WO2002074840A1 - Process for coating the surface of plastics - Google Patents
Process for coating the surface of plastics Download PDFInfo
- Publication number
- WO2002074840A1 WO2002074840A1 PCT/HU2002/000021 HU0200021W WO02074840A1 WO 2002074840 A1 WO2002074840 A1 WO 2002074840A1 HU 0200021 W HU0200021 W HU 0200021W WO 02074840 A1 WO02074840 A1 WO 02074840A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- reagent
- layer
- coating
- plastic
- coated
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 75
- 229920003023 plastic Polymers 0.000 title claims abstract description 63
- 239000004033 plastic Substances 0.000 title claims abstract description 63
- 230000008569 process Effects 0.000 title claims abstract description 58
- 238000000576 coating method Methods 0.000 title claims abstract description 55
- 239000011248 coating agent Substances 0.000 title claims abstract description 41
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 98
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000000654 additive Substances 0.000 claims abstract description 8
- 230000000996 additive effect Effects 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 38
- 125000000524 functional group Chemical group 0.000 claims description 25
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 claims description 18
- 229920002873 Polyethylenimine Polymers 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 9
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 8
- 238000010521 absorption reaction Methods 0.000 claims description 8
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 7
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 6
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005055 methyl trichlorosilane Substances 0.000 claims description 3
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 claims description 3
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims description 3
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 2
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 79
- 239000000463 material Substances 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 239000011247 coating layer Substances 0.000 description 20
- -1 polypropylene Polymers 0.000 description 18
- YBJHBAHKTGYVGT-ZKWXMUAHSA-N (+)-Biotin Chemical compound N1C(=O)N[C@@H]2[C@H](CCCCC(=O)O)SC[C@@H]21 YBJHBAHKTGYVGT-ZKWXMUAHSA-N 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 15
- 239000012153 distilled water Substances 0.000 description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 13
- 238000011534 incubation Methods 0.000 description 13
- 238000001291 vacuum drying Methods 0.000 description 12
- 239000004743 Polypropylene Substances 0.000 description 11
- 125000003277 amino group Chemical group 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 11
- 229920001155 polypropylene Polymers 0.000 description 11
- 239000000758 substrate Substances 0.000 description 11
- 238000004040 coloring Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 8
- 229960002685 biotin Drugs 0.000 description 8
- 235000020958 biotin Nutrition 0.000 description 8
- 239000011616 biotin Substances 0.000 description 8
- 229920002379 silicone rubber Polymers 0.000 description 8
- 239000004945 silicone rubber Substances 0.000 description 8
- 229910052709 silver Inorganic materials 0.000 description 8
- 239000004332 silver Substances 0.000 description 8
- 108010090804 Streptavidin Proteins 0.000 description 7
- LOKCTEFSRHRXRJ-UHFFFAOYSA-I dipotassium trisodium dihydrogen phosphate hydrogen phosphate dichloride Chemical compound P(=O)(O)(O)[O-].[K+].P(=O)(O)([O-])[O-].[Na+].[Na+].[Cl-].[K+].[Cl-].[Na+] LOKCTEFSRHRXRJ-UHFFFAOYSA-I 0.000 description 7
- 239000002953 phosphate buffered saline Substances 0.000 description 7
- 239000004753 textile Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- 230000003247 decreasing effect Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 239000004952 Polyamide Substances 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 238000010924 continuous production Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 229920002647 polyamide Polymers 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 4
- 238000001212 derivatisation Methods 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000004809 Teflon Substances 0.000 description 3
- 229920006362 Teflon® Polymers 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- ZKHQWZAMYRWXGA-KQYNXXCUSA-J ATP(4-) Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O)[C@@H](O)[C@H]1O ZKHQWZAMYRWXGA-KQYNXXCUSA-J 0.000 description 2
- ZKHQWZAMYRWXGA-UHFFFAOYSA-N Adenosine triphosphate Natural products C1=NC=2C(N)=NC=NC=2N1C1OC(COP(O)(=O)OP(O)(=O)OP(O)(O)=O)C(O)C1O ZKHQWZAMYRWXGA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- 238000004026 adhesive bonding Methods 0.000 description 2
- 150000008365 aromatic ketones Chemical class 0.000 description 2
- 230000000975 bioactive effect Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002773 nucleotide Substances 0.000 description 2
- 125000003729 nucleotide group Chemical group 0.000 description 2
- 239000003504 photosensitizing agent Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000010399 physical interaction Effects 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 2
