CN116693794A - 一种面料 - Google Patents
一种面料 Download PDFInfo
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- CN116693794A CN116693794A CN202310633452.2A CN202310633452A CN116693794A CN 116693794 A CN116693794 A CN 116693794A CN 202310633452 A CN202310633452 A CN 202310633452A CN 116693794 A CN116693794 A CN 116693794A
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- polyol
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- fabric
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- polytetrahydrofuran
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- 239000004744 fabric Substances 0.000 title claims abstract description 37
- 229920005862 polyol Polymers 0.000 claims abstract description 125
- 150000003077 polyols Chemical class 0.000 claims abstract description 123
- 238000000576 coating method Methods 0.000 claims abstract description 48
- 239000011248 coating agent Substances 0.000 claims abstract description 46
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 43
- 229920000909 polytetrahydrofuran Polymers 0.000 claims abstract description 36
- 239000007788 liquid Substances 0.000 claims abstract description 33
- 239000012948 isocyanate Substances 0.000 claims abstract description 27
- 229920001451 polypropylene glycol Polymers 0.000 claims abstract description 17
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 239000004970 Chain extender Substances 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 14
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229920001610 polycaprolactone Polymers 0.000 claims abstract description 8
- 239000004632 polycaprolactone Substances 0.000 claims abstract description 7
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 5
- 239000004417 polycarbonate Substances 0.000 claims abstract description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 75
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 73
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 54
