A laminated polyolefin material with imitation wood grain effect and its preparation method and application

Abstract

The present invention discloses a laminated polyolefin material with a wood-like grain effect, its preparation method, and use. The material comprises the following components, by weight: modified material A: 30-90 parts of a copolymer, 3-15 parts of maleic anhydride-grafted polypropylene, 5-20 parts of polypropylene, 2-30 parts of a colorant, and 1-5 parts of an additive; and modified material B: 55-99 parts of a polyolefin polymer, 0-35 parts of a filler modifier, and 1-10 parts of an abrasion-resistant modifier. Modified material A is added and mixed with modified material B, followed by heating and plasticization, and then directly extruded to form a film or sheet fused with the polymer and having a pattern similar to wood grain, forming a permanent pattern. The resulting wood-like grain material has better scratch resistance and is environmentally friendly and innovative than conventional materials.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and in particular relates to a laminated polyolefin material with imitation wood grain effect, a preparation method and application thereof. Background Art

[0002] Currently, the appearance effects used in extrusion molding processing are generally achieved by adding masterbatch and mixing with polymer, and then heating and plasticizing it through specific equipment to form products with a specific and uniform color appearance effect. Often, the carrier of the masterbatch must have good compatibility and dispersion properties with the polymer resin it is mixed with to achieve a uniform appearance and color effect.

[0003] However, currently in the wallpaper industry and furniture film industry, similar imitation wood grain effects are produced by extruding a specific uniform film material and then undergoing secondary printing, coating or water transfer printing to form a film material with a specific appearance pattern. This process is complicated, and the pattern is only formed on the outermost layer of the film, which is easily scratched and smeared, and has poor adhesion. Conventional polyolefin resins have low hardness and poor lubricity. As surface materials, they are also easily scratched, affecting the appearance. Therefore, it is necessary to improve the surface scratch resistance through modification. Therefore, there is an urgent need for a polyolefin material with high wear resistance and imitation wood grain effect to meet production needs. Summary of the Invention

[0004] The embodiment of the present invention provides a laminated polyolefin material with imitation wood grain effect, wherein the modified material A comprises the following components in parts by weight: 30-90 parts of a copolymer, such as 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90 parts, preferably 50-70 parts, the melt index of the copolymer is 15-80 g / 10 min, the test standard is GB / T3682.1-2018, the test conditions are 280 ° C, 2.16 kg ; 3-15 parts of maleic anhydride grafted polypropylene, such as 3, 5, 8, 10, 12, 15 parts, preferably 5-10 parts; 5-20 parts of polypropylene, such as 5, 8, 10, 12, 15, 18, 20 parts, preferably 10-15 parts; 2-30 parts of colorant, such as 2, 5, 10, 12, 15, 20, 25, 30 parts; 1-5 parts of auxiliary agent, such as 1, 2, 3, 4, 5 parts; modified material B includes the following components in parts by weight: 55-99 parts of polyolefin polymer, such as 55 , 60, 65, 70, 75, 80, 85, 90, 95, 99 parts, preferably 60-80 parts; 0-35 parts of filler modifier, such as 0, 1, 3, 5, 10, 15, 20, 25, 30, 35 parts, preferably 20-30 parts; 1-10 parts of wear-resistant modifier, such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 parts, preferably 4-8 parts; the weight ratio of modifying material A to modifying material B is (2-10): (90-98), preferably (2-5) : (95-98), the copolymer is a copolymer of polybutylene terephthalate and polytetramethylene ether or polyethylene glycol ether or polypropylene glycol ether, a copolymer of polybutylene terephthalate and polycaprolactone or propylene alginate or polylactic acid ester, polyethylene terephthalate-1,4 cyclohexanedimethanol ester, polyurethane, any one of polycyclohexyldimethylene terephthalate, preferably a copolymer of polybutylene terephthalate and polytetramethylene ether or polyethylene glycol ether or polypropylene glycol ether.

