WO2020108204A1 - Abs composite material - Google Patents

Abstract

Disclosed is an ABS composite material comprising the following components by weight: 34-78 parts of ABS resin, 0-20 parts of SAN resin, 0-10 parts of toughener, 12-20 parts of flame retardant, 3-6 parts of flame retardant synergist, 3-15 parts of inorganic filler, 0.1-0.5 part of anti-dripping agent and 0-2 parts of auxiliary agent. The average aspect ratio of the inorganic filler is ≥ 5:1. The ABS composite material has the following advantages: 1. high flame retardant grade of up to grade 1.8 mm 5VA; 2. excellent comprehensive performance, achieving a balance of strength and notched impact performance; 3. excellent appearance and high gloss; and 4. excellent thermal stability and large process window.

Description

ABS composite material Technical field

The invention relates to the technical field of engineering plastics, in particular to an ABS composite material.

Background technique

ABS resin is a yellowish solid with a density of about 1.04g/cm ^3. Because it organically unifies the properties of three different materials, acrylonitrile, butadiene, and styrene, it has moldability, rigidity, toughness, and comprehensive performance. Excellent and widely used. ABS is suitable for household appliances, such as TV housings, refrigerator linings, vacuum cleaners, etc., as well as plastic products for instruments, telephones, and the automotive industry.

Flame retardant ABS is one of the important directions of ABS modification. It is developed in response to the shortcoming of ordinary ABS resin that is easy to burn. The flame retardant grade increases from HB, V-2, V-1, V-0, 5VB to 5VA. Among them, the 5V test requires the sample to be burned five times for 5 seconds, and the afterflame or afterflame is extinguished within 30 seconds. The dripping cannot ignite cotton. 5VA also requires that the sample is not allowed to burn through. The thinner the spline, the more Not easy to reach.

Conventional modification methods, such as patents CN201310225994 and CN201310430476, disclose flame-retardant ABS and flame-retardant PC/ASA alloys, brominated or phosphorus-based flame retardants, but the thickness of the spline that achieves the flame retardant effect is large, generally above 3.0mm.

Patents CN200810066901 and CN201611212463 disclose PVC/ABS alloys, which can achieve high flame retardant grades, but due to poor thermal stability of PVC, the processing window is very narrow, which limits its application.

The patents CN201210470130 and CN201310743041 disclose high flame retardant ABS and its alloys, but due to the addition of glass fiber/carbon fiber, its appearance is not good.

Patent CN201480014209 discloses a filled polycarbonate composition, the flame retardant is bisphenol A-bis (diphenyl phosphate) compounded with a large amount of polytetrafluoroethylene, wollastonite particles, alumina particles or glass fibers And its mixture is filled, but the highest can only be 2.3mm 5VA.

Summary of the invention

The purpose of the present invention is to overcome the shortcomings of the prior art and provide an ABS composite material.

In order to achieve the above object, the technical solution adopted by the present invention is: an ABS composite material comprising the following parts by weight of components: ABS resin 34-78 parts, SAN resin 0-20 parts, toughening agent 0-10 parts, resistance 12-20 parts of fuel, 3-6 parts of flame retardant synergist, 3-15 parts of inorganic filler, 0.1-0.5 parts of anti-dripping agent, and 0-2 parts of auxiliary; the average long diameter of the inorganic filler Ratio ≥5:1.

AS resin uses high-viscosity SAN resin and inorganic filler with aspect ratio ≥5:1. The inorganic filler cannot be combusted. The inorganic filler with this aspect ratio can be staggered together to play the role of skeleton support. The material is not easy to burn through. The ABS composite material prepared by the above formula: 1. High flame retardant grade, up to 1.8mm5VA grade; 2. Good overall performance, balanced strength and notch impact performance; 3. Good appearance, high gloss; 4. Good thermal stability and wide processing window. The ABS composite material of the present invention can be used in the field of electronic appliances with high performance and flame retardant requirements.

As a preferred embodiment of the ABS composite material of the present invention, the inorganic filler is at least one of talc powder, inorganic salt whiskers, marble powder, mica powder, calcium metasilicate, kaolin and montmorillonite.

