CN111549540A - Method for manufacturing one-way solvent-free polyurethane resin artificial leather - Google Patents
Method for manufacturing one-way solvent-free polyurethane resin artificial leather Download PDFInfo
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- CN111549540A CN111549540A CN202010447467.6A CN202010447467A CN111549540A CN 111549540 A CN111549540 A CN 111549540A CN 202010447467 A CN202010447467 A CN 202010447467A CN 111549540 A CN111549540 A CN 111549540A
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- CN
- China
- Prior art keywords
- solvent
- free polyurethane
- polyurethane resin
- layer
- artificial leather
- 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
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- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 45
- 239000002649 leather substitute Substances 0.000 title claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 11
- 239000010410 layer Substances 0.000 claims abstract description 74
- 239000000758 substrate Substances 0.000 claims abstract description 27
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims abstract description 25
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims abstract description 25
- 239000008108 microcrystalline cellulose Substances 0.000 claims abstract description 25
- 229940016286 microcrystalline cellulose Drugs 0.000 claims abstract description 25
- 239000002344 surface layer Substances 0.000 claims abstract description 25
- 239000004814 polyurethane Substances 0.000 claims abstract description 23
- 229920002635 polyurethane Polymers 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 17
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 16
- 229920000570 polyether Polymers 0.000 claims abstract description 16
- 229920005862 polyol Polymers 0.000 claims abstract description 16
- 150000003077 polyols Chemical class 0.000 claims abstract description 16
- 239000002002 slurry Substances 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 238000005096 rolling process Methods 0.000 claims abstract description 8
- -1 cyclic isocyanate Chemical class 0.000 claims abstract description 7
- 239000012948 isocyanate Substances 0.000 claims abstract description 6
- 239000007822 coupling agent Substances 0.000 claims abstract description 5
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 7
- MOZWTGNQELYNHO-UHFFFAOYSA-N 5-isocyano-1-(isocyanomethyl)-1,3,3-trimethylcyclohexane Chemical compound CC1(C)CC([N+]#[C-])CC(C)(C[N+]#[C-])C1 MOZWTGNQELYNHO-UHFFFAOYSA-N 0.000 claims description 6
- 239000008096 xylene Substances 0.000 claims description 6
- LBAWETVNIZSRJM-UHFFFAOYSA-N N-[[dimethoxy(propan-2-yl)silyl]oxymethyl]ethanamine Chemical compound C(C)NCO[Si](OC)(OC)C(C)C LBAWETVNIZSRJM-UHFFFAOYSA-N 0.000 claims description 5
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 claims description 4
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- VZDIRINETBAVAV-UHFFFAOYSA-N 2,4-diisocyanato-1-methylcyclohexane Chemical compound CC1CCC(N=C=O)CC1N=C=O VZDIRINETBAVAV-UHFFFAOYSA-N 0.000 claims description 2
- LVACOMKKELLCHJ-UHFFFAOYSA-N 3-trimethoxysilylpropylurea Chemical compound CO[Si](OC)(OC)CCCNC(N)=O LVACOMKKELLCHJ-UHFFFAOYSA-N 0.000 claims description 2
- IIGAAOXXRKTFAM-UHFFFAOYSA-N N=C=O.N=C=O.CC1=C(C)C(C)=C(C)C(C)=C1C Chemical compound N=C=O.N=C=O.CC1=C(C)C(C)=C(C)C(C)=C1C IIGAAOXXRKTFAM-UHFFFAOYSA-N 0.000 claims description 2
- 239000010985 leather Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 239000004744 fabric Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 229920001046 Nanocellulose Polymers 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 238000005187 foaming Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000004753 textile Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 235000010980 cellulose Nutrition 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229920001410 Microfiber Polymers 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 235000019687 Lamb Nutrition 0.000 description 1
- 241001629511 Litchi Species 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- MAVBUZJIOYZMRX-UHFFFAOYSA-N aniline;trimethoxy(propyl)silane Chemical compound NC1=CC=CC=C1.CCC[Si](OC)(OC)OC MAVBUZJIOYZMRX-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006264 polyurethane film Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
- D06N3/145—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes two or more layers of polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4829—Polyethers containing at least three hydroxy groups
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
- D06N3/0061—Organic fillers or organic fibrous fillers, e.g. ground leather waste, wood bark, cork powder, vegetable flour; Other organic compounding ingredients; Post-treatment with organic compounds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
