EP0236478A1 - Decorative inlaid types of sheet materials. - Google Patents
Decorative inlaid types of sheet materials.Info
- Publication number
- EP0236478A1 EP0236478A1 EP86906054A EP86906054A EP0236478A1 EP 0236478 A1 EP0236478 A1 EP 0236478A1 EP 86906054 A EP86906054 A EP 86906054A EP 86906054 A EP86906054 A EP 86906054A EP 0236478 A1 EP0236478 A1 EP 0236478A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- product
- particles
- pvc
- substrate
- layer
- 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.)
- Granted
Links
- 239000000463 material Substances 0.000 title abstract description 19
- 239000002245 particle Substances 0.000 claims abstract description 84
- 239000011159 matrix material Substances 0.000 claims abstract description 34
- 238000000576 coating method Methods 0.000 claims abstract description 27
- 239000000853 adhesive Substances 0.000 claims abstract description 26
- 230000001070 adhesive effect Effects 0.000 claims abstract description 26
- 239000011248 coating agent Substances 0.000 claims abstract description 23
- 239000000758 substrate Substances 0.000 claims description 49
- 239000000203 mixture Substances 0.000 claims description 46
- 229920001944 Plastisol Polymers 0.000 claims description 43
- 239000004999 plastisol Substances 0.000 claims description 43
- 239000004800 polyvinyl chloride Substances 0.000 claims description 37
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 37
- 239000010410 layer Substances 0.000 claims description 34
- 229920005989 resin Polymers 0.000 claims description 28
- 239000011347 resin Substances 0.000 claims description 28
- 239000000976 ink Substances 0.000 claims description 17
- 239000003381 stabilizer Substances 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 16
- 239000011049 pearl Substances 0.000 claims description 16
- IRIAEXORFWYRCZ-UHFFFAOYSA-N n-butyl benzyl phthalate Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000000049 pigment Substances 0.000 claims description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000009472 formulation Methods 0.000 claims description 14
- -1 organic acid esters Chemical class 0.000 claims description 14
- 239000004014 plasticizer Substances 0.000 claims description 12
- 239000012790 adhesive layer Substances 0.000 claims description 11
- 239000010425 asbestos Substances 0.000 claims description 11
- 229920001577 copolymer Polymers 0.000 claims description 11
- 229910052895 riebeckite Inorganic materials 0.000 claims description 11
- SHLNMHIRQGRGOL-UHFFFAOYSA-N barium zinc Chemical compound [Zn].[Ba] SHLNMHIRQGRGOL-UHFFFAOYSA-N 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 10
- 229920001519 homopolymer Polymers 0.000 claims description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 9
- 239000004606 Fillers/Extenders Substances 0.000 claims description 9
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- 239000004408 titanium dioxide Substances 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- BJQHLKABXJIVAM-UHFFFAOYSA-N Diethylhexyl phthalate Natural products CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 5
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- 239000000839 emulsion Substances 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 239000003350 kerosene Substances 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 2
- 239000012964 benzotriazole Substances 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims 3
- 229920012485 Plasticized Polyvinyl chloride Polymers 0.000 claims 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 229920006026 co-polymeric resin Polymers 0.000 claims 1
- 235000015112 vegetable and seed oil Nutrition 0.000 claims 1
- 239000008158 vegetable oil Substances 0.000 claims 1
- 230000002087 whitening effect Effects 0.000 claims 1
- 238000013461 design Methods 0.000 abstract description 15
- 238000000034 method Methods 0.000 description 23
- 230000008569 process Effects 0.000 description 12
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 229920002554 vinyl polymer Polymers 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 6
- 239000011236 particulate material Substances 0.000 description 6
- 239000003086 colorant Substances 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 238000007639 printing Methods 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 239000000470 constituent Substances 0.000 description 4
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 3
- 125000006487 butyl benzyl group Chemical group 0.000 description 3
