Polycarbonate composite material, flocking-imitating master batch as well as preparation method and application of flocking-imitating master batch

Abstract

The invention relates to a polycarbonate composite material, a flocking-imitating master batch as well as a preparation method and application of the flocking-imitating master batch. The polycarbonate composite material is prepared from the following raw materials in percentage by mass: 80 to 95 percent of resin base material and 5 to 20 percent of flocking-imitating master batch, wherein the resin base material contains first PC resin; the flocking-imitating master batch comprises the following components in percentage by mass: 65.3%-90% of second PC resin, 5.3%-30% of fluff and 1.4%-4.7% of an auxiliary agent, wherein the total mass percentage of the flocking-imitating master batch is 100%. The polycarbonate composite material has a relatively good flocking-imitating effect and good flame retardance and mechanical properties.

Description

Technical Field

[0001] The present application relates to the field of polycarbonate materials, and in particular to a polycarbonate composite material, a flocking-like masterbatch, and a preparation method and application thereof. Background Art

[0002] In recent years, the application scope of polycarbonate (PC) resin materials has gradually expanded in the fields of consumer goods, electronic and electrical, and security monitoring. In traditional applications, polycarbonate is used as a substrate, and when a certain effect is finally presented, it often needs to be sprayed on the surface. However, surface spraying has problems such as complex process, long time consumption, high overall cost, large environmental pollution of the production line, high defect rate, and exposure of the substrate after the paint surface is damaged and peeled off. The spray-free material can be injection molded with the effect component to be presented and the resin at one time, which can meet the aesthetics of plastic parts while taking into account the application performance. In addition, the product does not require post-spraying treatment, is energy-saving and environmentally friendly, has a short production cycle, and high production efficiency. It can greatly reduce the overall cost of industrialization, and at the same time can give the product surface a rich aesthetic feel to meet different application scenarios and growing personalized requirements.

[0003] Plastic products with special aesthetic effects are becoming more and more popular. Among them, the imitation flocking effect is widely loved by consumers and manufacturers due to its unique and elegant texture, simulated three-dimensional fiber feeling and soft and skin-friendly visual effect. However, the current spray-free polycarbonate products still have the problem of not being able to combine good imitation flocking effect with flame retardancy and mechanical properties, which limits their further application. Summary of the invention

[0004] Based on this, some embodiments of the present application provide a polycarbonate composite material having good flocking effect and good flame retardancy and mechanical properties and a preparation method thereof.

[0005] In addition, other embodiments of the present application also provide a flocking-like masterbatch and a preparation method and application thereof.

[0006] A polycarbonate composite material, wherein the raw materials for preparing the polycarbonate composite material include, by mass percentage: 80% to 95% of a resin base material and 5% to 20% of a flocking-like masterbatch;

[0007] The resin base material contains a first PC resin; taking the total mass percentage of the flocking imitation masterbatch as 100%, the flocking imitation masterbatch includes: 65.3% to 90% of the first PC resin, 5.3% to 30% of the fluff, and 1.4% to 4.7% of the additive.

[0008] In some of the embodiments, in the flocking-like masterbatch, the mass percentage of the fluff is 10% to 25%.

[0009] In some embodiments, in the flocking-like masterbatch, the mass percentage of the second PC resin is 72% to 87%.

[0010] In some of the embodiments, the raw materials for preparing the polycarbonate composite material include, by mass percentage: 80% to 90% of a resin base material and 10% to 20% of a flocking-like masterbatch.

[0011] In some embodiments, the additives include 0.1% to 0.3% by mass of the second antioxidant, 0.1% to 0.4% by mass of the second lubricant, 0.2% to 1% by mass of the second flame retardant and 1% to 3% by mass of the second white masterbatch.

[0012] In some embodiments, the fluff includes one or more of fiber filaments, marble filaments and injection-molded fiber wool.

[0013] In some embodiments, the average fiber diameter of the fluff is 0.015 mm to 0.15 mm, and the average fiber length is 0.5 mm to 1.5 mm;

[0014] In some of these embodiments, the fluff includes a mixture of fluffs having different average fiber lengths and / or average fiber diameters.

[0015] In some embodiments, the fluff includes a first fluff, a second fluff and a third fluff in a mass ratio of 1: (0.5~1.5): (0.5~1), the average fiber diameter of the first fluff ≤ the average fiber diameter of the second fluff < the average fiber diameter of the third fluff, and the average fiber length of the first fluff > the average fiber length of the second fluff > the average fiber length of the third fluff.

[0016] In some of the embodiments, the resin base material includes, by weight: 80 to 95 parts of a first PC resin, 0 to 1 part of a first antioxidant, 0 to 4 parts of a first lubricant, 0 to 2 parts of a first flame retardant, 1 to 3 parts of a first white masterbatch, and 0.001 to 0.01 parts of a color powder.

[0017] In some embodiments, the resin base material includes, by weight: 80 to 90 parts of a first PC resin, 0.1 to 0.3 parts of a first antioxidant, 0.1 to 0.4 parts of a first lubricant, 0.2 to 1 parts of a first flame retardant, 1 to 3 parts of a first white masterbatch, and 0.001 to 0.01 parts of a color powder.

[0018] In some embodiments, the resin base material includes, by weight: 80 to 90 parts of a first PC resin, 0.1 to 0.3 parts of a first antioxidant, 0.1 to 0.4 parts of a first lubricant, 0.7 to 1 parts of a first flame retardant, 2 to 3 parts of a first white masterbatch, and 0.005 to 0.01 parts of a color powder.

[0019] In some embodiments, the resin base material includes a first PC resin, a first antioxidant, a first lubricant, a first flame retardant, a first white masterbatch and a color powder; in terms of weight percentage, the raw materials for preparing the polycarbonate composite material include: 5 to 20 parts of the flocking masterbatch, 80 to 95 parts of the first PC resin, 0 to 1 part of the first antioxidant, 0 to 4 parts of the first lubricant, 0 to 2 parts of the first flame retardant, 1 to 3 parts of the first white masterbatch and 0.001 to 0.01 parts of the color powder.

[0020] In some of the embodiments, the raw materials for preparing the polycarbonate composite material include, by weight: 10 to 20 parts of flocking masterbatch, 80 to 90 parts of a first PC resin, 0.1 to 0.3 parts of a first antioxidant, 0.1 to 0.4 parts of a first lubricant, 0.2 to 1 parts of a first flame retardant, 1 to 3 parts of a first white masterbatch and 0.001 to 0.01 parts of a color powder.

[0021] In some of the embodiments, the raw materials for preparing the polycarbonate composite material include, by weight: 10 to 20 parts of flocking masterbatch, 80 to 90 parts of a first PC resin, 0.1 to 0.3 parts of a first antioxidant, 0.1 to 0.4 parts of a first lubricant, 0.7 to 1 parts of a first flame retardant, 2 to 3 parts of a first white masterbatch and 0.005 to 0.01 parts of a color powder.

[0022] In some embodiments, when the test condition is 300° C. and the load is 1.2 kg, the melt flow index of the first PC resin and the second PC resin is independently 3 g / 10 min to 65 g / 10 min.

[0023] In some embodiments, when the test conditions are 300° C. and a load of 1.2 kg, the melt flow index of the first PC resin and the second PC resin are independently 5 g / 10 min to 40 g / 10 min.

[0024] In some embodiments, when the test conditions are 300° C. and a load of 1.2 kg, the melt flow index of the first PC resin and the second PC resin are independently 7 g / 10 min to 30 g / 10 min.

[0025] A method for preparing a polycarbonate composite material comprises the following steps:

[0026] The following raw materials are obtained by weight percentage: 80% to 95% of a resin base material and 5% to 20% of a flocking imitation masterbatch; wherein the resin base material contains a first PC resin; taking the total weight percentage of the flocking imitation masterbatch as 100%, the flocking imitation masterbatch includes: 65.3% to 90% of a first PC resin, 5.3% to 30% of fluff, and 1.4% to 4.7% of an additive;

[0027] The flocking-like masterbatch and the resin base material are mixed and injection-molded to prepare a composite material.

[0028] In some embodiments, the preparation steps of the flocking-like masterbatch include:

[0029] At a first rotation speed, the fluff and a portion of the second PC resin are mixed, and the remaining second PC resin and the additive are added and continued to mix;

[0030] The obtained mixture is extruded and granulated to prepare the flocking-like masterbatch;

[0031] The first rotation speed is smaller than the second rotation speed, and the second rotation speed is the rotation speed in the step of mixing the flocking-like masterbatch and the resin base material.

[0032] In some embodiments, the first rotation speed is 50 rpm to 80 rpm, and the second rotation speed is 100 rpm to 200 rpm.

