CN1521201A - Waterproof ventilated microporous membrane, its preparing method and use - Google Patents
Waterproof ventilated microporous membrane, its preparing method and use Download PDFInfo
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- CN1521201A CN1521201A CNA031152783A CN03115278A CN1521201A CN 1521201 A CN1521201 A CN 1521201A CN A031152783 A CNA031152783 A CN A031152783A CN 03115278 A CN03115278 A CN 03115278A CN 1521201 A CN1521201 A CN 1521201A
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Abstract
The present invention discloses one kind of waterproof and air permeable microporous membrane comprising synthetic resin, inorganic matter powder, plasticizer and lubricant, with the inorganic matter powder being nanometer level inorganic matter powder and/or inorganic matter powder with nanometer level micropores. The waterproof and air permeable microporous membrane has the advantages of even thickness, homogeneous micropore size and distribution and single-way air permeability.
Description
Technical field
The present invention relates to a kind of waterproof and breathable microporous membrane, the preparation method of this film and purposes.
Background technology
Waterproof ventilated membrane has purposes widely, for example can be used for high-performance apparel (as wind coat, submarine armour, biochemical defence suit, anorak, sports clothes etc.), sanitary product (as diaper, incontinence article, bandage etc.), outdoor tent, shield cap, and " can breathe emulational leather "." can breathe emulational leather " and be meant the artificial simulated leather that has microvoid structure, can air-moisture-permeable.
At present, microporous membrane mainly comprises polytetrafluoroethylene (PTFE) stretched film and polyolefine stretched film, and commercial mainly be the PTFE stretched film, it is widely used in making high-performance apparel, tent and sanitary product etc.; The polyolefine stretched film mainly is used to make sanitary product, sheet etc. based on polyethylene (PE) film.
CN1258305A discloses a kind of uniaxial orientation micro-porous permeable film and manufacture method thereof, and this film comprises the 40-65% mineral filler and comprises ethene and at least a C
4-C
8The multipolymer of 'alpha '-olefin monomers forms micropore through uniaxial extension.This film air penetrability is 300-4500g/m
2.d, the transverse breakage elongation is mainly used in and makes diaper, training pants, incontinence article etc. greater than 150%.
CN1203610 discloses a kind of PTFE microporous article that contains filler, and filler content is 5-50% in these goods, and filler is an oxide compound, mainly is titanium oxide.The manufacture method of the above-mentioned microporous article of being made up of PTFE and oxide compound is: at first make the film band, stretch then and make microporous membrane.This characteristic feature of an invention is that the microporous membrane wear resistance is good, UV resistant is shone, heat-resisting height, mainly as the fine filtering net.Similar patent also has EPA-0463106, USP4153661, USP4194040, and these INVENTION IN GENERAL are that the particle diameter that adds more than 25% in PTFE is the filler of 1-100 μ m, make sheet material after the mixing, stretch, and obtain the PTFE stretched film at last.
CN1034357C discloses a kind of manufacture method of waterproof breathable garment lining, and this invention principal feature is to carry out answer naturally of biaxial stretch-formed back with lower molecular weight PTFE, after this film and fabric is directly compound, make Air permenbility greater than 5000g/m
2.d, hydrostaticpressure is greater than 6mH
2O waterproof breathable garment lining.
CN1041167A discloses a kind of preparation method of flexible microporous membrane, this method is that mineral filler and molten the touching of processing aid of 10-15 μ m mixed with the polymkeric substance of alpha-olefin or multipolymer and 60-70% particle diameter, carry out the biaxial stretch-formed microporous membrane of making then, this film is mainly used in towel, sheet and hospital work clothes.Similar invention also has CN1014794B, USP3903234, USP498372 and EP-A-272026 etc.These patents all disclose with polyolefine or its multipolymer and auxiliary agent mixing, have stretched and make the method for microporous membrane, and this this microporous membrane is mainly used in towel, health napkin and leakage prevention sheet etc.
No matter foregoing invention is to adopt PTFE or olefin polymer, add mineral filler no matter be, still do not add mineral filler, all adopt the method for stretching pore-forming, maximum defective is that the size of gained microporous article mesopore can not accurately be controlled, inconsistent and the skewness of size meeting of each several part mesopore, the film Air permenbility, vapor transfer rate, watertight size and the tensile strength that further show as different piece in the same goods differ bigger, and promptly ununiformity is bigger.The bigger microporous membrane of this ununiformity will have a strong impact on the comfortableness of clothes as the clothes as waterproof and breathable.
Summary of the invention
An object of the present invention is to provide a kind of micropore and be evenly distributed, ventilative even with water vapour permeability, water pressure resistance height, the microporous membrane that tensile strength is high.