- D06N3/0095—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by inversion technique; by transfer processes
- D06N3/0097—Release surface, e.g. separation sheets; Silicone papers
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
- D06N3/146—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the macromolecular diols used
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
- D06N3/147—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the isocyanates used
- D06N3/148—(cyclo)aliphatic polyisocyanates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/10—Properties of the materials having mechanical properties
- D06N2209/103—Resistant to mechanical forces, e.g. shock, impact, puncture, flexion, shear, compression, tear
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/16—Properties of the materials having other properties
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/16—Properties of the materials having other properties
- D06N2209/1607—Degradability
- D06N2209/1621—Water-soluble, water-dispersible
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/16—Properties of the materials having other properties
- D06N2209/1642—Hardnes
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2211/00—Specially adapted uses
- D06N2211/12—Decorative or sun protection articles
- D06N2211/28—Artificial leather
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Textile Engineering (AREA)
- Dispersion Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Abstract
The invention discloses a method for manufacturing one-way solvent-free polyurethane resin artificial leather, which comprises a surface layer, a substrate layer and a solvent-free polyurethane layer coated between the surface layer and the substrate layer, and comprises the following steps: s1, mixing the unidirectional solvent-free polyurethane resin and the leveling agent, and heating to a molten state to obtain slurry; s2, coating the slurry prepared in the step S1 on a release layer, drying and curing to obtain a surface layer coated with a solvent-free polyurethane layer; s3, rolling and adhering the substrate layer on the surface of the surface layer coated with the solvent-free polyurethane layer, and drying and curing the surface layer to obtain the artificial leather; the unidirectional solvent-free polyurethane resin comprises the following raw materials in parts by weight based on the total weight of the polyurethane resin: 25-30 parts of polyether polyol, 58-65 parts of cyclic isocyanate, 5-8 parts of modified nano microcrystalline cellulose and 2-6 parts of aminosilane coupling agent. The manufacturing method is simple, low in cost and suitable for large-scale popularization.
Description
Technical Field
The invention relates to the technical field of artificial leather, in particular to a method for manufacturing one-way solvent-free polyurethane resin artificial leather.
Background
With the development of industrial technology, the manufacturing technology of artificial leather has been advanced, and polyurethane is used as a raw material, and different substrate layers (plain cloth, double-sided/four-sided stretch cloth, non-woven microfiber cloth, etc.) and appropriate processing methods are used to manufacture artificial leather with different characteristics and surface patterns, so that the artificial leather has the advantages of multiple functions and diversification compared with natural leather.
In the conventional artificial leather, solvent-based Polyurethane (PU) with a solid content of 40 to 60% is usually used as a main raw material of the leather surface of the artificial leather, and in the leather manufacturing process, in addition to an organic solvent (such as Dimethylformamide (DMF), dimethylacetamide (DMAc) or Methyl Ethyl Ketone (MEK)) contained in the Polyurethane resin itself, other solvents are usually used to adjust the viscosity of the Polyurethane resin so that the Polyurethane resin can be easily coated on a matrix layer, and finally, before the manufacturing process is finished, the solvent is removed by a drying method or a water bath replacement method to form the Polyurethane resin leather surface with a solidified phase.
However, the method for manufacturing artificial leather in the prior art is rather complicated and time-consuming, and is not economical, and the organic solvent involved in the manufacturing process and the organic solvent remained in the final product are not good for human health and environment, and do not meet the requirements of the current green chemical process and materials.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provides a method for manufacturing one-way solvent-free polyurethane resin artificial leather.
