A polymethyl methacrylate composite material and a preparation method and application thereof

Abstract

The present application relates to a kind of polymethyl methacrylate composite material and its preparation method and application, belong to polymer material technical field.The polymethyl methacrylate composite material of the present application includes the following weight parts of component:PMMA resin 70-99 parts, toughening agent 14-32 parts, black colorant 0.2-1.1 parts;Toughening agent is core-shell type acrylate resin, black colorant includes first colorant and second colorant, first colorant includes the solvent red and solvent green of mass ratio (4.9-7.5) : (1.7-4.1) ;The mass percentage of first colorant in black colorant is ≥90%.The polymethyl methacrylate composite material provided in the present application has higher infrared light transmittance, lower visible light transmittance, and can reduce processing color difference, and give consideration to certain toughness intensity, has higher application prospect in the field such as intelligent automobile.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, and in particular to a polymethyl methacrylate composite material, its preparation method, and its application. Background Technology

[0002] High-gloss black automotive interior and exterior trim pieces are gaining popularity among consumers. As smart cars rapidly evolve towards high automation and personalized interaction, the B-pillar trim is upgrading from a traditional decorative element to a smart interactive terminal, with a surge in demand for integrated biometric systems such as facial recognition and palm vein recognition. Infrared cameras, unaffected by ambient light, have become a core component of B-pillar biometric systems. To meet this application, B-pillar trim materials must maintain structural strength while possessing high transmittance in specific infrared bands.

[0003] Currently, the main type of paint-free high-gloss black material is polymethyl methacrylate (PMMA), which has advantages such as paint-free operation, high weather resistance, easy processing and molding, and low cost. However, after modification, the transmittance of PMMA material to infrared and visible light will be significantly reduced. To achieve intelligent interaction such as accurate facial recognition, an infrared transmittance of ≥87% is required; for door panel ambient lighting decorative parts, visible light transmittance is also required. However, because black has a strong absorption effect on light, light is difficult to pass through paint-free black PMMA material; in addition, the additives in the system also have an infrared absorption effect, making it difficult to meet the infrared transmittance requirements. On the other hand, PMMA molecular chains are rigid, resulting in insufficient toughness and low impact strength. To improve the toughness and impact performance of PMMA material, a common method is to mix toughening agents with PMMA material through physical modification and granulation. Generally, while toughening agents can improve the toughness of the material, they will reduce the light transmittance of PMMA material, failing to utilize the "acrylic glass" characteristics of PMMA material. In addition, modified PMMA often uses colorants such as carbon black, which have extremely high surface energy and a strong tendency to agglomerate, easily causing color differences during processing and affecting the appearance.

[0004] Therefore, there is an urgent need to develop a PMMA material that can achieve low color difference, good black appearance, and at the same time ensure high infrared transmittance and high toughness. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of existing technologies and provide a polymethyl methacrylate (PMMA) composite material, its preparation method, and its applications. The PMMA composite material provided by this invention achieves a balance of low processing color difference, high infrared transmittance, and high toughness.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows: In a first aspect, the present invention provides a polymethyl methacrylate composite material comprising the following components in parts by weight: 70-99 parts of PMMA resin, 14-32 parts of toughening agent, and 0.2-1.1 parts of black colorant; wherein the toughening agent is a core-shell type acrylate resin; The black colorant includes a first colorant and a second colorant. The first colorant includes solvent red and solvent green in a mass ratio of (4.9-7.5):(1.7-4.1). The mass percentage of the first colorant in the black colorant is ≥90%.

[0007] This invention provides a composite material based on polymethyl methacrylate (PMMA resin), wherein an acrylate resin with a core-shell structure is selected as a toughening agent to improve the toughness and structural strength of the composite material, and it has good compatibility with organic black colorants, which helps to achieve a good black appearance effect.

[0008] The polymethyl methacrylate (PMMA) composite material of this invention also optimizes the types of colorants used. By employing an organic black colorant that does not contain carbon black, the infrared transmittance of the material can be significantly improved, and color difference during processing can be reduced. This invention selects a first colorant mainly consisting of two dyes: solvent red and solvent green. By mixing them in the aforementioned proportions, a black effect can be achieved by replacing carbon black. In this invention, solvent red refers to a red solvent dye, and solvent green refers to a green solvent dye. Furthermore, this invention also balances the relationship between the blackness of the PMMA composite material and the transmittance of infrared and visible light by controlling the amount of colorant added, achieving the optimal overall effect of blackness and infrared transmittance.