[0033] In some embodiments, the mass percentage of the second PC resin to the total mass percentage of the second PC resin is 40% to 60%.

[0034] In some embodiments, in the step of extrusion granulation, the extrusion temperature is 270° C. to 300° C., and the screw speed is 200 rpm to 1000 rpm.

[0035] In some of the embodiments, in the injection molding step, the injection temperature is 290° C. to 310° C., the injection pressure is 50 MPa to 65 MPa, and the rotation speed of the injection molding machine is 200 rpm to 500 rpm.

[0036] Application of the polycarbonate composite material as described above or the polycarbonate composite material prepared by the preparation method as described above in the electronic and electrical fields, security monitoring fields, home appliance casing fields or consumer product fields.

[0037] In some of the embodiments, the polycarbonate composite material is used in the preparation of electronic and electrical products, security monitoring products, home appliance housings or consumer products.

[0038] A method for preparing flocking imitation masterbatch comprises the following steps:

[0039] The following raw materials were obtained by mass percentage: 65.3% to 90% of the second PC resin, 5.3% to 30% of the fluff, and 1.4% to 4.7% of the additive;

[0040] At a rotation speed of 50 rpm to 80 rpm, the fluff and a portion of the second PC resin are mixed, and the remaining second PC resin and the additive are added and continued to mix;

[0041] The obtained mixture is extruded and granulated to prepare the flocking-like masterbatch.

[0042] In some embodiments, in the step of extrusion granulation, the extrusion temperature is 270° C. to 300° C., and the screw speed is 200 rpm to 1000 rpm.

[0043] In some embodiments, the weight percentage of the second PC resin to the total second PC resin is 40% to 60%.

[0044] A flocking imitation masterbatch is prepared by the above-mentioned preparation method.

[0045] The present application study found that due to the high processing temperature of polycarbonate, if the traditional process is used to directly mix the fluff with the polycarbonate resin and additives, during the subsequent processing and molding process, the fluff will be cut into pieces and dyed due to poor shear resistance and heat resistance, and will not be able to maintain a good appearance effect, resulting in a poor imitation flocking effect of the spray-free polycarbonate product. In order to improve its imitation flocking effect, traditional technology usually increases the amount of fluff added, but at the same time it will lead to a significant decrease in the flame retardancy and mechanical properties of the polycarbonate material. Therefore, it is difficult for polycarbonate materials in traditional technology to have both good imitation flocking effect and good flame retardancy and mechanical properties. Based on this, some embodiments of the present application provide a polycarbonate composite material, including a resin base material and a flocking-like masterbatch, the resin base material contains a first PC resin, and the flocking-like masterbatch includes a certain ratio of fluff, a second PC resin and an additive. The fluff is added to the polycarbonate composite material in the form of a flocking-like masterbatch, and the proportion of each component is adjusted so that it is not easily cut into pieces during high-temperature, high-shear heat processing and molding. With a smaller amount added than traditional technology, a good and obvious matte flocking surface effect is achieved, and a realistic rock texture can be presented at multiple visual angles. At the same time, good mechanical properties and flame retardant properties are guaranteed, and the contradiction between the flocking effect with good length retention and the mechanical and flame retardant properties of the material is solved, providing a polycarbonate material with a flocking spray-free effect and excellent flame retardant and mechanical properties, which has an obvious, unique and elegant texture, simulated three-dimensional fiber feel and soft and skin-friendly visual effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required for use in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0047] Figure 1 A schematic diagram of a process flow of a method for preparing a polycarbonate composite material according to some embodiments of the present application;

[0048] Figure 2 This is an appearance rendering of the polycarbonate composite material prepared in Example 1 of the present application;

[0049] Figure 3 This is an appearance rendering of the polycarbonate composite material prepared in Example 3 of the present application;

[0050] Figure 4 This is an appearance effect diagram of the polycarbonate composite material prepared in Comparative Example 1 of the present application;

[0051] Figure 5 This is an appearance rendering of the polycarbonate composite material prepared in Comparative Example 2 of the present application. DETAILED DESCRIPTION

[0052] In order to facilitate the understanding of the present application, the present application will be described more comprehensively below in conjunction with the specific embodiments. The preferred embodiments of the present application are provided in the specific embodiments. However, the present application can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present application more thorough and comprehensive.

[0053] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art to which the present application belongs. The terms used herein in the specification of the present application are only for the purpose of describing specific embodiments and are not intended to limit the present application. The term "and / or" used herein includes any and all combinations of one or more related listed items.

[0054] Unless otherwise specified or there is a contradiction, the terms and phrases used in this application have the following meanings:

[0055] In this application, "first" and "second" are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Therefore, a feature defined as "first" or "second" may explicitly or implicitly include at least one of the features.

[0056] In the description of the present application, “plurality” means at least two, for example, two, three, etc., unless otherwise clearly and specifically defined.

[0057] In this application, "one or several" refers to any one, any two or more of the listed items. Among them, "several" refers to any two or more of the listed items.

[0058] In this application, the percentage concentration involved, unless otherwise specified, refers to the final concentration. The final concentration refers to the proportion of the added component in the system after the addition of the component.

[0059] In this document, "further", "further", "particularly", "for example", "such as", "example", "for example", etc. are used for descriptive purposes, indicating that the previous and subsequent technical solutions are related in terms of the content covered, but should not be understood as a limitation on the previous technical solution, nor can it be understood as a limitation on the protection scope of this document. In this document, unless otherwise specified, A (such as B) means that B is a non-limiting example of A, and it can be understood that A is not limited to B.

[0060] Herein, "optionally", "optional", and "optional" mean optional, that is, any one of the two parallel schemes of "yes" or "no". If multiple "optional" items appear in a technical solution, unless otherwise specified and there is no contradiction or mutual restriction, each "optional" item is independent of each other. In this application, descriptions such as "optionally contain", "optionally include", etc. mean "contain or not contain". "Optional component X" means that component X exists or does not exist, or means that component X is contained or not contained.

[0061] When a numerical range is disclosed in this application, the above range is considered to be continuous and includes the minimum and maximum values ​​of the range, as well as every value between such minimum and maximum values. Further, when a range refers to an integer, every integer between the minimum and maximum values ​​of the range is included. In addition, when multiple ranges are provided to describe features or characteristics, the ranges can be combined. In other words, unless otherwise indicated, all ranges disclosed in this application should be understood to include any and all subranges included therein.

[0062] In the present application, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.

[0063] The terms "including" and "having" and any variations thereof in the embodiments of the present application are intended to cover non-exclusive inclusions. For example, a process, method, system, product, or device that includes a series of steps or units is not limited to the listed steps or units, but may optionally include steps or units that are not listed, or may optionally include other steps or components that are inherent to these processes, methods, products, or devices.

[0064] Reference to "embodiments" in this application means that a particular feature, structure, or characteristic described in conjunction with the embodiments may be included in at least one embodiment of the present application. The appearance of the phrase in various locations in the specification does not necessarily refer to the same embodiment, nor is it an independent or alternative embodiment that is mutually exclusive with other embodiments. It is explicitly and implicitly understood by those skilled in the art that the embodiments described in this application may be combined with other embodiments.

[0065] The first aspect of the present application provides a polycarbonate composite material. The raw materials for preparing the polycarbonate composite material include, by mass percentage: 80% to 95% of a resin base material and 5% to 20% of a flocking-like masterbatch;

[0066] The resin base material contains a first PC resin; taking the total mass percentage of the flocking imitation masterbatch as 100%, the flocking imitation masterbatch includes: 65.3% to 90% of the second PC resin, 5.3% to 30% of the fluff, and 1.4% to 4.7% of the additive.

[0067] The present application study found that due to the high processing temperature of polycarbonate, if the traditional process is used to directly mix the fluff with the polycarbonate resin and additives, during the subsequent processing and molding process, the fluff will be cut into pieces and dyed to maintain a good appearance due to its poor shear resistance and heat resistance, resulting in a poor flocking effect of the spray-free polycarbonate product. In order to improve its flocking effect, the amount of fluff added is usually increased, but at the same time it will lead to a significant decrease in the flame retardancy and mechanical properties of the polycarbonate material, thereby affecting its application in the fields of electronic and electrical, security monitoring, home appliance housings, consumer products, etc. with strict performance requirements. Therefore, it is difficult for polycarbonate materials in traditional technologies to have both good flocking effects and good flame retardancy and mechanical properties.

