阅读说明：本技术 一种疏液薄膜及其制备方法和应用 (lyophobic film and preparation method and application thereof ) 是由 东为富 刘耘 李婷 汪洋 于 2018-06-08 设计创作，主要内容包括：本发明涉及一种疏液薄膜材料及其制备方法。疏液薄膜的组成包括：基体树脂100份,和水溶性树脂10～100份。制备方法包括：将基体树脂和水溶性树脂进行熔融共混后,将所述共混料熔融加工成膜并将其置于去离子水中将水溶性树脂溶解刻蚀后即得疏液薄膜材料。该疏液薄膜材料对多种液滴如水、牛奶、酸奶、咖啡、血液、尿液、酱油、醋或茶水有着良好的不浸润效果,因此可以在酸奶盖、塑料容器、封装材料、防水服、工作服、桌布、围裙中有良好的应用前景。(The invention relates to a lyophobic film material and a preparation method thereof. The lyophobic film comprises the following components: 100 parts of matrix resin and 10-100 parts of water-soluble resin. The preparation method comprises the following steps: and melting and blending matrix resin and water-soluble resin, melting and processing the blend into a film, placing the film into deionized water, and dissolving and etching the water-soluble resin to obtain the lyophobic film material. The lyophobic film material has good non-infiltration effect on various liquid drops such as water, milk, yoghourt, coffee, blood, urine, soy sauce, vinegar or tea, so the lyophobic film material has good application prospect in yoghourt covers, plastic containers, packaging materials, waterproof clothes, work clothes, tablecloths and aprons.)

1. The lyophobic film is characterized by being prepared by blending the following raw materials in parts by weight:

100 parts of matrix resin;

10-100 parts of water-soluble resin;

Wherein, the surface of the lyophobic film presents a mesh structure, and the contact angle of the film and water is 120-150 degrees.

2. The lyophobic film of claim 1, wherein the lyophobic film is obtained by blending raw materials comprising, by weight:

100 parts of matrix resin;

66-100 parts of water-soluble resin.

3. The lyophobic film of claim 1, wherein:

The matrix resin is at least one of polyethylene, polypropylene, polylactic acid, polyvinyl chloride, polymethyl methacrylate, acrylonitrile-butadiene-styrene copolymer, polystyrene, polycarbonate, polyamide, polyester, ethylene-vinyl acetate copolymer, polyphenyl ether, phenolic resin, melamine resin and unsaturated polyester.

4. The lyophobic film of claim 1, wherein:

The water-soluble resin is at least one of ethylene-acrylate copolymer, polyethylene oxide, polyacrylate, polymethacrylic acid salt, poly-N-vinyl pyrrolidone, polyvinyl alcohol, polyacrylamide, polyacrylic acid, polyethylene glycol, polymaleic anhydride, Arabic gum, soybean gum, bone glue, gelatin, xanthan gum, carboxymethyl starch and carboxymethyl cellulose.

5. The lyophobic film according to any one of claims 1 to 4, characterized by being prepared by a method comprising the steps of:

(1) Drying matrix resin and water-soluble resin, and then carrying out melt blending to obtain a blend;

(2) melting and processing the mixture into a film;

(3) And (3) placing the film in water to etch and remove the water-soluble resin, and drying in vacuum to obtain the lyophobic film.

6. A method for preparing a lyophobic film according to any one of claims 1 to 5, characterized by comprising the steps of:

(1) Drying matrix resin and water-soluble resin, and then carrying out melt blending to obtain a blend;

(2) Melting and processing the mixture into a film;

(3) And (3) placing the film in water to etch and remove the water-soluble resin, and drying in vacuum to obtain the lyophobic film.

7. The method for producing a lyophobic film according to claim 6, characterized in that:

In the step (1), the drying temperature is 60-100 ℃, and the melting temperature is 140-300 ℃.

