Halogen-free flame-retardant ABS material, preparation method and application thereof

Abstract

The application discloses a halogen-free flame-retardant ABS material and a preparation method and application thereof, and relates to the technical field of high polymer materials. The halogen-free flame-retardant ABS material comprises ABS resin, SAN resin, halogen-free flame retardant and laser marking agent. The melt flow rate of the ABS resin under the condition of 220 DEG C and 10 kg is 15-40 g / 10 min, and the impact strength is 15-27 KJ / m 2 2. The melt flow rate of the SAN resin under the condition of 220 DEG C and 10 kg is less than or equal to 40 g / 10 min. Through the synergistic effect of the raw material components, the material has high pencil hardness and high gloss, has good laser marking effect, and the mark is not easy to be abraded, and can be kept for a long time.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high polymer materials, and more particularly to a halogen-free flame-retardant ABS material, a preparation method and application thereof. BACKGROUND

[0002] Laser marking is a marking method that uses high-energy density laser to irradiate the workpiece locally, so that the surface layer material is vaporized or undergoes a chemical reaction to change color, thereby leaving a permanent mark.

[0003] ABS resin is a ternary graft copolymer of acrylonitrile-butadiene-styrene, has a mechanical property of rigid and tough balance, excellent chemical resistance, low temperature resistance and dimensional stability, and is easy to process and shape. Therefore, ABS resin is widely used in household appliances, electronics, electrical appliances and automobiles. However, the surface hardness of ABS products is low, and the pencil hardness is only 2B-B level, and after laser marking, the glossiness will decrease, and even the appearance problem of being scorched, yellow and black. In order to improve such appearance problems, a large amount of polymethyl methacrylate (PMMA) is usually added in the resin composition in the prior art.

[0004] For example, the patent CN104804360A of the white laser marking impact-resistant ABS resin composition and its preparation and application, which includes mass ratio (1-9): (1-9) ABS resin and PMMA, which effectively enhances the ability of the resin composition to heat and foam under laser radiation due to the acrylic structure, so that the white laser printing mark has higher whiteness and better clarity. However, the flame retardance of PMMA is low, which leads to the flame retardance of ABS / PMMA alloy material cannot reach V-2 level. It is urgent to develop an ABS resin material suitable for laser marking, which has high pencil hardness and high glossiness, and realizes halogen-free flame retardance above V-2 level. SUMMARY

[0005] The purpose of the present application is to overcome the defects and deficiencies that the existing ABS material cannot have high pencil hardness and high glossiness, and at the same time have halogen-free flame retardance above V-2 level, and to provide a halogen-free flame-retardant ABS material.

[0006] Another purpose of the present application is to provide a preparation method of a halogen-free flame-retardant ABS material.

[0007] Another purpose of the present application is to provide a halogen-free flame-retardant ABS material in the preparation of laser markable material.

[0008] The above purposes of the present application are achieved by the following technical solutions:

[0009] The present application protects a halogen-free flame-retardant ABS material, which comprises the following components by mass:

[0010]

[0011] The melt flow rate (ASTM D1238) of the ABS resin under the condition of 220℃, 10kg is ≥5g / 10min, and the Izod notched impact strength (ASTM D256) is ≤380J / m; the melt flow rate (ASTM D256) of the SAN resin under the condition of 220℃, 10kg is ≤40g / 10min.

[0012] The halogen-free flame-retardant ABS material of the present application uses ABS resin as the base resin and introduces SAN resin, so that the content of SAN in the whole ABS system can be controlled, thereby greatly improving the rigidity, gloss and chemical stability of the material, while avoiding the problems of poor compatibility and mechanical property loss caused by the introduction of heterogeneous resin. Meanwhile, the ABS material is compounded with a specific content of halogen-free flame retardant, so that the material can achieve V-2 level or above in flame retardancy while ensuring the mechanical properties; in addition, a certain amount of laser marking agent is added, so that the material can be efficiently laser marked; under the synergistic action of various raw material components, the material has high pencil hardness and high gloss, and has good laser marking effect and the mark is not easy to be worn, which can be maintained for a long time.

[0013] The Izod notched impact strength and the melt flow rate are parameters reflecting the ratio of butadiene monomer in the ABS resin, and the main role of butadiene monomer in the ABS resin is to improve the elasticity and toughness of the resin material. The higher the proportion of butadiene monomer, the higher the Izod notched impact strength and the lower the melt flow rate. The use of ABS resin with specific Izod notched impact strength and melt flow rate is conducive to controlling the content of SAN in the whole ABS system when introducing SAN resin, so as to improve the rigidity, gloss and chemical stability of the material.