[0068] Based on this, some embodiments of the present application provide a polycarbonate composite material, including a resin base material and a flocking-like masterbatch, the resin base material contains a first PC resin, and the flocking-like masterbatch includes a certain ratio of fluff, a second PC resin and an additive, by adding the fluff into the polycarbonate composite material in the form of a flocking-like masterbatch, and adjusting the proportion of each component, so that it is not easy to be cut into pieces during high-temperature, high-shear heat processing and molding, and a good and obvious matte flocking surface effect is achieved when the addition amount is less than that of traditional technology, and a realistic rock texture can be presented at a variety of visual angles, which adds beauty to the spray-free products. At the same time, good mechanical properties and flame retardant properties are guaranteed, and the contradiction between the flocking effect with good length retention and the mechanical and flame retardant properties of the material is solved, and a polycarbonate material with obvious, unique and elegant texture, simulated three-dimensional fiber feel and soft skin-friendly visual effect is provided. The flocking-free spraying effect and excellent flame retardant and mechanical properties are provided, which can be used in the fields of electronic and electrical, security monitoring, home appliance housing, consumer products, etc. with strict requirements on appearance, production process and performance, and has good economic development prospects and broad industrial application value.

[0069] In one example, in the raw materials for preparing the polycarbonate composite material, the mass percentage of the resin base material can be, but is not limited to, 80%, 82%, 84%, 85%, 86%, 88%, 90%, 92%, 94%, 95%, or a range consisting of any two of these values. Optionally, in the raw materials for preparing the polycarbonate composite material, the mass percentage of the resin base material is 80% to 90%.

[0070] In one example, in the raw material for preparing the polycarbonate composite material, the mass percentage of the flocking masterbatch can be, but is not limited to, 5%, 6%, 8%, 10%, 12%, 14%, 15%, 16%, 18%, 20%, or a range consisting of any two of these values. Optionally, in the raw material for preparing the polycarbonate composite material, the mass percentage of the flocking masterbatch is 10% to 20%.

[0071] In one of the embodiments, the raw materials for preparing the polycarbonate composite material include, by mass percentage: 80% to 90% of a resin base material and 10% to 20% of a flocking-like masterbatch.

[0072] In some embodiments, the resin base material includes a first PC resin, a first antioxidant, a first lubricant, a first flame retardant, a first white masterbatch and a color powder. In some embodiments, the resin base material includes, by weight: 80 to 95 parts of the first PC resin, 0 to 1 part of the first antioxidant, 0 to 4 parts of the first lubricant, 0 to 2 parts of the first flame retardant, 1 to 3 parts of the first white masterbatch and 0.001 to 0.01 parts of the color powder.

[0073] Optionally, the resin base material includes, by weight: 80 to 90 parts of a first PC resin, 0.1 to 0.3 parts of a first antioxidant, 0.1 to 0.4 parts of a first lubricant, 0.2 to 1 parts of a first flame retardant, 1 to 3 parts of a first white masterbatch and 0.001 to 0.01 parts of a color powder.

[0074] Optionally, the resin base material includes, by weight: 80 to 90 parts of a first PC resin, 0.1 to 0.3 parts of a first antioxidant, 0.1 to 0.4 parts of a first lubricant, 0.7 to 1 parts of a first flame retardant, 2 to 3 parts of a first white masterbatch and 0.005 to 0.01 parts of a color powder.

[0075] Furthermore, the resin base material includes, by weight: 80 to 90 parts of a first PC resin, 0.2 parts of a first antioxidant, 0.2 parts of a first lubricant, 0.7 to 1 parts of a first flame retardant, 2 to 3 parts of a first white masterbatch and 0.0062 parts of a color powder.

[0076] In one example, in the flocking-like masterbatch, the mass percentage of the second PC resin can be, but is not limited to, 65.3%, 68%, 70%, 72%, 75%, 80%, 85%, 86%, 87%, 88%, 89%, 90%, or a range consisting of any two of these values. Optionally, in the flocking-like masterbatch, the mass percentage of the second PC resin is 72% to 87%.

[0077] In one example, in the flocking-like masterbatch, the mass percentage of the fluff can be, but is not limited to, 5.3%, 6%, 7%, 8%, 9%, 10%, 15%, 20%, 25%, 30%, or a range consisting of any two of these values. Optionally, in the flocking-like masterbatch, the mass percentage of the fluff is 10% to 25%.

[0078] In some of the embodiments, taking the total mass percentage of the flocking imitation masterbatch as 100%, the flocking imitation masterbatch includes: 72% to 87% of the second PC resin, 10% to 25% of the fluff, and 1.4% to 4.7% of the additive.

[0079] In some embodiments of the present application, by optimizing the content of the fluff and the amount of flocking masterbatch, the prepared polycarbonate composite material can have good flocking effect, mechanical properties and flame retardant properties. Specifically, when the fluff content is too little, it is easy to be covered by additives such as white masterbatch and color powder, and the simulated three-dimensional fiber feeling and soft skin-friendly visual effect are not rich; when the fluff content is too much, the flame retardant properties of the polycarbonate composite material are significantly reduced. In addition, the fluff stays in the screw for a long time, and the shear heat accumulates a lot, which will cause the fluff color to fall off and cause the base color of the workpiece to change. At the same time, the average molecular weight of the prepared polycarbonate composite material is reduced, the melt index is increased, and the impact resistance of the material is weakened.

[0080] In some embodiments, the flock includes one or more of fiber filaments, marble filaments and injection-molded fiber wool. The above-mentioned flock is applied to the polycarbonate composite material to achieve a three-dimensional and rich flocking appearance effect.

[0081] In some embodiments, the average fiber diameter of the fluff is 0.015 mm to 0.15 mm, and the average fiber length is 0.5 mm to 1.5 mm. For example, the average fiber diameter of the fluff can be, but is not limited to, 0.015 mm, 0.02 mm, 0.03 mm, 0.05 mm, 0.06 mm, 0.08 mm, 0.1 mm, 0.12 mm, 0.14 mm, 0.15 mm, or a range consisting of any two of these values. The average fiber length can be, but is not limited to, 0.5 mm, 0.6 mm, 0.8 mm, 1 mm, 1.2 mm, 1.4 mm, 1.5 mm, or a range consisting of any two of these values.

[0082] In some embodiments, the fluff includes a mixture of fluffs having different average fiber lengths and / or average fiber diameters.

[0083] Optionally, the fluff includes a first fluff, a second fluff and a third fluff in a mass ratio of 1: (0.5~1.5): (0.5~1), the average fiber diameter of the first fluff ≤ the average fiber diameter of the second fluff < the average fiber diameter of the third fluff, and the average fiber length of the first fluff > the average fiber length of the second fluff > the average fiber length of the third fluff.

[0084] The above-mentioned arrangement of the flock compound is beneficial to further improve the flocking-like effect, mechanical properties and flame retardant properties of the prepared polycarbonate composite material.

[0085] In some embodiments, the additives include 0.1% to 0.3% of the second antioxidant, 0.1% to 0.4% of the second lubricant, 0.2% to 1% of the second flame retardant, and 1% to 3% of the second white masterbatch by mass percentage of the flocking masterbatch. Specifically, by mass percentage, the flocking masterbatch includes: 65.3% to 90% of the second PC resin, 5.3% to 30% of the fluff, 0.1% to 0.3% of the second antioxidant, 0.1% to 0.4% of the second lubricant, 0.2% to 1% of the second flame retardant, and 1% to 3% of the second white masterbatch.

[0086] In some embodiments, the first PC resin and the second PC resin each independently include one or more of aromatic polycarbonate, aliphatic polycarbonate and aromatic-aliphatic polycarbonate. Specifically, when the test condition is 300°C and the load is 1.2kg, the melt flow index (MFR) of the first PC resin and the second PC resin is independently 3g / 10min~65g / 10min. For example, when the test condition is 300°C and the load is 1.2kg, the melt flow index of the first PC resin and the second PC resin is independently 3g / 10min, 5g / 10min, 7g / 10min, 10g / 10min, 15g / 10min, 20g / 10min, 25g / 10min, 30g / 10min, 35g / 10min, 40g / 10min, 45 / 10min, 50g / 10min, 60g / 10min, 65g / 10min or a range consisting of any two of these values. Further, when the test conditions are 300° C. and the load is 1.2 kg, the melt flow index of the first PC resin and the second PC resin is independently 5 g / 10 min to 40 g / 10 min. Further, when the test conditions are 300° C. and the load is 1.2 kg, the melt flow index of the first PC resin and the second PC resin is independently 7 g / 10 min to 30 g / 10 min.

[0087] In one embodiment, the first PC resin and the second PC resin each independently include bisphenol A polycarbonate. For example, the first PC resin and the second PC resin each independently include one or more of Wanhua Chemical 2100, Wanhua Chemical 2150, and Wanhua Chemical 2220.

