A laminated wood-like polyolefin material and a method for its production and use

Abstract

The application discloses a kind of laminated wood grain polyolefin materials and its preparation method and application.The laminated wood grain polyolefin material includes modified material A and modified material B;The modified material A includes the following components by weight parts: copolymer 30-90 parts, maleic anhydride grafting polyethylene 3-15 parts, polyolefin resin 5-20 parts, colorant 2-30 parts, auxiliary agent 1-5 parts;The modified material B includes the following components by weight parts: polyolefin resin 80-100 parts, filling modifier 10-35 parts, anti-aging agent 0.2-2 parts;The mass ratio of modified material A and modified material B is (2-10) :(90-98).The wood grain effect of polyolefin material of the application is good, not easy to fade, strong stability, strong anti-aging performance, production process is simple, strong adhesion is not easy to be wiped off, good durability, high tensile strength retention rate after xenon lamp irradiation.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, and particularly relates to a laminated wood grain imitation polyolefin material, its preparation method and application. Background Technology

[0002] Extrusion molding is a simple, economical, and efficient technology widely used in the manufacturing of plastic products. Currently, the appearance achieved through extrusion molding is generally achieved by mixing masterbatch with polymers and then heating and plasticizing the mixture using specific equipment to create products with a uniform color and appearance. Special molds or surface treatment techniques are typically used during extrusion to give the plastic products a wood-like texture and feel. However, these surface treatment methods may affect the composition and structure of the material surface, influencing the distribution and effectiveness of anti-aging agents, thus impacting the overall anti-aging performance. Furthermore, traditional anti-aging agents can easily alter the optical properties of the material, affecting the clarity and realism of the texture and conflicting with the wood grain effect.

[0003] Therefore, there is an urgent need for a polyolefin material with excellent anti-aging properties and a good wood grain effect to meet consumers' demand for high-quality and durable products. Summary of the Invention

[0004] To address the shortcomings of existing technologies, this invention proposes a laminated wood-grain-like polyolefin material, its preparation method, and its applications.

[0005] This invention provides a polyolefin material, comprising modified material A and modified material B;

[0006] The modified material A, by weight, comprises the following components: 30-90 parts of copolymer, preferably 50-70 parts; 3-15 parts of maleic anhydride-grafted polyethylene, preferably 5-10 parts; 5-20 parts of polyolefin resin, preferably 10-15 parts; 2-30 parts of colorant; and 1-5 parts of additives.

[0007] The modified material B, by weight, comprises the following components: 80-100 parts of polyolefin resin, 10-35 parts of filler modifier, and 0.2-2 parts of anti-aging agent.

[0008] The anti-aging agent includes a composition of ultraviolet absorbers, light stabilizers, and antioxidants;

[0009] The mass ratio of modified material A to modified material B is (2-10):(90-98).

[0010] Furthermore, the ultraviolet absorber is one or more of the following: triazine-structured compounds, benzoxazinone-structured compounds, benzophenone-structured compounds, benzotriazole-structured compounds, oxalamide-structured compounds, and cyanoacrylate-structured compounds.

[0011] Furthermore, the light stabilizer is one of the hindered amine structure light stabilizers and the hindered benzoic acid ester structure light stabilizers.

[0012] Furthermore, the antioxidant is one of hindered phenolic antioxidants, thiobisphenol antioxidants, amine antioxidants, phosphite antioxidants, and thioester antioxidants.

[0013] Furthermore, the total mass ratio of the ultraviolet absorber and the light stabilizer to the antioxidant is 1:(0.1-5), preferably 1:(0.3-3).

[0014] Furthermore, the melting points of the ultraviolet absorber, light stabilizer, and antioxidant are all greater than 100°C, preferably 105–230°C. Using ultraviolet absorbers, light stabilizers, and antioxidants with melting points greater than 100°C provides better stability and reduces the occurrence of failure phenomena such as migration and blooming of the additives.

[0015] Furthermore, the weight ratio of the copolymer to maleic anhydride-grafted polyethylene (PE-g-MAH) is (5-30):1, preferably (8-16):1.

