CN112721364A - Mildew-proof wear-resistant environment-friendly PVC artificial leather and preparation method thereof - Google Patents
Mildew-proof wear-resistant environment-friendly PVC artificial leather and preparation method thereof Download PDFInfo
- Publication number
- CN112721364A CN112721364A CN202110076074.3A CN202110076074A CN112721364A CN 112721364 A CN112721364 A CN 112721364A CN 202110076074 A CN202110076074 A CN 202110076074A CN 112721364 A CN112721364 A CN 112721364A
- Authority
- CN
- China
- Prior art keywords
- parts
- artificial leather
- pvc
- vermiculite powder
- pvc artificial
- 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
- 239000002649 leather substitute Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 101
- 229920001971 elastomer Polymers 0.000 claims abstract description 64
- 239000000806 elastomer Substances 0.000 claims abstract description 63
- 229910052902 vermiculite Inorganic materials 0.000 claims abstract description 60
- 235000019354 vermiculite Nutrition 0.000 claims abstract description 60
- 239000010455 vermiculite Substances 0.000 claims abstract description 60
- 235000013162 Cocos nucifera Nutrition 0.000 claims abstract description 41
- 244000060011 Cocos nucifera Species 0.000 claims abstract description 41
- 239000004744 fabric Substances 0.000 claims abstract description 22
- 239000004014 plasticizer Substances 0.000 claims abstract description 18
- 239000004088 foaming agent Substances 0.000 claims abstract description 17
- 239000010410 layer Substances 0.000 claims abstract description 17
- 239000002344 surface layer Substances 0.000 claims abstract description 15
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 14
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 13
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000011347 resin Substances 0.000 claims abstract description 7
- 229920005989 resin Polymers 0.000 claims abstract description 7
- 230000007613 environmental effect Effects 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 41
- 229910021389 graphene Inorganic materials 0.000 claims description 41
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 36
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims description 33
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 33
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 28
- 239000007787 solid Substances 0.000 claims description 26
- 239000007900 aqueous suspension Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 18
- 239000012948 isocyanate Substances 0.000 claims description 18
- 150000002513 isocyanates Chemical class 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 18
- 239000003607 modifier Substances 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 238000000227 grinding Methods 0.000 claims description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 12
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000005187 foaming Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 238000007873 sieving Methods 0.000 claims description 10
- 238000004049 embossing Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 239000011265 semifinished product Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 5
- AGKBXKFWMQLFGZ-UHFFFAOYSA-N (4-methylbenzoyl) 4-methylbenzenecarboperoxoate Chemical compound C1=CC(C)=CC=C1C(=O)OOC(=O)C1=CC=C(C)C=C1 AGKBXKFWMQLFGZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- 239000004359 castor oil Substances 0.000 claims description 4
- 235000019438 castor oil Nutrition 0.000 claims description 4
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 claims description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- 235000011330 Armoracia rusticana Nutrition 0.000 claims description 3
- 240000003291 Armoracia rusticana Species 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- 235000003351 Brassica cretica Nutrition 0.000 claims description 3
- 235000003343 Brassica rupestris Nutrition 0.000 claims description 3
- 229920002101 Chitin Polymers 0.000 claims description 3
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- QKSKPIVNLNLAAV-UHFFFAOYSA-N bis(2-chloroethyl) sulfide Chemical compound ClCCSCCCl QKSKPIVNLNLAAV-UHFFFAOYSA-N 0.000 claims description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 3
- 235000013539 calcium stearate Nutrition 0.000 claims description 3
- 239000008116 calcium stearate Substances 0.000 claims description 3
- 238000003490 calendering Methods 0.000 claims description 3
- RWXOJQGSZWUIEJ-UHFFFAOYSA-K lanthanum(3+);octadecanoate Chemical compound [La+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O RWXOJQGSZWUIEJ-UHFFFAOYSA-K 0.000 claims description 3
- 235000010460 mustard Nutrition 0.000 claims description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- TXSUIVPRHHQNTM-UHFFFAOYSA-N n'-(3-methylanilino)-n-phenyliminobenzenecarboximidamide Chemical compound CC1=CC=CC(NN=C(N=NC=2C=CC=CC=2)C=2C=CC=CC=2)=C1 TXSUIVPRHHQNTM-UHFFFAOYSA-N 0.000 claims description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 2
- 239000008158 vegetable oil Substances 0.000 claims description 2
- 244000056139 Brassica cretica Species 0.000 claims 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims 1
- 238000012360 testing method Methods 0.000 abstract description 13
- 239000010985 leather Substances 0.000 abstract description 11
- 238000005299 abrasion Methods 0.000 abstract description 7
- 230000032683 aging Effects 0.000 abstract description 5
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 2
- 230000000704 physical effect Effects 0.000 abstract 1
- 238000007790 scraping Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 19
- 239000010903 husk Substances 0.000 description 18
- 230000010355 oscillation Effects 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 7
- 229920011687 Hytrel® 6356 Polymers 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 229920005610 lignin Polymers 0.000 description 3
- 229940049964 oleate Drugs 0.000 description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 3
- 239000004604 Blowing Agent Substances 0.000 description 2
- 241000219198 Brassica Species 0.000 description 2
- 229920010502 Hytrel® 5555HS Polymers 0.000 description 2
- 229920010930 Hytrel® 5556 Polymers 0.000 description 2
- 229920012530 Hytrel® 7246 Polymers 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009775 high-speed stirring Methods 0.000 description 2
- 230000002452 interceptive effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000035943 smell Effects 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- FJQXCDYVZAHXNS-UHFFFAOYSA-N methadone hydrochloride Chemical compound Cl.C=1C=CC=CC=1C(CC(C)N(C)C)(C(=O)CC)C1=CC=CC=C1 FJQXCDYVZAHXNS-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 125000004151 quinonyl group Chemical group 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000009044 synergistic interaction Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/02—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type
- B29B7/22—Component parts, details or accessories; Auxiliary operations
- B29B7/28—Component parts, details or accessories; Auxiliary operations for measuring, controlling or regulating, e.g. viscosity control
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/34—Auxiliary operations
- B29C44/60—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/009—Use of pretreated compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2266/00—Composition of foam
- B32B2266/02—Organic
- B32B2266/0214—Materials belonging to B32B27/00
- B32B2266/0221—Vinyl resin
- B32B2266/0235—Vinyl halide, e.g. PVC, PVDC, PVF, PVDF
-
- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
-
- 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
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
-
- 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
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Abstract
The invention relates to a mildew-proof wear-resistant environment-friendly PVC artificial leather and a preparation method thereof, wherein the PVC artificial leather comprises a base cloth layer and a PVC surface layer attached to the base cloth layer, and the PVC surface layer is prepared from the following raw materials in parts by weight: 100 parts of PVC resin, 20-30 parts of functional elastomer, 50-70 parts of plasticizer, 12-20 parts of coconut shell powder modified vermiculite powder, 4-12 parts of cross-linking agent, 1-5 parts of heat stabilizer, 1-3 parts of antibacterial agent and 0.2-4 parts of foaming agent. Compared with the prior art, the PVC artificial leather does not contain any volatile solvent, is good in environmental protection, smooth in hand feeling, strong in three-dimensional sense, high in glossiness and quality, excellent in mildew-proof, antibacterial and abrasion-resistant scraping performance, plump in hand feeling like real leather, long in service life, capable of achieving the test standard in physical property, capable of effectively overcoming the problems of easy aging, easy mildew and peeling and the like of the existing PVC leather, and good in economic practicability.
