CN115058190A - Antifouling and water-repellent composite leather and preparation method thereof - Google Patents
Antifouling and water-repellent composite leather and preparation method thereof Download PDFInfo
- Publication number
- CN115058190A CN115058190A CN202210766337.8A CN202210766337A CN115058190A CN 115058190 A CN115058190 A CN 115058190A CN 202210766337 A CN202210766337 A CN 202210766337A CN 115058190 A CN115058190 A CN 115058190A
- Authority
- CN
- China
- Prior art keywords
- layer
- water
- polysiloxane
- leather
- modified
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000010985 leather Substances 0.000 title claims abstract description 93
- 239000002131 composite material Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 47
- 239000005871 repellent Substances 0.000 title claims abstract description 28
- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 27
- 239000010410 layer Substances 0.000 claims abstract description 122
- -1 polysiloxane Polymers 0.000 claims abstract description 92
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 90
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 73
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 70
- 239000010703 silicon Substances 0.000 claims abstract description 70
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 67
- 239000004814 polyurethane Substances 0.000 claims abstract description 44
- 229920002635 polyurethane Polymers 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 102000008186 Collagen Human genes 0.000 claims abstract description 25
- 108010035532 Collagen Proteins 0.000 claims abstract description 25
- 229920001436 collagen Polymers 0.000 claims abstract description 25
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 21
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 11
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 8
- 239000011241 protective layer Substances 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 6
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 claims description 41
- 238000003756 stirring Methods 0.000 claims description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 34
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 34
- 239000005018 casein Substances 0.000 claims description 32
- 235000021240 caseins Nutrition 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 22
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 21
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 19
- 229920002554 vinyl polymer Polymers 0.000 claims description 19
- 229960003638 dopamine Drugs 0.000 claims description 18
- 235000012239 silicon dioxide Nutrition 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 17
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 239000000839 emulsion Substances 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 10
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 229920002545 silicone oil Polymers 0.000 claims description 9
- 235000011187 glycerol Nutrition 0.000 claims description 8
- 239000002077 nanosphere Substances 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- 239000007853 buffer solution Substances 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- 239000003607 modifier Substances 0.000 claims description 7
- 229920000734 polysilsesquioxane polymer Polymers 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 6
- 238000010409 ironing Methods 0.000 claims description 6
- 229920001184 polypeptide Polymers 0.000 claims description 6
- 102000004196 processed proteins & peptides Human genes 0.000 claims description 6
- 108090000765 processed proteins & peptides Proteins 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 239000005543 nano-size silicon particle Substances 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 description 38
- 230000002209 hydrophobic effect Effects 0.000 description 17
- 238000004132 cross linking Methods 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000002649 leather substitute Substances 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 9
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 230000002940 repellent Effects 0.000 description 3
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 240000002853 Nelumbo nucifera Species 0.000 description 2
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 2
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- VMAWODUEPLAHOE-UHFFFAOYSA-N 2,4,6,8-tetrakis(ethenyl)-2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O[Si](C)(C=C)O1 VMAWODUEPLAHOE-UHFFFAOYSA-N 0.000 description 1
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920001213 Polysorbate 20 Polymers 0.000 description 1
- LWZFANDGMFTDAV-BURFUSLBSA-N [(2r)-2-[(2r,3r,4s)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O LWZFANDGMFTDAV-BURFUSLBSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000004207 dermis Anatomy 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000011067 sorbitan monolaureate Nutrition 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000012546 transfer Methods 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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- 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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C11/00—Surface finishing of leather
- C14C11/003—Surface finishing of leather using macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C11/00—Surface finishing of leather
- C14C11/003—Surface finishing of leather using macromolecular compounds
- C14C11/006—Surface finishing of leather using macromolecular compounds using polymeric products of isocyanates (or isothiocyanates) with compounds having active hydrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The application relates to the field of leather materials, and particularly discloses antifouling and water-repellent composite leather and a preparation method thereof. The antifouling water-repellent composite leather comprises a leather layer and a protective layer, wherein the protective layer comprises a polyurethane layer and a hand feeling layer, the polyurethane layer and the hand feeling layer are sequentially coated on the leather layer from inside to outside, the hand feeling layer is made of an organic silicon finishing agent, and the organic silicon finishing agent comprises the following substances in parts by weight: 20-30 parts of polysiloxane, 0.2-2 parts of emulsifier, 1-5 parts of alcoholic solution, 1-3 parts of collagen and 300 parts of 200-water, wherein the polysiloxane is polysiloxane modified by graphene, and the graphene is graphene oxide modified by a silane coupling agent function; the preparation method comprises the following steps: s1, preparing an organic silicon finishing agent; s2, preparing the composite leather. The composite leather can be used in the fields of bags, clothes and the like, and has the advantages of water repellency, pollution resistance and smooth hand feeling.
Description
Technical Field
The application relates to the field of leather materials, in particular to antifouling and water-repellent composite leather and a preparation method thereof.
Background
The leather can be divided into animal leather and artificial leather, the artificial leather usually uses cloth base as substrate, the substrate is coated with polyurethane or silicon rubber, and is made by calendering PVC, the artificial leather usually has the advantages of soft and plump hand feeling, better elasticity, excellent processing performance, etc., therefore, the artificial leather on the market is widely used at present, most shoes, leather bags, furniture, etc. are made of artificial leather, and is popular with consumers.
In order to improve the processing performance of the artificial leather, a layer of polyurethane material is compounded on the animal leather to form a coating layer by part of traditional artificial leather manufacturers; meanwhile, in order to improve the hand feeling of the artificial leather, the surface treatment of the organic silicon is carried out on the artificial leather, and the treated product is called semi-silicon leather, namely composite leather.
In view of the above-mentioned related technologies, the inventor believes that the surface of the animal leather needs to be treated for many times, so that the active component in the organic silicon loses efficacy, so that the organic silicon is not easy to form a protective film on the surface of the leather, and meanwhile, the bonding effect between the organic silicon and the polyurethane on the surface of the animal leather is not good, that is, the coating layer loaded on the animal leather is easy to fall off, so that the composite leather has a poor water-repellent and stain-resistant effect.
Disclosure of Invention
In order to improve the defect that the water-repellent and anti-fouling effect of the composite leather is poor, the application provides the anti-fouling and water-repellent composite leather and the preparation method thereof.
