WO2018192005A1

WO2018192005A1 - Vapour-permeable barrier-type thermoplastic resin composition and thin film prepared therefrom

Info

Publication number: WO2018192005A1
Application number: PCT/CN2017/082435
Authority: WO
Inventors: 林裕卫; 吴耀根
Original assignee: 佛山金万达科技股份有限公司
Priority date: 2017-04-20
Filing date: 2017-04-28
Publication date: 2018-10-25
Also published as: CN108727774A

Abstract

Provided are a vapour-permeable barrier-type thermoplastic resin composition and a thin film prepared therefrom, wherein the thermoplastic resin composition comprises (in mass percentages): 1-99% of a thermoplastic elastomer resin material containing not less than 5% of hydrophilic segments, 0.01-99% of a polar thermoplastic resin material, and 0-30% of a thermoplastic resin material acting as a compatibiliser, wherein the thermoplastic resin composition is melt-blended and then flows onto a non-specular rough surface and is cast into one or two or more layers of a vapour-permeable barrier-type thermoplastic resin thin film by means of a film-forming mould. The thin film prepared by using the composition of the present invention has an excellent vapour permeability based on permeation diffusion principles, is structurally continuous, and can block substances with a size of more than 5 nm, such as solid dust, aerosols, bacteria, viruses and liquids; furthermore, a laminate resulting from same and a natural or chemical product can provide a good blocking effect, thereby having a protective function.

Description

Composition of vapor permeable barrier type thermoplastic resin and film prepared therefrom

Technical field

The present invention relates to a vapor permeable barrier type thermoplastic resin composition and a film prepared therefrom; more particularly, the present invention relates to a thermoplastic elastomer resin material having a high vapor permeability barrier property, a polar thermoplastic resin material and a phase A thermoplastic resin material composition of a bulking agent and a continuous vapor permeable barrier film prepared therefrom. This film is used for protective isolation.

Background technique

With the development of industry, the harsh climate and pollution have caused various human survival crises, such as various specific virus bacteria such as SARS, MERS, Ebola, haze, heavy rain, air pollution, etc., and human beings have re-entered from industrial urbanization. Outdoors, towards nature. Barrier-type thermoplastic resin materials have become the focus of research at home and abroad. Among them, selective gas permeable membrane materials are more concerned, especially the vapor-permeable barrier materials, while protecting and at the same time breathing. However, at present, both domestic and foreign are only focused on synthesis and modification development. There is no corresponding control on the molding process and the key control points in the later application, especially the control of the barrier effect. Some patented technologies are designed to increase the vapor permeability and smoothness. The addition of fillers also sacrifices barrier properties and creates a discontinuous structure, thus creating an unmatched technical barrier between production and end use, resulting in consumers not being able to properly understand and use the product.

CN101358020 discloses a modified formulation of a modified polyetherester film material which enhances the thermal stability of the product by the addition of an organic functional material. CN1032220C discloses a water vapor permeable thermoplastic film comprising a polyether ester amide as a main component, which film improves the moisture permeability and mechanical strength of the product. CN101346228 discloses a waterproof, water vapor permeable multilayer film having at least one first layer and a second layer, wherein all layers are selected from polyether esters, polyether amides or polyether urethanes The thermoplastic polymers of the type are composed and connected to each other. US 7,422,795 B2 discloses an elastomeric film having an organic soft segment and an organic hard segment. US 6,749,923 discloses a highly permeable film formed on a substrate. US 6,261,674 discloses a two layer breathable polymer film having a second layer having a lower moisture permeability than the first layer. US 6,114,024 discloses a five layer breathable film, the core layer and the adhesive layer being coextruded and stretched into a film. US 2016/0176168 A1 discloses a layer of non-hydrophilic material and a layer of hydrophilic material having a discontinuous structure. CN205167769U discloses a three-layer structure waterproof and moisture permeable film in which the intermediate layer is a non-polar resin material having a discontinuous structure. CN201220512715.1 discloses a three-layer knot The waterproof vapor permeable membrane has an intermediate layer of a polar resin material and a surface layer of a non-polar resin material. CN98812871.3 discloses a gas permeable film of a non-continuous structure having improved physical and barrier properties of a non-polar resin material excellent in water vapor permeability and excellent liquid permeation barrier property.