- 238000003490 calendering Methods 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 238000004049 embossing Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000565 sealant Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 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 2
- 239000004156 Azodicarbonamide Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 2
- 235000019399 azodicarbonamide Nutrition 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- HGAZMNJKRQFZKS-UHFFFAOYSA-N chloroethene;ethenyl acetate Chemical compound ClC=C.CC(=O)OC=C HGAZMNJKRQFZKS-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 1
- NVXYNWZJMIFTMV-UHFFFAOYSA-N 10-o-benzyl 1-o-butyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCC1=CC=CC=C1 NVXYNWZJMIFTMV-UHFFFAOYSA-N 0.000 description 1
- PACBIGNRUWABMA-UHFFFAOYSA-N 2-(2,3-dihydro-1,3-benzothiazol-2-yl)-6-dodecyl-4-methylphenol Chemical compound CCCCCCCCCCCCC1=CC(C)=CC(C2SC3=CC=CC=C3N2)=C1O PACBIGNRUWABMA-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene 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
- AUNAPVYQLLNFOI-UHFFFAOYSA-L [Pb++].[Pb++].[Pb++].[O-]S([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Mo]([O-])(=O)=O Chemical compound [Pb++].[Pb++].[Pb++].[O-]S([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Mo]([O-])(=O)=O AUNAPVYQLLNFOI-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007799 cork Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- HCQHIEGYGGJLJU-UHFFFAOYSA-N didecyl hexanedioate Chemical compound CCCCCCCCCCOC(=O)CCCCC(=O)OCCCCCCCCCC HCQHIEGYGGJLJU-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 238000009826 distribution Methods 0.000 description 1
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000008131 herbal destillate Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical compound O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- UMKARVFXJJITLN-UHFFFAOYSA-N lead;phosphorous acid Chemical compound [Pb].OP(O)O UMKARVFXJJITLN-UHFFFAOYSA-N 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- YAFOVCNAQTZDQB-UHFFFAOYSA-N octyl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OCCCCCCCC)OC1=CC=CC=C1 YAFOVCNAQTZDQB-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- PZTAGFCBNDBBFZ-UHFFFAOYSA-N tert-butyl 2-(hydroxymethyl)piperidine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCCCC1CO PZTAGFCBNDBBFZ-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- LPEBYPDZMWMCLZ-CVBJKYQLSA-L zinc;(z)-octadec-9-enoate Chemical compound [Zn+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O LPEBYPDZMWMCLZ-CVBJKYQLSA-L 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- D06N7/00—Flexible sheet materials not otherwise provided for, e.g. textile threads, filaments, yarns or tow, glued on macromolecular material
- D06N7/0005—Floor covering on textile basis comprising a fibrous substrate being coated with at least one layer of a polymer on the top surface
- D06N7/0028—Floor covering on textile basis comprising a fibrous substrate being coated with at least one layer of a polymer on the top surface characterised by colour effects, e.g. craquelé, reducing gloss
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- D06N7/00—Flexible sheet materials not otherwise provided for, e.g. textile threads, filaments, yarns or tow, glued on macromolecular material
- D06N7/0005—Floor covering on textile basis comprising a fibrous substrate being coated with at least one layer of a polymer on the top surface
- D06N7/0039—Floor covering on textile basis comprising a fibrous substrate being coated with at least one layer of a polymer on the top surface characterised by the physical or chemical aspects of the layers
- D06N7/0052—Compounding ingredients, e.g. rigid elements
- D06N7/0055—Particulate material such as cork, rubber particles, reclaimed resin particles, magnetic particles, metal particles, glass beads
Definitions
- the present invention relates to decorative inlaid sheet materials and the like. More particularly the invention is concerned with the use of polyvinyl chloride (hereinafter "PVC") polymerization agglomerates as decorative particles and their application on floor and wall covering substrates to produce realistic inlaid patterns, utilizing heretofore unobtainable design strategies and exhibiting superior properties.
- PVC polyvinyl chloride
- the particles can be spherical and, when such is the case, are hereinafter sometimes referred to as "pearls" .
- These pearls can be random-sifted on the substrate or applied in geometrical patterns. Also disclosed is the use of mixes or blends containing transparent or partly transparent pearls allowing visible underprinting as a further strategy for unique design variations.
