Adhesive film and preparation method thereof

Abstract

The invention discloses an adhesive film and a preparation method thereof, and relates to the field of polymeric membranes, the adhesive film comprises a polyvinyl base membrane, a cellulose / polylactic acid composite electrostatic spinning membrane and a ceramic particle layer which are arranged in sequence; wherein the porosity of the cellulose / polylactic acid composite electrostatic spinning membrane is 50%-80%, at least part of pores of the cellulose / polylactic acid composite electrostatic spinning membrane are filled with the polyvinyl base membrane, and the ceramic particle layer comprises micron-scale porous silicon dioxide particles and nano-scale porous silicon dioxide particles. According to the technical scheme, the mechanical property of the adhesive film can be effectively improved, and meanwhile the adhesive residue problem of the adhesive film is solved.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer membranes, and particularly relates to an adhesive film and a preparation method thereof. Background Art

[0002] The metal plates used in washing machines (such as the metal plates on the outer surface of the cabinet and the bottom of the inner cylinder) are generally coated with a film to prevent the metal plates from being scratched during transportation. In the prior art, a polyethylene (PE) film is usually used to coat the metal plates. During the film processing, the film is subjected to a dipping treatment with glue so that the film can be more closely adhered to the galvanized steel coil on the metal plate laminator; in the stamping factory, the coated coil is first cut into square or circular sheets, and then subjected to high-curvature and large-deformation stamping on the stamping production line. However, due to the poor deformability of the polyethylene film under rapid stamping (when the tensile deformation is greater than 50 cm / min), the film may be broken during stamping; moreover, when the stamped parts are assembled onto the washing machine, the coating film needs to be torn off, and at this time, it is easy to cause the adhesive components on the polyethylene film to transfer to the metal plate, resulting in the phenomenon of residual glue on the metal plate. Summary of the Invention

[0003] The main object of the present invention is to provide an adhesive film and a preparation method thereof, aiming to improve the mechanical properties and residual glue problems of the adhesive film used for coating metal plates in the prior art.

[0004] To achieve the above object, the adhesive film provided by the present invention includes a polyethylene-based film, a cellulose / polylactic acid composite electrospun film, and a ceramic particle layer arranged in sequence; wherein, the porosity of the cellulose / polylactic acid composite electrospun film is 50% - 80%, the polyethylene-based film fills at least part of the pores of the cellulose / polylactic acid composite electrospun film, and the ceramic particle layer includes micron-sized porous silica particles and nano-sized porous silica particles.

[0005] In one embodiment, the porosity of the cellulose / polylactic acid composite electrospun film is 55.8% - 72.4%; and / or,

[0006] In the ceramic particle layer, the mass ratio of the micron-sized porous silica particles to the nano-sized porous silica particles is 2:(3 - 5).

[0007] The present invention also provides a preparation method of an adhesive film, including the following steps:

[0008] Providing a cellulose spinning solution and a polylactic acid spinning solution;

[0009] Electrospinning the cellulose spinning solution and the polylactic acid spinning solution to obtain a cellulose / polylactic acid composite electrospun film;

[0010] Mix micron-sized porous silica particles, nano-sized porous silica particles with a cellulose solution to obtain a suspension;

[0011] Coat the suspension on one side of the cellulose / polylactic acid composite electrospun membrane and dry to obtain a ceramic particle layer;

[0012] Dissolve polyethylene in trichloroethylene to obtain a polyethylene solution;

[0013] Cast the polyethylene solution on the other side of the cellulose / polylactic acid composite electrospun membrane to form a polyethylene-based film and obtain a glue film.

[0014] In one embodiment, the step of providing the cellulose spinning solution and the polylactic acid spinning solution includes:

[0015] Dissolve cellulose in a lithium chloride / N,N-dimethylacetamide solvent system to obtain a cellulose spinning solution; and / or,

[0016] Dissolve polylactic acid in a mixed solvent to obtain a polylactic acid spinning solution; wherein, the mixed solvent includes dimethylformamide and dichloromethane with a volume ratio of 1:(2 - 6).

[0017] In one embodiment, in the step of providing the cellulose spinning solution and the polylactic acid spinning solution:

[0018] The mass ratio of cellulose in the cellulose spinning solution is 1.5% - 2.5%; and / or,

[0019] The mass ratio of polylactic acid in the polylactic acid spinning solution is 4.5% - 8.5%.

[0020] In one embodiment, in the step of electrospinning the cellulose spinning solution and the polylactic acid spinning solution to obtain a cellulose / polylactic acid composite electrospun membrane:

[0021] The voltage of the electrospinning is 13 kV - 15 kV; and / or,

[0022] The roller rotation speed of the electrospinning is 500 rmp; and / or,

[0023] The horizontal moving rate of the electrospinning is 10 cm / min; and / or,

[0024] The spinning solution flow rate of the electrospinning is 0.4 mL / h; and / or,

[0025] The receiving distance of the electrospinning is 12 cm - 14 cm.

[0026] In one embodiment, in the step of mixing the micron-sized porous silica particles, nano-sized porous silica particles with the cellulose solution to obtain a suspension:

[0027] The mass ratio of cellulose in the cellulose solution is 0.3% to 0.5%; and / or,

[0028] In the suspension, the sum of the mass ratios of the micron-sized porous silica particles and the nano-sized porous silica particles is 3.5% to 6.5%; and / or,

[0029] The mass ratio of the micron-sized porous silica particles to the nano-sized porous silica particles is 2:(3 - 5).

[0030] In one embodiment, the step of coating the suspension on one side of the cellulose / polylactic acid composite electrospun membrane, drying to obtain a ceramic particle layer includes:

[0031] Atomize the suspension, spray it on one side of the cellulose / polylactic acid composite electrospun membrane, and dry to obtain a ceramic particle layer.

[0032] In one embodiment, in the step of atomizing the suspension, spraying it on one side of the cellulose / polylactic acid composite electrospun membrane, drying to obtain a ceramic particle layer:

[0033] On one side of the cellulose / polylactic acid composite electrospun membrane, the spraying amount of the suspension is 15 g / m 2 ~20 g / m 2 ; and / or,

[0034] On one side of the cellulose / polylactic acid composite electrospun membrane, the suspension is sprayed multiple times.