Summary of the invention

The object of the present invention is a vapor-permeable barrier type thermoplastic resin composition and a film prepared therefrom, wherein the prepared film has a vapor permeability, a structural continuity, a solid dust having a size greater than 5 nm, and an aerosol having excellent permeation and diffusion principles. , bacteria, viruses and liquids, and its natural or chemical laminates can play a good barrier effect, play a protective role.

In one aspect, in order to achieve the above object of the present invention, the present invention provides a composition of a vapor permeable barrier type thermoplastic resin, wherein the composition comprises, by mass percentage, the composition comprises:

1-99% of a non-amorphous thermoplastic resin material containing a hydrophilic segment of 5% or more, 0.01 to 99% of a polar thermoplastic resin material, and 0 to 30% of a thermoplastic resin material serving as a compatibilizing agent. There is no inorganic filler in the composition.

In the above composition of the present invention, the thermoplastic elastomer resin material containing a hydrophilic segment of 5% or more may be one or a blend of any of the following resins: dicarboxylic acid and diol, Copolymers or blends of epoxy compounds, and/or copolymers or blends of bisamides and diols, epoxy compounds, and/or binary isocyanates and diols, epoxy compounds a copolymer or blend, and/or a hydrophilic group containing an ionic surfactant, such as a copolymer of a carboxylic acid group (-COOH), a sulfonic acid group (-SO3H), a sulfate group and a phosphate group, or Blending, and/or containing a cationic surfactant such as an amino (-NH2), a copolymer or blend of quaternary ammonium groups, and/or containing a nonionic surfactant, such as an ether group composed of an oxygen-containing group, Copolymer or blend of hydroxyl (-OH), aldehyde (-CHO) carbonyl, block polyether. The proportion of hydrophilic segments is preferably 5% ˉ 95%, more preferably 5% ˉ 90%, and the proportion of hydrophilic segments in the formulation will affect the vapor permeability, but too high will result in a film that cannot form a continuity. The mechanical strength is reduced.

In the above composition of the present invention, the other thermoplastic resin material containing a polar group is one or more thermoplastic resin materials selected from the group consisting of polyvinyl chloride resin, vinylidene chloride resin, vinyl acetate. Ester resin, polyvinyl alcohol, polyvinyl acetal, polystyrene, AS resin, SAN resin, SBS resin, ABS resin, acrylic resin, nylon resin, polyacetal resin, polyacetal resin, polycarbonate Resin (PC), agglomerated resin, Copolymers or blends and or modified resins of cellophane, cellulose acetate plastic, thermoplastic polyester, epoxy resin, thermoplastic acrylic resin, and the like.

In the above composition of the present invention, the thermoplastic resin material serving as a compatibilizing agent is one or more selected from the group consisting of a cyclic anhydride type (MAH) graft polymer or a blend, And/or carboxylic acid type graft polymer or co-mixture, and/or epoxy type graft polymer or co-mix, and/or oxazoline type graft polymer or co-mix, and/or imide type A graft polymer or co-mixture, and/or an isocyanate-type graft polymer or co-mixture, and/or a low molecular type reactive compatibilizer and mixtures thereof.

Preferably, the composition of the present invention is: 3 to 95% by weight of the thermoplastic elastomer resin material containing 5% or more of the hydrophilic segment, 1-99% of the polar thermoplastic resin material, 0-28 % of a thermoplastic resin material that acts as a compatibilizer. More preferably, the composition of the present invention is: 3 to 95% of a thermoplastic elastomer resin material containing 5% or more of a hydrophilic segment, 2 to 99% of a polar thermoplastic resin material, 0 to 25% of the composition A thermoplastic resin material of a compatibilizer.

In the present invention, when the thermoplastic resin composition comprises 30% to 60% of a polar thermoplastic resin material, a polar thermoplastic resin material serving as a compatibilizing agent should be used. In a preferred embodiment of the present invention, the composition of the present invention comprises: 40 to 70% of a thermoplastic elastomer resin material containing 5% or more of a hydrophilic segment, 30 to 60% of a polar thermoplastic resin material, 1 - 10% of a thermoplastic resin material acting as a compatibilizer.

