CN108727774A - The composition of saturating vapour isolation-type thermoplastic resin and its film of preparation - Google Patents
The composition of saturating vapour isolation-type thermoplastic resin and its film of preparation Download PDFInfo
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- CN108727774A CN108727774A CN201710262655.XA CN201710262655A CN108727774A CN 108727774 A CN108727774 A CN 108727774A CN 201710262655 A CN201710262655 A CN 201710262655A CN 108727774 A CN108727774 A CN 108727774A
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- Prior art keywords
- thermoplastic resin
- film
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- composition
- resin
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2400/00—Characterised by the use of unspecified polymers
- C08J2400/10—Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C08J2400/106—Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing nitrogen atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
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Abstract
The present invention provides a kind of vapour isolation-type thermoplastic resin composition and its films of preparation, wherein by mass percentage, which includes:The thermoplastic resin material for serving as compatilizer of the thermoplastic elastomer resin material for the hydrophilic segment that 1-99% contains 5% or more ratio, the polar thermoplastic resin material of 0.01-99%, 0-30%.Wherein, the thermoplastic resin composition by film die after melt blending by being cast to non-specular surface rough surface into single layer, two layers or more of saturating vapour isolation-type thermoplastic resin membrane.The film prepared using the present composition has the saturating vapour of excellent diffusion principle, structure are continuous, can obstruct size to be more than the substances such as 5nm solid dusts, aerosol, bacterium, virus and liquid, it is even more that can play good barriering effect with natural or chemicals laminates, plays protective action.
Description
Technical field
The present invention relates to a kind of composition of vapour isolation-type thermoplastic resin and its films of preparation；More particularly,
The present invention relates to a kind of thermoplastic elastomer resin material, polar thermoplastic resin material and phases with high vapour locking separating performance thoroughly
Hold the saturating vapour barrier film of continuity of the thermoplastic resin material composition and its preparation of agent.The film is isolated for protecting.
Background technology
With the development of industry, awful weather, pollution etc. cause the various crisis of survival of the mankind, such as various special diseases
Malicious bacterium such as SARS, MERS, Ebola, haze, heavy rain, air pollution etc., the mankind moved towards again from industrial urbanization it is outdoor,
Nature is moved towards.Isolation-type thermoplastic resin material becomes the research focus paid close attention to both at home and abroad, and wherein selective gas penetrates
Membrane material is even more concerned, the barrier material of especially saturating vapour, while protection, and can play the effect of breathing.But mesh
It is preceding to be focused only in synthesis and modified exploitation both at home and abroad, phase is not carried out to moulding process and later stage key application control point
The control of the control answered, especially barriering effect, some patented technologies are to increase steam permeability and smooth degree, add filler, together
When also sacrifice barrier property, produce discontinuous structure, therefore in production to formd between terminal use can not be matched
Technology barrier, product can not correctly be recognized and use by causing consumer.
CN101358020 discloses a kind of modified formula of modified polyether ester thin-film material, by adding organic functions
Material and the thermal stability for improving product.CN1032220C discloses one kind using polyether ester amides as main component, water permeable
The thermoplastic film of steam, the film improve the rate of perviousness and mechanical strength of product.CN101346228 discloses a kind of anti-
The multilayer film of water, porous steam has at least one first layer and a second layer, wherein all layers are all by being selected from polyethers
The thermoplastic polymer of esters, polyetheramides class or polyether urethane class is constituted, and is connected to each other.US 7,422,795
B2 discloses a kind of elastomer thin film with organic soft segment and organic hard section.US 6,749,923 discloses one kind on ground
The high moisture-inhibiting film of film forming.US 6,261,674, which discloses a kind of two layers, can breathe thin polymer film, and the film second layer is than the
One layer of rate of perviousness is low.US 6,114,024, which discloses a kind of 5 layers, can breathe film, and sandwich layer and adhesive-layer coextrusion stretch film forming.
2016/0176168 A1 of US disclose it is a kind of one layer not water wetted material and one layer of water wetted material composition have one layer it is discontinuous
Structure.CN205167769U discloses a kind of three-decker Waterproof & Moisture Permeable Film, and wherein middle layer is the non-pole of discontinuous structure
Property resin material.CN201220512715.1 discloses a kind of water-proof air-permeable film of three-decker, and wherein middle layer is polarity tree
Fat material, surface layer are non-polar resin material.CN98812871.3 discloses that a kind of excellent vapor is ventilative and excellent liquidproof
The breathable films for the discontinuous structure that the non-polar resin Material Physics and barrier property of permeation barrier improve.
Invention content
The purpose of the present invention is a kind of vapour isolation-type thermoplastic resin composition and its films of preparation, wherein prepared
Film with the saturating vapour with excellent diffusion principle, structure is continuous, can obstruct size more than 5nm solid dusts, gas
The substances such as colloidal sol, bacterium, virus and liquid are even more that can play good barrier with natural or chemicals laminates
Effect plays protective action.