Another object of the present invention provides the preparation method of above-mentioned microporous membrane.
A further object of the invention provides the purposes of above-mentioned microporous membrane.
The invention provides a kind of waterproof and breathable microporous membrane, this microporous membrane comprises synthetic resins, mineral powder, softening agent and lubricant, described mineral powder is nano grade inorganic powder and/or the non-nano level mineral powder with nano micropore structure capable, gross weight in synthetic resins and mineral powder, each components contents is as follows: synthetic resins 20-50 weight %, mineral powder 50-80 weight %, softening agent 2-45 weight %, lubricant 2-45 weight %.
Synthetic resins better is to be selected from polyolefine, polyvinyl chloride, polyester, Polyurethane, nylon or its mixture, is more preferably to be selected from polyethylene, polypropylene, polyvinyl chloride, poly terephthalic acid diester, thermoplastic polyurethane, nylon 6, nylon 66 or its mixture.The nano grade inorganic powder better is to be selected from a kind of in nanometer grade calcium carbonate, nano level barium sulfate, nano level calcium sulfate, nano level diatom soil, nano level magnesium oxide, nanometer grade silica, Nano titanium dioxide, nano level potter's clay, nano level talcum powder and the nano-kaoline or it is multiple; Non-nano level mineral powder with nano micropore structure capable better is to be selected from lime carbonate, barium sulfate, calcium sulfate, diatomite, magnesium oxide, silicon-dioxide, titanium dioxide, potter's clay, mica, kaolin, wollastonite, rhombspar and the lignin powder one or more.
Softening agent better is to be selected from Bisphthalate, phosphotriester, tris phosphite, di adipate, di azelate, polylactone, thermoplastic elastomer and the polyester plasticizer one or more, and lubricant better is to be selected from toluol sulfonamide, toluenesulphonic acids butyramide, chlorinatedpolyethylene, clorafin, mineral oil, the polyethylene wax one or more.
Preferably, waterproof and breathable microporous membrane of the present invention also comprises 0-20 weight % auxiliary agent, gross weight in synthetic resins and mineral powder, auxiliary agent better is to comprise in UV light absorber, mould inhibitor, stablizer and the tinting material one or more, is more preferably to be selected from zinc oxide, two (8-hydroxyl) the quinoline copper of Shuan phenoxarsine ether, N-(dichloro one fluorine methylthio group)-phthalic imidine, hexichol antimony-ethylhexoate, stearate, two-n-octyl thiolate, titanium dioxide, carbon black and color dye or the Masterbatch one or more.
Better be that the Air permenbility of microporous membrane one side of the present invention is greater than 0.5cm
3/ cm
2.s, the Air permenbility of another side is less than 0.1cm
3/ cm
2.s; The vapor transfer rate of one side is greater than 5000g/m
2.d, the vapor transfer rate of another side is less than 1000g/m
2.d; Hydrostaticpressure is greater than 5mH
2O.
The present invention also provides a kind of preparation method of waterproof and breathable microporous membrane, and this method comprises:
(1) earlier with synthetic resins, mineral powder, softening agent, lubricant and optional auxiliary agent mix, described mineral powder is nano grade inorganic powder and/or the non-nano level mineral powder with nano micropore structure capable, gross weight in synthetic resins and mineral powder, the consumption of each component is as follows: synthetic resins 20-50 weight %, mineral powder 50-80 weight %, softening agent 4-100 weight %, lubricant 4-200 weight %, auxiliary agent 0-20 weight %, again with gained mixture extrusion plasticizing, calendering formation, remove the softening agent and the lubricant of part then with solvent cleaning, realize the first step pore-forming, this moment, the volume porosity of material was 30-50%;
(2) material through the first step pore-forming is stretched, reach the volume porosity of 60-90%, realize the second step pore-forming, obtain the waterproof and breathable microporous membrane.
Solvent preferably is selected from one or more in ethanol, butanols, acetone, vinyl acetic monomer, toluene, hexanaphthene, trichloroethane, ethylene dichloride, trieline, normal hexane, methane amide, dimethylbenzene, Ethylene Dichloride, butanone, benzene, perhydronaphthalene, cresols and the gasoline.
In the preparation method of microporous membrane of the present invention, preferably removing softening agent and lubricant partly with solvent cleaning in the first step pore-forming is to carry out 2-30 minute in 30-150 ℃ temperature.
The present invention also provides the waterproof and breathable microporous membrane to be used for clothes, tent, sanitary product, bedclothes, towel, and alternative PVC leatheroid and/or PU use for synthetic leather in clothes, automobile furniture decorate, the purposes of case and bag.
