An acs composite and its use

Abstract

The application discloses an ACS composite material and application thereof, and belongs to the technical field of high polymer materials. By adding a specific amount of anisotropic silicate and a specific type of bromine-based flame retardant into ACS resin, good laser marking effect is obtained, laser marking color development is good, blackness is high, definition is good, and effect uniformity is good, and black pitting is less, so that the ACS composite material is suitable for being used as a laser marking material and can be used for preparing products with laser marking effect, such as electronic appliances, cosmetic packaging, automobile interior parts and instrument panels, computer keyboards and medical equipment housings.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, specifically relating to an ACS composite material and its applications. Background Technology

[0002] Laser marking technology is widely used in industry due to its advantages such as permanence, anti-counterfeiting, non-contact, wide applicability, high precision, and high processing efficiency. Laser marking utilizes laser radiation to ablate or momentarily heat the surface of a workpiece, causing a color change and thus marking the workpiece.

[0003] Acrylonitrile-vinylchloride-styrene polymer (ACS), developed to address the shortcomings of acrylonitrile-butadiene-styrene (ABS), replaces butadiene with chlorinated polyethylene (CPE), exhibiting excellent weather resistance, aging resistance, flame retardancy, and antistatic properties. It is widely used in electronic, electrical, and telecommunications products, as well as outdoor products such as vehicles, ships, and building materials. However, because ACS lacks easily oxidized double bonds, its color development during laser marking is poor, resulting in very blurry and almost unrecognizable markings. Even with the addition of laser marking agents, the effect remains unsatisfactory, with yellowish markings, rough edges, uneven marking, and black speckles. Currently, there are few literature reports on the use of ACS materials for laser marking; therefore, it is necessary to develop an ACS material with good laser marking performance. Summary of the Invention

[0004] The purpose of this invention is to provide an ACS composite material and its application, which has good laser marking effect, good laser marking color development, high blackness, good clarity, good uniformity of effect, and fewer black spots.

[0005] To achieve the above objectives, the present invention provides an ACS composite material comprising the following components in parts by weight:

[0006] ACS resin 78.5–89.5 parts,

[0007] 5.7–10.3 parts of brominated flame retardant,

[0008] Silicate 2.8–5.2 parts,

[0009] The brominated flame retardant includes at least one of decabromodiphenyl ethane, decabromodiphenyl ether, and bis(tetrabromophenyl o-dicarboximide);

[0010] The aspect ratio of the silicate is 2 to 21.

[0011] The ACS composite material exhibits excellent laser marking performance by adding specific amounts of silicates with specific aspect ratios and specific types of brominated flame retardants to the ACS resin. The laser markings show good color development, high blackness, good clarity, and good uniformity with fewer black specks. The silicates, with their high aspect ratio, readily absorb laser light and convert it into heat energy, promoting the decomposition and carbonization of the brominated flame retardants and ACS resin. Simultaneously, they effectively conduct heat, promoting uniform degradation of the brominated flame retardants and ACS resin, avoiding localized overheating that could lead to specks and reduced clarity. The specific type of brominated flame retardant, possibly containing an ortho-C-Br structure with low bond energy, can be excited, decomposed, and carbonized by laser light (e.g., at a wavelength of 1064 nm), resulting in a darker and clearer mark. Other brominated flame retardants, such as brominated triazine, brominated epoxy, octabromoether, brominated polystyrene, tetrabromobisphenol A, and brominated polycarbonate, produce poorer laser marking results.

[0012] In this application, the aspect ratio of the silicate is 2 to 21, such as 2, 5, 10, 15, 20, 21, etc. The aspect ratio of the silicate can be measured by the following method: After the sample is dried, a scanning electron microscope (SEM) is used to take a magnified image at 400-1000 times. The SEM image is opened using Nano Measurer software, the scale is set, 50 samples are selected from the SEM image of each sample, and their length and diameter are marked by the software. The software automatically generates a measurement report to obtain the average aspect ratio of the sample.