Description
Technical Field
The invention belongs to the technical field of leather processing, and relates to mildew-proof wear-resistant environment-friendly PVC artificial leather and a preparation method thereof.
Background
Artificial leather, also known as imitation leather or rubber, is a plastic product that looks and feels like leather and can replace it. The artificial leather is usually manufactured by foaming or film-covering PVC or PU with different formulas on a textile fabric base or a non-woven fabric base, can be processed and manufactured according to the requirements of different strength, abrasion resistance, cold resistance, color, luster, pattern and the like, and has the characteristics of various patterns, good waterproof performance, neat margin, high utilization rate and low price compared with genuine leather.
At present, for the production of PVC artificial leather, the following problems mainly exist: firstly, because some processing aids (such as plasticizers) with certain volatility are required to be used in the processing process, the final PVC artificial leather product has certain unpleasant smell, the normal use of the product is influenced, and potential harm is caused to the health of a human body; secondly, the existing PVC artificial leather products mostly have the phenomena of poor wear resistance and aging resistance, poor waterproofness, obvious aging, abrasion, skin falling, mildew and the like after being used for a long time, not only seriously affect the aesthetic degree of the leather products, but also greatly shorten the service life of the products.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the mildew-proof wear-resistant environment-friendly PVC artificial leather and the preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
according to one aspect of the invention, the mildew-proof wear-resistant environment-friendly PVC artificial leather comprises a base cloth layer and a PVC surface layer attached to the base cloth layer, wherein the PVC surface layer is prepared from the following raw materials in parts by weight: 100 parts of PVC resin, 20-30 parts of functional elastomer, 50-70 parts of plasticizer, 12-20 parts of coconut shell powder modified vermiculite powder, 4-12 parts of cross-linking agent, 1-5 parts of heat stabilizer, 1-3 parts of antibacterial agent and 0.2-4 parts of foaming agent.
In one embodiment, the functional elastomer is a graphene oxide modified thermoplastic polyurethane elastomer, and the graphene oxide is added in an amount of 5 to 15wt% based on the mass of the thermoplastic polyurethane elastomer.
As an embodiment, the functional elastomer is prepared by a method comprising: preparing 2-5 wt% of graphene oxide aqueous suspension, adding an isocyanate modifier and thermoplastic polyurethane elastomer particles into the graphene oxide aqueous suspension, carrying out ultrasonic reaction for 2-4 h at 65-80 ℃ under 100-120 KHz, carrying out centrifugal separation, retaining solids, washing, drying, grinding until 95% of the solid particles pass through a 400-mesh sieve, and thus obtaining the functional elastomer.
Further, the amount of the isocyanate-based modifier added is 0.4 to 1.8% by weight based on the mass of the thermoplastic polyurethane elastomer.
Preferably, the isocyanate-based modifier is selected from any one of hexamethylene diisocyanate, diphenylmethane diisocyanate or dicyclohexylmethane diisocyanate.
Preferably, the thermoplastic polyurethane elastomer may be selected from commercially available Hytrel 5555HS, 5556, 6356 or 7246.
As an embodiment, the preparation method of the coconut shell powder modified vermiculite powder comprises the following steps:
step i): centrifugally separating the vermiculite powder soaked in the hydrogen peroxide solution, keeping solids, washing the solids to be neutral by using deionized water, and drying to prepare pretreated vermiculite powder;
step ii): adding coconut shell powder and a silane coupling agent into a mixed solution of methyl isobutyl ketone, isopropanol and N, N-dimethylformamide, adding the dried pretreated vermiculite powder at 80-95 ℃ while stirring, continuing to stir at a constant temperature for reaction for 1-2 hours after the addition is finished, filtering, retaining solids, washing, drying, grinding to 90%, and sieving with a 2000-mesh sieve to obtain the coconut shell powder modified vermiculite powder.
Preferably, the addition amount of the coconut shell powder is 10-20% of the mass of the pretreated vermiculite powder, the addition amount of the silane coupling agent is 1-5% of the mass of the pretreated vermiculite powder, and the silane coupling agent is any one of gamma- (2, 3-glycidoxy) propyl trimethoxy silane or gamma-aminopropyl triethoxy silane.
Preferably, the mass ratio of the methyl isobutyl ketone to the isopropanol to the N, N-dimethylformamide in the mixed solution is 1:2-4:1, and the mass concentration of the pretreated vermiculite powder in the mixed solution is 0.4-0.8 g/mL.
In one embodiment, the plasticizer is selected from at least one of an aliphatic dibasic acid ester plasticizer or an epoxy vegetable oil plasticizer.
As an embodiment, the crosslinking agent is selected from at least one of 1, 1-di (t-butylperoxy) cyclohexane, di (4-methylbenzoyl) peroxide, or dibenzoyl peroxide.
As an embodiment, the heat stabilizer is selected from at least one of calcium stearate, calcium ricinoleate, zinc stearate, barium stearate, or lanthanum stearate.
As an embodiment, the antibacterial agent is selected from any one of chitin, mustard, castor oil or horseradish.
As an embodiment, the blowing agent is an AC blowing agent.
