PVC (polyvinyl chloride) film as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of high-molecular compounds, and particularly relates to a PVC film as well as a preparation method and application thereof. The PVC film is prepared from PVC resin, a polyolefin elastomer, fumed silica, a flame retardant, dicumyl peroxide and a plasticizer. The preparation method comprises the following steps: S1, mixing and stirring a polyolefin elastomer and PVC resin to obtain a resin mixture; s2, adding dicumyl peroxide and fumed silica into the resin mixture, and stirring to obtain a mixture; s3, mixing and stirring a flame retardant, a plasticizer, a light stabilizer, an ultraviolet diluent and an antioxidant to obtain an auxiliary mixture; s4, adding the auxiliary agent mixture into the mixed material, and continuously stirring to obtain a material; and S5, carrying out tape casting extrusion or calendaring on the material to form a film. Compared with the prior art, the PVC film disclosed by the invention is good in flame retardant property and excellent in mechanical property, and the prepared PVC decorative sheet is good in color persistence and not easy to fade.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer compounds, and in particular relates to a PVC film and a preparation method and application thereof. Background Art

[0002] PVC decorative sheets are made of PVC resin, plasticizer, stabilizer, filler and processing agent as main raw materials. They are made by formula design and calendering or extrusion molding, and are printed with various patterns on the surface. They can be coated on the surface of wood, steel, aluminum, ceiling or other substrates. PVC decorative sheets are widely used in various fields because of their light weight, heat insulation, thermal insulation, moisture resistance, flame retardancy, simple construction and high decorativeness. They are one of the most widely used decorative materials in plastic materials.

[0003] PVC decorative sheet mainly includes PVC base film, pattern printing layer and surface layer, among which the surface layer is mainly used to protect the pattern printing layer and increase the hardness of the material, thereby improving the durability of the product.

[0004] CN107513233A discloses a matte PVC decorative film that can reduce the brightness of the product surface. The film is made of the following components by weight: 100-120 parts of PVC resin powder, 15-100 parts of matting powder, 8-12 parts of calcium powder, 3-5 parts of hand feeling agent, 0.3-0.5 parts of titanium dioxide, 20-30 parts of plasticizer, 3-3.5 parts of barium zinc stabilizer, 0.2-0.4 parts of internal lubricant, 2-4 parts of processing aid, and 1-2 parts of anti-fouling agent. Compared with the existing matte PVC decorative film, the invention has better anti-fouling performance and effectively improves the problem of poor anti-fouling performance of traditional PVC decorative film.

[0005] CN114539737A discloses a PET laminating layer and a preparation method thereof, and a PVC composite decorative sheet, wherein the PET laminating layer comprises 60-70 parts by weight of PET resin and 10-15 parts of an anti-fingerprint composition, wherein the anti-fingerprint composition is a mixture of fluorosilane-modified phenolic resin, pectin and vegetable oil, and the mass ratio of the fluorosilane-modified phenolic resin, pectin and vegetable oil is (2-4):(0.3-0.5):1. The fluorosilane-modified phenolic resin is prepared by hydrolyzing a fluorosilane compound and reacting it with a phenolic resin to form a polymer, and then adding silica sol and mixing evenly. The PET laminating layer is prepared by mixing PET resin, polyetheretherketone, nano glass microspheres, an anti-fingerprint composition, a lubricant, a flame retardant and a defoaming agent evenly, and then extruding and stretching it into a film to obtain a PET laminating layer. The above-mentioned PET laminating layer is used to prepare a PVC composite decorative sheet, thereby improving the disadvantage of residual fingerprints in the PVC composite decorative sheet.

[0006] Although the above invention patent has improved the surface layer, the PVC film still has the problem of poor aging and yellowing resistance. After long-term use, the surface of the PVC decorative sheet will turn yellow, making the PVC decorative sheet no longer able to play a decorative role, greatly reducing the service life of the PVC decorative sheet. Summary of the invention

[0007] The present invention aims at the problems existing in the prior art and provides a PVC film and a preparation method and application thereof. The PVC film of the present invention has good aging and yellowing resistance, and solves the problem of surface aging and yellowing of PVC decorative sheets after long-term use.