[0014] The use of a mixed system of ABS high rubber powder and SAN resin can also be conducive to controlling the content of SAN in the whole ABS system; however, the inventors have found that a large amount of ABS high rubber powder is required in the mixing process of ABS high rubber powder and SAN resin, and too much powder is prone to uneven feeding and bridging problems in the process of extrusion granulation, and the uniformity of the product is poor, which is not suitable for application in laser markable materials. The present application uses ABS resin with specific melt flow rate and SAN resin to compound, which not only improves the processing performance, but also prepares a material with high rigidity, gloss and chemical stability.

[0015] In some embodiments, the melt flow rate (ASTM D1238) of the ABS resin under the condition of 220℃, 10kg is 5-45g / 10min, and the Izod notched impact strength (ASTM D256) is 150-380J / m.

[0016] Preferably, the ABS resin has a melt flow rate (ASTM D1238) of 8-40 g / 10 min at 220℃, 10 kg; preferably, the ABS resin has a Izod notched impact strength (ASTM D256) of 180-370 J / m; ABS resins meeting the above requirements include but are not limited to the products of ABSDG-MG94, ABSDG-417 and ABSDG-MG29 series of Tianjin Dagu Chemical Co., Ltd.

[0017] In some embodiments, the ABS resin can be present in an amount of 50 parts, 51 parts, 52 parts, 53 parts, 54 parts, 55 parts, 56 parts, 57 parts, 58 parts, 59 parts, 60 parts, 61 parts, 62 parts, 63 parts, 64 parts, 65 parts, 66 parts, 67 parts, 68 parts, 69 parts, 70 parts, or any range between the above values.

[0018] In some embodiments, the ABS resin can be present in an amount of 50 parts, 51 parts, 52 parts, 53 parts, 54 parts, 55 parts, 56 parts, 57 parts, 58 parts, 59 parts, 60 parts, 61 parts, 62 parts, 63 parts, 64 parts, 65 parts, 66 parts, 67 parts, 68 parts, 69 parts, 70 parts, or any range between the above values.

[0019] In some embodiments, the SAN resin has a melt flow rate (ASTM D1238) of 8-40 g / 10 min at 220℃, 10 kg. Controlling the melt flow rate range of the SAN resin is beneficial to improve the hardness of the material and improve the mechanical properties of the material.

[0020] Preferably, the SAN resin has a melt flow rate (ASTM D1238) of 20-35 g / 10 min at 220℃, 10 kg. ABS resins meeting the above requirements include but are not limited to SAN 350N A of Kingfa Plastics Group Co., Ltd. and SAN SA30 of LG Chemical (Huizhou) Chemical Co., Ltd.

[0021] In some embodiments, the SAN resin (styrene-acrylonitrile copolymer) can be present in an amount of 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts, 40 parts, or any range between the above values.

[0022] In some embodiments, the SAN resin can be present in an amount of 50 parts, 51 parts, 52 parts, 53 parts, 54 parts, 55 parts, 56 parts, 57 parts, 58 parts, 59 parts, 60 parts, 61 parts, 62 parts, 63 parts, 64 parts, 65 parts, 66 parts, 67 parts, 68 parts, 69 parts, 70 parts, or any range between the above values.

[0023] In some embodiments, the halogen-free flame retardant can be present in an amount of 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, or any range between these values.

[0024] In some embodiments, the halogen-free flame retardant comprises a phosphorus-based flame retardant and / or a nitrogen-based flame retardant.

[0025] Preferably, the phosphorus-based flame retardant is selected from the group consisting of phosphate ester-based flame retardants; more preferably, bisphenol A bis(diphenyl phosphate) (BDP).

[0026] Preferably, the nitrogen-based flame retardant is selected from the group consisting of ammonium salt-based flame retardants; more preferably, melamine cyanurate (MCA).

[0027] The laser marking agent is not particularly limited in the present application and can be any conventional material in the field of laser marking agents; including but not limited to black-on-white laser marking agents, white-on-black laser marking agents, preferably, the laser marking agent is at least one of phthalocyanine salts, dioxazine-based, anthraquinone-based, perinone-based, carbon black, titanium black, iron oxide black, and surface alkyl-modified silica.

[0028] Preferably, the phthalocyanine salt is copper phthalocyanine and / or aluminum phthalocyanine.

