Ethanol-resistant spraying-free high-brightness black ASA / PMMA material and preparation method thereof

Abstract

The invention discloses an ethanol-resistant, spraying-free and high-brightness black ASA / PMMA material and a preparation method thereof. The preparation method of the material comprises the following steps: 1) weighing 50-60% of polymethyl methacrylate resin, 10-20% of styrene-acrylonitrile resin, 0.5-1.5% of an antioxidant and 0.1-0.5% of a lubricant, adding into a high-speed mixer, uniformly mixing, and adding the mixed material into a main feeding port; 2) weighing 20%-30% of acrylonitrile-styrene-acrylate resin, 5%-15% of flexibilizer, 1%-2% of light stabilizer and 1%-2% of toner; and quantitatively adding from a side feeding port of an extruder, and melting, homogenizing, extruding and granulating by the extruder to obtain a final product. The alcohol-resistant, spraying-free and high-brightness black ASA / PMMA resin prepared by the invention has high-brightness black appearance and alcohol resistance, can be used as an outer part without paint spraying, has alcohol resistance, can be used for ornaments which can be in contact with various alcohol-containing cleaning agents, such as bumper decoration strips, rearview mirror shells, grilles, automobile lamp peripheral decoration strips, side skirt ornaments and the like, and has the advantages of simple preparation process and low cost. The material can also be used for shells of electronic and electrical equipment such as kitchen appliances.

Description

Technical Field

[0001] The present invention relates to the field of thermoplastic alloy materials with a spray-free, high-gloss black appearance and alcohol resistance, and in particular to an ethanol-resistant, spray-free, high-gloss black ASA / PMMA material and a preparation method thereof. Background Art

[0002] PMMA resin offers advantages such as high transparency, excellent dyeability, and high hardness. However, PMMA's brittleness limits its use in applications requiring toughness, such as appliance housings and most automotive exterior parts. ASA, an acrylonitrile-styrene-acrylate rubber copolymer, has excellent toughness due to its rubber phase. However, its low hardness and poor dyeability make it susceptible to scratch resistance when used directly as exterior components, and it cannot achieve a deep, high-gloss finish. ASA and PMMA, however, have similar solubility parameters and a degree of compatibility. Forming an alloy of the two materials can achieve a high-gloss black appearance while maintaining a certain degree of toughness, making them suitable for a wide range of applications. In industries such as automotive and home appliances, environmental awareness is gaining traction, and consumers are demanding higher standards for both appearance and health. Consequently, paint-free, high-gloss black ASA / PMMA materials are gaining widespread adoption. This meets manufacturers' cost reduction needs while addressing environmental concerns, eliminating painting and plating steps and effectively reducing environmental pollution. Currently, high-gloss black ASA / PMMA materials are widely used in automotive exterior trim, such as front fenders, grilles, fenders, and rearview mirror housings. This helps OEMs reduce production costs while also embracing environmental protection. Consumers often clean their cars after purchase, using a variety of cleaning agents. While some high-ethanol content cleaning agents can effectively remove dirt, they can also damage parts made with high-gloss black ASA / PMMA, causing the surface to appear slightly whitish and foggy, affecting both the aesthetics and the lifespan of the parts.

[0003] Patent CN202411306307.4 discloses a PC / ASA / PMMA ternary alloy material with scratch resistance and self-cleaning functions and its preparation method. By adding PC and perfluoropolymer, the material surface becomes resistant to pollution and highly hydrophobic. However, the addition of PC and perfluoropolymer will reduce the gloss and blackness of the material surface, and the weather resistance of the material will also decrease.

[0004] Patent CN201710749326.8 discloses a highly wear-resistant ASA / PMMA mixture with surface self-cleaning function and its preparation method. By adding PVDF resin, the wear resistance and surface hydrophobicity of the material are improved, and the surface self-cleaning function is achieved, but it also affects the blackness and glossiness of the surface of the ASA / PMMA material. Summary of the Invention

[0005] The object of the present invention is to improve the ethanol resistance of ASA / PMMA materials without affecting their gloss, blackness and properties, and to increase the service life and application scenarios of the materials. Therefore, a preparation method of ethanol-resistant, spray-free, high-brightness black ASA / PMMA materials is provided, which can be used in industries such as automobiles and household appliances, is not afraid of washing with ethanol cleaning agents, and does not require painting on the surface, achieving the effects of cost reduction and environmental protection.

