EP4165132A1 - Toy building element made of a polymeric polyester material - Google Patents
Toy building element made of a polymeric polyester materialInfo
- Publication number
- EP4165132A1 EP4165132A1 EP21731821.1A EP21731821A EP4165132A1 EP 4165132 A1 EP4165132 A1 EP 4165132A1 EP 21731821 A EP21731821 A EP 21731821A EP 4165132 A1 EP4165132 A1 EP 4165132A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polyester
- resin
- acid
- modified
- pet
- 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
- 229920000728 polyester Polymers 0.000 title claims abstract description 209
- 239000000463 material Substances 0.000 title claims abstract description 36
- 239000004609 Impact Modifier Substances 0.000 claims abstract description 158
- 229920005989 resin Polymers 0.000 claims abstract description 138
- 239000011347 resin Substances 0.000 claims abstract description 138
- 238000004519 manufacturing process Methods 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000012545 processing Methods 0.000 claims abstract description 20
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 131
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 131
- 239000000178 monomer Substances 0.000 claims description 112
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 102
- KKEYFWRCBNTPAC-UHFFFAOYSA-N terephthalic acid group Chemical group C(C1=CC=C(C(=O)O)C=C1)(=O)O KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 70
- -1 polyethylene terephthalate Polymers 0.000 claims description 55
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 44
- 239000000203 mixture Substances 0.000 claims description 42
- 239000000314 lubricant Substances 0.000 claims description 34
- 239000000654 additive Substances 0.000 claims description 33
- 238000001746 injection moulding Methods 0.000 claims description 28
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 24
- 150000002009 diols Chemical class 0.000 claims description 24
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 19
- 230000000996 additive effect Effects 0.000 claims description 19
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 18
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 18
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 16
- DNXDYHALMANNEJ-UHFFFAOYSA-N furan-2,3-dicarboxylic acid Chemical compound OC(=O)C=1C=COC=1C(O)=O DNXDYHALMANNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 9
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 9
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 9
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 8
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 claims description 8
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 claims description 8
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 8
- 239000001361 adipic acid Substances 0.000 claims description 8
- 235000011037 adipic acid Nutrition 0.000 claims description 8
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 8
- 229960002479 isosorbide Drugs 0.000 claims description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 8
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 claims description 8
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 8
- 235000013772 propylene glycol Nutrition 0.000 claims description 8
- 239000000945 filler Substances 0.000 claims description 7
- 239000002667 nucleating agent Substances 0.000 claims description 5
- 239000004970 Chain extender Substances 0.000 claims description 4
- 239000004150 EU approved colour Substances 0.000 claims description 4
- 239000012963 UV stabilizer Substances 0.000 claims description 4
- 230000000655 anti-hydrolysis Effects 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 239000003063 flame retardant Substances 0.000 claims description 4
- 229940006093 opthalmologic coloring agent diagnostic Drugs 0.000 claims description 4
- 239000000049 pigment Substances 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- 239000003607 modifier Substances 0.000 claims 2
- 229920003313 Bynel® Polymers 0.000 description 53
- 229920000642 polymer Polymers 0.000 description 50
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 42
- 239000000126 substance Substances 0.000 description 39
- 229910052799 carbon Inorganic materials 0.000 description 31
- 239000002114 nanocomposite Substances 0.000 description 29
- 229920013724 bio-based polymer Polymers 0.000 description 24
- 229920001225 polyester resin Polymers 0.000 description 23
- 239000004645 polyester resin Substances 0.000 description 23
- 238000006116 polymerization reaction Methods 0.000 description 23
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 21
- 239000005977 Ethylene Substances 0.000 description 21
- 239000003208 petroleum Substances 0.000 description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 17
- 229920003298 Nucrel® Polymers 0.000 description 15
- 229920001577 copolymer Polymers 0.000 description 13
- 239000002028 Biomass Substances 0.000 description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 11
- 229920003317 Fusabond® Polymers 0.000 description 10
- 239000011449 brick Substances 0.000 description 10
- 229920001971 elastomer Polymers 0.000 description 10
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 description 10
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical class CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 10
- 230000004048 modification Effects 0.000 description 10
- 238000012986 modification Methods 0.000 description 10
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 238000004064 recycling Methods 0.000 description 10
- 150000008064 anhydrides Chemical class 0.000 description 9
- 239000011469 building brick Substances 0.000 description 9
- 239000004927 clay Substances 0.000 description 9
- 238000013329 compounding Methods 0.000 description 9
- 239000011258 core-shell material Substances 0.000 description 9
- 239000011159 matrix material Substances 0.000 description 9
- 239000005060 rubber Substances 0.000 description 9
- 239000001993 wax Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 8
- 239000004926 polymethyl methacrylate Substances 0.000 description 8
- 229920001296 polysiloxane Polymers 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 229940035437 1,3-propanediol Drugs 0.000 description 7
- 239000004743 Polypropylene Substances 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 239000002991 molded plastic Substances 0.000 description 7
- 239000008188 pellet Substances 0.000 description 7
- 229920001155 polypropylene Polymers 0.000 description 7
- 230000002195 synergetic effect Effects 0.000 description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 7
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 150000002148 esters Chemical group 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 6
- 229920000578 graft copolymer Polymers 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 229920001903 high density polyethylene Polymers 0.000 description 5
- 239000004700 high-density polyethylene Substances 0.000 description 5
- 229920001684 low density polyethylene Polymers 0.000 description 5
- 239000004702 low-density polyethylene Substances 0.000 description 5
- 239000012170 montan wax Substances 0.000 description 5
- 230000002787 reinforcement Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229920001169 thermoplastic Polymers 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- 239000004610 Internal Lubricant Substances 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 description 4
- 239000002041 carbon nanotube Substances 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 210000004534 cecum Anatomy 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical compound [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 238000000197 pyrolysis Methods 0.000 description 4
- 239000004416 thermosoftening plastic Substances 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- PZWQOGNTADJZGH-SNAWJCMRSA-N (2e)-2-methylpenta-2,4-dienoic acid Chemical compound OC(=O)C(/C)=C/C=C PZWQOGNTADJZGH-SNAWJCMRSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 239000004605 External Lubricant Substances 0.000 description 3
- 239000004697 Polyetherimide Substances 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000005250 alkyl acrylate group Chemical group 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000010425 asbestos Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 3
- 229910002113 barium titanate Inorganic materials 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- QHZOMAXECYYXGP-UHFFFAOYSA-N ethene;prop-2-enoic acid Chemical class C=C.OC(=O)C=C QHZOMAXECYYXGP-UHFFFAOYSA-N 0.000 description 3
- 229920006228 ethylene acrylate copolymer Polymers 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000010445 mica Substances 0.000 description 3
- 229910052618 mica group Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000011236 particulate material Substances 0.000 description 3
- 229920001601 polyetherimide Polymers 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910052895 riebeckite Inorganic materials 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- FUSNPOOETKRESL-ZPHPHTNESA-N (z)-n-octadecyldocos-13-enamide Chemical compound CCCCCCCCCCCCCCCCCCNC(=O)CCCCCCCCCCC\C=C/CCCCCCCC FUSNPOOETKRESL-ZPHPHTNESA-N 0.000 description 2
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229920004482 WACKER® Polymers 0.000 description 2
- NXDJCCBHUGWQPG-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol;terephthalic acid Chemical compound OCC1CCC(CO)CC1.OC(=O)C1=CC=C(C(O)=O)C=C1 NXDJCCBHUGWQPG-UHFFFAOYSA-N 0.000 description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001408 amides Chemical group 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 229920003020 cross-linked polyethylene Polymers 0.000 description 2
- 239000004703 cross-linked polyethylene Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000004811 fluoropolymer Substances 0.000 description 2
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- 235000013305 food Nutrition 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
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- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 235000012254 magnesium hydroxide Nutrition 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- 150000002924 oxiranes Chemical class 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 239000002952 polymeric resin Substances 0.000 description 2
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- 239000004800 polyvinyl chloride Substances 0.000 description 2
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 2
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
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- LLVWLCAZSOLOTF-UHFFFAOYSA-N 1-methyl-4-[1,4,4-tris(4-methylphenyl)buta-1,3-dienyl]benzene Chemical compound C1=CC(C)=CC=C1C(C=1C=CC(C)=CC=1)=CC=C(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 LLVWLCAZSOLOTF-UHFFFAOYSA-N 0.000 description 1
- 229940114072 12-hydroxystearic acid Drugs 0.000 description 1
- VSIKJPJINIDELZ-UHFFFAOYSA-N 2,2,4,4,6,6,8,8-octakis-phenyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound O1[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si]1(C=1C=CC=CC=1)C1=CC=CC=C1 VSIKJPJINIDELZ-UHFFFAOYSA-N 0.000 description 1
- BVHIXHQSARSQAH-UHFFFAOYSA-N 2,2,4-trimethyl-4,6,6-triphenyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C1(=CC=CC=C1)[Si]1(O[Si](O[Si](O[SiH2]O1)(C)C)(C)C1=CC=CC=C1)C1=CC=CC=C1 BVHIXHQSARSQAH-UHFFFAOYSA-N 0.000 description 1
- IRVZFACCNZRHSJ-UHFFFAOYSA-N 2,4,6,8-tetramethyl-2,4,6,8-tetraphenyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound O1[Si](C)(C=2C=CC=CC=2)O[Si](C)(C=2C=CC=CC=2)O[Si](C)(C=2C=CC=CC=2)O[Si]1(C)C1=CC=CC=C1 IRVZFACCNZRHSJ-UHFFFAOYSA-N 0.000 description 1
- FDSYTWVNUJTPMA-UHFFFAOYSA-N 2-[3,9-bis(carboxymethyl)-3,6,9,15-tetrazabicyclo[9.3.1]pentadeca-1(15),11,13-trien-6-yl]acetic acid Chemical compound C1N(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC2=CC=CC1=N2 FDSYTWVNUJTPMA-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- OKTJSMMVPCPJKN-NJFSPNSNSA-N Carbon-14 Chemical compound [14C] OKTJSMMVPCPJKN-NJFSPNSNSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
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- 239000004287 Dehydroacetic acid Substances 0.000 description 1
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- 239000004594 Masterbatch (MB) Substances 0.000 description 1
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- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- ULBTUVJTXULMLP-UHFFFAOYSA-N butyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCCC ULBTUVJTXULMLP-UHFFFAOYSA-N 0.000 description 1
- 239000004295 calcium sulphite Substances 0.000 description 1
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- 239000001569 carbon dioxide Substances 0.000 description 1
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- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- HDERJYVLTPVNRI-UHFFFAOYSA-N ethene;ethenyl acetate Chemical group C=C.CC(=O)OC=C HDERJYVLTPVNRI-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000000216 gellan gum Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- YQEMORVAKMFKLG-UHFFFAOYSA-N glycerine monostearate Natural products CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 description 1
- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
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- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
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- 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 1
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
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- CPXCDEMFNPKOEF-UHFFFAOYSA-N methyl 3-methylbenzoate Chemical compound COC(=O)C1=CC=CC(C)=C1 CPXCDEMFNPKOEF-UHFFFAOYSA-N 0.000 description 1
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- 238000000465 moulding Methods 0.000 description 1
- VMRGZRVLZQSNHC-ZCXUNETKSA-N n-[(z)-octadec-9-enyl]hexadecanamide Chemical compound CCCCCCCCCCCCCCCC(=O)NCCCCCCCC\C=C/CCCCCCCC VMRGZRVLZQSNHC-ZCXUNETKSA-N 0.000 description 1
- 239000012802 nanoclay Substances 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
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- 239000005022 packaging material Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
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- 229920013716 polyethylene resin Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
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- 150000004760 silicates Chemical class 0.000 description 1
- 235000014214 soft drink Nutrition 0.000 description 1
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- TUNFSRHWOTWDNC-UHFFFAOYSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63H—TOYS, e.g. TOPS, DOLLS, HOOPS OR BUILDING BLOCKS
- A63H33/00—Other toys
- A63H33/04—Building blocks, strips, or similar building parts
- A63H33/06—Building blocks, strips, or similar building parts to be assembled without the use of additional elements
- A63H33/08—Building blocks, strips, or similar building parts to be assembled without the use of additional elements provided with complementary holes, grooves, or protuberances, e.g. dovetails
- A63H33/086—Building blocks, strips, or similar building parts to be assembled without the use of additional elements provided with complementary holes, grooves, or protuberances, e.g. dovetails with primary projections fitting by friction in complementary spaces between secondary projections, e.g. sidewalls
Definitions
- the present invention relates to a toy building element made of a polyester material and manufactured by processing of a resin comprising at least one polyester, at least one reactive impact modifier and at least one non-reactive impact modifier.
- the present invention also relates to a method for the manufacture of such toy building element.
- Polyesters are a category of polymers that contain an ester functional group in their main chain. They can be formed from the reaction of a diacid or acid anhydride and a diol with the elimination of water, or by ring-opening polymerization of cyclic (di-)esters. Polyesters are classified as aliphatic, semi aromatic and aromatic according to the composition of their main chain. In general, aromatic acids and diols improve the hardness, rigidity and heat resistance, whereas aliphatic acids and diols increase the flexibility, lower the melting or softening point and improve the processability.
- Common aliphatic diols are ethylene glycol, 1,4-butanediol and 1,3-propanediol. They are often reacted with aromatic diacids, such as terephthalic acid, phthalic acid, phthalic anhydride and naphthalene dicarboxylic acid. Glycerol and unsaturated acids (anhydrides) like maleic anhydride, are sometimes added to crosslink the polyester. In the case of unsaturated acids (anhydrides), crosslinking is achieved in a subsequent free radical chain polymerization. Double bonds in the backbone of the polyesters also improve the resistance to softening and deformation at elevated temperatures.
- Poly(ethylene terephthalate), also referred to as PET, is a common thermoplastic polymer resin. It can be produced by reaction of ethylene glycol and terephthalic acid.
- Today PET is widely used to make containers for food, water and carbonated water and soft drinks and the like due to its excellent combination of mechanical and gas barrier properties.
- the transparent water bottles are manufactured by blow moulding of amorphous PET.
- amorphous PET may be considered a low-cost raw material for the production of engineering compounds due to its widespread availability for example from recycled beverage bottles.
- PET was not originally considered as an injection moulding material because of high moisture sensitivity, poor impact strength and slow rate of crystallization, which slows the moulding process.
- the properties of PET can be modified and enhanced to such an extent that it can be used in industrial production of durable products.
- the slow crystallization rate can be improved by addition of nucleating agents and the poor impact strength can be improved by addition of glass, fibres, mineral or organic reinforcements, such as carbon nanotubes, graphene and graphite, and/or impact modifiers.
- Standard bottle grade PET typically has an intrinsic viscosity in the range of 0.75 to 0.85 dl/g.
- Copolymer modification (acid or glycol modification) has been used to decrease the crystallization rate and to decrease the PET melting temperature, thereby decreasing the energy demand in the production process.
- Standard PET bottle polymers with copolymer modification typically have between 0% and 3 mol% isophthalic acid (IPA) modification in order to reduce the crystallization rate and allow the production of clear amorphous preforms weighing up to 100 grams.
- IPA isophthalic acid
- Poly(ethylene furanoate), also referred to as PEF, is an aromatic thermoplastic polyester that can be easily moulded and thermoformed. It can be produced by polycondensation of ethylene glycol and 2,5-furandicarboxylic acid (FDCA). PEF has many attractive properties including high tensile strength and high puncture toughness, good heat resistance, as well as outstanding gas barrier properties, which are superior to PET. PEF also has a lower melting point and a higher glass transition temperature than PET and thus more attractive thermal and mechanical properties. Information with regard to the impact strength is very sparse.
- PEF is a known analogue to PET, which is capable of replacing PET because its chemical structure is very similar to the chemical structure of PET.
- the studies in recent years have been focused on the use of PEF for use as food and beverage packaging material, because of its better barrier properties, i.e. better ability to withstand gas (oxygen and carbon dioxide) permeability, as compared to PET.
- PEF can be recycled in very similar ways to PET recycling. Preliminary tests have shown that PEF has no material effect on the mechanical and physical properties of PET, such as strength and impact. It is therefore suggested that PEF is likely to be recycled in the PET recycling stream, at least in the transition period following the launch of PEF items on the market. It is considered that up to 2% PEF would be compatible in the existing PET recycling stream, and this upper limit of 2% PEF in the PET recycling stream has actually been granted by the European PET Bottle Platform.
- glycol modified polyethylene terephthalate also referred to as glycol modified polyethylene terephthalate or PETG
- PETG Poly(ethylene glycol-co-l,4-cyclohexanedimethanol terephthalate), also referred to as glycol modified polyethylene terephthalate or PETG
- CHDM 1,4-cyclohexanedimethanol
- glycol modified poly(ethylene terephthalate) copolyester is an amorphous thermoplastic that exhibits a glass transition temperature of about 80 degrees C, which is similar to the glass transition temperature of PET. In some studies, the glass transition temperature of PETG has been reported to be higher than for PET.
- the impact strength of PETG depends on the content of ethylene glycol and 1,4- cyclohexanedimethanol terephthalate, respectively. The higher the content of 1,4- cyclohexanedimethanol terephthalate the higher impact strength.
- Impact modifiers are known to improve the durability and toughness of polymer resins.
- Impact modifiers for PET are generally elastomeric compounds that increase impact strength and elongation while usually decreasing modulus.
- An effective way to enhance the impact strength is by the dispersion of a rubber phase within the PET matrix.
- the main role of the rubber particles is to induce an overall deformation mechanism rather than a localized phenomenon, thereby strongly increasing the amount of dissipated fracture energy.
- the effectiveness of rubber modification depends on the type of rubber, the rubber content, the rubber particle size and the interparticle distance.
- Impact modifiers may be characterized as reactive or non-reactive. Reactive impact modifiers are preferred for toughening of PET since these form a stable dispersed phase by grafting to the PET matrix. Non-reactive elastomers can be dispersed into PET by intensive compounding but may coalesce downstream in the compounder.
- Reactive impact modifiers have functionalized end groups. Functionalization serves two purposes: firstly to bond the impact modifier to the polymer matrix and secondly, to modify the interfacial energy between the polymer matrix and the impact modifier for enhanced dispersion.
- Non-reactive (unfunctionalized) elastomeric impact modifiers are not highly effective at toughening polyesters because they are unable to adequately interact with the polyester matrix so as to achieve optimally sized dispersed phases and strong interfacial bonding.
- Non-reactive impact modifiers may take a unique core shell structure. This structure is obtained by copolymerization of a hard shell around a soft rubber core and since the structure is typically obtained by emulsion copolymerization, it provides a well-defined particle size, which in turn leads to a well-controlled blend morphology.
- the soft rubber-core may be a butadiene core or an acrylic core, whereas the shell may be made of PMMA.
- Polyesters are an interesting material for use in the manufacture of toys, such as toy building elements.
- impact strength needs to be modified in order to satisfy the requirements of product safety and play experience and so that long- lasting toy building bricks can be produced, which do not break when for example dropped on the floor or when stepped on by an adult person.
- the improved impact strength need to be focused on injection moulded objects with complex geometries such as the geometry of a traditional LEGO® brick which has been on the market for many years when produced in conventional materials such as for example ABS.
- the inventors of the present invention have developed a new polyester resin for use in the manufacture of toy building elements, which provides improved impact strength of the manufactured elements.