[0029] In some embodiments, the mass ratio of the ABS resin to the SAN resin is (1.0-3.0):1, preferably (1.2-2.6):1, and more preferably (1.5-2.5):1.

[0030] In some embodiments, further comprising: 0.2-1 parts of an antioxidant and 0.2-1 parts of a processing aid.

[0031] Preferably, the antioxidant is composed of a hindered amine primary antioxidant and a phosphite auxiliary antioxidant.

[0032] More preferably, the hindered amine primary antioxidant is selected from antioxidant 1010.

[0033] More preferably, the phosphite auxiliary antioxidant is selected from antioxidant 168.

[0034] Preferably, the processing aid comprises at least one of a lubricant, a dispersant, white mineral oil, and a coupling agent.

[0035] More preferably, the lubricant is selected from zinc stearate.

[0036] More preferably, the coupling agent is selected from silane coupling agents.

[0037] This invention protects a method for preparing a halogen-free flame-retardant ABS material, comprising the following steps: mixing the raw material components in the specified amounts evenly, melting and extruding them together to obtain the halogen-free flame-retardant ABS material.

[0038] In some embodiments, the melt extrusion temperature is 180-220°C.

[0039] In some embodiments, the preparation method of halogen-free flame-retardant ABS material includes the following steps: mixing the raw material components in the formula in uniform amounts, and then melting and extruding them through a screw extruder at an extrusion temperature of 180-220℃, a rotation speed of 200-300rpm, and a feeding speed of 200-400kg / h to obtain the halogen-free flame-retardant ABS material.

[0040] This invention protects the application of a halogen-free flame-retardant ABS material in the preparation of laser-markable materials.

[0041] In some embodiments, the halogen-free flame-retardant ABS material is used in the manufacture of electronic appliances or household appliances.

[0042] Compared with the prior art, the beneficial effects of the present invention are:

[0043] This invention provides a halogen-free flame-retardant ABS material, using ABS resin as the base resin and introducing SAN resin. This increases the proportion of SAN in the overall ABS system, significantly improving the material's rigidity, gloss, and chemical stability, while avoiding the compatibility issues and mechanical property losses caused by introducing heterogeneous resins. Furthermore, the ABS material is compounded with a specific amount of halogen-free flame retardant, enabling it to achieve a flame retardancy rating of V-2 or higher while maintaining mechanical properties. The synergistic effect of the various raw material components gives the material high pencil hardness and high gloss, as well as good laser marking effects with markings that are not easily worn away and can be maintained for a long time. Detailed Implementation

[0044] The present invention will be further described below with reference to specific embodiments, but the embodiments do not limit the present invention in any way. Unless otherwise stated, the raw materials and reagents used in the embodiments of the present invention are conventionally purchased raw materials and reagents.

[0045] The raw materials used in the following examples and comparative examples are as follows:

[0046] ABS resin (acrylonitrile-butadiene-styrene terpolymer):

[0047] ABS resin 1: ABSDG-MG94, Tianjin Dagu Chemical Co., Ltd.; melt flow rate (ASTM D1238) at 220℃ and 10kg is 37g / 10min, and cantilever beam notched impact strength (ASTM D256) is 190J / m.

[0048] ABS resin 2: ABSDG-417, Tianjin Dagu Chemical Co., Ltd.; melt flow rate (ASTM D1238) at 220℃ and 10kg is 20g / 10min, and notched cantilever beam impact strength (ASTM D256) is 200J / m.

[0049] ABS resin 3: ABSDG-MG29, Tianjin Dagu Chemical Co., Ltd.; melt flow rate (ASTM D1238) at 220℃ and 10kg is 10g / 10min, and cantilever beam notched impact strength (ASTM D256) is 360J / m.

[0050] SAN resin (styrene-acrylonitrile copolymer):

[0051] SAN Resin 1: SAN 350N A, Kumho Sunny Plastics Co., Ltd.; melt flow rate (ASTM D1238) at 220°C and 10kg is 33g / 10min.

[0052] SAN Resin 2: SAN SA30, LG Chem (Huizhou) Chemical Co., Ltd.; melt flow rate (ASTM D1238) at 220°C and 10kg is 29g / 10min.

[0053] SAN Resin 3: SAN NX3400, Taiwan Chemical Fiber Co., Ltd.; melt flow rate (ASTM D1238) at 220°C and 10kg is 10g / 10min.

[0054] SAN Resin 4: SAN 320N A, Kumho Sunray Plastics Co., Ltd.; melt flow rate (ASTM D1238) at 220°C and 10kg is 110g / 10min.