- 239000005051 trimethylchlorosilane Substances 0.000 description 2
- YMXHPSHLTSZXKH-RVBZMBCESA-N (2,5-dioxopyrrolidin-1-yl) 5-[(3as,4s,6ar)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoate Chemical compound C([C@H]1[C@H]2NC(=O)N[C@H]2CS1)CCCC(=O)ON1C(=O)CCC1=O YMXHPSHLTSZXKH-RVBZMBCESA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000007836 KH2PO4 Substances 0.000 description 1
- 108091034117 Oligonucleotide Proteins 0.000 description 1
- 108010039918 Polylysine Proteins 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000013504 Triton X-100 Substances 0.000 description 1
- 229920004890 Triton X-100 Polymers 0.000 description 1
- JLCPHMBAVCMARE-UHFFFAOYSA-N [3-[[3-[[3-[[3-[[3-[[3-[[3-[[3-[[3-[[3-[[3-[[5-(2-amino-6-oxo-1H-purin-9-yl)-3-[[3-[[3-[[3-[[3-[[3-[[5-(2-amino-6-oxo-1H-purin-9-yl)-3-[[5-(2-amino-6-oxo-1H-purin-9-yl)-3-hydroxyoxolan-2-yl]methoxy-hydroxyphosphoryl]oxyoxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(6-aminopurin-9-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(6-aminopurin-9-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(6-aminopurin-9-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(6-aminopurin-9-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxyoxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(4-amino-2-oxopyrimidin-1-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(6-aminopurin-9-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(6-aminopurin-9-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(4-amino-2-oxopyrimidin-1-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(4-amino-2-oxopyrimidin-1-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(4-amino-2-oxopyrimidin-1-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(6-aminopurin-9-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(4-amino-2-oxopyrimidin-1-yl)oxolan-2-yl]methyl [5-(6-aminopurin-9-yl)-2-(hydroxymethyl)oxolan-3-yl] hydrogen phosphate Polymers Cc1cn(C2CC(OP(O)(=O)OCC3OC(CC3OP(O)(=O)OCC3OC(CC3O)n3cnc4c3nc(N)[nH]c4=O)n3cnc4c3nc(N)[nH]c4=O)C(COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3CO)n3cnc4c(N)ncnc34)n3ccc(N)nc3=O)n3cnc4c(N)ncnc34)n3ccc(N)nc3=O)n3ccc(N)nc3=O)n3ccc(N)nc3=O)n3cnc4c(N)ncnc34)n3cnc4c(N)ncnc34)n3cc(C)c(=O)[nH]c3=O)n3cc(C)c(=O)[nH]c3=O)n3ccc(N)nc3=O)n3cc(C)c(=O)[nH]c3=O)n3cnc4c3nc(N)[nH]c4=O)n3cnc4c(N)ncnc34)n3cnc4c(N)ncnc34)n3cnc4c(N)ncnc34)n3cnc4c(N)ncnc34)O2)c(=O)[nH]c1=O JLCPHMBAVCMARE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 229920001586 anionic polysaccharide Polymers 0.000 description 1
- 150000004836 anionic polysaccharides Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229960000633 dextran sulfate Drugs 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 description 1
- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000005499 meniscus Effects 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 150000002482 oligosaccharides Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000000678 plasma activation Methods 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000656 polylysine Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- PIEPQKCYPFFYMG-UHFFFAOYSA-N tris acetate Chemical compound CC(O)=O.OCC(N)(CO)CO PIEPQKCYPFFYMG-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 230000003442 weekly effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/02—Polyamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
Definitions
- the invention relates to a new process for coating the surface of plastics.
- plastics are manufactured in huge quantities and applied in all areas of economy and life for the most different purposes.
- surface of the material should have entirely different properties than the material itself. It is a common problem when applying plastics that a plastic may have ideal properties from a certain aspect but at the same time it is inadequate from other aspects of the application.
- an indifferent plastic is an excellent structural material but its colorability is poor, its sticking properties are inadequate, the formation of chemical functional groups on its surface is difficult, its permeability to gas is too high or it is imperfect in other ways.
- the problem can be solved by modifying the surface of the plastics, e. g. coating the surface with an appropriate layer.
- the coat is formed by an immersion process.
- the substrate to be coated is immersed in a solution of a first coating compound having reactive groups and then dried.
- the coated substrate is subjected to an interfacial contact reaction with a second coating composition having at least one low-energy functional group and a reactive functional group that reacts with the functional group in the first coating compound.
- the interfacial contact reaction between the reactive functional groups in the first and second coating compositions fixes the low-energy functional groups to the substrate surface thereby reducing the surface energy of the substrate surface. In this way a stable binding of the layer is achieved.
- This method has some disadvantages, e. g. it is laborious, material-intensive and time-consuming.
