained in the first step and cellulose at a temperature of 150 to 240 C (second step).
(8) The method for producing a thermoplastic composition according to (7), further including kneading and molding the mixture obtained in the second step in an extruder (third step).
(9) A method for producing a thermoplastic composition, the method including mixing cellulose, a hydroxycarboxylic acid, and a monosaccharide and/or a disaccharide in an extruder at a temperature of 150 to 240 C.
(10) A thermoplastic pellet formed of the thermoplastic composition according to any one of (1) to (6).
That is, the present invention provides the following aspects (1) to (11).
(1) A thermoplastic composition including: cellulose; and an eutectic mixture of a monosaccharide and/or a disaccharide and a hydroxycarboxylic acid.
(2) The thermoplastic composition according to (1), in which the eutectic mixture is a mixture of lactic acid and glucose.
(3) The thermoplastic composition according to (1) or (2), further comprising hemicellulose and/or lignin, wherein the cellulose is plant-derived cellulose.
(4) The thermoplastic composition according to any one of (1) to (3), in which the composition includes 0.05 to 60.0% by mass of the cellulose.
(5) The thermoplastic composition according to any one of (1) to (4), in which the composition has a mass ratio of the hydroxycarboxylic acid : the monosaccharide and/or the disaccharide in a range of 1:2 to 6:1.
(6) The thermoplastic composition according to any one of (1) to (5), further including one or more substances selected from the group consisting of an inorganic filler, a natural thermoplastic resin, a synthetic thermoplastic resin, and a biodegradable resin.
(7) A method for producing a thermoplastic composition, the method including:
mixing a hydroxycarboxylic acid and a monosaccharide and/or a disaccharide at a temperature of 150 to 240 C (first step); and mixing the mixture obtained in the first step and cellulose at a temperature of 150 to 240 C (second step).
(8) The method for producing a thermoplastic composition according to (7), further including kneading and molding the mixture obtained in the second step in an extruder (third step).
(9) A method for producing a thermoplastic composition, the method including mixing cellulose, a hydroxycarboxylic acid, and a monosaccharide and/or a disaccharide in an extruder at a temperature of 150 to 240 C.
(10) A thermoplastic pellet formed of the thermoplastic composition according to any one of (1) to (6).
(11) A molded product formed of the thermoplastic composition according to any one of (1) to (6).
Effects of the Invention [0011]
A thermoplastic composition of the present invention is thermoplastic while being a cellulose-based composition and thus has a good mechanical property derived from the cellulose and excellent moldability. Therefore, the thermoplastic composition is suitable as a material for various molded products and is useful as an industrial material such as a thermoplastic pellet. In addition, the thermoplastic composition has an advantage of not requiring disposal of a solvent or use of an environmentally hazardous substance such as a halide-containing substance in a manufacturing process.
Furthermore, the thermoplastic composition of the present invention and a method for producing the thermoplastic composition can be utilized for waste disposal since cellulose containing an impurity, for example, wood waste such as sawdust or waste paper can also be used as a raw material.
Therefore, the composition and the method are useful from the perspective of global environmental conservation PREFERRED MODE FOR CARRYING OUT THE INVENTION
Effects of the Invention [0011]
A thermoplastic composition of the present invention is thermoplastic while being a cellulose-based composition and thus has a good mechanical property derived from the cellulose and excellent moldability. Therefore, the thermoplastic composition is suitable as a material for various molded products and is useful as an industrial material such as a thermoplastic pellet. In addition, the thermoplastic composition has an advantage of not requiring disposal of a solvent or use of an environmentally hazardous substance such as a halide-containing substance in a manufacturing process.
Furthermore, the thermoplastic composition of the present invention and a method for producing the thermoplastic composition can be utilized for waste disposal since cellulose containing an impurity, for example, wood waste such as sawdust or waste paper can also be used as a raw material.
Therefore, the composition and the method are useful from the perspective of global environmental conservation PREFERRED MODE FOR CARRYING OUT THE INVENTION
[0012]
The present invention will be described in detail with reference to embodiments.
The present invention will be described in detail with reference to embodiments.
[0013]
[Thermoplastic composition]
A first aspect of the present invention is a thermoplastic composition including cellulose; and an eutectic mixture of a monosaccharide and/or a disaccharide, together with a hydroxycarboxylic acid. First, these components will be described in detail. Note that, the phrase "monosaccharide and/or disaccharide", as used herein, may be collectively referred to as "sugar".
[Thermoplastic composition]
A first aspect of the present invention is a thermoplastic composition including cellulose; and an eutectic mixture of a monosaccharide and/or a disaccharide, together with a hydroxycarboxylic acid. First, these components will be described in detail. Note that, the phrase "monosaccharide and/or disaccharide", as used herein, may be collectively referred to as "sugar".
[0014]
<Cellulose>
Cellulose constituting a thermoplastic composition of the present invention is not particularly limited, and various known cellulose may be used. Examples thereof include, but are not limited to, natural cellulose derived from, for example, a plant; modified cellulose including cellulose acetate, carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, or hydroxypropylmethyl cellulose; or regenerated cellulose.
Furthermore, the cellulose may be included in not only wood pulp or non-wood pulp, but also those less refined, or even waste such as sawdust, waste wood, or waste paper.
<Cellulose>
Cellulose constituting a thermoplastic composition of the present invention is not particularly limited, and various known cellulose may be used. Examples thereof include, but are not limited to, natural cellulose derived from, for example, a plant; modified cellulose including cellulose acetate, carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, or hydroxypropylmethyl cellulose; or regenerated cellulose.
Furthermore, the cellulose may be included in not only wood pulp or non-wood pulp, but also those less refined, or even waste such as sawdust, waste wood, or waste paper.
[0015]
The cellulose is a polysaccharide, a type of carbohydrate, and a main component of plant fiber. The cellulose is usually present in a plant as lignocellulose bound to or mixed with hemicellulose or lignin. In general, a plant-derived cellulose fiber has a configuration in which bundles of 30 to 40 molecules of cellulose form ultrafine, highly crystalline microfibrils with a diameter of about 3 nm and a length of several hundred nanometers to several tens of micrometers and the microfibrils are further bundled together via soft non-crystalline portions.
The cellulose is a polysaccharide, a type of carbohydrate, and a main component of plant fiber. The cellulose is usually present in a plant as lignocellulose bound to or mixed with hemicellulose or lignin. In general, a plant-derived cellulose fiber has a configuration in which bundles of 30 to 40 molecules of cellulose form ultrafine, highly crystalline microfibrils with a diameter of about 3 nm and a length of several hundred nanometers to several tens of micrometers and the microfibrils are further bundled together via soft non-crystalline portions.
[0016]
The cellulose constituting the thermoplastic composition of the present invention is preferably plant-derived cellulose. The composition of the present invention exhibits a resin-like property and thermoplasticity even if the cellulose is, for example, the above-described lignocellulose.
Therefore, pulp, etc. can be used without refining, and waste such as waste paper can be used as a raw material. In one preferred embodiment of the present invention, the cellulose is plant-derived and further includes hemicellulose and/or lignin.
The cellulose constituting the thermoplastic composition of the present invention is preferably plant-derived cellulose. The composition of the present invention exhibits a resin-like property and thermoplasticity even if the cellulose is, for example, the above-described lignocellulose.
Therefore, pulp, etc. can be used without refining, and waste such as waste paper can be used as a raw material. In one preferred embodiment of the present invention, the cellulose is plant-derived and further includes hemicellulose and/or lignin.
[0017]
The plant-derived cellulose is not particularly limited.
Examples include, but are not limited to, those derived from wood, bamboo, hemp, jute, kenaf, and agricultural waste including wheat or rice straw, corn, a stem of cotton, or sugar cane. Cellulose derived from sawdust, wood chips, waste wood, waste paper, waste cloth, re-formed bedding cotton, recycled pulp, etc. may also be used. Depending on an application of the thermoplastic composition, wood-derived cellulose, especially wood pulp, is generally preferred from the viewpoints of appearance, a mechanical property, and quality stability of the composition, and easy availability of raw materials. The wood pulp is advantageous in terms of a small seasonal fluctuation in supply, and cost.
The plant-derived cellulose is not particularly limited.
Examples include, but are not limited to, those derived from wood, bamboo, hemp, jute, kenaf, and agricultural waste including wheat or rice straw, corn, a stem of cotton, or sugar cane. Cellulose derived from sawdust, wood chips, waste wood, waste paper, waste cloth, re-formed bedding cotton, recycled pulp, etc. may also be used. Depending on an application of the thermoplastic composition, wood-derived cellulose, especially wood pulp, is generally preferred from the viewpoints of appearance, a mechanical property, and quality stability of the composition, and easy availability of raw materials. The wood pulp is advantageous in terms of a small seasonal fluctuation in supply, and cost.
[0018]
As desired, hemicellulose or lignin may be removed from the plant-derived cellulose. For example, kraft pulp, highly pure cellulose that has been chemically treated with caustic soda to remove hemicellulose and lignin, may be used.
As desired, hemicellulose or lignin may be removed from the plant-derived cellulose. For example, kraft pulp, highly pure cellulose that has been chemically treated with caustic soda to remove hemicellulose and lignin, may be used.
[0019]
In the thermoplastic composition of the present invention, a portion of hydroxy groups in a cellulose molecule may be acetylated or carboxylated or a hydrogen atom in the hydroxy group may be substituted with a metal ion such as sodium or potassium, or an ammonium ion.
In the thermoplastic composition of the present invention, a portion of hydroxy groups in a cellulose molecule may be acetylated or carboxylated or a hydrogen atom in the hydroxy group may be substituted with a metal ion such as sodium or potassium, or an ammonium ion.
