CN111849014B - Weak acid antistatic waterproof breathable film and preparation method thereof - Google Patents
Weak acid antistatic waterproof breathable film and preparation method thereof Download PDFInfo
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- CN111849014B CN111849014B CN202010696515.5A CN202010696515A CN111849014B CN 111849014 B CN111849014 B CN 111849014B CN 202010696515 A CN202010696515 A CN 202010696515A CN 111849014 B CN111849014 B CN 111849014B
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Abstract
The invention provides a weakly acidic antistatic waterproof breathable film and a preparation method thereof, and belongs to the technical field of PE waterproof breathable films. The weak-acidic antistatic waterproof breathable film is subjected to melt tape casting or blow molding of breathable master batches to form a film, then a PE breathable film is obtained through longitudinal stretching, then surface plasma treatment is carried out on the single surface of the PE breathable film to obtain a pretreated PE breathable film, then surface grafting is carried out on the pretreated PE breathable film, and then the PE breathable film subjected to surface grafting is washed and dried to obtain the weak-acidic antistatic waterproof breathable film. The pH value of the waterproof breathable film prepared by the invention is 6.5-7.3, so that the waterproof breathable film is more beneficial to the health of human skin, and meanwhile, the waterproof breathable film is endowed with good antistatic property, so that the product is more skin-friendly.
Description
Technical Field
The invention belongs to the technical field of PE waterproof breathable films, and particularly relates to a weakly acidic antistatic waterproof breathable film and a preparation method thereof.
Background
The polyethylene waterproof breathable film is a microporous film which allows water vapor to diffuse and permeate but blocks liquid water from leaking, is mainly used for manufacturing sanitary protective products at present, and has wide application in the fields of medical treatment, health care, personal care and the like. At present, the production process of the polyethylene breathable film mainly comprises the following steps: the special material for the breathable film is made into a film by a casting or blowing mode, and finally, the film is subjected to single or two-way stretching action to separate the polymer matrix from the surfaces of the filler particles and develop mutually communicated micro channels among the filler particles, so that the microporous breathable film is formed.
The forming principle of the polyethylene waterproof breathable film is that 40-60% of calcium carbonate is added into PE material to serve as a pore-forming agent, and the waterproof breathable film is prepared through longitudinal stretching and pore forming, wherein the calcium carbonate is alkalescent, so that the pH value of the breathable film is 7.5-10 generally. The skin of the infant is weakly acidic, and the weakly acidic skin is beneficial to resisting the invasion of foreign bacteria; the sanitary towel, which is an indispensable consumer product for women in the physiological period, also needs to be weakly acidic so as to effectively ensure the health of women. In addition, when the existing polyethylene waterproof breathable film is applied, static electricity is easily generated due to dry weather in winter, and the skin-friendly property is poor, so that the research on the weak-acid antistatic waterproof breathable film is very important.
Disclosure of Invention
Based on the prior art, the invention aims to provide a weakly acidic antistatic waterproof breathable film and a preparation method thereof, the pH value of the prepared waterproof breathable film is 6.5-7.3, the waterproof breathable film is more beneficial to the health of human skin, and meanwhile, the waterproof breathable film is endowed with good antistatic property, so that the product is more skin-friendly.
In order to achieve the above purpose, the invention adopts the technical scheme that:
the invention provides a preparation method of a weakly acidic antistatic waterproof breathable film, which comprises the following steps:
step one, film preparation: performing melt tape casting or blow molding on the breathable master batch to form a film, and then performing longitudinal stretching to obtain a PE breathable film;
step two, pretreatment: performing surface plasma treatment on one side of the PE breathable film obtained in the step one to obtain a pretreated PE breathable film;
step three, surface grafting reaction: putting the PE breathable film obtained in the step two into an aqueous solution containing a grafting monomer, and reacting for 2min-1h under the protection of inert gas in a low-temperature environment to obtain a surface-grafted PE breathable film;
step four, post-treatment: and (4) washing the grafted surface of the PE breathable film grafted on the surface obtained in the step three, removing unreacted monomers, cleaning and drying to obtain the weak-acid antistatic waterproof breathable film.
Further, the thickness of the PE breathable film in the step one is 18-30 μm.
Furthermore, the specific parameters of the surface plasma treatment in the second step are as follows: the argon flow is 20-35 pa, the power is 70-300 w, and the treatment time is 2-10 min.
Furthermore, the grafting monomer in the third step is at least one of dimethyl diallyl ammonium chloride, tetra allyl ammonium chloride, trimethyl allyl ammonium chloride and acrylamide.
Furthermore, the mass concentration of the monomer in the aqueous solution of the grafting monomer is 5-20%.
And furthermore, in the third step, high-purity nitrogen is introduced into the ice water bath to discharge oxygen for gas protection.
The invention also provides the weakly acidic antistatic waterproof breathable film prepared by the preparation method of the weakly acidic antistatic waterproof breathable film.
The grafting monomer adopted by the invention can easily generate free hydrogen ions in hydrolysis reaction, so that the pH value is weakly acidic, and can be kept in the range of 6.5-7.5 according to different grafting rates.