- resin materials having low-surface energy are treated with photosensitizers and ultraviolet radiation.
- a silane or siloxane Applying a silane or siloxane, a transitional layer is formed which has a higher surface energy than that of the material to be coated.
- the transitional layer serves as a basis of the further coating (primarily painting).
- the polyolefin to be coated is soaked in a solution of an aromatic ketone photosensitizer. After removing the solvent, the surface is coated with a second solution comprising (i) a monomer selected from the group consisting of an unsaturated organic acid, an unsaturated organosulfonic acid, a vinyl monomer, (ii) an aromatic ketone photosensitiser and (iii) a low boiling point alcohol or ketone.
- the coated polyolefin is exposed to irradiation, washed and dried. The layer formed from the monomer makes the polyolefin capable to be glued.
- the main disadvantage of the above two processes is the need for an extra device.
- carrying out homogeneous ultraviolet radiation is very complicated even with objects of regular shape.
- the coating can be produced after multistep pre-treatment, only.
- the surface is activated by ultraviolet irradiation and plasma treatment, respectively. After activation a filmlike coating is formed by immersion into a coating material. The coating is bound to the surface by chemical adsorption and by ionic bond, respectively.
- the disadvantage of these processes is that they allow formation of film-like coatings only, since the binding is formed between the activated surface and the coating material contacting directly the activated surface.
- coating is formed on polymeric fabric in order to reduce the adsorption of proteins by the polymeric fabric.
- Fabrics are treated with solutions of various surfactants and exposed to corona discharge.
- the disadvantages of the method are that the coating on the fibres constituting the fabric is inhomogeneous and the process demands an extra device.
- polypropylene nucleophile (preferably amino) groups are formed by exposing the polypropylene to plasma energy, then biopolymers (peptides, oligonucleotides, proteins, oligosaccharides) are attached to these groups by covalent bond.
- biopolymers peptides, oligonucleotides, proteins, oligosaccharides
- plasma activation is applicable only in the case of plain surfaces, e.g. sheets, films and fibres.
- a polyamine of high average molecular weight is adsorbed on the surface to be coated and it is stabilized simultaneously with the adsorption or in a separate step by cross-linking with crotonaldehyde.
- the first layer thus obtained is treated with an anionic polysaccharide (for instance with dextran sulfate) to form a second layer.
- anionic polysaccharide for instance with dextran sulfate
- a second layer is formed by turns.
- a polyamine layer without cross-linking is formed.
- a coating containing free amino groups is formed which may be used to form ionic or covalent bonds.
- the serious disadvantage of the method is that the layer thus formed is not stable enough, since only a part of the bonds holding the layer together is covalent.
- cross-linking simultaneously with the adsorption, a loose precipitate-like layer is created, while in the two-step process a very thin monomolecular layer is formed. Because of the several repeated steps this process is quite long and difficult.
- the surface of the polymer to be coated is treated with a polymeric surfactant which is then cross-linked thereon to form a first layer.
- the first layer through its remaining cross-linking groups, covalently binds to a second layer which has functional groups capable of covalently binding to biologically active substances.
- the process is quite long, it consists of several steps and is suitable for forming very thin, film-like coatings, only.
- coating plastics is a frequent task.
- the coating can be accomplished by several methods, e. g. by means of spraying, immersion, brushing, adsorption, chemical reaction, plasma energy, nebulisation.
- Coating neutral plastics is very difficult as the application of both the coating methods based on physical interaction and the coating methods based on chemical interaction are difficult or impossible because of their small surface- energy and the lack of reactive functional groups, respectively.
- the task is especially difficult if the object to be coated has a geometrical shape other than plain.
- the object of the present invention is to provide a process for coating plastics which eliminates the above described problems and allows carrying out coating tasks which cannot be accomplished or can be accomplished only with difficulties by the traditional methods.
- the process should be suitable for coating objects of complicated geometrical shape.
- Another important object of the present invention is to provide a process suitable for coating also neutral plastics which is a very difficult task.
- Another aim of the invention is to create a coating on the surface of a plastic which contains, when necessary, reactive functional groups which allow to form (with or without chemical treatment) a layer with requested physical or chemical properties.
- a further purpose was to achieve these aims by the simplest way and at the lowest costs possible.
- the invention is based on the recognition of the fact that the surface of plastics can be coated with a layer which is formed in a reaction between an internal reagent absorbed in the plastic and an external reagent which is in the space contacting the plastic.
- the plastic substrates - depending on their properties - can absorb large quantities of reactive materials, then release them in an unchanged form. We have found that this phenomenon can be used to produce coatings.
