CN106752899A - A kind of extrusion coating paper and composite plastic film packaging material preparation method with double-hydrophobic surface - Google Patents

Abstract

A method for preparing a composite paper and composite plastic film packaging material with an amphiphobic surface. Small balls with a diameter of 0.01 to 50 microns are evenly dispersed in a liquid adhesive to prepare a coating solution, and a layer of diameter is uniformly coated on the surface of paper and plastic film. It is a small ball of 0.01-50 microns. After curing, the small ball adheres to the surface of paper or plastic film to form a micro-nano rough surface structure; the surface of the small ball layer is coated with silicone resin or fluorine-containing resin solution, after heat or light curing A low surface energy layer with a thickness of 30 to 500 nm is formed to protect the formed micro-nano rough structure. After being placed for 7-10 days; the low surface energy surface of the composite paper and composite plastic film has amphiphobic properties: the water contact angle is greater than 140°, and the water rolling angle is less than 10°; the oil contact angle is greater than 130°, and the oil rolling angle is less than 10°. Composite paper or composite plastic film is used as the packaging material for liquid or pasty substances. The liquid and pasty packaged substances are easy to take out from the package, and the packaged liquid or paste has little adhesion on the amphiphobic surface layer.

Description

A kind of preparation method of composite paper and composite plastic film packaging material with amphiphobic surface

technical field

The invention relates to a method for preparing composite paper and composite plastic film packaging materials with an amphiphobic surface, belonging to the field of packaging materials.

Background technique

Surface wettability is an important feature of the surface of a solid material. The degree of wettability of a liquid to a solid is usually characterized by the contact angle. When the contact angle between a solid surface and water is greater than 90°, it is called a hydrophobic surface, and when it is greater than 150°, it is called a hydrophobic surface. superhydrophobic surface. When the contact angle between solid surface and oil is greater than 90°, it is called oleophobic surface, and when it is greater than 150°, it is called superoleophobic surface. Amphobic surface refers to the surface whose contact angle with water and oil is greater than 90°. Amphobic surface has the advantages of waterproof, anti-fog, anti-snow, anti-pollution, anti-adhesion, anti-oxidation, anti-corrosion, etc. It can be widely used in agriculture, Fields such as military industry, construction, transportation, textile, medical treatment, anticorrosion and daily life have been extensively studied, and many technical preparation methods have been proposed for amphiphobic and superamphiphobic surfaces. The technical requirements are too high, and it is not suitable for the preparation of large-area amphiphobic surfaces, which limits the industrial application of amphiphobic surfaces.

This patent application proposes a way to protect the micro-nano surface rough structure formed by coating small balls, and then coating the surface of the small ball layer with silicone resin or fluorine-containing resin, which solves the problem of large-area industrial production. and durability issues of the double-hydrophobic surface. The composite paper and composite plastic film obtained by this patent application do not reach the performance standards of superhydrophobic and superoleophobic, but the water contact angle and oil contact angle are close to the performance of superamphiphobic. There is almost no adhesion to the paste-like packaged substance on the amphiphobic surface, and the adhesion amount is very small.

Contents of the invention

This patent application proposes a method for preparing composite paper and composite plastic film packaging materials with an amphiphobic surface. The specific steps are:

Step 1: uniformly disperse small balls with a diameter of 0.01-50 microns in a liquid adhesive to prepare a coating solution, and uniformly coat a layer of small balls with a diameter of 0.01-50 microns on the surface of paper and plastic film, after drying and curing, The small balls are attached to the surface of paper or plastic film to form a surface with micro-nano rough structure;

Step 2: Coating a silicone resin or fluorine-containing resin solution with low surface energy on the surface of the bead layer, and curing by heat or light to form a low surface energy film layer with a thickness of 30 to 500 nm to protect the formed micro-nano rough structure;

Step 3, placing the prepared composite paper or composite plastic film for 7-10 days to relax the stress;

Step 4, the prepared composite paper or composite plastic film is used as liquid substance or pasty substance packaging material, the liquid and pasty substance to be packaged is easy to take out from the package, and the packaged liquid or pasty substance is placed on the amphiphobic surface layer The amount of adhesion is very small.

Fig. 1 is the structural representation of the composite paper and composite plastic film packaging material that this patent application proposes, and 1 is commonly used paper and plastic film, is called base material layer; 2 is the adhesive layer of sticking bead after coating solution solidifies; 3 It is a small ball layer formed after curing, and the surface has a micro-nano rough structure; 4 is a low surface energy layer formed by coating, and the low surface energy layer is uniform in thickness. After coating the low surface energy layer, the surface of the composite paper or composite plastic film remains The micro-nano rough structure formed by the original small balls is maintained.

