CN106633305A - High permeability rate composite gas-permeable membrane and preparation method thereof - Google Patents

High permeability rate composite gas-permeable membrane and preparation method thereof Download PDF

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Publication number
CN106633305A
CN106633305A CN201611194212.3A CN201611194212A CN106633305A CN 106633305 A CN106633305 A CN 106633305A CN 201611194212 A CN201611194212 A CN 201611194212A CN 106633305 A CN106633305 A CN 106633305A
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parts
layer
resin
high air
air penetrability
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张直
黄云华
刘武
李静波
李龙山
杨信强
罗义果
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Gongga Sichuan Snow New Materials Ltd By Share Ltd
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Gongga Sichuan Snow New Materials Ltd By Share Ltd
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/023—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets using multilayered plates or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/28—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of blown tubular films, e.g. by inflation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C69/00—Combinations of shaping techniques not provided for in a single one of main groups B29C39/00 - B29C67/00, e.g. associations of moulding and joining techniques; Apparatus therefore
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
    • B29C71/02—Thermal after-treatment
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    • B32—LAYERED PRODUCTS
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/266—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by an apertured layer, the apertures going through the whole thickness of the layer, e.g. expanded metal, perforated layer, slit layer regular cells B32B3/12
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    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2007/00—Flat articles, e.g. films or sheets
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2009/00—Layered products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54—Yield strength; Tensile strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/582—Tearability
    • B32B2307/5825—Tear resistant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
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    • B32B2307/73—Hydrophobic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
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    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
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    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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    • C08J2423/04—Homopolymers or copolymers of ethene
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K2201/003—Additives being defined by their diameter
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    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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Abstract

The invention belongs to the field of new material and plastic processing, and discloses composition of a high permeability rate composite gas-permeable membrane and a preparation method of the membrane. The high permeability rate composite gas-permeable membrane is prepared from master batch composed of polyolefin resin, ultrathin inorganic powder, an interface modifier, an inorganic powder dispersant and a processing lubricant, and processing rheological master batch composed of polyolefin resin, a processing rheological agent, a dispersant and an anti-aging agent, and after the master batch and the processing rheological master batch are mixed with at least one of optional polyolefin resin and copolyolefin resin, the high permeability rate composite gas-permeable membrane is obtained through three-layer composite co-extrusion equipment. The prepared composite gas-permeable membrane has the advantages of being high in gas permeation rate, hydrophilic in surface, free of electrostatic generation, good in penetration resistance, high in tensile strength and the like; the three-layer co-extrusion preparation technology increases the production line speed of the composite gas-permeable membrane and has the advantages of being high in productivity and low in unit product energy consumption, and the prepared composite gas-permeable membrane has the advantages of being high in strength, less in defect and free of stimulation.

Description

A kind of high air penetrability compound breath film and preparation method thereof
Technical field
The invention belongs to field of new, discloses raw material composition and its preparation side of a kind of high air penetrability compound breath film Method and the high air penetrability compound breath film prepared by the raw material.
Background technology
Conventional plastic sheeting is air-locked, by the modified plastics of the ultra tiny inorganic particle of uniaxial or biaxial stretching Film forms the micropore of countless intercommunications（Per square metre there are about 1010Micropore of the individual aperture at 0.1 μm～5 μm）, so as to air and Water vapour has good permeability, but has barrier to liquid because liquid there is surface tension, and this film is referred to as Breathable microporous film, abbreviation ventilated membrane.Its principle is that the modified plastic sheeting of ultra tiny inorganic particle is made in appropriate force-extension With under, polymeric matrix and rigid inorganic powder interface peel, polymer extends and to form aperture and mutually pass through at 0.1 μm～5 μm The micropore worn, polymer can not be restPosed due to creep with relaxing, and form permanent micropore.Ventilated membrane extensively should In daily life, medical treatment, special industrial protection, agricultural production, industrial packaging field, only 2015 above-mentioned fields are to ventilative The demand of film is just more than 350,000 tons.