[0035] In one embodiment, in the step of dissolving polyethylene in trichloroethylene to obtain a polyethylene solution:

[0036] The mass ratio of polyethylene in the polyethylene solution is 10% to 15%.

[0037] In the technical solution provided by the present invention, a cellulose / polylactic acid composite electrospun membrane and a ceramic particle layer including micron-sized porous silica particles and nano-sized porous silica particles are sequentially arranged on a polyethylene film. The cellulose / polylactic acid composite electrospun membrane can improve the mechanical properties of the adhesive film, and the polyethylene film fills at least part of the pores of the cellulose / polylactic acid composite electrospun membrane, which can enhance the stability of the composite of the cellulose / polylactic acid composite electrospun membrane and the polyethylene film and improve the mechanical properties of the adhesive film. At the same time, the ceramic particle layer includes micron-sized porous silica particles and nano-sized porous silica particles, and the porosity of the cellulose / polylactic acid composite electrospun membrane is 50% to 80%, which can form a micro-nano structure on the surface of the cellulose / polylactic acid composite electrospun membrane. When an adhesive is coated subsequently, the ceramic particle layer can adsorb more adhesive. After being bonded to a metal plate, due to the adsorption effect of the micro-nano structure and the porous silica, the transfer of the adhesive to the metal plate during stamping can be reduced, and the residual adhesive problem of the adhesive film can be improved. Therefore, the mechanical properties of the adhesive film can be effectively improved, and at the same time, the residual adhesive problem of the adhesive film can be improved. Detailed implementation manners

[0038] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Those not specified in the embodiments are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments not specified by the manufacturer are all conventional products that can be obtained through commercial purchase. In addition, the meaning of "and / or" appearing throughout the text includes three parallel solutions. Taking "A and / or B" as an example, it includes solution A, or solution B, or a solution where A and B are satisfied simultaneously. In addition, the technical solutions between the various embodiments can be combined with each other, but it must be based on the fact that those skilled in the art can implement them. When the combination of technical solutions is contradictory or cannot be implemented, it should be considered that such a combination of technical solutions does not exist and is not within the protection scope required by the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the protection scope of the present invention.

[0039] The metal plates used in washing machines (such as the metal plates on the outer surface of the cabinet and the bottom of the inner cylinder) are generally covered with a film to prevent scratches on the metal plates during transportation. In the prior art, polyethylene (PE) film is usually used to cover the metal plates. During film processing, the film is treated with dipping glue to make the film fit more closely with the galvanized steel coil on the metal plate laminator; in the stamping factory, the laminated coil is first cut into square or circular sheets and then subjected to high-curvature and large-deformation stamping on the stamping production line. However, due to the poor deformability of the polyethylene film under rapid stamping (when the tensile deformation is greater than 50 cm / min), stamping broken film will occur; moreover, when the stamped parts are assembled onto the washing machine, the film needs to be torn off, and at this time, it is easy for the adhesive components on the polyethylene film to transfer to the metal plate, resulting in the phenomenon of residual glue on the metal plate.

[0040] In view of this, the present invention proposes an adhesive film, which can effectively improve the mechanical properties of the adhesive film and at the same time improve the problem of residual glue of the adhesive film.

[0041] In an embodiment of the present invention, the adhesive film includes a polyethylene-based film, a cellulose / polylactic acid composite electrospun film, and a ceramic particle layer arranged in sequence; wherein, the porosity of the cellulose / polylactic acid composite electrospun film is 50% to 80%, and the polyethylene-based film fills at least part of the pores of the cellulose / polylactic acid composite electrospun film, and the ceramic particle layer includes micron-sized porous silica particles and nano-sized porous silica particles.

[0042] In the technical solution provided by the present invention, by sequentially arranging a cellulose / polylactic acid composite electrospun film and a ceramic particle layer including micron-sized porous silica particles and nano-sized porous silica particles on the polyethylene-based film, the cellulose / polylactic acid composite electrospun film can improve the mechanical properties of the adhesive film, and the polyethylene-based film fills at least part of the pores of the cellulose / polylactic acid composite electrospun film, which can enhance the stability of the composite of the cellulose / polylactic acid composite electrospun film and the polyethylene-based film and improve the mechanical properties of the adhesive film; at the same time, the ceramic particle layer includes micron-sized porous silica particles and nano-sized porous silica particles, and the porosity of the cellulose / polylactic acid composite electrospun film is 50% to 80%, which can form a micro-nano structure on the surface of the cellulose / polylactic acid composite electrospun film. When the adhesive is coated subsequently, the ceramic particle layer can adsorb more adhesive. After bonding with the metal plate, due to the adsorption effect of the micro-nano structure and the porous silica, the transfer of the adhesive to the metal plate during stamping can be reduced, and the problem of residual glue of the adhesive film can be improved; thus, the mechanical properties of the adhesive film can be effectively improved, and at the same time, the problem of residual glue of the adhesive film can be improved.

[0043] It should be noted that the filling of at least part of the pores of the cellulose / polylactic acid composite electrospun membrane by the polyvinyl film means that one side of the polyvinyl film that fits the cellulose / polylactic acid composite electrospun membrane is embedded into the pores of the cellulose / polylactic acid composite electrospun membrane to fill at least part of the pores of the cellulose / polylactic acid composite electrospun membrane. It can be that the polyvinyl film fills part of the pores of the cellulose / polylactic acid composite electrospun membrane, or it can be that the polyvinyl film fills all the pores of the cellulose / polylactic acid composite electrospun membrane; the porosity of the cellulose / polylactic acid composite electrospun membrane is 50% - 80%, which is beneficial to constructing the micro-nano structure (the ceramic particle layer) on its surface; the porosity of the cellulose / polylactic acid composite electrospun membrane can be 50%, 55%, 60%, 65%, 70%, 75% or 80%.

[0044] In the embodiment of the present invention, the porosity of the cellulose / polylactic acid composite electrospun membrane is 55.8% - 72.4%. When the porosity of the cellulose / polylactic acid composite electrospun membrane is within the above range, it can further be beneficial to constructing the micro-nano structure on its surface. The porosity of the cellulose / polylactic acid composite electrospun membrane can be 55.8%, 59.6%, 65.1%, 70.4% or 72.4%.