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 36
- 239000011527 polyurethane coating Substances 0.000 claims description 33
- 239000002987 primer (paints) Substances 0.000 claims description 23
- 239000007787 solid Substances 0.000 claims description 20
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 10
- 229920005906 polyester polyol Polymers 0.000 claims description 10
- 239000010410 layer Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000002344 surface layer Substances 0.000 claims description 6
- ZVYSYCLZXICWLH-UHFFFAOYSA-N 1,3-dioxetan-2-one Chemical compound O=C1OCO1 ZVYSYCLZXICWLH-UHFFFAOYSA-N 0.000 claims description 5
- 239000004677 Nylon Substances 0.000 claims description 4
- 229920001778 nylon Polymers 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- -1 lactone polyol Chemical class 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- 229940031098 ethanolamine Drugs 0.000 claims 5
- 229920000747 poly(lactic acid) Polymers 0.000 claims 1
- 239000004626 polylactic acid Substances 0.000 claims 1
- 239000004814 polyurethane Substances 0.000 abstract description 17
- 229920002635 polyurethane Polymers 0.000 abstract description 17
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000003973 paint Substances 0.000 abstract 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000001361 adipic acid Substances 0.000 description 5
- 235000011037 adipic acid Nutrition 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 3
- 229920006264 polyurethane film Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000009194 climbing Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
- 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
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- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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- 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
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- 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