- the inventors of the present invention have surprisingly found that markedly improved impact strength is obtained when a resin comprising one or more polyester(s), a reactive impact modifier and a non-reactive impact modifier is processed into toy building elements.
- a synergistic effect is observed when processing such polyester resins as compared to polyester resins comprising only the reactive impact modifier or the non-reactive impact modifier.
- the present invention is directed to a toy building element made of a polyester material and manufactured by processing of a resin comprising at least one polyester, at least one reactive impact modifier and at least one non reactive impact modifier, wherein the polyester is a poly(ethylene terephthalate) polyester (PET polyester) or a modified PET polyester, which has been modified by replacing all or parts of the terephthalic acid groups of the PET polyester with a diacid monomer selected from the group consisting of adipic acid, succinic acid, isophthalic acid, furandicarboxylic acid, phthalic acid, 4,4 ' -biphenyl dicarboxylic acid, 2,6-naphthalenedicarboxylic acid and mixtures thereof; and/or all or parts of the ethylene glycol groups of the PET polyester with a diol monomer selected from the group consisting of isosorbide, 1,4- cyclohexanedimethanol, 2,2,4,4-tetramehyl-l,3-cycl
- the present invention is directed to a method for the manufacture of a toy building element comprising the steps of a) providing a resin comprising at least one polyester, at least one reactive impact modifier and at least one non-reactive impact modifier, wherein the polyester is a polyethylene terephthalate) polyester (PET polyester) or a modified PET polyester, which has been modified by replacing all or parts of the terephthalic acid groups of the PET polyester with a diacid monomer selected from the group consisting of adipic acid, succinic acid, isophthalic acid, furandicarboxylic acid, phthalic acid, 4,4 ' -biphenyl dicarboxylic acid, 2,6-naphthalenedicarboxylic acid and mixtures thereof; and/or all or parts of the ethylene glycol groups of the PET polyester with a diol monomer selected from the group consisting of isosorbide, 1,4- cyclohexanedimethanol, 2,2,4,4-tetramehyl
- Figure 1 shows a traditional box-shaped LEGO® 2*4 brick.
- the present invention is directed to a toy building element made of a polyester material and manufactured by processing of a resin comprising at least one polyester, at least one reactive impact modifier and at least one non-reactive impact modifier.
- toy building element includes the traditional toy building elements in the form of box-shaped building bricks provided with knobs on the upper side and complementary tubes on the lower side.
- a traditional box shaped toy building brick is shown in Figure 1.
- the traditional box-shaped toy building bricks were disclosed for the first time in US 3,005,282 and are widely sold under the tradenames LEGO® and LEGO® DUPLO®.
- the term also includes other similar box-shaped building bricks, which are produced by other companies than The LEGO Group and therefore sold under other trademarks than the trademark LEGO.
- toy building element also includes other kinds of toy building elements that form part of a toy building set which typically comprises a plurality of building elements that are compatible with and hence can be interconnected with each other.
- Such toy building sets are also sold under the trademark LEGO, such as for example LEGO® bricks, LEGO® Technic and LEGO® DUPLO®.
- Some of these toy building sets includes toy building figures, such as for example LEGO® Minifigures (see for example US 05/877,800), having complementary tubes on the lower side so that the figure can be connected to other toy building elements in the toy building set.
- Such toy building figures are also encompassed by the term "toy building element”.
- the term also includes similar toy building elements, which are produced by other companies than The LEGO Group and therefore sold under other trademarks than the trademark LEGO.
- LEGO® bricks are available in a large variety of shapes, sizes and colours.
- LEGO® DUPLO® bricks are twice the size of a LEGO® brick in all dimensions.
- the size of the traditional box-shaped LEGO® toy building brick having 4*2 knobs on the upper side is about 3.2 cm in length, about 1.6 cm in width and about 0.96 cm in height (excluding knobs), and the diameter of each knob is about 0.48 cm.
- the size of a LEGO® DUPLO® brick having 4*2 knobs on the upper side is about 6.4 cm in length, about 3.2 cm in width and about 1.92 cm in height (excluding knobs), and the diameter of each knob is about 0.96 cm.
- the toy building elements are manufactured either by injection moulding or by additive manufacturing or by a combination of injection moulding and additive manufacturing.
- Injection moulding of toy building elements is the traditional way of manufacturing toy building bricks. This manufacturing technique has been used for many years and is very well known to a skilled person.
- the toy building element is manufactured by injection moulding of a polyester resin.
- the toy building element is manufactured by two- component injection moulding, where one of the components is a polyester resin.
- additive manufacturing or “additively manufactured” as used herein is meant that the brick is built in an additive fashion, i.e. by adding new material on top of either a substrate or on top of newly added material, by repeated solidification of a thin liquid layer or droplet on a substrate or on a previously solidified liquid layer or droplet, or by repeated printing with a thermoplastic polymeric material on a substrate or on a previously printed plastics material, or by repeated soldering in an additive fashion of plastics material e.g. by use of laser.
- the toy building element is manufactured by injection moulding. In other embodiments the toy building element is manufactured by additive manufacturing. In yet other embodiments the toy building element is manufactured by a combination of injection moulding and additive manufacturing. Such combined manufacturing technique is described for example in WO 2014/005591 where a toy building element with high degree of design individuality is manufactured by adding material in the layer-by-layer fashion on the surface of a traditional injection moulded box-shaped building brick.
- the toy building element is made of a polyester material and manufactured by processing of a resin comprising at least one polyester, at least one reactive impact modifier and at least one non-reactive impact modifier.
- polyester as used herein includes both PET polyesters and modified PET polyesters and mixtures thereof.
- the modified PET polyester has been modified by replacing all or parts of the terephthalic acid groups of the PET polyester with a diacid monomer selected from the group consisting of adipic acid, succinic acid, isophthalic acid, furandicarboxylic acid, phthalic acid, 4,4 ' -biphenyl dicarboxylic acid, 2,6-naphthalenedicarboxylic acid and mixtures thereof; and/or all or parts of the ethylene glycol groups of the PET polyester with a diol monomer selected from the group consisting of isosorbide, 1,4- cyclohexanedimethanol, 2,2,4,4-tetramehyl-l,3-cyclobutanediol, diethylene glycol, 1,2-propanediol, neopentylene glycol, 1,3-propanediol, 1,4 butanedio
- polyester resin as used herein is meant a resin comprising at least one polyester as defined above, at least one reactive impact modifier and at least one non-reactive impact modifier.
- the PET polyester is produced by polymerization of the monomers ethylene glycol and terephthalic acid.
- the modified PET polyester may be produced in three different ways. First of all, the modified PET polyester may be produced by polymerization of the monomers ethylene glycol, terephthalic acid and one or more further comonomer(s), which is/are a diacid monomer and/or a diol monomer thereby producing a diacid modification, a diol modification or a diacid/diol modification.
- the modified PET polyester may be produced by polymerization of the monomer ethylene glycol and one or more further comonomer(s), which is/are one or more diacid monomer(s) and optionally one or more diol monomer(s).
- the modified PET polyester may be produced by polymerization of the monomer terephthalic acid and one or more further comonomer(s), which is/are one or more diol monomer(s) and optionally one or more diacid monomer(s).
- the diacid monomer is selected from the group consisting of adipic acid, succinic acid, isophthalic acid, furandicarboxylic acid, phthalic acid, 4,4 ' -biphenyl dicarboxylic acid, 2,6-naphthalenedicarboxylic acid and mixtures thereof and the diol monomer is selected from the group consisting of isosorbide, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramehyl-l,3- cyclobutanediol, diethylene glycol, 1,2-propanediol, neopentylene glycol, 1,3- propanediol, 1,4 butanediol and mixtures thereof.
- the resin comprises PET polyester.
- the PET polyester is produced by reaction of ethylene glycol and terephthalic acid.
- the polyester is PET polyester.
- the resin comprises a modified PET polyester, which has been produced by reaction of ethylene glycol and terephthalic acid and the comonomer 1,4-cyclohexanedimethanol.
- the resin comprises a modified PET polyester, which has been produced by reaction of ethylene glycol and terephthalic acid and the comonomer isophthalic acid.
- the resin comprises a modified PET polyester which has been produced by reaction of ethylene glycol and terephthalic acid and the comonomer 2,2,4,4-tetramehyl-l,3-cyclobutanediol.
- the resin comprises a modified PET polyester which has been produced by reaction of terephthalic acid and 1,4-cyclohexanedimethanol. In yet other embodiments the resin comprises a modified PET polyester, which has been produced by reaction of terephthalic acid, isophthalic acid and 1,4-cyclohexanedimethanol. In other embodiments the resin comprises a modified PET polyester, which has been produced by reaction of ethylene glycol, terephthalic acid, and 2,5- furandicarboxylic acid.
- the resin comprises poly(ethylene terephthalate-co- isophthalate) polyester.
- the poly(ethylene terephthalate-co-isophthalate) polyester is produced by reaction of ethylene glycol, terephthalic acid and isophthalic acid.
- the polyester in the resin is a modified PET polyester, which is polyethylene terephthalate-co-isophthalate) polyesters.
- the amount of isophthalic acid in the poly(ethylene terephthalate-co- isophthalate) polyesters is typically 0.5-12 mol% and preferably 1-3 mol%.
- the chemical composition of poly(ethylene terephthalate-co-isophthalate) polyesters i.e. the amount of isophthalic acid in the poly(terephthalate-co- isophthalate) polyester, may be characterised by 13C Nuclear Magnetic Resonance spectroscopy (C NMR) according to the method described in "Martinez de Ilarduya, A.; Kint, D. P.; Muhoz-Guerra, S. Sequence Analysis of Poly (ethylene terephthalate-co-isophthalate) Copolymers by 13C NMR. Macromolecules 2000 33, 4596-4598". Accordingly, the amount of isophthalic acid may be measured using this C NMR method.
- C NMR Nuclear Magnetic Resonance spectroscopy
- the intrinsic viscosity which is measured in dl/g, is found by extrapolating the relative viscosity to zero concentration. It depends on the length of the PET polymer chains. The longer the polymer chains the more entanglements between chains and therefore the higher the viscosity. The average length of a particular batch of PET resin can be controlled during the polymerization process.
- the PET Intrinsic Viscosity (IV) may be measured according to ASTM D4603.
- High IV homo- and copolymer PET compositions are difficult to process in injection moulding due to their high viscosity.
- the IV of the PET polyester ranges from 0.6-1.1 dl/g, such as 0.7-0.9 dl/g, preferably from 0.75-0.85 dl/g.
- the modified PET polyester is PET of bottle grade.
- bottle grade is well known in the technical area and refers to PET starting materials that can easily be processed into bottles.
- the "bottle grade" PET is made of polyethylene terephthalate-co-isophthalate) polyesters comprising 1-3 mol% of isophthalic acid.
- the IV is typically in the range of 0.70-0.78 dl/g for non-carbonated water, and in the range of 0.78-0.85 for carbonated water.
- PET grades which are also commercial available include bottle grade EASTLON PET CB-600, CB-602 and CB-608 supplied by Far Eastern New Century (FENC), commercial grade post-consumer rPET CB-602R supplied by FENC, partially bio-based bottle grade PET CB-602AB supplied by FENC and homopolymer PET grade 6020 supplied by Invista.
- FENC Far Eastern New Century
- FENC commercial grade post-consumer rPET CB-602R supplied by FENC
- partially bio-based bottle grade PET CB-602AB supplied by FENC and homopolymer PET grade 6020 supplied by Invista.
- the resin comprises a modified PET polyester, which has been produced by reaction of ethylene glycol and terephthalic acid and the comonomer 1,4-cyclohexanedimethanol.
- the resin comprises poly(ethylene glycol-co-l,4-cyclohexanedimethanol terephthalate) polyesters, also referred to as glycol modified polyethylene terephthalate or PETG.
- the polyester is a modified PET polyester, which is PETG.
- the amount of 1,4-cyclohexanedimethanol in the PETG is typically 0.1-25 mol%.
- the resin comprises ethylene glycol modified poly(cyclohexylenedimethylene terephthalate) also referred to as PCTG.
- the polyester is a modified PET polyester, which is PETG.
- the amount of 1,4-cyclohexanedimethanol in the PETG is typically 25-49.99 rmol%.
- the resin comprises a modified PET polyester which has been produced by reaction of ethylene glycol and terephthalic acid and the comonomer 2,2,4,4-tetramehyl-l,3-cyclobutanediol.
- the resin comprises poly(ethylene glycol-co-2,2,4,4-tetramethyl-l,3-cyclobutanediol terephthalate) also referred to as PETT.
- the resin comprises a modified PET polyester which has been produced by reaction of terephthalic acid and 1,4-cyclohexanedimethanol.
- the resin comprises poly(cyclohexanedimethylene terephthalate) also referred to as PCT.
- the resin comprises a modified PET polyester, which has been produced by reaction of terephthalic acid, isophthalic acid and 1,4- cyclohexanedimethanol.
- the resin comprises isophthalic acid modified poly(cyclohexanedimethylene terephthalate) also referred to as PCTA.
- the amount of isophthalic acid is typically 0.1-50 mol%, more typically 0.1- 5 mol%.
- the resin comprises poly(ethylene furanoate-co-ethylene terephthalate) polyester.
- the poly(ethylene furanoate-co-ethylene terephthalate) polyester is produced by reaction of ethylene glycol, terephthalic acid and 2,5- furandicarboxylic acid.
- the amount of 2,5-furandicarboxylic acid in the modified PET polyester is typically 0.5-12 mol% and preferably 1-3 mol%.
- the resin comprises polyethylene furanoate) polyester, also referred to as PEF.
- the poly(ethylene furanoate) polyester is produced by reaction of ethylene glycol and furandicarboxylic acid.
- the polyester is a modified PET polyester, which is PEF.
- the resin comprises a mixture of poly(ethylene terephthalate) polyester and poly(ethylene furanoate) polyester. In other embodiments the resin comprises a mixture of poly(ethylene terephthalate-co- isophthalate) polyester and poly(ethylene furanoate) polyester. In yet other embodiments the resin comprises a mixture of poly(ethylene terephthalate) polyester, poly(ethylene terephthalate-co-isophthalate) polyester and poly(ethylene furanoate) polyester. In any of these mixtures the amount of poly(ethylene furanoate) polyester is typically 0.1-10% (wt/wt), such as for example 0.1-5% (wt/wt) or 0.1-2% (wt/wt) based on total amount of polyesters.
- the polyester resin is an unfilled polyester resin.
- unfilled polyester resin as used herein is meant a polyester resin which does not comprise reinforcing and filling material, such as glass, glass beads, fibres, mineral reinforcements, such as aluminum silicate, talc, asbestos, mica and calcium carbonate, and organic reinforcements, such as aramid fibres, carbon nanotubes, graphene and graphite.
- reinforcing and filling material such as glass, glass beads, fibres, mineral reinforcements, such as aluminum silicate, talc, asbestos, mica and calcium carbonate, and organic reinforcements, such as aramid fibres, carbon nanotubes, graphene and graphite.
- the polyester resin does not contain glass, glass beads and/or glass fibres. In one embodiment the polyester resin does not contain fibres. In one embodiment the polyester resin does not contain inorganic reinforcements, such as aluminum silicate, asbestos, talc, mica and calcium carbonate. In one embodiment the polyester resin does not contain organic reinforcements, such as aramid fibres, carbon nanotubes, graphene and graphite. In one embodiment the polyester resin does not contain glass and fibres.
- the polyester resin further comprises one or more filler(s) in an amount of up to 5% (wt/wt) relative to the total weight of the resin, such as from 0.1-5% (wt/wt), more preferred from 0.2-4% (wt/wt), most preferred from 0.5-3% (wt/wt).
- the one or more filler(s) may be inorganic particulate material or a nanocomposite or a mixture thereof.
- inorganic particulate material examples include inorganic oxides, such as glass, MgO, Si02, Ti02 and Sb203; hydroxides, such as AI(OH)3 and Mg(OH)2; salts, such as CaC03, BaS04, CaS04 and phosphates; silicates, such as talc, mica, kaolin, wollastonite, montmorillonite, nanoclay, feldspar and asbestos; metals, such as boron and steel; carbon - graphite, such as carbon fibers, graphite fibers and flakes, carbon nanotubes and carbon black.
- inorganic oxides such as glass, MgO, Si02, Ti02 and Sb203
- hydroxides such as AI(OH)3 and Mg(OH)2
- salts such as CaC03, BaS04, CaS04 and phosphates
- silicates such as talc, mica, kaolin, wollastonite, montmorillonite, nanoclay, feld
- Suitable examples of inorganic particulate material also include surface treated and/or surface modified Si02 and Ti02, such as for example alumina surface modified Ti02.
- Suitable examples of nanocomposites include clay filled polymers, such as clay/low density polyethylene (LDPE) nanocomposites, clay/high density polyethylene (HDPE) nanocomposites, acrylonitrile-butadiene-styrene (ABS)/clay nanocomposites, polyimide (PI)/clay nanocomposites, epoxy/clay nanocomposites, polypropylene (PP)/clay nanocomposites, poly (methyl methacrylate) (PMMA)/clay nanocomposites and polyvinyl chloride (PVC)/clay nanocomposites; alumina filled polymers, such as epoxy/alumina nanocomposites, PMMA/alumina nanocomposites, PI/alumina nanocomposites, PP/alumina nanocomposites, LDPE/alumina nanocomposites and cross-linked polyethylene (
- the resin comprises polyester in an amount of at least 50% (wt/wt) relative to the total weight of the resin. In other embodiments the resin comprises polyester in an amount of at least 60% or 70% or 80% (wt/wt) relative to the total weight of the resin. In preferred embodiments the resin comprises polyester in an amount of at least 85%, such as at least 90% (wt/wt) relative to the total weight of the resin, more preferred at least 95% or 97% or 99% (wt/wt) relative to the total weight of the resin.
- the resin comprises polyester in an amount of 50-99.5% (wt/wt) relative to the total weight of the resin. In other embodiments the resin comprises polyester in an amount of 60-97% or 70-95% (wt/wt) relative to the total weight of the resin. In a preferred embodiment the resin comprises polyester in an amount of 75-95%, more preferred 77-92%, even more preferred 80-90% (wt/wt) relative to the total weight of the resin.
- the polyester in the resin may be a bio-based polymer, a hybrid bio-based polymer or a petroleum-based polymer, or a mixture thereof.
- bio-based polymer as used herein is meant a polymer, which is produced by chemical, or biochemical polymerization of monomers derived from biomass.
- Bio-based polymers include polymers produced by polymerization of one type of monomer derived from biomass as well as polymers produced by polymerization of at least two different monomers derived from biomass.
- bio-based polymer is produced by chemical or biochemical polymerization of monomers, which are all derived from biomass.
- Bio-based polymers according to the present invention include
- Polymers produced by biochemical polymerization i.e. for example by use of microorganisms.
- the monomers are produced using biomass as substrate.
- the monomers are produced using biomass as substrate.
- the bio-based polymer is produced by biochemical polymerization. In other embodiments the bio-based polymer is produced by chemical polymerization. In yet other embodiments the bio-based polymers are produced by biochemical or chemical polymerization.
- the bio-based polymer may also be produced by a combination of biochemical and chemical polymerization, for example in cases where two monomers are combined to a dimer by a biochemical reaction path and then the dimers are polymerized by use of chemical reaction.
