EP2643410A1 - Use of di(2-ethylhexyl)terephthalate (deht) in expandable pvc formulations - Google Patents
Use of di(2-ethylhexyl)terephthalate (deht) in expandable pvc formulationsInfo
- Publication number
- EP2643410A1 EP2643410A1 EP11788082.3A EP11788082A EP2643410A1 EP 2643410 A1 EP2643410 A1 EP 2643410A1 EP 11788082 A EP11788082 A EP 11788082A EP 2643410 A1 EP2643410 A1 EP 2643410A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- foamable composition
- composition according
- foam
- polymer
- foamable
- 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.)
- Withdrawn
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 77
- RWPICVVBGZBXNA-UHFFFAOYSA-N bis(2-ethylhexyl) benzene-1,4-dicarboxylate Chemical compound CCCCC(CC)COC(=O)C1=CC=C(C(=O)OCC(CC)CCCC)C=C1 RWPICVVBGZBXNA-UHFFFAOYSA-N 0.000 title description 19
- RWPICVVBGZBXNA-BGYRXZFFSA-N Bis(2-ethylhexyl) terephthalate Natural products CCCC[C@H](CC)COC(=O)C1=CC=C(C(=O)OC[C@H](CC)CCCC)C=C1 RWPICVVBGZBXNA-BGYRXZFFSA-N 0.000 title description 17
- 239000004807 Di(2-ethylhexyl)terephthalate Substances 0.000 title description 17
- 238000009472 formulation Methods 0.000 title description 8
- 239000006260 foam Substances 0.000 claims abstract description 51
- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 41
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 40
- 239000004014 plasticizer Substances 0.000 claims abstract description 35
- 229920000642 polymer Polymers 0.000 claims abstract description 26
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 11
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 9
- 229920001577 copolymer Polymers 0.000 claims abstract description 8
- 229920001328 Polyvinylidene chloride Polymers 0.000 claims abstract description 6
- 239000005033 polyvinylidene chloride Substances 0.000 claims abstract description 6
- 239000003381 stabilizer Substances 0.000 claims abstract description 6
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 claims abstract description 5
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002649 leather substitute Substances 0.000 claims abstract description 5
- 239000004088 foaming agent Substances 0.000 claims description 11
- 239000000049 pigment Substances 0.000 claims description 10
- 239000000945 filler Substances 0.000 claims description 8
- 239000004872 foam stabilizing agent Substances 0.000 claims description 7
- 239000000839 emulsion Substances 0.000 claims description 6
- -1 viscosity regulators Substances 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 4
- 239000003017 thermal stabilizer Substances 0.000 claims description 4
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 claims description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 2
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000000314 lubricant Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 229920001944 Plastisol Polymers 0.000 description 56
- 239000004999 plastisol Substances 0.000 description 56
- 238000005187 foaming Methods 0.000 description 24
- 238000005259 measurement Methods 0.000 description 16
- 238000012545 processing Methods 0.000 description 14
- 239000000126 substance Substances 0.000 description 14
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 13
- KKEYFWRCBNTPAC-UHFFFAOYSA-N benzene-dicarboxylic acid Natural products OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 11
- 239000000047 product Substances 0.000 description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 238000001879 gelation Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- BBVARVTURNYWGV-UHFFFAOYSA-N 7-methyloctyl benzoate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1 BBVARVTURNYWGV-UHFFFAOYSA-N 0.000 description 5
- 239000004604 Blowing Agent Substances 0.000 description 5
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 5
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 5
- 239000003380 propellant Substances 0.000 description 5
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 4
- 239000004156 Azodicarbonamide Substances 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 235000019399 azodicarbonamide Nutrition 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 239000005711 Benzoic acid Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 235000010233 benzoic acid Nutrition 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000003503 terephthalic acid derivatives Chemical class 0.000 description 3
- 239000012463 white pigment Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 2
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004049 embossing Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 150000003022 phthalic acids Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000005496 tempering Methods 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 1
- OMVSWZDEEGIJJI-UHFFFAOYSA-N 2,2,4-Trimethyl-1,3-pentadienol diisobutyrate Chemical compound CC(C)C(=O)OC(C(C)C)C(C)(C)COC(=O)C(C)C OMVSWZDEEGIJJI-UHFFFAOYSA-N 0.000 description 1
- KESQFSZFUCZCEI-UHFFFAOYSA-N 2-(5-nitropyridin-2-yl)oxyethanol Chemical compound OCCOC1=CC=C([N+]([O-])=O)C=N1 KESQFSZFUCZCEI-UHFFFAOYSA-N 0.000 description 1
- OILUAKBAMVLXGF-UHFFFAOYSA-N 3,5,5-trimethyl-hexanoic acid Chemical compound OC(=O)CC(C)CC(C)(C)C OILUAKBAMVLXGF-UHFFFAOYSA-N 0.000 description 1
- NBOCQTNZUPTTEI-UHFFFAOYSA-N 4-[4-(hydrazinesulfonyl)phenoxy]benzenesulfonohydrazide Chemical compound C1=CC(S(=O)(=O)NN)=CC=C1OC1=CC=C(S(=O)(=O)NN)C=C1 NBOCQTNZUPTTEI-UHFFFAOYSA-N 0.000 description 1
- QDTDKYHPHANITQ-UHFFFAOYSA-N 7-methyloctan-1-ol Chemical compound CC(C)CCCCCCO QDTDKYHPHANITQ-UHFFFAOYSA-N 0.000 description 1
- XZOYHFBNQHPJRQ-UHFFFAOYSA-N 7-methyloctanoic acid Chemical compound CC(C)CCCCCC(O)=O XZOYHFBNQHPJRQ-UHFFFAOYSA-N 0.000 description 1
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 1
- SHOAYVKYQLOSFO-UHFFFAOYSA-N CCCCC(CC)CO.OOO Chemical compound CCCCC(CC)CO.OOO SHOAYVKYQLOSFO-UHFFFAOYSA-N 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- OOCMUZJPDXYRFD-UHFFFAOYSA-L calcium;2-dodecylbenzenesulfonate Chemical compound [Ca+2].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O.CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O OOCMUZJPDXYRFD-UHFFFAOYSA-L 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 239000004148 curcumin Substances 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical class OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- PPSZHCXTGRHULJ-UHFFFAOYSA-N dioxazine Chemical compound O1ON=CC=C1 PPSZHCXTGRHULJ-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229960002479 isosorbide Drugs 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- BAZQYVYVKYOAGO-UHFFFAOYSA-M loxoprofen sodium hydrate Chemical group O.O.[Na+].C1=CC(C(C([O-])=O)C)=CC=C1CC1C(=O)CCC1 BAZQYVYVKYOAGO-UHFFFAOYSA-M 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002674 ointment Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003534 oscillatory effect Effects 0.000 description 1
- 230000021715 photosynthesis, light harvesting Effects 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000006077 pvc stabilizer Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000010022 rotary screen printing Methods 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical class [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000008256 whipped cream Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0023—Use of organic additives containing oxygen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
-
- C—CHEMISTRY; METALLURGY
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- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K13/02—Organic and inorganic ingredients
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- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
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- D—TEXTILES; PAPER
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- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
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- B32B2307/10—Properties of the layers or laminate having particular acoustical properties
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- B32B2607/00—Walls, panels
- B32B2607/02—Wall papers, wall coverings
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
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- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
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- E04F15/107—Flooring or floor layers composed of a number of similar elements of other materials, e.g. fibrous or chipped materials, organic plastics, magnesite tiles, hardboard, or with a top layer of other materials composed of several layers, e.g. sandwich panels
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Definitions
- the invention relates to a foamable composition containing at least one polymer selected from the group consisting of polyvinyl chloride, polyvinylidene chloride, polyvinyl butyrate, polyalkyl (meth) acrylate and copolymers thereof, a foaming agent and / or foam stabilizer and di-2-ethylhexyl tereph-thalate (DEHT) as a plasticizer.
- polyvinyl chloride (PVC) is one of the most economically important polymers and is used both as rigid PVC as well as soft PVC in a variety of applications. Important applications include cable sheathing, floor coverings, wallpapers and frames for plastic windows. To increase elasticity, plasticizers are added to the PVC.
- plasticizers include, for example, phthalic acid esters such as di-2-ethylhexyl phthalate (DEHP), diisononyl phthalate (DINP) and diisodecyl phthalate (DIDP).
- DEHP di-2-ethylhexyl phthalate
- DIDP diisononyl phthalate
- DIDP diisodecyl phthalate
- terephthalic acid esters such as di-2-ethylhexyl terephthalate (DEHT) or cyclohexanoic acid esters such as diisonone-1,2-cyclohexanedicarboxylic acid ester (DINCH) have recently been discussed as possible alternatives.
- DEHT di-2-ethylhexyl terephthalate
- DICH diisonone-1,2-cyclohexanedicarboxylic acid ester
- EP 1 505 104 describes a foamable composition which contains isononyl benzoate as plasticizer.
- the use of benzoic acid isonon esters as plasticizers has the considerable disadvantage that isononyl benzoate are very volatile and therefore escape from the polymer during processing and also with increasing storage and use time. This provides considerable problems, in particular in applications, for example indoors. Therefore, in the prior art, the isononyl benzoates are frequently used as plasticizer admixtures with customary other plasticizers, for example phthalic acid esters. Isononyl benzoates are also known as
- EP 1 808 457 A1 describes the use of terephthalic acid dialkyl esters, which are characterized in that the alkyl radicals have a longest carbon chain of at least four carbon atoms and have a total number of carbon atoms per alkyl radical of five. It is stated that terephthalic acid esters having four to five C atoms in the longest carbon chain of the alcohol are well suited as PVC fast-curing plasticizers. It is also described that this was particularly surprising because prior art such terephthalic acid esters were considered incompatible with PVC. The document further states that the terephthalic acid dialkyl esters are also mixed or mechanically foamed layers or in compact layers or primers can be used. But even these plasticizers are classified as relatively volatile fast gelators, so that the above problems persist in principle.
- di-2-ethylhexyl terephthalate has been known for decades as a plasticizer for PVC and other polymers.
- Application technical data for this product are described in numerous publications, in particular in the form of conference reports and presentations.
- Don Beeler Tephthalate esters, a new class of plasticizers for poly (vinyl chloride)
- the object of the invention is to identify such plasticizers, which show even without the use of Schnellgelierern foaming properties that are equal to those of the DINP and therefore the above difficulties of faster viscosity increase of the corresponding plastisols with time (storage stability) and the clearly no longer show much higher volatility.
- these plastisols should also be readily processable, ie show a viscosity similar to that of the current standard DINP, because otherwise the viscosity of the plastisol would have to be adjusted by increased addition of thinners and then the thinner would have to be thermally expelled again during processing, which is economically and ecologically disadvantageous.
- a foamable composition containing at least one polymer selected from the group consisting of polyvinyl chloride, polyvinylidene chloride, polyvinyl butyrate, polyalkyl (meth) acrylate and copolymers thereof, a foaming agent and / or foam stabilizer and di-2-ethylhexyl terephthalate (DEHT) as plasticizers.
- polymer selected from the group consisting of polyvinyl chloride, polyvinylidene chloride, polyvinyl butyrate, polyalkyl (meth) acrylate and copolymers thereof, a foaming agent and / or foam stabilizer and di-2-ethylhexyl terephthalate (DEHT) as plasticizers.
- DEHT di-2-ethylhexyl terephthalate
- compositions containing di-2-ethylhexyl terephthalate (DEHT) and a foaming agent or foam stabilizer are suitable for the production of foams or foamed layers which exhibit significantly greater expansion behavior over corresponding DINP-containing compositions at the same temperature and residence time although the gelling speed is lowered.
- DEHT di-2-ethylhexyl terephthalate
- foaming agent or foam stabilizer are suitable for the production of foams or foamed layers which exhibit significantly greater expansion behavior over corresponding DINP-containing compositions at the same temperature and residence time although the gelling speed is lowered.
- di-2-ethylhexyl terephthalate according to the invention is significantly less volatile than isononyl benzoate used in the prior art in foamable compositions.
- the possibility of dispensing with-as a rule-volatile, fast gelators also facilitates the use for interior applications since the plasticizers of the composition according to the invention are less volatile and less readily escape from the plastic.
- At least one polymer contained in the foamable composition is selected from the group consisting of polyvinyl chloride, polyvinylidene chloride, polyvinyl butyrate, polyalkyl (meth) acrylate, and copolymers thereof.
- the polymer may be a copolymer of vinyl chloride with one or more monomers selected from the group consisting of vinylidene chloride, vinyl butyrate, methyl (meth) acrylate, ethyl (meth) acrylate or butyl (meth) acrylate.
- the amount of diisononyl-1, 2-cyclohexanedicarboxylic acid ester in the foamable composition is 5 to 150 parts by mass, preferably 10 to 100 parts by mass, more preferably 10 to 80 parts by mass and most preferably 15 to 90 parts by mass per 100 parts by mass of polymer.
- the foamable composition may optionally contain further additional plasticizers other than di-2-ethylhexyl terephthalate.
- the solvation and / or gelling ability of the additional plasticizers may in this case be higher, equal to or lower than those of the di-2-ethylhexyl terephthalates according to the invention.
- the mass ratio of the additional plasticizers used to the di-2-ethylhexyl terephthalates used according to the invention is in particular between 1:10 and 10: 1, preferably between 1:10 and 8: 1, more preferably between 1:10 and 5: 1 and in particular preferably between 1:10 and 1: 1.
- the additional plasticizers are esters of orthophthalic acid, isophthalic acid, terephthalic acid (excluding di-2-ethylhexyl terephthalate), cyclohexanedicarboxylic acid, trimellitic acid, citric acid, benzoic acid, isononanoic acid, 2-ethylhexanoic acid, Octanoic acid, 3,5,5-trimethylhexanoic acid and / or esters of butanol, pentanol, octanol, 2-ethylhexanol, isononanol, decanol, dodecanol, tridecanol, glycerol and / or isosorbide and their derivatives and mixtures.
- citric acid esters such as acetyl tributyl citrate or benzoates can be used.
- the foamable composition can be foamed chemically or mechanically.
- chemical foaming is understood to mean that the foamable composition contains a foaming agent which forms gaseous components by thermal decomposition at a higher temperature, which then cause the foaming.
- the foamable composition according to the invention contains a foaming agent.
- This foaming agent may be a gas bubble developing compound optionally containing a kicker.
- Kicker metal compounds are called, which catalyze the thermal decomposition of the gas bubbles developing component and cause the foaming agent decomposes to gas evolution and the foamable composition is foamed.
- Foaming agents are also referred to as blowing agents.
- a gas bubble-developing component a compound is preferably used, which under the influence of heat gaseous constituents disintegrate, causing the composition to expand. A typical representative of such compounds is z.