- the internal reagent should be able to enrich in the plastic substrate and, when the conditions has been changed, to outdiffuse and react with the external reagent to form a reaction product capable of immobilizing on the surface of the plastic substrate to be coated as a layer.
- the invention provides a process for coating the surface of plastics comprising the steps of i) absorbing one or more internal reagent(s) in the plastic to be coated, ii) contacting one or more external reagent(s) with the surface of said plastic, iii) forming an immobilised coating by a chemical reaction between the internal reagent(s) and the external reagent(s) both diffusing to the boundary layer of said plastic, preferably in the presence of an additive.
- one or more internal reagents and one or more external reagents can be used.
- the formation of the coating layer can be accomplished in two different ways. It can be either a step-by- step process wherein the absorption and the contacting occur consecutively, or a continuous process wherein the absorption and the contacting take place simultaneously.
- the step-by-step process can always be implemented while the continuous process is feasible only in special cases.
- the formation of the coating layer can be accomplished by a continuous process if the surface for the absorption of the internal reagent and the surface to be coated can be separated. In these cases the internal reagent diffuses through the plastic to be coated.
- the inner surface of tubes can be coated in a way that the external reagent is fed into the inner part of the tube while the internal reagent is in contact with its outer surface. The internal reagent permeates through the tube material and reacts with the external reagent on the inner surface of the tube. In the case of forming outer coating the process is carried out in the reverse direction.
- the coating should be accomplished by a step-by- step process.
- the first step is the absorption of the internal reagent in the plastic to be coated.
- the formation of the coating layer occurs in a separate step when the plastic object is contacted with the external reagent which reacts with the outdiffusing internal reagent.
- any compound can be used which is capable to absorb in the plastic to be coated.
- any compound can be used which is capable to react with the internal reagent and form a reaction product capable to immobilise on the surface of the plastic.
- external reagent preferably a compound having two or more functional groups is used.
- Said compound is preferably a polimer.
- the internal reagent is preferably selected from the group consisting of oxalyl chloride, sulfuryl chloride, thionyl chloride, phosgene, dimethyldichlorosilane, methyltrichlorosilane, tetrachlorosilane, phosphorus oxychloride, phosphorus trichloride, acetaldehyde and ethylenediamine.
- the process according to the invention can be used for coating the surface of all kinds of plastic, independently of their chemical character, shape, etc.
- the properties of the plastic to be coated have to be taken into account.
- the internal reagent is applied together with an inert solvent which promotes its diffusion.
- Dilution of reactive materials of high diffusibility e.g. phosgene, dimethyldichlorosilane
- phosgene dimethyldichlorosilane
- additives also together with the external reagent in order to improve the properties of the coating layer.
- an additive decreasing surface tension can improve the adhering properties of the coating.
- inert materials and polymers having reactive functional groups e.g. polyvinyl alcohol
- the external reagent is a solution of a polymer with several reactive functional groups being capable of enriching to some extent on the surface of the plastic to be coated.
- the aqueous solution of polyethylenimine (PEI) and polypropylene can be given.
- the hydrophobic part of the PEI molecules is directed towards the plastic surface, while their hydrophilic part towards the solution, creating a transitional layer the surface-energy of which gradually increases.
- This boundary layer can be "in situ” fixed by cross-linking of the amino groups of the polyethylenimine with the internal reagent (which outdiffuses from the plastic substrate). Cross-linking can be formed e.g.
- oxalyl chloride which forms bridges between the amino groups of the polyethylenimine.
- Tertiary amines of the polyethylenimine do not react with the oxalyl chloride, furthermore - if the external reagent is added in excess - not every primary and secondary amino group reacts with the internal reagent.
- a layer containing primary, secondary and tertiary amines; cross-linked with -CO-CO- bridges
- This layer makes the surface of the polypropylene hydrophilic, therefore it will be suitable to be painted and glued.
- the amino groups are suitable for further derivatization, or, without derivatization, the layer can serve as an ion exchanger.
- the main advantage of the process according to the invention - which radically differs from all processes of similar aim applied up to now - is that it makes possible carrying out coating tasks which cannot be accomplished or can be accomplished only with difficulties by other methods.
- the coating layer prepared by the process according to the invention is formed on the boundary layer of the material to be coated, it is possible to coat objects of complicated geometrical shape. For instance, it is possible to coat the internal surface of capillary tubes made from a neutral plastic material.
- the conventional coating processes based on physical interaction cannot be applied for the internal surface of the tube because of the influence of the capillary forces and the small surface energy, while the application of conventional chemical methods for coating is impossible because of the lack of functional groups.
- forming of functional groups is not possible in the case of objects of special geometrical shapes. According to the process proposed by the invention, coating these objects can be carried out easily, even by the continuous process.
