Waterproof 3D film and preparation method thereof

Abstract

The invention discloses a waterproof 3D film and a preparation method thereof, and belongs to the technical field of plastics, the waterproof 3D film provided by the invention comprises the following components in parts by weight: 30-80 parts of an ethylene-vinyl acetate copolymer, 5-30 parts of a modified organic silicon elastomer and 0-20 parts of a filler, the modified organic silicon elastomer takes amino silicon oil as a main chain, and the modified organic silicon elastomer is an organic silicon elastomer; long-carbon-chain binary fatty acid and 3, 4-dihydroxybenzoic acid are introduced through amidation reaction, and zinc ions are used as a cross-linking agent. The preparation method comprises the following steps: adding amino silicon oil as a main chain into an EVA material, introducing long-carbon-chain binary fatty acid and 3, 4-dihydroxybenzoic acid through amidation reaction, and mixing with an organic silicon elastomer which takes zinc ions as a cross-linking agent, so that the prepared EVA colloidal particles meet the performance requirements of good ductility, light transmission, adhesion resistance and the like of the waterproof 3D film.

Description

Technical Field

[0001] The present invention relates to the field of plastic technology, in particular to a waterproof 3D film and a preparation method thereof. Background Art

[0002] Waterproof 3D film refers to a thin film material made of specific materials and processes, which has waterproof properties and three-dimensional visual effects. It can be used in packaging materials, automotive interior materials, home decoration materials and many other aspects. Common materials used for 3D films include polyvinyl chloride (PVC), polyethylene (PE) or ethylene-vinyl acetate copolymer (EVA). Among them, EVA has good flexibility, transparency and moisture resistance, can be easily bent and shaped, and has a high light transmittance. The light transmittance of pure EVA material can reach 80%-95%, which can ensure efficient light transmission and provide a solid foundation for presenting bright and realistic 3D images. Moreover, the haze of EVA material can be controlled by adjusting the formula and processing technology, so that it can maintain low haze in application scenarios that require clear images, reduce light scattering, and improve image clarity; in some special applications such as 3D scene construction that simulates fog effects, the haze can be appropriately increased to enhance the sense of atmosphere. However, the vinyl acetate segment in the EVA molecular chain has a strong polarity, which makes it highly adhesive to itself or other substances. The EVA film is easily adhered to the pressure roller during the embossing process, resulting in blistering, wrinkles, etc., and the product yield is low. In addition, after being made into a coil, EVA itself will also have adhesion, resulting in ink transfer, affecting the final effect of the printed film. In the prior art, the anti-sticking and slippery properties of EVA can often be provided by adding anti-sticking agents or slipping agents. Commonly used anti-sticking agents or slipping agents include silicon dioxide or erucic acid amide, but the addition of silicon dioxide often affects the transparency and ductility of the EVA film, and erucic acid amide, as a small molecule, is prone to precipitation problems, which will increase the adhesion of the EVA film surface. Summary of the invention

[0003] In order to overcome the shortcomings of the above-mentioned prior art, the present invention provides a waterproof 3D film and a preparation method thereof, by adding amino silicone oil as the main chain to the EVA material, introducing long carbon chain dibasic fatty acids and 3,4-dihydroxybenzoic acid through an amidation reaction, and mixing together with a silicone elastomer using zinc ions as a cross-linking agent, so that the prepared EVA particles meet the performance requirements of the waterproof 3D film such as good ductility, light transmittance, and anti-stickiness.

[0004] The technical solution for achieving the purpose of the present invention is as follows:

[0005] A waterproof 3D film, calculated by weight, comprises the following components: 30-80 parts of ethylene-vinyl acetate copolymer, 5-30 parts of modified silicone elastomer, and 0-20 parts of filler. The modified silicone elastomer is an organic silicone elastomer with amino silicone oil as the main chain, long carbon chain dibasic fatty acids and 3,4-dihydroxybenzoic acid are introduced through amidation reaction, and zinc ions are used as cross-linking agents.

[0006] In a specific embodiment, the amino content of the amino silicone oil is 0.4-0.8 mmol / g.