- Bio-based polymers also include polymers having the same molecular structure as petroleum-based polymers, but which have been produced by chemical and/or biochemical polymerization of monomers derived from biomass.
- petroleum-based polymers as used herein is meant a polymer produced by chemical polymerization of monomers derived from petroleum, petroleum by-products or petroleum-derived feedstocks.
- hybrid bio-based polymer as used herein is meant a polymer, which is produced by polymerization of at least two different monomers, where at least one monomer is derived from biomass and at least one monomer is derived from petroleum, petroleum by-products or petroleum-derived feedstocks.
- the polymerization process is typically a chemical polymerization process.
- the hybrid bio-based polymers may also be characterized by their content of bio based carbon per total carbon content.
- bio-based carbon refers to the carbon atoms that originate from the biomass that is used as substrate in the production of monomers, which form part of the bio-based polymers and/or the hybrid bio-based polymers.
- the content of bio-based carbon in the hybrid bio-based polymer can be determined by Carbon-14 isotope content as specified in ASTM D6866 or CEN/TS 16137 or an equivalent protocol.
- the content of bio-based carbon in the hybrid bio-based polymer is at least 25% based on the total carbon content of the hybrid bio-based polymer, such as for example at least 30% or at least 40%. In other embodiments the content of bio-based carbon in the hybrid bio-based polymer is at least 50% based on the total carbon content, such as at least 60% for example at least 70%, such as at least 80% based on the total carbon content of the hybrid bio-based polymer.
- the ethylene glycol monomers and/or the diol monomers are bio-based monomers whereas the terephthalic acid monomers and/or the diacid monomers are not bio-based monomers, such as for example petroleum-based monomers.
- the terephthalic acid monomers and/or the diacid monomers are bio-based monomers whereas the ethylene glycol monomers and/or the diol monomers are not bio-based monomers.
- the ethylene glycol monomers and/or the diol monomers and the terephthalic acid monomers and/or the diacid monomers are bio-based monomers.
- neither the ethylene glycol monomers nor the diol monomers nor the terephthalic acid monomers nor the diacid monomers are bio-based monomers.
- the ethylene glycol monomers and/or the diol monomers are bio-based monomers derived from biomass and having a content of bio-based carbon equal to 100% based on the total carbon content in the ethylene glycol monomers and/or diol monomers.
- the ethylene glycol monomers and/or diol monomers have a content of bio-based carbon of at least 25% based on the total carbon content in the ethylene glycol monomers and/or diol monomers, such as for example at least 50%, preferably at least 70%, more preferred at least 90% and most preferred at least 95%.
- the terephthalic acid monomers and/or diacid monomers are bio-based monomers derived from biomass and having a content of bio-based carbon equal to 100% based on the total carbon content in the terephthalic acid monomers and/or diacid monomers.
- the terephthalic acid monomers and/or diacid monomers have a content of bio-based carbon of at least 25% based on the total carbon content in the terephthalic acid monomers and/or diacid monomers, such as for example at least 50%, preferably at least 70%, more preferred at least 90% and most preferred at least 95%.
- the content of bio-based carbon in the polyester is at least 25% based on the total carbon content in the polyester. In other embodiments the content of bio-based carbon in the polyester is at least 50% based on the total carbon content, such as at least 60% for example at least 70%, preferably at least 80%, more preferably at least 90%, even more preferably at least 95%. In the most preferred embodiment the content of bio-based carbon in the polyester is 100% based on the total carbon content in the polyester.
- the content of bio-based carbon in the resin is at least 25% based on the total carbon content in the resin. In other embodiments the content of bio-based carbon in the resin is at least 50% based on the total carbon content in the resin, such as at least 60% for example at least 70%, preferably at least 75%, more preferably at least 80%, even more preferably at least 85%. In the most preferred embodiment the content of bio-based carbon in the resin is 90% based on the total carbon content in the resin.
- bio-based polymer also include recycled polymers and recycled material comprising "bio-based polymer”, “hybrid bio-based polymer” and “petroleum-based polymer”.
- recycled material refers to a material, which is obtained by processing of a resin comprising recycled polymers.
- the recycled polymers are obtained from waste materials.
- the waste material can be mechanically recycled material or chemically recycled material.
- Mechanical recycled material refers to material which has been recovered by mechanically recycling of material. Mechanical recycling involves only mechanical processes, such as for example grinding, washing, separating, drying, re granulating and compounding. In a typical recycling process, the waste material is collected and washed in order to remove contaminants. The cleaned plastic is then grinded into flakes, which can be compounded and pelletized or reprocessed into granulate.
- “Chemically recycled material” includes materials which has been obtained by pyrolysis, chemical depolymerisation, solvent dissolution or any other suitable chemical recycling process.
- Polyrolysis refers to breakdown of the material to crude oil at elevated temperature in the absence of oxygen. New virgin-like polymers can then be made from the resulting oil by known polymerization processes.
- “Chemical depolymerisation” refers to the process of breaking down of a polymer into either monomers, mixtures of monomers or intermediates thereof using a chemical agent. New virgin-like polymers can be produced by polymerization of the monomers.
- solvent dissolution refers to the selective extraction of polymers using solvents.
- the extracted polymers are recovered by precipitation of the polymer or by evaporation of the solvent.
- the polymer chain and structure is not broken down.
- recycled polymer refers to the polymer comprised in the mechanically recycled waste material or the polymer, which is chemically recovered from the waste material in the solvent dissolution process.
- virgin-like polymer which is produced in the pyrolysis recycling process or the chemical depolymerisation recycling process.
- virgin-like polymers then it also includes polymers where only one or two of the monomers have been recycled by pyrolysis or chemical depolymerisation.
- the resin comprises mechanically recycled polyesters.
- the resin comprises mechanically recycled polyesters and biobased polyesters.
- the resin comprises mechanically recycled polyesters and hybrid bio-based polyesters.
- the resin comprises mechanically recycled polyesters and petroleum-based polyesters. In still other embodiments the resin comprises mechanically recycled polyesters, bio-based polyesters and petroleum-based polyesters. In still other embodiments the resin comprises mechanically recycled polyesters, hybrid biobased polyesters and petroleum-based polyesters. In yet other embodiments the resin comprises mechanically recycled polyesters, bio-based polyesters and hybrid bio-based polyesters. And in other embodiments the resin comprises mechanically recycled polyesters, bio-based polyesters, hybrid bio-based polyesters and petroleum-based polyesters.
- the amount of mechanically recycled polyester in the resin is at least 10% (wt/wt) based on the total weight of the resin, such as at least 20%, or for example at least 30%, such as at least 40% or for example at least 50%. In other embodiments, the amount of mechanically recycled polyester in the resin is at least 60% (wt/wt) based on the total weight of the resin, such as at least 70%, or for example at least 75%, such as at least 80% or for example at least 85%.
- the polyester comprises chemically recycled monomers. In other embodiments the polyester comprises chemically recycled monomers and bio-based monomers. In other embodiments the polyester comprises chemically recycled monomers and hybrid bio-based monomers. In yet other embodiments the polyester comprises chemically recycled monomers and petroleum-based monomers. In still other embodiments the polyester comprises chemically recycled monomers, bio-based monomers and petroleum-based monomers. In still other embodiments the polyester comprises chemically recycled monomers, hybrid bio-based monomers and petroleum-based monomers. In yet other embodiments the polyester comprises chemically recycled monomers, bio-based monomers and hybrid bio-based monomers. And in other embodiments the polyester comprises chemically recycled monomers, bio-based monomers, hybrid bio-based monomers and petroleum-based monomers.
- the amount of chemically recycled monomers in the polyester is at least 10% (wt/wt) based on the total weight of the polyester, such as at least 20%, or for example at least 30%, such as at least 40% or for example at least 50%. In other embodiments, the amount of chemically recycled monomers in the polyester is at least 60% (wt/wt) based on the total weight of the polyester, such as at least 70%, or for example at least 80%, such as at least 90% or for example at least 95%.
- the resin comprises a mixture of recycled poly(ethylene terephthalate) polyester and recycled polyethylene furanoate) polyester. In other embodiments the resin comprises a mixture of recycled poly(ethylene terephthalate-co-isophthalate) polyester and recycled polyethylene furanoate) polyester. In yet other embodiments the resin comprises a mixture of recycled poly(ethylene terephthalate) polyester, recycled poly(ethylene terephthalate-co- isophthalate) polyester and recycled poly(ethylene furanoate) polyester.
- the polyester resin comprises at least one reactive impact modifier and at least one non-reactive impact modifier.
- impact modifier an agent that increases the impact strength of the produced toy building element.
- the impact strength is measured using the Charpy v-notch test as defined below.
- reactive impact modifier an impact modifier having functionalized end groups. These functionalized end groups serve two purposes: 1) to bond the impact modifier to the polymer matrix and 2) to modify the interfacial energy between the polymer matrix and the impact modifier for enhanced dispersion.
- functionalized end groups include glycidyl methacrylates, maleic anhydrides and carboxylic acids.
- the reactive impact modifier is a copolymer of the formula X/Y/Z where X is aliphatic or aromatic hydrocarbon polymer having 2-8 carbon atoms, Y is a moiety comprising an acrylate or methacrylate having 3-6 and 4-8 carbon atoms, respectively, and Z is a moiety comprising methacrylic acid, glycidyl methacrylate, maleic anhydride or carboxylic acid.
- the reactive impact modifier may be described by the formula : where n is an integer from 1 to 4, m is an integer from 0 to 5, k is an integer from 0 to 5, and R is an alkyl of 1 to 5 carbon or 1 hydrogen atom.
- X constitutes 40-90% (wt/wt) of the impact modifier
- Y constitutes 0-50% (wt/wt), such as 10-40% (wt/wt), preferably 15-35% (wt/wt), most preferably 20-35% (wt/wt) of the impact modifier
- Z constitutes 0.5-20% (wt/wt), preferably 2-10% (wt/wt), most preferably 3-8% (wt/wt) of the reactive impact modifier.
- X constitutes 70-99.5% (wt/wt) of the reactive impact modifier, preferably 80-95% (wt/wt), most preferably 92-97% (wt/wt) and Y constitutes 0% (wt/wt) of the impact modifier, and Z constitutes 0.5-30%
- Suitable examples of specific reactive impact modifiers that can be used in the resin of the present invention include ethylene-ethylene acrylate-glycidyl methacrylate and ethylene-butyl acrylate-glycidyl methacrylate.
- Commercial available impact modifiers include ParaloidTM EXM-2314 (an acrylic copolymer from Dow Chemical Company), Lotader® AX8700, Lotader® AX8900, Lotader AX8750®, Lotader® AX8950 and Lotader® AX8840 (manufactured by Arkema) and Elvaloy® PTW (manufactured by DuPont).
- Suitable examples of specific reactive impact modifiers that can be used in the resin of the present invention include anhydride modified ethylene acrylates.
- Commercial available impact modifiers include Lotader® 3210, Lotader® 3410, Lotader® 4210, Lotader® 3430, Lotader® 4402, Lotader® 4503, Lotader® 4613, Lotader® 4700, Lotader® 5500, Lotader® 6200, Lotader® 8200, Lotader® HX8210, Lotader® HX8290, Lotader® LX4110, Lotader® TX8030 (manufactured by Arkema), Bynel® 21E533, Bynel® 21E781, Bynel® 21E810 and Bynel® 21E830 (manufactured by DuPont).
- the reactive impact modifier is a modified ethylene vinyl acetate, such as for example Bynel® 1123 or Bynel® 1124 (manufactured by DuPont), an acid modified ethylene acrylate, such as for example Bynel® 2002 or Bynel® 2022 (manufactured by DuPont), a modified ethylene acrylate, such as for example Bynel® 22E757, Bynel® 22E780 or Bynel® 22E804 (manufactured by DuPont), an anhydride modified ethylene vinyl acetate, such as for example Bynel® 30E670, Bynel® 30E671, Bynel® 30E753 or Bynel® 30E783 (manufactured by DuPont), and acid/acrylate modified ethylene vinyl acetate, such as for example Bynel® 3101 or Bynel® 3126 (manufactured by DuPont), an anhydride modified ethylene vinyl a
- Suitable reactive impact modifiers include maleic anhydride grafted impact modifiers.
- reactive impact modifiers include chemically modified ethylene acrylate copolymers, such as Fusabond® A560 (manufactured by DuPont), an anhydride modified polyethylene, such as Fusabond® E158 (manufactured by DuPont), an anhydride modified polyethylene resin, such as for example Fusabond® E564 or Fusabond® E589 or Fusabond® E226 or Fusabond® E528 (manufactured by DuPont), an anhydride modified high density polyethylene, such as for example Fusabond ® E100 or Fusabond ® E265 (manufactured by DuPont), an anhydride modified ethylene copolymer, such as for example Fusabond ® N525 (manufactured by DuPont), or a chemically modified propylene copolymer, such as for example Fusabond ® E353
- ethylene-acid copolymer resins such as ethylene-methacrylic acid (EMAA) based copolymers and ethylene- acrylic acid (EAA) based copolymers.
- EAA ethylene-methacrylic acid
- Specific examples of ethylene-methacrylic acid based copolymer impact modifiers include Nucrel® 403, Nucrel® 407FIS, Nucrel® 411HS, Nucrel® 0609FISA, Nucrel® 0903, Nucrel® 0903FIC, Nucrel® 908FIS, Nucrel® 910, Nucrel® 910FIS, Nucrel® 1202FIC, Nucrel® 599, Nucrel® 699, Nucrel® 925 and Nucrel® 960 (manufactured by DuPont).
- ethylene-acrylic acid based copolymers Nucrel® 30707, Nucrel® 30907, Nucrel® 31001, Nucrel® 3990 and Nucrel® AE (manufactured by DuPont).
- Other specific examples of ethylene of ethylene-acrylic acid (EAA) based copolymers include EscorTM 5000, EscorTM 5020, EscorTM 5050, EscorTM 5080, EscorTM 5100, EscorTM 5200 and EscorTM 6000 (manufactured by ExonMobile Chemical).
- Still other suitable reactive impact modifiers include ionomers of ethylene acid copolymers.
- Specific examples of such impact modifiers include Surlyn® 1601, Surlyn® 1601-2, Surlyn® 1601-2LM, Surlyn® 1605, Surlyn® 8150, Surlyn® 8320, Surlyn® 8528 and Surlyn® 8660 (manufactured by DuPont).
- the reactive impact modifier is an alkyl methacrylate- silicone/alkyl acrylate graft copolymer.
- the "alkyl methacrylate” of the graft copolymer may be one selected from the group consisting of methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate and butyl methacrylate.
- the "silicone/alkyl acrylate” in the graft copolymer refers to a polymer obtained by polymerizing a mixture of a silicone monomer and an alkyl acrylate monomer.
- the silicone monomer may be selected from the group consisting of dimethylsiloxane, hexamethylcyclotrisiloxane, octamethylcyclo- tetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotetrasiloxane, tetramethyltetraphenylcyclotetrasiloxane and octaphenylcyclotetrasiloxane.
- the alkyl monomer may be selected from the group consisting of methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate and butyl methacrylate.
- the graft copolymer is in the form of core-shell rubber and has a graft rate of 5 to 90% (wt/wt), a glass transition temperature of the core of -150 to -20 degrees C, and a glass transition temperature of the shell of 20 to 200 degrees C.
- the graft copolymer is methyl methacrylate- silicone/butyl acrylate graft copolymer. Specific examples include S-2001, S-2100, S-2200 and S-2501 manufactured by Mitsubishi Rayon Co., Ltd. In Japan.
- Suitable reactive impact modifiers include the siloxane polymers mentioned in US 4,616,064, which contain siloxane units, and at least one of carbonate, urethane or amide units.
- Suitable reactive and non-reactive impact modifiers also include those mentioned in WO 2018/089573 paragraphs [0043]-[0072],
- non-reactive impact modifier an impact modifier, which does not have functionalized end groups and therefore cannot form covalent chemical bonds with the polymer matrix.
- the non-reactive impact modifiers are typically dispersed into the polymer matrix by intensive compounding but may coalesce downstream in the compounder.
- Non-reactive impact modifiers may take a unique core-shell structure. This structure is obtained by copolymerization of a hard shell around a soft rubber core and since the structure is typically obtained by emulsion copolymerization, it provides a well-defined particle size, which in turn leads to a well-controlled blend morphology.
- Suitable examples of non-reactive core-shell impact modifiers include those mentioned in US 5,409,967, i.e.
- core-shell impact modifiers with a core comprised mainly of a rubbery core polymer such as a copolymer containing a diolefin, preferably a 1,3-diene, and a shell polymer comprised mainly of a vinyl aromatic monomer, such as styrene, and hydroxylalkyl (meth)acrylate or, in the alternative, another functional monomer which acts in a manner similar to the hydroxylalkyl (meth)acrylate.
- a soft rubber-core such as for example a butadiene core, an acrylic core or a silicone-acrylic core, and a shell made of polymethyl (methacrylate) (PMMA).
- the reactive impact modifier has a functionalized end group, which is selected from the group consisting of glycidyl methacrylate, maleic anhydride and carboxylic acid.
- the functionalized group of the reactive impact modifier is glycidyl methacrylate.
- the reactive impact modifier has a functionalized end group, which is selected from the group consisting of glycidyl methacrylate, maleic anhydride and carboxylic acid, and the non-reactive impact modifier is a core shell impact modifier.
- the reactive impact modifier has a functionalized end group, which is glycidyl methacrylate, and the non-reactive impact modifier is a core shell impact modifier.
- the non-reactive impact modifier is a core shell impact modifier.
- the non-reactive impact modifier is a core shell impact modifier with a butadiene core, an acrylic core or a silicone-acrylic core, and a shell made of polymethyl (methacrylate) (PMMA).
- the reactive impact modifier has a functionalized end group, which is selected from the group consisting of glycidyl methacrylate, maleic anhydride and carboxylic acid, and the non-reactive impact modifier is an ethylene-acrylate co-polymer.
- the reactive impact modifier has a functionalized end group, which is glycidyl methacrylate, and the non-reactive impact modifier is an ethylene-acrylate co-polymer.
- the amount of reactive impact modifier in the polyester resin is 0.25-10% (wt/wt) based on the total weight of the resin. In preferred embodiments the amount of reactive impact modifier in the polyester resin is 0.5- 5% (wt/wt) based on the total weight of the resin, such as 1-3% (wt/wt) based on the total weight of the resin.
- the amount of non-reactive impact modifier in the polyester resin is 0.25-15% (wt/wt) based on the total weight of the resin. In preferred embodiments the amount of non-reactive impact modifier in the polyester resin is 0.5-10% (wt/wt) based on the total weight of the resin, such as 1-3% (wt/wt) based on the total weight of the resin.
- the total amount of impact modifier in the polyester resin is 0.5-25% (wt/wt) based on the total weight of the resin. In some embodiments the total amount of impact modifiers is 2-15% (wt/wt), such as 2-5% (wt/wt) or 5-8% (wt/wt) or 8-12% (wt/wt) based on the total weight of the resin.
- the resin may in addition to fillers and impact modifiers further comprise lubricants.
- Lubricants are typically added to the resin in order to improve the processability and demoulding performance of the resin and prevent damage to the injection moulding equipment by reducing friction (external lubricants) and by reducing viscosity and heat dissipation (internal lubricants).