In one aspect, the present invention also provides a vapor-permeable barrier type thermoplastic resin film prepared from the above composition, which film has a thickness of from 1 to 250 μmm, preferably from 2 to 100 μmm, more preferably 2-80μmm is optimal. According to the ASTM E96-2000D method, the vapor permeability of the film of the invention should be above 100g/m ² *24h, preferably at 600g/m ² *24h, 1000g/m ² *24h or more, wherein the ultra-high permeability is transparent. More preferably, it is 1200 g/m ² *24h or more.

For example, the thermoplastic resin composition of the present invention can be formed by melt-blending and casting through a film-forming mold to a non-mirror rough surface to form a single layer or more of a vapor-permeable barrier type thermoplastic resin film having a thickness of from 1 μm to 250 μm.

In the present invention, the vapor permeability of the film has a large relationship with the ratio of the thermoplastic elastomer resin material of the composition and the thermoplastic resin material of the polar thermoplastic resin material and the compatibilizing agent, especially the compatibilizer and the compatibilizer. To adjust the phase incompatibility of the two materials, the more compatible, the less vapor permeable, but if not at all compatible will result in a decrease in the mechanical strength of the film.

In the present invention, the vapor permeability and barrier properties of the film are also related to the thickness and the process. The thicker the thickness, the lower the air permeability, the stronger the barrier property, and the more the destructive force on the film in the process and transportation, such as the pressure roller, the roller surface cleaning, etc., the barrier property will be reduced.

A vapor-permeable barrier type thermoplastic resin film prepared from the composition of the present invention, which has a continuous structure and has a vapor permeable principle and a continuous structure as shown in FIG.

In the present invention, the vapor-permeable barrier type thermoplastic resin film may be a single layer or a structure of two or more layers, wherein each layer of the two or more layers adopts the same composition, and the vapor permeability level is uniform, so that the number of layers is not Increase and change the ability of vapor permeability, and there will be no delamination and discontinuity due to different materials. When there are two or more layers, there are no discontinuous layers, all of which are continuous structures, and there is no physical gap. The more the number of layers, the stronger the barrier property, and as long as the thickness is constant, the ventilation comfort will not decrease.

The vapor-permeable barrier type thermoplastic resin film of the present invention can block solid dust and substances having a size larger than 5 nm, substances such as bacteria, viruses, and liquids, and is preferably a substance having a barrier of 20 nm or more, and more preferably 80 nm or more.

As a specific embodiment of the present invention, the vapor-permeable barrier type thermoplastic resin composition of the present invention may comprise: 5% to 95% of a thermoplastic elastomer resin material containing a hydrophilic segment of 5% or more, 5 to 95% A polar thermoplastic resin material, and 0 to 25% of a thermoplastic resin material serving as a compatibilizer.

As another embodiment of the present invention, the vapor-permeable barrier type thermoplastic resin composition of the present invention may comprise: 5% to 95% of a thermoplastic elastomer resin material containing a hydrophilic segment of 5% or more, 10-90 % of a polar thermoplastic resin material, and 1-25% of a thermoplastic resin material serving as a compatibilizer.

In the present invention, the above composition may be mechanically mixed by a twin screw or a single screw, and then subjected to premixed melt granulation or directly melt-extruded into a film, which is preferably carried out according to different formulations.

In the present invention, a plurality of extruders may be co-extruded to form a multilayer structure, or a multilayer cavity or a multilayer wind ring structure may be used to form a multilayer structure, or a multilayer distributor may be used to form a multilayer structure. It may be a multilayer structure formed by one, two or three of the above three methods, preferably a continuous film structure of 3 or more layers. The number of extruders corresponding to the cavity or the air ring or the distributor may be one, and may be plural, and preferably two or more.

In the present invention, the thermoplastic resin composition has a melt processing temperature of 10 degrees Celsius higher than the highest melting point of the three thermoplastic resins, and is 10 degrees Celsius lower than the lowest decomposition temperature of the three thermoplastic resins, thereby avoiding unmelting due to a low processing temperature. The appearance of substances or glue spots causes discontinuous holes in the film, and also avoids excessive processing temperatures. Degradation of the material, even perforation.

