US3876735A - Method of manufacturing an artificial paper - Google Patents
Method of manufacturing an artificial paper Download PDFInfo
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- US3876735A US3876735A US158060A US15806071A US3876735A US 3876735 A US3876735 A US 3876735A US 158060 A US158060 A US 158060A US 15806071 A US15806071 A US 15806071A US 3876735 A US3876735 A US 3876735A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 229920000642 polymer Polymers 0.000 claims abstract description 31
- 229920000098 polyolefin Polymers 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims description 51
- 230000008569 process Effects 0.000 claims description 48
- 239000000203 mixture Substances 0.000 claims description 47
- 229920001577 copolymer Polymers 0.000 claims description 24
- 239000000155 melt Substances 0.000 claims description 23
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 22
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 20
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 18
- -1 ETHYLENE, PROPYLENE Chemical class 0.000 claims description 17
- 239000002671 adjuvant Substances 0.000 claims description 17
- 229920001903 high density polyethylene Polymers 0.000 claims description 16
- 239000004700 high-density polyethylene Substances 0.000 claims description 16
- 238000001125 extrusion Methods 0.000 claims description 15
- 229920001519 homopolymer Polymers 0.000 claims description 13
- 238000004381 surface treatment Methods 0.000 claims description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 10
- 238000003490 calendering Methods 0.000 claims description 9
- 238000011282 treatment Methods 0.000 claims description 9
- 239000011256 inorganic filler Substances 0.000 claims description 8
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 8
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 8
- 239000004743 Polypropylene Substances 0.000 claims description 7
- 239000007844 bleaching agent Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000003086 colorant Substances 0.000 claims description 7
- 239000000314 lubricant Substances 0.000 claims description 7
- 238000009994 optical bleaching Methods 0.000 claims description 7
- 229920001155 polypropylene Polymers 0.000 claims description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 230000003064 anti-oxidating effect Effects 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- 239000005662 Paraffin oil Substances 0.000 claims description 5
- 238000001033 granulometry Methods 0.000 claims description 5
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 5
- 239000000049 pigment Substances 0.000 claims description 5
- 229920001083 polybutene Polymers 0.000 claims description 5
- 229940088417 precipitated calcium carbonate Drugs 0.000 claims description 5
- 239000003017 thermal stabilizer Substances 0.000 claims description 5
- 239000002216 antistatic agent Substances 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical class OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 3
- FCSHMCFRCYZTRQ-UHFFFAOYSA-N N,N'-diphenylthiourea Chemical compound C=1C=CC=CC=1NC(=S)NC1=CC=CC=C1 FCSHMCFRCYZTRQ-UHFFFAOYSA-N 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 3
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 3
- 239000008116 calcium stearate Substances 0.000 claims description 3
- 235000013539 calcium stearate Nutrition 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000004049 embossing Methods 0.000 claims description 3
- 235000019239 indanthrene blue RS Nutrition 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 3
- 239000001095 magnesium carbonate Substances 0.000 claims description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 3
- 235000019359 magnesium stearate Nutrition 0.000 claims description 3
- 239000006069 physical mixture Substances 0.000 claims description 3
- 239000004014 plasticizer Substances 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 claims description 3
- 239000000454 talc Substances 0.000 claims description 3
- 229910052623 talc Inorganic materials 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 229940012185 zinc palmitate Drugs 0.000 claims description 3
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 claims description 3
- GJAPSKMAVXDBIU-UHFFFAOYSA-L zinc;hexadecanoate Chemical compound [Zn+2].CCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCC([O-])=O GJAPSKMAVXDBIU-UHFFFAOYSA-L 0.000 claims description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical class CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 2
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 claims description 2
- BLXLSQIOCCHAHJ-UHFFFAOYSA-N [2,3,4-tri(nonyl)phenyl] dihydrogen phosphite Chemical compound CCCCCCCCCC1=CC=C(OP(O)O)C(CCCCCCCCC)=C1CCCCCCCCC BLXLSQIOCCHAHJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- RAVAZXZOSFZIRB-UHFFFAOYSA-L barium(2+);hexadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCC([O-])=O RAVAZXZOSFZIRB-UHFFFAOYSA-L 0.000 claims description 2
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 claims description 2
- GWOWVOYJLHSRJJ-UHFFFAOYSA-L cadmium stearate Chemical compound [Cd+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O GWOWVOYJLHSRJJ-UHFFFAOYSA-L 0.000 claims description 2
- DNLGWCVZSDBXAH-UHFFFAOYSA-L cadmium(2+);hexadecanoate Chemical compound [Cd+2].CCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCC([O-])=O DNLGWCVZSDBXAH-UHFFFAOYSA-L 0.000 claims description 2
- 238000004040 coloring Methods 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 abstract description 11
- 229920002678 cellulose Polymers 0.000 abstract description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 8
- 239000005977 Ethylene Substances 0.000 description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000004594 Masterbatch (MB) Substances 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920002994 synthetic fiber Polymers 0.000 description 3
- 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 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229920002367 Polyisobutene Polymers 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229920005549 butyl rubber Polymers 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- HXIQYSLFEXIOAV-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1SC1=CC(C(C)(C)C)=C(O)C=C1C HXIQYSLFEXIOAV-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004429 Calibre Substances 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000011354 acetal resin Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002730 additional effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 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 1
- 230000009172 bursting Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 239000004794 expanded polystyrene Substances 0.000 description 1
- 238000007647 flexography Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
- C08L23/0815—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic 1-olefins containing one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/10—Copolymers of styrene with conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
Definitions
- the present invention relates to the production of artificial paper of improved physical characteristics yet [52] U.S. Cl. 264/22; 260/4243; 260/4246; which retains the advantageous properties of cellulose 260/4256; 260/889; 260/897 A; 260/897 B; paper. 260/897 C; 264/80; 264/83; 264/234; 264/284
- This novel artificial paper is comprised of (a) at least [Sl] ll'lt.
- the present invention relates to a film resembling paper and to processes for'the manufacture thereof.
- cellulose paper is characterized by lower specific strengths and elongations at break and .by greater rigidity. Moreover. the resistance to tearing of cellulose paper is relatively poor and practically equal in both directions of the plane of the paper. Apart from these measurable properties. cellulose paper is characterized by some specific properties, namely:
- the synthetic materials may provide additional properties not possessed by cellulose paper. such as impermeability to water vapor and gases. resistance to greases. dimensional stability under various atmospheric conditions. and scalability.
- a synthetic film may for example be treated by one of the following processes:
- the base polymer in the film provides the mechanical properties. This film may or may not be oriented.
- paper-like films which are simple films the paper-like feel of which is obtained by a controlled melt fracture phenomenon during extrusion. These films are normally manufactured to form a film imitating tissuepaper.
- spun-bonded artificial papers also exist, which are papers manufactured with synthetic fibres instead of cellulose fibres. These papers may also be subsequently coated.
- Another type of artificial paper is obtained from a composition containing at least one high density polyethylene, a copolymer of ethylene and a vinyl compound (for example vinyl acetate. acrylic ester. etc.). mineral fillers, and unmodified polystyrene. This mixture must first be calendered before its extrusion.
- an artificial paper composed of (a) olefinic resins. (b) resins of the group comprising styrene resins, acrylic resins, acetal resins. phenol resins. (c) fillers and (d) optionally a synthetic elastomer. this mixture likewise being calendered. extruded, and then additionally subjected to biorientation.