- External lubricants migrate to the interface between the molten resin and the surface of the processing equipment and reduce friction during processing, reduce the resin's adhesion to the surface of the mould and prevent melt fracture.
- external lubricants reduce the coefficient of friction and often improve the scratch resistance of the moulded parts.
- Internal lubricants promote the flow of the resin and facilitate mould filing.
- Suitable lubricants that can be used in the resins of the present invention include fatty alcohols with chain length from C12 to C22 produced either by hydrogenation of fatty acids or from ethylene via Ziegler process. These fatty alcohols may also be subjected to esterification with dicarboxylic acids. These lubricants are effective internal lubricants.
- Suitable lubricants include those sold under trade names Abrilube and Abriflo (manufactured by Abril Industrial Waxes), Interlite (manufactured by Akros Chemical), Baerolub (manufactured by Baerlocher GmBH), Naftolub (manufactured by Chemson Polymer-Additive Ges.mbH), Loxiol (manufactured by Cognis Deutchland GmbH), Ligalub (manufactured by Peter Greven Fettchermie), Atrmer (manufactured by Uniqema) and Marklube (manufactured by Witco Vinyl Additives GmbH).
- Abrilube and Abriflo manufactured by Abril Industrial Waxes
- Interlite manufactured by Akros Chemical
- Baerolub manufactured by Baerlocher GmBH
- Naftolub manufactured by Chemson Polymer-Additive Ges.mbH
- Loxiol manufactured by Cognis Deutchl
- Suitable lubricants include fatty acid esters of short-chain alcohols, such as for example esters of fatty acid glycerides. Suitable examples include liquid glycerol monoleate and solid glycerol monostearate and triglyceride esters of 12- hydroxystearic acid (hydrogenated castor oil). Other suitable examples include the stearic acid esters of trimethylol propane and pentaerythritol, and N-butyl stearate and isobutyl stearate. These are known to act as internal lubricants.
- Suitable lubricants include those sold under trade names Interlite (manufactured by Akros Chemical), Baerolub (manufactured by Baerlocher GmBH), Naftolub (manufactured by Chemson Polymer-Additive Ges.mbH), Loxiol (manufactured by Cognis Deutchland GmbH), Lubriol (manufactured by Comiel (Morton International Group)), Syncrolube (manufactured by Croda Oleochemicals), Petrac waxes (manufactured by Ferro Corporation), Tegomer 9xx (manufactured by Th. Goldschmidt AG), Glycolub, Glycostat and Polyaldo (manufactured by Lonza Benelux B.V.), Radia and Radiasurf (manufactured by Fina Chemicals N.V.),
- Ligalub (manufactured by Peter Greven Fettchemie), Realub (manufactured by Reagens Societa per Azioni Industria), Waxso (manufactured by SO.GJ.S. Industria Chimica S. p. a.), Atmer and Estol (manufactured by Uniqema) and Marklube (manufactured by Witco Vinyl Additives GmbH).
- Fatty acids such as stearic acid
- suitable lubricants include those sold under trade names Interlite (manufactured by Akros Chemical), Baerolub (manufactured by Baerlocher GmBH), Naftozin (manufactured by Chemson Polymer-Additive Ges.mbH), Loxiol (manufactured by Cognis Deutchland GmbH), Lubriol (manufactured by Comiel (Morton International Group)), Crodacid (manufactured by Croda Oleochemicals), Stavinor (manufactured by Ceca), Petrac waxes (manufactured by Ferro Carporation), Radiacid (manufactured by Fina Chemicals N.V.), Ligalub (manufactured by Peter Greven Fettchemie), Waxso (manufactured by SO.GJ
- Fatty acid amides are yet another example of suitable lubricants to be used in the resins of the present invention.
- suitable lubricants include oleic acid amide and erucamide as well as bis(stearyol)ethylenediamine, generally known as amide wax. These lubricants show a distinct slip effect.
- Suitable lubricants include those sold under trade names Abrilube and Abriflo (manufactured by Abril Industrial Waxes), Armoslip (manufactured by Akzo Nobel Chemicals), Licowax (manufactured by Clariant GmbH), Loxamid (manufactured by Cognis Deutchland GmbH), Lubriol (manufactured by Comiel (Morton International Group)), Crodamid (manufactured by Croda Oleochemicals), Stavinor (manufactured by Ceca), Acrawax and Glycolub (manufactured by Lonza Benelux B.V.), Ligalub (manufactured by Peter Greven Fettchemie), Realub (manufactured by Reagens Societa per Azioni Industria), Waxso (manufactured by SO.GJ.S. Industria Chimica S. p. a.), Unislip and
- Metal soaps are also suitable for use as lubricants in the resins of the present invention. These lubricants are known to stabilize plastics and also act as release agents. Suitable lubricants include those sold under trade names Haro Chem (manufactured by Akros Chemical), Baerolub (manufactured by Baerlocher GmBH), Lstab (manufactured by Chemson Polymer- Additive Ges.mbH), Licowax (manufactured by Clariant GmbH), Loxiol (manufactured by Cognis Deutchland GmbH), Lubriol (manufactured by Comiel (Morton International Group)), stavinor (manufactured by Ceca), Glycolub, Glycosperse, Lonzest and Pegosperse (manufactured by Lonza Benelux B.V.), Radiastar (manufactured by Fina Chemicals N.V.),
- montan waxes An important group of lubricants is the montan waxes. Crude montan wax is a by product of some, but not all, lignites. The chemistry of montan wax is comparable to the chemistry of fatty acids. Esters of long-chain alcohols, esters of mono- and polyfunctional short-chain alcohols and oligomeric (complex) esters are synthesized from montan wax acid. In addition, saponified products and several metal soaps also find applications as lubricants. Montan waxes are known to act as release agents and reduce viscosity.
- Suitable lubricants include those sold under trade names Interlite (manufactured by Akros Chemical), Luwax (manufactured by BASF AG), Licowax (manufactured by Clariant GmbH), and Stavinor (manufactured by Ceca).
- Polar PE and PP waxes are also examples of suitable lubricants to be used in the resins of the present invention.
- Polar PE waxes are typically produced by introducing oxygen-containing polar groups into hydrocarbon by oxidation in air.
- Polar PP waxes are typically produced by grafting with maleic anhydride.
- Suitable lubricants include those sold under trade names Interlite (manufactured by Akros Chemical), Baerolub (manufactured by Baerlocher GmBH), Luwax (manufactured by BASF AG), Naftolub (manufactured by Chemson Polymer-Additive Ges.mbH), Licowax (manufactured by Clariant GmbH), Loxiol (manufactured by Cognis Deutchland GmbH), Vestowax (manufactured by Creanova), Epolene (manufactured by Eastman Chemicals International AG), Petrac waxes (manufactured by Ferro Carporation), A-C Polyethylene, AClyn Ionomers and Acumist (manufactured by Honeywell), LE-Wachs (manufactured by Leuna Polymer GmbH) and Marklube (manufactured by Witco Vinyl Additives GmbH).
- Fluoropolymers i.e. polytetrafluoroethylene or oligomers having the general structure -(F2C-CF2)n-, are yet another example of suitable lubricants to be used in the resin of the present invention. Fluoropolymers improve the frictional properties. Suitable lubricants include those sold under trade name Dyneon PTFE Mikropulver (manufactured by Dyneon GmbH).
- lubricants include silicone-based lubricants, i.e. polysiloxanes. These lubricants are based on molecules with the general structure (-R2Si-0-SiR2)n-, where R denotes an organic group, typically methyl or phenyl or a mixture thereof, and n represents the number of repeat units. It is known that silicone-based lubricants, and in particular polydimethylsiloxane (PDMS) improves mould filling, surface appearance, mould release, surface lubricity and wear resistance. Suitable lubricants include those sold under trade names Tegopren (manufactured by Th. Goldsmith AG) and Genioplast (manufactured by Wacker Chemical Corporation).
- Tegopren manufactured by Th. Goldsmith AG
- Genioplast manufactured by Wacker Chemical Corporation
- the total amount of lubricants in the polyester resin is 0.1- 5% (wt/wt) based on the total weight of the resin. In some embodiments the total amount of lubricants is 0.2-5 % (wt/wt), such as 0.5-4% (wt/wt) more preferred 1-3.5% (wt/wt), even more preferred 2-3 % (wt/wt) based on the total weight of the resin.
- the resin may in addition to fillers, impact modifiers and lubricants also comprise other additives, such as nucleating agents, anti-hydrolysis additives, release agent, UV stabilizers, flame retardants, chain extenders, processing stabilizers, antioxidants and colouring agents or pigments.
- additives such as nucleating agents, anti-hydrolysis additives, release agent, UV stabilizers, flame retardants, chain extenders, processing stabilizers, antioxidants and colouring agents or pigments.
- the inventors of the present invention have also surprisingly found that in some cases beneficial effects are obtained when using non-reactive impact modifiers alone without the presence of reactive impact modifiers.
- the present invention relates to a toy building element made of a polyester material and manufactured by processing of a resin comprising at least one polyester and at least one non-reactive impact modifier, wherein the polyester is a poly(ethylene terephthalate) polyester (PET polyester) or a modified PET polyester, which has been modified by replacing all or parts of the terephthalic acid groups of the PET polyester with a diacid monomer selected from the group consisting of adipic acid, succinic acid, isophthalic acid, furandicarboxylic acid, phthalic acid, 4,4 ' -biphenyl dicarboxylic acid, 2,6-naphthalenedicarboxylic acid and mixtures thereof; and/or all or parts of the ethylene glycol groups of the PET polyester with a diol monomer selected from the group consisting of isosorbide, 1,4- cyclohexanedimethanol, 2,2,4,4-tetramehyl-l,3-cyclobut
- the inventors of the present invention has surprisingly found that better flow properties can be obtained when using only non-reactive impact modifiers as compared with the use of a combination of reactive and non-reactive impact modifiers. It has also proven to be easier to control the compounding of non reactive impact modifiers instead of carrying out a reactive compounding process with reactive impact modifiers.
- the present invention is also directed to a method for the manufacture of a toy building element comprising the steps of a) providing a resin comprising at least one polyester, at least one reactive impact modifier and at least one non-reactive impact modifier, wherein the polyester is a PET polyester or a modified PET polyester, which has been modified by replacing all or parts of the terephthalic acid groups of the PET polyester with a diacid monomer selected from the group consisting of adipic acid, succinic acid, isophthalic acid, furandicarboxylic acid, phthalic acid, 4,4 ' -biphenyl dicarboxylic acid, 2,6-naphthalenedicarboxylic acid and mixtures thereof; and/or all or parts of the ethylene glycol groups of the PET polyester with a diol monomer selected from the group consisting of isosorbide, 1,4- cyclohexanedimethanol, 2,2,4,4-tetramehyl-l,3-cyclobutanediol,
- Suitable resins to be provided and processed in the method include those described above. Suitable examples of PET polyesters, modified PET polyesters, reactive impact modifiers and non-reactive impact modifiers include those mentioned above.
- the total amount of impact modifiers is typically up to 25% (w/w) based on the total weight of the resin. In some embodiments the total amount of impact modifiers is 2-15% (wt/wt), such as 2-5% (wt/wt) or 5-8% (wt/wt) or 8-12% (wt/wt) based on the total weight of the resin. In some embodiments the amount of reactive impact modifier is in the range of 0.25-10% (wt/wt) based on total weight of resin. In other embodiments the total amount of non-reactive impact modifier is in the range of 0.25-15% (wt/wt) based on total weight of resin.
- the toy building element is manufactured by injection moulding.
- the impact modifiers are mixed with the polyester during feeding of the injection moulding machine.
- the total amount of impact modifier is preferably at most 3% (wt/wt) based on the total weight of the resin so that suitable dispersion of the impact modifier in the resin is obtained.
- the reactive impact modifier is mixed with the polyester during feeding of the injection moulding machine.
- the amount of reactive impact modifier is preferably at most 3% (wt/wt) based on the total weight of the resin so that suitable dispersion of the reactive impact modifier in the resin is obtained.
- the amount of reactive impact modifier is at most 9% (wt/wt), for example at most 6% (wt/wt), based on the total weight of the resin.
- the impact modifiers are mixed with the polyester prior to feeding the mixture to the injection moulding machine.
- the mixing may be performed by dry mixing or by compounding.
- the impact modifiers and the polyester are dry mixed prior to feeding of the injection moulding machine.
- the total amount of impact modifiers is preferably at most 5% (w/w) based on the total weight of the resin so that suitable dispersion of the impact modifier in the resin is obtained.
- the impact modifiers and the polyester are mixed by compounding prior to feeding it to the injection moulding machine. In such cases the resin is brought to its melted state and then thoroughly mixed to ensure sufficient dispersion of the impact modifier in the polyester and then the mixture is cooled, transformed into pellets and the pellets are then fed to the injection moulding machine.
- the total amount of impact modifiers is typically up to 25% (w/w) based on the total weight of the resin. In some embodiments the total amount of impact modifiers is 2-15% (wt/wt), such as 2-5% (wt/wt) or 5-8% (wt/wt) or 8- 12% (wt/wt) based on the total weight of the resin.
- the impact modifiers and the polyester are compounded by thoroughly mixing to ensure sufficient dispersion and then fed directly into the injection moulding machine.
- polyester and the impact modifiers may be mixed into a masterbatch which is then mixed with the rest of the resin during feeding of the injection moulding machine.
- Additives such as fillers, nucleating agents, anti-hydrolysis additives, release agents, lubricants, UV stabilizers, flame retardants, chain extenders processing stabilizers, antioxidants and colouring agents or pigments, may be added and mixed with the impact modifiers and the polyester either prior to or during feeding to the injection moulding machine.
- the toy building element is manufactured by additive manufacturing.
- additive manufacturing techniques are those in which the toy building element is built by photopolymerization additive manufacturing or thermoplastic additive manufacturing, such as liquid-based additive manufacturing, toner-based additive manufacturing, powder-based additive manufacturing or granulate-based additive manufacturing.
- Moulded plastic rods with dimensions of 6.0 x 4.0 x 50.0 mm 3 , B x W x H, and in the relevant material to be tested were cut according to ISO 179-1/1 eA with a notch cutter (ZNO, Zwick, Germany) with a notch tip diameter of 0.5 mm.
- the notched specimens were placed with v-notch opposite pendulum and tested in a pendulum impact machine (HOT, Zwick, Germany) according to the principles described in ISO 179-1:2010.
- Post-consumer bottle grade PET with an IV of 0.80 dl/g was dried at 150 degrees C to a moisture content of 50-100 ppm.
- the PET was dry blended with the impact modifiers ParaloidTM EXL-3691J (an unreactive impact modifier from Dow Chemical Company) and ELVALOYTM PTW (a reactive random terpolymer of ethylene, butyl acrylate and glycidyl methacrylate (epoxide functional) from Dow/Dupont Chemical Company).
- the quantities of each impact modifier are listed in the table below. Blends were processed via twin screw extrusion into pellets followed by injection moulding into tensile and impact bars. The obtained impact bars were tested in the Charpy v-notch test, as described above. The results are shown in the table below.
- the injection moulding parameters were as follows:
- extrusion processing parameters were as follows:
- a moulded plastic rod made of a resin containing 4% (wt/wt) ELVALOYTM PTW as the only impact modifier has a Charpy v-notch value of 15 kJ/m2 and a resin containing 5% (wt/wt) ParaloidTM EXL-3691J as the only impact modifier has a Charpy v-notch value of 8 kJ/m2.
- the results show that a moulded plastic rod made of a resin comprising both impact modifiers in the same quantities, i.e.
- the material samples were dry blended with the impact modifiers ParaloidTM EXL-3330 (unreactive impact modifier from Dow Chemical Company) and ELVALOYTM PTW (which is a reactive random terpolymer of ethylene, butyl acrylate and glycidyl methacrylate (epoxide functional) from Dow/Dupont Chemical Company) according to the table below. Blends were processed via twin screw extrusion into pellets followed by injection moulding into tensile and impact bars. The obtained impact bars were tested in the Charpy v-notch test, as described above. The results are shown in the table below.
- ParaloidTM EXL-3330 unreactive impact modifier from Dow Chemical Company
- ELVALOYTM PTW which is a reactive random terpolymer of ethylene, butyl acrylate and glycidyl methacrylate (epoxide functional) from Dow/Dupont Chemical Company
- the injection moulding parameters were as follows: Melt temperature: 290 degrees C Hot runner temperature: 295 degrees C Mould temperature: 30 degrees C
- the extrusion processing parameters were as follows:
- a moulded plastic rod made of a resin containing PETG and no impact modifier has a sharpy v-notch value of 9.4 kJ/m2.
- the PETG-containing resin has a Charpy v-notch value of 11.0 kJ/m2 and when adding 5% (wt/wt) ParaloidTM EXL-3330 as the only impact modifier the PETG-containing resin has a Charpy v-notch value of 12.9 kJ/m2.
- the results show that a moulded plastic rod made of a resin, which contains PETG and comprising both 2.5% (wt/wt) ELVALOYTM PTW and 5% (wt/wt) ParaloidTM EXL-3330 has a Charpy v-notch value of 21.6 kJ/m2.
- the results show that a synergistic effect is obtained when combining the reactive impact modifier and the non-reactive impact modifier.
- a moulded plastic rod made of a resin containing PETT and no impact modifier has a sharpy v-notch value of 4.5 kJ/m2.
- the PETT-containing resin has a Charpy v-notch value of 7.5 kJ/m2
- the PETG-containing resin has a Charpy v-notch value of 7.6 kJ/m2.
- the results show that a moulded plastic rod made of a resin, which contains PETG and comprising both 2.5% (wt/wt) ELVALOYTM PTW and 5% (wt/wt) ParaloidTM EXL-3330 has a Charpy v-notch value of 106.4 kJ/m2.
- the results show that a synergistic effect is obtained when combining the reactive impact modifier and the non-reactive impact modifier.
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Abstract
The present invention relates to a toy building element made of a polyester material and manufactured by processing of a resin comprising at least one polyester, at least one reactive impact modifier and at least one non-reactive impact modifier. The present invention also relates to a method for the manufacture of such toy building element.
Description
TOY BUILDING ELEMENT MADE OF A POLYMERIC POLYESTER MATERIAL
FIELD OF THE INVENTION The present invention relates to a toy building element made of a polyester material and manufactured by processing of a resin comprising at least one polyester, at least one reactive impact modifier and at least one non-reactive impact modifier. The present invention also relates to a method for the manufacture of such toy building element. BACKGROUND
Polyesters are a category of polymers that contain an ester functional group in their main chain. They can be formed from the reaction of a diacid or acid anhydride and a diol with the elimination of water, or by ring-opening polymerization of cyclic (di-)esters. Polyesters are classified as aliphatic, semi aromatic and aromatic according to the composition of their main chain. In general, aromatic acids and diols improve the hardness, rigidity and heat resistance, whereas aliphatic acids and diols increase the flexibility, lower the melting or softening point and improve the processability.