[0055] SAN Resin 5: SAN SA50, LG Chem (Huizhou) Chemical Co., Ltd.; melt flow rate (ASTM D1238) at 220°C and 10kg is 55g / 10min.

[0056] Polymethyl methacrylate (PMMA): PMMA LG, Sumitomo Chemical Singapore Pte. Ltd.

[0057] Flame retardant: WSFR-PX-220, Zhejiang Wansheng Technology Co., Ltd.

[0058] Laser marking agent: Carbon black Ensaco 250G, Hong Kong Haiyi Company.

[0059] Antioxidants: RIANOX 1010 and RIANOX 168 in a 1:1 mass ratio, from Rianon Corporation.

[0060] Processing aids: EBS B50, PT.CMS CHEMICAL INDONESIA.

[0061] The following examples and comparative methods for preparing halogen-free flame-retardant ABS materials include the following steps: mixing the raw material components in the formula amount evenly, and then melting and extruding them through a screw extruder at an extrusion temperature of 200°C, a rotation speed of 250 rpm, and a feeding speed of 300 kg / h to obtain the halogen-free flame-retardant ABS material.

[0062] Examples 1-8

[0063] This embodiment provides a halogen-free flame-retardant ABS material, the composition of which is shown in Table 1.

[0064] Table 1 Examples 1-8 (parts by weight)

[0065]

[0066] Comparative Examples 1-7

[0067] This comparative example provides a halogen-free flame-retardant ABS material, the composition of which is shown in Table 2.

[0068] Table 2 Comparative Examples 1-7 (parts by weight)

[0069]

[0070]

[0071] Performance testing

[0072] The halogen-free flame-retardant ABS material samples from Examples 1-8 and Comparative Examples 1-7 were tested for impact strength, pencil hardness, surface scratch resistance, gloss, flame retardancy, and laser marking effect. The test results are shown in Table 3.

[0073] Impact strength: Tested according to standard ISO 180.

[0074] Pencil hardness: Tested according to ASTM D3363 standard. The specific method is as follows: Prepare a 70mm × 40mm × 3mm square injection-molded template of ABS material and place it on a fixed horizontal surface. Hold a pencil at a 45° angle to the coating (pointing in the opposite direction to the tester) and push the pencil away from the tester, drawing a line 6.5mm long. This process starts with the hardest pencil and continues until the pencil no longer scratches the template surface; the corresponding pencil hardness is the template pencil hardness.

[0075] Surface scratch resistance: Scratch resistance was evaluated using a color fastness tester for rubbing. A 70mm × 40mm × 3mm square injection-molded sample was prepared from ABS material. The sample was rubbed back and forth 500 times with gauze. The depth of the scratches was observed under a Leica microscope at 200x magnification. Shallower scratches were considered the best, and deeper scratches the worst. The evaluation grading was: Worst --, Poor --, Average 0, Good +, Best ++.

[0076] Gloss: Tested according to standard GB / T 8807-1988.

[0077] Flame retardancy: Tested according to standard UL94.

[0078] Laser marking effect: The laser-marked pattern was observed and evaluated under a Leica microscope at 200x magnification. The clearer the edges of the laser engraving and the smoother the pattern, the better the laser marking effect. The evaluation grading for this test is: worst --, poor -, average 0, good +, best ++. This test used a UV marking machine, model UV-3X, with parameters of 365nm and 3W.

[0079] Table 3

[0080]

[0081]

[0082] As shown in Table 3, the impact strength of the halogen-free flame-retardant ABS material of the present invention is ≥10KJ / m. 2 The pencil has a hardness of F or higher, a gloss level of 90 or higher at 60°, a flame retardancy rating of V-2, and a surface scratch resistance and laser marking effect rating of ++.

[0083] Compared with Example 1, Comparative Example 1, which does not contain SAN resin, has a pencil hardness of only B grade, a decrease in 60° gloss, and poor surface scratch resistance and laser marking effect.

[0084] Compared with Example 1, Comparative Example 2 uses PMMA instead of SAN resin. Although it has better surface scratch resistance and laser marking effect, PMMA has lower flame retardancy, which means that the flame retardancy of the material cannot reach the V-2 level.

[0085] Compared with Example 1, when ABS resin 3 with low melt flow rate and high cantilever beam notched impact strength was used in Comparative Example 3, its pencil hardness was only HB grade, and the surface scratch resistance and laser marking effect were reduced.