[0005] This technical solution uses a specific copolymer and maleic anhydride grafted material, and adds a wear-resistant modifier to material B, so that the resulting material has both wood-grain imitation effects and wear resistance, while also maintaining the processing stability and mechanical properties of the film product. A polypropylene substrate is used in component A of the modified material, and maleic anhydride grafted polypropylene (PP-g-MAH) is used to enhance the melting of the polypropylene substrate so that the two have better compatibility and maintain mechanical properties; in addition, when the flow pattern is formed on the surface of the material, the PP substrate has higher hardness and scratch resistance than other types of polyolefins. The copolymer is modified by compounding with PP-g-MAH, so that the modified material A and the modified material B have sufficient compatibility after blending, while maintaining the processing stability and mechanical properties of the film product. In addition, by adding a wear-resistant modifier, the film product obtained has better scratch resistance, which expands the scope of use and durability of this type of film material, and the addition of a colorant can enhance the contrast effect of the wood grain appearance and improve the wood grain effect.

[0006] Furthermore, the wear-resistant modifier is one or more of polytetrafluoroethylene, fatty acid amide, silicon dioxide, and silicone, preferably a combination of four.

[0007] Furthermore, the polypropylene has a melt index of ≤60 g / 10 min at 230° C. and 2.16 kg according to the GB / T3682.1-2018 test standard, and preferably has a melt index of <30 g / 10 min.

[0008] Furthermore, the filler modifier is selected from one or more of calcium carbonate, talc, wollastonite, diatomaceous earth, kaolin, mica powder, glass beads, graphite, and barium sulfate. Calcium carbonate and talc are preferably compounded, and the preferred compounding ratio is (0.5-1.5):1.

[0009] Furthermore, the grafting rate of maleic anhydride in the maleic anhydride grafted polypropylene is ≤1.35%, preferably ≤1.05%; the maleic anhydride grafting rate test method is as follows: weigh about 0.5g of maleic anhydride grafted polypropylene and place it in a 250mL distillation flask, add 80mL of xylene, and heat under reflux for 30 minutes. After the grafted solvent cools, add an excess of 0.05mol / L KOH-ethanol standard solution (10mL) and heat to 80°C for 2 hours. Cool to below the boiling point of ethanol, use phenolphthalein as an indicator, and while hot, use 0.05mol / L HCL-isopropanol standard solution to backtitrate the excess KOH-ethanol standard solution, record the amount of excess alkali consumed and the amount of acid neutralized, and calculate the grafting rate according to formula (1): G MAH =9.806(V1C1-V2C2) / 2m(1);

[0010] G MAH —MAH mass fraction on 1g PP grafted material (%);

[0011] C1—concentration of KOH-ethanol standard solution mol / L;

[0012] C2—HCL-isopropanol standard solution concentration mol / L;

[0013] V1—volume of excess KOH-ethanol standard solution added (mL);

[0014] V2—volume of HCL-isopropanol standard solution consumed by back titration and alkali neutralization (mL);

[0015] m—mass of the refined grafted sample in g.

[0016] Furthermore, the weight ratio of the copolymer to the maleic anhydride grafted polypropylene is (2-30):1, preferably (5-10):1.

[0017] Furthermore, the polyolefin polymer is any one or more of polyethylene, polypropylene or POE, preferably any one or more of polyethylene or polypropylene.

[0018] Furthermore, the melt index of the polyolefin polymer is ≤64 g / 10 min, preferably <20 g / 10 min, and the melt index is tested according to the test standard of GB / T3682.1-2018 at 230° C. and 2.16 kg.

[0019] Furthermore, the weight ratio of the total weight of polytetrafluoroethylene, silicon dioxide and silicone in the wear-resistant modifier to the fatty acid amide is 3:(0.5-1.5).

[0020] Furthermore, the sphericity of the silicon dioxide is greater than 95%, and the testing standard is GB / T32661-2016.

[0021] Furthermore, the auxiliary agent includes an antioxidant and a dispersant.

[0022] Furthermore, the dispersant includes at least one of polyethylene wax, polyester wax, amide wax, modified ethylene wax or stearate.