- the process according to the invention for the manufacture of an artificial paper requiring neither calendering nor biorientation comprises homogenizing in a conventional rotary mixer a composition containing the following:
- At least one rigid polyolefin (A) selected from the group consisting of homopolymers and copolymers of ethylene. propylene, and butylene. and also mixtures thereof, having a melt index of at most 1 decigramme per minute:
- adjuvants (E) selected from the group consisting of antioxidizing agents. heat stabilizers. optical bleaching agents. pigments, coloring agents, antistatic agents and lubricants, in that the mixture thus homogenized is subjected to extrusion in order to obtain an artificial paper. and that the artificial paper thus obtained. if desired. is subjected to surface treatment.
- adjuvants (E) selected from the group consisting of antioxidizing agents. heat stabilizers. optical bleaching agents. pigments, coloring agents, antistatic agents and lubricants, in that the mixture thus homogenized is subjected to extrusion in order to obtain an artificial paper. and that the artificial paper thus obtained. if desired. is subjected to surface treatment.
- rigid polyolefin (A) is understood a high density polyethylene. an isotactic polypropylene. or an isotactic polybutene which has a melt index (M.l.) of at most I decigramme/minute. preferably lower than 0.2 decigramme per minute. measured according to the standard ASTM D l238/57T. Nevertheless. the rigid polyolefin (A) may also consist of a physical mixture of these homopolymers with one another. or of copolymers obtained from ethylene. propylene. and/or butene.
- the polyolefin (A) has a modulus of elasticity higher than 2000 kg per cm measured according to the standard ASTM D 882/6lT.
- the polyolefin (A) is used in the composition according to the invention at the rate of 94.8 percent by weight. preferably from 40 to 80 percent by weight; it provides the artificial paper of the invention with rigidity and constitutes its framework.
- the polymer (B) which is incompatible with the rigid polyolefin (A) and which when extruded by itself supplies a brittle. hard. fragile film. is obtained by polymerization of a preponderant quantity of a polymerizable.
- ethylene-unsaturated monomer having the end group CH- C selected particularly from the group consisting of styrene. styrene haloand alkylsubstituted on the side chain or on the nucleus.
- the polymer (B) imparts hardness and tearability to the artificial paper manufactured from this composition.
- the properties of the polymer (B) may be modified by the conjoint utilisation of minor amounts of olefinic or diolefinic elastomers. derived for example from isobutylene. butadiene. isoprene. etc.. in a proportion representing at most 49 percent by weight of the polymer (B). It is also possible to modify the polymer (B) by external plastification with conventional plasticizers for vinyl resins. such as for example dioctyl phthalate. tricresyl phosphate. in an amount from 0.1 to 30 percent by weight of the polymer (B).
- the M.l. of the polymer (B) must be lower than l0 decigrammes per minute. preferably lower than 5.
- the polymer (B) is used in an amount from 0.l to percent by weight. preferably from 5 to 30 percent by weight. of the total composition of the invention.
- the macromolecular material (C) provides compatibility in the molten state between the polyolefin (A) and the polymer (B). It is obtained in two ways: l by copolymerisation of two monomers, one of which is compatible with the polyolefin (A). for example ethylene. propylene. or butylene. and the other is compatible with the polymer (B). for example isobutylene. bu-
- macromolecular materials (C) mention'will be made of a 50/50 ethylene/isobutylene copolymer.
- the macromolecular material (C) must be of at most 2 decigrammes per minute. preferably lower than 1 decigramme per minute. It is used in the composition of the invention at the rate of 0.1 to 35 percent by weight of the total mixture. preferably at the rate of 0.l to 25 percent by weight.
- the inorganic filler (D) is selected from inorganic substances which impart opaqueness and a suitable surface structure to the artificial paper of the invention. It may consist of talc. titanium dioxide. kaolin. zeolites. silica. zinc oxide. natural or precipitated calcium carbonate. magnesium carbonate. barytine. etc.
- the granulometry of the inorganic filler will as a maximum amount to 50 microns. Granulometry higher than this limit is disadvantageous because of the formation of grains which are detrimental to the uniformity of the artificial paper.
- the amount of inorganic filler added represents from 5 to 45 percent by weight of the total composition of the artificial paper of the invention. preferably from 5 to 25 percent by weight.
- the adjuvants (E) are constituted by:
- thermal stabilizers such as diphenylthiourea. alphaphenyl-indol. barium. cadmium. or zinc palmitate or stearate. tris-nonlyphenyl phosphite. etc.
- antioxidizing agents such as 4.4'-thio-bis(6-t-butylmetacresol 4.4-methylene-bis( 2.6-di-tbutylphenol). butylated hydroxytoluenes. etc.
- optical bleaching agents such as sulfonated derivatives of stilbene.
- organic coloring agents such as the phthalocyanines. disazoic coloring agents. chlorinated indanthrenes. etc.
- inorganic pigments such as zinc chromate. cadmium sulfide. iron oxide. etc.
- lubricants such as magnesium and calcium stearate.
- adjuvants (E) are added to the composition of the artificial paper according to the invention in an amount ranging from 0 to 10 percent by weight.
- the components (A). (B). (C). (D), and (E) are mixed together in a mixer of conventional construction. preferably in an ordinary rotary mixer.
- the composition of the invention therefore makes it possible to eliminate calendering and subsequent granulation before extrusion. which constitutes a considerable saving in manufacturing costs.
- a suitable way of preparing this mixture consists in adding components (A). (B). and (C) with a lubricant to the rotary mixer. then adding to the resulting mixture the components (D) and (E), which are in the form of a powder. This technique is not necessary if the components (D) and (E) are added in the form of a master batch.
- the length of the operation of mixing in the rotary mixer amounts at most to 60 minutes and is preferably from to 45 minutes. at ambient temperature.
- the homogeneous mixture thus obtained is subjected to extrusion in an apparatus of conventional design. in which the mixture is brought to a temperature achieving at most 290C.
- the extrusion temperature may vary between 100 and 290C in dependence on the composition of the mixture. Moreover. while remaining within the temperature limits specified above. temperature EXAMPLE I.
- a high density polyethylene having a melt index of l dg/min (component A) percent by weight of a mixture of the impact polystyrene type containing 90 percent polystyrene and 10 percent polybutadiene. with a melt index of 3 dg/min under a pressure of 100 psi (7 kg/cm") (comgradients may exist from the supply zone of the ex- 15 ponen't B) truder to the end zone of the extrusion die. percent by weight of a 50/50 mixture of polyethyl-
- the extruder may contain one or more extrusion ene and polyisobutylene with a melt index of 0.2
- the g/min (component C) composition obtained should be perfectly homogene- 10 percent by weight of titanium dioxide passing ous at the outlet of the die. through a 50 micron screen (component D)
- the die should in turn be constructed so that the ex- 4 percent by weight of precipitated calcium carbonate truded film has a regular final calibre. passing through a 50 micron screen (component D)
- the properties of the artificial paper ob- 1 percent by weight of paraffin oil (component E). tained at the outlet of the die are such that subsequent The components (A). (B), and (C) are wetted with biorientation is unnecessary, which provides a second 25 the compound (E) before incorporating the fillers (D).
- the artificial paper according to the invention may is then passed into a laboratory extruder of the type L then undergo surface treatment to improve subsequent 20 D, with a round die, at a temperature of 235C;
- Softening temperature Start C 121 Total 133 Dimensional variations in SM nil in 24h in water at 20C ST nil SM machine direction S'l transversal direction number of ml of air passing through a l m film. with a pressure difference of 1 atmosphere between the faces of the film. in 24 hours.
- This treatment which is well knownin the field of plastics. may consist in subjecting the paper to the action of a flame. corona effect. oxidizing chemical agents. etc.
- the surface treatment of the paper as described above may bepreceded by an operation of em-
- the properties of tearability, impact resistance, rigidity, and permeabilities are properties which depend on the thickness of the paper, while the breaking load, elongation at break, and modulus of elasticity are properties independent of the thickness of the paper.