[0013] In this application, the ACS composite material comprises 78.5 to 89.5 parts by weight of ACS resin, such as 79 parts by weight, 80 parts by weight, 82 parts by weight, 84 parts by weight, 86 parts by weight, 88 parts by weight, 89 parts by weight, etc.; comprises 5.7 to 10.3 parts by weight of brominated flame retardant, such as 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, etc.; and comprises 2.8 to 5.2 parts by weight of silicate, such as 3 parts by weight, 4 parts by weight, 5 parts by weight, etc.

[0014] In some embodiments, the mass percentage of ACS resin in the ACS composite material is 75% or more, such as 75%, 78%, 80%, 85%, 90%, 90.8%, etc.

[0015] The mass ratio of the brominated flame retardant to the silicate is (1.1–3.7):1, such as 1.1:1, 1.5:1, 2:1, 3:1, 3.7:1, etc. In some embodiments, the mass ratio of the brominated flame retardant to the silicate is (1.7–2.3):1, such as 1.7:1, 1.8:1, 1.9:1, 2:1, 2.1:1, 2.2:1, 2.3:1, etc., so that the resulting ACS composite material has better laser marking effect, better color rendering effect, higher blackness, and fewer pinholes.

[0016] In some embodiments, the method further includes a silane coupling agent containing at least one of epoxy groups and base groups, the silane coupling agent being coated on the surface of the silicate. Coating the silicate surface with a silane coupling agent containing at least one of epoxy groups and base groups not only improves its compatibility with the resin matrix but also enhances dispersion, preventing silicate agglomeration, resulting in better laser marking and clearer laser markings. Simultaneously, the silane coupling agent can absorb acidic gases such as hydrogen chloride produced by the decomposition of chlorinated polyethylene in ACS resin and hydrogen bromide produced by the decomposition of brominated flame retardants, thus preventing yellowing of the substrate and improving the blackness of the laser marking.

[0017] As an example, the bases include nitrogenous bases. Nitrogenous bases include amino groups, etc.

[0018] As an example, the silane coupling agent includes, but is not limited to, at least one of 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-n-butyl-3-aminopropyltriethoxysilane and anilinemethyltriethoxysilane.

[0019] In some embodiments, the silane coupling agent is 0.03 to 0.5 parts by weight, such as 0.03 parts by weight, 0.05 parts by weight, 0.1 parts by weight, 0.3 parts by weight, or 0.5 parts by weight, to obtain better laser marking effect. In one embodiment, the silane coupling agent is 0.08 to 0.2 parts by weight, such as 0.08 parts by weight, 0.11 parts by weight, 0.13 parts by weight, 0.15 parts by weight, 0.17 parts by weight, 0.19 parts by weight, or 0.2 parts by weight, to further improve the laser marking effect and increase the blackness of the marking.

[0020] In some embodiments, a method for preparing silicates with surfaces coated with coupling agents includes the following steps: mixing silicates and coupling agents to obtain silicates with surfaces modified with coupling agents.

[0021] In some embodiments, the silicate has a layered, acicular, and / or columnar structure. Silicates with a layered structure include, but are not limited to, at least one of talc, mica, and montmorillonite; silicates with a acicular and / or columnar structure include, but are not limited to, wollastonite.

[0022] In one embodiment, the silicate includes at least one of talc, mica, wollastonite, and montmorillonite.

[0023] In some embodiments, the silicate particle size Dv50 is 1-50 μm, such as talc powder particles with a Dv50 of 1-50 μm, mica powder particles with a Dv50 of 5-50 μm, wollastonite powder particles with a Dv50 of 2-20 μm, and montmorillonite particles with a Dv50 of 5-30 μm.

[0024] The particle size Dv50 of the silicate can be measured using a laser particle size analyzer according to GB / T 19077-2016.