- Another advantage of the process according to the invention is that it allows to form coatings with a reactive functional group on their surface.
- the reagent to be in excess can be chosen, thereby determining the functional groups on the surface of the layer.
- These functional groups can be further modified, therefore, it is possible to form surfaces with required physical properties.
- modification of the functional groups the chemical characteristics of the coated object can be modified. For example, a neutral carrier may be transformed into an ion exchanger or can be modified in such a way that it will be capable to bind bioactive compounds by a covalent bond.
- the molecules of the external reagent are immobilized in the position which is energetically the most stable state.
- the coating process so to say, "freezes in” the state at the moment of the coating, therefore, the coating layer forms a stable (e.g. nonpolar-polar) transition between the plastic to be coated and the medium of the external reagent.
- a great advantage of the invention is the possibility of its wide-ranging applicability.
- the use of the process put forward by the invention allows to solve a lot of problems - modification of physical properties of plastic objects by a simple coating layer, immobilization of biologically active materials, coating the surface of plastic objects by a metal layer, etc.
- An open vessel of 2 ml is placed into a vessel of 20 ml with a screw cap.
- the internal reagents are placed into the open vessel of 2 ml.
- the plastic objects to be coated are placed into the vessel of 20 ml next to the vessel containing the reagent. After closing the external vessel, the system is incubated for a period of time. By this arrangement it is ensured that the reagent does not, only its vapours contact directly with the plastic to be coated.
- Pieces of silicone rubber tubes having external diameter of 12 mm and wall thickness of 2 mm are placed into three vessels, as described in Example 1.
- the pieces of tubes are saturated with 100 ⁇ l of the following reagents: (2a) trimethylchlorosilane, (2b) dimethyldichlorosilane, and (2c) methyltrichlorosilane.
- (2a) trimethylchlorosilane (2b) dimethyldichlorosilane
- (2c) methyltrichlorosilane 2a) trimethylchlorosilane
- the tubes are placed into a 0.1 M NaOH solution. This solution is stirred overnight, then the pieces of tubes are washed three times with distilled water and dried for 6 hours at 150°C temperature in a vacuum drying oven.
- the results of the weightings have shown that the silicone plastic to be coated is capable to absorb a significant quantity (5.9 to 8.6% by weight) of the reagent.
- the internal reagents - depending on the number of chlorine atoms - have one, two or three reactive functional groups.
- the external reagent - in this case the water - can react with the internal reagent in a fast reaction (X-CI + HOH - X-OH + HCI) and in a slow reaction (X-OH + X-OH -> X-O-X + H 2 0).
- the function of NaOH solved in the external reagent is to bind HCI forming as by-product.
- Example 1 In an experimental set-up as described in Example 1 a piece of tube of known weight, made of silicone rubber, having external diameter of 12 mm and wall thickness of 2 mm, is saturated with 100 ⁇ l of dimethyldichlorosilane. After incubation of 2.5 hours the increase in weight of the plastic tube is measured, then the piece of tube is placed into a 1% aqueous solution of polyvinyl alcohol. This solution is stirred overnight, then the piece of tube is washed three times with distilled water and dried for 5 hours at 150°C temperature in a vacuum drying oven.
- a piece of silicone rubber tube of properties given in the above examples is coated first by the process identified in Example 3, then by the process identified in Example 2c. Both the visual observation of the tube and the results of weightings (Table I, 4/a, 4/b) prove that the two layers formed have different properties. Consequently, it is possible to create new layers on plastic objects which already have a coating layer and the different layers may be constituted of different reaction products.
- Example 2c The process as described in Example (2c) is repeated.
- the time of absorption of the internal reagent is the same but the incubation time is decreased from 6 hours to 1.5 hours.
- the results of the weightings show that - as expected -the weight of the coating layer formed will be smaller with decreasing incubation time. Since the geometrical dimensions of the tubes are the same, the lesser weight means that the layer is thinner.
- the thickness of the coating layer may be increased or decreased by changing the quantity of the absorbed internal reagent. Since the coating process is repeatable (see Example 4), coating layers with various thickness can be created by means of changing the parameters of the process suggested by the invention.
- a piece of textile constituted of polyamide fibres is placed (as described in Example 1) into confined space filled with the vapours of a reagent of a mixture of dimethyldichlorosilane and trimethylchlorosilane in 1 :1 ratio. After overnight incubation, the weight of the material to be coated becomes significantly greater.
- This piece of polyamide textile saturated with reagents is placed into a 5% aqueous solution of polyethylenimine. This solution is stirred overnight, then the polyamide textile is washed several times with distilled water and dried overnight at 60°C temperature in a vacuum drying oven.