According to another aspect of the present invention, there is provided a method for preparing the above-mentioned mildewproof, wear-resistant and environment-friendly PVC artificial leather, comprising the steps of:
step 1): adding the preparation raw materials of the PVC surface layer into a high-speed stirrer according to parts by weight, and carrying out high-speed mixing and stirring to obtain a mixture;
step 2): transferring the mixture prepared in the step 1) into an internal mixer for mixing, transferring into an open mill for plasticating after mixing is finished, and then conveying to a calender for calendering into a sheet;
step 3): and (3) attaching the sheet prepared in the step 2) to a base fabric layer to prepare a semi-finished product, and transferring the semi-finished product to a foaming embossing machine for foaming embossing treatment to prepare the PVC artificial leather.
Preferably, in the high-speed mixing and stirring in the step 1), the stirring temperature is 100-110 ℃, and the stirring time is 2-5 min.
Preferably, the mixing temperature in the step 2) is 120-140 ℃, and the plastication is performed by sequentially passing through two open mills and performing plastication under the temperature condition of 130-150 ℃.
Preferably, the temperature of the foaming embossing treatment in step 3) is 180-.
Compared with the prior art, the invention has the following characteristics:
1) the functional elastomer is introduced into the material system of the PVC artificial leather, and is a thermoplastic polyurethane elastomer modified by graphene oxide, because the surface of the graphene oxide has rich active functional groups, the graphene oxide is combined into the thermoplastic polyurethane elastomer by utilizing the isocyanate modifier, not only is beneficial to improving the compatibility between the thermoplastic polyurethane elastomer and the PVC base material, improves the dispersion uniformity of the thermoplastic polyurethane elastomer particles in the PVC base material, can effectively enhance the wear resistance and the scratch resistance of a material system, moreover, the introduction of the graphene oxide is beneficial to improving the flame retardance and aging resistance of the material system, and meanwhile, the graphene oxide can also have synergistic interaction with an antibacterial agent in the material system, the antibacterial and bacteriostatic effects can be played together, and the phenomenon that the surface of the artificial leather is easy to mildew in plum rain weather can be inhibited or prevented;
2) the coconut husk powder modified vermiculite powder is introduced into the material system of the PVC artificial leather, and because the coconut husk powder contains lignin and cellulose, the lignin and the cellulose contain rich aromatic ring structures, aliphatic and aromatic hydroxyl groups, quinone groups and other active groups, the lignin and the cellulose can be combined to the surface of the vermiculite powder through a silane coupling agent, the dispersibility of the vermiculite powder in a PVC base material can be improved, the agglomeration of vermiculite powder particles can be effectively prevented, the vermiculite powder modified by the coconut husk powder has outstanding adsorbability and antiseptic antibacterial property, the odor emission of the PVC artificial leather can be effectively inhibited, in addition, a stable cross-linked structure can be formed between the coconut husk powder modified vermiculite powder and a functional elastomer, and the strength and wear and scratch resistance of the material system can be obviously improved on the premise of keeping the flexibility of the material system;
3) the PVC artificial leather disclosed by the invention does not contain any volatile solvent, is good in environmental protection property, smooth in hand feeling, strong in three-dimensional sense, high in glossiness and quality, excellent in mildew-proof, antibacterial and abrasion-resistant performances, plump in hand feeling of a product like real leather, long in service life, and capable of effectively overcoming the problems of easiness in aging, easiness in mildew and peeling and the like of the conventional PVC leather, and has good economic practicability.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Further, in this document, it should be understood that where an available, suitable, etc. concentration range is listed or described, it is intended that any and every concentration within that range (including the endpoints) should be considered to have been stated. For example, "a range of from 1 to 10" should be understood to mean every and every possible number in succession between about 1 and about 10. Thus, even if specific data points within the range, or even no data points within the range, are explicitly identified or refer to only a few specific points, it is to be understood that any and all data points within the range are to be considered explicitly stated.
Although numerical ranges and parameters setting forth the broad scope of the invention are approximate, the values set forth in the specific examples are presented as precisely as possible. Any numerical value, however, inherently contains certain standard deviations found in their respective testing measurements. As used herein, "about" generally means that the actual value is within plus or minus 10%, 5%, 1%, or 0.5% of a particular value or range. Alternatively, the term "about" means that the actual value falls within the acceptable standard error of the mean, as considered by those skilled in the art. Except in the experimental examples, or where otherwise expressly indicated, it is to be understood that all ranges, amounts, values and percentages herein used (e.g., to describe amounts of materials, length of time, temperature, operating conditions, quantitative ratios, and the like) are to be modified by the word "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, these numerical parameters are to be understood as meaning the number of significant digits recited and the number resulting from applying ordinary carry notation.
The present invention will be described in detail with reference to specific examples.
Example 1:
the mould-proof wear-resistant environment-friendly PVC artificial leather comprises a base cloth layer and a PVC surface layer attached to the base cloth layer, wherein the PVC surface layer is prepared from the following components in parts by weight: 100 parts of PVC resin, 20 parts of functional elastomer, 50 parts of plasticizer, 12 parts of coconut shell powder modified vermiculite powder, 4 parts of cross-linking agent, 1 part of heat stabilizer, 1 part of antibacterial agent and 0.2 part of foaming agent.
The functional elastomer used in this embodiment is a graphene oxide-modified thermoplastic polyurethane elastomer, and the amount of the added graphene oxide is 5wt% based on the mass of the thermoplastic polyurethane elastomer, and the specific preparation method is as follows: preparing a graphene oxide aqueous suspension with the content of 2wt%, adding an isocyanate modifier and thermoplastic polyurethane elastomer particles into the graphene oxide aqueous suspension, carrying out ultrasonic reaction for 4 hours at 65 ℃ and 100 KHz, carrying out centrifugal separation, retaining solids, washing, drying, grinding to 95%, and sieving with a 400-mesh sieve to obtain the functional elastomer.
In the process of preparing the functional elastomer, the preparation method of the graphene oxide water suspension comprises the following steps: fully grinding and dispersing graphene oxide and deionized water at the rotating speed of 30000 r/min for 30 min at the temperature of below 10 ℃, and then carrying out ultrasonic oscillation at the temperature of 50 ℃, wherein the frequency of the ultrasonic oscillation is controlled to be 75 kHz, and carrying out ultrasonic oscillation for 25 min to obtain the graphene oxide water suspension.
The adopted thermoplastic polyurethane elastomer is commercially available Hytrel 5555HS, the adopted isocyanate modifier is hexamethylene diisocyanate, and the using amount of the isocyanate modifier is 0.4 wt% of the mass of the thermoplastic polyurethane elastomer.