Common aliphatic diols are ethylene glycol, 1,4-butanediol and 1,3-propanediol. They are often reacted with aromatic diacids, such as terephthalic acid, phthalic acid, phthalic anhydride and naphthalene dicarboxylic acid. Glycerol and unsaturated acids (anhydrides) like maleic anhydride, are sometimes added to crosslink the polyester. In the case of unsaturated acids (anhydrides), crosslinking is achieved in a subsequent free radical chain polymerization. Double bonds in the backbone of the polyesters also improve the resistance to softening and deformation at elevated temperatures. Poly(ethylene terephthalate), also referred to as PET, is a common thermoplastic polymer resin. It can be produced by reaction of ethylene glycol and terephthalic acid. Today PET is widely used to make containers for food, water and carbonated
water and soft drinks and the like due to its excellent combination of mechanical and gas barrier properties. The transparent water bottles are manufactured by blow moulding of amorphous PET. Hence, amorphous PET may be considered a low-cost raw material for the production of engineering compounds due to its widespread availability for example from recycled beverage bottles.
PET was not originally considered as an injection moulding material because of high moisture sensitivity, poor impact strength and slow rate of crystallization, which slows the moulding process.
The properties of PET can be modified and enhanced to such an extent that it can be used in industrial production of durable products. The slow crystallization rate can be improved by addition of nucleating agents and the poor impact strength can be improved by addition of glass, fibres, mineral or organic reinforcements, such as carbon nanotubes, graphene and graphite, and/or impact modifiers.
Standard bottle grade PET typically has an intrinsic viscosity in the range of 0.75 to 0.85 dl/g. Copolymer modification (acid or glycol modification) has been used to decrease the crystallization rate and to decrease the PET melting temperature, thereby decreasing the energy demand in the production process. Standard PET bottle polymers with copolymer modification typically have between 0% and 3 mol% isophthalic acid (IPA) modification in order to reduce the crystallization rate and allow the production of clear amorphous preforms weighing up to 100 grams.
Poly(ethylene furanoate), also referred to as PEF, is an aromatic thermoplastic polyester that can be easily moulded and thermoformed. It can be produced by polycondensation of ethylene glycol and 2,5-furandicarboxylic acid (FDCA). PEF has many attractive properties including high tensile strength and high puncture toughness, good heat resistance, as well as outstanding gas barrier properties, which are superior to PET. PEF also has a lower melting point and a higher glass transition temperature than PET and thus more attractive thermal and mechanical properties. Information with regard to the impact strength is very sparse.
PEF is a known analogue to PET, which is capable of replacing PET because its chemical structure is very similar to the chemical structure of PET. In particular, the studies in recent years have been focused on the use of PEF for use as food
and beverage packaging material, because of its better barrier properties, i.e. better ability to withstand gas (oxygen and carbon dioxide) permeability, as compared to PET.
It has been demonstrated that PEF can be recycled in very similar ways to PET recycling. Preliminary tests have shown that PEF has no material effect on the mechanical and physical properties of PET, such as strength and impact. It is therefore suggested that PEF is likely to be recycled in the PET recycling stream, at least in the transition period following the launch of PEF items on the market. It is considered that up to 2% PEF would be compatible in the existing PET recycling stream, and this upper limit of 2% PEF in the PET recycling stream has actually been granted by the European PET Bottle Platform.
Studies have not yet been focused on improving impact strength and toughness of PEF. Flowever, because of its chemical similarity with PET it is credible that the impact strength of PEF may be improved in a similar way as for PET, when adding the same types and amounts of impact modifiers.
Poly(ethylene glycol-co-l,4-cyclohexanedimethanol terephthalate), also referred to as glycol modified polyethylene terephthalate or PETG, is prepared by partially replacing the ethylene glycol groups of PET with 1,4-cyclohexanedimethanol (CHDM) groups. In contrast to semicrystalline PET, glycol modified poly(ethylene terephthalate) copolyester is an amorphous thermoplastic that exhibits a glass transition temperature of about 80 degrees C, which is similar to the glass transition temperature of PET. In some studies, the glass transition temperature of PETG has been reported to be higher than for PET.
The impact strength of PETG depends on the content of ethylene glycol and 1,4- cyclohexanedimethanol terephthalate, respectively. The higher the content of 1,4- cyclohexanedimethanol terephthalate the higher impact strength.
Impact modifiers are known to improve the durability and toughness of polymer resins. Impact modifiers for PET are generally elastomeric compounds that increase impact strength and elongation while usually decreasing modulus. An effective way to enhance the impact strength is by the dispersion of a rubber phase within the PET matrix. The main role of the rubber particles is to induce an
overall deformation mechanism rather than a localized phenomenon, thereby strongly increasing the amount of dissipated fracture energy. The effectiveness of rubber modification depends on the type of rubber, the rubber content, the rubber particle size and the interparticle distance.
Impact modifiers may be characterized as reactive or non-reactive. Reactive impact modifiers are preferred for toughening of PET since these form a stable dispersed phase by grafting to the PET matrix. Non-reactive elastomers can be dispersed into PET by intensive compounding but may coalesce downstream in the compounder.
Reactive impact modifiers have functionalized end groups. Functionalization serves two purposes: firstly to bond the impact modifier to the polymer matrix and secondly, to modify the interfacial energy between the polymer matrix and the impact modifier for enhanced dispersion.
Non-reactive (unfunctionalized) elastomeric impact modifiers are not highly effective at toughening polyesters because they are unable to adequately interact with the polyester matrix so as to achieve optimally sized dispersed phases and strong interfacial bonding. Non-reactive impact modifiers may take a unique core shell structure. This structure is obtained by copolymerization of a hard shell around a soft rubber core and since the structure is typically obtained by emulsion copolymerization, it provides a well-defined particle size, which in turn leads to a well-controlled blend morphology. The soft rubber-core may be a butadiene core or an acrylic core, whereas the shell may be made of PMMA.
Polyesters are an interesting material for use in the manufacture of toys, such as toy building elements. However, impact strength needs to be modified in order to satisfy the requirements of product safety and play experience and so that long- lasting toy building bricks can be produced, which do not break when for example dropped on the floor or when stepped on by an adult person. The improved impact strength need to be focused on injection moulded objects with complex geometries such as the geometry of a traditional LEGO® brick which has been on the market for many years when produced in conventional materials such as for example ABS.
SUMMARY OF THE INVENTION
The inventors of the present invention have developed a new polyester resin for use in the manufacture of toy building elements, which provides improved impact strength of the manufactured elements.
In particular, the inventors of the present invention have surprisingly found that markedly improved impact strength is obtained when a resin comprising one or more polyester(s), a reactive impact modifier and a non-reactive impact modifier is processed into toy building elements. In fact, a synergistic effect is observed when processing such polyester resins as compared to polyester resins comprising only the reactive impact modifier or the non-reactive impact modifier.
In a first aspect the present invention is directed to a toy building element made of a polyester material and manufactured by processing of a resin comprising at least one polyester, at least one reactive impact modifier and at least one non reactive impact modifier, wherein the polyester is a poly(ethylene terephthalate) polyester (PET polyester) or a modified PET polyester, which has been modified by replacing all or parts of the terephthalic acid groups of the PET polyester with a diacid monomer selected from the group consisting of adipic acid, succinic acid, isophthalic acid, furandicarboxylic acid, phthalic acid, 4,4 '-biphenyl dicarboxylic acid, 2,6-naphthalenedicarboxylic acid and mixtures thereof; and/or all or parts of the ethylene glycol groups of the PET polyester with a diol monomer selected from the group consisting of isosorbide, 1,4- cyclohexanedimethanol, 2,2,4,4-tetramehyl-l,3-cyclobutanediol, diethylene glycol, 1,2-propanediol, neopentylene glycol, 1,3-propanediol, 1,4 butanediol and mixtures thereof, with the proviso that not all of the terephthalic acid groups and all of the ethylene glycol groups can be replaced at the same time.
In a second aspect the present invention is directed to a method for the manufacture of a toy building element comprising the steps of a) providing a resin comprising at least one polyester, at least one reactive impact modifier and at least one non-reactive impact modifier, wherein the
polyester is a polyethylene terephthalate) polyester (PET polyester) or a modified PET polyester, which has been modified by replacing all or parts of the terephthalic acid groups of the PET polyester with a diacid monomer selected from the group consisting of adipic acid, succinic acid, isophthalic acid, furandicarboxylic acid, phthalic acid, 4,4 '-biphenyl dicarboxylic acid, 2,6-naphthalenedicarboxylic acid and mixtures thereof; and/or all or parts of the ethylene glycol groups of the PET polyester with a diol monomer selected from the group consisting of isosorbide, 1,4- cyclohexanedimethanol, 2,2,4,4-tetramehyl-l,3-cyclobutanediol, diethylene glycol, 1,2-propanediol, neopentylene glycol, 1,3-propanediol, 1,4 butanediol and mixtures thereof, with the proviso that not all of the terephthalic acid groups and all of the ethylene glycol groups can be replaced at the same time, and b) processing said resin.
BRIEF DESCRIPTION OF THE FIGURES
Figure 1 shows a traditional box-shaped LEGO® 2*4 brick.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is directed to a toy building element made of a polyester material and manufactured by processing of a resin comprising at least one polyester, at least one reactive impact modifier and at least one non-reactive impact modifier.
The term "toy building element" as used herein includes the traditional toy building elements in the form of box-shaped building bricks provided with knobs on the upper side and complementary tubes on the lower side. A traditional box shaped toy building brick is shown in Figure 1. The traditional box-shaped toy building bricks were disclosed for the first time in US 3,005,282 and are widely sold under the tradenames LEGO® and LEGO® DUPLO®. The term also includes other similar box-shaped building bricks, which are produced by other companies
than The LEGO Group and therefore sold under other trademarks than the trademark LEGO.
The term "toy building element" also includes other kinds of toy building elements that form part of a toy building set which typically comprises a plurality of building elements that are compatible with and hence can be interconnected with each other. Such toy building sets are also sold under the trademark LEGO, such as for example LEGO® bricks, LEGO® Technic and LEGO® DUPLO®. Some of these toy building sets includes toy building figures, such as for example LEGO® Minifigures (see for example US 05/877,800), having complementary tubes on the lower side so that the figure can be connected to other toy building elements in the toy building set. Such toy building figures are also encompassed by the term "toy building element". The term also includes similar toy building elements, which are produced by other companies than The LEGO Group and therefore sold under other trademarks than the trademark LEGO.
The toy building elements are available in a large variety of shapes, sizes and colours. One difference between LEGO® bricks and LEGO® DUPLO® bricks is the size in that a LEGO® DUPLO® brick is twice the size of a LEGO® brick in all dimensions. The size of the traditional box-shaped LEGO® toy building brick having 4*2 knobs on the upper side is about 3.2 cm in length, about 1.6 cm in width and about 0.96 cm in height (excluding knobs), and the diameter of each knob is about 0.48 cm. In contrast, the size of a LEGO® DUPLO® brick having 4*2 knobs on the upper side is about 6.4 cm in length, about 3.2 cm in width and about 1.92 cm in height (excluding knobs), and the diameter of each knob is about 0.96 cm.
The toy building elements are manufactured either by injection moulding or by additive manufacturing or by a combination of injection moulding and additive manufacturing.
Injection moulding of toy building elements is the traditional way of manufacturing toy building bricks. This manufacturing technique has been used for many years and is very well known to a skilled person. In some embodiments the toy building element is manufactured by injection moulding of a polyester
resin. In other embodiments the toy building element is manufactured by two- component injection moulding, where one of the components is a polyester resin.
In recent years, the new additively manufacturing technique for building objects in for example polymeric material has been developed. By the term "additive manufacturing" or "additively manufactured" as used herein is meant that the brick is built in an additive fashion, i.e. by adding new material on top of either a substrate or on top of newly added material, by repeated solidification of a thin liquid layer or droplet on a substrate or on a previously solidified liquid layer or droplet, or by repeated printing with a thermoplastic polymeric material on a substrate or on a previously printed plastics material, or by repeated soldering in an additive fashion of plastics material e.g. by use of laser.
In some embodiments the toy building element is manufactured by injection moulding. In other embodiments the toy building element is manufactured by additive manufacturing. In yet other embodiments the toy building element is manufactured by a combination of injection moulding and additive manufacturing. Such combined manufacturing technique is described for example in WO 2014/005591 where a toy building element with high degree of design individuality is manufactured by adding material in the layer-by-layer fashion on the surface of a traditional injection moulded box-shaped building brick.
Hence, the toy building element is made of a polyester material and manufactured by processing of a resin comprising at least one polyester, at least one reactive impact modifier and at least one non-reactive impact modifier.
The term "polyester" as used herein includes both PET polyesters and modified PET polyesters and mixtures thereof. The modified PET polyester has been modified by replacing all or parts of the terephthalic acid groups of the PET polyester with a diacid monomer selected from the group consisting of adipic acid, succinic acid, isophthalic acid, furandicarboxylic acid, phthalic acid, 4,4 '-biphenyl dicarboxylic acid, 2,6-naphthalenedicarboxylic acid and mixtures thereof; and/or all or parts of the ethylene glycol groups of the PET polyester with a diol monomer selected from the group consisting of isosorbide, 1,4-
cyclohexanedimethanol, 2,2,4,4-tetramehyl-l,3-cyclobutanediol, diethylene glycol, 1,2-propanediol, neopentylene glycol, 1,3-propanediol, 1,4 butanediol and mixtures thereof, with the proviso that not all of the terephthalic acid groups and all of the ethylene glycol groups can be replaced at the same time.
By the term "polyester resin" as used herein is meant a resin comprising at least one polyester as defined above, at least one reactive impact modifier and at least one non-reactive impact modifier.
The PET polyester is produced by polymerization of the monomers ethylene glycol and terephthalic acid. The modified PET polyester may be produced in three different ways. First of all, the modified PET polyester may be produced by polymerization of the monomers ethylene glycol, terephthalic acid and one or more further comonomer(s), which is/are a diacid monomer and/or a diol monomer thereby producing a diacid modification, a diol modification or a diacid/diol modification. Secondly, the modified PET polyester may be produced by polymerization of the monomer ethylene glycol and one or more further comonomer(s), which is/are one or more diacid monomer(s) and optionally one or more diol monomer(s). Thirdly, the modified PET polyester may be produced by polymerization of the monomer terephthalic acid and one or more further comonomer(s), which is/are one or more diol monomer(s) and optionally one or more diacid monomer(s). In all cases the diacid monomer is selected from the group consisting of adipic acid, succinic acid, isophthalic acid, furandicarboxylic acid, phthalic acid, 4,4'-biphenyl dicarboxylic acid, 2,6-naphthalenedicarboxylic acid and mixtures thereof and the diol monomer is selected from the group consisting of isosorbide, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramehyl-l,3- cyclobutanediol, diethylene glycol, 1,2-propanediol, neopentylene glycol, 1,3- propanediol, 1,4 butanediol and mixtures thereof.
In some embodiments the resin comprises PET polyester. The PET polyester is produced by reaction of ethylene glycol and terephthalic acid. In a preferred embodiment the polyester is PET polyester.
In some embodiments the resin comprises a modified PET polyester, which has been produced by reaction of ethylene glycol and terephthalic acid and the
comonomer 1,4-cyclohexanedimethanol. In other embodiments the resin comprises a modified PET polyester, which has been produced by reaction of ethylene glycol and terephthalic acid and the comonomer isophthalic acid. In other embodiments the resin comprises a modified PET polyester which has been produced by reaction of ethylene glycol and terephthalic acid and the comonomer 2,2,4,4-tetramehyl-l,3-cyclobutanediol. In other embodiments the resin comprises a modified PET polyester which has been produced by reaction of terephthalic acid and 1,4-cyclohexanedimethanol. In yet other embodiments the resin comprises a modified PET polyester, which has been produced by reaction of terephthalic acid, isophthalic acid and 1,4-cyclohexanedimethanol. In other embodiments the resin comprises a modified PET polyester, which has been produced by reaction of ethylene glycol, terephthalic acid, and 2,5- furandicarboxylic acid.
In preferred embodiments the resin comprises poly(ethylene terephthalate-co- isophthalate) polyester. The poly(ethylene terephthalate-co-isophthalate) polyester is produced by reaction of ethylene glycol, terephthalic acid and isophthalic acid. In a preferred embodiment the polyester in the resin is a modified PET polyester, which is polyethylene terephthalate-co-isophthalate) polyesters. The amount of isophthalic acid in the poly(ethylene terephthalate-co- isophthalate) polyesters is typically 0.5-12 mol% and preferably 1-3 mol%.
The chemical composition of poly(ethylene terephthalate-co-isophthalate) polyesters, i.e. the amount of isophthalic acid in the poly(terephthalate-co- isophthalate) polyester, may be characterised by 13C Nuclear Magnetic Resonance spectroscopy (C NMR) according to the method described in "Martinez de Ilarduya, A.; Kint, D. P.; Muhoz-Guerra, S. Sequence Analysis of Poly (ethylene terephthalate-co-isophthalate) Copolymers by 13C NMR. Macromolecules 2000 33, 4596-4598". Accordingly, the amount of isophthalic acid may be measured using this C NMR method.
An important characteristic of PET is the intrinsic viscosity (IV). The intrinsic viscosity, which is measured in dl/g, is found by extrapolating the relative viscosity to zero concentration. It depends on the length of the PET polymer chains. The longer the polymer chains the more entanglements between chains
and therefore the higher the viscosity. The average length of a particular batch of PET resin can be controlled during the polymerization process.
The PET Intrinsic Viscosity (IV) may be measured according to ASTM D4603.
High IV homo- and copolymer PET compositions are difficult to process in injection moulding due to their high viscosity.
In some embodiments the IV of the PET polyester ranges from 0.6-1.1 dl/g, such as 0.7-0.9 dl/g, preferably from 0.75-0.85 dl/g.
In preferred embodiments the modified PET polyester is PET of bottle grade. The term "bottle grade" is well known in the technical area and refers to PET starting materials that can easily be processed into bottles. In most embodiments the "bottle grade" PET is made of polyethylene terephthalate-co-isophthalate) polyesters comprising 1-3 mol% of isophthalic acid. In bottle grade PET the IV is typically in the range of 0.70-0.78 dl/g for non-carbonated water, and in the range of 0.78-0.85 for carbonated water.
Suitable examples of PET grades which are also commercial available include bottle grade EASTLON PET CB-600, CB-602 and CB-608 supplied by Far Eastern New Century (FENC), commercial grade post-consumer rPET CB-602R supplied by FENC, partially bio-based bottle grade PET CB-602AB supplied by FENC and homopolymer PET grade 6020 supplied by Invista.
In some embodiments the resin comprises a modified PET polyester, which has been produced by reaction of ethylene glycol and terephthalic acid and the comonomer 1,4-cyclohexanedimethanol. In some embodiments the resin comprises poly(ethylene glycol-co-l,4-cyclohexanedimethanol terephthalate) polyesters, also referred to as glycol modified polyethylene terephthalate or PETG. In a preferred embodiment the polyester is a modified PET polyester, which is PETG. The amount of 1,4-cyclohexanedimethanol in the PETG is typically 0.1-25 mol%. In other embodiments the resin comprises ethylene glycol modified poly(cyclohexylenedimethylene terephthalate) also referred to as PCTG. In a preferred embodiment the polyester is a modified PET polyester, which is PETG.
The amount of 1,4-cyclohexanedimethanol in the PETG is typically 25-49.99 rmol%.
