Abs composite material, its preparation method and application

Abstract

The application discloses an ABS composite material and a preparation method and application thereof, and relates to the technical field of engineering plastics.The raw material of the ABS composite material comprises the following components in parts by weight: SAN resin 44-67 parts; high glue powder 13-26 parts; nylon resin 9-32 parts; surface modifier 0.8-7 parts; the high glue powder is ABS high glue powder; the surface modifier comprises oleic acid amide and erucic acid amide, and the mass ratio of the oleic acid amide to the erucic acid amide is (1-5):(1-5). The ABS composite material has excellent softness, and also has excellent scratch resistance and stain resistance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of plastics, in particular to an ABS composite material and a preparation method and application thereof. BACKGROUND

[0002] The commonly used materials of building block toy materials are polypropylene, ABS, transparent ABS, etc. The ABS material has a high rubber content, and during the building block splicing process, the rubber is squeezed and shrunk, which endows the material with a good soft feel. Therefore, the commonly used material of toy building blocks is ABS material. In order to obtain a better soft feel, a large amount of rubber is often added to the ABS material for building blocks, but this will cause the scratch resistance of the material to decrease significantly. Therefore, it is necessary to develop a new ABS material that has excellent soft feel and excellent scratch resistance. SUMMARY

[0003] The present application aims to overcome the shortcomings of the prior art and provides an ABS composite material and a preparation method and application thereof. The ABS composite material has excellent softness, excellent scratch resistance, and excellent stain resistance.

[0004] To achieve the above-mentioned purposes, the technical solutions adopted by the present application are as follows:

[0005] In a first aspect, the present application provides an ABS composite material, the raw materials of the ABS composite material comprising the following components in parts by weight:

[0006] SAN resin 44-67 parts; high rubber powder 13-26 parts; nylon resin 9-32 parts; surface modifier 0.8-7 parts; the high rubber powder is ABS high rubber powder; the surface modifier comprises oleic acid amide and erucic acid amide, and the mass ratio of the oleic acid amide and the erucic acid amide is (1-5):(1-5).

[0007] The SAN resin is a styrene-acrylonitrile copolymer.

[0008] The application can improve the softness of the material by adding nylon resin in the composite material, so that the building blocks are easier to pull out, and the material has better soft hand feeling, and the content of high glue powder in the ABS composite material is reduced, and the scratch resistance of the material is improved. At the same time, the surface modifier is added as an external lubricant to migrate to the surface of the material, reduce the surface energy of the material, and improve the hydrophobic performance of the material, thereby improving the stain resistance of the material. Moreover, the ABS high glue powder, the nylon resin and the surface modifier are compounded, so that the composite material has excellent scratch resistance and gloss. At the same time, the specific proportion of oleic acid amide and erucic acid amide is compounded, which is beneficial to reduce the surface energy of the material, thereby further improving the hydrophobic performance of the composite material.

[0009] Therefore, by using ABS high glue powder, nylon resin and specific proportion of oleic acid amide and erucic acid amide, the application not only improves the scratch resistance and stain resistance of the composite material, but also makes the composite material have excellent softness.

[0010] Preferably, the nylon resin is PA6.

[0011] Preferably, the melt flow rate of the PA6 is 5-15 g / 10 min under 235 DEG C / 1.2 kg load according to ISO 1133-2011.

[0012] Preferably, the weight content of acrylonitrile in the SAN resin is 24-26%, and the weight average molecular weight is 80-120 thousand, and the melt flow rate of the SAN resin is 30-40 g / 10 min under 220 DEG C / 10 kg load according to ISO 1133-2011.

[0013] The test method of acrylonitrile content in the SAN resin is infrared quantitative method: the ratio K of the characteristic peak 1600 cm -1 of benzene ring in the infrared spectrum of the substance with known parameters to the characteristic peak 2237 cm -1 of acrylonitrile, the calibration curve of acrylonitrile content and ratio K is obtained, and the acrylonitrile content of the unknown substance is obtained according to the ratio of 1600 / 2237.

[0014] Preferably, the sum of the mass percentage content of SAN resin and high glue powder in the ABS composite material is not less than 55%.