[0008] To achieve the above purpose, the technical solution adopted by the present invention is as follows:

[0009] In a first aspect, the present invention provides a PVC film comprising a PVC resin, a polyolefin elastomer, fumed silica, a flame retardant, dicumyl peroxide and a plasticizer.

[0010] Preferably, the mass ratio of the PVC resin, the polyolefin elastomer, the fumed silica, the flame retardant, the dicumyl peroxide and the plasticizer is 100:5-10:2-5:2-5:0.1-1:40-50.

[0011] In the present invention, the polyolefin elastomer is polyolefin elastomer POE, the flame retardant is magnesium hydroxide, and the plasticizer is tributyl citrate.

[0012] In some embodiments, the PVC film further comprises at least one of a light stabilizer, a UV diluent, and an antioxidant.

[0013] Preferably, the PVC film comprises, by weight, 0.1-0.4 parts of light stabilizer, 0.1-0.5 parts of UV diluent and 0.3-0.5 parts of antioxidant.

[0014] In the present invention, the light stabilizer is bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, the ultraviolet absorber is 2-hydroxy-4-n-octyloxybenzophenone, and the antioxidant is β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate.

[0015] In some embodiments, the PVC film comprises the following components, by weight: 100 parts of PVC resin, 5-10 parts of polyolefin elastomer, 2-5 parts of fumed silica, 2-5 parts of flame retardant, 0.1-1 part of dicumyl peroxide, 40-50 parts of plasticizer, 0.1-0.4 part of light stabilizer, 0.1-0.5 part of UV diluent and 0.3-0.5 part of antioxidant.

[0016] In a second aspect, the present invention provides a method for preparing the aforementioned PVC film, comprising the following steps:

[0017] S1, mixing a polyolefin elastomer and a PVC resin according to a certain proportion to obtain a resin mixture;

[0018] S2, adding dicumyl peroxide and fumed silica to the resin mixture obtained in step S1 and stirring to obtain a mixture;

[0019] S3, mixing and stirring the flame retardant, plasticizer, light stabilizer, ultraviolet diluent and antioxidant to obtain an additive mixture;

[0020] S4, adding the auxiliary agent mixture obtained in step S3 to the mixed material obtained in step S2, and continuing stirring to obtain a material;

[0021] S5: Casting, extruding or calendering the material obtained in step S4 into a film to obtain the PVC film.

[0022] In a third aspect, the present invention further provides a PVC decorative sheet, comprising a PVC base film, a printing layer located on one side of the PVC base film, and a PVC face mask located on one side of the printing layer, wherein the PVC face mask is the aforementioned PVC film.

[0023] In a fourth aspect, the present invention provides use of the above-mentioned PVC film or PVC decorative sheet in decoration engineering.

[0024] In a fifth aspect, the present invention provides an ornament comprising the above-mentioned PVC film or PVC decorative sheet.

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] (1) The PVC film of the present invention has good flame retardancy and excellent mechanical properties, and the prepared PVC decorative sheet has good color durability and is not easy to fade.

[0027] (2) Experiments have shown that, in the technical solution claimed in the present invention, the addition of fumed silica having an oil absorption value of 310-340 mL / 100 g can prevent the prepared PVC decorative sheet from fading and turning yellow, thereby improving the aging and yellowing resistance of the PVC film. DETAILED DESCRIPTION

[0028] The present invention is described below through specific embodiments to make the technical solution of the present invention easier to understand and grasp, but the present invention is not limited thereto, and the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments.