[0009] This invention provides a polymethyl methacrylate (PMMA) composite material that combines improved blackness, high infrared transmittance, high toughness and strength, and low processing color difference. The material provided by this invention is suitable for manufacturing automotive parts, especially for door panel ambient lighting decorations, and has high practical value.

[0010] Preferably, the polymethyl methacrylate composite material comprises 70-99 parts of PMMA resin, for example, it can be one or any two of the following values: 70 parts, 71 parts, 72 parts, 73 parts, 74 parts, 75 parts, 76 parts, 77 parts, 78 parts, 79 parts, 80 parts, 81 parts, 82 parts, 83 parts, 84 parts, 85 parts, 86 parts, 87 parts, 88 parts, 89 parts, 90 parts, 91 parts, 92 parts, 93 parts, 94 parts, 95 parts, 96 parts, 97 parts, 98 parts, and 99 parts.

[0011] Preferably, the polymethyl methacrylate composite material includes 14-32 parts of toughening agent, for example, it can be one or any two of the following values: 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, and 32 parts.

[0012] Preferably, the polymethyl methacrylate composite material includes 0.2-1.1 parts of black colorant, for example, it can be one or any two of the following values: 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1.0 parts, and 1.1 parts.

[0013] Preferably, the black colorant comprises solvent red and solvent green in a mass ratio of (4.9-7.5):(1.7-4.1), for example, it can be one or any two of the following: 7.5:1.7, 7.4:1.8, 7:2, 6:3, 5:4, 4.9:4.1.

[0014] Preferably, the solvent red can be at least one of purine solvent dyes, azo solvent dyes, and anthraquinone solvent dyes; specifically, the solvent red can be at least one of solvent red 179 and solvent red 195.

[0015] Preferably, the solvent green is an anthraquinone solvent dye; specifically, the solvent green is at least one of solvent green 3 and solvent green 28.

[0016] Preferably, the mass percentage of PMMA resin in the polymethyl methacrylate composite material is ≥65%.

[0017] Preferably, the mass percentage of PMMA resin in the polymethyl methacrylate composite material is 68-90%.

[0018] Preferably, the toughening agent in the polymethyl methacrylate composite material has a mass percentage content of 11-32%.

[0019] Preferably, the mass percentage of black colorant in the polymethyl methacrylate composite material is 0.2-1.1%.

[0020] Preferably, according to ISO 1133-1:2022, the melt flow rate of the PMMA resin at 230°C and 3.8 kg is 1-20 g / 10 min, for example, 1.0 g / 10 min, 2.0 g / 10 min, 2.5 g / 10 min, 3.0 g / 10 min, 3.5 g / 10 min, 4.0 g / 10 min, 4.5 g / 10 min, 5.0 g / 10 min, 5.5 g / 10 min, 6.0 g / 10 min, 6.5 g / 10 min, 7.0 g / 10 min, etc. The range of values ​​is one or both of the following: 7.5g / 10min, 8.0g / 10min, 8.5g / 10min, 9.0g / 10min, 9.5g / 10min, 10.0g / 10min, 11g / 10min, 12g / 10min, 13g / 10min, 14g / 10min, 15g / 10min, 16g / 10min, 17g / 10min, 18g / 10min, 19g / 10min, and 20g / 10min.

[0021] The core-shell type acrylate toughening agent of the present invention refers to a toughening agent having an acrylate polymer in the core and / or shell; specifically, the core of the core-shell type acrylate resin is selected from at least one of polybutadiene, butadiene-styrene copolymer, and acrylate polymer, and the shell of the core-shell type acrylate resin is selected from at least one of acrylate polymer and acrylonitrile-styrene copolymer.

[0022] Specifically, the toughening agent is at least one of a full acrylate polymer, MBS resin, and ASA resin.

[0023] Preferably, the average particle size of the core-shell type acrylate resin rubber phase is 50-350 nm.

[0024] Specifically, the average particle size of the MBS resin rubber phase is 200-350 nm, for example, it can be one or any two of 200 nm, 250 nm, 300 nm, and 350 nm. Specifically, the average particle size of the ASA resin rubber phase is 100-300 nm, for example, it can be one or any two of 100 nm, 150 nm, 160 nm, 200 nm, 250 nm, and 300 nm.

[0025] The average particle size of both ASA resin and MBS resin refers to the average particle size of the rubber phase, and the test method is dynamic light scattering (refer to ISO 22412).

[0026] Preferably, the toughening agent comprises ASA resin and a full acrylate polymer or MBS resin, wherein the mass ratio of the full acrylate polymer or MBS resin to the ASA resin is (3-4):(1-2), for example, it can be one of 3:2, 3.5:1.5, 4:1, or any combination thereof.