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- 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
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/0015—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using fibres of specified chemical or physical nature, e.g. natural silk
- D06N3/0034—Polyamide fibres
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- 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
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- 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
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Abstract
本发明涉及一种面料,其包括面料主体和由液型聚氨酯涂料形成的涂层,涂层包括形成在面料主体上的底涂层以及形成在底涂层上的面涂层,液型聚氨酯涂料的制备方法为:(1)将异氰酸酯、第一多元醇、第二多元醇以及第三多元醇进行预聚反应;(2)向步骤(1)反应完成后的体系中加入溶剂、聚四氢呋喃多元醇以及扩链剂进行扩链反应,所述的第一多元醇为聚四氢呋喃多元醇、聚碳酸酯多元醇、聚己内酯多元醇中的一种或多种,所述的第二多元醇为聚环氧丙烷多元醇、四氢呋喃和环氧丙烷共聚多元醇、环氧丙烷和环氧乙烷共聚多元醇中的一种或多种。本发明的面料具有优异的耐寒性、回弹性和柔韧性,且更加轻便,具有经济、环保的优点。
Description
本发明是申请日为2020年8月31日、申请号为2020108942336、发明名称为一种液型聚氨酯涂料及其制备方法和应用的分案申请。
技术领域
本发明具体涉及一种面料。
背景技术
目前市面上服装革涂层耐低温只停留在零下20~30℃,因此市面上流行的羽绒服、登山服以及帐篷和睡袋等的耐寒温度最低约为零下20~30℃。在极寒环境中(零下30~45℃),现有服装革涂层的耐寒性能无法满足使用需求,而且在极寒天气下,人体对服装的舒适感要求的提高,因此还需提高面料的柔软性和回弹性。此外,现有耐低温聚氨酯涂料的涂覆量较高,大约为150~210g/m2,用于服装或帐篷和睡袋时,面料较厚较重,不方便折叠携带。
发明内容
本发明的目的是提供一种液型聚氨酯涂料的制备方法,制备的液型聚氨酯涂料具有优异的耐寒性、回弹性和柔韧性。
为达到上述目的,本发明采用的技术方案是:
本发明第一方面提供一种液型聚氨酯涂料的制备方法,包括如下步骤:
(1)将异氰酸酯、第一多元醇、第二多元醇以及第三多元醇进行预聚反应;
(2)向步骤(1)反应完成后的体系中加入溶剂、聚四氢呋喃多元醇以及扩链剂进行扩链反应,
所述的第一多元醇为聚四氢呋喃多元醇、聚碳酸酯多元醇、聚己内酯多元醇中的一种或多种,所述的第二多元醇为聚环氧丙烷多元醇、四氢呋喃和环氧丙烷共聚多元醇、环氧丙烷和环氧乙烷共聚多元醇中的一种或多种。
本发明中,所述的聚碳酸酯多元醇为PCDL。
本发明中,所述的聚己内酯多元醇为PCL。
本发明中,使用的第一多元醇具有耐寒性优、耐水性优、机械强度较高、结晶性良好等特点,而使用的第二多元醇虽也具有较优的耐寒性能以及较高的机械强度,但结晶性差。
优选地,控制步骤(1)的反应温度为80~95℃。
优选地,控制步骤(2)的反应温度为80~95℃。
优选地,所述的异氰酸酯为MDI、TDI、HMDI中的一种或多种;
优选地,所述的第三多元醇为聚碳酸亚内酯多元醇、聚酯多元醇、聚乙二醇中的一种或多种。
本发明中,所述的聚碳酸亚内酯多元醇为PPC,是由二氧化碳和环氧丙烷共聚形成的。
本发明中,所述的聚酯多元醇由己二酸、乙二醇、1,4-丁二醇按摩尔比5~6:1.5~2.5:2~4缩合而成,所述摩尔比更优选为5.01:2:3。
本发明中,步骤(1)中使用的聚四氢呋喃多元醇、聚环氧丙烷多元醇以及其他多元醇的数均分子量为1500~3000,优选为1800~2500,更优选为2000左右。