8. The method for producing a lyophobic film according to claim 6, characterized in that:

in the step (2), the melting temperature is 140-300 ℃, and the thickness of the film is 0.005-0.5 mm.

9. The method for producing a lyophobic film according to claim 6, characterized in that:

In the step (3), the etching temperature is 25-100 ℃, and the etching time is 2-24 hours; the vacuum drying temperature is 60-80 ℃, and the drying time is 2-30 hours.

10. The lyophobic film of any one of claims 1 to 5, which is applied to a material or a product for preventing infiltration or permeation of a liquid, wherein the liquid is at least one of water, milk, yogurt, coffee, blood, urine, soy sauce, vinegar or tea, and the product is at least one of a yogurt cover, a plastic container, a packaging material, a waterproof garment, a coverlet, a tablecloth, and an apron.

Technical Field

The invention relates to the field of film materials, in particular to a lyophobic film and a preparation method and application thereof.

Background

A superhydrophobic surface refers to a surface having a contact angle with water of greater than 150 ° and a sliding angle of less than 10 °. Super-hydrophobic surfaces have been produced in the long-term evolution of natural organisms, and many animal and plant surfaces (such as lotus leaves, rice leaves, cicada wings and water strider legs) have super-hydrophobic and self-cleaning effects, and the most typical representative is the so-called "lotus effect". The lotus leaf effect is mainly benefited by the special micro-nano composite structure existing on the lotus leaf surface, and the low-surface-energy wax-like substance is also present on the papilla of the micro-nano structure, and the composite structure is just because the composite structure exists, so that the lotus leaf effect shows excellent super-hydrophobicity. Through research on the phenomenon of superhydrophobicity in nature, it is found that superhydrophobicity is mainly related to two properties: roughness and surface energy of the material surface. Superhydrophobic surfaces can therefore generally be prepared by two methods: firstly, a rough structure is constructed on the surface of a low-surface-energy material; secondly, a low surface energy substance is modified on the rough surface. Wherein, the influence of the surface rough structure is more obvious.

The field of superhydrophobic research is mainly focused on water infiltration research at present, but many liquids closely related to us in life, such as milk, yogurt, coffee, blood, urine, soy sauce, vinegar or tea water, and the like, exist. If the surface of the film material can simultaneously achieve a good non-infiltration effect on the liquid, namely, the lyophobic film material, the application fields of the material, such as a yoghourt cover, a plastic container, a packaging material, waterproof clothes, work clothes, tablecloth, apron and the like, can be necessarily widened.

polyethylene is a general-purpose plastic with no toxicity, no odor, excellent performance, good extensibility, electric insulation, chemical stability, processability and low temperature resistance (can resist-70 ℃). As one of five synthetic resins, the polyester resin is a variety with the largest capacity and the largest import quantity in the synthetic resins in China, and is widely applied to film products, such as films for agriculture, films for packaging and blown films for liquid packaging; medical appliances, packaging materials for medicines and foods, pipes, injection-molded articles, electric wire wrapping layers, and the like. Therefore, if the polyethylene film can be endowed with more excellent hydrophobic and lyophobic performances, the application field of the polyethylene film must be greatly widened.