Waterproof microporous membrane of the present invention has following advantage: thickness evenly, the size of micropore and be evenly distributed, ventilation property and water vapour permeability is even, water pressure resistance is high, the tensile strength height, and have one-way ventilating (wetting) property, promptly ventilative (wetting) property of film one side is than the big several times of another side.
The preparation method who uses microporous membrane of the present invention can prepare the microporous membrane with above-mentioned plurality of advantages well.And this two step hole forming methods adopt the first pore-forming film forming that stretches as requested then, make thickness, aperture, porosity, ventilative (wetting) property, the water pressure resistance of microporous membrane can be adjusted control in the scope of broad.
Embodiment
The synthetic resins that adopts in the waterproof and breathable microporous membrane of the present invention comprises polyolefine, polyethylene (particularly ultrahigh molecular weight polyethylene(UHMWPE)) preferably, polypropylene; Polyvinyl chloride; Polyester, poly terephthalic acid diester preferably, good especially is polyethylene terephthalate, polybutylene terephthalate, poly terephthalic acid hexylene glycol ester; Polyurethane better is a thermoplastic polyurethane; Nylon, preferably nylon 6, nylon 66 etc.In these materials, polyolefin resin is particularly suitable for making water pressure resistance height, ventilative, saturating wet microporous membrane, this film can be used on health sheet, leakproof articles for use, tent, clothes (for example wind coat, Leisure Sport clothes, anorak, submarine armour, biochemical defence suit) etc., sanitary product, also can be used to substitute used PVC leatheroid and PU synthetic leather; Polyvinyl chloride and urethane are particularly suitable for making imitation leather, are used for automotive trim, case and bag, footwear etc.; Nylon and polyester are particularly suitable for making air-permeable envelope, are used for tent, towel, bandage etc.
In the waterproof and breathable microporous membrane of the present invention, nano grade inorganic powder and/or the non-nano level mineral powder with nano micropore structure capable add as weighting material, and consumption is 50-80 weight %, in the gross weight of synthetic resins and mineral powder.The nano-grade inorganics particle diameter is generally 5-100nm, better is 10-80nm, is preferably the following nanometer grade powder of 60nm.Particle diameter with non-nano level mineral powder of nano micropore structure capable is generally 1-45 μ m, better is 5-20 μ m, has 100-800m
2/ g specific surface area, and have nanometer level microporous skeleton structure.If the add-on of mineral powder is less than 50 weight %, and then porosity is low, lack of homogeneity; If exceed 80 weight %, then tensile strength is low, and resistance to tearing is poor, and is flexible poor.
The used mineral powder of microporous membrane of the present invention can be the nano grade inorganic powder, also can be the non-nano level mineral powder with nano micropore structure capable, or the two mixture.The nano grade inorganic powder is with the key distinction with non-nano level mineral powder of nano micropore structure capable: the nano grade inorganic powder has littler micropore, the flowability and the processibility of material can not only be improved after adding as filler, and tensile strength, elongation at break and the antioxidant property of product can be improved; Has nano micropore structure capable although have the non-nano level mineral powder of nano micropore structure capable, but size is big than the former, particle diameter and micropore size distribution broad, adsorption between the particle is less, thereby prepared product compares with nano grade inorganic powder products obtained therefrom, easily stretch and intensity relatively low.In actual applications, above-mentioned two kinds of mineral powders can be used in combination, can control the pore size and the distribution thereof of product, thereby control mechanical property, processing characteristics and the antioxidant property of products obtained therefrom by the ratio of controlling them.
The softening agent that the present invention adopts preferably can be selected from one or more of following material: Bisphthalate better is phthalic acid two (C
1-C
12Alkyl) ester is more preferably diethyl phthalate, dibutyl phthalate, dioctyl phthalate (DOP); Phosphotriester better is a tributyl phosphate; Tris phosphite better is a tributyl phosphate; Di adipate better is a diisodecyl adipate; Di azelate better is a diisooctyl azelate; Polylactone better is a polycaprolactone; Thermoplastic elastomer better is Thermoplastic Elastomer, Olefinic (TPR); Polyester plasticizer better is the vinylformic acid oligomer ester.
The lubricant that the present invention adopts preferably can be selected from one or more in toluol sulfonamide, toluenesulphonic acids butyramide, chlorinatedpolyethylene, clorafin, mineral oil, the polyethylene wax.Lubricant can be used to improve the flowability of material system in the course of processing.