In the present invention, the thermoplastic resin composition is cast through a film forming mold to a non-mirror rough surface by melt blending, and may be a rough roll, a rough paper tape, or a rough plastic resin tape. It can also be a rough metal strip. At the time of molding, there is a device for pressing the cast slurry to a non-mirror rough surface, and the pressure for pressing is 0.01 to 0.6 MPa, preferably 0.1 to 0.5 MPa, and more preferably 0.1 to 0.45 MPa. Too low will cause the rough surface of the film to fail to form, and too high will cause the film to be perforated.

In the present invention, the non-mirror rough surface may have a surface temperature of from 0 ° C to the lowest softening point in the composition of claim 1 5 when cooled to form a film, and more preferably 5 ° C below the minimum softening point. More preferably, it is 10 ° C below the minimum softening point. In the present invention, if the temperature of the non-mirror rough surface is too high, the adhesion problem of the film is liable to occur, and damage is caused therefrom, and the production speed is lowered. Too low and easy to cause the texture of the film is not clear, the film and film adhesion, which is not conducive to later use.

In the present invention, the non-mirror rough surface may be various patterns and textures, such as random, sand, pattern, logo, lattice, leather, etc., alone or in a mixed shape;

In the present invention, the non-mirror rough surface has a rough surface depth of 0.1 μm or more, more preferably 0.5 μm or more, and most preferably 1 μm or more.

In the present invention, the vapor-permeable barrier type thermoplastic resin film prepared by the non-mirror rough surface has a rough surface conforming to a non-specular surface.

In the present invention, various processing steps may be intermediate special processes, trimming, slitting, slitting into rolls, etc., preferably any of the processes are combined or separately performed, wherein the intermediate special processes may be surface treatment, solvent cleaning, printing, Online curing, coating or gluing, etc., preferably surface treatment, printing, sizing, in-line aging. The surface treatment method is on-line or offline, preferably on-line, and the method includes imprinting pigment, pattern, and matte molding; sizing is mainly a coating process of coating, glue, etc. according to requirements; performing various online curing methods, preferably For online mode matching production line speed, as described in CN101767465A.

In the present invention, the intermediate special process changes the properties of the product, especially in terms of moisture permeability, appearance, strength, hand feeling, toughness and the like.

In the present invention, the prepared vapor-permeable barrier type thermoplastic resin film, wherein the film has a barrier function, can pass a liquid barrier test having a Dyne value of less than 50, can pass a blood barrier test (ASTM F1670), can Through the virus bacterial barrier test (ASTM F1671), the test results can be blocked by hydrostatic pressure of 1400mmH2O or above. (AATCC 127), can block solid particles above 5nm, aerosol (YY/T0506.5-2009).

In still another aspect, in order to achieve the object of the present invention, the present invention also provides a laminate of a vapor-permeable barrier type thermoplastic resin film, wherein the laminate comprises:

At least one layer of a vapor-permeable barrier type thermoplastic resin continuous structure film according to the present invention;

At least one layer having a natural or chemical layer;

Wherein the natural or chemical product is a discontinuous film, and/or a nonwoven article, and/or an adhesive article, and/or a woven fiber article.

Wherein the thermoplastic resin product layer is a thermoplastic resin film or a thermoplastic resin fiber product, and the thermoplastic resin fiber product is a textile fiber and/or a nonwoven material.

Preferably, the textile fiber is a fiber material selected from the group consisting of polyester and its derivative fibers, nylon and its derivative fibers, spandex and its derivative fibers, and polypropylene and its derivative fibers.

Preferably, the nonwoven article is selected from the group consisting of wet weaving, stitchbonding, synthetic leather, membrane cracking, spunbonding, meltblowing, hydroentangling , acupuncture, thermal bonding, chemical bonding, etc. Preferably, the nonwoven article itself has some resistance to leakage.

Films and laminates prepared using the polyetherester thermoplastic elastomer composition of the present invention have the same barrier effect and provide protection.

The film and laminate prepared by using the vapor-permeable barrier thermoplastic resin composition of the present invention have excellent performance in terms of gas permeability, moisture permeability, wet resistance value, and mechanical properties.

