Flame-retardant PC / ABS material as well as preparation method and application thereof

Abstract

The invention belongs to the field of plastic materials, and particularly discloses a flame-retardant PC / ABS (polycarbonate / acrylonitrile butadiene styrene) material as well as a preparation method and application thereof. The flame-retardant PC / ABS material comprises the following components in parts by weight: 44 to 71 parts of PC, 4 to 16 parts of ABS, 23 to 42 parts of mica powder, 0.9 to 5.3 parts of hollow glass beads, 2.9 to 11 parts of glass fibers, 3.9 to 11 parts of a flame retardant, 0.29 to 2.9 parts of an anti-dripping agent and 0 to 2.5 parts of a processing aid. According to the flame-retardant PC / ABS material disclosed by the invention, the glass fibers, the mica powder and the hollow glass beads are compounded and mutually matched, so that the toughness of the material is obviously improved and the warping degree of the material is reduced on the basis of improving the rigidity of the flame-retardant PC / ABS material, and the flame-retardant PC / ABS material with low warping and rigidity-toughness balance is comprehensively realized.

Description

Technical Field

[0001] The invention belongs to the field of plastics, and in particular relates to a flame retardant PC / ABS material and a preparation method and application thereof. Background Art

[0002] Flame retardant PC / ABS is a commonly used plastic alloy with excellent mechanical properties, flame retardant properties, weather resistance and heat resistance, etc. It is widely used in the automotive, office, home appliance and other industries. With the development demand of thin-wall and lightweight in the industry, the performance requirements of the industry for traditional flame retardant PC / ABS alloys are getting higher and higher. In order to improve the rigidity of flame retardant PC / ABS, the more common way is to add flaky or fibrous inorganic fillers such as glass fiber and talcum powder. However, the degree to which these inorganic fillers improve the rigidity of the material is often insufficient, and the compatibility of inorganic fillers with polymers is poor, which easily leads to a decrease in the impact toughness of the material. In addition, these flaky or fibrous inorganic fillers, such as glass fiber, generally have a high aspect ratio, and have obvious anisotropy themselves. They are also easy to show anisotropy in the material system. When the temperature changes before and after processing and molding, the material as a whole will produce uneven changes, and this uneven change causes the material to warp significantly. Therefore, it is difficult for flame retardant PC / ABS in the prior art to take into account the characteristics of low warpage and rigid-toughness balance. Summary of the invention

[0003] The purpose of the present invention is to overcome the defect that flame retardant PC / ABS in the prior art is difficult to take into account the characteristics of low warpage and rigidity-toughness balance. The present invention will provide a flame retardant PC / ABS material and its preparation method and application.

[0004] To achieve the above purpose, the following technical solutions are specifically included:

[0005] In one aspect, the present invention provides a flame retardant PC / ABS material, comprising the following components in parts by weight:

[0006] PC 44-71 parts, ABS 4-16 parts, mica powder 23-42 parts, hollow glass microspheres 0.9-5.3 parts, glass fiber 2.9-11 parts, flame retardant 3.9-11 parts, anti-dripping agent 0.29-2.9 parts, processing aid 0-2.5 parts.

[0007] The inventors of the present invention have found through experimental research that the presence of mica and glass fiber in PC / ABS materials, the cooperation of the two can make the material obtain sufficiently good rigidity and flame retardancy; at the same time, in order to overcome the obvious decrease in the toughness of the material caused by mica and glass fiber, and the fact that flaky mica and high aspect ratio glass fiber are easily oriented along the flow direction during processing, the material has high anisotropy, and thus the defect of the material being prone to warping; the inventors of the present invention added hollow glass microbeads to the system. Perhaps because the hollow glass microbeads have a spherical morphology, the mica powder has a flaky morphology, and the glass fiber has a fibrous morphology, each with a different morphology, the three cooperate with each other. On the basis of maintaining good rigidity and toughness, the orientation effect of mica and glass fiber can be well suppressed, the warping behavior of the material is reduced, and a flame-retardant PC / ABS material with low warping and a balance of rigidity and toughness is comprehensively realized.