The ventilated membrane defect of existing Recipe production is more, such as：Tensile strength≤8MPa, not puncture resistant；Have big The micropore of metering-orifice footpath >=30 μm causes liquid permeable mistake；Average water vapor transmittance≤120000g/ ㎡ 24h, made by once Sex aids allow when in use people to feel sultry；From inorganic particle deal with improperly, cause ventilated membrane surface to have powder to come off thorn Sharp skin etc..Inventor for current ventilated membrane deficiency, the particularly not high problem of water vapor transmittance in use, there is provided Plant the raw material scheme and production preparation scheme of brand-new high air penetrability compound breath film.
The content of the invention
First technical problem to be solved by this invention is to provide a kind of raw material of high air penetrability compound breath film.It is high saturating Gas rate compound breath film is at least by more than two-layer constituting, and the raw material that its A layer and B layers are adopted is as follows：
A layer raw materials are to include following components by portion rate：
Ultra tiny inorganic powder mother material：55-75 parts；
Processing rheology masterbatch：3-8 parts；
Vistanex：55-85 parts；
Copolyalkenamer resin：2-5 parts；
B layer raw materials are to include following components by portion rate：
Ultra tiny inorganic powder mother material：75-90 parts；
Processing rheology masterbatch：0.5-1 parts；
Vistanex：15-35 parts；
Copolyalkenamer resin：35-45 parts.
Specifically, the ultra tiny inorganic powder mother material in above-mentioned A layers and B layer raw materials is to include following components by portion rate, And extruding pelletization is obtained after double screw extruder or mixer mixing after being stirred by following components：
Vistanex：12-22 parts；
Ultra tiny inorganic particle：90-100 parts；
Interface modifier：5-10 parts；
Inorganic particle dispersant：3-8 parts；
Lubricant：3-5 parts；
Preferably, the vistanex for constituting ultra tiny inorganic powder mother material is ldpe resin of the melting means 5 ~ 10 （LDPE）, linear low density polyethylene resin of the melting means 16 ~ 20（LLDPE）, LDPE resin and LLDPE resins by weight 1：Any one in 1 mixing gained；Ultra tiny inorganic particle is Paris white, sulfuric acid of the particle size between 2 μm ~ 5 μm Barium powder, by weight talcum powder, by weight calcium carbonate and the mixing gained of 1 ︰ of barium sulfate 1, calcium carbonate and the ︰ 1 of talcum powder 1 are mixed Close at least one in gained；Interface modifier is maleic anhydride grafted ethene/alpha olefin copolymer（POE-g-MAH）, maleic acid Acid anhydride grafted ethene acetate ethylene copolymer（EVA-g-MAH）In at least one；Inorganic particle dispersant is different by weight Aluminium propoxide and stearic acid 1：1 mixing gained, ethylene bis stearamide（EBS）, trimethoxysilane, dodecyl front three At least one in TMOS, gamma-aminopropyl-triethoxy-silane, stearic acid；Lubricant be low molecular weight polyethylene, At least one in paraffin, white oil.
Specifically, the processing rheology masterbatch in above-mentioned A layers and B layer raw materials be by portion rate include following components, and by with Lower component be well mixed after through double screw extruder mixing after extruding pelletization obtain：
Vistanex：80-90 parts；
Processing rheological agent：8-12 parts；
Dispersant：5-8 parts；
Age resistor：0.5-1 parts
Preferably, the vistanex of composition processing rheology masterbatch is ldpe resin of the melting means 2 ~ 2.5（LDPE）、 Linear low density polyethylene resin of the melting means 1.5 ~ 4（LLDPE）, LDPE resin and LLDPE resins 1 by weight：0.5 mixes Close any one in gained；Processing rheological agent is organic siliconresin, fluoropolymer, dimethyl of the molecular weight 10,000 ~ 30,000 At least one in silicone oil, low molecule pa resin；Dispersant is ethylene bis stearamide（EBS）, the ethoxy of γ-aminopropyl three Base silane, lauryl amine APEO, Du Pont's Entira SD100 additives, neopelex, stearic acid list At least one in acid anhydride ester；Age resistor be four [β-（3,5- di-tert-butyl-hydroxy phenyls）Propionic acid] pentaerythritol ester, three [2.4- di-tert-butyl-phenyls] phosphite ester, N, N '-bis- [β-(3,5- di-tert-butyl-hydroxy phenyl) propionyl] hydrazine, 2,4- bis- At least one in (dodecylthiomethyl) -6- methylphenols.