On the one hand, in order to realize the purpose of aforementioned present invention, the present invention provides a kind of vapour isolation-type thermoplastic resins
Composition, wherein by mass percentage, the composition includes:
1-99% contains the polarity of the thermoplastic elastomer resin material of the hydrophilic segment of 5% or more ratio, 0.01-99%
The thermoplastic resin material for serving as compatilizer of thermoplastic resin material, 0-30%.Without inorganic filler.
On the one hand, in order to realize the purpose of aforementioned present invention, the hydrophilic segment of the present invention containing 5% or more ratio
Thermoplastic elastomer resin material can be following resin one or any a variety of blend：Dicarboxylic acids and binary
Alcohol, the copolymer of epoxide or blend, and/or binary amide and dihydric alcohol, the copolymer of epoxide or blending
Object, and/or binary isocyanic acid and dihydric alcohol, the copolymer of epoxide or blend, and/or contain ionic surface active agent
Hydrophilic group (group), such as carboxylic acid group (- COOH), sulfonic group (- SO3H), sulfate and the copolymer of phosphate or be blended
Object, and/or contain cationic surfactant, such as amino (- NH2), the copolymer of quaternary ammonium group or blend, and/or containing non-
Ionic surface active agent, the ether being such as made of oxygen-containing group, hydroxyl (- OH), aldehyde radical (- CHO) carbonyl, block polyether are total to
Polymers or blend.The ratio of hydrophilic segment is preferably 5%~95%, is more preferably 5%~90%, hydrophilic segment with
Accounting will influence moisture vapor transmission in side, but it is too high will cause that successional film can not be formed, mechanical strength reduces.
On the one hand, of the present invention to contain the other thermoplastic resins of polar group in order to realize the purpose of aforementioned present invention
Fat material is one or more kinds of selected from the thermoplastic resin material such as next group：Corvic, inclined two chloroethene
Olefine resin, vinyl acetate resin, polyvinyl alcohol, polyvinyl acetal, polystyrene, AS resins, SAN resins, SBS trees
Fat, acryl resin, nylon resin, polyacetal resin, acetal resin, polycarbonate resin (PC), gathers and mocks tree ABS resin
The copolymer of fat, celluloid, cellulose acetate plastics, thermoplasticity polyester, epoxy resin, thermoplastic acrylic resin etc. is total
Mixed object and/or modified resin.
On the one hand, in order to realize the purpose of aforementioned present invention, the thermoplastic resin material of the present invention for serving as compatilizer
Material is to be one or more kinds of selected from following one or any a variety of blend：Cyclic acid anhydride type (MAH) grafting is poly-
Close object either blend, and/or carboxylic acid type graft polymers or concurrent mixture, and/or epoxy type graft polymers or total
Mixture, and/or oxazoline type graft polymers either concurrent mixture, and/or imide-type graft polymers or co-blended
Object, and/or isocyanate-based graft polymers or concurrent mixture, and/or low molecule type response type compatilizer and its mixture.
On the one hand, in order to realize the purpose of aforementioned present invention, composition of the present invention by mass percentage, the group
Object is closed to be preferably:3-95% contains the pole of the thermoplastic elastomer resin material of the hydrophilic segment of 5% or more ratio, 1-99%
The thermoplastic resin material for serving as compatilizer of property thermoplastic resin material, 0-28%.More preferably it is:3-95% contains
The thermoplastic elastomer resin material of the hydrophilic segment of 5% or more ratio, polar thermoplastic resin material, the 0-25% of 2-99%
The thermoplastic resin material for serving as compatilizer.
On the one hand, goal of the invention to realize the present invention, the present invention provides a kind of saturating vapour prepared by above-mentioned composition
The thickness of isolation-type thermoplastic resin membrane, the film are 1-250 μm of m, and preferably 2-100 μm of m, more preferably 2-80 μm of m are most
It is excellent.It is tested using ASTM E96-2000D methods, the moisture vapor transmission of film of the present invention should be in 100g/m2* for 24 hours more than, preferably in 600g/
m2* for 24 hours, 1000g/m2* above for 24 hours more excellent, wherein superelevation moisture-inhibiting moisture-inhibiting is more highly preferred to 1200g/m2* for 24 hours more than.
In the present invention, the thermoplastic elastomer resin material and polar thermoplastic resinous wood of film moisture vapor transmission and composition
The ratio of the thermoplastic resin material of material and compatilizer has larger relationship, especially compatilizer, and compatilizer is for adjusting two
The mutually incompatible degree of a material, if more mutually compatible, by more steam-proof, but if the completely mutually not compatible machine that will cause film
Tool intensity declines.
In the present invention, film moisture vapor transmission and barrier property also have relationship with thickness and technique.The thicker air penetrability of thickness declines,
Barrier property is reinforced, and has the link of destructive power more film in technique and transport, such as press bonding roller, roll surface cleaning, barrier
Property will reduce.