[0029] The endpoints and any value of the scope disclosed in this article are not limited to the accurate scope or value, and these scopes or values ​​should be understood to include values ​​close to these scopes or values. For numerical ranges, between the endpoint values ​​of each scope, between the endpoint values ​​of each scope and a separate point value, and between separate point values, one or more new numerical ranges can be combined with each other, and these numerical ranges should be considered as specifically disclosed in this article. Unless the context clearly indicates otherwise, the singular form "one", "a kind of" and "described" as used herein include singular and plural indicators. The numerical range described by the endpoint is included in all numerical values ​​and fractions within the corresponding range, as well as the described endpoint.

[0030] Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work should fall within the scope of protection of the present invention. The experimental methods described in the following embodiments are conventional methods unless otherwise specified; the reagents and materials described are commercially available unless otherwise specified.

[0031] The fumed silica in this embodiment is hydrophobic fumed silica with a specific surface area of ​​110±20 m 2 / g, oil absorption value is 310-340mL / 100g, water content is ≤0.7% (2 hours at 105°C), and the flame retardant is magnesium hydroxide.

[0032] Examples 1-3 and Comparative Examples 1-3

[0033] The PVC film was prepared according to the formulation in Table 1 and the following preparation method.

[0034] Preparation method:

[0035] S1, mixing a polyolefin elastomer, a PVC resin, dicumyl peroxide, and fumed silica in proportion to obtain a resin mixture;

[0036] S2, blending the resin mixture obtained in step S1 at 170° C. for 10 min to obtain a mixture;

[0037] S3, mixing and stirring the flame retardant, plasticizer, light stabilizer, ultraviolet diluent and antioxidant to obtain an additive mixture;

[0038] S4, adding the auxiliary agent mixture obtained in step S3 to the mixed material obtained in step S2, and blending at 180° C. for 15 min to obtain a material;

[0039] S5: Calendering the material obtained in step S4 into a film to obtain the PVC film.

[0040] Table 1 Formula of PVC film of Examples 1-3 and Comparative Examples 1-3 (Unit: parts by weight)

[0041] Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 PVC resin 100 100 100 107 80 100 Polyolefin elastomer 5 10 7 / 27 7 Fumed Silica 2 5 3 / 10 3* Flame retardants 2 5 3 3 3 3 Dicumyl peroxide 0.1 1 0.5 0.5 0.5 0.5 Plasticizers 40 50 45 48 38 45 Light Stabilizer 0.2 0.2 0.2 0.2 0.2 0.2 UV Dilution 0.3 0.3 0.3 0.3 0.3 0.3 Antioxidants 0.4 0.4 0.4 0.4 0.4 0.4

[0042] Note: 1. " / " in the table means the added amount is zero;

[0043] 2. “*” in the table indicates fumed silica, with a specific surface area of ​​110±20m 2 / g, oil absorption value is 210-240mL / 100g, water content ≤0.7% (2 hours at 105℃).

[0044] Example 4 PVC decorative film

[0045] The preparation method of the PVCZ decorative film is as follows:

[0046] (1) Texture printing: PVC film is used as a carrier, and the ink penetrates into the PVC film under pressure during printing;

[0047] (2) Drying: The printed PVC film is dried at 50-70°C;

[0048] (3) Compounding: Compounding the dried PVC film with the release paper coated with glue.

[0049] The sample (thickness 2.5 mm) prepared in Example 4 was pasted on a substrate with a combustion performance of Class A1, and the substrate was installed close to the backing plate. Both the substrate and the backing plate were calcium silicate boards with a thickness of 12 mm and a density of 900 kg / m3. The combustion performance was tested, and the results are shown in Table 2.

[0050] Table 2

[0051]

[0052] This indicates that the PVC film prepared by the present invention has good flame retardant properties.

[0053] The mechanical properties of the sample prepared in Example 4 were investigated according to QB / T2028-1994 "Soft polyvinyl chloride decorative film (sheet)". The results are shown in Table 3.