Specifically, the vistanex that a kind of high air penetrability compound breath film is selected is that melting means is low between 1.0-2.0 Density Polyethylene Resin（LDPE）, linear low density polyethylene resin of the melting means between 1.8-4.5（LLDPE）, melting means be less than 2 High density polyethylene (HDPE)（HDPE）In at least one.
Specifically, the copolyalkenamer resin that a kind of high air penetrability compound breath film is selected is VA contents in 8%-20% and melting means Ethylene vinyl acetate copolymer between 1 ~ 6（EVA）Resin.
Second technical problem to be solved by this invention is to provide a kind of processing technology of high air penetrability compound breath film Method.A kind of technological process of high air penetrability compound breath film for " raw material → dryings feed intake → tri- layers of extrusion → inflation cool down → Fold traction → cold stretch → annealing and surface treatment → finished product ", specific process parameter is as follows：
A, above-mentioned A layers or B layer raw materials are fully dried and are well mixed in plastics mixer, baking temperature at 70 DEG C -80 DEG C, Drying time at least 30min；
, by three-layer co-extruded film blowing device in 145 DEG C -165 DEG C of processing temperature, blow-up ratio 2.5 ~ 2.8 is led for b, A layer and B layers raw material Draw the film embryo for blowing out that thickness is 80 μm -150 μm than 5.8 ~ 6.2 times；
, to 65 DEG C -85 DEG C, then by unidirectional or two-way cold stretch, it is 1.8-4.5 to control cold stretch ratio, will be cold drawn for c, heating film embryo The film for obtaining 3 ~ 5min of constant temperature annealings at 65 DEG C ~ 85 DEG C are stretched, and surface hydrophilic antistatic treatment is carried out with corona, received Packaging obtains final product high air penetrability compound breath film after volume.
3rd technical problem to be solved by this invention is by above-mentioned high air penetrability composite ventilating film raw material and processing work The high air penetrability compound breath film that skill is prepared.
Specifically, above-mentioned high air penetrability compound breath film is the three-layer composite structure of " A | B | A ", and thickness is 15 μm ~ 45 μm, Moisture permeability is 12000g/ ㎡ 24h ~ 15000 g/ ㎡ 24h, and air air penetrability is 3500cm3/(cm2·KPa·24h)~ 5500cm3/(cm2KPa24h), 80 DEG C of percent thermal shrinkage≤3%, 25 DEG C of resistance to hydrostatics are 30mmHg ~ 38mmHg, tensile strength For 9.5MPa ~ 12MPa, breathable microporous par is 1010Individual/m2~1012Individual/m2, breathable microporous aperture is 0.01 μm ~ 15 μm.
Compared with prior art, gas permeability height, the safety and sanitation of high air penetrability compound breath film of the invention, long-time is contacted Human body will not stimulate skin, and tensile strength is high, puncture-resistant, in daily life, medical treatment, special industrial protection, agricultural production, industry Packaging field has more comfortable practical effect.
Specific embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated.
Embodiment 1
1. put in proportion in 110L banburies according to following recipe ingredient and knead after 24min, then Jing draw ratios 24:1 Φ The Single screw extrusions of 210/ Φ 190, Jing flour millings are earnestly granulated, and after air cooling ultra tiny inorganic powder mother material is obtained：
LDPE 1F7B resins：15 parts；
D97=4.6 μm of super fine calcium carbonate powder：95 parts；
The light E625 modifying agent of energy：6 parts；
KH550 dispersants：5 parts；
Yanshan Petrochemical LP1000：4 parts；
Mixing temperature 1 area's temperature 2 area's temperature 3 area's temperature 4 area's temperature Head temperature Engine speed Pelletizing rotating speed
148℃ 135℃ 145℃ 150℃ 155℃ 150℃ 258r/min 125r/min
2. put in 200L homogenizers according to following recipe ingredient and stir after 5min, then Jing draw ratios 44:1 Φ 72 is in the same direction Double screw extruder is extruded, the water cooled rear pelletizing of tie rod, then 80 DEG C of Jing ebullated beds are dried 5min and obtain processing rheology masterbatch：
Yanshan Petrochemical LD362 resin：90 parts；
EVONIK Tegopren 5885：8 parts；
Glycerin monostearate：5 parts；
Antioxidant 1010：0.5 part
1 area's temperature 2 area's temperature 3 area's temperature 4 area's temperature 5 area's temperature 6 area's temperature 7 area's temperature 8 area's temperature 9 area's temperature 10 area's temperature Head temperature Engine speed
145℃ 165℃ 170℃ 175℃ 175℃ 170℃ 165℃ 165℃ 160℃ 160℃ 165℃ 230r/min
3. according to dry mixed 30min in following recipe ingredient input SZG-350 double conic rotary vacuum dryers, vacuum is adjusted For 0.02MPa, the outer layer of high ventilative compound breath film is obtained（A layers）Raw material：
Ultra tiny inorganic powder mother material：60 parts；
Processing rheology masterbatch：6 parts；
LDPE LD100AC resins：55 parts；
EVA YG1001 resins：2 parts；
4. according to dry mixed 30min in following recipe ingredient input SZG-350 double conic rotary vacuum dryers, vacuum is adjusted For 0.02MPa, the inner sandwich layer of high ventilative compound breath film is obtained（B layers）Raw material：
Ultra tiny inorganic powder mother material：80 parts；
Processing rheology masterbatch：0.5 part；
LDPE 2426H resins：15 parts；
EVA 18J3 resins：35 parts.