[0020]
A content of the cellulose is preferably about 0.05 to 60.0% by mass, more preferably about 0.1 to 50.0% by mass, and further preferably about 0.2 to 40.0% by mass relative to 100%
by mass of a total thermoplastic composition of the present invention. The thermoplastic composition of the present invention exhibits texture or excellent mechanical strength resulting from cellulose even when the content of the cellulose is as small as about 0.05% by mass. Furthermore, satisfactory thermoplasticity is ensured when the content of the cellulose is about 60.0% by mass or less. Note that, when the thermoplastic composition of the present invention contains hemicellulose and/or lignin, these components are materials constituting lignocellulose, so amounts thereof shall be included in the content of the cellulose.
A content of the cellulose is preferably about 0.05 to 60.0% by mass, more preferably about 0.1 to 50.0% by mass, and further preferably about 0.2 to 40.0% by mass relative to 100%
by mass of a total thermoplastic composition of the present invention. The thermoplastic composition of the present invention exhibits texture or excellent mechanical strength resulting from cellulose even when the content of the cellulose is as small as about 0.05% by mass. Furthermore, satisfactory thermoplasticity is ensured when the content of the cellulose is about 60.0% by mass or less. Note that, when the thermoplastic composition of the present invention contains hemicellulose and/or lignin, these components are materials constituting lignocellulose, so amounts thereof shall be included in the content of the cellulose.
[0021]
Herein, the content of the cellulose is preferably about 0.05 to 20.0% by mass, particularly 0.1 to 10.0% by mass, further 0.2 to 5.0% by mass, and especially 0.4 to 2.0% by mass relative to 100% by mass of a total thermoplastic composition of the present invention in order to improve molding processability of the thermoplastic composition or when the thermoplastic composition is produced in a small amount in a low-shear mixer. On the other hand, the content is preferably about 5.0 to 60.0% by mass, for example, 10.0 to 50.0% by mass, particularly 15.0 to 40.0% by mass, further 18.0 to 30.0% by mass, and especially 20.0 to 25.0% by mass in order to improve heat resistance or a mechanical property of the thermoplastic composition or from the viewpoint of utilizing more cellulose waste.
Herein, the content of the cellulose is preferably about 0.05 to 20.0% by mass, particularly 0.1 to 10.0% by mass, further 0.2 to 5.0% by mass, and especially 0.4 to 2.0% by mass relative to 100% by mass of a total thermoplastic composition of the present invention in order to improve molding processability of the thermoplastic composition or when the thermoplastic composition is produced in a small amount in a low-shear mixer. On the other hand, the content is preferably about 5.0 to 60.0% by mass, for example, 10.0 to 50.0% by mass, particularly 15.0 to 40.0% by mass, further 18.0 to 30.0% by mass, and especially 20.0 to 25.0% by mass in order to improve heat resistance or a mechanical property of the thermoplastic composition or from the viewpoint of utilizing more cellulose waste.
[0022]
<Eutectic mixture>
The thermoplastic composition of the present invention contains, in addition to the above-described cellulose, an eutectic mixture of a hydroxycarboxylic acid and a sugar. This eutectic mixture can act like a deep eutectic solvent, loosening cellulose to near a level of a nanofiber and even dissolving or microdispersing it to form a nearly homogeneous mixture. This eutectic mixture can also form a composition that is solid at room temperature and is thermoplastic when mixed with cellulose, etc. This is an unexpected phenomenon that does not occur in the above-described deep eutectic solvent such as imidazole/ammonium chloride. The reason why the composition of the invention results in such a thermoplastic material is unknown, but it is believed that a hydroxycarboxylic acid and a sugar may interact with cellulose at the same time that they form a eutectic crystal. However, the present invention is not limited to a certain theory.
<Eutectic mixture>
The thermoplastic composition of the present invention contains, in addition to the above-described cellulose, an eutectic mixture of a hydroxycarboxylic acid and a sugar. This eutectic mixture can act like a deep eutectic solvent, loosening cellulose to near a level of a nanofiber and even dissolving or microdispersing it to form a nearly homogeneous mixture. This eutectic mixture can also form a composition that is solid at room temperature and is thermoplastic when mixed with cellulose, etc. This is an unexpected phenomenon that does not occur in the above-described deep eutectic solvent such as imidazole/ammonium chloride. The reason why the composition of the invention results in such a thermoplastic material is unknown, but it is believed that a hydroxycarboxylic acid and a sugar may interact with cellulose at the same time that they form a eutectic crystal. However, the present invention is not limited to a certain theory.
[0023]
In the present invention, the eutectic mixture forms a thermoplastic composition together with cellulose as described above, and does not need to be separated and removed after a cellulose material is prepared (for example, as in the preparation method described in Non-Patent document 2).
Therefore, labor and cost for separation, waste solvent treatment, etc. can be reduced. The eutectic mixture in the thermoplastic composition of the present invention is constituted of halogen-free natural products, that is, a hydroxycarboxylic acid and a monosaccharide and/or a disaccharide. This also is a reason why the eutectic mixture is an excellent material that does not burden the global environment.
In the present invention, the eutectic mixture forms a thermoplastic composition together with cellulose as described above, and does not need to be separated and removed after a cellulose material is prepared (for example, as in the preparation method described in Non-Patent document 2).
Therefore, labor and cost for separation, waste solvent treatment, etc. can be reduced. The eutectic mixture in the thermoplastic composition of the present invention is constituted of halogen-free natural products, that is, a hydroxycarboxylic acid and a monosaccharide and/or a disaccharide. This also is a reason why the eutectic mixture is an excellent material that does not burden the global environment.
[0024]
(Hydroxycarboxylic acid) A hydroxycarboxylic acid in the present invention may be any compound as long as it forms an eutectic mixture with a monosaccharide and/or a disaccharide, and a type thereof is not particularly limited. Examples thereof include, but are not limited to, an aliphatic hydroxycarboxylic acid such as glycolic acid, lactic acid, tartronic acid, glyceric acid, hydroxybutyric acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, gamma-hydroxybutyric acid, malic acid, tartaric acid, citramalic acid, citric acid, isocitric acid, leucinic acid, mevalonic acid, pantoic acid, ricinoleic acid, ricinelaidic acid, cerebronic acid, quinic acid, or shikimic acid; an aromatic hydroxycarboxylic acid such as salicylic acid, creosotic acid, vanillic acid, syringic acid, pyrocatechuic acid, resorcylic acid, protocatechuic acid, gentisic acid, orsellinic acid, gallic acid, mandelic acid, benzylic acid, atrolactic acid, cinnamic acid, melilotic acid, phloretic acid, cumaric acid, umbellic acid, caffeic acid, ferulic acid, or sinapic acid, etc. Depending on a combination of a monosaccharide and/or a disaccharide, a plurality of hydroxycarboxylic acids may also be used in combination.
(Hydroxycarboxylic acid) A hydroxycarboxylic acid in the present invention may be any compound as long as it forms an eutectic mixture with a monosaccharide and/or a disaccharide, and a type thereof is not particularly limited. Examples thereof include, but are not limited to, an aliphatic hydroxycarboxylic acid such as glycolic acid, lactic acid, tartronic acid, glyceric acid, hydroxybutyric acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, gamma-hydroxybutyric acid, malic acid, tartaric acid, citramalic acid, citric acid, isocitric acid, leucinic acid, mevalonic acid, pantoic acid, ricinoleic acid, ricinelaidic acid, cerebronic acid, quinic acid, or shikimic acid; an aromatic hydroxycarboxylic acid such as salicylic acid, creosotic acid, vanillic acid, syringic acid, pyrocatechuic acid, resorcylic acid, protocatechuic acid, gentisic acid, orsellinic acid, gallic acid, mandelic acid, benzylic acid, atrolactic acid, cinnamic acid, melilotic acid, phloretic acid, cumaric acid, umbellic acid, caffeic acid, ferulic acid, or sinapic acid, etc. Depending on a combination of a monosaccharide and/or a disaccharide, a plurality of hydroxycarboxylic acids may also be used in combination.
[0025]
The hydroxycarboxylic acid is preferably a compound having one hydroxy group and one carboxy group in a molecule or an aliphatic hydroxycarboxylic acid. More preferably, a hydroxycarboxylic acid having 2 to 4 carbon atoms is used.
Such a hydroxycarboxylic acid easily forms a deep eutectic solvent with a monosaccharide or a disaccharide and a composition containing such a hydroxycarboxylic acid and cellulose exhibits good thermoplasticity. Lactic acid is particularly preferred. Note that, lactic acid may be in any form such as a D-form, an L-form, or a DL-form.
The hydroxycarboxylic acid is preferably a compound having one hydroxy group and one carboxy group in a molecule or an aliphatic hydroxycarboxylic acid. More preferably, a hydroxycarboxylic acid having 2 to 4 carbon atoms is used.
Such a hydroxycarboxylic acid easily forms a deep eutectic solvent with a monosaccharide or a disaccharide and a composition containing such a hydroxycarboxylic acid and cellulose exhibits good thermoplasticity. Lactic acid is particularly preferred. Note that, lactic acid may be in any form such as a D-form, an L-form, or a DL-form.
[0026]
(Monosaccharide) A monosaccharide in the present invention may be any compound as long as it forms an eutectic mixture with a hydroxycarboxylic acid, and a type thereof is not particularly limited. Examples thereof include, but are not limited to, aldose such as glyceraldehyde, erythrose, threose, ribose, lixose, xylose, arabinose, allose, talose, gulose, glucose, altrose, mannose, galactose, or idose; ketose such as dihydroxyacetone, erythrulose, xylulose, ribulose, psicose, fructose, sorbose, or tagatose. Depending on a combination with a hydroxycarboxylic acid, a plurality of monosaccharides may also be used in combination.
(Monosaccharide) A monosaccharide in the present invention may be any compound as long as it forms an eutectic mixture with a hydroxycarboxylic acid, and a type thereof is not particularly limited. Examples thereof include, but are not limited to, aldose such as glyceraldehyde, erythrose, threose, ribose, lixose, xylose, arabinose, allose, talose, gulose, glucose, altrose, mannose, galactose, or idose; ketose such as dihydroxyacetone, erythrulose, xylulose, ribulose, psicose, fructose, sorbose, or tagatose. Depending on a combination with a hydroxycarboxylic acid, a plurality of monosaccharides may also be used in combination.