[0045] In the embodiment of the present invention, in the ceramic particle layer, the mass ratio of the micron-sized porous silica particles to the nano-sized porous silica particles is 2:(3 - 5). When the mass ratio of the micron-sized porous silica particles to the nano-sized porous silica particles is within the above range, the problem of residual glue of the glue film can be avoided. The mass ratio of the micron-sized porous silica particles to the nano-sized porous silica particles can be 2:3, 2:3.5, 2:4, 2:4.5 or 2:5.

[0046] The present invention also proposes a method for preparing a glue film, which includes the following steps:

[0047] S1. Provide a cellulose spinning solution and a polylactic acid spinning solution;

[0048] S2. Perform electrospinning on the cellulose spinning solution and the polylactic acid spinning solution to obtain a cellulose / polylactic acid composite electrospun membrane;

[0049] S3. Mix the micron-sized porous silica particles, the nano-sized porous silica particles with a cellulose solution to obtain a suspension;

[0050] S4. Coat the suspension on one side of the cellulose / polylactic acid composite electrospun membrane and dry it to obtain a ceramic particle layer;

[0051] S5. Dissolve polyethylene in trichloroethylene to obtain a polyethylene solution;

[0052] S6. Cast the polyethylene solution on the other side of the cellulose / polylactic acid composite electrospun membrane to form a polyethylene-based membrane, thereby obtaining a glue film.

[0053] First, prepare a cellulose / polylactic acid composite electrospun membrane by electrospinning. Then, prepare a ceramic particle layer including micron-sized porous silica particles and nano-sized porous silica particles on one side of the cellulose / polylactic acid composite electrospun membrane. After that, cast a polyethylene solution on the other side of the cellulose / polylactic acid composite electrospun membrane to prepare a polyethylene-based membrane, and allow the polyethylene solution to penetrate into the pores of the cellulose / polylactic acid composite electrospun membrane, thereby obtaining a glue film. The obtained glue film can effectively improve the mechanical properties and simultaneously improve the problem of residual glue.

[0054] It should be noted that step S3 can be carried out before step S1, before step S2, simultaneously with step S1 or simultaneously with step S2. Step S5 can be carried out before step S1, before step S2, before step S3, before step S4, simultaneously with step S1, simultaneously with step S2, simultaneously with step S3 or simultaneously with step S4.

[0055] It can be understood that in step S2, the cellulose spinning solution and the polylactic acid spinning solution can be electrospun through a double-needle electrospinning device; in step S5, polyethylene can be dissolved in trichloroethylene by heating; specifically, step S6 can be to fix the cellulose / polylactic acid composite electrospun membrane loaded with the ceramic particle layer at the bottom of the mold, with the ceramic particle layer facing down, and then cast the polyethylene solution on the other side of the cellulose / polylactic acid composite electrospun membrane.

[0056] In the embodiment of the present invention, step S1 includes: S11. Dissolve cellulose in a lithium chloride / N,N-dimethylacetamide solvent system to obtain a cellulose spinning solution. By the above steps, the cellulose spinning solution for electrospinning can be obtained, which can ensure the quality of the cellulose / polylactic acid composite electrospun membrane.

[0057] In the embodiment of the present invention, step S1 includes: S12. Dissolve polylactic acid in a mixed solvent to obtain a polylactic acid spinning solution; wherein, the mixed solvent includes dimethylformamide and dichloromethane with a volume ratio of 1:(2 - 6). By the above steps, the polylactic acid spinning solution for electrospinning can be obtained, which can ensure the quality of the cellulose / polylactic acid composite electrospun membrane. The volume ratio of dimethylformamide to dichloromethane in the mixed solvent can be 1:2, 1:3, 1:4, 1:5 or 1:6.

[0058] It should be noted that step S11 is used to provide a cellulose spinning solution, step S12 is used to provide a polylactic acid spinning solution, step S11 can be carried out before step S12, after step S12 or simultaneously with step S12.

[0059] In an embodiment of the present invention, in step S1, the mass ratio of cellulose in the cellulose spinning solution is 1.5% - 2.5%. When the mass ratio of cellulose in the cellulose spinning solution is within the above range, the quality of the cellulose / polylactic acid composite electrospun membrane can be ensured. The mass ratio of cellulose in the cellulose spinning solution can be 1.5%, 1.8%, 2%, 2.2% or 2.5%.

[0060] In an embodiment of the present invention, in step S1, the mass ratio of polylactic acid in the polylactic acid spinning solution is 4.5% - 8.5%. When the mass ratio of polylactic acid in the polylactic acid spinning solution is within the above range, the quality of the cellulose / polylactic acid composite electrospun membrane can be ensured. The mass ratio of polylactic acid in the polylactic acid spinning solution can be 4.5%, 5.5%, 6.5%, 7.5% or 8.5%.

[0061] In an embodiment of the present invention, in step S2, the voltage of the electrospinning is 13 kV - 15 kV. When the voltage of the electrospinning is within the above range, it is beneficial to obtain a cellulose / polylactic acid composite electrospun membrane with an appropriate porosity. The voltage of the electrospinning can be 13 kV, 14 kV or 15 kV.

[0062] In an embodiment of the present invention, in step S2, the rotational speed of the roller of the electrospinning is 500 rmp. When the rotational speed of the roller of the electrospinning is the above value, it is beneficial to obtain a cellulose / polylactic acid composite electrospun membrane with an appropriate porosity.

[0063] In an embodiment of the present invention, in step S2, the horizontal moving rate of the electrospinning is 10 cm / min. When the horizontal moving rate of the electrospinning is the above value, it is beneficial to obtain a cellulose / polylactic acid composite electrospun membrane with an appropriate porosity.

[0064] In an embodiment of the present invention, in step S2, the flow rate of the spinning solution of the electrospinning is 0.4 mL / h. When the flow rate of the spinning solution of the electrospinning is the above value, it is beneficial to obtain a cellulose / polylactic acid composite electrospun membrane with an appropriate porosity.