- the piece of polyamide textile - along with an untreated control piece - is placed into a solution consisting of 0.1 g Coomassie Brillant Blue dye (manufacturer: Loba Chemie, Austria), 50 ml methanol, 10 ml acetic acid and 40 ml distilled water for 5 minutes.
- the pieces of polyamide textile are washed with a solution consisting of 50 ml methanol, 10 ml acetic acid and 40 ml distilled water for 5 minutes, then aired at ambient temperature.
- the treated piece of textile becomes coloured deep blue, while the untreated control textile remains uncoloured.
- the layer formed in the inside of the pipette tips is made visible by the colouring method as described in Example 6.
- the layer containing amino groups formed in the inside of the pipette tips becomes coloured uniform dark blue in that part of the tips which was filled with polyethylenimine solution.
- Example 1 In an experimental set-up as described in Example 1 two pieces of thin-wall PCR tubes (200 ⁇ l) made of polypropylene are placed into confined space filled with the vapours of 50 ⁇ l sulfuryl chloride for 2 hours. After weighting (Table I, Example 8), 100 ⁇ l of 5% aqueous solution of polyethylenimine, as external reagent, is filled into the tubes. After one hour of incubation, the solution is removed, the tubes are washed several times and, finally, are dried for 3 hours at 80°C temperature in a vacuum drying oven. The layer formed in the inside of the tubes is made visible by the colouring method as described in Example 6. The layer containing amino groups formed in the inside of the tubes becomes coloured blue up in that part of the vessels which was filled with the solution of external reagent. This layer is inhomogeneous to some extent at the height of the meniscus of the external reagent.
- Example 8 The process as described in Example 8 is repeated with the difference that more internal reagent is used, moreover, a mixture of 100 ⁇ l of 5% aqueous solution of polyethylenimine (external reagent) and 1 ⁇ l of 10% aqueous solution of polyvinyl alcohol (additive) is filled into the tubes to be coated.
- the layer after applying the same colouring method as described in Example 8, is perfectly homogenous and its colour is darker (Table I, Example 9).
- Pipette tips are coated as described in Example 7 but instead of testing the colouring process, the applicability of using the coating layer as ion exchanger is tested, according to the following method.
- 25 ⁇ l of titrant is sucked into the pipette tips having ion exchange layer changed for acetate form and the tips are incubated for 5 minutes. After incubation, the liquids in the tips are transferred into a scintillation vial and the tips are washed with distilled water and alcohol. 25 ⁇ l of 1 M Tris-base is sucked into the pipette tips and the tips are incubated for 5 minutes. After incubation, the liquids in the tips are transferred into another scintillation vial.
- a Teflon tube of 1 m length, 0.5 mm of inner diameter and 1 mm of outer diameter is conducted through a closed glass vessel of 100 ml volume in a way that the tube is hermetically sealed at the inlet and outlet, ensuring airtight connections.
- An 80 cm piece of the whole length of the tube wound into loop is placed into the vessel.
- 10 ml of trichloroethylene (solvent) and - through a vacuum system - 0.1 ml of phosgene (internal reagent) are added into the vessel.
- a part of the capillary tube wound into loop is placed in the liquid and the other part of it being outside of the liquid is in contact with the vapours of the reagent, only.
- Example 13 An 5% polyethylenimine solution is circulated in the Teflon tube for 2 hours. After dismounting the system, the tube is washed with distilled water, then dried in a vacuum drying oven at 105 °C for 5 hours. After drying, the tube is coloured and rinsed according to the method described in Example 6. As a result of colouring a uniform blue layer is visible on the internal surface of the tube.
- Example 13 An 5% polyethylenimine solution is circulated in the Teflon tube for 2 hours. After dismounting the system, the tube is washed with distilled water, then dried in a vacuum drying oven at 105 °C for 5 hours. After drying, the tube is coloured and rinsed according to the method described in Example 6. As a result of colouring a uniform blue layer is visible on the internal surface of the tube. Example 13
- Example 12 The process as described in Example 12 is repeated but different internal reagents (oxalyl chloride, phosgene), different external reagents (polylysine, poly(phenylalanine-lysine), polyethylenimine) and tubes made of different materials (Teflon, polyethylene, polypropylene) are used. Performing the process with all of the variations of internal reagents, external reagents and tube materials resulted in uniformly coloured layers of different intensity.