The coconut husk powder modified vermiculite powder used in the example is prepared by the following steps:
step i): centrifugally separating the vermiculite powder soaked in the hydrogen peroxide solution, keeping solids, washing the solids to be neutral by using deionized water, and drying to prepare pretreated vermiculite powder;
step ii): adding coconut shell powder and a silane coupling agent into a mixed solution of methyl isobutyl ketone, isopropanol and N, N-dimethylformamide, adding the dried pretreated vermiculite powder at 80 ℃ while stirring, continuing stirring at a constant temperature for reaction for 2 hours after the addition is finished, filtering, retaining solids, washing, drying, grinding to 90%, and sieving with a 2000-mesh sieve to obtain the coconut shell powder modified vermiculite powder.
In the process of preparing the coconut husk powder modified vermiculite powder, the addition amount of the coconut husk powder is 10 wt%, the addition amount of the silane coupling agent is 1 wt%, and the silane coupling agent is gamma-aminopropyltriethoxysilane; the hydrogen peroxide solution used in step i) was a 15wt% hydrogen peroxide solution, the mass ratio of methyl isobutyl ketone, isopropyl alcohol and N, N-dimethylformamide in the mixed solution used in step ii) was 1:2:1, and the mass concentration of the pretreated vermiculite powder in the mixed solution was 0.4 g/mL.
In this example, the plasticizer used was dioctyl phthalate, the crosslinking agent used was 1, 1-di (t-butylperoxy) cyclohexane, the heat stabilizer used was calcium stearate, the antibacterial agent used was chitin, and the foaming agent used was AC foaming agent.
Example 2:
the mould-proof wear-resistant environment-friendly PVC artificial leather comprises a base cloth layer and a PVC surface layer attached to the base cloth layer, wherein the PVC surface layer is prepared from the following components in parts by weight: 100 parts of PVC resin, 23 parts of functional elastomer, 57 parts of plasticizer, 15 parts of coconut shell powder modified vermiculite powder, 6 parts of cross-linking agent, 2 parts of heat stabilizer, 1 part of antibacterial agent and 1 part of foaming agent.
The functional elastomer used in the embodiment is a graphene oxide modified thermoplastic polyurethane elastomer, and the addition amount of graphene oxide is 7 wt% based on the mass of the thermoplastic polyurethane elastomer, and the specific preparation method comprises the following steps: preparing 4 wt% of graphene oxide aqueous suspension, adding an isocyanate modifier and thermoplastic polyurethane elastomer particles into the graphene oxide aqueous suspension, carrying out ultrasonic reaction for 3 hours at 76 ℃ and 110 KHz, carrying out centrifugal separation, retaining solids, washing, drying, grinding to 95%, and sieving with a 400-mesh sieve to obtain the functional elastomer.
In the process of preparing the functional elastomer, the preparation method of the graphene oxide water suspension comprises the following steps: fully grinding and dispersing graphene oxide and deionized water at the rotating speed of 30000 r/min for 30 min at the temperature of below 10 ℃, and then carrying out ultrasonic oscillation at the temperature of 50 ℃, wherein the frequency of the ultrasonic oscillation is controlled to be 75 kHz, and carrying out ultrasonic oscillation for 25 min to obtain the graphene oxide water suspension.
The adopted thermoplastic polyurethane elastomer is commercially available Hytrel 5556, the adopted isocyanate modifier is diphenylmethane diisocyanate, and the using amount of the isocyanate modifier is 0.8 wt% of the mass of the thermoplastic polyurethane elastomer.
The coconut husk powder modified vermiculite powder used in the example is prepared by the following steps:
step i): centrifugally separating the vermiculite powder soaked in the hydrogen peroxide solution, keeping solids, washing the solids to be neutral by using deionized water, and drying to prepare pretreated vermiculite powder;
step ii): adding coconut shell powder and a silane coupling agent into a mixed solution of methyl isobutyl ketone, isopropanol and N, N-dimethylformamide, adding the dried pretreated vermiculite powder at 89 ℃ while stirring, continuing stirring at a constant temperature for reaction for 2 hours after the addition is finished, filtering, retaining solids, washing, drying, grinding to 90%, and sieving with a 2000-mesh sieve to obtain the coconut shell powder modified vermiculite powder.
In the process of preparing the coconut husk powder modified vermiculite powder, the addition amount of the coconut husk powder is 15wt%, the addition amount of the silane coupling agent is 3 wt%, and the silane coupling agent is gamma-aminopropyltriethoxysilane; the hydrogen peroxide solution used in step i) was a 12wt% hydrogen peroxide solution, the mass ratio of methyl isobutyl ketone, isopropyl alcohol and N, N-dimethylformamide in the mixed solution used in step ii) was 1:3:1, and the mass concentration of the pretreated vermiculite powder in the mixed solution was 0.5 g/mL.
In this example, the plasticizer used was butyl epoxy oleate, the crosslinking agent used was bis (4-methylbenzoyl) peroxide, the heat stabilizer used was calcium castor oil, the antibacterial agent used was castor oil, and the foaming agent used was an AC foaming agent.
Example 3:
the mould-proof wear-resistant environment-friendly PVC artificial leather comprises a base cloth layer and a PVC surface layer attached to the base cloth layer, wherein the PVC surface layer is prepared from the following components in parts by weight: 100 parts of PVC resin, 26 parts of functional elastomer, 60 parts of plasticizer, 18 parts of coconut shell powder modified vermiculite powder, 10 parts of cross-linking agent, 4 parts of heat stabilizer, 2 parts of antibacterial agent and 3 parts of foaming agent.
The functional elastomer used in this embodiment is a graphene oxide-modified thermoplastic polyurethane elastomer, and the amount of the added graphene oxide is 10 wt% based on the mass of the thermoplastic polyurethane elastomer, and the specific preparation method is as follows: preparing 5wt% of graphene oxide aqueous suspension, adding an isocyanate modifier and thermoplastic polyurethane elastomer particles into the graphene oxide aqueous suspension, carrying out ultrasonic reaction for 2 hours at 80 ℃ and 120 KHz, carrying out centrifugal separation, retaining solids, washing, drying, grinding to 95%, and sieving with a 400-mesh sieve to obtain the functional elastomer.
In the process of preparing the functional elastomer, the preparation method of the graphene oxide water suspension comprises the following steps: fully grinding and dispersing graphene oxide and deionized water at the rotating speed of 30000 r/min for 30 min at the temperature of below 10 ℃, and then carrying out ultrasonic oscillation at the temperature of 50 ℃, wherein the frequency of the ultrasonic oscillation is controlled to be 75 kHz, and carrying out ultrasonic oscillation for 25 min to obtain the graphene oxide water suspension.