- EXAMPLE 2 The following are mixed in an ordinary rotary mixer: 35 percent by weight of a high density polyethylene having a melt index of 0.4 dg/min (component A) l4 percent by weight of a styrene-butadiene (90/10) copolymer having a melt index of 3.5 dg/min under a pressure of 100 psi (7 kg/cm (component B) percent by weight of an ethylene-isobutylene (50/50) copolymer having a melt index of 0.2 dg/min (component C) 20 percent by weight of a master batch of titanium dioxide and of high density polyethylene (60/40) having a melt index of 8 dg/min (components A and D) [0 percent by weight of a master batch of calcium carbonate and of high density polyethylene (50/50) having a melt index of4 dg/min (components A and D) percent by weight of antistatic agent (component E) consisting ofa mixture ofC C
- the artificial paper obtained in this manner possesses characteristics similar to those of the paper prepared in Example 1.
- a master batch consisting of a 50/50 mixture of titanium dioxide and high density polyethylene with a melt index equal to 5 dg/min (component A D).
- optical bleaching agent component E
- the properties of the artificial paper obtained are similar to those of the paper prepared in Example I.
- the artificial paper of the invention can be printed in particular by the following processes: offset, li-tho, letterpress, gravure, flexography, silk screen, it can be impulse or heat sealed, it can be stuck on ordinary paper with glues normally suitable for polyethylene, it can be laminated on different types of film, on cellophane, etc., with the aid of standard glues, it is thermoformable, so that embossing can be carried out and any desired surface structures obtained by simply passing over heated rollers.
- the artificial paper manufactured according to the present invention can be used for making maps of any kind: tourist maps, topographical maps. road maps, etc., for printing instructions on official documents (driving licenses, hunting permits, fishing permits), for forms, catalogues. etc.
- the synthetic paper according to the invention can also be used for any artistic printing application and for posters displayed outdoors.
- [t can also be used for printing childrens' books because the pages are washable with water.
- the synthetic paper of the invention does not form dust, it is recommended for special applications in certain industries (for example the manufacture of transistors) where the presence of dust is not allowable.
- the artificial paper of the invention is very particularly recommended for use in places where oil or grease is found, for example as manuals for the greasing of cars. machines, etc.. as self-adhesive labels resisting oils and greases. etc.
- a process for the manufacture of artificial paper requiring neither calendering nor biorientation which comprises homogenizing in a conventional rotary mixer a composition containing:
- At least one rigid polyolefin (A) selected from the group consisting of homopolymers and copolymers of ethylene, propylene, and butylene, and also mixtures thereof, and
- melt index of at most 1 dg./min.
- polymer (B) which is incompatible with the rigid polyolefin (A) and which when extruded by itself produces a brittle film which has a melt index lower than l0 dg./min..
- the polymer (B) being selected from the group consisting of homopolymers and copolymers containing a preponderant amount of styrene an amount within the range of 20 to 25 percent by weight of a macromolecular material (C), said amount being sufficient to produce compatibility between (A) and (B), selected from the group consisting of:
- said macromolecular material having a melt index of at most 2 dg/min.:
- adjuvants (E) selected from the group consisting of antioxidizing agents. thermal stabilizers. optical bleaching agents. pigments. coloring materials, antistatic agents. and lubricants.
- the mixture thus homogenized being subjected to extrusion to obtain an artificial paper and the artificial paper thus obtained. if desired, being subjected to surface treatment.
- polyolefin (A) is selected from the group consisting of high density polyethylene. isotactic polypropylene. and isotactic polybutene.
- polyolefin (A) is a physical mixture of at least two polyolefins selected from the group consisting of high density polyethylene. isotactic polypropylene. and isotactic polybutene.
- polyolefin (A) is a copolymer obtained from at least two olefins selected from the group consisting of ethylene. propylene and butylene.
- polymer (B) is constituted by a mixture containing a major amount of a homopolymer of styrene and a minor amount of a homopolymer obtained by polymerization of an olefinic compound selected from the group consisting of isobutylene. butadiene. and isoprene.
- polymer (B) is a copolymer obtained by copolymerization of a major amount of styrene and a minor amount of a polymerizable olefinic monomer selected from the group consisting of isobutylene. butadiene. and isoprene.
- the macromolecular material (C) is selected from the group consisting of a 50/50 ethylene-isobutylene copolymer and a 75/25 ethylene-butadiene copolymer.
- the inorganic filler (D) is selected from the group consisting of talc. titanium dioxide. kaolin. zeolites. silica. zinc oxide. natural or precipitated calcium carbonate. magnesium carbonate. and barytine.
- thermal stabilizer used as adjuvant (E) is selected from the group consisting of diphenylthiourea. alpha-phenylindol. barium palmitate. cadmium palmitate, zinc palmitate, barium stearate, cadmium stearate. zinc stearate. and tris-nonylphenyl phosphite.
- antioxidizing agent used as adjuvant (E) is selected from the group consisting of 4,4'-thio-bis(6-t-butyl-metacresol). 4.4'-methylene-bis(2,6-di-t-butylphenol), and butylated hydroxytoluenes.
- optical bleaching agent used as adjuvant (E) is selected from the class of sulfonated derivatives of stilbene.
- organic coloring agent used as adjuvant (E) is selected from the group consisting of phthalocyanines. disazoic coloring agents. and chlorinated indanthrenes.
- pigment used as adjuvant (E) is selected from the group consisting of zinc chromate. cadmium sulfide. and iron oxide.
- lubricant used as adjuvant (E) is selected from the group consisting of magnesium stearate. calcium stearate. and paraffin oil.
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Abstract
The present invention relates to the production of artificial paper of improved physical characteristics yet which retains the advantageous properties of cellulose paper. This novel artificial paper is comprised of (a) at least one of a specific class of rigid polyolefins, (b) at least one specific class of polymers incompatible with the rigid polyolefin and (c) at least one of a specific class of macromolecular materials which produce compatability of (a) and (b).
Description
United States Patent Bontinck et al. Apr. 8, 1975 [54] METHOD OF MANUFACTURING AN 3.632.674 l/l972 Aishima et al. 260/897 A X ARTIFICIAL PAPER 7 [75] lnventors: Walter Bontinck, St. I igfi i li gg OR APPLICATIONS Martens-Leerne; Willy De Custer, l' l x Gem both of B g 1,240,586 7/l97l United Kingdom [73] Assignee: U.C.B. Societe Anony ne,
suim GmeS Iez BruXeles Belgium Primary E.\amn zer-Morr1s Liehman Assistant Examiner-J. H. Derrmgton l l Flledi June 29, 1971 Attorney, Agent, or Firm--Wenderoth, Lind & Ponack [21] App]. No.: 158,060
5 [30] Foreign Application Priority Data 7] ABSTRACT July 3, 1970 Belgium 725917 The present invention relates to the production of artificial paper of improved physical characteristics yet [52] U.S. Cl. 264/22; 260/4243; 260/4246; which retains the advantageous properties of cellulose 260/4256; 260/889; 260/897 A; 260/897 B; paper. 260/897 C; 264/80; 264/83; 264/234; 264/284 This novel artificial paper is comprised of (a) at least [Sl] ll'lt. 829C one of a specific Class of polyoicfins at least [58] held of segrch g lf 2 897 one specific class of polymers incompatible with the 60/897 284 rigid polyolefin and (c) at least one of a specific class of macromolecular materials which produce [56] References cued compatability of (a) and (h).
UNITED STATES PATENTS 3,154.46l l0/l964 Johnson lollllo 21 Claims, No Drawings METHOD OF MANUFACTURING AN ARTIFICIAL PAPER The present invention relates to a film resembling paper and to processes for'the manufacture thereof.