[0027] Preferably, the solvent red in the black colorant has a mass percentage content of 50-74%, for example, it can be one or any two of the following values: 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%.

[0028] Preferably, the solvent green in the black colorant has a mass percentage content of 18-40%, for example, it can be one or any two of the following values: 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%.

[0029] Preferably, the second colorant includes at least one of solvent yellow, solvent blue, and solvent violet. In this invention, solvent yellow refers to a yellow solvent dye, solvent blue refers to a blue solvent dye, and solvent violet refers to a purple solvent dye; the solvent yellow, solvent blue, and solvent violet can all be selected from anthraquinone solvent dyes.

[0030] Preferably, the second colorant has a mass percentage content of 8-10% in the black colorant, for example, it can be a range of one or any two of 8.0%, 8.5%, 9.0%, 9.5%, 10.0%.

[0031] Preferably, the second colorant comprises solvent yellow and solvent purple in a mass ratio of (0.8-1.2):(0.8:1.2).

[0032] Preferably, the polymethyl methacrylate composite material further includes 0.1-2 parts by weight of additives.

[0033] The polymethyl methacrylate composite material provided by the present invention does not particularly limit the types of additives, and commonly used additives in the art can be selected, such as antioxidants, lubricants, light stabilizers, etc.

[0034] Secondly, the present invention provides a method for preparing the above-mentioned polymethyl methacrylate composite material, comprising the following steps: The components are mixed to obtain a premix, which is then melt-blended, extruded and granulated to obtain the polymethyl methacrylate composite material.

[0035] Preferably, a twin-screw extruder is used for melt blending, wherein the screw temperature of the twin-screw extruder is 80-270℃, the length-to-diameter ratio is (38-50):1, and the screw speed is 200-400 rpm.

[0036] Thirdly, the present invention provides the application of the above-mentioned polymethyl methacrylate composite material in an infrared camera module.

[0037] Fourthly, the present invention provides a component made of the above-mentioned polymethyl methacrylate composite material.

[0038] Preferably, the component is a smart identification module part or an infrared camera module part.

[0039] Compared with the prior art, the beneficial effects of the present invention are as follows: This invention provides a polymethyl methacrylate (PMMA) composite material. Through screening and optimization of the types and ratios of toughening agents and colorants, a good black effect of PMMA resin material is achieved without adding carbon black. It also significantly improves the infrared light transmittance of the material, as well as its toughness and impact performance, and reduces color difference during processing at lower locations. This is beneficial for balancing structural strength, improving product appearance consistency, achieving superior blackness, high visible light transmittance, and high infrared light transmittance, and can meet the application needs in functional parts such as automotive intelligent recognition. Detailed Implementation

[0040] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions in the embodiments of this application will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. Based on the embodiments in this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.

[0041] In this application, the technical features described in an open-ended manner include both closed technical solutions consisting of the listed features and open technical solutions that include the listed features.

[0042] In this application, numerical ranges are referred to as continuous unless otherwise specified, and include the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when the range refers to integers, it includes every integer between the minimum and maximum values ​​of the range. Additionally, when multiple ranges are provided to describe a feature or characteristic, the ranges may be merged. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges to which they are incorporated.

[0043] The raw materials used in the examples and comparative examples are described below: PMMA-1: Polymethyl methacrylate, ACRYPET VH5, Nantong Mitsubishi Chemical, according to ISO 1133-1:2022 standard, the melt flow rate at 230℃ and 3.8kg is 5.5g / 10min.

[0044] PMMA-2: Polymethyl methacrylate, ACRYPET VH 001, Nantong Mitsubishi Chemical, according to ISO 1133-1:2022 standard, the melt flow rate is 2 g / 10 min at 230℃ and 3.8 kg.

[0045] PMMA-3: Polymethyl methacrylate, ACRYPET TF8, Nantong Mitsubishi Chemical, according to ISO 1133-1:2022 standard, the melt flow rate is 10 g / 10 min at 230℃ and 3.8 kg.

[0046] PMMA-4: Polymethyl methacrylate, SUMIPEX LG2, Sumitomo Chemicals, Japan, according to ISO 1133-1:2022 standard, melt flow rate is 15 g / 10 min at 230°C and 3.8 kg.

[0047] Toughening Agent-1: Full acrylate toughening agent, M-210, Kanekachi, Japan, with a rubber content of 60%.

[0048] Toughening agent-2: MBS type toughening agent, M-701, Kanekachi, Japan, with a rubber content of 60%.

[0049] Toughening agent-3: ASA type toughening agent, LP 2065X, Guangzhou Entropy Energy, with a rubber content of 50%.