Fig. 2 is one of the representative schematic diagrams of the distribution of beads on the surface of paper or plastic film substrate in this patent application, and the scanning electron micrograph of the surface of composite paper or composite plastic film. 5 is a dense stack of coated pellets. The dense piles of small balls are randomly distributed on the surface of the substrate, and the distance between the dense piles of small balls and the push is 30-200 microns.

Figure 3 is one of the representative schematic diagrams of the distribution of pellets on the surface of the paper or plastic film substrate in this patent application, and a scanning electron micrograph of the surface of the composite paper or composite plastic film. 6 is a coated pellet. The pellets are evenly distributed on the surface of the substrate, covering the entire substrate.

Fig. 4 is one of the representative schematic diagrams of the distribution of pellets on the surface of paper or plastic film substrate in this patent application, and a scanning electron micrograph of the surface of composite paper or composite plastic film. 7 is a coated pellet. Beads of different sizes are used, which cover the entire substrate.

Fig. 5 is one of the representative distribution diagrams of nanometer-sized silica balls on the surface of paper or plastic film substrate in this patent application, the scanning electron micrograph of composite paper or composite plastic film surface, and 8 is a coated ball . The pellets cover the entire substrate.

A layer of small balls with a diameter of 0.01-50 microns uniformly coated on the surface of paper and plastic film. The material of the small balls is polymethyl methacrylate or polystyrene or glass or silicon dioxide or titanium dioxide or zinc oxide or calcium carbonate or alumina.

Coat the surface of the bead layer with a silicone resin or fluorine-containing resin solution with low surface energy, and form a low surface energy film layer with a thickness of 30 to 500 nm after curing to protect the micro-nano rough structure formed by the bead from being easily damaged. Moreover, the durability of the surface's hydrophobic and oleophobic properties is further improved. Moreover, the low surface energy film layer further improves the barrier properties of the composite paper and composite plastic film to oxygen and water vapor.

Paper materials include coated paper, kraft paper and various cardboards and cardboards; plastic film materials include polyethylene, polyvinyl chloride, polypropylene, polyvinyl alcohol, polystyrene, polyethylene vinyl acetate, polyethylene terephthalate Glycol ester, polyamide, PTFE, polycarbonate.

Relying on the rough structure formed by micron or nanometer sized balls and the low surface energy layer of silicone or fluorine-containing resin on the surface, the low surface energy surface of composite paper and composite plastic film has amphiphobic properties. The water contact angle is greater than 140°, and the water rolling angle is less than 10°; the oil contact angle test is carried out with n-hexadecane, and the contact angle is greater than 130°, and the oil rolling angle is less than 10°.

The prepared composite paper or composite plastic film is used as the packaging material for liquid or pasty substances. The liquid and pasty packaged substances are easy to take out from the package. The amount of liquid or pasty packaged substances attached to the amphiphobic surface of the packaging material rare.

The method adopts a coating method to coat a layer of small balls on the surface of paper or commonly used plastic films to form a micro-nano rough structure, and then prepare a layer of low surface energy film on the surface of the small ball layer to protect the micro-nano rough structure formed by the small balls, which overcomes the Commonly used amphiphobic surface preparation process is complex, high cost and difficult for industrialized mass production, and the surface micro-nano structure is easily damaged during use, resulting in the application defect that the amphiphobic properties cannot be maintained continuously. It is used as a liquid or paste substance The advanced packaging material overcomes the defect that the packaged liquid or pasty substance adheres too much on the surface of commonly used packaging materials.

Description of drawings

Fig. 1 is the structural representation of the composite paper and composite film packaging materials proposed in this patent application, in which 1 is the base material layer, 2 is the adhesive layer where the coating solution is cured and adheres to the small balls, and 3 is the small ball layer formed after curing , 4 is the low surface energy layer.

Fig. 2 is one of the representative schematic diagrams of the distribution of pellets on the surface of paper or plastic film substrate in this patent application, and a scanning electron micrograph of the surface of composite paper or composite plastic film, and 5 in the figure is a dense pile of coated pellets.

Fig. 3 is one of representative distribution schematic diagrams of pellets on the surface of paper or plastic film substrate in this patent application, the scanning electron micrograph of composite paper or composite plastic film surface, 6 is coated pellets.

Fig. 4 is one of representative distribution schematic diagrams of pellets on the surface of paper or plastic film base material in this patent application, the scanning electron micrograph of composite paper or composite plastic film surface, 7 is coated pellets.

Fig. 5 is one of the representative distribution diagrams of nanometer-sized silica balls on the surface of paper or plastic film substrate in this patent application, the scanning electron micrograph of composite paper or composite plastic film surface, and 8 is a coated ball .

detailed description

The present invention will be further described below with specific embodiment.

