CN103910969A - Water-resistant air-permeable polyurethane film and preparation method thereof - Google Patents
Water-resistant air-permeable polyurethane film and preparation method thereof Download PDFInfo
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- CN103910969A CN103910969A CN201410157481.7A CN201410157481A CN103910969A CN 103910969 A CN103910969 A CN 103910969A CN 201410157481 A CN201410157481 A CN 201410157481A CN 103910969 A CN103910969 A CN 103910969A
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Abstract
The invention discloses a water-resistant air-permeable polyurethane film and a preparation method thereof. The polyurethane film comprises a water-based polyurethane resin, and 10-30 wt% of acrylate monomer, 0.4-0.6 wt% of leveling agent, 0.4-0.6 wt% of peeling assistant, 1-2 wt% of extinction powder, 0.1-1 wt% of catalyst, 2-10 wt% of opening agent and 20-60 wt% of solvent on the basis of the water-based polyurethane resin. The water-resistant air-permeable polyurethane film comprises the water-based polyurethane resin, acrylate monomer, leveling agent, peeling assistant, extinction powder, catalyst, opening agent and solvent. By optimizing the contents of the raw material, the polyurethane film has favorable water resistance, air permeability, softness, wear resistance, mechanical properties and tactile sensation.
Description
Technical field
The technical field that the present invention relates to polyurethane film, relates in particular to a kind of waterproof ventilation polyurethane film and preparation method thereof.
Background technology
Urethane full name is polyurethane(s), is the general designation that contains the macromolecular cpd of repetition carbamate groups on main chain.It is to be formed by organic diisocyanate or polyisocyanates and dihydroxyl or polyol addition polymerization.Polyurethane material purposes is very wide, can replace rubber, plastics, nylon etc., be widely used in automobile making, refrigerator manufacture, footwear, synthetic leather, fabric,, many fields such as petrochemical complex, mining machinery, aviation, medical treatment, agricultural.The mechanical property of urethane has very large adjustability, the excellent properties such as that its goods have is wear-resisting, heatproof, sealing, sound insulation, good processability, degradable.Aqueous polyurethane is using water as dispersion medium, there is the advantages such as nontoxic, and can more intactly retain the characteristic of solvent borne polyurethane, therefore become one of preferred material of fabric coating finish, but in aqueous polyurethane molecular chain, contain hydrophilic chain link, can affect the water resistance of coating substance, and feel is partially hard when low temperature.
Polyurethane film is applied to the preparation of ready-made clothes and fashionable dress more and more in recent years, and the clothes that adopt ventilative thin polyurethane mould material to prepare not only have respiratory function, can also be antistatic; Polyurethane film in sportwear and goods with making the fabrics such as submarine armor, swim suit, rhythm clothing and air Landing clothes, Aerated water bed, ball inner bag, boat, safety buoy and material inside.More than room temperature, can there is good water vapour permeability.It is good that thermoplasticity polyurethane film has soft feel, and intensity is high, windproof ventilative, outstanding features such as environmental protection and be widely used in textile composite fabric, and for Sport & Casual, the fields such as special type protection.The polyurethane film of prior art mostly is the film of hydrophilic, and its water-repellancy is poor, shows as water-swellable, and its ventilation property, oil-proofness are also poor in addition.
Summary of the invention
In view of this, one aspect of the present invention provides a kind of polyurethane film of waterproof and breathable, and this polyurethane film has good water-repellancy, ventilation property, flexibility, wear resistance, mechanical property and better sense of touch.
A kind of waterproof ventilation polyurethane film, comprise waterborne polyurethane resin, and in the quality of waterborne polyurethane resin, 10～30% acrylic ester monomer, 0.4～0.6% flow agent, 0.4～0.6% help stripping agent, 1～2% flatting silica, 0.1～1% catalyzer, 2～10% opening agent, 20～60% solvent.
Preferably, comprise waterborne polyurethane resin, in the quality of waterborne polyurethane resin, 25% acrylic ester monomer, 0.5% flow agent, 0.5% help stripping agent, 1.5% flatting silica, 0.5% catalyzer, 7% opening agent, 50% solvent, with the deionized water of surplus.