[0027]
(Disaccharide) A disaccharide in the present invention is not particularly limited. Examples thereof include, but are not limited to, sucrose, lactulose, lactose, maltose, trehalose, or cellobiose. It is also possible to use two or more disaccharides in combination or a monosaccharide and a disaccharide in combination.
(Disaccharide) A disaccharide in the present invention is not particularly limited. Examples thereof include, but are not limited to, sucrose, lactulose, lactose, maltose, trehalose, or cellobiose. It is also possible to use two or more disaccharides in combination or a monosaccharide and a disaccharide in combination.
[0028]
Among the above-described sugars, a monosaccharide is preferred. The disaccharide is more preferably aldose and further preferably aldohexose. Such a monosaccharide easily forms an eutectic mixture with a hydroxycarboxylic acid and a composition containing such a monosaccharide and cellulose exhibits good thermoplasticity. Among aldohexoses, glucose, allose, mannose, or galactose, especially glucose is preferred. In other words, an eutectic mixture constituting the thermoplastic composition of the present invention is especially preferably a mixture of lactic acid and glucose. A
monosaccharide such as glucose has several optical isomers, but any structure can be used in the present invention.
Among the above-described sugars, a monosaccharide is preferred. The disaccharide is more preferably aldose and further preferably aldohexose. Such a monosaccharide easily forms an eutectic mixture with a hydroxycarboxylic acid and a composition containing such a monosaccharide and cellulose exhibits good thermoplasticity. Among aldohexoses, glucose, allose, mannose, or galactose, especially glucose is preferred. In other words, an eutectic mixture constituting the thermoplastic composition of the present invention is especially preferably a mixture of lactic acid and glucose. A
monosaccharide such as glucose has several optical isomers, but any structure can be used in the present invention.
[0029]
<Composition of thermoplastic composition>
For the thermoplastic composition of the present invention, contents of a hydroxycarboxylic acid a sugar are not particularly limited. For example, a mass ratio of the hydroxycarboxylic acid to the sugar may be selected in a range of 1:4 to 99:1. However, in the present invention, the mass ratio of the hydroxycarboxylic acid to the monosaccharide and/or the disaccharide is preferably in a range of 1:2 to 6:1, more preferably in a range of 1:1 to 4:1, and further preferably in a range of 2:1 to 3:1. When the mass ratio is in the above-described range, an eutectic mixture is easily formed and a composition containing them and cellulose exhibits good thermoplasticity. In an especially preferred embodiment of the present invention, lactic acid and glucose are contained in a mass ratio of 1:1 to 4:1, in particular, a mass ratio of 2:1 to 3:1.
<Composition of thermoplastic composition>
For the thermoplastic composition of the present invention, contents of a hydroxycarboxylic acid a sugar are not particularly limited. For example, a mass ratio of the hydroxycarboxylic acid to the sugar may be selected in a range of 1:4 to 99:1. However, in the present invention, the mass ratio of the hydroxycarboxylic acid to the monosaccharide and/or the disaccharide is preferably in a range of 1:2 to 6:1, more preferably in a range of 1:1 to 4:1, and further preferably in a range of 2:1 to 3:1. When the mass ratio is in the above-described range, an eutectic mixture is easily formed and a composition containing them and cellulose exhibits good thermoplasticity. In an especially preferred embodiment of the present invention, lactic acid and glucose are contained in a mass ratio of 1:1 to 4:1, in particular, a mass ratio of 2:1 to 3:1.
[0030]
In one preferred embodiment of the thermoplastic composition of the present invention, cellulose is contained in an amount of 0.05 to 20.0% by mass, a hydroxycarboxylic acid is contained in an amount of 20.0 to 99.0% by mass, and a sugar is contained in an amount of 1.0 to 80.0% by mass; more preferably, cellulose is contained in an amount of 0.1 to 5.0%
by mass, a hydroxycarboxylic acid is contained in an amount of 50.0 to 90.0% by mass, and a sugar is contained in an amount of 5.0 to 50.0% by mass; and further preferably cellulose is contained in an amount of 0.2 to 2.0% by mass, a hydroxycarboxylic acid is contained in an amount of 60 to 80%
by mass, and a sugar is contained in an amount of 20 to 40% by mass relative to 100% by mass of a total of cellulose, a hydroxycarboxylic acid, and a sugar. Such a composition can make the thermoplastic composition of the present invention be a thermoplastic composition that has, in particular, excellent texture and molding processability, for example, that melts or solidifies at a temperature of 50 to 230 C, typically 60 to 200 C, and especially about 70 to 150 C.
In one preferred embodiment of the thermoplastic composition of the present invention, cellulose is contained in an amount of 0.05 to 20.0% by mass, a hydroxycarboxylic acid is contained in an amount of 20.0 to 99.0% by mass, and a sugar is contained in an amount of 1.0 to 80.0% by mass; more preferably, cellulose is contained in an amount of 0.1 to 5.0%
by mass, a hydroxycarboxylic acid is contained in an amount of 50.0 to 90.0% by mass, and a sugar is contained in an amount of 5.0 to 50.0% by mass; and further preferably cellulose is contained in an amount of 0.2 to 2.0% by mass, a hydroxycarboxylic acid is contained in an amount of 60 to 80%
by mass, and a sugar is contained in an amount of 20 to 40% by mass relative to 100% by mass of a total of cellulose, a hydroxycarboxylic acid, and a sugar. Such a composition can make the thermoplastic composition of the present invention be a thermoplastic composition that has, in particular, excellent texture and molding processability, for example, that melts or solidifies at a temperature of 50 to 230 C, typically 60 to 200 C, and especially about 70 to 150 C.
[0031]
In another preferred embodiment of the thermoplastic composition of the present invention, cellulose is contained in an amount of 5 to 60% by mass, a hydroxycarboxylic acid is contained in an amount of 20 to 80% by mass, and a sugar is contained in an amount of 5 to 50% by mass; more preferably, cellulose is contained in an amount of 10 to 50% by mass, a hydroxycarboxylic acid is contained in an amount of 30 to 60%
by mass, and a sugar is contained in an amount of 10 to 40% by mass; and further preferably cellulose is contained in an amount of 20 to 45% by mass, a hydroxycarboxylic acid is contained in an amount of 35 to 50% by mass, and a sugar is contained in an amount of 15 to 30% by mass relative to 100%
by mass of a total of cellulose, a hydroxycarboxylic acid, and a sugar. Such a composition can make the thermoplastic composition of the present invention be a thermoplastic composition that has, in particular, excellent texture, heat resistance, or mechanical property, for example, that melts or solidifies at a temperature of 150 to 240 C, typically 160 to 230 C, particularly about 170 to 220 C, and especially 180 to 210 C.
In another preferred embodiment of the thermoplastic composition of the present invention, cellulose is contained in an amount of 5 to 60% by mass, a hydroxycarboxylic acid is contained in an amount of 20 to 80% by mass, and a sugar is contained in an amount of 5 to 50% by mass; more preferably, cellulose is contained in an amount of 10 to 50% by mass, a hydroxycarboxylic acid is contained in an amount of 30 to 60%
by mass, and a sugar is contained in an amount of 10 to 40% by mass; and further preferably cellulose is contained in an amount of 20 to 45% by mass, a hydroxycarboxylic acid is contained in an amount of 35 to 50% by mass, and a sugar is contained in an amount of 15 to 30% by mass relative to 100%
by mass of a total of cellulose, a hydroxycarboxylic acid, and a sugar. Such a composition can make the thermoplastic composition of the present invention be a thermoplastic composition that has, in particular, excellent texture, heat resistance, or mechanical property, for example, that melts or solidifies at a temperature of 150 to 240 C, typically 160 to 230 C, particularly about 170 to 220 C, and especially 180 to 210 C.
[0032]
<Additive>
The thermoplastic composition of the present invention may further contain one or more substances selected from the group consisting of an inorganic filler, a natural thermoplastic resin, a synthetic thermoplastic resin, and a biodegradable resin, in addition to the cellulose, the hydroxycarboxylic acid, and the sugar as described above. When an inorganic filler is contained, a physical property of the thermoplastic composition, for example, a mechanical property such as hardness or strength, or heat resistance may be controlled.
Furthermore, when any of various resins is contained, a melting or solidification temperature, or a physical property of the thermoplastic composition can be also controlled.
<Additive>
The thermoplastic composition of the present invention may further contain one or more substances selected from the group consisting of an inorganic filler, a natural thermoplastic resin, a synthetic thermoplastic resin, and a biodegradable resin, in addition to the cellulose, the hydroxycarboxylic acid, and the sugar as described above. When an inorganic filler is contained, a physical property of the thermoplastic composition, for example, a mechanical property such as hardness or strength, or heat resistance may be controlled.
Furthermore, when any of various resins is contained, a melting or solidification temperature, or a physical property of the thermoplastic composition can be also controlled.
[0033]
(Inorganic filler) An inorganic filler to be incorporated in the thermoplastic composition of the present invention is not particularly limited. Examples thereof include, but are not limited to, a carbonate, a sulfate, a silicate, a phosphate, a borate, an oxide of calcium, magnesium, aluminum, titanium, iron, zinc, barium, etc., or a hydrate thereof in a powder form, specifically calcium carbonate, magnesium carbonate, zinc oxide, titanium oxide, silica, alumina, clay, talc, kaolin, aluminum hydroxide, magnesium hydroxide, aluminum silicate, magnesium silicate, calcium silicate, aluminum sulfate, magnesium sulfate, calcium sulfate, magnesium phosphate, barium sulfate, silica sand, carbon black, zeolite, molybdenum, diatomaceous earth, sericite, shirasu, calcium sulfite, sodium sulfate, potassium titanate, bentonite, wollastonite, dolomite, graphite, etc. The inorganic filler may be synthetic or derived from natural mineral and may be contained alone or as a combination of two or more thereof.