5. by outer layer（A layers）Raw material and inner sandwich layer（B layers）Raw material sucks three-layer co-extruded extruder with suction feeder respectively In the hopper of A, B extruder of group, carry out three-layer co-extruded blown film and obtain the film embryo that thickness is 60 μm；
Outer layer extruder（A extruders）Parameter is as follows：
Draw ratio Diameter 1 area's temperature 2 area's temperature 3 area's temperature 4 area's temperature Melt pump temperature Machine neck temperature Engine speed
30：1 Φ90 145℃ 150℃ 155℃ 155℃ 160℃ 155℃ 35r/min
Inner sandwich layer extruder（B extruders）Parameter is as follows：
Draw ratio Diameter 1 area's temperature 2 area's temperature 3 area's temperature 4 area's temperature 5 area's temperature Melt pump temperature Machine neck temperature Engine speed
36：1 Φ65 135℃ 155℃ 160℃ 160℃ 160℃ 160℃ 160℃ 22r/min
Blown film parameter is as follows：
Core rod diameter 1 section of temperature 2 sections of temperature 3 sections of temperature Blow-up ratio Draw ratio Film flake thickness degree Cooling air quantity
Φ600 165℃ 160℃ 150℃ 2.65 5.9 60μm 62%
6. film embryo is introduced into infrared heating drawing zone by carry-over pinch rolls, stretching orientation is obtained the film with micropore, and reheating is moved back Fire is processed, and is packaged to be high air penetrability compound breath film：
Draft temperature Draw ratio Annealing temperature Annealing time
72℃ 1.9 80℃ 5min
The high air penetrability composite ventilating film properties of the present embodiment gained are as follows：Structure is the three-layer composite structure of " A | B | A ", and thickness is 35 μm, moisture permeability is 12300g/ ㎡ 24h, and air air penetrability is 3700cm3/(cm2KPa24h), percent thermal shrinkage 1.2%, 25 DEG C of resistance to hydrostatics are 35mmHg, and tensile strength is 10.8MPa, it is measured microscopically breathable microporous par for 2.7 × 1011Individual/m2, breathable microporous maximum diameter of hole is measured microscopically for 8.6 μm.