On the one hand, goal of the invention to realize the present invention, the present invention provides a kind of saturating vapour prepared by above-mentioned composition
The structure of isolation-type thermoplastic resin membrane, the film are continuous, have saturating vapour principle and continuous structure such as attached drawing 9.Such as right
It is required that the saturating vapour isolation-type thermoplastic resin membrane is single layer or two layers or more structure, wherein two layers or more structure
Same composition is all made of per layer material, saturating carbonated drink is flat consistent, will not change vapour ability because of the increase of the number of plies, simultaneously
It will not lead to occur layering and discontinuous because of the difference of material.When wherein two layers or more structure, there is no there is discontinuity layer,
It is continuous structure, physical clearance is not present.The number of plies is more, and barrier property is stronger, as long as while constant thickness, moisture vapor transmission comfort level
It would not decline.
On the one hand, goal of the invention to realize the present invention, the present invention provides a kind of saturating vapour prepared by above-mentioned composition
Isolation-type thermoplastic resin membrane, the film can obstruct size and be more than 5nm solid dusts and substance, bacterium, virus and liquid etc.
Substance preferably obstructs 20nm or more substances, is more preferably 80nm or more.
As the specific implementation mode of the present invention, saturating vapour isolation-type thermoplastic resin composition of the invention may include:
The thermoplastic elastomer resin material of the hydrophilic segment containing 5% or more ratio of 5%-95%, the polar thermoplastic of 5-95%
The thermoplastic resin material for serving as compatilizer of resin material and 0-25%.
As another embodiment of the present invention, saturating vapour isolation-type thermoplastic resin composition of the invention can wrap
It includes:The thermoplastic elastomer resin material of the hydrophilic segment containing 5% or more ratio of 5%-95%, the polarity heat of 10-90%
The thermoplastic resin material for serving as compatilizer of plastic resin material and 1-25%.
In the present invention, it can use twin-screw or single screw rod by above-mentioned composition after mechanical mixture, carry out premix melting and make
Grain or directly melting extrusion film forming, carry out preferred according to different formulations.
In the present invention, can be that more extruder co-extrusions form multilayered structure, can also be multilayer die cavity or multilayer wind
Ring structure forms multilayered structure, can also be that multilayer distributor forms multilayered structure, can also be the one of three kinds of above-mentioned methods
The multilayered structures that the arbitrary combination of kind, two kinds or three kinds is formed, preferably 3 layers or more of continuity membrane structure.It is corresponding
The extruder of die cavity or vane or distributor can be 1, can be more, preferably 2 or more.
In the present invention, thermoplastic resin composition's melt processing temperature is that than three kinds thermoplastic resin highests are molten
That puts is 10 degrees Celsius high, 10 degrees Celsius lower than the lowest decomposition temperature of three kinds of thermoplastic resins, avoids because processing temperature is too low
Cause not melt the appearance of substance or glue point so that discontinuous hole occurs in film, while also avoiding processing temperature excessively high, makes
At the degradation of material, or even perforation.
In the present invention, the thermoplastic resin composition by film die after melt blending by being cast to non-mirror
Face rough surface can be matte roll, can also be coarse paper tape, can also be coarse plastic resin band, can also be thick
Rough metal steel strap.At the time of molding, there is the slurry pressing that will be cast out to the device of non-specular surface rough surface, the pressure of pressing is
0.01-0.6MPa, preferably 0.1-0.5MPa are more preferably 0.1-0.45MPa, the too low coarse table that will lead to film
Face can not be formed, excessively high to lead to film holed technique.
In the present invention, the non-specular surface rough surface, in cooling form a film, surface temperature can be 0 DEG C and want to right
The minimum softening point in the composition described in 1~5 is sought, 5 DEG C of minimum softening point is more optimizedly less than；More optimizedly it is less than minimum soft
Change 10 DEG C of point.What if the excessively high adhesion problems for be easy to causeing film of the temperature of non-specular surface rough surface in the present invention, produced from
It is raw to destroy, reduce speed of production.Texture that is too low and be easy to causeing film is unintelligible, and adhesion between film and film is unfavorable for the later stage
It uses.
In the present invention, the non-specular surface rough surface can be various patterns and texture, such as random dotted, sand shape, flower
Line, Logo, grid, leather patterns etc. individually or mixed type shape；
In the present invention, the roughness depth of the non-specular surface rough surface, surface should be more shallow than the thickness of the film
0.1 μm or more, more preferably shallow 0.5 μm or more, optimal shallow 1 μm or more.
In the present invention, the saturating vapour isolation-type thermoplastic resin membrane that prepared by the non-specular surface rough surface have with it is non-
The consistent rough surface of specular surface.