- Sheet materials in particular sheet vinyl flooring products, made with chips or particulate material, are commonly referred to as inlaids. These products and processes for their manufacture are well known in the floorcovering business and originate back to the early linoleum times where through patterned floorcoverings, based on linseed oil, cork dust and resins were developed by the industry. The process was later modified for vinyl.
- Vinyl inlaid floorcovering consists of coarse colored particles, such as chips or dry blends, which are "laid on” a substrate and then sintered by heat, or "laid in” a transparent liquid or solid matrix and fused by heat.
- the chips are produced from pre-gelled or fused spread, calendered or extruded compounds cut into geometrically regular profiles or ground into randomly shaped particles.
- the dry blends are made by mixing fine PVC powder with plasticizer, filler and color pigments and heating above the PVC compound's softening temperature.
- the small origin particles "grow” and form a loose, porous, coarse, fluffy mass.
- the inlaid floorcoverings are normally characterized as those which maintain their decorative appearance as the surface is worn or abraded away. This characteristic makes such products particularly suitable for use in light commercial areas where significant wear is encountered.
- Resilients include a substantially continuous layer of foam and are usually made by incorporating solid particulate material into a plastisol coating, followed by gelling and fusing.
- Non-resilients do not contain a foam layer and usually are made by sintering and/or calendering, or otherwise compacting, particulate material.
- non-resilient products commercially offered are those containing large (about 1/8 inch) square chips in a clear matrix and those containing small (about 0.004 inch) dry blend resin particles made by sintering and/or c ⁇ mpacting normal dry blend resins. It is believed that the reason no products containing chips, granules, or particles of an intermediate particle size (eg. ranging from about 0.004 inch to about 0.040 inch) are offered results from limitations inherent in current inlaid manufacturing technology, discussed more fully hereinafter.
- Resilient inlaids are usually made by embedding ground plastic particulate material in a plastisol coating.
- United States Patent 4, 212,691 exemplifies such products and methods for their manufacture.
- the thickness of the particles of the decorative chips or flakes is stated to be from about 3 mils to about 25 mils (eg. see column 7, lines 62-64).
- the products disclosed all contain embedded chips or flakes ground from plastic sheet stock, even when chips or flakes from other stock materials are added (eg. see column 8, lines 4 et seq). These chips or flakes characteristically have a high aspect ratio (ie. length/thickness).
- products formed by compacting or sintering dry blends have always shown limited particle distinction due to process limitations and available particle sizes.
- the particles tend to lose their identity due to agglomeration or lumping caused by the sintering process.
- a decorative, inlaid floor or wall covering product which incorporates as the essential elements thereof (i) resinous particles having an aspect ratio significantly lower than those currently employed in inlaids commercially offered in the United States and a particle size, preferably falling within the range of from about 0.004 inch to about 0.040 inch, (ii) an adhesive matrix in which said particles are embedded, and (iii) a substrate which supports these and any other optional elements of the product, such as a substrate coating or sealant, a print layer, and a wear layer.
- resinous particles having an aspect ratio significantly lower than those currently employed in inlaids commercially offered in the United States and a particle size, preferably falling within the range of from about 0.004 inch to about 0.040 inch
- an adhesive matrix in which said particles are embedded preferably falling within the range of from about 0.004 inch to about 0.040 inch
- a substrate which supports these and any other optional elements of the product, such as a substrate coating or sealant, a print layer, and a wear layer.
- the particles employed in this invention have an aspect ratio of no greater than about 2:1 and, preferably, no greater than about 1.5:1.
- Particles having an aspect ratio of about 1:1 and, in particular, spheroidal particles, are especially preferred because of the excellent results achieved therewith, as discussed more fully hereinafter.
- the use of particles which are essentially as thick as they are flat, ie. having a low aspect ratio, provides a product that will not lose its pattern due to wear in use, thus preserving the unique property which characterizes true inlaids.
