CN112646346B

CN112646346B - Paint-spraying-resistant PC/ABS alloy material and preparation method thereof

Info

Publication number: CN112646346B
Application number: CN202011558720.1A
Authority: CN
Inventors: 林荣涛; 黄险波; 叶南飚; 王琪; 孙付宇; 李文龙; 杨波; 丁正亚
Original assignee: Kingfa Science and Technology Co Ltd
Current assignee: Kingfa Science and Technology Co Ltd
Priority date: 2020-12-24
Filing date: 2020-12-24
Publication date: 2022-12-02
Anticipated expiration: 2040-12-24
Also published as: CN112646346A

Abstract

The invention discloses a paint spraying resistant PC/ABS alloy material and a preparation method thereof, belonging to the technical field of high polymer materials. The PC/ABS alloy material resistant to paint spraying comprises the following components in parts by weight: 30 to 70 parts of polycarbonate resin, 30 to 70 parts of acrylonitrile-butadiene-styrene resin, 0.5 to 10 parts of corrosion-resistant assistant, 1 to 5 parts of compatilizer, 0.1 to 1 part of antioxidant and 0.1 to 1 part of lubricant; the corrosion-resistant aid comprises polyketone. The PC/ABS alloy material prepared by the formula has good paint-spraying resistance, a painted surface is intact, no crack exists, the adhesive force of a paint layer is good, and the PC/ABS alloy material has good mechanical property and can be used for preparing automobile interior and exterior parts.

Description

Paint-spraying-resistant PC/ABS alloy material and preparation method thereof

Technical Field

The invention belongs to the technical field of high polymer materials, and particularly relates to a paint-spraying-resistant PC/ABS alloy material and a preparation method thereof.

Background

With the development of technology and the improvement of living standard, the automobile is no longer just a simple tool for riding instead of walk. Appearance design and driving experience of automobiles are gradually valued by people, and selling points are also dug in the aspects of the appearance design and the driving experience by various large automobile host factories, so that the appearance design and the driving experience attract eyes and favor of consumers. The diversification and customization of automobile colors are an important aspect attracting automobile consumers, and automobile colors are mainly white and black over ten years ago, and nowadays automobiles have various choices such as sapphire blue, fast red and the like. Diversification and customization of automobile colors can not be left in automobile spraying.

The plastic has the advantages of low density, good flexibility, low manufacturing energy consumption and the like, and is widely applied to the manufacturing of automobile parts. However, the corrosion resistance and weather resistance of the plastic are poor, so that the surface of the plastic product can be endowed with better corrosion resistance and weather resistance by spraying paint, and meanwhile, the appearance and decoration of the product can be improved by various paint color effects. Common plastic painted parts of automobiles include bumpers, rearview mirror housings, guide plates, door handles, and the like. PC/ABS belongs to polar non-qualitative high molecular polymer, and is easily excessively corroded by ester, ketone, ether and benzene solvents in paint due to poor chemical resistance, so that appearance defects often appear in paint spraying application.

CN 106832851A discloses a method for improving PC/ABS painting defects: 3-5 parts of talcum powder is added to be separated out on the surface of a workpiece during injection molding, so that the oil paint etching resistance of the workpiece is improved, and the problems of paint-spraying bottom biting and cracking are solved. However, the talc powder used in this method has a small particle size and a limited improvement effect, and is not suitable for paint systems with very strong corrosive forces. If the addition amount of the talcum powder is increased, the appearance of the material is adversely affected. CN103342886B utilizes the addition of high-flow SAN resin in PC/ABS, so that the internal stress formed by the part in the injection molding process is lower, and the possibility of cracking of the plastic substrate due to the release of the internal stress after spraying is reduced, thereby improving the paint spraying performance of the PC/ABS material. However, SAN itself has very poor corrosion resistance to paint solvents, and even if the internal stress of the system is reduced, the resistance of PC/ABS to solvents cannot be improved, and the risk of paint defects is still high. CN101508833A discloses a method for improving the solvent resistance of a PC/ABS alloy by modifying PC/ABS with PBT and an acrylic toughening agent. But in practice, the addition of PBT generally needs to reach more than 10% to play a role, and the shrinkage rate of the material is obviously changed, which brings difficulty to practical application.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provide a PC/ABS alloy material with excellent paint spraying resistance and a preparation method thereof.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows: the PC/ABS alloy material resistant to paint spraying comprises the following components in parts by weight: 30 to 70 parts of polycarbonate resin, 30 to 70 parts of acrylonitrile-butadiene-styrene resin, 0.5 to 10 parts of corrosion-resistant auxiliary agent, 1 to 5 parts of compatilizer, 0.1 to 1 part of antioxidant and 0.1 to 1 part of lubricant; the corrosion-resistant auxiliary agent comprises polyketone, the structural formula of the polyketone is shown as a formula (I), wherein the ratio of n to m is 0.01-0.5; x is one of propylene, butene, hexene, octene, decene, styrene, alpha-methylstyrene, cyclopentene, norbornene, tetracyclododecene, tricyclodecene, pentacyclopentadecene, pentacyclohexadecene, ethylene chloride and ethylene fluoride;

