A housing material, its preparation method and application

Abstract

The present invention provides a housing material, a preparation method thereof and an application. The housing material comprises the following raw materials by weight parts: 50-80 parts of recycled polycarbonate resin; 5-76 parts of silicone-containing polycarbonate resin; 5-10 parts of recycled acrylonitrile / butadiene / styrene copolymer resin; 6-12 parts of flame retardant; 2-4 parts of toughening agent; 2-4 parts of compatibilizer; 0.2-1.0 part of antioxidant; 0.3-3 parts of lubricant; 1-3 parts of coupling agent modified effect powder. The present invention can prepare a spray-free halogen-free flame retardant material by combining the inorganic mineral effect powder modified by the coupling agent with the recycled PC / ABS material. Through injection molding, plastic parts with natural texture effects such as starry sky can be produced. By optimizing the formula, the problems that the performance of recycled PC / ABS is poor compared with that of the virgin material and the effect powder affects the mechanical properties of the material are solved, and a recycled PC / ABS material with excellent mechanical properties, low defects, spray-free and halogen-free flame retardant is obtained.

Description

Technical Field

[0001] The present invention relates to the technical field of materials, and in particular to a housing material, a preparation method thereof, and an application thereof. Background Art

[0002] Plastic products are widely used in daily necessities, household appliances, 3C digital products, automotive interiors, packaging products, etc. As an alternative to painting, spray-free has the advantages of environmental friendliness, one-step molding, cost reduction, and production cycle shortening. It can directly achieve high gloss, metallic texture and other effects through injection molding. With the development of spray-free materials, many spray-free products have emerged on the market. However, current spray-free products are prone to surface defects such as flow marks, weld lines, and bright and dark lines, which limit the application of spray-free technology.

[0003] On the other hand, in order to obtain better appearance effects, spray-free plastics usually introduce some inorganic material effect powders to achieve appearance effects such as starry sky and terrazzo. Materials with special appearance requirements can be directly obtained through injection molding, eliminating the process of spraying paint. However, the poor compatibility between inorganic materials and the plastic matrix will further reduce the mechanical properties of the materials. When applied to components, component structure strengthening is required to meet the use requirements, which brings great limitations and cannot completely eliminate risks, and mechanical failures still occur from time to time.

[0004] At the same time, due to the wide application of plastic products, the global consumption of plastic products has increased year by year, and plastic waste has caused irreversible damage and pollution to the earth's environment. In order to slow down the trend of resource reduction and environmental deterioration, the recycling and reuse of consumed plastic products have received increasing attention, and relevant regulations have been formulated one after another to encourage the addition of recycled materials to virgin materials to reduce raw material costs and meet environmental protection requirements. Plastics containing recycled components have lower mechanical properties than virgin materials due to the lower performance of recycled plastics. How to improve the mechanical properties of recycled plastics is the main difficulty in the current plastic recycling and reuse. Summary of the Invention

[0005] In view of this, the technical problem to be solved by the present invention is to provide a housing material, a preparation method thereof, and an application thereof. The prepared housing material is a spray-free material and has the characteristics of low defects, excellent mechanical properties and flame retardant properties.

[0006] To achieve the above object, the present invention provides a housing material, which comprises the following raw materials by weight:

[0007]

[0008] The recycled polycarbonate resin used in the present invention can be a generally recycled polycarbonate resin, and there are no special restrictions on its source. Preferably, the recycled polycarbonate resin has a melt index of 10-20 g / 10 min when tested under the conditions of 300 °C * 1.2 kg.

[0009] The weight content of the recycled polycarbonate resin is 50-80 parts by weight, specifically 50, 60, 74 or 80 parts by weight.

[0010] The recycled acrylonitrile / butadiene / styrene copolymer resin can be a generally recycled acrylonitrile / butadiene / styrene copolymer resin, and there are no special restrictions on its source. Preferably, the content of the polybutadiene segment is 15%-25%, and the content is in mole fraction. The melt index of the recycled acrylonitrile / butadiene / styrene copolymer resin is preferably 15-35 g / 10 min when tested under the conditions of 220 °C * 10 kg.

