CN103044850A - Black highlight acrylonitrile butadiene styrene (ABS) alloy and preparation method thereof - Google Patents

Abstract

The invention relates to a dazzling black high-gloss ABS alloy and a preparation method thereof. The high-performance ABS resin, permeable SAN, PMMA, black masterbatch, light stabilizer and processing aid are mixed according to weight ratio: high-performance ABS resin 60 -90 parts, 10~40 parts of permeability SAN, 0~5 parts of PMMA, 0-10 parts of toughening agent, 1~10 parts of black masterbatch, 0.2~2 parts of light stabilizer, 0.2~5 parts of processing aid; and respectively Drying, stir evenly in a high-speed mixer, fully mix, send into a twin-screw extruder, knead, extrude, pull strands, cool, pelletize, dry, and obtain raw materials and finished products. The dazzling black high-gloss ABS alloy of the present invention has good glossiness, permeability and dazzling black effect. At the same time, it also has high fluidity, good impact strength and high hardness, and can be used in various injection molding products, especially It is used in products that have high requirements for viewing in the household appliance industry, such as TV front shells, etc.

Description

A kind of dazzling black high-gloss ABS alloy and preparation method thereof

technical field

The invention relates to a high-performance high-gloss ABS resin with a dazzling black effect and a preparation method thereof, which is mainly applied to the appearance of large thin shells with high requirements on product appearance (including gloss, weld marks, flow marks, color, etc.) Injection molded parts (such as TV front shells, etc.), with low production cost and excellent comprehensive performance, have broad market prospects.

Background technique

ABS (Acrylonitrile butadiene Styrene) resin is a terpolymer with excellent comprehensive properties composed of acrylonitrile, butadiene and styrene. Because of the synergistic performance of the three components, ABS resin has good fluidity, toughness, good low temperature impact resistance, good creep resistance, good dimensional stability, small molding shrinkage, good gloss, and excellent formability. It is widely used in household appliances, mechanical parts, office supplies, electronic devices, automobile industry and other fields, and has become the mainstream plastic raw material favored by major enterprises and research institutions.

With people's pursuit of high-quality life, the elegant, stable and elegant appearance has become one of the important means to attract consumers. At the same time, in the large-scale thin-shell product industry, especially in the home appliance industry, the green injection molding process is constantly innovating. , higher requirements are put forward for the hardness, heat resistance, scratch resistance, gloss, permeability and color of the product. Enterprises and research institutions have also done a lot of work to continuously modify the original ABS. Cater to the needs of the market.

PMMA (polymethyl methacrylate) has been attracting attention as an ideal modified blend for scratch-resistant, high-gloss ABS alloys. In 2012, Longjia (Shanghai) Industrial Co., Ltd. developed a high-scratch-resistant and high-toughness alloy material by using a high ratio of PMMA and MBS, and applied for a patent 201210288752.3 "A spray-free high-transparency and high-gloss ABS material and its preparation Method"; Kingfa Science and Technology applied for patent 201210037436 "A thermoplastic resin blend with weather resistance, scratch resistance, high gloss and high heat resistance and its preparation method", the PMMA content is as high as 33-80%. In 2011, Sichuan Changhong Electric Co., Ltd. successfully developed high hardness (H grade, even 3H grade) ABS alloy material, and applied for patent 201110398087.9 "ABS/PMMA composite material and its preparation method". In 2010, Silver Jubilee Engineering Plastics (Dongguan) Co., Ltd. applied for patent 201010213189.4 "High-gloss, high-hardness, dust-proof ABS alloy material for electronic appliances and its preparation method", with a PMMA content of 23-60%; Shanghai Pulit Composites Co., Ltd. applied Patent 201010611626.8 "A transparent, high-hardness, impact-resistant ABS plastic alloy composition", Shenzhen Keju New Materials Co., Ltd. applied for patent 201010296190.8 "A flame-retardant high-gloss ABS alloy and its preparation method", Weilin Engineering, Shunde District, Foshan City Plastic Co., Ltd. "A PMMA/ABS alloy with dazzling black and colorful effects and its preparation method" all achieve the purpose of high gloss and scratch resistance by adding a large ratio of PMMA and AS to cooperate. In addition, patents 200910196729.X, 200810241237.3, 200810241325.3, and 200810203577.7 all use high-ratio PMMA to develop high-toughness, high-hardness, scratch-resistant, and excellent comprehensive performance high-gloss ABS alloy raw materials. Although the addition of PMMA can significantly improve the performance of ABS alloys (high gloss, high hardness, high strength, scratch resistance, etc.) The cost of raw materials affects its market competitiveness.

