CN101381962A - Water proof and moisture permeable artificial leather and method for making same - Google Patents
Water proof and moisture permeable artificial leather and method for making same Download PDFInfo
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- CN101381962A CN101381962A CNA2008101672852A CN200810167285A CN101381962A CN 101381962 A CN101381962 A CN 101381962A CN A2008101672852 A CNA2008101672852 A CN A2008101672852A CN 200810167285 A CN200810167285 A CN 200810167285A CN 101381962 A CN101381962 A CN 101381962A
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- Prior art keywords
- artificial leather
- moisture permeable
- waterproof
- permeable artificial
- polyurethane resin
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- 239000002649 leather substitute Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title description 43
- 239000004744 fabric Substances 0.000 claims abstract description 54
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 49
- 229920005989 resin Polymers 0.000 claims abstract description 45
- 239000011347 resin Substances 0.000 claims abstract description 45
- 239000012948 isocyanate Substances 0.000 claims abstract description 25
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 24
- 239000004970 Chain extender Substances 0.000 claims abstract description 23
- 239000011248 coating agent Substances 0.000 claims abstract description 23
- 238000000576 coating method Methods 0.000 claims abstract description 23
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 22
- 230000009477 glass transition Effects 0.000 claims abstract description 22
- 230000035699 permeability Effects 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000010985 leather Substances 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 229920005862 polyol Polymers 0.000 claims abstract description 6
- 150000003077 polyols Chemical class 0.000 claims abstract description 6
- 239000002798 polar solvent Substances 0.000 claims abstract description 5
- 230000001112 coagulating effect Effects 0.000 claims abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- 150000005846 sugar alcohols Polymers 0.000 claims description 23
- 239000002202 Polyethylene glycol Substances 0.000 claims description 18
- 229920001223 polyethylene glycol Polymers 0.000 claims description 18
- 238000000465 moulding Methods 0.000 claims description 13
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 9
- 238000009738 saturating Methods 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- -1 oxirane adipate ester Chemical class 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims description 5
- 150000002009 diols Chemical class 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
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- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- 238000012360 testing method Methods 0.000 description 17
- 239000002904 solvent Substances 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 10
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- 238000012546 transfer Methods 0.000 description 9
- 239000002759 woven fabric Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
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- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 238000009954 braiding Methods 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
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- 238000004078 waterproofing Methods 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000003495 polar organic solvent Substances 0.000 description 2
- 230000001846 repelling effect Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 210000004243 sweat Anatomy 0.000 description 2
- KJAMZCVTJDTESW-UHFFFAOYSA-N tiracizine Chemical compound C1CC2=CC=CC=C2N(C(=O)CN(C)C)C2=CC(NC(=O)OCC)=CC=C21 KJAMZCVTJDTESW-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 150000001279 adipic acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- QVHQGRAPTXUURC-UHFFFAOYSA-N butane-1,1-diol;hexane-1,6-diol Chemical compound CCCC(O)O.OCCCCCCO QVHQGRAPTXUURC-UHFFFAOYSA-N 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
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- 125000004185 ester group Chemical group 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
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- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
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- 235000019634 flavors Nutrition 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
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- 230000003238 somatosensory effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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Landscapes
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Laminated Bodies (AREA)
Abstract
The invention relates to a waterproof and moisture permeable artificial leather with real comfort. The technical proposal is that the artificial leather consists of a base fabric which is at least one surface of the artificial leather and a resin film layer prepared by a reaction of isocyanate, polyol and a chain extender, wherein the glass transition temperature is between 20 DEG C below zero and 20 DEG C, and the content of ethylene oxide chain is at least 7.0mol/kg. The artificial leather is characterized in that the ratio of the high temperature moisture permeability to the low temperature moisture permeability is 1.4 or more than 1.4. Meanwhile, the invention also discloses a preparation method for the waterproof and moisture permeable artificial leather, which is characterized by comprising the following steps that a polyurethane resin is dissolved in a polar solvent, and then a polyurethane resin solution is coated on one surface of fabrics and the coating is solidified by a wet method in a coagulating basin to obtain a film layer; or the polyurethane resin is dissolved in a polar solvent and then the polyurethane resin solution with a volatile organic solvent is coated on release paper to form a polyurethane resin film, and then the polyurethane resin film coated with a bonding resin is laminated on one surface of a leather base cloth and the release paper is stripped.