[0088] It is understood that in this application, the first PC resin and the second PC resin may be the same or different. The expressions "first" and "second" are only used to distinguish the PC resin in the resin base and the flocking masterbatch, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of indicated technical features. Similarly, the first antioxidant, the second antioxidant, etc. also have similar meanings and will not be repeated.

[0089] In some embodiments, the first antioxidant and the second antioxidant each independently include one or more of hindered phenols, phosphites, thioesters, benzofurans, acryl-modified phenols and hydroxylamines. In one embodiment, the first antioxidant and the second antioxidant each independently include one or more of hindered phenols and phosphites. In one example, the first antioxidant and the second antioxidant each independently include one or more of antioxidant 1076, antioxidant 1010 and antioxidant 168. Antioxidant 1076, antioxidant 1010 and antioxidant 168 can be commercially available, for example, the first antioxidant and the second antioxidant each independently include one or more of Irganox 1076, Irganox 1010 and Irganox 168 of BASF. In a specific example, the first antioxidant and the second antioxidant each independently include antioxidant 1076 and antioxidant 168.

[0090] In some embodiments, the first lubricant and the second lubricant independently include one or more of fatty alcohols, metal soaps, fatty acids, fatty acid esters, montanic acid and its derivatives, amide waxes, saturated hydrocarbons, polyolefin waxes and its derivatives, silicones and silicone powders, and organic fluorines. In one embodiment, the first lubricant and the second lubricant independently include one or more of fatty acid esters and silicones. Further, the first lubricant and the second lubricant independently include fatty acid esters. For example, the first lubricant and the second lubricant independently include pentaerythritol stearate (PETS).

[0091] In some embodiments, the first flame retardant and the second flame retardant each independently include one or more of a phosphorus flame retardant, a silicon flame retardant, a sulfonate flame retardant, and a bromine flame retardant. Among them, the phosphorus flame retardant includes one or more of ammonium phosphate and phosphonate. In one example, the first flame retardant and the second flame retardant each independently include one or more of a sulfonate flame retardant. For example, the first flame retardant and the second flame retardant each independently include one or more of KSS and KFR-KKS.

[0092] In some embodiments, the toner includes one or more of carbon black and titanium yellow pigment. In one example, the toner includes carbon black 50L and titanium yellow pigment 1038. It can be understood that only two common toners are given above, but it is not limited thereto, and the type of toner can also be adjusted according to the color and purpose of the polycarbonate composite material to be prepared.

[0093] It is understood that the raw materials and reagents used in this application can be purchased through commercial channels unless otherwise specified.

[0094] In some embodiments, the resin base material includes a first PC resin, a first antioxidant, a first lubricant, a first flame retardant, a first white masterbatch and a color powder; in terms of weight percentage, the raw materials for preparing the polycarbonate composite material include: 5 to 20 parts of the flocking masterbatch, 80 to 95 parts of the first PC resin, 0 to 1 part of the first antioxidant, 0 to 4 parts of the first lubricant, 0 to 2 parts of the first flame retardant, 1 to 3 parts of the first white masterbatch and 0.001 to 0.01 parts of the color powder.

[0095] Optionally, the raw materials for preparing the polycarbonate composite material include, by weight: 10 to 20 parts of flocking masterbatch, 80 to 90 parts of a first PC resin, 0.1 to 0.3 parts of a first antioxidant, 0.1 to 0.4 parts of a first lubricant, 0.2 to 1 parts of a first flame retardant, 1 to 3 parts of a first white masterbatch and 0.001 to 0.01 parts of a color powder.

[0096] Optionally, the raw materials for preparing the polycarbonate composite material include, by weight: 10 to 20 parts of flocking masterbatch, 80 to 90 parts of a first PC resin, 0.1 to 0.3 parts of a first antioxidant, 0.1 to 0.4 parts of a first lubricant, 0.7 to 1 parts of a first flame retardant, 2 to 3 parts of a first white masterbatch and 0.001 to 0.01 parts of a color powder.

[0097] Furthermore, the raw materials for preparing the polycarbonate composite material include, by weight: 10 to 20 parts of flocking masterbatch, 80 to 90 parts of a first PC resin, 0.2 parts of a first antioxidant, 0.2 parts of a first lubricant, 0.7 to 1 parts of a first flame retardant, 2 to 3 parts of a first white masterbatch and 0.0062 parts of a color powder.

[0098] By optimizing the composition and ratio of polycarbonate composite materials, it is beneficial to achieve better spray-free flocking effect, mechanical properties and flame retardant properties.

[0099] The raw materials prepared from the above-mentioned polycarbonate composite material can be made into a spray-free appearance part with imitation flocking effect after injection molding. It can achieve a good and obvious matte flocking surface effect during the high temperature and high shear heat processing and molding process, and can present a realistic rock texture at a variety of visual angles, adding beauty to the spray-free products, and can maintain good mechanical properties and flame retardant properties. It can be used in electronic and electrical, security monitoring, home appliance casings, consumer products and other fields with strict requirements on appearance, production process and performance.

[0100] A second aspect of the present application provides a method for preparing a polycarbonate composite material, comprising the following steps:

[0101] The following raw materials are obtained by weight percentage: 80% to 95% of resin base material and 5% to 20% of flocking masterbatch; wherein the resin base material contains the first PC resin; taking the total weight percentage of the flocking masterbatch as 100%, the flocking masterbatch includes: 65.3% to 90% of the second PC resin, 5.3% to 30% of the fluff and 1.4% to 4.7% of the additive;

[0102] The flocking-like masterbatch and the resin base material are mixed and injection-molded to prepare a composite material.

[0103] The preparation method of the above-mentioned polycarbonate composite material is to mix a certain ratio of resin base material and imitation flocking masterbatch and then perform injection molding. The fluff is added in the form of imitation flocking masterbatch, which can achieve a good and obvious matte flocking surface effect in high temperature and high shear heat extrusion and molding, and can present a realistic rock texture at a variety of visual angles, adding beauty to the spray-free products, and can maintain good mechanical properties and flame retardant properties; at the same time, it has the advantages of high stability of extrusion and molding processes, low comprehensive industrialization costs, and high feasibility of mass production and expansion. The obtained spray-free polycarbonate composite material with imitation flocking effect and flame retardancy can be used in the fields of electronics and electrical, security monitoring, home appliance housing, consumer products, etc. with strict requirements on appearance, production process and performance.

[0104] In some embodiments, the preparation steps of the flocking-like masterbatch include:

[0105] At a first speed, the fluff and a portion of the second PC resin are mixed, and the remaining second PC resin and the additive are added and continued to mix;

[0106] The obtained mixture is extruded and granulated to prepare flocking masterbatch;

[0107] The first rotation speed is smaller than the second rotation speed, and the second rotation speed is the rotation speed in the step of mixing the flocking imitation masterbatch and the resin base material.

[0108] In some embodiments, the first rotational speed is 50rpm~80rpm, and the second rotational speed is 100rpm~200rpm. For example, the first rotational speed may be, but is not limited to, 50rpm, 55rpm, 60rpm, 65rpm, 70rpm, 75rpm, 80rpm, or a range consisting of any two of these values. The second rotational speed may be, but is not limited to, 100rpm, 120rpm, 140rpm, 150rpm, 160rpm, 180rpm, 200rpm, or a range consisting of any two of these values. With the above arrangement, the lighter fluff is fully mixed with part of the second PC resin powder before extrusion to form a certain coating, so that the color and size of the fluff are kept better during the extrusion granulation process.

[0109] In some embodiments, the mass percentage of the second PC resin in the total second PC resin is 40% to 60%. For example, the mass percentage of the second PC resin in the total second PC resin can be, but is not limited to, 40%, 42%, 45%, 48%, 50%, 52%, 55%, 58%, 60%, or a range consisting of any two of these values.

[0110] In some embodiments, the total mixing time before the mixture is subjected to the step of extrusion granulation is 40s to 100s. For example, the total mixing time can be, but is not limited to, 40s, 50s, 60s, 70s, 80s, 90s, 100s, or a range consisting of any two of these values.

[0111] In some of the embodiments, in the step of extrusion granulation, the extrusion temperature is 270°C to 300°C, and the screw speed is 200rpm to 1000rpm. Specifically, in the step of extrusion granulation, the temperature is set in sections from the feed port to the die head: the feed port temperature is 245°C to 265°C, and the first to seventh sections are each independently 275°C to 290°C. It can be understood that the temperatures of the first to seventh sections may be the same or different. Optionally, in one of the examples, the temperature of the first to sixth sections is 285°C, and the temperature of the seventh section is 280°C.