In a first aspect, the application provides an antifouling and water-repellent composite leather, which adopts the following technical scheme:
the antifouling water-repellent composite leather comprises a leather layer and a protective layer, wherein the protective layer comprises a polyurethane layer and a hand feeling layer, the polyurethane layer and the hand feeling layer are sequentially coated on the leather layer from inside to outside, the hand feeling layer is made of an organic silicon finishing agent, and the organic silicon finishing agent comprises the following substances in parts by weight: 20-30 parts of polysiloxane, 0.2-2 parts of emulsifier, 1-5 parts of alcoholic solution, 1-3 parts of collagen and 300 parts of water, wherein the polysiloxane is polysiloxane modified by graphene, and the graphene is graphene oxide modified by a silane coupling agent function.
Through adopting above-mentioned technical scheme, at first, graphite alkene carries out modification treatment to polysiloxane, because graphite alkene is two-dimensional lamellar structure, higher surface activity for graphite alkene can form composite construction with organic silicon, forms continuous cross-linking structure, has improved the degree of compactness on the layer of feeling, and the lamellar structure of graphite alkene can pile up the hole on the cover polyurethane layer, has effectively improved composite leather's water-proof effects. Meanwhile, the graphene has a good conductive effect, so that the hand feeling agent obtains good conductivity, namely the hand feeling layer obtains an anti-static effect, the retention of dirt on the hand feeling layer is reduced, and the water-repellent and anti-fouling effects of the composite leather are effectively improved.
Secondly, according to the technical scheme, polysiloxane is modified by graphene modified by a silane coupling agent, and graphene oxide is subjected to coupling modification by the silane coupling agent, so that the dispersion uniformity of the graphene in the organic silicon finishing agent is improved, and the organic silicon finishing agent obtains a uniform waterproof effect.
Finally, the collagen is added into the organic silicon finishing agent, and the inside of collagen molecules and the collagen molecules can be crosslinked, so that the viscosity of the organic silicon finishing agent can be increased, and the bonding performance between the hand feeling layer and the polyurethane layer is enhanced; and the compactness of a membrane structure formed by the organic silicon finishing agent can be enhanced, and the waterproof effect of the composite leather is further improved. In addition, collagen has the infiltration effect of preferred to polyurethane, can further infiltrate the pore structure who forms on the polyurethane layer, and can connect through covalent bond combination's mode between collagen and the polyurethane, has further improved the combination effect between feeling layer and the polyurethane layer, feels the layer and can load for a long time on the genuine leather layer promptly, stably improves the water-proof effects of compound leather.
Preferably, the polysiloxane comprises one or two of long-chain alkyl modified polysiloxane and thiolated hydroxyl-terminated vinyl polysiloxane.
By adopting the technical scheme, firstly, the long-chain alkyl modified polysiloxane is preferably added into the organic silicon finishing agent, the long-chain alkyl group is a hydrophobic group, and in the film forming process of the hand feeling agent, the long-chain alkyl group can induce the polysiloxane to form a cross-linked reticular hydrophobic structure, so that the cross-linking density in the hand feeling layer is improved, and the hydrophobic effect of the hand feeling layer is improved. And the reticular hydrophobic structure can form interpenetration with a three-dimensional cross-linking structure in the polyurethane, so that the bonding strength between the polyurethane layer and the hand feeling layer is further improved.
And secondly, preferably, the thiolated hydroxyl-terminated vinyl polysiloxane is added into the organic silicon finishing agent, and the n-dodecyl mercaptan is grafted on the polysiloxane, so that the silicon-containing chain segment in the organic silicon finishing agent is increased, and the hydrophobicity of the organic silicon finishing agent is further improved. Meanwhile, active groups on the thiolated hydroxyl-terminated vinyl polysiloxane can form grafting with polyurethane, so that the bonding strength between the hand feeling layer and the polyurethane layer is enhanced. And because the surface energy of the thiolated hydroxyl-terminated vinyl polysiloxane is lower, in the film forming process of the hand feeling layer, the silicon-containing chain segment is transferred towards the surface of the hand feeling layer, so that the roughness of the hand feeling layer is increased, the hand feeling layer can form a surface structure similar to a lotus leaf, and the hydrophobic effect of the hand feeling layer is effectively improved.
Finally, long-chain alkyl modified polysiloxane and thiolated hydroxyl-terminated vinyl polysiloxane are matched to serve as polysiloxane, and the combination strength between the hand feeling layer and the polyurethane layer can be further improved, the possibility of peeling of the hand feeling layer is reduced, and the waterproof aging of the composite leather is prolonged through the interpenetration of the network-shaped hydrophobic structure and the three-dimensional cross-linking structure in the polyurethane layer and the grafting between the active groups on the thiolated hydroxyl-terminated vinyl polysiloxane and the polyurethane. Moreover, the hydrophobic effect of the composite leather is synergistically improved through surface transfer of the silicon-containing chain segment and the matching of alkyl groups and through a hydrophobic functional group and a lotus leaf-like hydrophobic structure on the surface.
Preferably, the polysiloxane further comprises polysilsesquioxane nanosphere modified polysiloxane.
By adopting the technical scheme, the nano microspheres in the polysilsesquioxane nanosphere modified polysiloxane can be uniformly adsorbed to the surface of the polyurethane layer in a single layer, the nano microspheres can be filled into a pore structure on the polyurethane layer to block a path of water drops entering the corium layer, and a micro rough structure is further formed on the surface of the hand feeling layer, so that the construction of a super-hydrophobic surface is realized, and the hydrophobic effect of the composite leather is further improved.
Preferably, the graphene oxide is modified by a modifier, and the modifier comprises one or two of silicon dioxide and dopamine.
By adopting the technical scheme, the graphene oxide is modified by adopting the silicon dioxide in the technical scheme, the silicon dioxide can be coated on the surface of the graphene oxide, and the insulating layer is formed on the surface of the graphene oxide, so that on one hand, the surface energy of the graphene oxide is reduced, and the dispersibility of the graphene oxide is improved, on the other hand, the silicon dioxide can be inserted into a graphene oxide lamellar structure, the agglomeration of the graphene oxide is reduced, the graphene oxide can be uniformly dispersed in polysiloxane, and namely the hydrophobicity and the binding property of the polysiloxane can be uniformly improved by the graphene oxide.