A manufacturing method of one-way solvent-free polyurethane resin artificial leather comprises a surface layer, a substrate layer and a solvent-free polyurethane layer coated between the surface layer and the substrate layer, and the method comprises the following steps:
s1, mixing the unidirectional solvent-free polyurethane resin and the leveling agent, and heating to a molten state to obtain slurry;
s2, coating the slurry prepared in the step S1 on a release layer, drying and curing to obtain a surface layer coated with a solvent-free polyurethane layer;
s3, rolling and adhering the substrate layer on the surface of the surface layer coated with the solvent-free polyurethane layer, and drying and curing the surface layer to obtain the artificial leather;
the unidirectional solvent-free polyurethane resin comprises the following raw materials in parts by weight based on the total weight of the polyurethane resin: 25-30 parts of polyether polyol, 58-65 parts of cyclic isocyanate, 5-8 parts of modified nano microcrystalline cellulose and 2-6 parts of aminosilane coupling agent.
Further, the polyether polyol is one or a combination of more than two of the polyether polyol with the functionality of more than 4 and the number average molecular weight of 2000-6000 g/mol.
Further, the cyclic isocyanate is one or a combination of two or more of 4, 4-dicyclohexylmethane diisocyanate, 1, 4-cyclohexane diisocyanate, 1-methyl-2, 4-diisocyanatocyclohexane, 1-isocyanomethyl-3-isocyano-1, 5, 5-trimethylcyclohexane, xylene diisocyanate and tetramethyl xylene diisocyanate.
Furthermore, the aminosilane coupling agent is one or the combination of more than two of N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane, N-ethylaminoisopropyl trimethoxysilane, anilinopropyltrimethoxysilane and gamma-ureidopropyl trimethoxysilane.
Further, the preparation method of the modified nano microcrystalline cellulose comprises the following steps: adding nano microcrystalline cellulose into an ethanol solution containing sodium hydroxide, keeping the reaction at 20-25 ℃ for 0.5-1 h to prepare alkalized nano microcrystalline cellulose, then adding isopropanol into a reaction system, heating to 70-80 ℃, continuing the reaction for 5-10 min, cooling, filtering and washing to prepare the modified nano microcrystalline cellulose, wherein the mass percent ratio of the sodium hydroxide, the isopropanol, the nano microcrystalline cellulose and the ethanol is 10-18: 3-5: 6-9: 100.
Furthermore, the diameter of the nano microcrystalline cellulose is 15-45 nm, and the length of the nano microcrystalline cellulose is 0.8-2 mu m.
Further, the mass of the unidirectional solvent-free polyurethane resin coated on the release layer is 20-100g/m2。
Compared with the prior art, the invention has the following beneficial effects:
(1) the polyether polyol with the functionality of more than 4 is selected, and the polyether polyol with the functionality of more than 4 is high-activity polyether polyol, has strong lipophilicity and self activity, can react with cyclic isocyanate under the condition of no catalyst, can react with water vapor in preference to water vapor due to lipophilicity, has advantages in competition with water due to high activity, can effectively inhibit foaming rate and water resistance, and controls the foaming rate and hydrolysis resistance within a certain range, so that the finally obtained artificial leather has good soft touch, softness and hydrolysis resistance;
(2) nanocrystalline cellulose is a rod-like cellulose crystal, with a diameter of less than 100nm, which is the smallest physical structural unit of cellulose. Nanocrystalline cellulose is a highly crystalline cellulose structure that is often used as a filler in composite materials to enhance the mechanical properties of the material. In the invention, the nano microcrystalline cellulose is modified and then added into the polyurethane resin, so that the mechanical property of the unidirectional solvent-free polyurethane resin can be greatly improved.
(3) The artificial leather manufactured by the invention has excellent performance in all aspects, simple manufacturing method and low cost, and is suitable for large-scale popularization.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples.
The term "substrate layer" as used herein can be any layer that forms an adhesive bond with the polyurethane of the present invention, such as a fabric substrate layer, a batt substrate layer, a fiber substrate layer, a foil substrate layer, a leather layer (preferably split leather), a textile layer, a shoe substrate layer, or a luggage substrate layer. The textile substrate layer may consist of one or more identical or different sub-layers which are closely interconnected to one another, for example of a small-or large-pore woven, knitted, braided or meshed fabric, for example: elastic cloth, knitted cloth, plain cloth, microfiber cloth, water repellent cloth, etc. The batt-based layer is a sheet-like structure of randomly placed fibers (examples are felts and webs), preferably bonded together by an adhesive. The batt substrate layer is typically a cellulosic batt or a textile batt reinforced with a non-water soluble impregnant. The fibrous matrix layer is a fabricated object of plastic reinforced loose randomly placed fibers used as a binder, obtained, for example, by adhering together leather fibers (preferably obtainable from leather waste such as from vegetable tanned leather) and the binder. The textile layer may be manufactured from the following materials: cotton, linen, polyester, polyamide and/or polyurethane.