[0112] In one embodiment, in the step of extrusion granulation, the vacuum degree of the vacuum pump of the twin-screw metering section is controlled to be less than -0.8 bar, and the temperature of the cooling water tank is 30°C to 80°C.

[0113] In some of the embodiments, the mass moisture content of the first PC resin and the second PC resin is independently less than 0.5%, and optionally, the mass moisture content of the first PC resin and the second PC resin is independently less than 0.3%. The above arrangement is helpful to reduce appearance defects during the molding process. Specifically, the first PC resin and the second PC resin are dried before use so that their mass moisture content meets the above requirements. In one example, the drying temperature is 80℃~120℃, and optionally, the drying temperature is 100℃~120℃.

[0114] In some embodiments, in the step of mixing the flocking masterbatch and the resin base material, the mixing time is 30s to 90s. For example, the mixing time can be, but is not limited to, 30s, 40s, 50s, 60s, 70s, 80s, 90s, or a range consisting of any two of these values.

[0115] In some embodiments, in the step of injection molding, the injection temperature is 290°C to 310°C, the injection pressure is 50MPa to 65MPa, and the speed of the injection molding machine is 200rpm to 500rpm. For example, the injection temperature may be, but is not limited to, 290°C, 295°C, 300°C, 305°C, 310°C, or a range consisting of any two of these values. The injection pressure may be, but is not limited to, 50MPa, 52MPa, 54MPa, 55MPa, 56MPa, 58MPa, 60MPa, 62MPa, 64MPa, 65MPa, or a range consisting of any two of these values. The speed of the injection molding machine may be, but is not limited to, 200rpm, 250rpm, 300rpm, 350rpm, 400rpm, 450rpm, 500rpm, or a range consisting of any two of these values.

[0116] In some embodiments, the steps for preparing the resin base material may be commonly used in the art, for example, mixing the components and then extruding and granulating them. Specifically, the steps for preparing the resin base material include:

[0117] The following raw materials are mixed by weight: 80 to 95 parts of a first PC resin, 0 to 1 part of a first antioxidant, 0 to 4 parts of a first lubricant, 0 to 2 parts of a first flame retardant, 1 to 3 parts of a first white masterbatch and 0.001 to 0.01 parts of a color powder; the obtained mixture is extruded and granulated to obtain a resin base material.

[0118] In one embodiment, during the preparation of the resin base material, the toner and the first white masterbatch are first mixed, and the first PC resin, the first antioxidant, the first lubricant and the first flame retardant are added and stirred and mixed continuously;

[0119] Specifically, in the step of preparing the resin base material, the extrusion temperature is 270°C to 300°C, and the screw speed is 200rpm to 1000rpm. Specifically, in the step of extrusion granulation, the temperature is set in sections from the feed port to the die head: the feed port temperature is 245°C to 265°C, and the first to seventh sections are each independently 275°C to 290°C. It can be understood that the temperatures of the first to seventh sections can be the same or different. Optionally, in one of the examples, the temperature of the first to sixth sections is 285°C, and the temperature of the seventh section is 280°C.

[0120] In one embodiment, in the step of preparing the resin base material, the vacuum degree of the vacuum pumping device of the twin-screw metering section is controlled to be less than -0.8 bar, and the temperature of the cooling water tank is 30°C~80°C.

[0121] See also Figure 1 In some embodiments, the method for preparing the polycarbonate composite material comprises the following steps:

[0122] Step S110: Mix the following raw materials by mass: 80 to 95 parts of a first PC resin, 0 to 1 part of a first antioxidant, 0 to 4 parts of a first lubricant, 0 to 2 parts of a first flame retardant, 1 to 3 parts of a first white masterbatch, and 0.001 to 0.01 parts of a color powder; and extrude and granulate the obtained first mixture to obtain a resin base material.

[0123] Step S120: Obtain the following raw materials by mass percentage: 65.3% to 90% of the second PC resin, 5.3% to 30% of the fluff, and 1.4% to 4.7% of the additive; at a first rotation speed, mix the fluff and part of the second PC resin, add the remaining second PC resin and the additive and continue mixing, extrude and granulate the obtained second mixture to prepare a flocking masterbatch.

[0124] In one embodiment, the first rotation speed is 50 rpm to 80 rpm. The mixing time of step S120 is 40 s to 100 s.

[0125] Specifically, the mass moisture content of the first PC resin and the second PC resin is each independently less than 0.5%. Optionally, the mass moisture content of the first PC resin and the second PC resin is each independently less than 0.3%.

[0126] Specifically, in the extrusion granulation steps of step S110 and step S120, the extrusion temperature is independently 270°C to 300°C, and the screw speed is independently 200rpm to 1000rpm. Specifically, in the extrusion granulation step, the temperature is set in sections from the feed port to the die head: the feed port temperature is 245°C to 265°C, and the first to seventh sections are independently 275°C to 290°C. It can be understood that the temperatures of the first to seventh sections can be the same or different. Optionally, in one of the examples, the temperature of the first to sixth sections is 285°C, and the temperature of the seventh section is 280°C.

[0127] In one embodiment, in the extrusion granulation steps of step S110 and step S120, the vacuum degree of the vacuum pumping device of the twin-screw metering section is controlled to be less than -0.8 bar, and the temperature of the cooling water tank is 30°C to 80°C.

[0128] Step S130: obtaining the following raw materials by mass percentage: 80% to 95% of a resin base material and 5% to 20% of a flocking-like masterbatch; mixing the flocking-like masterbatch and the resin base material at a second rotation speed.

[0129] In one embodiment, the second rotation speed is 100 rpm to 200 rpm. The mixing time of step S130 is 30 s to 90 s.

[0130] Step S140: injection molding the mixed material of the flocking imitation masterbatch and the resin base material to prepare a polycarbonate composite material.

[0131] Among them, the injection temperature is 290℃~310℃, the injection pressure is 50MPa~65MPa, and the injection molding machine speed is 200rpm~500rpm.

[0132] The preparation method of the polycarbonate composite material in the above-mentioned embodiment solves the contradiction between the flocking effect with good length retention and the mechanical and flame retardant properties of the material, and provides a polycarbonate material with a flocking spray-free effect and excellent flame retardant and mechanical properties with obvious, unique and elegant texture, simulated three-dimensional fiber feel and soft and skin-friendly visual effect, thereby overcoming the application limitations of traditional technologies.

[0133] It should be understood that Figure 1 This is a schematic diagram of a process for preparing a polycarbonate composite material according to an embodiment of the present invention. Figure 1 The steps in the flowchart are shown in sequence as indicated by the arrows, but the steps are not necessarily performed in the order indicated by the arrows. Unless otherwise specified herein, the execution of the steps is not strictly limited in order and can be performed in other orders. For example, step S110 and step S120 can be performed simultaneously, or step S120 can be performed first and then step S110. Figure 1 At least part of the steps may include multiple sub-steps or multiple stages. These sub-steps or stages are not necessarily executed at the same time, but can be executed at different times. The order of execution is not necessarily sequential, but can be executed in turn or alternately with other steps or at least part of other sub-steps or stages.

[0134] It can be understood that, when the raw materials for preparing the polycarbonate composite material include, by weight, 5-20 parts of flocking masterbatch, 80-95 parts of the first PC resin, 0-1 part of the first antioxidant, 0-4 parts of the first lubricant, 0-2 parts of the first flame retardant, 1-3 parts of the first white masterbatch and 0.001-0.01 parts of the color powder, the first PC resin, the first antioxidant, the first lubricant, the first flame retardant, the first white particles and the color powder are mixed to prepare the resin base material, and then mixed with the flocking masterbatch and injection molded. The specific process is as described above and will not be repeated here.

[0135] The third aspect of the present application provides an application of the above-mentioned polycarbonate composite material or the polycarbonate composite material prepared by the above-mentioned preparation method in the electronic and electrical fields, security monitoring fields, home appliance casing fields or consumer product fields.

[0136] For example, polycarbonate composite materials are used in the preparation of electronic and electrical products, security monitoring products, home appliance casings or consumer products.

[0137] The fourth aspect of the present application also provides a method for preparing a flocking-like masterbatch, comprising the following steps:

[0138] The following raw materials were obtained by mass percentage: 65.3% to 90% of the second PC resin, 5.3% to 30% of the fluff, and 1.4% to 4.7% of the additive;

[0139] At a speed of 50 rpm to 80 rpm, mix the fluff and part of the second PC resin, add the remaining second PC resin and additives and continue mixing;

[0140] The obtained mixture is extruded and granulated to prepare flocking masterbatch.