As a preferred embodiment of the ABS composite material of the present invention, the inorganic salt whiskers are calcium sulfate whiskers and/or basic magnesium sulfate whiskers.

As a preferred embodiment of the ABS composite material of the present invention, the average aspect ratio of the inorganic filler is ≥10:1, and D50≤8 μm.

As a preferred embodiment of the ABS composite material of the present invention, the flame retardant is tetrabromobisphenol A, tris(tribromophenoxy)triazine, brominated epoxy, decabromodiphenylethane, brominated At least one of polyimide, brominated polystyrene, polybrominated styrene, brominated polycarbonate, and brominated polyacrylate.

The flame retardant may be a halogen flame retardant, preferably a bromine flame retardant; more preferably the above bromine flame retardant.

As a preferred embodiment of the ABS composite material of the present invention, the flame retardant is a mixture of tris(tribromophenoxy)triazine and brominated epoxy or decabromodiphenylethane. When the flame retardant is tri(tribromophenoxy)triazine compounded with brominated epoxy or decabromodiphenylethane, the flame retardant effect is better than other types of flame retardants.

As a more preferred embodiment of the ABS composite material of the present invention, the weight ratio of the tris(tribromophenoxy)triazine to brominated epoxy or decabromodiphenylethane is: tris(tribromophenoxy) Radical) triazine: brominated epoxy or decabromodiphenylethane = 1:4 ~ 4:1. It has been repeatedly experimented by the inventor that the flame retardant effect is better when the flame retardant is used especially when compounded with the above ratio.

As a preferred embodiment of the ABS composite material of the present invention, in the ABS resin, the weight percentage of acrylonitrile is 15 to 30%, the weight percentage of butadiene is 20 to 40%, and the weight of styrene The percentage content is 30 to 65%.

The ABS resin may be ABS resin produced by a one-step polymerization process with a core-shell structure, or two steps of acrylonitrile-styrene copolymer (AS resin, SAN) blended with ABS rubber powder graft-polymerized by an emulsion method ABS resin produced by the process; commercially available ABS resin can be used as the matrix resin, or a certain amount and ratio of the blend of ABS grafted rubber powder and SAN can be used as the matrix resin, but the composition of the ABS resin matrix needs to meet Only in this way can a better flame retardant effect be achieved.

As a preferred embodiment of the ABS composite material of the present invention, the weight percentage of the butadiene in the ABS resin is 28 to 35%. After repeated experiments and researches by the inventors, it is found that under the same amount of ABS resin, when the weight percentage of butadiene in the ABS resin is 28 to 35%, a better flame retardant effect can be achieved, and the resistance The impact performance is good, the combustion is not easy to drip (5VA), and the performance and appearance are more balanced.

As a preferred embodiment of the ABS composite material of the present invention, the toughening agent is ABS grafted rubber powder, chlorinated polyethylene, silicone rubber, styrene-butadiene-styrene block copolymer, oil-extended SBS , SEBS, nitrile rubber, EPDM, cis-butadiene rubber, natural rubber, styrene-butadiene rubber, acrylic resin, methyl methacrylate-butadiene-styrene copolymer, styrene butyl acrylate binary At least one of graft-modified ethylene-propylene rubber, ethylene-acrylate copolymer, EAA, ethylene-acrylate copolymer, and EVA.

As a preferred embodiment of the ABS composite material of the present invention, the toughening agent is at least one of linear or star SBS and linear or star SEBS. In particular, when the above-mentioned toughening agent is used, it can complement each other with the inorganic filler, which can more effectively increase the viscosity of the material in the molten state and help to improve the flame retardant level.

As a preferred embodiment of the ABS composite material of the present invention, the ABS composite material contains the following parts by weight of components: ABS resin 34-78 parts, SAN resin 0-20 parts, toughener 0-10 parts, flame retardant 12 to 20 parts of agent, 3 to 6 parts of flame retardant synergist, 3 to 15 parts of inorganic filler, 0.1 to 0.5 parts of anti-drip agent and 0 to 2 parts of auxiliary.