Secondly, the dopamine is coated on the graphene oxide, and after the dopamine is coated on the graphene oxide, an adsorption layer can be formed on the surface of the graphene oxide, so that the compatibility between the graphene oxide and polysiloxane is further improved, the modification effect of the graphene oxide on the polysiloxane is improved, the adsorption strength between the organic silicon finishing agent and the polyurethane layer can be enhanced, and the long-acting hydrophobic effect of the composite leather is obtained.
Finally, dopamine and silicon dioxide are matched to modify graphene oxide, the adsorption effect of dopamine can enhance the bonding strength between the silicon dioxide and the graphene oxide, and the graphene oxide obtains excellent dispersibility, so that each component in the organic silicon modifier obtains uniform suspension dispersibility, namely, a hand feeling layer obtains uniform hydrophobic effect.
Preferably, the modification treatment comprises the following steps: respectively weighing 0.5-2 parts by weight of ethyl orthosilicate, 0.05-0.2 part by weight of dopamine, 0.1-0.5 part by weight of graphene oxide and 300 parts by weight of 200-plus buffer solution, stirring and mixing the graphene oxide and water to obtain a dispersion liquid, adding the ethyl orthosilicate into the dispersion liquid, stirring and reacting at room temperature, and performing suction filtration, washing and freeze drying to obtain primary modified graphene; dispersing the primary modified graphene in a buffer solution, adding dopamine, stirring at room temperature for reaction, filtering, retaining solids, washing, and drying to obtain the modified graphene oxide.
By adopting the technical scheme, the modification sequence of the silicon dioxide and the dopamine to the graphene oxide is optimized, so that the graphene oxide is sequentially coated with the silicon dioxide layer and the dopamine adsorption layer, the insulating layer is coated on the graphene oxide, and the dispersion uniformity of the graphene oxide is improved; the adsorption layer can be wrapped on the insulating layer, the combination firmness of the insulating layer and the graphene oxide can be enhanced by the adsorption layer, the adsorption combination effect between the organic silicon finishing agent and the polyurethane layer is enhanced simultaneously, and the composite leather is enabled to obtain a lasting and uniform hydrophobic effect and an antifouling effect.
Preferably, the organosilicon finishing agent further comprises one or more of collagen polypeptide, casein and glycerol, wherein the casein is modified by a film forming agent and comprises acrylate monomers and caprolactam.
By adopting the technical scheme, the collagen polypeptide is added into the organic silicon finishing agent, so that the compatibility among all components in the organic silicon finishing agent can be enhanced, the stability of the organic silicon finishing agent is improved, and the emulsification effect in the organic silicon finishing agent can be promoted.
And secondly, casein is added into the organic silicon finishing agent, has good film forming property and adhesive force, can improve the film forming effect of the organic silicon finishing agent, enables the hand feeling layer to obtain a compact cross-linking structure, and improves the bonding strength between the hand feeling layer and the polyurethane layer.
And thirdly, glycerol is added into the organic silicon finishing agent, the glycerol can lubricate components in the organic silicon finishing agent, the ductility of the hand feeling layer is improved, meanwhile, the compatibility between the glycerol and polyurethane is good, and the bonding strength between the hand feeling layer and the polyurethane layer can be further improved.
Collagen polypeptide, casein and glycerine are added to the organic silicon finishing agent in a matching manner, so that the film forming speed and viscosity of the organic silicon finishing agent can be improved, the organic silicon finishing agent can permeate into the polyurethane layer, the polyurethane layer and the hand feeling layer are promoted to form cross-linking, and the composite leather can obtain long-acting hydrophobic and antifouling effects.
Finally, the technical scheme of the application adopts the acrylate monomer and the caprolactam to modify the casein, and under the self-crosslinking action of the caprolactam, the acrylate monomer is grafted to the casein, so that the softness of a casein film is improved, the toughness of a hand feeling layer is improved, and the hand feeling layer is favorable for uniformly wrapping the composite leather.
Preferably, the film forming agent further comprises one or more of a silane coupling agent, vinyl silicone oil and nano silicon dioxide.
By adopting the technical scheme, the silane coupling agent is added into the film forming agent, the appearance and the size of latex particles in the casein are regulated, so that the casein obtains a shell-core structure, the film forming effect of the casein is maintained through the structure of a soft core and a hard shell, the hardness and the wear resistance of the hand feeling layer can be improved, and the possibility that the water resistance of the composite leather is poor due to the breakage of the hand feeling layer is reduced.
And secondly, vinyl silicone oil is added into the film forming agent, and a flexible long-chain structure on the vinyl silicone oil can be grafted on casein, so that the flexibility of a film structure formed by the casein is improved, and the film forming effect of the hand feeling agent is further improved.
Finally, the nano silicon dioxide is adopted to modify the casein, the nano silicon dioxide can wrap the surface of the casein latex particle, the hardness of the shell of the latex particle is enhanced, the viscosity of the casein is optimized, the dispersion uniformity among all components in the casein molecule is improved, and the crosslinking uniformity of the hand feeling layer is effectively improved.
In addition, the silane coupling agent, the vinyl silicone oil and the nano silicon dioxide are matched to be used as the film forming agent to modify the casein, a flexible chain segment can be grafted on the casein, a hard shell and soft core structure is formed, the stability of the organic silicon finishing agent is effectively improved, and the toughness and the water resistance of the hand feeling layer are improved.
Preferably, the alcohol solution comprises any one of ethanol, n-propanol, isopropanol and n-pentanol.
By adopting the technical scheme, the polysiloxane is dissolved by adopting the alcohol solution in the technical scheme of the application, and the active groups in the polysiloxane have strong electron-withdrawing induction effect and electron-withdrawing conjugation effect, so that the alcohol solution and the polysiloxane can react and prevent the crosslinking and curing of the organic silicon, and the stability of the organic silicon finishing agent is improved.