Among them, calcium carbonate, clay, talc, kaolin, etc. are preferred from the viewpoints of safety and cost. Calcium carbonate is especially preferred since it is commercially available in a variety of particle sizes and shapes and one appropriate for a physical property targeted for the thermoplastic composition may be selected. Use of eggshell-derived calcium carbonate from a food factory can contribute to waste reduction.
(Inorganic filler) An inorganic filler to be incorporated in the thermoplastic composition of the present invention is not particularly limited. Examples thereof include, but are not limited to, a carbonate, a sulfate, a silicate, a phosphate, a borate, an oxide of calcium, magnesium, aluminum, titanium, iron, zinc, barium, etc., or a hydrate thereof in a powder form, specifically calcium carbonate, magnesium carbonate, zinc oxide, titanium oxide, silica, alumina, clay, talc, kaolin, aluminum hydroxide, magnesium hydroxide, aluminum silicate, magnesium silicate, calcium silicate, aluminum sulfate, magnesium sulfate, calcium sulfate, magnesium phosphate, barium sulfate, silica sand, carbon black, zeolite, molybdenum, diatomaceous earth, sericite, shirasu, calcium sulfite, sodium sulfate, potassium titanate, bentonite, wollastonite, dolomite, graphite, etc. The inorganic filler may be synthetic or derived from natural mineral and may be contained alone or as a combination of two or more thereof.
Among them, calcium carbonate, clay, talc, kaolin, etc. are preferred from the viewpoints of safety and cost. Calcium carbonate is especially preferred since it is commercially available in a variety of particle sizes and shapes and one appropriate for a physical property targeted for the thermoplastic composition may be selected. Use of eggshell-derived calcium carbonate from a food factory can contribute to waste reduction.
[0034]
When the inorganic filler is incorporated into the thermoplastic composition of the present invention, a content thereof is not particularly limited, but is preferably about to 400% by mass, further about 20 to 200% by mass, especially about 30 to 100% by mass relative to 100% by mass of a total of cellulose, a hydroxycarboxylic acid, and a sugar. Such a content allows a physical property such as hardness to be controlled without impairing a melt processability of the thermoplastic composition.
When the inorganic filler is incorporated into the thermoplastic composition of the present invention, a content thereof is not particularly limited, but is preferably about to 400% by mass, further about 20 to 200% by mass, especially about 30 to 100% by mass relative to 100% by mass of a total of cellulose, a hydroxycarboxylic acid, and a sugar. Such a content allows a physical property such as hardness to be controlled without impairing a melt processability of the thermoplastic composition.
[0035]
(Resin) A natural thermoplastic resin, a synthetic thermoplastic resin, or a biodegradable resin to be incorporated in the thermoplastic composition of the present invention is not particularly limited. Examples thereof include, but are not limited to, a polyolefin resin such as a polyethylene resin, a polypropylene resin, polymethyl-l-pentene, or an ethylene-cyclic olefin copolymer; a functional group-containing polyolefin resin such as an ethylene-vinyl acetate copolymer, an ethylene-acrylic acid copolymer, an ethylene-methacrylic acid copolymer, a metal salt of an ethylene-(meth)acrylic acid copolymer (ionomer), an ethylene-acrylic acid alkyl ester copolymer, an ethylene-methacrylic acid alkyl ester copolymer, maleic acid-modified polyethylene, or maleic acid modified polypropylene; a polyamide resin such as nylon-6, nylon-6,6, nylon-6,10, or nylon-6,12; an aromatic polyester resin such as polyethylene terephthalate or a copolymer thereof, polyethylene naphthalate, or polybutylene terephthalate; a thermoplastic polyester resin such as an aliphatic polyester resin including polyvinyl acetate, polybutylene succinate, polylactic acid, or a poly(3-hydroxybutyrate/3-hydroxyvalerate) copolymer (PHBV); an acrylic resin such as poly(meth)acrylic acid (ester) or polyacrylonitrile; a polycarbonate resin such as aromatic polycarbonate or aliphatic polycarbonate; a polystyrene resin such as atactic polystyrene, syndiotactic polystyrene, a acrylonitrile-styrene (AS) copolymer, or an acrylonitrile-butadiene-styrene (ABS) copolymer; a polyvinyl chloride resin such as polyvinyl chloride or polyvinylidene chloride; polyphenylene sulfide; a polyether resin such as polyether sulfone, polyether ketone, or polyether ether ketone; and various known thermoplastic resins such as polyvinyl alcohol, rosin, a cellulose acetate thermoplastic resin, a petroleum hydrocarbon resin, a coumarone indene resin, etc. A plurality of thermoplastic resins may be used in combination. Furthermore, an elastomer component such as a styrene-butadiene copolymer, a styrene-isoprene copolymer, a styrene-butadiene-ethylene copolymer, a styrene-isoprene-ethylene copolymer, an acrylonitrile-butadiene copolymer, or a fluoroelastomer may be included.
(Resin) A natural thermoplastic resin, a synthetic thermoplastic resin, or a biodegradable resin to be incorporated in the thermoplastic composition of the present invention is not particularly limited. Examples thereof include, but are not limited to, a polyolefin resin such as a polyethylene resin, a polypropylene resin, polymethyl-l-pentene, or an ethylene-cyclic olefin copolymer; a functional group-containing polyolefin resin such as an ethylene-vinyl acetate copolymer, an ethylene-acrylic acid copolymer, an ethylene-methacrylic acid copolymer, a metal salt of an ethylene-(meth)acrylic acid copolymer (ionomer), an ethylene-acrylic acid alkyl ester copolymer, an ethylene-methacrylic acid alkyl ester copolymer, maleic acid-modified polyethylene, or maleic acid modified polypropylene; a polyamide resin such as nylon-6, nylon-6,6, nylon-6,10, or nylon-6,12; an aromatic polyester resin such as polyethylene terephthalate or a copolymer thereof, polyethylene naphthalate, or polybutylene terephthalate; a thermoplastic polyester resin such as an aliphatic polyester resin including polyvinyl acetate, polybutylene succinate, polylactic acid, or a poly(3-hydroxybutyrate/3-hydroxyvalerate) copolymer (PHBV); an acrylic resin such as poly(meth)acrylic acid (ester) or polyacrylonitrile; a polycarbonate resin such as aromatic polycarbonate or aliphatic polycarbonate; a polystyrene resin such as atactic polystyrene, syndiotactic polystyrene, a acrylonitrile-styrene (AS) copolymer, or an acrylonitrile-butadiene-styrene (ABS) copolymer; a polyvinyl chloride resin such as polyvinyl chloride or polyvinylidene chloride; polyphenylene sulfide; a polyether resin such as polyether sulfone, polyether ketone, or polyether ether ketone; and various known thermoplastic resins such as polyvinyl alcohol, rosin, a cellulose acetate thermoplastic resin, a petroleum hydrocarbon resin, a coumarone indene resin, etc. A plurality of thermoplastic resins may be used in combination. Furthermore, an elastomer component such as a styrene-butadiene copolymer, a styrene-isoprene copolymer, a styrene-butadiene-ethylene copolymer, a styrene-isoprene-ethylene copolymer, an acrylonitrile-butadiene copolymer, or a fluoroelastomer may be included.
[0036]
Incorporation of such a resin can variously change a physical property of the thermoplastic composition of the present invention. For example, incorporation of rosin can improve water resistance of the thermoplastic composition.
Furthermore, incorporation of a biodegradable resin such as polylactic acid or PHBV can facilitate biodegradation when the thermoplastic composition is disposed of and contribute to environment aspects.
Incorporation of such a resin can variously change a physical property of the thermoplastic composition of the present invention. For example, incorporation of rosin can improve water resistance of the thermoplastic composition.
Furthermore, incorporation of a biodegradable resin such as polylactic acid or PHBV can facilitate biodegradation when the thermoplastic composition is disposed of and contribute to environment aspects.
[0037]
From the viewpoint of making the most of a physical property and processability of the thermoplastic composition of the present invention, as well as texture resulting from cellulose, not incorporating the thermoplastic resin is also possible. Furthermore, when such a thermoplastic resin is incorporated, a content thereof is preferably about 5 to 120%
by mass, further about 10 to 100% by mass, especially about 20 to 80% by mass relative to 100% by mass of a total of cellulose, a hydroxycarboxylic acid, and a sugar.
From the viewpoint of making the most of a physical property and processability of the thermoplastic composition of the present invention, as well as texture resulting from cellulose, not incorporating the thermoplastic resin is also possible. Furthermore, when such a thermoplastic resin is incorporated, a content thereof is preferably about 5 to 120%
by mass, further about 10 to 100% by mass, especially about 20 to 80% by mass relative to 100% by mass of a total of cellulose, a hydroxycarboxylic acid, and a sugar.
[0038]
In another preferred embodiment of the thermoplastic composition of the present invention different from the above-described embodiment, cellulose is contained in an amount of 5 to 40% by mass, a hydroxycarboxylic acid is contained in an amount of 5 to 40% by mass, a sugar is contained in an amount of 3 to 25% by mass, and a resin or a filler is contained in an amount of 20 to 80% by mass; more preferably cellulose is contained in an amount of 10 to 35% by mass, a hydroxycarboxylic acid is contained in an amount of 10 to 35%
by mass, a sugar is contained in an amount of 5 to 20% by mass, a resin or a filler is contained in an amount of 30 to 70% by mass; and further preferably cellulose is contained in an amount of 15 to 30% by mass, a hydroxycarboxylic acid is contained in an amount of 15 to 30% by mass, a sugar is contained in an amount of 7 to 15% by mass, a resin or a filler is contained in an amount of 35 to 60% by mass. Such a composition can result in a thermoplastic composition having, in particular, excellent texture, heat resistance, water resistance, or mechanical property.