[0054] Table 3

[0055]

[0056] The results show that the PVC film prepared by the present invention has good mechanical properties. By comparing Comparative Examples 1 and 2, it can be seen that when the amount relationship of PVC resin, polyolefin elastomer and fumed silica is changed, the effect on the prepared PVC film is greater, and the right-angle tear strength of Comparative Examples 1 and 2 is lower than 40 MPa.

[0057] The sample prepared in Example 4 was left for 6 months and its yellowing was investigated. The results are shown in Table 4.

[0058] Yellowing Example 1 Bright colors, no yellowing Example 2 Bright colors, no yellowing Example 3 Bright colors, no yellowing Comparative Example 1 Fading, yellowing Comparative Example 3 Fading, yellowing

[0059] The results show that the PVC film prepared by the present invention has good adhesion, and the prepared PVC decorative sheet has good color durability and is not easy to fade. Comparison of Comparative Examples 1 and 3 shows that in the technical solution claimed by the present invention, adding fumed silica with an oil absorption value of 310-340 mL / 100 g can prevent the prepared PVC decorative sheet from fading and yellowing, thereby improving the aging and yellowing resistance of the PVC film.

[0060] Finally, it should be noted that the above content is only used to illustrate the technical solution of the present invention, rather than to limit the scope of protection of the present invention. Simple modifications or equivalent substitutions of the technical solution of the present invention by ordinary technicians in this field do not deviate from the essence and scope of the technical solution of the present invention.

Claims

1. A PVC film, characterized in that: It includes PVC resin, polyolefin elastomer, fumed silica, flame retardant, dicumyl peroxide and plasticizer.

2. The PVC film according to claim 1, characterized in that The mass ratio of the PVC resin, the polyolefin elastomer, the fumed silica, the flame retardant, the dicumyl peroxide and the plasticizer is 100:5-10:2-5:2-5:0.1-1:40-50.

3. The PVC film according to claim 1, characterized in that The polyolefin elastomer is polyolefin elastomer POE, and the plasticizer is tributyl citrate.

4. The PVC film according to claim 1, characterized in that Also included is at least one of a light stabilizer, an ultraviolet diluent, and an antioxidant.

5. The PVC film according to claim 4, characterized in that The invention comprises the following components by weight: 100 parts of PVC resin, 5-10 parts of polyolefin elastomer, 2-5 parts of fumed silica, 2-5 parts of flame retardant, 0.1-1 parts of dicumyl peroxide, 40-50 parts of plasticizer, 0.1-0.4 parts of light stabilizer, 0.1-0.5 parts of ultraviolet diluent and 0.3-0.5 parts of antioxidant.

6. The PVC film according to claim 4, characterized in that The light stabilizer is bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, the ultraviolet absorber is 2-hydroxy-4-n-octyloxybenzophenone, and the antioxidant is β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate octadecyl alcohol.

7. The method for preparing a PVC film according to any one of claims 1 to 6, characterized in that: The steps include: S1, mixing a polyolefin elastomer and a PVC resin according to a certain proportion to obtain a resin mixture; S2, adding dicumyl peroxide and fumed silica to the resin mixture obtained in step S1 and stirring to obtain a mixture; S3, mixing and stirring the flame retardant, plasticizer, light stabilizer, ultraviolet diluent and antioxidant to obtain an additive mixture; S4, adding the auxiliary agent mixture obtained in step S3 to the mixed material obtained in step S2, and continuing stirring to obtain a material; S5: The material obtained in step S4 is cast, extruded or calendered into a film to obtain the PVC film.

8. A PVC decorative sheet, comprising a PVC base film, a printing layer located on one side of the PVC base film, and a PVC face film located on one side of the printing layer, characterized in that: The PVC facial mask is the PVC film described in any one of claims 1-6.

9. Use of the PVC film according to any one of claims 1 to 6 or the PVC decorative sheet according to claim 8 in decorative engineering.

10. A kind of ornament, characterized in that: A PVC film comprising the PVC film according to any one of claims 1 to 6.

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