In a second aspect, the application provides a preparation method of antifouling and water repellent composite leather, which adopts the following technical scheme:
a preparation method of antifouling and water-repellent composite leather comprises the following steps: s1, preparing an organic silicon finishing agent: respectively taking polysiloxane, an emulsifier, an alcoholic solution, water and collagen according to a formula, stirring and mixing the polysiloxane, the emulsifier and the alcoholic solution to obtain a premixed emulsion, and stirring and mixing the premixed emulsion, the collagen and the water to obtain an organic silicon finishing agent; s2, preparing the composite leather: coating polyurethane on the leather layer, drying to obtain semi-finished leather, spraying the organic silicon finishing agent on the semi-finished leather, drying, ironing, standing, softening, vibrating, softening, ironing, and vacuum drying to obtain the composite leather.
By adopting the technical scheme, the polysiloxane is dissolved in the alcohol solution in advance, and the completely emulsified premixed emulsion is obtained by emulsifying the polysiloxane with the emulsifier; and then adding collagen and water into the premixed emulsion, so that the viscosity of the organic silicon finishing agent can be slowly adjusted, the components in the organic silicon finishing agent are uniformly dispersed, are not easy to crosslink and solidify and can be stably kept to be not easy to settle, and a hand feeling layer which is compact in crosslinking and stably combined with a polyurethane layer is formed by the organic silicon finishing agent, so that the composite leather can obtain a uniform and long-acting waterproof effect.
In summary, the present application has the following beneficial effects:
1. according to the application, the graphene oxide modified polysiloxane modified by the silane coupling agent function is adopted, and after the silane coupling agent is modified, the coupling group is grafted on the graphene oxide, so that the dispersion uniformity of the graphene oxide in the polysiloxane is improved, and the two-dimensional lamellar structure of the graphene can be compounded with the polysiloxane to form a continuous structure, so that a continuous and uniform hydrophobic structure is obtained in a hand feeling layer formed by the organic silicon finishing agent, a better anti-static effect is given to the hand feeling layer, and the attachment of dirt is reduced; and the collagen is added into the organic silicon finishing agent, so that the bonding strength between the hand feeling layer and the polyurethane is effectively enhanced, and the possibility of peeling of the hand feeling layer is reduced, therefore, the composite leather has excellent and long-acting water-repellent and anti-fouling effects.
2. Preferentially adopt the film-forming agent to modify casein in this application, through graft flexible chain segment on casein, form soft core crust structure, form the nano particle coating outside the micelle, can effectively improve the film forming effect of casein, improve the pliability and the wearability on feeling the layer, improve the parcel integrality of feeling the layer to compound leather to reduce the possibility that the layer of feeling peels off because of the friction, consequently, compound leather has obtained even and long-term water repellent effect.
3. According to the method, polysiloxane is diluted and emulsified in advance, the viscosity of the premixed emulsion is adjusted, water and collagen are added into the premixed liquid, the viscosity of the organic silicon finishing agent is slowly adjusted, the possibility that the viscosity of the organic silicon finishing agent is increased greatly due to the fact that the collagen is directly added is reduced, the suspension dispersibility and the stability of the organic silicon finishing agent are effectively improved, and therefore the composite leather obtains a uniform and stable waterproof effect.
Detailed Description
The present application will be described in further detail with reference to examples.
Preparation example
Preparation of Long chain alkyl-modified polysiloxane
Preparation example 1
Respectively taking 3kg of side chain type hydrogen-containing silicone oil, 1kg of 2-hydroxypropyl carboxyethyl ether, 1kg of 1-octadecene (brand: SIGMA) and 0.5kg of platinum catalyst, stirring and mixing the side chain type hydrogen-containing silicone oil, the 2-hydroxypropyl carboxyethyl ether and the 1-octadecene, heating to 75 ℃, adding the platinum catalyst, continuously stirring, releasing heat of a system, cooling to 85 ℃, and reacting at constant temperature for 3 hours to obtain the long-chain alkyl modified polysiloxane.
Preparation of thiolated hydroxyl-terminated vinyl polysiloxane
Preparation example 2
1.05kg of octamethylcyclotetrasiloxane (D) were each taken 4 ) 4g of tetramethylammonium hydroxide, 18.6kg of tetravinyltetramethylcyclotetrasiloxane (V) 4 ) 2kg of tetrahydrofuran, 6.3kg of n-dodecylmercaptan, 2g of azobisisobutyronitrile. Get D 4 、V 4 And tetramethylammonium hydroxide, stirring and reacting for 3h at 110 ℃, heating to 170 ℃, and distilling under reduced pressure for 3h to obtain hydroxyl-terminated vinyl Polysiloxane (PDMS). Mixing 0.05kg of PDMS and tetrahydrofuran, stirring for dissolving, adding n-dodecyl mercaptan and azobisisobutyronitrile, stirring and refluxing for 10h at 80 ℃, cooling to room temperature, dripping methanol for precipitation, filtering, and retaining solids, namely the thiolated hydroxyl-terminated vinyl polysiloxane.
Preparation of polysilsesquioxane nanosphere modified polysiloxane
Preparation example 3
1kg of Sodium Dodecyl Sulfate (SDS), 1kg of fatty alcohol-polyoxyethylene ether (AEO-3), 30kg of water, 1kg of Methyltriethoxysilane (MTES), 0.2kg of silane coupling agent KH-560, 1kg of Gelatio brand HD-109 type coupling agent, 0.05kg of Tetramethylammonium Hydroxide (THMA), octamethylcyclotetrasiloxane (D) 4 ) 1kg of Dadi HD-121 type coupling agent, 10kg of acetone, 0.08kg of methyltrimethoxysilane (MTMS).
Mixing SDS, water and AEO-3 under stirring to obtain a mixture, adding ammonia water to adjust the pH of the mixture to 8, adding MTES and KH-560, stirring at room temperature for 12h, centrifuging, retaining precipitate, washing with ethanol and deionized water for 2 times, drying, and grinding to obtain nanospheres (PGMSQ).
Taking HD-109, acetone, water and THMA, stirring and mixing, adding to 55 ℃, keeping the temperature to react for 3 hours, and distilling under reduced pressure to remove the solvent to obtain the precursor. Mixing the precursor with D 4 HD-121, MTMS are stirred and mixed,heating to 90 ℃, adding THMA, reacting for 0.5h under heat preservation, heating to 110 ℃, reacting for 6h under heat preservation, continuing heating to 135 ℃, decomposing the catalyst, and distilling under reduced pressure to remove low-boiling-point substances to obtain the cross-linked long-chain alkyl amino silicon (JRASO).