- a decorative, inlaid floor or wall covering which comprises: a) a substrate, b) a printed layer, generally comprising a printable substrate coating or sealant, onto which is printed a pattern in an ink suitable for floor or wall covering applications, applied over and in contact with said substrate, and c) an adhesive matrix, overlaying said printed layer, and in contact therewith, in which are embedded the resinous particles, said matrix being sufficiently transparent or transluscent to permit the underprint to show through.
- the inlaid products of this invention offer unique design advantages. Further, cost advantages can also be realized by utilizing raw materials which are believed to be unique to inlaid manufacture.
- certain of the novel products of the invention incorporate an adhesive matrix consisting essentially of a plastisol layer containing a high loading of transparent and/or transluscent and colored, spheroidal resinous particles, which, preferably, range in size from about 0.004 inches to about 0.040 inches. When this matrix is applied over a printed pattern, a unique visual effect is produced.
- Such particles can be made in uniform controlled sizes by employing technology described in United States Patent 3,856,900, the entire contents of which are incorporated herein by reference.
- special large particle size dry blend resinous particles either screened to the desired size ranges of this invention from oversized material obtained from normal production variations, or specially made particles in the desired size range, can be utilized .
- Another, and preferred, embodiment of this invention is a decorative, inlaid floor covering which comprises:
- the product is comprised of a base supporting material, which, optionally, may be precoated with a plastisol to enhance printability, a print layer offering decoration, and an adhesive matrix containing transparent and pigmented resin particles, which are preferably spherical or spheroidal.
- the resulting product has an additional coating on its top surface to enhance surface properties, such as gloss and the like, and insure there is no residual porosity resulting from the process of embedding the particulates in the adhesive matrix.
- One of the advantages of this invention is that it employs ingredients and processing technology well known to those skilled in the art. Also, by employing a fluid plastisol as the matrix material binding the particles together, the product can be manufactured without the need for the high pressures or temperatures characteristic of the calendering or agglomeration steps of the prior art processes. This processing characteristic also distinguishes the subject process from those of the prior art which employ only dry blend resins, which are agglomerated through heat sintering.
- the substrate is a relatively flat fibrous or non-fibrous backing sheet material, such as a fibrous, felted or matted, relatively flat sheet of overlapping, intersecting fibers, usually of non-asbestos origin.
- the substrate can, if desired, be asbestos or non-asbestos felts or papers, woven or non-woven; knitted or otherwise fabricated textile material or fabrics comprised of cellulose, glass, natural or synthetic organic fibers, or natural or synthetic inorganic fibers, or supported or non-supported webs or sheets made therefrom or filled or unfilled thermoplastic or thermoset polymeric materials.
- the substrate or base material can be coated to improve the print quality of the substrate.
- coatings can be plastisols, organosols, lacquers, filled or unfilled latex coatings, or other coatings conventionally employed as preprint sealants in the manufacture of floor or wall covering products.
- plastisol is intended to cover a relatively high molecular weight polyvinyl chloride resin dispersed in one or more plasticizers.
- the plastisol upon heating or curing forms a tough plasticized solid.
- plastisol compositions are intended to include organosols, which are similar dispersed polyvinyl chloride resin materials that, in addition, contain one or more volatile liquids that are driven off upon heating.
- the substrate coating employed in the products of this invention is a resinous polymer composition, preferably, a polyvinyl chloride plastisol which is substantially uniformly applied to the substrate surface, for example by means of a conventional reverse roll coater or wire wound bar, eg. a Meyer Rod Coater, wherein the grooves provided by the wires assist in metering the flow of the plastisol.
- a conventional reverse roll coater or wire wound bar eg. a Meyer Rod Coater
- any suitable coating means can be employed.
- Exemplary of other coating means are knife-over roll coater, rotary screen, direct roll coater and the like.
- the thickness of the resinous polymer composition or plastisol, as it is applied to the surface of the substrate, is substantially uniform, and is in the range of about 3 mils to about 30 mils, 30 mils to about 100 mils being especially preferred.
- the substrate can be thinner or thicker as may be required by the particular product application.