[0008] Preferably, the flame retardant PC / ABS material comprises the following components in parts by weight: 45-70 parts of PC, 5-15 parts of ABS, 25-40 parts of mica powder, 1-5 parts of hollow glass microspheres, 3-10 parts of glass fiber, 4-10 parts of flame retardant, 0.3-2.5 parts of anti-dripping agent, and 0-2 parts of processing aid.

[0009] Preferably, in the flame-retardant PC / ABS material, the mass percentage of the PC (polycarbonate) is not less than 30%, more preferably not less than 40%, and even more preferably not less than 45%.

[0010] The system of the present invention has no restriction on the type of PC. The polycarbonate is preferably bisphenol A polycarbonate. Homemade PC can also be used. For example, the melt mass flow rate of the polycarbonate can be 1-60 g / 10 min, wherein the melt mass flow rate is tested according to ISO 1133-1 2011 standard, and the test conditions are 300° C. and 1.2 kg. More specifically, the melt mass flow rate of the polycarbonate can be 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60 g / 10 min, etc., as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the said range.

[0011] ABS is a terpolymer of acrylonitrile, butadiene and styrene. The system of the present invention has no restrictions on the type of ABS. Commercially available conventional ABS can be used, and homemade ABS can also be used. For example, ABS with a melt mass flow rate of 1-30 g / 10 min tested at 220°C and 10 kg according to GB / T3682-2000 can be used. More specifically, the melt mass flow rate of ABS can be 1, 3, 9, 12, 15, 18, 21, 24, 27, 30 g / 10 min, etc., as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention will no longer exhaustively list the specific point values ​​included in the range.

[0012] In the system of the present invention, the mesh number of the mica powder is preferably 200-800 mesh, and the mesh number of the mica powder is further preferably 300-600 mesh, and can be specifically 200, 225, 250, 275, 300, 325, 350, 375, 400, 425, 450, 475, 500, 525, 550, 575, 600, 625, 650, 275, 700, 725, 750, 775, 800 mesh, etc., as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0013] The mesh size of the mica powder is measured using a conventional method, and the mesh size of the mica powder of the present invention can be measured by a grid screening method.

[0014] In the system of the present invention, the average particle size of the hollow glass microspheres is preferably 20-60 μm, and the average particle size of the hollow glass microspheres is further preferably 30-45 μm, specifically 20, 25, 30, 35, 40, 45, 50, 55, 60 μm, etc., as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0015] The average particle size of the hollow glass microspheres was measured by laser particle size analysis.

[0016] Preferably, the mass ratio of the mica powder to the hollow glass microspheres is (28-32): (1-5), specifically 28:1, 29:1, 30:1, 31:1, 32:1, 28:3, 29:3, 30:3, 31:3, 32:3, 28:5, 29:5, 30:5, 31:5, 32:5, etc., as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the said range.

[0017] Preferably, the glass fiber is a conventional round glass fiber or a flat glass fiber, and the average diameter of the glass fiber is 1-20 μm, specifically 1, 2, 4, 6, 8, 10, 12, 14, 16, 18, 20 μm, etc., as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0018] Preferably, the flame retardant is a phosphorus-based flame retardant, and more preferably, the flame retardant includes at least one of bisphenol A diphenyl phosphate, resorcinol diphenyl phosphate, triphenyl phosphate, and 4,4'-(isopropylidene diphenyl)bis(diphenyl phosphate).

[0019] Preferably, the anti-drip agent comprises polytetrafluoroethylene.

[0020] Preferably, the processing aid comprises the following components in parts by weight: 0.1-1 part of antioxidant and 0.1-1 part of lubricant.

[0021] More preferably, the antioxidant is a hindered phenol antioxidant.