[0007] In a specific embodiment, the long carbon chain dibasic fatty acid is a straight chain dibasic fatty acid having 8 to 16 carbon atoms.

[0008] In a specific embodiment, the filler is at least one of calcium carbonate, talc, silicon dioxide or titanium dioxide.

[0009] Preferably, the filler is silicon dioxide, and the particle size of the silicon dioxide is 1 to 30 μm, more preferably 1 to 10 μm.

[0010] In a specific embodiment, the molar ratio of the dibasic fatty acid to 3,4-dihydroxybenzoic acid is (2-3): (4-6).

[0011] In a specific embodiment, the vinyl acetate content of the ethylene-vinyl acetate copolymer is 5 wt % to 15 wt %.

[0012] Preferably, the modified EVA particles also include 0.1 to 2 parts of an antioxidant and 0.1 to 5 parts of a lubricant; the lubricant is at least one of zinc stearate, calcium stearate, and stearic acid; and the antioxidant is at least one of antioxidant 1010 and antioxidant 168.

[0013] In a specific embodiment, the preparation method of the modified silicone elastomer is as follows: under a nitrogen atmosphere, amino silicone oil, 3,4-dihydroxybenzoic acid and long carbon chain fatty dibasic acid are dissolved in tetrahydrofuran, refluxed and stirred at 60-80°C for 6-12 hours to obtain a prepolymer solution, zinc chloride is dissolved in tetrahydrofuran, and then added to the prepolymer solution, and stirring reaction is continued at 60-80°C for a period of time. After the reaction is completed, the solution is cast onto a polytetrafluoroethylene mold, volatilized at room temperature, and dried to obtain a modified silicone elastomer.

[0014] Another object of the present invention is to protect the preparation method of the waterproof 3D film, which includes the following steps: mixing ethylene-vinyl acetate copolymer, modified silicone elastomer, and filler in proportion and stirring to obtain a semi-gelled mixture, shearing and kneading the semi-gelled mixture to obtain colloid particles; filtering the obtained colloid particles to obtain modified EVA colloid particles, casting the modified EVA colloid particles to obtain a film sheet; printing and embossing the film sheet to obtain a waterproof 3D film.

[0015] Specifically, the printing and embossing are to print the pattern on the front or back of the film by a rotary gravure printing machine or a lithographic printing machine, control the expansion ratio by 1 to 8% to design printing dots or lines under different conditions, and use an embossing machine to emboss the film with the printed pattern to produce a three-dimensional sense of the product and a 3D effect in which the color varies depending on the viewing angle.

[0016] Preferably, the stirring speed is 580-1160 rpm and the stirring temperature is 85-105°C.

[0017] Preferably, the filtration is performed using a filter, the filter uses a 80-200 mesh filter screen to filter the colloid particles, and the screw speed of the filter is controlled below 60 rpm.

[0018] Preferably, the tape casting is carried out by using a tape casting machine, pushing the rubber particles to the die head of the tape casting machine for extrusion molding, and the temperature difference between the die head of the tape casting machine and the cooling roller is not less than 40° C.

[0019] Preferably, the temperature of the traction wheel is 150-180°C, and the temperature of the cooling roller is 10-25°C.

[0020] Preferably, the speed of the embossing machine is 10-20 m / min, and the temperature of the embossing machine is 140-180°C.

[0021] Another object of the present invention is to provide a shower curtain prepared from the above-mentioned waterproof 3D film.

[0022] Beneficial Effects

[0023] The present invention provides a waterproof 3D film and its preparation method and application, by adding amino silicone oil as the main chain to EVA material, introducing long carbon chain dibasic fatty acid and 3,4-dihydroxybenzoic acid through amidation reaction, and mixing with zinc ions as a crosslinking agent, and then casting, printing and embossing to obtain a waterproof 3D film, wherein 3,4-dihydroxybenzoic acid and zinc ions in the modified silicone elastomer can form a metal-ligand bond dynamic crosslinking network, as the hard segment of the modified silicone elastomer, providing rigidity for the film, and the long carbon chain as a soft segment ensures the resilience and fluidity of the modified silicone elastomer, improves the elongation at break of the film, and ensures the ductility of the film. In addition, the addition of the modified silicone elastomer can also ensure the light transmission effect of the film, and the use of silicon dioxide in a certain number of parts can adjust the transparency and haze of the film, and the silicone main chain can also improve the hydrophobic effect and anti-sticking and smooth effect of the EVA material, and improve the processing performance of the waterproof 3D film. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 Schematic diagram of the synthesis route of the modified silicone elastomer 1;