[0023] Furthermore, the colorant is one or more of an inorganic pigment, an organic pigment, a metallic effect pigment, or a fluorescent dye. The inorganic pigment may be an inorganic metal oxide, such as iron yellow, iron red, titanium yellow, ultramarine, etc. The organic pigment may be phthalocyanine, condensed azo, isoindolinone, pyrrolopyrrole, etc. The metallic effect pigment may be metallic aluminum powder, pearlescent pigment, etc.

[0024] The present invention also provides a method for preparing the polyolefin material, comprising the following steps:

[0025] S1: Weigh each component of modified material A according to parts by weight, stir and mix them evenly in a high-speed mixer, transfer them to a continuous plasticizing and mixing equipment with a plasticizing temperature of 240-270°C for plasticization and uniform dispersion, extrude them into strips, and pelletize them after sufficient cooling to obtain modified material A;

[0026] S2: Weigh each component of modified material B according to parts by weight, stir and mix them evenly in a high-speed mixer, and transfer them to a continuous plasticizing and mixing equipment with a plasticizing temperature of 200-230°C for plasticization and uniform dispersion, extrude them into strips, and pelletize them after sufficient cooling to obtain modified material B;

[0027] S3: mixing modified material A and modified material B according to the mixing ratio or adding them to an extruder having a die shape, heating and melting them, plasticizing and laminating them to obtain the laminated polyolefin material with imitation wood grain effect;

[0028] The speed of the high-speed mixer is 800-1200 r / min, and the stirring time is 200-300 seconds.

[0029] Modified material A and modified material B are compounded and plasticized by heating and then directly extruded to form a film material that is integrated with the polymer and has a pattern similar to imitation wood. This not only eliminates the complicated process of printing and coating, but is also energy-saving and environmentally friendly. The formed pattern will not disappear due to scratching and smearing, forming a permanent pattern. The formed pattern texture has a unique effect that cannot be replicated, and has good uprightness and durability as well as environmental protection and innovation.

[0030] The present invention also provides the use of the polyolefin material in preparing extrusion cast film materials, sheets, extrusion pipe materials or extrusion profiles.

[0031] In summary, compared with the prior art, the present invention achieves the following technical effects:

[0032] (1) The polyolefin material provided by the present invention has a good imitation wood grain appearance, a smooth surface and uniform color distribution;

[0033] (2) The polyolefin material provided by the present invention has excellent scratch resistance;

[0034] (3) The scratch-resistant polyolefin material provided by the present invention has both mechanical properties and a high tensile strength retention rate. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 This is a wood grain effect diagram of Example 1 of the present invention.

[0036] Figure 2 This is a wood grain effect diagram of comparative example 1 of the present invention. DETAILED DESCRIPTION

[0037] In order to enable those skilled in the art to better understand the solutions of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention and the comparative examples.

[0038] Example

[0039] The present invention is further described below with reference to specific examples and comparative examples. The following specific examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the following examples, and are particularly not limited to the types of the various component raw materials used in the following specific examples.

[0040] 1. The sources of raw materials for the embodiments and comparative examples are as follows:

[0041] Copolymer #1: polybutylene terephthalate copolymer with polytetramethylene ether, H63DMG, copolymer, Hechuang Technology;

[0042] Copolymer #2: polyethylene terephthalate-1,4-cyclohexanedimethanol, JN200, copolymer, SK, Korea;

[0043] Copolymer #3: Polyurethane, TPU C90A, copolymer, BASF, Germany;

[0044] Homopolymer #4: Polycarbonate, PC K1300, homopolymer, Teijin, Japan;

[0045] PP-g-MAH#1: Maleic anhydride grafted polypropylene, PC-1, grafting rate 0.8-1.05%, Nanhai Baichen Polymer Materials;

[0046] PP-g-MAH#2: Maleic anhydride grafted polypropylene, AD-105, grafting rate 1.05-1.35%, Nanhai Baichen Polymer Materials;