As softening agent and the lubricant that raw material adds, some can be removed by solvent cleaning in microporous membrane preparation method's of the present invention the first step pore forming process, thereby forms hole.Still leave softening agent and lubricant in the microporous film products of gained, softening agent can be used to improve the tensile property of product.In microporous film products, the content of softening agent is 2-45 weight %, be more preferably 4-20 weight %, the content of lubricant is 2-45 weight %, is more preferably 4-20 weight %, in the gross weight of synthetic resins and mineral powder, this can record by the following method: take by weighing about 2g sample and placed in 104-110 ℃ the loft drier 2 hours, be cooled to room temperature, accurately take by weighing quality, record.Sample is placed liquid-liquid extractor, add 600 milliliters of solvents and a small amount of zeolite, be heated to boiling, keep after 1 hour taking out, put into 104-110 ℃ loft drier 2 hours, taking-up is put into moisture eliminator and is cooled to room temperature, take by weighing quality, calculate loss of weight, be softening agent or lubricant content.
Can add multiple auxiliary agent in the waterproof and breathable microporous membrane of the present invention, these auxiliary agents comprise UV light absorber, mould inhibitor, thermo-stabilizer, tinting material etc.UV light absorber is such as but not limited to 2-(2 '-hydroxyphenyl) benzotriazole, zinc oxide, titanium oxide, and consumption is generally 0.5-8 weight %, in the gross weight of synthetic resins and mineral powder.Mould inhibitor includes but not limited to two (8-hydroxyl) the quinoline copper of two phenoxarsine ethers, N-(two chloro-fluorine methylthio groups)-phthalic imidine, hexichol antimony-ethylhexoate etc., consumption is generally 0.2-5 weight %, in the gross weight of synthetic resins and mineral powder.Stablizer comprises but is not limited to lead stearate, calcium stearate, two-n-octyl thiolate etc. that consumption is 0.5-4 weight %, in the gross weight of synthetic resins and mineral powder.Tinting material includes but not limited to the mineral dye and the Masterbatch of titanium dioxide, carbon black and other different colours, and consumption can be determined as requested.
Microporous membrane of the present invention adopts two step hole forming methods to make.Earlier each component is mixed, extrusion plasticizing (extrusion temperature is generally 100-300 ℃), and compression moulding again, such as but not limited to being pressed into sheet material, sheet thickness is generally the 0.15-1.0 millimeter.Use solvent cleaning then, realize the first step pore-forming, the volume porosity is controlled at 30-50%, and the aperture is roughly in the scope of 10-100 nanometer; Carry out the second step pore-forming with drawing process as required again.
In preparation method of the present invention, nano grade inorganic powder and/or the non-nano level mineral powder with nano micropore structure capable all have porous skeleton structure.Be filled into and still keep this structure in the synthetic resins, the fluent meterial (as softening agent, lubricant) that adds is absorbed among the micropore by mineral powder, the fluent meterial that will absorb in the micropore by solvent extraction cleans out, and becomes hole and the powder micropore remained; On the other hand, some fluent meterials are miscible in synthetic resins, and this part fluent meterial also cleans out by extraction and forms hole.Finish the first step pore-forming thus.
The solvent that adopts in the first step pore-forming can be softening agent and lubricant can be cleaned out by extraction but can not cause dysgenic any solvent to the present invention.These solvents include but not limited to: ethanol, butanols, acetone, vinyl acetic monomer, toluene, hexanaphthene, trichloroethane, ethylene dichloride, trieline, normal hexane, methane amide, dimethylbenzene, Ethylene Dichloride, butanone, benzene, perhydronaphthalene, cresols, gasoline.These solvents can use separately or two or more are used in combination.The temperature of solvent cleaning is controlled at 30-150 ℃, and the time is generally 2-30 minute.
The second step pore-forming can carry out with drawing process well known to those skilled in the art.Preferably adopt biaxial stretch-formed.Be stretching under 50-160 ℃ the temperature and carry out, stretching ratio can determine as required, better be 2-10 doubly, the volume porosity of gained microporous membrane is generally 60-90%, the aperture is the 100-1000 nanometer, and micropore is evenly distributed.
Because the non-nano level powder that the present invention uses the nano grade inorganic powder or has nano micropore structure capable as filler, has therefore guaranteed that the poromerics that obtains is the nanometer micropore material of a kind of micro-pore diameter less than 100nm after extrusion calendaring and solvent cleaning.This poromerics can aperture formed by stretching be the air-moisture-permeable film of hundreds of nanometers.
The two step hole forming methods that the present invention adopts can be adjusted thickness, aperture, porosity, ventilative (wetting) property and the water pressure resistance of control gained microporous membrane as required in the scope of broad.The present invention can prepare thickness in 0.02-0.15 millimeter scope, and the aperture is in the 50-500 nanometer range, and porosity is 50-90%, and the film Air permenbility is at 0.5cm
3/ cm
2More than, water vapour permeability is at 5000g/m
2.d more than, the film of water pressure resistance more than the 5m water column, but be not limited to these films that above parameter limits.The inventive method also can prepare the film of aperture more than 500 nanometers, at this moment can select the mineral powder of granularity more than 100 nanometers for use.