- As azodicarbonamide which releases mainly thermal decomposition N 2 and CO. The decomposition temperature of the propellant can be reduced by the kicker.
- pp '-Oxybisibenzolsulfonhydrazid Another usable propellant is called pp '-Oxybisibenzolsulfonhydrazid), also OBSH. This is characterized by a lower compared to azodicarbonamide decomposition temperature. Further information on propellants can be found in the "Handbook of Vinyl Formulating", Second Edition, John Wiley Publication (ISBN 978-0-471 -71046-2), pages 379. The most preferred blowing agent is azodicarbonamide.
- foam stabilizers are preferably used in mechanical foams.
- Commercially available foam stabilizers may be present in the composition according to the invention as foam stabilizers.
- foam stabilizers may e.g. based on silicone or soap and are used e.g. under the brand names BYK (Byk-Chemie) offered.
- the foamable compositions according to the invention can be, for example, plastisols which can be prepared by mixing emulsion or microsuspension PVC with liquid components such as plasticizers. It is further preferred that the foamable composition contains an emulsion PVC. Most preferably, the foamable composition according to the invention comprises an emulsion PVC which has a molecular weight expressed as K value (Fikent's constant) of 60 to 95 and more preferably of 65 to 90.
- K value Fikent's constant
- the foamable composition may furthermore preferably comprise additional additives which are in particular selected from the group consisting of fillers, pigments, heat stabilizers, antioxidants, viscosity regulators, (further) foam stabilizers, flame retardants, adhesion promoters and lubricants.
- additional additives which are in particular selected from the group consisting of fillers, pigments, heat stabilizers, antioxidants, viscosity regulators, (further) foam stabilizers, flame retardants, adhesion promoters and lubricants.
- the thermal stabilizers neutralize u. a. hydrochloric acid split off during and / or after the processing of the PVC and prevent thermal degradation of the polymer.
- Suitable thermal stabilizers are all customary PVC stabilizers in solid and liquid form, for example based on Ca / Zn, Ba / Zn, Pb, Sn or organic compounds (OBS), and also acid-binding phyllosilicates such as hydrotalcite.
- the mixtures according to the invention may have a content of from 0.5 to 10, preferably from 1 to 5, particularly preferably from 1.5 to 4, parts by mass per 100 parts by mass of polymer to thermal stabilizers.
- pigments both inorganic and organic pigments can be used in the context of the present invention.
- the content of pigments is between 0.01 to 10 mass%, preferably 0.05 to 5 mass%, particularly preferably 0, 1 to 3 mass% per 100 mass parts of polymer.
- examples of inorganic pigments are CdS, C0O / Al2O3, Cr 2 O 3.
- Known organic pigments are, for example, azo dyes, phthalocyanine pigments, dioxazine pigments and aniline pigments.
- TXIB 2,2,4-trimethyl-1,3-pentanediol diisobutyrate
- Viscosity reducing reagents are added in proportions of 0.5 to 30, preferably 1 to 20, more preferably 2 to 15 parts by mass per 100 parts by mass of polymer.
- Special viscosity-lowering additives are offered, for example, under the trade name Viskobyk (Byk-Chemie).
- Another object of the present application is the use of the foamable composition for floor coverings, wallpaper or artificial leather.
- Another object of the invention is a floor covering containing the foamable composition of the invention, a wall wallpaper containing the foamable composition of the invention or artificial leather containing the foamable inventive composition.
- Di-2-ethylhexyl terephthalate is prepared industrially either by transesterifying dimethyl terephthalate with the bulky oxo-alcohol 2-ethylhexanol or by esterifying terephthalic acid with this alcohol. Another possibility is the conversion of PET recycling material with 2-ethylhexanol. Corresponding preparation processes are described, for example, in WO 2008094396, US 2007038001 or in Huagong Jinzhan (2008), 27 (1), 143-146. For example, DEHT is commercially available from the Eastman Chemical Company under the designation Eastman 168.
- the preparation of the foamable composition according to the invention can be carried out in various ways. In general, however, the composition is prepared by intensive mixing of all components in a suitable mixing container. Here, the components are preferably added successively (see also EJ Wickson, "Handbook of PVC Formulating", John Wiley and Sons, 1993, p. 727).
- the foamable composition according to the invention can be used for the production of foamed moldings which contain at least one polymer selected from the group polyvinyl chloride or polyvinylidene chloride or copolymers thereof.
- foamed products are, for example, imitation leather, floors or wall-mounted wallpaper, in particular the use of the foamed products in cushion vinyl floors and wallpapers.
- the foamed products of the foamable composition according to the invention are prepared by first applying the foamable composition to a support or another polymer layer and foaming the composition before or after application and finally thermally processing the applied and / or foamed composition ,
- the foam in contrast to the mechanical foam, in the case of chemical foams, the foam is formed only during processing, as a rule in a gelling channel, ie, the unfoamed composition is applied to the carrier, preferably by brushing.
- a profiling of the foam can be achieved by selective application of inhibitor solutions, for example via a rotary screen printing machine. At the sites where the inhibitor solution was applied, expansion of the plastisol during processing either does not take place at all or only delayed.
- chemical foaming is used to a much greater extent than mechanical ones. For more information on chemical and mechanical foaming, see, for example, EJ Wickson, Handbook of PVC Formulating, 1993, John Wiley & Sons.
- profiling can also be achieved subsequently by means of the so-called mechanical embossing, for example by means of an embossing roller.
- the carriers can also be only temporary carriers, from which the foams produced can be removed again as foam layers.
- Such carriers may be, for example, metal bands or release paper (duplex paper).
- the final thermal processing takes place in both cases in a so-called gelation channel, usually a furnace, which is passed through by the applied on the support layer of the composition according to the invention or in which the provided with the layer carrier is briefly introduced.
- the gelling channel can be combined with a device used to produce the foam, for example, it is possible to use only one gelling channel, in which: the foam is chemically generated in the front part at a first temperature by decomposition of a gas-forming component and this foam is transferred into the semifinished product or end product in the rear part of the gelling channel at a second temperature, which is preferably higher than the first temperature It is also possible that gelation and
- Typical processing temperatures are in the range of 130 to 280 ° C, preferably in the range of 150 to 250 ° C. Gelation is preferably carried out such that the foamed composition is treated at the stated gelling temperatures for a period of 0.5 to 5 minutes, preferably for a period of 0.5 to 3 minutes. The duration of the temperature treatment can be adjusted in continuous processes by the length of the gelling channel and the speed at which the foam-containing carrier passes through it.
- Typical foaming temperatures (chemical foam) are in the range of 160 to 240 ° C, preferably 180 to 220 ° C.
- the individual layers are usually first fixed in their form by a so-called pre-gelation of the applied plastisol at a temperature which is below the decomposition temperature of the propellant, after which further layers (for example a cover layer) can be applied.
- a cover layer When all layers have been applied, gelation is carried out at a higher temperature - and, in the case of chemical foaming, also foaming. By this procedure, the desired profile can also be transferred to the cover layer.
- the foamable compositions according to the invention have the advantage over the prior art that they can be processed either at the same temperatures faster or alternatively at lower temperatures, and thus the efficiency of the production process of the PVC foams is considerably improved.
- the plasticizers used in the PVC foam are less volatile than, for example, the benzoic acid isononyl esters mentioned in the prior art, and thus the PVC foam is particularly suitable in particular for interior applications.
- Carrier gas helium Injection volume: 3 microliters
- the viscosity of the PVC plastisols was measured using a Physica MCR 101 (Anton Paar) using the rotation mode and the measuring system "Z3" (DIN 25 mm).
- the plastisol was first homogenized manually in the batch tank using a spatula, then filled into the measuring system and measured isothermally at 25 ° C. During the measurement the following points were activated: 1. A pre-shear of 100 s "1 for the period of 60 s at which no measured values were recorded (to level any thixotropic effects that may occur).
- a shear rate down ramp starting at 200 s "1 and ending at 0, 1 s " 1 , divided into a logarithmic series with 30 steps each with a 5 second measurement point duration.
- the measurements were usually carried out (unless stated otherwise) after storage / maturation of the plastisols of 24 h. Between measurements, the plastisols were stored at 25 ° C.
- Heating / cooling rate 5 K / min
- Oscillation frequency 4 - 0, 1 Hz ramp (logarithmic)
- the foaming behavior was determined with the aid of a thickness cutter suitable for soft PVC measurements (KXL047, Mitutoyo) with an accuracy of 0.01 mm 5.
- a thickness cutter suitable for soft PVC measurements KXL047, Mitutoyo
- the roll doctor of a Mathis Labcoaters type:
- LTE-TS Long Term Evolution-TS
- Manufacturer Fa. W. Mathis AG
- a doctor gap of 1 mm. This was checked with a feeler gauge and readjusted if necessary.
- the plastisols were knife-coated onto a release paper clamped in a frame (Warran Release Paper, Sappi Ltd.) using the doctor blade of Mathis Labcoater.
- a gelled and unfoamed film was first produced at 200 ° C./30 seconds dwell time.
- the measurement of the thickness was carried out at three different locations of the film.
- the yellow value (index YD 1925) is a measure of yellow discoloration of a specimen.
- the color measurement of the foam films was carried out with a Spectro Guide from the Byk-Gardner company.
- the background for the color measurements was a white reference tile. The following parameters have been set: Light type: C / 2 °
- the advantages of the plastisols according to the invention are to be clarified on the basis of a filler and pigment-containing thermally expandable PVC plastisol.
- the following plastisols according to the invention are, inter alia, examples of thermally expandable plastisols which are used in the production of floor coverings.
- the following plastisols according to the invention are exemplary of foam layers which are used as printable and / or inhibitable top foams in multilayer PVC floors.
- the used weights of the components for the different plastisols are shown in the following table (1). The liquid and solid formulation components were weighed separately into a suitable PE cup each time.
- the mixture was stirred with an ointment spatula so that no unwetted powder was present.
- the plastisols were mixed with a Kreiss dissolver VDKV30-3 (manufacturer Fa. Niemann).
- the mixing cup was clamped in the clamping device of the dissolver stirrer.
- the sample was homogenized using a mixer disk (toothed disk, finely toothed, 0: 50 mm).
- the speed of the dissolver was continuously increased from 330 rpm to 2000 rpm and stirred until the temperature at the digital readout of the thermocouple reached 30.0 ° C.
- VESTOLIT P1352 K emulsion PVC (homopolymer) with a K value (determined according to DIN EN ISO 1628-2) of 68; Fa. Vestolit GmbH & Co. KG
- Eastman 168 di-2-ethylhexyl terephthalate; Fa. Eastman Chemical
- VESTINOL® 9 diisononyl (ortho) phthalate (DINP), plasticizer; Fa. Evonik Oxeno GmbH
- Unifoam AZ Ultra 1035 azodicarbonamide; thermally activated blowing agent; Fa. Hebron S.A.
- Calcilit 8G calcium carbonate; Filler; Fa. Alpha Calcite.
- KRONOS 2220 rutile pigment (TiO 2 ) stabilized with Al and Si; White pigment; Company Kroenos Worldwide Inc.
- Isopropanol Cosolvent for lowering the plastisol viscosity and additive for improving the foam structure (Brenntag AG).
- Zinc oxide active ® ZnO
- Thermal decomposition catalyst which lowers the substractive decomposition temperature of the blowing agent, but also acts as a stabilizer, for better distribution the zinc oxide was treated with the appropriate plasticizer (mass ratio 1: 2) and rubbed on a 3-roll mill; Fa. Lanxess AG
- DEHT has a worse Gelierner than the DINP.
- thermally expandable plastisols with fillers are made available which, despite obvious disadvantages in gelling behavior (see Example 3), have advantages in terms of thermal expandability.
- the completeness of the decomposition of the blowing agent used, and thus the progress of the expansion process can also be read off from the color of the foam produced (despite the content of white pigment). The lower the yellowing of the foam, the further the expansion process is completed.
- Example 4 The yellowness of the polymer foams or foam foils prepared in Example 4, determined according to the analysis, item 5 (see above), is shown in the following Table (5). TABLE 5 Yellow values (YI D1925) of the polymer foams prepared according to Example 4.
- the plastisols prepared on the basis of the composition according to the invention have a significantly lower color number in the foamed state (from 120 s).
- the value at 60 s is of practically no importance due to the fact that foaming is just beginning.
- filled plastisols are provided which, despite apparent disadvantages in gelation, allow a faster processing speed and / or lower processing temperatures with respect to foaming.
- filler here chalk
- 0 i.e., unfilled but pigmented system
- 133 phr i.e., highly filled formulation
- Vestolit E 7012 S emulsion PVC (homopolymer) with a K value (determined according to DIN EN ISO 1628-2) of 67; Fa. Vestolit GmbH & Co. KG.
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Abstract
The invention relates to an expandable composition containing a polymer selected from among the group consisting of polyvinyl chloride, polyvinylidene chloride, polyvinyl butyrate, polyalkyl (meth)acrylate, and copolymers thereof, an expanding agent and/or foam stabilizer, and di-2-ethylhexyl terephthalate as a plasticizer. The invention further relates to expanded molded articles and the use of the expandable composition for floor coverings, wallpapers, or synthetic leather.
Description
Verwendung von Di(2-ethylhexyl)terephthalat (DEHT) in verschäumbaren PVC- Formulierungen Use of di (2-ethylhexyl) terephthalate (DEHT) in foamable PVC formulations
Gegenstand der Erfindung ist eine schäumbare Zusammensetzung enthaltend mindes- tens ein Polymer ausgewählt aus der Gruppe bestehend aus Polyvinylchlorid, Polyvinyl- idenchlorid, Polyvinylbutyrat, Polyalkyl(meth)acrylat und Copolymeren davon, einen Schaumbildner und/oder Schaumstabilisator und Di-2-ethylhexyltereph-thalat (DEHT) als Weichmacher. Polyvinylchlorid (PVC) ist eines der wirtschaftlich bedeutendsten Polymere und wird sowohl als Hart-PVC wie auch als Weich-PVC in vielfältigen Anwendungen eingesetzt. Wichtige Anwendungsbereiche sind beispielsweise Kabelummantelungen, Fußbodenbeläge, Tapeten sowie Rahmen für Kunststofffenster. Zur Erhöhung der Elastizität werden dem PVC Weichmacher zugesetzt. Zu diesen üblichen Weichmachern gehören beispielsweise Phthalsäureester wie Di-2-ethylhexylphthalat (DEHP), Diisononylphthalat (DINP) und Diisodecylphthalat (DIDP). The invention relates to a foamable composition containing at least one polymer selected from the group consisting of polyvinyl chloride, polyvinylidene chloride, polyvinyl butyrate, polyalkyl (meth) acrylate and copolymers thereof, a foaming agent and / or foam stabilizer and di-2-ethylhexyl tereph-thalate (DEHT) as a plasticizer. Polyvinyl chloride (PVC) is one of the most economically important polymers and is used both as rigid PVC as well as soft PVC in a variety of applications. Important applications include cable sheathing, floor coverings, wallpapers and frames for plastic windows. To increase elasticity, plasticizers are added to the PVC. These conventional plasticizers include, for example, phthalic acid esters such as di-2-ethylhexyl phthalate (DEHP), diisononyl phthalate (DINP) and diisodecyl phthalate (DIDP).