[0011] The weight content of the recycled acrylonitrile / butadiene / styrene copolymer resin is 5-10 parts by weight, specifically 5 or 10 parts by weight.

[0012] The present invention uses recycled polycarbonate resin (PC) and recycled acrylonitrile / butadiene / styrene copolymer resin (ABS) as raw materials, which not only reduces the raw material cost but also meets the environmental protection requirements. However, the recycled PC / ABS material has the defect of low mechanical properties, and introducing the effect powder will further reduce the mechanical properties of the material.

[0013] In order not to affect the mechanical properties of the material, the effect powder is modified with a coupling agent in this application. Optionally, in the coupling agent-modified effect powder, the coupling agent is selected from epoxy-functionalized oligosiloxanes, more preferably 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane or 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. The effect powder is preferably a flaky silicate mineral.

[0014] The coupling agent-modified effect powder is prepared by mixing and reacting the coupling agent and the effect powder; during the reaction process, the coupling agent and the effect powder undergo a coupling reaction through hydroxyl groups.

[0015] The present invention uses 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane or 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane to pretreat the flaky silicate minerals. The organic substances on the surface are beneficial to the compatibility of the flaky silicate minerals, improve their dispersibility in the recycled PC / ABS material, and thus reduce the generation of material defects. Compared with the metal effect, the appearance defects are lower. At the same time, the coupling agent contains an active functional group, epoxy group, which can react with the end groups of PC and the compatibilizer acrylonitrile / styrene copolymer resin grafted with maleic anhydride. The oligosiloxyl groups are beneficial to improving the flame retardant performance of the material. The test results show that the effect powder after the above special modification is added to the recycled PC / ABS material, which well maintains the mechanical properties of the material, especially the impact resistance, and obtains excellent flame retardant performance. At the same time, using environmentally friendly flaky silicate minerals and recycled PC / ABS as raw materials reduces plastic pollution and carbon emissions, which has a positive significance for environmental protection.

[0016] The addition amount of the coupling agent is preferably 1 wt% - 10 wt% of the effect powder. Under this ratio condition, the coupling agent-modified effect powder prepared can obtain the best mechanical properties of the material.

[0017] The weight content of the coupling agent-modified effect powder is 1 - 3 parts by weight.

[0018] Meanwhile, the present application also adjusts other components in the material.

[0019] A silicone-containing polycarbonate resin is also added to the housing material. The content of polysiloxane in the silicone-containing polycarbonate resin is preferably 4% - 10% (molar content), and the melt index is preferably 10 - 20 g / 10 min when tested under the conditions of 300°C * 1.2 kg.

[0020] The weight content of the silicone-containing polycarbonate resin is preferably 5 - 76 parts by weight, and it can be 5, 20, 35 or 76 parts by weight.

[0021] The silicone-containing polycarbonate has better comprehensive mechanical properties, more excellent impact resistance, and the silicone and phosphorus-based flame retardants have a synergistic flame retardant performance, with higher flame retardant efficiency. At the same time, the added toughening agent plays a toughening effect, and the compatibilizer can improve the dispersion of the coupling agent-modified effect powder and enhance the material properties. Finally, a low-defect natural texture effect spray-free halogen-free flame retardant PC / ABS material is obtained, which takes into account the mechanical properties and excellent flame retardant performance. It can be injection molded once to produce plastic parts with natural texture effects such as starry sky feeling, and the surface of the products has no defects and a high yield.

[0022] The housing material further includes a flame retardant, which is preferably a phosphorus-based flame retardant, more preferably one or more of triphenyl phosphate and resorcinol bis(diphenyl phosphate). Using a phosphorus-based flame retardant can achieve a synergistic flame retardant effect with the silicon-containing polycarbonate, enabling the material to obtain more excellent flame retardant properties.

[0023] The weight content of the flame retardant is preferably 6 to 12 parts, specifically 6 or 12 parts by weight.

[0024] The housing material further includes a toughening agent, which is preferably a copolymerized methyl methacrylate-butadiene-styrene core-shell type impact modifier, and the content of the polybutadiene chain segment is preferably 50% to 70% (molar content).

[0025] The weight content of the toughening agent is preferably 2 to 4 parts, specifically 2, 3 or 4 parts by weight.