[0141] By adopting the above preparation method, the lighter fluff is fully mixed with part of the second PC resin powder before extrusion to form a certain coating, so that the color and size of the fluff are well maintained during the extrusion granulation process.

[0142] In some embodiments, the mass percentage of the second PC resin to the total second PC resin is 40%-60%.

[0143] In some embodiments, the total mixing time before the mixture is subjected to the step of extrusion granulation is 40s to 100s. For example, the total mixing time can be, but is not limited to, 40s, 50s, 60s, 70s, 80s, 90s, 100s, or a range consisting of any two of these values.

[0144] In some of the embodiments, in the step of extrusion granulation, the extrusion temperature is 270°C to 300°C, and the screw speed is 200rpm to 1000rpm. Specifically, in the step of extrusion granulation, the temperature is set in sections from the feed port to the die head: the feed port temperature is 245°C to 265°C, and the first to seventh sections are each independently 275°C to 290°C. It can be understood that the temperatures of the first to seventh sections may be the same or different. Optionally, in one of the examples, the temperature of the first to sixth sections is 285°C, and the temperature of the seventh section is 280°C.

[0145] In one embodiment, in the step of extrusion granulation, the vacuum degree of the vacuum pump of the twin-screw metering section is controlled to be less than -0.8 bar, and the temperature of the cooling water tank is 30°C to 80°C.

[0146] The fifth aspect of the present application also provides a flocking-like masterbatch, which is prepared by the preparation method of the fourth aspect.

[0147] In order to make the purpose and advantages of the present application clearer, the polycarbonate composite material of the present application and its effects are further described in detail in conjunction with specific examples. It should be understood that the specific examples described herein are only used to explain the present application and shall not be used to limit the present application. The following examples do not include other components except inevitable impurities unless otherwise specified. The drugs and instruments used in the examples are conventionally selected in the art unless otherwise specified. The experimental methods for which specific conditions are not specified in the examples are implemented according to conventional conditions, such as the conditions described in the literature and books or the methods recommended by the manufacturer.

[0148] In the following examples and comparative examples, the sources of the main raw materials are shown in Table 1 below:

[0149] Table 1 Raw material source information

[0150]

[0151] Among them, the average fiber diameter of fluff 1205 (denoted as 1#) is 0.015mm, and the average fiber length is 1.5mm; the average fiber diameter of fluff 3002 (denoted as 2#) is 0.015mm, and the average fiber length is 1mm; the average fiber diameter of fluff 9C-0.5 (denoted as 3#) is 0.03mm, and the average fiber length is 0.5mm.

[0152] In the following examples and comparative examples, the processing equipment used is as follows:

[0153] The twin-screw extruder was: KraussMaffei ZE28 x40D BP, with a screw aspect ratio of 40, a screw diameter of 28 cm, and a screw speed of 0-1200 rpm.

[0154] Example 1

[0155] This embodiment provides a composite material, and the raw materials for preparation include, by mass, 97.1062 parts of resin base material and 5 parts of flocking masterbatch (i.e., the mass percentages of resin base material and flocking masterbatch are 95% and 5%, respectively). Among them, by mass, the resin base material includes the following raw materials: 95 parts of PC resin, 0.2 parts of antioxidant, 0.2 parts of lubricant, 0.7 parts of flame retardant, 0.0062 parts of toner and 1 part of white masterbatch, totaling 97.1062 parts. By mass percentage, the flocking masterbatch includes the following raw materials: 66.9% PC resin, 30% fluff, 0.7% flame retardant, 2% white masterbatch, 0.2% antioxidant and 0.2% lubricant. Among them, the fluff is a mixture of fluff 1#, fluff 2# and fluff 3# in a mass ratio of 1:0.5:1. The PC resin, antioxidant, lubricant, flame retardant and white masterbatch in the resin base are the same as the polycarbonate resin, antioxidant, lubricant, flame retardant and white masterbatch in the flocking masterbatch. The PC resin is dried before use to make its mass moisture content less than 0.3%. The specific raw materials are shown in Table 2 below.

[0156] The preparation steps of the polycarbonate composite material of this embodiment are as follows:

[0157] (1) Preparation of resin base material: First, stir and mix the color powder and white masterbatch, then add PC resin, antioxidant, lubricant and flame retardant and continue to stir and mix. The mixed material is extruded and granulated by a twin-screw extruder to obtain the resin base material. The twin-screw extrusion temperature is set as follows: the temperature from the feed port to the die is set as follows: 285°C for the first to sixth sections, 280°C for the seventh section, the screw speed is 200rpm~1000rpm, the vacuum degree of the vacuum device of the twin-screw metering section is less than -0.8bar, and the cooling water tank temperature is 30~80°C.

[0158] (2) Preparation of flocking masterbatch: Mix the fluff and 50% PC resin and feed them through the side feed port, then mix the remaining 50% PC resin with antioxidant, lubricant, flame retardant and white masterbatch. A low-speed mixer is used for mixing, the mixing speed is 50rpm~80rpm, and the total mixing time is 40s~100s. The mixed material is melt-extruded and granulated by a twin-screw extruder to obtain flocking masterbatch. The twin-screw extrusion temperature is set as follows: the temperature is set from the feed port to the die: 285℃ for sections 1 to 6, 280℃ for section 7, the screw speed is 200rpm~1000rpm, the vacuum degree of the vacuum device of the twin-screw metering section is less than -0.8bar, and the cooling water tank temperature is 30~80℃.

[0159] (3) Material mixing: The resin base material and the flocking imitation masterbatch are blended in a high-speed mixer, wherein the mixing speed is 100 rpm to 200 rpm and the mixing time is 30 s to 90 s to obtain a mixed material.

[0160] (4) Injection molding: The mixed material is injection molded to obtain a polycarbonate composite material, wherein the injection molding temperature is 290°C to 310°C, the injection molding pressure is 50MPa to 65MPa, and the speed of the injection molding machine is 200rpm to 500rpm.

[0161] Example 2

[0162] The present embodiment provides a composite material, and the raw materials for preparation include, by weight: 93.1062 parts of resin base material and 10 parts of flocking masterbatch (i.e., the mass percentages of resin base material and flocking masterbatch are 90% and 10%, respectively). Among them, by weight, the resin base material includes the following raw materials: 90 parts of PC resin, 0.2 parts of antioxidant, 0.2 parts of lubricant, 0.7 parts of flame retardant, 0.0062 parts of color powder and 2 parts of white masterbatch, totaling 93.1062 parts. The flocking masterbatch includes the following raw materials: 66.9% PC resin, 30% fluff, 0.7% flame retardant, 2% white masterbatch, 0.2% antioxidant and 0.2% lubricant. Among them, the fluff is a mixture of fluff 1#, fluff 2# and fluff 3# in a mass ratio of 1:0.5:1. The PC resin, antioxidant, lubricant, flame retardant and white masterbatch in the resin base are the same as those in the flocking masterbatch. The PC resin is dried before use to make its mass moisture content less than 0.3%. The specific raw materials are shown in Table 2 below.

[0163] The steps for preparing the composite material of this embodiment are the same as those of Embodiment 1 and will not be described in detail.

[0164] Example 3

[0165] The present embodiment provides a composite material, and the raw materials for preparation include, by weight: 80% resin base material and 20 parts of flocking masterbatch (i.e., the mass percentages of the resin base material and the flocking masterbatch are 81% and 19%, respectively). Among them, by weight, the base material includes the following raw materials: 80 parts of PC resin, 0.2 parts of antioxidant, 0.2 parts of lubricant, 1 part of flame retardant, 0.0062 parts of toner and 3 parts of white masterbatch. By weight percentage, the flocking masterbatch includes the following raw materials: 66.9% PC resin, 30% fluff, 0.7% flame retardant, 2% white masterbatch, 0.2% antioxidant and 0.2% lubricant. Among them, the fluff is a mixture of fluff 1#, fluff 2# and fluff 3# in a mass ratio of 1:0.5:1. The PC resin, antioxidant, lubricant, flame retardant and white masterbatch in the resin base are the same as those in the flocking masterbatch. The PC resin is dried before use to make its mass moisture content less than 0.3%. The specific raw materials are shown in Table 2 below.

[0166] The steps for preparing the composite material of this embodiment are the same as those of Embodiment 1 and will not be described in detail.