In other embodiments the resin comprises a modified PET polyester which has been produced by reaction of ethylene glycol and terephthalic acid and the comonomer 2,2,4,4-tetramehyl-l,3-cyclobutanediol. In some embodiments the resin comprises poly(ethylene glycol-co-2,2,4,4-tetramethyl-l,3-cyclobutanediol terephthalate) also referred to as PETT.
In other embodiments the resin comprises a modified PET polyester which has been produced by reaction of terephthalic acid and 1,4-cyclohexanedimethanol. In some embodiments the resin comprises poly(cyclohexanedimethylene terephthalate) also referred to as PCT.
In yet other embodiments the resin comprises a modified PET polyester, which has been produced by reaction of terephthalic acid, isophthalic acid and 1,4- cyclohexanedimethanol. In some embodiments the resin comprises isophthalic acid modified poly(cyclohexanedimethylene terephthalate) also referred to as PCTA. The amount of isophthalic acid is typically 0.1-50 mol%, more typically 0.1- 5 mol%.
In some embodiments the resin comprises poly(ethylene furanoate-co-ethylene terephthalate) polyester. The poly(ethylene furanoate-co-ethylene terephthalate) polyester is produced by reaction of ethylene glycol, terephthalic acid and 2,5- furandicarboxylic acid. The amount of 2,5-furandicarboxylic acid in the modified PET polyester is typically 0.5-12 mol% and preferably 1-3 mol%.
In some embodiments the resin comprises polyethylene furanoate) polyester, also referred to as PEF. The poly(ethylene furanoate) polyester is produced by reaction of ethylene glycol and furandicarboxylic acid. In a preferred embodiment the polyester is a modified PET polyester, which is PEF.
In other embodiments the resin comprises a mixture of poly(ethylene terephthalate) polyester and poly(ethylene furanoate) polyester. In other embodiments the resin comprises a mixture of poly(ethylene terephthalate-co- isophthalate) polyester and poly(ethylene furanoate) polyester. In yet other
embodiments the resin comprises a mixture of poly(ethylene terephthalate) polyester, poly(ethylene terephthalate-co-isophthalate) polyester and poly(ethylene furanoate) polyester. In any of these mixtures the amount of poly(ethylene furanoate) polyester is typically 0.1-10% (wt/wt), such as for example 0.1-5% (wt/wt) or 0.1-2% (wt/wt) based on total amount of polyesters.
In some embodiments the polyester resin is an unfilled polyester resin.
By the term "unfilled polyester resin" as used herein is meant a polyester resin which does not comprise reinforcing and filling material, such as glass, glass beads, fibres, mineral reinforcements, such as aluminum silicate, talc, asbestos, mica and calcium carbonate, and organic reinforcements, such as aramid fibres, carbon nanotubes, graphene and graphite.
In one embodiment the polyester resin does not contain glass, glass beads and/or glass fibres. In one embodiment the polyester resin does not contain fibres. In one embodiment the polyester resin does not contain inorganic reinforcements, such as aluminum silicate, asbestos, talc, mica and calcium carbonate. In one embodiment the polyester resin does not contain organic reinforcements, such as aramid fibres, carbon nanotubes, graphene and graphite. In one embodiment the polyester resin does not contain glass and fibres.
In another preferred embodiment the polyester resin further comprises one or more filler(s) in an amount of up to 5% (wt/wt) relative to the total weight of the resin, such as from 0.1-5% (wt/wt), more preferred from 0.2-4% (wt/wt), most preferred from 0.5-3% (wt/wt). The one or more filler(s) may be inorganic particulate material or a nanocomposite or a mixture thereof.
Suitable examples of inorganic particulate material include inorganic oxides, such as glass, MgO, Si02, Ti02 and Sb203; hydroxides, such as AI(OH)3 and Mg(OH)2; salts, such as CaC03, BaS04, CaS04 and phosphates; silicates, such as talc, mica, kaolin, wollastonite, montmorillonite, nanoclay, feldspar and asbestos; metals, such as boron and steel; carbon - graphite, such as carbon fibers, graphite fibers and flakes, carbon nanotubes and carbon black. Suitable examples of inorganic particulate material also include surface treated and/or surface modified Si02 and Ti02, such as for example alumina surface modified Ti02.
Suitable examples of nanocomposites include clay filled polymers, such as clay/low density polyethylene (LDPE) nanocomposites, clay/high density polyethylene (HDPE) nanocomposites, acrylonitrile-butadiene-styrene (ABS)/clay nanocomposites, polyimide (PI)/clay nanocomposites, epoxy/clay nanocomposites, polypropylene (PP)/clay nanocomposites, poly (methyl methacrylate) (PMMA)/clay nanocomposites and polyvinyl chloride (PVC)/clay nanocomposites; alumina filled polymers, such as epoxy/alumina nanocomposites, PMMA/alumina nanocomposites, PI/alumina nanocomposites, PP/alumina nanocomposites, LDPE/alumina nanocomposites and cross-linked polyethylene (XLPE)/alumina nanocomposites; barium titanate filled polymers, such as HDPE/barium titanate nanocomposites and polyetherimide (PEI)/barium titanate nanocomposites; silica filled polymers, such as PP/silica nanocomposites, epoxy/silica nanocomposites, PVC/silica nanocomposites, PEI/silica nanocomposites, Pi/silica nanocomposites, ABS/silica nanocomposites, and PMMA/silica nanocomposites; and zinc oxide filled polymers, such as LDPE/zinc oxide nanocomposites, PP/zinc oxide nanocomposites, epoxy/zinc oxide nanocomposites and PMMA/zinc oxide nanocomposites.
In one embodiment the resin comprises polyester in an amount of at least 50% (wt/wt) relative to the total weight of the resin. In other embodiments the resin comprises polyester in an amount of at least 60% or 70% or 80% (wt/wt) relative to the total weight of the resin. In preferred embodiments the resin comprises polyester in an amount of at least 85%, such as at least 90% (wt/wt) relative to the total weight of the resin, more preferred at least 95% or 97% or 99% (wt/wt) relative to the total weight of the resin.
In another embodiment the resin comprises polyester in an amount of 50-99.5% (wt/wt) relative to the total weight of the resin. In other embodiments the resin comprises polyester in an amount of 60-97% or 70-95% (wt/wt) relative to the total weight of the resin. In a preferred embodiment the resin comprises polyester in an amount of 75-95%, more preferred 77-92%, even more preferred 80-90% (wt/wt) relative to the total weight of the resin.
The polyester in the resin may be a bio-based polymer, a hybrid bio-based polymer or a petroleum-based polymer, or a mixture thereof.
By the term "bio-based polymer" as used herein is meant a polymer, which is produced by chemical, or biochemical polymerization of monomers derived from biomass. Bio-based polymers include polymers produced by polymerization of one type of monomer derived from biomass as well as polymers produced by polymerization of at least two different monomers derived from biomass.
In a preferred embodiment the bio-based polymer is produced by chemical or biochemical polymerization of monomers, which are all derived from biomass.
Bio-based polymers according to the present invention include
Polymers produced by biochemical polymerization, i.e. for example by use of microorganisms. The monomers are produced using biomass as substrate. Polymers produced by chemical polymerization, i.e. by chemical synthesis. The monomers are produced using biomass as substrate.
In some embodiments, the bio-based polymer is produced by biochemical polymerization. In other embodiments the bio-based polymer is produced by chemical polymerization. In yet other embodiments the bio-based polymers are produced by biochemical or chemical polymerization. The bio-based polymer may also be produced by a combination of biochemical and chemical polymerization, for example in cases where two monomers are combined to a dimer by a biochemical reaction path and then the dimers are polymerized by use of chemical reaction.
Bio-based polymers also include polymers having the same molecular structure as petroleum-based polymers, but which have been produced by chemical and/or biochemical polymerization of monomers derived from biomass.
By the term "petroleum-based polymers" as used herein is meant a polymer produced by chemical polymerization of monomers derived from petroleum, petroleum by-products or petroleum-derived feedstocks.
By the term "hybrid bio-based polymer" as used herein is meant a polymer, which is produced by polymerization of at least two different monomers, where at least one monomer is derived from biomass and at least one monomer is derived from
petroleum, petroleum by-products or petroleum-derived feedstocks. The polymerization process is typically a chemical polymerization process.
The hybrid bio-based polymers may also be characterized by their content of bio based carbon per total carbon content. The term "bio-based carbon" as used herein refers to the carbon atoms that originate from the biomass that is used as substrate in the production of monomers, which form part of the bio-based polymers and/or the hybrid bio-based polymers. The content of bio-based carbon in the hybrid bio-based polymer can be determined by Carbon-14 isotope content as specified in ASTM D6866 or CEN/TS 16137 or an equivalent protocol.
In some embodiments the content of bio-based carbon in the hybrid bio-based polymer is at least 25% based on the total carbon content of the hybrid bio-based polymer, such as for example at least 30% or at least 40%. In other embodiments the content of bio-based carbon in the hybrid bio-based polymer is at least 50% based on the total carbon content, such as at least 60% for example at least 70%, such as at least 80% based on the total carbon content of the hybrid bio-based polymer.
In one embodiment the ethylene glycol monomers and/or the diol monomers are bio-based monomers whereas the terephthalic acid monomers and/or the diacid monomers are not bio-based monomers, such as for example petroleum-based monomers. In another embodiment the terephthalic acid monomers and/or the diacid monomers are bio-based monomers whereas the ethylene glycol monomers and/or the diol monomers are not bio-based monomers. In yet another embodiment the ethylene glycol monomers and/or the diol monomers and the terephthalic acid monomers and/or the diacid monomers are bio-based monomers. In even yet another embodiment neither the ethylene glycol monomers nor the diol monomers nor the terephthalic acid monomers nor the diacid monomers are bio-based monomers.
In one preferred embodiment the ethylene glycol monomers and/or the diol monomers are bio-based monomers derived from biomass and having a content of bio-based carbon equal to 100% based on the total carbon content in the ethylene glycol monomers and/or diol monomers. In other embodiments the ethylene glycol monomers and/or diol monomers have a content of bio-based
carbon of at least 25% based on the total carbon content in the ethylene glycol monomers and/or diol monomers, such as for example at least 50%, preferably at least 70%, more preferred at least 90% and most preferred at least 95%.
In one preferred embodiment the terephthalic acid monomers and/or diacid monomers are bio-based monomers derived from biomass and having a content of bio-based carbon equal to 100% based on the total carbon content in the terephthalic acid monomers and/or diacid monomers. In other embodiments the terephthalic acid monomers and/or diacid monomers have a content of bio-based carbon of at least 25% based on the total carbon content in the terephthalic acid monomers and/or diacid monomers, such as for example at least 50%, preferably at least 70%, more preferred at least 90% and most preferred at least 95%.
In some embodiments the content of bio-based carbon in the polyester is at least 25% based on the total carbon content in the polyester. In other embodiments the content of bio-based carbon in the polyester is at least 50% based on the total carbon content, such as at least 60% for example at least 70%, preferably at least 80%, more preferably at least 90%, even more preferably at least 95%. In the most preferred embodiment the content of bio-based carbon in the polyester is 100% based on the total carbon content in the polyester.
In some embodiments the content of bio-based carbon in the resin is at least 25% based on the total carbon content in the resin. In other embodiments the content of bio-based carbon in the resin is at least 50% based on the total carbon content in the resin, such as at least 60% for example at least 70%, preferably at least 75%, more preferably at least 80%, even more preferably at least 85%. In the most preferred embodiment the content of bio-based carbon in the resin is 90% based on the total carbon content in the resin.
The terms "bio-based polymer", "hybrid bio-based polymer" and "petroleum- based polymer" also include recycled polymers and recycled material comprising "bio-based polymer", "hybrid bio-based polymer" and "petroleum-based polymer".
The term "recycled material" as used herein refers to a material, which is obtained by processing of a resin comprising recycled polymers. The recycled polymers are
obtained from waste materials. The waste material can be mechanically recycled material or chemically recycled material.
"Mechanically recycled material" refers to material which has been recovered by mechanically recycling of material. Mechanical recycling involves only mechanical processes, such as for example grinding, washing, separating, drying, re granulating and compounding. In a typical recycling process, the waste material is collected and washed in order to remove contaminants. The cleaned plastic is then grinded into flakes, which can be compounded and pelletized or reprocessed into granulate.
"Chemically recycled material" includes materials which has been obtained by pyrolysis, chemical depolymerisation, solvent dissolution or any other suitable chemical recycling process.
"Pyrolysis" refers to breakdown of the material to crude oil at elevated temperature in the absence of oxygen. New virgin-like polymers can then be made from the resulting oil by known polymerization processes.
"Chemical depolymerisation" refers to the process of breaking down of a polymer into either monomers, mixtures of monomers or intermediates thereof using a chemical agent. New virgin-like polymers can be produced by polymerization of the monomers.
"Solvent dissolution" refers to the selective extraction of polymers using solvents. The extracted polymers are recovered by precipitation of the polymer or by evaporation of the solvent. The polymer chain and structure is not broken down.
The term "recycled polymer" refers to the polymer comprised in the mechanically recycled waste material or the polymer, which is chemically recovered from the waste material in the solvent dissolution process. The term also refers to the virgin-like polymer, which is produced in the pyrolysis recycling process or the chemical depolymerisation recycling process. When the term refers to virgin-like polymers then it also includes polymers where only one or two of the monomers have been recycled by pyrolysis or chemical depolymerisation.
In some embodiments the resin comprises mechanically recycled polyesters. In other embodiments the resin comprises mechanically recycled polyesters and biobased polyesters. In other embodiments the resin comprises mechanically recycled polyesters and hybrid bio-based polyesters. In yet other embodiments the resin comprises mechanically recycled polyesters and petroleum-based polyesters. In still other embodiments the resin comprises mechanically recycled polyesters, bio-based polyesters and petroleum-based polyesters. In still other embodiments the resin comprises mechanically recycled polyesters, hybrid biobased polyesters and petroleum-based polyesters. In yet other embodiments the resin comprises mechanically recycled polyesters, bio-based polyesters and hybrid bio-based polyesters. And in other embodiments the resin comprises mechanically recycled polyesters, bio-based polyesters, hybrid bio-based polyesters and petroleum-based polyesters.
In some embodiments, the amount of mechanically recycled polyester in the resin is at least 10% (wt/wt) based on the total weight of the resin, such as at least 20%, or for example at least 30%, such as at least 40% or for example at least 50%. In other embodiments, the amount of mechanically recycled polyester in the resin is at least 60% (wt/wt) based on the total weight of the resin, such as at least 70%, or for example at least 75%, such as at least 80% or for example at least 85%.
In some embodiments the polyester comprises chemically recycled monomers. In other embodiments the polyester comprises chemically recycled monomers and bio-based monomers. In other embodiments the polyester comprises chemically recycled monomers and hybrid bio-based monomers. In yet other embodiments the polyester comprises chemically recycled monomers and petroleum-based monomers. In still other embodiments the polyester comprises chemically recycled monomers, bio-based monomers and petroleum-based monomers. In still other embodiments the polyester comprises chemically recycled monomers, hybrid bio-based monomers and petroleum-based monomers. In yet other embodiments the polyester comprises chemically recycled monomers, bio-based monomers and hybrid bio-based monomers. And in other embodiments the polyester comprises chemically recycled monomers, bio-based monomers, hybrid bio-based monomers and petroleum-based monomers.
In some embodiments, the amount of chemically recycled monomers in the polyester is at least 10% (wt/wt) based on the total weight of the polyester, such as at least 20%, or for example at least 30%, such as at least 40% or for example at least 50%. In other embodiments, the amount of chemically recycled monomers in the polyester is at least 60% (wt/wt) based on the total weight of the polyester, such as at least 70%, or for example at least 80%, such as at least 90% or for example at least 95%.
In some embodiments the resin comprises a mixture of recycled poly(ethylene terephthalate) polyester and recycled polyethylene furanoate) polyester. In other embodiments the resin comprises a mixture of recycled poly(ethylene terephthalate-co-isophthalate) polyester and recycled polyethylene furanoate) polyester. In yet other embodiments the resin comprises a mixture of recycled poly(ethylene terephthalate) polyester, recycled poly(ethylene terephthalate-co- isophthalate) polyester and recycled poly(ethylene furanoate) polyester.
The polyester resin comprises at least one reactive impact modifier and at least one non-reactive impact modifier.
By the term "impact modifier" as used herein is meant an agent that increases the impact strength of the produced toy building element. The impact strength is measured using the Charpy v-notch test as defined below.
By the term "reactive impact modifier" as used herein is meant an impact modifier having functionalized end groups. These functionalized end groups serve two purposes: 1) to bond the impact modifier to the polymer matrix and 2) to modify the interfacial energy between the polymer matrix and the impact modifier for enhanced dispersion. Preferred examples of such functionalized end groups include glycidyl methacrylates, maleic anhydrides and carboxylic acids.
In a preferred embodiment the reactive impact modifier is a copolymer of the formula X/Y/Z where X is aliphatic or aromatic hydrocarbon polymer having 2-8 carbon atoms, Y is a moiety comprising an acrylate or methacrylate having 3-6 and 4-8 carbon atoms, respectively, and Z is a moiety comprising methacrylic acid, glycidyl methacrylate, maleic anhydride or carboxylic acid.
In one preferred embodiment the reactive impact modifier may be described by the formula :
where n is an integer from 1 to 4, m is an integer from 0 to 5, k is an integer from 0 to 5, and R is an alkyl of 1 to 5 carbon or 1 hydrogen atom.
X constitutes 40-90% (wt/wt) of the impact modifier, and Y constitutes 0-50% (wt/wt), such as 10-40% (wt/wt), preferably 15-35% (wt/wt), most preferably 20-35% (wt/wt) of the impact modifier, and Z constitutes 0.5-20% (wt/wt), preferably 2-10% (wt/wt), most preferably 3-8% (wt/wt) of the reactive impact modifier.
In other embodiments, X constitutes 70-99.5% (wt/wt) of the reactive impact modifier, preferably 80-95% (wt/wt), most preferably 92-97% (wt/wt) and Y constitutes 0% (wt/wt) of the impact modifier, and Z constitutes 0.5-30%
(wt/wt), preferably 5-20% (wt/wt), most preferably 3-8% (wt/wt) of the reactive impact modifier.
Suitable examples of specific reactive impact modifiers that can be used in the resin of the present invention include ethylene-ethylene acrylate-glycidyl methacrylate and ethylene-butyl acrylate-glycidyl methacrylate. Commercial available impact modifiers include Paraloid™ EXM-2314 (an acrylic copolymer from Dow Chemical Company), Lotader® AX8700, Lotader® AX8900, Lotader
AX8750®, Lotader® AX8950 and Lotader® AX8840 (manufactured by Arkema) and Elvaloy® PTW (manufactured by DuPont).
Other suitable examples of specific reactive impact modifiers that can be used in the resin of the present invention include anhydride modified ethylene acrylates. Commercial available impact modifiers include Lotader® 3210, Lotader® 3410, Lotader® 4210, Lotader® 3430, Lotader® 4402, Lotader® 4503, Lotader® 4613, Lotader® 4700, Lotader® 5500, Lotader® 6200, Lotader® 8200, Lotader® HX8210, Lotader® HX8290, Lotader® LX4110, Lotader® TX8030 (manufactured by Arkema), Bynel® 21E533, Bynel® 21E781, Bynel® 21E810 and Bynel® 21E830 (manufactured by DuPont).