The adopted thermoplastic polyurethane elastomer is commercially available Hytrel 6356, the adopted isocyanate modifier is dicyclohexylmethane diisocyanate, and the using amount of the isocyanate modifier is 1.2 wt% of the mass of the thermoplastic polyurethane elastomer.
The coconut husk powder modified vermiculite powder used in the example is prepared by the following steps:
step i): centrifugally separating the vermiculite powder soaked in the hydrogen peroxide solution, keeping solids, washing the solids to be neutral by using deionized water, and drying to prepare pretreated vermiculite powder;
step ii): adding coconut shell powder and a silane coupling agent into a mixed solution of methyl isobutyl ketone, isopropanol and N, N-dimethylformamide, adding the dried pretreated vermiculite powder at 95 ℃ while stirring, continuing stirring at a constant temperature for reaction for 1 hour after the addition is finished, filtering, retaining solids, washing, drying, grinding to 90 percent, and sieving with a 2000-mesh sieve to obtain the coconut shell powder modified vermiculite powder.
In the process of preparing the coconut husk powder modified vermiculite powder, the addition amount of the coconut husk powder is 18 wt%, the addition amount of the silane coupling agent is 5wt%, and the silane coupling agent is gamma-aminopropyltriethoxysilane; the hydrogen peroxide solution used in step i) was a 15wt% hydrogen peroxide solution, the mass ratio of methyl isobutyl ketone, isopropyl alcohol and N, N-dimethylformamide in the mixed solution used in step ii) was 1:4:1, and the mass concentration of the pretreated vermiculite powder in the mixed solution was 0.6 g/mL.
In this example, the plasticizer used was a mixture of octyl epoxy oleate and n-butyl phthalate at a mass ratio of 1:1, the crosslinking agent used was di (4-methylbenzoyl) peroxide, the heat stabilizer used was zinc stearate, the antibacterial agent used was horseradish, and the foaming agent used was an AC foaming agent.
Example 4:
the mould-proof wear-resistant environment-friendly PVC artificial leather comprises a base cloth layer and a PVC surface layer attached to the base cloth layer, wherein the PVC surface layer is prepared from the following components in parts by weight: 100 parts of PVC resin, 30 parts of functional elastomer, 70 parts of plasticizer, 20 parts of coconut shell powder modified vermiculite powder, 12 parts of cross-linking agent, 5 parts of heat stabilizer, 3 parts of antibacterial agent and 4 parts of foaming agent.
The functional elastomer used in this embodiment is a graphene oxide-modified thermoplastic polyurethane elastomer, and the amount of the added graphene oxide is 15wt% based on the mass of the thermoplastic polyurethane elastomer, and the specific preparation method is as follows: preparing 5wt% of graphene oxide aqueous suspension, adding an isocyanate modifier and thermoplastic polyurethane elastomer particles into the graphene oxide aqueous suspension, carrying out ultrasonic reaction for 4 hours at 72 ℃ under 100 KHz, carrying out centrifugal separation, keeping solids, washing, drying, grinding to 95%, and sieving with a 400-mesh sieve to obtain the functional elastomer.
In the process of preparing the functional elastomer, the preparation method of the graphene oxide water suspension comprises the following steps: fully grinding and dispersing graphene oxide and deionized water at the rotating speed of 30000 r/min for 30 min at the temperature of below 10 ℃, and then carrying out ultrasonic oscillation at the temperature of 50 ℃, wherein the frequency of the ultrasonic oscillation is controlled to be 75 kHz, and carrying out ultrasonic oscillation for 25 min to obtain the graphene oxide water suspension.
The adopted thermoplastic polyurethane elastomer is commercially available Hytrel 7246, the adopted isocyanate modifier is hexamethylene diisocyanate, and the using amount of the isocyanate modifier is 1.8 wt% of the mass of the thermoplastic polyurethane elastomer.
The coconut husk powder modified vermiculite powder used in the example is prepared by the following steps:
step i): centrifugally separating the vermiculite powder soaked in the hydrogen peroxide solution, keeping solids, washing the solids to be neutral by using deionized water, and drying to prepare pretreated vermiculite powder;
step ii): adding coconut shell powder and a silane coupling agent into a mixed solution of methyl isobutyl ketone, isopropanol and N, N-dimethylformamide, adding the dried pretreated vermiculite powder at 90 ℃ while stirring, continuing stirring at a constant temperature for reaction for 1.5 hours after the addition is finished, filtering, retaining solids, washing, drying, grinding to 90%, and sieving with a 2000-mesh sieve to obtain the coconut shell powder modified vermiculite powder.
In the process of preparing the coconut husk powder modified vermiculite powder, the addition amount of the coconut husk powder is 20 wt%, the addition amount of the silane coupling agent is 4 wt%, and the silane coupling agent is gamma-aminopropyltriethoxysilane; the hydrogen peroxide solution used in step i) was a 15wt% hydrogen peroxide solution, the mass ratio of methyl isobutyl ketone, isopropyl alcohol and N, N-dimethylformamide in the mixed solution used in step ii) was 1:2:1, and the mass concentration of the pretreated vermiculite powder in the mixed solution was 0.8 g/mL.
In this embodiment, the plasticizer used is decyl epoxy oleate, the crosslinking agent used is dibenzoyl peroxide, the heat stabilizer used is lanthanum stearate, the antibacterial agent used is mustard, and the foaming agent used is an AC foaming agent.
Comparative example 1:
the raw material components of the PVC artificial leather of the comparative example do not contain the functional elastomer and the coconut husk powder modified vermiculite powder, and the rest is the same as the example 3.
Comparative example 2:
in the raw material components of the PVC artificial leather for the comparative example, commercial Hytrel 6356 elastomer was used in place of the functional elastomer, and the rest is the same as example 3.
Comparative example 3:
in the raw material components of the PVC artificial leather of the comparative example, commercially available vermiculite powder is used to replace coconut husk powder modified vermiculite powder, and the rest is the same as in example 3.