[0047] Polypropylene #1: PP Z30S, melt index 25g / 10min, Sinopec;

[0048] Polypropylene #2: PP HP740T, melt index 60 g / 10 min, Basel;

[0049] Colorant: Iron oxide red, 120M, Bayer;

[0050] Additives: Antioxidant 1010, Beijing Tiangang;

[0051] Dispersant 1105A, Mitsui;

[0052] Polyolefin polymer #1: polyethylene, HDPE 5000S, melt index 1 g / 10 min; Sinopec;

[0053] Polyolefin polymer #2: polypropylene, PP M60T, melt index 64 g / 10 min, Sinopec;

[0054] Polyolefin polymer #3: polyolefin elastomer, POE 6202, melt index 9 g / 10 min, ExxonMobil;

[0055] Filling modifier: talc, HS778, Guangyuan Chemical;

[0056] Calcium carbonate, HS-2500, Guangyuan Chemical;

[0057] Wear-resistant modifier: silicone masterbatch, HY100POE, Dongguan Huiyi Chemical;

[0058] Polytetrafluoroethylene micropowder, F330, Hefei Qihong Polymer;

[0059] Fatty acid amide, WK1890, Jiangxi Weike;

[0060] Silica #1: VK-SP30T, 97% sphericity, Jingrui New Materials;

[0061] Silica #2: RD60, sphericity less than 10%, Jiangsu Jinyi New Materials Co., Ltd.

[0062] The preparation method of the polyolefin material of the embodiment of the present invention and the comparative example comprises the following steps:

[0063] S1: Weigh each component of modified material A according to parts by weight, stir and mix them evenly in a high-speed mixer, transfer them to a continuous plasticizing and mixing equipment with a plasticizing temperature of 240-270°C for plasticization and uniform dispersion, extrude them into strips, and pelletize them after sufficient cooling to obtain modified material A;

[0064] S2: Weigh each component of modified material B according to parts by weight, stir and mix them evenly in a high-speed mixer, and transfer them to a continuous plasticizing and mixing equipment with a plasticizing temperature of 200-230°C for plasticization and uniform dispersion, extrude them into strips, and pelletize them after sufficient cooling to obtain modified material B;

[0065] S3: Mixing modified material A and modified material B according to the mixing ratio or adding them to an extruder having a die shape, heating and melting, plasticizing and laminating to obtain a product with a wood grain appearance pattern; wherein the speed of the mixer is 800-1200 r / min, and the stirring time is 200-300 seconds;

[0066] Examples 16-17 and Comparative Example 2 use the component formula of Example 1, except that the ratio of modified materials A and B is different from that of Example 1.

[0067] 2. Various performance test methods

[0068] (1) Imitation wood grain appearance test: Multiple testers visually judge the texture uniformity, obviousness, surface appearance, etc. to comprehensively evaluate the appearance effect. The specific method is: 4 testers judge the imitation wood grain appearance effect and take the average value; the evaluation criteria are:

[0069] Level 0: The film has a completely uniform color and no texture pattern effect, or the film is severely damaged or has poor film-forming properties;

[0070] Level 1: Imitation wood grain appearance is unqualified, the film surface has a texture pattern but it is uneven or there are obvious holes or blocky unmelted matter;

[0071] Level 1.5: The imitation wood grain has a flawed appearance. The texture pattern can be formed, but there are obvious crystal points and fish eyes, and the thickness uniformity is obviously beyond the range.

[0072] Level 2: The imitation wood grain appearance is acceptable, the film's crystal points, fish eyes, and thickness uniformity are all under control, but the texture uniformity is poor;

[0073] Level 2.5: good imitation wood grain appearance, good overall membrane surface appearance, poor control of grain size;

[0074] Level 3: Excellent imitation wood grain effect, flawless film appearance, uniform and aesthetically pleasing texture.