In recent years, on the basis of PMMA-modified high-gloss ABS alloys, a number of new high-gloss ABS alloy modifiers with low PMMA content (or even PMMA-free) have gradually emerged and gradually occupied market share. Shenzhen Keju New Material Co., Ltd. applied for patents 201010296190.8 "A Flame-Retardant High-gloss ABS Alloy and Its Preparation Method" and 200910110381.8 "High Heat-Resisting, High-Gloss, Flame-Retardant ABS Modified Material and Its Preparation Method", which were applied by Kingfa Technology Patent 200910199794.8 "A super-high flow flame-retardant ABS modified resin", Fujian Aofeng Technology Co., Ltd. applied for patent 201010568964.8 "High-gloss flame-retardant and heat-resistant ABS alloy and its preparation method", and China National Petroleum Corporation applied for patent 200910243758.7 "A ABS resin composition with excellent flow properties". The above-mentioned inventions reduce the amount of PMMA to varying degrees, or even completely abandon the modification method of PMMA, and achieve high-gloss ABS alloy through the synergistic effect of high-ratio SAN, flame retardant, toughening agent, heat-resistant agent and other modification additives. High scratch resistance, high gloss and excellent comprehensive mechanical properties. Although the above invention has changed the traditional high-ratio PMMA blended high-gloss ABS alloy preparation method, it is mainly used in fields with high heat resistance and flame retardancy requirements, and the introduction of flame retardants, heat stabilizers and other additives The cost is much higher than PMMA.

At present, the injection molding materials of high-gloss plastic parts with electrical appearance in my country are mostly ABS/PMMA alloys (also known as high-gloss ABS alloys), but they face the problem of high cost of high-content PMMA, and as the thickness of plastic parts becomes smaller and smaller, the existing ABS When the /PMMA alloy is used to form thin-shell plastic parts, the blackness effect of the plastic part is significantly reduced, which affects the overall appearance quality of the plastic part. CN102311590A patent discloses a flame-retardant high-gloss ABS alloy and its preparation method. The flame-retardant high-gloss ABS alloy consists of the following components by weight percentage: SAN30-40%; PMMA10-14%; ABS12-34%; toughening agent 8 -12%; liquid flame retardant 1-2.5%; solid flame retardant 16-18%; lubricant 1-2%. Although the invention has adopted the modification method of replacing part of PMMA with SAN, its PMMA content still exceeds 10%, and the ratio of expensive toughening agent to flame retardant is too high, which not only increases the cost of the alloy system, but also affects The temperature control of the blending process puts forward more stringent requirements. Therefore, for the general-purpose high-gloss ABS used in most of the current electrical appearance parts in my country, it is urgent to seek an improvement of a high-gloss ABS alloy with a dazzling black effect that can reduce costs and meet the high mechanical properties and appearance quality requirements of injection-molded electrical thin-shell appearance parts. sexual means. In response to the above problems, this patent uses low-cost, high-permeability, and high-hardness SAN to replace the high-cost PMMA in a large proportion, and adjusts the ratio of other additives. Through reasonable physical modification methods and processes, the preparation is obtained. A high-performance, high-gloss ABS alloy with a dazzling black effect, which has achieved the mechanical properties and appearance quality of the original ABS/PMMA alloy, and significantly reduced the cost of the PMMA-modified high-gloss ABS alloy.

Contents of the invention

The purpose of the present invention is to provide a dazzling black high-gloss ABS alloy and its preparation method. With high-performance ABS as the main body, the content of PMMA with high cost can be reduced by adjusting the ratio of other ingredients and the process, and the scratch resistance of the product can be guaranteed. and gloss requirements.