preferably, the paint-resistant PC/ABS alloy material comprises the following components in parts by weight: 40 to 60 portions of polycarbonate resin, 40 to 60 portions of acrylonitrile-butadiene-styrene resin, 2 to 5 portions of corrosion-resistant auxiliary agent, 2 to 4 portions of compatilizer, 0.1 to 1 portion of antioxidant and 0.1 to 1 portion of lubricant.

Preferably, the polycarbonate resin is bisphenol A polycarbonate having a melt flow rate of 2 to 25g/10min at 300 ℃ under 1.2 kg. The melt flow rate of the acrylonitrile-butadiene-styrene resin is 5-30 g/10min at the temperature of 220 ℃ and under the condition of 10kg, wherein the content of acrylonitrile is 5-35 wt.%, the content of butadiene is 10-60 wt.%, and the content of styrene is 30-70 wt.%.

Preferably, the melt flow rate of the polycarbonate resin is 3-15 g/10min at 300 ℃ and 1.2 kg; the melt flow rate of the acrylonitrile-butadiene-styrene resin is 10-20 g/10min at the temperature of 220 ℃ under the condition of 10 kg.

Preferably, the compatibilizer comprises at least one of methacrylate-butadiene-styrene terpolymer, polyethylene grafted maleic anhydride, polypropylene grafted maleic anhydride, polyacrylonitrile-styrene grafted maleic anhydride polymer, polyacrylonitrile-butadiene-styrene grafted maleic anhydride polymer, styrene-N, phenylmaleimide-maleic anhydride terpolymer.

Preferably, the compatilizer is a mixture of a polyacrylonitrile-styrene grafted maleic anhydride polymer and a polyacrylonitrile-butadiene-styrene grafted maleic anhydride polymer, and the mass ratio of the polyacrylonitrile-styrene grafted maleic anhydride polymer to the polyacrylonitrile-butadiene-styrene grafted maleic anhydride polymer is 1.

Preferably, the antioxidant comprises at least one of monophenols, bisphenols, phosphites, sulphur-containing species, amines, semi-hindered phenolic antioxidants.

Preferably, the lubricant comprises at least one of silicone, ester, amide, polyethylene, stearic, wax, fatty acid type lubricants.

Meanwhile, the invention also discloses a preparation method of the PC/ABS alloy material, which comprises the following steps: uniformly mixing polycarbonate resin, acrylonitrile-butadiene-styrene resin, a corrosion-resistant auxiliary agent, a compatilizer, an antioxidant and a lubricant, adding the mixture into a double-screw extruder, melting and mixing, extruding and granulating to obtain the spray-resistant PC/ABS alloy material.

Preferably, in the preparation method, the melting and mixing temperature is 160-260 ℃, and the screw rotation speed is 350-450 r/min.

Compared with the prior art, the invention has the beneficial effects that: the risk of appearance defects after PC/ABS alloy is painted is effectively reduced by selecting the proportion of each component, the corrosion-resistant auxiliary agent and the compatilizer; meanwhile, the PC/ABS alloy material still has good mechanical properties.

Detailed Description

To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.

The materials used in the examples and comparative examples are as follows:

polycarbonate resin: bisphenol A polycarbonate, LG chemical, PC1 melt flow rate of 12g/10min, PC2 melt flow rate of 22g/10min, melt flow rate at 300 ℃,1.2 kg;

acrylonitrile-butadiene-styrene resin: qimei, the melt flow rate of ABS1 is 6g/10min, the acrylonitrile content is 15%, the butadiene content is 30%, and the styrene content is 55%; the melt flow rate of ABS2 is 15g/10min, the acrylonitrile content is 21%, the butadiene content is 16%, and the styrene content is 63%; the melt flow rate of ABS3 was 30g/10min, the acrylonitrile content was 22%, the butadiene content was 12%, and the styrene content was 66%. The melt flow rates were all measured at 220 ℃ under 10 kg.

Polyketone: xiao xing in Korea, n/m value 0.05, X is propylene;

polyacrylonitrile-styrene graft maleic anhydride polymer: wen in China;

polyacrylonitrile-butadiene-styrene graft maleic anhydride polymer: dow, USA;

bisphenol antioxidants: antioxidant 1010, sanfeng chemical industry;

phosphite ester antioxidant: antioxidant 168, sanfeng chemical industry;

lubricant: pentaerythritol tetrastearate, usa lool.