- the preferred and typical substrate coating is a polyvinyl chloride homopolymer resin
- other vinyl chloride resins can be employed.
- Exemplary are a vinyl chloride-vinyl acetate copolymer, a vinyl chloridevinylidene chloride copolymer, and copolymers of vinyl chloride with other vinyl esters, such as, vinyl butyrate, vinyl propionate, and alkyl substituted vinyl esters, wherein the alkyl moiety preferably is lower alkyl containing between about 1-4 carbons.
- synethetic resins such as polystyrene, substituted polystyrene, preferably wherein the substituents are selected from the group consisting of alkyl (C 1 -C 10 , preferably C 1 -C 4 ), aryl (preferably, C 6 -C 14 ) , polyolefins such as polyethylene and polypropylene, acrylates and methacrylates, polyamides, polyesters, and any other natural or synethetic resin capable of being applied to the substrate or base coatings of this invention to provide a smooth and uniform surface and/or to improve the print quality of the substrate or base coating surface, are also applicable; provided such resin is otherwise compatible with the overall product composition and, therefor, within the principles of this invention.
- Organosols and aqueous latices are also of use, employing as the dispersing or suspending media, organic solvents and water, respectively, rather than plasticizers, as in the case of a plastisol.
- plasticizers which can be used are dibutyl sebacate, butyl benzyl sebacate, dibenzyl sebacate, dioctyl adipate, didecyl adipate, dibutyl phthlate, dioctyl phthlate, dibutoxy ethyl phthlate, butyl benzyl phthlate, dibenzyl phthlate, di (2-ethylhexyl) phthlate, alkyl or aryl modified phthalate esters, alkyl, aryl, or alkylaryl hydrocarbons, tricresyl phosphate, octyl diphenyl phosphate, dipropylene glycol dibenzoate, dibasic acid glycol esters, and the like.
- a blowing or foaming agent such as azodicarbonamide (if a blowing or foaming procedure is desired), conventional stabilizers/ accelerators, initiators, catalysts, etc., such as zinc oleate, dibasic lead phosphite, etc., conventional heat or light stabilizers, such as metallic soaps, etc., UV absorbers, colorants, dyes or pigments, notably, titanium oxide, solvents and diluents, such as methyl ethyl ketone, methyl isobutyl ketone, dodecyl benzene, etc., fillers, such as clay, limestone, etc, viscosity modifiers, antioxidants, ba ⁇ teriostats and bacteriosides, and the like.
- azodicarbonamide if a blowing or foaming procedure is desired
- conventional stabilizers/ accelerators, initiators, catalysts, etc. such as zinc oleate, dibasic lead phosphite, etc.
- Suitable inks include those normally used in the manufacture of floor covering, preferably resilient floor covering. These include plastisol, solvent based systems and water based systems. Such systems can include a chemical suppressant in those cases where the substrate to which the ink is to be applied is a foamable plastisol or organosol. Such suppressants are well known in the art (eg. see U.S. Patent 3,293,094).
- Printing onto the substrate can be effected by rotogravure, flexigraphic, screen printing, or other printing techniques conventionally employed in making floor ⁇ r wall covering products.
- the adhesive layer is normally a plastisol or organosol additonally containing a plasticizer system, associated diluents, viscosity control aids and stabilizers. Those discussed above are exemplary. When underprinting is present, the adhesive would not normally contain colors or pigments which would render the adhesive layer opaque.
- the resinous particles of this invention can be of various sizes and geometric shapes, spherical and essentially spherical, (sometimes referred to herein as "spheroidal") being especially preferred as having the low aspect ratios discussed herein required to obtain the desirable design effects this invention is capable of providing.
- Each transluscent or opaque particle can contain its own individual colorant, dye or pigment, provided that at least some of the particles must be sufficiently transparent or sufficiently transluscent, to permit the printing on the print layer to show through.
- the particles employed in this invention can have a wide variety of geometric shapes, provided that the aspect ratios of such particles fall within the ranges discussed herein.
- Exemplary of other geometric shapes are squares, triangles, circles, annuli, other polygons, etc, or irregular sizes and shapes, or a mixture of any or all of such shapes, including spheroidal.