[0022] On the other hand, the present invention provides a method for preparing the flame retardant PC / ABS material, comprising the following steps:

[0023] The raw materials are sequentially mixed, melted, extruded and granulated to obtain the flame retardant PC / ABS material.

[0024] Preferably, the melting temperature is 210-250°C.

[0025] Preferably, the rotation speed during melting is 200 to 600 rpm.

[0026] The present invention also provides an application of the flame-retardant PC / ABS material in the preparation of automotive parts, office supplies, and household appliances, and can be specifically applied to the preparation of printer housings, projector housings, or chargers, etc.

[0027] Compared with the prior art, the present invention has the following beneficial effects: the present invention compounds glass fiber, mica powder and hollow glass microspheres, and the components cooperate with each other. On the basis of improving the rigidity of the flame-retardant PC / ABS material, the toughness of the material is significantly improved and the warpage of the material is reduced, thereby comprehensively realizing a flame-retardant PC / ABS material with low warpage and balanced rigidity and toughness. DETAILED DESCRIPTION

[0028] In order to better illustrate the purpose, technical scheme and advantages of the present invention, the present invention will be further described below through specific examples. The test methods used in the examples and / or comparative examples are conventional methods unless otherwise specified; the materials, reagents, etc. used can be obtained from commercial channels unless otherwise specified. The components and raw materials used in the examples and comparative examples of the present invention are the same unless otherwise specified.

[0029] The raw material information involved in the following examples and comparative examples:

[0030] PC resin: PC 1300 10NP, LG Chemical Co., Ltd., South Korea;

[0031] ABS resin: 275, Shanghai Gaoqiao;

[0032] Mica powder 1:200 mesh, Huajing Mica;

[0033] Mica powder 2: 300 mesh, obtained by grinding and sieving mica powder 1;

[0034] Mica powder 3: 500 mesh, obtained by grinding and sieving mica powder 1;

[0035] Mica powder 4: 600 mesh, obtained by grinding and sieving mica powder 1;

[0036] Mica powder 5: 800 mesh, obtained by grinding and sieving mica powder 1;

[0037] Hollow glass microspheres 1: iM16K, average particle size 20 μm, manufacturer 3M;

[0038] Hollow glass microspheres 2: S28HS, average particle size 30 μm, manufacturer 3M;

[0039] Hollow glass microspheres 3: S35, average particle size 40 μm, manufacturer 3M;

[0040] Hollow glass microspheres 4: K37, average particle size 45 μm, manufacturer 3M;

[0041] Hollow glass microspheres 5: K20, average particle size 60 μm, manufacturer 3M;

[0042] Talc: average particle size after grinding and sieving is 500 mesh (28 μm), Shandong Kaiwell;

[0043] Glass fiber: ECS13-4.5-534A, average diameter 13 microns, length 4.5 mm, China Jushi Co., Ltd.

[0044] Phosphorus flame retardant: BDP (bisphenol A-bis(diphenyl phosphate)), Wansheng;

[0045] Anti-drip agent: polytetrafluoroethylene, commercially available;

[0046] Processing aid: Antioxidant 1010, commercially available.

[0047] Examples 1-13 and Comparative Examples 1-5

[0048] A method for preparing a flame retardant PC / ABS material comprises the following steps:

[0049] (1) According to the amounts of raw material components in Table 1-2, each component is stirred and blended in a high-speed mixer to obtain a premix;

[0050] (2) feeding the premix into a twin-screw extruder through a main feed port, melt-mixing and extruding granulation in the twin-screw extruder to obtain the flame-retardant PC / ABS material, wherein the screw aspect ratio is 45:1, the barrel temperature is 210-250° C., and the screw speed is 300 rpm.