Furthermore, polyethylene is a typical low surface energy polymer which has certain lyophobic properties by itself, but still does not meet the current use requirements. Therefore, modification treatment is needed, but since polyethylene is a relatively inert material and has no relatively active reactive groups in the molecular structure, the construction of a rough micro-nano structure on the surface of polyethylene becomes a key for making the polyethylene lyophobic. At present, a plurality of methods for preparing lyophobic polyethylene films are available, such as a microphase separation method, a solvent-nonsolvent method, a plasma etching method, a vapor deposition method and the like, for example, Xiaooying Lu and the like adopt the solvent-nonsolvent method to prepare and obtain a super-hydrophobic polyethylene film (Macromolecular Rapid Communications, 2010, 25(18):1606-1610), the porous micro-nano structure is formed by mainly controlling the crystallization behavior of LDPE through adjusting the crystallization time and the nucleation rate, and the obtained polyethylene hydrophobic material has good hydrophobic performance; etching the surface of polyethylene by using oxygen plasma to increase the roughness of the polyethylene surface, and then depositing a plasma polymerized fluorocarbon film on the surface of the polyethylene surface to obtain a super-hydrophobic surface (research on water drop impact performance of the plasma nano-textured polyethylene super-hydrophobic surface [ D ], university of great physics, 2015); yuanxi et al prepared nanostructured superhydrophobic surfaces by depositing a candle ash coating on the surface of a Low Density Polyethylene (LDPE) substrate (package letters, 2017, 9(2): 25-29); chinese patent publication No. CN101157768 discloses a method for preparing a super-hydrophobic high-density polyethylene film by dissolving high-density polyethylene in xylene as a solvent and adding a non-solvent ethanol into the solution. However, in the practical application process, the preparation process is complex, the cost is high, and industrialization is difficult to realize. Therefore, a simple, safe and environment-friendly preparation method capable of large-area industrial production is urgently needed for the development and application of the lyophobic material at present.

Disclosure of Invention

In order to solve the problems, the invention provides a lyophobic film and a preparation method and application thereof.

One of the purposes of the invention is to provide a lyophobic film, the surface of which presents a porous reticular structure, the contact angle of the film and water is 120-150 degrees, the contact angle of the film and yoghourt is 110-140 degrees,

the lyophobic film is prepared by blending the following raw materials in parts by weight:

100 parts of matrix resin;

10-100 parts of water-soluble resin; preferably 66 to 100 parts.

Among them, the matrix resin is preferably at least one of polyethylene, polypropylene, polylactic acid, polyvinyl chloride, polymethyl methacrylate, acrylonitrile-butadiene-styrene copolymer (ABS), polystyrene, polycarbonate, polyamide, polyester, ethylene-vinyl acetate copolymer, polyphenylene oxide, phenol resin, melamine resin, and unsaturated polyester, and more preferably polyethylene.

The water-soluble resin is preferably at least one of ethylene-acrylate copolymer, polyethylene oxide, polyacrylate, polymethacrylic acid salt, poly-N-vinyl pyrrolidone, polyvinyl alcohol, polyacrylamide, polyacrylic acid, polyethylene glycol, polymaleic anhydride, Arabic gum, soybean gum, bone gum, gelatin, xanthan gum, carboxymethyl starch and carboxymethyl cellulose, and more preferably ethylene-acrylate copolymer.

The lyophobic film can be added with various common additives in the field according to the processing requirements, such as a stabilizer, a lubricant, an antioxidant and the like, and the dosage of the additives is conventional or adjusted according to the requirements of actual conditions.

The stabilizer can comprise diphosphites, phosphate derivatives, calcium zinc stabilizers, basic lead salts, metal soaps, organic tin stabilizers, organic stabilizers, composite stabilizers and the like.

The lubricant may include paraffin wax, PE wax, stearates, silicones, ethylene bis stearamide, fatty amides, stearic acids, and the like.

The antioxidant can comprise antioxidant 264, antioxidant 2246, antioxidant 1010, thioester, phosphite ester and the like.

The second purpose of the invention is to provide a preparation method of the lyophobic film, which comprises the following steps:

(1) drying matrix resin and water-soluble resin, and then carrying out melt blending to obtain a blend;

(2) melting and processing the mixture into a film;

(3) And (3) placing the film in water to etch and remove the water-soluble resin, and drying in vacuum to obtain the lyophobic film.

preferably, the first and second liquid crystal materials are,

The melting process in the step (1) is at least one process commonly used in the field, preferably selected from torque rheometer blending, single-screw extrusion, twin-screw extrusion, open mill mixing and internal mixer mixing.

the drying temperature in the step (1) is 60-100 ℃, and the processing temperature is 140-300 ℃.