[0006] To achieve the above object, the technical solution used in the present invention is as follows:

[0007] An ethanol-resistant, spray-free, high-brightness black ASA / PMMA material is prepared from the following raw materials by weight percentage

[0008] as follows:

[0009] 50%-60% of PMMA resin,

[0010] 20%-30% of ASA resin,

[0011] 10-20% of AS resin,

[0012] 5-15% of toughening agent,

[0013] 0.5%-1.5% of antioxidant,

[0014] 1%-2% of light stabilizer,

[0015] 0.1%-0.5% of lubricant,

[0016] 1%-2% of color powder.

[0017] In the above ASA / PMMA material, the PMMA resin is a mixture of high melt index PMMA and low melt index PMMA. Among them, for the high melt index PMMA, under the test conditions of 230°C * 3.8 kg, the melt flow rate ranges from 7 to 10 g / 10 min, and for the low melt index PMMA, under the test conditions of 230°C * 3.8 kg, the melt flow rate ranges from 2 to 5 g / 10 min. The mixing ratio is high melt index PMMA: low melt index PMMA = 1:1.

[0018] The particle size of the ASA resin is 300-500 μm, and the acrylate content is 50-60%.

[0019] The acrylonitrile content of the AS resin is 30-40%.

[0020] The toughening agent is a mixture of a fully acrylate toughening agent and a silicone-acrylate toughening agent. Among them, the refractive index of the fully acrylate toughening agent is 1.49, and the mixing ratio is: fully acrylate toughening agent: silicone-acrylate toughening agent = 2:1.

[0021] The antioxidant is a complex of a hindered phenol antioxidant and a phosphite antioxidant, and the compounding ratio is: hindered phenol antioxidant: phosphite antioxidant = 1:2.

[0022] The light stabilizer is used by compounding a hindered amine light stabilizer and a benzotriazole light stabilizer, and the compounding ratio is: hindered amine light stabilizer: benzotriazole light stabilizer = 1:2.

[0023] The lubricant is pentaerythritol stearate.

[0024] The color powder is compounded by one or more kinds.

[0025] Another object of the present invention is to provide a preparation method of ethanol-resistant, spray-free, high-brightness black ASA / PMMA material: 1) Weigh polymethyl methacrylate (PMMA) resin, styrene-acrylonitrile (AS) resin, antioxidant, and lubricant, add them to a high-speed mixer and mix evenly, and add the mixed materials to the main feed port; 2) Weigh acrylonitrile-styrene-acrylate (ASA) resin, toughening agent, light stabilizer, and color powder, mix them evenly in a high-speed mixer, and quantitatively add them from the side feed port of the extruder. After melting, homogenizing, extruding, and pelletizing by the extruder, the final product is obtained.

[0026] The present invention has the following beneficial effects:

[0027] 1. A certain amount of AS resin with a relatively high acrylonitrile content is added to the present invention. The relatively high acrylonitrile content increases the binding force between molecular chains, hinders the penetration of ethanol molecules, and the AS resin does not affect the transparency and dyeability of PMMA.

[0028] 2. The present invention reduces the certain dosage of ASA rubber powder and adds two toughening agents: a fully acrylate toughening agent and a silicon-acrylate toughening agent. Through a suitable ratio, it can hinder the diffusion of ethanol in the material and at the same time prevent the diffusion of stress cracks, and further improve the ethanol resistance of the ASA / PMMA material without affecting the appearance of the material.

[0029] 3. The pentaerythritol stearate lubricant added in the present invention takes into account the effects of internal and external lubrication, can reduce the stress generated during the injection molding process of the material, and reduce the risk of stress cracking caused by ethanol erosion.