In vielen PVC-Artikeln ist es üblich, durch Aufbringen von Schaumschichten das Gewicht der Produkte und somit auch die Kosten auf Grund des geringeren Materialein- satzes zu reduzieren. Für den Anwender kann ein geschäumtes Produkt, beispielsweise bei Fußbodenbelägen, den Vorteil einer besseren Trittschalldämmung mit sich bringen. Die Güte der Verschäumung ist innerhalb der Formulierung von vielen Komponenten abhängig, neben Art und Menge des Schaumbildners spielen auch der verwendete PVC-Typ und der Weichmacher eine wichtige Rolle. So ist bekannt, dass besonders dann eine gute Verschäumung erreicht werden kann, wenn gut gelierende Weichmacher (sog. Schnellgelierer) wie BBP (Benzyl-butyl-phthalat) zumindest anteilig in der Rezeptur verwendet werden. In vielen Fällen ist jedoch die alleinige Verwendung von DINP auch aus Kostengründen etabliert. Im Zusammenhang mit der Diskussion um ortho-Phthalate im Kinderspielzeug sind verschiedene gesetzliche Maßnahmen zur Regulierung dieser Stoffgruppe erlassen wor-
den, und eine weitere Verschärfung ist prinzipiell nicht auszuschließen. Somit arbeitet die Industrie intensiv an der Entwicklung neuer ortho-Phthalat freier Weichmacher, die toxikologisch unbedenklich sind und auch in ihren technischen Eigenschaften den Phthalaten ebenbürtig sind. So sind in neuerer Zeit Terephthalsäureester wie bei- spielsweise Di-2-ethylhexylterephthalat (DEHT) oder Cyclohexansäureester wie Diiso- nonyl-1 ,2-cyclohexandicarbonsäureester (DINCH) als mögliche Alternativen diskutiert worden. In many PVC articles, it is customary to reduce the weight of the products and thus also the costs due to the lower use of material by applying foam layers. For the user, a foamed product, for example in the case of floor coverings, can bring the advantage of better footfall sound insulation. The quality of the foaming is dependent on the formulation of many components, in addition to the type and amount of the foaming agent and the PVC type used and the plasticizer play an important role. Thus, it is known that good foaming can be achieved especially when well-gelling plasticizers (so-called rapid gels) such as BBP (benzyl-butyl-phthalate) are used at least proportionally in the formulation. In many cases, however, the sole use of DINP is also established for cost reasons. In connection with the discussion about ortho-phthalates in children's toys, various legal measures have been adopted to regulate this substance group. and further tightening can not be ruled out in principle. Thus, the industry is working intensively on the development of new ortho-phthalate-free plasticizers, which are toxicologically safe and in their technical properties equal to the phthalates. For example, terephthalic acid esters such as di-2-ethylhexyl terephthalate (DEHT) or cyclohexanoic acid esters such as diisonone-1,2-cyclohexanedicarboxylic acid ester (DINCH) have recently been discussed as possible alternatives.
Die EP 1 505 104 beschreibt eine schäumbare Zusammensetzung, die als Weichmacher Benzoesäureisononylester enthält. Die Verwendung von Benzoesäureisonony- lestern als Weichmacher hat jedoch den erheblichen Nachteil, dass Benzoesäureisononylester sehr flüchtig sind und daher während der Verarbeitung und auch mit zunehmender Lager- und Benutzungszeit aus dem Polymer entweichen. Dies liefert insbesondere bei Anwendungen beispielsweise in Innenräumen erhebliche Probleme. Es werden daher im Stand der Technik die Benzoesäureisononylester häufig als Weichmacherbeimischungen mit üblichen anderen Weichmachern verwendet wie beispielsweise Phthalsäureestern. Benzoesäureisononylester werden weiterhin auch als EP 1 505 104 describes a foamable composition which contains isononyl benzoate as plasticizer. The use of benzoic acid isonon esters as plasticizers, however, has the considerable disadvantage that isononyl benzoate are very volatile and therefore escape from the polymer during processing and also with increasing storage and use time. This provides considerable problems, in particular in applications, for example indoors. Therefore, in the prior art, the isononyl benzoates are frequently used as plasticizer admixtures with customary other plasticizers, for example phthalic acid esters. Isononyl benzoates are also known as
Schnellgelierer verwendet. Weiterhin würde die Verwendung von Schnellgelierern wie BBP oder auch Benzoesäureisononylester einen zu starken Anstieg der Viskosität des entsprechenden Plastisols mit der Zeit verursachen. Fast gelator used. Furthermore, the use of rapid gellants such as BBP or also benzoic isononyl ester would cause an excessive increase in the viscosity of the corresponding plastisol with time.
Als weitere Weichmacher sind im Stand der Technik auch gewisse Terephthalsäuralky- lester für den Einsatz in PVC bekannt. So beschreibt die EP 1 808 457 A1 den Einsatz von Terephthalsäuredialkylestern, die dadurch gekennzeichnet sind, dass die Alkylreste eine längste Kohlenstoffkette von zumindest vier Kohlenstoffatomen aufweisen und eine Gesamtzahl an Kohlenstoffatomen pro Alkylrest von fünf aufweisen. Es wird angegeben, dass Terephthalsäureester mit vier bis fünf C-Atomen in der längsten Kohlenstoffkette des Alkohols als schnellgelierende Weichmacher für PVC gut geeignet sind. Es wird auch beschrieben, dass dies insbesondere überraschend war, da vorher im Stand der Technik solche Terephthalsäureester mit PVC als unverträglich angesehen wurden. Die Druckschrift gibt weiterhin an, dass die Terephthalsäuredialkylester auch in che-
misch oder mechanisch geschäumten Schichten oder in Kompaktschichten bzw. Grundierungen eingesetzt werden können. Aber auch diese Weichmacher sind als relativ flüchtige Schnellgelierer zu klassifizieren, so dass die o.g. Probleme prinzipiell weiter bestehen. Other plasticizers also known in the art are certain terephthalic acid alkyl esters for use in PVC. Thus, EP 1 808 457 A1 describes the use of terephthalic acid dialkyl esters, which are characterized in that the alkyl radicals have a longest carbon chain of at least four carbon atoms and have a total number of carbon atoms per alkyl radical of five. It is stated that terephthalic acid esters having four to five C atoms in the longest carbon chain of the alcohol are well suited as PVC fast-curing plasticizers. It is also described that this was particularly surprising because prior art such terephthalic acid esters were considered incompatible with PVC. The document further states that the terephthalic acid dialkyl esters are also mixed or mechanically foamed layers or in compact layers or primers can be used. But even these plasticizers are classified as relatively volatile fast gelators, so that the above problems persist in principle.
Das bereits oben erwähnte Di-2-ethylhexylterephthalat (DEHT) ist seit Jahrzehnten als Weichmacher für PVC und andere Polymere bekannt. Anwendungstechnische Daten zu diesem Produkt sind in zahlreichen Veröffentlichungen, insbesondere auch in Form von Konferenzberichten und Präsentationen beschrieben. Hier seien beispielhaft die Veröf- fentlichung von Don Beeler („Terephthalate esters, a new class of plasticizers for po- ly(vinyl Chloride") in Technical Papers - Society of Plastics Engineers (1976), 22 613-15, sowie die Präsentation von M. Stimpson und M. Holt auf der PVC Formulation- Konferenz im März 2009 in Köln mit dem Titel„DEHT: an Alternative to ortho-Phthalates in flexible PVC Compound Applications" genannt. Hier wurde beispielsweise auch auf die im Vergleich zu DINP geringere Gelierfähigkeit des DEHT hingewiesen. Auch auf zahlreichen weiteren Konferenzen wurden Versuchsergebnisse zu diesem Produkt vorgestellt. Angaben über die Eignung in DEHT als Weichmacher für oder in schäumbaren Zusammensetzungen sind bisher jedoch nicht bekannt. Es ist jedoch davon auszugehen, dass sich das schlechtere Gelierverhalten von DEHT im Vergleich zu DINP negativ auf die Verschäumbarkeit, d.h. die prozentuale Aufschäumung pro Zeiteinheit bei gegebener Temperatur auswirken wird. Dies ist auch aus einer Aussage in dem bekannten Fachbuch„Handbook of Vinyl Formulating", Second Edition, Verlag John Wiley (ISBN 978-0-471 -71046-2), S. 384, zu schließen, dass näm- lieh („...with slower fusing plasticizers.., it may be necessary to... run at higher oven temperatures") schlechter gelierende Weichmacher für Verschäumungen höhere Temperaturen benötigen. Höhere Temperaturen allerdings sind für den Verarbeiter nachteilig, da zum einen die Energiekosten steigen und zum anderen das Produkt durch thermisches Altern verfärbt wird.
Somit besteht die Aufgabe der Erfindung darin, solche Weichmacher zu identifizieren, die auch ohne die Verwendung von Schnellgelierern Verschäumungseigenschaften zeigen, die denen des DINP ebenbürtig sind und die daher die oben genannten Schwierigkeiten des schnelleren Viskositätsanstiegs der entsprechenden Piastisole mit der Zeit (Lagerstabilität) und die deutlich höhere Flüchtigkeit nicht mehr zeigen. Gleichermaßen sollten auch diese Piastisole gut verarbeitbar sein, d.h. eine Viskosität zeigen, die ähnlich der des derzeitigen Standards DINP liegt, weil sonst wieder durch vermehrte Zugabe von Verdünnern die Viskosität des Plastisols eingestellt und danach der Verdünner bei der Verarbeitung wieder thermisch ausgetrieben werden müsste, was ökonomisch und ökologisch nachteilig ist. The already mentioned above di-2-ethylhexyl terephthalate (DEHT) has been known for decades as a plasticizer for PVC and other polymers. Application technical data for this product are described in numerous publications, in particular in the form of conference reports and presentations. For example, the publication of Don Beeler ("Terephthalate esters, a new class of plasticizers for poly (vinyl chloride)" in Technical Papers - Society of Plastics Engineers (1976), 22613-15, and the presentation of M. Stimpson and M. Holt at the PVC Formulation Conference in Cologne in March 2009 with the title "DEHT: an alternative to ortho-phthalates in flexible PVC compound applications", where, for example, the lower gelling ability compared to DINP Test results for this product have also been presented at numerous other conferences, but no information is currently available on the suitability of DEHT as a plasticizer for or in foamable compositions, but DEHT's poorer gelling behavior is expected to be comparable to DINP negative on the foamability, ie the percentage foaming per unit time at a given temperature will affect is also from a statement in the well-known textbook "Handbook of Vinyl Formulating", Second Edition, Publisher John Wiley (ISBN 978-0-471 -71046-2), p. 384, to conclude that it lent (".. . with slower fusing plasticizers.), poorer gelling plasticizers require higher temperatures for foaming. Higher temperatures, however, are disadvantageous for the processor, on the one hand the energy costs increase and on the other hand the product is discolored by thermal aging. Thus, the object of the invention is to identify such plasticizers, which show even without the use of Schnellgelierern foaming properties that are equal to those of the DINP and therefore the above difficulties of faster viscosity increase of the corresponding plastisols with time (storage stability) and the clearly no longer show much higher volatility. Likewise, these plastisols should also be readily processable, ie show a viscosity similar to that of the current standard DINP, because otherwise the viscosity of the plastisol would have to be adjusted by increased addition of thinners and then the thinner would have to be thermally expelled again during processing, which is economically and ecologically disadvantageous.
Diese technische Aufgabe wird gelöst durch eine schäumbare Zusammensetzung enthaltend mindestens ein Polymer ausgewählt aus der Gruppe bestehend aus Polyvinylchlorid, Polyvinylidenchlorid, Polyvinylbutyrat, Polyalkyl(meth)acrylat und Copolymeren davon, einem Schaumbildner und/oder Schaumstabilisator und Di-2- ethylhexylterephthalat (DEHT) als Weichmacher. This technical object is achieved by a foamable composition containing at least one polymer selected from the group consisting of polyvinyl chloride, polyvinylidene chloride, polyvinyl butyrate, polyalkyl (meth) acrylate and copolymers thereof, a foaming agent and / or foam stabilizer and di-2-ethylhexyl terephthalate (DEHT) as plasticizers.
Völlig überraschend wurde gefunden, dass Zusammensetzungen, die Di-2- ethylhexylterephthalat (DEHT) und einen Schaumbildner oder einen Schaumstabilisator enthalten, zur Herstellung von Schäumen oder geschäumten Schichten geeignet sind, die gegenüber entsprechenden DINP haltigen Zusammensetzungen bei gleicher Temperatur und Verweilzeit deutlich stärkeres Expansionsverhalten zeigen, obwohl die Geliergeschwindigkeit herabgesetzt ist. Hierdurch ist es möglich, entweder die Verarbeitungstemperatur abzusenken oder bei der gleichen Temperatur die Verweilzeit im Ofen abzusenken, was zu einem höheren und somit für den Verarbeiter vorteilhaften Produktausstoß pro Zeiteinheit führt. Dies ist insofern überraschend, als dies im Widerspruch zur gängigen Lehrbuchmeinung (z.B.„Handbook of Vinyl Formulating", Second Edition, Verlag John Wiley (ISBN 978-0-471 -71046-2), Seite 384) steht, dass besser gelierende Weichmacher auch zu höheren Expansionsraten bei der Verschäumung füh- ren.
Ein weiterer Vorteil ist es, dass die schäumbaren Zusammensetzungen bei niedrigeren Temperaturen verarbeitet werden können und daher auch einen deutlich geringeren Gelbwert zeigen. Auch bei gleicher Verarbeitungstemperatur ist der Gelbwert der entsprechenden Schaumfolien aus den erfindungsgemäßen Zusammensetzungen geringer als der einer entsprechenden DINP-Rezeptur, so dass hier weniger Weißpigment zur Kaschierung der Gelbfärbung eingesetzt werden kann. Quite surprisingly, it has been found that compositions containing di-2-ethylhexyl terephthalate (DEHT) and a foaming agent or foam stabilizer are suitable for the production of foams or foamed layers which exhibit significantly greater expansion behavior over corresponding DINP-containing compositions at the same temperature and residence time although the gelling speed is lowered. This makes it possible to lower either the processing temperature or lower the residence time in the oven at the same temperature, resulting in a higher and thus advantageous for the processor product output per unit time. This is surprising inasmuch as this is in contradiction to the common textbook opinion (eg "Handbook of Vinyl Formulating", Second Edition, John Wiley Verlag (ISBN 978-0-471 -71046-2), page 384) that better gelling plasticizers also lead to higher expansion rates during foaming. Another advantage is that the foamable compositions can be processed at lower temperatures and therefore also have a much lower yellow value. Even at the same processing temperature, the yellow value of the corresponding foam films of the compositions according to the invention is lower than that of a corresponding DINP formulation, so that less white pigment can be used here for lamination of the yellow coloration.