Description
Technical field
The present invention relates to artificial leather and preparation method thereof, in particular, what the present invention paid close attention to is a kind of comfortable waterproof, moisture permeable artificial leather and preparation method thereof, and this artificial leather can correspondingly be controlled poisture-penetrability and hot retentivity to heat, cold sensation according to human body.
Background technology
Traditional method that makes artificial leather not only have poisture-penetrability but also water proofing property is arranged mainly is to improve the moisture of poisture-penetrability to prevent to produce in the motion process, maintains water proofing property simultaneously.Yet, with the high poisture-penetrability waterproof artificial leather of conventional method preparation, owing to have higher poisture-penetrability, thereby warmth retention property is relatively poor.When environment temperature was low, it is colder that people can feel.On the other hand, the wet thoroughly leather of common water proofing property, because poisture-penetrability is relatively poor, when environment temperature is higher and after the motion, people have wet, hot sensation again.Therefore, conventional method does not possess makes artificial leather have real comfort level, when promptly environment temperature is low, keeps heat not scatter and disappear, and when environment temperature is high, has can discharge sweat and keep the function of feeling nice and cool.
Summary of the invention
The purpose of this invention is to provide a kind of waterproof, moisture permeable artificial leather and preparation method thereof.This waterproof, moisture permeable artificial leather have higher hot retentivity under low temperature environment; Under high environment temperature, high poisture-penetrability is arranged, to keep nice and cool.Thereby, possess real comfortableness is arranged.
In order to achieve the above object, the present invention adopts following technical scheme:
Waterproof, moisture permeable artificial leather are by the fabric base cloth, provide this artificial leather at least one surface, resin film layer, make by isocyanates, polyalcohol and chain extender reaction, glass transition temperature is-20 to 20 ℃, ethylene oxide segment content is at least 7.0mol/kg two parts to be formed, and it is characterized in that its high temperature moisture permeability is 1.4 or higher with the ratio of low temperature moisture permeability.
Polyol component is made up of polyethylene glycol, polytetrahydrofuran diol, polyethylene glycol adipate glycol, and molecular weight is 500-3000.
Above-mentioned resin molding is a porous.
Above-mentioned resin molding is an atresia.
The heat of above-mentioned waterproof, saturating wet leather keeps performance and environment temperature on every side to be inversely proportional to, and poisture-penetrability is 1000g/m in low temperature environment
224hr or lower is 8000g/m under hot environment
224hr or higher.
Waterproof, moisture permeable artificial leather provide at least one surface of this base cloth by the fabric base cloth; Resin film layer, make by different hydrogen acid ether (hydrogen acid ester) and polyalcohol and chain extender reaction, glass transition temperature is-20 to 20 ℃, and ethylene oxide segment content is at least 7.0mol/kg two parts to be formed, and it is characterized in that: its high temperature moisture permeability is 1.4 or higher with the ratio of low temperature moisture permeability.
Polyol component is by polyethylene glycol and PTMG, and the oxirane adipate ester is formed, and molecular weight is 500-3000.
Above-mentioned resin molding is a porous.
Above-mentioned resin molding is an atresia.
The poisture-penetrability of above-mentioned waterproof, saturating wet leather is 1000g/m in low temperature environment
224hr or lower is 8000g/m under hot environment
224hr or higher.
The heat conservation rate and the ambient temperature of saturating wet leather are inversely proportional to.
The preparation method of waterproof, moisture permeable artificial leather, comprise following steps: will be by isocyanates and polyalcohol and chain extender reaction, glass transition temperature is at-20 to 20 ℃, the polyurethane resin that ethylene oxide segment content is at least 7.0mol/kg is dissolved in the polar solvent, and with its coating on a surface of fabric, this coating wet method is set in obtains rete in the coagulating basin.
Comprise following steps: will be by isocyanates and polyalcohol and chain extender reaction, glass transition temperature is at-20 to 20 ℃, the polyurethane resin that ethylene oxide segment content is at least 7.0mol/kg is dissolved in the polarity volume, and it is coated in film forming on the release liners, then this film is sticked to fabric face and form leather.
