Environment-friendly self-repairing high-hydrophobicity wear-resistant decorative film as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of decorative films, and particularly relates to an environment-friendly self-repairing high-hydrophobicity wear-resistant decorative film as well as a preparation method and application thereof. The preparation method comprises the following steps: (1) adding an acrylic emulsion, nano titanium dioxide and modified diatomite into deionized water, and stirring at the rotating speed of 500-800rpm for 30-60 minutes to obtain a mixture; (2) adding a slow-release antibacterial agent into the mixture, stirring for 20-30 minutes at the rotating speed of 300-500 rpm, then adding fluorine-containing polymer microcapsules, and stirring for 25-35 minutes at the rotating speed of 200-400 rpm to obtain a coating; (3) the obtained coating is filtered through a filter screen of 200-300 meshes, vacuum defoaming is carried out, the vacuum degree ranges from-0.08 MPa to 0.1 MPa, and the defoaming time ranges from 10 min to 15 min; and (4) coating release paper with the defoamed coating by using a small coating machine, drying at 110-130 DEG C for 3-7 minutes, coating a layer of PVC film by using an automatic film laminating machine, and curing at 35-45 DEG C for 3 days after film laminating to obtain the decorative film. The prepared membrane is excellent in performance and wide in application prospect.

Description

Technical Field

[0001] The present invention belongs to the technical field of decorative films. More specifically, it relates to an environmentally friendly self-healing highly hydrophobic and wear-resistant decorative film, a preparation method thereof, and an application thereof. Background Art

[0002] At present, decorative films are widely used in various interior decorations and furniture finishes, but generally suffer from insufficient surface hardness and poor waterproof and anti-fouling properties. Traditional decorative films are usually based on solvent-based coatings, which can provide a certain degree of protection, but are prone to scratches under high-frequency contact, and are difficult to resist the penetration of water stains and oil stains, resulting in a significant increase in the workload of cleaning and maintenance, seriously affecting the aesthetics and durability of the decorative film.

[0003] The hardness of existing decorative film materials is generally low, and they are prone to wear and scratches when facing sharp objects or long-term friction; their waterproof and anti-fouling properties are limited, and they cannot effectively resist the attachment of pollutants, shortening the cleaning cycle and increasing the maintenance cost.

[0004] To improve the performance of decorative films, the industry has tried to add hard particles to increase wear resistance, or use fluorides to improve hydrophobicity. However, these methods often sacrifice transparency or color performance, and are not easy to produce on a large scale and conflict with environmental protection standards.

[0005] The present invention provides an environmentally friendly self-healing highly hydrophobic and wear-resistant decorative film with good surface hardness, good wear resistance, strong waterproof and anti-fouling ability, and relatively good durability and reliability. Summary of the Invention

[0006] The technical problem to be solved by the present invention is to overcome the defects and deficiencies of the prior art, and provide an environmentally friendly self-healing highly hydrophobic and wear-resistant decorative film, a preparation method thereof, and an application thereof. The preparation method includes the following steps: (1) adding acrylic emulsion, nano-titanium dioxide, and modified diatomaceous earth to deionized water, and stirring at a rotation speed of 500-800 rpm for 30-60 min to obtain a mixture; (2) then adding a sustained-release antibacterial agent to the mixture, stirring at a rotation speed of 300-500 rpm for 20-30 min, and then adding fluoropolymer microcapsules, stirring at a rotation speed of 200-400 rpm for 25-35 min to obtain a coating; (3) filtering the obtained coating through a 200-300 mesh filter screen, performing vacuum defoaming, with a vacuum degree of -0.08 to 0.1 MPa and a defoaming time of 10-15 min; (4) coating the defoamed coating on a release paper with a small coater, drying at 110-130°C for 3-7 min, then covering a layer of PVC film with an automatic laminating machine, and curing at 35-45°C for 3 days after laminating to obtain a decorative film. The prepared film has excellent performance and broad application prospects.

[0007] The object of the present invention is to provide a preparation method of an environmentally friendly self-repairing highly hydrophobic and wear-resistant decorative film.

[0008] Another object of the present invention is to provide an environmentally friendly self-repairing highly hydrophobic and wear-resistant decorative film.

[0009] Another object of the present invention is to provide a use of an environmentally friendly self-repairing highly hydrophobic and wear-resistant decorative film.