Weiterhin ist festzustellen, dass Di-2-ethylhexylterephthalat gemäß der Erfindung deutlich weniger flüchtig ist als Benzoesäureisononylester, die im Stand der Technik in schäumbaren Zusammensetzungen verwendet werden. Durch die Möglichkeit des Verzichts auf - in der Regel - flüchtige Schnellgelierer wird auch der Einsatz für Anwendungen in Innenräumen erleichtert, da die Weichmacher aus der erfindungsgemäßen Zusammensetzung weniger flüchtig sind und weniger stark aus dem Kunststoff entweichen. It should also be noted that di-2-ethylhexyl terephthalate according to the invention is significantly less volatile than isononyl benzoate used in the prior art in foamable compositions. The possibility of dispensing with-as a rule-volatile, fast gelators also facilitates the use for interior applications since the plasticizers of the composition according to the invention are less volatile and less readily escape from the plastic.
Mindestens ein Polymer, das in der schäumbaren Zusammensetzung enthalten ist, ist ausgewählt aus der Gruppe bestehend aus Polyvinylchlorid, Polyvinylidenchlorid, Poly- vinylbutyrat, Polyalkyl(meth)acrylat und Copolymeren davon. In einer weiteren bevorzugten Ausführungsform kann das Polymer ein Copolymer von Vinylchlorid mit einem oder mehreren Monomeren ausgewählt aus der Gruppe bestehend aus Vinylidenchlorid, Vinylbutyrat, Methyl(meth)acrylat, Ethyl(meth)acrylat oder Butyl(meth)acrylat sein. In bevorzugter Weise ist die Menge an Diisononyl-1 ,2-cyclohexandicarbonsäure-ester in der schäumbaren Zusammensetzung 5 bis 150 Massenteile, bevorzugt 10 bis 100 Massenteile, besonders bevorzugt 10 bis 80 Massenteile und ganz besonders bevorzugt 15 bis 90 Massenteile pro 100 Massenteile Polymer. In der schäumbaren Zusammensetzung können gegebenenfalls weitere zusätzliche Weichmacher, ausgenommen Di-2-ethylhexylterephthalat, enthalten sein.
Die Solvatations- und/oder Gelierfähigkeit der zusätzlichen Weichmacher können hierbei höher, gleich oder niedriger sein als die der erfindungsgemäßen Di-2- ethylhexylterephthalate. Das Massenverhältnis der eingesetzten zusätzlichen Weich- macher zu den eingesetzten erfindungsgemäßen Di-2-ethylhexylterephthalaten liegt insbesondere zwischen 1 : 10 und 10:1 , bevorzugt zwischen 1 : 10 und 8: 1 , besonders bevorzugt zwischen 1 : 10 und 5: 1 und insbesondere bevorzugt zwischen 1 : 10 und 1 : 1 . At least one polymer contained in the foamable composition is selected from the group consisting of polyvinyl chloride, polyvinylidene chloride, polyvinyl butyrate, polyalkyl (meth) acrylate, and copolymers thereof. In a further preferred embodiment, the polymer may be a copolymer of vinyl chloride with one or more monomers selected from the group consisting of vinylidene chloride, vinyl butyrate, methyl (meth) acrylate, ethyl (meth) acrylate or butyl (meth) acrylate. Preferably, the amount of diisononyl-1, 2-cyclohexanedicarboxylic acid ester in the foamable composition is 5 to 150 parts by mass, preferably 10 to 100 parts by mass, more preferably 10 to 80 parts by mass and most preferably 15 to 90 parts by mass per 100 parts by mass of polymer. The foamable composition may optionally contain further additional plasticizers other than di-2-ethylhexyl terephthalate. The solvation and / or gelling ability of the additional plasticizers may in this case be higher, equal to or lower than those of the di-2-ethylhexyl terephthalates according to the invention. The mass ratio of the additional plasticizers used to the di-2-ethylhexyl terephthalates used according to the invention is in particular between 1:10 and 10: 1, preferably between 1:10 and 8: 1, more preferably between 1:10 and 5: 1 and in particular preferably between 1:10 and 1: 1.
Insbesondere handelt es sich bei den zusätzlichen Weichmachern um Ester der ortho- Phthalsäure, der Isophthalsäure, der Terephthalsäure (ausgenommen Di-2- ethylhexylterephthalat), der Cyclohexandicarbonsäure, der Trimellitsäure, der Zitronensäure, der Benzoesäure, der Isononansäure, der 2-Ethylhexansäure, der Octansäure, der 3,5,5-Trimethylhexansäure und/oder um Ester des Butanol, Pentanol, Octanol, 2- Ethylhexanol, Isononanol, Decanol, Dodecanol, Tridecanol, Glycerin und/oder Isosorbid sowie deren Derivate und Mischungen. Bevorzugt können Zitronensäureester wie beispielsweise Acetyl-tributyl-citrat oder Benzoate verwendet werden. In particular, the additional plasticizers are esters of orthophthalic acid, isophthalic acid, terephthalic acid (excluding di-2-ethylhexyl terephthalate), cyclohexanedicarboxylic acid, trimellitic acid, citric acid, benzoic acid, isononanoic acid, 2-ethylhexanoic acid, Octanoic acid, 3,5,5-trimethylhexanoic acid and / or esters of butanol, pentanol, octanol, 2-ethylhexanol, isononanol, decanol, dodecanol, tridecanol, glycerol and / or isosorbide and their derivatives and mixtures. Preferably, citric acid esters such as acetyl tributyl citrate or benzoates can be used.
Grundsätzlich kann die schäumbare Zusammensetzung chemisch oder mechanisch aufgeschäumt werden. Hierbei wird unter einem chemischen Aufschäumen verstanden, dass die schäumbare Zusammensetzung einen Schaumbildner enthält, der durch thermischen Zerfall bei höherer Temperatur gasförmige Komponenten bildet, die dann das Aufschäumen bewirken. In principle, the foamable composition can be foamed chemically or mechanically. Here, chemical foaming is understood to mean that the foamable composition contains a foaming agent which forms gaseous components by thermal decomposition at a higher temperature, which then cause the foaming.
Es ist daher weiterhin bevorzugt, dass die schäumbare Zusammensetzung gemäß der Erfindung einen Schaumbildner enthält. Dieser Schaumbildner kann eine Gasblasen entwickelnde Verbindung, die optional einen Kicker enthält, sein. Als solche Kicker werden Metallverbindungen bezeichnet, die den thermischen Zerfall der Gasblasen entwickelnden Komponente katalysieren und dazu führen, dass der Schaumbildner unter Gasentwicklung zerfällt und die schäumbare Zusammensetzung aufgeschäumt wird. Schaumbildner werden auch als Treibmittel bezeichnet. Als Gasblasen entwickelnde Komponente wird vorzugsweise eine Verbindung verwendet, die unter Wärmeeinfluss in
gasförmige Bestandteile zerfällt und damit ein Aufblähen der Zusammensetzung bewirkt. Ein typischer Vertreter solcher Verbindungen ist z. B. Azodicarbonamid, welches beim thermischen Zerfall überwiegend N2 und CO freisetzt. Die Zerfallstemperatur des Treibmittels kann durch den Kicker verringert werden. It is therefore further preferred that the foamable composition according to the invention contains a foaming agent. This foaming agent may be a gas bubble developing compound optionally containing a kicker. As such Kicker metal compounds are called, which catalyze the thermal decomposition of the gas bubbles developing component and cause the foaming agent decomposes to gas evolution and the foamable composition is foamed. Foaming agents are also referred to as blowing agents. As a gas bubble-developing component, a compound is preferably used, which under the influence of heat gaseous constituents disintegrate, causing the composition to expand. A typical representative of such compounds is z. As azodicarbonamide, which releases mainly thermal decomposition N 2 and CO. The decomposition temperature of the propellant can be reduced by the kicker.
Ein weiteres einsetzbares Treibmittel ist p.p'-Oxybisibenzolsulfonhydrazid), auch OBSH genannt. Dieses zeichnet sich durch eine im Vergleich zu Azodicarbonamid niedrigere Zersetzungstemperatur aus. Weitere Informationen zu Treibmitteln können dem„Handbook of Vinyl Formulating", Second Edition, Verlag John Wiley (ISBN 978-0-471 -71046- 2), Seiten 379 ff entnommen werden. Besonders bevorzugt handelt es sich bei dem Treibmittel um Azodicarbonamid. Another usable propellant is called pp '-Oxybisibenzolsulfonhydrazid), also OBSH. This is characterized by a lower compared to azodicarbonamide decomposition temperature. Further information on propellants can be found in the "Handbook of Vinyl Formulating", Second Edition, John Wiley Publication (ISBN 978-0-471 -71046-2), pages 379. The most preferred blowing agent is azodicarbonamide.
Im Gegensatz zum chemischen Aufschäumen wird beim mechanischen Aufschäumen der Schaum dadurch hergestellt, dass ein Gas, bevorzugt Luft, durch starkes Rühren, ähnlich dem Herstellen von Schlagsahne, in die Zusammensetzung eingetragen wird (sog. Schlagschaum). Der Schaum wird dann beispielsweise auf einen Träger aufgetragen und danach durch die hohe Verarbeitungstemperatur fixiert. Um den Zerfall der Schaumblasen mit der Zeit zu verhindern, werden bevorzugt in mechanischen Schäumen Schaumstabilisatoren eingesetzt. Als Schaumstabilisatoren können handelsübliche Schaumstabilisatoren in der erfindungsgemäßen Zusammensetzung vorhanden sein. Solche Schaumstabilisatoren können z.B. auf Silikon oder Seife basieren und werden z.B. unter den Markennamen BYK (Fa. Byk-Chemie) angeboten. Diese werden in Mengen von 1 bis 10, bevorzugt 1 bis 8, besonders bevorzugt 2 bis 4 Massenteilen pro 100 Massenteilen Polymer eingesetzt. Weitere Details zu einsetzbaren Schaumstabilisato- ren (z. B. Calciumdodecylbenzolsulfonat) werden beispielsweise in der DE 10026234 C1 genannt. In contrast to chemical foaming, the foam is produced by mechanical foaming in that a gas, preferably air, is introduced into the composition by vigorous stirring, similar to the production of whipped cream (so-called whipped foam). The foam is then applied, for example, to a support and then fixed by the high processing temperature. In order to prevent the disintegration of the foam bubbles over time, foam stabilizers are preferably used in mechanical foams. Commercially available foam stabilizers may be present in the composition according to the invention as foam stabilizers. Such foam stabilizers may e.g. based on silicone or soap and are used e.g. under the brand names BYK (Byk-Chemie) offered. These are used in amounts of 1 to 10, preferably 1 to 8, particularly preferably 2 to 4 parts by mass per 100 parts by mass of polymer. Further details on usable foam stabilizers (for example calcium dodecylbenzenesulfonate) are mentioned, for example, in DE 10026234 C1.
Grundsätzlich kann es sich bei den erfindungsgemäßen schäumbaren Zusammensetzungen beispielsweise um Piastisole handeln, die durch Mischen von Emulsions- oder Mikrosuspensions-PVC mit flüssigen Komponenten wie Weichmachern hergestellt werden können.
Es ist weiterhin bevorzugt, dass die schäumbare Zusammensetzung ein Emulsions- PVC enthält. Ganz besonders bevorzugt weist die erfindungsgemäße schäumbare Zusammensetzung ein Emulsions-PVC auf, das ein Molekulargewicht angegeben als K- Wert (Fikentscher Konstante) von 60 bis 95 und besonders bevorzugt von 65 bis 90 aufweist. In principle, the foamable compositions according to the invention can be, for example, plastisols which can be prepared by mixing emulsion or microsuspension PVC with liquid components such as plasticizers. It is further preferred that the foamable composition contains an emulsion PVC. Most preferably, the foamable composition according to the invention comprises an emulsion PVC which has a molecular weight expressed as K value (Fikent's constant) of 60 to 95 and more preferably of 65 to 90.
Die schäumbare Zusammensetzung kann weiterhin bevorzugt zusätzliche Additive enthalten, die insbesondere ausgewählt sind aus der Gruppe bestehend aus Füllstoffen, Pigmenten, Thermostabilisatoren, Antioxidantien, Viskositätsregulierer, (weitere) Schaumstabilisatoren, Flammschutzmittel, Haftvermittler und Gleitmittel. The foamable composition may furthermore preferably comprise additional additives which are in particular selected from the group consisting of fillers, pigments, heat stabilizers, antioxidants, viscosity regulators, (further) foam stabilizers, flame retardants, adhesion promoters and lubricants.
Die Thermostabilisatoren neutralisieren u. a. während und/oder nach der Verarbeitung des PVCs abgespaltene Salzsäure und verhindern einen thermischen Abbau des Poly- meren. Als Thermostabilisatoren kommen alle üblichen PVC-Stabilisatoren in fester und flüssiger Form in Betracht, beispielsweise auf Basis von Ca/Zn, Ba/Zn, Pb, Sn oder organischer Verbindungen (OBS), sowie auch säurebindende Schichtsilikate wie Hydrotalcit. Die erfindungsgemäßen Gemische können einen Gehalt von 0,5 bis 10, bevorzugt 1 bis 5, besonders bevorzugt von 1 ,5 bis 4 Massenteilen pro 100 Massenteile Po- lymer an Thermostabilisatoren aufweisen. The thermal stabilizers neutralize u. a. hydrochloric acid split off during and / or after the processing of the PVC and prevent thermal degradation of the polymer. Suitable thermal stabilizers are all customary PVC stabilizers in solid and liquid form, for example based on Ca / Zn, Ba / Zn, Pb, Sn or organic compounds (OBS), and also acid-binding phyllosilicates such as hydrotalcite. The mixtures according to the invention may have a content of from 0.5 to 10, preferably from 1 to 5, particularly preferably from 1.5 to 4, parts by mass per 100 parts by mass of polymer to thermal stabilizers.