Heating and stirring 0.15kg of PGMSQ, 1kg of JRASO and 3kg of isopropanol to 52 ℃, reacting for 4h, and distilling under reduced pressure to obtain semitransparent liquid, namely the polysilsesquioxane nanosphere modified polysiloxane.
Preparation of polysiloxane
Preparation examples 4 to 7
Respectively weighing long-chain alkyl modified polysiloxane, thiolated hydroxyl-terminated vinyl polysiloxane and polysilsesquioxane nanosphere modified polysiloxane, stirring and mixing to obtain polysiloxane 1-4, wherein the specific mass is shown in table 1.
TABLE 1 preparation examples 4-7 polysiloxane compositions
Graphene oxide preparation example
Preparation examples 8 to 12
Tetraethoxysilane, dopamine, graphene oxide, a buffer solution (Tris-HCl buffer solution), ethanol and water are respectively weighed, and the specific mass is shown in Table 2.
Taking graphene oxide, water and ethanol, stirring and mixing, carrying out 400W ultrasonic dispersion for 1h to obtain a dispersion, adding ammonia water to adjust the pH of the dispersion to 8, carrying out magnetic stirring, adding tetraethoxysilane, stirring at room temperature for 12h, carrying out suction filtration and washing with deionized water to neutrality, and carrying out freeze drying to obtain the primary modified graphene. Stirring and mixing 0.3kg of primary modified graphene and a buffer solution, carrying out 400W ultrasonic dispersion for 30min to obtain a suspension, adding dopamine into the suspension, carrying out vigorous stirring at room temperature for 48h, washing with deionized water and ethanol for 3 times respectively, and drying at 80 ℃ for 10h to obtain modified graphene oxide 1-5.
Table 2 preparation examples 8 to 12 modified graphene oxide compositions
Preparation example 13
And (3) taking 0.01kg of graphene oxide and 0.1kg of silane coupling agent KH560, stirring, mixing and drying to obtain graphene oxide 1 modified by the silane coupling agent function.
Preparation examples 14 to 18
The difference from preparation 13 is that: graphene oxide 2-6 functionally modified with a silane coupling agent was prepared by using modified graphene oxide 1-5 instead of graphene oxide in preparation example 13.
Preparation of alcohol solution
Preparation example 19
Taking 100kg of ethanol as the alcoholic solution, it is worth mentioning that the alcoholic solution includes, but is not limited to, any one of ethanol, n-propanol, isopropanol, and n-pentanol.
Preparation of casein
Preparation example 20
Casein, caprolactam, triethanolamine, water, butyl acrylate, methyl methacrylate and ammonium persulfate are taken, and the specific mass is shown in Table 3. Mixing casein, triethanolamine and water under stirring, heating to 65 deg.C, stirring at constant temperature, and reacting for 2 hr to obtain intermediate solution. Adding 1/3 mass of butyl acrylate, methyl methacrylate and ammonium persulfate into the intermediate liquid, and stirring and mixing to form the seed emulsion. And (3) dropwise adding the residual butyl acrylate into the seed emulsion, and reacting for 2h at 75 ℃ to obtain the modified casein 1.
Preparation example 21
The difference from preparation example 20 is that: and (3) reacting the residual butyl acrylate and a silane coupling agent KH-570 for 2 hours at the temperature of 75 ℃ to obtain the modified casein 2. The proportions of the components are shown in Table 3.
Preparation example 22
The difference from preparation example 20 is that: respectively taking casein, triethanolamine, vinyl silicone oil and water, stirring and mixing, heating to 65 ℃, stirring and reacting at constant temperature for 2 hours to obtain intermediate liquid, and preparing the modified casein 3. The mass of each component is shown in Table 3.
Preparation example 23
The difference from preparation 22 is that: respectively taking casein, triethanolamine, vinyl silicone oil, tetraethoxysilane, silane coupling agent KH-570 and water, stirring and mixing, heating to 65 ℃, stirring and reacting at constant temperature for 2 hours to obtain intermediate liquid, and preparing modified casein 4. The mass of each component is shown in Table 3.
TABLE 3 preparation examples 20-23 modified casein compositions
Preparation of graphene-modified polysiloxane
Preparation example 24
Taking 0.1kg of graphene oxide 1 modified by the silane coupling agent function, ultrasonically dispersing the graphene oxide 1 in 10kg of water, adding 19.9kg of polysiloxane and 1.6kg of triethylamine, and carrying out sol-gel reaction at normal temperature to obtain the graphene-modified polysiloxane 1.
Wherein, the preparation of the polysiloxane comprises the following steps: 1kgD4, 0.9g of catalyst tetramethylammonium hydroxide and 4g of epoxy blocking agent, stirring and mixing, adding 0.04kg of silane coupling agent KH550 and 0.04kg of isopropanol, reacting at 110 ℃ for 1 hour under heat preservation, heating to 140 ℃ to destroy the catalyst, distilling under reduced pressure to remove water and low-boiling-point substances, and stopping the reaction to obtain the polysiloxane.
Preparation examples 25 to 28
The difference from preparation 24 is that: graphene-modified polysiloxanes 2-5 were prepared using polysiloxanes 1-4 instead of the polysiloxane of preparation 24.
Preparation examples 29 to 33
The difference from preparation 24 is that: graphene-modified polysiloxane 6-10 was prepared by using graphene oxide 2-6 functionally modified with a silane coupling agent instead of graphene oxide 1 functionally modified with a silane coupling agent in preparation example 24.
Examples
Examples 1 to 3
In one aspect, the application provides a compound leather is refused to antifouling water, including corium layer and protective layer, the protective layer includes polyurethane layer and the layer of feeling of cladding on corium layer in order from inside to outside, the layer of feeling is made by including organosilicon finishing agent, organosilicon finishing agent includes following substance: polysiloxane, emulsifier, alcohol solution, collagen and water, and the specific mass is shown in Table 4. Wherein the polysiloxane is polysiloxane 1 modified by graphene. The emulsifier is span 20 and tween 20 with equal mass.