[0026] The housing material further includes a compatibilizer, which is preferably an acrylonitrile / styrene copolymer resin grafted with maleic anhydride, and its melt index is 5 to 20 g / 10 min when tested under the conditions of 200°C * 5 kg. The above compatibilizer can improve the dispersion performance of the coupling agent-modified powder, thereby enhancing the mechanical properties of the material.

[0027] The weight content of the compatibilizer is preferably 2 to 4 parts, specifically 2, 3 or 4 parts by weight.

[0028] The housing material further includes an antioxidant, which is preferably one or more of antioxidant 1076 and antioxidant 168; more preferably antioxidant 1076 and antioxidant 168. The weight content of antioxidant 1076 is preferably 0.1 to 0.5 parts by weight, and the weight content of antioxidant 168 is preferably 0.1 to 0.5 parts by weight. More preferably, the mass ratio of antioxidant 1076 to antioxidant 168 is 1:1.

[0029] The weight content of the antioxidant is preferably 0.2 to 1.0 parts.

[0030] The housing material further includes a lubricant, which is preferably pentaerythritol stearate.

[0031] The weight content of the lubricant is preferably 0.3 to 3 parts.

[0032] The housing material further includes a drip retardant, which is preferably polytetrafluoroethylene particles.

[0033] The weight content of the drip retardant is preferably 0.5 to 1 part.

[0034] The housing material further includes a weathering agent, which is preferably hydroxyphenylbenzotriazoles.

[0035] The weight content of the weathering agent is preferably 0.3 to 1 part.

[0036] When the material needs to have a certain color, color powder can also be added to the housing material.

[0037] The present invention does not specifically limit the color powder, which can be adjusted according to the color requirements of the product, including but not limited to carbon powder, or color powder of other colors, etc.

[0038] The addition amount of the color powder can be adjusted according to the material and color, and specifically can be 0.1 to 1.5 parts.

[0039] The present invention provides a preparation method of the above housing material, including the following steps:

[0040] A) Pretreat the effect powder with a coupling agent to obtain a coupling agent-modified effect powder;

[0041] B) Mix the recycled polycarbonate resin, silicon-containing polycarbonate resin, recycled acrylonitrile / butadiene / styrene copolymer resin, flame retardant, toughening agent, compatibilizer, antioxidant, lubricant and coupling agent-modified effect powder, and perform melt extrusion granulation to obtain the housing material.

[0042] The step A) is preferably specifically:

[0043] Place the effect powder in a mechanical stirrer, dropwise add the coupling agent while stirring, the stirring speed of the mechanical stirrer is preferably 50 to 100 r / min, the coupling agent is added dropwise at a constant speed, and the dropping is completed in 5 to 10 minutes. After the dropping is completed, continue to stir for 5 to 20 minutes, and the reaction is completed to obtain the coupling agent-modified effect powder.

[0044] Then weigh the recycled polycarbonate resin, silicon-containing polycarbonate resin, recycled acrylonitrile / butadiene / styrene copolymer resin, flame retardant, toughening agent, compatibilizer, antioxidant, lubricant and coupling agent-modified effect powder by weight parts, add them to a blender for pre-dispersion, the stirring speed is preferably 30 to 80 r / min, after mixing evenly, add them to a twin-screw extruder for melt extrusion granulation.

[0045] The parameter settings of the twin-screw extruder are preferably: the temperatures of the first to fifth extrusion zones are 220°C, 230°C, 240°C, 240°C, and 250°C in sequence, and the twin-screw rotation speed is 300 - 500 r / min. The setting of these parameters can ensure a high qualified rate of the material.

[0046] The above housing material can obtain the product through injection molding, and is applicable to common plastic products, such as household appliances, computers, decorative parts, etc., such as desktop and all-in-one decorative structural parts.

[0047] The present invention also provides a plastic product housing, which is prepared from the above-mentioned housing material.

[0048] Due to the addition of the effect powder, the above-mentioned plastic product housing can obtain an appearance similar to that of the starry sky or marble texture, making the product more beautiful. At the same time, it has excellent mechanical properties (especially impact resistance) and flame retardant properties, which can optimize the structural design of electronic products.