Effect of the present invention is: the invention provides a kind of waterproof, moisture permeable artificial leather, it comprises textile fabric, and provide the surface of this fabric, a kind of resin film layer is provided, it comprises polyurethane resin, made by isocyanates and polyalcohol and chain extender reaction, glass transition temperature is-20 to 20 ℃, and ethylene oxide segment content is at least 7.0mol/kg.
Further, the invention provides the preparation method of waterproof, moisture permeable artificial leather, comprise following steps: will be by isocyanates and polyalcohol and chain extender reaction, the vitrifying glass transition temperature is-20 to 20 ℃, the polyurethane resin that ethylene oxide segment content is at least 7.0mol/kg is dissolved in the polarity volume, and with its coating on a surface of fabric, this coating wet method is set in obtains rete in the coagulating basin, maybe will be dissolved in polyurethane resin solution in the polarity volume, be coated in film forming on the release liners, then this film sticked to fabric face.
Waterproof of the present invention, moisture permeable artificial leather have higher hot retentivity under low temperature environment; Under high environment temperature, high poisture-penetrability is arranged, to keep nice and cool.Thereby, possess real comfortableness is arranged.
The present invention is described further below in conjunction with not limiting embodiment.
The specific embodiment
Waterproof, moisture permeable artificial leather, it comprises textile fabric and polyurethane resin rete, it is characterized in that described polyurethane resin rete is made by isocyanates and polyalcohol and chain extender reaction, glass transition temperature is-20 to 20 ℃, and ethylene oxide segment content is at least 7.0mol/kg.
Can be used for textile fabric of the present invention comprises: chemical fibre, as polyester, polyamide, acrylic acid or nylon fiber; Natural fabric is as cotton, hair or their blending thing.Can be woven, braiding or non-weaving be made into.
Can be used for polyurethane resin of the present invention, is to be made by isocyanates and polyalcohol and chain extender reaction, and it contains the rigid structure of restriction molecule chain movement, and this structure makes the glass transition temperature of polyurethane resin-20 to 20 ℃ of scopes.Therefore, compensated the shortcoming of fabric moisture-penetrability height dependence environment temperature.
For preparing polyurethane resin of the present invention, need isocyanate component.Isocyanates commonly used comprises: 4,4 '-methyl diphenylene diisocyanate (MDI); Hydrogenation MDI; Isophorone diisocyanate; 1,3 '-Xylene Diisocyanate; 2,4 '-toluene di-isocyanate(TDI).They can also can mix use separately.Consider that from the hard segment structure of molecule MDI and hydrogenation MDI are better.
The present invention also uses chain extender, and chain extender comprises preferably: ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexylene glycol, ethylenediamine, pentanediamine, isophorone diamine and water.They can also can mix use separately.Consider from the hard section of molecule,, ethylene glycol, propylene glycol, water is better.
The polyol component that the present invention uses comprises: high molecular weight diol as polyethylene glycol, is ethylene oxide homopolymerization product; Ethylene oxide and tetrahydrofuran copolymer; The polymer of ethylene oxide and bisphenol-A; Aliphatic acid and ethylene oxide product.The high molecular weight diol of oxygen-free ethene segment is as polytetramethylene glycol; Polyoxypropyleneglycol; PCDL; Polycaprolactone glycol; The PPA glycol; Poly-adipic acid butanediol hexylene glycol etc.They can use separately also can mix use.
The molecular weight of polyalcohol is in the 500---3000 scope preferably.Molecular weight was less than 500 o'clock, and not good by the elastic behavior of its polyurethane resin of making, persistence is poor.On the other hand, molecular weight was greater than 3000 o'clock, and the condition of synthetic polyalcohol is restricted, when filming with polyurethane resin prepared therefrom, and the opaque or generation fish-eye shaped defective of film.
The present invention tends to use mixed alcohol: as polyethylene glycol and polytetramethylene glycol; Or polyethylene glycol and contain the poly-adipic acid series polyester polyol of vinyl segment.The molecular weight ranges of these polyalcohols is 500-3000.
The ethyoxyl mass contg that polyurethane resin of the present invention contains is to be controlled at 7.0mol/kg or more by adjusting polyalcohol, isocyanates, chain extender consumption.
Polyurethane resin of the present invention is with one-step method or pre-polymerization method or polymerisation in solution in solvent.