If the properties of an ordinary cellulose paper are compared with those 'of any film of synthetic materials. for example of polyethylene. polypropylene. polyvinyl chloride. polystyrene, etc.. it is found that the cellulose paper is characterized by lower specific strengths and elongations at break and .by greater rigidity. Moreover. the resistance to tearing of cellulose paper is relatively poor and practically equal in both directions of the plane of the paper. Apart from these measurable properties. cellulose paper is characterized by some specific properties, namely:
l. appearance.
. touch.
. permanent deformation after folding.
. absence of or a low static electricity charge.
. ability to be written on by a pencil. pen. ballpen,
etc.
6. ability to be printed on by various processes: letterpress. offset. photogravure. etc.
If it isdesired to produce a synthetic film resembling paper. it is therefore necessary to provide the specific properties characterizing the latter. At the same time. the synthetic materials may provide additional properties not possessed by cellulose paper. such as impermeability to water vapor and gases. resistance to greases. dimensional stability under various atmospheric conditions. and scalability.
Various means have i already been adopted in attempts to imitate cellulose paper.
Some have attempted to imitate appearance alone. by surface treatment. A synthetic film may for example be treated by one of the following processes:
a. sand blasting;
b. passing over a rough heated roller;
c. chemical treatment: passing the film through a bath of solvent. followed by passage through a bath containing a non-solvent for the polymer which is however miscible with the first solvent;
d. coating the film with a highly pigmented layer;
c. extrusion by a specific method.
By these surface treatments the opaqueness and the feel of paperare obtained. The base polymer in the film provides the mechanical properties. This film may or may not be oriented.
By chemical treatment with the system comprising the solvent and the non-solvent it is also possible to obtain a certain porosity. but an important advantage of plastics paper. that is to say its impermeability and resistance to liquids. is then partly lost.
One of the first attempts to make a synthetic paper consisted in producing a porous film by incorporating. during extrusion. an expansion agent which forms cavities in the film (for example expanded polystyrene). This film however is difficult to print on and it suffers both from poor impermeability and from poor resistance to liquids (spongy effect).
There are also so-called paper-like films. which are simple films the paper-like feel of which is obtained by a controlled melt fracture phenomenon during extrusion. These films are normally manufactured to form a film imitating tissuepaper.
So-called spun-bonded artificial papers also exist, which are papers manufactured with synthetic fibres instead of cellulose fibres. These papers may also be subsequently coated.
Another type of artificial paper is obtained from a composition containing at least one high density polyethylene, a copolymer of ethylene and a vinyl compound (for example vinyl acetate. acrylic ester. etc.). mineral fillers, and unmodified polystyrene. This mixture must first be calendered before its extrusion.
More recently there has been proposed an artificial paper composed of (a) olefinic resins. (b) resins of the group comprising styrene resins, acrylic resins, acetal resins. phenol resins. (c) fillers and (d) optionally a synthetic elastomer. this mixture likewise being calendered. extruded, and then additionally subjected to biorientation.
Without prejudging the quality of the various artificial papers obtained by the processes mentioned above. it will be noted that the cost of manufacture is burdened by operations such as calendering. which consumes a large amount of energy. and biorientation. which requires special equipment and an elaborate technique. 1
An important technical and economic improvement would be made if it were possible to manufacture an artificial paper having the maximum resemblance to cellulose paper. while the cost of manufacture is reduced to a minimum. In other words. it would inparticular be necessary to be able to develop an artificial paper composition permitting the direct production of the desired paper by simply mixing the components and by simple extrusion. without calendering or biorientation. The present invention relates to the solution of this problem.
The process according to the invention for the manufacture of an artificial paper requiring neither calendering nor biorientation comprises homogenizing in a conventional rotary mixer a composition containing the following:
30-94.8 percent by weight of at least one rigid polyolefin (A) selected from the group consisting of homopolymers and copolymers of ethylene. propylene, and butylene. and also mixtures thereof, having a melt index of at most 1 decigramme per minute:
0.1 to 35 percent by weight of at least one polymer (B) which is incompatible with the rigid polyolefin (A) and which when extruded by itself produces a brittle film and which has a melt index lower than 10 decigrammes/minute. the polymer (B) being selected from the group consisting of homopolymers and copolymers containing a preponderant amount of a polymerizable. ethylenically unsaturated monomer. containing a terminal vinylidene group CH =C selected from the group consisting of styrene. styrene haloor alkylsubstituted on the side chain or on the nucleus, vinyl chloride, vinylidene chloride. acrylic acid esters and methacrylic acid esters of alkanols containing 1 to 3 carbon atoms;
0.] to 35 percent by weight ofa macromolecular material (C) producing compatibility between (A) and (B). selected from the group consisting of l copolymers containing at least one monomer selected from the group consisting of ethylene. propylene. and butylene. and at least one monomer selected from the group consisting of isobutylene. butadiene. and isoprene. and (2) a mixture prepared in advance from at least one homopolymer of ethylene. propylene. or butylene and at least one homopolymer of isobutylene. butadiene. or isoprene. this material having a melt index of at most 2 dg/minute;
545 percent by weight of an inorganic filler (D) having a granulometry lower than 50 microns;
0 to by weight of adjuvants (E) selected from the group consisting of antioxidizing agents. heat stabilizers. optical bleaching agents. pigments, coloring agents, antistatic agents and lubricants, in that the mixture thus homogenized is subjected to extrusion in order to obtain an artificial paper. and that the artificial paper thus obtained. if desired. is subjected to surface treatment.
By rigid polyolefin (A) is understood a high density polyethylene. an isotactic polypropylene. or an isotactic polybutene which has a melt index (M.l.) of at most I decigramme/minute. preferably lower than 0.2 decigramme per minute. measured according to the standard ASTM D l238/57T. Nevertheless. the rigid polyolefin (A) may also consist of a physical mixture of these homopolymers with one another. or of copolymers obtained from ethylene. propylene. and/or butene.
ln the form ofa film the polyolefin (A) has a modulus of elasticity higher than 2000 kg per cm measured according to the standard ASTM D 882/6lT. The polyolefin (A) is used in the composition according to the invention at the rate of 94.8 percent by weight. preferably from 40 to 80 percent by weight; it provides the artificial paper of the invention with rigidity and constitutes its framework.
The polymer (B). which is incompatible with the rigid polyolefin (A) and which when extruded by itself supplies a brittle. hard. fragile film. is obtained by polymerization of a preponderant quantity of a polymerizable. ethylene-unsaturated monomer having the end group CH- =C selected particularly from the group consisting of styrene. styrene haloand alkylsubstituted on the side chain or on the nucleus. vinyl chloride. vinylidene chloride. acrylic acid and methacrylic acid esters of alkanols containing 1 to 3 carbon atoms. etc. In the composition of the invention the polymer (B) imparts hardness and tearability to the artificial paper manufactured from this composition. Nevertheless. the properties of the polymer (B) may be modified by the conjoint utilisation of minor amounts of olefinic or diolefinic elastomers. derived for example from isobutylene. butadiene. isoprene. etc.. in a proportion representing at most 49 percent by weight of the polymer (B). It is also possible to modify the polymer (B) by external plastification with conventional plasticizers for vinyl resins. such as for example dioctyl phthalate. tricresyl phosphate. in an amount from 0.1 to 30 percent by weight of the polymer (B). The M.l. of the polymer (B) must be lower than l0 decigrammes per minute. preferably lower than 5. The polymer (B) is used in an amount from 0.l to percent by weight. preferably from 5 to 30 percent by weight. of the total composition of the invention.