On the other hand, the application provides a preparation method of the antifouling water-repellent composite leather, which comprises the following steps:
preparing an organic silicon finishing agent: stirring and mixing polysiloxane, an emulsifier and an alcohol solution to obtain a premixed emulsion, and stirring and mixing the premixed emulsion, collagen and water to obtain an organic silicon finishing agent;
coating polyurethane on a dermis layer, drying to obtain semi-finished leather, spraying an organic silicon finishing agent on the semi-finished leather, drying at 80 ℃ for 3min, ironing at 130 ℃ and under the pressure of 30kgf, standing for 4h, milling for 2h, vibrating and softening the semi-finished leather with the strength of 6 agents, ironing at 120 ℃ and under the pressure of 5kgf, and vacuum drying at 80 ℃ for 15s to obtain the composite leather 1-3.
Table 4 examples 1-3 silicone finish compositions
Examples 4 to 7
The difference from example 2 is that: composite leathers 4 to 7 were prepared using graphene-modified polysiloxane 2 to 5 instead of graphene-modified polysiloxane 1 in example 2.
Examples 8 to 12
The difference from example 2 is that: composite leathers 8 to 12 were prepared using the graphene-modified polysiloxane 6 to 10 instead of the graphene-modified polysiloxane 1 of example 2.
Examples 13 to 16
The difference from example 2 is that: the organic silicon finishing agent also comprises collagen polypeptide, modified casein 1 and glycerol, the specific mass is shown in table 5, and composite leather 13-16 is prepared.
Table 5 examples 13-16 silicone finish remaining component compositions
Examples 17 to 19
The differences from example 16 are: composite leathers 17 to 19 were prepared using modified casein 2 to 4 instead of modified casein 1 in example 16.
Example 20
The difference from example 16 is that: composite leather 20 was prepared using casein in place of modified casein 1 in example 16.
Comparative example
Comparative example 1
The comparative example is different from example 2 in that the polysiloxane was not graphene-modified in the comparative example, and the composite leather 21 was prepared.
Comparative example 2
The comparative example is different from example 3 in that graphene in the comparative example is commercially available graphene, and the composite leather 22 is prepared.
Performance test
(1) And (3) waterproof testing: and detecting the surface water contact angle of the composite leather by using a water contact angle tester.
(2) And (3) detecting the adhesion performance: the adhesion of the hand layer was tested according to "QB/T2537-2001 leather colour fastness test reciprocating crocking colour fastness".
TABLE 6 Performance test of examples 1-24 and comparative examples 1-2
The comparison of the performance tests in combination with the table 6 can find that:
(1) by combining examples 1-3 with comparative examples 1-2, it can be found that: the waterproof property and the adhesiveness of the composite leather prepared in the embodiments 1 to 3 are improved, which shows that the graphene modified polysiloxane is adopted and matched with the collagen, so that a lamellar structure is added into the organic silicon finishing agent, a continuous structure is added into the hand feeling layer, and the antistatic effect of the hand feeling layer is improved; the crosslinking property and the caking property of the organic silicon finishing agent can be improved, and the bonding strength between the hand feeling layer and the polyurethane layer is improved, so that the composite leather has excellent and long-acting antifouling and water repellent effects. As can be seen from table 6, the composite leather prepared in example 2 has a good waterproof effect and a good adhesion effect of the hand layer, which indicates that the proportions of the components in the silicone finishing agent are suitable.
(2) A comparison of examples 4 to 7 with example 2 shows that: the waterproof property and the adhesiveness of the composite leather prepared in the embodiments 4 to 7 are improved, which indicates that the long-chain alkyl modified polysiloxane, the thiolated hydroxyl-terminated vinyl polysiloxane, and the polysilsesquioxane nanosphere modified polysiloxane are adopted as the polysiloxane, and that the hydrophobic network structure formed by the long-chain alkyl groups and the three-dimensional crosslinking structure in the polyurethane layer form interpenetration, and the silicon-containing chain segments are transferred on the hand feeling layer to form a hydrophobic surface structure, fill the nanoparticles, and adsorb the polyurethane layer, so that the bonding strength between the hand feeling layer and the polyurethane layer can be effectively improved, the hydrophobic effect of the hand feeling layer is improved, and the possibility of peeling off the hand feeling layer is reduced. As can be seen from table 6, the composite leather obtained in example 7 is excellent in the water-repellent effect and the hand layer adhesion effect, and the proportions of the components in the polysiloxane are appropriate at this time.
(3) Combining example 8, example 9, examples 10-12 and example 2, it can be found that: the waterproof performance and the adhesiveness of the composite leather are improved in examples 8-12, which shows that the graphene oxide is modified by matching silicon dioxide and dopamine, the silicon dioxide is firstly coated on the graphene oxide to form an insulating layer in a graphene oxide lamellar layer, the possibility of graphene oxide agglomeration is reduced, and then the graphene oxide is coated on the dopamine through the adsorption effect of polydopamine to form a graphene oxide-silicon dioxide-dopamine composite structure, so that the dopamine adsorption layer not only can firmly bond the silicon dioxide and the graphene oxide, but also can enhance the bonding strength between an organic silicon modifier and a polyurethane layer, and the possibility of peeling of a hand feeling layer is further reduced. As can be seen from table 6, the composite leather obtained in example 11 is excellent in the water-repellent effect and the adhesion effect of the hand layer, and the proportions of the components in the modifier are appropriate at this time.
(4) A comparison of examples 13 to 16 with example 2 shows that: the waterproof property and the adhesiveness of the composite leather prepared in examples 13 to 16 are improved, which shows that the composite leather prepared in the present application adopts collagen polypeptide, casein and glycerin to be added to the organic silicon finishing agent in a matching manner, so that on one hand, the film forming speed and the viscosity of the organic silicon finishing agent are improved, on the other hand, the permeation effect of the organic silicon finishing agent to the polyurethane layer is increased, the cross-linking between the polyurethane layer and the hand feeling layer is promoted, and the composite leather can obtain a long-acting hydrophobic effect. As can be seen from table 6, the composite leather produced in example 15 has a good waterproof effect and a good adhesion effect of the hand layer, which indicates that the proportions of the components in the silicone finishing agent are suitable.
(5) A comparison of examples 17 to 19, example 20 and example 2 shows that: the waterproof property and the adhesion of the composite leather prepared in the examples 17-20 are improved, which shows that the application adopts the film forming agent to modify the casein, and the flexibility and the anti-blocking effect of the hand feeling layer are improved by grafting the flexible chain segment on the casein, forming a soft core hard shell colloidal particle structure and further adding the hardening and adsorbing layer on the hard shell structure.