[0010] The above objects of the present invention are achieved by the following technical solutions:

[0011] A preparation method of an environmentally friendly self-repairing highly hydrophobic and wear-resistant decorative film, the preparation method comprising the following steps:

[0012] (1) Add acrylic emulsion, nano-titanium dioxide and modified diatomite to deionized water, and stir at a speed of 500 - 800 rpm for 30 - 60 min to obtain a mixture;

[0013] (2) Then add a slow-release antibacterial agent to the mixture, stir at a speed of 300 - 500 rpm for 20 - 30 min, and then add fluoropolymer microcapsules, and stir at a speed of 200 - 400 rpm for 25 - 35 min to obtain a coating;

[0014] (3) Filter the obtained coating through a 200 - 300 mesh filter screen, perform vacuum defoaming, the vacuum degree is -0.08 - 0.1 MPa, and the defoaming time is 10 - 15 min;

[0015] (4) Coat the defoamed coating on a release paper with a small coater, dry at 110 - 130 °C for 3 - 7 min, then cover with a layer of PVC film with an automatic laminating machine, and cure at 35 - 45 °C for 3 d to obtain a decorative film.

[0016] In the present invention, in a preferred scheme, between step (3) and step (4), it further includes: an aqueous solution of 0.1 - 0.5 wt% gold nanoparticles and an ethanol solution of 5 - 9 wt% dodecyl mercaptan are stirred at 30 - 50 °C for 1 - 3 h to obtain a mixed solution, 10 g of the obtained mixed solution is coated on a release paper, and then dried to constant weight at 60 °C. By self-assembly on the release paper, an ultrathin and dense functional interface is constructed to enhance the adhesion between the coating and the substrate.

[0017] In the present invention, in a preferred scheme, by weight, 60 - 80 parts of acrylic emulsion; 5 - 15 parts of nano-titanium dioxide; 5 - 10 parts of modified diatomite; 20 - 30 parts of deionized water; 0 - 3 parts of slow-release antibacterial agent; 0 - 5 parts of fluoropolymer microcapsules; the particle size of the nano-titanium dioxide is 10 - 100 nm.

[0018] In the present invention, a further preferred embodiment is that in step (1), the preparation method of the diatomaceous earth includes the following steps: adding diatomaceous earth and a silane coupling agent to ethanol, reacting at 60 - 80°C for 1 - 3 h, filtering, washing, and drying at 90 - 110°C for 2 - 4 h to obtain modified diatomaceous earth. As a filling material, the diatomaceous earth is uniformly dispersed in the coating, and a coating with a closed protective layer and excellent protective effect can be formed.

[0019] Preferably, the mass ratio of the diatomaceous earth to the silane coupling agent is 100:7 - 11; the particle size of the diatomaceous earth is 1 - 5 μm; the silane coupling agent is at least one of KH-550, KH-560, and KH-570.

[0020] In a preferred embodiment, in step (2), the fluoropolymer microcapsule is one of polytetrafluoroethylene (PTFE), fluorinated ethylene propylene copolymer (FEP), perfluoroalkoxy alkane (PFA), polyvinylidene fluoride (PVDF), and fluororubber (FKM), and the particle size is 10 - 50 μm.

[0021] In the present invention, a further more preferred embodiment is that in step (2), the preparation method of the sustained-release antibacterial agent includes: immersing 10 g of a carrier in 100 mL of a silver nitrate solution with a concentration of 2 g / mL, stirring for 30 - 50 min, and then directly drying to constant weight at 80 - 100°C to obtain the sustained-release antibacterial agent, where the carrier is silica. By adding the sustained-release antibacterial agent, bio-inspired antibacterial technology can be utilized to inhibit the growth of bacteria and prevent the accumulation of microorganisms.

[0022] In a further preferred embodiment, in step (4), the thickness of the coated film is 0.03 - 0.05 mm, and the thickness of the PVC film is 0.06 - 0.1 mm.

[0023] An environmentally friendly self-healing highly hydrophobic and wear-resistant decorative film prepared by the preparation method of an environmentally friendly self-healing highly hydrophobic and wear-resistant decorative film described above.

[0024] Application of an environmentally friendly self-healing highly hydrophobic and wear-resistant decorative film described above in the field of decoration.

[0025] The present invention has the following beneficial effects:

[0026] 1) The environmentally friendly self-healing highly hydrophobic and wear-resistant decorative film prepared by the present invention significantly improves the surface hardness of the decorative film, greatly reduces wear and scratches, and enhances the scratch resistance performance;

[0027] 2) It enhances the waterproof and anti-fouling capabilities, reduces the cleaning frequency, and simplifies the daily maintenance process;

[0028] 3) The integration of long-acting antibacterial and self-healing functions extends the service life of the decorative film and ensures hygiene and safety;

[0029] 4) The selection of environmentally friendly materials meets the requirements of sustainable development and is beneficial to ecological environment protection.