[0015] Preferably, the rubber content in the high glue powder is 40-60%, and the average particle size of the rubber is 300-400 nm.

[0016] The rubber particle size in the high glue powder is tested by dynamic light scattering method.

[0017] Preferably, the raw materials of the ABS composite material include the following components in parts by weight:

[0018] SAN resin 50-65 parts; high glue powder 18-22 parts; nylon resin 15-25 parts; surface modifier 2-5 parts.

[0019] Preferably, the ABS composite material further includes 0.3-1 parts of an antioxidant and 0-1 parts of an additive.

[0020] Preferably, the antioxidant is a hindered phenolic antioxidant, and specifically can be antioxidant 1010, antioxidant 1076, antioxidant SONOX 1076.

[0021] Preferably, the additive includes a colorant and other lubricants, the other lubricants are amide lubricants or PETS lubricants, and specifically can be lubricant EBS B50, LOXIOL P 861 / 3.5; the colorant includes organic dyes and inorganic dyes, and specifically can be anthraquinone blue, anthraquinone purple, titanium dioxide, carbon black.

[0022] In a second aspect, the present application further provides a method for preparing an ABS composite material, including the following steps:

[0023] After uniformly mixing the components, melt blending extrusion is performed on a twin-screw extruder, and after underwater pelletizing and drying, the ABS composite material is obtained.

[0024] Preferably, the processing temperature of the twin-screw extruder is 200-260℃, and the rotation speed is 350-600 rpm.

[0025] Preferably, the twin-screw extruder has a temperature of 200-210℃ in the first to second zones, a temperature of 220-230℃ in the third to fifth zones, and a temperature of 230-260℃ in the fifth to tenth zones, and a screw rotation speed of 450-550 rpm.

[0026] In a third aspect, the present application further provides an application of the ABS composite material in building blocks.

[0027] The ABS composite material has excellent softness, excellent scratch resistance and stain resistance, and is suitable for use in toy building blocks.

[0028] Compared with the prior art, the present application has the following beneficial effects:

[0029] The ABS composite material and the preparation method thereof have the advantages that by adding the nylon resin in the composite material, the softness of the material can be improved, the material has better soft hand feeling, the content of the high glue powder in the ABS composite material is reduced, and the scratch resistance of the material is improved. Meanwhile, by adding the surface modifier as the external lubricant to migrate to the surface of the material, the surface energy of the material is reduced, the hydrophobic property of the material is improved, and the stain resistance of the material is improved. DETAILED DESCRIPTION

[0030] In order to better illustrate the purpose, technical scheme and advantages of the present application, the present application will be further described below in combination with specific examples, but the protection scope and implementation mode of the present application are not limited thereto.

[0031] In the following examples, the materials, reagents and the like used are commercially available reagents and materials unless otherwise specified.

[0032] Examples 1-12

[0033] The composition of the ABS composite material is shown in Table 1.

[0034] The preparation method of the ABS composite material comprises the following steps:

[0035] After the components are uniformly mixed, melt blending extrusion is performed on a twin-screw extruder, and after underwater cutting and drying, the ABS composite material is obtained.

[0036] The temperature of the twin-screw extruder is divided into ten zones, the temperature of the first and second zones is 200-210 DEG C, the temperature of the third to fifth zones is 220-230 DEG C, the temperature of the fifth to tenth zones is 230-260 DEG C, and the screw rotation speed is 450-550 rpm.

[0037] Comparative Examples 1-9

[0038] The only difference between the comparative examples and the examples is that the types and proportions of the components are different, as shown in Table 2.

[0039] In the components of each example and comparative example:

[0040] The SAN resin 1 is from Liaoning Jinfa, the model number is KFA-130, the acrylonitrile content is 24%, and the weight average molecular weight is 80,000;

[0041] The SAN resin 2 is from Tianjin Dagu, the model number is DG-AS106, the acrylonitrile content is 26%, and the weight average molecular weight is 120,000.

[0042] The high rubber powder 1 is ABS high rubber powder, the manufacturer is South Korea Kim Hu, the brand is ABS POW HR181, the rubber content is 40%, and the average particle size is 300 nm;

[0043] The high rubber powder 2 is ABS high rubber powder, the manufacturer is Shandong Yigong, the brand is ABS high rubber powder EB-168, the rubber content is 60%, and the average particle size is 400 nm.