Examples 1 to 9

The formulations of the paint-resistant PC/ABS alloy materials of the embodiments 1-9 of the paint-resistant PC/ABS alloy material of the invention are shown in Table 1, and the preparation method is as follows: uniformly mixing polycarbonate resin, acrylonitrile-butadiene-styrene resin, a corrosion-resistant auxiliary agent, a compatilizer, an antioxidant and a lubricant, adding the mixture into a double-screw extruder, melting and mixing at the temperature of 200 ℃ and the screw rotating speed of 400 ℃, and extruding and granulating to obtain the spray-painting-resistant PC/ABS alloy material.

Comparative example 1

The formula of the PC/ABS alloy material is shown in Table 1, and the preparation method is the same as that of the embodiment.

Table 1 formula table (parts by weight)

Performance testing

1) Paint spray resistance test

The PC/ABS alloy materials described in examples 1 to 9 and comparative example 1 were injection-molded into rectangular 100X 3mm test pieces which were used for the evaluation of the paint-resistance. The test method comprises the following steps: and spraying paint on the surface of the rectangular sample plate by using a spray pen, baking the sample plate in an oven at 90 ℃ for 1h, and after the paint is cured, judging the risk degree of the paint spraying defect by evaluating the appearance change grade of the surface of the sample plate. The specific appearance and painting risk levels are illustrated in table 2, and the painting defect risk test results are shown in table 3. The model of the spray pen is HS08ADC-K; the paint is X-20C which is Rongxin in the Yangyin.

TABLE 2

TABLE 3

Item

Example 1

Example 2

EXAMPLE 3

Example 4

Example 5

Example 6

Example 7

Fruit 8

Example 9

To 1

Risks

In (1)

Is low in

In

In (1)

Extremely low

Super high

2) Mechanical Property measurement

Testing flexural modulus with reference to ISO 178-2019; testing the notch impact strength of the simply supported beam by referring to ISO 180-2019; the paint adhesion was tested with reference to ISO 2409-2013. The test results are shown in table 4.

TABLE 4

Comparative example 1 has a very high risk of paint defects, and the paint layer has poor adhesion, and in addition, the flexural modulus and impact strength are poor, and the practicability is poor; in the embodiments 2-4, the risk of paint spraying defects is low, and the mechanical property is better; in contrast, the risk of painting defects was slightly higher for examples 6-8; example 9, the risk of paint defects was minimal, the paint adhesion was good, and the mechanical properties were also most excellent.

Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims

1. The PC/ABS alloy material with paint spraying resistance is characterized by comprising the following components in parts by weight: 40 to 50 parts of polycarbonate resin, 50 to 60 parts of acrylonitrile-butadiene-styrene resin, 2 to 5 parts of corrosion-resistant additive, 2 to 4 parts of compatilizer, 0.1 to 1 part of antioxidant and 0.1 to 1 part of lubricant; the corrosion-resistant auxiliary agent comprises polyketone; the compatilizer is a mixture of a polyacrylonitrile-styrene grafted maleic anhydride polymer and a polyacrylonitrile-butadiene-styrene grafted maleic anhydride polymer, and the mass ratio of the polyacrylonitrile-styrene grafted maleic anhydride polymer to the polyacrylonitrile-butadiene-styrene grafted maleic anhydride polymer is 1; the melt flow rate of the polycarbonate resin is 3-15 g/10min under the conditions of 300 ℃ and 1.2 kg; the melt flow rate of the acrylonitrile-butadiene-styrene resin is 10-20 g/10min at the temperature of 220 ℃ under the condition of 10 kg.

2. The paint spray resistant PC/ABS alloy material of claim 1, wherein the antioxidant comprises at least one of monophenolic, bisphenolic, phosphite, sulfur-containing, amine, and semi-hindered phenolic antioxidants.

3. The paint resistant PC/ABS alloy material of claim 1 wherein the lubricant comprises at least one of a silicone based, ester based, amide based, polyethylene based, stearic acid based, wax, fatty acid based lubricant.

4. A method for preparing the paint-resistant PC/ABS alloy material according to any of claims 1 to 3, characterized in that the method comprises: uniformly mixing polycarbonate resin, acrylonitrile-butadiene-styrene resin, corrosion-resistant auxiliary agent, compatilizer, antioxidant and lubricant, adding the mixture into a double-screw extruder, melting and mixing, extruding and granulating to obtain the spray-resistant PC/ABS alloy material.

5. The method according to claim 4, wherein the melt-kneading temperature is 160 to 260 ℃ and the screw rotation speed is 350 to 450r/min.