Example 1

Coat a layer of polymethyl methacrylate microspheres with a diameter of 10-30 microns on the surface of kraft paper in a roll-to-roll manner. The distribution of the microspheres on the surface of the paper is similar to that shown in Figure 2. After curing, use Coating method Coating a layer of coating solution mainly composed of polydimethylsiloxane, cured at 120°C for 30 seconds to form a low surface energy layer with a thickness of about 200nm, after 7 days at room temperature, test the compound The water contact angle of the paper low surface energy surface is 143°, and the water rolling angle is 4°. The oil contact angle tested by n-hexadecane is 140°, and the oil rolling angle is 6°. Print graphics and text on the paper surface of the composite paper, then cut it into bags, and use it as a packaging bag for traditional Chinese medicine ointment. The amphiphobic layer of the composite paper is in contact with the viscous Chinese medicine ointment. Packed viscous herbal ointment that hardly adheres.

Example 2

A layer of glass microspheres with a diameter of 10-30 microns is coated on the surface of a 12-micron thick polyvinyl alcohol film in a roll-to-roll manner. The distribution of the microspheres on the surface of the polyvinyl alcohol film is similar to that shown in Figure 3. The surface of the spherical layer is coated with a layer of emulsion mainly composed of hydroxyl-terminated polydimethylsiloxane, tetraethyl orthosilicate and hydrogen-containing polymethylsiloxane by coating method, and cured at 120°C for 60 seconds , forming a low surface energy layer with a thickness of about 300nm. After 7 days at room temperature, the water contact angle of the low surface energy surface of the composite film was tested to be 155°, and the water rolling angle was 4°. The oil contact angle tested by n-hexadecane is 135°, and the oil rolling angle is 8°. Print graphics on the plastic side of the composite film, then cut it into bags, and use it as a packaging bag for milk. The amphiphobic side of the composite film contacts the milk. After drinking the milk, the amphiphobic side of the packaging bag hardly adheres to the packaged food. milk.

Example 3

A layer of polymethyl methacrylate microspheres with a diameter of 10-30 microns is coated on the surface of a 12-micron thick polypropylene film in a roll-to-roll manner. The distribution of the microspheres on the surface of the polypropylene film is similar to that shown in Figure 4. After curing , on the surface of the bead layer, a layer is coated with polydimethylsiloxane containing mercapto, hydroxyl-terminated polydimethylsiloxane and γ-methacryloxypropyltrimethoxy The coating solution mainly composed of silane, photoinitiator and reactive diluent is cured under ultraviolet light to form a low surface energy layer with a thickness of about 80nm. After 10 days at room temperature, the water contact of the low surface energy surface of the composite film is tested. The angle is 151°, and the water rolling angle is 4°. The oil contact angle tested by n-hexadecane is 146°, and the oil rolling angle is 6°. Print graphics and text on the plastic side of the composite film, then cut it into bags, and use it as the packaging cover film of yogurt. The low surface energy layer of the composite plastic film contacts the yogurt, and the cover film of the yogurt cup is torn off, and the inner surface of the yogurt cup cover film is low. The packaged yoghurt hardly adheres to the surface of the energy layer.

Example 4

A layer of polymethyl methacrylate microspheres with a diameter of 10-30 microns is coated on the surface of a polyethylene film with a thickness of 12 microns in a roll-to-roll manner. The distribution of the microspheres on the surface of the polyethylene film is similar to that shown in Figure 2. After curing , on the surface of the bead layer, a layer of polymethylhydrogensiloxane terminated with fluorine-containing acrylate, trifluoropropyl and alkenyl modified polydimethylsiloxane, and methoxysilane is coated by a coating method The coating solution mainly composed of alkanes is cured at 120°C for 60 seconds to form a low surface energy layer with a thickness of about 250nm. The angle is 8°. The oil contact angle tested by n-hexadecane is 142°, and the oil rolling angle is 5°. Print graphics and text on the plastic surface of the composite film, then cut it into bags, and use it as a packaging bag for fruit juice. The low surface energy layer of the composite plastic film contacts the fruit juice. After drinking the juice, the surface of the amphiphobic layer in the packaging bag is hardly adhered to. Packaged juice.