本发明中,步骤(2)中使用的聚四氢呋喃多元醇的数均分子量为1500~3000,优选为1800~2500,更优选为2000左右。
优选地,所述的溶剂为二甲基甲酰胺、二甲基乙酰胺中的一种或多种。
优选地,所述的扩链剂为乙醇胺、一缩二乙二醇、乙二醇、1,4-丁二醇、新戊二醇中的一种或多种。
优选地,所述的制备方法还包括扩链反应完成后,分批加入异氰酸酯进行反应至所需粘度,然后加入链终止剂终止反应的步骤。
本发明中,粘度范围优选为3~20万cps/65℃,优选为5~11万cps/65℃。
进一步优选地,所述的链终止剂为乙二醇、苹果酸中的一种或多种。
进一步优选地,所述的制备方法还包括终止反应后,向反应体系中加入溶剂调整固含量的步骤。
本发明中,固含量调整范围优选为20%~60%,更优选为28%~52%。
优选地,步骤(1)在溶剂的存在下进行反应。
根据一种具体实施方式,当所述的液型聚氨酯涂料为面层涂料时,步骤(1)中的异氰酸酯、第一多元醇、第二多元醇以及第三多元醇的摩尔比为10~15:2~5:0.5~1:1;步骤(2)中的聚四氢呋喃多元醇和扩链剂的摩尔比为0.05~0.2:1;步骤(1)中的第一多元醇与步骤(2)中的聚四氢呋喃多元醇的摩尔比为0.5~2:1。
优选地,当所述的液型聚氨酯涂料为面层涂料时,所述的第一多元醇为聚四氢呋喃多元醇;所述的第二多元醇为聚环氧丙烷多元醇;所述的第三多元醇为聚碳酸亚内酯多元醇;所述的扩链剂为乙醇胺、一缩二乙二醇的混合物。
进一步优选地,所述的乙醇胺、一缩二乙二醇的摩尔比为1~2:1。
根据一种具体实施方式,当所述的液型聚氨酯涂料为底层涂料时,步骤(1)中的异氰酸酯、第一多元醇、第二多元醇以及第三多元醇的摩尔比为2~8:0.5~1.5:0.1~0.5:1;步骤(2)中的聚四氢呋喃多元醇和扩链剂的摩尔比为0.05~0.1:1;步骤(1)中的第一多元醇与步骤(2)中的聚四氢呋喃多元醇的摩尔比为1~3:1。
优选地,当所述的液型聚氨酯涂料为底层涂料时,所述的第一多元醇为聚四氢呋喃多元醇;所述的第二多元醇为聚环氧丙烷多元醇;所述的第三多元醇为聚酯多元醇;所述的扩链剂为乙二醇、乙醇胺、一缩二乙二醇的混合物。
进一步优选地,所述的乙二醇、乙醇胺、一缩二乙二醇的摩尔比为0.5~1:0.1~0.6:1。
本发明第二方面还提供一种使用上述制备方法制得的液型聚氨酯涂料。
本发明第三方面还提供一种使用上述制备方法制得的液型聚氨酯涂料在面料涂层中的应用。
本发明中,将上述底层涂料先涂覆在面料上形成底涂层,然后再将上述面层涂料涂覆在所述的底涂层上形成面涂层。
本发明的第四方面还提供一种面料,其包括由上述涂料形成的涂层。
进一步地,所述涂层包括形成在面料本体上的底涂层以及形成在底涂层上的面涂层。
本发明第五方面还提供一种面料涂层的制备方法,将使用上述制备方法制得的液型聚氨酯涂料涂覆在面料上,经干燥回收溶剂得到涂层。
优选地,所述的液型聚氨酯涂料在所述的面料上的涂覆量为50~120g/m2。
本发明中,底层和面层的涂覆量之和为50~120g/m2,在生产面料时,可根据需要选择面层和底层的具体涂覆量。
本发明的聚氨酯涂料为液型,树脂稳定性佳,制备时无需加入固化剂、交联剂等成膜助剂,操作更加方便。
本发明通过先使用软链段原料第一多元醇(聚四氢呋喃多元醇、聚碳酸酯多元醇、聚己内酯多元醇中的一种或多种)、第二多元醇(聚环氧丙烷多元醇、四氢呋喃和环氧丙烷共聚多元醇、环氧丙烷和环氧乙烷共聚多元醇中的一种或多种)以及第三多元醇进行预聚后,再使用软链段原料聚四氢呋喃多元醇和硬链段原料扩链剂进行扩链,与传统一步法合成的聚氨酯涂料相比,耐寒性能显著提高,且回弹性和柔韧性也得到提高。
本发明的液型聚氨酯涂料的制备方法,可使用二甲基甲酰胺或二甲基乙酰胺作为反应溶剂,制得的液型聚氨酯涂料直接涂覆在面料上,经干燥得到涂层,反应溶剂可在干燥过程中回收再利用,节约了资源,降低了成本,并且本发明的制备方法在工业生产时无废气、废液产生,更加环保。
本发明的液型聚氨酯涂料可应用于服装涂层,人使用由此制备得到的服装在自然恶劣条件下能够提高身体的舒适感。而且本发明的液型聚氨酯涂料在面料上的涂覆量为50~120g/m2,相对市面上的涂料涂覆量少,因此使用本发明的液型聚氨酯涂料的面料不仅防水及防寒性能优越,而且轻便易折、方便携带,更适用于军工迷彩服。
由于上述技术方案运用,本发明与现有技术相比具有下列优点:
使用本发明方法制备的液型聚氨酯涂料具有优异的耐寒性、回弹性和柔韧性,且涂覆量低,可使面料更加轻便;本发明的制备方法操作时无废气、废液产生,溶剂可回收再利用,具有经济、环保的优点,更适合工业化生产。
具体实施方式