In another preferred embodiment of the thermoplastic composition of the present invention different from the above-described embodiment, cellulose is contained in an amount of 5 to 40% by mass, a hydroxycarboxylic acid is contained in an amount of 5 to 40% by mass, a sugar is contained in an amount of 3 to 25% by mass, and a resin or a filler is contained in an amount of 20 to 80% by mass; more preferably cellulose is contained in an amount of 10 to 35% by mass, a hydroxycarboxylic acid is contained in an amount of 10 to 35%
by mass, a sugar is contained in an amount of 5 to 20% by mass, a resin or a filler is contained in an amount of 30 to 70% by mass; and further preferably cellulose is contained in an amount of 15 to 30% by mass, a hydroxycarboxylic acid is contained in an amount of 15 to 30% by mass, a sugar is contained in an amount of 7 to 15% by mass, a resin or a filler is contained in an amount of 35 to 60% by mass. Such a composition can result in a thermoplastic composition having, in particular, excellent texture, heat resistance, water resistance, or mechanical property.
[0039]
(Other additives) Additives other than those above-described may be incorporated in the thermoplastic composition of the present invention, as desired. Examples thereof include, but are not limited to, a colorant, a lubricant, a coupling agent, a flow modifier (flow regulator), a crosslinking agent, a dispersing agent, an antioxidant, a UV absorber, a flame retardant, a stabilizer, an antistatic agent, a foaming agent, a plasticizer, starch, casein, etc. These additives may be used alone or two or more thereof may be used in combination.
Furthermore, the additives may be incorporated in the below-described kneading step or may be incorporated in raw materials in advance before the kneading step. For example, a coupling agent may be included by applying it on a surface of cellulose or an inorganic filler.
(Other additives) Additives other than those above-described may be incorporated in the thermoplastic composition of the present invention, as desired. Examples thereof include, but are not limited to, a colorant, a lubricant, a coupling agent, a flow modifier (flow regulator), a crosslinking agent, a dispersing agent, an antioxidant, a UV absorber, a flame retardant, a stabilizer, an antistatic agent, a foaming agent, a plasticizer, starch, casein, etc. These additives may be used alone or two or more thereof may be used in combination.
Furthermore, the additives may be incorporated in the below-described kneading step or may be incorporated in raw materials in advance before the kneading step. For example, a coupling agent may be included by applying it on a surface of cellulose or an inorganic filler.
[0040]
Contents of the other additives in the thermoplastic composition of the present invention may be freely set in accordance with a target physical property or processability, but preferably each of the other additives is contained in an amount of about 0 to 10% by mass and especially about 0.05 to 5% by mass and a total of the other additives is contained in an amount of 20% by mass or less, for example, 0.05 to 20% by mass relative to 100% by mass of a total of cellulose, a hydroxycarboxylic acid, and a sugar.
Contents of the other additives in the thermoplastic composition of the present invention may be freely set in accordance with a target physical property or processability, but preferably each of the other additives is contained in an amount of about 0 to 10% by mass and especially about 0.05 to 5% by mass and a total of the other additives is contained in an amount of 20% by mass or less, for example, 0.05 to 20% by mass relative to 100% by mass of a total of cellulose, a hydroxycarboxylic acid, and a sugar.
[0041]
[Method for producing thermoplastic composition]
The thermoplastic composition of the present invention can be produced by mixing components. The method is not particularly limited. For example, three components, that is, cellulose, a hydroxycarboxylic acid, and sugar, as well as an additive such as an inorganic filler or other resin components may be kneaded simultaneously or two components of the three components may be kneaded in advance and then other components may be added thereto and kneaded together.
[Method for producing thermoplastic composition]
The thermoplastic composition of the present invention can be produced by mixing components. The method is not particularly limited. For example, three components, that is, cellulose, a hydroxycarboxylic acid, and sugar, as well as an additive such as an inorganic filler or other resin components may be kneaded simultaneously or two components of the three components may be kneaded in advance and then other components may be added thereto and kneaded together.
[0042]
Here, in order to improve molding processability of the thermoplastic composition or when the thermoplastic composition is produced in a small amount in a low-shear mixer, for example, it is preferred that a hydroxycarboxylic acid and a sugar be melt-kneaded and then cellulose be kneaded therewith. Since the hydroxycarboxylic acid and the sugar can form an eutectic mixture, when the above-described two components are mixed in advance, the subsequent mixing can be performed at a mild temperature and under a low shear condition, reducing an energy consumption amount and preventing an organic matter from degrading at a high temperature.
Here, in order to improve molding processability of the thermoplastic composition or when the thermoplastic composition is produced in a small amount in a low-shear mixer, for example, it is preferred that a hydroxycarboxylic acid and a sugar be melt-kneaded and then cellulose be kneaded therewith. Since the hydroxycarboxylic acid and the sugar can form an eutectic mixture, when the above-described two components are mixed in advance, the subsequent mixing can be performed at a mild temperature and under a low shear condition, reducing an energy consumption amount and preventing an organic matter from degrading at a high temperature.
[0043]
The present invention also encompasses a method for producing a thermoplastic composition, the method including a first step of mixing a hydroxycarboxylic acid and a monosaccharide and/or a disaccharide at a temperature of 150 to 240 C; and a second step of mixing the mixture obtained in the first step with cellulose at a temperature of 150 to 240 C
(hereinafter, this method may be referred to as "Production method-A"). For example, when a thermoplastic composition containing cellulose in about 0.05 to 20.0% by mass relative to a total amount of thermoplastic composition is produced, Production method-A is effectively used.
The present invention also encompasses a method for producing a thermoplastic composition, the method including a first step of mixing a hydroxycarboxylic acid and a monosaccharide and/or a disaccharide at a temperature of 150 to 240 C; and a second step of mixing the mixture obtained in the first step with cellulose at a temperature of 150 to 240 C
(hereinafter, this method may be referred to as "Production method-A"). For example, when a thermoplastic composition containing cellulose in about 0.05 to 20.0% by mass relative to a total amount of thermoplastic composition is produced, Production method-A is effectively used.
[0044]
A method for mixing components in the method of the present invention, for example, Production method-A is not particularly limited. For example, a method in which the components are mixed in a common kneader such as an extruder, a kneader, a Banbury mixer, a planetary mixer, a Henschel mixer, or a heated roll, etc. at a temperature of 150 to 240 C, especially 160 to 200 C may be used, but is not limited thereto. In the case of a small batch, the components may be mixed in a flask with a stirrer as described below.
A method for mixing components in the method of the present invention, for example, Production method-A is not particularly limited. For example, a method in which the components are mixed in a common kneader such as an extruder, a kneader, a Banbury mixer, a planetary mixer, a Henschel mixer, or a heated roll, etc. at a temperature of 150 to 240 C, especially 160 to 200 C may be used, but is not limited thereto. In the case of a small batch, the components may be mixed in a flask with a stirrer as described below.
[0045]
However, when mixing is performed on more than a certain scale (not only in the below-described Production method-B, but also in Production method-A), an extruder, especially a twin-screw extruder is preferably used. The extruder can uniformly disperse components by the action of high shear force upon mixing and the first step and the second step can be performed in a single device by adding cellulose at an extrusion stage. Of course, the first step and the second step may be, for example, performed in separate devices at different times. Furthermore, the first step and the second step may be performed in a kneader and the resulting mixture may be further kneaded in an extruder and molded.
However, when mixing is performed on more than a certain scale (not only in the below-described Production method-B, but also in Production method-A), an extruder, especially a twin-screw extruder is preferably used. The extruder can uniformly disperse components by the action of high shear force upon mixing and the first step and the second step can be performed in a single device by adding cellulose at an extrusion stage. Of course, the first step and the second step may be, for example, performed in separate devices at different times. Furthermore, the first step and the second step may be performed in a kneader and the resulting mixture may be further kneaded in an extruder and molded.
[0046]
In one embodiment of Production method-A of the present invention, for example, the first step and the second step are performed in a twin screw extruder or a kneader, and the resulting mixture is extruded by a single- or twin-screw extruder. Thus, the thermoplastic composition of the present invention may be extruded into, for example, a strand shape and cut into a prism or cylinder shape having a size of, for example, about 2 to 5 mm square by a pelletizer, resulting in a thermoplastic composition having the above-described composition in a pellet form. The present invention also encompasses a method for producing a thermoplastic composition, the method further including a third step in which the mixture obtained in the second step is kneaded and molded in an extruder.
In one embodiment of Production method-A of the present invention, for example, the first step and the second step are performed in a twin screw extruder or a kneader, and the resulting mixture is extruded by a single- or twin-screw extruder. Thus, the thermoplastic composition of the present invention may be extruded into, for example, a strand shape and cut into a prism or cylinder shape having a size of, for example, about 2 to 5 mm square by a pelletizer, resulting in a thermoplastic composition having the above-described composition in a pellet form. The present invention also encompasses a method for producing a thermoplastic composition, the method further including a third step in which the mixture obtained in the second step is kneaded and molded in an extruder.
[0047]
The thermoplastic composition of the present invention may also be produced by kneading cellulose, a hydroxycarboxylic acid, and a sugar simultaneously (this method may be referred to as "Production method-B"). For example, when a thermoplastic composition containing cellulose in about 5 to 60% by mass relative to a total amount of the thermoplastic composition is produced, Production method-B is advantageously employed using a high-shear mixer. Here, the high-shear mixer is not particularly limited. For example, the mixer may be an extruder, a kneader, a Banbury mixer, etc. with an extruder, especially a twin screw extruder being preferred. Such a mixer can mix a hydroxycarboxylic acid and a sugar with a high shear force and thus form a deep eutectic solvent even in the presence of another component. Therefore, a step of mixing only the above-described two components in advance may be omitted.
The thermoplastic composition of the present invention may also be produced by kneading cellulose, a hydroxycarboxylic acid, and a sugar simultaneously (this method may be referred to as "Production method-B"). For example, when a thermoplastic composition containing cellulose in about 5 to 60% by mass relative to a total amount of the thermoplastic composition is produced, Production method-B is advantageously employed using a high-shear mixer. Here, the high-shear mixer is not particularly limited. For example, the mixer may be an extruder, a kneader, a Banbury mixer, etc. with an extruder, especially a twin screw extruder being preferred. Such a mixer can mix a hydroxycarboxylic acid and a sugar with a high shear force and thus form a deep eutectic solvent even in the presence of another component. Therefore, a step of mixing only the above-described two components in advance may be omitted.