Example 5

Coat a layer of silicon dioxide microspheres with a diameter of 10-30 nanometers on the surface of polyethylene vinyl acetate film with a thickness of 12 microns by roll-to-roll method. The distribution of microspheres on the surface of polyethylene vinyl acetate film is similar to that in Figure 5 After curing, a layer of vinyl-terminated polydimethylsiloxane, polymethylhydrogensiloxane, 1,3-divinyltetramethyldimethicone is coated on the surface of the ball layer by a coating method. The coating solution mainly composed of siloxane was cured at 120°C for 60 seconds to form a low surface energy layer with a thickness of about 150nm. After 10 days at room temperature, the water contact angle of the low surface energy surface of the composite film was tested to be 154°. The water roll angle is 6°. The oil contact angle tested by n-hexadecane is 142°, and the oil rolling angle is 5°. Print graphics and text on the plastic surface of the composite film, then cut it into bags, and use it as a packaging cover film for yogurt. The low surface energy layer of the composite film contacts the yogurt, tear off the cover film of the yogurt cup, and the low surface energy inside the cover film of the yogurt cup The layer hardly adheres to the packaged yoghurt.

Based on the above embodiments, this application proposes to coat a layer of small balls on paper and plastic substrates to construct a surface micro-nano rough structure, and then prepare a layer of low surface energy on the surface of the small ball layer to protect the surface micro-nano rough structure , improve the durability of the surface amphiphobic properties, and at the same time be easy to industrialized mass production. The above embodiments are only used to illustrate and not limit the technical solution of this patent application. Those skilled in the art can understand that various changes and equivalent replacements are made to the technical solution of this patent application, such as changing materials, spherical nano-sized carbon dioxide Replacing silicon with titanium dioxide, aluminum oxide, and zinc oxide powders, without departing from the principle and scope of the technical solution of this patent application, should be covered within the scope of the claims of this patent application.

Claims (6)

1. a method for preparing composite paper and composite plastic film packaging material with an amphiphobic surface, comprising the following steps: Step 1: uniformly disperse small balls with a diameter of 0.01-50 microns in a liquid adhesive to prepare a coating solution, and uniformly coat a layer of small balls with a diameter of 0.01-50 microns on the surface of paper and plastic film, after drying and curing, The small balls are attached to the surface of paper or plastic film to form a surface with micro-nano rough structure; Step 2: Coating a silicone resin or fluorine-containing resin solution with low surface energy on the surface of the ball layer, and forming a film layer with a thickness of 30 to 500nm and a low surface energy after curing by heat or light to protect the formed micro-nano rough structure ; Step 3, placing the prepared composite paper or composite plastic film for 7-10 days to relax the stress; Step 4, the prepared composite paper or composite plastic film is used as liquid substance or pasty substance packaging material, the liquid and pasty substance to be packaged is easy to take out from the package, and the packaged liquid or pasty substance is placed on the amphiphobic surface layer The amount of adhesion is very small. 2. A kind of composite paper and composite plastic film packaging material preparation method with amphiphobic surface according to claim 1, is characterized in that, evenly coating one deck diameter on paper and plastic film surface is 0.01-50 micron small The balls are made of polymethyl methacrylate or polystyrene or glass or silicon dioxide or titanium dioxide or zinc oxide or calcium carbonate or aluminum oxide. 3. a kind of composite paper and composite plastic film packaging material preparation method with amphiphobic surface according to claim 1, is characterized in that, has the organosilicon resin of low surface energy or fluorine-containing resin at pellet layer surface coating Solution, after heat or light curing, a low surface energy film layer with a thickness of 30 to 500nm is formed, and the surface of the film layer still has a micro-nano rough structure. Destruction, thereby improving the durability of the surface amphiphobic properties; moreover, the low surface energy film layer further improves the barrier properties of composite paper and composite plastic film to oxygen and water vapor. 4. a kind of composite paper and composite plastic film packaging material preparation method with amphiphobic surface according to claim 1 is characterized in that, the material of paper comprises coated paper, kraft paper and various cardboard, cardboard; Materials include polyethylene, polyvinyl chloride, polypropylene, polyvinyl alcohol, polystyrene, polyethylene vinyl acetate, polyethylene terephthalate, polyamide, polytetrafluoroethylene, polycarbonate. 5. a kind of composite paper and composite plastic film packaging material preparation method with amphiphobic surface according to claim 1, is characterized in that, rely on the micron or the roughness structure that the bead of nanometer size forms and the organosilicon or the organic silicon containing on the surface The low surface energy layer of fluororesin realizes that the low surface energy surface of composite paper and composite plastic film has amphiphobic properties; the water contact angle is greater than 140°, and the water rolling angle is less than 10°; the oil contact angle test is carried out with n-hexadecane, and the contact angle Greater than 130°, the oil rolling angle is less than 10°. 6. a kind of composite paper and composite plastic film packaging material preparation method with amphiphobic surface according to claim 1 is characterized in that, the composite paper or composite plastic film of preparation is used as liquid substance or pasty substance packaging material , The liquid and pasty packaged substances are easy to take out from the packaging, and the amount of liquid or pasty packaged substances attached to the amphoteric surface of the packaging material is very small.