- the size of the particles employed in carrying out this invention have a pronounced effect on the results obtained.
- Use of relatively small particles eg. ranging from about 150 microns (100 mesh) to about 600 microns (30 mesh) are most advantageous in producing the desired design effects.
- the ratio of transparent to colored particles determines the visibility of the printed pattern underneath the resulting adhesive matrix. Generally, 50% or less, and preferably 0-30 %, transparent to colored particle loading is preferred. The amount actually used will, of course, depend upon the type of end-use application and design effect desired. Good results have even been achieved in the range of 0-lOX transparent to colored particle loading. Wearlayer
- the optional overcoat or wearlayer is preferably a plastisol of the same or similar type as that discussed above in connection with the resins employed in the substrate coat and the adhesive layer or matrix.
- the formulations generally include materials to enhance special specific properties, for example gloss, wear, stain resistance, and scuff resistance.
- the decorative, inlaid floor or wall coverings comprise:
- Example 1 is intended to demonstrate preferred embodiments of this invention without limiting the scope thereof. In the following examples all parts and percentages are by weight.
- a floor covering substrate sheet of conventional type non-asbestos felt (Tarkett Inc., Whitehall, Pa.), approximately 32 mils thick, was bar coated (wire wound bar) with approximately 3 mils of a layer of white printable plastisol, the composition of which was as follows:
- PVC extender k value 60 30
- the resulting smooth surface is gravure printed on a flat print press using Series 125 inks from American Inks, Inc..
- an adhesive layer about 10 mils thick was applied by drawdown bar and an excess of premixed plastisol pearls (produced in Example 3 and having the composition set forth hereinafter), about half of which were transparent and the remainder colored, were evenly distributed on the surface of the wet, tacky adhesive layer from a vibrating pan ( SYNTRON vibrator manufactured by FMC Corp.).
- the composition of the adhesive mix was:
- the composition of the pearl particles was:
- the PEVIKON S658 GK resin had an aspect ratio of about 1 (the particles were round) and the particle size was found by microscopic observation to average about 600 microns (approximately 30 mesh). Screen analysis was as follows:
- the surface of the matrix was then bar coated using a drawdown bar with a transparent plastisol wearlayer having the following composition:
- the wearlayer was fused in a hot air oven at about 300°F. for 3.5 minutes and then embossed between a cooled embossing roll and a rubber pressure roll.
- the resultant wearlayer has a thickness of about 15 mils.
- the wear characteristics of the decorative inlaid product thereby produced are set forth in the following Table I and compared with leading competitive products.
- a floorcovering substrate sheet of conventional type non-asbestos felt (Tarkett Inc., Whitehall, Pa.) approximately 32 mils thick was coated with a foamable plastisol the composition of which was as follows:
- PVC extender resin k value 60 30
- TXIB Texanol isobutyrate
- the coated substrate is then pregelled in a hot oven at 275°F. for 2.5 minutes.
- the surface is then gravure printed on a flat bed press using inks having the same composition as those of Example 1 except that the inks used to cover the plate printing the valley areas of the pattern (ie. the grouts) contain additionally 140 parts benzotriazole, a chemical suppressant, to inhibit in these selected areas the expansion of the foamable plastisol.
- an adhesive layer having the same composition as that of Example 1 was applied by a drawdown bar.
- Premixed colored and transparent pearls, in the same ratio Example 3 were evenly distributed, gelled and smoothed as described in Example 1.
- the thickness of the resulting matrix containing the pearls (15 mils) embedded in the adhesive (5 mils) was about 20 mils.
- Approximately 10 mils of a transparent wearlayer having the same composition as that of Example 1 was applied with a drawdown bar.
- the resulting product was then fused and expanded (ie. foamed) in a hot air oven at 380°F. for 3 minutes.
- the floorcovering produced shows a relief structure (embossing) in register with the printed areas.
- the decorative inlaid product thereby produced has an overall thickness of about 82 mils and exhibited excellent wear and design characteristics.