[0016] Further, the copolymer is any one or more of polybutylene terephthalate and polytetrahydrofuran ether or polyethylene glycol ether or polypropylene glycol ether, polybutylene terephthalate and polycaprolactone or propylene glycol alginate or polylactic acid ester, polyethylene glycol terephthalate-1,4-cyclohexanediol ester and polyurethane, preferably a copolymer of polybutylene terephthalate and polytetrahydrofuran ether or polyethylene glycol ether or polypropylene glycol ether.

[0017] Furthermore, the polyolefin resin comprises a polymer formed by copolymerization of one or more monomers of ethylene, butene, hexene, and octene; the melt index of the polyolefin resin is ≤64g / 10min, preferably 0.4~20g / 10min (190℃, 2.16kg), and the test standard is GB / T 3682.1-2018.

[0018] Furthermore, the colorant is one or more compound compositions of inorganic pigments, organic pigments, metallic effect pigments, or fluorescent dyes; the inorganic pigments can be inorganic metal oxides, such as iron yellow, iron red, titanium yellow, ultramarine, etc.; the organic pigments can be phthalocyanines, condensed azo compounds, isoindolinones, pyrrolopyrroles, etc.; and the metallic effect pigments can be metallic aluminum powder, pearlescent pigments, etc. The introduction of the colorant can better facilitate the creation of contrast in the wood grain effect appearance and enhance the wood grain effect.

[0019] Furthermore, the filler modifier is one or more of calcium carbonate, talc, wollastonite, diatomaceous earth, kaolin, mica, glass microspheres, graphite, barium sulfate, and silica. By adding filler modifiers and anti-aging agents, the resulting membrane products have higher stiffness and anti-aging properties, expanding the application range and durability of this type of membrane material.

[0020] Furthermore, the additive includes a dispersant, which is one or more of polyethylene wax, polyester wax, amide wax, modified ethylene wax, and stearate.

[0021] This solution utilizes specific copolymers and maleic anhydride-grafted polyethylene. The copolymers, in particular, effectively control the melting characteristics and thermorheological properties of the material at certain temperatures. By compounding with maleic anhydride-grafted polyethylene, the processing stability and mechanical properties of the film products are maintained. Simultaneously, by controlling the specific ratio of UV absorbers, light stabilizers, and antioxidants in the B-component anti-aging agent, the material achieves a wood-grain effect while maintaining excellent anti-aging properties.

[0022] This invention also provides a method for preparing the laminated wood grain polyolefin material, comprising the following steps:

[0023] (1) Weigh each component of modified material A according to the weight parts, put them into a high-speed mixer, set the speed to 40-50 Hz, stir and mix at high speed for 3 minutes, put them into a high-speed continuous internal mixer extruder for plasticizing, mixing, dispersing and granulation, set the temperature to 220-250℃, the mixing speed to 400 rpm, and after cooling to below 70℃, granulate to obtain modified material A;

[0024] (2) Weigh each component of modified material B according to the weight parts, mix them evenly in a mixer, transfer them to a continuous plasticizing internal mixing equipment for plasticizing and dispersing evenly, press them out, and cool them fully to obtain modified material B;

[0025] (3) After uniformly mixing modified material A and modified material B, the mixture is fed into the extrusion casting equipment. The extrusion screw and barrel temperature is set to 180–220℃, the runner and die temperature is set to 190–260℃, the ABC screw speed is set to 60 rpm, and the film thickness is adjusted to 150 μm by adjusting the traction speed. The extruded casting product can then obtain a film product with a wood grain appearance and good anti-aging properties.

[0026] After being compounded with modified material A and modified material B and heated and plasticized, the mixture is directly extruded to form a film material that is integrated with the polymer and has a pattern similar to wood. This process eliminates the complex printing and coating process, saves energy and is environmentally friendly. The resulting pattern will not disappear due to smearing or other processes, forming a permanent pattern. Furthermore, the pattern formation mechanism has a unique effect that cannot be replicated, and it has good stiffness, durability and environmental innovation.

[0027] In summary, compared with the prior art, the present invention achieves the following technical effects:

[0028] (1) The polyolefin material of the present invention has a good wood grain effect, is not easy to fade, has strong stability and strong anti-aging properties.