In other embodiments the reactive impact modifier is a modified ethylene vinyl acetate, such as for example Bynel® 1123 or Bynel® 1124 (manufactured by DuPont), an acid modified ethylene acrylate, such as for example Bynel® 2002 or Bynel® 2022 (manufactured by DuPont), a modified ethylene acrylate, such as for example Bynel® 22E757, Bynel® 22E780 or Bynel® 22E804 (manufactured by DuPont), an anhydride modified ethylene vinyl acetate, such as for example Bynel® 30E670, Bynel® 30E671, Bynel® 30E753 or Bynel® 30E783 (manufactured by DuPont), and acid/acrylate modified ethylene vinyl acetate, such as for example Bynel® 3101 or Bynel® 3126 (manufactured by DuPont), an anhydride modified ethylene vinyl acetate, such as for example Bynel® E418, Bynel® 3810, Bynel® 3859, Bynel® 3860 or Bynel® 3861 (manufactured by DuPont), an anhydride modified ethylene vinyl acetate, such as for example Bynel® 3930 or Bynel® 39E660 (manufactured by DuPont), and anhydride modified high density polyethylene, such as for example Bynel® 4033 or Bynel® 40E529 (manufactured by DuPont), an anhydride modified linear low density polyethylene, such as for example Bynel® 4104, Bynel® 4105, Bynel® 4109, Bynel® 4125, Bynel® 4140, Bynel® 4157, Bynel® 4164, Bynel® 41E556,
Bynel® 41E687, Bynel® 41E710, Bynel® 41E754, Bynel® 41E755, Bynel® 41E762, Bynel® 41E766, Bynel® 41E850, Bynel® 41E865 or Bynel® 41E871 (manufactured by DuPont) an anhydride modified low density polyethylene, such as for example Bynel® 4206, Bynel® 4208, Bynel® 4288 or Bynel® 42E703 (manufactured by DuPont) or an anhydride modified polypropylene, such as for example Bynel® 50E571, Bynel® 50E662, Bynel® 50E725, Bynel® 50E739, Bynel® 50E803 or Bynel® 50E806 (manufactured by DuPont).
Other suitable reactive impact modifiers include maleic anhydride grafted impact modifiers. Specific examples of such reactive impact modifiers include chemically modified ethylene acrylate copolymers, such as Fusabond® A560 (manufactured by DuPont), an anhydride modified polyethylene, such as Fusabond® E158 (manufactured by DuPont), an anhydride modified polyethylene resin, such as for example Fusabond® E564 or Fusabond® E589 or Fusabond® E226 or Fusabond® E528 (manufactured by DuPont), an anhydride modified high density polyethylene, such as for example Fusabond ® E100 or Fusabond ® E265 (manufactured by DuPont), an anhydride modified ethylene copolymer, such as for example Fusabond ® N525 (manufactured by DuPont), or a chemically modified propylene copolymer, such as for example Fusabond ® E353 (manufactured by DuPont).
Yet other suitable reactive impact modifiers include ethylene-acid copolymer resins, such as ethylene-methacrylic acid (EMAA) based copolymers and ethylene- acrylic acid (EAA) based copolymers. Specific examples of ethylene-methacrylic acid based copolymer impact modifiers include Nucrel® 403, Nucrel® 407FIS, Nucrel® 411HS, Nucrel® 0609FISA, Nucrel® 0903, Nucrel® 0903FIC, Nucrel® 908FIS, Nucrel® 910, Nucrel® 910FIS, Nucrel® 1202FIC, Nucrel® 599, Nucrel® 699, Nucrel® 925 and Nucrel® 960 (manufactured by DuPont). Specific examples of ethylene-acrylic acid based copolymers Nucrel® 30707, Nucrel® 30907, Nucrel® 31001, Nucrel® 3990 and Nucrel® AE (manufactured by DuPont). Other specific examples of ethylene of ethylene-acrylic acid (EAA) based copolymers include Escor™ 5000, Escor™ 5020, Escor™ 5050, Escor™ 5080, Escor™ 5100, Escor™ 5200 and Escor™ 6000 (manufactured by ExonMobile Chemical).
Still other suitable reactive impact modifiers include ionomers of ethylene acid copolymers. Specific examples of such impact modifiers include Surlyn® 1601, Surlyn® 1601-2, Surlyn® 1601-2LM, Surlyn® 1605, Surlyn® 8150, Surlyn® 8320, Surlyn® 8528 and Surlyn® 8660 (manufactured by DuPont).
In other embodiments the reactive impact modifier is an alkyl methacrylate- silicone/alkyl acrylate graft copolymer. The "alkyl methacrylate" of the graft copolymer may be one selected from the group consisting of methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate and butyl
methacrylate. The "silicone/alkyl acrylate" in the graft copolymer refers to a polymer obtained by polymerizing a mixture of a silicone monomer and an alkyl acrylate monomer. The silicone monomer may be selected from the group consisting of dimethylsiloxane, hexamethylcyclotrisiloxane, octamethylcyclo- tetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotetrasiloxane, tetramethyltetraphenylcyclotetrasiloxane and octaphenylcyclotetrasiloxane. The alkyl monomer may be selected from the group consisting of methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate and butyl methacrylate. The graft copolymer is in the form of core-shell rubber and has a graft rate of 5 to 90% (wt/wt), a glass transition temperature of the core of -150 to -20 degrees C, and a glass transition temperature of the shell of 20 to 200 degrees C. In one embodiment of the present invention, the graft copolymer is methyl methacrylate- silicone/butyl acrylate graft copolymer. Specific examples include S-2001, S-2100, S-2200 and S-2501 manufactured by Mitsubishi Rayon Co., Ltd. In Japan.
Other suitable reactive impact modifiers include the siloxane polymers mentioned in US 4,616,064, which contain siloxane units, and at least one of carbonate, urethane or amide units.
Suitable reactive and non-reactive impact modifiers also include those mentioned in WO 2018/089573 paragraphs [0043]-[0072],
By the term "non-reactive impact modifier" as used herein is meant an impact modifier, which does not have functionalized end groups and therefore cannot form covalent chemical bonds with the polymer matrix. The non-reactive impact modifiers are typically dispersed into the polymer matrix by intensive compounding but may coalesce downstream in the compounder.
Non-reactive impact modifiers may take a unique core-shell structure. This structure is obtained by copolymerization of a hard shell around a soft rubber core and since the structure is typically obtained by emulsion copolymerization, it provides a well-defined particle size, which in turn leads to a well-controlled blend morphology.
Suitable examples of non-reactive core-shell impact modifiers include those mentioned in US 5,409,967, i.e. core-shell impact modifiers with a core comprised mainly of a rubbery core polymer such as a copolymer containing a diolefin, preferably a 1,3-diene, and a shell polymer comprised mainly of a vinyl aromatic monomer, such as styrene, and hydroxylalkyl (meth)acrylate or, in the alternative, another functional monomer which acts in a manner similar to the hydroxylalkyl (meth)acrylate. Other suitable examples include impact modifiers with a soft rubber-core, such as for example a butadiene core, an acrylic core or a silicone-acrylic core, and a shell made of polymethyl (methacrylate) (PMMA).
In some embodiments the reactive impact modifier has a functionalized end group, which is selected from the group consisting of glycidyl methacrylate, maleic anhydride and carboxylic acid. In a preferred embodiment the functionalized group of the reactive impact modifier is glycidyl methacrylate.
In some embodiments the reactive impact modifier has a functionalized end group, which is selected from the group consisting of glycidyl methacrylate, maleic anhydride and carboxylic acid, and the non-reactive impact modifier is a core shell impact modifier. In a preferred embodiment the reactive impact modifier has a functionalized end group, which is glycidyl methacrylate, and the non-reactive impact modifier is a core shell impact modifier.
In some embodiments the non-reactive impact modifier is a core shell impact modifier. In a preferred embodiment the non-reactive impact modifier is a core shell impact modifier with a butadiene core, an acrylic core or a silicone-acrylic core, and a shell made of polymethyl (methacrylate) (PMMA).
In some embodiments the reactive impact modifier has a functionalized end group, which is selected from the group consisting of glycidyl methacrylate, maleic anhydride and carboxylic acid, and the non-reactive impact modifier is an ethylene-acrylate co-polymer. In a preferred embodiment the reactive impact modifier has a functionalized end group, which is glycidyl methacrylate, and the non-reactive impact modifier is an ethylene-acrylate co-polymer.
In some embodiments the amount of reactive impact modifier in the polyester resin is 0.25-10% (wt/wt) based on the total weight of the resin. In preferred
embodiments the amount of reactive impact modifier in the polyester resin is 0.5- 5% (wt/wt) based on the total weight of the resin, such as 1-3% (wt/wt) based on the total weight of the resin.
In some embodiments the amount of non-reactive impact modifier in the polyester resin is 0.25-15% (wt/wt) based on the total weight of the resin. In preferred embodiments the amount of non-reactive impact modifier in the polyester resin is 0.5-10% (wt/wt) based on the total weight of the resin, such as 1-3% (wt/wt) based on the total weight of the resin.
In some embodiments the total amount of impact modifier in the polyester resin is 0.5-25% (wt/wt) based on the total weight of the resin. In some embodiments the total amount of impact modifiers is 2-15% (wt/wt), such as 2-5% (wt/wt) or 5-8% (wt/wt) or 8-12% (wt/wt) based on the total weight of the resin.
The resin may in addition to fillers and impact modifiers further comprise lubricants. Lubricants are typically added to the resin in order to improve the processability and demoulding performance of the resin and prevent damage to the injection moulding equipment by reducing friction (external lubricants) and by reducing viscosity and heat dissipation (internal lubricants). External lubricants migrate to the interface between the molten resin and the surface of the processing equipment and reduce friction during processing, reduce the resin's adhesion to the surface of the mould and prevent melt fracture. In addition, external lubricants reduce the coefficient of friction and often improve the scratch resistance of the moulded parts. Internal lubricants promote the flow of the resin and facilitate mould filing.
Suitable lubricants that can be used in the resins of the present invention include fatty alcohols with chain length from C12 to C22 produced either by hydrogenation of fatty acids or from ethylene via Ziegler process. These fatty alcohols may also be subjected to esterification with dicarboxylic acids. These lubricants are effective internal lubricants. Suitable lubricants include those sold under trade names Abrilube and Abriflo (manufactured by Abril Industrial Waxes), Interlite (manufactured by Akros Chemical), Baerolub (manufactured by Baerlocher GmBH), Naftolub (manufactured by Chemson Polymer-Additive Ges.mbH), Loxiol (manufactured by Cognis Deutchland GmbH), Ligalub
(manufactured by Peter Greven Fettchermie), Atrmer (manufactured by Uniqema) and Marklube (manufactured by Witco Vinyl Additives GmbH).
Other suitable lubricants include fatty acid esters of short-chain alcohols, such as for example esters of fatty acid glycerides. Suitable examples include liquid glycerol monoleate and solid glycerol monostearate and triglyceride esters of 12- hydroxystearic acid (hydrogenated castor oil). Other suitable examples include the stearic acid esters of trimethylol propane and pentaerythritol, and N-butyl stearate and isobutyl stearate. These are known to act as internal lubricants. Suitable lubricants include those sold under trade names Interlite (manufactured by Akros Chemical), Baerolub (manufactured by Baerlocher GmBH), Naftolub (manufactured by Chemson Polymer-Additive Ges.mbH), Loxiol (manufactured by Cognis Deutchland GmbH), Lubriol (manufactured by Comiel (Morton International Group)), Syncrolube (manufactured by Croda Oleochemicals), Petrac waxes (manufactured by Ferro Corporation), Tegomer 9xx (manufactured by Th. Goldschmidt AG), Glycolub, Glycostat and Polyaldo (manufactured by Lonza Benelux B.V.), Radia and Radiasurf (manufactured by Fina Chemicals N.V.),
Ligalub (manufactured by Peter Greven Fettchemie), Realub (manufactured by Reagens Societa per Azioni Industria), Waxso (manufactured by SO.GJ.S. Industria Chimica S. p. a.), Atmer and Estol (manufactured by Uniqema) and Marklube (manufactured by Witco Vinyl Additives GmbH).
Fatty acids, such as stearic acid, can also act as suitable lubricants in the resins of the present invention. These are known to have good release effect. Suitable lubricants include those sold under trade names Interlite (manufactured by Akros Chemical), Baerolub (manufactured by Baerlocher GmBH), Naftozin (manufactured by Chemson Polymer-Additive Ges.mbH), Loxiol (manufactured by Cognis Deutchland GmbH), Lubriol (manufactured by Comiel (Morton International Group)), Crodacid (manufactured by Croda Oleochemicals), Stavinor (manufactured by Ceca), Petrac waxes (manufactured by Ferro Carporation), Radiacid (manufactured by Fina Chemicals N.V.), Ligalub (manufactured by Peter Greven Fettchemie), Waxso (manufactured by SO.GJ.S. Industria Chimica S. p. a.), and Prifrac and Pristerene (manufactured by Uniqema).
Fatty acid amides are yet another example of suitable lubricants to be used in the resins of the present invention. Examples include oleic acid amide and erucamide
as well as bis(stearyol)ethylenediamine, generally known as amide wax. These lubricants show a distinct slip effect. Suitable lubricants include those sold under trade names Abrilube and Abriflo (manufactured by Abril Industrial Waxes), Armoslip (manufactured by Akzo Nobel Chemicals), Licowax (manufactured by Clariant GmbH), Loxamid (manufactured by Cognis Deutchland GmbH), Lubriol (manufactured by Comiel (Morton International Group)), Crodamid (manufactured by Croda Oleochemicals), Stavinor (manufactured by Ceca), Acrawax and Glycolub (manufactured by Lonza Benelux B.V.), Ligalub (manufactured by Peter Greven Fettchemie), Realub (manufactured by Reagens Societa per Azioni Industria), Waxso (manufactured by SO.GJ.S. Industria Chimica S. p. a.), Unislip and Uniwax (manufactured by Uniqema) and Marklube (manufactured by Witco Vinyl Additives GmbH).
Metal soaps, especially the soaps of alkaline earth metals, are also suitable for use as lubricants in the resins of the present invention. These lubricants are known to stabilize plastics and also act as release agents. Suitable lubricants include those sold under trade names Haro Chem (manufactured by Akros Chemical), Baerolub (manufactured by Baerlocher GmBH), Lstab (manufactured by Chemson Polymer- Additive Ges.mbH), Licowax (manufactured by Clariant GmbH), Loxiol (manufactured by Cognis Deutchland GmbH), Lubriol (manufactured by Comiel (Morton International Group)), stavinor (manufactured by Ceca), Glycolub, Glycosperse, Lonzest and Pegosperse (manufactured by Lonza Benelux B.V.), Radiastar (manufactured by Fina Chemicals N.V.), Ligalub (manufactured by Peter Greven Fettchemie), Realub (manufactured by Reagens Societa per Azioni Industria) and Waxso (manufactured by SO.GJ.S. Industria Chimica S. p. a.).
An important group of lubricants is the montan waxes. Crude montan wax is a by product of some, but not all, lignites. The chemistry of montan wax is comparable to the chemistry of fatty acids. Esters of long-chain alcohols, esters of mono- and polyfunctional short-chain alcohols and oligomeric (complex) esters are synthesized from montan wax acid. In addition, saponified products and several metal soaps also find applications as lubricants. Montan waxes are known to act as release agents and reduce viscosity. Suitable lubricants include those sold under trade names Interlite (manufactured by Akros Chemical), Luwax (manufactured by BASF AG), Licowax (manufactured by Clariant GmbH), and Stavinor (manufactured by Ceca).
Polar PE and PP waxes are also examples of suitable lubricants to be used in the resins of the present invention. Polar PE waxes are typically produced by introducing oxygen-containing polar groups into hydrocarbon by oxidation in air. Polar PP waxes are typically produced by grafting with maleic anhydride. Suitable lubricants include those sold under trade names Interlite (manufactured by Akros Chemical), Baerolub (manufactured by Baerlocher GmBH), Luwax (manufactured by BASF AG), Naftolub (manufactured by Chemson Polymer-Additive Ges.mbH), Licowax (manufactured by Clariant GmbH), Loxiol (manufactured by Cognis Deutchland GmbH), Vestowax (manufactured by Creanova), Epolene (manufactured by Eastman Chemicals International AG), Petrac waxes (manufactured by Ferro Carporation), A-C Polyethylene, AClyn Ionomers and Acumist (manufactured by Honeywell), LE-Wachs (manufactured by Leuna Polymer GmbH) and Marklube (manufactured by Witco Vinyl Additives GmbH).
Fluoropolymers, i.e. polytetrafluoroethylene or oligomers having the general structure -(F2C-CF2)n-, are yet another example of suitable lubricants to be used in the resin of the present invention. Fluoropolymers improve the frictional properties. Suitable lubricants include those sold under trade name Dyneon PTFE Mikropulver (manufactured by Dyneon GmbH).
Yet other suitable examples of lubricants include silicone-based lubricants, i.e. polysiloxanes. These lubricants are based on molecules with the general structure (-R2Si-0-SiR2)n-, where R denotes an organic group, typically methyl or phenyl or a mixture thereof, and n represents the number of repeat units. It is known that silicone-based lubricants, and in particular polydimethylsiloxane (PDMS) improves mould filling, surface appearance, mould release, surface lubricity and wear resistance. Suitable lubricants include those sold under trade names Tegopren (manufactured by Th. Goldsmith AG) and Genioplast (manufactured by Wacker Chemical Corporation).
Specific examples of commercially available lubricants which are suitable for use in the resins of the present invention include, but are not limited to, Crodamide ER, Crodamide VRX, Crodamid OR, Crodamid ORX, Crodamid 212, Crodamid EBS, and Crodamid EBSV (manufactured by Croda), IncroMold K, IncroMold T (manufactured by Croda) and IncroMax PET 100 (manufactured by Croda),
GENIOPLAST® PELLET P PLUS, GENIOPLAST® PELLET S, GENIOPLAST® FLUID 110 and GENIOPLAST® PELLET 345 (manufactured by Wacker Chemical Corporation), Kemamide E-180 (stearyl erucamide), Kemamide® P-181 (oleyl palmitamide) and Kemamide W-20 (manufactured by PMC Biogenix Inc).
In some embodiments the total amount of lubricants in the polyester resin is 0.1- 5% (wt/wt) based on the total weight of the resin. In some embodiments the total amount of lubricants is 0.2-5 % (wt/wt), such as 0.5-4% (wt/wt) more preferred 1-3.5% (wt/wt), even more preferred 2-3 % (wt/wt) based on the total weight of the resin.
The resin may in addition to fillers, impact modifiers and lubricants also comprise other additives, such as nucleating agents, anti-hydrolysis additives, release agent, UV stabilizers, flame retardants, chain extenders, processing stabilizers, antioxidants and colouring agents or pigments.
The inventors of the present invention have also surprisingly found that in some cases beneficial effects are obtained when using non-reactive impact modifiers alone without the presence of reactive impact modifiers.