[0048]
The present invention also encompasses a method for producing a thermoplastic composition, the method including mixing cellulose, a hydroxycarboxylic acid, and a monosaccharide and/or a disaccharide in an extruder at a temperature of 150 to 240 C. Such Production method-B allows a thermoplastic composition with excellent heat resistance or mechanical property to be easily produced and enables utilization of more cellulose waste.
The present invention also encompasses a method for producing a thermoplastic composition, the method including mixing cellulose, a hydroxycarboxylic acid, and a monosaccharide and/or a disaccharide in an extruder at a temperature of 150 to 240 C. Such Production method-B allows a thermoplastic composition with excellent heat resistance or mechanical property to be easily produced and enables utilization of more cellulose waste.
[0049]
The extruder to be used in Production method-B is not particularly limited. A twin screw extruder is preferably used, but is not limited thereto. Furthermore, any type of twin screw extruder may be used. A kneading or extruding condition is also not limited and may be a temperature of 150 to 240 C, particularly 160 to 230 C, and especially 170 to 210 C. Furthermore, a component such as an inorganic filler or a resin may be kneaded simultaneous with three components, that is, cellulose, a hydroxycarboxylic acid, and a sugar or may be kneaded with a mixture of the three components. For example, only the above three components or a portion of other components may be kneaded by Production method-B with an extruder and then the remaining components may be kneaded in a mixer such as an extruder or a kneader.
The extruder to be used in Production method-B is not particularly limited. A twin screw extruder is preferably used, but is not limited thereto. Furthermore, any type of twin screw extruder may be used. A kneading or extruding condition is also not limited and may be a temperature of 150 to 240 C, particularly 160 to 230 C, and especially 170 to 210 C. Furthermore, a component such as an inorganic filler or a resin may be kneaded simultaneous with three components, that is, cellulose, a hydroxycarboxylic acid, and a sugar or may be kneaded with a mixture of the three components. For example, only the above three components or a portion of other components may be kneaded by Production method-B with an extruder and then the remaining components may be kneaded in a mixer such as an extruder or a kneader.
[0050]
In Production method-B, a kneaded product may be formed directly into a molded product by extrusion from an extruder or may be molded into a pellet form. Furthermore, the resulting mixture may be subjected to a step similar to the third step in the above-described Production method-A. For example, the mixture obtained by Production method-B may be extruded by a single- or twin-screw extruder into a strand shape and cut into a prism or cylinder shape having a size of about 2 to 5 mm square by, for example, a pelletizer, resulting in a thermoplastic composition having the above-described composition in a pellet form.
In Production method-B, a kneaded product may be formed directly into a molded product by extrusion from an extruder or may be molded into a pellet form. Furthermore, the resulting mixture may be subjected to a step similar to the third step in the above-described Production method-A. For example, the mixture obtained by Production method-B may be extruded by a single- or twin-screw extruder into a strand shape and cut into a prism or cylinder shape having a size of about 2 to 5 mm square by, for example, a pelletizer, resulting in a thermoplastic composition having the above-described composition in a pellet form.
[0051]
[Molded product]
The present invention further encompasses a thermoplastic pellet made of the above-described thermoplastic composition.
The thermoplastic composition of the present invention has excellent moldability since it melts or solidifies generally at a temperature of 50 to 230 C, specifically, in the case where the content of cellulose is about 0.05 to 20.0% by mass, at a temperature of about 60 to 200 C, further about 70 to 150 C, especially about 70 to 100 C, and in the case where the content of cellulose is about 5 to 60% by mass, at a temperature of about 150 to 240 C, further about 160 to 230 C, especially about 170 to 210 C, as described above. Therefore, the thermoplastic pellet of the present invention is suitable as a thermoplastic polymer material.
[Molded product]
The present invention further encompasses a thermoplastic pellet made of the above-described thermoplastic composition.
The thermoplastic composition of the present invention has excellent moldability since it melts or solidifies generally at a temperature of 50 to 230 C, specifically, in the case where the content of cellulose is about 0.05 to 20.0% by mass, at a temperature of about 60 to 200 C, further about 70 to 150 C, especially about 70 to 100 C, and in the case where the content of cellulose is about 5 to 60% by mass, at a temperature of about 150 to 240 C, further about 160 to 230 C, especially about 170 to 210 C, as described above. Therefore, the thermoplastic pellet of the present invention is suitable as a thermoplastic polymer material.
[0052]
The thermoplastic composition of the present invention has a good thermoplasticity as described above and thus can be molded into various shapes. The present invention also encompasses a molded product made of the thermoplastic composition. A shape or size of the molded product is not particularly limited, and the molded product may be any shape such as sheet, tube, strand, or any other shape for any purpose. A method for molding the composition is also not particularly limited, any molding method such as extrusion molding, injection molding, roll molding, transfer molding, or blow molding may be used. For example, the above-described thermoplastic pellet of the present invention may be molded into a desired shape using an extruder or an injection molding device or the thermoplastic composition may be extruded without pelletizing and molded into a sheet or tubular product. It is also possible to combine it with another material using calendar molding.
The thermoplastic composition of the present invention has a good thermoplasticity as described above and thus can be molded into various shapes. The present invention also encompasses a molded product made of the thermoplastic composition. A shape or size of the molded product is not particularly limited, and the molded product may be any shape such as sheet, tube, strand, or any other shape for any purpose. A method for molding the composition is also not particularly limited, any molding method such as extrusion molding, injection molding, roll molding, transfer molding, or blow molding may be used. For example, the above-described thermoplastic pellet of the present invention may be molded into a desired shape using an extruder or an injection molding device or the thermoplastic composition may be extruded without pelletizing and molded into a sheet or tubular product. It is also possible to combine it with another material using calendar molding.
[0053]
Application of the thermoplastic composition of the present invention or the molded product is not particularly limited. For example, it may be used for a daily necessity such as a toy, a toothbrush, or a bath product; a housing for a home appliance; or a polymeric material for transportation equipment such as an automobile or a train. In particular, when a refined product such as kraft pulp is used as a cellulose material, it can be used for a medical or food application. Since cellulose, a hydroxycarboxylic acid, a monosaccharide, and a disaccharide are highly safe materials, the thermoplastic composition of the present invention made of these components is suitable for a medical or food application. The thermoplastic composition of the present invention can also be considered a natural product-derived material on the basis of a concept different from a conventional biodegradable resin, and can be utilized as an additive to another material for the purpose of increasing a biomass content.
EXAMPLES
Application of the thermoplastic composition of the present invention or the molded product is not particularly limited. For example, it may be used for a daily necessity such as a toy, a toothbrush, or a bath product; a housing for a home appliance; or a polymeric material for transportation equipment such as an automobile or a train. In particular, when a refined product such as kraft pulp is used as a cellulose material, it can be used for a medical or food application. Since cellulose, a hydroxycarboxylic acid, a monosaccharide, and a disaccharide are highly safe materials, the thermoplastic composition of the present invention made of these components is suitable for a medical or food application. The thermoplastic composition of the present invention can also be considered a natural product-derived material on the basis of a concept different from a conventional biodegradable resin, and can be utilized as an additive to another material for the purpose of increasing a biomass content.
EXAMPLES
[0054]
The present invention will be more specifically described with reference to Examples. Note that, these Examples are described only for the purpose of illustrating certain aspects and embodiments in order to facilitate a better understanding of the concept and scope of the invention as disclosed herein and described in the appended claims, and the invention is not limited in any way to these Examples.
The present invention will be more specifically described with reference to Examples. Note that, these Examples are described only for the purpose of illustrating certain aspects and embodiments in order to facilitate a better understanding of the concept and scope of the invention as disclosed herein and described in the appended claims, and the invention is not limited in any way to these Examples.
[0055]
[Example 1]
(First step/Production method-A) A flask with a stirrer was charged with 100 g of lactic acid and 40 g of glucose and stirred at a temperature of 150 to 200 C for 30 min. The resulting mixture was liquid at room temperature and had become a 100% natural deep eutectic solvent.
[Example 1]
(First step/Production method-A) A flask with a stirrer was charged with 100 g of lactic acid and 40 g of glucose and stirred at a temperature of 150 to 200 C for 30 min. The resulting mixture was liquid at room temperature and had become a 100% natural deep eutectic solvent.
[0056]
(Second step/Production method-A) A flask with a stirrer was charged with 100 g of the mixture obtained in the first step and heated to 150 to 200 C.
Then, 0.5 g of pulp was added thereto and stirred at about 150 to 200 C for 1 hour or longer, resulting in a nearly homogeneous brown liquid. The heating and the stirring at the above-described temperature were performed for a total of 8 hours. Then, once the liquid was transferred onto a clean aluminum plate, it solidified into a solid.
(Second step/Production method-A) A flask with a stirrer was charged with 100 g of the mixture obtained in the first step and heated to 150 to 200 C.
Then, 0.5 g of pulp was added thereto and stirred at about 150 to 200 C for 1 hour or longer, resulting in a nearly homogeneous brown liquid. The heating and the stirring at the above-described temperature were performed for a total of 8 hours. Then, once the liquid was transferred onto a clean aluminum plate, it solidified into a solid.
[0057]
(Property of composition) The solid obtained in the second step had a resin-like appearance and feel. When the solid was hammered by a clean hammer, it became powdery. The resulting powder melted at a temperature of about 150 C and solidified again when cooled to near room temperature. Furthermore, the powder was able to be molded into a dumbbell specimen by injection molding. In other words, the composition obtained in this Example was demonstrated to be thermoplastic.
(Property of composition) The solid obtained in the second step had a resin-like appearance and feel. When the solid was hammered by a clean hammer, it became powdery. The resulting powder melted at a temperature of about 150 C and solidified again when cooled to near room temperature. Furthermore, the powder was able to be molded into a dumbbell specimen by injection molding. In other words, the composition obtained in this Example was demonstrated to be thermoplastic.