As a preferred embodiment of the ABS composite material of the present invention, the ABS composite material includes the following parts by weight of components: ABS resin 34-78 parts, SAN resin 3-20 parts, toughener 1-10 parts, flame retardant 12 to 20 parts of agent, 3 to 6 parts of flame retardant synergist, 3 to 15 parts of inorganic filler, 0.1 to 0.5 parts of anti-drip agent and 0 to 2 parts of auxiliary.

As a preferred embodiment of the ABS composite material of the present invention, the flame retardant synergist includes antimony compound, polysiloxane and inorganic powder, and the weight percentage of the antimony compound in the flame retardant synergist The content is 20～80%;

The antimony compound is at least one of antimony trioxide, colloidal antimony pentoxide, sodium antimonate, antimony trichloride, antimony pentachloride, antimony phosphite, antimony polyphosphate and complex antimony;

The polysiloxane is methyl polysiloxane, phenyl polysiloxane, vinyl polysiloxane, amido polysiloxane, epoxy polysiloxane, isobutyl polysiloxane , At least one of styryl polysiloxane and cyclic structure polysiloxane;

The inorganic powder is at least one of talc powder, magnesium carbonate, barium sulfate, marble powder, mica powder, natural silica, wollastonite powder, kaolin, sepiolite, whiskers, montmorillonite and feldspar powder.

The flame retardant synergist is more preferably the flame retardant synergist in CN20121045503.8.

As a preferred embodiment of the ABS composite material of the present invention, in the SAN resin, the weight average molecular weight is 1×10 ⁵ to 1.5×10 ⁵ g/mol.

As a preferred embodiment of the ABS composite material of the present invention, the anti-dripping agent is polytetrafluoroethylene; the auxiliary agent includes at least one of an antioxidant, a lubricant, a weathering agent, and a colorant.

As a preferred embodiment of the ABS composite material of the present invention, the antioxidant includes a hindered phenolic antioxidant and a phosphite antioxidant; the lubricant includes an amide lubricant and a stearate lubricant , At least one of ester lubricants and silicone lubricants; the weathering agent includes at least one of benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers and hindered amine light stabilizers Species. The colorant includes at least one of a pigment type, a dye type, and other colorants with special aesthetic effects.

The invention also provides a method for preparing the ABS composite material, including the following steps:

a. Mix the raw materials of each component in the high-speed mixer for 5-10 minutes according to the ratio;

b. The above mixture is transported to the twin-screw extruder through a precision metering feeding device. The screw temperature of each section of the extruder is controlled between 180 and 220°C, and the length-diameter ratio of the twin-screw extruder is 30 to 45. The screw speed is 200-800 rpm, under the shearing, mixing and conveying of the screw, the material can be fully melted and compounded, and then extruded, granulated and dried to obtain ABS composite material.

The beneficial effect of the present invention is that the present invention provides an ABS composite material. The ABS composite material of the present invention: 1. High flame retardant grade, up to 1.8mm5VA grade; 2. Good overall performance, balanced strength and notch impact performance; 3. Good appearance, high gloss; 4. Thermal stability Good performance and wide processing window.

detailed description

In the raw materials of the examples and comparative examples, PA-747S and PA-757 of Chimei Industries of Taiwan are used as the ABS resin; the weight percentage of butadiene in PA-747S is 28-35%, butadiene in PA-757 The weight percentage of olefin is less than 20%;

SAN resin is selected from D-168 of Zhenjiang Chimei Chemical Co., Ltd. and SAN 350 of Kumho Chemical Co., Ltd.; D-168 is a high-viscosity SAN, and the weight average molecular weight of D-168 is 1.4×10 ⁵ g/mol; It is a common SAN. The weight average molecular weight of SAN-350 is 0.85×10 ⁵ g/mol.