[0050] Toughening agent-4: ASA type toughening agent, LP 2068, Guangzhou Entropy Energy, with a rubber content of 50%.

[0051] Toughening Agent-5 (Non-acrylate Toughening Agent): High-rubber powder, ABS POW HR181, Kumho Petrochemical, with a rubber content of 60%.

[0052] Solvent Red 179: 14H-benzo[4,5]isoquinoline[2,1-a]piperidin-14-one, commercially available.

[0053] Solvent Red 195: 4-[(4-aminophenyl)azo]-3-methyl-N-(2-methylphenyl)benzenesulfonamide, commercially available.

[0054] Solvent Green 3: 1,4-di-p-tolueneaminoanthraquinone, commercially available.

[0055] Solvent Green 28: 1,4-Di[[4-(1,1-dimethylethyl)phenyl]amino]-5,8-dihydroxyanthraquinone, commercially available.

[0056] Solvent Yellow 114: 2-(3-hydroxy-2-quinolinyl)indan-1,3-dione, commercially available.

[0057] Solvent Blue 104: 1,4-bis[(2,4,6-trimethylphenyl)amino]anthraquinone, commercially available.

[0058] Solvent Violet 13: 1-hydroxy-4-(p-toluidine)anthraquinone, commercially available.

[0059] Carbon black: M717, Cabot Corporation, USA.

[0060] The formulations of the black colorant-1 to black colorant-14 are shown in Table 1 below (the table shows the mass percentage content).

[0061] Table 1 Unless otherwise specified, all components and raw materials used in the embodiments and comparative examples of this invention are commercially available, and the same type of components and raw materials are used in each parallel experiment.

[0062] Examples 1-19, Comparative Examples 1-11 The formulations of polymethyl methacrylate composite materials in Examples 1-19 and Comparative Examples 1-11 are shown in Tables 2 and 3 (all figures are parts by weight).

[0063] The preparation methods of the polymethyl methacrylate composite materials in Examples 1-19 and Comparative Examples 1-11 all include the following steps: According to the formula, each component is weighed and mixed evenly with a high-speed mixer to obtain a premix. The premix is ​​then fed into a twin-screw extruder through the main feeding device. The components are mixed and dispersed through conveying, melting, shearing and dispersing. After extrusion granulation, cooling and drying, the polymethyl methacrylate composite material is obtained. The process conditions for the twin-screw extruder are as follows: Zone 1 temperature is 90℃, Zone 2 temperature is 120℃, Zone 3 temperature is 200℃, Zone 4 temperature is 240℃, Zone 5 temperature is 250℃, Zone 6 temperature is 255℃, Zone 7 temperature is 255℃, Zone 8 temperature is 250℃, Zone 9 temperature is 250℃, and the die head temperature is 250℃; the length-to-diameter ratio is 42:1, and the screw speed is 300 rpm.

[0064] Table 2 Table 3 Performance testing To investigate the properties of the polymethyl methacrylate composite material provided by this invention, the composite materials in the examples and comparative examples were subjected to the following tests: (1) Room temperature impact strength: Tested according to ISO 179:2023, injection molded into a standard specimen, the pendulum energy is 4J; (2) Visible light transmittance and infrared transmittance: The light transmittance of the injection-molded color plate with a thickness of 3mm was tested by a spectrophotometer, where the infrared wavelength was 850nm; (3) L value: The color difference meter was tested using D65 light source SCI mode. The lower the L value, the darker the color and the more prominent the effect. (4) Color difference during processing: The material is placed in the injection molding machine and 100 mold color plates are continuously injected. The color difference ΔE between the first mold and the 100th mold color plate is measured with a colorimeter.

[0065] Table 4 As can be seen from the table: Compared with the comparative example, the polymethyl methacrylate composite material provided by the present invention in the examples has higher structural toughness and a room temperature impact strength of 50 kJ / m. 2 The above-mentioned properties are achieved; the visible light transmittance is above 18%, and the infrared transmittance is basically above 87%, enabling intelligent recognition and interaction; in addition, the L value can be below 24, the color difference during processing is <0.5, it has a good black effect, and the appearance is consistent, which significantly improves the defects of existing PMMA modified materials.

[0066] The black colorant formulation used in Comparative Example 1 lacked solvent green, and the black colorant formulation used in Comparative Example 2 lacked solvent red. The transmittance of visible and infrared light of the composite material decreased significantly, and the L value and color difference increased significantly. Neither of them could achieve a good black appearance and high transmittance.