[0065] In an embodiment of the present invention, in step S2, the receiving distance of the electrospinning is 12 cm - 14 cm. When the receiving distance of the electrospinning is within the above range, it is beneficial to obtain a cellulose / polylactic acid composite electrospun membrane with an appropriate porosity. The receiving distance of the electrospinning can be 12 cm, 13 cm or 14 cm.

[0066] In an embodiment of the present invention, in step S3, the mass ratio of cellulose in the cellulose solution is 0.3% to 0.5%. When the mass ratio of cellulose in the cellulose solution is within the above range, the quality of the ceramic particle layer can be ensured. The mass ratio of cellulose in the cellulose solution can be 0.3%, 0.35%, 0.4%, 0.45% or 0.5%.

[0067] In an embodiment of the present invention, in step S3, in the suspension, the sum of the mass ratios of the micron-sized porous silica particles and the nano-sized porous silica particles is 3.5% to 6.5%. When the sum of the mass ratios of the micron-sized porous silica particles and the nano-sized porous silica particles in the prepared suspension is within the above range, the quality of the ceramic particle layer can be ensured. In the suspension, the sum of the mass ratios of the micron-sized porous silica particles and the nano-sized porous silica particles can be 3.5%, 4%, 4.5%, 5%, 5.5%, 6% or 6.5%. It can be understood that the sum of the mass ratios of the micron-sized porous silica particles and the nano-sized porous silica particles in the suspension refers to the mass ratio of the total amount of the micron-sized porous silica particles and the nano-sized porous silica particles in the suspension.

[0068] In an embodiment of the present invention, in step S3, the mass ratio of the micron-sized porous silica particles to the nano-sized porous silica particles is 2:(3 - 5). When the mass ratio of the micron-sized porous silica particles to the nano-sized porous silica particles is within the above range, the problem of residual glue on the glue film can be avoided. The mass ratio of the micron-sized porous silica particles to the nano-sized porous silica particles can be 2:3, 2:3.5, 2:4, 2:4.5 or 2:5.

[0069] In an embodiment of the present invention, step S4 includes: atomizing the suspension and spraying it on one side of the cellulose / polylactic acid composite electrospun membrane, and then drying to obtain a ceramic particle layer. Depositing the suspension on one side of the cellulose / polylactic acid composite electrospun membrane by atomizing and spraying is beneficial to ensuring the quality of the ceramic particle layer. It can be understood that the suspension can be atomized by an atomizer.

[0070] In an embodiment of the present invention, in step S4, on one side of the cellulose / polylactic acid composite electrospun membrane, the spraying amount of the suspension is 15 g / m 2 ~20 g / m 2 . When the spraying amount of the suspension is within the above range, the problem of residual glue on the glue film can be avoided. The spraying amount of the suspension can be 15 g / m 2 、16 g / m2 、 17 g / m 2 、 18 g / m 2 、 19 g / m 2 or 20 g / m 2 。

[0071] In an embodiment of the present invention, in step S4, on one side of the cellulose / polylactic acid composite electrospun membrane, the suspension is sprayed multiple times. Spraying the suspension multiple times to form a ceramic particle layer is beneficial to improving the quality of the ceramic particle layer and can avoid the problem of residual glue on the glue film.

[0072] In an embodiment of the present invention, in step S5, the mass ratio of polyethylene in the polyethylene solution is 10% - 15%. When the mass ratio of polyethylene in the polyethylene solution is within the above range, the quality of the polyethylene-based membrane can be guaranteed, and it is also beneficial for the polyethylene solution to penetrate into the pores of the cellulose / polylactic acid composite electrospun membrane. The mass ratio of polyethylene in the polyethylene solution can be 10%, 11%, 12%, 13%, 14% or 15%.

[0073] The technical solutions of the present invention will be further described in detail below in conjunction with specific embodiments. It should be understood that the following embodiments are only used to explain the present invention and are not used to limit the present invention.

[0074] Example 1

[0075] A method for preparing a glue film, comprising the following steps:

[0076] S11. Preparation of cellulose spinning solution: Add cotton fibers to a solvent system of anhydrous lithium chloride / N,N-dimethylacetamide, stir and dissolve to prepare a cellulose spinning solution with a concentration of 1.5 wt%.

[0077] S12. Preparation of polylactic acid spinning solution: Add polylactic acid to a mixed solvent of dimethylformamide and dichloromethane with a volume ratio of 1:4 to prepare a polylactic acid spinning solution with a concentration of 4.5 wt%.

[0078] S2. Preparation of cellulose / polylactic acid composite electrospun membrane: Add the cellulose spinning solution and the polylactic acid spinning solution to a double-needle electrospinning device for electrospinning. The parameters of electrospinning are: voltage 15 kV, roller speed 500 rmp, horizontal movement rate 10 cm / min, spinning solution flow rate 0.4 mL / h, receiving distance 14 cm, to obtain a cellulose / polylactic acid composite electrospun membrane with a porosity of 55.8%.

[0079] S3. Preparation of micro-nano silica particle suspension: Add micro-porous silica particles and nano-porous silica particles into a cellulose solution with a concentration of 0.5 wt%, stir and disperse evenly to obtain a micro-nano silica particle suspension with a concentration of 3.5 wt%. Among them, the mass ratio of micro-porous silica particles to nano-porous silica particles is 2:5;

[0080] S4. Composite of cellulose / polylactic acid composite electrospun membrane and ceramic particle layer: Add the micro-nano silica particle suspension into an atomizer, and evenly spray and deposit the micro-nano silica particle suspension onto one side of the cellulose / polylactic acid composite electrospun membrane. Spray multiple times and dry to obtain a cellulose / polylactic acid composite electrospun membrane with a ceramic particle layer loaded on one side. Among them, the spraying amount of the micro-nano silica particle suspension on the surface of the cellulose / polylactic acid composite electrospun membrane is 20 g / m 2 ;

[0081] S5. Preparation of polyethylene solution: Heat and dissolve polyethylene in trichloroethylene to obtain a polyethylene solution with a concentration of 10 wt%;

[0082] S6. Preparation of adhesive film: Fix the cellulose / polylactic acid composite electrospun membrane with a ceramic particle layer loaded on one side at the bottom of the mold, and the side with the ceramic particle layer facing down. Cast the polyethylene solution on the side without the ceramic particle layer to obtain an adhesive film.