Preferably, acrylic ester monomer is compositions a kind of in methyl acrylate, ethyl propenoate, isobutyl acrylate, 2-methyl methacrylate, ethyl 2-methacrylate or at least 2 kinds, and described solvent is compositions a kind of in butanone, toluene, dimethyl formamide or at least 2 kinds.
Preferably, flow agent is C
1～10alkyl-modified organo-siloxane, described in help stripping agent be polyether-modified polydimethylsiloxane, described flatting silica OK-412 flatting silica.
Preferably, catalyzer is compositions a kind of in dibutyl tin laurate, stannous octoate, dibutyltin diacetate or at least 2 kinds, and opening agent is compositions a kind of in amine hydroxybenzene, silicon-dioxide AB905, silicon-dioxide AB702 or at least 2 kinds.
In the feed composition of above polyurethane film, the deionized water adding is dispersion medium, is understandable that, " surplus " is only enough to make flatting silica fully to soak or dissolve the effect that it is fully disperseed to reach.The amount that it is concrete, those skilled in the art can obtain by simple practice.
Flatting silica is the glossiness that reduces mould material, makes it reach half light or unglazed effect.OK-412 flatting silica is a kind of white powder, and taking silicon-dioxide as main component, composition is up to more than 98%, and its median size is at several microns.It has advantages of that easy dispersion, extinction are good, increase slip, suspension is good.
Flow agent is to impel glue in drying and forming-film process, to form smooth, smooth, a uniform film.C
1～ 10alkyl-modified organopolysiloxane is in macromolecular chain, to contain the polymkeric substance that a class of alkyl contains silicon-oxide structure unit.Alkyl wherein can improve thermostability, consistency and foam stability not, even has their defoaming function.
Help stripping agent to be called again release agent, add that can to impel dry film to be easy to from coated substrate separated.Polyether-modified polydimethylsiloxane is to adopt ethers oligopolymer and polydimethylsiloxane to carry out condensation reaction to obtain.It had both been dissolvable in water oil type solvent, was dissolvable in water again water.It can anti, increases wear resistance, increases separate-type paper and obtain access times and can obviously improve glossiness, weathering resistance and the vividness of coating, and this external enwergy gives leather smooth feel, can effectively improve the dispersiveness of pigment and filler, improves the homogeneity of color; Can be used as the waterproof processing of fabric coating.
Opening agent is to form taking vegetables oil as Raw material processing, good with resin-phase dissolubility, to heat, oxygen, UV stable, there is typical polarity and non-polar molecule structure, have anti stick, smooth, increase the effects such as cunning, levelling, waterproof, damp proof, anti-precipitation, fouling resistance, antistatic and dispersion.It is a kind of nonionogenic tenside of nontoxic corrosion-free, excellent performance.
Acrylate is the general name of the ester class of vinylformic acid and homologue thereof.Important have methyl acrylate,
Ethyl propenoate, 2-methyl methacrylate and ethyl 2-methacrylate.Can autohemagglutination or and other monomer copolymerizations, be the monomer of manufacturing tackiness agent, synthetic resins, specialty elastomer and plastics.Its multipolymer has the characteristics such as good oil resistant, thermotolerance, tint retention, uvioresistant variable color.
The present invention provides a kind of method of preparing above-mentioned waterproof ventilation polyurethane film on the other hand, and the waterproof ventilation polyurethane film that the method obtains has good water-repellancy, ventilation property, flexibility, wear resistance, mechanical property and better sense of touch.
Prepare the method as above-mentioned waterproof ventilation polyurethane film, comprise the following steps:
(1) by the same waterborne polyurethane resin quality in waterborne polyurethane resin, 10～30% acrylic ester monomer, 0.4～0.6% flow agent, 0.4～0.6% help stripping agent, 0.1～1% catalyzer, 2～10% opening agent, 20～60% solvent are fully mixed and made into hybrid resin, and 1～2% flatting silica and deionized water are fully mixed and made into mixed solution;
(2) mixed solution is added in hybrid resin, be thoroughly mixed to form glue, glue is inserted to foaming in foaming machine and form foam;
(3) after foam is coated on coated substrate, coated substrate is dried, obtains waterproof ventilation polyurethane film.