Embodiment 2
1. put in proportion in 90L banburies according to following recipe ingredient and knead after 23min, then Jing draw ratios 26:1 Φ 160/ The Single screw extrusions of Φ 145, Jing flour millings are earnestly granulated, and after air cooling ultra tiny inorganic powder mother material is obtained：
The resins of LLDPE 7144：16 parts；
D97=2.5 μm of talcum powder：92 parts；
The light N408 modifying agent of energy：8 parts；
Aluminium isopropoxide and stearic acid 1：1 mixing：5 parts；
75# paraffin：3 parts；
Mixing temperature 1 area's temperature 2 area's temperature 3 area's temperature 4 area's temperature Head temperature Engine speed Pelletizing rotating speed
142℃ 130℃ 135℃ 135℃ 135℃ 140℃ 230r/min 110r/min
2. put in 200L homogenizers according to following recipe ingredient and stir after 5min, then Jing draw ratios 40:1 Φ 65 is in the same direction Double screw extruder is extruded, the water cooled rear pelletizing of tie rod, then 80 DEG C of Jing ebullated beds are dried 5min and obtain processing rheology masterbatch：
7042 resins：85 parts；
Lanpoly 2800：10 parts；
Entira SD100：8 parts；
Antioxidant 1024：0.6 part
1 area's temperature 2 area's temperature 3 area's temperature 4 area's temperature 5 area's temperature 6 area's temperature 7 area's temperature 8 area's temperature 9 area's temperature 10 area's temperature Head temperature Engine speed
145℃ 165℃ 170℃ 180℃ 175℃ 170℃ 170℃ 165℃ 165℃ 160℃ 165℃ 200r/min
3. according to dry mixed 30min in following recipe ingredient input SZG-350 double conic rotary vacuum dryers, vacuum is adjusted For 0.02MPa, the outer layer of high ventilative compound breath film is obtained（A layers）Raw material：
Ultra tiny inorganic powder mother material：70 parts；
Processing rheology masterbatch：5 parts；
7001 resins：60 parts；
EVA 18J3 resins：2 parts；
4. according to dry mixed 30min in following recipe ingredient input SZG-350 double conic rotary vacuum dryers, vacuum is adjusted For 0.02MPa, the inner sandwich layer of high ventilative compound breath film is obtained（B layers）Raw material：
Ultra tiny inorganic powder mother material：90 parts；
Processing rheology masterbatch：0.5 part；
7042 resins：15 parts；
The resins of EVA 2520：42 parts.
5. by outer layer（A layers）Raw material and inner sandwich layer（B layers）Raw material extrudes three layers altogether with suction feeder suction two-shipper respectively In the hopper of A, B extruder of extrusion unit, carry out three-layer co-extruded blown film and obtain the film embryo that thickness is 80 μm；
Outer layer extruder（A extruders）Parameter is as follows：
Draw ratio Diameter 1 area's temperature 2 area's temperature 3 area's temperature 4 area's temperature Melt pump temperature Machine neck temperature Engine speed
30：1 Φ90 150℃ 155℃ 155℃ 160℃ 160℃ 155℃ 45r/min
Inner sandwich layer extruder（B extruders）Parameter is as follows：
Draw ratio Diameter 1 area's temperature 2 area's temperature 3 area's temperature 4 area's temperature 5 area's temperature Melt pump temperature Machine neck temperature Engine speed
36：1 Φ65 135℃ 155℃ 160℃ 160℃ 160℃ 160℃ 160℃ 28r/min
Blown film parameter is as follows：
Core rod diameter 1 section of temperature 2 sections of temperature 3 sections of temperature Blow-up ratio Draw ratio Film flake thickness degree Cooling air quantity
Φ600 165℃ 160℃ 155℃ 2.55 6.0 80μm 85%
6. film embryo is introduced into infrared heating drawing zone by carry-over pinch rolls, stretching orientation is obtained the film with micropore, and reheating is moved back Fire is processed, and is packaged to be high air penetrability compound breath film：
Draft temperature Draw ratio Annealing temperature Annealing time
75℃ 2.8 82℃ 5min
The high air penetrability composite ventilating film properties of the present embodiment gained are as follows：Structure is the three-layer composite structure of " A | B | A ", and thickness is 30 μm, moisture permeability is 14700g/ ㎡ 24h, and air air penetrability is 3900cm3/(cm2KPa24h), percent thermal shrinkage 1.5%, 25 DEG C of resistance to hydrostatics are 30mmHg, and tensile strength is 11.2MPa, it is measured microscopically breathable microporous par for 7.2 × 1010Individual/m2, breathable microporous maximum diameter of hole is measured microscopically for 11.8 μm.
Three-layer co-extruded equipment used is to reduce merging one on the type units of Germany W@H VAREX II 3 in above-described embodiment Outer layer extruder, it is 36 to increase inner layer extruder draw ratio:Obtain after 1；But during actual preparation, it is not limited to the model, The equipment of the type, the three-layer co-extruded film blowing device and three-layer co-extruded casting apparatus of other similar structures are equally applicable to this It is bright.