The present invention is further described with reference to the accompanying drawings and specific embodiments.

DRAWINGS

1 is a schematic view of a single layer extrusion process in accordance with an embodiment of the present invention;

2 is a schematic illustration of a two or more layer extrusion process in accordance with another embodiment of the present invention.

3 is a schematic illustration of a multilayer dispenser extrusion process in accordance with another embodiment of the present invention.

4 is a schematic view of a multi-layer in-mold extrusion process in accordance with another embodiment of the present invention.

Figure 5 is a schematic view of a belt film formation according to another embodiment of the present invention.

Figure 6 is a schematic view of roll forming film according to another embodiment of the present invention.

Figure 7 is a schematic diagram of the continuity of the same material of two or more layers of film

Figure 8 is a schematic view of the SEM of the continuous surface roughness of the film

Figure 9 is a schematic diagram of the permeation-diffusion vapor transmission of the film

detailed description

In the following specific embodiments, the test methods such as gram weight, peeling force, flatness, and moisture permeability are as follows:

(1) Thickness test standards:

A) Testing equipment: analytical balance, accuracy 0.001g;

B) Sampling standard: sampling at a distance of about 15 mm from the side in the width direction, sampling every 300 mm in the longitudinal direction. The sample size is 100x100mm, and the number of sample blocks is 100 pieces in width and length direction;

(2) Barrier blood test standards:

A) Test standard: ASTM F 1670;

B) Sampling standards:

1. Randomly select 3 samples for each material, composition, location (when non-uniform material is designed) or other conditions;

2. If the material has a sealing layer sandwiched between the two fiber layers, the capillary action at the edge of the material may cause false positives in the experimental results, resulting in unsatisfactory results. At this point, the edges of the test sample should be sealed to avoid capillary effects. The sample should be sealed with an adhesive, a sealant, a paraffin wax or a foam with a binder before the experiment;

3. Seal only the sample on the edge, leaving the open area of the center 57mm for testing;

4. If the sample is to be sterilized when it is finished, the sample should be disinfected. The anti-virus process can not affect the performance of the sample and must meet the manufacturer's requirements;

5. The sample should be treated for at least 24 hours at a temperature of (21 ± 5) ° C and a relative humidity of 30 ˉ 80% before the experiment. 6. If allowed, other pretreatment conditions (such as sterilization) can be used to evaluate performance;

C) Test method: The sample was subjected to a penetration test of simulated body fluid (synthetic blood) under a specified time and pressure (first holding at 0 kPa for 5 minutes, then at 13.8 kPa for 1 minute, and then at 0 kPa for 54 minutes). The occurrence of infiltration was judged by visual observation. Any evidence of penetration of synthetic blood constitutes a failure. The results report is reflected as pass/fail.

(3) Barrier virus standards:

A) Test standard: ASTM F 1671;

B) Sampling standards:

C) Test method: The sample was subjected to a penetration test of the phage liquid Phi-X174 at a specified time and pressure (first at 0 kPa for 5 minutes, then at 13.8 kPa for 1 minute, and then at 0 kPa for 54 minutes). When no liquid permeation occurs, an analytical procedure is used to determine if the virus passes the sample to the other side. There is a liquid or virus penetration evidence that fails. The results report is reflected as pass/fail.

(4) Moisture permeability:

Simulated ASTM E96 distilled water positive cup D method test, wind speed of 1m / s, humidity of 50%, temperature of 38 degrees Celsius, moisture permeability equipment produced by Toyo Seiki Co., Ltd.

(5) Hydrostatic pressure test standards:

A) Test standard: GB/T 4744-2013

B) This standard indicates the resistance encountered by water through the fabric by the hydrostatic pressure experienced by the fabric. Under standard atmospheric conditions, one side of the sample is subjected to a continuously rising water pressure until three water seepage points appear on the other side, and the pressure value at the third water seepage point is recorded, and the water resistance of the sample is evaluated. For the film product test, a layer of nylon or polyester mesh having a mesh size of about 50 mesh must be applied to the surface of the film.