The macromolecular material (C) provides compatibility in the molten state between the polyolefin (A) and the polymer (B). It is obtained in two ways: l by copolymerisation of two monomers, one of which is compatible with the polyolefin (A). for example ethylene. propylene. or butylene. and the other is compatible with the polymer (B). for example isobutylene. bu-
tadiene. isoprene. or else (2) by a previous mixing of a polymer compatible with the polyolefin (A) and a polymer compatible with the polymer (B). As examples of macromolecular materials (C) mention'will be made of a 50/50 ethylene/isobutylene copolymer. or a 75/25 ethylene-butadiene copolymer; as examples of mixtures of the polymer compatible with (A) and of another polymer compatible with (B) mention will be made of a mixture of high or low density polyethylene and polyisobutylene in a 50/50 ratio, a mixture of high or low density polyethylene and polybutadiene in a 75/25 ratio, a /30 mixture of high density polyethylene and butyl rubber. etc. Through its presence the macromolecular material (C) (copolymer or mixture of polymers) makes it possible to obtain a homogeneous composition according to the invention without using calendering. the homogeneity of the composition of the invention being simply obtained in the mixer and the extruder itself. The M.l. of the macromolecular material (C) must be of at most 2 decigrammes per minute. preferably lower than 1 decigramme per minute. It is used in the composition of the invention at the rate of 0.1 to 35 percent by weight of the total mixture. preferably at the rate of 0.l to 25 percent by weight.
The inorganic filler (D) is selected from inorganic substances which impart opaqueness and a suitable surface structure to the artificial paper of the invention. It may consist of talc. titanium dioxide. kaolin. zeolites. silica. zinc oxide. natural or precipitated calcium carbonate. magnesium carbonate. barytine. etc.
The granulometry of the inorganic filler will as a maximum amount to 50 microns. Granulometry higher than this limit is disadvantageous because of the formation of grains which are detrimental to the uniformity of the artificial paper. The amount of inorganic filler added represents from 5 to 45 percent by weight of the total composition of the artificial paper of the invention. preferably from 5 to 25 percent by weight.
The adjuvants (E) are constituted by:
a. thermal stabilizers such as diphenylthiourea. alphaphenyl-indol. barium. cadmium. or zinc palmitate or stearate. tris-nonlyphenyl phosphite. etc.
b. antioxidizing agents such as 4.4'-thio-bis(6-t-butylmetacresol 4.4-methylene-bis( 2.6-di-tbutylphenol). butylated hydroxytoluenes. etc.
c. optical bleaching agents. such as sulfonated derivatives of stilbene.
(1. organic coloring agents such as the phthalocyanines. disazoic coloring agents. chlorinated indanthrenes. etc.
e. inorganic pigments such as zinc chromate. cadmium sulfide. iron oxide. etc.
f. lubricants such as magnesium and calcium stearate.
paraffin oil. etc.
These adjuvants (E) are added to the composition of the artificial paper according to the invention in an amount ranging from 0 to 10 percent by weight.
The components (A). (B). (C). (D), and (E) are mixed together in a mixer of conventional construction. preferably in an ordinary rotary mixer. The composition of the invention therefore makes it possible to eliminate calendering and subsequent granulation before extrusion. which constitutes a considerable saving in manufacturing costs.
A suitable way of preparing this mixture consists in adding components (A). (B). and (C) with a lubricant to the rotary mixer. then adding to the resulting mixture the components (D) and (E), which are in the form of a powder. This technique is not necessary if the components (D) and (E) are added in the form of a master batch. As a rule the length of the operation of mixing in the rotary mixer amounts at most to 60 minutes and is preferably from to 45 minutes. at ambient temperature.
The homogeneous mixture thus obtained is subjected to extrusion in an apparatus of conventional design. in which the mixture is brought to a temperature achieving at most 290C. The extrusion temperature may vary between 100 and 290C in dependence on the composition of the mixture. Moreover. while remaining within the temperature limits specified above. temperature EXAMPLE I.
The following are mixed in a rotary mixer:
50 percent by weight of a high density polyethylene having a melt index of l dg/min (component A) percent by weight of a mixture of the impact polystyrene type containing 90 percent polystyrene and 10 percent polybutadiene. with a melt index of 3 dg/min under a pressure of 100 psi (7 kg/cm") (comgradients may exist from the supply zone of the ex- 15 ponen't B) truder to the end zone of the extrusion die. percent by weight of a 50/50 mixture of polyethyl- The extruder may contain one or more extrusion ene and polyisobutylene with a melt index of 0.2
screws; it is merely important in each case that the g/min (component C) composition obtained should be perfectly homogene- 10 percent by weight of titanium dioxide passing ous at the outlet of the die. through a 50 micron screen (component D) The die should in turn be constructed so that the ex- 4 percent by weight of precipitated calcium carbonate truded film has a regular final calibre. passing through a 50 micron screen (component D) If desired. the properties of the artificial paper ob- 1 percent by weight of paraffin oil (component E). tained at the outlet of the die are such that subsequent The components (A). (B), and (C) are wetted with biorientation is unnecessary, which provides a second 25 the compound (E) before incorporating the fillers (D). considerable saving in the manufacturing process acand the ingredients are mixed for minutes at ambicording to the invention. ent temperature. The mixture obtained in this manner The artificial paper according to the invention may is then passed into a laboratory extruder of the type L then undergo surface treatment to improve subsequent 20 D, with a round die, at a temperature of 235C;
Table 1 Thickness of paper microns 150 Density of paper 1 Breaking load SM kg/cm 190 (ASTM D 882/61T) ST 115 Elongation at break SM 71 13 (ASTMD 882/6IT) ST 11 Apparent elastic limit SM kg/cm nil (ASTM D 882/61T) ST Modulus of elasticity SM kg/cm 7.600
(at a traction speed of ST 7.400
10 mm/min) Resistance to tearing SM g/sheet 67 (ASTM D 1922/6IT) ST 74 Resistance to bursting Kg 1.85
(Mullen Burst. ASTM 774/67) sag mm 3.7
Impact resistance (ASTM D 1709/67) g to Rigidity SM mg/sheet 87 (ASTM D 747/63) ST 113 C oefficient of friction static 05 Film on film (ASTM D 1894/63) dynamic 0.3
Permeability to water vapor g/m'-'/24h 2 (ASTM E 96/66T) Permeability to air mI/m /atm/24h 90 (ASTM D 1434/58) Dimensional variations in 7! SM 75C +0.04
at the temperature of ST +0.17 SM 100C 1.23 ST 0.l6
Softening temperature Start C 121 Total 133 Dimensional variations in SM nil in 24h in water at 20C ST nil SM machine direction S'l transversal direction number of ml of air passing through a l m film. with a pressure difference of 1 atmosphere between the faces of the film. in 24 hours.
profiled heated rollers. thus making it possible to impart to the film a grainy appearance. a linen paper apprintability. This treatment. which is well knownin the field of plastics. may consist in subjecting the paper to the action of a flame. corona effect. oxidizing chemical agents. etc.
If desired. the surface treatment of the paper as described above may bepreceded by an operation of em- In this table the properties of tearability, impact resistance, rigidity, and permeabilities are properties which depend on the thickness of the paper, while the breaking load, elongation at break, and modulus of elasticity are properties independent of the thickness of the paper.
This table shows that the artificial paper according to the invention possesses mechanical properties similar to those of a cellulose paper and that in this regard it is very different from an ordinary film of plastics material. in addition, foldability and tearability are likewise of the same kind as those of glazed paper. Nevertheless, the paper of the invention has the advantage over cellulose paper of possessing better impermeability to water vapor and air and of having remarkable dimensional stability under variable climatic conditions. Moreover, unlike ordinary paper, it withstands water perfectly.