The technical scheme that the present invention takes is:

A kind of dazzling black high-gloss ABS alloy, its weight ratio is composed of:

Described dazzing black high gloss ABS alloy, its weight ratio composition is preferred:

Described dazzling black high-gloss ABS alloy, its weight ratio composition is further preferred:

The above-mentioned ABS resins are acrylonitrile-butadiene-styrene graft copolymer (ABS), acrylonitrile-ethylene propylene elastomer-styrene graft copolymer (ABS), acrylonitrile-styrene-acrylic acid terpolymer One or several blends of ASA, such as Chimei's 757K, LG Yongxing's 121H, Korea Kumho's 750, Shanghai Gaoqiao's 8391, Jilin Petrochemical's 0215A, Taiwan Taihua's AG15A1 , BASF's GP22, etc. The mass content of acrylonitrile in ABS resin is between 20%-30%, the mass content of butadiene is between 13-20%, and the mass content of styrene is between 40-60%.

The melt flow coefficient of the permeable SAN should be between 20-40g/10min (220°C, 10kg), the light transmittance should be greater than 85%, it has high hardness and excellent comprehensive performance.

The PMMA is high hardness and high transparency polymethyl methacrylate, its average molecular weight is 80,000-300,000, and the mass content of acrylic acid is 98-100%. The content of the added PMMA depends on product requirements, in the present invention because of adjusting the content and technology of other batching, reduce the consumption of PMMA as far as possible, the addition amount can be reduced to zero when necessary.

The selected tougheners are methyl methacrylate-butadiene-styrene graft copolymer (MBS), chlorinated polyethylene, acrylic-butadiene-styrene copolymer, methyl or ethyl acrylate copolymer One or more mixtures of compounds and their derivatives, MBS is the preferred toughening agent, and the rubber content should be between 50-60%.

The selected black masterbatch should be high-precision and bright grade. Even if the general color masterbatch meets the blackness requirements, it will have a certain impact on gloss and fluidity, and then affect the processing performance. The black masterbatch can be special grade or general grade, and can be any one or a mixture of PE base, EVA base, ABS base, AS base, but the special black masterbatch based on ABS is preferred .

The amount of black masterbatch should be added theoretically according to the appearance of the products produced, but for large thin shell parts with high appearance requirements (such as TV front shells, etc.), the amount should not be less than 3% (the carbon black content should be greater than 40%, the allowable saturation of black masterbatch should not be less than 3%), especially when the color transparency of the selected ABS base material is not very good.

The light stabilizer is one or a mixture of alkylated monophenol, alkylated polyphenol, diphenyl phosphite, triphenyl phosphite, hindered phenol or hydroxybenzotriazole.

The processing aids include one or more mixtures of lubricants, brighteners, dispersants, white mineral oil, glycerin and coupling agents. The processing aid is preferably compounded with lubricant, brightener and dispersant to ensure sufficient dispersion of the color masterbatch and meet the requirements of bright and dazzling black surface appearance.

The preparation method of the above-mentioned dazzling black high-gloss ABS alloy comprises the following steps:

Mix high-performance ABS resin, permeability AS (SAN), PMMA, black masterbatch, light stabilizer and processing aids in proportion and dry them separately, stir them evenly in a high-speed mixer, mix them thoroughly, and send them to the twin-screw extruder In the machine, kneading, extruding, drawing, cooling, pelletizing, drying, and obtaining raw materials and finished products.

In the twin-screw extrusion process, the temperature of each zone is controlled between 180-240°C, and the frequency of the main engine is between 30-45Hz.

The invention takes high-performance ABS as the main body, and reduces the content of PMMA with high cost by adjusting the ratio of other ingredients and processes, and can reduce the content of the two to zero in specific applications, and ensure the scratch resistance and gloss of the product degree requirements. At the same time, aiming at the problem that the casing injection molded parts (such as TV front casings, etc.) with high appearance requirements in the industry gradually become thinner and affect the blackness effect, the selection and proportion of black masterbatch are controlled to obtain a high-performance , high-gloss ABS alloy material with dazzling black effect.