The grafting monomer has surface activity, free ends are hydrophilic, and the free ends have good conductivity after absorbing water. Since only one side of the film of the PE breathable film is subjected to plasma treatment and the other side is not subjected to plasma pretreatment, the PE breathable film cannot form free radicals to perform a grafting reaction. Therefore, the breathable film prepared by the invention has hydrophilic one side and hydrophobic one side.
Advantageous effects
The weakly acidic antistatic waterproof breathable film prepared by the preparation method has good antistatic performance, the pH value of the film can reach 6.5-7.5, and when the film is used as a sanitary article or a medical material, the health of human skin can be effectively protected, and the film is more skin-friendly.
Drawings
FIG. 1 is a schematic view of the preparation process of the weakly acidic antistatic waterproof breathable film of the invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
The preparation method of the weakly acidic antistatic waterproof breathable film comprises the following steps:
step one, membrane preparation: performing melt casting or blow molding on the breathable master batch to form a film, and stretching the film into a PE breathable film with the thickness of 18 microns by an MDO (longitudinal stretching) device;
step two, pretreatment: introducing argon gas with the flow of 20pa into cold plasma modification equipment, and performing single-side surface treatment on the breathable film at the power of 70w for 2 min;
step three, surface grafting reaction: putting the pretreated breathable film into an aqueous solution prepared by taking trimethyl allyl ammonium chloride as a grafting monomer, wherein the monomer concentration in the aqueous solution is 5%, introducing high-purity nitrogen gas to discharge oxygen gas for gas protection in an ice water bath, and reacting for 2min to obtain a surface-grafted PE breathable film;
step four, post-treatment: and (3) washing the grafted surface (plasma treated surface) of the grafted PE breathable film with distilled water for 1h, removing unreacted monomers, and drying the film after cleaning to obtain the weakly acidic antistatic waterproof breathable film.
Example 2
The preparation method of the weakly acidic antistatic waterproof breathable film comprises the following steps:
step one, film preparation: performing melt casting or blow molding on the breathable master batch to form a film, and stretching the film into a PE breathable film with the thickness of 18 microns by an MDO (longitudinal stretching) device;
step two, pretreatment: introducing argon gas with the flow of 25pa by using cold plasma modification equipment, and carrying out single-side surface treatment on the breathable film at the power of 100w for 4 min;
step three, surface grafting reaction: putting the pretreated breathable film into an aqueous solution prepared by taking trimethyl allyl ammonium chloride as a grafting monomer, wherein the monomer concentration in the aqueous solution is 10%, introducing high-purity nitrogen gas to discharge oxygen gas for gas protection in an ice water bath, and reacting for 10min to obtain a surface-grafted PE breathable film;
step four, post-treatment: and (3) washing the grafted surface (plasma treated surface) of the grafted PE breathable film with distilled water for 1h, removing unreacted monomers, and drying the film after cleaning to obtain the weakly acidic antistatic waterproof breathable film.
Example 3
The preparation method of the weakly acidic antistatic waterproof breathable film comprises the following steps:
step one, film preparation: performing melt casting or blow molding on the breathable master batch to form a film, and stretching the film into a PE breathable film with the thickness of 30 microns by using an MDO (longitudinal stretching) device;
step two, pretreatment: introducing argon gas with the flow of 30pa by using cold plasma modification equipment, and performing single-side surface treatment on the breathable film at the power of 200w for 8 min;
step three, surface grafting reaction: putting the pretreated breathable film into an aqueous solution prepared by taking acrylamide as a grafting monomer, wherein the monomer concentration in the aqueous solution is 15%, introducing high-purity nitrogen to discharge oxygen in an ice-water bath for gas protection, and reacting for 30min to obtain a surface-grafted PE breathable film;
step four, post-treatment: and (3) washing the grafted surface (plasma treated surface) of the grafted PE breathable film with distilled water for 1h, removing unreacted monomers, and drying the film after cleaning to obtain the weakly acidic antistatic waterproof breathable film.
Example 4
The preparation method of the weakly acidic antistatic waterproof breathable film comprises the following steps:
step one, membrane preparation: performing melt casting or blow molding on the breathable master batch to form a film, and stretching the film into a PE breathable film with the thickness of 30 microns by using an MDO (longitudinal stretching) device;
step two, pretreatment: introducing argon gas with the flow of 35pa by using cold plasma modification equipment, and carrying out single-side surface treatment on the breathable film at the power of 300w for 10 min;
step three, surface grafting reaction: putting the pretreated breathable film into an aqueous solution prepared by taking acrylamide as a grafting monomer, wherein the monomer concentration in the aqueous solution is 20%, introducing high-purity nitrogen to discharge oxygen in an ice-water bath for gas protection, and reacting for 60min to obtain a surface-grafted PE breathable film;
step four, post-treatment: and (3) washing the grafted surface (plasma treated surface) of the grafted PE breathable film with distilled water for 1h, removing unreacted monomers, and drying the film after cleaning to obtain the weakly acidic antistatic waterproof breathable film.