[0025] Figure 2 This is the infrared spectrum of the modified silicone elastomer 1. DETAILED DESCRIPTION

[0026] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0027] In the examples, the experimental methods used are conventional methods unless otherwise specified, and the materials, reagents, etc. used are all commercially available unless otherwise specified.

[0028] The raw materials used in the embodiments and comparative examples are described as follows:

[0029] Ethylene-vinyl acetate copolymer: vinyl acetate content 14%, melt index 2g / 10min at 190℃ and 2.16kg; brand 14J2, Yanshan Petrochemical;

[0030] Amino silicone oil 1: DY-N322, amino content 0.5-0.56 mmol / g, viscosity (25°C, cp)>500; purchased from Shandong Dayi Chemical Co., Ltd.;

[0031] Amino silicone oil 2: DY-N323, amino content 0.9-1 mmol / g, viscosity 20-100 (25°C, cp), purchased from Shandong Dayi Chemical Co., Ltd.;

[0032] Amino silicone oil 3: DY-N322D2, amino content 0.2-0.3 mmol / g, viscosity 200-1000 (25°C, cp), purchased from Shandong Dayi Chemical Co., Ltd.;

[0033] 3,4-Dihydroxybenzoic acid: purity 99%, Guangdong Wengjiang Chemical Reagent Co., Ltd.;

[0034] Adipic acid: purity 99.5%, Shanghai Aladdin Biochemical Technology Co., Ltd.;

[0035] Sebacic acid: purity 99%, Shanghai MacLean Biochemical Technology Co., Ltd.;

[0036] Dodecanedioic acid: purity 99%, Shanghai MacLean Biochemical Technology Co., Ltd.;

[0037] Octadecanedioic acid: purity 99%, Shanghai Siying Chemical Technology Co., Ltd.;

[0038] Zinc chloride: purity 99.95%, Shanghai MacLean Biochemical Technology Co., Ltd.;

[0039] Lubricant: calcium stearate, commercially available;

[0040] Filler: silicon dioxide, 1 μm, Brofos-Si02-W01, Bohuasi Nanotechnology (Ningbo) Co., Ltd.

[0041] Modified silicone elastomer 1: Homemade, the preparation method is as follows:

[0042] In a nitrogen atmosphere, 10 mol parts of amino silicone oil with an amino content, 4 mol parts of 3,4-dihydroxybenzoic acid and 3 mol parts of sebacic acid were weighed and dissolved in tetrahydrofuran, and then added under condensation reflux stirring at 60°C for 12 hours to obtain a prepolymer solution. 2 mol parts of zinc chloride were dissolved in tetrahydrofuran and then added to the prepolymer solution. The stirring reaction was continued at 60°C for 30 minutes. After the reaction was completed, the solution was cast onto a polytetrafluoroethylene mold and evaporated at room temperature for 24 hours. The film was placed in a vacuum oven at 40°C until it reached a constant weight to obtain a modified silicone elastomer.

[0043] Modified silicone elastomer 2: The preparation method is different from that of modified silicone elastomer 1 in that the amino silicone oil 1 is replaced by amino silicone oil 2;

[0044] Modified silicone elastomer 3: The preparation method is different from that of modified silicone elastomer 1 in that the amino silicone oil 1 is replaced by amino silicone oil 3;

[0045] Modified silicone elastomer 4: The preparation method is different from that of modified silicone elastomer 1, except that the sebacic acid used is replaced by adipic acid;

[0046] Modified silicone elastomer 5: The preparation method is different from that of modified silicone elastomer 1, except that the sebacic acid used is replaced by dodecanedioic acid;