[0051] The testing methods for various properties of the flame retardant PC / ABS materials of the embodiments of the present invention and the comparative examples are as follows:

[0052] (1) Flexural modulus test: performed according to ASTM D790-2010, with a bending rate of 2 mm / min; a flexural modulus of 9000-12000 MPa is considered qualified;

[0053] (2) Impact test: Test the material’s Izod notched impact strength according to ASTM D256-2018; the impact strength is considered qualified if it remains between 35 and 60 J / m;

[0054] (3) Warpage test: Each product is injection molded into a 100*100*1.5mm square plate. After being laid out and cooled naturally, the warpage of the sample is observed and the maximum warpage height is tested (the square plate is placed on a marble flat plate, one corner is fixed close to the marble plane, and the distance between the diagonal position of the square plate and the marble plane is measured); a warpage height ≤2mm is considered qualified;

[0055] (2) Flame retardant grade: The flammability test is carried out in accordance with the "Flammability Test of Plastic Materials, UL94-2019" regulations. The flame retardant grade is derived based on the burning rate, extinguishing time, ability to resist dripping, and whether the dripping is burning. The sample used for the test: 125mm long, 13mm wide, the thickness of the present invention is selected as 1.5mm during the test. According to the UL94-2019 regulations, the flame retardant grade of the material can be classified as UL94 V0, V1, V2, etc.; the flame retardant grade of V-1 or above is considered qualified; the test results are shown in Table 3.

[0056] Table 1 (parts by weight)

[0057]

[0058]

[0059] Table 2 (parts by weight)

[0060] Group / Raw Material Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 PC 55 55 55 55 55 ABS 10 10 10 10 10 Mica powder 3 - 33 30 30 - talcum powder - - - - 30 Hollow glass microspheres 3 33 - 3 12 3 Glass Fiber 8 8 - 8 8 BDP 5 5 5 5 5 Anti-drip agent 0.5 0.5 0.5 0.5 0.5 Processing Aids 0.1 0.1 0.1 0.1 0.1

[0061] Table 3

[0062]

[0063]

[0064] It can be seen from the above embodiments that the PC / ABS material of the present invention has a flexural modulus of 9000-11500 MPa, an impact strength of 35-58 J / m, a warpage height of less than 2 mm, and a flame retardant grade of V-1 or above.

[0065] In Example 2, Example 1, Example 3, Example 4 and Example 5, the mesh number of mica powder gradually increases (the mesh number of mica powder gradually decreases), the flexural modulus and impact strength first increase and then decrease, and because the mesh number of mica powder is small, its size is too large, and the degree to which the material effectively migrates to the combustion surface during the combustion process to participate in carbonization decreases, making the flame retardant performance relatively worse, so, as the mesh number of mica powder increases, the size gradually becomes smaller, which is more conducive to migration and participation in carbonization, and therefore, the flame retardancy increases; as the mesh number of mica powder increases, the size of mica powder becomes smaller, and mica is more likely to flow along the processing direction and oriented, resulting in an increase in material anisotropy and obvious material warping. Therefore, in the system of the present invention, the mesh number of mica powder can be selected to be 200-800 mesh, and preferably the mesh number is 300-500 mesh, which can have the characteristics of excellent flame retardancy, rigidity, toughness and good low warping.

[0066] In Example 6, Example 7, Example 1, Example 8 and Example 9, the average particle size of the hollow glass microspheres gradually increases, and the bending modulus and impact strength first increase and then decrease. This is because, within a certain range, the particle size of the hollow glass microspheres cooperates well with mica and glass fiber, can construct a skeleton structure, and enhance its bending modulus and impact strength. However, as its particle size further increases, the particle size of the glass microspheres is too large, and it is easy to break during processing and form defect points in the material, resulting in a decrease in the bending modulus and impact strength. At the same time, as the particle size of the hollow glass microspheres increases, the degree of oriented flow of mica and glass fiber is increased, that is, the orientation effect is significantly inhibited, which can significantly reduce the warping of the material. However, as its particle size continues to increase, the magnitude of the reduction in warping is not large.