Hence, in alternative embodiments, the present invention relates to a toy building element made of a polyester material and manufactured by processing of a resin comprising at least one polyester and at least one non-reactive impact modifier, wherein the polyester is a poly(ethylene terephthalate) polyester (PET polyester) or a modified PET polyester, which has been modified by replacing all or parts of the terephthalic acid groups of the PET polyester with a diacid monomer selected from the group consisting of adipic acid, succinic acid, isophthalic acid, furandicarboxylic acid, phthalic acid, 4,4 '-biphenyl dicarboxylic acid, 2,6-naphthalenedicarboxylic acid and mixtures thereof; and/or all or parts of the ethylene glycol groups of the PET polyester with a diol monomer selected from the group consisting of isosorbide, 1,4- cyclohexanedimethanol, 2,2,4,4-tetramehyl-l,3-cyclobutanediol, diethylene glycol, 1,2-propanediol, neopentylene glycol, 1,3-propanediol, 1,4 butanediol and mixtures thereof,
with the proviso that not all of the terephthalic acid groups and all of the ethylene glycol groups can be replaced at the same time, and with the proviso that the resin does not contain any reactive impact modifier.
The inventors of the present invention has surprisingly found that better flow properties can be obtained when using only non-reactive impact modifiers as compared with the use of a combination of reactive and non-reactive impact modifiers. It has also proven to be easier to control the compounding of non reactive impact modifiers instead of carrying out a reactive compounding process with reactive impact modifiers.
The present invention is also directed to a method for the manufacture of a toy building element comprising the steps of a) providing a resin comprising at least one polyester, at least one reactive impact modifier and at least one non-reactive impact modifier, wherein the polyester is a PET polyester or a modified PET polyester, which has been modified by replacing all or parts of the terephthalic acid groups of the PET polyester with a diacid monomer selected from the group consisting of adipic acid, succinic acid, isophthalic acid, furandicarboxylic acid, phthalic acid, 4,4 '-biphenyl dicarboxylic acid, 2,6-naphthalenedicarboxylic acid and mixtures thereof; and/or all or parts of the ethylene glycol groups of the PET polyester with a diol monomer selected from the group consisting of isosorbide, 1,4- cyclohexanedimethanol, 2,2,4,4-tetramehyl-l,3-cyclobutanediol, diethylene glycol, 1,2-propanediol, neopentylene glycol, 1,3-propanediol, 1,4 butanediol and mixtures thereof, with the proviso that not all of the terephthalic acid groups and all of the ethylene glycol groups can be replaced at the same time, and b) processing said resin.
Suitable resins to be provided and processed in the method include those described above. Suitable examples of PET polyesters, modified PET polyesters, reactive impact modifiers and non-reactive impact modifiers include those mentioned above.
The total amount of impact modifiers is typically up to 25% (w/w) based on the total weight of the resin. In some embodiments the total amount of impact modifiers is 2-15% (wt/wt), such as 2-5% (wt/wt) or 5-8% (wt/wt) or 8-12% (wt/wt) based on the total weight of the resin. In some embodiments the amount of reactive impact modifier is in the range of 0.25-10% (wt/wt) based on total weight of resin. In other embodiments the total amount of non-reactive impact modifier is in the range of 0.25-15% (wt/wt) based on total weight of resin.
In some embodiments the toy building element is manufactured by injection moulding.
In some embodiments the impact modifiers are mixed with the polyester during feeding of the injection moulding machine. In such embodiments the total amount of impact modifier is preferably at most 3% (wt/wt) based on the total weight of the resin so that suitable dispersion of the impact modifier in the resin is obtained.
In preferred embodiments at least the reactive impact modifier is mixed with the polyester during feeding of the injection moulding machine. In such embodiments the amount of reactive impact modifier is preferably at most 3% (wt/wt) based on the total weight of the resin so that suitable dispersion of the reactive impact modifier in the resin is obtained. In other embodiments the amount of reactive impact modifier is at most 9% (wt/wt), for example at most 6% (wt/wt), based on the total weight of the resin.
In other embodiments the impact modifiers are mixed with the polyester prior to feeding the mixture to the injection moulding machine. The mixing may be performed by dry mixing or by compounding.
In some embodiments the impact modifiers and the polyester are dry mixed prior to feeding of the injection moulding machine. In such embodiments the total amount of impact modifiers is preferably at most 5% (w/w) based on the total weight of the resin so that suitable dispersion of the impact modifier in the resin is obtained.
In other embodiments the impact modifiers and the polyester are mixed by compounding prior to feeding it to the injection moulding machine. In such cases the resin is brought to its melted state and then thoroughly mixed to ensure sufficient dispersion of the impact modifier in the polyester and then the mixture is cooled, transformed into pellets and the pellets are then fed to the injection moulding machine.
In embodiments where the impact modifiers and the polyester are mixed by compounding, the total amount of impact modifiers is typically up to 25% (w/w) based on the total weight of the resin. In some embodiments the total amount of impact modifiers is 2-15% (wt/wt), such as 2-5% (wt/wt) or 5-8% (wt/wt) or 8- 12% (wt/wt) based on the total weight of the resin.
In some embodiments the impact modifiers and the polyester are compounded by thoroughly mixing to ensure sufficient dispersion and then fed directly into the injection moulding machine.
In other embodiments the polyester and the impact modifiers may be mixed into a masterbatch which is then mixed with the rest of the resin during feeding of the injection moulding machine.
Additives, such as fillers, nucleating agents, anti-hydrolysis additives, release agents, lubricants, UV stabilizers, flame retardants, chain extenders processing stabilizers, antioxidants and colouring agents or pigments, may be added and mixed with the impact modifiers and the polyester either prior to or during feeding to the injection moulding machine.
In some embodiments the toy building element is manufactured by additive manufacturing. Suitable examples of additive manufacturing techniques are those in which the toy building element is built by photopolymerization additive manufacturing or thermoplastic additive manufacturing, such as liquid-based additive manufacturing, toner-based additive manufacturing, powder-based additive manufacturing or granulate-based additive manufacturing.
EXAMPLES
In the examples below it is described how a toy building brick is manufactured by injection moulding. The manufactured bricks were subsequently tested by the "Charpy v-notch test".
Charpy v-notch test
Moulded plastic rods with dimensions of 6.0 x 4.0 x 50.0 mm3, B x W x H, and in the relevant material to be tested were cut according to ISO 179-1/1 eA with a notch cutter (ZNO, Zwick, Germany) with a notch tip diameter of 0.5 mm. The notched specimens were placed with v-notch opposite pendulum and tested in a pendulum impact machine (HOT, Zwick, Germany) according to the principles described in ISO 179-1:2010.
Example 1. Modification of PET with Paraloid™ EXL-3691J and ELVALOY™ PTW
Post-consumer bottle grade PET with an IV of 0.80 dl/g was dried at 150 degrees C to a moisture content of 50-100 ppm. Upon ambient cooling of the dried PET material to below 50 degrees C, the PET was dry blended with the impact modifiers Paraloid™ EXL-3691J (an unreactive impact modifier from Dow Chemical Company) and ELVALOY™ PTW (a reactive random terpolymer of ethylene, butyl acrylate and glycidyl methacrylate (epoxide functional) from Dow/Dupont Chemical Company). The quantities of each impact modifier are listed in the table below. Blends were processed via twin screw extrusion into pellets followed by injection moulding into tensile and impact bars. The obtained impact bars were tested in the Charpy v-notch test, as described above. The results are shown in the table below.
The injection moulding parameters were as follows:
Melt temperature: 295 degrees C Hot runner temperature: 300 degrees C Mould temperature: 20 degrees C
The extrusion processing parameters were as follows:
Barrel temperature: 290 degrees C Melt temperature: 295-300 degrees C
When comparing trials 1-3, 1-8 and 1-5 it is seen that a moulded plastic rod made of a resin containing 4% (wt/wt) ELVALOY™ PTW as the only impact modifier has a Charpy v-notch value of 15 kJ/m2 and a resin containing 5% (wt/wt) Paraloid™ EXL-3691J as the only impact modifier has a Charpy v-notch value of 8 kJ/m2. Very surprisingly, the results show that a moulded plastic rod made of a resin comprising both impact modifiers in the same quantities, i.e. 4% (wt/wt) ELVALOY™ PTW and 5% (wt/wt) Paraloid™ EXL-3691J has a Charpy v-notch value of 65 kJ/m2. In other words, the results show that a synergistic effect is obtained when combining the reactive impact modifier and the non-reactive impact modifier.
A similar synergistic effect is also seen when comparing trials 1-2, 1-9 and 1-6.
To sum up, the results clearly show that a synergistic effect on the Charpy v- notch values is obtained when combining a reactive impact modifier (ELVALOY™ PTW) with an unreactive impact modifier (Paraloid™ EXL-3691J).
Example 2. Modification of PETG and PETT with Paraloid™ EXL-3330 and ELVALOY™ PTW
Two different types of co-polyesters were tested in compounding trials with different types of impact modifiers. One common type of co-polyester is
SkyGreen™ KN100 from SK Chemicals, which is a poly(ethylene glycol-co-1,4- cyclohexanedimethanol terephthalate) (PETG). Another type of co-polyester is Eastman™ GMX201 Natural from Eastman, which is a poly (ethylene glycol-co- 2,2,4,4-tetramethyl-l,3-cyclobutanediol terephthalate) (PETT). Samples of PETG and PETT were dried at 70 degrees C to a moisture content of 50-100 ppm. Upon ambient cooling of the dried materials to below 50 degrees C, the material samples were dry blended with the impact modifiers Paraloid™ EXL-3330 (unreactive impact modifier from Dow Chemical Company) and ELVALOY™ PTW (which is a reactive random terpolymer of ethylene, butyl acrylate and glycidyl methacrylate (epoxide functional) from Dow/Dupont Chemical Company) according to the table below. Blends were processed via twin screw extrusion into pellets followed by injection moulding into tensile and impact bars. The obtained impact bars were tested in the Charpy v-notch test, as described above. The results are shown in the table below.
The injection moulding parameters were as follows: Melt temperature: 290 degrees C Hot runner temperature: 295 degrees C Mould temperature: 30 degrees C
The extrusion processing parameters were as follows:
Barrel temperature: 290 degrees C Melt temperature: 295-300 degrees C
When comparing trials 2-1, 2-3, 2-4 and 2-5 it is seen that a moulded plastic rod made of a resin containing PETG and no impact modifier has a sharpy v-notch value of 9.4 kJ/m2. When adding 2.5% (wt/wt) ELVALOY™ PTW as the only impact modifier the PETG-containing resin has a Charpy v-notch value of 11.0 kJ/m2 and when adding 5% (wt/wt) Paraloid™ EXL-3330 as the only impact modifier the PETG-containing resin has a Charpy v-notch value of 12.9 kJ/m2.
Very surprisingly, the results show that a moulded plastic rod made of a resin, which contains PETG and comprising both 2.5% (wt/wt) ELVALOY™ PTW and 5% (wt/wt) Paraloid™ EXL-3330 has a Charpy v-notch value of 21.6 kJ/m2. In other words, the results show that a synergistic effect is obtained when combining the reactive impact modifier and the non-reactive impact modifier.
When comparing trials 2-2, 2-6, 2-7 and 2-8 it is seen that a moulded plastic rod made of a resin containing PETT and no impact modifier has a sharpy v-notch value of 4.5 kJ/m2. When adding 2.5% (wt/wt) ELVALOY™ PTW as the only impact modifier the PETT-containing resin has a Charpy v-notch value of 7.5 kJ/m2 and when adding 5% (wt/wt) Paraloid™ EXL-3330 as the only impact modifier the PETG-containing resin has a Charpy v-notch value of 7.6 kJ/m2. Very surprisingly, the results show that a moulded plastic rod made of a resin, which contains PETG and comprising both 2.5% (wt/wt) ELVALOY™ PTW and 5% (wt/wt) Paraloid™ EXL-3330 has a Charpy v-notch value of 106.4 kJ/m2. In other words, the results show that a synergistic effect is obtained when combining the reactive impact modifier and the non-reactive impact modifier.
To sum up: The results clearly show that a marked synergistic effect on the Charpy v-notch values is obtained when mixing a PETG-containing resin or a PETT-containing resin with both a reactive impact modifier (ELVALOY™ PTW) and an unreactive impact modifier Paraloid™ EXL-3330.
Claims
1. A toy building element made of a polyester material and manufactured by processing of a resin comprising at least one polyester, at least one reactive impact modifier and at least one non-reactive impact modifier, wherein the polyester is a polyethylene terephthalate) polyester (PET polyester) or a modified PET polyester, which has been modified by replacing all or parts of the terephthalic acid groups of the PET polyester with a diacid monomer selected from the group consisting of adipic acid, succinic acid, isophthalic acid, furandicarboxylic acid, phthalic acid, 4,4 '-biphenyl dicarboxylic acid, 2,6-naphthalenedicarboxylic acid and mixtures thereof; and/or all or parts of the ethylene glycol groups of the PET polyester with a diol monomer selected from the group consisting of isosorbide, 1,4- cyclohexanedimethanol, 2,2,4,4-tetramehyl-l,3-cyclobutanediol, diethylene glycol, 1,2-propanediol, neopentylene glycol, 1,3-propanediol, 1,4 butanediol and mixtures thereof, with the proviso that not all of the terephthalic acid groups and all of the ethylene glycol groups can be replaced at the same time.
2. The toy building element according to claim 1, wherein the polyester is a PET polyester or a modified PET polyester, which has been modified by replacing all or parts of the terephthalic acid groups of the PET polyester with isophthalic acid.
3. The toy building element according to claim 1, wherein the polyester is a modified PET polyester, which has been modified by replacing all of the terephthalic acid groups of the PET polyester with furandicarboxylic acid groups.
4. The toy building element according to claim 1, wherein the polyester is a mixture of a PET polyester or a modified PET polyester, which has been modified by replacing all or parts of the terephthalic acid groups of the PET polyester with isophthalic acid, and a modified PET polyester, which has been modified by replacing all of the terephthalic acid groups of the PET polyester with furandicarboxylic acid groups.
5. The toy building element according to claim 1, wherein the polyester is a modified PET polyester, which has been modified by replacing parts of the ethylene glycol groups of the PET polyester with 1,4-cyclohexanedimethanol.
6. The toy building block according to any one of the preceding claims, wherein the amount of the PET polyester or the modified PET polyester is in the range of 75-95% (wt/wt) based on total weight of resin.
7. The toy building block according to any one of the preceding claims, wherein the amount of the reactive impact modifier is in the range of 0.25-10% (wt/wt) based on total weight of the resin.
8. The toy building block according to any one of the preceding claims, wherein the amount of the non-reactive impact modifier is in the range of 0.25-15% (wt/wt) based on total weight of the resin.
9. The toy building block according to any one of the preceding claims, wherein the resin further comprises an additive selected from the group consisting of fillers, nucleating agents, anti-hydrolysis additives, release agent, lubricants, UV stabilizers, flame retardants, chain extenders, processing stabilizers, antioxidants and colouring agents and/or pigments and mixtures thereof.
10. A method for the manufacture of a toy building element comprising the steps of a) providing a resin comprising at least one polyester, at least one reactive impact modifier and at least one non-reactive impact modifier, wherein the polyester is a PET polyester or a modified PET polyester, which has been modified by replacing all or parts of the terephthalic acid groups of the PET polyester with a diacid monomer selected from the group consisting of adipic acid, succinic acid, isophthalic acid, furandicarboxylic acid, phthalic acid, 4,4 '-biphenyl dicarboxylic acid, 2,6-naphthalenedicarboxylic acid and mixtures thereof; and/or all or parts of the ethylene glycol groups of the PET polyester with a diol monomer selected from the group consisting of isosorbide, 1,4-
cyclohexanedimethanol, 2,2,4,4-tetramehyl-l,3-cyclobutanediol, diethylene glycol, 1,2-propanediol, neopentylene glycol, 1,3-propanediol, 1,4 butanediol and mixtures thereof, with the proviso that not all of the terephthalic acid groups and all of the ethylene glycol groups can be replaced at the same time, and b) processing said resin.
11. The method according to claim 10, wherein the toy building element is manufactured by injection moulding and/or additive manufacturing of the resin comprising at least one polyester, at least one reactive impact modifier and at least one non-reactive impact modifier.
12. The method according to any one of claims 10 or 11, wherein the resin further comprises an additive selected from the group consisting of fillers, nucleating agents, anti-hydrolysis additives, release agent, lubricants, UV stabilizers, flame retardants, chain extenders, processing stabilizers, antioxidants and colouring agents and/or pigments and mixtures thereof.
13. The method according to any one of claims 10 to 12, wherein the impacts modifiers are mixed with the polyester(s) during feeding of the injection moulding machine.
14. The method according to any one of claims 10 to 13, wherein the impacts modifiers are mixed with the polyester(s) prior to feeding the mixture to the injection moulding machine.
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EP20180141 | 2020-06-16 | ||
PCT/EP2021/066247 WO2021255098A1 (en) | 2020-06-16 | 2021-06-16 | Toy building element made of a polymeric polyester material |
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EP4165132A1 true EP4165132A1 (en) | 2023-04-19 |
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EP21731821.1A Pending EP4165132A1 (en) | 2020-06-16 | 2021-06-16 | Toy building element made of a polymeric polyester material |
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EP (1) | EP4165132A1 (en) |
JP (1) | JP2023530350A (en) |
KR (1) | KR20230023740A (en) |
CN (1) | CN115943183A (en) |
MX (1) | MX2022016146A (en) |
WO (1) | WO2021255098A1 (en) |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
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US3005282A (en) | 1958-01-28 | 1961-10-24 | Interlego Ag | Toy building brick |
US4616064A (en) | 1983-04-26 | 1986-10-07 | Raychem Corporation | Polymeric compositions suitable for use in the medical field and comprising a thermoplastic olefin, a siloxane polymer, and an elastomer |
US5321056A (en) | 1992-06-19 | 1994-06-14 | Rohm And Haas Company | Amorphous, aromatic polyester containing impact modifier |
GB9318804D0 (en) | 1993-09-10 | 1993-10-27 | Ici Plc | Optical data recordal |
FR2801597B1 (en) * | 1999-11-26 | 2005-03-11 | Atofina | COMPOSITIONS OF THERMOPLASTIC POLYESTERS WITH IMPROVED SHOCK PROPERTIES |
US7015261B1 (en) * | 2000-11-17 | 2006-03-21 | Arkema Inc. | Impact modifier combination for polymers |
WO2014005591A1 (en) | 2012-07-04 | 2014-01-09 | Lego A/S | A method for the manufacture of a plastics product and a product made by the method |
CN110168005B (en) | 2016-11-11 | 2023-07-28 | 伊士曼化工公司 | Cellulose ester and impact modifier compositions and articles made using these compositions |
CN111432905A (en) * | 2017-12-01 | 2020-07-17 | 乐高公司 | Toy building blocks made of biopolymer material |
DK3717086T3 (en) * | 2017-12-01 | 2024-03-25 | Lego As | TOY BUILDING ELEMENT MADE OF A POLYMERIC PET MATERIAL |
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2021
- 2021-06-16 EP EP21731821.1A patent/EP4165132A1/en active Pending
- 2021-06-16 MX MX2022016146A patent/MX2022016146A/en unknown
- 2021-06-16 JP JP2022577472A patent/JP2023530350A/en active Pending
- 2021-06-16 CN CN202180043260.5A patent/CN115943183A/en active Pending
- 2021-06-16 WO PCT/EP2021/066247 patent/WO2021255098A1/en unknown
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JP2023530350A (en) | 2023-07-14 |
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