In the present invention, various manufacturing procedures can be coiled etc. for intermediate special procedure, trimming, bundling, cutting, preferably wherein
Arbitrary process is combined or is individually carried out, wherein intermediate special procedure can be surface treatment, solvent cleaning, printing, on-line curing, painting
Cloth coating or gluing etc., preferably surface treatment, printing, starching, on-line curing.Wherein surface treatment mode has online or line
Under, preferably online, mode includes coining pigment, pattern, mute chemical conversion type；Starching mainly carries out coating, glue according to demand
Deng brush coating process；Carry out various on-line curing modes, preferably with the matched online mode of line speed, such as
Mode described in CN101767465A.
In the present invention, intermediate special procedure causes to change to the performance of product, especially in rate of perviousness, appearance, intensity, hand
Sense, toughness etc..
In the present invention, the saturating vapour isolation-type thermoplastic resin membrane of the preparation, wherein the film has barrier
Function, can by liquid barrier test of dyne value less than 50, test (ASTM F1670) can be obstructed by blood, can be with
The test result for obstructing test (ASTM F1671) by virus and bacteria, 1400mmH2O or more being obstructed by hydrostatic pressing
(AATCC 127), 5nm or more solid particles, aerosol (YY/T 0506.5-2009) can be obstructed.
In another aspect, in order to realize the goal of the invention of the present invention, the present invention also provides a kind of vapour isolation-type thermoplasticity
The laminates of resin film, wherein the laminates include：
The film of at least one layer of vapour isolation-type thermoplastic resin continuous structure of the present invention；
At least one layer has natural or chemicals layer；
Wherein, the natural or chemicals is discontinuous film, and/or nonwoven articles, and/or viscose system
Product, and/or Textile Fibre Product.
Wherein, thermoplastic articles layer is thermoplastic resin membrane or thermoplastic resin fibre's product, the thermoplasticity
Resin fibre product is textile fabric and/or non-woven material.
Preferably, the textile fabric is selected from such as next group of fibrous material：Polyester and its derivant fiber, nylon
And its derivant fiber, spandex and its derivant fiber and polypropylene fibre and its derivant fiber.
Preferably, the nonwoven articles are selected from such as next group：Wet laid nonwoven method, Stitchbonded nonmoven method, synthesis
Leather method, film split method nonwoven process, spun-bond process, meltblown, spun lacing method, needle point method, thermal bonding, chemical adhesion method etc..Preferably,
Nonwoven articles itself have certain antiseep.
Film and laminates prepared by polyether ester thermoplastic elastomer composition using the present invention has same resistance
Every effect, protective action is played.
Film and laminates prepared by vapour barrier thermoplastic resin composition using the present invention, in gas permeability
Energy, water vapour permeability, wet impedance value and mechanical properties, there is excellent performance.
In the following, in conjunction with the drawings and specific embodiments, the present invention is further illustrated, but these specific implementation modes
Just for the explanation of the certain specific specific implementation modes of the present invention, it is not limited to the present invention.
Description of the drawings
Fig. 1 is the schematic diagram of single layer expressing technique according to an embodiment of the present invention；
Fig. 2 is the schematic diagram according to another embodiment two or more layers expressing technique of the present invention.
Fig. 3 is the schematic diagram according to another embodiment multilayer distributor expressing technique of the present invention.
Fig. 4 is the schematic diagram according to expressing technique in another embodiment multilayer film of the present invention.
Fig. 5 is according to another embodiment party's belt film forming schematic diagram of the present invention
Fig. 6 is according to another embodiment party's roll-type film forming schematic diagram of the present invention
Fig. 7 two or more layers film identical material continuity schematic diagrames
Fig. 8 film continuity rough surface protrusion SEM schematic diagrames
The saturating vapour schematic diagram of diffusion of Fig. 9 films
Specific implementation mode
In following each specific implementation mode, the test methods such as grammes per square metre, peeling force, flatness, rate of perviousness are as follows:
(1) Thickness sensitivity standard：
A) detecting instrument：Assay balance, precision 0.001g；
B) standard for manual sampling：Breadth direction far from side 15mm rise, often at a distance of about 60mm sample, in the longitudinal direction every
300mm is sampled.Sample ruler cun is referred to as 100x100mm, and sampling block number is totally 100 pieces on breadth and length direction；
(2) blood testing standard is obstructed：
A) examination criteria：ASTM F 1670；
B) standard for manual sampling：
1, each material forms, and 3 samples are randomly selected under position (when heterogencity design of material) or other conditions；
If 2, material is to accompany one layer of sealant in two fibrous layers, the capillarity of edge of materials can lead to reality
It tests result and false positive occurs, and cause result unqualified.The edge of laboratory sample should be sealed at this time, to avoid capillarity shadow
It rings.It should be with adhesive, sealing compound, solid paraffin or paying has the foam of bonding agent to carry out sealing to sample before experiment carries out；
3, only to the sample at edge, the open area for leaving center 57mm is tested for sealing；
If to pass through sterilization processing when 4, sample makes finished product, need to carry out antivirus processing to sample.Antivirus process cannot
Influence the performance of sample, it is necessary to meet the requirement of manufacturing firm；
5, sample is before experiment, should be (21 ± 5) DEG C in temperature, relative humidity 30~80% under conditions of handle at least 24
Hour.6, if it is allowed, other pretreatment conditions (as sterilized) can be used, performance is evaluated；
C) detection method：(0kPa first is kept for 5 minutes sample, is protected later with 13.8kPa under pressure at the appointed time
Hold 1 minute, then kept for 54 minutes with 0kPa again) bear the penetration test of simulated body fluid (synthesis blood).Judged with visually observing
The generation of infiltration.Dextran has any evidence that penetrates then to constitute failure.As a result report is presented as qualified/unqualified.