- the PVC resin (at 70°F.) was charged to a high intensity mixer running at 3500 RPM and mixed until the batch temperature reached 160°F. (about 10 minutes). The speed of the mixer was then reduced to 500 revolutions per minute and the pigment pastes, plasticizer and stabilizer were added slowly over a period of about 5 minutes. The speed was then increased to 2000-3000 rpm and the material mixed until the batch temperature reached 260°F. (approximately 15 minutes additional). The speed was then reduced to 500 RPM and the material was mixed until the batch temperature cooled to 70-9Q°F. (about 30 additional minutes).
- the pearls produced were essentially spherical, dry and free running; did not exceed 0.60 inch in diameter, and had a particle size distribution range of .004 to .040.
- Examples 1 and 2 demonstrate decorative, inlaid floor coverings which constitute highly preferred embodiments of this invention and which comprise:
- PVC extender preferably having a k value about 60
- a plasticizer preferably a phthlate such as di (2-ethylhexyl) phthlate or butyl benzyl phthalate,
- a pigment preferably titanium dioxide
- a print layer of one or more inks made from effective amounts of a formulation comprising:
- a solvent preferably consisting essentially of methyl ethyl ketone and xylene
- a gelled adhesive layer made from effective amounts of a formulation comprising:
- PVC dispersion preferably having a relative viscosity about 2.5
- PVC extender preferably having a k value about 60
- plasticizer preferably butyl benzyl phthalate or di-isononyl phthalate
- plasticizer preferably butyl benzyl phthalate
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Laminated Bodies (AREA)
- Finishing Walls (AREA)
- Paints Or Removers (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US77398485A | 1985-09-09 | 1985-09-09 | |
US773984 | 1985-09-09 | ||
PCT/US1986/001849 WO1987001334A1 (en) | 1985-09-09 | 1986-09-09 | Decorative inlaid types of sheet materials |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0236478A1 true EP0236478A1 (en) | 1987-09-16 |
EP0236478A4 EP0236478A4 (en) | 1988-02-01 |
EP0236478B1 EP0236478B1 (en) | 1997-01-15 |
Family
ID=25099902
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP86906054A Expired - Lifetime EP0236478B1 (en) | 1985-09-09 | 1986-09-09 | Decorative inlaid types of sheet materials |
Country Status (10)
Country | Link |
---|---|
EP (1) | EP0236478B1 (en) |
CN (1) | CN1018622B (en) |
AT (1) | ATE147680T1 (en) |
AU (1) | AU6406886A (en) |
CA (1) | CA1283815C (en) |
DE (1) | DE3650594T2 (en) |
ES (1) | ES2002286A6 (en) |
IE (1) | IE76461B1 (en) |
PT (1) | PT83337B (en) |
WO (1) | WO1987001334A1 (en) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5178912A (en) * | 1990-03-29 | 1993-01-12 | Congoleum Corporation | Use of reverse roll coater to make flooring material |
YU77891A (en) * | 1990-05-03 | 1994-05-10 | Lcv International Limited | PRINTING COLOR AND PRINTING PROCEDURE |
EP2182135A1 (en) * | 2008-10-28 | 2010-05-05 | Tarkett GDL S.A. | Removable surface covering |
KR101679171B1 (en) * | 2008-12-19 | 2016-11-23 | 플로어링 인더스트리즈 리미티드 에스에이알엘 | Coated panel comprising foam or polyvinyl chloride and method for manufacturing |
BE1018680A5 (en) | 2008-12-19 | 2011-06-07 | Flooring Ind Ltd Sarl | METHODS FOR MANUFACTURING PANELS AND PANEL OBTAINED HEREBY |
EP2727725A1 (en) * | 2012-10-31 | 2014-05-07 | Tarkett GDL S.A. | Low cost synthetic floor covering |