The toughening agent is the irregular spherical high-rubber powder ABS 60P of Taiwan Guoqiao Petrochemical Co., Ltd., and the linear SBS and star SEBS of China Petrochemical Corporation Baling Branch; the flame retardant is the Israeli Dead Sea Bromine Company. Tris(tribromophenoxy)triazine FR-245 and South Korea Yujin’s brominated epoxy CXB-714C; the flame retardant synergist is antimony trioxide, produced by Huachang Antimony Co., Ltd.; flame retardant synergy The agent is prepared by the following method: mix 60 grams of talc powder, 15 grams of dimethyl polysiloxane, and 25 grams of antimony trioxide in a high-mixer for 20 minutes to prepare it, and record it as KF-1; For the inorganic filler, IMIFABI talcum powder HTPUltra5L, Yingkou Wesk Chemical Co., Ltd. basic magnesium sulfate whisker HTPUltra5L talcum powder and Guangzhou Huangpu Tiantai Chemical Light Co., Ltd. precipitated barium sulfate AB-3000N1, The average aspect ratio of HTPUltra5L is ≥5:1, the average aspect ratio of basic magnesium sulfate whiskers is ≥5:1, the average aspect ratio of precipitated barium sulfate is about 1:1; the anti-dripping agent is Guangzhou Entropy SN80-SA7; additives are antioxidants and lubricants, wherein the weight ratio of antioxidants and lubricants is: antioxidants: lubricants = 3:5, antioxidants are selected from Shanghai Ciba Refining and Chemical Company The produced antioxidant 1010 and antioxidant 168 are compounded in a weight ratio of 1:2. The lubricant is ethylene bisstearic acid amide (EBS) provided by Beijing Shidafeng Trading Co., Ltd.

The preparation method of the ABS composite material of the embodiment and the comparative example is the same, specifically: firstly, the raw materials are added into a high-speed mixer for uniform mixing, and then the above mixture is sent into a twin-screw extruder for kneading, extrusion, drawing, Water cooling and pelletizing; among them, the length-to-diameter ratio of the twin screw extruder is 40:1; the barrel temperature is set to: the temperature in the first zone is 80 ℃, the temperature in the second zone is 160 ℃, the temperature in the third zone is 200 ℃, and the temperature in the fourth zone is 200 ℃, five zone temperature 200 ℃, six zone temperature 200 ℃, seven zone temperature 200 ℃, eight zone temperature 200 ℃, nine zone temperature 200 ℃, ten zone temperature 200 ℃, head temperature 220 ℃; screw speed is 300 rpm Minutes to get ABS composite material.

In order to better explain the purpose, technical solution and advantages of the present invention, the present invention will be further described in combination with specific embodiments below.

Examples 1-9

The formulations of the ABS composite materials of Examples 1-9 are shown in Table 1.

Table 1 ABS composite material formulations of Examples 1-9

"-" means no addition.

Examples 10 to 15 and Comparative Examples 1 to 4

The formulations of the ABS composite materials of Examples 10 to 15 and Comparative Examples 1 to 4 are shown in Table 2.

Table 2 ABS composite material formulations of Examples 10 to 15 and Comparative Examples 1 to 4

Examples 16-22

The ABS composite material formulations of Examples 16 to 22 differ from Example 7 only in the types of flame retardants. The ABS composite material formulations of Examples 16 to 22 are shown in Table 3.

Table 3 ABS composite material formulations of Examples 16-22

Examples 22 to 23 The ABS composite formulations of Examples 22 to 23 differ from Example 6 only in the types of tougheners. The types of Examples 22 to 23 are shown in Table 4.

Table 4 Types of tougheners of Examples 22 to 23

Examples	Types of tougheners
Example 22	Linear SBS
Example 23	Star SEBS

Example 24

See Table 5 for product performance test methods.

Table 5 Performance test methods

Performance	Test Conditions	Test Methods
Tensile Strength	50mm/min	ISO527
Bending strength	2mm/min	ISO178
IZOD notched impact strength	23℃	ISO 180
Flame retardant test	1.8-3.0mm	UL94
Gloss	60°	ASTM D523

The ABS composite materials prepared in the above examples and comparative examples are first injected into standard test strips according to the standard size, and then each performance test is performed according to the test standards shown in Table 5 above; each example and comparative test The performance test data of this kind are shown in Table 6-9.