The high air penetrability compound breath film and existing ventilated membrane for now preparing embodiment 1 and embodiment 2 is carried out The comparison of gas performance, see the table below 1：
Table 1
As can be seen from Table 1, compound breath film of the present invention is in air penetrability, needle pore defect, tensile strength, glossiness, resistant to liquids Several aspects such as static pressure, percent thermal shrinkage are all substantially better than existing ventilated membrane.So, high air penetrability prepared by the inventive method is answered Ventilated membrane is closed, is had in daily life, medical treatment, special industrial protection, agricultural production, industrial packaging field more comfortable using effect Really.

Claims (9)

1. a kind of high air penetrability compound breath film, it is characterised in that：
A, a kind of high air penetrability compound breath film are constituted by three layers, its A layer（Superficial layer）With B layers（Sandwich layer）Using raw material composition It is as follows：
A layer raw materials are to include following components by portion rate：
Ultra tiny inorganic powder mother material：55-75 parts；
Processing rheology masterbatch：3-8 parts；
Vistanex：55-85 parts；
Copolyalkenamer resin：2-5 parts
B layer raw materials are to include following components by portion rate：
Ultra tiny inorganic powder mother material：75-90 parts；
Processing rheology masterbatch：0.5-1 parts；
Vistanex：15-35 parts；
Copolyalkenamer resin：35-45 parts
B, A layer and B layer raw materials be well mixed respectively after under 140 DEG C -170 DEG C of processing temperature, set by three-layer co-extruded technique It is standby to prepare film embryo of the thickness at 50 μm -150 μm；
C, film embryo is heated in 65 DEG C -95 DEG C of temperature range, then obtained after uniaxial or biaxial stretching thickness 15 μm - 30 μm, the high air penetrability compound breath film of water vapor transmittance >=12000g/ ㎡ 24h, draw ratio is in the range of 1.8-4.5.
2. high air penetrability compound breath film according to claim 1, it is characterised in that：In step a, described ultra tiny nothing Machine powder mother material is to include following components by portion rate：
Vistanex：12-22 parts；
Ultra tiny inorganic particle：90-100 parts；
Interface modifier：5-10 parts；
Inorganic particle dispersant：3-8 parts；
Lubricant：3-5 parts；
And extruding pelletization is obtained after twin-screw or mixer mixing by said components.
3. high air penetrability compound breath film according to claim 2, it is characterised in that：In step a, constitute ultra tiny inorganic The vistanex of powder mother material is ldpe resin（LDPE）, linear low density polyethylene resin（LLDPE）, by weight Amount is than meter LDPE resin and LLDPE resins 1：0.5 to 1：Any one in 2 mixing gained；Ultra tiny inorganic particle is particle diameter Paris white, blanc fixe, talcum powder, glass microballoon, by weight calcium carbonate and sulfuric acid of the size between 2 μm ~ 5 μm At least one in the mixing gained of 1 ︰ of barium 1, by weight calcium carbonate and the mixing gained of 1 ︰ of talcum powder 1；Interface modifier is horse Maleic anhydride grafted ethylene/alpha olefin polymer（POE-g-MAH）, ethylene-vinylacetate grafting maleic anhydride copolymer（EVA-g- MAH）In at least one；Inorganic particle dispersant is aluminium isopropoxide and stearic acid 1 by weight：1 mixing gained, ethylene are double Stearmide（EBS）, trimethoxysilane, dodecyltrimethoxysilane, gamma-aminopropyl-triethoxy-silane, At least one in stearic acid；Lubricant is at least one in low molecular weight polyethylene, paraffin, white oil.
4. high air penetrability compound breath film according to claim 1, it is characterised in that：In step a, described processing rheology Masterbatch is to include following components by portion rate：
Vistanex：80-90 parts；
Processing rheological agent：8-12 parts；
Dispersant：5-8 parts；
Age resistor：0.5-1 parts
And extruding pelletization is obtained after twin-screw mixer by said components.