[0058]
Note that, when a simple experiment similar to in Example 1 was performed using another deep eutectic solvent instead of lactic acid and glucose in the first step, pulp was not uniformly microdispersed in the second step and did not exhibit thermoplasticity (see, Comparative Example 1).
Although it is not possible to say for certain because of the simple experiment without precise temperature control during mixing, it is suggested that a thermoplastic material like the thermoplastic material of the present invention cannot be obtained merely by heating and mixing cellulose with a deep eutectic solvent.
Note that, when a simple experiment similar to in Example 1 was performed using another deep eutectic solvent instead of lactic acid and glucose in the first step, pulp was not uniformly microdispersed in the second step and did not exhibit thermoplasticity (see, Comparative Example 1).
Although it is not possible to say for certain because of the simple experiment without precise temperature control during mixing, it is suggested that a thermoplastic material like the thermoplastic material of the present invention cannot be obtained merely by heating and mixing cellulose with a deep eutectic solvent.
[0059]
[Example 2]
The powder obtained in Example 1 (thermoplastic composition) and starch were put into a small twin screw extruder at a mass ratio of 7:3 and kneaded and extruded at 80 to 120 C into a pellet. The resulting pellet was able to be molded into a dumbbell specimen by injection molding, as in Example 1.
[Example 2]
The powder obtained in Example 1 (thermoplastic composition) and starch were put into a small twin screw extruder at a mass ratio of 7:3 and kneaded and extruded at 80 to 120 C into a pellet. The resulting pellet was able to be molded into a dumbbell specimen by injection molding, as in Example 1.
[0060]
[Example 3]
The powder obtained in Example 1 (thermoplastic composition) and talc were put into a small twin screw extruder at a mass ratio of 6:4, and a pellet was produced in the same manner as in Example 2. The resulting pellet was able to be molded into a dumbbell specimen by injection molding, as in Examples 1 and 2.
[Example 3]
The powder obtained in Example 1 (thermoplastic composition) and talc were put into a small twin screw extruder at a mass ratio of 6:4, and a pellet was produced in the same manner as in Example 2. The resulting pellet was able to be molded into a dumbbell specimen by injection molding, as in Examples 1 and 2.
[0061]
[Example 4]
The pellet obtained in Example 2 and poly(3-hydroxybutyrate/3-hydroxyvalerate) (PHBV, biodegradable resin) were put into a small twin screw extruder at a mass ratio of 1:1, and a pellet was produced in the same manner as in Example 2. The resulting pellet was able to be molded into a dumbbell specimen by injection molding, as in Examples 1 to 3.
[Example 4]
The pellet obtained in Example 2 and poly(3-hydroxybutyrate/3-hydroxyvalerate) (PHBV, biodegradable resin) were put into a small twin screw extruder at a mass ratio of 1:1, and a pellet was produced in the same manner as in Example 2. The resulting pellet was able to be molded into a dumbbell specimen by injection molding, as in Examples 1 to 3.
[0062]
[Example 5]
The pellet obtained in Example 3 and gum rosin were put into a small twin screw extruder at a mass ratio of 8:2, and a pellet was produced in the same manner as in Example 3. The resulting pellet was able to be molded into a dumbbell specimen by injection molding, as in Examples 1 to 4.
[Example 5]
The pellet obtained in Example 3 and gum rosin were put into a small twin screw extruder at a mass ratio of 8:2, and a pellet was produced in the same manner as in Example 3. The resulting pellet was able to be molded into a dumbbell specimen by injection molding, as in Examples 1 to 4.
[0063]
[Example 6]
A pellet was produced in the same manner as in Example 5, except that lignin (Vanillex (registered trademark) ON
manufactured by Nippon Paper Industries Co., Ltd.) was used instead of gum rosin. The resulting pellet was able to be molded into a dumbbell specimen by injection molding, as in Examples 1 to 5.
[Example 6]
A pellet was produced in the same manner as in Example 5, except that lignin (Vanillex (registered trademark) ON
manufactured by Nippon Paper Industries Co., Ltd.) was used instead of gum rosin. The resulting pellet was able to be molded into a dumbbell specimen by injection molding, as in Examples 1 to 5.
[0064]
[Example 7]
A twin screw extruder (twin screw kneader extruder, manufactured by TECHNOVEL CORPORATION, p 15mm, L/D = 50) was charged with 40 parts by mass of cedar wood flour, 50 parts by mass of lactic acid, 25 parts by mass of glucose, and 50 parts by mass of talc and extruded in a strand shape with kneading at a set temperature of 160 to 220 C (to thereby prepare a thermoplastic composition as described in Production method-B). Then, the strand was cut with a pelletizer to thereby form a pellet of the thermoplastic composition.
[Example 7]
A twin screw extruder (twin screw kneader extruder, manufactured by TECHNOVEL CORPORATION, p 15mm, L/D = 50) was charged with 40 parts by mass of cedar wood flour, 50 parts by mass of lactic acid, 25 parts by mass of glucose, and 50 parts by mass of talc and extruded in a strand shape with kneading at a set temperature of 160 to 220 C (to thereby prepare a thermoplastic composition as described in Production method-B). Then, the strand was cut with a pelletizer to thereby form a pellet of the thermoplastic composition.
[0065]
Then, the resulting pellet was injection molded by an injection molding device (HAAKE Process 11 manufactured by Thermo Fisher Scientific, Inc.) and was able to be molded into a specimen for a bending test according to JIS K7171 (IS0178) (80 x 10 x 4mm) and a dumbbell specimen for a tensile test according to JIS K7161-2 at 180 to 220 C. It was revealed that the composition of the present example was thermoplastic and exhibited a good molding processability although it contained a large amount of a cellulose component.
Then, the resulting pellet was injection molded by an injection molding device (HAAKE Process 11 manufactured by Thermo Fisher Scientific, Inc.) and was able to be molded into a specimen for a bending test according to JIS K7171 (IS0178) (80 x 10 x 4mm) and a dumbbell specimen for a tensile test according to JIS K7161-2 at 180 to 220 C. It was revealed that the composition of the present example was thermoplastic and exhibited a good molding processability although it contained a large amount of a cellulose component.
[0066]
Next, three of each of these specimens were subjected to a bending test according to JIS K7171 (test speed: 2 mm/min) and a tensile test according to JIS K7161-2 (tensile speed: 5 mm/min) to evaluate their mechanical strength. Furthermore, water resistance was also evaluated. Note that, water resistance was evaluated by adding the resulting thermoplastic resin pellet and the dumbbell specimen to a glass beaker containing water, visually observing for change in shape, and grading based on the following criteria.
(Evaluation criteria of water resistance) Good (indicated by circle symbol (o)): No change in shape was observed. Fair (indicated by triangle symbol (A)):
Specimen was changed in shape, but was not broken down. Poor (indicated by cross symbol (x)): Specimen was broken down in water and its shape was not retained. Evaluation results are shown in Table 1 below along with compositions of the thermoplastic compositions.
Next, three of each of these specimens were subjected to a bending test according to JIS K7171 (test speed: 2 mm/min) and a tensile test according to JIS K7161-2 (tensile speed: 5 mm/min) to evaluate their mechanical strength. Furthermore, water resistance was also evaluated. Note that, water resistance was evaluated by adding the resulting thermoplastic resin pellet and the dumbbell specimen to a glass beaker containing water, visually observing for change in shape, and grading based on the following criteria.
(Evaluation criteria of water resistance) Good (indicated by circle symbol (o)): No change in shape was observed. Fair (indicated by triangle symbol (A)):
Specimen was changed in shape, but was not broken down. Poor (indicated by cross symbol (x)): Specimen was broken down in water and its shape was not retained. Evaluation results are shown in Table 1 below along with compositions of the thermoplastic compositions.
[0067]
[Examples 8 to 13]
Rosin or PHBV was used along with the components used in Example 7, and the same operations were performed as in Example 7. The composition of each of the thermoplastic compositions and evaluation results are shown in Table 1.
[Examples 8 to 13]
Rosin or PHBV was used along with the components used in Example 7, and the same operations were performed as in Example 7. The composition of each of the thermoplastic compositions and evaluation results are shown in Table 1.
[0068]
[Table 1 Composition and evaluation result of samples]
Exam- Exam- Exam- Exam- Exam- Exam- Exam-Example pie 7 pie 8 pie 9 pie 10 pie 11 pie 12 pie 13 Ceder wood flour Lactic acid *Compo-Glucose 25 25 25 25 25 25 sition of Talc 50 50 50 50 50 50 sample Rosin - 25 50 75 - --24.2 25.0 22.2 20.0 25.0 22.2 20.0 Cellulose amount' (35) (40) (40) (40) (40) (40) (40) Tensile 3.1 9.8 11.2 13.9 7.2 10.6 13.1 strength#
Evalu-ationBending 2.3 13.8 14.9 16.1 8.9 9.1 11.2 strength#
result Water resistance * Unit:Part(s) by mass x unit: % by mass (Number within parentheses denotes % by mass relative to a total of three components, cellulose, lactic acid, and glycol) # Unit: MPa
[Table 1 Composition and evaluation result of samples]
Exam- Exam- Exam- Exam- Exam- Exam- Exam-Example pie 7 pie 8 pie 9 pie 10 pie 11 pie 12 pie 13 Ceder wood flour Lactic acid *Compo-Glucose 25 25 25 25 25 25 sition of Talc 50 50 50 50 50 50 sample Rosin - 25 50 75 - --24.2 25.0 22.2 20.0 25.0 22.2 20.0 Cellulose amount' (35) (40) (40) (40) (40) (40) (40) Tensile 3.1 9.8 11.2 13.9 7.2 10.6 13.1 strength#
Evalu-ationBending 2.3 13.8 14.9 16.1 8.9 9.1 11.2 strength#
result Water resistance * Unit:Part(s) by mass x unit: % by mass (Number within parentheses denotes % by mass relative to a total of three components, cellulose, lactic acid, and glycol) # Unit: MPa
[0069]
The above examples show that the compositions of the present invention each containing cellulose and an eutectic mixture of a hydroxycarboxylic acid and a sugar exhibit thermoplasticity and can be thermally melted and kneaded with various materials to provide various thermoplastic resin-like CA 03240134 2024 6 materials. In view of the fact that simply mixing cellulose with a deep eutectic solvent did not result in a thermoplastic material (Comparative Example 1), the present invention is considered to be a thermoplastic material that exhibits an unexpected property.