EXAMPLE 2 The following are mixed in an ordinary rotary mixer: 35 percent by weight of a high density polyethylene having a melt index of 0.4 dg/min (component A) l4 percent by weight of a styrene-butadiene (90/10) copolymer having a melt index of 3.5 dg/min under a pressure of 100 psi (7 kg/cm (component B) percent by weight of an ethylene-isobutylene (50/50) copolymer having a melt index of 0.2 dg/min (component C) 20 percent by weight of a master batch of titanium dioxide and of high density polyethylene (60/40) having a melt index of 8 dg/min (components A and D) [0 percent by weight of a master batch of calcium carbonate and of high density polyethylene (50/50) having a melt index of4 dg/min (components A and D) percent by weight of antistatic agent (component E) consisting ofa mixture ofC C alkylamines, at ambient temperature for a period of minutes. The homogenized mixture obtained in this manner is extruded in the same extruder and with the same conditions of operation as in Example 1.
The artificial paper obtained in this manner possesses characteristics similar to those of the paper prepared in Example 1.
EXAMPLE 3 The following are mixed in a rotary mixer:
12 percent by weight of isotactic polypropylene having a melt index equal to 1 dg/min and 39 percent by weight of high density polyethylene having a melt index equal to l dg/min (component A),
l0 percent by weight of a mixture of polystyrene and polybutadiene (80/20) having a melt index equal to 4 dg/min under a pressure of 300 psi (2l kglcm (component B),
23 percent by weight of a mixture of high density polyethylene and butyl rubber (70/30) with a melt index equal to 2 dg/min (component C),
10 percent by weight of a master batch consisting of a 50/50 mixture of titanium dioxide and high density polyethylene with a melt index equal to 5 dg/min (component A D).
5 percent by weight of precipitated calcium carbonate (component D),
0.9 percent by weight of paraffin oil (component E),
and
0.1 percent by weight of optical bleaching agent (component E),
at ordinary temperature for a period of 35 minutes. The
homogenized mixture obtained in this manner is extruded in the same extruder and under the same conditions of operation as in Example 1.
The properties of the artificial paper obtained are similar to those of the paper prepared in Example I.
The artificial paper of the invention can be printed in particular by the following processes: offset, li-tho, letterpress, gravure, flexography, silk screen, it can be impulse or heat sealed, it can be stuck on ordinary paper with glues normally suitable for polyethylene, it can be laminated on different types of film, on cellophane, etc., with the aid of standard glues, it is thermoformable, so that embossing can be carried out and any desired surface structures obtained by simply passing over heated rollers.
The artificial paper manufactured according to the present invention can be used for making maps of any kind: tourist maps, topographical maps. road maps, etc., for printing instructions on official documents (driving licenses, hunting permits, fishing permits), for forms, catalogues. etc.
The synthetic paper according to the invention can also be used for any artistic printing application and for posters displayed outdoors.
[t can also be used for printing childrens' books because the pages are washable with water. As the synthetic paper of the invention does not form dust, it is recommended for special applications in certain industries (for example the manufacture of transistors) where the presence of dust is not allowable.
The artificial paper of the invention is very particularly recommended for use in places where oil or grease is found, for example as manuals for the greasing of cars. machines, etc.. as self-adhesive labels resisting oils and greases. etc.
We claim:
1. A process for the manufacture of artificial paper requiring neither calendering nor biorientation, which comprises homogenizing in a conventional rotary mixer a composition containing:
40 to percent by weight of at least one rigid polyolefin (A) selected from the group consisting of homopolymers and copolymers of ethylene, propylene, and butylene, and also mixtures thereof, and
having a melt index of at most 1 dg./min.;
5 to 30 percent by weight of at least one polymer (B) which is incompatible with the rigid polyolefin (A) and which when extruded by itself produces a brittle film which has a melt index lower than l0 dg./min.. the polymer (B) being selected from the group consisting of homopolymers and copolymers containing a preponderant amount of styrene an amount within the range of 20 to 25 percent by weight of a macromolecular material (C), said amount being sufficient to produce compatibility between (A) and (B), selected from the group consisting of:
copolymers of at least one monomer selected from the group consisting of ethylene, propylene, and butylene, and at least one monomer selected from the group consisting of isobutylene. butadiene, and isoprene, and
said macromolecular material having a melt index of at most 2 dg/min.:
to 45 percent by weight of an inorganic filler (D) having a granulometry lower tnan 50 microns;
0 to percent by weight of adjuvants (E) selected from the group consisting of antioxidizing agents. thermal stabilizers. optical bleaching agents. pigments. coloring materials, antistatic agents. and lubricants.
the mixture thus homogenized being subjected to extrusion to obtain an artificial paper and the artificial paper thus obtained. if desired, being subjected to surface treatment.
2. A process according to claim 1., in which the polyolefin (A) is selected from the group consisting of high density polyethylene. isotactic polypropylene. and isotactic polybutene.
3. A process according to claim 1, in which the polyolefin (A) is a physical mixture of at least two polyolefins selected from the group consisting of high density polyethylene. isotactic polypropylene. and isotactic polybutene.
4. A process according to claim I. in which the polyolefin (A) is a copolymer obtained from at least two olefins selected from the group consisting of ethylene. propylene and butylene.
5. A process according to claim 1. in which the polymer (B) is constituted by a mixture containing a major amount of a homopolymer of styrene and a minor amount of a homopolymer obtained by polymerization of an olefinic compound selected from the group consisting of isobutylene. butadiene. and isoprene.
6. A process according to claim 1. in which the polymer (B) is a copolymer obtained by copolymerization of a major amount of styrene and a minor amount of a polymerizable olefinic monomer selected from the group consisting of isobutylene. butadiene. and isoprene.
7. A process according to claim 1. in which the polymer (B) is plasticized with 0.1 to percent by weight of a plasticizer.
8. A process according to claim 1. in which the macromolecular material (C) is selected from the group consisting of a 50/50 ethylene-isobutylene copolymer and a 75/25 ethylene-butadiene copolymer.
9. A process according to claim 1. in which the inorganic filler (D) is selected from the group consisting of talc. titanium dioxide. kaolin. zeolites. silica. zinc oxide. natural or precipitated calcium carbonate. magnesium carbonate. and barytine.
10. A process according to claim 1, in which the thermal stabilizer used as adjuvant (E) is selected from the group consisting of diphenylthiourea. alpha-phenylindol. barium palmitate. cadmium palmitate, zinc palmitate, barium stearate, cadmium stearate. zinc stearate. and tris-nonylphenyl phosphite.
11. A process according to claim 1, in which the antioxidizing agent used as adjuvant (E) is selected from the group consisting of 4,4'-thio-bis(6-t-butyl-metacresol). 4.4'-methylene-bis(2,6-di-t-butylphenol), and butylated hydroxytoluenes.
12. A process according to claim 1, in which the optical bleaching agent used as adjuvant (E) is selected from the class of sulfonated derivatives of stilbene.
13. A process according to claim 1, in which the organic coloring agent used as adjuvant (E) is selected from the group consisting of phthalocyanines. disazoic coloring agents. and chlorinated indanthrenes.
14. A process according to claim 1. in which the pigment used as adjuvant (E) is selected from the group consisting of zinc chromate. cadmium sulfide. and iron oxide.
15. A process according to claim 1, in which the lubricant used as adjuvant (E) is selected from the group consisting of magnesium stearate. calcium stearate. and paraffin oil.
16. A process according to claim 1, in which the mixing of the components A.B.C.D. and E in the rotary mixer is carried out at ambient temperature.