[0030] 4. The preparation method of the present invention is that the pellets enter the extruder from the main feed, and the powder is quantitatively fed into the extruder from the side feed port, so that the pellets and the powder are mixed evenly, and a stable and uniform-performance ASA / PMMA material is obtained. Specific embodiments

[0031] The following further illustrates the present invention with reference to embodiments, but it is not used as a basis for limiting the present invention.

[0032] Embodiments of the present invention

[0033] The raw material components used below have the following structure:

[0034] The PMMA resin is a blend of high melt index PMMA and low melt index PMMA. Among them, for the high melt index PMMA, under the test conditions of 230°C * 3.8 kg, the melt flow rate ranges from 7 to 10 g / 10 min. For the low melt index PMMA, under the test conditions of 230°C * 3.8 kg, the melt flow rate ranges from 2 to 5 g / 10 min. The blending ratio is high melt index PMMA: low melt index PMMA = 1:1.

[0035] The particle size of the ASA resin is 300 - 500 μm, and the acrylate content is 50 - 60%.

[0036] The acrylonitrile content in the AS resin is 30 - 40%.

[0037] The toughening agent is a blend of a fully acrylate toughening agent and a silicon - acrylate toughening agent. Among them, the refractive index of the fully acrylate toughening agent is 1.49, and the blending ratio is fully acrylate toughening agent: silicon - acrylate toughening agent = 2:1.

[0038] The antioxidant is a blend of a hindered phenol antioxidant and a phosphite antioxidant, and the blending ratio is: hindered phenol antioxidant: phosphite antioxidant = 1:2.

[0039] The light stabilizer is a blend of a hindered amine light stabilizer and a benzotriazole light stabilizer, and the blending ratio is: hindered amine light stabilizer: benzotriazole light stabilizer = 1:2.

[0040] The lubricant is pentaerythritol stearate.

[0041] The color powder is blended through one or more components.

[0042] Example 1:

[0043] PMMA resin 60%,

[0044] ASA resin 22%,

[0045] AS resin 10%,

[0046] Toughening agent 5%, fully acrylate toughening agent: silicon - acrylate toughening agent = 2:1

[0047] Antioxidant 1%,

[0048] Light stabilizer 1%,

[0049] Lubricant 0.3%,

[0050] Toner 1%

[0051] Weigh the PMMA resin, AS resin, antioxidant, and lubricant, add them to a high-speed mixer and mix evenly. Then add the mixed materials to the main feed port. 2) Weigh the ASA resin, toughening agent, light stabilizer, and toner, mix them evenly in a high-speed mixer, and quantitatively add them through the side feed port of the extruder. After melting, homogenizing, extruding, and pelletizing by the extruder, the final product is obtained.

[0052] Example 2:

[0053] PMMA resin 55%

[0054] ASA resin 22%

[0055] AS resin 15%

[0056] Toughening agent 5%, all-acrylate toughening agent: silicone-acrylate toughening agent = 2:1

[0057] Antioxidant 1%

[0058] Light stabilizer 1%

[0059] Lubricant 0.3%

[0060] Toner 1%

[0061] Weigh the PMMA resin, AS resin, antioxidant, and lubricant, add them to a high-speed mixer and mix evenly. Then add the mixed materials to the main feed port. 2) Weigh the ASA resin, toughening agent, light stabilizer, and toner, mix them evenly in a high-speed mixer, and quantitatively add them through the side feed port of the extruder. After melting, homogenizing, extruding, and pelletizing by the extruder, the final product is obtained.

[0062] Example 3:

[0063] PMMA resin 50%

[0064] ASA resin 22%

[0065] AS resin 20%

[0066] Toughening agent 5%, all-acrylate toughening agent: silicone-acrylate toughening agent = 2:1

[0067] Antioxidant 1%

[0068] Light stabilizer 1%

[0069] Lubricant 0.3%

[0070] Toner 1%

[0071] Weigh the PMMA resin, AS resin, antioxidant, and lubricant, add them to a high-speed mixer and mix evenly, then add the mixed materials to the main feeding port; 2) Weigh the ASA resin, toughening agent, light stabilizer, and color powder, mix them evenly in a high-speed mixer, and quantitatively add them through the side feeding port of the extruder. After melting, homogenizing, extruding, and pelletizing by the extruder, the final product is obtained.