5. high air penetrability compound breath film according to claim 4, it is characterised in that：In step a, composition processing rheology is female The vistanex of material is ldpe resin（LDPE）, linear low density polyethylene resin（LLDPE）, by weight LDPE resin and LLDPE resins 1：Any one in 0.5 mixing gained；Processing rheological agent is polyphosphazene polymer siloxanes, fluorine-containing At least one in polymer, dimethicone, low molecule pa resin；Dispersant is ethylene bis stearamide（EBS）、 Gamma-aminopropyl-triethoxy-silane, lauryl amine APEO, Du Pont's Entira SD100 additives, detergent alkylate At least one in sodium sulfonate, stearic acid list acid anhydride ester；Age resistor be four [β-（3,5- di-tert-butyl-hydroxy phenyls）Propionic acid] season Doutrate, three [2.4- di-tert-butyl-phenyls] phosphite esters, N, N '-bis- [β-(3,5- di-tert-butyl-hydroxy phenyl) third Acyl] hydrazine, at least one in 2,4- bis- (dodecylthiomethyl) -6- methylphenols.
6. high air penetrability compound breath film according to claim 1, it is characterised in that：In step a, described polyolefin tree Fat is ldpe resin of the melting means between 1.0-2.0（LDPE）, linea low density of the melting means between 1.8-4.5 gather Vinyl（LLDPE）, melting means less than 2 high density polyethylene (HDPE)（HDPE）In at least one, described copolyalkenamer resin For the ethylene vinyl acetate copolymer that VA contents are in 8%-20% and melting means is less than 10（EVA）Resin.
7. high air penetrability compound breath film according to claim 1, it is characterised in that：In step b, the three-layer co-extruded work Skill is three-layer co-extruded blown film process or three-layer co-extruded cast film technique；Wherein A layers are superficial layer, and B layers are sandwich layer, high saturating Gas rate compound breath film is the composite construction of " A | B | A ".
8. the ventilated membrane that the preparation method of the high air penetrability compound breath film by described in any one of claim 1～7 is obtained is special Material.
9. the water vapor transmittance that the preparation method of the high air penetrability compound breath film by described in any one of claim 1～8 is obtained The ventilated membrane product of >=12000g/ ㎡ 24h.
CN201611194212.3A 2016-12-21 2016-12-21 High permeability rate composite gas-permeable membrane and preparation method thereof Pending CN106633305A (en)

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CN108250538A (en) * 2017-12-29 2018-07-06 黎明职业大学 A kind of ventilated membrane filler parent granule and preparation method thereof
CN108382034A (en) * 2017-12-25 2018-08-10 福建恒安卫生材料有限公司 A kind of soft colored ventilated membrane
CN111875864A (en) * 2020-07-31 2020-11-03 湖北宏裕新型包材股份有限公司 Polyethylene PE microporous breathable film for medical protective clothing and preparation method thereof
CN111890767A (en) * 2020-07-31 2020-11-06 湖北宏裕新型包材股份有限公司 Ultrathin polyethylene microporous breathable film and preparation method thereof
CN112238620A (en) * 2020-09-25 2021-01-19 福建琦峰科技有限公司 One-step breathable film and preparation method thereof
CN114621516A (en) * 2022-03-07 2022-06-14 金发科技股份有限公司 High-water-repellency polyolefin composition, breathable film, and preparation method and application thereof

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108382034A (en) * 2017-12-25 2018-08-10 福建恒安卫生材料有限公司 A kind of soft colored ventilated membrane
CN108250538A (en) * 2017-12-29 2018-07-06 黎明职业大学 A kind of ventilated membrane filler parent granule and preparation method thereof
CN111875864A (en) * 2020-07-31 2020-11-03 湖北宏裕新型包材股份有限公司 Polyethylene PE microporous breathable film for medical protective clothing and preparation method thereof
CN111890767A (en) * 2020-07-31 2020-11-06 湖北宏裕新型包材股份有限公司 Ultrathin polyethylene microporous breathable film and preparation method thereof
CN111875864B (en) * 2020-07-31 2023-03-10 湖北宏裕新型包材股份有限公司 Polyethylene PE microporous breathable film for medical protective clothing and preparation method thereof
CN112238620A (en) * 2020-09-25 2021-01-19 福建琦峰科技有限公司 One-step breathable film and preparation method thereof
CN114621516A (en) * 2022-03-07 2022-06-14 金发科技股份有限公司 High-water-repellency polyolefin composition, breathable film, and preparation method and application thereof

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