Further specify the present invention below in conjunction with specific embodiment, but the present invention is not limited to these embodiment.
Embodiment 1
With listed each component of table 1 in high-speed mixer (Beijing plastics machinery factory, GH-50DY) mix in, use forcing machine (Keya Industry Co., Ltd., Nanjing then, TP-50) in 100-170 ℃ of extrusion plasticizing, being pressed into thickness with rolling press (Shanghai rubber machine factory, model is the tri-roll press machine of XY3F-1120A) is 0.8 millimeter sheet coiled material.Then, cleaned 20 minutes in 50 ℃, form volumetric porosity and be 45%, average pore diameter is the poromerics of 50nm with ethanol.Then, with biaxial stretch-formed machine (Guilin east occasion membrane equipment company limited) the gained poromerics is carried out biaxial stretch-formedly, stretching ratio is about 5 times, makes microporous membrane, and the volume porosity of this film is 70%, and the aperture is 150nm, and thickness is 0.1mm.Observation post gets microporous membrane with electron microscope (Shimadzu Corp), finds the big or small more consistent of micropore and is evenly distributed.With the content of softening agent and lubricant in this paper preceding method measurement gained microporous membrane, softening agent is 32 grams, and lubricant is 2 grams.Other performance index are shown in table 2.Performance index in the table 2 obtain according to GB/T 5453-1997, GB/T 4757-1997 standard detection.
Embodiment 2
Listed each component of table 1 is mixed in high-speed mixer, then in forcing machine in 170-220 ℃ of extrusion plasticizing, being pressed into thickness with rolling press is 0.35 millimeter sheet coiled material.Then, cleaned 30 minutes in 30 ℃, make volumetric porosity and be 30%, mean pore size is the poromerics of 30nm with acetone.Then, with drawing machine the gained poromerics is carried out biaxial stretch-formedly, stretching ratio is 10 times, makes microporous membrane, and the volume porosity of this film is 75%, and the aperture is 150nm, and thickness is 0.08mm.Observation post gets microporous membrane with electron microscope, finds the big or small more consistent of micropore and is evenly distributed.With the content of softening agent and lubricant in this paper preceding method measurement gained microporous membrane, softening agent is 10 grams, and lubricant is 11 grams.Other performance index are shown in table 2.This microporous membrane flexibility is good, elasticity is high, feel is level and smooth, be applicable to all use fields of wet-type PU synthetic leather, and its ventilation property reaches 0.5cm
3/ cm
2.s more than, considerably beyond wet-type PU synthetic leather 0.05cm
3/ cm
2.s ventilation property index.
Embodiment 3
Listed each component of table 1 is mixed in high-speed mixer, uses then in the forcing machine in 200-300 ℃ of extrusion plasticizing, with rolling press be pressed into that the volume porosity is 50%, thickness is 0.18 millimeter sheet coiled material.Then, in 90 ℃ of cleanings 25 minutes, make the poromerics that mean pore size is 30nm with toluene.Then, with drawing machine the gained poromerics is carried out biaxial stretch-formedly, stretching ratio is 2 times, makes microporous membrane, and the volume porosity of this film is 60%, and the aperture is 240nm, and thickness is 0.06mm.Observation post gets microporous membrane with electron microscope, finds the big or small more consistent of micropore and is evenly distributed.With the content of softening agent and lubricant in this paper preceding method measurement gained microporous membrane, softening agent is 2 grams, and lubricant is 32 grams.Other performance index are shown in table 2.
Embodiment 4
Listed each component of table 1 is mixed in high-speed mixer, then in forcing machine in 130-210 ℃ of extrusion plasticizing, being pressed into thickness with rolling press is 0.25 millimeter sheet coiled material.Then, cleaned 8 minutes in 40 ℃, make volume porosity 50%, mean pore size is the poromerics of 50nm with the mixed solvent of hexanaphthene and normal hexane.Then, with drawing machine the gained poromerics is carried out biaxial stretch-formedly, stretching ratio is 6 times, makes microporous membrane, and the volume porosity of this film is 90%, and the aperture is 300nm, and thickness is 0.08mm.Observation post gets microporous membrane with electron microscope, finds the big or small more consistent of micropore and is evenly distributed.With the content of softening agent and lubricant in this paper preceding method measurement gained microporous membrane, softening agent is 45 grams, and lubricant is 45 grams.Other performance index are shown in table 2.