[0044] The ASA rubber powder, the manufacturer is South Korea Kim Hu, the brand is ASA POW XC640, the rubber content is 68%, and the average particle size of the rubber is 400 nm.

[0045] The nylon resin 1 is PA6, the manufacturer is Guangdong Xinhui Meida, the brand is PA M3400, and the melt flow rate under the condition of 235 DEG C / 1.2 kg load according to ISO 1133-2011 is 5 g / 10 min;

[0046] The nylon resin 2 is PA6, the manufacturer is Jiangsu Hongsheng New Material Co., Ltd., the brand is PA6 BE3280, and the melt flow rate under the condition of 235 DEG C / 1.2 kg load according to ISO 1133-2011 is 10 g / 10 min;

[0047] The nylon resin 3 is PA6, the manufacturer is Guangdong Xinhui Meida, the brand is PA6 M2400, and the melt flow rate under the condition of 235 DEG C / 1.2 kg load according to ISO 1133-2011 is 15 g / 10 min.

[0048] The surface modifier 1 comprises oleic acid amide and erucic acid amide, and the mass ratio of the two is 1:5;

[0049] The surface modifier 2 comprises oleic acid amide and erucic acid amide, and the mass ratio of the two is 1:1;

[0050] The surface modifier 3 comprises oleic acid amide and erucic acid amide, and the mass ratio of the two is 5:1;

[0051] The surface modifier 4 comprises oleic acid amide and erucic acid amide, and the mass ratio of the two is 1:6;

[0052] The surface modifier 5 comprises oleic acid amide and erucic acid amide, and the mass ratio of the two is 6:1;

[0053] The surface modifier 6 comprises oleic acid amide and ethylene bis-stearamide, and the mass ratio of the two is 1:1;

[0054] The surface modifier 7 comprises ethylene bis-stearamide and erucic acid amide, and the mass ratio of the two is 1:1;

[0055] The surface modifier 8 is oleic acid amide;

[0056] The surface modifier 9 is erucamide;

[0057] The oleic acid amide is commercially available; the erucamide is commercially available; the ethylene bis-stearamide is commercially available.

[0058] The antioxidant is a hindered phenol antioxidant, which is commercially available.

[0059] The other lubricant is a PETS lubricant, which is commercially available.

[0060] The colorant is anthraquinone blue.

[0061] The components used in the embodiments and the comparative examples of the present application are commercially available unless otherwise specified, and the components used in each parallel experiment are the same.

[0062] Table 1

[0063]

[0064] Table 2

[0065]

[0066] In order to verify the performance of the ABS composite material described in the present application, the ABS composite material prepared in each embodiment and comparative example is injection molded into a sample bar for testing the following performance.

[0067] Performance test method:

[0068] 1. Plug-in force: After injection molding 2x4 blocks (length 32 mm, width 16 mm, height 10 mm), the plug-in force of the blocks is tested on a full-automatic plug-in force machine (model TG-9250); the plug-in force range is 20-40 N, and the smaller the plug-in force, the better the softness.

[0069] 2. Scratch resistance: After injection molding a color plate, the pencil hardness is tested on a pencil hardness tester, and the test is performed in accordance with the standard GB / T6739-2006.

[0070] 3. Hydrophobicity: The rolling angle of water on the material is tested on a contact angle measuring instrument, and the equipment model of the contact angle measuring instrument is OSA200. The smaller the rolling angle, the better the hydrophobicity.

[0071] The performance parameters obtained by the above tests are shown in Tables 3 and 4.

[0072] Table 3

[0073]

[0074] Table 4

[0075]

[0076] According to Examples 1-12, the ABS composite material has a plug force of less than 30 N, a pencil hardness of B or above, and a rolling angle of less than 30°, and has excellent softness, scratch resistance, and hydrophobicity.