Als Pigmente können im Rahmen der vorliegenden Erfindung sowohl anorganische als auch organische Pigmente eingesetzt werden. Der Gehalt an Pigmenten liegt zwischen 0,01 bis 10 Massen-%, bevorzugt 0,05 bis 5 Massen-%, besonders bevorzugt 0, 1 bis 3 Massen-% pro 100 Massenteile Polymer. Beispiele für anorganische Pigmente sind CdS, C0O/AI2O3, Cr2O3. Bekannte organische Pigmente sind beispielsweise Azo- farbstoffe, Phthalocyaninpigmente, Dioxazinpigmente sowie Anilinpigmente. As pigments, both inorganic and organic pigments can be used in the context of the present invention. The content of pigments is between 0.01 to 10 mass%, preferably 0.05 to 5 mass%, particularly preferably 0, 1 to 3 mass% per 100 mass parts of polymer. Examples of inorganic pigments are CdS, C0O / Al2O3, Cr 2 O 3. Known organic pigments are, for example, azo dyes, phthalocyanine pigments, dioxazine pigments and aniline pigments.
Als viskositätssenkende Reagenzien können aliphatische oder aromatische Kohlenwasserstoffe aber auch Carbonsäurederivate wie beispielsweise das als TXIB (Fa. Eastman) bekannte 2, 2, 4-Trimethyl-1 ,3-pentandiol-diisobutyrat eingesetzt werden. Letz-
teres lässt sich auch auf Grund ähnlicher Eigenviskosität sehr leicht durch Benzoesäu- reisononylester substituieren. Bedingt durch die ähnliche Viskosität von Piastisolen auf Basis der erfindungsgemäßen Zusammensetzung ist der zusätzliche Verbrauch an vis- kositätssenkenden Reagenzien eher gering. Viskositätssenkende Reagenzien werden in Anteilen von 0,5 bis 30, bevorzugt 1 bis 20, besonders bevorzugt 2 bis 15 Massenteilen pro 100 Massenteile Polymer zugegeben. Spezielle, die Viskosität absenkende Additive werden beispielsweise unter dem Handelsnamen Viskobyk (Fa. Byk-Chemie) angeboten. Ein weiterer Gegenstand der vorliegenden Anmeldung ist die Verwendung der schäumbaren Zusammensetzung für Fußbodenbeläge, Tapeten oder Kunstleder. Ein weiterer Gegenstand der Erfindung ist ein Fußbodenbelag enthaltend die schäumbare erfindungsgemäße Zusammensetzung, eine Wandtapete enthaltend die schäumbare erfindungsgemäße Zusammensetzung oder Kunstleder enthaltend die schäumbare erfin- dungsgemäße Zusammensetzung. Aliphatic or aromatic hydrocarbons, but also carboxylic acid derivatives such as, for example, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate known as TXIB (Eastman), can be used as viscosity-reducing reagents. Letz- Due to its similar intrinsic viscosity, teres can easily be substituted by benzoic-isonononyl esters. Due to the similar viscosity of plastisols based on the composition according to the invention, the additional consumption of viscosity-reducing reagents is rather low. Viscosity reducing reagents are added in proportions of 0.5 to 30, preferably 1 to 20, more preferably 2 to 15 parts by mass per 100 parts by mass of polymer. Special viscosity-lowering additives are offered, for example, under the trade name Viskobyk (Byk-Chemie). Another object of the present application is the use of the foamable composition for floor coverings, wallpaper or artificial leather. Another object of the invention is a floor covering containing the foamable composition of the invention, a wall wallpaper containing the foamable composition of the invention or artificial leather containing the foamable inventive composition.
Di-2-ethylhexylterephthalat (DEHT) wird technisch entweder durch Umestern von Di- methylterephthalat mit dem großvolumigen Oxo-Alkohol 2-Ethylhexanol oder durch Ve- restern von Terephthalsäure mit diesem Alkohol hergestellt. Eine weitere Herstellmög- lichkeit bietet auch die Umsetzung von PET-Recyclingmaterial mit 2-Ethylhexanol. Entsprechende Herstellverfahren sind beispielsweise in WO 2008094396, US 2007038001 oder in Huagong Jinzhan (2008), 27(1 ), 143-146, beschrieben. DEHT ist kommerziell beispielsweise erhältlich bei dem amerikanischen Hersteller Eastman Chemical unter der Bezeichnung Eastman 168. Di-2-ethylhexyl terephthalate (DEHT) is prepared industrially either by transesterifying dimethyl terephthalate with the bulky oxo-alcohol 2-ethylhexanol or by esterifying terephthalic acid with this alcohol. Another possibility is the conversion of PET recycling material with 2-ethylhexanol. Corresponding preparation processes are described, for example, in WO 2008094396, US 2007038001 or in Huagong Jinzhan (2008), 27 (1), 143-146. For example, DEHT is commercially available from the Eastman Chemical Company under the designation Eastman 168.
Die Herstellung der erfindungsgemäßen schäumbaren Zusammensetzung kann auf verschiedene Weisen erfolgen. In der Regel wird jedoch die Zusammensetzung durch intensives Mischen aller Komponenten in einem geeigneten Mischbehälter hergestellt. Hierbei werden die Komponenten bevorzugt nacheinander zugegeben (siehe auch E. J. Wickson,„Handbook of PVC Formulating", John Wiley and Sons, 1993, S. 727).
Die erfindungsgemäße schäumbare Zusammensetzung kann zur Herstellung von geschäumten Formkörpern, die zumindest ein Polymer ausgewählt aus der Gruppe Polyvinylchlorid oder Polyvinylidenchlorid oder Copolymere davon enthalten, eingesetzt werden. The preparation of the foamable composition according to the invention can be carried out in various ways. In general, however, the composition is prepared by intensive mixing of all components in a suitable mixing container. Here, the components are preferably added successively (see also EJ Wickson, "Handbook of PVC Formulating", John Wiley and Sons, 1993, p. 727). The foamable composition according to the invention can be used for the production of foamed moldings which contain at least one polymer selected from the group polyvinyl chloride or polyvinylidene chloride or copolymers thereof.
Als solche geschäumte Produkte sind beispielsweise Kunstleder, Fußböden oder Wandtapeten zu nennen, insbesondere die Verwendung der geschäumten Produkte in Cushion-Vinylfußböden und Tapeten. Die geschäumten Produkte aus der schäumbaren Zusammensetzung gemäß der Erfindung werden so hergestellt, dass zunächst die schäumbare Zusammensetzung auf einen Träger oder eine weitere Polymerschicht aufgebracht wird und die Zusammensetzung vor oder nach dem Aufbringen geschäumt wird und die aufgebrachte und / oder geschäumte Zusammensetzung abschließend thermisch verarbeitet wird. Such foamed products are, for example, imitation leather, floors or wall-mounted wallpaper, in particular the use of the foamed products in cushion vinyl floors and wallpapers. The foamed products of the foamable composition according to the invention are prepared by first applying the foamable composition to a support or another polymer layer and foaming the composition before or after application and finally thermally processing the applied and / or foamed composition ,
Im Unterschied zum mechanischen Schaum wird bei chemischen Schäumen der Schaum erst bei der Verarbeitung, in der Regel in einem Gelierkanal, gebildet, d. h., dass die noch ungeschäumte Zusammensetzung auf den Träger, bevorzugt durch Aufstreichen, aufgebracht wird. Bei dieser Ausführungsart des Verfahrens kann eine Profi- lierung des Schaums durch selektive Auftragung von Inhibitorlösungen, beispielsweise über eine Rotationssiebdruckanlage, erreicht werden. An den Stellen, auf denen die Inhibitorlösung aufgetragen wurde, findet die Expansion des Plastisols während der Verarbeitung entweder überhaupt nicht oder nur verzögert statt. In der Praxis wird die chemische Verschäumung gegenüber der mechanischen in deutlich stärkerem Masse eingesetzt. Weitere Informationen über das chemische und mechanische Schäumen können z.B. E.J. Wickson, "Handbook of PVC Formulating", 1993, John Wiley & Sons, entnommen werden. Gegebenenfalls kann auch im Anschluss durch das sogenannte mechanische Prägen bspw. mittels einer Prägewalze eine Profilgebung erreicht werden. Bei beiden Verfahren können als Träger solche Materialien verwendet werden, die mit dem hergestellten Schaum fest verbunden bleiben, wie z.B. Gewebe- oder Vliesbah-
nen. Ebenso können die Träger aber auch nur temporäre Träger sein, von denen die hergestellten Schäume als Schaumschichten wieder entfernt werden können. Solche Träger können z.B. Metallbänder oder Release-Papier (Duplex-Papier) sein. Ebenfalls kann eine weitere, ggf. schon ganz oder teilweise (= vorgelierte) ausgelierte Polymer- schicht als Träger fungieren. Dies wird insbesondere bei CV-Fußböden praktiziert, die aus mehreren Schichten aufgebaut sind. In contrast to the mechanical foam, in the case of chemical foams, the foam is formed only during processing, as a rule in a gelling channel, ie, the unfoamed composition is applied to the carrier, preferably by brushing. In this embodiment of the method, a profiling of the foam can be achieved by selective application of inhibitor solutions, for example via a rotary screen printing machine. At the sites where the inhibitor solution was applied, expansion of the plastisol during processing either does not take place at all or only delayed. In practice, chemical foaming is used to a much greater extent than mechanical ones. For more information on chemical and mechanical foaming, see, for example, EJ Wickson, Handbook of PVC Formulating, 1993, John Wiley & Sons. Optionally, profiling can also be achieved subsequently by means of the so-called mechanical embossing, for example by means of an embossing roller. In both processes, it is possible to use those materials which remain firmly bonded to the foam produced, such as woven or nonwoven webs. NEN. Likewise, however, the carriers can also be only temporary carriers, from which the foams produced can be removed again as foam layers. Such carriers may be, for example, metal bands or release paper (duplex paper). Likewise, another, possibly even completely or partially (= pre-gelled), gelled polymer layer can act as a carrier. This is especially practiced on CV floors that are built up of multiple layers.
Die abschließende thermische Verarbeitung erfolgt in beiden Fällen in einem sogenannten Gelierkanal, in der Regel ein Ofen, der von der auf dem Träger aufgebrachten Schicht aus der erfindungsgemäßen Zusammensetzung durchlaufen wird oder in den der mit der Schicht versehene Träger kurzzeitig eingeführt wird. Die abschließende thermische Verarbeitung dient der„Verfestigung" der geschäumten Schicht. Bei der chemischen Verschäumung kann der Gelierkanal mit einer Vorrichtung, die zur Erzeugung des Schaums dient, kombiniert werden. So ist es z.B. möglich, nur einen Gelier- kanal zu verwenden, bei dem im vorderen Teil bei einer ersten Temperatur durch Zersetzung einer Gas bildenden Komponente chemisch der Schaum erzeugt wird und dieser Schaum im hinteren Teil des Gelierkanals bei einer zweiten Temperatur, die vorzugsweise höher als die erste Temperatur ist, ins Halbzeug oder Endprodukt überführt wird. Je nach Zusammensetzung ist es außerdem möglich, dass Gelierung und The final thermal processing takes place in both cases in a so-called gelation channel, usually a furnace, which is passed through by the applied on the support layer of the composition according to the invention or in which the provided with the layer carrier is briefly introduced. In chemical foaming, the gelling channel can be combined with a device used to produce the foam, for example, it is possible to use only one gelling channel, in which: the foam is chemically generated in the front part at a first temperature by decomposition of a gas-forming component and this foam is transferred into the semifinished product or end product in the rear part of the gelling channel at a second temperature, which is preferably higher than the first temperature It is also possible that gelation and
Schaumbildung zeitgleich bei einer einzigen Temperatur erfolgen. Typische Verarbeitungstemperaturen (Geliertemperaturen) liegen im Bereich von 130 bis 280 °C, vorzugsweise im Bereich von 150 bis 250 °C. Die Gelierung erfolgt vorzugsweise so, dass die geschäumte Zusammensetzung bei den genannten Geliertemperaturen für eine Dauer von 0,5 bis 5 Minuten, vorzugsweise für eine Dauer von 0,5 bis 3 Minuten be- handelt wird. Die Dauer der Temperaturbehandlung kann dabei bei kontinuierlich arbeitenden Verfahren durch die Länge des Gelierkanals und die Geschwindigkeit, mit der der den Schaum aufweisende Träger durch diesen hindurch läuft, eingestellt werden. Typische Schaumbildungstemperaturen (chemischer Schaum) liegen im Bereich von 160 bis 240 °C, bevorzugt 180 bis 220 °C.
Bei mehrschichtigen Systemen werden in der Regel die einzelnen Schichten zuerst durch eine sogenannte Vorgelierung des aufgetragenen Plastisols bei einer Temperatur, die unter der Zersetzungstemperatur des Treibmittels liegt, in ihrer Form fixiert, danach können weitere Schichten (zum Beispiel eine Deckschicht) aufgetragen werden. Wenn alle Schichten aufgetragen sind, wird bei einer höheren Temperatur die Gelierung - und im Falle der chemischen Verschäumung auch die Schaumbildung - durchgeführt. Durch diese Verfahrensweise kann die gewünschte Profilierung auch an die Deckschicht übertragen werden. Die erfindungsgemäßen schäumbaren Zusammensetzungen haben gegenüber dem Stand der Technik den Vorteil, dass sie entweder bei gleichen Temperaturen schneller oder alternativ bei tieferen Temperaturen verarbeitet werden können und damit die Effizienz des Herstellungsprozesses der PVC-Schäume erheblich verbessert wird. Weiterhin sind die im PVC-Schaum verwendeten Weichmacher weniger flüchtig als beispiels- weise die im Stand der Technik erwähnten Benzoesäureisononylester und damit ist der PVC-Schaum insbesondere auch für Innenraumanwendungen besonders geeignet.
Foaming takes place at the same time at a single temperature. Typical processing temperatures (gelling temperatures) are in the range of 130 to 280 ° C, preferably in the range of 150 to 250 ° C. Gelation is preferably carried out such that the foamed composition is treated at the stated gelling temperatures for a period of 0.5 to 5 minutes, preferably for a period of 0.5 to 3 minutes. The duration of the temperature treatment can be adjusted in continuous processes by the length of the gelling channel and the speed at which the foam-containing carrier passes through it. Typical foaming temperatures (chemical foam) are in the range of 160 to 240 ° C, preferably 180 to 220 ° C. In multilayer systems, the individual layers are usually first fixed in their form by a so-called pre-gelation of the applied plastisol at a temperature which is below the decomposition temperature of the propellant, after which further layers (for example a cover layer) can be applied. When all layers have been applied, gelation is carried out at a higher temperature - and, in the case of chemical foaming, also foaming. By this procedure, the desired profile can also be transferred to the cover layer. The foamable compositions according to the invention have the advantage over the prior art that they can be processed either at the same temperatures faster or alternatively at lower temperatures, and thus the efficiency of the production process of the PVC foams is considerably improved. Furthermore, the plasticizers used in the PVC foam are less volatile than, for example, the benzoic acid isononyl esters mentioned in the prior art, and thus the PVC foam is particularly suitable in particular for interior applications.