(6) Fine particle test standards:

A) Test standard: YY/T 0506.5-2009

B) This test was carried out on test pieces each fixed to a container. In these containers, 5 containers carrying Bacillus talc powder, 1 added unstained talc The powder container was used as a control. Insert one petri dish at a distance from the bottom of each container at a distance from the bottom of each container. The apparatus for supporting the container was oscillated by a gas ball type oscillator, and the talc powder penetrating the test piece was all dropped on the culture dish, and the culture dish was taken out and cultured. The growing colonies were counted. The samples were conditionally adjusted and tested at 20 ° C ± 2 ° C and 65% ± 5% relative humidity. No powder penetration is passed the test.

(7) Pinhole test standard:

A) Test standard: self-matching penetrating liquid;

B) Sampling criteria: 3 samples are randomly selected for each material;

C) The penetrating liquid is brushed to the suture, and if it appears after 60 minutes, it will fail. If there is no exudate, no pores will be produced.

Example one to eleven

As shown in Table 1, the metered mixture of Examples 1 to 11 was directly poured into three extruders and melted, and the film was formed by a rough roll having a roughness depth of 0.5 μm and a temperature of 30 ° C (see Fig. 5). The temperature is 30 ° C higher than the highest melting point component, and the surface treatment process, trimming, winding, and finally prepared into a 9 μm fog point (see Figure 8) continuity (see Figure 7), a vapor barrier thermoplastic resin film finished product ( See Figure 8), film speed 80m / min. The film has a high vapor permeability of 2500, 2430, 2500, 2255, 2000, 500, 700, 800, 1100, 1300, 3120g/m ² * 24h, respectively, except that the hydrostatic pressure of the formula 11 is only 1200mmH2O. The remaining hydrostatic pressure barriers have reached the test result of 6000mmH2O or more (AATCC 127, screening test), with barrier function. Except that formula 11 can not pass, the rest can pass the liquid barrier test of Dyne value 42, can pass the blood barrier test (ASTM F1670), can pass the virus bacterial barrier test (ASTM F1671), can block solid particles above 5nm, gas Sol (YY/T 0506.5-2009). It is indicated that the polar thermoplastic resin material in the formulation of the film has an influence within a certain proportion range, especially with the increase of the ratio, which has a negative effect, and the degree of phase separation has a certain help to the vapor permeability.

Example twelve to sixteen

Example 12, Example 13 and Example 14 are respectively the sample after metering of the sample of Example 4, which is directly put into a single extruder for melting, through a three-layer distributor (see Fig. 3), a single layer mold, a single layer. Three-layer mold of distributor (see Figure 4), three-layer mold of three-layer distributor, Example 15 and Example 16 are three-layer mold single-layer mold melting into three extruders, three extruders The three-layer distributor three-layer mold is melted, and the remaining four parts are finally prepared into a 12 μm fog-like three-layer, three-layer, nine-layer, nine-layer, twenty-seven-layer surface fog-like continuous vapor barrier. The finished thermoplastic resin film has a film forming speed of 80 m/min. The film has a high vapor permeability of 2200, 2350, 2321, 2334g/m ² *24h, and the hydrostatic pressure barrier reaches test results of 9000, 9000, 9250, 9250, 10000mmH2O or more (AATCC 127, screening Test), with blocking function. The rest can pass the dyne value of 42 liquid barrier test, can pass the blood barrier test (ASTM F1670), can pass the virus bacterial barrier test (ASTM F1671), can block solid particles above 5nm, aerosol (YY/T 0506.5-2009 ). It is shown that the number of layers of the film has no effect on the vapor permeability and is beneficial to the barrier properties.