[0067] In Example 10, Example 1 and Example 11, the total weight of mica powder and hollow glass microspheres is the same, but the mass ratio of the two is 28:5, 30:3, and 32:1, respectively. As the content of mica powder increases, the content of hollow glass microspheres decreases, the bending modulus and impact strength first increase and then decrease, and the warpage gradually increases. It can be seen that the mass ratio of mica powder and hollow glass microspheres has an effect on the mechanics and warpage of the material. The mass ratio of the two can be selected as (28-32): (1-5). At this time, the material has higher rigidity and toughness and lower warpage.

[0068] Comparative Example 1 does not add mica powder, but contains 33 parts of hollow glass microspheres, the bending modulus is low, the impact strength is extremely low, the material rigidity and toughness are insufficient, and the flame retardant performance is poor; Comparative Example 2 does not add hollow glass microspheres, but contains 33 parts of mica powder, the bending modulus, impact strength and flame retardant are good, but the orientation effect of mica and glass fiber cannot be suppressed, and the warping height is too large; Comparative Example 3 is a material without adding glass fiber, the bending modulus is low, the rigidity is poor, and the flame retardant performance decreases; It can be seen from Example 1 and Comparative Examples 1-3 that when mica powder, hollow glass microspheres and glass fiber are present in the material at the same time, it can have good rigidity, toughness, flame retardant and low warping characteristics at the same time. In addition, when more hollow glass microspheres are added in Comparative Example 4, the hollow glass microspheres are easy to gather and rub against each other to cause breakage, which leads to lower bending modulus and impact strength of the material, and increased warping. Therefore, in the material system, when the weight of the hollow glass microspheres is selected from 1 to 5 parts, the rigidity and toughness of the material are better, and the warping degree is lower. Adding 30 parts of talc in Comparative Example 5 will lead to a decrease in the impact strength and deterioration of the flame retardant properties of the material.

[0069] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present invention.

Claims

1. A flame retardant PC / ABS material, characterized in that: The composition comprises the following components in parts by weight: PC 44-71 parts, ABS 4-16 parts, mica powder 23-42 parts, hollow glass microspheres 0.9-5.3 parts, glass fiber 2.9-11 parts, flame retardant 3.9-11 parts, anti-dripping agent 0.29-2.9 parts, processing aid 0-2.5 parts.

2. The flame retardant PC / ABS material according to claim 1, characterized in that: The mesh size of the mica powder is 200-800 meshes.

3. The flame retardant PC / ABS material according to claim 2, characterized in that: The mesh size of the mica powder is 300-600 meshes.

4. The flame retardant PC / ABS material according to claim 1, characterized in that: The average particle size of the hollow glass microspheres is 20-60 μm.

5. The flame retardant PC / ABS material according to claim 4, characterized in that: The average particle size of the hollow glass microspheres is 30-45 μm.

6. The flame retardant PC / ABS material according to claim 1, characterized in that: The mass ratio of the mica powder to the hollow glass microspheres is (28-32):(1-5).

7. The flame retardant PC / ABS material according to claim 1, characterized in that: The flame retardant includes at least one of bisphenol A diphenyl phosphate, resorcinol diphenyl phosphate, triphenyl phosphate, and 4,4'-(isopropylidene diphenyl)bis(diphenyl phosphate); and the anti-dripping agent includes polytetrafluoroethylene.

8. The flame retardant PC / ABS material according to claim 1, characterized in that: The processing aid comprises the following components in parts by weight: 0.1-1 part of antioxidant and 0.1-1 part of lubricant.

9. A method for preparing the flame retardant PC / ABS material according to any one of claims 1 to 8, characterized in that: The method comprises the following steps: mixing, melting, extruding and granulating the raw materials in sequence to obtain the flame retardant PC / ABS material.

10. Use of the flame retardant PC / ABS material according to any one of claims 1 to 8 in the preparation of automotive parts, office supplies and household appliances.

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