[0029] (2) The laminated wood grain polyolefin material of the present invention has a simple production process, strong adhesion, is not easily coated off, has good durability, and has a high tensile strength retention rate after xenon lamp irradiation. Detailed Implementation

[0030] To enable those skilled in the art to better understand the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the comparative examples.

[0031] I. The sources of the equipment, instruments, and raw materials used in the embodiments of this invention are as follows:

[0032] Twin-screw extrusion system, Coperon (Nanjing) Machinery Co., Ltd., length-to-diameter ratio 48:1;

[0033] High-speed mixer, HS-400L, Zhangjiagang Yili;

[0034] ABC three-layer casting equipment with a screw diameter of 35mm, Guangzhou Putong Experimental Analytical Instruments Co., Ltd.

[0035] Xenon lamp aging equipment, model CI4000, manufacturer ATLAS;

[0036] Spectrophotometer / colorimeter, model CE7000A, X-Rite, USA;

[0037] Standard lightbox, model SPLQC, manufactured by X-Rite, USA;

[0038] Electronic universal testing machine, EUT5000 (Shenzhen Sansi).

[0039] Copolymer A: Polybutylene terephthalate and polytetrahydrofuran ether copolymer, H63DMG, copolymer, Hechuang Technology;

[0040] Copolymer B: Polyethylene terephthalate-1,4-cyclohexanediol ester, JN200, copolymer, SK Korea;

[0041] Homopolymers: PMMA, CM-205, homopolymer, Chimei;

[0042] Maleic anhydride-grafted polyethylene (PE-g-MAH): BYNEL 4109DOW CHENMICAL;

[0043] Maleic anhydride-grafted polypropylene (PP-g-MAH) PC-1, Nanhai Baichen Polymer Materials;

[0044] Polyolefin resin A: HDPE 5000S, Sinopec;

[0045] Polyolefin resin B: PP T03 compound, Sinopec;

[0046] Anti-aging agents:

[0047] Ultraviolet absorber A: Benzotriazole, UV-327, melting point 156℃, Tiangang additive;

[0048] Ultraviolet absorber B: Benzophenone derivative, UV-531, melting point 49℃, Tiangang additive;

[0049] Light stabilizer A: Hindered amine light stabilizer, HS-944, melting point 105~125℃, Tiangang additive;

[0050] Light stabilizer B: Hindered amine light stabilizer, IRESORB 770, melting point 80-85℃, Liansheng Technology;

[0051] Antioxidants:

[0052] The melting point of hindered phenolic antioxidant 1010 is between 110 and 125°C, and the melting point of phosphite antioxidant 168 is between 180 and 186°C.

[0053] Antioxidant A: Antioxidant 1010 and Antioxidant 168, Beijing Tiangang; Antioxidant 1010 and Antioxidant 168 are added in a 1:1 ratio;

[0054] Antioxidant B: Melting point 50-55℃, brand name IRGANOX 1076, BASF;

[0055] Colorant: Iron oxide red, 120M, Bayer;

[0056] Additives: Antioxidants: Antioxidant 1010, Antioxidant 168, Beijing Tiangang; Antioxidant 1010: Antioxidant 168 are added in a ratio of 20:1;

[0057] Dispersants: EBS (Hetai), 1105A (Mitsui);

[0058] Filler Modifier A: Talc, HS778, Guangyuan Chemical;

[0059] Filler Modifier B: Calcium carbonate, HS-2500, Guangyuan Chemical;

[0060] Filler modifier C: Silica, E-1011, Tosoh Corporation, Japan.