(3) Virus Standard is obstructed：
A) examination criteria：ASTM F 1671；
B) standard for manual sampling：
1, each material forms, and 3 samples are randomly selected under position (when heterogencity design of material) or other conditions；
If 2, material is to accompany one layer of sealant in two fibrous layers, the capillarity of edge of materials can lead to reality
It tests result and false positive occurs, and cause result unqualified.The edge of laboratory sample should be sealed at this time, to avoid capillarity shadow
It rings.It should be with adhesive, sealing compound, solid paraffin or paying has the foam of bonding agent to carry out sealing to sample before experiment carries out；
3, only to the sample at edge, the open area for leaving center 57mm is tested for sealing；
If to pass through sterilization processing when 4, sample makes finished product, need to carry out antivirus processing to sample.Antivirus process cannot
Influence the performance of sample, it is necessary to meet the requirement of manufacturing firm；
5, sample is before experiment, should be (21 ± 5) DEG C in temperature, relative humidity 30~80% under conditions of handle at least 24
Hour.6, if it is allowed, other pretreatment conditions (as sterilized) can be used, performance is evaluated；
C) detection method：(0kPa first is kept for 5 minutes sample, is protected later with 13.8kPa under pressure at the appointed time
Hold 1 minute, then kept for 54 minutes with 0kPa again) bear the penetration test of bacteriophage liquid Phi-X174.When there is no generation liquid
When body phenomenon of osmosis, determine virus whether by sample to another side by a kind of analysis program.There are liquid or virus to penetrate
Evidence then fails.As a result report is presented as qualified/unqualified.
(4) rate of perviousness：
The positive cup D methods test of ASTM E96 distilled water is simulated, wind speed 1m/s, humidity 50%, temperature is 38 degrees Celsius, east
The moisture-inhibiting equipment of Yang Jing machines company production.
(5) hydrostatic pressing testing standard：
A) examination criteria：GB/T 4744-2013
B) hydrostatic pressing that this standard is born with fabric indicates that water penetrates the resistance that is encountered of fabric.In standard atmosphere condition
Under, the hydraulic pressure for bearing to continue rising on one side of sample records seepage point at third until seepage point at three occurs in another side
Pressure value when appearance, and evaluate with this water resistance of sample.It must add on the membrane surface when being tested for film product
One layer of mesh number is the nylon or terylene net of 50 mesh or so.
(6) fine particle testing standard：
A) examination criteria：YY/T 0506.5-2009
B) this experiment is carried out on the test specimen on being separately fixed at a container.In these containers, 5 carryings are withered
The container of straw bacterium talcum powder, 1 container that non-microbiological contamination talcum powder is added is as a contrast.It is close from below test specimen in each container bottom
Distance is inserted into 1 culture dish.The equipment of support container makes its oscillation by 1 gas ball-type oscillator, penetrates the talcum powder of test specimen
It all falls on culture dish, take out culture dish and cultivates.The bacterium colony of growth is counted.Sample is at 20 DEG C ± 2 DEG C and 65%
Status adjustment and experiment are carried out under ± 5% relative humidity.It is to pass through test that no powder, which penetrates,.
(7) pin hole testing standard：
A) examination criteria：Autogamy penetrability liquid；
B) standard for manual sampling：Each material randomly selects 3 samples；
C) penetrability liquid brush is applied to suture, fails if there is sepage after 60min, if without sepage, that is, imporosity production
It is raw.