Preferably, the described mixed solution of step (2) successively divides and is added in hybrid resin for three times according to 30%, 30% and 40% add-on, and the blowing ratio of described foaming is 4～6, and flow is 7～12g/s.
Preferably, in step (1) and step (2), mixing process is all carried out in 50～80 DEG C of water-baths.
Preferably, in step (3), the glue spread of coating is 100～200g/m
2, coated substrate is separate-type paper, drying process is that coated substrate is inserted in the baking oven of 80～140 DEG C and passed through baking oven with the speed of 10～20m/min.
Preferably, step (3) afterwards, also comprises that step (4) utilizes central coiling machine that waterproof ventilation polyurethane film is separated with separate-type paper, batches rolling.
In waterproof ventilation polyurethane film of the present invention, comprise waterborne polyurethane resin, acrylic ester monomer, flow agent, help stripping agent, flatting silica, catalyzer, opening agent and solvent.By the content optimization to each feed composition, make polyurethane film there is good waterproof and breathable, soft type, wear-resisting, mechanical property and better sense of touch.
Embodiment
The present invention is described in further detail in conjunction with the embodiments respectively below.
In below implementing, related each industrial chemicals is commercially available.
Embodiment 1: the present embodiment waterproof ventilation polyurethane film comprises waterborne polyurethane resin, and in the following component of waterborne polyurethane resin quality:
This waterproof ventilation polyurethane film adopts following methods to make:
Under 70 DEG C of water bath condition, by waterborne polyurethane resin (DL-1537, Bayer A.G produces) together with acrylic ester monomer, acrylic ester monomer, flow agent, help stripping agent, catalyzer, opening agent, the stirrer that solvent is 1000rpm at rotating speed is fully mixed and made into hybrid resin under stirring, the stirrer that flatting silica and deionized water are 1500rpm at rotating speed is fully mixed and made into mixed solution under stirring, mixed solution is successively according to 30%, 30% and 40% add-on is divided to be added to for three times in hybrid resin and in the stirrer that is 300rpm at rotating speed to continue to stir and is obtained glue.Then, glue is inserted in foaming machine, and when the flow of 7～12g/s some time of foaming obtains aqueous polyurethane foam to the foaming according to 4～6.Then, by aqueous polyurethane foam according to 150g/m
2glue spread is coated in separate-type paper, passes through the oven drying of 110 DEG C with the speed of 10～20m/min, obtains waterproof ventilation polyurethane film.Finally, utilize central coiling machine that waterproof ventilation polyurethane film is separated and obtain the finished product from separate-type paper.
Embodiment 2: the present embodiment waterproof ventilation polyurethane film comprises waterborne polyurethane resin, and in the following component of waterborne polyurethane resin quality:
This waterproof ventilation polyurethane film adopts following methods to make:
Under 70 DEG C of water bath condition, by waterborne polyurethane resin (DL-1537, Bayer A.G produces) together with acrylic ester monomer, acrylic ester monomer, flow agent, help stripping agent, catalyzer, opening agent, the stirrer that solvent is 1000rpm at rotating speed is fully mixed and made into hybrid resin under stirring, the stirrer that flatting silica and deionized water are 1500rpm at rotating speed is fully mixed and made into mixed solution under stirring, mixed solution is successively according to 30%, 30% and 40% add-on is divided to be added to for three times in hybrid resin and in the stirrer that is 300rpm at rotating speed to continue to stir and is obtained glue.Then, glue is inserted in foaming machine, and when the flow of 7～12g/s some time of foaming obtains aqueous polyurethane foam to the foaming according to 4～6.Then, by aqueous polyurethane foam according to 150g/m
2glue spread is coated in separate-type paper, passes through the oven drying of 110 DEG C with the speed of 10～20m/min, obtains waterproof ventilation polyurethane film.Finally, utilize central coiling machine that waterproof ventilation polyurethane film is separated and obtain the finished product from separate-type paper.