[0061] The preparation method of the laminated wood grain imitation polyolefin material in the embodiments and comparative examples of the present invention includes the following steps:

[0062] (1) Weigh each component of modified material A according to the weight parts, put them into a high-speed mixer, set the speed to 40-50 Hz, stir and mix at high speed for 3 minutes, put them into a high-speed continuous internal mixer extruder for plasticizing, mixing, dispersing and granulation, set the temperature to 220-250℃, the mixing speed to 400 rpm, and after cooling to below 70℃, granulate to obtain modified material A;

[0063] (2) Weigh each component of modified material B according to the weight parts, mix them evenly in a mixer, transfer them to a continuous plasticizing internal mixing equipment for plasticizing and dispersing evenly, press them out, and cool them fully to obtain modified material B;

[0064] (3) After uniformly mixing modified material A and modified material B, the mixture is fed into the extrusion casting equipment. The extrusion screw and barrel temperature is set to 180–220℃, the runner and die temperature is set to 190–260℃, the ABC screw speed is set to 60 rpm, and the film thickness is adjusted to 150 μm by adjusting the traction speed. The extruded casting product can then obtain a film product with a wood grain appearance and good anti-aging properties.

[0065] II. Performance Testing Methods

[0066] 1. Evaluation of the wood grain appearance: The appearance effect is comprehensively evaluated by multiple testers through visual judgment of texture uniformity, clarity, surface appearance, etc. The specific method is as follows:

[0067] The wood grain appearance effect was judged by four testers, and the average value was taken.

[0068] The evaluation criteria are as follows: Level 0: almost no wood grain appearance effect (if the film appearance color is completely uniform without texture pattern effect, or the film is severely damaged and has poor film-forming performance, it is defined as Level 0); Level 1: unqualified wood grain appearance effect (texture pattern is formed on the film surface, but it is uneven, with obvious holes or blocky unmelted matter); Level 1.5: flawed wood grain appearance effect (texture pattern can be formed, but there are obvious crystal points and fish eyes and the thickness uniformity is significantly out of range); Level 2: qualified wood grain appearance effect (crystal points and fish eyes on the film, thickness uniformity is controlled, but texture uniformity is poor); Level 2.5: good wood grain appearance effect (overall film surface appearance effect is good, texture size and occurrence are poorly controlled); Level 3: excellent wood grain effect (film appearance is flawless, texture is uniform and aesthetically pleasing).

[0069] 2. Thin film thickness fluctuation: Using a thickness gauge (micrometer screw gauge, Deli brand), divide the film laterally into 10 equally spaced test points and measure the thickness at each point. Then, calculate the thickness fluctuation at each point by comparing the thickness value at each point with the arithmetic mean of the 10 points. That is, thin film thickness fluctuation = (D...) / (...) n -D 平 ) / (D 平 Then analyze the thickness fluctuation range.

[0070] 3. Tensile strength retention of the film: Comparison of tensile strength performance between the film material prepared by adding modified material A and the film material made of pure polymer resin;

[0071] Strength retention rate R2 = (tensile strength after xenon lamp irradiation) (改性材料A：改性材料B) Tensile strength before xenon lamp irradiation (改性材料A：改性材料B) *100%; Xenon lamp irradiation test method is according to ISO4892-2-2013 0.51W / cm² 2 @340nm test, continuous test time 2000 hours; tensile strength properties can be measured by electronic universal testing machine EUT5000 (Shenzhen Sansi), and the test standard is in accordance with ISO527-3-2012.

[0072] 4. Anti-aging performance evaluation was conducted using xenon lamp aging, adhering to the standard ISO4892-2-2013 0.51W / cm². 2 @340nm test, continuous test time 2000 hours, measure the color difference change of the sample before and after anti-aging CIELAB DE value. The smaller the DE, the better the anti-aging performance. Usually DE<3 indicates that it has a good anti-aging effect.

[0073] Table 1. Technical solutions of the embodiments (parts by weight)

[0074]

[0075]

[0076] Table 2 Comparative examples of technical solutions (parts by weight)

[0077]

[0078] Table 3 shows the detection results of the embodiments.

[0079]

[0080] Table 4 shows the test results of the comparative examples.

[0081]

[0082]

[0083] All comparative examples use a single variable compared to Example 1. Comparative Example 1 uses pure resin raw materials without modification; Comparative Example 2 does not contain anti-aging agents; Comparative Example 3 does not contain filler modifiers; Comparative Example 4 contains excessive filler modifiers; Comparative Example 5 contains excessive anti-aging agents; Comparative Example 6 does not contain UV absorbers; Comparative Example 7 does not contain light stabilizers; Comparative Example 8 does not contain antioxidants; Comparative Example 9 uses maleic anhydride-grafted polypropylene; Comparative Example 10 uses homopolymer PMMA; and Comparative Example 11 uses different proportions of modified material A and modified material B. None of the above comparative examples can achieve a good wood grain effect while maintaining good weather resistance and color stability.