The process parameters for preparing the weakly acidic antistatic waterproof breathable film, as well as the pH and surface charge density of the film in examples 1 to 4 of the present invention are shown in the following table 1, wherein the test method for the average pH value is: GB/T7573-1987; the method for testing the surface charge density of the film comprises the following steps: GB/T12703-1997.
Table 1 examples 1 to 4 process parameters and test data for preparing weak acid antistatic waterproof breathable films
Example 1 | Example 2 | Example 3 | Example 4 | |
Monomer concentration (%) | 5 | 10 | 15 | 20 |
Grafting reaction time (min) | 2 | 10 | 30 | 60 |
Pretreatment time (min) | 2 | 4 | 8 | 10 |
Average pH value | 7.5 | 7.1 | 6.7 | 6.5 |
Surface charge density (uC/m)2) | 6.8 | 5.5 | 4.3 | 2.6 |
As can be seen from the above table, as the monomer concentration increases, the grafting reaction time increases, and the pretreatment time increases, the grafting yield increases accordingly, and the pH value and the surface charge density decrease accordingly. Therefore, different pH values and surface charge densities can be achieved by controlling the grafting reaction conditions so as to adapt to different product requirements. The weakly acidic antistatic waterproof breathable film prepared according to the process parameters has good antistatic performance, and the pH value of the film can reach 6.5-7.5.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. The preparation method of the weakly acidic antistatic waterproof breathable film is characterized by comprising the following steps of:
step one, film preparation: performing melt tape casting or blow molding on the breathable master batch to form a film, and then performing longitudinal stretching to obtain a PE breathable film;
step two, pretreatment: performing surface plasma treatment on one side of the PE breathable film obtained in the step one to obtain a pretreated PE breathable film;
step three, surface grafting reaction: putting the PE breathable film obtained in the second step into an aqueous solution containing a grafting monomer, wherein the grafting monomer is at least one of dimethyldiallylammonium chloride, tetraallylammonium chloride and trimethylallylammonium chloride, and reacting for 2min-1h under the protection of inert gas in an ice-water bath environment to obtain a surface-grafted PE breathable film;
step four, post-treatment: and (4) washing the grafted surface of the PE breathable film grafted on the surface obtained in the step three, removing unreacted monomers, cleaning and drying to obtain the weak-acid antistatic waterproof breathable film.
2. The method for preparing a weakly acidic antistatic waterproof breathable film as claimed in claim 1, wherein the thickness of the PE breathable film in the step one is 18-30 μm.
3. The method for preparing a weakly acidic antistatic waterproof breathable film according to claim 1 or 2, wherein the specific parameters in the surface plasma treatment in the second step are as follows: the argon flow is 20-35 pa, the power is 70-300 w, and the treatment time is 2-10 min.
4. The method for preparing a weakly acidic antistatic waterproof breathable film as claimed in claim 1, wherein the mass concentration of the monomer in the aqueous solution of the grafting monomer is 5% -20%.
5. The preparation method of the weakly acidic antistatic waterproof breathable film as claimed in claim 1 or 2, wherein in the third step, high-purity nitrogen is introduced into the ice water bath to discharge oxygen for gas protection.
6. A weakly acidic antistatic waterproof breathable film obtained by the method for producing a weakly acidic antistatic waterproof breathable film according to any one of claims 1 to 5.
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Citations (5)
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JPH11106552A (en) * | 1997-09-30 | 1999-04-20 | Tonen Kagaku Kk | Microporous hydrophilized polyolefin membrane and its production |
CN1827658A (en) * | 2006-03-28 | 2006-09-06 | 广州市合诚化学有限公司 | Materials dedicated for antibacterial and permeable polyolefin film and preparation method thereof |
CN101921536A (en) * | 2010-08-11 | 2010-12-22 | 武汉华卫科技有限公司 | Waterborne polyurethane film and preparation technology thereof |
CN102786708A (en) * | 2012-08-20 | 2012-11-21 | 太原理工大学 | Method for preparing antimicrobial medical polymer material |
CN103496239A (en) * | 2013-09-29 | 2014-01-08 | 佛山华韩卫生材料有限公司 | Special WVTR (water vapour transmission rate) breathable film and production process thereof |
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Publication number | Priority date | Publication date | Assignee | Title |
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JPH11106552A (en) * | 1997-09-30 | 1999-04-20 | Tonen Kagaku Kk | Microporous hydrophilized polyolefin membrane and its production |
CN1827658A (en) * | 2006-03-28 | 2006-09-06 | 广州市合诚化学有限公司 | Materials dedicated for antibacterial and permeable polyolefin film and preparation method thereof |
CN101921536A (en) * | 2010-08-11 | 2010-12-22 | 武汉华卫科技有限公司 | Waterborne polyurethane film and preparation technology thereof |
CN102786708A (en) * | 2012-08-20 | 2012-11-21 | 太原理工大学 | Method for preparing antimicrobial medical polymer material |
CN103496239A (en) * | 2013-09-29 | 2014-01-08 | 佛山华韩卫生材料有限公司 | Special WVTR (water vapour transmission rate) breathable film and production process thereof |
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