Analytik: analytics:
1. Bestimmung der Reinheit 1. Determination of purity
Die Bestimmung der Reinheit des hergestellten Esters mittels GC erfolgt mit einem GC- Automaten „6890N" von Agilent Technologies unter Verwendung einer DB-5-Säule (Länge: 20m, Innendurchmesser: 0,25 mm, Filmdicke 0,25 μηι) von J&W Scientific und einem Flammenionisationsdetektor bei folgenden Rahmenbedingungen: Starttemperatur Ofen: 150 °C Endtemperatur Ofen: 350 °C The determination of the purity of the ester produced by GC is carried out with a GC machine "6890N" from Agilent Technologies using a DB-5 column (length: 20m, inner diameter: 0.25 mm, film thickness 0.25 μm) from J & W Scientific and a flame ionization detector under the following conditions: Start temperature oven: 150 ° C Final temperature oven: 350 ° C
(1 ) Heizrate 150-300 °C: 10 K/min (2) Isotherm : 10 min. bei 300 °C (1) heating rate 150-300 ° C: 10 K / min (2) isothermal: 10 min. at 300 ° C
(3) Heizrate 300-350 °C: 25 K/min. (3) Heating rate 300-350 ° C: 25 K / min.
Gesamtlaufzeit: 27 min. Eingangstemperatur Einspritzblock: 300 °C Splittverhältnis: 200: 1 Total running time: 27 min. Inlet temperature injection block: 300 ° C split ratio: 200: 1
Splitfluss: 121 , 1 ml/min Gesamtfluss: 124,6 ml/min. Split flow: 121, 1 ml / min total flow: 124.6 ml / min.
Trägergas: Helium Injektionsvolumen: 3 Mikroliter Carrier gas: helium Injection volume: 3 microliters
Detektortemperatur: 350 °C Brenngas: Wasserstoff Detector temperature: 350 ° C Fuel gas: hydrogen
Flussrate Wasserstoff: 40 ml/min. Flussrate Luft: 440 ml/min. Flow rate of hydrogen: 40 ml / min. Flow rate air: 440 ml / min.
Makeup-Gas: Helium Fluorite Makeup-Gas: 45 ml/min. Makeup Gas: Helium Fluorite Makeup Gas: 45 ml / min.
Die Auswertung der erhaltenen Gaschromatogramme erfolgt manuell gegen vorhandene Vergleichssubstanzen, die Angabe der Reinheit erfolgt in Flächenprozent. Auf Grund der hohen Endgehalte an Zielsubstanz von > 99,7 % ist der zu erwartende Fehler durch fehlende Kalibrierung auf die jeweilige Probensubstanz gering.
2. Bestimmung der Plastisolviskosität The evaluation of the gas chromatograms obtained is done manually against existing reference substances, the indication of the purity is in area percent. Due to the high final contents of target substance of> 99.7%, the expected error due to lack of calibration to the respective sample substance is low. 2. Determination of plastisol viscosity
Die Messung der Viskosität der PVC-Plastisole wurde mit einem Physica MCR 101 (Fa. Anton-Paar) durchgeführt, wobei der Rotationsmodus und das Meßsystem„Z3" (DIN 25 mm) verwendet wurden. The viscosity of the PVC plastisols was measured using a Physica MCR 101 (Anton Paar) using the rotation mode and the measuring system "Z3" (DIN 25 mm).
Das Plastisol wurde zunächst im Ansatzbehälter unter Verwendung eines Spatels manuell homogenisiert, anschließend in das Messsystem eingefüllt und isotherm bei 25 °C vermessen. Während der Messung wurden folgende Punkte angesteuert: 1 . Eine Vorscherung von 100 s"1 für den Zeitraum von 60 s, bei der keine Messwerte aufgenommen wurden (zur Nivellierung eventuell auftretender thixotroper Effekte). The plastisol was first homogenized manually in the batch tank using a spatula, then filled into the measuring system and measured isothermally at 25 ° C. During the measurement the following points were activated: 1. A pre-shear of 100 s "1 for the period of 60 s at which no measured values were recorded (to level any thixotropic effects that may occur).
2. Eine Scherraten-Abwärtsrampe, beginnend bei 200 s"1 und endend bei 0, 1 s"1, aufgeteilt in eine logarithmische Reihe mit 30 Schritten mit jeweils 5 Sekunden Messpunkt- dauer. 2. A shear rate down ramp, starting at 200 s "1 and ending at 0, 1 s " 1 , divided into a logarithmic series with 30 steps each with a 5 second measurement point duration.
Die Messungen wurden in der Regel (wenn nicht anders angegeben) nach einer Lagerung / Reifung der Plastisole von 24h durchgeführt. Zwischen den Messungen wurden die Plastisole bei 25 °C gelagert. The measurements were usually carried out (unless stated otherwise) after storage / maturation of the plastisols of 24 h. Between measurements, the plastisols were stored at 25 ° C.
3. Bestimmung der Geliergeschwindigkeit 3. Determination of the gelling speed
Die Untersuchung des Gelierverhaltens der Plastisole wurde im Physica MCR 101 im Oszillationsmodus mit einem Platte-Platte Meßsystem (PP25), welches schubspan- nungsgesteuert betrieben wurde, vorgenommen. Eine zusätzliche Temperierhaube wurde an das Gerät angeschlossen, um die bestmögliche Wärmeverteilung zu erreichen.
Messparameter: The investigation of the gelling behavior of the plastisols was carried out in the Physica MCR 101 in oscillation mode with a plate-plate measuring system (PP25), which was operated under shear stress control. An additional tempering hood was connected to the device to achieve the best possible heat distribution. Measurement parameters:
Modus: Temperatur-Gradient (Temperaturrampe linear) Mode: temperature gradient (temperature ramp linear)
Start-Temperatur: 25 °C Start temperature: 25 ° C
End-Temperatur: 180 °C End temperature: 180 ° C
Heiz/Kühl rate: 5 K/min Heating / cooling rate: 5 K / min
Oszillations-Frequenz: 4 - 0, 1 Hz Rampe (logarithmisch) Oscillation frequency: 4 - 0, 1 Hz ramp (logarithmic)
Kreisfrequenz Omega: 10 1/s Angular frequency Omega: 10 1 / s
Anzahl Messpunkte: 63 Number of measuring points: 63
Messpunktdauer: 0,5 min Measuring point duration: 0.5 min
keine automatische Spaltnachführung no automatic gap tracking
konstante Messpunktdauer constant measuring point duration
Spaltweite 0,5 mm Durchführung der Messung: Gap width 0.5 mm Carrying out the measurement:
Auf die untere Messsystemplatte wurde mit dem Spatel ein Tropfen des zu messenden Plastisols luftblasenfrei aufgetragen. Dabei wurde darauf geachtet, dass nach dem Zusammenfahren des Messsystems etwas Plastisol gleichmäßig aus dem Messsystem herausquellen konnte (nicht mehr als ca. 6 mm rundum). Anschließend wurde die Tem- perierhaube über der Probe positioniert und die Messung gestartet. On the lower measuring system plate, a drop of the plastisol to be measured was applied with the spatula free of air bubbles. Care was taken to ensure that, after moving the measuring system, some plastisol could evenly escape from the measuring system (no more than approx. 6 mm around). Subsequently, the tempering hood was positioned over the sample and the measurement started.
Bestimmt wurde die sog. komplexe Viskosität des Plastisols in Abhängigkeit von der Temperatur. Ein Einsetzen des Geliervorganges war in einem plötzlichen starken Anstieg der komplexen Viskosität zu erkennen. Je früher dieser Viskositätsanstieg einsetzte, desto besser war die Gelierfähigkeit des Systems. The so-called complex viscosity of the plastisol was determined as a function of the temperature. Onset of gelling was evident in a sudden sharp increase in complex viscosity. The earlier this increase in viscosity began, the better the gelling ability of the system.
Aus den erhaltenen Messkurven wurden durch Interpolation für jedes Plastisol die Temperaturen bestimmt, bei der eine komplexe Viskosität von 1000 Pa*s bzw. 10.000 Pa*s erreicht war. Zusätzlich wurde mittels Tangentenmethode die im vorliegenden Versuchsaufbau maximal erreichte Plastisolviskosität bestimmt, sowie durch Fällen eines Lotes die Temperatur, ab der die maximale Plastisolviskosität auftritt.
4. Herstellung der Schaumfolien und Bestimmung der Expansionsrate From the measured curves obtained, the temperatures at which a complex viscosity of 1000 Pa * s or 10,000 Pa * s was reached were determined by interpolation for each plastisol. In addition, by means of a tangent method, the maximum plastisol viscosity achieved in the present experimental setup was determined, and by precipitating a solder, the temperature at which the maximum plastisol viscosity occurs. 4. Preparation of the foam films and determination of the expansion rate
Das Aufschäumverhalten wurde mit Hilfe eines Dickenschneilmessers mit Eignung für Weich-PVC Messungen (KXL047, Fa. Mitutoyo) mit einer Genauigkeit von 0,01 mm 5 bestimmt. Für die Folienherstellung wurde am Rollrakel eines Mathis Labcoaters (Typ: The foaming behavior was determined with the aid of a thickness cutter suitable for soft PVC measurements (KXL047, Mitutoyo) with an accuracy of 0.01 mm 5. For the film production, the roll doctor of a Mathis Labcoaters (type:
LTE-TS; Hersteller: Fa. W. Mathis AG) ein Rakelspalt von 1 mm eingestellt. Dieser wurde mit einer Fühlerblattlehre kontrolliert und ggf. nachgestellt. Die Plastisole wurden auf ein in einem Rahmen plan eingespanntes Trennpapier (Warran Release Paper; Fa. Sappi Ltd.) mittels dem Rollrakel des Mathis Labcoaters aufgerakelt. Um die prozentuale) le Aufschäumung errechnen zu können, wurde bei 200 °C / 30 Sekunden Verweilzeit zunächst eine angelierte und nicht geschäumte Folie hergestellt. Die Foliendicke (= Ausgangsdicke) dieser Folie betrug bei dem angegebenen Rakelspalt in allen Fällen zwischen 0,74 und 0,77 mm. Die Messung der Dicke wurde an drei unterschiedlichen Stellen der Folie durchgeführt. LTE-TS; Manufacturer: Fa. W. Mathis AG) set a doctor gap of 1 mm. This was checked with a feeler gauge and readjusted if necessary. The plastisols were knife-coated onto a release paper clamped in a frame (Warran Release Paper, Sappi Ltd.) using the doctor blade of Mathis Labcoater. In order to calculate the percentage foaming, a gelled and unfoamed film was first produced at 200 ° C./30 seconds dwell time. The film thickness (= initial thickness) of this film was at the indicated blade gap in all cases between 0.74 and 0.77 mm. The measurement of the thickness was carried out at three different locations of the film.
15 Anschließend wurden ebenfalls mit dem bzw. im Mathis-Labcoater die geschäumten Folien (Schäume) bei 4 unterschiedlichen Ofen-Verweilzeiten (60s, 90s, 120s und 150s) hergestellt. Nach Abkühlung der Schäume wurden die Dicken ebenfalls an drei unterschiedlichen Stellen vermessen. Der Mittelwert der Dicken und die Ausgangsdicke wurden für die Berechnung der Expansion benötigt. (Beispiel: (Schaumdicke- 20 Ausgangsdicke)/Ausgangsdicke*100% = Expansion). 15 Subsequently, the foamed foils (foams) were also produced with the Mathis-Labcoater at 4 different oven residence times (60s, 90s, 120s and 150s). After cooling the foams, the thicknesses were also measured at three different locations. The mean of the thicknesses and the initial thickness were needed to calculate the expansion. (Example: (foam thickness-20 initial thickness) / initial thickness * 100% = expansion).
5. Bestimmung des Gelbwertes 5. Determination of the yellow value
Der Gelbwert (Index YD 1925) ist ein Maß für Gelbverfärbung eines Probekörpers. Bei der Beurteilung von Schaumfolien ist der Gelbwert in zweierlei Hinsicht von Interesse. 25 Zum einen zeigt er den Zersetzungsgrad des Treibmittels (= gelb im unzersetzten Zustand) an, zum anderen ist er ein Maß für die Thermostabilität (Verfärbungen in Folge thermischer Belastung). Die Farbmessung der Schaumfolien erfolgte mit einem Spectro Guide der Fa. Byk-Gardner. Als Hintergrund für die Farbmessungen wurde eine weiße Referenz-Kachel benutzt. Folgende Parameter wurden eingestellt:
Lichtart: C/2° The yellow value (index YD 1925) is a measure of yellow discoloration of a specimen. When evaluating foamed sheets, yellowness is of interest in two respects. 25 On the one hand it indicates the degree of decomposition of the propellant (= yellow in the undecomposed state), on the other hand it is a measure of the thermal stability (discoloration due to thermal stress). The color measurement of the foam films was carried out with a Spectro Guide from the Byk-Gardner company. The background for the color measurements was a white reference tile. The following parameters have been set: Light type: C / 2 °
Anzahl Messungen: 3 Number of measurements: 3
Anzeige: CIE L*a*b* Display: CIE L * a * b *
Messindex: YD 1925 Measurement index: YD 1925
Die Messungen selbst wurden an 3 unterschiedlichen Stellen der Proben (für Effekt- und Glattschäume bei einer Plastisol-Rakeldicke von 200 pm) durchgeführt. Die Werte aus den 3 Messungen wurden gemittelt. The measurements themselves were carried out at 3 different points of the samples (for effect and smooth foams with a plastisol squeegee thickness of 200 μm). The values from the 3 measurements were averaged.
Die nachfolgenden Beispiele sollen die Erfindung näher erläutern. The following examples are intended to explain the invention in more detail.