[0167] Example 4

[0168] This embodiment provides a composite material, and the raw materials for preparation include, by mass, 84.4062 parts of resin base material and 20 parts of flocking masterbatch (i.e., the mass percentages of resin base material and flocking masterbatch are 81% and 19%, respectively). Among them, by mass, the resin base material includes the following raw materials: 80 parts of PC resin, 0.2 parts of antioxidant, 0.2 parts of lubricant, 1 part of flame retardant, 0.0062 parts of toner and 3 parts of white masterbatch. By mass percentage, the flocking masterbatch includes the following raw materials: 90% PC resin, 6.9% fluff, 0.7% flame retardant, 2% white masterbatch, 0.2% antioxidant and 0.2% lubricant. Among them, the fluff is a mixture of fluff 1#, fluff 2# and fluff 3# in a mass ratio of 1:1.5:0.5. The PC resin, antioxidant, lubricant, flame retardant and white masterbatch in the resin base are the same as those in the flocking masterbatch. The PC resin is dried before use to make its mass moisture content less than 0.3%. The specific raw materials are shown in Table 2 below.

[0169] Example 5

[0170] This embodiment provides a composite material, and the raw materials for preparation include, by weight: 84.4062 parts of resin base material and 20 parts of flocking masterbatch (i.e., the mass percentages of resin base material and flocking masterbatch are 81% and 19%, respectively). Among them, by weight, the base material includes the following raw materials: 80 parts of PC resin, 0.2 parts of antioxidant, 0.2 parts of lubricant, 1 part of flame retardant, 0.0062 parts of toner and 3 parts of white masterbatch. By weight percentage, the flocking masterbatch includes the following raw materials: 80% PC resin, 16.9% fluff, 0.7% flame retardant, 2% white masterbatch, 0.2% antioxidant and 0.2% lubricant. Among them, the fluff is a mixture of fluff 1#, fluff 2# and fluff 3# in a mass ratio of 1:1:0.75. The PC resin, antioxidant, lubricant, flame retardant and white masterbatch in the resin base are the same as those in the flocking masterbatch. The PC resin is dried before use to make its mass moisture content less than 0.3%. The specific raw materials are shown in Table 2 below.

[0171] Comparative Example 1

[0172] Comparative Example 1 provides a composite material, and the raw materials for preparation include, by weight: 90 parts of PC resin, 0.2 parts of lubricant, 0.7 parts of flame retardant, 0.2 parts of antioxidant, 1 part of white masterbatch, 0.0062 of color powder and 10 parts of fluff 3#. The specific raw materials are shown in Table 2 below.

[0173] The preparation steps of the composite material of Comparative Example 1 are as follows:

[0174] (1) Preparation of mixed pellets: Mix the fluff, color powder and white masterbatch, then add PC resin (the weight ratio of powder to pellets in PC resin = 85:5), antioxidant, lubricant and flame retardant and continue to mix and stir. The resulting mixture is extruded and granulated by a twin-screw extruder to obtain mixed pellets. In the mixing step, the speed is 100rpm~200rpm, the time is 30s~90s, and in the extrusion granulation step, the twin-screw extrusion temperature is set as follows: the temperature from the feed port to the die is set to: 285℃ for sections 1 to 6, 280℃ for section 7, the screw speed is 200rpm~1000rpm, the vacuum degree of the vacuum device in the twin-screw metering section is less than -0.8bar, and the cooling water tank temperature is 30-80℃.

[0175] (2) Injection molding: The mixed pellets are injection molded to obtain a polycarbonate composite material, wherein the injection molding temperature is 290°C to 310°C, the injection molding pressure is 50MPa to 65MPa, and the speed of the injection molding machine is 200rpm to 500rpm.

[0176] Comparative Example 2

[0177] Comparative Example 2 provides a composite material, and the raw materials for preparation include, by weight: 90 parts of PC resin, 0.2 parts of lubricant, 0.7 parts of flame retardant, 0.2 parts of antioxidant, 2 parts of white masterbatch, 0.0062 parts of color powder, 5 parts of fluff 2# and 5 parts of fluff 3#. The specific raw materials are shown in Table 2 below.

[0178] The preparation steps of the composite material of Comparative Example 2 are the same as those of Comparative Example 1, and will not be repeated herein.

[0179] Comparative Example 3

[0180] Comparative Example 3 provides a composite material, and the raw materials for preparation include, by weight dispersion, 90 parts of PC resin, 0.2 parts of lubricant, 0.7 parts of flame retardant, 0.2 parts of antioxidant, 3 parts of white masterbatch, 0.0062 parts of color powder, 8 parts of fluff 1# and 2 parts of fluff 3#. The specific raw materials are shown in Table 2 below.

[0181] The preparation steps of the composite material of Comparative Example 3 are the same as those of Comparative Example 1, and will not be repeated herein.

[0182] The types and amounts of raw materials used in the above embodiments and comparative examples are shown in Table 2 below.

[0183] Table 2 Types and amounts of raw materials in Examples 1 to 5 and Comparative Examples 1 to 3 (unit: mass fraction)

[0184]

[0185] In the above embodiments and comparative examples, the performance testing method of the composite material is as follows:

[0186] Melt index (PC): in accordance with ASTM D1238 test standard, test conditions 300℃ / 1.2kg;

[0187] Izod notched impact strength: in accordance with ISO 180 test standard, test conditions are 23°C;

[0188] Glow Wire Flammability Index: According to UL94-2018 test standard, the test condition is GWFI-1.1mm.

[0189] Appearance effect: The polycarbonate composite materials prepared in the above embodiments and comparative examples were injection molded into 90mm×55mm×3mm fine leather grain color plates, which were observed under D65 light, and the changes in the base color and the length, amount and obviousness of the villi were rated respectively, with the best being grade V and the worst being grade I; grade V means that the villi are long, evenly distributed, numerous, and have a very obvious three-dimensional effect visually; grade I means that the villi are almost invisible, too short and too few, or the base color smudge changes seriously.

[0190] The test results of Examples 1 to 5 and Comparative Examples 1 to 3 are shown in Table 3.

[0191] Table 3 Performance and appearance of products of Examples 1 to 5 and Comparative Examples 1 to 3

[0192]

[0193] The appearance of the polycarbonate composite material prepared in Example 1 is as follows: Figure 2 The appearance of the polycarbonate composite material prepared in Example 3 is shown in Figure 3 The appearance of the polycarbonate composite material prepared in Comparative Example 1 is shown in Figure 4 The appearance of the polycarbonate composite material prepared in Comparative Example 2 is shown in Figure 5 shown.

[0194] From the performance test results in Table 3 and Figure 2~Figure 5It can be seen from the appearance effect that the spray-free polycarbonate composite materials of each embodiment of the present application can achieve a good spray-free imitation flocking effect in twin-screw extrusion shearing and injection molding, and the appearance rating is above level III, and some embodiments can reach level IV or even level V, with elegant texture, simulated three-dimensional fiber feel and soft skin-friendly visual plastic imitation flocking effect; and the flame retardant performance is relatively good, all above V1, and some embodiments can reach V0 level. In the comparative example, the traditional extrusion process is adopted, and it is difficult to obtain a good appearance effect due to the poor shear resistance of the fluff. Although the imitation flocking effect can be improved to a certain extent by increasing the amount of fluff added, the flame retardancy and impact resistance are obviously poor, which limits its application. In some embodiments of the present application, by designing suitable extrusion, injection molding processes and the proportion of each component, the shear resistance and heat resistance of the system can be effectively improved, so that the color, size and appearance uniformity of the fluff are kept good.

[0195] In addition, it can be seen from the examples of the present application that by optimizing the ratio of each component, the prepared polycarbonate composite material can have better spray-free flocking effect, mechanical properties and flame retardant properties.

[0196] Therefore, the polycarbonate composite material and the preparation method thereof provided in some embodiments of the present application have at least the following advantages over the conventional technology:

[0197] (1) The traditional polycarbonate system has the problem of high gloss of the parts. The polycarbonate composite material provided in some embodiments of the present application can achieve a plastic flocking effect with elegant texture, simulated three-dimensional fiber feeling and soft and skin-friendly visual effect in the polycarbonate system.

[0198] (2) The traditional technology used in the production of fluff has poor shear resistance and will significantly affect the mechanical properties and flame retardant properties of the material. In some embodiments of the present application, the shear resistance and heat resistance of the fluff system are improved by designing appropriate combinations of components and optimizing the preparation method, so that the color, size and appearance of the fluff are kept uniform. At the same time, the composite materials of some embodiments of the present application also have excellent flame retardant properties and mechanical properties.

[0199] (3) The flame-retardant PC spray-free composite materials with flocking-like effects provided in some embodiments of the present application can be injection molded in one step without the need for subsequent spraying treatment, which is energy-saving and environmentally friendly, has a short production cycle, greatly improves production efficiency, and significantly reduces the overall cost of industrialization. At the same time, it can give the product surface a rich aesthetic appearance and is widely used in the fields of electronic and electrical, security monitoring, consumer products, etc. with strict performance requirements.