In the invention, the unidirectional type unidirectional solvent-free polyurethane resin can contact the substrate layer in a release transfer mode. The release-transfer method is to coat the molten polyurethane resin on the release layer before the contact step, and then to contact the substrate layer. Suitable release layers include, but are not limited to, metallic release layers or paper release layers, such as: the metal foil, the PET release layer, the RCPP release layer or the paper release layer and the like, and the release layer can be recycled for 10 to 20 times according to needs. The release layer is not limited to bright surface, matte surface, litchi pattern, lamb skin pattern or other patterns.
Example 1
Mixing the unidirectional solvent-free polyurethane resin and the flatting agent, and heating to a molten state to obtain slurry; coating the slurry prepared in the step S1 on a release layer, drying and curing to obtain a surface layer coated with a solvent-free polyurethane layer, rolling and attaching a substrate layer on the surface of the surface layer coated with the solvent-free polyurethane layer, and drying and curing to obtain the artificial leather; the unidirectional solvent-free polyurethane resin is prepared from the following raw materials in parts by weight: 25 parts of polyether polyol with the functionality of 4 and the number average molecular weight of 4000, 65 parts of a mixture consisting of 4, 4-dicyclohexylmethane diisocyanate and 1, 4-cyclohexane diisocyanate in a mass ratio of 3:1, 5 parts of modified nano microcrystalline cellulose and 5 parts of N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane, wherein the preparation method comprises the following steps: mixing a mixture consisting of polyether polyol, 4-dicyclohexylmethane diisocyanate and 1, 4-cyclohexane diisocyanate, N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane and modified nano microcrystalline cellulose, stirring and heating to 65 ℃, keeping for 3.0h, and cooling to obtain the unidirectional solvent-free polyurethane resin;
the preparation method of the modified nano microcrystalline cellulose comprises the following steps: adding nano microcrystalline cellulose with the diameter of 35nm and the length of 1 mu m into ethanol solution containing sodium hydroxide, keeping the reaction at 25 ℃ for 1h to prepare alkalized nano microcrystalline cellulose, then adding isopropanol into the reaction system, heating to 80 ℃, continuing the reaction for 10min, cooling, filtering and washing to prepare the modified nano microcrystalline cellulose, wherein the mass percent ratio of the sodium hydroxide, the isopropanol, the nano microcrystalline cellulose and the ethanol is 15: 5: 9:100.
Example 2
Mixing the unidirectional solvent-free polyurethane resin and the flatting agent, and heating to a molten state to obtain slurry; coating the slurry prepared in the step S1 on a release layer, drying and curing to obtain a surface layer coated with a solvent-free polyurethane layer, rolling and attaching a substrate layer on the surface of the surface layer coated with the solvent-free polyurethane layer, and drying and curing to obtain the artificial leather; the unidirectional solvent-free polyurethane resin is prepared from the following raw materials in parts by weight: 30 parts of polyether polyol with the functionality of 5 and the number average molecular weight of 2000, 58 parts of mixture of 1-methyl-2, 4-diisocyanate cyclohexane, 1-isocyanomethyl-3-isocyano-1, 5, 5-trimethylcyclohexane and xylene diisocyanate, 8 parts of modified nanocrystalline cellulose (same as in example 1), and 4 parts of mixture of N-ethylaminoisopropyl trimethoxy silane, phenylaminopropyl trimethoxy silane and gamma-urea propyl trimethoxy silane, and the preparation method is the same as in example 1.