The above examples 1 to 4 and comparative examples 1 to 3 prepared PVC artificial leather by the following method:
step 1): adding the preparation raw materials of the PVC surface layer into a high-speed stirrer according to parts by weight, and carrying out high-speed mixing and stirring to obtain a mixture;
step 2): transferring the mixture prepared in the step 1) into an internal mixer for mixing, transferring into an open mill for plasticating after mixing is finished, and then conveying to a calender for calendering into a sheet;
step 3): the sheet prepared in the step 2) is attached to the base cloth layer to prepare a semi-finished product, and the semi-finished product is transferred to a foaming embossing machine for foaming embossing treatment to prepare the PVC artificial leather.
The process conditions used in the above preparation methods in the respective examples and comparative examples are shown in table 1 below.
TABLE 1 Process conditions
| Item | High speed stirring temperature | High speed stirring time | Mixing temperature | Plastication temperature | Temperature of foaming embossing |
| Example 1 | 100℃ | 5 min | 120℃ | 130℃ | 180℃ |
| Example 2 | 106℃ | 4 min | 128℃ | 138℃ | 185℃ |
| Example 3 | 108℃ | 4 min | 136℃ | 145℃ | 192℃ |
| Example 4 | 110℃ | 2 min | 140℃ | 150℃ | 200℃ |
| Comparative example 1 | 108℃ | 4 min | 136℃ | 145℃ | 192℃ |
| Comparative example 2 | 108℃ | 4 min | 136℃ | 145℃ | 192℃ |
| Comparative example 3 | 108℃ | 4 min | 136℃ | 145℃ | 192℃ |
And (3) performance testing:
the artificial leathers obtained in the above examples and comparative examples were subjected to abrasion resistance and dry-wet rub resistance tests in the following specific methods.
And (3) testing the abrasion resistance: cutting the prepared artificial leather into a circle with the diameter of 12cm as a sample; and (3) placing the sample on a Martindale wear-resistant tester to test the wear resistance. The conditions of the test were: load 1kg, rotate 50 turns. The samples were observed for fuzzing, flaking, slushing and cracking of the coating.
Dry and wet rub resistance test: placing the prepared artificial leather as a sample in a constant temperature and humidity box with the temperature of 20 ℃ and the humidity of 65% for 48 hours; taking out the sample and placing the sample in a leather color fastness instrument; fixing the lining cloth on a leather color fastness instrument, and wiping the sample by the lining cloth; after wiping, the wiped samples were compared using a standard gray sample card to determine the dry-wet rub rating.
Wherein, the experimental operation process of dry wiping and wet wiping is the same, and the conditions of the dry wiping test are as follows: the lining cloth is dry and white, and the wiping times are set to be 25 times; and wet wiping conditions: the lining cloth is wet and white, the water content is 70-75%, and the wiping times are set to be 20 times.
The results of the above abrasion resistance and dry and wet rub resistance tests are shown in table 2 below.
TABLE 2 test results
| Item | Phenomenon of wear | Dry rub resistance rating | Wet rub resistance rating |
| Example 1 | No fluffing, shelling, pulp dropping and breaking through phenomena | 5 | 5 |
| Example 2 | No fluffing, shelling, pulp dropping and breaking through phenomena | 5 | 5 |
| Example 3 | No fluffing, shelling, pulp dropping and breaking through phenomena | 5 | 5 |
| Example 4 | No fluffing, shelling, pulp dropping and breaking through phenomena | 5 | 5 |
| Comparative example 1 | The fluffing phenomenon is serious, the shelling occurs at a plurality of positions, and the pulp falling is serious | 3 | 3 |
| Comparative example 2 | Has slight fluffing phenomenon, and has no peeling, pulp falling and piercing | 4 | 4-5 |
| Comparative example 3 | Has slight fluffing phenomenon, small point pulp falling in a scattered way, no peeling and no broken penetration | 3-4 | 4 |
The artificial leathers prepared in the above examples and comparative examples were tested for odor grade with reference to VDA270, and the grade evaluation: 1, no odor; 2 smells but does not interfere; 3 has a clear odor, but still no interference; 4 has an interfering odor; 5 strong interfering odor; 6 has an intolerable odour. The test results are shown in Table 3 below.
TABLE 3 test results
| Item | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Odor grade (40 ℃, 24 h) | 1 | 1 | 1 | 1 | 3 | 1 | 2 |
Although the present invention has been described in detail, modifications within the spirit and scope of the invention will be apparent to those skilled in the art. Furthermore, it should be understood that the various aspects recited, portions of different embodiments, and various features recited may be combined or interchanged either in whole or in part. In the various embodiments described above, those embodiments that refer to another embodiment may be combined with other embodiments as appropriate, as will be appreciated by those skilled in the art. Furthermore, those skilled in the art will appreciate that the foregoing description is by way of example only, and is not intended to limit the invention.
Claims (10)
1. The utility model provides a mould proof wear-resisting environmental protection PVC synthetic leather, including the base cloth layer and with the PVC surface course that the base cloth layer was laminated mutually, its characterized in that, the PVC surface course is prepared by the raw materials that contain following component and part by weight content: 100 parts of PVC resin, 20-30 parts of functional elastomer, 50-70 parts of plasticizer, 12-20 parts of coconut shell powder modified vermiculite powder, 4-12 parts of cross-linking agent, 1-5 parts of heat stabilizer, 1-3 parts of antibacterial agent and 0.2-4 parts of foaming agent.
2. The mould-proof wear-resistant environment-friendly PVC artificial leather according to claim 1, wherein the functional elastomer is a graphene oxide modified thermoplastic polyurethane elastomer, and the addition amount of the graphene oxide is 5-15wt% based on the mass of the thermoplastic polyurethane elastomer.
3. The mould-proof wear-resistant environment-friendly PVC artificial leather according to claim 2, wherein the preparation method of the functional elastomer comprises the following steps: preparing 2-5 wt% of graphene oxide aqueous suspension, adding an isocyanate modifier and thermoplastic polyurethane elastomer particles into the graphene oxide aqueous suspension, carrying out ultrasonic reaction for 2-4 h at 65-80 ℃ under 100-120 KHz, carrying out centrifugal separation, retaining solids, washing, drying, grinding until 95% of the solid particles pass through a 400-mesh sieve, and thus obtaining the functional elastomer.
4. The mildewproof, wear-resistant and environment-friendly PVC artificial leather according to claim 3, wherein the isocyanate modifier is added in an amount of 0.4 to 1.8 wt% based on the mass of the thermoplastic polyurethane elastomer, and is selected from any one of hexamethylene diisocyanate, diphenylmethane diisocyanate or dicyclohexylmethane diisocyanate.