[0030] In summary, the technical solution provides a new solution with strong comprehensive protection ability and ecological friendliness for decorative materials in high-frequency contact environments. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 The preparation flow chart of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0032] The present invention will be further described below in conjunction with specific embodiments, but the embodiments do not limit the present invention in any form. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the technical field.

[0033] The solid content of the acrylic emulsion is 50 wt%, the viscosity is 2000 - 3000 mPa·s, the pH value is 8.0 - 9.0, the minimum film formation temperature (MFFT) is 15 - 20 °C, and the glass transition temperature (Tg) is 10 - 20 °C.

[0034] Unless otherwise specified, the reagents and materials used in the following examples are all commercially available.

[0035] EXAMPLE

[0036] A preparation method of an environmentally friendly self-repairing highly hydrophobic and wear-resistant decorative film, the preparation method comprising the following steps:

[0037] (1) Add acrylic emulsion, nano-titanium dioxide (the particle size of the nano-titanium dioxide is 80 nm) and modified diatomite to 25 parts of deionized water, and stir at a speed of 600 rpm for 50 min to obtain a mixture; the preparation method of the diatomite comprises the following steps: Add 100 g of diatomite with a particle size of 1 - 5 μm and 9 g of KH-560 to 150 mL of ethanol, react at 70 °C for 2 h, filter, wash, and dry at 100 °C for 3 h to obtain modified diatomite.

[0038] (2) Then, add the slow-release antibacterial agent to the mixture and stir it at a speed of 400 rpm for 25 min. Then, add the fluoropolymer microcapsules and stir at a speed of 300 rpm for 30 min to obtain the coating; the fluoropolymer microcapsules are polytetrafluoroethylene (PTFE) with a particle size of 30 μm; the preparation method of the slow-release antibacterial agent includes: impregnating 10 g of silica in 100 mL of silver nitrate solution with a concentration of 2 g / mL, stirring for 40 min, and then directly drying it to constant weight at 90 °C to obtain the slow-release antibacterial agent.

[0039] (3) Filter the obtained coating through a 200-300 mesh filter screen, perform vacuum degassing with a vacuum degree of -0.09 MPa and a degassing time of 14 min;

[0040] (4) Coat the degassed coating on the release paper with a small coater, with a coating film thickness of 0.04 mm. Dry it at 120 °C for 5 min, and then cover it with a layer of PVC film with an automatic laminating machine. The thickness of the PVC film is 0.08 mm. After laminating, cure it at 40 °C for 3 d to obtain the decorative film.

[0041] By weight, 60-80 parts of acrylic emulsion; 5-15 parts of nano-titanium dioxide; 5-10 parts of modified diatomite; 20-30 parts of deionized water; 0-3 parts of slow-release antibacterial agent; 0-5 parts of fluoropolymer microcapsules.

[0042] Examples 1-5 and Comparative Examples 1-3 are basically the same as the examples, except for the specific descriptions in Examples 1-5 and Comparative Examples 1-3.

[0043] Example 1

[0044] By weight, 70 parts of acrylic emulsion; 10 parts of nano-titanium dioxide; 5 parts of modified diatomite (diatomite particle size is 3 μm); 1 part of slow-release antibacterial agent; 0 part of fluoropolymer microcapsules.

[0045] Example 2

[0046] By weight, 70 parts of acrylic emulsion; 10 parts of nano-titanium dioxide; 5 parts of modified diatomite (diatomite particle size is 3 μm); 1 part of slow-release antibacterial agent; 3 parts of fluoropolymer microcapsules.

[0047] Example 3

[0048] By weight, 70 parts of acrylic emulsion; 10 parts of nano-titanium dioxide; 5 parts of modified diatomite (diatomite particle size is 3 μm); 0 part of slow-release antibacterial agent; 0 part of fluoropolymer microcapsules.

[0049] Example 4

[0050] By weight, 70 parts of acrylic emulsion; 10 parts of nano-titanium dioxide; 8 parts of modified diatomaceous earth (diatomaceous earth particle size is 5μm); 3 parts of slow-release antibacterial agent; 0 parts of fluoropolymer microcapsules.