The specific embodiments are only for explaining the present application and are not limiting to the present application, and those skilled in the art can make modifications to the embodiments without inventive contribution as required after reading the present specification, but all the embodiments are protected by patent law within the scope of the claims of the present application.
Claims (9)
1. The antifouling water-repellent composite leather is characterized by comprising a leather layer and a protective layer, wherein the protective layer comprises a polyurethane layer and a hand feeling layer, the polyurethane layer and the hand feeling layer are sequentially coated on the leather layer from inside to outside, the hand feeling layer is made of an organic silicon finishing agent, and the organic silicon finishing agent comprises the following substances in parts by weight: 20-30 parts of polysiloxane, 0.2-2 parts of emulsifier, 1-5 parts of alcoholic solution, 1-3 parts of collagen and 300 parts of water, wherein the polysiloxane is polysiloxane modified by graphene, and the graphene is graphene oxide modified by a silane coupling agent function.
2. The antifouling and water-repellent composite leather according to claim 1, characterized in that: the polysiloxane comprises one or two of long-chain alkyl modified polysiloxane and thiolated hydroxyl-terminated vinyl polysiloxane.
3. The antifouling water-repellent composite leather according to claim 2, characterized in that: the polysiloxane also comprises polysilsesquioxane nanosphere modified polysiloxane.
4. The antifouling and water-repellent composite leather according to claim 1, characterized in that: the graphene oxide is modified by a modifier, and the modifier comprises one or two of silicon dioxide and dopamine.
5. The antifouling and water-repellent composite leather according to claim 4, wherein: the modification treatment comprises the following steps: respectively weighing 0.5-2 parts by weight of ethyl orthosilicate, 0.05-0.2 part by weight of dopamine, 0.1-0.5 part by weight of graphene oxide and 300 parts by weight of 200-plus buffer solution, stirring and mixing the graphene oxide and water to obtain a dispersion liquid, adding the ethyl orthosilicate into the dispersion liquid, stirring and reacting at room temperature, and performing suction filtration, washing and freeze drying to obtain primary modified graphene; dispersing the primary modified graphene in a buffer solution, adding dopamine, stirring at room temperature for reaction, filtering, retaining solids, washing, and drying to obtain the modified graphene oxide.
6. The antifouling and water-repellent composite leather according to claim 1, characterized in that: the organic silicon finishing agent also comprises one or more of collagen polypeptide, casein and glycerin, wherein the casein is modified by a film forming agent and comprises an acrylate monomer and caprolactam.
7. The antifouling and water-repellent composite leather according to claim 6, characterized in that: the film forming agent also comprises one or more of silane coupling agent, vinyl silicone oil and nano silicon dioxide.
8. The antifouling and water-repellent composite leather according to claim 1, characterized in that: the alcoholic solution comprises any one of ethanol, n-propanol, isopropanol and n-pentanol.
9. The preparation method of the antifouling and water-repellent composite leather according to any one of claims 1 to 8, characterized by comprising the following steps:
s1, preparing an organic silicon finishing agent: taking polysiloxane, an emulsifier, an alcohol solution, water and collagen according to a formula, respectively, stirring and mixing the polysiloxane, the emulsifier and the alcohol solution to obtain a premixed emulsion, and stirring and mixing the premixed emulsion, the collagen and the water to obtain an organic silicon finishing agent;
s2, preparing the composite leather: coating polyurethane on the leather layer, drying to obtain semi-finished leather, spraying the organic silicon finishing agent on the semi-finished leather, drying, ironing, standing, softening, vibrating, softening, ironing, and vacuum drying to obtain the composite leather.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210766337.8A CN115058190A (en) | 2022-07-01 | 2022-07-01 | Antifouling and water-repellent composite leather and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210766337.8A CN115058190A (en) | 2022-07-01 | 2022-07-01 | Antifouling and water-repellent composite leather and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115058190A true CN115058190A (en) | 2022-09-16 |
Family
ID=83203402
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210766337.8A Pending CN115058190A (en) | 2022-07-01 | 2022-07-01 | Antifouling and water-repellent composite leather and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115058190A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115503320A (en) * | 2022-09-26 | 2022-12-23 | 东莞市赛越新材料科技有限公司 | Artificial imitation leather film and preparation method thereof |
| CN115947947A (en) * | 2022-12-26 | 2023-04-11 | 浙江震东新材料有限公司 | Functional finishing agent copolymer and preparation method thereof |
| CN116213226A (en) * | 2023-04-21 | 2023-06-06 | 兴业皮革科技股份有限公司 | Leather coating process with high water resistance |
| CN116285311A (en) * | 2023-01-17 | 2023-06-23 | 北京交通大学 | Novel polyurethane water shutoff grouting material and preparation method thereof |
| CN116589808A (en) * | 2023-03-24 | 2023-08-15 | 青岛天晟防水建材有限公司 | Flake graphene fluorocarbon film, self-adhesive waterproof coiled material and preparation method |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009055874A1 (en) * | 2007-11-02 | 2009-05-07 | Ifinder Pty Ltd | A locating device |
| CN105061781A (en) * | 2015-09-08 | 2015-11-18 | 陕西科技大学 | Long-acting mildew-proof polyacrylate modified casein composite emulsion and preparation method thereof |
| CN106916529A (en) * | 2017-03-07 | 2017-07-04 | 陕西科技大学 | A kind of super-hydrophobic leather coating of durability polysilsesquioxane nano hybridization and preparation method thereof |
| CN108610936A (en) * | 2018-05-23 | 2018-10-02 | 芜湖市创源新材料有限公司 | A kind of preparation method of environmental protection collagen-polyurethane coating |