The dazzling black high-gloss ABS alloy of the present invention has good glossiness, permeability and dazzling black effect. At the same time, it also has high fluidity, good impact strength and high hardness, and can be used in various injection molding products, especially It is used in products that have high requirements for viewing in the household appliance industry, such as TV front shells, etc. The invention has simple ingredients, is prepared by a twin-screw extrusion process, and has the advantages of simple and continuous process, high production efficiency and stable product quality.

The present invention has the following beneficial effects:

1. The present invention uses ABS, PMMA, AS, high-precision bright black masterbatch and related processing aids to make high-gloss ABS with high gloss.

2. The high-gloss ABS alloy prepared by the present invention solves the problem of affecting the blackness effect of plastic parts due to the gradual thinning of large thin-shell parts, and achieves the dazzling black effect of thin-shell plastic parts through the selection and dosage control of color masterbatch.

3. The high-gloss ABS alloy prepared by the present invention not only ensures the excellent appearance of the molded plastic parts, but also combines other excellent physical and mechanical properties of the material, such as high impact strength, excellent scratch resistance, and high fluidity. Sex, etc., by adjusting the ratio of ingredients and processes, reducing the number of expensive materials, reducing costs while maintaining excellent performance, in line with market demand.

4. The preparation process of a high-gloss ABS alloy mentioned in the present invention is simple and low in cost.

Detailed ways

For the convenience of further understanding of the present invention, the present invention is described in detail in conjunction with specific embodiments now,

As the base material, ABS with high flow rate and excellent performance is selected, AS (SAN) and PMMA with good hardness and permeability are used, and the selected toughening agent is methyl methacrylate-butadiene-styrene bonded branch copolymer (MBS).

The raw materials used in the present invention are all commercially available commodities, which are convenient for popularization.

Example 1

Dazzling black high-gloss ABS alloy, its composition by weight is shown in Table 1.

Acrylonitrile-styrene-butadiene graft copolymer is selected as ABS resin, the melt flow rate is greater than 18g/10min, and the comprehensive performance is excellent, such as BASF GP22, Jilin Petrochemical 0215A, etc.;

The selected PMMA has high transparency and high scratch resistance, such as Taiwan Chimei CM207, CM205, etc.;

The selected AS has high transparency and high melt flow rate, which should be greater than 25g/10min, such as BASF 310TR;

The selected toughening agent is the core-shell structure toughening agent MBS, and the rubber particle size should not be greater than 400nm, such as EM500 and EM500A of South Korea's LG;

The selected color masterbatch is imported general-purpose color masterbatch, such as Cabot UN2014, British Colloids UN606, etc.;

Dry ABS resin, PMMA, SAN, toughening agent, black masterbatch, light stabilizer and processing aid separately, mix evenly by high-speed stirring, and then feed the above mixture into the extruder through a precisely metered feeder, Under the action of screw conveying and shearing, it is fully melted and compounded, and then extruded through the machine head, drawn, cooled, pelletized, dried, and finally packed.

The temperature of each zone of the twin-screw extruder is controlled between 180-240 ° C, the pressure is 16 MPa, the speed is 250-300 rpm, and the dwell time is 2-3 minutes.

The injection molding machine injects into standard test specimens under the conditions of 210-230°C and mold temperature of 110°C, and places the test specimens at room temperature for 24 hours before testing.

Example 2

Dazzling black high-gloss ABS alloy, its composition by weight is shown in Table 1.

Example 2 and Example 1 use imported general-purpose color masterbatches, the difference being that the content of PMMA is different.

Example 3

Dazzling black high-gloss ABS alloy, its composition by weight is shown in Table 1.

Compared with Examples 1 and 2, Example 3 has different grades of base material ABS and AS, and domestic ABS-based high-precision bright color masterbatch is used. The ABS substrate adopts Taiwan Taihua's AG15A1, the AS is Taiwan Taihua's NF2200, and the black masterbatch is 2016C of fine bright pigment color masterbatch.