下面通过具体实施例来进一步阐述本发明,但并不是对本发明的限制,仅做示例说明。实施例中采用的实施条件可以根据具体使用的不同要求做进一步调整,未注明的实施条件为本行业中的常规条件。
本发明中使用的试剂、材料均可通过市售获得。
实施例1:
聚氨酯面层涂料:
(1)将异氰酸酯(MDI)0.432摩尔、聚四氢呋喃多元醇(数均分子量约为2000)0.104摩尔、聚环氧丙烷多元醇(数均分子量约为2000)0.024摩尔、聚碳酸亚内酯多元醇(数均分子量约为2000)0.032摩尔以及二甲基甲酰胺150g加入反应容器中,在80~85℃下反应2h。
(2)向步骤(1)反应完成后的体系中加入二甲基甲酰胺470g、聚四氢呋喃多元醇(数均分子量约为2000)0.08摩尔、乙醇胺0.5摩尔以及一缩二乙二醇0.32摩尔,在80~85℃下反应1.5h。
(3)向步骤(2)反应完成后的体系中分3个批次投入异氰酸酯(MDI),第一次投料量为0.314摩尔、第二次投料量0.209摩尔、第三次投料量0.105摩尔,在80~85℃下反应,取样,采用NDJ-4粘度计检测反应液的粘度,当反应液粘度为8~11万cps/65℃时,加入乙二醇0.04摩尔终止反应。
(4)向步骤(3)终止反应后的体系中加入二甲基甲酰胺调整固含量至30±1%,采用GB1725-79甲法测定固含量。
实施例2:
聚氨酯面层涂料:
(1)将异氰酸酯(MDI)0.432摩尔、聚四氢呋喃多元醇(数均分子量约为2000)0.084摩尔、聚环氧丙烷多元醇(数均分子量约为2000)0.024摩尔、聚碳酸亚内酯多元醇(数均分子量约为2000)0.032摩尔以及二甲基甲酰胺150g加入反应容器中,在80~85℃下反应2h。
(2)向步骤(1)反应完成后的体系中加入二甲基甲酰胺470g、聚四氢呋喃多元醇(数均分子量约为2000)0.1摩尔、乙醇胺0.5摩尔以及一缩二乙二醇0.32摩尔,在80~85℃下反应1.5h。
(3)向步骤(2)反应完成后的体系中分3个批次投入异氰酸酯(MDI),第一次投料量为0.314摩尔、第二次投料量为0.209摩尔、第三次投料量为0.105摩尔,在80~85℃下反应至反应液的粘度为8~11万cps/65℃,加入乙二醇0.04摩尔终止反应。
(4)向步骤(3)终止反应后的体系中加入二甲基甲酰胺调整固含量至30±1%。
本实施例中,粘度及固含量检测方法同实施例1。
实施例3:
聚氨酯面层涂料:
(1)将异氰酸酯(MDI)0.432摩尔、聚四氢呋喃多元醇(数均分子量约为2000)0.104摩尔、聚环氧丙烷多元醇(数均分子量约为2000)0.024摩尔以及聚碳酸亚内酯多元醇(数均分子量约为2000)0.032摩尔加入反应容器中,80~85℃下反应2h。
(2)向步骤(1)反应完成后的体系中加入二甲基甲酰胺620g、聚四氢呋喃多元醇(数均分子量约为2000)0.08摩尔、乙醇胺0.5摩尔以及一缩二乙二醇0.32摩尔,在80~85℃下反应1.5h。
(3)向步骤(2)反应完成后的体系中分3个批次投入异氰酸酯(MDI),第一次投料量为0.314摩尔、第一次投料量为0.209摩尔、第一次投料量为0.105摩尔,在80~85℃下反应至反应液的粘度为8~11万cps/65℃,加入乙二醇0.04摩尔终止反应。
(4)向步骤(3)终止反应后的体系中加入二甲基甲酰胺调整固含量至30±1%。
本实施例中,粘度及固含量检测方法同实施例1。
对比例1:
聚氨酯面层涂料:
(1)将异氰酸酯(MDI)0.432摩尔、聚四氢呋喃多元醇(数均分子量约为2000)0.184摩尔、聚环氧丙烷多元醇(数均分子量约为2000)0.024摩尔、聚碳酸亚内酯多元醇(数均分子量约为2000)0.032摩尔、乙醇胺0.5摩尔、一缩二乙二醇0.32摩尔以及二甲基甲酰胺150g加入反应容器中,在80~85度下反应2小时。
(2)向步骤(1)反应完成后的体系中投入异氰酸酯(MDI)0.628摩尔,在80~85℃下反应至反应液的粘度为8~11万cps/65℃,加入乙二醇0.04摩尔终止反应。
(3)向步骤(2)终止反应后的体系中加入二甲基甲酰胺、甲苯,调整固含量至30±1%。
本对比例中,粘度及固含量检测方法同实施例1。
实施例4:
聚氨酯底层涂料:
(1)将异氰酸酯(TDI)0.654摩尔、聚四氢呋喃多元醇(数均分子量约为2000)0.1565摩尔、聚环氧丙烷多元醇(数均分子量约为2000)0.0463摩尔、聚酯多元醇(由己二酸、乙二醇、1,4-丁二醇按摩尔比为5.01:2:3聚合而成,数均分子量约为2000)0.139摩尔以及二甲基甲酰胺190g加入反应容器中,在90~95℃下反应2h。