[0083] Example 2

[0084] A method for preparing an adhesive film, comprising the following steps:

[0085] S11. Preparation of cellulose spinning solution: Add cotton fibers into a solvent system of anhydrous lithium chloride / N,N-dimethylacetamide, stir and dissolve to prepare a cellulose spinning solution with a concentration of 2.5 wt%;

[0086] S12. Preparation of polylactic acid spinning solution: Add polylactic acid into a mixed solvent of dimethylformamide and dichloromethane with a volume ratio of 1:4 to prepare a polylactic acid spinning solution with a concentration of 8.5 w%;

[0087] S2. Preparation of cellulose / polylactic acid composite electrospun membrane: Add the cellulose spinning solution and the polylactic acid spinning solution into a double-needle electrospinning device for electrospinning. The parameters of electrospinning are: voltage 13 kV, roller speed 500 rmp, horizontal moving speed 10 cm / min, spinning solution flow rate 0.4 mL / h, receiving distance 12 cm, to obtain a cellulose / polylactic acid composite electrospun membrane with a porosity of 72.4%;

[0088] S3. Preparation of micro-nano silica particle suspension: Add micro-scale porous silica particles and nano-scale porous silica particles into a cellulose solution with a concentration of 0.3 wt%, stir and disperse evenly to obtain a micro-nano silica particle suspension with a concentration of 6.5 wt%. Among them, the mass ratio of micro-scale porous silica particles to nano-scale porous silica particles is 2:3;

[0089] S4. Composite of cellulose / polylactic acid composite electrospun membrane and ceramic particle layer: Add the micro-nano silica particle suspension into an atomizer, and evenly spray and deposit the micro-nano silica particle suspension onto one side of the cellulose / polylactic acid composite electrospun membrane. Spray multiple times and dry to obtain a cellulose / polylactic acid composite electrospun membrane with a ceramic particle layer loaded on one side. Among them, the spraying amount of the micro-nano silica particle suspension on the surface of the cellulose / polylactic acid composite electrospun membrane is 15 g / m 2 ;

[0090] S5. Preparation of polyethylene solution: Heat and dissolve polyethylene in trichloroethylene to obtain a polyethylene solution with a concentration of 15 wt%;

[0091] S6. Preparation of adhesive film: Fix the cellulose / polylactic acid composite electrospun membrane with a ceramic particle layer loaded on one side at the bottom of the mold, and the side loaded with the ceramic particle layer faces down. Cast the polyethylene solution on the side without the ceramic particle layer to obtain an adhesive film.

[0092] Example 3

[0093] A method for preparing an adhesive film, comprising the following steps:

[0094] S11. Preparation of cellulose spinning solution: Add cotton fibers into a solvent system of anhydrous lithium chloride / N,N-dimethylacetamide, stir and dissolve to prepare a cellulose spinning solution with a concentration of 1.8 wt%;

[0095] S12. Preparation of polylactic acid spinning solution: Add polylactic acid into a mixed solvent of dimethylformamide and dichloromethane with a volume ratio of 1:4 to prepare a polylactic acid spinning solution with a concentration of 5.5 wt%;

[0096] S2. Preparation of cellulose / polylactic acid composite electrospun membrane: Add the cellulose spinning solution and the polylactic acid spinning solution into a double-needle electrospinning device for electrospinning. The parameters of electrospinning are: voltage 13 kV, roller speed 500 rmp, horizontal moving rate 10 cm / min, spinning solution flow rate 0.4 mL / h, receiving distance 14 cm, to obtain a cellulose / polylactic acid composite electrospun membrane with a porosity of 59.6%;

[0097] S3. Preparation of micro-nano silica particle suspension: Add micron-sized porous silica particles and nano-sized porous silica particles into a cellulose solution with a concentration of 0.45 wt%, stir and disperse evenly to obtain a micro-nano silica particle suspension with a concentration of 4.5 wt%. Among them, the mass ratio of micron-sized porous silica particles to nano-sized porous silica particles is 2:4.5;

[0098] S4. Composite of cellulose / polylactic acid composite electrospun membrane and ceramic particle layer: Add the micro-nano silica particle suspension into an atomizer, and evenly spray and deposit the micro-nano silica particle suspension onto one side of the cellulose / polylactic acid composite electrospun membrane. Spray multiple times and dry to obtain a cellulose / polylactic acid composite electrospun membrane with a ceramic particle layer loaded on one side. Among them, the spraying amount of the micro-nano silica particle suspension on the surface of the cellulose / polylactic acid composite electrospun membrane is 18 g / m 2 ;

[0099] S5. Preparation of polyethylene solution: Heat and dissolve polyethylene in trichloroethylene to obtain a polyethylene solution with a concentration of 12 wt%;

[0100] S6. Preparation of adhesive film: Fix the cellulose / polylactic acid composite electrospun membrane with a ceramic particle layer loaded on one side at the bottom of the mold, and the side with the ceramic particle layer facing down. Cast the polyethylene solution on the side without the ceramic particle layer to obtain an adhesive film.

[0101] Example 4

[0102] A method for preparing an adhesive film, comprising the following steps:

[0103] S11. Preparation of cellulose spinning solution: Add cotton fibers into a solvent system of anhydrous lithium chloride / N,N-dimethylacetamide, stir and dissolve to prepare a cellulose spinning solution with a concentration of 2.2 wt%;

[0104] S12. Preparation of polylactic acid spinning solution: Add polylactic acid into a mixed solvent of dimethylformamide and dichloromethane with a volume ratio of 1:4 to prepare a polylactic acid spinning solution with a concentration of 7 wt%;

[0105] S2. Preparation of cellulose / polylactic acid composite electrospun membrane: Add the cellulose spinning solution and the polylactic acid spinning solution into a double-needle electrospinning device for electrospinning. The parameters of electrospinning are: voltage 15 kV, roller speed 500 rmp, horizontal moving speed 10 cm / min, spinning solution flow rate 0.4 mL / h, receiving distance 14 cm, to obtain a cellulose / polylactic acid composite electrospun membrane with a porosity of 65.1%;