Example 4

Dazzling black high-gloss ABS alloy, its composition by weight is shown in Table 1.

The difference between embodiment 4 and embodiment 3 is that when the content of PMMA and the toughening agent are all zero, the type and content of black masterbatch are changed.

Table 1 Material ratio

The test standard and performance test results of the dazzling black high-gloss ABS alloy of the present invention are shown in Tables 2 and 3.

Table 2 Test Standards

According to the ratio in Table 1, different ABS base materials are selected, and various properties will have certain differences. The test results are shown in Table 3.

Table 3 performance test results

According to the test results of Example 1 and Example 2 in Table 3, it can be seen that if an appropriate AS (SAN) can be selected, under a certain process, the expensive PMMA content can be reduced, or even reduced to zero. The performance of the plastic part has little effect; through the observation of the appearance of the plastic part, it can be seen that the content of PMMA has little effect on the appearance of the plastic part (welding marks, flow marks, permeability, etc.). Therefore, under a certain application range and a specific process, the amount of PMMA added can be completely reduced or eliminated, thereby achieving the purpose of reducing costs.

According to the test results of Example 3 and Example 4 in Table 3, it can be seen that if the base materials ABS and AS (SAN) with excellent performance are selected, when the impact strength is not high, when PMMA and toughening agent are completely canceled, The fluidity of the material and the tensile and bending properties of the plastic parts are improved. In addition, it can also be known from the comparison of the examples that the use of different base black masterbatches and the adjustment of their content have a greater impact on the blackness of appearance.

The scope of the invention is not to be limited by the specific embodiments described, which are intended only as single examples illustrating various aspects of the inventive concept, and functionally equivalent methods and components are also intended to be within the scope of the invention. In addition to the content described herein, those skilled in the art can easily grasp various modifications, equivalent replacements and improvements of the present invention by referring to the above description, all of which should be included in the protection scope of the present invention.

Claims (10)

1. A dazzling black high-gloss ABS alloy, characterized in that its weight ratio consists of:

. 2. The dazzling black high-gloss ABS alloy according to claim 1 is characterized in that, its weight ratio consists of:

3. The dazzling black high-gloss ABS alloy according to claim 2 is characterized in that its weight ratio consists of: 4. The dazzling black high-gloss ABS alloy according to claim 1, 2 or 3 is characterized in that, in the described ABS resin, the mass content of acrylonitrile is between 20%-30%, and the mass content of butadiene is between 20% and 30%. Between 13-20%, the mass content of styrene is between 40-60%. the 5. The dazzling black high-gloss ABS alloy according to claim 1, 2 or 3, characterized in that the melt flow coefficient of the permeable SAN should be between 20-40g/10min at 220°C/10kg , SAN light rate should be greater than 85%. the 6. The dazzling black high-gloss ABS alloy according to claim 1, 2 or 3, characterized in that, the PMMA is high hardness and high transparency polymethyl methacrylate with an average molecular weight of 80,000-300,000, wherein acrylic acid The mass content is 98-100%. the 7. The dazzling black high-gloss ABS alloy according to claim 1, 2 or 3, wherein the processing aid is one or more of lubricant, brightener, white mineral oil, glycerin and coupling agent A mixture of several. the 8. The dazzling black high-gloss ABS alloy according to claim 1, 2 or 3, characterized in that the selected black masterbatch is a high-precision bright grade, which is any one or more of PE-based, EVA-based, ABS-based, AS-based mixture of species. the 9. The preparation method of the dazzling black high-gloss ABS alloy according to claim 1 is characterized in that high-performance ABS resin, permeability SAN, PMMA, black masterbatch, light stabilizer and processing aid are proportioned and respectively Drying, stir evenly in a high-speed mixer, fully mix, send into a twin-screw extruder, knead, extrude, pull strands, cool, pelletize, dry, and obtain raw materials and finished products. the 10. The preparation method of the dazzling black high-gloss ABS alloy according to claim 9, characterized in that, in the twin-screw extrusion process, the temperature of each zone is controlled between 180-240°C. the