Among the present invention, the above-mentioned polyurethane resin that obtains that relates to can use with other carbamic acid mixed with resin.For example they can be that glass transition temperature is at-20 ℃ or lower common carbamic acid resin, as the carbamate resins of ether-containing key; The carbamate resins that contains ester group; Polycarbonate resin; Contain amino modified resin; Fluorine-containing modified resin.
The product made from the used leather of the present invention is when being used in garment industry, from guaranteeing to consider that the ratio of the vapor permeability of high temperature and low temperature is 1.4 or higher discharging under sweat and the low temperature environment the warm comfortableness of somatosensory under high temperature, the high humidity environment.A numerical value represented in the term here " vapor permeability ", refer under probe temperature, and water-fast force value, unit is mmHg." at low temperatures " the hungry temperature in the expression clothes is at 0-20 ℃, and the temperature in " at high temperature " expression clothes is at 20-50 ℃.Traditional waterproof, saturating wet leather have the wet thoroughly value ratio of higher poisture-penetrability and high temperature/low temperature, so when high temperature, fabric discharges steam energetically; Meanwhile, the heat when potential water evaporates also is released when low temperature, and comfortableness so just is provided easily.Yet poisture-penetrability is also higher at low temperatures, and the heat during potential water evaporation is also taken out of external, so the heat retention is relatively poor.On the other hand, the waterproof fabric of traditional low-moisture permeability, because poisture-penetrability is poor, steam is difficult for being distributed to external when low temperature, keep heat in vivo but assemble, but under the high temperature, low poisture-penetrability can make the people that the sensation of humidity, adhesion is arranged.
During high temperature poisture-penetrability more during high and low temperature poisture-penetrability low more, the wet thoroughly ratio of high more high temperature/low temperature, temperature will depend on poisture-penetrability more in the body.That is to say that it is few strong more with the tendency that keeps heat that steam discharges actively that steam discharges when preventing that clothes from having flavor, low temperature during high temperature.
Among the present invention, poisture-penetrability is according to JISL 1099A-1 standard testing.Test condition is: 5 ℃ of low temperature, humidity 90%; 40 ℃ of high temperature, humidity 90%.
The temperature of testing when high temperature, low temperature, humidity neither be absolute.Temperature, humidity depend on the variation of operating condition in the clothes, get final product so long as guarantee the poisture-penetrability height of high temperature/low temperature.
The poisture-penetrability of waterproof of the present invention, moisture permeable artificial leather is at 40 ℃, under the high temperature test condition of humidity 90% and 5 ℃, is respectively 8000g/m under the low-temperature test condition of humidity 90%
2.24h or slightly many and 1000g/m
2.24h or many slightly.Water pressure resistance is about 1000mmH
2O or many slightly.
Steam is discharged into the outside energetically and is retained under what temperature, can realize by the glass transition temperature of regulating polyurethane resin.Consider that from guaranteeing common work and motion comfortableness the glass transition temperature of the polyurethane resin that the present invention uses is-20 to 20 ℃ of scopes.
Waterproof of the present invention, moisture permeable artificial leather have higher poisture-penetrability under high temperature, high humidity environment; Heat retentivity is preferably arranged again under low temperature environment, make temperature, humidity to regulate.
The manufacture method of waterproof of the present invention, moisture permeable artificial leather is described below:
1, makes waterproof, moisture permeable artificial leather with wet method.
Polyurethane resin fat is dissolved in the polar solvent, and with its coating on a surface of fabric, coated weight is 3-50g/m preferably
2, solidify like this and remove solvent all than being easier to.In order to keep good hand feeling, the coated weight of polyurethane resin 3-10g/m preferably after oven dry
2The water pressure resistance performance of the leather of the importance that in the middle of using, will consider, by said method, polyurethane resin wet method solidify with dry run in further formation.On choice of Solvent, consider the resin dissolubility therein and the easy eccysis of solvent, mainly tend to from water-soluble polar organic solvent to select polar organic solvent as solvent, dimethyl formamide (hereinafter to be referred as DMF) for example, dimethylacetylamide and N-Methyl pyrrolidone.In addition, also might in resin liquid, add isocyanate crosslinking, surfactant etc.This isocyanate crosslinking is the cross-linked structure that is used for forming film, thereby helps to improve film strength and durability.