[0200] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0201] The above-described embodiments only express several implementation methods of the present application, which is convenient for understanding the technical solutions of the present application in detail, but it cannot be understood as limiting the scope of protection of the invention patent. It should be pointed out that for ordinary technicians in this field, without departing from the concept of the present application, several modifications and improvements can be made, which all belong to the protection scope of the present application. It should be understood that the technical solutions obtained by those skilled in the art through logical analysis, reasoning or limited experiments on the basis of the technical solutions provided in the present application are all within the protection scope of the claims attached to the present application. Therefore, the scope of protection of the patent of this application shall be based on the contents of the attached claims, and the description and drawings can be used to explain the contents of the claims.

Claims

1. A polycarbonate composite material, characterized in that: The raw materials for preparing the polycarbonate composite material include, by mass percentage: 80% to 95% of a resin base material and 5% to 20% of a flocking-like masterbatch; The resin base material contains a first PC resin; taking the total mass percentage of the flocking imitation masterbatch as 100%, the flocking imitation masterbatch includes: 65.3% to 90% of a second PC resin, 5.3% to 30% of fluff, and 1.4% to 4.7% of an additive.

2. The polycarbonate composite material according to claim 1, characterized in that: Meet one or more of the following conditions: (1) In the flocking-like masterbatch, the mass percentage of the fluff is 10% to 25%; (2) In the flocking-like masterbatch, the mass percentage of the second PC resin is 72% to 87%; (3) Calculated by mass percentage, the raw materials for preparing the polycarbonate composite material include: 80% to 90% of a resin base material and 10% to 20% of a flocking-like masterbatch; (4) The auxiliary agent includes 0.1% to 0.3% by weight of the second antioxidant, 0.1% to 0.4% by weight of the second lubricant, 0.2% to 1% by weight of the second flame retardant and 1% to 3% by weight of the second white masterbatch; (5) When the test conditions are 300° C. and the load is 1.2 kg, the melt flow index of the first PC resin and the second PC resin are independently 3 g / 10 min to 65 g / 10 min; Optionally, when the test conditions are 300° C. and a load of 1.2 kg, the melt flow index of the first PC resin and the second PC resin are independently 5 g / 10 min to 40 g / 10 min; Optionally, when the test conditions are 300° C. and a load of 1.2 kg, the melt flow index of the first PC resin and the second PC resin are independently 7 g / 10 min to 30 g / 10 min.

3. The polycarbonate composite material according to claim 1 or 2, characterized in that: The fluff meets one or more of the following conditions: (1) The fluff includes one or more of fiber filaments, marble filaments and injection-molded fiber wool; (2) The average fiber diameter of the fluff is 0.015 mm to 0.15 mm, and the average fiber length is 0.5 mm to 1.5 mm; (3) The fluff comprises a mixture of fluffs having different average fiber lengths and / or average fiber diameters; Optionally, the fluff includes a first fluff, a second fluff and a third fluff in a mass ratio of 1: (0.5~1.5): (0.5~1), the average fiber diameter of the first fluff ≤ the average fiber diameter of the second fluff < the average fiber diameter of the third fluff, and the average fiber length of the first fluff > the average fiber length of the second fluff > the average fiber length of the third fluff.

4. The polycarbonate composite material according to claim 1 or 2, characterized in that: The resin base material comprises, by weight: 80 to 95 parts of a first PC resin, 0 to 1 part of a first antioxidant, 0 to 4 parts of a first lubricant, 0 to 2 parts of a first flame retardant, 1 to 3 parts of a first white masterbatch and 0.001 to 0.01 parts of a color powder; Optionally, the resin base material includes, by weight: 80 to 90 parts of a first PC resin, 0.1 to 0.3 parts of a first antioxidant, 0.1 to 0.4 parts of a first lubricant, 0.2 to 1 parts of a first flame retardant, 1 to 3 parts of a first white masterbatch, and 0.001 to 0.01 parts of a toner; Optionally, the resin base material includes, by weight: 80 to 90 parts of a first PC resin, 0.1 to 0.3 parts of a first antioxidant, 0.1 to 0.4 parts of a first lubricant, 0.7 to 1 parts of a first flame retardant, 2 to 3 parts of a first white masterbatch and 0.005 to 0.01 parts of a color powder.

5. The polycarbonate composite material according to claim 1 or 2, characterized in that: The resin base material includes a first PC resin, a first antioxidant, a first lubricant, a first flame retardant, a first white masterbatch and a color powder; the raw materials for preparing the polycarbonate composite material include, by weight: 5 to 20 parts of the flocking masterbatch, 80 to 95 parts of the first PC resin, 0 to 1 part of the first antioxidant, 0 to 4 parts of the first lubricant, 0 to 2 parts of the first flame retardant, 1 to 3 parts of the first white masterbatch and 0.001 to 0.01 parts of the color powder; Optionally, the raw materials for preparing the polycarbonate composite material include, by weight: 10 to 20 parts of flocking masterbatch, 80 to 90 parts of a first PC resin, 0.1 to 0.3 parts of a first antioxidant, 0.1 to 0.4 parts of a first lubricant, 0.2 to 1 parts of a first flame retardant, 1 to 3 parts of a first white masterbatch, and 0.001 to 0.01 parts of a color powder; Optionally, the raw materials for preparing the polycarbonate composite material include, by weight: 10 to 20 parts of flocking masterbatch, 80 to 90 parts of a first PC resin, 0.1 to 0.3 parts of a first antioxidant, 0.1 to 0.4 parts of a first lubricant, 0.7 to 1 parts of a first flame retardant, 2 to 3 parts of a first white masterbatch and 0.005 to 0.01 parts of a color powder.

6. A method for preparing a polycarbonate composite material, characterized in that: The steps include: The following raw materials are obtained by weight percentage: 80% to 95% of a resin base material and 5% to 20% of a flocking imitation masterbatch; wherein the resin base material contains a first PC resin; taking the total weight percentage of the flocking imitation masterbatch as 100%, the flocking imitation masterbatch includes: 65.3% to 90% of a second PC resin, 5.3% to 30% of fluff, and 1.4% to 4.7% of an additive; The flocking-like masterbatch and the resin base material are mixed and injection-molded to prepare a composite material.

7. The method for preparing the polycarbonate composite material according to claim 6, characterized in that: One or more of the following conditions are met: (1) The preparation steps of the flocking-like masterbatch include: At a first rotation speed, the fluff and a portion of the second PC resin are mixed, and the remaining second PC resin and the additive are added and continued to mix; The obtained mixture is extruded and granulated to prepare the flocking-like masterbatch; Wherein, the first rotation speed is less than the second rotation speed, and the second rotation speed is the rotation speed in the step of mixing the flocking masterbatch and the resin base material; Optionally, the first rotation speed is 50 rpm to 80 rpm, and the second rotation speed is 100 rpm to 200 rpm; Optionally, the mass percentage of the part of the second PC resin to the total second PC resin is 40% to 60%; Optionally, in the step of extrusion granulation, the extrusion temperature is 270°C to 300°C, and the screw speed is 200rpm to 1000rpm; (2) In the injection molding step, the injection temperature is 290°C to 310°C, the injection pressure is 50MPa to 65MPa, and the speed of the injection molding machine is 200rpm to 500rpm.

8. Use of the polycarbonate composite material according to any one of claims 1 to 5 or the polycarbonate composite material prepared by the preparation method according to any one of claims 6 to 7 in the field of electronics and electrical, security monitoring, home appliance housing or consumer products; Optionally, the polycarbonate composite material is used in the preparation of electronic and electrical products, security monitoring products, home appliance casings or consumer products.

9. A method for preparing flocking imitation masterbatch, characterized in that: The steps include: The following raw materials were obtained by mass percentage: 65.3% to 90% of the second PC resin, 5.3% to 30% of the fluff, and 1.4% to 4.7% of the additive; At a rotation speed of 50 rpm to 80 rpm, the fluff and a portion of the second PC resin are mixed, and the remaining second PC resin and the additive are added and continued to mix; The obtained mixture is extruded and granulated to prepare the flocking-like masterbatch; Optionally, the preparation method satisfies one or more of the following conditions: (1) In the step of extrusion granulation, the extrusion temperature is 270°C to 300°C, and the screw speed is 200 rpm to 1000 rpm; (2) The mass percentage of the second PC resin in the total second PC resin is 40% to 60%.

10. A flocking-like masterbatch, characterized in that: It is prepared by the preparation method described in claim 9.

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