- internal reagents oxalyl chloride, phosgene
- different external reagents polylysine, poly(phenylalanine-lysine), polyethylenimine
- tubes made of different materials Teflon, polyethylene, polypropylene
- Example 12 The coating process as described in Example 12 is repeated but instead of colouring 10 mM solution of biotin N-hydroxysuccinimide ester in dimethyl sulfoxide is added. After 2 hours of incubation, the tube is washed with dimethyl sulfoxide, ethanol and water, then dried. As a result of the treatment, biotin is bound by covalent bond to the free amino groups of the layer formed. Binding of the biotin was proved by titration with labelled 25 l-streptavidine solution.
- 125 l- streptavidin/PBS (Phosphate Buffered Saline) solution (pH 7,4) of 400,000 cpm/ml radioactive concentration is added into a piece of tube of 10 cm length and then it is incubated for 1 hour at ambient temperature.
- the composition of the PBS solution is as follows: 8 g NaCI, 0.2 g KCI, 1.15 g Na 2 HPO 4 -2H 2 0, 0.2 g KH 2 PO 4 , diluted with distilled water to a volume of 3 litres; pH is adjusted with NaOH to 7.4. After removing the titrant, the tube is washed three times with PBS solution (pH 7,4), then its radioactivity is measured. It was established that the tube has bound 97.4% of the labelled streptavidin. Consequently, the process described in the example is suitable for the formation of a layer containing functional groups; the layer can be modified by appropriate reagents.
- PBS 0.01 mg/ml concentration
- the layer coated with biotin is transformed into a layer coated with streptavidin. Since one streptavidin molecule is capable of binding four biotin molecules, the immobilized streptavidin layer is capable of binding further biotin molecules or further molecules labelled with biotin.
- the immobilized streptavidin layer is detected with an oligomer (dT 25 ) labelled with biotin on its 5' end and with P-32 isotope on its 3' end.
- oligomer labelled with biotin on its 5' end and with P-32 isotope on its 3' end.
- a piece of tube of 10 cm length is incubated with the solution of the labelled oligomer (40,000 Bq/ ⁇ l, 1 pmole/ ⁇ l) for 2 hours. After incubation, the labelled solution is removed and the tube is washed with 1 M NaCI solution containing 0.1% Triton X-100 detergent (manufacturer: Reanal, Budapest, Hungary). The quantity of bound oligomer is measured by Cherenkow radiation.
- the layer formed by the process of the invention is suitable for the immobilization of bioactive compounds after a proper derivatization.
- Example 1 In an experimental set-up as described in Example 1 two pieces of thin-wall PCR tubes (200 ⁇ l) made of polypropylene are placed into confined space filled with the vapours of 50 ⁇ l oxalyl chloride overnight. After weighting (Table I, Example 16), BSA solution of 1 mg/ml concentration is filled into the tubes. The tubes are closed with caps and incubated overnight at ambient temperature. After the BSA solution is removed the tubes are washed three times with PBS buffer solution containing a detergent, then dried for 3 hours at 80°C temperature in a vacuum drying oven. The tubes are coloured according to the method as described in Example 6.
- Example 1 In an experimental set-up as described in Example 1 two pieces of silicone rubber tube of known weight are incubated in oxalyl chloride vapours for 2.5 hours. After weighting, one of the pieces is placed into confined space filled with the vapours of ethylenediamine (Table I, Example 17a), the other one is placed into 2 M aqueous solution of ethylenediamine (Table I, Example 17b). The pieces of tubes are incubated overnight, then washed with distilled water, finally dried for 2.5 hours at 80°C temperature in a vacuum drying oven. In both cases a whitish coating layer is formed at the end of the process. The pieces of tube lose their slippery, "silicone-like" nature and become suitable for gluing. In this way it was demonstrated that the external reagent - if the conditions are suitable - can be applied in both vapour phase and liquid phase.
- Example 17 The process as described in Example 17 is carried out with the reagents reversed, i.e. pieces of silicone rubber tube are incubated in ethylenediamine overnight, then - after weighting (Table I, Example 18) - placed into oxalyl chloride vapours for 20 minutes. In order to ensure the excess of ethylenediamine, the incubation continues in the open air for 2 hours. Then the tube is washed with distilled water, dried for 2.5 hours at 80°C temperature in a vacuum drying oven. At the end of the process - like in the process described in Example 17 - a whitish coating layer forms which can be glued well. This example demonstrates that the internal and external reagents - in certain cases - are interchangeable.
- Example 19 demonstrates that the internal and external reagents - in certain cases - are interchangeable.