[0047] Modified silicone elastomer 6: The preparation method is different from that of modified silicone elastomer 1, except that the sebacic acid used is replaced by octadecanedioic acid;

[0048] Modified silicone elastomer 7: The preparation method is different from that of modified silicone elastomer 1, except that: the amount of 3,4-dihydroxybenzoic acid added is 3 mol parts, the amount of sebacic acid added is changed to 3.5 mol parts, and the amount of zinc chloride added is 1.5 mol parts;

[0049] Modified silicone elastomer 8: The preparation method is different from that of modified silicone elastomer 1, except that: the amount of 3,4-dihydroxybenzoic acid added is 6 molar parts, the amount of sebacic acid added is 2 molar parts, and the amount of zinc chloride added is 3 molar parts;

[0050] Modified silicone elastomer 9: The preparation method is different from that of modified silicone elastomer 1, except that: the amount of 3,4-dihydroxybenzoic acid added is 10 parts by mole, sebacic acid is not added, and the amount of zinc chloride added is 5 parts by mole;

[0051] Modified silicone elastomer 10: The preparation method is the same as that of modified silicone elastomer 1, except that: 3,4-dihydroxybenzoic acid is not added, the amount of sebacic acid added is 5 parts by mole, and zinc chloride is not added;

[0052] Modified silicone elastomer 11: The preparation method is different from that of modified silicone elastomer 1 in that: no zinc chloride is added;

[0053] Antioxidant: a compound of antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1, commercially available;

[0054] Unless otherwise specified, the components and raw materials used in the embodiments and comparative examples of the present invention are all commercially available raw materials, and the components and raw materials used in each parallel experiment are all of the same kind.

[0055] Examples and Comparative Examples

[0056] A waterproof 3D film, the preparation method of which comprises the following steps: mixing ethylene-vinyl acetate copolymer, modified silicone elastomer and filler in proportion and stirring to obtain a semi-gelled mixture, shearing and kneading the semi-gelled mixture to obtain colloid particles; filtering the obtained colloid particles; obtaining modified EVA colloid particles, the stirring speed is 800 rpm, and the stirring temperature is 105° C.; filtering is performed by a filter, the filter uses a 100-mesh filter screen to filter the colloid particles, and the screw speed of the filter is controlled at 40 rpm; casting the modified EVA colloid particles to obtain a film sheet with a thickness of 0.15 mm; printing the film sheet to obtain a waterproof 3D film; the specific components and portions of the waterproof 3D film are shown in Table 1;

[0057] Table 1 Specific components and quantities of waterproof 3D film

[0058]

[0059]

[0060]

[0061] The prepared sheet was subjected to the following performance tests, and the results are shown in Table 2:

[0062] (1) Tensile strength and elongation at break: The tensile properties and elongation at break of the material were tested in accordance with ISO 527-2012 “Determination of tensile properties of plastics” at 23°C and a tensile rate of 50 mm / min.

[0063] (2) Hydrophobicity: The hydrophobicity of the sheet is evaluated by measuring the water contact angle of the sheet in the air. The larger the contact angle, the less likely the film surface is to be wetted, and the better the hydrophobicity.

[0064] (3) Light transmittance: Test the light transmittance of the film according to the standard GB / T 2410-2008 “Determination of light transmittance and haze of transparent plastics”;

[0065] (4) Film friction coefficient test: The dynamic coefficient of friction (COF) of the film was tested according to the ASTM D 1894-73 standard.

[0066] (5) Film adhesion test: The film adhesion was tested according to ASTM D 1893-67.

[0067] Table 2 Performance test results of waterproof 3D film

[0068]

[0069]

[0070] It can be seen from Examples 1 to 3 that when the silica content is high, the light transmittance of the film will decrease. When no silica is added to the film material, the light transmittance of the film can be as high as 95%. Therefore, in actual production, the ratio of silica and modified silicone elastomer can be adjusted as needed to obtain a film material with the desired transmittance and haze effect.