Example 3
Mixing the unidirectional solvent-free polyurethane resin and the flatting agent, and heating to a molten state to obtain slurry; coating the slurry prepared in the step S1 on a release layer, drying and curing to obtain a surface layer coated with a solvent-free polyurethane layer, rolling and attaching a substrate layer on the surface of the surface layer coated with the solvent-free polyurethane layer, and drying and curing to obtain the artificial leather; the unidirectional solvent-free polyurethane resin is prepared from the following raw materials in parts by weight: 26 parts of polyether polyol with the functionality of 4 and the number average molecular weight of 6000, 62 parts of a mixture of 1-isocyanomethyl-3-isocyano-1, 5, 5-trimethylcyclohexane and xylene diisocyanate, 8 parts of modified nanocrystalline cellulose (same as in example 1) and 4 parts of a mixture of aniline propyl trimethoxy silane and gamma-urea propyl trimethoxy silane, and the preparation method is the same as in example 1.
Example 4
Mixing the unidirectional solvent-free polyurethane resin and the flatting agent, and heating to a molten state to obtain slurry; coating the slurry prepared in the step S1 on a release layer, drying and curing to obtain a surface layer coated with a solvent-free polyurethane layer, rolling and attaching a substrate layer on the surface of the surface layer coated with the solvent-free polyurethane layer, and drying and curing to obtain the artificial leather; the unidirectional solvent-free polyurethane resin is prepared from the following raw materials in parts by weight: 25 parts of polyether polyol with the functionality of 4 and the number average molecular weight of 3000, 65 parts of a mixture consisting of 1-isocyanomethyl-3-isocyano-1, 5, 5-trimethylcyclohexane, xylene diisocyanate and tetramethylxylene diisocyanate, 8 parts of modified nanocrystalline cellulose (same as in example 1) and 2 parts of a mixture consisting of N-ethylaminoisopropyltrimethoxysilane and anilinopropyltrimethoxysilane, which are prepared by the same method as in example 1.
Example 5
Mixing the unidirectional solvent-free polyurethane resin and the flatting agent, and heating to a molten state to obtain slurry; coating the slurry prepared in the step S1 on a release layer, drying and curing to obtain a surface layer coated with a solvent-free polyurethane layer, rolling and attaching a substrate layer on the surface of the surface layer coated with the solvent-free polyurethane layer, and drying and curing to obtain the artificial leather; the unidirectional solvent-free polyurethane resin is prepared from the following raw materials in parts by weight: 28 parts of polyether polyol with the functionality of 6 and the number average molecular weight of 5000, 60 parts of a mixture consisting of 4, 4-dicyclohexylmethane diisocyanate and 1-isocyanomethyl-3-isocyano-1, 5, 5-trimethylcyclohexane, 6 parts of modified nanocrystalline cellulose (same as in example 1) and 6 parts of N-ethylaminoisopropyltrimethoxysilane, and the preparation method is the same as in example 1.
Performance detection
1. Detection of one-way type solvent-free polyurethane resin
And (3) viscosity measurement: after the polyurethane resin obtained in the above examples 1-5 was hot-melted in an oven at a constant temperature of 100 ℃, the viscosity value was measured by a rotary viscometer.
Determination of the isocyanate group content (NCO%): dissolving the di-n-butylamine in ethyl acetate, reacting with isocyanate groups (-NCO) in the sample, titrating the excessive di-n-butylamine by using hydrochloric acid standard solution, and measuring the content of the isocyanate groups in the sample, wherein the unit is weight percent.
And (3) measuring mechanical properties: coating a resin on a release layer to obtain a polyurethane film with a thickness of 0.02mm, cutting and inspecting according to ASTM D412, setting a tensile rate of 10mm/min by a tensile tester, and comparing the modulus of 100% deformation in Kg/cm2)。
Hydrolysis resistance test: the measurement is carried out according to the standard of ASTM D3690-02, the film sample is placed in a constant temperature and humidity box, the set conditions are 70 ℃ and RH 95%, and after 5 weeks, the film sample is taken out and dried, and the modulus retention rate of 100% deformation of the film sample is tested to be more than 80%, preferably the standard.
2. Detection of artificial leather characteristics
Hand feeling determination: according to CNS12915 cut pieces and detection, the artificial leather sample is cut into strips with a width of 3cm and a length of 20cm, and the strips are placed on a platform for vertical stop detection, while the vertical stop degree is higher, the better hand feeling is judged.
And (3) measuring the foaming ratio: the expansion ratio (thickness of the artificial leather after foaming/thickness of the artificial leather before foaming). The measurement precision is 0.01 mm.