Example seventeen to twenty

The seventeenth embodiment, the eighteenth embodiment, the nineteenth embodiment, and the twenty-eighth embodiment are the metered mixture of the sample of the fourth example, which are directly put into a single extruder and melted through a single layer distributor (see Fig. 1). Layer mold, a rough roll forming film with a rough depth of 9 μm, a temperature of 30 ° C, a roughness of 0.5 μm, a 0.1 mm × 0.1 mm square-shaped rough roll formed at a temperature of 30 ° C, a roughness depth of 0.5 μm μm, temperature 160 °C (the lowest softening point of one component), a fog-rolled rough roll forming film, a roughness depth of 0.5 μm, a fog-point rough high-temperature belt formed film at a temperature of 100 ° C (see Fig. 6), and the rest is finally prepared as 9 μm in the same manner as in the fourth embodiment. The mist-like single-layer surface has a matte-shaped, square-shaped, vapor-barrier-type thermoplastic resin film which cannot be formed into a film or a mist, and has a film forming speed of 80 m/min. The films described therein have a high vapor transmission rate of 3345, 2192, no data, 2334g/m ² *24h, and the hydrostatic pressure barrier reaches 10, 9000, no data, 8900mmH2O test results (AATCC 127, screening test) ). Except for the seventeenth embodiment and the nineteenth embodiment, all of them can pass the liquid barrier test of dyne value 42, can pass the blood barrier test (ASTM F1670), can pass the virus bacterial barrier test (ASTM F1671), can block more than 5nm Solid particles, aerosol (YY/T0506.5-2009). It is indicated that the roughness depth of the molding facility is too high, which will cause the barrier property to drop greatly. The surface morphology has some influence on the vapor permeability rate. If the temperature is too high during molding, film formation or roll film formation can be achieved.

Example twenty to twenty seven

Example 20 to Example 26 are respectively the sample metered mixture of Example 4, which is directly put into a single extruder for melting, through a single layer distributor (see Fig. 1), a single layer mold, and the rest is the same as in the fourth embodiment. A continuous vapor-permeable barrier thermoplastic resin film having a haze-like single-layer surface of 2 μm, 5 μm, 12 μm, 15 μm, 25 μm, 33 μm, and 50 μm was prepared at a film forming speed of 80 m/min. The film has a high vapor permeability of 2933, 2789, 2203, 2105, 1988, 1671, 1100g/m ² *24h, and the hydrostatic pressure barrier reaches 1000, 3000, 12000, 18000, 30,000, 35000, 45000mmH2O. Test results (AATCC 127, screening test). Except for the twenty-th embodiment, all can pass the liquid barrier test of dyne value 42, can pass the blood barrier test (ASTM F1670), can pass the virus bacterial barrier test (ASTM F1671), can block solid particles above 5nm, aerosol (YY/T 0506.5-2009). It shows that the thinner the thickness, the worse the barrier property, and the thicker the vapor permeability, the lower the vapor permeability. However, if the film continuity is maintained, there is still a certain barrier property.

Example twenty-seven one to thirty-two

As shown in Table 2, the formulation of Example 27 to Example 32 was metered out, and the rest was the same as in Example 4, and finally prepared into a 9 μm fog point (see Figure 8) continuity (see Figure 7). The finished thermoplastic resin film (see Figure 8) has a film forming speed of 80 m/min. The film has a high vapor permeability of 2630, 2100, 500, 2123, 2278, 780, 2550g/m ² * 24h, respectively, except that the hydrostatic pressure of the formula 32 is only 1800mmH2O, and the rest of the hydrostatic pressure barriers are It has reached the test result of 6000mmH2O or above (AATCC 127, screening test) and has a barrier function. Both can pass the liquid barrier test of Dyne value 42, can pass the blood barrier test (ASTM F1670), can pass the virus bacterial barrier test (ASTM F1671), can block solid particles above 5nm, aerosol (YY/T 0506.5-2009) . It is indicated that the addition of the compatibilizer in the formulation of the film is beneficial to the vapor permeation. When the proportion is increased, the vapor permeation is slightly decreased. If the proportion is increased too much, the vapor permeation will be greatly reduced. In addition to the compatibilizer, two When the components are phase separated, the addition of the compatibilizer is beneficial to the improvement of the barrier property, but has an effect on the vapor permeability.