Example one~11
As shown in table 1, by mixture after the formula metering of example one to example 11, it is molten that three extruders are direct plungeed into
Melt, through 0.5 μm of roughness depth, the cloud point matte roll form film (see Fig. 5) of 30 DEG C of temperature, processing temperature be than peak melting point at
Divide 30 DEG C high, surface treated manufacturing procedure, trimming, winding to be finally prepared into 9 μm of cloud point shape (see Fig. 8) continuitys (see Fig. 7)
Saturating vapour isolation-type thermoplastic resin membrane finished product (see Fig. 8), film speed 80m/min.Wherein the film is respectively provided with
2500、2430、2500、2255、2000、500、700、800、1100、1300、3120g/m2* high moisture vapor transmission for 24 hours, except formula
11 hydrostatic pressing only has outside 1200mmH2O, remaining hydrostatic pressing obstructs the test result for having reached 6000mmH2O or more
(AATCC 127, screening test), has barriers function.Except formula 11 can not be in addition to, remaining can pass through dyne value 42
Liquid barrier test can be obstructed test (ASTM F1670) by blood, can obstruct test (ASTM by virus and bacteria
F1671 5nm or more solid particles, aerosol (YY/T 0506.5-2009) can), be obstructed.In the formula for illustrating film
Polar thermoplastic resin material can have an impact in certain proportional region again, especially with the increase of ratio, there is negative work
With phase separation degree has certain help to saturating vapour degree.
Example 12~16
Embodiment 12, embodiment 13, embodiment 14 are by mixture after the formula metering of example four, directly respectively
Put into the melting of separate unit extruder, through three layers of three Layer assignment device (see Fig. 3) monolayer molds, single layer distributor mold (see Fig. 4), three layers
Three layers of mold of distributor, embodiment 15 and embodiment 16 are that three three Layer assignment device monolayer molds of extruder of input are molten
Melt, three extruder three Layer assignment devices, three layers of die melts, remaining is finally prepared into 12 μm of three layers of cloud point shapes, three with example IV
Layer, nine layers, nine layers, the continuous saturating vapour isolation-type thermoplastic resin membrane's finished product of each layer of 27 layers of surface cloud point shape, system
Film speed 80m/min.The wherein described film is respectively provided with 2200,2350,2321,2334g/m2* high moisture vapor transmission for 24 hours, it is quiet
Hydraulic pressure barrier has reached test result (AATCC 127, the screening survey of 9000,9000,9250,9250,10000mmH2O or more
Examination), there is barriers function.Remaining can be tested by the liquid barrier of dyne value 42, can obstruct test (ASTM by blood
F1670 test (ASTM F1671)), can be obstructed by virus and bacteria, can obstruct 5nm or more solid particles, aerosol
(YY/T 0506.5-2009).Illustrate that the number of plies of film does not influence moisture vapor transmission, it is beneficial to barrier property.
Example 17~20
Embodiment 17, embodiment 18, embodiment 19, embodiment 20 are respectively will be after the formula metering of example four
Mixture direct plunges into the melting of separate unit extruder, through single layer distributor (see Fig. 1) monolayer mold, respectively in 9 μm of roughness depth,
The 0.1mm*0.1mm specifications of 0.5 μm of the cloud point matte roll form film of 30 DEG C of temperature, roughness depth, 30 DEG C of temperature are grid-like thick
Rough roller form film, 0.5 μm μm of roughness depth, the cloud point matte roll of 160 DEG C of temperature (one of which point minimum softening point) at
0.5 μm of type film, roughness depth, the coarse height temperate zone form film (see Fig. 6) of cloud point that 100 DEG C of temperature, remaining same example IV
It is final be prepared into 9 μm of cloud point shape monolayer surface cloud point shapes, it is grid-like, can not form a film, the saturating vapour isolation-type thermoplastic resin of cloud point shape
Membrane of lipoprotein finished product, film speed 80m/min.The wherein described film is respectively provided with 3345,2192, no data, 2334g/m2*
High moisture vapor transmission for 24 hours, hydrostatic pressing barrier reached 10,9000, no data, 8900mmH2O test result (AATCC 127, adds
Net test).In addition to embodiment 17 and embodiment 19, remaining can pass through the test of the liquid barrier of dyne value 42, Ke Yitong
Cross blood barrier test (ASTM F1670), can by virus and bacteria obstruct test (ASTM F1671), can obstruct 5nm with
Upper solid particle, aerosol (YY/T 0506.5-2009).Barrier property will be caused by illustrating that the roughness depth of molding facility is excessively high
Decline severe, configuration of surface has some influences to moisture vapor transmission, and temperature is excessively high when molding will lead to not form a film, band-like film forming or
Roll forms a film.
Example 20~27
Embodiment 20 to embodiment 26 is that mixture after the formula metering of example four is direct plungeed into separate unit respectively
Extruder melts, through single layer distributor (see Fig. 1) monolayer mold, remaining be finally prepared into example IV 2 μm, 5 μm, 12 μm,
Continuous vapour isolation-type thermoplastic resin membrane's finished product of 15 μm, 25 μm, 33 μm, 50 μm cloud point shape monolayer surface cloud point shapes, system
Film speed 80m/min.The wherein described film is respectively provided with 2933,2789,2203,2105,1988,1671,1100g/m2*
High moisture vapor transmission for 24 hours, hydrostatic pressing barrier reached 1000,3000,12000,18000,30000,35000,45000mmH2O
Test result (AATCC 127, screening test).In addition to embodiment 20, remaining can be surveyed by the liquid barrier of dyne value 42
Examination, test (ASTM F1670) can be obstructed by blood, test (ASTM F1671) can be obstructed by virus and bacteria, can be with
Obstruct 5nm or more solid particles, aerosol (YY/T 0506.5-2009).Illustrate that the thinner barrier property of thickness is poorer, it is thicker
Vapour rate is lower, but if the continuity of film is kept still to have certain obstructing capacity.