17. A process according to claim 1. in which the extrusion is carried out at a temperature between and 290C.
18. A process according to claim 1, in which the surface treatment to which the artificial paper is subjected is a flame treatment.
19. A process according to claim 1, in which the surface treatment to which the artificial paper is subjected is a treatment by corona effect.
20. A process according to claim 1. in which the surface treatment to which the artificial paper is subjected is a treatment by oxidizing agents.
21. A process according to claim 1. in which the artificial paper is additionally subjected to an embossing operation.
Claims (21)
1. A PROCESS FOR THE MANUFACTURE OF ARTIFICIAL PAPER REQUIRING NEITHER CALENDERING NOR BIORIENTATION, WHICH COMPRISES HOMOGENIZING IN A CONVENTIONAL ROTARY MIXER A COMPOSITION CONTAINING: 40 TO 80 PERCENT BY WEIGHT OF AT LEAST ONE RIGID POLYOLEFIN (A) SELECTED FROM THE GROUP CONSISTING OF HOMOPOLYMERS AND COPOLYMERS OF ETHYLENE, PROPYLENE, AND BUTYLENE AND ALSO MIXTURES THEREOF, AND HAVING A MELT INDEX OF AT MOST 1 DG./MIN., 5 TO 30 PERCENT BY WEIGHT OF AT LEAST ONE POLYMER (B) WHICH IS INCOMPATIBLE WITH THE RIGID POLYOLEFIN (A) AND WHICH WHEN EXTRUDED BY ITSELF PRODUCES A BRITTLE FILM WHICH HAS A MELT INDEX LOWER THAN 10 DG./MIN., THE POLYMER (B) BEING SELECTED FROM THE GROUP CONSISTING OF HOMOPOLYMERS AND COPOLYMERS CONTAINING A PREPONDERANT AMOUNT OF STYRENE AN AMOUNT WITHIN THE RANGE OF 20 TO 25 PERCENT BY WEIGHT OF A MACROMOLECULAR MATERIAL (C), SAID AMOUNT BEING SUFFICIENT TO PRODUCE COMPATIBILITY BETWEEN (A) AND (B), SELECTED FROM THE GROUP CONSISTING OF: COPOLYMERS OF T LEAST ONE MONOMER SELECTED FROM THE GROUP CONSISTING OF ETHYLENE, PROPYLENE, AND GROUP CONAND AT LEAST ONE MONOMER SELECTED FROM THE GROUP CONSISTING OF ISOBUTYLENE, BUTADIENE, AND ISOPRENE, AND SAID MACROMOLECULAR MATERIAL HAVING A MELT INDEX OF AT MOST 2 DG/MIN., 5 TO 45 PERCENT BY WEIGHT OF AN INORGANIC FILLER (D) HAVING A GRANULOMETRY LOWER THAN 50 MICRONS, 0 TO 10 PERCENT BY WEIGHT OF ADJUVANTS (E) SELECTED FROM THE GROUP CONSISTING OF ANTIOXIDIZING AGENTS, THERMAL STABILIZERS, OPTICAL BLEACHING AGENT, PIGMENTS, COLORING MATERIALS, ANTISTATIC AGENTS, AND LUBRICANTS, THE MIXTURE THUS HOMOGENIZED BEING SUBJECTED TO EXTRUSION TO OBTAIN AN ARTIFICAL PAPER AND THE ARTIFICAL PAPER THUS, OBTAINED, IF DESIRED, BEING SUBJECTED TO SURFACE TREATMENT.
2. A process according to claim 1, in which the polyolefin (A) is selected from the group consisting of high density polyethylene, isotactic polypropylene, and isotactic polybutene.
3. A process according to claim 1, in which the polyolefin (A) is a physical mixture of at least two polyolefins selected from the group consisting of high density polyethylene, isotactic polypropylene, and isotactic polybutene.
4. A process according to claim 1, in which the polyolefin (A) is a copolymer obtained from at least two olefins selected from the group consisting of ethylene, propylene and butylene.
5. A process according to claim 1, in which the polymer (B) is constituted by a mixture containing a major amount of a homopolymer of styrene and a minor amount of a homopolymer obtained by polymerization of an olefinic compound selected from the group consisting of isobutylene, butadiene, and isoprene.
6. A process according to claim 1, in which the polymer (B) is a copolymer obtained by copolymerization of a major amount of styrene and a minor amount of a polymerizable olefinic monomer selected from the group consisting of isobutylene, butadiene, and isoprene.
7. A process according to claim 1, in which the polymer (B) is plasticized with 0.1 to 30 percent by weight of a plasticizer.
8. A process according to claim 1, in which the macromolecular material (C) is selected from the group consisting of a 50/50 ethylene-isobutylene copolymer and a 75/25 ethylene-butadiene copolymer.
9. A process according to claim 1, in which the inorganic filler (D) is selected from the group consisting of talc, titanium dioxide, kaolin, zeolites, silica, zinc oxide, natural or precipitated calcium carbonate, magnesium carbonate, and barytine.
10. A process according to claim 1, in which the thermal stabilizer used as adjuvant (E) is selected from the group consisting of diphenylthiourea, alpha-phenyl-indol, barium palmitate, cadmium palmitate, zinc palmitate, barium stearate, cadmium stearate, zinc stearate, and tris-nonylphenyl phosphite.
11. A process according to claim 1, in which the antioxidizing agent used as adjuvant (E) is selected from the group consisting of 4,4''-thio-bis(6-t-butyl-meta-cresol), 4,4''-methylene-bis(2,6-di-t-butylphenol), and butylated hydroxytoluenes.
12. A process according to claim 1, in which the optical bleaching agent used as adjuvant (E) is selected from the class of sulfonated derivatives of stilbene.
13. A process according to claim 1, in which the organic coloring agent used as adjuvant (E) is selected from the group consisting of phthalocyanines, disazoic coloring agents, and chlorinated indanthrenes.
14. A process according to claim 1, in which the pigment used as adjuvant (E) is selected from the group consisting of zinc chromate, cadmium sulfide, and iron oxide.
15. A process according to claim 1, in which the lubricant used as adjuvant (E) is selected from the group consisting of magnesium stearate, calcium stearate, and paraffin oil.
16. A process according to claim 1, in which the mixing of the components A,B,C,D, and E in the rotary mixer is carried out at ambient temperature.
17. A process according to claim 1, in which the extrusion is carried out at a temperature between 100.degree. and 290.degree.C.
18. A process according to claim 1, in which the surface treatment to which the artificial paper is subjected is a flame treatment.
19. A process according to claim 1, in which the surface treatment to which the artificial paper is subjected is a treatment by corona effect.
20. A process according to claim 1, in which the surface treatment to which the artificial paper is subjected is a treatment by oxidizing agents.