[0049] Compared with the prior art, the present invention provides a housing material. The present invention uses an inorganic mineral effect powder modified by a coupling agent in combination with recycled PC / ABS material to prepare a spray-free halogen-free flame retardant material. Through injection molding, plastic parts with natural texture effects such as starry sky can be produced. By optimizing the formula, the problems of the poor performance of recycled PC / ABS compared to virgin materials and the influence of the effect powder on the mechanical properties of the material are solved, and a recycled PC / ABS material with excellent mechanical properties, low defects, spray-free and halogen-free flame retardant is obtained. It can be injection molded once to produce plastic parts with natural texture effects such as starry sky, and the surface of the products has no defects and a high yield. Description of the Drawings

[0050] Figure 1 Appearance diagram of the PC / ABS material prepared in Example 1. Detailed Embodiments

[0051] In order to further illustrate the present invention, the housing material provided by the present invention, its preparation method and application will be described in detail below with reference to the embodiments.

[0052] Example 1

[0053] (1) Pretreat the effect powder with a coupling agent:

[0054] Place the sprinkling effect powder in a mechanical stirrer, where the addition amount of the coupling agent is 1 wt% of the effect powder. While stirring, drop the coupling agent. The stirring speed of the mechanical stirrer is 80 r / min, and the coupling agent is dropped at a uniform speed and finished dropping in 10 minutes. After dropping, continue to stir for 10 minutes and set aside after completion.

[0055] (2) Prepare a low-defect spray-free halogen-free flame retardant PC / ABS material, and weigh according to parts by weight:

[0056]

[0057] The above raw materials are mechanically mixed evenly at a stirring speed of 50 r / min. After mixing evenly, add them to a twin-screw extruder. The temperatures of the first to fifth zones of the extruder are 220 °C, 230 °C, 240 °C, 240 °C, and 250 °C in sequence, and the twin-screw speed is 500 r / min, thus obtaining the described low-defect natural texture effect spray-free halogen-free flame retardant PC / ABS material.

[0058] The recycled polycarbonate resin has a melt index of 10 g / 10 min when tested under the conditions of 300 °C * 1.2 kg;

[0059] The content of polysiloxane in the silicone-containing polycarbonate resin is 4%, and the melt index is 10 g / 10 min when tested under the conditions of 300 °C * 1.2 kg;

[0060] The recycled acrylonitrile / butadiene / styrene copolymer resin contains 20% polyacrylonitrile and 15% polybutadiene chain segments, and has a melt index of 20 g / 10 min when tested under the conditions of 220 °C * 10 kg;

[0061] The coupling agent is epoxy-functionalized oligomeric siloxane Dynasylan 2926, and its addition amount is 1% of the effect powder;

[0062] The flame retardant is triphenyl phosphate;

[0063] The toughening agent is a copolymerized methyl methacrylate-butadiene-styrene core-shell type impact modifier with a polybutadiene chain segment content of 50%;

[0064] The compatibilizer is acrylonitrile / styrene copolymer resin grafted with maleic anhydride, and it has a melt index of 5 g / 10 min when tested under the conditions of 200 °C * 5 kg;

[0065] The lubricant is pentaerythritol stearate;

[0066] The weathering agent is UV-P;

[0067] The color powder is carbon black;

[0068] The pretreated effect powder is sheet silicate.

[0069] Example 2

[0070] The difference between Example 2 and Example 1 is that 50 parts of the recycled polycarbonate resin and 35 parts of the silicone-containing polycarbonate resin are used.

[0071] Example 3

[0072] The difference between Example 3 and Example 1 is that 60 parts of the recycled polycarbonate resin, 20 parts of the silicone-containing polycarbonate resin, and 10 parts of the recycled acrylonitrile / butadiene / styrene copolymer resin are used.

[0073] Example 4

[0074] The difference between Example 4 and Example 1 is that 74 parts of the recycled polycarbonate resin and 12 parts of the flame retardant are used.

[0075] Example 5

[0076] Example 5 is different from Example 1 in that 76 parts of the silicone-containing polycarbonate resin, 4 parts of the toughening agent, and 4 parts of the compatibilizer are used.