Example 20 July 1st~32
As shown in table 2, by mixture after the formula metering of example 27 to example 32, remaining same example IV,
It is final to be prepared into 9 μm of cloud point shape (see Fig. 8) continuitys (see Fig. 7) vapour isolation-type thermoplastic resin membrane finished product (see Fig. 8) thoroughly, system
Film speed 80m/min.The wherein described film is respectively provided with 2630,2100,500,2123,2278,780,2550g/m2*24h
High moisture vapor transmission, except formula 32 hydrostatic pressing there was only 1800mmH2O in addition to, remaining hydrostatic pressing barrier reaches
The test result (AATCC 127, screening test) of 6000mmH2O or more, has barriers function.The liquid of dyne value 42 can be passed through
Body barrier test can be obstructed test (ASTM F1670) by blood, can obstruct test (ASTM by virus and bacteria
F1671 5nm or more solid particles, aerosol (YY/T 0506.5-2009) can), be obstructed.In the formula for illustrating film
The polar part that is added thereto of compatilizer is conducive to vapour, and saturating vapour is declined slightly after ratio increase, and ratio increase excessively will be big
Width reduces saturating vapour, and in two ingredients phase separation in addition to compatilizer, the addition of compatilizer is conducive to the raising of barrier property, but
Have an impact to moisture vapor transmission.
Claims (14)
1. a kind of thermoplastic resin composition being used to prepare vapour isolation-type film, wherein by mass percentage, the thermoplastic
Property resin combination includes:
1-99% contains the non-unformed elastomer resin material of thermoplasticity of the hydrophilic segment of 5% or more ratio, 0.01-99%
The thermoplastic resin material for serving as compatilizer of polar thermoplastic resin material, 0-30%；
Wherein, which is formed by being cast to non-specular surface rough surface by film die after melt blending
The saturating vapour isolation-type thermoplastic resin membrane of 1 μm -250 μm of the thickness of single layer or more.
2. composition as described in claim 1, wherein the thermoplasticity of the hydrophilic segment containing 5% or more ratio is non-
Unformed elastomer resin material can be one or any a variety of blend of following resin：Dicarboxylic acids and dihydric alcohol,
The copolymer or blend, and/or binary amide and dihydric alcohol of epoxide, the copolymer of epoxide or blend,
And/or binary isocyanic acid and dihydric alcohol, the copolymer of epoxide or blend, and/or contain ionic surface active agent
Hydrophilic group (group), such as carboxylic acid group (- COOH), sulfonic group (- SO3H), sulfate and phosphate copolymer or blend,
And/or contain cationic surfactant, such as amino (- NH2), the copolymer of quaternary ammonium group or blend, and/or containing it is non-from
Sub- surfactant, the copolymerization of the ether, hydroxyl (- OH), aldehyde radical (- CHO) carbonyl, block polyether that are such as made of oxygen-containing group
Object or blend.
3. composition as described in claim 1, wherein described is one kind containing the other thermoplastic resin materials of polar group
Or more than one the thermoplastic resin material being selected from such as next group：Corvic, vinylidene resin, acetic acid second
Enester resin, polyvinyl alcohol, polyvinyl acetal, polystyrene, AS resins, SAN resins, SBS resins, ABS resin, pressure gram
Power resin, polyacetal resin, acetal resin, polycarbonate resin (PC), gathers and mocks resin, celluloid, acetic acid fibre nylon resin
The copolymer or blend of the plain plastics of dimension, thermoplasticity polyester, epoxy resin, thermoplastic acrylic resin etc..
4. composition as described in claim 1, wherein the thermoplastic resin material for serving as compatilizer is one kind or one
Kind or more selected from following one or any a variety of blend：Cyclic acid anhydride type (MAH) graft polymers or blending
Object, and/or carboxylic acid type graft polymers either concurrent mixture, and/or epoxy type graft polymers or concurrent mixture, and/or
Oxazoline type graft polymers either concurrent mixture, and/or imide-type graft polymers or concurrent mixture, and/or isocyanide
Acid esters type graft polymers or concurrent mixture, and/or low molecule type response type compatilizer and its mixture.
5. composition as described in claim 1, wherein by mass percentage, the composition includes:3-95% contains 5%
The thermoplastic elastomer resin material of the hydrophilic segment of the above ratio, the polar thermoplastic resin material of 1-99%, 0-28%
Serve as the thermoplastic resin material of compatilizer.