Table 6 Performance test data of the samples of Examples 1-9

Table 7 Performance test data of samples of Examples 10 to 15 and Comparative Examples 1 to 4

Generally speaking, when the tensile strength is greater than 38MPa, the bending strength is greater than 56MPa, the IZOD notch impact strength is greater than 12kJ/m ² and the gloss is greater than 80, the comprehensive mechanical properties of the material are better, and the impact strength is the most critical factor. It can be seen from the data in Tables 6 and 7 that the ABS composite material of the present invention has better flame retardancy and better impact resistance. From the comparison between Example 7 and Comparative Example 1, it can be seen that the flame retardant effect and mechanical properties of butadiene with a weight percentage of 28 to 35% are better than that of ABS resin with a lower butadiene content. It can be seen from the comparison between Example 7 and Comparative Example 2 that the high-viscosity SAN resin has a higher flame retardant grade than the ordinary SAN resin. It can be seen from the comparison between Example 7 and Comparative Example 3 that the flame retardant effect of using KF-1 is better than the general flame retardant synergist. It can be seen from the comparison between Example 7 and Comparative Example 4 that when the aspect ratio of the inorganic filler is greater than 5:1, the flame retardant effect is better. As can be seen from the comparison of Examples 4 to 9, as the content of the inorganic filler increases, the content of the ABS resin decreases, the flame retardant grade of the ABS composite increases, and the tensile strength, bending strength, and notch impact strength decrease. When the content of the inorganic filler is greater than 12 parts by weight, the increase in the flame retardant grade is not obvious, and the toughness decreases, so the content of the inorganic filler is preferably 8 to 12 parts by weight. It can be seen from the results of Examples 5, 7, 10 to 13 that as the content of the high-viscosity SAN resin increases, the impact strength decreases, but the tensile strength and bending strength increase. When the high-viscosity SAN resin is greater than When it is 3 parts by weight, it can meet the balance of impact performance and strength. It can be seen from the comparison between Example 7 and Examples 14 and 15 that the toughening agent can improve the problem of reduction in impact strength caused by the high-viscosity SAN resin.

Table 8 Performance test data of the samples of Examples 16 to 22

It can be seen from the comparison of Examples 7, 16 to 22 in Tables 6 and 8 that when tri(tribromophenoxy)triazine and brominated epoxy compound are used as flame retardants, the flame retardant effect is better, Especially when the weight ratio of tris(tribromophenoxy)triazine to brominated epoxy is: tris(tribromophenoxy)triazine: brominated epoxy=1:4～4:1, the resistance Burning effect is better. The inventors used the same method to test the compound of tris(tribromophenoxy)triazine and decabromodiphenylethane. The results showed that when tris(tribromophenoxy)triazine and decabromodiphenylethyl When the compound is used as a flame retardant, the flame retardant effect is better, especially when the weight ratio of tris(tribromophenoxy)triazine to decabromodiphenylethane is: tris(tribromophenoxy) Triazine: decabromodiphenylethane = 1:4 ~ 4:1, the flame retardant effect is better.

Table 9 Performance Test Data of Examples 22 to 23 Samples

It can be seen from the comparison of Examples 6, 22, and 23 in Tables 6 and 9 that when the toughening agent is changed from spherical high rubber powder to linear or star SBS or SEBS, the flame retardant effect of the composite material is better.

Finally, it should be noted that the above embodiments are only for illustrating the technical solutions of the present invention rather than limiting the protection scope of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, persons of ordinary skill in the art should understand that The technical solutions of the present invention may be modified or equivalently replaced without departing from the spirit and scope of the technical solutions of the present invention.

Claims (10)