[0077] Example 6

[0078] Example 6 is different from Example 1 in that 1 part of the anti-dripping agent is used.

[0079] Example 7

[0080] Example 7 is different from Example 1 in that 0.5 part of antioxidant 1# and 0.5 part of antioxidant 2# are used.

[0081] Example 8

[0082] Example 8 is different from Example 1 in that 3 parts of the lubricant are used.

[0083] Example 9

[0084] Example 9 is different from Example 1 in that 1 part of the weathering agent is used.

[0085] Example 10

[0086] Example 10 is different from Example 1 in that the addition amount of the coupling agent is 10% of the effect powder.

[0087] Example 11

[0088] Example 11 is different from Example 1 in that the recycled polycarbonate resin has a melt index of 20 g / 10 min when tested under the conditions of 300 °C * 1.2 kg.

[0089] Example 12

[0090] Example 12 is different from Example 1 in that the content of polysiloxane in the silicone-containing polycarbonate resin is 10%.

[0091] Example 13

[0092] Example 13 is different from Example 1 in that the silicone-containing polycarbonate resin has a melt index of 20 g / 10 min when tested under the conditions of 300 °C * 1.2 kg.

[0093] Example 14

[0094] Example 14 is different from Example 1 in that the recycled acrylonitrile / butadiene / styrene copolymer resin has a polybutadiene content of 25%.

[0095] Example 15

[0096] Example 15 is different from Example 1 in that the recycled acrylonitrile / butadiene / styrene copolymer resin has a melt index of 30 g / 10 min when tested under the conditions of 220 °C * 10 kg.

[0097] Example 16

[0098] Example 16 is different from Example 1 in that the flame retardant is resorcinol bis(diphenyl phosphate).

[0099] Example 17

[0100] Example 17 is different from Example 1 in that the toughening agent is a copolymerized methyl methacrylate-butadiene-styrene core-shell impact modifier with a polybutadiene content of 70%.

[0101] Example 18

[0102] Example 18 is different from Example 1 in that the compatibilizer is acrylonitrile / styrene copolymer resin grafted with maleic anhydride, which has a melt index of 20 g / 10 min when tested under the conditions of 200 °C * 5 kg.

[0103] Comparative Example 1

[0104] The recycled polycarbonate resin, recycled acrylonitrile / butadiene / styrene copolymer, flame retardant, toughening agent, compatibilizer, anti-dripping agent, antioxidant 1#, antioxidant 2#, lubricant, weathering agent, color powder, and effect powder were mechanically mixed evenly at a stirring speed of 50 r / min. After mixing evenly, they were added to a twin-screw extruder. The temperatures of the first to fifth zones of the extruder were 220 °C, 230 °C, 240 °C, 240 °C, and 250 °C in sequence, and the twin-screw rotation speed was 500 r / min, thus obtaining the described low-defect natural texture effect spray-free halogen-free flame-retardant PC / ABS material;

[0105] Weigh according to parts by weight:

[0106]

[0107] The recycled polycarbonate resin has a melt index of 10 g / 10 min when tested under the conditions of 300 °C * 1.2 kg;

[0108] The recycled acrylonitrile / butadiene / styrene copolymer resin contains 20% polyacrylonitrile and 15% polybutadiene content, and has a melt index of 20 g / 10 min when tested under the conditions of 220 °C * 10 kg.

[0109] The flame retardant is triphenyl phosphate;

[0110] The toughener is a copolymerized methyl methacrylate-butadiene-styrene core-shell impact modifier with a polybutadiene content of 50%;

[0111] The compatibilizer is acrylonitrile / styrene copolymer resin grafted with maleic anhydride, and its melt index is 5 g / 10 min when tested under the conditions of 200 °C * 5 kg;

[0112] The anti-dripping agent is polytetrafluoroethylene particles;

[0113] The antioxidant No. 1 is antioxidant 1076;

[0114] The antioxidant No. 2 is antioxidant 168;

[0115] The lubricant is pentaerythritol stearate;

[0116] The weathering agent is UV-P;

[0117] The color powder is carbon black;

[0118] Comparative Example 2

[0119] The difference between Comparative Example 2 and Comparative Example 1 is that 1 part of the effect powder is added.