[0072] Example 4:

[0073] PMMA resin 50%,

[0074] ASA resin 20%,

[0075] AS resin 20%,

[0076] Toughening agent 7%, all-acrylate toughening agent: silicone-acrylate toughening agent = 2:1

[0077] Antioxidant 1%,

[0078] Light stabilizer 1%,

[0079] Lubricant 0.3%,

[0080] Color powder 1%,

[0081] Weigh the PMMA resin, AS resin, antioxidant, and lubricant, add them to a high-speed mixer and mix evenly, then add the mixed materials to the main feeding port; 2) Weigh the ASA resin, toughening agent, light stabilizer, and color powder, mix them evenly in a high-speed mixer, and quantitatively add them through the side feeding port of the extruder. After melting, homogenizing, extruding, and pelletizing by the extruder, the final product is obtained.

[0082] Comparative Example 1:

[0083] PMMA resin 65%,

[0084] ASA resin 27%,

[0085] Toughening agent 5%, all-acrylate toughening agent: silicone-acrylate toughening agent = 1:2

[0086] Antioxidant 1%,

[0087] Light stabilizer 1%,

[0088] Lubricant 0.3%,

[0089] Color powder 1%,

[0090] Weigh the PMMA resin, antioxidant, and lubricant, add them to a high-speed mixer and mix evenly. Then add the mixed materials to the main feeding port. 2) Weigh the ASA resin, toughening agent, light stabilizer, and color powder, mix them evenly in a high-speed mixer, and then quantitatively add them through the side feeding port of the extruder. After melting, homogenizing, extruding, and pelletizing by the extruder, the final product is obtained.

[0091] Comparative Example 2:

[0092] 67% PMMA resin

[0093] 30% ASA resin

[0094] 1% antioxidant

[0095] 1% light stabilizer

[0096] 1% color powder

[0097] Weigh the PMMA resin, antioxidant, and lubricant, add them to a high-speed mixer and mix evenly. Then add the mixed materials to the main feeding port. 2) Weigh the ASA resin, light stabilizer, and color powder, mix them evenly in a high-speed mixer, and then quantitatively add them through the side feeding port of the extruder. After melting, homogenizing, extruding, and pelletizing by the extruder, the final product is obtained.

[0098] Comparative Example 3:

[0099] 67% PMMA resin

[0100] 30% ASA resin

[0101] 1% antioxidant

[0102] 1% light stabilizer

[0103] 1% color powder

[0104] 0.3% lubricant

[0105] Weigh the PMMA resin, antioxidant, and lubricant, add them to a high-speed mixer and mix evenly. Then add the mixed materials to the main feeding port. 2) Weigh the ASA resin, light stabilizer, and color powder, mix them evenly in a high-speed mixer, and then quantitatively add them through the side feeding port of the extruder. After melting, homogenizing, extruding, and pelletizing by the extruder, the final product is obtained.

[0106] The materials prepared in the above Examples 1-5 and Comparative Examples 1-2 were respectively made into splines, and then according to the ISO standard, their Vicat softening temperature, notched impact strength, tensile strength, and heat distortion temperature (1.8 Mpa) were tested; the tensile splines were tested for the cracking time under the force of contacting alcohol at 1% strain; they were injection-molded into color plates of 150*100*2.5 mm, and their blackness was tested in the SCE mode with an integrating sphere spectrophotometer, and they were soaked in 75% concentration of alcohol, and the surface whitening situation was observed. The specific data are shown in Table 1 below.

[0107] Table 1 Test Results of Examples

[0108]

[0109]

[0110] It can be seen from the results in Table 1 that the ASA / PMMA material prepared by modification of the present invention has greatly improved the ethanol resistance of the material itself with very little change in blackness, extended the service life of the material, and will not reduce the high-brightness black appearance effect of the material after cleaning with an ethanol cleaning agent. It can be widely applied to automobiles, household appliances, etc., and scenarios that require a high-brightness black appearance without painting.