[0106] S3. Preparation of micro-nano silica particle suspension: Add micro-scale porous silica particles and nano-scale porous silica particles into a cellulose solution with a concentration of 0.35 wt%, stir and disperse evenly to obtain a micro-nano silica particle suspension with a concentration of 5.5 wt%. Among them, the mass ratio of micro-scale porous silica particles to nano-scale porous silica particles is 2:3.5;

[0107] S4. Composite of cellulose / polylactic acid composite electrospun membrane and ceramic particle layer: Add the micro-nano silica particle suspension into an atomizer, and evenly spray and deposit the micro-nano silica particle suspension onto one side of the cellulose / polylactic acid composite electrospun membrane. Spray multiple times and dry to obtain a cellulose / polylactic acid composite electrospun membrane with a ceramic particle layer loaded on one side. Among them, the spraying amount of the micro-nano silica particle suspension on the surface of the cellulose / polylactic acid composite electrospun membrane is 16 g / m 2 ;

[0108] S5. Preparation of polyethylene solution: Heat and dissolve polyethylene in trichloroethylene to obtain a polyethylene solution with a concentration of 14 wt%;

[0109] S6. Preparation of adhesive film: Fix the cellulose / polylactic acid composite electrospun membrane with a ceramic particle layer loaded on one side at the bottom of the mold, and the side with the ceramic particle layer facing down. Cast the polyethylene solution on the side without the ceramic particle layer to obtain an adhesive film.

[0110] Example 5

[0111] A method for preparing an adhesive film, comprising the following steps:

[0112] S11. Preparation of cellulose spinning solution: Add cotton fibers into a solvent system of anhydrous lithium chloride / N,N-dimethylacetamide, stir and dissolve to prepare a cellulose spinning solution with a concentration of 2 wt%;

[0113] S12. Preparation of polylactic acid spinning solution: Add polylactic acid into a mixed solvent of dimethylformamide and dichloromethane with a volume ratio of 1:4 to prepare a polylactic acid spinning solution with a concentration of 6.5 wt%;

[0114] S2. Preparation of cellulose / polylactic acid composite electrospun membrane: Add the cellulose spinning solution and the polylactic acid spinning solution into a double-needle electrospinning device for electrospinning. The parameters of electrospinning are: voltage 14 kV, roller speed 500 rmp, horizontal moving rate 10 cm / min, spinning solution flow rate 0.4 mL / h, receiving distance 13 cm, to obtain a cellulose / polylactic acid composite electrospun membrane with a porosity of 70.4%;

[0115] S3. Preparation of micro-nano silica particle suspension: Add micron-sized porous silica particles and nano-sized porous silica particles into a cellulose solution with a concentration of 0.4 wt%, stir and disperse evenly to obtain a micro-nano silica particle suspension with a concentration of 5 wt%. Among them, the mass ratio of micron-sized porous silica particles to nano-sized porous silica particles is 2:4;

[0116] S4. Composite of cellulose / polylactic acid composite electrospun membrane and ceramic particle layer: Add the micro-nano silica particle suspension into an atomizer, and evenly spray and deposit the micro-nano silica particle suspension onto one side of the cellulose / polylactic acid composite electrospun membrane. Spray multiple times and dry to obtain a cellulose / polylactic acid composite electrospun membrane with a ceramic particle layer loaded on one side. Among them, the spraying amount of the micro-nano silica particle suspension on the surface of the cellulose / polylactic acid composite electrospun membrane is 17 g / m 2 ;

[0117] S5. Preparation of polyethylene solution: Heat and dissolve polyethylene in trichloroethylene to obtain a polyethylene solution with a concentration of 13 wt%;

[0118] S6. Preparation of adhesive film: Fix the cellulose / polylactic acid composite electrospun membrane with a ceramic particle layer loaded on one side at the bottom of the mold, with the side loaded with the ceramic particle layer facing down, and cast the polyethylene solution on the side without the ceramic particle layer to obtain an adhesive film.

[0119] Comparative Example 1

[0120] The preparation method of the adhesive film includes the following steps:

[0121] S11. Preparation of cellulose spinning solution: Add cotton fibers into a solvent system of anhydrous lithium chloride / N,N-dimethylacetamide, stir and dissolve to prepare a cellulose spinning solution with a concentration of 2 wt%;

[0122] S12. Preparation of polylactic acid spinning solution: Add polylactic acid into a mixed solvent of dimethylformamide and dichloromethane with a volume ratio of 1:4 to prepare a polylactic acid spinning solution with a concentration of 6.5 wt%;

[0123] S2. Preparation of cellulose / polylactic acid composite electrospun membrane: Add the cellulose spinning solution and the polylactic acid spinning solution into a double-needle electrospinning device for electrospinning. The parameters of electrospinning are: voltage 14 kV, roller speed 500 rmp, horizontal movement rate 10 cm / min, spinning solution flow rate 0.4 mL / h, receiving distance 13 cm, to obtain a cellulose / polylactic acid composite electrospun membrane with a porosity of 95.2%;

[0124] S3. Preparation of micro-nano silica particle suspension: Add micron-sized porous silica particles and nano-sized porous silica particles into a cellulose solution with a concentration of 0.4 wt%, stir and disperse evenly to obtain a micro-nano silica particle suspension with a concentration of 5 wt%. Among them, the mass ratio of micron-sized porous silica particles to nano-sized porous silica particles is 2:4;

[0125] S4. Composite of cellulose / polylactic acid composite electrospun membrane and ceramic particle layer: Add the micro-nano silica particle suspension into an atomizer, and evenly spray and deposit the micro-nano silica particle suspension on one side of the cellulose / polylactic acid composite electrospun membrane. Spray multiple times and dry to obtain a cellulose / polylactic acid composite electrospun membrane with a ceramic particle layer loaded on one side. Among them, the spraying amount of the micro-nano silica particle suspension on the surface of the cellulose / polylactic acid composite electrospun membrane is 17 g / m 2 ;

[0126] S5. Preparation of polyethylene solution: Heat and dissolve polyethylene in trichloroethylene to obtain a polyethylene solution with a concentration of 13 wt%;

[0127] S6. Preparation of adhesive film: Fix the cellulose / polylactic acid composite electrospun membrane with a ceramic particle layer loaded on one side at the bottom of the mold, and the side with the ceramic particle layer facing down. Cast the polyethylene solution on the side without the ceramic particle layer to obtain an adhesive film.