[0120] Comparative Example 3

[0121] The difference between Comparative Example 3 and Comparative Example 1 is that 1 part of the coupling agent-modified effect powder identical to that in Example 1 is added.

[0122] Comparative Example 4

[0123] The difference between Comparative Example 4 and Comparative Example 1 is that 1 part of the unpretreated effect powder is added and 5 parts of a silicone-containing polycarbonate resin are added.

[0124] The content of polysiloxane in the silicone-containing polycarbonate resin is 4%, and its melt index is 10 g / 10 min when tested under the conditions of 300 °C * 1.2 kg.

[0125] Tests show that the unmodified effect powder causes obvious flow marks during the injection molding of the prepared material.

[0126] Performance test:

[0127] The mechanical properties of Examples 1-18 and Comparative Examples 1-4 were tested.

[0128] Test method:

[0129] Table 1 Test conditions and test standards

[0130]

[0131]

[0132] The test results are shown in Table 2 as follows:

[0133] Table 2 Test results of various performances of Examples 1-18 and Comparative Examples 1-4

[0134]

[0135]

[0136] The description of the above embodiments is only used to help understand the method and its core idea of the present invention. It should be noted that for those of ordinary skill in the art of this technology, without departing from the principle of the present invention, several improvements and modifications can be made to the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.

Claims

1. A housing material, by weight, comprises the following raw materials: In the coupling agent-modified effect powder, the coupling agent is 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane or 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; the effect powder is selected from sheet silicate minerals; The compatibilizer is selected from acrylonitrile / styrene copolymer resin grafted maleic anhydride; The epoxy group in the structure of the coupling agent reacts with the end groups of the recycled polycarbonate resin and the acrylonitrile / styrene copolymer resin grafted maleic anhydride of the compatibilizer, improving the flame retardancy and impact resistance of the material.

2. The housing material according to claim 1, characterized in that, The coupling agent-modified effect powder is prepared by mixing the coupling agent and the effect powder for reaction; The addition amount of the coupling agent is 1wt% - 10wt% of the effect powder.

3. The housing material according to claim 1, wherein The recycled polycarbonate resin has a melt index of 10 - 20 g / 10min when tested under the conditions of 300°C * 1.2 kg; In the silicon-containing polycarbonate resin, the molar percentage content of polysiloxane is 4% - 10%, and the melt index is 10 - 20 g / 10min when tested under the conditions of 300°C * 1.2 kg; The recycled acrylonitrile / butadiene / styrene copolymer resin has a polybutadiene chain segment content of 15% - 25%, and the melt index is 15 - 35 g / 10min when tested under the conditions of 220°C * 10 kg.

4. The housing material according to claim 1, characterized in that, The flame retardant is selected from one or more of triphenyl phosphate and resorcinol bis(diphenyl phosphate).

5. The housing material according to claim 1, wherein The toughening agent is selected from copolymerized methyl methacrylate-butadiene-styrene core-shell impact modifiers, in which the molar percentage content of the polybutadiene chain segment is 50% - 70%.

6. The housing material according to claim 1, characterized in that, The acrylonitrile / styrene copolymer resin grafted maleic anhydride has a melt index of 5 - 20 g / 10min when tested under the conditions of 200°C * 5 kg.

7. The housing material according to claim 1, wherein The antioxidant is selected from one or more of antioxidant 1076 and antioxidant 168; The lubricant is pentaerythritol stearate; The raw materials further include an anti-dripping agent; The anti-dripping agent is selected from polytetrafluoroethylene particles; The raw materials further include a weathering agent; The weathering agent is a hydroxyphenylbenzotriazole type.

8. The preparation method of the housing material according to any one of claims 1 to 7, comprising the following steps: A) Pretreat the effect powder with a coupling agent to obtain a coupling agent-modified effect powder; B) Mix the recycled polycarbonate resin, the silicon-containing polycarbonate resin, the recycled acrylonitrile / butadiene / styrene copolymer resin, the flame retardant, the toughening agent, the compatibilizer, the antioxidant, the lubricant and the coupling agent-modified effect powder and melt-extrude and pelletize them to obtain the housing material.

9. A plastic product housing prepared from the housing material according to any one of claims 1 to 7.

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