| CN108823340A (en) * | 2018-07-13 | 2018-11-16 | 广东天跃新材料股份有限公司 | Corium silastic polymer synthetic leather and its manufacturing technology |
| CN109651945A (en) * | 2018-11-20 | 2019-04-19 | 兴业皮革科技股份有限公司 | A kind of preparation method and applications method of the graphene-based leather finishing agent of high physical property |
| CN110494509A (en) * | 2017-04-14 | 2019-11-22 | 爱克发有限公司 | Decorate natural leather |
| CN112724813A (en) * | 2020-12-29 | 2021-04-30 | 苏州德达材料科技有限公司 | Leather coating material and preparation method thereof |
| CN113045974A (en) * | 2021-04-13 | 2021-06-29 | 江苏天沃重工科技有限公司 | Preparation method of impact-resistant graphene polyurea composite coating for impeller surface |
-
2022
- 2022-07-01 CN CN202210766337.8A patent/CN115058190A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009055874A1 (en) * | 2007-11-02 | 2009-05-07 | Ifinder Pty Ltd | A locating device |
| CN105061781A (en) * | 2015-09-08 | 2015-11-18 | 陕西科技大学 | Long-acting mildew-proof polyacrylate modified casein composite emulsion and preparation method thereof |
| CN106916529A (en) * | 2017-03-07 | 2017-07-04 | 陕西科技大学 | A kind of super-hydrophobic leather coating of durability polysilsesquioxane nano hybridization and preparation method thereof |
| CN110494509A (en) * | 2017-04-14 | 2019-11-22 | 爱克发有限公司 | Decorate natural leather |
| CN108610936A (en) * | 2018-05-23 | 2018-10-02 | 芜湖市创源新材料有限公司 | A kind of preparation method of environmental protection collagen-polyurethane coating |
| CN108823340A (en) * | 2018-07-13 | 2018-11-16 | 广东天跃新材料股份有限公司 | Corium silastic polymer synthetic leather and its manufacturing technology |
| CN109651945A (en) * | 2018-11-20 | 2019-04-19 | 兴业皮革科技股份有限公司 | A kind of preparation method and applications method of the graphene-based leather finishing agent of high physical property |
| CN112724813A (en) * | 2020-12-29 | 2021-04-30 | 苏州德达材料科技有限公司 | Leather coating material and preparation method thereof |
| CN113045974A (en) * | 2021-04-13 | 2021-06-29 | 江苏天沃重工科技有限公司 | Preparation method of impact-resistant graphene polyurea composite coating for impeller surface |
Non-Patent Citations (3)
| Title |
|---|
| 叶丽谢也娃等: "《皮革涂饰的理论基础与实用方法》", 31 January 1961, 轻工业出版社 * |
| 雷颖: "高形变、疏水性聚硅氧烷柔性材料的制备及应用研究", 《中国优秀硕士学位论文全文数据库 （工程科技Ⅰ辑）》 * |
| 韩长日等: "《造纸用化学品生产工艺与技术》", 31 May 2019, 北京：科学技术文献出版社 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115503320A (en) * | 2022-09-26 | 2022-12-23 | 东莞市赛越新材料科技有限公司 | Artificial imitation leather film and preparation method thereof |
| CN115503320B (en) * | 2022-09-26 | 2023-06-30 | 东莞市赛越新材料科技有限公司 | Artificial leather-like film and preparation method thereof |
| CN115947947A (en) * | 2022-12-26 | 2023-04-11 | 浙江震东新材料有限公司 | Functional finishing agent copolymer and preparation method thereof |
| CN115947947B (en) * | 2022-12-26 | 2023-10-31 | 浙江震东新材料有限公司 | Functional finishing agent copolymer and preparation method thereof |
| CN116285311A (en) * | 2023-01-17 | 2023-06-23 | 北京交通大学 | Novel polyurethane water shutoff grouting material and preparation method thereof |
| CN116589808A (en) * | 2023-03-24 | 2023-08-15 | 青岛天晟防水建材有限公司 | Flake graphene fluorocarbon film, self-adhesive waterproof coiled material and preparation method |
| CN116589808B (en) * | 2023-03-24 | 2023-12-15 | 青岛天晟防水建材有限公司 | Flake graphite fluorocarbon film, self-adhesive waterproof coiled material and preparation method |
| CN116213226A (en) * | 2023-04-21 | 2023-06-06 | 兴业皮革科技股份有限公司 | Leather coating process with high water resistance |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN115058190A (en) | Antifouling and water-repellent composite leather and preparation method thereof | |
| CN105622944B (en) | A kind of quaternized organic silicone oil and preparation method thereof | |
| CN109762454B (en) | Preparation method of silicon-modified two-component waterborne polyurethane composite coating for automobile varnish | |
| US20120296029A1 (en) | Fluorine-containing multifunctional microspheres and uses thereof | |
| JP2819417B2 (en) | Method for producing antibacterial silicone rubber granules | |
| CN104262639B (en) | The preparation method of super-hydrophobic cross linking polysiloxane-polysilsesquioxane nanosphere hybrid material | |
| CN103214993B (en) | Acrylic ester electrostatic flocking binding agent and preparation method thereof | |
| CN106916529B (en) | A kind of super-hydrophobic leather coating of durability polysilsesquioxane nano hybridization and preparation method thereof | |
| CN105536639B (en) | A kind of ion liquid functionalization snowman anisotropic composite material and its preparation method and application | |
| CN109651945A (en) | A kind of preparation method and applications method of the graphene-based leather finishing agent of high physical property | |
| CN102504131A (en) | Double in-situ method for preparing casein-based nano silicon dioxide composite leather finishing agent | |
| CN113512890B (en) | Silicone rubber leather material for outdoor furniture and preparation method thereof | |
| JP2022533624A (en) | Coating composition and its use | |
| CN114164655A (en) | Antibacterial finishing process of rayon fabric | |
| JPH0367145B2 (en) | ||
| CN103059233B (en) | Method for preparing acrylate/ silane coupling agent shared modified casein leather finishing agent by adopting soap-free polymerization method | |
| CN114481682B (en) | Antibacterial anti-sticking agent for gum dipping process and preparation method thereof | |
| CN1806023B (en) | Coating composition | |
| CN109651816A (en) | A kind of compound emulsion method of graphene-based polysiloxanes | |
| JP3087105B2 (en) | Coating agent consisting of silicone oil and polyalkyl methacrylate | |
| US20210238422A1 (en) | Porous spherical silicone rubber particles, porous silicone composite particles, and method for producing these particles | |
| CN107325322A (en) | Modifying agent comprising nano material | |
| CN110105769A (en) | A kind of high-mechanical property silicon rubber and preparation method thereof of POSS enhancing | |
| CN106221473B (en) | A kind of compound resin and preparation method thereof | |
| CN105647251B (en) | A kind of waterproofing agent preparation method and applications for fibrous plate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220916 |