- Example 1 In an experimental set-up as described in Example 1 a piece of silicone rubber tube of known weight is incubated in ethylenediamine vapours for 6 hours. After weighting (Table I, Example 19), the piece of tube is placed into polyethylene vial containing 5 ml of Tollens reagent which is prepared as follows: 1 g AgN0 3 is solved in 10 ml of water and 1 g NaOH is solved in 10 ml of water; 1 ml NaOH solution is added to 1 ml AgNO 3 solution; cc. ammonium hydroxide is added to the reagent until the precipitated Ag 2 O is dissolved. In a few minutes the precipitation of metallic silver begins on the whole surface of the silicone rubber tube.
- Tollens reagent which is prepared as follows: 1 g AgN0 3 is solved in 10 ml of water and 1 g NaOH is solved in 10 ml of water; 1 ml NaOH solution is added to 1 ml AgNO 3 solution; cc. ammoni
- the vial is shaken for an hour, then the coated tube is rinsed with distilled water and finally it is dried for 2.5 hours at 80°C temperature in a vacuum drying oven.
- the whole surface of the tube is coated with a silver layer. Due to the gradient created by the reducing reagent diffusing out from the plastic tube, the whole surface of the plastic tube is coated, while the walls of the plastic vial are not coated with silver.
- Example 21 In an experimental set-up as described in Example 1 a piece of polyethylene tube of 15 cm length, of 0.5 mm inner diameter and 1 mm outer diameter is incubated in acetaldehyde vapours overnight. After weighting (Table I, Example 20), the end of the tube is pulled on a pipette tip. By means of the pipette Tollens reagent is sucked into the polyethylene tube. The formation of the silver layer begins in a few minutes. By means of the pipette the Tollens reagent is supplied from time to time. After incubation of 1 hour the tube is rinsed with distilled water and then dried for 2 hours at 80°C temperature in a vacuum drying oven. As a result of the coating process, the inside of the tube is coated with a silver mirror layer.
- Example 21 Example 21
Abstract
Description
Claims
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EP02704995A EP1383827A1 (en) | 2001-03-21 | 2002-03-20 | Process for coating the surface of plastics |
JP2002573843A JP2004528433A (en) | 2001-03-21 | 2002-03-20 | Plastic surface coating method |
CA002440441A CA2440441A1 (en) | 2001-03-21 | 2002-03-20 | Process for coating the surface of plastics |
US10/469,710 US6926930B2 (en) | 2001-03-21 | 2002-03-20 | Process for coating the surface of plastics |
NO20033658A NO20033658L (en) | 2001-03-21 | 2003-08-19 | Process for coating the plastic surface |
IL15759503A IL157595A0 (en) | 2001-03-21 | 2003-08-26 | Process for coating the surface of plastics |
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EP (1) | EP1383827A1 (en) |
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JP3389754B2 (en) * | 1994-11-14 | 2003-03-24 | 松下電器産業株式会社 | Method of forming chemisorption film |
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2001
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2002
- 2002-03-20 JP JP2002573843A patent/JP2004528433A/en active Pending
- 2002-03-20 WO PCT/HU2002/000021 patent/WO2002074840A1/en active Application Filing
- 2002-03-20 US US10/469,710 patent/US6926930B2/en not_active Expired - Fee Related
- 2002-03-20 EP EP02704995A patent/EP1383827A1/en not_active Withdrawn
- 2002-03-20 CA CA002440441A patent/CA2440441A1/en not_active Abandoned
-
2003
- 2003-08-19 NO NO20033658A patent/NO20033658L/en unknown
- 2003-08-26 IL IL15759503A patent/IL157595A0/en unknown
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US3720540A (en) * | 1970-07-14 | 1973-03-13 | R Wimmer | Production of glass fiber-reinforced plastic articles |
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See also references of EP1383827A1 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002090372A2 (en) * | 2001-05-10 | 2002-11-14 | Izotóp Intézet Kft. | Products containing charged biomaterials and method for the preparation thereof |
WO2002090372A3 (en) * | 2001-05-10 | 2003-07-31 | Izotop Intezet Kft | Products containing charged biomaterials and method for the preparation thereof |
Also Published As
Publication number | Publication date |
---|---|
JP2004528433A (en) | 2004-09-16 |
US6926930B2 (en) | 2005-08-09 |
WO2002074840B1 (en) | 2003-01-03 |
HU225723B1 (en) | 2007-07-30 |
NO20033658L (en) | 2003-11-10 |
EP1383827A1 (en) | 2004-01-28 |
HU0101145D0 (en) | 2001-05-28 |
NO20033658D0 (en) | 2003-08-19 |
HUP0101145A2 (en) | 2003-01-28 |
CA2440441A1 (en) | 2002-09-26 |
IL157595A0 (en) | 2004-03-28 |
US20040146651A1 (en) | 2004-07-29 |
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