Removing of hardening of resin and solvent can realize by the method that conventional wet is solidified.The suitable solidification liquid of doing of the solution of above-mentioned solvent and water.For the diameter of adjusting pore-forming in the resin molding in suitable scope, setting temperature is preferably from 5 ℃ to 50 ℃.Water is the most handy material of dispeling solvent.The temperature optimum range that removes solvent is 10 ℃ to 80 ℃.To remove from office the base cloth oven dry with conventional method then.In this case, bake out temperature is preferably 60 ℃ to 140 ℃.And,, after leather base cloth drying, carry out WATER RESISTANCE as required and handle in order to give leather persistent water repelling property.In WATER RESISTANCE is handled, may draw the water repelling property that conforms to known conclusion.In addition, in order to improve the quality of product, should be for further processing.Base cloth can carry out anti-water treatment or calendering processing before coated with resins.
The resin molding that is made by wet method easily forms cellular provides the waterproof and moisture permeability leather good poisture-penetrability.
2, polyurethane resin is coated on the release liners and makes waterproof, moisture permeable artificial leather in the method that is pasted on the fabric base cloth.
In the dry run of the Water-proof artificial leather of producing, the resin solution that contains volatile organic solvent of above-mentioned polyurethane resin is coated in and forms urethane resin film on the release liners, and its consumption is 50--200g/m preferably
2Then, a kind of binding resin is applied on the resin molding, the words that need then are laminated to it on surface of leather base cloth 40 ℃ to 150 ℃ dryings, and release liners is peeled off.Dried polyurethane resin coated weight is preferably in 10-50g/m
2, in the example of first-selection, volatile solvent comprises toluene, MEK, isopropyl alcohol and dimethyl formamide.Ultra-violet absorber, antioxidant, blowing agent etc. can add in the resin liquid.In the process of drying, porous resin film and atresia resin molding can produce.In addition, isocyanate crosslinking, surfactant etc. also can add in the resin liquid.This isocyanate crosslinking is the crosslinked mechanism that is used for forming film, thereby helps to improve film strength and durability.
In addition, in dry run, according to the present invention, on the Water-proof artificial leather resin surface that this resin molding can be applied to be made by traditional polyurethane resin.The waterproof that makes by this method, its water pressure resistance of moisture permeable artificial leather are 10000mmH
2O or higher.
According to the present invention, the poisture-penetrability of waterproof, moisture permeable artificial leather depends on temperature.Specifically, when temperature is low, the motion of aqueous vapor, latent energy motion is just tended to heat and is kept performance; When temperature was high, steam actively discharged latent energy by the leather fabric, prevented to produce to perspire and the temperature rising.Therefore, use Water-proof artificial leather of the present invention at wind formula disintegrating machine, skiwear, work clothes, footwear etc., before motion or motion early stage, when health does not also warm up, can provide the clothing water resistance, shows good heat maintenance performance; In motion process or after motion finishes, keep high water vapour permeability when body heat is got up, can not cause perspiration, refrigerant sensation can be provided, comfortable and good feel arranged.
With reference now to the following experiment description that the present invention is detailed.
In following example, poisture-penetrability and water pressure resistance performance test respectively according to JISL 1099A-1 and JISL 1092 that (it is 2000mmH that low hydraulic pressure method is fit to the product water pressure resistance
2O or lower; It is 20000mmH that high hydraulic pressure method is fit to the product water pressure resistance
2O or higher).
Experiment 1
Polyester ponzee woven fabric (75D-72F) all is warp and parallel, end cabin spacing: 101 yarn/inches, select at interval: 80 yarn/inches) by 10% the aqueous solution of Asahi Guard AG710 as a fluorine-containing waterproof filler, the woven fabric of Tian Chonging is dried and repairs then.
Polyalcohol is dissolved among the DMF under 50 ℃ of stirring conditions, then adds vulcabond.The mixture stir about made prepolymer in 1 hour, and then, chain extending reaction takes place in the chain extender the inside that joins dropwise, prepares DMF25% solution with this weight by polyurethane resin.Above-mentioned polyurethane resin with DMI as isocyanates, molecular weight is that 2000,1200 polyethylene glycol, polyethylene glycol adipate glycol are as polyalcohol, 1, the 4-butanediol is as chain extender, and the mixed of 3.4:0.5:0.5:2.5 reaction in molar ratio makes.The glass transformation temperature of polyurethane resin is 0.2 ℃, and the content of ethylene oxide segment is 8.4Mol/kg.