[0086] Compared with Example 1, the SAN resin with a higher melt flow rate used in Comparative Examples 4-5 showed a decrease in pencil hardness, surface scratch resistance, and laser marking effect.

[0087] Compared with Example 1, the amount of SAN resin added in Comparative Examples 6-7 was too low, which failed to effectively improve the pencil hardness, surface scratch resistance and laser marking effect; when the amount of SAN resin added was too high, it would result in low impact strength and poor toughness.

[0088] The above embodiments of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the implementation of the present invention. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively describe all possible implementations here. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the claims of the present invention.

Claims

1. A halogen-free flame-retardant ABS material, characterized in that, The ABS resin has a melt flow rate of ≥20 g / 10 min at 220℃ under a 10 kg load and a notched Izod impact strength of ≤380 J / m. The SAN resin has a melt flow rate of ≤40 g / 10 min at 220℃ under a 10 kg load. The ABS resin has a melt flow rate of 20-40 g / 10 min at 220℃ under a 10 kg load and a notched Izod impact strength of 180-370 J / m. The SAN resin has a melt flow rate of 20-35 g / 10 min at 220℃ under a 10 kg load. The ABS resin and the SAN resin have a mass ratio of (1.0-3.0) :

1. The halogen-free flame retardant comprises a phosphorus-based flame retardant and / or a nitrogen-based flame retardant. The laser marking agent is at least one of a phthalocyanine salt, a dioxazine-based, an anthraquinone-based, a perinone-based, carbon black, titanium black, iron oxide black, and surface alkyl-modified silica.

2. The halogen-free flame-retardant ABS material according to claim 1, characterized in that, The laser marking agent is at least one of a phthalocyanine salt, a dioxazine-based, an anthraquinone-based, a perinone-based, carbon black, titanium black, iron oxide black, and surface alkyl-modified silica.

3. The halogen-free flame-retardant ABS material according to claim 1, characterized in that, The laser marking agent is at least one of a phthalocyanine salt, a dioxazine-based, an anthraquinone-based, a perinone-based, carbon black, titanium black, iron oxide black, and surface alkyl-modified silica.

4. The halogen-free flame-retardant ABS material according to claim 1, characterized in that, The laser marking agent is at least one of a phthalocyanine salt, a dioxazine-based, an anthraquinone-based, a perinone-based, carbon black, titanium black, iron oxide black, and surface alkyl-modified silica.

5. The halogen-free flame-retardant ABS material according to claim 1, characterized in that, The laser marking agent is at least one of a phthalocyanine salt, a dioxazine-based, an anthraquinone-based, a perinone-based, carbon black, titanium black, iron oxide black, and surface alkyl-modified silica.

6. The halogen-free flame-retarded ABS material according to claim 1, characterized in that, The laser marking agent is at least one of a phthalocyanine salt, a dioxazine-based, an anthraquinone-based, a perinone-based, carbon black, titanium black, iron oxide black, and surface alkyl-modified silica.

7. The halogen-free flame-retarded ABS material according to claim 1, characterized in that, The laser marking agent is at least one of a phthalocyanine salt, a dioxazine-based, an anthraquinone-based, a perinone-based, carbon black, titanium black, iron oxide black, and surface alkyl-modified silica. The laser marking agent is at least one of a phthalocyanine salt, a dioxazine-based, an anthraquinone-based, a perinone-based, carbon black, titanium black, iron oxide black, and surface alkyl-modified silica.

8. A process for the preparation of a halogen-free flame-retardant ABS material according to any one of claims 1 to 7, characterized in that, The laser marking agent is at least one of a phthalocyanine salt, a dioxazine-based, an anthraquinone-based, a perinone-based, carbon black, titanium black, iron oxide black, and surface alkyl-modified silica.

9. The process for preparing halogen-free flame-retardant ABS material according to claim 8, characterized in that, The laser marking agent is at least one of a phthalocyanine salt, a dioxazine-based, an anthraquinone-based, a perinone-based, carbon black, titanium black, iron oxide black, and surface alkyl-modified silica. The laser marking agent is at least one of a phthalocyanine salt, a dioxazine-based, an anthraquinone-based, a perinone-based, carbon black, titanium black, iron oxide black, and surface alkyl-modified silica. The laser marking agent is at least one of a phthalocyanine salt, a dioxazine-based, an anthraquinone-based, a perinone-based, carbon black, titanium black, iron oxide black, and surface alkyl-modified silica. The laser marking agent is at least one of a phthalocyanine salt, a d

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