6. saturating vapour isolation-type thermoplastic resin membrane prepared by a kind of composition by described in one of claim 1-5, the film
With single layer or two layers or more structure, the thickness of the film is 1-250 μm of m, preferably 2-100 μm of m.
7. vapour isolation-type thermoplastic resin membrane thoroughly as claimed in claim 6, wherein every layer material of two layers or more structure is equal
Using same composition, saturating carbonated drink is flat consistent.
8. vapour isolation-type thermoplastic resin membrane thoroughly as claimed in claim 6, wherein the surface of single layer or two layers or more is equal
For continuous structure.
9. vapour isolation-type thermoplastic resin membrane thoroughly as claimed in claim 6, wherein after the composition is by melt blending
It is cast to non-specular surface rough surface by film die by forms film.
10. vapour isolation-type thermoplastic resin membrane thoroughly as claimed in claim 9, wherein in cooling form a film, surface temperature is 0
DEG C to the minimum softening point in the composition, more optimizedly it is less than 5 DEG C of minimum softening point.
11. vapour isolation-type thermoplastic resin membrane thoroughly as claimed in claim 9, wherein the roughness depth on surface should be than described
Shallow 0.1 μm of thickness of film or more, more preferably shallow 0.5 μm or more, optimal shallow 1 μm or more.
12. vapour isolation-type thermoplastic resin membrane thoroughly as claimed in claim 6, wherein the film has 300g/m2*24h
Or more moisture vapor transmission (ASTM E96-2000D methods), preferably 700g/m2* rate of perviousness for 24 hours or more, more preferably
For 1000g/m2* high moisture vapor transmission for 24 hours or more.
13. a kind of laminates of vapour isolation-type thermoplastic resin membrane, wherein the laminates include：
At least one layer of saturating vapour isolation-type thermoplastic resin membrane as described in claim 6-12；
At least one layer of natural or chemicals layer；
Wherein, the natural or chemicals is discontinuous film, nonwoven articles, viscose product, and/or textile fabric
Product.
14. laminates as claimed in claim 13, wherein the textile fabric is selected from such as next group of fibrous material：
Polyester and its derivant fiber, nylon and its derivant fiber, spandex and its derivant fiber and polypropylene fibre and its derivative are fine
Dimension, polyolefin and its derivant fiber etc..
Priority Applications (2)
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| CN201710262655.XA CN108727774A (en) | 2017-04-20 | 2017-04-20 | The composition of saturating vapour isolation-type thermoplastic resin and its film of preparation |
| PCT/CN2017/082435 WO2018192005A1 (en) | 2017-04-20 | 2017-04-28 | Vapour-permeable barrier-type thermoplastic resin composition and thin film prepared therefrom |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710262655.XA CN108727774A (en) | 2017-04-20 | 2017-04-20 | The composition of saturating vapour isolation-type thermoplastic resin and its film of preparation |
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| WO (1) | WO2018192005A1 (en) |
Cited By (1)
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|---|---|---|---|---|
| CN111925552A (en) * | 2020-08-04 | 2020-11-13 | 佛山金万达科技股份有限公司 | Surface treatment of thermoplastic resin film and resulting product |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| FR3115790B1 (en) * | 2020-11-03 | 2023-07-07 | Prochimir | single layer monolithic breathable waterproof film |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101358020A (en) * | 2008-09-28 | 2009-02-04 | 华南理工大学 | Nonporous moisture permeable and water-repellent modified polyether ester functional film material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2721320B1 (en) * | 1994-06-20 | 1996-08-14 | Atochem Elf Sa | Waterproof-breathable film. |
| CA2256624A1 (en) * | 1996-05-29 | 1997-12-04 | E.I. Du Pont De Nemours And Company | Breathable composite sheet structure and absorbent articles utilizing same |
| WO2011116475A1 (en) * | 2010-03-25 | 2011-09-29 | Ibco Srl | Breathable coated fabric |
| EP2723568B1 (en) * | 2011-06-23 | 2017-09-27 | Fiberweb, LLC | Vapor permeable, substantially water impermeable multilayer article |
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2017
- 2017-04-20 CN CN201710262655.XA patent/CN108727774A/en active Pending
- 2017-04-28 WO PCT/CN2017/082435 patent/WO2018192005A1/en active Application Filing
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101358020A (en) * | 2008-09-28 | 2009-02-04 | 华南理工大学 | Nonporous moisture permeable and water-repellent modified polyether ester functional film material and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111925552A (en) * | 2020-08-04 | 2020-11-13 | 佛山金万达科技股份有限公司 | Surface treatment of thermoplastic resin film and resulting product |
| CN111925552B (en) * | 2020-08-04 | 2022-11-22 | 佛山金万达科技股份有限公司 | Surface treatment of thermoplastic resin film and resulting product |
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Application publication date: 20181102 |