The melt processing technology in the step (2) is at least one of a calendering film forming method, a tape casting film forming method, a blown film method, a stretched film method and a biaxial stretched film method.

The melting temperature in the step (2) is 140-300 ℃, and the thickness of the film is 0.005-0.5 mm.

The etching temperature in the step (3) is 25-100 ℃, and the etching time is 2-24 hours; the vacuum drying temperature is 60-80 ℃, and the drying time is 2-30 hours.

the third purpose of the invention is to apply the lyophobic film in materials or products for preventing liquid infiltration or permeation, wherein the liquid is at least one of water, milk, yoghourt, coffee, blood, urine, soy sauce, vinegar or tea, and the products can be at least one of yoghourt covers, plastic containers, packaging materials, waterproof clothes, work clothes, tablecloths and aprons.

In general, polyethylene film materials used in daily life generally adopt two processes of blowing and casting. The films prepared by the two methods have smooth surfaces and only have limited hydrophobic and lyophobic capacities of polyethylene, so that the key for improving the lyophobic performance is to change the roughness of the polyethylene surface. The preferred ethylene-acrylate copolymer is an ionic polymer which has good compatibility with polyethylene and can be dissolved in water at 100 ℃. The two polymers are melted and blended to form a blend, and then the ethylene-acrylate copolymer is etched in hot water to form a rough net-shaped hole structure on the surface of the polyethylene.

The polyethylene film prepared by the invention has lyophobic performance, and can be used as a material for preventing liquid such as water, milk, yoghourt, coffee, blood, urine, soy sauce, vinegar or tea water from infiltrating or permeating.

The invention has the following beneficial effects:

1. The lyophobic film prepared by the melt processing method provided by the invention has the advantages of simple operation process, environmental protection, no need of any expensive equipment and suitability for large-scale industrial application.

2. The raw materials and reagents used in the invention all meet the requirements of environmental protection and have no pollution to the environment.

Drawings

FIG. 1 is a photograph of the static water contact angle of the untreated polyethylene surface of comparative example 1.

fig. 2 is a picture of the static yogurt contact angle of the untreated polyethylene surface of comparative example 1.

FIG. 3 is a scanning electron micrograph of the surface of the untreated polyethylene in comparative example 1.

Fig. 4 is a photograph of the static water contact angle of the lyophobic polyethylene surface prepared in example 1.

Fig. 5 is a picture of the static yogurt contact angle of the lyophobic polyethylene surface prepared in example 1.

Fig. 6 is a scanning electron micrograph of the surface of lyophobic polyethylene prepared in example 1.

fig. 7 is a photograph of the static water contact angle of the lyophobic polyethylene surface prepared in example 3.

Fig. 8 is a picture of the static yogurt contact angle of the lyophobic polyethylene surface prepared in example 3.

Fig. 9 is a scanning electron micrograph of the surface of lyophobic polyethylene prepared in example 3.

Detailed Description

The present invention will be further described with reference to the following specific examples. It should be understood that these examples are only for illustrating the present invention and are not intended to limit the scope of application of the present invention. The methods are conventional unless otherwise specified, and the starting materials used are commercially available from public sources.

Comparative example 1

50g of polyethylene (Shanghai Shishi @ Q281) is weighed into a vacuum oven for drying, then melt processing is carried out, and the obtained polyethylene material is prepared into a 0.5mm film on a calender at 170 ℃. The film surface was tested for wettability using an OCA20 contact angle tester and tested for static water contact angle and yogurt contact angle, with the contact angle test results listed in table 1.

The water contact angle of the untreated polyethylene film was 94.6 ° (as shown in fig. 1), the yogurt contact angle was 83.9 ° (as shown in fig. 2), and the scanning electron microscope of the film surface is shown in fig. 3, which shows that the untreated film surface was smoother and the contact angle was smaller.