1. An ABS composite material, characterized by comprising the following parts by weight of components: ABS resin 34-78 parts, SAN resin 0-20 parts, toughener 0-10 parts, flame retardant 12-20 parts, flame retardant 3-6 parts of synergist, 3-15 parts of inorganic filler, 0.1-0.5 parts of anti-dripping agent and 0-2 parts of auxiliary; the average aspect ratio of the inorganic filler is ≥5:1.
2. The ABS composite material according to claim 1, wherein the inorganic filler is at least one of talc powder, inorganic salt whiskers, marble powder, mica powder, calcium metasilicate, kaolin and montmorillonite.
3. The ABS composite material according to claim 1, wherein the average aspect ratio of the inorganic filler is ≥10:1 and D50≤8 μm.
4. The ABS composite material according to claim 1, wherein the flame retardant is tetrabromobisphenol A, tris(tribromophenoxy)triazine, brominated epoxy, decabromodiphenylethane, bromine At least one of polyimide, brominated polystyrene, polybrominated styrene, brominated polycarbonate, and brominated polyacrylate; the flame retardant is tris(tribromophenoxy) tri A mixture of azine and brominated epoxy or decabromodiphenylethane; more preferably, the weight ratio of the tris(tribromophenoxy)triazine to brominated epoxy or decabromodiphenylethane is: Tris(tribromophenoxy)triazine: brominated epoxy or decabromodiphenylethane=1:4～4:1.
5. The ABS composite material according to claim 1, wherein in the ABS resin, the weight percentage of acrylonitrile is 15-30%, the weight percentage of butadiene is 20-40%, and the weight of styrene The weight percentage content is 30 to 65%; preferably, the weight percentage content of the butadiene in the ABS resin is 28 to 35%.
6. The ABS composite material according to claim 1, wherein the toughening agent is ABS grafted rubber powder, chlorinated polyethylene, silicone rubber, styrene-butadiene-styrene block copolymer, oil-extended SBS, SEBS, nitrile rubber, EPDM, cis-butadiene rubber, natural rubber, styrene-butadiene rubber, acrylic resin, methyl methacrylate-butadiene-styrene copolymer, styrene butyl acrylate Meta-grafted modified ethylene propylene rubber, ethylene-acrylate copolymer, EAA, ethylene-acrylate copolymer and at least one of EVA; preferably, the toughening agent is linear or star SBS and linear Or at least one of star SEBS.
7. The ABS composite material according to claim 1, characterized by comprising the following parts by weight of components: ABS resin 34-78 parts, SAN resin 0-20 parts, toughening agent 0-10 parts, flame retardant 12-20 Parts, flame retardant synergist 3 to 6 parts, inorganic filler 3 to 15 parts, anti-dripping agent 0.1 to 0.5 parts and auxiliary agent 0 to 2 parts; preferably, the ABS composite material contains the following parts by weight of the group Points: ABS resin 34-78 parts, SAN resin 3-20 parts, toughening agent 1-10 parts, flame retardant 12-20 parts, flame retardant synergist 3-6 parts, inorganic filler 3-15 parts, Anti-dripping agent 0.1～0.5 parts and auxiliary agent 0～2 parts.
8. The ABS composite material according to claim 1, wherein the flame retardant synergist comprises antimony compound, polysiloxane and inorganic powder, and the antimony compound has a weight of 100% in the flame retardant synergist The content is 20～80%;

   The antimony compound is at least one of antimony trioxide, colloidal antimony pentoxide, sodium antimonate, antimony trichloride, antimony pentachloride, antimony phosphite, antimony polyphosphate and complex antimony;

   The polysiloxane is methyl polysiloxane, phenyl polysiloxane, vinyl polysiloxane, amido polysiloxane, epoxy polysiloxane, isobutyl polysiloxane , At least one of styryl polysiloxane and cyclic structure polysiloxane;

   The inorganic powder is at least one of talc powder, magnesium carbonate, barium sulfate, marble powder, mica powder, natural silica, wollastonite powder, kaolin, sepiolite, whiskers, montmorillonite and feldspar powder.
9. The ABS composite material according to claim 1, wherein the SAN resin has a weight average molecular weight of 1×10 ⁵ to 1.5×10 ⁵ g/mol.
10. The ABS composite material according to claim 1, wherein the anti-dripping agent is polytetrafluoroethylene; the auxiliary agent includes at least one of antioxidant, lubricant, weathering agent and colorant; preferably Ground, the antioxidants include hindered phenol antioxidants and phosphite antioxidants; the lubricants include amide lubricants, stearate lubricants, ester lubricants and silicone lubricants At least one of; the weathering agent includes at least one of a benzophenone ultraviolet absorber, a benzotriazole ultraviolet absorber, and a hindered amine light stabilizer.