Embodiment 5
Listed each component of table 1 is mixed in high-speed mixer, then in forcing machine in 140-260 ℃ of extrusion plasticizing, being pressed into thickness with rolling press is 0.2 millimeter sheet coiled material.Then, cleaned 15 minutes in 120 ℃, make volume porosity 50%, mean pore size is the poromerics of 50nm with Ethylene Dichloride.Then, with drawing machine the gained poromerics is carried out biaxial stretch-formedly, stretching ratio is 10 times, makes microporous membrane, and the volume porosity of this film is 90%, and the aperture is 150nm, and thickness is 0.02mm.Observation post gets microporous membrane with electron microscope, finds the big or small more consistent of micropore and is evenly distributed.With the content of softening agent and lubricant in this paper preceding method measurement gained microporous membrane, softening agent is 4 grams, and lubricant is 20 grams.Other performance index are shown in table 2.This microporous membrane flexibility is good, wear resistance is high, feel is level and smooth, be applicable to all use fields of wet-type PU synthetic leather, and its ventilation property reaches 0.6cm
3/ cm
2.s more than, considerably beyond wet-type PU synthetic leather 0.08cm
3/ cm
2.s ventilation property index.
Embodiment 6
Listed each component of table 1 is mixed in high-speed mixer, use then in the forcing machine in 180-300 ℃ of extrusion plasticizing, being pressed into thickness with rolling press is 0.15 millimeter sheet coiled material.Then, cleaned 2 minutes in 150 ℃, make volume porosity 35%, mean pore size is the poromerics of 50nm with cresols.Then, with drawing machine the gained poromerics is carried out biaxial stretch-formedly, stretching ratio is 8 times, makes microporous membrane, and the volume porosity of this film is 60%, and the aperture is 200nm, and thickness is 0.06mm.Observation post gets microporous membrane with electron microscope, finds the big or small more consistent of micropore and is evenly distributed.With the content of softening agent and lubricant in this paper preceding method measurement gained microporous membrane, softening agent is 20 grams, and lubricant is 4 grams.Other performance index are shown in table 2.
The film that embodiment 1 and embodiment 2 make is soft, be especially suitable for use as poromeric material, make the leatheroid clothes, wear more comfortable with it, and have good heat retaining property, be particularly suitable for cold district insulation garment in winter, automotive trim and furniture decoration etc.
What embodiment 3 and embodiment 6 adopted is the higher resin of thermotolerance, through biaxial stretch-formed oriented crystalline, has higher physical strength and thermotolerance, and the Air permenbility of gained microporous membrane is greater than 0.5cm
3/ cm
2.s, water vapour permeability reaches 6000g/m
2.d, the sports clothes and open-air tent, the footwear etc. that are particularly useful for vigorous exercise.
Embodiment 4 and embodiment 5 adopt the nonpolar polyolefin hydrocarbon resin, and the ventilation property of gained microporous membrane is greater than 0.6cm
3/ cm
2.s, water vapour permeability is greater than 6000g/m
2.d, water pressure resistance is greater than 8mH
2O, and good heat preservation performance, clothes, diving suit and tent etc. are suitable for climbing the mountain.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| Synthetic resins | ??- | ??- | ????- | ??- | ??- | ??- |
| Polyvinyl chloride | ??30 | ??- | ????- | ??- | ??- | ??- |
| Thermoplastic polyurethane | ??- | ??50 | ????- | ??- | ??- | ??- |
| Poly terephthalic acid hexylene glycol ester | ??- | ??- | ????20 | ??- | ??- | ??- |
| Polypropylene | ??- | ??- | ????- | ??35 | ??- | ??- |
| Ultrahigh molecular weight polyethylene(UHMWPE) | ??- | ??- | ????- | ??- | ??25 | ??- |
| Nylon 6 | ??- | ??- | ????- | ??- | ??- | ??40 |
| Mineral powder | ??- | ??- | ????- | ??- | ??- | ??- |
| Nanometer grade calcium carbonate | ??70 | ??- | ????- | ??- | ??- | ??- |
| Non-nano level calcium sulfate with nanometer micropore structure | ??- | ??50 | ????- | ??- | ??- | ??- |
| Nanometer grade silica | ??- | ??- | ????80 | ??- | ??- | ??- |
| Non-nano level kaolin with nanometer micropore structure | ??- | ??- | ????- | ??65 | ??40 | ??- |
| Nano level diatom soil | ??- | ??- | ????- | ??- | ??35 | ??- |
| The nano level talcum | ??- | ??- | ????- | ??- | ??- | ??60 |
| Softening agent | ||||||