Resin dissolves is by weight calculation, adds 10 parts DMF and 1 part of ResamineNE in 100 parts of resins as isocyanate crosslinking, mixes mutually, and coating is on the surface of above-mentioned fabrics, and coated weight is 15g/m
2Coating was solidified in the aqueous solution 5 minutes, and after this, solvent is replaced by water in the time of 25 ℃.Coated fabric is washed, and drying is repelled processing by fluorinated water.Carry out last processing at 150 ℃ then, the dried coated weight of polyurethane resin is 5g/m
2Testing coating fabric, thereby acquisition amount poisture-penetrability, water pressure resistance, resistance and vapor transfer rate ratio (poisture-penetrability that depends on environment) see Table 1.
Experiment 2
Polyester ponzee woven fabric (75D-72F) all is warp and parallel; end cabin spacing: 101 yarn/inches; select at interval: the aqueous solution silver-colored protection liquid 710 and the fluorinated water repulsion that 80 yarn/inches) are subjected to filling with 10% are handled, and make the dry and repairing of the braiding of filling up.
Polyalcohol is dissolved among the DMF under 50 ℃ of stirring conditions, then adds vulcabond.The mixture stir about made prepolymer in 1 hour, and then, chain extending reaction takes place in the chain extender the inside that joins dropwise, prepares DMF25% solution with this weight by polyurethane resin.Above-mentioned polyurethane resin with DMI as isocyanates, molecular weight is that 2000,1200 polyethylene glycol, polyethylene glycol adipate glycol are as polyalcohol, 1, the 4-butanediol is as chain extender, and the mixed of 1.2:0.7:0.7:0.2 reaction in molar ratio makes.The glass transformation temperature of polyurethane resin is 3.0 ℃, and the content of ethylene oxide segment is 11.3Mol/kg.
Resin dissolves is by weight calculation, adds 10 parts DMF and 1 part of ResamineNE in 100 parts of resins as isocyanate crosslinking, mixes mutually, and coating is on the surface of above-mentioned fabrics, and coated weight is 15g/m
2Coating was solidified in the aqueous solution 5 minutes, and after this, solvent is replaced by water in the time of 25 ℃.Coated fabric is washed, and drying is repelled processing by fluorinated water.Carry out last processing at 150 ℃ then, the dried coated weight of polyurethane resin is 5g/m
2Testing coating fabric, thereby acquisition amount poisture-penetrability, water pressure resistance, resistance and vapor transfer rate ratio (poisture-penetrability that depends on environment) see Table 1.
Experiment 3
Polyester ponzee woven fabric (75D-72F) all is warp and parallel, holds the cabin spacing: 101 yarn/inches, select at interval: the aqueous solution silver protection liquid and the fluorinated water repulsion that 80 yarn/inches) are subjected to filling with 10% are handled, and make the braiding of filling dry and perfect.
Polyalcohol is dissolved among the DMF under 50 ℃ of stirring conditions, then adds vulcabond.The mixture stir about made prepolymer in 1 hour, and then, chain extending reaction takes place in the chain extender the inside that joins dropwise, prepares DMF25% solution with this weight by polyurethane resin.Above-mentioned polyurethane resin with DMI as isocyanates, molecular weight is that 2000,1200 polyethylene glycol, polyethylene glycol adipate glycol are as polyalcohol, 1, the 4-butanediol is as chain extender, and the mixed of 3.3:0.5:0.5:2.4 reaction in molar ratio makes.The glass transformation temperature of polyurethane resin is-8.5 ℃, and the content of ethylene oxide segment is 7.4Mol/kg.