21. A process according to claim 1, in which the artificial paper is additionally subjected to an embossing operation.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BE1002327 | 1970-07-03 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US428743A Division US3882061A (en) | 1970-07-03 | 1973-12-12 | Method of manufacturing an artificial paper |
Publications (1)
Publication Number | Publication Date |
---|---|
US3876735A true US3876735A (en) | 1975-04-08 |
Family
ID=3862612
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US158060A Expired - Lifetime US3876735A (en) | 1970-07-03 | 1971-06-29 | Method of manufacturing an artificial paper |
Country Status (15)
Country | Link |
---|---|
US (1) | US3876735A (en) |
AT (1) | AT318930B (en) |
BE (1) | BE752917A (en) |
CA (1) | CA978685A (en) |
CH (1) | CH544185A (en) |
DE (1) | DE2132510A1 (en) |
DK (1) | DK132090C (en) |
FR (1) | FR2097165B1 (en) |
GB (1) | GB1336492A (en) |
HU (1) | HU166037B (en) |
LU (1) | LU63443A1 (en) |
NL (1) | NL7108905A (en) |
PL (1) | PL81823B1 (en) |
RO (1) | RO63330A (en) |
ZA (1) | ZA714301B (en) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4024323A (en) * | 1975-02-06 | 1977-05-17 | Evans Products Company | Battery separator |
US4151159A (en) * | 1973-06-13 | 1979-04-24 | Bakelite Xylonite Limited | Plastics shaped articles |
US4265960A (en) * | 1978-12-26 | 1981-05-05 | Mobil Oil Corporation | Films produced from LDPE encapsulated CaCO3 |
US4447479A (en) * | 1975-05-08 | 1984-05-08 | Plastona (John Waddington) Ltd. | Plastics sheet material and articles produced therefrom |
US4911985A (en) * | 1989-02-21 | 1990-03-27 | Allied-Signal Inc. | High density polyethylene compositions containing polyisobutylene rubber and filler |
US5049441A (en) * | 1989-02-21 | 1991-09-17 | Paxon Polymer Company, Lp | High density polyethylene compositions |
US5153039A (en) * | 1990-03-20 | 1992-10-06 | Paxon Polymer Company, L.P. | High density polyethylene article with oxygen barrier properties |
US5536468A (en) * | 1993-11-26 | 1996-07-16 | Arjobex Limited | Method of making watermarks on synthetic paper |
WO2008124906A2 (en) * | 2007-04-16 | 2008-10-23 | FUNDAçAÕ UNIVERSIDADE FEDERAL DE SAÕ CARLOS-UFSCAR | Compositions for synthetic papers and ecological films for writing and printing. |
US20220204708A1 (en) * | 2020-12-30 | 2022-06-30 | Taiwan Lung Meng Advanced Composite Materials Co., Ltd. | Waterproof corrugated paper |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2310205A1 (en) * | 1976-05-07 | 1976-12-03 | Plastona Waddington Ltd John | Sheet material contg. polyolefin and granular inorganic material - melted by mechanical working, and sheeted ,as paper or cardboard substitute esp. for food and drink containers |
DE2646298C2 (en) * | 1976-10-14 | 1982-09-16 | Wacker-Chemie GmbH, 8000 München | Paper-like foils made from highly filled polyethylene masses |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3154461A (en) * | 1960-03-07 | 1964-10-27 | Minnesota Mining & Mfg | Matte-finish polymeric film and method of forming the same |
US3632674A (en) * | 1967-11-02 | 1972-01-04 | Itsuho Aishima | Blend of ethylene polymer crystalline polypropylene polymer and crystalline ethylene-propylene block copolymer |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1425566A (en) * | 1963-12-24 | 1966-01-24 | Union Carbide Corp | Film-forming polymer compositions and films obtained from these compositions |
GB1257512A (en) * | 1968-06-10 | 1971-12-22 | ||
DE1934096B2 (en) * | 1968-07-06 | 1976-02-05 | Sekisui Kagaku Kogyo KJC., Osaka (Japan) | PROCESS FOR MANUFACTURING ARTIFICIAL PAPER FROM THERMOPLASTIC POLYMER BLENDS |
-
1970
- 1970-07-03 BE BE752917D patent/BE752917A/en unknown
-
1971
- 1971-06-28 NL NL7108905A patent/NL7108905A/xx unknown
- 1971-06-29 CA CA117,036A patent/CA978685A/en not_active Expired
- 1971-06-29 PL PL1971149111A patent/PL81823B1/pl unknown
- 1971-06-29 US US158060A patent/US3876735A/en not_active Expired - Lifetime
- 1971-06-29 FR FR7124041A patent/FR2097165B1/fr not_active Expired
- 1971-06-29 RO RO7100067495A patent/RO63330A/en unknown
- 1971-06-29 DK DK319571A patent/DK132090C/en active
- 1971-06-30 DE DE19712132510 patent/DE2132510A1/en active Pending
- 1971-06-30 ZA ZA714301A patent/ZA714301B/en unknown
- 1971-06-30 LU LU63443D patent/LU63443A1/xx unknown
- 1971-06-30 GB GB3064871A patent/GB1336492A/en not_active Expired
- 1971-07-01 CH CH972971A patent/CH544185A/en not_active IP Right Cessation
- 1971-07-02 AT AT05750/71A patent/AT318930B/en not_active IP Right Cessation
- 1971-07-02 HU HUUI176A patent/HU166037B/hu unknown
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3154461A (en) * | 1960-03-07 | 1964-10-27 | Minnesota Mining & Mfg | Matte-finish polymeric film and method of forming the same |
US3632674A (en) * | 1967-11-02 | 1972-01-04 | Itsuho Aishima | Blend of ethylene polymer crystalline polypropylene polymer and crystalline ethylene-propylene block copolymer |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4151159A (en) * | 1973-06-13 | 1979-04-24 | Bakelite Xylonite Limited | Plastics shaped articles |
US4024323A (en) * | 1975-02-06 | 1977-05-17 | Evans Products Company | Battery separator |
US4447479A (en) * | 1975-05-08 | 1984-05-08 | Plastona (John Waddington) Ltd. | Plastics sheet material and articles produced therefrom |
US4265960A (en) * | 1978-12-26 | 1981-05-05 | Mobil Oil Corporation | Films produced from LDPE encapsulated CaCO3 |
US4911985A (en) * | 1989-02-21 | 1990-03-27 | Allied-Signal Inc. | High density polyethylene compositions containing polyisobutylene rubber and filler |
US5049441A (en) * | 1989-02-21 | 1991-09-17 | Paxon Polymer Company, Lp | High density polyethylene compositions |
US5153039A (en) * | 1990-03-20 | 1992-10-06 | Paxon Polymer Company, L.P. | High density polyethylene article with oxygen barrier properties |
US5536468A (en) * | 1993-11-26 | 1996-07-16 | Arjobex Limited | Method of making watermarks on synthetic paper |
WO2008124906A2 (en) * | 2007-04-16 | 2008-10-23 | FUNDAçAÕ UNIVERSIDADE FEDERAL DE SAÕ CARLOS-UFSCAR | Compositions for synthetic papers and ecological films for writing and printing. |
WO2008124906A3 (en) * | 2007-04-16 | 2009-02-12 | Fundacao Universidade Fed De S | Compositions for synthetic papers and ecological films for writing and printing. |
US20100119799A1 (en) * | 2007-04-16 | 2010-05-13 | Fundacao Universidade Federal De Sao Carlo- Ufscar And Vitopel Do Brasil Ltda | Compositions for synthetic papers and ecologic films for writing and printing, synthetic papers and films obtained from such compositions, and uses thereof |
US20220204708A1 (en) * | 2020-12-30 | 2022-06-30 | Taiwan Lung Meng Advanced Composite Materials Co., Ltd. | Waterproof corrugated paper |
Also Published As
Publication number | Publication date |
---|---|
GB1336492A (en) | 1973-11-07 |
AT318930B (en) | 1974-11-25 |
LU63443A1 (en) | 1972-03-22 |
ZA714301B (en) | 1972-03-29 |
PL81823B1 (en) | 1975-10-31 |
FR2097165B1 (en) | 1974-08-19 |
HU166037B (en) | 1974-12-28 |
RO63330A (en) | 1978-06-15 |
DE2132510A1 (en) | 1972-01-05 |
CH544185A (en) | 1973-11-15 |
CA978685A (en) | 1975-11-25 |
FR2097165A1 (en) | 1972-03-03 |
BE752917A (en) | 1971-01-04 |
NL7108905A (en) | 1972-01-05 |
DK132090C (en) | 1976-03-22 |
DK132090B (en) | 1975-10-20 |
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