5. The mould-proof wear-resistant environment-friendly PVC artificial leather according to claim 1, wherein the preparation method of the coconut shell powder modified vermiculite powder is as follows:
step i): centrifugally separating the vermiculite powder soaked in the hydrogen peroxide solution, keeping solids, washing the solids to be neutral by using deionized water, and drying to prepare pretreated vermiculite powder;
step ii): adding coconut shell powder and a silane coupling agent into a mixed solution of methyl isobutyl ketone, isopropanol and N, N-dimethylformamide, adding the dried pretreated vermiculite powder at 80-95 ℃ while stirring, continuing to stir at a constant temperature for reaction for 1-2 hours after the addition is finished, filtering, retaining solids, washing, drying, grinding to 90%, and sieving with a 2000-mesh sieve to obtain the coconut shell powder modified vermiculite powder.
6. The mould-proof wear-resistant environment-friendly PVC artificial leather according to claim 5, wherein the addition amount of the coconut shell powder is 10-20% of the mass of the pretreated vermiculite powder, the addition amount of the silane coupling agent is 1-5% of the mass of the pretreated vermiculite powder, and the silane coupling agent is any one of gamma- (2, 3-epoxypropoxy) propyl trimethoxysilane or gamma-aminopropyltriethoxysilane.
7. The mould-proof wear-resistant environment-friendly PVC artificial leather according to claim 5, wherein the mass ratio of methyl isobutyl ketone, isopropanol and N, N-dimethylformamide in the mixed solution is 1:2-4:1, and the mass concentration of the pretreated vermiculite powder in the mixed solution is 0.4-0.8 g/mL.
8. The PVC artificial leather with characteristics of mold resistance, wear resistance and environmental protection as claimed in claim 1, wherein the plasticizer is at least one selected from aliphatic dibasic acid ester plasticizers or epoxy vegetable oil plasticizers, the cross-linking agent is at least one selected from 1, 1-di (t-butylperoxy) cyclohexane, di (4-methylbenzoyl) peroxide or dibenzoyl peroxide, the heat stabilizer is at least one selected from calcium stearate, calcium ricinoleate, zinc stearate, barium stearate or lanthanum stearate, the antibacterial agent is any one selected from chitin, mustard, castor oil or horseradish, and the foaming agent is an AC foaming agent.
9. The method for preparing mildewproof, wear-resistant and environment-friendly PVC artificial leather according to any one of claims 1 to 8, which comprises the following steps:
step 1): adding the preparation raw materials of the PVC surface layer into a high-speed stirrer according to parts by weight, and carrying out high-speed mixing and stirring to obtain a mixture;
step 2): transferring the mixture prepared in the step 1) into an internal mixer for mixing, transferring into an open mill for plasticating after mixing is finished, and then conveying to a calender for calendering into a sheet;
step 3): and (3) attaching the sheet prepared in the step 2) to a base fabric layer to prepare a semi-finished product, and transferring the semi-finished product to a foaming embossing machine for foaming embossing treatment to prepare the PVC artificial leather.
10. The method for preparing the mildewproof, wear-resistant and environment-friendly PVC artificial leather according to the claim 9, wherein in the step 1), the high-speed mixing and stirring are carried out at the stirring temperature of 100 ℃ and 110 ℃ for 2-5 min; the mixing temperature in the step 2) is 120-140 ℃, and the plastication is performed by sequentially passing through two open mills and performing plastication at the temperature of 130-150 ℃; the temperature of the foaming embossing treatment in the step 3) is 180-200 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110076074.3A CN112721364A (en) | 2021-01-20 | 2021-01-20 | Mildew-proof wear-resistant environment-friendly PVC artificial leather and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110076074.3A CN112721364A (en) | 2021-01-20 | 2021-01-20 | Mildew-proof wear-resistant environment-friendly PVC artificial leather and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112721364A true CN112721364A (en) | 2021-04-30 |
Family
ID=75593828
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110076074.3A Pending CN112721364A (en) | 2021-01-20 | 2021-01-20 | Mildew-proof wear-resistant environment-friendly PVC artificial leather and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112721364A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113308065A (en) * | 2021-06-08 | 2021-08-27 | 江阴嘉思特车业有限公司 | Bicycle saddle |
| CN118087284A (en) * | 2024-04-15 | 2024-05-28 | 英德市宏利皮革有限公司 | Scratch-resistant artificial leather and preparation method thereof |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103820787A (en) * | 2014-02-20 | 2014-05-28 | 铜陵祥云消防科技有限责任公司 | Antirust agent containing modified vermiculite powder |
| CN105238323A (en) * | 2015-09-25 | 2016-01-13 | 安徽大松树脂有限公司 | High peel strength adhesive for shoes |
| CN107100013A (en) * | 2017-05-12 | 2017-08-29 | 佛山高明骏宏塑胶有限公司 | A kind of mould proof PVC artificial leather and preparation method thereof |
| CN207331343U (en) * | 2017-06-15 | 2018-05-08 | 江门市大丰皮革有限公司 | A kind of mould proof PVC artificial leather |
| CN108892887A (en) * | 2018-05-25 | 2018-11-27 | 中山圣洛迪新材料有限公司 | Outdoor wood-plastic floor and manufacturing method thereof |
| CN108998988A (en) * | 2018-06-22 | 2018-12-14 | 安徽索亚装饰材料有限公司 | A kind of degradable PVC decorative artificial leather of Environment-friendlywear-resistant wear-resistant |
| CN108997736A (en) * | 2018-05-21 | 2018-12-14 | 南京宜凯瑞新材料有限公司 | A kind of environmentally-friendly flame retardant thermoplastic polyurethane elastomer |
| CN109281188A (en) * | 2018-11-12 | 2019-01-29 | 南通薇星纺织科技有限公司 | The efficiently PVC artificial leather and preparation method thereof of release anion |
| CN111455684A (en) * | 2020-04-14 | 2020-07-28 | 昆山阿基里斯新材料科技有限公司 | High-durability antibacterial mildew-proof polyvinyl chloride artificial leather and preparation method thereof |