Embodiment 3: the present embodiment waterproof ventilation polyurethane film comprises waterborne polyurethane resin, and in the following component of waterborne polyurethane resin quality:
This waterproof ventilation polyurethane film adopts following methods to make:
Under 70 DEG C of water bath condition, by waterborne polyurethane resin (DL-1537, Bayer A.G produces) together with acrylic ester monomer, acrylic ester monomer, flow agent, help stripping agent, catalyzer, opening agent, the stirrer that solvent is 1000rpm at rotating speed is fully mixed and made into hybrid resin under stirring, the stirrer that flatting silica and deionized water are 1500rpm at rotating speed is fully mixed and made into mixed solution under stirring, mixed solution is successively according to 30%, 30% and 40% add-on is divided to be added to for three times in hybrid resin and in the stirrer that is 300rpm at rotating speed to continue to stir and is obtained glue.Then, glue is inserted in foaming machine, and when the flow of 7～12g/s some time of foaming obtains aqueous polyurethane foam to the foaming according to 4～6.Then, by aqueous polyurethane foam according to 150g/m
2glue spread is coated in separate-type paper, passes through the oven drying of 110 DEG C with the speed of 10～20m/min, obtains waterproof ventilation polyurethane film.Finally, utilize central coiling machine that waterproof ventilation polyurethane film is separated and obtain the finished product from separate-type paper.
Embodiment 4: the present embodiment waterproof ventilation polyurethane film comprises waterborne polyurethane resin, and in the following component of waterborne polyurethane resin quality:
This waterproof ventilation polyurethane film adopts following methods to make:
Under 70 DEG C of water bath condition, by waterborne polyurethane resin (DL-1537, Bayer A.G produces) together with acrylic ester monomer, acrylic ester monomer, flow agent, help stripping agent, catalyzer, opening agent, the stirrer that solvent is 1000rpm at rotating speed is fully mixed and made into hybrid resin under stirring, the stirrer that flatting silica and deionized water are 1500rpm at rotating speed is fully mixed and made into mixed solution under stirring, mixed solution is successively according to 30%, 30% and 40% add-on is divided to be added to for three times in hybrid resin and in the stirrer that is 300rpm at rotating speed to continue to stir and is obtained glue.Then, glue is inserted in foaming machine, and when the flow of 7～12g/s some time of foaming obtains aqueous polyurethane foam to the foaming according to 4～6.Then, by aqueous polyurethane foam according to 150g/m
2glue spread is coated in separate-type paper, passes through the oven drying of 110 DEG C with the speed of 10～20m/min, obtains waterproof ventilation polyurethane film.Finally, utilize central coiling machine that waterproof ventilation polyurethane film is separated and obtain the finished product from separate-type paper.
The waterproof ventilation polyurethane film that embodiment 1～4 is obtained and commercially available polyurethane film carry out following test: according to ASTM D737 standard, ventilation property (taking vapor transfer rate as index) is tested; According to JIS L1099B standard to water-repellancy (taking resistance to hydrostatic pressure as index); Endwise tensile strength and transverse tensile strength are tested according to GB/T4757-1997; Sticking power is tested according to GB/9286; Wear resistance is according to EN530(sand paper specification GRIT100) test 5000 turns.
Test result is as following table:
As can be seen from the above table, the polyurethane film of embodiment 1～4 has better water-proof breathable properties, mechanical property, sticking power and wear resistance compared with commercially available polyurethane film.
Meanwhile, the relatively commercially available hydrophilic film of the waterproof breathable membrane of preparation compare there is the water not swelling of chance, more soft, sense of touch better and nontoxic to human body, meets the advantages such as environmental protection concept.
Should be noted that and understand, in the case of not departing from the spirit and scope of accompanying claim the present invention for required protection, can make various amendments and improvement to the present invention of foregoing detailed description.Therefore, the scope of claimed technical scheme is not subject to the restriction of given any specific exemplary teachings.
Applicant's statement, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, and the selections of the equivalence replacement to the each raw material of product of the present invention and the interpolation of ancillary component, concrete mode etc., within all dropping on protection scope of the present invention and open scope.
Claims (10)
1. a waterproof ventilation polyurethane film, it is characterized in that, comprise waterborne polyurethane resin, and in the quality of waterborne polyurethane resin, 10～30% acrylic ester monomer, 0.4～0.6% flow agent, 0.4～0.6% help stripping agent, 1～2% flatting silica, 0.1～1% catalyzer, 2～10% opening agent, 20～60% solvent.