[0084] Based on the test data in Tables 3-4 regarding the wood grain appearance, 150μm film thickness fluctuation, tensile strength retention, and anti-aging properties, the polyolefin material prepared in the examples exhibits a good wood grain effect with an appearance grade of 2.5 or higher, a film thickness fluctuation within ±5%, a high tensile strength retention rate (R2 not less than 71%), and good anti-aging properties (DE value not higher than 2.6). Compared to the comparative example, it has significant advantages and can effectively meet the high standards required by customers and the market.

[0085] The above description is only a partial embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A polyolefin material, characterized in that, Including modified material A and modified material B; The modified material A, by weight, comprises the following components: 30-90 parts of copolymer, 3-15 parts of maleic anhydride-grafted polyethylene, 5-20 parts of polyolefin resin, 2-30 parts of colorant, and 1-5 parts of additives. The modified material B, by weight, comprises the following components: 80-100 parts of polyolefin resin, 10-35 parts of filler modifier, and 0.2-2 parts of anti-aging agent; The anti-aging agent is a composition of ultraviolet absorber, light stabilizer and antioxidant; The mass ratio of modified material A to modified material B is (2~10):(90~98). The copolymer is a copolymer of polybutylene terephthalate and polytetrahydrofuran ether or polyethylene terephthalate-1,4-cyclohexanediol ester. The total mass ratio of the ultraviolet absorber and light stabilizer to the antioxidant is 1:(0.1~5).

2. The polyolefin material according to claim 1, characterized in that, The ultraviolet absorber is one or more of the following: triazine-structured compounds, benzoxazinone-structured compounds, benzophenone-structured compounds, benzotriazole-structured compounds, oxalamide-structured compounds, and cyanoacrylate-structured compounds.

3. The polyolefin material according to claim 1, characterized in that, The light stabilizer is one or more of the hindered amine structure light stabilizers and the hindered benzoic acid ester structure light stabilizers.

4. The polyolefin material according to claim 1, characterized in that, The antioxidant is one or more of the following: hindered phenolic antioxidants, thiobisphenol antioxidants, amine antioxidants, phosphite antioxidants, and thioester antioxidants.

5. The polyolefin material according to claim 1, characterized in that, The total mass ratio of the ultraviolet absorber and light stabilizer to the antioxidant is 1:(0.3~3).

6. The polyolefin material according to claim 1, characterized in that, The melting points of the ultraviolet absorber, light stabilizer, and antioxidant are all greater than 100°C.

7. The polyolefin material according to claim 1, characterized in that, The melting points of the ultraviolet absorber, light stabilizer, and antioxidant are all 105~230℃.

8. The polyolefin material according to claim 1, characterized in that, The weight ratio of the copolymer to maleic anhydride-grafted polyethylene is (5~30):

1.

9. The polyolefin material according to claim 1, characterized in that, The weight ratio of the copolymer to maleic anhydride-grafted polyethylene is (8~16):

1.

10. A method for preparing the polyolefin material according to any one of claims 1 to 9, characterized in that, Includes the following steps: (1) Weigh each component of modified material A according to the weight parts, stir and mix them evenly in a mixer, transfer them to a continuous plasticizing internal mixing equipment for plasticizing and dispersing evenly, press out, and cool fully to obtain modified material A; (2) Weigh each component of modified material B according to the weight parts, mix them evenly in a mixer, transfer them to a continuous plasticizing internal mixing equipment for plasticizing and dispersing evenly, press them out, and cool them fully to obtain modified material B; (3) Mix or add modified material A and modified material B into an extrusion device with a die shape, heat and melt, and plasticize and laminate to obtain the polyolefin material.

11. The use of the polyolefin material according to any one of claims 1 to 9 in extruded cast films, sheets, extruded pipes or extruded profiles.

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