(2)向步骤(1)反应完成后的体系中加入二甲基甲酰胺470g、聚四氢呋喃多元醇(数均分子量约为2000)0.075摩尔、乙二醇0.37摩尔、乙醇胺0.185摩尔以及一缩二乙二醇0.485摩尔,在90~95℃下反应1.5h。
(3)向步骤(2)反应完成后的体系中分3个批次投入异氰酸酯(MDI),第一次投加量为0.4014摩尔、第二次投加量为0.2676摩尔、第三次投加量为0.1338摩尔,在80~85℃下反应至反应液的粘度为5~6万cps/65℃,加入乙二醇0.04摩尔终止反应。
(4)向步骤(3)终止反应后的体系中加入二甲基甲酰胺调整固含量至50±1%。
本实施例中,粘度及固含量检测方法同实施例1。
实施例5:
聚氨酯底层涂料:
(1)将异氰酸酯(TDI)0.654摩尔、聚四氢呋喃多元醇(数均分子量约为2000)0.139摩尔、聚环氧丙烷多元醇(数均分子量约为2000)0.0463摩尔、聚酯多元醇(己二酸、乙二醇、1,4-丁二醇按摩尔比5.01:2:3聚合而成,数均分子量约为2000)0.139摩尔以及二甲基甲酰胺190g加入反应容器中,在90~95℃下反应2h。
(2)向步骤(1)反应完成后的体系中加入二甲基甲酰胺470g、聚四氢呋喃多元醇(数均分子量约为2000)0.0925摩尔、乙二醇0.37摩尔、乙醇胺0.185摩尔以及一缩二乙二醇0.485摩尔,在90~95℃下反应1.5h。
(3)向步骤(2)反应完成后的体系中分3个批次投入异氰酸酯(MDI),第一次投加量为0.4014摩尔、第二次投加量为0.2676摩尔、第三次投加量为0.1338摩尔,在80~85℃下反应至反应液的粘度为5~6万cps/65℃,加入乙二醇0.04摩尔终止反应。
(4)向步骤(3)终止反应后的体系中加入二甲基甲酰胺调整固含量至50±1%。
本实施例中,粘度及固含量检测方法同实施例1。
实施例6:
聚氨酯底层涂料:
(1)将异氰酸酯(TDI)0.654摩尔、聚四氢呋喃多元醇(数均分子量约为2000)0.139摩尔、聚环氧丙烷多元醇(数均分子量约为2000)0.0463摩尔以及聚酯多元醇(己二酸、乙二醇、1,4-丁二醇按摩尔比5.01:2:3聚合而成,数均分子量约为2000)0.139摩尔加入反应容器中,在90~95℃下反应2h。
(2)向步骤(1)反应完成后的体系中加入二甲基甲酰胺660g、聚四氢呋喃多元醇(数均分子量约为2000)0.0925摩尔、乙二醇0.37摩尔、乙醇胺0.185摩尔以及一缩二乙二醇0.485摩尔,在90~95℃下反应1.5h。
(3)向步骤(2)反应完成后的体系中分3个批次投入异氰酸酯(MDI),第一次投加量为0.4014摩尔、第二次投加量为0.2676摩尔、第三次投加量为0.1338摩尔,在80~85℃下反应至反应液的粘度为5~6万cps/65℃,加入乙二醇0.04摩尔终止反应。
(4)向步骤(3)终止反应后的体系中加入二甲基甲酰胺调整固含量至50±1%。
本实施例中,粘度及固含量检测方法同实施例1。
对比例2:
聚氨酯底层涂料:
(1)将异氰酸酯(TDI)0.654摩尔、聚四氢呋喃多元醇(数均分子量约为2000)0.2315摩尔、聚环氧丙烷多元醇(数均分子量约为2000)0.0463摩尔、聚酯多元醇(己二酸、乙二醇、1,4-丁二醇按摩尔比5.01:2:3聚合而成,数均分子量约为2000)0.139摩尔、乙二醇0.37摩尔、乙醇胺0.185摩尔、一缩二乙二醇0.485摩尔以及二甲基甲酰胺190g加入反应容器中,在90~95℃下反应2小时。
(2)向步骤(1)反应完成后的体系中投入异氰酸酯(MDI)0.8028摩尔,在80~85℃下反应至反应液的粘度为5~6万cps/65℃,加入乙二醇0.04摩尔终止反应。
(3)向步骤(2)终止反应后的体系中加入二甲基甲酰胺、甲苯,调整固含量至50±1%。
本对比例中,粘度及固含量检测方法同实施例1。
将实施例4的聚氨酯底层涂料按常规方法涂覆在尼龙布的正面,经常规方法干燥后得到聚氨酯底层涂层,将实施例1的聚氨酯面层涂料按常规方法涂覆在聚氨酯底层涂层上,经常规方法干燥后得到聚氨酯面层涂层,最终得到正面带有聚氨酯涂层的尼龙布产品,记作成品1,底层和面层的总涂覆量约为80g/m2,二甲基甲酰胺在干燥过程中回收再用。同样地,采用与成品1相同的涂覆量及涂覆方式,将实施例1~6按表1的组合方式制作成品2~9;采用与成品1相同的涂覆量及涂覆方式,使用对比例1和对比例2制作成品10。采用FZ/T01007-2008对成品1~10进行耐折牢度性能测试,测试项目及测试结果见表1。
表1
将实施例1、实施例2、实施例3、对比例1的聚氨酯面层涂料,实施例4、实施例5、实施例6、对比例2的聚氨酯底层涂料分别用10dmm线棒按常规涂覆方式涂覆在平面离型纸上,按常规方法干燥制得厚度为6dmm的聚氨酯薄膜,取下聚氨酯薄膜,用GB/T1040-2006对各聚氨酯薄膜进行拉伸性能测试,测试项目及测试结果见表2和表3。