WO2016008783A1 (en) * | 2014-07-15 | 2016-01-21 | Tarkett Gdl S.A. | Low cost surface covering tiles and the process for their manufacture |
EP3106301A1 (en) * | 2015-06-18 | 2016-12-21 | Tarkett GDL S.A. | Low cost surface covering tiles and the process for their manufacture |
PL3693180T3 (en) * | 2019-02-05 | 2024-06-10 | Unilin Bv | Method for manufacturing a decorative foil and a panel comprising such foil |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3239364A (en) * | 1959-11-18 | 1966-03-08 | Congoleum Nairn Inc | Process for producing decorative plastic surface coverings |
US4440826A (en) * | 1983-01-24 | 1984-04-03 | Armstrong World Industries, Inc. | Decorative surface covering |
US4450194A (en) * | 1982-07-29 | 1984-05-22 | Armstrong World Industries, Inc. | Decorative laminate |
FR2572022A1 (en) * | 1984-10-24 | 1986-04-25 | Armstrong World Ind Inc | Prodn. of decorative laminate, especially flooring |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3856900A (en) * | 1972-12-27 | 1974-12-24 | Gaf Corp | Production of spherical polyvinyl chloride particles |
US4239797A (en) * | 1978-09-29 | 1980-12-16 | Gaf Corporation | Non-skid floor tile |
US4196243A (en) * | 1978-09-29 | 1980-04-01 | Gaf Corporation | Non-skid floor covering |
US4212691A (en) * | 1978-11-21 | 1980-07-15 | Congoleum Corporation | Methods and apparatus for making decorative inlaid types of resilient sheet materials and the like |
JPS58110751A (en) * | 1981-12-24 | 1983-07-01 | 大日本印刷株式会社 | Synthetic resin sheet for floor |
-
1986
- 1986-09-05 IE IE237786A patent/IE76461B1/en not_active IP Right Cessation
- 1986-09-05 ES ES8601679A patent/ES2002286A6/en not_active Expired
- 1986-09-08 CA CA000517656A patent/CA1283815C/en not_active Expired - Lifetime
- 1986-09-09 AT AT86906054T patent/ATE147680T1/en active
- 1986-09-09 AU AU64068/86A patent/AU6406886A/en not_active Abandoned
- 1986-09-09 PT PT83337A patent/PT83337B/en not_active IP Right Cessation
- 1986-09-09 EP EP86906054A patent/EP0236478B1/en not_active Expired - Lifetime
- 1986-09-09 WO PCT/US1986/001849 patent/WO1987001334A1/en active IP Right Grant
- 1986-09-09 DE DE3650594T patent/DE3650594T2/en not_active Expired - Fee Related
- 1986-09-09 CN CN86106829.7A patent/CN1018622B/en not_active Expired
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3239364A (en) * | 1959-11-18 | 1966-03-08 | Congoleum Nairn Inc | Process for producing decorative plastic surface coverings |
US4450194A (en) * | 1982-07-29 | 1984-05-22 | Armstrong World Industries, Inc. | Decorative laminate |
US4440826A (en) * | 1983-01-24 | 1984-04-03 | Armstrong World Industries, Inc. | Decorative surface covering |
FR2572022A1 (en) * | 1984-10-24 | 1986-04-25 | Armstrong World Ind Inc | Prodn. of decorative laminate, especially flooring |
Non-Patent Citations (1)
Title |
---|
See also references of WO8701334A1 * |
Also Published As
Publication number | Publication date |
---|---|
DE3650594T2 (en) | 1997-05-28 |
AU6406886A (en) | 1987-03-24 |
CN86106829A (en) | 1987-05-27 |
ES2002286A6 (en) | 1988-08-01 |
EP0236478A4 (en) | 1988-02-01 |
CA1283815C (en) | 1991-05-07 |
IE862377L (en) | 1987-03-09 |
IE76461B1 (en) | 1997-10-22 |
DE3650594D1 (en) | 1997-02-27 |
WO1987001334A1 (en) | 1987-03-12 |
PT83337A (en) | 1986-10-01 |
EP0236478B1 (en) | 1997-01-15 |
PT83337B (en) | 1993-01-29 |
CN1018622B (en) | 1992-10-14 |
ATE147680T1 (en) | 1997-02-15 |
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