Resin dissolves is by weight calculation, adds MEK and 80 parts of toluene of 20 parts in 100 parts of PU resins, mixes them mutually, and coating is in the surface of release liners, and coated weight is 80g/m
2Coating is 120 ℃ of dryings.Then, in 100 parts of PU resins, add 60 parts of toluene and 10 parts of ResamineNE crosslinking agent, mix mutually as isocyanates, coating is crushed to film on film, push after 24 hours, release liners is peeled off from fabric, is 15g/m after the polyurethane resin drying of covering
2Testing coating fabric, thereby acquisition amount poisture-penetrability, water pressure resistance, resistance and vapor transfer rate ratio (poisture-penetrability that depends on environment) see Table 1.
Experiment 4
The stand-by mode that rolls woven fabric is according to experiment 3, go out a polyester knitting (through becoming textiles 30d and 20) and be used as woven fabric, above-mentioned polyurethane resin is with MDI vulcabond the most, molecular weight is that 2000 polyethylene glycol, polytetrahydrofuran diol are as polyalcohol, ethylene glycol is chain extender, and the mixed reaction for 3.30:0.55:0.45:2.40 in molar ratio makes.The glass transition temperature of polyurethane resin is-18 ℃, and the content of ethylene oxide segment is 7.8Mol/kg.Test the woven fabric of this laminated board, thus acquisition amount poisture-penetrability, water pressure resistance, resistance and vapor transfer rate ratio (water permeability that depends on environment) see Table 1.
Experiment 5
The solution of hybrid resin: at the identical fabric in experiment 4 surfaces, coating is solidified as 5 minutes in the aqueous solution with the synthetic coating.After this at 25 ℃, solution is water-washed away, and coating is dried then, is covered as 27g/m to provide a fabric to have perforated membrane
2Then, fabric has perforated membrane and no pore film and prepares to use resin and the method identical with example 4.Test the woven fabric of this laminated board, thus acquisition amount poisture-penetrability, water pressure resistance, resistance and vapor transfer rate ratio (water permeability that depends on environment) see Table 1.
Similitude test 1
Coated fabric adopts experiment 2 same modes to prepare, MDI, and polyethylene glycol, polyethylene glycol adipate diol and 2, the mol ratio of 4-butanediol is 3.3:0.3:0.7:2.4.The glass transition temperature of polyurethane resin is 0.8 ℃, and the content of ethylene oxide segment is 4.54Mol/kg.Testing coating fabric, thereby acquisition amount poisture-penetrability, the pressure of water, resistance and vapor transfer rate ratio (water permeability that depends on environment), the result sees Table 1.
Similitude test 2
The preparation of coated fabric is adopted in a like fashion, promptly tests 2 and removes the used glass transition temperature of polyurethane resin and be-50 ℃, testing coating fabric, thereby acquisition amount poisture-penetrability, the pressure of water, resistance and vapor transfer rate ratio (water permeability that depends on environment), the result sees Table 1.
Similitude test 3
The preparation of coated fabric is adopted and is tested 2 identical modes, and the used glass transition temperature of polyurethane resin is-50 ℃, high poisture-penetrability.This laminated fabric is tested, thus acquisition amount poisture-penetrability, the pressure of water, resistance and vapor transfer rate ratio (water permeability that depends on environment), the result sees Table 1.
Similitude experiment 4
The preparation of coated fabric is adopted in the same way, promptly tests 4, and the used glass transition temperature of polyurethane resin is-50 ℃, high poisture-penetrability.This laminated fabric is tested, thus acquisition amount poisture-penetrability, the pressure of water, resistance and vapor transfer rate ratio (water permeability that depends on environment), the result sees Table 1.
| Glass transition temperature (Tg, ℃) | The molar fraction of ethylene oxide | Poisture-penetrability | Water pressure resistance | Anti-vapour pressure | The water pressure resistance ratio | |
| Example 1 | 0.2 | 8.4 | 6800 | 11232 | 1200 | 1.44 |
| Example 2 | 3.0 | 11.3 | 7060 | 15432 | 1000 | 1.55 |
| Example 3 | -8.5 | 7.4 | 5250 | 15000 | 1200 | 1.56 |
| Example 4 | -18 | 7.8 | 6240 | 16000 | 1500 | 1.53 |
Claims (13)
1, waterproof, moisture permeable artificial leather are by the fabric base cloth, provide this artificial leather at least one surface, resin film layer, make by isocyanates, polyalcohol and chain extender reaction, glass transition temperature is-20 to 20 ℃, ethylene oxide segment content is at least 7.0mol/kg two parts to be formed, and it is characterized in that its high temperature moisture permeability is 1.4 or higher with the ratio of low temperature moisture permeability.