Beispiele: Examples:
Beispiel 1 : Example 1 :
Herstellung von expandierbaren / schäumbaren PVC-Plastisolen enthaltend das erfindungsgemäß verwendete Di-2-ethylhexylterephthalat (DEHT) (unter Verwendung von Füllstoff und Pigment) Preparation of expandable / foamable PVC plastisols containing the di-2-ethylhexyl terephthalate (DEHT) used according to the invention (using filler and pigment)
Im Folgenden sollen die Vorteile der erfindungsgemäßen Piastisole an Hand eines Füllstoff und Pigment enthaltenden thermisch expandierbaren PVC-Plastisols verdeutlicht werden. Die nachstehenden erfindungsgemäßen Piastisole stehen dabei u.a. beispielhaft für thermisch expandierbare Piastisole, die bei der Herstellung von Fußbodenbelä- gen zum Einsatz kommen. Insbesondere sind die nachstehenden erfindungsgemäßen Piastisole beispielhaft für Schaumschichten welche als bedruckbare und/oder inhibierbare Oberseitenschäume in mehrschichtig aufgebauten PVC-Fußböden Verwendung finden. Die verwendeten Einwaagen der Komponenten für die verschiedenen Piastisole sind der nachfolgenden Tabelle (1 ) zu entnehmen. Die flüssigen und festen Formulierungs-
bestandteile wurden getrennt in je einem geeigneten PE-Becher eingewogen. Von Hand wurde die Mischung mit einem Salbenspatel so eingerührt, dass kein unbenetztes Pulver mehr vorhanden war. Das Mischen der Piastisole erfolgte mit einem Kreiss- Dissolver VDKV30-3 (Hersteller Fa. Niemann). Der Mischbecher wurde in die Klemm- Vorrichtung des Dissolverrührers eingespannt. Mit einer Mischerscheibe (Zahnscheibe, fein gezahnt, 0: 50 mm) wurde die Probe homogenisiert. Dabei wurde die Drehzahl des Dissolvers von 330 U/min kontinuierlich bis 2000 U/min erhöht, und so lange gerührt, bis die Temperatur an der Digitalanzeige des Thermofühlers 30,0 °C (Temperaturerhöhung in Folge der Friktionsenergie / Energiedissipation; siehe beispielsweise N.P.Cheremisinoff:„An Introduction to Polymer Rheology and Processing"; CRC Press; London; 1993) erreichte. Damit war sicher gestellt, dass die Homogenisierung des Plastisols bei einem definierten Energieeintrag erreicht wurde. Danach wurde das Plastisol sofort auf 25,0 °C temperiert. Tabelle 1 : Zusammensetzung der gefüllten und pigmentierten expandierbaren PVC- Plastisole gemäß Beispiel 1 . [Alle Angaben in phr (= Massenteile pro 100 Massenteile PVC)] In the following, the advantages of the plastisols according to the invention are to be clarified on the basis of a filler and pigment-containing thermally expandable PVC plastisol. The following plastisols according to the invention are, inter alia, examples of thermally expandable plastisols which are used in the production of floor coverings. In particular, the following plastisols according to the invention are exemplary of foam layers which are used as printable and / or inhibitable top foams in multilayer PVC floors. The used weights of the components for the different plastisols are shown in the following table (1). The liquid and solid formulation components were weighed separately into a suitable PE cup each time. By hand, the mixture was stirred with an ointment spatula so that no unwetted powder was present. The plastisols were mixed with a Kreiss dissolver VDKV30-3 (manufacturer Fa. Niemann). The mixing cup was clamped in the clamping device of the dissolver stirrer. The sample was homogenized using a mixer disk (toothed disk, finely toothed, 0: 50 mm). The speed of the dissolver was continuously increased from 330 rpm to 2000 rpm and stirred until the temperature at the digital readout of the thermocouple reached 30.0 ° C. (temperature increase as a result of the friction energy / energy dissipation, see, for example, NPCheremisinoff: "An Introduction to Polymer Rheology and Processing" (CRC Press; London; 1993), which ensured that plastisol homogenization was achieved at a defined energy input, and then the plastisol was immediately heated to 25.0 ° C 1: Composition of the filled and pigmented expandable PVC plastisols according to Example 1. [All data in phr (= parts by mass per 100 parts by mass of PVC)]
** = Vergleichsbeispiel * = erfindungsgemäß ** = Comparative Example * = according to the invention
Die verwendeten Stoffe und Substanzen werden im Folgenden näher erläutert:
VESTOLIT P1352 K: Emulsions-PVC (Homopolymer) mit einem K-Wert (bestimmt gemäß DIN EN ISO 1628-2) von 68; Fa. Vestolit GmbH & Co. KG The substances and substances used are explained in more detail below: VESTOLIT P1352 K: emulsion PVC (homopolymer) with a K value (determined according to DIN EN ISO 1628-2) of 68; Fa. Vestolit GmbH & Co. KG
Eastman 168: Di-2-ethylhexylterephthalat; Fa. Eastman Chemical Eastman 168: di-2-ethylhexyl terephthalate; Fa. Eastman Chemical
VESTINOL® 9: Diisononyl(ortho)phthalat (DINP), Weichmacher; Fa. Evonik Oxeno GmbH VESTINOL® 9: diisononyl (ortho) phthalate (DINP), plasticizer; Fa. Evonik Oxeno GmbH
Unifoam AZ Ultra 1035: Azodicarbonamid; thermisch aktivierbares Treibmittel; Fa. Hebron S.A. Unifoam AZ Ultra 1035: azodicarbonamide; thermally activated blowing agent; Fa. Hebron S.A.
Calcilit 8G: Calciumcarbonat; Füllstoff; Fa. Alpha Calcit. Calcilit 8G: calcium carbonate; Filler; Fa. Alpha Calcite.
KRONOS 2220: Mit AI und Si stabilisiertes Rutilpigment (TiO2); Weißpigment; Fa. Kro- nos Worldwide Inc. KRONOS 2220: rutile pigment (TiO 2 ) stabilized with Al and Si; White pigment; Company Kroenos Worldwide Inc.
Isopropanol: Colösungsmittel zur Absenkung der Plastisolviskosität sowie Additiv zur Verbesserung der Schaumstruktur (Fa. Brenntag AG). Isopropanol: Cosolvent for lowering the plastisol viscosity and additive for improving the foam structure (Brenntag AG).
Zinkoxid aktiv®: ZnO; Zersetzungskatalysator („Kicker") für thermisches Treibmittel; setzt die substanzeigene Zersetzungstemperatur des Treibmittels herab; wirkt gleichzei- tig auch als Stabilisator; zur besseren Verteilung wurde das Zinkoxid mit dem entsprechenden Weichmacher (Massenverhältnis 1 :2) angebatcht und über einem 3 Walzenstuhl abgerieben; Fa. Lanxess AG Zinc oxide active ® : ZnO; Thermal decomposition catalyst ("kicker") which lowers the substractive decomposition temperature of the blowing agent, but also acts as a stabilizer, for better distribution the zinc oxide was treated with the appropriate plasticizer (mass ratio 1: 2) and rubbed on a 3-roll mill; Fa. Lanxess AG
Beispiel 2: Example 2:
Bestimmung der Plastisolviskosität der gefüllten und pigmentierten thermisch expandierbaren Plastisole aus Beispiel 1 nach einer Lagerdauer von 24 h (bei 25°C). Determination of the plastisol viscosity of the filled and pigmented thermally expandable plastisols from Example 1 after a storage time of 24 hours (at 25 ° C.).
Die Messung der Viskositäten der in Beispiel 1 hergestellten Plastisole erfolgte wie unter Analytik, Punkt 2 (siehe oben) beschrieben, mit einem Rheometer Physica MCR 101 (Fa. Anton Paar). Die Ergebnisse werden in der nachfolgenden Tabelle (2) exemplarisch für die Schergeschwindigkeiten 100/s und 10/s dargestellt.
Tabelle 2: Scherviskosität der Plastisole aus Beispiel 1 nach 24h Lagerung bei 25 °C. The measurement of the viscosities of the plastisols prepared in Example 1 was carried out as described under Analysis, Item 2 (see above), using a Rheometer Physica MCR 101 (Anton Paar). The results are shown in the following table (2) as an example for the shear rates 100 / s and 10 / s. Shear viscosity of the plastisols from Example 1 after 24 h storage at 25 ° C.
= Vergleichsbeispiel * = erfindungsgemäß = Comparative Example * = According to the invention
Die Plastisolviskositäten der erfindungsgemäßen Zusammensetzung sind zwar höher, aber in einer vergleichbaren Größenordnung wie die des Vergleichsbeispiels. Somit wäre die Menge an zusätzlich notwendigem Viskositätserniedriger begrenzt. Beispiel 3: The plastisol viscosities of the composition according to the invention, although higher, but in a comparable order of magnitude as those of the comparative example. Thus, the amount of additionally necessary lower viscosity would be limited. Example 3:
Bestimmung des Gelierverhaltens der gefüllten und pigmentierten thermisch expandierbaren Plastisole aus Beispiel 1 Determination of the gelling behavior of the filled and pigmented thermally expandable plastisols from Example 1
Die Untersuchung des Gelierverhaltens der in Beispiel 1 hergestellten gefüllten und pigmentierten thermisch expandierbaren Plastisole erfolgte wie unter Analytik, Punkt 3 (siehe oben) beschrieben, mit einem Physica MCR 101 im Oszillationsmodus nach einer Lagerung der Plastisole bei 25 °C für 24h. Die Ergebnisse werden in der nachfolgenden Tabelle (3) dargestellt. Tabelle 3: Aus den Gelierkurven (Viskositätskurven) bestimmte Eckpunkte des Gelierverhaltens der gemäß Beispiel 1 hergestellten gefüllten und pigmentierten expandierbaren Plastisole.
Plastisolrezeptur 2* Examination of the gelling behavior of the filled and pigmented thermo-expandable plastisols prepared in Example 1 was carried out as described under Analysis, Item 3 (see above) with a Physica MCR 101 in oscillatory mode after storage of the plastisols at 25 ° C. for 24 h. The results are shown in the following Table (3). Table 3: From the gelation curves (viscosity curves) certain cornerstones of the gelling behavior of the filled and pigmented expandable plastisols prepared according to Example 1. Plastisol recipe 2 *
(gemäß Bsp. 1 ) (according to Ex. 1)
Erreichen einer Plasti- 80 83 Achieving a plastic 80 83
solviskosität von sol viscosity of
1 .000 Pa*s bei [°C] 1 .000 Pa * s at [° C]
Erreichen einer Plasti- 84 106 Achieving a plastic 84 106
solviskosität von sol viscosity of
10.000 Pa*s bei [°C] 10,000 Pa * s at [° C]
Maximale Plasti- 39700 32900 Maximum plastic 39700 32900
solviskosität [Pa*s] sol viscosity [Pa * s]
Temperatur beim Er127 132 Temperature at Er127 132
reichen der max. the max.
Plastisolviskosität [°C] Plastisol viscosity [° C]
= Vergleichsbeispiel * = erfindungsgemäß = Comparative Example * = According to the invention
Hiermit kann nochmals gezeigt werden, dass, wie auch schon im Stand der Technik genannt, DEHT eine schlechtere Gelierneigung aufweist als das DINP. Hereby can be shown again that, as already mentioned in the prior art, DEHT has a worse Gelierneigung than the DINP.
Beispiel 4: Example 4:
Herstellung der Schaumfolien und Bestimmung des Expansions- bzw. Aufschäumverhaltens der in Beispiel 1 hergestellten thermisch expandierbaren Plastisole bei 200 °C. Preparation of the foam films and determination of the expansion or foaming behavior of the thermo-expandable plastisols prepared in Example 1 at 200 ° C.
Die Herstellung der Schaumfolien und die Bestimmung des Expansionsverhaltens erfolgte analog zu der unter Analytik, Punkt 4 beschriebenen Verfahrensweise jedoch unter Verwendung der in Beispiel 1 hergestellten gefüllten und pigmentierten Plastisole. Die Ergebnisse werden in der nachfolgenden Tabelle (4) dargestellt.
Tabelle 4: Expansion der aus den gefüllten und pigmentierten thermisch expandierbaren Piastisolen (gemäß Bsp. 6) bei unterschiedlichen Ofen-Verweilzeiten im Mathis Labcoater (bei 200 °C) hergestellten Polymerschäume bzw. Schaumfolien. The preparation of the foam films and the determination of the expansion behavior was carried out analogously to the procedure described under Analytical Item 4, but using the filled and pigmented plastisols prepared in Example 1. The results are shown in Table (4) below. Table 4: Expansion of the polymer foams or foam foils produced from the filled and pigmented thermally expandable plastisols (according to Ex. 6) at different furnace residence times in Mathis Labcoater (at 200 ° C.).
Es werden mit den Piastisolen, welche das erfindungsgemäß verwendete Di-2- ethylhexylterephthalat enthalten, im Vergleich mit entsprechenden Piastisolen enthaltend den Standard-Weichmacher DINP nach einer Verweilzeit von 120 und 150 Sekun- den höhere Schaumhöhen bzw. Expansionsraten erreicht. With the plastisols which comprise the di-2-ethylhexyl terephthalate used according to the invention, higher foam heights or expansion rates are achieved after comparison with corresponding plastisols containing the standard plasticizer DINP after a residence time of 120 and 150 seconds.
Es werden somit thermisch expandierbare Piastisole mit Füllstoffen zur Verfügung gestellt, die trotz augenscheinlicher Nachteile beim Gelierverhalten (siehe Beispiel 3) Vorteile bei der thermischen Expandierbarkeit aufweisen. Bei Piastisolen mit Füllstoffen lässt sich (trotz des Gehaltes an Weißpigment) die Vollständigkeit der Zersetzung des verwendeten Treibmittels und damit der Fortschritt des Expansionsprozesses auch an der Farbe des hergestellten Schaumes ablesen. Je geringer die Gelbfärbung des Schaumes, desto weiter ist der Expansionsprozess abgeschlossen. Thus, thermally expandable plastisols with fillers are made available which, despite obvious disadvantages in gelling behavior (see Example 3), have advantages in terms of thermal expandability. In the case of plastisols with fillers, the completeness of the decomposition of the blowing agent used, and thus the progress of the expansion process, can also be read off from the color of the foam produced (despite the content of white pigment). The lower the yellowing of the foam, the further the expansion process is completed.
Der gemäß Analytik, Punkt 5 (siehe oben) bestimmte Gelbwert der in Beispiel 4 hergestellten Polymerschäume bzw. Schaumfolien ist in der nachfolgenden Tabelle (5) dargestellt.
Tabelle 5: Gelbwerte (Yl D1925) der gemäß Beispiel 4 hergestellten Polymerschäume. The yellowness of the polymer foams or foam foils prepared in Example 4, determined according to the analysis, item 5 (see above), is shown in the following Table (5). TABLE 5 Yellow values (YI D1925) of the polymer foams prepared according to Example 4.