[0111] The above description of the embodiments is to enable those of ordinary skill in the art to understand and apply the present invention. Obviously, those skilled in the art can easily make various modifications to these embodiments and apply the general principles described herein to other embodiments without creative efforts. Therefore, the present invention is not limited to the embodiments herein, and the improvements and modifications made by those skilled in the art without departing from the scope of the present invention according to the disclosure of the present invention should be within the protection scope of the present invention.

Claims

1. A kind of ethanol-resistant, spray-free, high-brightness black ASA / PMMA material, characterized in that, Prepared from the following raw materials by weight percentage: PMMA resin 50%-60%, ASA resin 20%-30%, AS resin 10-20%, Toughening agent 5-15%, Antioxidant 0.5%-1.5%, Light stabilizer 1%-2%, Lubricant 0.1%-0.5%, Color powder 1%-2%.

2. The ethanol-resistant, spray-free, high-brightness black ASA / PMMA material according to claim 1, characterized in that The PMMA resin is a mixture of high melt index PMMA and low melt index PMMA. Among them, for the high melt index PMMA, under the test conditions of 230°C * 3.8 kg, the melt flow rate ranges from 7 to 10 g / 10 min. For the low melt index PMMA, under the test conditions of 230°C * 3.8 kg, the melt flow rate ranges from 2 to 5 g / 10 min. The mixing ratio is high melt index PMMA: low melt index PMMA = 1:

1.

3. The ethanol-resistant, spray-free, high-brightness black ASA / PMMA material according to claim 1, characterized in that, The particle size of the ASA resin is 300-500 μm, and the acrylate content is 50-60%.

4. The ethanol-resistant, spray-free, high-brightness black ASA / PMMA material according to claim 1, characterized in that, The acrylonitrile content of the AS resin is 30-40%.

5. The ethanol-resistant, spray-free, high-brightness black ASA / PMMA material according to claim 1, wherein The toughening agent is a mixture of a fully acrylate toughening agent and a silicone-acrylate toughening agent. Among them, the refractive index of the fully acrylate toughening agent is 1.

49. The mixing ratio is: fully acrylate toughening agent: silicone-acrylate toughening agent = 2:

1.

6. The ethanol-resistant, spray-free, high-brightness black ASA / PMMA material according to claim 1, wherein The antioxidant is a mixture of a hindered phenol antioxidant and a phosphite antioxidant. The mixing ratio is: hindered phenol antioxidant: phosphite antioxidant = 1:

2.

7. The ethanol-resistant, spray-free, high-brightness black ASA / PMMA material according to claim 1, wherein The light stabilizer is a mixture of a hindered amine light stabilizer and a benzotriazole light stabilizer. The mixing ratio is: hindered amine light stabilizer: benzotriazole light stabilizer = 1:

2.

8. The ethanol-resistant, spray-free, high-brightness black ASA / PMMA material according to claim 1, wherein The lubricant is pentaerythritol stearate.

9. The ethanol-resistant, spray-free, high-brightness black ASA / PMMA material according to claim 1, wherein The color powder is prepared by mixing one or more kinds.

10. The preparation method of the ethanol-resistant, spray-free, high-brightness black ASA / PMMA material according to any one of claims 1-9, characterized in that, The preparation steps are as follows: 1) Weigh polymethyl methacrylate (PMMA) resin, styrene-acrylonitrile (AS) resin, antioxidant, and lubricant, add them to a high-speed mixer and mix evenly, and then add the mixed materials to the main feeding port; 2) Weigh acrylonitrile-styrene-acrylate (ASA) resin, toughening agent, light stabilizer, and color powder, mix them evenly in a high-speed mixer, and then quantitatively add them through the side feeding port of the extruder. After melting, homogenizing, extruding, and pelletizing by the extruder, the final product is obtained.

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