[0025] In some embodiments, the melt flow rate of the ACS resin under test conditions of 220°C and 10kg is 4.5–51 g / 10min, such as 5 g / 10min, 8 g / 10min, 10 g / 10min, 15 g / 10min, 20 g / 10min, 25 g / 10min, 30 g / 10min, 35 g / 10min, 40 g / 10min, 45 g / 10min, and 50 g / 10min. In this embodiment, the ACS composite material exhibits good laser marking effect, with good color development, high blackness, good clarity, and few black specks. The melt flow rate of the ACS resin was measured according to standard ISO 1133-1-2022.

[0026] In some embodiments, the ACS resin contains 10%-40% acrylonitrile by mass; 15%-40% chlorinated polyethylene by mass; and 20%-75% styrene by mass.

[0027] In one embodiment, the product further comprises the following components in parts by weight: 2.8 to 5.2 parts of flame retardant synergist, 0.08 to 0.52 parts of anti-dripping agent, and 0.01 to 2.1 parts by weight of other additives. The flame retardant synergist includes, but is not limited to, antimony compounds, including, but not limited to, at least one of antimony trioxide, colloidal antimony pentoxide, sodium antimonate, antimony trichloride, antimony pentachloride, antimony phosphite, antimony polyphosphate, and complexed antimony; the anti-dripping agent includes, but is not limited to, polytetrafluoroethylene; other additives include, but are not limited to, at least one of antioxidants, lubricants, weathering agents, and colorants, the antioxidants including, but not limited to, hindered phenolic antioxidants and phosphite esters, preferably with a weight ratio of hindered phenolic antioxidants to phosphite esters of 1:(1-3); the lubricant includes, but is not limited to, at least one of amide lubricants, stearate lubricants, ester lubricants, and silicone lubricants; the weathering agent includes, but is not limited to, at least one of benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, and hindered amine light stabilizers; the colorant includes, but is not limited to, at least one of pigment-type, dye-type, and other colorants with special aesthetic effects.

[0028] In one embodiment, the method for preparing the ACS composite material includes the following steps:

[0029] All raw materials except silicates are mixed according to the specified proportions to obtain a mixture;

[0030] The composition is added through the main feed port of the screw extruder, and the silicate is added through the side feed port of the screw extruder. The mixture is melted, extruded, granulated, and dried to obtain the ACS composite material.

[0031] The screw extruder includes, but is not limited to, a twin-screw extruder. In one specific embodiment, when preparing the mixture, all component raw materials except silicate are mixed in a high-speed mixer for 5-10 minutes. In one specific embodiment, silicate is added through the side feed port of the sixth zone of the screw extruder.

[0032] In one specific embodiment, the screw temperature of each section of the screw extruder is controlled within the range of 180 to 220°C, the length-to-diameter ratio of the screw extruder is 30 to 45:1, and the screw speed is 200 to 800 rpm.

[0033] This application also provides the application of the ACS composite material in laser-markable materials. The ACS composite material can be used as a laser marking material and can be used to prepare products with laser marking effects, such as electronic appliances, cosmetic packaging, automotive interior parts and dashboards, computer keyboards, and medical device housings.

[0034] Compared with the prior art, the beneficial effects of this application are as follows: This application has a good laser marking effect by adding a specific amount of silicate and a specific type of bromine flame retardant to ACS resin. The laser marking has good color development, high blackness, good clarity, good uniformity, and fewer black spots. It is suitable as a laser marking material and can be used to prepare products with laser marking effects such as electronic appliances, cosmetic packaging, automotive interior parts and dashboards, computer keyboards and medical equipment shells. Detailed Implementation

[0035] To better illustrate the purpose, technical solution, and advantages of this invention, the invention will be further described below with reference to specific embodiments and comparative examples. The purpose of this description is to provide a detailed understanding of the invention, not to limit its scope. All other embodiments obtained by those skilled in the art without inventive effort are within the protection scope of this invention. Unless otherwise specified, the experimental reagents and instruments involved in the implementation of this invention are commonly used reagents and instruments.