[0077] According to Comparative Examples 7-9 and Example 2, Comparative Example 7 uses ASA powder as a high powder, a nylon resin, and a surface modifier, and the composite material has lower scratch resistance than Example 2. Comparative Example 8 does not contain a nylon resin, and the softness of the composite material is affected. Comparative Example 9 does not contain a surface modifier, and the hydrophobicity of the composite material is lower than Example 2. In Example 2, ABS high powder, a nylon resin, and a surface modifier are used to make the composite material have excellent scratch resistance and softness, and also have excellent hydrophobicity.

[0078] According to Comparative Examples 3-6 and Example 2, Comparative Example 5 contains only oleic acid amide, and Comparative Example 6 contains only erucic acid amide. The hydrophobicity of the composite material in Comparative Examples 5-6 is lower than Example 2, and the scratch resistance and softness are also lower than Example 2. This shows that using only oleic acid amide or erucic acid amide with a nylon resin and a surface modifier cannot make the composite material have excellent softness, scratch resistance, and hydrophobicity. Comparative Examples 3-4 use oleic acid amide or erucic acid amide with ethylene bis-stearamide, and the performance of the composite material is also lower than Example 2. This shows that only using oleic acid amide and erucic acid amide can make the composite material have excellent softness, scratch resistance, and hydrophobicity.

[0079] According to Comparative Examples 1-2 and Example 2, the mass ratio of oleic acid amide and erucic acid amide in Comparative Examples 1-2 is not within the range defined in the present application, and the performance of the composite material is lower than Example 2. This shows that by controlling the mass ratio of acid amide and erucic acid amide, the surface energy of the material can be reduced, thereby further improving the hydrophobicity of the composite material, and also improving the softness of the composite material.

[0080] According to Examples 4-6, as the content of the nylon resin increases, the plug force decreases and the rolling angle increases. This shows that by controlling the content of the nylon resin, the composite material can have excellent hydrophobicity and softness.

[0081] Finally, it should be noted that the above examples are merely intended to illustrate the technical solutions of the present application and not to limit the protection scope of the present application. Although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can be modified or equivalently replaced without departing from the essence and scope of the technical solutions of the present application.

Claims

1. An ABS composite material, characterized in that, The raw materials of the ABS composite material include the following components in parts by weight: 44-67 parts of SAN resin; 13-26 parts of high-rubber powder; 9-32 parts of nylon resin; 0.8-7 parts of surface modifier; the high-rubber powder is ABS high-rubber powder; the surface modifier includes oleamide and erucamide, and the mass ratio of oleamide to erucamide is (1-5):(1-5).

2. The ABS composite material as described in claim 1, characterized in that, The nylon resin is PA6, and the melt flow rate of PA6 at 235℃ / 1.2kg load is 5-15 g / 10min according to ISO 1133-2011.

3. The ABS composite material as described in claim 1, characterized in that, The high-rubber powder contains 40-60% rubber, and the average particle size of the rubber is 300-400 nm.

4. The ABS composite material as described in claim 1, characterized in that, The SAN resin contains 24-26% acrylonitrile by weight and has a weight-average molecular weight of 80,000-120,000.

5. The ABS composite material as described in claim 1, characterized in that, The SAN resin, according to ISO 1133-2011, has a melt flow rate of 30-40 g / 10 min at 220°C / 10 kg load.

6. The ABS composite material as described in claim 1, characterized in that, The raw materials of the ABS composite material include the following components in parts by weight: 50-65 parts SAN resin; 18-22 parts high-polymer powder; 15-25 parts nylon resin; 2-5 parts surface modifier.

7. The ABS composite material as described in claim 1, characterized in that, The ABS composite material also includes 0-1 parts of additives.

8. The ABS composite material as described in claim 1, characterized in that, The ABS composite material also includes 0.3-1 parts of antioxidant.

9. The ABS composite material as described in claim 8, characterized in that, The antioxidant is a hindered phenolic antioxidant.

10. The ABS composite material as described in claim 7, characterized in that, The additives include colorants and other lubricants.

11. The method for preparing the ABS composite material according to any one of claims 1-10, characterized in that, Includes the following steps: After the components are uniformly mixed, they are melt-blended and extruded on a twin-screw extruder. After underwater pelletizing and drying, the ABS composite material is obtained.

12. The application of the ABS composite material as described in any one of claims 1-10 in building blocks.

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