[0075] (2) Film thickness fluctuation test: The thickness of the film in the transverse direction is measured at multiple points using a thickness gauge (micrometer screw, Deli brand): 10 test points are equally spaced in the transverse direction of the film and the thickness value of each point is measured. The thickness fluctuation of each point is then calculated by calculating the difference between the thickness value of each point and the arithmetic mean of the accumulated 10 points, i.e., film thickness fluctuation = ((D n -D 平 )) / D 平 )*100%, and then analyze the thickness fluctuation range.

[0076] (3) Film tensile strength retention test: The tensile strength performance of the film material prepared by adding modified material A and modified material B is compared with that of the film material made by modified material B. Strength retention = (tensile strength (添加改性材料A+B) / Tensile Strength 改性材料B )*100%, wherein the tensile strength performance can be measured by electronic universal testing machine EUT5000 (Shenzhen Sansi), and the testing standard is implemented according to ISO527-3-2012.

[0077] (4) Scratch resistance test: The scratch test was conducted using the Volkswagen PV3952-2002 test method. The CIELAB DE value of the color difference before and after the sample was scratched was measured. The smaller the DE, the better the scratch resistance. Generally, DE < 3 indicates good scratch resistance.

[0078] Table 1. Example components (parts by weight)

[0079]

[0080] Table 1 continued. Example components (parts by weight)

[0081]

[0082]

[0083] Table 2. Performance test of examples (Examples 1-15 modified material A: modified material B = 4:96)

[0084]

[0085] Table 2 continued. Example performance test (Example 16 modified material A: B = 2:98; Example 17 modified material A: B = 10:90)

[0086]

[0087] Table 3. Comparative Examples Components and Effects (Parts by Weight) (Comparative Example 2 Modified Material A:B = 20:80, Other Comparative Examples Modified Material A:B = 4:96)

[0088]

[0089]

[0090] Comparative Examples 1-5 are compared with Example 1. In Comparative Example 1, no maleic anhydride grafted polypropylene is added, resulting in a polarity difference between the copolymer and the polyolefin resin. The two still have phase separation in the molten state, resulting in the inability to achieve good compatibility after the modified material A is added to the modified material B, resulting in film delamination, uneven thickness and even perforation. Figure 2As shown; in Comparative Example 2, modified material A: modified material B = 20:80. Since the modified material A is added in too much proportion, a homogenized phase is formed, and a good contrast cannot be formed, resulting in unclear texture; in Comparative Example 3, no wear-resistant modifier is added, and the scratch resistance is significantly reduced; in Comparative Example 4, no modified material B is added, and only the modified material A component is extruded to form a film. Since it is extruded and homogenized to form a uniform modified material, the prepared film is also a uniform modified material film, which cannot form a good flow effect; and in Comparative Example 5, the polymer added is a homopolymer, which makes it impossible for the polymer to be well compounded with maleic anhydride grafted polypropylene, resulting in reduced mechanical properties. At the same time, due to the problem of film uniformity, the wear resistance is poor; Comparative Example 6 is compared with Example 15. Too much wear-resistant modifier is added, the content of silicone masterbatch is too high, there is a heterogeneous stratification phenomenon, and the film thickness fluctuates. In addition, the silicone masterbatch is concentrated on the surface of the film. Although the scratch performance is improved, there is stratification and peeling from the main substrate, which affects the mechanical properties of the material. The above comparative examples are unable to achieve a good imitation wood grain appearance effect and maintain the scratch resistance of the material while having good mechanical properties.

[0091] Based on the test data of the imitation wood grain appearance effect, film thickness fluctuation, film tensile strength retention and scratch resistance in Tables 2 and 3, the polyolefin materials prepared by Examples 1-17 can achieve a good imitation wood grain appearance effect while ensuring production and processing molding performance. The imitation wood grain effect reaches level 2 or above, the film thickness fluctuation range is within ±6%, and the material can maintain good scratch resistance and mechanical properties. The film tensile strength retention rate is 85% or above, and the scratch resistance performance is within DE 3 or less. Compared with the comparative example, it has obvious advantages and can effectively meet the high standards of customers and the market.