[0067] In Comparative Examples 3 and 4, the ratio of the first colorant solvent red and solvent green in the black colorant formulation was unsuitable, resulting in poor light transmittance. Both visible and infrared transmittance were low, and color difference during processing was significantly increased, affecting appearance consistency. In Comparative Example 5, carbon black was used instead of the composite colorant in this invention, and the material failed to achieve light transmittance. In Comparative Example 6, the proportion of the first colorant solvent red and solvent green in the black colorant was too low, failing to achieve good light transmittance. Infrared transmittance decreased significantly, L increased, blackness was poor, and color difference during processing was significantly increased, affecting appearance consistency.

[0068] In Comparative Examples 7 and 8, the amounts of PMMA and toughening agent were adjusted to be outside the specified range. In Comparative Example 7, insufficient toughening agent resulted in significantly poor structural toughness and a substantial decrease in room temperature impact strength. In Comparative Example 8, excessive toughening agent and insufficient PMMA enhanced the structural toughness of the composite material, but the light transmittance failed to meet the usage requirements. In Comparative Example 11, replacing the toughening agent with ABS failed to improve the structural toughness, and the visible and infrared light transmittance of the composite material was significantly reduced, failing to meet the usage requirements.

[0069] In Comparative Example 9, the total amount of colorant added was insufficient. Although the light transmittance was good, a good black appearance could not be achieved, and the L value was significantly increased. In Comparative Example 10, the total amount of colorant added was excessive. Although the L value was low, the transmittance of both visible light and infrared light was greatly reduced, and the transmittance requirements for intelligent recognition could not be met.

[0070] In summary, this invention provides a polymethyl methacrylate (PMMA) composite material. Through the rational formulation of toughening agents, the toughness and structural strength of the PMMA resin material are improved, and it has good compatibility with colorants, which helps to achieve a good black appearance. At the same time, the types of colorants are optimized, significantly improving the infrared transmittance of the material and improving the color difference during processing. The relationship between the blackness of the PMMA composite material and the transmittance of infrared and visible light is balanced, achieving the best overall effect of blackness and infrared transmittance.

[0071] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A polymethyl methacrylate composite material, characterized in that, The product comprises the following components in parts by weight: 70-99 parts PMMA resin, 14-32 parts toughening agent, and 0.2-1.1 parts black colorant; wherein the toughening agent is a core-shell type acrylate resin. The black colorant includes a first colorant and a second colorant. The first colorant includes solvent red and solvent green in a mass ratio of (4.9-7.5):(1.7-4.1). The mass percentage of the first colorant in the black colorant is ≥90%.

2. The polymethyl methacrylate composite material as described in claim 1, characterized in that, The PMMA resin has a melt flow rate of 1-20 g / 10 min at 230°C and 3.8 kg.

3. The polymethyl methacrylate composite material as described in claim 1, characterized in that, The core of the core-shell acrylate resin is selected from at least one of polybutadiene, butadiene-styrene copolymer, and acrylate polymers, and the shell of the core-shell acrylate resin is selected from at least one of acrylate polymers and acrylonitrile-styrene copolymers; And / or, the average particle size of the core-shell type acrylate resin rubber phase is 50-350 nm.

4. The polymethyl methacrylate composite material as described in claim 3, characterized in that, The toughening agent is at least one of a full acrylate polymer, MBS resin, and ASA resin.

5. The polymethyl methacrylate composite material as described in claim 4, characterized in that, The toughening agent includes ASA resin and a full acrylate polymer or MBS resin, wherein the mass ratio of the full acrylate polymer or MBS resin to the ASA resin is (3-4):(1-2).

6. The polymethyl methacrylate composite material as described in claim 1, characterized in that, The solvent red in the black colorant has a mass percentage content of 50-74%; And / or, the solvent red is at least one of purpurone solvent dyes, azo solvent dyes, and anthraquinone solvent dyes; And / or, the solvent green in the black colorant has a mass percentage content of 18-40%; And / or, the solvent green is an anthraquinone solvent dye.

7. The polymethyl methacrylate composite material as described in claim 1, characterized in that, The second colorant includes at least one of solvent yellow, solvent blue, and solvent violet; And / or, the second colorant has a mass percentage content of 8-10% in the black colorant.

8. The method for preparing the polymethyl methacrylate composite material according to any one of claims 1-7, characterized in that, Includes the following steps: The components are mixed to obtain a premix, which is then melt-blended, extruded and granulated to obtain the polymethyl methacrylate composite material.

9. The application of the polymethyl methacrylate composite material as described in any one of claims 1-7 in an infrared camera module.

10. A component, characterized in that, It is prepared using the polymethyl methacrylate composite material according to any one of claims 1-7.

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