[0071] It can be seen from Examples 3 to 5 that the amino content of amino silicone oil has a certain influence on the ductility, light transmittance, hydrophobicity and adhesion of the film material. This is because the amino content directly affects the crosslinking density of the modified silicone elastomer, which leads to slight differences in the various properties of the film. Therefore, amino silicone oil with an amino content in the range of 0.4 to 0.8 mmol / g is preferably used as the main chain of the modified silicone elastomer to achieve the best overall performance of the film.

[0072] It can be seen from Examples 3 and 6 to 8 that when the carbon chain length of the long carbon chain dibasic fatty acid is in the range of 8 to 16, the overall performance of the film is the best.

[0073] It can be seen from Examples 3, 9, 10 and Comparative Examples 1 and 2 that when the ratio of the hard segment to the soft segment of the modified silicone elastomer is within a certain range, the overall performance of the film material is the best.

[0074] It can be seen from Comparative Example 3 that when zinc chloride is not used for crosslinking in the modified silicone elastomer, although there is hydrogen bonding between the hydroxyl groups of 3,4-dihydroxybenzoic acid, the hydrophobic properties of the waterproof 3D film will deteriorate due to the polar effect of the hydroxyl groups.

[0075] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific implementation methods described. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A waterproof 3D film, characterized in that: The waterproof 3D film comprises the following components in parts by weight: 30-80 parts of ethylene-vinyl acetate copolymer, 10-50 parts of modified silicone elastomer, and 0-20 parts of filler. The modified silicone elastomer is a silicone elastomer with amino silicone oil as the main chain, long carbon chain dibasic fatty acids and 3,4-dihydroxybenzoic acid are introduced through amidation reaction, and zinc ions are used as cross-linking agents.

2. The waterproof 3D film according to claim 1, characterized in that: The amino content of the amino silicone oil is 0.4-0.8 mmol / g.

3. The waterproof 3D film according to claim 1, characterized in that: The long carbon chain dibasic fatty acid is a straight chain dibasic fatty acid having 8 to 16 carbon atoms.

4. The waterproof 3D film according to claim 1, characterized in that: The filler is at least one of calcium carbonate, talc, silicon dioxide or titanium dioxide.

5. The waterproof 3D film according to claim 1, characterized in that: The molar ratio of the dibasic fatty acid to 3,4-dihydroxybenzoic acid is (2-3):(4-6).

6. The waterproof 3D film according to claim 1, characterized in that: The vinyl acetate content of the ethylene-vinyl acetate copolymer is 5wt% to 15wt%.

7. The waterproof 3D film according to claim 1, characterized in that: The preparation method of the modified silicone elastomer is as follows: in a nitrogen atmosphere, amino silicone oil, 3,4-dihydroxybenzoic acid and long carbon chain fatty dibasic acid are dissolved in tetrahydrofuran, refluxed and stirred at 60-80° C. for 6-12 hours to obtain a prepolymer solution, zinc chloride is dissolved in tetrahydrofuran, and then added to the prepolymer solution, stirring and reacting at 60-80° C. for a period of time, and after the reaction is completed, the solution is cast on a polytetrafluoroethylene mold, volatilized at room temperature, and dried to obtain the modified silicone elastomer.

8. The method for preparing a waterproof 3D film according to any one of claims 1 to 7, characterized in that: The following steps are involved: Ethylene-vinyl acetate copolymer, modified silicone elastomer and filler are mixed in proportion and stirred to obtain a semi-gelled mixture, and the semi-gelled mixture is sheared and kneaded to obtain rubber particles; the obtained rubber particles are filtered to obtain modified EVA rubber particles, and the modified EVA rubber particles are cast to obtain film sheets; the film sheets are printed and embossed to obtain a waterproof 3D film.

9. The method for preparing a waterproof 3D film according to claim 8, characterized in that: The printing and embossing are to print the pattern on the front or back of the film by a rotary gravure printing machine or a lithographic printing machine, control the expansion ratio by 1 to 8% to design printing dots or lines under different conditions, and use an embossing machine to emboss the film with the printed pattern to produce a three-dimensional sense of the product and a 3D effect in which the color varies depending on the viewing angle.

10. A shower curtain, characterized in that: Prepared from the waterproof 3D film according to any one of claims 1 to 7.

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