[0036] Examples and Comparative Examples

[0037] Each embodiment and comparative example provides an ACS composite material, the composition of which is shown in Tables 1-3, and the preparation method includes the following steps:

[0038] All raw materials, except silicates or silicates coated with silane coupling agents, are mixed in a high-speed mixer for 8 minutes according to the specified proportions to obtain a mixture.

[0039] The above composition is added through the main feed port of a twin-screw extruder. Silicates or silicates coated with a silane coupling agent are added through the sixth-zone side feed port of the twin-screw extruder. The screw temperature of each section of the extruder is controlled between 180 and 220°C. The length-to-diameter ratio of the twin-screw extruder is 40:1, and the screw speed is 200-400 rpm. Under the shearing, mixing, and conveying action of the screws, the materials are fully melted and compounded. After extrusion granulation and drying, the ACS material is obtained. The preparation method of silicates coated with a silane coupling agent includes the following steps: mixing silicates and a silane coupling agent in a high-speed mixer for 8 minutes to obtain silicates coated with a silane coupling agent. Unless otherwise specified, the steps and process parameters of each embodiment and comparative example are the same.

[0040] The component information used in the above embodiments and comparative examples is as follows:

[0041] ACS Resin 1: Melt flow rate of 5 g / 10 min, ACS-3005, Liaoning Kingfa Science & Technology Co., Ltd.;

[0042] ACS Resin 2: Melt flow rate of 21 g / 10 min, high impact grade ACS, Ningbo Zhenyang Chemical Development Co., Ltd.

[0043] ACS Resin 3: Melt flow rate of 50 g / 10 min, ACS-2050, Liaoning Kingfa Science & Technology Co., Ltd.

[0044] Bromine-based flame retardant 1: Decabromodiphenyl ethane, 8010, Albemarle Chemicals, USA;

[0045] Bromine-based flame retardant 2: Decabromodiphenyl ether, 102E, Albemarle Chemicals, USA;

[0046] Brominated flame retardant 3: Ethyl-bis(tetrabromophenyl o-dicarboximide), BT-93, Albemarle Chemicals, USA;

[0047] Bromine-based flame retardant 4: Tris(tribromophenoxy)triazine, FR-245, Dead Sea Bromine Company, Israel;

[0048] Silicate 1: Wollastonite powder, aspect ratio in the range of 15-20, particle size Dv50 of 3μm, GY-4000, Jiangxi Guangyuan Chemical Co., Ltd.;

[0049] Silicate 2: Wollastonite powder, aspect ratio = 9, particle size Dv50 is 5.9μm, WFC5-4101, Hubei Fengjiashan Silicon Fiber Co., Ltd.;

[0050] Silicate 3: Wollastonite powder, aspect ratio = 2.5, particle size Dv50 is 8μm, NYAD MD 400, Shanghai Huazhongrong Industry & Trade Co., Ltd.;

[0051] Silicate 4: Talc, aspect ratio = 5, particle size Dv50 is 1.3μm, HTP05L, IMIFABI, Italy;

[0052] Silicate 5: Mica powder, aspect ratio = 8, particle size Dv50 is 45μm, mica powder - P325 mesh, Jiangmen Jingda Mica Materials Co., Ltd.;

[0053] Silicate 6: Montmorillonite, aspect ratio = 2, particle size Dv50 is 16μm, I.44P, Nanocor Corporation, USA;

[0054] Silicate 7: Spherical boron, sodium, and calcium silicate, aspect ratio = 1, particle size Dv50 is 1.8μm, R-80, Guangdong Chuangna New Materials Co., Ltd.;

[0055] Silicate 8: Spherical boron, sodium, and calcium silicate, aspect ratio = 1, particle size Dv50 is 35μm, N48, Zhongke Huaxing New Materials Co., Ltd.;

[0056] Silicate 9: Spherical boron, sodium, and calcium silicate, aspect ratio = 1, particle size Dv50 is 55μm, N24, Zhongke Huaxing New Materials Co., Ltd.;