| Dibutyl phthalate | ??70 | ??- | ????- | ??- | ??- | ??- |
| Tributyl phosphate | ??- | ??25 | ????- | ??- | ??- | ??- |
| Polycaprolactone | ??- | ??- | ????4 | ??- | ??- | ??- |
| Diisooctyl azelate | ??- | ??- | ????- | ??100 | ??- | ??- |
| Thermoplastic Elastomer, Olefinic (TPR) | ??- | ??- | ????- | ??- | ??12 | ??- |
| The vinylformic acid oligomer ester | ??- | ??- | ????- | ??- | ??- | ??50 |
| Lubricant | ||||||
| Toluol sulfonamide | ??4 | ??- | ????- | ??- | ??- | ??- |
| The toluenesulphonic acids butyramide | ??- | ??55 | ????- | ??- | ??- | ??- |
| Chlorinatedpolyethylene | ??- | ??- | ????140 | ??- | ??- | ??- |
| Clorafin | ??- | ??- | ????- | ??200 | ??- | ??- |
| Mineral oil | ??- | ??- | ????- | ??- | ??110 | ??- |
| Polyethylene wax | ??- | ??- | ????- | ??- | ??- | ??30 |
| Auxiliary agent | ??- | |||||
| Zinc oxide | ??6 | ??- | ????- | ??6 | ??- | ??- |
| 2-(2 '-hydroxyphenyl) benzotriazole | ??- | ??8 | ????- | ??- | ??- | ??- |
| Two (8-hydroxyl) the quinoline copper of Shuan phenoxarsine ether | ??- | ??- | ????- | ??4 | ??0.5 | ??- |
| Hexichol antimony-ethylhexoate | ??5 | ??- | ????- | ??- | ??- | ??- |
| Calcium stearate | ??- | ??- | ????- | ??4 | ??- | ??- |
| The di-n-octyl sodium mercaptides | ??4 | ??- | ????1 | ??- | ??- | ??- |
| Titanium dioxide | ??- | ??- | ????- | ??6 | ??- | ??- |
Annotate: data shown in the table 1 are consumption, in weight part.
Table 2
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | ||
| Air permenbility (cm 3/cm 2·s) | Simultaneously | ??0.63 | ??0.57 | ??0.58 | ??0.69 | ??0.68 | ??0.59 |
| Another side | ??0.08 | ??0.07 | ??0.08 | ??0.09 | ??0.09 | ??0.09 | |
| Vapor transfer rate (g/m 2·d) | Simultaneously | ??5765 | ??5532 | ??6124 | ??6450 | ??6400 | ??6225 |
| Another side | ??827 | ??719 | ??825 | ??845 | ??850 | ??830 | |
| Water pressure resistance (static state) (m water column) | ??6.2 | ??6.9 | ??7.7 | ??8.2 | ??8.0 | ??7.5 | |
| Tensile strength (Mpa) | ??5.2 | ??6.4 | ??9.7 | ??7.2 | ??7.4 | ??10.1 | |
Comparative example 1
With 30 weight part polyvinyl chloride, 70 weight part nanometer grade calcium carbonates, 6 part by weight of zinc oxide, 5 weight part hexichol antimony-ethylhexoates and 4 weight part di-n-octyl sodium sulfate in high-speed mixer (Beijing plastics machinery factory, GH-50DY) mix in, use forcing machine (Keya Industry Co., Ltd., Nanjing then, TP-50) in 100-170 ℃ of extrusion plasticizing, (Shanghai rubber machine factory, model is the tri-roll press machine of XY3F-1120A) is pressed into the sheet like membrane material with rolling press.The volume porosity of this film is 50%, and mean pore size is 100nm, and thickness is 0.1mm.Observation post gets microporous membrane with electron microscope (Shimadzu Corp), finds that the not of uniform size of micropore causes and skewness.
The microporous membrane of this comparative example is divided into 50 sample areas, measures Air permenbility, vapor transfer rate, water pressure resistance and the tensile strength of these sample areas respectively, calculate the mean value and the standard deviation sigma of these performances.The microporous membrane of embodiment 1 also is divided into 50 sample areas, carries out identical performance test, and calculate the mean value and the standard deviation sigma of these performances.Gained the results are shown in table 3.
Table 3
| Embodiment 1 | Comparative example 1 | ||||
| Mean value | Standard deviation | Mean value | Standard deviation | ||
| Air permenbility (cm 3/cm 2·s) | Simultaneously | ????0.63 | ????4.5％ | ????0.14 | ????13.4％ |
| Another side | ????0.08 | ????2.2％ | ????0.03 | ????5.2％ | |
| Vapor transfer rate (g/m 2·d) | Simultaneously | ????5765 | ????6.4％ | ????1250 | ????16.8％ |
| Another side | ????827 | ????3.7％ | ????176 | ????4.8％ | |
| Water pressure resistance (static state) (m water column) | ????6.2 | ????2.5％ | ????9.8 | ????3.2％ | |
| Tensile strength (Mpa) | ????5.2 | ????1.8％ | ????6.9 | ????2.5％ | |
Claims (10)
1. waterproof and breathable microporous membrane, this microporous membrane comprises synthetic resins, mineral powder, softening agent and lubricant, described mineral powder is nano grade inorganic powder and/or the non-nano level mineral powder with nano micropore structure capable, gross weight in synthetic resins and mineral powder, each components contents is as follows: synthetic resins 20-50 weight %, mineral powder 50-80 weight %, softening agent 2-45 weight %, lubricant 2-45 weight %.