[0128] Comparative Example 2

[0129] A method for preparing an adhesive film, comprising the following steps:

[0130] S1. Preparation of cellulose spinning solution: Add cotton fibers into a solvent system of anhydrous lithium chloride / N,N-dimethylacetamide, stir and dissolve to prepare a cellulose spinning solution with a concentration of 2 wt%;

[0131] S2. Preparation of cellulose electrospun membrane: Add the cellulose spinning solution into an electrospinning device for electrospinning. The parameters of electrospinning are: voltage 14 kV, roller speed 500 rmp, horizontal moving rate 10 cm / min, spinning solution flow rate 0.4 mL / h, receiving distance 13 cm, to obtain a cellulose electrospun membrane with a porosity of 69.6%;

[0132] S3. Preparation of micro-nano silica particle suspension: Add micron-sized porous silica particles and nano-sized porous silica particles into a cellulose solution with a concentration of 0.4 wt%, stir and disperse evenly to obtain a micro-nano silica particle suspension with a concentration of 5 wt%. Among them, the mass ratio of micron-sized porous silica particles to nano-sized porous silica particles is 2:4;

[0133] S4. Composite of cellulose electrospun membrane and ceramic particle layer: Add the micro-nano silica particle suspension into an atomizer, and evenly spray and deposit the micro-nano silica particle suspension onto one side of the cellulose electrospun membrane. Spray multiple times and then dry to obtain a cellulose electrospun membrane with a ceramic particle layer loaded on one side; wherein, the spraying amount of the micro-nano silica particle suspension on the surface of the cellulose electrospun membrane is 17 g / m 2 ;

[0134] S5. Preparation of polyethylene solution: Heat and dissolve polyethylene in trichloroethylene to obtain a polyethylene solution with a concentration of 13 wt%.

[0135] S6. Preparation of adhesive film: Fix the cellulose electrospun membrane with a ceramic particle layer loaded on one side at the bottom of a mold, with the side loaded with the ceramic particle layer facing downwards, and cast the polyethylene solution on the side without the ceramic particle layer loaded to obtain an adhesive film.

[0136] Comparative Example 3

[0137] Method for preparing an adhesive film, comprising the following steps:

[0138] S11. Preparation of cellulose spinning solution: Add cotton fibers into a solvent system of anhydrous lithium chloride / N,N-dimethylacetamide, stir and dissolve to prepare a cellulose spinning solution with a concentration of 2 wt%.

[0139] S12. Preparation of polylactic acid spinning solution: Add polylactic acid into a mixed solvent of dimethylformamide and dichloromethane with a volume ratio of 1:4 to prepare a polylactic acid spinning solution with a concentration of 6.5 wt%.

[0140] S2. Preparation of cellulose / polylactic acid composite electrospun membrane: Add the cellulose spinning solution and the polylactic acid spinning solution into a double-needle electrospinning device for electrospinning. The parameters of electrospinning are: voltage 14 kV, roller rotation speed 500 rmp, horizontal movement rate 10 cm / min, spinning solution flow rate 0.4 mL / h, receiving distance 13 cm, to obtain a cellulose / polylactic acid composite electrospun membrane with a porosity of 75.2%.

[0141] S3. Preparation of nano-silica particle suspension: Add nano-porous silica particles into a cellulose solution with a concentration of 0.4 wt%, stir and disperse evenly to obtain a nano-silica particle suspension with a concentration of 5 wt%.

[0142] S4. Composite of Cellulose / Polylactic Acid Composite Electrospun Membrane and Ceramic Particle Layer: Add the nano-silica particle suspension into an atomizer, and evenly spray and deposit the nano-silica particle suspension onto one side of the electrospun membrane. Spray multiple times and then dry to obtain a cellulose / polylactic acid composite electrospun membrane with a ceramic particle layer loaded on one side; wherein, the spraying amount of the nano-silica particle suspension on the surface of the cellulose / polylactic acid composite electrospun membrane is 17 g / m 2 ;

[0143] S5. Preparation of Polyethylene Solution: Heat and dissolve polyethylene in trichloroethylene to obtain a polyethylene solution with a concentration of 13 wt%.

[0144] S6. Preparation of Glue Film: Fix the cellulose / polylactic acid composite electrospun membrane with a ceramic particle layer loaded on one side at the bottom of a mold, with the side loaded with the ceramic particle layer facing down, and cast the polyethylene solution on the side without the ceramic particle layer loaded to obtain a glue film.

[0145] Comparative Example 4

[0146] A method for preparing a glue film, comprising the following steps:

[0147] S11. Preparation of Cellulose Spinning Solution: Add cotton fibers into a solvent system of anhydrous lithium chloride / N,N-dimethylacetamide, stir and dissolve to prepare a cellulose spinning solution with a concentration of 2 wt%.

[0148] S12. Preparation of Polylactic Acid Spinning Solution: Add polylactic acid into a mixed solvent of dimethylformamide and dichloromethane with a volume ratio of 1:4 to prepare a polylactic acid spinning solution with a concentration of 6.5 wt%.

[0149] S2. Preparation of Cellulose / Polylactic Acid Composite Electrospun Membrane: Add the cellulose spinning solution and the polylactic acid spinning solution into a double-needle electrospinning device for electrospinning. The parameters of electrospinning are: voltage 14 kV, roller rotation speed 500 rmp, horizontal moving rate 10 cm / min, spinning solution flow rate 0.4 mL / h, receiving distance 13 cm, to obtain a cellulose / polylactic acid composite electrospun membrane with a porosity of 74.8%.

[0150] S3. Preparation of Polyethylene Solution: Heat and dissolve polyethylene in trichloroethylene to obtain a polyethylene solution with a concentration of 13 wt%.

[0151] S4. Preparation of Glue Film: Fix the cellulose / polylactic acid composite electrospun membrane at the bottom of a mold, and cast the polyethylene solution to obtain a glue film.