[0051] Example 5

[0052] By weight, 70 parts of acrylic emulsion; 10 parts of nano-titanium dioxide; 5 parts of modified diatomaceous earth (diatomaceous earth particle size is 5μm); 3 parts of slow-release antibacterial agent; 0 parts of fluoropolymer microcapsules. Between step (3) and step (4), it also includes: mixing 10 mL of an aqueous solution of 0.3 wt% gold nanoparticles with 10 mL of an ethanol solution of 7 wt% dodecyl mercaptan, stirring at 40°C for 2 h to obtain a mixed solution, coating 10 g of the obtained mixed solution on a release paper, and then drying at 60°C to constant weight.

[0053] Comparative Example 1

[0054] By weight, 65 parts of acrylic emulsion; 15 parts of nano-titanium dioxide; 12 parts of modified diatomaceous earth (diatomaceous earth particle size is 7μm); 0.5 part of slow-release antibacterial agent; 0 parts of fluoropolymer microcapsules.

[0055] Comparative Example 2

[0056] By weight, 75 parts of acrylic emulsion; 5 parts of nano-titanium dioxide; 12 parts of modified diatomaceous earth (diatomaceous earth particle size is 7μm); 4 parts of slow-release antibacterial agent; 0 parts of fluoropolymer microcapsules.

[0057] Comparative Example 3

[0058] By weight, 75 parts of acrylic emulsion; 5 parts of nano-titanium dioxide; 4 parts of modified diatomaceous earth (diatomaceous earth particle size is 7μm); 4 parts of slow-release antibacterial agent; 1 part of graphene nano-additive is used to replace the fluoropolymer microcapsules.

[0059] Testing method:

[0060] (1) Self-healing performance test

[0061] First, place the superhydrophobic surface on a flat table, use a knife to evenly apply force perpendicular to the surface of the sample, smoothly draw a vertical cross "plus" pattern, and place it in an oven at 120°C for 30 min, and observe whether the scratch is repaired.

[0062] (2) Abrasion resistance test

[0063] Using sandpaper (1200 mesh) as the wear surface and the superhydrophobic surface as the surface to be worn, under a pressure of 12.5 kPa, pull the sample to be tested at a speed of 3 cm / s, the test distance is 15 cm, and this experimental process is repeated 20 times. After the test, measure the surface contact angle.

[0064] (3) Adhesion Test

[0065] The adhesion test adopts the cross - cut tape test method. Specifically, refer to "Cross - cut test for adhesion of paints and varnishes" (GB / T9286 - 1998). First, place the super - hydrophobic surface on a flat table. Use a cross - cut knife to apply even force perpendicular to the surface of the sample and steadily draw at least 6 parallel cutting lines. Then, draw 6 parallel lines perpendicular to the first - drawn lines at a 90° angle to form a grid pattern. It should be noted here that all cuts need to penetrate to the surface of the substrate. After cleaning the lines in the grid, apply tape in the center of the grid and ensure it is in full contact with the paint film. Lift the tape to form an angle of about 60° with the sample and continuously and steadily withdraw the tape. Then observe the peeling situation of the paint film in the grid. The corresponding adhesion grades for the number of peeled grids being 0, less than 5%, 5% - 15%, 15% - 35%, 35% - 65%, and more than 65% are grades 1 - 5 respectively.

[0066] (4) Contact Angle Test

[0067] Use a contact angle measuring instrument to measure the contact angle of the surface with water. The size of the water droplet is 5 μL, and each sample is measured 5 times, and the average value is taken.

[0068] The specific test results are shown in Table 1:

[0069] Table 1

[0070] Contact Angle / ° Contact Angle after Friction / ° Adhesion Force Whether Scratch Can Be Repaired Example 1 154.5 146.6 1 Yes Example 2 157.2 148.4 2 Yes Example 3 151.4 152.3 1 Yes Example 4 156.8 155.4 1 Yes Example 5 155.9 157.6 1 Yes Comparative Example 1 153.2 121.2 3 No Comparative Example 2 158.4 116.5 4 No Comparative Example 3 154.8 118.2 1 Yes

[0071] As can be seen from Table 1, an environmentally friendly self - healing highly hydrophobic and wear - resistant decorative film prepared by the present invention has excellent hydrophobic properties, adhesion, and the scratches can self - heal. That is, the film prepared by the present invention has excellent performance and broad application prospects.