2, waterproof according to claim 1, moisture permeable artificial leather is characterized in that, polyol component is made up of polyethylene glycol, polytetrahydrofuran diol, polyethylene glycol adipate glycol, and molecular weight is 500-3000.
3, waterproof according to claim 1, moisture permeable artificial leather is characterized in that, above-mentioned resin molding is a porous.
4, waterproof according to claim 1, moisture permeable artificial leather is characterized in that, above-mentioned resin molding is an atresia.
5, waterproof according to claim 1, moisture permeable artificial leather is characterized in that, the heat of above-mentioned waterproof, saturating wet leather keeps performance and environment temperature on every side to be inversely proportional to, and poisture-penetrability is 1000g/m in low temperature environment
224hr or lower is 8000g/m under hot environment
224hr or higher.
6, waterproof of the present invention, moisture permeable artificial leather provide at least one surface of this base cloth by the fabric base cloth; Resin film layer, make by different hydrogen acid ether (hydrogen acid ester) and polyalcohol and chain extender reaction, glass transition temperature is-20 to 20 ℃, and ethylene oxide segment content is at least 7.0mol/kg two parts to be formed, and it is characterized in that: its high temperature moisture permeability is 1.4 or higher with the ratio of low temperature moisture permeability.
7, waterproof according to claim 6, moisture permeable artificial leather is characterized in that, polyol component is by polyethylene glycol and PTMG, and the oxirane adipate ester is formed, and molecular weight is 500-3000.
8, waterproof according to claim 7, moisture permeable artificial leather is characterized in that, above-mentioned resin molding is a porous.
9, waterproof according to claim 8, moisture permeable artificial leather is characterized in that, above-mentioned resin molding is an atresia.
10, waterproof according to claim 8, moisture permeable artificial leather is characterized in that, the poisture-penetrability of above-mentioned waterproof, saturating wet leather is 1000g/m in low temperature environment
224hr or lower is 8000g/m under hot environment
224hr or higher.
11, waterproof according to claim 7, moisture permeable artificial leather is characterized in that, the heat conservation rate and the ambient temperature of saturating wet leather are inversely proportional to.
12, the preparation method of waterproof of the present invention, moisture permeable artificial leather, comprise following steps: will be by isocyanates and polyalcohol and chain extender reaction, glass transition temperature is at-20 to 20 ℃, the polyurethane resin that ethylene oxide segment content is at least 7.0mol/kg is dissolved in the polar solvent, and with its coating on a surface of fabric, this coating wet method is set in obtains rete in the coagulating basin.
13, the preparation method of waterproof of the present invention, moisture permeable artificial leather, comprise following steps: will be by isocyanates and polyalcohol and chain extender reaction, glass transition temperature is at-20 to 20 ℃, the polyurethane resin that ethylene oxide segment content is at least 7.0mol/kg is dissolved in the polarity volume, and it is coated in film forming on the release liners, then this film is sticked to fabric face and form leather.
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| CNA2008101672852A CN101381962A (en) | 2008-10-20 | 2008-10-20 | Water proof and moisture permeable artificial leather and method for making same |
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| CN102677480B (en) * | 2012-05-28 | 2015-05-20 | 佛山市高明尚昂科技有限公司 | Production method of novel artificial leather |
| CN102677480A (en) * | 2012-05-28 | 2012-09-19 | 佛山市高明尚昂科技有限公司 | Production method of novel artificial leather |
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| CN105461887A (en) * | 2016-01-13 | 2016-04-06 | 江苏东邦科技有限公司 | Method for preparing PU film for high-grade sportswear |
| CN107938377A (en) * | 2017-12-29 | 2018-04-20 | 上海市纺织科学研究院有限公司 | A kind of cold-proof breathable cloth |
| CN112030578A (en) * | 2020-08-28 | 2020-12-04 | 佛山市智布互联纺织有限公司 | Single-sided moisture permeable cotton-containing knitted fabric and processing technology thereof |
| CN112341591A (en) * | 2020-10-27 | 2021-02-09 | 上海伊纯实业有限公司 | Polyurethane material and preparation method and application thereof |
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