| CN111501368A (en) * | 2020-04-14 | 2020-08-07 | 昆山阿基里斯新材料科技有限公司 | Antibacterial and antiviral polyvinyl chloride artificial leather and preparation method thereof |
| CN111764179A (en) * | 2020-06-01 | 2020-10-13 | 广西鑫深科技有限公司 | Environment-friendly antibacterial artificial leather |
| CN111926583A (en) * | 2020-09-08 | 2020-11-13 | 清远市腾翔皮革有限公司 | Environment-friendly PVC artificial leather and preparation method thereof |
| CN111943198A (en) * | 2020-08-18 | 2020-11-17 | 湖州民强炭业有限公司 | Preparation method of coconut shell carbon molecular sieve with high specific surface area |
| CN112851188A (en) * | 2021-02-24 | 2021-05-28 | 中国路桥工程有限责任公司 | Prestressed duct grouting agent and preparation method thereof |
-
2021
- 2021-01-20 CN CN202110076074.3A patent/CN112721364A/en active Pending
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103820787A (en) * | 2014-02-20 | 2014-05-28 | 铜陵祥云消防科技有限责任公司 | Antirust agent containing modified vermiculite powder |
| CN105238323A (en) * | 2015-09-25 | 2016-01-13 | 安徽大松树脂有限公司 | High peel strength adhesive for shoes |
| CN107100013A (en) * | 2017-05-12 | 2017-08-29 | 佛山高明骏宏塑胶有限公司 | A kind of mould proof PVC artificial leather and preparation method thereof |
| CN207331343U (en) * | 2017-06-15 | 2018-05-08 | 江门市大丰皮革有限公司 | A kind of mould proof PVC artificial leather |
| CN108997736A (en) * | 2018-05-21 | 2018-12-14 | 南京宜凯瑞新材料有限公司 | A kind of environmentally-friendly flame retardant thermoplastic polyurethane elastomer |
| CN108892887A (en) * | 2018-05-25 | 2018-11-27 | 中山圣洛迪新材料有限公司 | Outdoor wood-plastic floor and manufacturing method thereof |
| CN108998988A (en) * | 2018-06-22 | 2018-12-14 | 安徽索亚装饰材料有限公司 | A kind of degradable PVC decorative artificial leather of Environment-friendlywear-resistant wear-resistant |
| CN109281188A (en) * | 2018-11-12 | 2019-01-29 | 南通薇星纺织科技有限公司 | The efficiently PVC artificial leather and preparation method thereof of release anion |
| CN111455684A (en) * | 2020-04-14 | 2020-07-28 | 昆山阿基里斯新材料科技有限公司 | High-durability antibacterial mildew-proof polyvinyl chloride artificial leather and preparation method thereof |
| CN111501368A (en) * | 2020-04-14 | 2020-08-07 | 昆山阿基里斯新材料科技有限公司 | Antibacterial and antiviral polyvinyl chloride artificial leather and preparation method thereof |
| CN111764179A (en) * | 2020-06-01 | 2020-10-13 | 广西鑫深科技有限公司 | Environment-friendly antibacterial artificial leather |
| CN111943198A (en) * | 2020-08-18 | 2020-11-17 | 湖州民强炭业有限公司 | Preparation method of coconut shell carbon molecular sieve with high specific surface area |
| CN111926583A (en) * | 2020-09-08 | 2020-11-13 | 清远市腾翔皮革有限公司 | Environment-friendly PVC artificial leather and preparation method thereof |
| CN112851188A (en) * | 2021-02-24 | 2021-05-28 | 中国路桥工程有限责任公司 | Prestressed duct grouting agent and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 田维亮;葛振红;穆金城;陈明鸽;李秀敏;王秋玉;曹婉婧;: "天然蛭石PVC热稳定剂的制备和性能研究", 现代化工 * |
| 阮林光;李志君;郑辉林;赵红磊;: "椰壳粉/PVC复合材料的结构及动态力学性能研究", 塑料科技 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113308065A (en) * | 2021-06-08 | 2021-08-27 | 江阴嘉思特车业有限公司 | Bicycle saddle |
| CN118087284A (en) * | 2024-04-15 | 2024-05-28 | 英德市宏利皮革有限公司 | Scratch-resistant artificial leather and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE102008041987A1 (en) | Solvent-free polyurethane-based artificial leather with the structure of human skin and method for producing the same | |
| CN112721364A (en) | Mildew-proof wear-resistant environment-friendly PVC artificial leather and preparation method thereof | |
| CN103015185B (en) | Wear-resistant superfine fiber napped leather and preparation method thereof | |
| CN102965964B (en) | Manufacturing method of artificial super-soft abrasion-proof polyurethane shoe lining leather | |
| CN112873892A (en) | Stain-resistant antibacterial environment-friendly PVC artificial leather and preparation method thereof | |
| CN112900109B (en) | High-performance environment-friendly PVC artificial leather and preparation method thereof | |
| CN114456447B (en) | Preparation method and application of never-drying children color mud | |
| CN113338051A (en) | Preparation method of solvent-free waterborne polyurethane microfiber synthetic leather with high R value | |
| CN104018359A (en) | Surface self-extinction artificial leather material | |
| CN112680085A (en) | High-gloss scratch-resistant surface-enhanced artificial leather and preparation method thereof | |
| CN110684173B (en) | Super-soft hydrolysis-resistant wet polyurethane resin and preparation method thereof | |
| CN1957787A (en) | Artificial flowers, and preparation method | |
| CN116442619A (en) | Mildew-proof wear-resistant PVC (polyvinyl chloride) artificial leather and preparation method thereof | |
| CN105986489A (en) | Soft wear-resistant superfine polyurethane imitation-leather automobile seat fabric and production method thereof | |
| CN110725136A (en) | Processing method of environment-friendly superfine fiber synthetic leather for automotive interior | |
| CN111441176B (en) | Technological method for manufacturing waterborne polyurethane suede synthetic leather | |
| CN103757926A (en) | Surface treating agent applied to luggage leather and preparation method thereof | |
| CN111286564B (en) | Real leather for leather bags and finishing method thereof | |
| CN108867079B (en) | Manufacturing method of high-simulation slow-rebound superfine fiber synthetic leather | |
| CN113402691A (en) | Modified waterborne polyurethane and preparation method and application thereof | |
| CN114085351A (en) | Composition for preparing waterborne polyurethane, preparation method and application of waterborne polyurethane, and method for preparing microfiber leather | |
| CN112280316A (en) | Environment-friendly resin composite material for textiles | |
| CN105986487A (en) | Anti-ultravilet-aging superfine fiber polyurethane artificial automobile leather and making method thereof | |
| CN117820842B (en) | Environment-friendly sponge, preparation method thereof and application thereof in insoles | |
| CN117867859A (en) | Optically-variable bicolor suede microfiber leather and preparation method thereof |
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: 20210430 |