[0057] Barium sulfate: AB-3000N1, aspect ratio = 1, particle size Dv50 is 1.5μm, Heshan Chemical Co., Ltd.;

[0058] Silane coupling agent 1: 3-glycidyl etheroxypropyltrimethoxysilane, JH-O187, Hubei Jianghan New Material Co., Ltd.;

[0059] Silane coupling agent 2: 3-aminopropyltriethoxysilane, JH-A110, Hubei Jianghan New Material Co., Ltd.;

[0060] Silane coupling agent 3: N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, JH-A112, Hubei Jianghan New Material Co., Ltd.;

[0061] Silane coupling agent 4: N-n-butyl-3-aminopropyltriethoxysilane, JH-A1151, Hubei Jianghan New Material Co., Ltd.;

[0062] Silane coupling agent 5: Aniline methyltriethoxysilane, UP-73, Nanjing Youpu Chemical Co., Ltd.;

[0063] Other coupling agents: titanate coupling agent, TMC-931, Tianchang Green Chemical Additives Factory;

[0064] Flame retardant synergist: Antimony trioxide;

[0065] Anti-dripping agent: polytetrafluoroethylene;

[0066] Antioxidant: A mixture of hindered phenolic antioxidant 1010 and phosphite antioxidant 168, in a mass ratio of 1:2;

[0067] Lubricant: Ethylene bis-stearamide (EBS);

[0068] Colorant: Titanium dioxide.

[0069] When the ACS composite materials of the examples and comparative examples contain both silicates and coupling agents, these coupling agents are used to surface-coat the corresponding silicates, i.e., to prepare silicates with surfaces coated with coupling agents.

[0070] The melt flow rates of ACS resins 1 to 3 were measured according to standard ISO 1133-1-2022, under the following conditions: 220℃ and a load of 10kg.

[0071] Unless otherwise specified, all components and raw materials used in the embodiments and comparative examples of this application are commercially available, and the same type of components and raw materials are used in each parallel experiment.

[0072] The performance of the ACS composite materials obtained in each embodiment and comparative example was tested using the following test methods:

[0073] The laser marking uses the TFL-M20 semiconductor-pumped fiber laser marking system manufactured by Teder Laser, with a laser wavelength of 1064nm, a laser power of 20W, a frequency of 40KHz, and a speed of 1000mm / s.

[0074] (1) Blackness of laser marking: A 30×30mm square area is marked with a laser. The color difference meter (UltraScan XE type, produced by Hunter Lab, USA) is used to test the color change of the square marking area and record the △L value to characterize the blackness of the laser marking (the higher the better).

[0075] (2) Clarity and pitting of laser markings: The laser markings were magnified using a two-dimensional microscope, and the edge lines were visually inspected. The clarity was categorized as good, medium, or poor based on the severity of jagged protrusions or defects in the edge lines. A 0.25cm sample was randomly selected from the center of the laser marking. 2 For each area, magnify it using a 2D method and count the number of pits with a diameter greater than or equal to 0.2mm. Fewer than 3 pits are good, 3-10 are medium, and more than 10 pits are poor.

[0076] Acceptance requirements: ΔL value ≥ 40, clarity rating is medium or good, and noise level rating is medium or good.

[0077] The test results are shown in Table 4.

[0078] Table 1

[0079]

[0080] Table 2

[0081]

[0082]

[0083] Table 3

[0084]

[0085]

[0086] Table 4

[0087]

[0088]

[0089] As shown in Table 4, the ACS composite materials obtained in each embodiment of this application have good laser marking effect, good laser marking color development, ΔL value above 40, and medium or good clarity and pitting. They are suitable for preparing products with laser marking effect such as electronic appliances, cosmetic packaging, automotive interior parts and dashboards, computer keyboards and medical equipment shells. In particular, when the mass ratio of bromine flame retardant to silicate is in the range of (1.7 to 2.3):1, the laser marking color development is better, the blackness is higher, and there are fewer pits.