[0152] Performance Test

[0153] (1) Tensile property test: Refer to GB / T 3923.1-2013 "Textiles - Tensile properties of fabrics", where the tensile speed is 100 mm / min;

[0154] (2) Tear property test: Refer to GB / T 3917.3-2009 "Textiles - Tear properties of fabrics - Part 3: Determination of tear force of trapezoid specimens";

[0155] (3) Bursting strength test: Refer to GB / T 19976-2005 "Textiles - Determination of bursting strength - Steel ball method";

[0156] (4) Peel strength test: Coat the adhesive on the side of the adhesive film away from the polyethylene film, refer to FZ / T01010-2012;

[0157] (5) Residual adhesive test: Test plate: glass panel; Test size: 170 mm * 100 mm; Test conditions: 85 °C / 60 RH%; After storing the panel with the spline in the temperature and humidity of the test conditions for 48 h, extract it with methanol and observe the residual adhesive situation.

[0158] The adhesive films prepared in Examples 1 to 5 and Comparative Examples 1 to 4 were respectively subjected to the above performance tests, and the results are shown in Table 1.

[0159] Table 1 Performance test results of the adhesive films obtained in each example and comparative example

[0160]

[0161]

[0162] It can be seen from Table 1 that compared with Comparative Examples 1 to 4, the adhesive films prepared in Examples 1 to 5 have better mechanical properties and no residual adhesive, indicating that the adhesive films provided by the present application can effectively improve the mechanical properties and avoid the problem of residual adhesive at the same time.

[0163] The above are only exemplary embodiments of the present invention, and do not limit the patent scope of the present invention. Any equivalent structural transformation made using the content of the specification of the present invention under the technical concept of the present invention, or direct / indirect application in other related technical fields, is included in the patent protection scope of the present invention.

Claims

1. A film, characterized in that: It includes a polyethylene-based membrane, a cellulose / polylactic acid composite electrospinning membrane and a ceramic particle layer which are arranged in sequence; wherein the porosity of the cellulose / polylactic acid composite electrospinning membrane is 50% to 80%, the polyethylene-based membrane fills at least part of the pores of the cellulose / polylactic acid composite electrospinning membrane, and the ceramic particle layer includes micron-sized porous silica particles and nano-sized porous silica particles.

2. The adhesive film according to claim 1, characterized in that: The porosity of the cellulose / polylactic acid composite electrospinning membrane is 55.8% to 72.4%; and / or, In the ceramic particle layer, the mass ratio of the micron-sized porous silica particles to the nano-sized porous silica particles is 2:(3-5).

3. A method for preparing an adhesive film as claimed in claim 1 or 2, characterized in that: The following steps are involved: Provide cellulose spinning solution and polylactic acid spinning solution; Electrospinning the cellulose spinning solution and the polylactic acid spinning solution to obtain a cellulose / polylactic acid composite electrospinning membrane; mixing micrometer-sized porous silica particles, nanometer-sized porous silica particles and a cellulose solution to obtain a suspension; Applying the suspension on one side of the cellulose / polylactic acid composite electrospinning membrane and drying it to obtain a ceramic particle layer; Dissolving polyethylene in trichloroethylene to obtain a polyethylene solution; A polyethylene solution is cast on the other side of the cellulose / polylactic acid composite electrospinning membrane to form a polyethylene-based membrane to obtain a rubber film.

4. The method for preparing the adhesive film according to claim 3, characterized in that: The step of providing cellulose spinning solution and polylactic acid spinning solution comprises: dissolving cellulose in a lithium chloride / N,N-dimethylacetamide solvent system to obtain a cellulose spinning solution; and / or, The polylactic acid is dissolved in a mixed solvent to obtain a polylactic acid spinning solution; wherein the mixed solvent comprises dimethylformamide and dichloromethane in a volume ratio of 1:(2-6).

5. The method for preparing the adhesive film according to claim 3 or 4, characterized in that: In the step of providing cellulose spinning solution and polylactic acid spinning solution: The mass percentage of cellulose in the cellulose spinning solution is 1.5% to 2.5%; and / or, The mass proportion of polylactic acid in the polylactic acid spinning solution is 4.5% to 8.5%.

6. The method for preparing the adhesive film according to claim 3, characterized in that: In the step of electrospinning the cellulose spinning solution and the polylactic acid spinning solution to obtain a cellulose / polylactic acid composite electrospinning membrane: The voltage of the electrospinning is 13 kV to 15 kV; and / or, The electrospinning drum speed is 500 rpm; and / or, The horizontal movement rate of the electrospinning is 10 cm / min; and / or, The electrospinning solution flow rate is 0.4 mL / h; and / or, The receiving distance of the electrostatic spinning is 12 cm to 14 cm.

7. The method for preparing the adhesive film according to claim 3, characterized in that: In the step of mixing the micron-sized porous silica particles, the nano-sized porous silica particles and the cellulose solution to obtain a suspension: The mass percentage of cellulose in the cellulose solution is 0.3% to 0.5%; and / or, In the suspension, the sum of the mass proportions of the micron-sized porous silica particles and the nano-sized porous silica particles is 3.5% to 6.5%; and / or, The mass ratio of the micron-sized porous silica particles to the nano-sized porous silica particles is 2:(3-5).

8. The method for preparing the adhesive film according to claim 3, characterized in that: The step of applying the suspension to one side of the cellulose / polylactic acid composite electrospinning membrane and drying to obtain a ceramic particle layer comprises: The suspension is atomized, sprayed on one side of the cellulose / polylactic acid composite electrospinning membrane, and dried to obtain a ceramic particle layer.

9. The method for preparing the adhesive film according to claim 8, characterized in that: In the step of atomizing the suspension, spraying it on one side of the cellulose / polylactic acid composite electrospinning membrane, and drying it to obtain a ceramic particle layer: On one side of the cellulose / polylactic acid composite electrospinning membrane, the spraying amount of the suspension is 15 g / m 2 ~20g / m 2 and / or, The suspension is sprayed multiple times on one side of the cellulose / polylactic acid composite electrospinning membrane.

10. The method for preparing the adhesive film according to claim 3, characterized in that: In the step of dissolving polyethylene in trichloroethylene to obtain a polyethylene solution: The weight percentage of polyethylene in the polyethylene solution is 10% to 15%.

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