[0072] The above - mentioned embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above - mentioned embodiments. Any other changes, modifications, substitutions, combinations, and simplifications made without departing from the spirit and principle of the present invention shall be equivalent replacement methods and are all included in the protection scope of the present invention.

Claims

1. A preparation method of an environment-friendly self-repairing highly hydrophobic and wear-resistant decorative film, characterized in that: The preparation method comprises the following steps: (1) Add acrylic emulsion, nano-titanium dioxide and modified diatomite into deionized water, and stir at a speed of 500 - 800 rpm for 30 - 60 min to obtain a mixture; (2) Then add a slow-release antibacterial agent to the mixture, stir at a speed of 300 - 500 rpm for 20 - 30 min, and then add fluoropolymer microcapsules, stir at a speed of 200 - 400 rpm for 25 - 35 min to obtain a coating; (3) Filter the obtained coating through a filter screen with 200 - 300 meshes, and perform vacuum defoaming. The vacuum degree is -0.08 - 0.1 MPa, and the defoaming time is 10 - 15 min; (4) Coat the defoamed coating on a release paper with a small coater, dry at 110 - 130 °C for 3 - 7 min, then cover a layer of PVC film with an automatic laminating machine, and cure at 35 - 45 °C for 3 d to obtain a decorative film.

2. The preparation method of the environment-friendly self-healing highly hydrophobic and wear-resistant decorative film according to claim 1, characterized in that: Between step (3) and step (4), it also includes: Mix an aqueous solution of 0.1 - 0.5 wt% gold nanoparticles and an ethanol solution of 5 - 9 wt% dodecyl mercaptan at 30 - 50 °C and stir for 1 - 3 h to obtain a mixed solution. Coat 10 g of the obtained mixed solution on a release paper, and then dry at 60 °C to constant weight.

3. The preparation method of an environmentally friendly self-healing highly hydrophobic and wear-resistant decorative film according to claim 1, characterized in that: By weight, 60 - 80 parts of acrylic emulsion; 5 - 15 parts of nano-titanium dioxide; 5 - 10 parts of modified diatomite; 20 - 30 parts of deionized water; 0 - 3 parts of slow-release antibacterial agent; 0 - 5 parts of fluoropolymer microcapsules; the particle size of the nano-titanium dioxide is 10 - 100 nm.

4. The preparation method of an environmentally friendly self-repairing highly hydrophobic and wear-resistant decorative film according to claim 1, wherein: In step (1), the preparation method of the diatomite includes the following steps: Add diatomite and a silane coupling agent into ethanol, react at 60 - 80 °C for 1 - 3 h, filter, wash, and dry at 90 - 110 °C for 2 - 4 h to obtain modified diatomite.

5. The preparation method of an environmentally friendly self-repairing highly hydrophobic and wear-resistant decorative film according to claim 4, wherein: The mass ratio of the diatomite to the silane coupling agent is 100:7 - 11; the particle size of the diatomite is 1 - 5 μm; the silane coupling agent is at least one of KH-550, KH-560, and KH-570.

6. The preparation method of an environmentally friendly self-repairing highly hydrophobic and wear-resistant decorative film according to claim 1 or 3, characterized in that: In step (2), the fluoropolymer microcapsule is one of polytetrafluoroethylene (PTFE), fluorinated ethylene propylene copolymer (FEP), perfluoroalkoxy alkane (PFA), polyvinylidene fluoride (PVDF), and fluororubber (FKM), and the particle size is 10 - 50 μm.

7. The preparation method of an environmentally friendly self-healing highly hydrophobic and wear-resistant decorative film according to claim 1, characterized in that: In step (2), the preparation method of the slow-release antibacterial agent includes: Immerse 10 g of a carrier in 100 mL of a silver nitrate solution with a concentration of 2 g / mL, stir for 30 - 50 min, and then directly dry to constant weight at 80 - 100 °C to obtain a slow-release antibacterial agent. The carrier is silica.

8. The preparation method of an environmentally friendly self-repairing highly hydrophobic and wear-resistant decorative film according to claim 1, characterized in that: In step (4), the thickness of the coated film is 0.03 - 0.05 mm, and the thickness of the PVC film is 0.06 - 0.1 mm.

9. An environmentally friendly self-repairing highly hydrophobic and wear-resistant decorative film prepared by the preparation method of an environmentally friendly self-repairing highly hydrophobic and wear-resistant decorative film according to any one of claims 1 - 8.

10. Application of an environmentally friendly self-repairing highly hydrophobic and wear-resistant decorative film according to claim 9 in the field of decoration.

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