The above examples show that the compositions of the present invention each containing cellulose and an eutectic mixture of a hydroxycarboxylic acid and a sugar exhibit thermoplasticity and can be thermally melted and kneaded with various materials to provide various thermoplastic resin-like CA 03240134 2024 6 materials. In view of the fact that simply mixing cellulose with a deep eutectic solvent did not result in a thermoplastic material (Comparative Example 1), the present invention is considered to be a thermoplastic material that exhibits an unexpected property.
[0070]
[Examples 14 to 19]
Polypropylene (PP) or polyethylene (PE) was used instead of rosin or PHBV, and the same operations were performed as in Examples 8 to 13. The composition of each of the thermoplastic compositions and evaluation results are shown in Table 2.
[Examples 14 to 19]
Polypropylene (PP) or polyethylene (PE) was used instead of rosin or PHBV, and the same operations were performed as in Examples 8 to 13. The composition of each of the thermoplastic compositions and evaluation results are shown in Table 2.
[0071]
[Table 2 Composition and evaluation result of samples]
Exam- Exam- Exam- Exam- Exam- Exam- Exam-Example pie 7 pie 14 pie 15 pie 16 pie 17 pie 18 pie 19 Ceder wood flour Lactic acid 50 50 50 50 50 50 *Compo-Glucose 25 25 25 25 25 25 sition of Talc sample -24.2 25.0 22.2 20.0 25.0 22.2 20.0 Cellulose amount' (35) (40) (40) (40) (40) (40) (40) Tensile 3.1 10.8 13.8 15.7 7.5 8.1 9.6 strength#
Evalu-ationBending 2.3 8.4 10.1 13.9 6.3 7.2 8.8 strength#
result Water A 0 0 0 0 0 resistance * Unit:Part(s) by mass x unit: % by mass (Number within parentheses denotes % by mass relative to a total of three components, cellulose, lactic acid, and glycol) # Unit: MPa
[Table 2 Composition and evaluation result of samples]
Exam- Exam- Exam- Exam- Exam- Exam- Exam-Example pie 7 pie 14 pie 15 pie 16 pie 17 pie 18 pie 19 Ceder wood flour Lactic acid 50 50 50 50 50 50 *Compo-Glucose 25 25 25 25 25 25 sition of Talc sample -24.2 25.0 22.2 20.0 25.0 22.2 20.0 Cellulose amount' (35) (40) (40) (40) (40) (40) (40) Tensile 3.1 10.8 13.8 15.7 7.5 8.1 9.6 strength#
Evalu-ationBending 2.3 8.4 10.1 13.9 6.3 7.2 8.8 strength#
result Water A 0 0 0 0 0 resistance * Unit:Part(s) by mass x unit: % by mass (Number within parentheses denotes % by mass relative to a total of three components, cellulose, lactic acid, and glycol) # Unit: MPa
[0072]
It is shown that the thermoplastic composition of the present invention can also contain a general-purpose resin such as polypropylene or polyethylene and thus improve a physical property such as a mechanical property or water resistance. Thus, the thermoplastic composition of the present invention can include a large amount of various resins or an inorganic filler and thus improve a physical property such as water resistance or reduce cost. For example, it was confirmed that up to 175 parts by mass of rosin was able to be incorporated to increase water resistance as in Examples 8 to 10.
It is shown that the thermoplastic composition of the present invention can also contain a general-purpose resin such as polypropylene or polyethylene and thus improve a physical property such as a mechanical property or water resistance. Thus, the thermoplastic composition of the present invention can include a large amount of various resins or an inorganic filler and thus improve a physical property such as water resistance or reduce cost. For example, it was confirmed that up to 175 parts by mass of rosin was able to be incorporated to increase water resistance as in Examples 8 to 10.
[0073]
As described above, the thermoplastic composition of the present invention exhibits thermoplastic even when a large amount of cellulose is contained and useful for a recycling application of cellulose waste. The thermoplastic composition of the present invention can also be mixed with a petroleum-based resin including polyethylene to increase a biomass content. The thermoplastic composition of the present invention can also be mixed with a biodegradable resin including PHBV to increase a waste utilization rate without reducing a physical property, as well as to reduce a cost. In other words, the thermoplastic composition of the present invention can be used like a bulking agent. In addition, the thermoplastic composition of the present invention does not require disposal of a solvent or use of an environmentally hazardous substance such as a halide-containing substance in a manufacturing process. Considering such points, the effect of this invention is remarkable.
As described above, the thermoplastic composition of the present invention exhibits thermoplastic even when a large amount of cellulose is contained and useful for a recycling application of cellulose waste. The thermoplastic composition of the present invention can also be mixed with a petroleum-based resin including polyethylene to increase a biomass content. The thermoplastic composition of the present invention can also be mixed with a biodegradable resin including PHBV to increase a waste utilization rate without reducing a physical property, as well as to reduce a cost. In other words, the thermoplastic composition of the present invention can be used like a bulking agent. In addition, the thermoplastic composition of the present invention does not require disposal of a solvent or use of an environmentally hazardous substance such as a halide-containing substance in a manufacturing process. Considering such points, the effect of this invention is remarkable.
Claims (11)
1. A thermoplastic composition comprising:
cellulose; and an eutectic mixture of a monosaccharide and/or a disaccharide and a hydroxycarboxylic acid.
cellulose; and an eutectic mixture of a monosaccharide and/or a disaccharide and a hydroxycarboxylic acid.
2. The thermoplastic composition according to claim 1, wherein the eutectic mixture is a mixture of lactic acid and glucose.
3. The thermoplastic composition according to claim 1 or 2, further comprising hemicellulose and/or lignin, wherein the cellulose is plant-derived cellulose.
4. The thermoplastic composition according to claim 1 or 2, wherein the composition comprises 0.05 to 60.0% by mass of the cellulose.
5. The thermoplastic composition according to claim 1 or 2, wherein the composition has a mass ratio of the hydroxycarboxylic acid : the monosaccharide and/or the disaccharide in a range of 1:2 to 6:1.
6. The thermoplastic composition according to claim 1 or 2, further comprising one or more substances selected from the group consisting of an inorganic filler, a natural thermoplastic resin, a synthetic thermoplastic resin, and a biodegradable resin.
7. A method for producing a thermoplastic composition, the method comprising:
a first step of mixing a hydroxycarboxylic acid and a monosaccharide and/or a disaccharide at a temperature of 150 to 240 C; and a second step of mixing the mixture obtained in the first step and cellulose at a temperature of 150 to 240 C.
a first step of mixing a hydroxycarboxylic acid and a monosaccharide and/or a disaccharide at a temperature of 150 to 240 C; and a second step of mixing the mixture obtained in the first step and cellulose at a temperature of 150 to 240 C.
8. The method for producing a thermoplastic composition according to claim 7, further comprising a third step of kneading and molding the mixture obtained in the second step in an extruder.
9. A method for producing a thermoplastic composition, the method comprising mixing cellulose, a hydroxycarboxylic acid, and a monosaccharide and/or a disaccharide in an extruder at a temperature of 150 to 240 C.
10. A thermoplastic pellet formed of the thermoplastic composition according to claim 1 or 2.
11. A molded product formed of the thermoplastic composition according to claim 1 or 2.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022013398 | 2022-01-31 | ||
| JP2022-013398 | 2022-01-31 | ||
| JP2022130009A JP2023111812A (en) | 2022-01-31 | 2022-08-17 | thermoplastic composition |
| JP2022-130009 | 2022-08-17 | ||
| PCT/JP2023/002990 WO2023145958A1 (en) | 2022-01-31 | 2023-01-31 | Thermoplastic composition |
Publications (1)
| Publication Number | Publication Date |
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| CA3240134A1 true CA3240134A1 (en) | 2023-08-03 |
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|---|---|---|---|
| CA3240134A Pending CA3240134A1 (en) | 2022-01-31 | 2023-01-31 | Thermoplastic composition |
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| WO (1) | WO2023145958A1 (en) |
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| JPH1192503A (en) * | 1997-09-22 | 1999-04-06 | Canon Inc | Polymer compound containing sugar chain polymer compound and its decomposition method |
| JPH11193524A (en) * | 1997-12-26 | 1999-07-21 | Kankyo Create:Kk | Treatment method and agent for existing concrete pile head |
| ES2732298T3 (en) * | 2005-07-26 | 2019-11-21 | Knauf Insulation Gmbh | A method of manufacturing fiberglass insulation products |
| WO2008143322A1 (en) * | 2007-05-23 | 2008-11-27 | Okayama Prefecture Industrial Promotion Foundation | Cellulose derivative, cellulose derivative-polylactic acid graft copolymer and method for producing the same, and polylactic acid resin composition |
| US9593230B2 (en) * | 2013-11-01 | 2017-03-14 | 3M Innovative Properties Company | Plasticized polymeric composition |
| CN103951852A (en) * | 2014-05-21 | 2014-07-30 | 季国良 | Manufacturing method of high-strength starch-base degradable environment-friendly material |
| WO2018038669A1 (en) * | 2016-08-24 | 2018-03-01 | Organoclick Ab | Bio-based polyelectrolyte complex compositions comprising non-water soluble particles |
| US20190075807A1 (en) * | 2017-09-08 | 2019-03-14 | DuPont Nutrition USA, Inc. | Colloidal compositions of microcrystalline cellulose and alginate, their preparation and products obtained therefrom |
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