Then, measuring the strength: the artificial leather was cut into a 3 cm-wide strip sample, and the peel strength of the leather layer and the substrate was measured in N/3cm by setting the tensile rate of 100mm/min in a tensile testing machine.
And (3) wear resistance test: the machine type is TABER5135, the wheel number is H-22, the load is 1Kg, and the wear-resisting times of the qualified standard is 300 circles.
And (3) bending resistance test: the measurement is carried out according to the ENISO32100 standard, a sample is cut into test pieces with the width of 4.5 cm and the length of 7cm, the bending resistance test is tested at the temperature of 25 ℃ and 20 ℃ below zero, the surface of the artificial leather is observed every 10000 times, and the damage does not exist for more than 20 ten thousand and 6 ten thousand times respectively according to the qualified standard.
The results are shown in tables 1 and 2, respectively.
TABLE 1
Table 2.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (7)
1. A manufacturing method of one-way solvent-free polyurethane resin artificial leather comprises a surface layer, a substrate layer and a solvent-free polyurethane layer coated between the surface layer and the substrate layer, and is characterized by comprising the following steps:
s1, mixing the unidirectional solvent-free polyurethane resin and the leveling agent, and heating to a molten state to obtain slurry;
s2, coating the slurry prepared in the step S1 on a release layer, drying and curing to obtain a surface layer coated with a solvent-free polyurethane layer;
s3, rolling and adhering the substrate layer on the surface of the surface layer coated with the solvent-free polyurethane layer, and drying and curing the surface layer to obtain the artificial leather;
the unidirectional solvent-free polyurethane resin comprises the following raw materials in parts by weight based on the total weight of the polyurethane resin: 25-30 parts of polyether polyol, 58-65 parts of cyclic isocyanate, 5-8 parts of modified nano microcrystalline cellulose and 2-6 parts of aminosilane coupling agent.
2. The method for producing one-way solvent-free polyurethane resin artificial leather according to claim 1, wherein the polyether polyol is one or a combination of two or more of a polyether polyol having a functionality of 4 or more and a number average molecular weight of 2000 to 6000 g/mol.
3. The method for producing one-way type solvent-free polyurethane resin artificial leather according to claim 1, wherein the cyclic isocyanate is one or a combination of two or more of 4, 4-dicyclohexylmethane diisocyanate, 1, 4-cyclohexane diisocyanate, 1-methyl-2, 4-diisocyanatocyclohexane, 1-isocyanomethyl-3-isocyano-1, 5, 5-trimethylcyclohexane, xylene diisocyanate and tetramethylxylene diisocyanate.
4. The method for producing one-way solvent-free polyurethane resin artificial leather according to claim 1, wherein the aminosilane coupling agent is one or a combination of two or more of N- (β -aminoethyl) - γ -aminopropylmethyldimethoxysilane, N-ethylaminoisopropyl trimethoxysilane, anilinopropyltrimethoxysilane and γ -ureidopropyl trimethoxysilane.
5. The manufacturing method of one-way type solvent-free polyurethane resin artificial leather as claimed in claim 1, wherein the preparation method of the modified nano microcrystalline cellulose comprises the following steps: adding nano microcrystalline cellulose into an ethanol solution containing sodium hydroxide, keeping the reaction at 20-25 ℃ for 0.5-1 h to prepare alkalized nano microcrystalline cellulose, then adding isopropanol into a reaction system, heating to 70-80 ℃, continuing the reaction for 5-10 min, cooling, filtering and washing to prepare the modified nano microcrystalline cellulose, wherein the mass percent ratio of the sodium hydroxide, the isopropanol, the nano microcrystalline cellulose and the ethanol is 10-18: 3-5: 6-9: 100.
6. The method for manufacturing the unidirectional solvent-free polyurethane resin artificial leather as claimed in claim 5, wherein the diameter of the nano microcrystalline cellulose is 15-45 nm, and the length of the nano microcrystalline cellulose is 0.8-2 μm.
7. The manufacturing method of the one-way solvent-free polyurethane resin artificial leather as claimed in any one of claims 1 to 6, wherein the mass of the one-way solvent-free polyurethane resin coated on the release layer is 20-100 g/m2。
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