[0090] Comparative Examples 1 and 2, due to the absence of brominated flame retardants or the use of non-specific brominated flame retardants, resulted in lower blackness and poorer clarity of the laser markings.

[0091] Comparative Examples 3-5 used spherical silicates with a low aspect ratio, which is not conducive to heat conduction. This leads to uneven degradation of the flame retardant and ACS resin, local overheating, and problems such as decreased clarity.

[0092] Comparative Example 6 used barium sulfate, which did not significantly improve the laser marking effect. The laser marking had low blackness, poor clarity, and many pits.

[0093] Comparative Example 7, lacking silicates, is not conducive to the decomposition and carbonization of flame retardants and ACS resin, as well as heat conduction, resulting in lower blackness, poorer clarity, and more pitting in the laser markings.

[0094] In Comparative Example 8, excessive silicate was used. Due to the large polarity difference between inorganic materials and the ACS organic matrix, silicate easily agglomerates and disperses unevenly during processing, resulting in pitting. At the same time, it also prevents the heat from being effectively and evenly conducted during the laser marking process, preventing the ACS from being uniformly carbonized, thus reducing blackness and resulting in poor clarity.

[0095] A comparison of Examples 15 with Examples 2 and 16-24 shows that modification of the silicate surface with a silane coupling agent containing at least one of epoxy groups and base groups can improve the laser marking effect. However, when the silicate surface is modified with a small amount of silane coupling agent containing at least one of epoxy groups and base groups, the improvement in the laser marking effect is low because the silane coupling agent is insufficient to wet the silicate. When the silicate surface is modified with a large amount of silane coupling agent containing at least one of epoxy groups and base groups, the high reactivity of siloxanes makes them prone to condensation when their content is high, reducing the probability of their combination with silicate and thus reducing the improvement in the laser marking effect. Therefore, it is preferable to use 0.08-0.2 parts by weight of silicate and silane coupling agent containing at least one of epoxy groups and base groups to obtain a better laser marking effect.

[0096] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. An ACS composite material, characterized by, The ACS composite material comprises the following components by weight: ACS resin 78.5~89.5 parts, Bromine-based flame retardant 5.7~10.3 parts, Silicate 2.8~5.2 parts, The bromine-based flame retardant comprises at least one of decabromodiphenyl ethane, decabromodiphenyl ether and bis(tetrabromophthalimide); The silicate has an aspect ratio of 2~21.

2. The ACS composite of claim 1, wherein, The mass ratio of the bromine-based flame retardant to the silicate is (1.7~2.3):

1.

3. The ACS composite of claim 1, wherein, A silane coupling agent containing at least one of an epoxy group and a base group is further included, and the silane coupling agent is coated on the surface of the silicate.

4. The ACS composite of claim 3, wherein, The silane coupling agent is 0.03~0.5 parts by weight.

5. The ACS composite of claim 3, wherein, The silane coupling agent comprises at least one of 3-glycidyloxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-n-butyl-3-aminopropyltriethoxysilane and anilinomethyltriethoxysilane.

6. The ACS composite of claim 1, wherein, The silicate has a layered, needle-like and / or columnar structure.

7. The ACS composite of claim 6, wherein, The silicate comprises at least one of talc powder, mica powder, wollastonite powder and montmorillonite.

8. The ACS composite of claim 1, wherein, The ACS resin has a melt flow rate of 4.5~51 g / 10 min under a test condition of 220℃ and a load of 10 kg.

9. The ACS composite of claim 1, wherein, Further components by weight include: flame retardant synergist 1.8~4.2 parts, anti-dripping agent 0.08~0.52 parts, and other auxiliary agents 0.01~2.1 parts; the other auxiliary agents comprise at least one of an antioxidant, a lubricant, a weather-resistant agent and a coloring agent.

10. Use of the ACS composite material according to any one of claims 1~9 in laser markable materials.

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