2. microporous membrane as claimed in claim 1, it is characterized in that described synthetic resins is selected from polyolefine, polyvinyl chloride, polyester, Polyurethane, nylon or its mixture, be more preferably and be selected from polyethylene, polypropylene, polyvinyl chloride, poly terephthalic acid diester, thermoplastic polyurethane, nylon 6, nylon 66 or its mixture.
3. microporous membrane as claimed in claim 1 is characterized in that described nano grade inorganic powder is selected from a kind of in nanometer grade calcium carbonate, nano level barium sulfate, nano level calcium sulfate, nano level diatom soil, nano level magnesium oxide, nanometer grade silica, Nano titanium dioxide, nano level potter's clay, nano level talcum powder and the nano-kaoline or it is multiple; Described non-nano level mineral powder with nano micropore structure capable is selected from one or more in lime carbonate, barium sulfate, calcium sulfate, diatomite, magnesium oxide, silicon-dioxide, titanium dioxide, potter's clay, mica, kaolin, wollastonite, rhombspar and the lignin powder.
4. microporous membrane as claimed in claim 1, it is characterized in that described softening agent is selected from one or more in Bisphthalate, phosphotriester, tris phosphite, di adipate, di azelate, polylactone, thermoplastic elastomer and the polyester plasticizer, described lubricant is selected from one or more in toluol sulfonamide, toluenesulphonic acids butyramide, chlorinatedpolyethylene, clorafin, mineral oil, the polyethylene wax.
5. microporous membrane as claimed in claim 1, it is characterized in that described microporous membrane also comprises 0-20 weight % auxiliary agent, gross weight in synthetic resins and mineral powder, described auxiliary agent better is to comprise UV light absorber, mould inhibitor, in stablizer and the tinting material one or more are more preferably and are selected from two (8-hydroxyl) the quinoline copper of zinc oxide Shuan phenoxarsine ether, N-(dichloro one fluorine methylthio group)-phthalic imidine, hexichol antimony-ethylhexoate, stearate, two-n-octyl thiolate, titanium dioxide, in carbon black and color dye or the Masterbatch one or more.
6. microporous membrane as claimed in claim 1, the Air permenbility that it is characterized in that described microporous membrane one side is greater than 0.5cm
3/ cm
2S, the Air permenbility of another side is less than 0.1cm
3/ cm
2S; The vapor transfer rate of one side is greater than 5000g/m
2D, the vapor transfer rate of another side is less than 1000g/m
2D; Hydrostaticpressure is greater than 5mH
2O.
7. the preparation method of the described waterproof and breathable microporous membrane of claim 1, this method comprises:
(1) earlier with synthetic resins, mineral powder, softening agent, lubricant and optional auxiliary agent mix, described mineral powder is nano grade inorganic powder and/or the non-nano level mineral powder with nano micropore structure capable, gross weight in synthetic resins and mineral powder, the consumption of each component is as follows: synthetic resins 20-50 weight %, mineral powder 50-80 weight %, softening agent 4-100 weight %, lubricant 4-200 weight %, auxiliary agent 0-20 weight %, again with gained mixture extrusion plasticizing, calendering formation, remove the softening agent and the lubricant of part then with solvent cleaning, realize the first step pore-forming, this moment, the volume porosity of material was 30-50%;
(2) material through the first step pore-forming is stretched, reach the volume porosity of 60-90%, realize the second step pore-forming, obtain the waterproof and breathable microporous membrane.
8. method as claimed in claim 7 is characterized in that described solvent is to be selected from ethanol, butanols, acetone, vinyl acetic monomer, toluene, hexanaphthene, trichloroethane, ethylene dichloride, trieline, normal hexane, methane amide, dimethylbenzene, Ethylene Dichloride, butanone, benzene, perhydronaphthalene, cresols and the gasoline one or more.
9. as claim 7 or 8 described methods, it is characterized in that removing softening agent and lubricant partly with solvent cleaning in the described the first step pore-forming is to carry out 2-30 minute in 30-150 ℃ temperature.
10. the described waterproof and breathable microporous membrane of claim 1 is used for clothes, tent, sanitary product, bedclothes, towel, and alternative PVC leatheroid and/or PU use for synthetic leather in clothes, automobile furniture decorate, the purposes of case and bag.
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