Claims

An inorganic filler-free thermoplastic resin composition for producing a vapor-permeable barrier film, wherein the thermoplastic resin composition comprises, by mass percentage, of:

1-99% of a non-amorphous thermoplastic resin material containing a hydrophilic segment of 5% or more, 0.01 to 99% of a polar thermoplastic resin material, and 0 to 30% of a thermoplastic resin material serving as a compatibilizing agent.
The composition according to claim 1, wherein said thermoplastic non-amorphous elastomer resin material containing 5% or more of hydrophilic segments may be one or a blend of any of the following resins: a copolymer or blend of a dicarboxylic acid and a glycol, an epoxy compound; a copolymer or blend of a diamide and a glycol, an epoxy compound; a divalent isocyanic acid and a glycol, a ring a copolymer or blend of oxygen compounds; a copolymer or blend of hydrophilic groups containing an ionic surfactant; a copolymer or blend containing cationic surfactant groups; and/or a nonionic surface A copolymer or blend of active agent groups.
The composition according to claim 2, wherein the hydrophilic group of the ionic surfactant is a carboxylic acid group, a sulfonic acid group, a sulfuric acid group or a phosphoric acid group; and the cationic surfactant has a group of An amino group or a quaternary ammonium group; the group of the nonionic surfactant is an ether group, a hydroxyl group, an aldehyde group, a carbonyl group, or a block polyether group composed of an oxygen-containing group.
The composition according to claim 1, wherein said polar thermoplastic resin material is one or more thermoplastic resin materials selected from the group consisting of polyvinyl chloride resins, vinylidene chloride resins, Vinyl acetate resin, polyvinyl alcohol, polyvinyl acetal, polystyrene, AS resin, SAN resin, SBS resin, ABS resin, acrylic resin, nylon resin, polyacetal resin, polyacetal resin, poly Carbonate resin (PC), agglomerate resin, cellophane, cellulose acetate plastic, thermoplastic polyester, epoxy resin, thermoplastic acrylic resin, or a copolymer or blend thereof.
The composition according to claim 1, wherein said thermoplastic resin material serving as a compatibilizing agent is one or more selected from the group consisting of cyclic anhydride type (MAH) graft polymerization. Or blend; carboxylic acid type graft polymer or co-mix; epoxy type graft polymer or co-mix; oxazoline type graft polymer or co-mix Imide type graft polymer or co-mixture; isocyanate type graft polymer or co-mixture; and / or low molecular type reactive compatibilizer and mixtures thereof.
The composition according to claim 1, wherein the composition comprises, by mass percentage, a thermoplastic elastomer resin material having a hydrophilic chain of from 5% to 5% by weight, and a polarity of from 1 to 99%. A thermoplastic resin material, 0 to 28% of a thermoplastic resin material serving as a compatibilizer.
The composition according to claim 6, wherein the composition comprises, by mass%, 40 to 70% of a thermoplastic elastomer resin material having a hydrophilic segment of 5% or more, 30-60% of a pole A thermoplastic resin material, 1-10% of a thermoplastic resin material serving as a compatibilizer.
A vapor-permeable barrier type thermoplastic resin film prepared from the composition according to any one of claims 1 to 7, which has a single layer or a structure of two or more layers, and the film has a thickness of from 1 to 250 μmm, preferably from 2 to 100 μm. .
The vapor-permeable barrier type thermoplastic resin film according to claim 6, wherein the single layer or the two or more layers have a continuous structure.
The vapor-permeable barrier type thermoplastic resin film according to claim 9, wherein the surface temperature at the time of cooling film formation is from 0 ° C to the lowest softening point in the composition, and more preferably from 5 ° C below the minimum softening point.
The vapor-permeable barrier type thermoplastic resin film according to claim 9, wherein the rough surface depth is 0.1 μm or more, more preferably 0.5 μm or more, and most preferably 1 μm or more.
The vapor-permeable barrier type thermoplastic resin film according to claim 8, wherein said film has a vapor permeability of 300 g/m 2 * 24 h or more (ASTM E96-2000 D method), preferably 700 g/m 2 * The moisture permeability of 24 h or more is more preferably a high vapor permeability of 1000 g/m 2 * 24 h or more.
A laminate of a vapor permeable barrier type thermoplastic resin film, wherein the laminate comprises:

At least one layer of a vapor permeable barrier type thermoplastic resin film according to claims 8-12;

At least one layer of natural or chemical;

Wherein the natural or chemical product is a discontinuous film, a nonwoven article, an adhesive article, and/or a textile fiber article.
The laminate according to claim 13, wherein said textile fiber is a fiber material selected from the group consisting of polyester and its derivative fiber, nylon and its derivative fiber, spandex and its derivative fiber, And polypropylene and its derivative fibers, polyolefins and their derivative fibers.