Die auf Basis der erfindungsgemäßen Zusammensetzung hergestellten Plastisole weisen im aufgeschäumten Zustand (ab 120 s) eine deutlich niedrigere Farbzahl auf. Dem Wert bei 60 s kommt aufgrund der gerade beginnenden Verschäumung praktisch keine Bedeutung bei. Es werden somit gefüllte Plastisole zur Verfügung gestellt, die trotz augenscheinlicher Nachteile bei der Gelierung eine schnellere Verarbeitungsgeschwindigkeit und/oder niedrigere Verarbeitungstemperaturen bezüglich der Verschäumung erlauben. The plastisols prepared on the basis of the composition according to the invention have a significantly lower color number in the foamed state (from 120 s). The value at 60 s is of practically no importance due to the fact that foaming is just beginning. Thus, filled plastisols are provided which, despite apparent disadvantages in gelation, allow a faster processing speed and / or lower processing temperatures with respect to foaming.
Beispiel 5 (variierter Füllgrad) Example 5 (varied degree of filling)
Um die Breite der Erfindung weiter zu untermauern, werden in einer weiteren Serie unter Verwendung eines anderen PVC-Typs die Mengen an Füllstoff (hier Kreide) von 0 (d.h. ungefülltes, aber pigmentiertes System bis 133 phr (d.h. hochgefüllte Formulierung) variiert. To further underline the breadth of the invention, in another series using a different PVC type, the amounts of filler (here chalk) are varied from 0 (i.e., unfilled but pigmented system to 133 phr (i.e., highly filled formulation).
Die Herstellung der Plastisole und der hieraus produzierten Schaumfolien sowie die Bestimmung der Expansionsrate und der Gelbwerte wurden analog zu den oberen Beispielen durchgeführt.
Tabelle 6: Rezepturen The production of the plastisols and the foams produced therefrom as well as the determination of the expansion rate and the yellowness values were carried out analogously to the above examples. Table 6: Recipes
V1 V2 V3 V4 V5 E1 E2 E3 E4 E5V1 V2 V3 V4 V5 E1 E2 E3 E4 E5
Vestolit E 100 100 100 100 100 100 100 100 100 100Vestolit E 100 100 100 100 100 100 100 100 100 100
7012 S 7012 p
Calibrite 0 33 67 100 133 0 33 67 100 133 Calibrite 0 33 67 100 133 0 33 67 100 133
OG OG
Kronos 7 7 7 7 7 7 7 7 7 7 Kronos 7 7 7 7 7 7 7 7 7 7
2220 2220
Unifoam 2,5 2,5 2,5 2,5 2,5 2,5 2,5 2,5 2,5 2,5 Unifoam 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5
AZ Ultra AZ Ultra
1035 1035
ZnO 1 ,5 1 ,5 1 ,5 1 ,5 1 ,5 1 ,5 1 ,5 1 ,5 1 ,5 1 ,5 ZnO 1, 5 1, 5 1, 5 1, 5 1, 5 1, 5 1, 5 1, 5 1, 5 1, 5
Isopropanol 3,3 3,3 3,3 3,3 3,3 3,3 3,3 3,3 3,3 3,3Isopropanol 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3
VESTINOL 73 73 73 73 73 VESTINOL 73 73 73 73 73
9 9
Eastman 73 73 73 73 73 Eastman 73 73 73 73 73
168 Vestolit E 7012 S: Emulsions-PVC (Homopolymer) mit einem K-Wert (bestimmt gemäß DIN EN ISO 1628-2) von 67; Fa. Vestolit GmbH & Co. KG. 168 Vestolit E 7012 S: emulsion PVC (homopolymer) with a K value (determined according to DIN EN ISO 1628-2) of 67; Fa. Vestolit GmbH & Co. KG.
Calibrite OG: Mineralischer Füllstoff ; Fa. Omya GmbH Alle anderen Rezepturbestandteile wurden im ersten Beispiel bereits detailliert beschrieben. Calibrite OG: mineral filler; Fa. Omya GmbH All other recipe ingredients have already been described in detail in the first example.
Von den im o.a. Beispiel hergestellten Schaumfolien wurde jeweils die Dicke der aufgeschäumten Folie ermittelt und hieraus die Expansionsrate in Prozent errechnet.
Tabelle 7: Expansion der aus den gefüllten und pigmentierten thermisch expandierbaren Piastisolen (gemäß Bsp. 5) bei unterschiedlichen Ofen-Verweilzeiten im Mathis Labcoater (bei 200 °C) hergestellten Polymerschäume bzw. Schaumfolien. Of the foam films produced in the example above, the thickness of the foamed film was determined in each case and from this the expansion rate in percent was calculated. Table 7: Expansion of the polymer foams or foam foils produced from the filled and pigmented thermally expandable plastisols (according to Ex. 5) at different furnace residence times in the Mathis Labcoater (at 200 ° C.).
Alle Angaben zu Expansionsraten in Prozent All data on expansion rates in percent
Aus der in Tabelle 7 aufgeführten Beispielen ist klar zu kennen, dass das Verschäu- mungsverhalten von DEHT enthaltenden Zusammensetzungen (E1 bis E5), ausgedrückt durch die Expansionsraten in % durchweg besser beurteilt werden kann als die vergleichbaren Zusammensetzungen mit dem Weichmacher DINP (Stand der Technik, V1 bis V5) From the examples given in Table 7, it is to be clearly understood that the foaming behavior of DEHT-containing compositions (E1 to E5), expressed by the% expansion rates, can be rated consistently better than the comparable compositions with the plasticizer DINP (prior art , V1 to V5)
Diese Aussage wird noch unterstrichen durch die mit den erfindungsgemäßen Zusammensetzungen erhältlichen niedrigeren Gelbwerten (Yellowness Indices), siehe Tabelle 8: This statement is further emphasized by the yellowness indices obtainable with the compositions according to the invention, see Table 8:
Alle Angaben zu Yl-Werten sind dimensionslos
Somit konnte gezeigt werden, dass bei Verwendung der erfindungsgemäßen Zusammensetzungen deutlich bessere Ergebnisse erzielt werden. All information on Yl values are dimensionless Thus it could be shown that significantly better results are achieved when using the compositions according to the invention.
Überraschend ist, dass DEHT trotz des etwas schlechteren Gelierverhaltens im Gegen- satz zur gängigen Lehrbuchmeinung diese Effekte zeigt.
It is surprising that DEHT shows these effects in spite of the somewhat poorer gelling behavior in contrast to the usual textbook opinion.
Claims
1 . Schäumbare Zusammensetzung enthaltend minestens ein Polymer ausgewählt aus der Gruppe bestehend aus Polyvinylchlorid, Polyvinylidenchlorid, Polyvinyl- butyrat, Polyalkyl(meth)acrylat und Copolymeren davon, einen Schaumbildner und/oder Schaumstabilisator und Di-2-ethylhexylterephthalat als Weichmacher. 1 . Foamable composition comprising at least one polymer selected from the group consisting of polyvinyl chloride, polyvinylidene chloride, polyvinyl butyrate, polyalkyl (meth) acrylate and copolymers thereof, a foaming agent and / or foam stabilizer and di-2-ethylhexyl terephthalate as plasticizer.
2. Schäumbare Zusammensetzung nach Anspruch 1 , dadurch gekennzeichnet, dass das Polymer Polyvinylchlorid ist. 2. Foamable composition according to claim 1, characterized in that the polymer is polyvinyl chloride.
3. Schäumbare Zusammensetzung nach Anspruch 1 , dadurch gekennzeichnet, dass das Polymer ein Copolymer von Vinylchlorid mit einem oder mehreren Monomeren ausgewählt aus der Gruppe bestehend aus Vinylidenchlorid, Vinylbuty- rat, Methyl(meth)acrylat, Ethyl(meth)acrylat oder Butyl(meth)acrylat ist. 3. Foamable composition according to claim 1, characterized in that the polymer is a copolymer of vinyl chloride with one or more monomers selected from the group consisting of vinylidene chloride, Vinylbuty- rat, methyl (meth) acrylate, ethyl (meth) acrylate or butyl (meth ) acrylate.
4. Schäumbare Zusammensetzung nach einem oder mehreren der Ansprüche 1 bis4. Foamable composition according to one or more of claims 1 to
3, dadurch gekennzeichnet, dass die Menge an Di-2-ethylhexylterephthalat 5 bis 150 Massenteile pro 100 Massenteile Polymer beträgt. 3, characterized in that the amount of di-2-ethylhexyl terephthalate is 5 to 150 parts by mass per 100 parts by mass of polymer.
5. Schäumbare Zusammensetzung nach einem oder mehreren der Ansprüche 1 bis5. Foamable composition according to one or more of claims 1 to
4, dadurch gekennzeichnet, dass zusätzlich weitere Weichmacher ausgenommen Di-2-ethylhexylterephthalat in der schäumbaren Zusammensetzung enthalten sind. 4, characterized in that additional plasticizers other than di-2-ethylhexyl terephthalate are additionally contained in the foamable composition.
6. Schäumbare Zusammensetzung nach einem oder mehreren der Ansprüche 1 bis6. Foamable composition according to one or more of claims 1 to
5, dadurch gekennzeichnet, dass die Zusammensetzung eine Gasblasen entwickelnde Komponente als Schaumbildner und optional einen Kicker enthält. 5, characterized in that the composition contains a gas bubble developing component as a foaming agent and optionally a kicker.
7. Schäumbare Zusammensetzung nach einem oder mehreren der Ansprüche 1 bis7. Foamable composition according to one or more of claims 1 to
6, dadurch gekennzeichnet, dass die Zusammensetzung Emulsions-PVC enthält. 6, characterized in that the composition contains emulsion PVC.
8. Schäumbare Zusammensetzung nach einem oder mehreren der Ansprüche 1 bis8. Foamable composition according to one or more of claims 1 to
7, dadurch gekennzeichnet, dass die Zusammensetzung Additive aufweist ausgewählt aus der Gruppe bestehend aus Füllstoffen, Pigmenten, Thermostabilisatoren, Antioxidantien, Viskositätsregulierer, Schaumstabilisatoren und Gleitmittel. 7, characterized in that the composition comprises additives selected from the group consisting of fillers, pigments, thermal stabilizers, antioxidants, viscosity regulators, foam stabilizers and lubricants.
9. Verwendung der schäumbaren Zusammensetzung gemäß den Ansprüchen 1 bis 8 für Fußbodenbeläge, Tapeten oder Kunstleder. 9. Use of the foamable composition according to claims 1 to 8 for floor coverings, wallpaper or artificial leather.
10. Geschäumter Formkörper enthaltend die schäumbare Zusammensetzung gemäß den Ansprüchen 1 bis 8. 10. Foamed molded article containing the foamable composition according to claims 1 to 8.
1 1 . Fußbodenbelag enthaltend die schäumbare Zusammensetzung in geschäumtem Zustand gemäß den Ansprüchen 1 bis 8. 1 1. Floor covering containing the foamable composition in the foamed state according to claims 1 to 8.
12. Wandtapete enthaltend die schäumbare Zusammensetzung in geschäumtem Zustand gemäß den Ansprüchen 1 bis 8. 12. wall wallpaper containing the foamable composition in the foamed state according to claims 1 to 8.
13. Kunstleder enthaltend die schäumbare Zusammensetzung in geschäumtem Zustand gemäß den Ansprüchen 1 bis 8. 13. Synthetic leather containing the foamable composition in the foamed state according to claims 1 to 8.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102010061866A DE102010061866A1 (en) | 2010-11-24 | 2010-11-24 | Use of di (2-ethylhexyl) terephthalate (DEHT) in foamable PVC formulations |
PCT/EP2011/069135 WO2012069287A1 (en) | 2010-11-24 | 2011-10-31 | Use of di(2-ethylhexyl)terephthalate (deht) in expandable pvc formulations |
Publications (1)
Publication Number | Publication Date |
---|---|
EP2643410A1 true EP2643410A1 (en) | 2013-10-02 |
Family
ID=45044536
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP11788082.3A Withdrawn EP2643410A1 (en) | 2010-11-24 | 2011-10-31 | Use of di(2-ethylhexyl)terephthalate (deht) in expandable pvc formulations |
Country Status (12)
Country | Link |
---|---|
US (1) | US20130310472A1 (en) |
EP (1) | EP2643410A1 (en) |
JP (1) | JP2014503616A (en) |
KR (1) | KR20130116296A (en) |
CN (1) | CN103314050A (en) |
CA (1) | CA2817803A1 (en) |
DE (1) | DE102010061866A1 (en) |
MX (1) | MX2013005506A (en) |
MY (1) | MY186878A (en) |
RU (1) | RU2013128415A (en) |
SG (1) | SG190329A1 (en) |
WO (1) | WO2012069287A1 (en) |
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KR102554521B1 (en) | 2014-02-20 | 2023-07-11 | 프레제니우스 카비 도이치란트 게엠베하 | Medical containers and system components with non-dehp plasticizers for storing red blood cell products, plasma and platelets |
TW201619120A (en) * | 2014-10-09 | 2016-06-01 | 巴斯夫歐洲公司 | Plasticizer composition which comprises cycloalkyl esters of saturated dicarboxylic acids and terephthalic esters |
KR101889540B1 (en) * | 2014-10-22 | 2018-08-17 | 한화케미칼 주식회사 | Plasticizer composition comprising di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate and citrates, and vinylchloride resin composition comprising the same |
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- 2011-10-31 JP JP2013540293A patent/JP2014503616A/en active Pending
- 2011-10-31 CA CA2817803A patent/CA2817803A1/en not_active Abandoned
- 2011-10-31 KR KR1020137016201A patent/KR20130116296A/en not_active Application Discontinuation
- 2011-10-31 MX MX2013005506A patent/MX2013005506A/en not_active Application Discontinuation
- 2011-10-31 WO PCT/EP2011/069135 patent/WO2012069287A1/en active Application Filing
- 2011-10-31 US US13/988,873 patent/US20130310472A1/en not_active Abandoned
- 2011-10-31 EP EP11788082.3A patent/EP2643410A1/en not_active Withdrawn
- 2011-10-31 RU RU2013128415/05A patent/RU2013128415A/en not_active Application Discontinuation
- 2011-10-31 MY MYPI2013001822A patent/MY186878A/en unknown
- 2011-10-31 SG SG2013038302A patent/SG190329A1/en unknown
- 2011-10-31 CN CN2011800658519A patent/CN103314050A/en active Pending
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Also Published As
Publication number | Publication date |
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CN103314050A (en) | 2013-09-18 |
MY186878A (en) | 2021-08-26 |
MX2013005506A (en) | 2013-07-05 |
JP2014503616A (en) | 2014-02-13 |
SG190329A1 (en) | 2013-06-28 |
RU2013128415A (en) | 2015-01-10 |
CA2817803A1 (en) | 2012-05-31 |
WO2012069287A1 (en) | 2012-05-31 |
US20130310472A1 (en) | 2013-11-21 |
KR20130116296A (en) | 2013-10-23 |
DE102010061866A1 (en) | 2012-05-24 |
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