表2
表3
表1显示成品1~9在-45℃下低温耐折性完全复合国家标准,成品10在-45℃下的低温耐折性未达国家标准;表2显示常温下实施例1~3相比对比例1具有更高的伸长率,实施例4~6相比对比例2也具有更高的伸长率,结合表1、表2和表3的结果可知,本发明的制备方法能够有效提高聚氨酯涂层的耐寒性、回弹性和柔韧性。
以上实例仅为本发明的示例性实施例,不用于限制本发明,本发明的保护范围由权利要求书限定。本领域技术人员可以在本发明的实质和保护范围内,对本发明做出各种修改或等同替换,这种修改或等同替换也应视为落在本发明的保护范围内。
Claims (10)
1.一种面料,其包括面料主体和由液型聚氨酯涂料形成的涂层,所述涂层包括形成在所述的面料主体上的底涂层以及形成在所述的底涂层上的面涂层,其特征在于:所述的液型聚氨酯涂料的制备方法的步骤为:
(1)将异氰酸酯、第一多元醇、第二多元醇以及第三多元醇进行预聚反应;
(2)向步骤(1)反应完成后的体系中加入溶剂、聚四氢呋喃多元醇以及扩链剂进行扩链反应;
(3)扩链反应完成后,分批加入异氰酸酯进行反应至所需粘度,然后加入链终止剂终止反应;
(4)选择性地向反应体系中加入溶剂调整固含量,
所述的第一多元醇为聚四氢呋喃多元醇、聚碳酸酯多元醇、聚己内酯多元醇中的一种或多种,所述的第二多元醇为聚环氧丙烷多元醇、四氢呋喃和环氧丙烷共聚多元醇、环氧丙烷和环氧乙烷共聚多元醇中的一种或多种,所述的第三多元醇为聚碳酸亚内酯多元醇、聚酯多元醇、聚乙二醇中的一种或多种,所述的链终止剂为乙二醇、苹果酸中的一种或多种,
当所述的液型聚氨酯涂料为面层涂料时,步骤(1)中的异氰酸酯、第一多元醇、第二多元醇以及第三多元醇的摩尔比为10~15:2~5:0.5~1:1;步骤(2)中的聚四氢呋喃多元醇和扩链剂的摩尔比为0.05~0.2:1;步骤(1)中的第一多元醇与步骤(2)中的聚四氢呋喃多元醇的摩尔比为0.5~2:1;
当所述的液型聚氨酯涂料为底层涂料时,步骤(1)中的异氰酸酯、第一多元醇、第二多元醇以及第三多元醇的摩尔比为2~8:0.5~1.5:0.1~0.5:1;步骤(2)中的聚四氢呋喃多元醇和扩链剂的摩尔比为0.05~0.1:1;步骤(1)中的第一多元醇与步骤(2)中的聚四氢呋喃多元醇的摩尔比为1~3:1。
2.根据权利要求1所述的面料,其特征在于:控制步骤(1)的反应温度为80~95℃;控制步骤(2)的反应温度为80~95℃。
3.根据权利要求1所述的面料,其特征在于:所述的异氰酸酯为MDI、TDI、HMDI中的一种或多种;
所述的第三多元醇为聚碳酸亚内酯多元醇、聚酯多元醇、聚乙二醇中的一种或多种;
所述的溶剂为二甲基甲酰胺、二甲基乙酰胺中的一种或多种;
所述的扩链剂为乙醇胺、一缩二乙二醇、乙二醇、1,4-丁二醇、新戊二醇中的一种或多种。
4.根据权利要求1所述的面料,其特征在于:步骤(3)中,所述的粘度的范围为3~20万cps/65℃;步骤(4)中,所述的固含量调整范围为20%~60%,所述的溶剂为二甲基甲酰胺。
5.根据权利要求1所述的面料,其特征在于:步骤(1)在溶剂的存在下进行反应。
6.根据权利要求1至5中任一项所述的面料,其特征在于:
当所述的液型聚氨酯涂料为面层涂料时,所述的第一多元醇为聚四氢呋喃多元醇;所述的第二多元醇为聚环氧丙烷多元醇;所述的第三多元醇为聚碳酸亚内酯多元醇;所述的扩链剂为乙醇胺、一缩二乙二醇的混合物;
当所述的液型聚氨酯涂料为底层涂料时,所述的第一多元醇为聚四氢呋喃多元醇;所述的第二多元醇为聚环氧丙烷多元醇;所述的第三多元醇为聚酯多元醇;所述的扩链剂为乙二醇、乙醇胺、一缩二乙二醇的混合物。
7.根据权利要求6所述的面料,其特征在于:当所述的液型聚氨酯涂料为面层涂料时,所述的乙醇胺、一缩二乙二醇的摩尔比为1~2:1,当所述的液型聚氨酯涂料为底层涂料时,所述的乙二醇、乙醇胺、一缩二乙二醇的摩尔比为0.5~1:0.1~0.6:1。
8.根据权利要求1所述的面料,其特征在于:先将所述的底层涂料涂覆在面料上,经干燥回收溶剂形成所述的底涂层,然后再所述的面层涂料涂覆在所述的底涂层上,经干燥回收溶剂形成所述的面涂层。
9.根据权利要求8所述的面料,其特征在于:所述的面料主体为尼龙布。
10.根据权利要求1所述的面料,其特征在于:所述的液型聚氨酯涂料在所述的面料主体上的涂覆量为50~120g/m2。
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