2. waterproof ventilation polyurethane film according to claim 1, it is characterized in that, in the quality of waterborne polyurethane resin, 25% acrylic ester monomer, 0.5% flow agent, 0.5% help stripping agent, 1.5% flatting silica, 0.5% catalyzer, 7% opening agent, 50% solvent and the deionized water of surplus.
3. waterproof ventilation polyurethane film according to claim 1, it is characterized in that, described acrylic ester monomer is compositions a kind of in methyl acrylate, ethyl propenoate, isobutyl acrylate, 2-methyl methacrylate, ethyl 2-methacrylate or at least 2 kinds, and described solvent is compositions a kind of in butanone, toluene, dimethyl formamide or at least 2 kinds.
4. waterproof ventilation polyurethane film according to claim 1, is characterized in that, described flow agent is C
1～10alkyl-modified organo-siloxane, described in help stripping agent be polyether-modified polydimethylsiloxane, described flatting silica OK-412 flatting silica.
5. waterproof ventilation polyurethane film according to claim 1, it is characterized in that, described catalyzer is compositions a kind of in dibutyl tin laurate, stannous octoate, dibutyltin diacetate or at least 2 kinds, and opening agent is compositions a kind of in amine hydroxybenzene, silicon-dioxide AB905, silicon-dioxide AB702 or at least 2 kinds.
6. prepare a method for waterproof ventilation polyurethane film as claimed in claim 1, it is characterized in that, comprise the following steps:
(1) by the same waterborne polyurethane resin quality in waterborne polyurethane resin, 10～30% acrylic ester monomer, 0.4～0.6% flow agent, 0.4～0.6% help stripping agent, 0.1～1% catalyzer, 2～10% opening agent, 20～60% solvent are fully mixed and made into hybrid resin, and 1～2% flatting silica and deionized water are fully mixed and made into mixed solution;
(2) mixed solution is added in hybrid resin, be thoroughly mixed to form glue, glue is inserted to foaming in foaming machine and form foam;
(3) after foam is coated on coated substrate, coated substrate is dried, obtains waterproof ventilation polyurethane film.
7. method according to claim 6, is characterized in that, mixed solution described in step (2) successively divides and is added in hybrid resin for three times according to 30%, 30% and 40% add-on, and the blowing ratio of described foaming is 4～6, and flow is 7～12g/s.
8. method according to claim 6, is characterized in that, in step (1) and step (2), mixing process is all carried out in 50～80 DEG C of water-baths.
9. method according to claim 6, is characterized in that, the glue spread of the described coating of step (3) is 100～200g/m
2, coated substrate is separate-type paper, described drying process is that coated substrate is inserted in the baking oven of 80～140 DEG C and passed through baking oven with the speed of 10～20m/min.
10. method according to claim 6, is characterized in that, described step (3) afterwards, also comprises that step (4) utilizes central coiling machine that waterproof ventilation polyurethane film is separated with separate-type paper, batches rolling.
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| CN104788712A (en) * | 2015-03-25 | 2015-07-22 | 嘉兴学院 | Pore-filling polyurethane waterproof and moisture permeable membrane and preparation method thereof |
| CN106823862A (en) * | 2017-03-05 | 2017-06-13 | 河北工业大学 | A kind of dry-forming method of microporous polyurethane film |
| CN114106264A (en) * | 2021-11-24 | 2022-03-01 | 天津工业大学 | Polyester modified organic silicon coating leveling agent and preparation method thereof |
| CN115142196A (en) * | 2021-08-18 | 2022-10-04 | 张家港市宏裕新材料有限公司 | Polyurethane film and preparation method thereof |
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| CN106823862A (en) * | 2017-03-05 | 2017-06-13 | 河北工业大学 | A kind of dry-forming method of microporous polyurethane film |
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| CN114106264A (en) * | 2021-11-24 | 2022-03-01 | 天津工业大学 | Polyester modified organic silicon coating leveling agent and preparation method thereof |
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Application publication date: 20140709 |