[0092] The above embodiments are merely examples for clarity of explanation and are not intended to limit the embodiments. Those skilled in the art will appreciate that other variations or modifications can be made based on the above descriptions, such as changes in the formulation color, the shape of the extruded product, and the lamination combination. It is not necessary and impossible to enumerate all the embodiments here, and obvious variations or modifications derived therefrom remain within the scope of protection of the present invention.

Claims

1. A polyolefin material, characterized in that: The modified material A comprises the following components in parts by weight: 30-90 parts of a copolymer, 3-15 parts of maleic anhydride grafted polypropylene, 5-20 parts of polypropylene, 2-30 parts of a colorant, and 1-5 parts of an additive; the modified material B comprises the following components in parts by weight: 55-99 parts of a polyolefin polymer, 0-35 parts of a filler modifier, and 1-10 parts of a wear-resistant modifier; wherein the weight ratio of the modified material A to the modified material B is (2-10):(90-98), and the copolymer is any one of a copolymer of polybutylene terephthalate and polytetramethylene ether, polyethylene terephthalate-1,4-cyclohexanedimethanol ester, and polyurethane.

2. The polyolefin material according to claim 1, characterized in that The wear-resistant modifier is one or more of polytetrafluoroethylene, fatty acid amide, silicon dioxide and silicone.

3. The polyolefin material according to claim 1, characterized in that The wear-resistant modifier is a compound of polytetrafluoroethylene, fatty acid amide, silicon dioxide and silicone.

4. The polyolefin material according to claim 1, characterized in that The melt index of the polypropylene is ≤60 g / 10 min, and the melt index is tested according to the GB / T3682.1-2018 test standard at 230° C. and 2.16 kg.

5. The polyolefin material according to claim 1, characterized in that The filler modifier is selected from any one or more of calcium carbonate, talc, wollastonite, diatomaceous earth, kaolin, mica powder, glass beads, graphite, and barium sulfate.

6. The polyolefin material according to claim 5, characterized in that The filling modifier is selected from a compound of talc and calcium carbonate.

7. The polyolefin material according to claim 6, characterized in that The compounding ratio of the talc powder to calcium carbonate is (0.5-1.5):

1.

8. The polyolefin material according to claim 1, characterized in that The grafting rate of maleic anhydride in the maleic anhydride grafted polypropylene is ≤1.35%.

9. The polyolefin material according to claim 1, characterized in that The weight ratio of the copolymer to the maleic anhydride grafted polypropylene is (5-10):

1.

10. The polyolefin material according to claim 1, characterized in that: The polyolefin polymer is any one or more of polyethylene, polypropylene or POE.

11. The polyolefin material according to claim 1, characterized in that: The melt index of the polyolefin polymer is ≤64 g / 10 min, and the melt index is tested at 230° C. and 2.16 kg in accordance with the test standard of GB / T3682.1-2018.

12. The polyolefin material according to claim 2, characterized in that: The weight ratio of the total weight of polytetrafluoroethylene, silicon dioxide and silicone in the wear-resistant modifier to the fatty acid amide is 3:(0.5-1.5).

13. The method for preparing a polyolefin material according to any one of claims 1 to 12, characterized in that: The steps include: S1: Weigh each component of modified material A according to parts by weight, stir and mix them evenly in a blender, transfer them to a continuous plasticizing and mixing equipment for plasticization and uniform dispersion, extrude them into strips, and pelletize them after sufficient cooling to obtain modified material A; S2: Weigh each component of modified material B according to parts by weight, stir and mix them evenly in a blender, transfer them to a continuous plasticizing and mixing device for plasticization and uniform dispersion, extrude them into strips, and pelletize them after sufficient cooling to obtain modified material B; S3: mixing modified material A and modified material B according to the mixing ratio or adding them into a molding extrusion device with a die shape, heating and melting, plasticizing and laminating to obtain the laminated polyolefin material with imitation wood grain effect.

14. Use of the polyolefin material according to any one of claims 1 to 12 in extruded cast films, sheets, extruded pipes or extruded profiles.

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